JP7450218B2 - Cross-linked polysiloxane adhesive - Google Patents

Description

The present invention relates to crosslinked polysiloxane adhesives.

While general adhesives harden and exhibit adhesive properties due to solvent volatilization or chemical reactions, hot melt adhesives can be bonded through a cycle of heating, melting, and cooling to solidify, and can complete bonding in a short time. . Hot melt adhesives are generally composed of olefin-based polyesters, ethylene vinyl acetate copolymers (EVA), synthetic rubbers, polyamides, urethane-based polymers, and the like as main components.
In general, linear siloxane polymers have good wettability to substrates with low surface free energy and excellent heat resistance, but they are oil or wax-like and have very weak adhesive strength, so they are not used as adhesives. When used, adhesion has been achieved by modifying the terminals of the siloxane polymer and actively crosslinking it by, for example, hydrosilylation reaction using vinyl groups and silane, urethanization reaction using isocyanate and alcoholic hydroxyl groups, moisture curing, etc.

As the silicone adhesive, for example, Patent Document 1 describes (A) 100 parts by weight of a heat-curable organopolysiloxane composition, (B) 1 to 100 parts by weight of reinforcing fine silica powder, and (C) adhesive properties. A silicone rubber adhesive composition for a moving object is disclosed, which contains 0.1 to 50 parts by weight of an imparting component.
Furthermore, Patent Document 2 discloses that the reactivity exhibits good gap-filling properties even in low-pressure thermocompression bonding to adherends with large surface irregularities, and hardens to firmly adhere to the adherends. The objective is to provide a hot-melt silicone adhesive, (A) an organopolysiloxane resin with a softening point of 40 to 250°C, (B) an alkenyl group-containing organopolysiloxane that is liquid or rubber-like at 25°C, ( C) (i) an organopolysiloxane containing a silicon-bonded hydrogen atom and (ii) an organosilicon compound containing a silicon-bonded alkoxy group, or (iii) an organopolysiloxane containing a silicon-bonded hydrogen atom and a silicon-bonded alkoxy group; A hot-melt silicone adhesive has been proposed that comprises at least (D) a hydrosilylation reaction catalyst and (E) a hydrosilylation reaction inhibitor.

On the other hand, the present inventors have developed a siloxane polymer having a structure in which a cage-shaped bifunctional silsesquioxane derived from a double-decker silsesquioxane and a linear siloxane are bonded, and whose glass transition temperature is 30°C. We have developed an adhesive containing a siloxane polymer that has a temperature of 200°C or less. This adhesive is a hot-melt polysiloxane adhesive that does not use a crosslinking agent and can be reversibly attached and detached by heating.

Japanese Patent Application Publication No. 2004-331820 Japanese Patent Application Publication No. 2006-274007 Japanese Patent Application Publication No. 2019-044107

An object of the present invention is to provide a polysiloxane adhesive that can be irreversibly bonded.

The present inventors have developed a siloxane polymer containing a silicon-bonded hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or alkyne, by siloxane crosslinking at the hydrogen atom or at the terminal alkene or alkyne. The present invention was completed based on the discovery that an irreversibly bondable adhesive can be obtained by reacting an adhesive and performing a crosslinking reaction.

Ｒ^０は、独立して、炭素数６～２０のアリール又は炭素数５～６のシクロアルキルを表し、前記炭素数６～２０のアリール及び前記炭素数５～６のシクロアルキルは、任意の水素原子が独立してフッ素原子又は炭素数１～２０のアルキルで置き換えられてもよく；
Ｒ^１は、独立して、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、又は炭素数１～４０のアルキルを表し、前記炭素数６～２０のアリール、前記炭素数５～６のシクロアルキル及び前記炭素数７～４０のアリールアルキル中のアリールは、任意の水素原子が独立してフッ素原子又は炭素数１～２０のアルキルで置き換えられてもよく、前記炭素数７～４０のアリールアルキル中のアルキレンは、任意の水素原子がフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－、－ＣＨ＝ＣＨ－、又は炭素数５～２０のシクロアルキレンで置き換えられてもよく、前記炭素数１～４０のアルキルは、任意の水素原子が独立してフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－又は炭素数５～２０のシクロアルキレンで置き換えられてもよく；
Ｒ²は、独立して、水素原子または末端アルケンもしくは末端アルキンを含む炭素数２～４０の脂肪族炭化水素基、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、又は炭素数１～４０のアルキルを表し、少なくとも１つが水素原子または末端アルケンもしくは末端アルキンを含む炭素数２～４０の脂肪族炭化水素基であり、
前記末端アルケンもしくは末端アルキンを含む炭素数２～４０の脂肪族炭化水素基は、任意の水素原子がフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－で置き換えられてもよく、
前記炭素数６～２０のアリール、前記炭素数５～６のシクロアルキル及び前記炭素数７～４０のアリールアルキル中のアリールは、任意の水素原子が独立してフッ素原子又は炭素数１～２０のアルキルで置き換えられてもよく、前記炭素数７～４０のアリールアルキル中のアルキレンは、任意の水素原子がフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－、－ＣＨ＝ＣＨ－、又は炭素数５～２０のシクロアルキレンで置き換えられてもよく、前記炭素数１～４０のアルキルは、任意の水素原子が独立してフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－又は炭素数５～２０のシクロアルキレンで置き換えられてもよく、
ｘは１～３０の整数を表し、ｍが重量平均分子量２，０００～１０，０００，０００を満たす数字を表す。
［２］シロキサンポリマー（Ａ）の構成単位－（OSi（R²）₂）_ｘ－は、下記の構成単位（I-1）と構成単位（I-2）を含む、［１］に記載の接着剤。

（I-1）

（I-2）
Ｒ²¹は、独立して、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、又は炭素数１～４０のアルキルを表し、
前記炭素数６～２０のアリール、前記炭素数５～６のシクロアルキル及び前記炭素数７～４０のアリールアルキル中のアリールは、任意の水素原子が独立してフッ素原子又は炭素数１～２０のアルキルで置き換えられてもよく、前記炭素数７～４０のアリールアルキル中のアルキレンは、任意の水素原子がフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－、－ＣＨ＝ＣＨ－、又は炭素数５～２０のシクロアルキレンで置き換えられてもよく、前記炭素数１～４０のアルキルは、任意の水素原子が独立してフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－又は炭素数５～２０のシクロアルキレンで置き換えられてもよい。
Ｒ²²は、水素原子または末端アルケンもしくは末端アルキンを含む炭素数２～４０の脂肪族炭化水素基を表し、
前記末端アルケンもしくは末端アルキンを含む炭素数２～４０の脂肪族炭化水素基は、任意の水素原子がフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－で置き換えられてもよい。
［３］Ｒ⁰が独立してフェニル又はシクロヘキシルを表し、
Ｒ¹が独立してメチル又はフェニルを表し、
Ｒ^２1が独立してメチル又はフェニルを表し、
Ｒ^２２が独立して水素、ビニル又はアリルを表す、
［２］に記載の接着剤。
［４］下記シロキサンポリマー（Ａ’）であって末端に置換基（II）を有するシロキサン
ポリマー（Ａ’）およびシロキサン架橋剤（Ｂ）を含む接着剤であって、置換基（II）がＲ^４として水素原子を含むときはシロキサン架橋剤（Ｂ）は末端アルケンまたはアルキンを含む炭素数２～４０の脂肪族炭化水素基を２つ以上含むシロキサン化合物であり、置換基（II）がＲ^４として末端アルケンまたはアルキンを含む炭素数２～４０の脂肪族炭化水素基を含むときはシロキサン架橋剤（Ｂ）はＳｉＨ基を２つ以上含むシロキサン化合物である、接着剤。

（II）
Ｒ^０は、独立して、炭素数６～２０のアリール又は炭素数５～６のシクロアルキルを表し、前記炭素数６～２０のアリール及び前記炭素数５～６のシクロアルキルは、任意の水素原子が独立してフッ素原子又は炭素数１～２０のアルキルで置き換えられてもよく；
Ｒ^１は、独立して、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、又は炭素数１～４０のアルキルを表し、前記炭素数６～２０のアリール、前記炭素数５～６のシクロアルキル及び前記炭素数７～４０のアリールアルキル中のアリールは、任意の水素原子が独立してフッ素原子又は炭素数１～２０のアルキルで置き換えられてもよく、前記炭素数７～４０のアリールアルキル中のアルキレンは、任意の水素原子がフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－、－ＣＨ＝ＣＨ－、又は炭素数５～２０のシクロアルキレンで置き換えられてもよく、前記炭素数１～４０のアルキルは、任意の水素原子が独立してフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－又は炭素数５～２０のシクロアルキレンで置き換えられてもよく；
Ｒ^2１は、独立して、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、又は炭素数１～４０のアルキルを表し、
前記炭素数６～２０のアリール、前記炭素数５～６のシクロアルキル及び前記炭素数７～４０のアリールアルキル中のアリールは、任意の水素原子が独立してフッ素原子又は炭素数１～２０のアルキルで置き換えられてもよく、前記炭素数７～４０のアリールアルキル中のアルキレンは、任意の水素原子がフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－、－ＣＨ＝ＣＨ－、又は炭素数５～２０のシクロアルキレンで置き換えられてもよく、前記炭素数１～４０のアルキルは、任意の水素原子が独立してフッ素
原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－又は炭素数５～２０のシクロアルキレンで置き換えられてもよい。
Ｒ^４は独立して、水素原子または末端アルケンもしくは末端アルキンを含む炭素数２～４０の脂肪族炭化水素基、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、又は炭素数１～４０のアルキルを表し、少なくとも１つが水素原子または末端アルケンもしくは末端アルキンを含む炭素数２～４０の脂肪族炭化水素基であり、
前記末端アルケンもしくは末端アルキンを含む炭素数２～４０の脂肪族炭化水素基は、任意の水素原子がフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－で置き換えられてもよく、
前記炭素数６～２０のアリール、前記炭素数５～６のシクロアルキル及び前記炭素数７～４０のアリールアルキル中のアリールは、任意の水素原子が独立してフッ素原子又は炭素数１～２０のアルキルで置き換えられてもよく、前記炭素数７～４０のアリールアルキル中のアルキレンは、任意の水素原子がフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－、－ＣＨ＝ＣＨ－、又は炭素数５～２０のシクロアルキレンで置き換えられてもよく、前記炭素数１～４０のアルキルは、任意の水素原子が独立してフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－又は炭素数５～２０のシクロアルキレンで置き換えられてもよく、
ｘは１～３０の整数を表し、ｍが重量平均分子量２，０００～１０，０００，０００を満たす数字を表す。
［５］シロキサン架橋剤（Ｂ）が（III）または（IV）である、［１］～［４］のいずれかに記載の接着剤。

（III）

（IV）
Ｒ⁵は、独立して、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、又は炭素数１～４０のアルキルを表し、前記炭素数６～２０のアリール、前記炭素数５～６のシクロアルキル及び前記炭素数７～４０のアリールアルキル中のアリールは、任意の水素原子が独立してフッ素原子又は炭素数１～２０のアルキルで置き換えられてもよく、前記炭素数７～４０のアリールアルキル中のアルキレンは、任意の水素原子がフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－、－ＣＨ＝ＣＨ－、又は炭素数５～２０のシクロアルキレンで置き換えられてもよく、前記炭素数１～４０のアルキルは、任意の水素原子が独立してフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－又は炭素数５～２０のシクロアルキレンで置き換えられてもよく；
Ｒ⁶は、独立して、水素原子または末端アルケンもしくは末端アルキンを含む炭素数２～４０の脂肪族炭化水素基を表し、前記末端アルケンあるいはアルキンを含む炭素数２～４
０のアルキル任意の水素原子がフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－で置き換えられてもよく；
ｐは０～３０の整数を表し、ｑは２～３０の整数を表す。
［６］Ｒ⁵が独立して、メチル又はフェニルを表し、Ｒ⁶が独立して、水素、ビニル又はアリルを表す、［５］に記載の接着剤。
［７］さらに溶剤を含む、［１］～［６］のいずれかに記載の接着剤。
［８］さらに触媒を含む、［１］～［７］のいずれかに記載の接着剤。
［９］ガラス基板、金属酸化物基板、セラミック基板、プラスチックフィルム、フッ素樹脂基板、フッ素樹脂積層基板、金属基板、シリコンウェハに接着可能である、［１］～［８］のいずれかに記載に記載の接着剤。
［１０］引張せん断強度が１ＭＰa以上である、［１］～［９］のいずれかに記載の接着剤。 That is, the embodiment of the present invention includes the following configuration.
[1] An adhesive containing the following siloxane polymer (A) and siloxane crosslinking agent (B), and when the siloxane polymer (A) contains a hydrogen atom as ^R2 , the siloxane crosslinking agent (B) is a terminal alkene or alkyne. is a siloxane compound containing two or more aliphatic hydrocarbon groups having 2 to 40 carbon atoms, including a siloxane polymer (A) containing an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or alkyne as ^R2 . When included, the siloxane crosslinking agent (B) is a siloxane compound containing two or more SiH groups.

R ⁰ independently represents an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms, and the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms are any hydrogen Atom may be independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms;
R ¹ independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms; 20 aryl, the cycloalkyl having 5 to 6 carbon atoms, and the aryl in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- , or cycloalkylene having 5 to 20 carbon atoms, and in the alkyl having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms;
R ² is independently a hydrogen atom or a C2-40 aliphatic hydrocarbon group containing a terminal alkene or terminal alkyne, a C6-20 aryl, a C5-6 cycloalkyl, a C7 ~40 arylalkyl, or an alkyl having 1 to 40 carbon atoms, at least one of which is a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne,
In the aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-. It's okay to be beaten,
In the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently a fluorine atom or a fluorine atom or a carbon atom. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH-, or cycloalkylene having 5 to 20 carbon atoms may be substituted, and any hydrogen atom of the alkyl having 1 to 40 carbon atoms may be independently replaced with a fluorine atom, or any -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms,
x represents an integer from 1 to 30, and m represents a number satisfying a weight average molecular weight of 2,000 to 10,000,000.
[2] The structural unit -(OSi(R ² ) ₂ ) _x - of the siloxane polymer (A) includes the following structural unit (I-1) and structural unit (I-2), as described in [1]. glue.

(I-1)

(I-2)
R ²¹ independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms;
In the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently a fluorine atom or a fluorine atom or a aryl having 1 to 20 carbon atoms. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH-, or cycloalkylene having 5 to 20 carbon atoms may be substituted, and any hydrogen atom of the alkyl having 1 to 40 carbon atoms may be independently replaced with a fluorine atom, or any -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms.
R ²² represents a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne;
In the aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-. It's okay to be hit.
[3] R ⁰ independently represents phenyl or cyclohexyl,
R ¹ independently represents methyl or phenyl;
R ²¹ independently represents methyl or phenyl;
^R22 independently represents hydrogen, vinyl or allyl,
The adhesive according to [2].
[4] An adhesive comprising the following siloxane polymer (A') having a substituent (II) at the terminal and a siloxane crosslinking agent (B), wherein the substituent (II) is R When the siloxane crosslinking agent (B) contains a hydrogen atom as ⁴ , the siloxane crosslinking agent (B) is a siloxane compound containing two or more aliphatic hydrocarbon groups having 2 to 40 carbon atoms containing a terminal alkene or alkyne, and the substituent (II) is R ⁴ When the adhesive contains an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or alkyne, the siloxane crosslinking agent (B) is a siloxane compound containing two or more SiH groups.

(II)
R ⁰ independently represents an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms, and the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms are any hydrogen Atom may be independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms;
R ¹ independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms; 20 aryl, the cycloalkyl having 5 to 6 carbon atoms, and the aryl in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- , or cycloalkylene having 5 to 20 carbon atoms, and in the alkyl having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms;
R ²¹ independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms;
In the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently a fluorine atom or a fluorine atom or a carbon atom. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- or cycloalkylene having 5 to 20 carbon atoms may be substituted, and any hydrogen atom of the alkyl having 1 to 40 carbon atoms may be independently replaced with a fluorine atom; -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms.
R ⁴ is independently a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or alkyne, an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, or a cycloalkyl group having 7 to 6 carbon atoms. 40 arylalkyl or alkyl having 1 to 40 carbon atoms, at least one of which is a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne,
In the aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-. It's okay to be beaten,
In the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently a fluorine atom or a fluorine atom or a carbon atom. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- or cycloalkylene having 5 to 20 carbon atoms may be substituted, and any hydrogen atom of the alkyl having 1 to 40 carbon atoms may be independently replaced with a fluorine atom; -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms,
x represents an integer from 1 to 30, and m represents a number satisfying a weight average molecular weight of 2,000 to 10,000,000.
[5] The adhesive according to any one of [1] to [4], wherein the siloxane crosslinking agent (B) is (III) or (IV).

(III)

(IV)
R ⁵ independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms; 20 aryl, the cycloalkyl having 5 to 6 carbon atoms, and the aryl in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- , or cycloalkylene having 5 to 20 carbon atoms, and in the alkyl having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms;
R ⁶ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or alkyne;
0 alkyl Any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-;
p represents an integer from 0 to 30, and q represents an integer from 2 to 30.
[6] The adhesive according to [5], wherein R ⁵ independently represents methyl or phenyl, and R ⁶ independently represents hydrogen, vinyl, or allyl.
[7] The adhesive according to any one of [1] to [6], further comprising a solvent.
[8] The adhesive according to any one of [1] to [7], further comprising a catalyst.
[9] According to any one of [1] to [8], which can be bonded to a glass substrate, a metal oxide substrate, a ceramic substrate, a plastic film, a fluororesin substrate, a fluororesin laminated substrate, a metal substrate, or a silicon wafer. Adhesives listed.
[10] The adhesive according to any one of [1] to [9], which has a tensile shear strength of 1 MPa or more.

The present invention provides adhesives that are irreversibly bondable with high tensile shear strength.

Hereinafter, embodiments of the present invention will be described in detail, but the following description is an example (representative example) of the embodiments of the present invention, and the present invention is not limited to these contents at all. Furthermore, the embodiments of the present invention can be combined as appropriate.
Note that the terms used in this specification are defined as follows. Alkyl and alkylene may be either straight-chain groups or branched groups. This means that even if any hydrogen in these groups is replaced with a halogen or cyclic group, any -CH ₂ - can be replaced with -O-, -CH=CH-, cycloalkylene, cycloalkenylene, phenylene. The same applies if it is replaced with etc. "Arbitrary" as used in the present invention indicates that not only the position but also the number is arbitrary. When there is a plurality of groups, each group may be replaced with a different group. For example, when two -CH ₂ - groups in alkyl are replaced by -O- and -CH=CH-, it indicates alkoxyalkenyl or alkenyloxyalkyl. Any of the alkoxy, alkenylene, alkenyl, and alkylene groups in this case may be a straight chain group or a branched group. However, when describing that any -CH ₂ - is replaced with -O-, a plurality of consecutive -CH ₂ -s are not replaced with -O-. That is, for example, -CH ₂ -CH ₂ - is never replaced by -OO-.

The adhesive of the present invention is an adhesive containing the following siloxane polymer (A) and siloxane crosslinking agent (B), and when the siloxane polymer (A) contains a hydrogen atom as ^R2 , the siloxane crosslinking agent (B) is an adhesive at the terminal. A siloxane compound containing two or more aliphatic hydrocarbon groups having 2 to 40 carbon atoms containing an alkene or alkyne, in which the siloxane polymer (A) is an aliphatic carbonization group having 2 to 40 carbon atoms containing a terminal alkene or alkyne as ^R2 . When containing hydrogen groups, the siloxane crosslinking agent (B) is an adhesive that is a siloxane compound containing two or more SiH groups.

Siloxane polymer (A)
The siloxane polymer (A) is characterized by containing a repeating unit represented by the following formula.

In formula (A),
R ⁰ independently represents an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms, and the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms are any hydrogen Atom may be independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms;
R ¹ independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms; 20 aryl, the cycloalkyl having 5 to 6 carbon atoms, and the aryl in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- , or cycloalkylene having 5 to 20 carbon atoms, and in the alkyl having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms;
R ² is each independently a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or alkyne, aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, or represents arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms, at least one of which is a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne;
In the aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-. In the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may independently be a fluorine atom or a carbon atom. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with an alkyl having 1 to 20 carbon atoms. It may be substituted with -O-, -CH=CH-, or cycloalkylene having 5 to 20 carbon atoms, and the alkyl having 1 to 40 carbon atoms may be substituted with any hydrogen atom independently replaced with a fluorine atom. and any -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms;
x represents an integer from 1 to 30, and m represents a number satisfying a weight average molecular weight of 2,000 to 10,000,000.

(R ⁰ )
R ⁰ independently represents aryl having 6 to 20 carbon atoms or cycloalkyl having 5 to 6 carbon atoms.
Examples of the aryl having 6 to 20 carbon atoms include phenyl, naphthyl, anthryl, phenanthryl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, perylenyl, and the like. Among these, phenyl, naphthyl, anthryl, and phenanthryl are preferred, and phenyl, naphthyl, and anthryl are more preferred.
Examples of cycloalkyl having 5 to 6 carbon atoms include cyclopentyl and cyclohexyl.
Any hydrogen atom in the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms may be independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms.
R ⁰ is preferably phenyl or cyclohexyl.

(R ¹ )
R ¹ independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms.
Aryl having 6 to 20 carbon atoms and cycloalkyl having 5 to 6 carbon atoms include the same ones as explained for R ⁰ .
Examples of the arylalkyl having 7 to 40 carbon atoms include benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4- Examples include phenylbutyl and 5-phenylpentyl.
Examples of alkyl having 1 to 40 carbon atoms include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, sec-pentyl, iso- Examples include pentyl, tert-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, dodecyl, and octadecyl.
In the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently a fluorine atom or a fluorine atom or a carbon atom. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- or cycloalkylene having 5 to 20 carbon atoms may be substituted, and any hydrogen atom of the alkyl having 1 to 40 carbon atoms may be independently replaced with a fluorine atom; -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms.
R ¹ is preferably selected from phenyl, cyclohexyl, and alkyl having 1 to 5 carbon atoms, preferably phenyl or methyl.

( ^R2 )
R ² is each independently a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne, aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, carbon It represents arylalkyl having 7 to 40 carbon atoms or alkyl having 1 to 40 carbon atoms, and at least one is a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne.
Since at least one of R ² is a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne, crosslinking can be performed using a siloxane crosslinking agent described below.

The aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne is not particularly limited, but preferably has 2 to 10 carbon atoms, and specifically, vinyl and allyl are preferable. Note that the aliphatic hydrocarbon group having 2 to 40 carbon atoms may contain one or more double bonds or triple bonds in addition to the terminal.

Aryl having 6 to 20 carbon atoms and cycloalkyl having 5 to 6 carbon atoms include the same ones as explained for R ⁰ .
As the arylalkyl having 7 to 40 carbon atoms, the same ones as explained for R ¹ can be mentioned.
Examples of the alkyl having 1 to 40 carbon atoms include those described for R ¹ .
In the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently a fluorine atom or a fluorine atom or a carbon atom. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- or cycloalkylene having 5 to 20 carbon atoms may be substituted, and any hydrogen atom of the alkyl having 1 to 40 carbon atoms may be independently replaced with a fluorine atom; -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms.

"At least one of R ² is a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne" means that at least one of the R ² groups contained in the polymer is a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms. This means that it is an aliphatic hydrocarbon ^group having 2 _{to 40} carbon atoms containing a terminal alkene or a terminal alkyne. In this case, one or two, preferably one, of the two R ² contained in this structural unit may be a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne. On the other hand, two or more types of the structural unit - ⁽ OSi(R ² ) _{2 )} may include aliphatic hydrocarbon groups having 2 to 40 carbon atoms, including

（I-1）

（I-2） Preferably, the structural unit -(OSi(R ² ) ₂ ) _x - of the siloxane polymer (A) includes the following (I-1) and (I-2).

(I-1)

(I-2)

R ²¹ independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms;
In the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently a fluorine atom or a fluorine atom or a carbon atom. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- or cycloalkylene having 5 to 20 carbon atoms may be substituted, and any hydrogen atom of the alkyl having 1 to 40 carbon atoms may be independently replaced with a fluorine atom; -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms.
R ²¹ is preferably selected from phenyl, cyclohexyl, and alkyl having 1 to 5 carbon atoms, more preferably selected from phenyl and methyl.

R ²² independently represents a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne; In the group, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-.
R ²² is preferably selected from hydrogen, vinyl, and allyl.

(x, m)
In the repeating unit represented by formula (A), x represents a real number from 1 to 30, but from the viewpoint of production and handling, x is preferably 20 or less, more preferably 8 or less.
m represents a number satisfying a weight average molecular weight of 2,000 to 10,000,000, preferably 10,000 to 1,000,000.

（II）
ここで、Ｒ^４はそれぞれ独立して、水素原子または末端アルケンもしくは末端アルキンを含む炭素数２～４０の脂肪族炭化水素基、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、又は炭素数１～４０のアルキルを表す。
末端アルケンもしくは末端アルキンを含む炭素数２～４０の脂肪族炭化水素基としては、Ｒ^２で説明したものと同様のものが挙げられる。
炭素数６～２０のアリール、炭素数５～６のシクロアルキルは、Ｒ^０で説明したものと同様のものが挙げられる。
炭素数７～４０のアリールアルキルとしては、Ｒ^１で説明したものと同様のものが挙げられる。
炭素数１～４０のアルキルとしては、Ｒ^１で説明したものと同様のものが挙げられる。
Ｒ^４は好ましくはメチル、水素、ビニル又はアリルである。 The terminal of the siloxane polymer containing the repeating unit represented by formula (A) according to the present invention is not particularly limited, and may be a hydroxyl group, but may have the following group.

(II)
Here, R ⁴ is each independently a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or alkyne, aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, Represents arylalkyl having 7 to 40 carbon atoms or alkyl having 1 to 40 carbon atoms.
Examples of the aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne include those similar to those explained for R ² .
Aryl having 6 to 20 carbon atoms and cycloalkyl having 5 to 6 carbon atoms include the same ones as explained for R ⁰ .
As the arylalkyl having 7 to 40 carbon atoms, the same ones as explained for R ¹ can be mentioned.
Examples of the alkyl having 1 to 40 carbon atoms include those described for R ¹ .
R ⁴ is preferably methyl, hydrogen, vinyl or allyl.

（II） Siloxane polymer (A')
According to another aspect of the present invention, the siloxane polymer contained in the adhesive of the present invention has a crosslinkable functional group (a silicon-bonded hydrogen atom, a terminal alkene, or a carbon number of 2 to 40 containing a terminal alkyne) only at the terminal. aliphatic hydrocarbon group).
That is, another embodiment of the adhesive of the present invention is an adhesive comprising the following siloxane polymer (A') having a substituent (II) at the terminal and a siloxane crosslinking agent (B). When the substituent (II) contains a hydrogen atom as ^R4 , the siloxane crosslinking agent (B) is a siloxane compound containing two or more aliphatic hydrocarbon groups having 2 to 40 carbon atoms containing a terminal alkene or alkyne. When the substituent (II) contains an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or alkyne as R ⁴ , the siloxane crosslinking agent (B) is a siloxane compound containing two or more SiH groups. , is an adhesive.

(II)

R ⁰ is a group defined similarly to R ⁰ in formula (A), and preferred examples are also the same.
R ¹ is a group defined similarly to R ¹ in formula (A), and preferred examples are also the same.

R ²¹ is a group defined similarly to R ¹ in formula (II-1), and preferred examples are also the same.

In the siloxane polymer (A') having a substituent (II) at the terminal, R ⁴ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or alkyne, or a C 6 Represents an aryl having ~20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, an arylalkyl having 7 to 40 carbon atoms, or an alkyl having 1 to 40 carbon atoms, in which at least one has a hydrogen atom or a terminal alkene or a terminal alkyne, and has a carbon number of 2. ~40 aliphatic hydrocarbon group, and in the alkyl having 2 to 40 carbon atoms including the terminal alkene or alkyne, any hydrogen atom may be replaced with a fluorine atom, and any --CH ₂ -- is independently The aryl in the above aryl having 6 to 20 carbon atoms, the above cycloalkyl having 5 to 6 carbon atoms, and the above arylalkyl having 7 to 40 carbon atoms may be substituted with and may be replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms, and in the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any - CH ₂ - may be independently replaced with -O-, -CH=CH-, or cycloalkylene having 5 to 20 carbon atoms, and the alkyl having 1 to 40 carbon atoms may be independently replaced with any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O- or a cycloalkylene having 5 to 20 carbon atoms.
The siloxane polymer (A') is crosslinked with a siloxane crosslinking agent (B) via a silicon-bonded hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne, which is present at the terminal. Ru.

In formula (A'), x represents an integer of 1 to 30, and m represents a number satisfying a weight average molecular weight of 2,000 to 10,000,000.

In addition, in the siloxane polymer (A) and the siloxane polymer (A') having a substituent (II) at the terminal, the mass percentage occupied by the repeating unit represented by the formula (A) or (A') is usually 10%. The above is preferably 30% or more, more preferably 50% or more, particularly preferably 70% or more, and usually less than 100, preferably 99% or less. That is, units other than the repeating unit represented by formula (1) may be included as long as the effects of the present invention are not significantly impaired. Such units include, for example, -(CH ₂ -CH ₂ )-, -(CH=CH)-, -(O-SiMe ₂ -C ₆ H ₄ -SiMe ₂ )
- is mentioned.

The weight average molecular weight (Mw) of the siloxane polymer (A) and the siloxane polymer (A') having a substituent (II) at the terminal is not particularly limited, but is preferably 2,000 or more, more preferably 10,000 or more. , preferably 10,000,000 or less, more preferably 1,000,000 or less. The weight average molecular weight is determined by calculating a chromatogram obtained by gel permeation chromatography (GPC) using a calibration curve obtained using a molecular weight standard sample, as described in the Examples below.

Method for producing siloxane polymer The method for producing the siloxane polymer represented by formula (A) or (A') is not particularly limited, but for example, it is produced by a method including the following step (i) or the following step (ii). can do.
(i): A step of reacting a compound represented by formula (a) with a compound represented by formula (b).
(ii): A step of reacting a compound represented by formula (a), a compound represented by formula (b1), and a compound represented by formula (b2).

The siloxane polymer represented by formula (A) or (A') can also be produced by a production method including the following step (iii).
(iii): A step of reacting the silicon compound represented by formula (a) with the silicon compound represented by formula (c).

Alternatively, the terminals may be modified by adding a compound represented by formula (d) to the siloxane polymer obtained in step (i), (ii) or (iii) above and causing the reaction to occur.

Ｒ^０は式（Ａ）におけるＲ^０と同様に定義される基であり、好ましい例も同様である。
Ｒ^１は式（Ａ）におけるＲ^１と同様に定義される基であり、好ましい例も同様である。
式（ａ）で表される化合物は、例えば、特開２００６－０２２２０７号公報の記載を参照して合成することができ、以下に示される化合物が好ましい。 (Compound represented by formula (a))

R ⁰ is a group defined similarly to R ⁰ in formula (A), and preferred examples are also the same.
R ¹ is a group defined similarly to R ¹ in formula (A), and preferred examples are also the same.
The compound represented by formula (a) can be synthesized, for example, with reference to the description in JP-A No. 2006-022207, and the compounds shown below are preferred.

（ｂ）

（ｂ１）

（ｂ２）

（ｃ） (Compounds represented by formulas (b), (b1), (b2), (c))

(b)

(b1)

(b2)

(c)

R ² in formula (b) is a group defined similarly to R ² in formula (A), and preferred examples are also the same. n is an integer from 2 to 30.

The definition of R ²¹ in formula (b1) is the same as in formula (I-1), and the preferred type of R ²¹ is also the same as in formula (I-1). n1 is an integer from 2 to 30.

Examples of the compound represented by formula (b1) include 2,2,4,4,6,6-hexamethylcyclotrisiloxane, 2,4,6-triethyl-2,4,6-trimethylcyclotrisiloxane , 2,2,4,4,6,6-hexaethylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tripropylcyclotrisiloxane, 2,4,6-triethyl-2,4 , 6-tripropylcyclotrisiloxane, 2,2,4,4,6,6-hexapropylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tris(1-methylethyl)cyclotrisiloxane Siloxane, 2,4,6-triethyl-2,4,6-tris(1-methylethyl)cyclotrisiloxane 2,2,4,4,6,6-hexakis(1-methylethyl)cyclotrisiloxane, 2 , 4,6-tributyl-2,4,6-trimethylcyclotrisiloxane, 2,4,6-tributyl-2,4,6-triethylcyclotrisiloxane, 2,2,4,4,6,6-hexane Butylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tris(1,1-dimethylethyl)cyclotrisiloxane, 2,46-triethyl-2,4,6-tris(1,1- dimethylethyl)cyclotrisiloxane, 2,4,6-tris(1,1-dimethylethyl)-2,4,6-tripropylcyclotrisiloxane, 2,2,4,4,6,6-hexakis(1 , 1-dimethylethyl) cyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tris(trifluoromethyl)cyclotrisiloxane, 2,2,4,4,6,6-hexakis(trifluoro methyl)cyclotrisiloxane, 2,2,4,4,6,6-hexakis(1,1,2,2,2-pentafluoroethyl)cyclotrisiloxane, 2,4,6-trimethyl-2,4, 6-tris(3,3,3-trifluoropropyl)cyclotrisiloxane, 2,2,4,4,6,6-hexakis(3,3,3-trifluoropropyl)cyclotrisiloxane, 2,4, 6-trimethyl-2,4,6-triphenylcyclotrisiloxane, 2,2,4,4,6,6-hexaphenylcyclotrisiloxane, 2,4,6-tricyclohexyl-2,4,6- Trimethylcyclotrisiloxane, 2,2,4,4,6,6-hexacyclohexylcyclotrisiloxane, 2,2,4,4,6,6-hexavinylcyclotrisiloxane, 2,4,6-trimethyl- 2,4,6-trivinylcyclotrisiloxane, 2,2,4,4,6,6,8,8-octamethylcyclotetrasiloxane, 2,4,6,8-tetraethyl-2,4,6, 8-tetramethylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octaethylcyclotrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetra Propylcyclotetrasiloxane, 2,4,6,8-tetraethyl-2,4,6,8-tetrapropylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octapropylcyclotetrasiloxane , 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(1-methylethyl)cyclotetrasiloxane, 2,4,6,8-tetraethyl-2,4,6,8-tetrakis (1-methylethyl)cyclotetrasiloxane 2,2,4,4,6,6,8,8-octakis(1-methylethyl)cyclotetrasiloxane, 2,4,6,8-tetrabutyl-2,4, 6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetrabutyl-2,4,6,8-tetraethylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octa Butylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(1,1-dimethylethyl)cyclotetrasiloxane, 2,4,6,8-tetraethyl-2,4 , 6,8-tetrakis(1,1-dimethylethyl)cyclotetrasiloxane, 2,4,6,8-tetrakis(1,1-dimethylethyl)-2,4,6,8-tetrapropylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octakis(1,1-dimethylethyl)cyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetrakis( trifluoromethyl)cyclotetrasiloxane, 2,2,4,4,6,6,8,8-octakis(trifluoromethyl)cyclotetrasiloxane, 2,2,4,4,6,6,8,8- Octakis(1,1,2,2,2-pentafluoroethyl)cyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(3,3,3-trifluoropropyl) ) cyclotetrasiloxane, 2,2,4,4,6,6,8,8-octakis(3,3,3-trifluoropropyl)cyclotetrasiloxane, 2,4,6,8-tetramethyl-2, 4,6,8-tetraphenylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octaphenylcyclotetrasiloxane, 2,4,6,8-tetracyclohexyl-2,4, 6,8-tetramethylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octacyclohexylcyclotetrasiloxane, 2,2,4,4,6,6,8,8-octa Vinylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,6-diethynyl-2,4,4,6,8,8-hexamethyl Cyclotetrasiloxane, 2,2,4,4,6,6,8,8,10,10-decamethylcyclopentasiloxane, 2,4,6,8,10-pentaethyl-2,4,6,8, 10-pentamethylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decaethylcyclotrisiloxane, 2,4,6,8.10-pentamethyl-2,4, 6,8-pentapropylcyclopentasiloxane, 2,4,6,8,10-pentaethyl-2,4,6,8,10-pentapropylcyclopentasiloxane, 2,2,4,4,6,6, 8,8,10,10-decapropylcyclopentasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentakis(1-methylethyl)cyclopentasiloxane, 2,4 ,6,8,10-pentaethyl-2,4,6,8,10-pentakis(1-methylethyl)cyclopentasiloxane 2,2,4,4,6,6,8,8,10,10-decakis (1-Methylethyl)cyclopentasiloxane, 2,4,6,8,10-pentabyl-2,4,6,8,10-pentamethylcyclopentasiloxane, 2,4,6,8,10-pentabyl- 2,4,6,8,10-pentaethylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decabutylcyclopentasiloxane, 2,4,6,8, 10,10-pentamethyl-2,4,6,8,10,10-pentakis(1,1-dimethylethyl)cyclopentasiloxane, 2,4,6,8,10-pentaethyl-2,4,6,8 , 10-pentakis(1,1-dimethylethyl)cyclopentasiloxane, 2,4,6,8,10-pentakis(1,1-dimethylethyl)-2,4,6,8,10-pentapropylcyclopenta Siloxane, 2,2,4,
4,6,6,8,8,10,10-decakis(1,1-dimethylethyl)cyclopentasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8-pentakis(trimethyl) fluoromethyl)cyclopentasiloxane, 2,2,4,4,6,6,8,8,10.10-decakis(trifluoromethyl)cyclopentasiloxane, 2,2,4,4,6,6,8 , 8,10,10-decakis(1,1,2,2,2-pentafluoroethyl)cyclopentasiloxane, 2,4,6,8,10,10-pentamethyl-2,4,6,8-pentakis (3,3,3-trifluoropropyl)cyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decakis(3,3,3-trifluoropropyl)cyclopentasiloxane , 2,4,6,8,10-pentamethyl-2,4,6,8-pentaphenylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decaffenylcyclo Pentasiloxane, 2,4,6,8,10-pentacyclohexyl-2,4,6,8,10-pentamethylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10 , 10-decacyclohexylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10-decavinylcyclopentasiloxane, 2,4,6,8,10-pentamethyl-2, Examples include 4,6,8,10-pentavinylcyclopentasiloxane, and among them, low molecular weight cyclic siloxanes in which R ² is alkyl having 1 to 40 carbon atoms are preferred, such as hexamethylcyclotrisiloxane (D3), octamethylcyclo Cyclic siloxanes such as tetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) are more preferred, and from the viewpoint of ease of availability, cost, and handling, octamethylcyclotetrasiloxane is preferred. Particularly preferred.

The definitions of R ²¹ and R ²² in formula (b2) are the same as in formula (I-2), and the preferred types of R ²¹ and R ²² are also the same as in formula (I-2). n2 is an integer from 2 to 30.

Examples of the compound represented by formula (b2) include 2,4,6-trimethylcyclotrisiloxane, 2,4,6-triethylcyclotrisiloxane, 2,4,6-tris(1-methylethyl)cyclo Trisiloxane, tripropylcyclotrisiloxane, 2,4,6-tris(1,1-dimethylethyl)cyclotrisiloxane, 2,4,6-tris(1,1-dimethylethyl)cyclotrisiloxane, 2,4 , 6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetraethylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, 2,4,6,8,10- Pentaethylcyclopentasiloxane is mentioned.

The definitions of R ²¹ and R ²² in formula (c) are the same as those of formulas (I-1) and (II-2), and the preferable types of R ²¹ and R ²² are also the same as those of formulas (I-1) and (II-2). ). n1 and n2 are integers from 2 to 30.

Examples of the compound represented by formula (c) include 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,1,3,5,5,7,7,7 -nonamethyltetrasiloxane, 1,1,1,3,5,5,5-heptaphenyltrisiloxane, 1,1,1,3,5,5,7,7,7-nonaphenyltetrasiloxane, manufactured by Gelest HMS-031, HMS-071, HMS-151, HMS-301, HMS-501, HAM-301 (when d=1): HMS-991, HMS-992, HMS-993 manufactured by Gelest.

（ｄ）
式（ｄ）中、Ｒ^３は、それぞれ独立して、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、又は炭素数１～４０のアルキルを表し、前記炭素数６～２０のアリール、前記炭素数５～６のシクロアルキル及び前記炭素数７～４０のアリールアルキル中のアリールは、任意の水素原子が独立してフッ素原子又は炭素数１～２０のアルキルで置き換えられてもよく、前記炭素数７～４０のアリールアルキル中のアルキレンは、任意の水素原子がフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－、－ＣＨ＝ＣＨ－、又は炭素数５～２０のシクロアルキレンで置き換えられてもよく、前記炭素数１～４０のアルキルは、任意の水素原子が独立してフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－又は炭素数５～２０のシクロアルキレンで置き換えられてもよい。
Ｒ^４は独立して、水素原子または末端アルケンもしくは末端アルキンを含む炭素数２～４０の脂肪族炭化水素基、炭素数６～２０のアリール、炭素数５～６のシクロアルキル、炭素数７～４０のアリールアルキル、又は炭素数１～４０のアルキルを表し、前記末端アルケンもしくはアルキンを含む炭素数２～４０のアルキルは、任意の水素原子がフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－で置き換えられてもよく、前記炭素数６～２０のアリール、前記炭素数５～６のシクロアルキル及び前記炭素数７～４０のアリールアルキル中のアリールは、任意の水素原子が独立してフッ素原子又は炭素数１～２０のアルキルで置き換えられてもよく、前記炭素数７～４０のアリールアルキル中のアルキレンは、任意の水素原子がフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－、－ＣＨ＝ＣＨ－、又は炭素数５～２０のシクロアルキレンで置き換えられてもよく、前記炭素数１～４０のアルキルは、任意の水素原子が独立してフッ素原子で置き換えられてもよく、任意の－ＣＨ_２－が独立して－Ｏ－又は炭素数５～２０のシクロアルキレンで置き換えられてもよい。
ｎは１～３０の整数を表す。
式（ｄ）で表される化合物としては、例えば、ヘキサメチルジシロキサン、オクタメチルトリシロキサン、デカメチルテトラシロキサン、ヘキサフェニルジシロキサン、オクタフェニルトリシロキサン、デカフェニルテトラシロキサン、Ｇｅｌｅｓｔ製 ＤＭＡ－Ｔ０７Ｒが挙げられる。 (Compound represented by formula (d))
A compound represented by formula (d) can be used to modify the terminal end of a siloxane polymer.

(d)
In formula (d), R ³ each independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms. In the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently a fluorine atom or a fluorine atom or In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O -, -CH=CH-, or cycloalkylene having 5 to 20 carbon atoms, and any hydrogen atom of the alkyl having 1 to 40 carbon atoms may be independently replaced with a fluorine atom. , any -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms.
R ⁴ is independently a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or alkyne, an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, or a cycloalkyl group having 7 to 6 carbon atoms. 40 arylalkyl or an alkyl having 1 to 40 carbon atoms, and in the alkyl having 2 to 40 carbon atoms containing the terminal alkene or alkyne, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, and the aryl in the above aryl having 6 to 20 carbon atoms, the above cycloalkyl having 5 to 6 carbon atoms, and the above arylalkyl having 7 to 40 carbon atoms may be optionally substituted with -O-. hydrogen atoms may be independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms, and alkylene in the arylalkyl having 7 to 40 carbon atoms may have any hydrogen atom replaced with a fluorine atom. Often, any -CH ₂ - may be independently replaced with -O-, -CH=CH-, or cycloalkylene having 5 to 20 carbon atoms, and said alkyl having 1 to 40 carbon atoms may be replaced with any A hydrogen atom may be independently replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O- or a cycloalkylene having 5 to 20 carbon atoms.
n represents an integer from 1 to 30.
Examples of the compound represented by formula (d) include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexaphenyldisiloxane, octaphenyltrisiloxane, decafenyltetrasiloxane, and DMA-T07R manufactured by Gelest. Can be mentioned.

In the above steps (i), (ii) or (iii), a solvent such as tetrahydrofuran, toluene, ethyl acetate, etc. may be used. Preferably, the reaction is carried out in the presence of an acid such as sulfuric acid. Preferably, the reaction is carried out under an inert atmosphere such as nitrogen (N ₂ ). Moreover, it is preferable to carry out the reaction while stirring.

(Siloxane crosslinking agent)
The siloxane crosslinking agent (B) used in the present invention is a silicon-bonded hydrogen atom, a terminal alkene, or a terminal alkyne contained in the siloxane polymer (A) and the siloxane polymer (A') having a substituent (II) at the terminal. The siloxane compound is not particularly limited as long as it has two or more groups that react with an aliphatic hydrocarbon group having 2 to 40 carbon atoms, including siloxane polymer (A) or siloxane polymer (II) having a substituent group at the terminal ( When A') contains a hydrogen atom bonded to silicon, select a crosslinking agent containing a siloxane compound having two or more groups that react with a terminal alkene or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkyne. However, when the siloxane polymer (A) or the siloxane polymer (A') having a substituent (II) at the terminal contains a group that reacts with an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne, selects a crosslinking agent containing a siloxane compound having two or more silicon-bonded hydrogen atoms.

（III）

（IV） As the crosslinking agent, for example, a siloxane compound represented by the following formula (III) or (IV) can be used.

(III)

(IV)

R ⁵ independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms; 20 aryl, the cycloalkyl having 5 to 6 carbon atoms, and the aryl in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- , or cycloalkylene having 5 to 20 carbon atoms, and in the alkyl having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms;
R ⁶ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne; In the group, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-.
p represents an integer from 0 to 30, and q represents an integer from 2 to 30.
R ⁵ is selected from phenyl, cyclohexyl, and alkyl having 1 to 5 carbon atoms, more preferably selected from alkyl having 1 to 5 carbon atoms.
R ⁶ is preferably a hydrogen atom, vinyl or allyl.

One type of crosslinking agent may be used, or two or more types may be used.
The amount of the crosslinking agent added is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and usually 20% by mass or less, preferably It is 10% by mass or less, more preferably 5% by mass or less. When using two or more types of crosslinking agents, it is preferable that the total content is within the above range.

(solvent)
The adhesive of the present invention preferably contains a solvent.
The solvent is not particularly limited as long as it can dissolve the siloxane polymer and/or siloxane crosslinking agent. Preferred solvents include hydrocarbon solvents such as butane, hexane, heptane, octane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and anisole; diethyl ether, diisopropyl ether, and 1,2-dimethoxyethane. , tetrahydrofuran (THF), ether solvents such as dioxane; halogenated hydrocarbon solvents such as methylene chloride, carbon tetrachloride; ester solvents such as ethyl acetate; glycol ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) ; Nitrogen-containing solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), and pyridine; Alcohol-based solvents such as methanol, ethanol, isopropanol, and butanol; acetone, These include ketone solvents such as methyl ethyl ketone. Preferred are toluene, mesitylene, anisole, tetrahydrofuran, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate, and 2-(2-ethoxyethoxy)ethyl acetate, and more preferred are toluene and propylene glycol monomethyl ether acetate (PGMEA). One type of solvent may be used, or two or more types may be used. Further, the solvent may be used after being dehydrated. The amount of the solvent used is not particularly limited, but it is usually 10% by mass or more, preferably 20% by mass or more, and usually 1000% by mass or less, preferably 500% by mass or less, based on the siloxane polymer. .

(catalyst)
It is preferable to use a catalyst for the reaction between the siloxane polymer and the siloxane crosslinking agent. Therefore, the adhesive of the present invention preferably contains a catalyst. The catalyst used in this embodiment may be appropriately selected depending on the crosslinking agent, and examples thereof include organometallic compounds containing metals such as tin, titanium, zirconium, zinc, and bismuth; acidic compounds; basic compounds, etc. can be used.
Such metal compounds are preferably organic tin catalysts such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin acetylacetonate, dibutyltin oxide, tin octoate; tetrabutyl titanate, tetra Alkoxy titaniums such as propyl titanate, tetraisopropyl titanate, and titanium tetraacetylacetonate can be mentioned.
Examples of acidic compounds include phosphoric acid, toluenesulfonic acid, sulfuric acid, nitric acid, acetic acid, and benzoic acid.
Examples of the basic compound include triethylamine, tributylamine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo [5.4.0] Undec-7-ene, N,N-bis(N,N-dimethyl-2-aminoethyl)methylamine, N,N-dimethylcyclohexylamine, N,N-dimethylphenylamine and N - Ethylmorpholinine.
One type of catalyst may be used, or two or more types may be used.
The amount of the catalyst added is usually 0.001% by mass or more, preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and usually 10% by mass or less, preferably It is 5% by mass or less, more preferably 3% by mass or less. When using two or more types of catalysts, the total content is preferably within the above range.

The adhesive of the present invention may include an embodiment in which the siloxane polymer and the crosslinking agent are contained separately and are mixed at the time of use, or an embodiment in which the siloxane polymer and the crosslinking agent are mixed in advance. Further, the siloxane polymer and the crosslinking agent may be dissolved in a solvent, or may be dissolved in a solvent before use. Preferably, the catalyst is added at the time of use.

(How to use)
The adhesive of the present invention can be used, but is not particularly limited, by mixing the siloxane polymer and a crosslinking agent in a solvent, preferably adding a catalyst, and heating the mixture to advance the crosslinking reaction. be able to perform its functions.
Specifically, in the heat treatment step, the mixture of the siloxane polymer and crosslinking agent may be applied to the base material, and then heated using an oven or the like.
The temperature and time of the heat treatment step are not particularly limited as long as the siloxane polymer can be formed into a desired crosslinked product, and are, for example, 50 to 250°C. The heating time is preferably 10 minutes to 3 hours.
The base material to be bonded is not particularly limited as long as it can withstand the temperature of the heat treatment process and the crosslinked body formed on the base material can be peeled off from the base material and taken out as a self-supporting film.For example, quartz, barium borosilicate, etc. Glass substrates such as acid glass and aluminoborosilicate glass; Calcium fluoride substrates; Metal oxide substrates such as ITO (indium tin oxide); Ceramic substrates; Polycarbonate (PC) film, silicone film, polyethylene terephthalate (PET) Plastic films such as film, polyethylene naphthalate (PEN) film, cycloolefin polymer (COP) film, polypropylene film, polyethylene film, acrylic polymer film, polyvinyl alcohol film, triacetyl cellulose film, polyimide (PI) film; polytetrafluoro A fluororesin substrate such as ethylene (PTFE) or perfluoroalkoxyalkane (PFA); a laminated substrate made of glass or the like coated with a fluororesin; a metal substrate such as SUS or copper; a silicon wafer, etc. can be used.

(Characteristics of the adhesive of the present invention)
The adhesive of the invention has high adhesive properties and transparency. For example, a substrate bonded using the adhesive of the present invention has a tensile shear strength of 1 MPa or more and a total light transmittance of 90% or more.
The tensile shear strength and total light transmittance are measured, for example, by the method described in the Examples below.

The present invention will be explained in more detail below with reference to Examples, but the scope of the present invention is not limited by these descriptions.

The reagents used in the examples are shown below.
・Octamethylcyclotetrasiloxane (D4, manufactured by Tokyo Chemical Industry Co., Ltd.)
・2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.)
・Toluene (manufactured by Nacalai Tesque Co., Ltd.)
・Sulfuric acid (manufactured by Nacalai Tesque Co., Ltd.)
・Hexamethyldisiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.)
・Sodium hydrogen carbonate (manufactured by Nacalai Tesque Co., Ltd.)
・Hexane (manufactured by Nacalai Tesque Co., Ltd.)
・Kyoward 500SN (manufactured by Kyowa Chemical Industry Co., Ltd.)
・Methanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
・THF (manufactured by Nacalai Tesque Co., Ltd.)
・1,1,3,3,5,5,7,7-octamethyltetrasiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.)
・PT-VTSC-3.0X (product name, manufactured by Umicore Japan)
・1,1,1,3,3,3-hexamethyldisilazane (manufactured by Tokyo Chemical Industry Co., Ltd.)
・Chromium (III) acetylacetonate (Cr(acac) ₃ , manufactured by Tokyo Kasei Kogyo Co., Ltd.)

化合物（α）は、以下の化合物（４）と化合物（５）とを反応させ、さらに加水分解することにより合成した（例えば、特開２００６－０２２２０７号公報の００３２段落参照。）。

Compound (α) was synthesized by reacting the following compound (4) with compound (5) and further hydrolyzing it (see, for example, paragraph 0032 of JP-A No. 2006-022207).

The weight average molecular weight can be determined by gel permeation chromatography (GPC), and more specifically, under the following conditions.
<GPC measurement conditions>
Column: Shodex KF-806M manufactured by Showa Denko K.K.
Mobile phase: THF (manufactured by Nacalai Tesque Co., Ltd.)
Flow rate: 1ml/min
Temperature: 45℃
Detector: UV
Molecular weight standard sample: polystyrene with known molecular weight

The 5% weight loss temperature can be determined by thermogravimetric analysis (TGA), and more specifically, can be determined under the following conditions.
<TGA measurement conditions>
Equipment name: Rigaku corp. Thermo olus Evo II differential type differential thermal balance TG-DTA TG 8120
Atmosphere: Air (0.5MPa)
Temperature increase rate: 10℃/min.
Measurement temperature: 25-800℃

< ^1H -NMR measurement conditions>
Equipment: JNM-EX400 manufactured by JEOL
Accumulated number of times: 64

< ²⁹ Si-NMR measurement conditions>
Equipment: JNM-EX400 manufactured by JEOL
Accumulation count: 800
Relaxation Delay: 0.1s
Relaxation reagent: Cr(acac)3 10wt%

ディーンスターク管、還流管、温度計を設置した四つ口丸底フラスコにスターラーチップ入れ、化合物（α）５０．０ｇ、オクタメチルシクロテトラシロキサン（Ｄ４、東京化成工業（株）製) ２５．０ｍＬ、２，４，６，８－テトラメチル－２，４，６，８－テトラビニルシクロテトラシロキサン（東京化成工業（株）製) ５．８ ｍＬ、トルエン（ナカライテスク製）１２５ｍＬを加え、１時間還流脱水した。硫酸（ナカライテスク製）２．１ｍＬを加え、３時間還流後、８０℃まで冷却しヘキサメチルジシロキサン（東京化成工業（株）製) ０．７ｍＬ加え、さらに3時間撹拌した。加熱を停止し、純水を加え分液後、有機層に飽和炭酸水素ナトリウム（ナカライテスク製)水溶液を加え中和洗浄した。その後数回純水で洗浄し、有機層をフィルターでろ過し、ロータリーエバポレーターで
濃縮した。トルエン ２０ｍＬ、ヘキサン（ナカライテスク製）２０００ｍＬを加え撹拌することで白色沈殿を析出させた。沈殿を乾燥させシロキサンポリマー（β）１６．８gを得た。１Ｈ－ＮＭＲよりビニル基の存在が確認され、２９Ｓｉ－ＮＭＲ測定により求めた（ｐ, ｐ’）は、平均４．２、（ｑ, ｑ’）は、平均０．７０であった。ＧＰＣによる重量平均分子量は、４５，０００であった。ＴＧＡによる５％重量減少温度は４８３℃であった。 Synthesis example Siloxane polymer (β)

A stirrer chip was placed in a four-necked round-bottomed flask equipped with a Dean-Stark tube, a reflux tube, and a thermometer, and 50.0 g of compound (α) and 25.0 mL of octamethylcyclotetrasiloxane (D4, manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added. , 5.8 mL of 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 125 mL of toluene (manufactured by Nacalai Tesque) were added, and 1 It was dehydrated under reflux for an hour. 2.1 mL of sulfuric acid (manufactured by Nacalai Tesque) was added, and after refluxing for 3 hours, the mixture was cooled to 80°C, 0.7 mL of hexamethyldisiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was further stirred for 3 hours. Heating was stopped, pure water was added to separate the layers, and a saturated aqueous solution of sodium hydrogen carbonate (manufactured by Nacalai Tesque) was added to the organic layer for neutralization and washing. Thereafter, it was washed several times with pure water, and the organic layer was filtered and concentrated using a rotary evaporator. 20 mL of toluene and 2000 mL of hexane (manufactured by Nacalai Tesque) were added and stirred to precipitate a white precipitate. The precipitate was dried to obtain 16.8 g of siloxane polymer (β). The presence of vinyl groups was confirmed by 1H-NMR, and (p, p') determined by 29Si-NMR measurement was 4.2 on average, and (q, q') was 0.70 on average. The weight average molecular weight by GPC was 45,000. The 5% weight loss temperature by TGA was 483°C.

( ^1H -NMR measurement results)
1H-NMR (400MHz, CO(CD3)2) δ (ppm): 7.12-7.66 (Ph), 5.70-6.13 (SiCH=CH ₂ ), 0.22-0.46 ( Me), -0.04 to -0.19 (Me)
( ²⁹ Si-NMR measurement results)
29Si-NMR (79MHz, THF-d8) δ(ppm): -18.5 to -22.0, -34.5 to -35.8, -64.6 to 65.1, -78.8, - 78.9, -79.2, -79.4

オクタメチルシクロテトラシロキサン ３０ ｇ、２，４，６，８－テトラメチル－２，４，６，８－テトラビニルシクロテトラシロキサン ５．０ｇ、 ヘキサメチルジシロキサン ０．３８ｇ、トルエン ５５．６ｇを２００ｍＬ ４つ口丸底フラスコに加え、還流管、スターラー、オイルバスをセット。窒素をフローし、撹拌した。硫酸１．７ ｇを加え５時間還流した。加熱を停止し、多量の飽和食塩水を加え、水層を捨て、数回飽和食塩水で洗浄し分液した。有機層に、キョーワード500ＳＮを加え1時間撹拌後、減圧ろ過によりキョーワード500ＳＮを除き、50 ℃程度で濃縮した。濃縮液にメタノールを撹拌しながら加え、上層をデカンテーションで除去し、下層を数回メタノールで洗浄した。下層を60 ℃で減圧乾燥し、６．５ｇの無色透明液体、シロキサンポリマー（γ）を得た。^２９Ｓｉ－ＮＭＲより求めたｐは、平均６．２、ｑは、平均１であった。ＧＰＣより重量平均分子量は８，２００であった。ＴＧＡによる５％重量減少温度は３５８℃であった。 Synthesis example (comparative example) Siloxane polymer (γ)

200 mL of octamethylcyclotetrasiloxane 30 g, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane 5.0 g, hexamethyldisiloxane 0.38 g, toluene 55.6 g In addition to a 4-neck round bottom flask, a reflux tube, stirrer, and oil bath are included. Fluid with nitrogen and stir. 1.7 g of sulfuric acid was added and the mixture was refluxed for 5 hours. Heating was stopped, a large amount of saturated brine was added, the aqueous layer was discarded, and the mixture was washed several times with saturated brine and separated. Kyoward 500SN was added to the organic layer, and after stirring for 1 hour, Kyoward 500SN was removed by vacuum filtration, and the mixture was concentrated at about 50°C. Methanol was added to the concentrated solution while stirring, the upper layer was removed by decantation, and the lower layer was washed several times with methanol. The lower layer was dried under reduced pressure at 60° C. to obtain 6.5 g of a colorless transparent liquid, siloxane polymer (γ). The average value of p determined by ²⁹ Si-NMR was 6.2, and the average value of q was 1. The weight average molecular weight was found to be 8,200 by GPC. The 5% weight loss temperature by TGA was 358°C.

( ^1H -NMR measurement results)
¹ H-NMR (500 MHz, CDCl ₃ ) δ (ppm): 6.02-6.14 (SiCH=CH ₂ ), 5.88-5.93 (SiCH=CH ₂ ), 0.25-0.26 (SiMe ₃ ), 0.18-0.20 (SiMe ₂ ).

( ²⁹ Si-NMR measurement results)
²⁹ Si-NMR (99 MHz, CDCl ₃ ) δ (ppm): 7.3, -21.4 to -21.3, -21.9 to -21.8, -35.5, -35.8.

Preparation of adhesive 0.5 g of siloxane polymer (β or γ), 136 μL of 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, and 0.5 mL of toluene were dissolved with stirring at room temperature, and then PT 1.69 μL of a solution prepared by diluting -VTSC-3.0X (trade name, manufactured by Umicore Japan) 2000 times with toluene was added and stirred until uniform.

Test piece creation: An aluminum substrate approximately 45 mm long, 7 mm wide, and 0.5 mm thick was ultrasonically cleaned with acetone for 30 minutes, dried, and then treated with UV ozone for 10 minutes to form an adherend (first base material). used as. Adhesive was placed on a 5 mm long x 7 mm wide area from the edge of this aluminum substrate, and a 5 mm long x 7 mm wide area from the edge of another substrate of the same type was attached and fixed with eyeball clips. It was heated in an oven at 70°C for 20 minutes, 100°C for 20 minutes, and 200°C for 2 hours. After heating, it was taken out of the oven, left to cool for 5 minutes at room temperature in an air atmosphere, and the eyeball clip was removed to prepare a test piece.

A stainless steel substrate approximately 50 mm long, 10 mm wide, and 0.5 mm thick was ultrasonically cleaned with acetone for 30 minutes, dried, and then treated with UV ozone for 10 minutes, and used as an adherend (first base material). . Adhesive was placed on a 6 mm long x 10 mm wide area from the edge of this stainless steel substrate, and a 6 mm long x 10 mm wide area from the edge of another substrate of the same type was attached and fixed with eyeball clips. It was heated in an oven at 70°C for 20 minutes, 100°C for 20 minutes, and 200°C for 2 hours. After heating, it was taken out of the oven, left to cool for 5 minutes at room temperature in an air atmosphere, and the eyeball clip was removed to prepare a test piece.

A glass substrate with a length of about 40 mm, a width of 8 mm, and a thickness of 1 mm was ultrasonically cleaned with acetone for 30 minutes, dried, and then treated with UV ozone for 10 minutes, and used as an adherend (first base material). An adhesive was placed on a 5 mm long x 8 mm wide area from the edge of this glass substrate, and a 5 mm long x 8 mm wide area from the edge of another glass substrate of the same type was pasted together and fixed with eyeball clips. It was heated in an oven at 70°C for 20 minutes, 100°C for 20 minutes, and 200°C for 2 hours. After heating, it was taken out of the oven, left to cool for 5 minutes at room temperature in an air atmosphere, and the eyeball clip was removed to prepare a test piece.

Hydrophobization in hydrophobized glass is carried out by immersing the same glass substrate as above in 1,1,1,3,3,3-hexamethyldisilazane for more than one day, taking it out, washing it with water, and dipping it in 100% It was prepared by baking at ℃ for 1 hour.

Using the obtained test piece, tensile shear stress was measured using EZ-LX (manufactured by Shimadzu Corporation) according to the method of JIS K6850. The tensile speed was 1 mm/min, and the test temperature was room temperature of 25-27°C. The thickness of the polymer is shown in the table. The results are shown in Tables 1 and 2.

Transparency evaluation An adhesive made of siloxane polymer (β) was sandwiched between two pieces of glass with a length of 50 mm, a width of 50 mm, and a thickness of 0.7 mm, and the adhesive made of siloxane polymer (β) was held down with eyeball clips. Heat in oven for 20 minutes at 200° C. for 2 hours. After heating, it was taken out of the oven and allowed to cool in the air, and then the eyeball clip was removed to prepare a sample (solidified adhesive). The total light transmittance of this sample was measured using a haze meter (NDH 5000, manufactured by Nippon Denshoku Industries Co., Ltd.). The film thickness of the polymer (adhesive layer) was 150 μm. As a reference, two sheets of glass made of the same type of base material were used. The total light transmittance of the sample was 91%.

In addition to high adhesiveness and transparency after solidification, the adhesive according to the present invention has a structure in which cage-shaped silsesquioxane is bonded with chain siloxane and has excellent heat resistance, so it requires not only homogeneous adhesion but also heterogeneous adhesion. It can be suitably used in the electronics field.

Claims (10)

An adhesive containing the following siloxane polymer (A) and siloxane crosslinking agent (B), and when the siloxane polymer (A) contains a hydrogen atom as ^R2 , the siloxane crosslinking agent (B) is a terminal alkene or a carbon containing alkyne. A siloxane compound containing two or more aliphatic hydrocarbon groups of 2 to 40 carbon atoms, and when the siloxane polymer (A) contains an aliphatic hydrocarbon group of 2 to 40 carbon atoms containing a terminal alkene or alkyne as R ² The siloxane crosslinking agent (B) is an adhesive that is a siloxane compound containing two or more SiH groups.

R ⁰ independently represents an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms, and the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms are any hydrogen Atom may be independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms;
R ¹ independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms; 20 aryl, the cycloalkyl having 5 to 6 carbon atoms, and the aryl in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- , or cycloalkylene having 5 to 20 carbon atoms, and in the alkyl having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms;
R ² is independently a hydrogen atom or a C2-40 aliphatic hydrocarbon group containing a terminal alkene or terminal alkyne, a C6-20 aryl, a C5-6 cycloalkyl, a C7 ~40 arylalkyl, or an alkyl having 1 to 40 carbon atoms, at least one of which is a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne,
In the aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-. It's okay to be beaten,
In the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently a fluorine atom or a fluorine atom or a carbon atom. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- or cycloalkylene having 5 to 20 carbon atoms may be substituted, and any hydrogen atom of the alkyl having 1 to 40 carbon atoms may be independently replaced with a fluorine atom; -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms,
x represents an integer from 1 to 30, and m represents a number satisfying a weight average molecular weight of 2,000 to 10,000,000. The adhesive according to claim 1, wherein the structural unit -(OSi(R ² ) ₂ ) _x - of the siloxane polymer (A) includes the following structural unit (I-1) and structural unit (I-2).

(I-1)

(I-2)
R ²¹ independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms;
In the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently a fluorine atom or a fluorine atom or a carbon atom. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- or cycloalkylene having 5 to 20 carbon atoms may be substituted, and any hydrogen atom of the alkyl having 1 to 40 carbon atoms may be independently replaced with a fluorine atom; -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms.
R ²² represents a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne;
In the aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-. It's okay to be hit. In the siloxane polymer (A) according to claim 1,
R ⁰ is independently phenyl or cyclohexyl;
R ¹ is independently methyl or phenyl;
In the structural unit (I-1) and the structural unit (I-2), ^R21 is independently methyl or phenyl,
R ²² is independently hydrogen, vinyl or allyl;
The adhesive according to claim 2. An adhesive containing the following siloxane polymer (A') having a substituent (II) at the terminal and a siloxane crosslinking agent (B) (excluding those having structure (V)) When the substituent (II) contains a hydrogen atom as R ⁴ , the siloxane crosslinking agent (B) is a siloxane compound containing two or more aliphatic hydrocarbon groups having 2 to 40 carbon atoms containing a terminal alkene or alkyne. When the substituent (II) contains an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or alkyne as R ⁴ , the siloxane crosslinking agent (B) is a siloxane compound containing two or more SiH groups. Yes, there is adhesive.

R ⁰ independently represents an aryl having 6 to 20 carbon atoms or a cycloalkyl having 5 to 6 carbon atoms, and the aryl having 6 to 20 carbon atoms and the cycloalkyl having 5 to 6 carbon atoms are any hydrogen Atom may be independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms;
R ¹ independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms; 20 aryl, the cycloalkyl having 5 to 6 carbon atoms, and the aryl in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- , or cycloalkylene having 5 to 20 carbon atoms, and in the alkyl having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms;
R ²¹ independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms;
In the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently a fluorine atom or a fluorine atom or a carbon atom. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- or cycloalkylene having 5 to 20 carbon atoms may be substituted, and any hydrogen atom of the alkyl having 1 to 40 carbon atoms may be independently replaced with a fluorine atom; -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms.
R ⁴ is independently a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or alkyne, an aryl having 6 to 20 carbon atoms, a cycloalkyl having 5 to 6 carbon atoms, or a cycloalkyl group having 7 to 6 carbon atoms. 40 arylalkyl or alkyl having 1 to 40 carbon atoms, at least one of which is a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne,
In the aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or a terminal alkyne, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-. It's okay to be beaten,
In the aryl having 6 to 20 carbon atoms, the cycloalkyl having 5 to 6 carbon atoms, and the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently a fluorine atom or a fluorine atom or a aryl having 1 to 20 carbon atoms. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH-, or cycloalkylene having 5 to 20 carbon atoms may be substituted, and any hydrogen atom of the alkyl having 1 to 40 carbon atoms may be independently replaced with a fluorine atom, or any -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms,
x represents an integer from 1 to 30, and m represents a number satisfying a weight average molecular weight of 2,000 to 10,000,000. The adhesive according to any one of claims 1 to 4, wherein the siloxane crosslinking agent (B) is (III) or (IV).

(III)

(IV)
R ⁵ independently represents aryl having 6 to 20 carbon atoms, cycloalkyl having 5 to 6 carbon atoms, arylalkyl having 7 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms; 20 aryl, the cycloalkyl having 5 to 6 carbon atoms, and the aryl in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom is independently replaced with a fluorine atom or an alkyl having 1 to 20 carbon atoms. In the alkylene in the arylalkyl having 7 to 40 carbon atoms, any hydrogen atom may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-, -CH=CH- , or cycloalkylene having 5 to 20 carbon atoms, and in the alkyl having 1 to 40 carbon atoms, any hydrogen atom may be independently replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O- or cycloalkylene having 5 to 20 carbon atoms;
R ⁶ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 2 to 40 carbon atoms containing a terminal alkene or alkyne; may be replaced with a fluorine atom, and any -CH ₂ - may be independently replaced with -O-;
p represents an integer from 0 to 30, and q represents an integer from 2 to 30. 6. Adhesive according to claim ⁵ , wherein R5 independently represents methyl or phenyl and ^R6 independently represents hydrogen, vinyl or allyl. The adhesive according to any one of claims 1 to 6, further comprising a solvent. Adhesive according to any one of claims 1 to 7, further comprising a catalyst. The method according to any one of claims 1 to 8, which can be bonded to a glass substrate, a metal oxide substrate, a ceramic substrate, a plastic film, a fluororesin substrate, a fluororesin laminated substrate, a metal substrate, or a silicon wafer. glue. The adhesive according to any one of claims 1 to 9, having a tensile shear strength of 1 MPa or more.