TWI691574B - Method for producing curd product, curd product, and a laminate containing the cured product - Google Patents

Abstract

The present invention provides a cured product having excellent thermal resistance, crack resistance (or cold-heat shock resistance) and adhesion and close attaching properties to an adhered article.

The cured product of this invention is obtained by carrying out a thermal treatment, which gradually changes curing-temperature, to a curing composition containing a compound having a polymerizable group, the degree of cure is 85% or less after a first stage of the thermal treatment, and allows the degree of cure to be over 85% by the second or the following stage of the thermal treatment. The compound having a polymerizable group is preferably a compound having a group selected from the group consisting of an epoxy group, an oxetanyl group, an ethylether group, and an ethylphenyl group, and especially preferably an epoxy-group modified polyorganosilsesquioxane.

Description

Manufacturing method of hardened product, hardened product, and laminate containing the aforementioned hardened product

The present invention relates to a method for manufacturing a hardened product, a hardened product obtained by the aforementioned method, and a laminate having a structure in which the hardened product is subsequently adhered. This case claims priority based on Japanese Patent Application No. 2015-122349 filed in Japan on June 17, 2015, and invokes its content.

Adhesives used for lamination of semiconductors and bonding of electronic parts are known to contain benzocyclobutene (BCB), novolac epoxy resin, or epoxy-modified polyorganosilsesquioxane. Agent (Patent Document 1).

However, in order to harden the thermosetting adhesive containing BCB, it needs to be heated at a high temperature of about 200 to 350°C, which may cause damage to the adhesive body due to exposure to the aforementioned high temperature. In addition, when thermosetting adhesives containing novolac-based epoxy resins are subjected to high-temperature steps such as lead-free reflow (for example, 260 to 280°C), the adhesives decompose to generate outgassing, so there is a problem of reduced adhesion.

On the other hand, compared with thermosetting adhesives containing BCB, thermosetting adhesives containing epoxy-modified polyorganosilicon silsesquioxane can be hardened at low temperature, and can form adhesion and adhesion to the substrate Excellent hardening. In addition, the adhesion can be maintained even when the high-temperature step is performed. However, the cured product of the thermosetting adhesive containing epoxy-modified polyorganosilicon silsesquioxane has the problem that it is prone to cracking due to the hot and cold shock.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2010-226060

Therefore, an object of the present invention is to provide a hardened product excellent in heat resistance, crack resistance (or hot and cold impact resistance), adhesion to an adherend, and adhesion.

Another object of the present invention is to provide a laminate having a structure that passes through the hardened material and then is adhered.

Another object of the present invention is to provide a method for manufacturing the aforementioned hardened product.

The present inventors have worked hard to solve the above-mentioned problems, and as a result, they have found that the curable composition is subjected to heat treatment in which the hardening temperature is changed stepwise and cured, and the curing degree at the end of the first-stage heat treatment is 85% or less In addition, a hardened product excellent in heat resistance, crack resistance (or cold and hot impact resistance), adhesion to an adherend, and adhesion can be obtained. this The invention is based on these findings.

That is, the present invention provides a hardened product obtained by subjecting a hardenable composition containing a compound having a polymerizable group to a heat treatment in which the hardening temperature is changed stepwise, and the degree of hardening at the end of the first heat treatment is 85% In the following, the degree of hardening exceeds 85% by heat treatment after the second stage.

Furthermore, the present invention provides the aforementioned hardened product, wherein the polymerizable group in the compound having a polymerizable group is one selected from the group consisting of an epoxy group, an oxetanyl group, a vinyl ether group, and a vinyl phenyl group More than one kind of base.

In addition, the present invention provides the aforementioned hardened product, wherein the compound having a polymerizable group is an epoxy-modified polyorganosilsesquioxane. The characteristics of the epoxy-modified polyorganosilsesquioxane are: The structural unit represented by the formula (1) and the molar ratio of the structural unit represented by the following formula (I) and the structural unit represented by the following formula (II) [the structural unit represented by the formula (I)/ The structural unit represented by formula (II)] is 5 or more; the structural unit represented by the above formula (1) and the following formula (4) with respect to the total amount of siloxane constituent units (100 mol%) The ratio of the constituent units is 55 to 100 mol %, the number average molecular weight is 1000 to 3000, and the molecular weight dispersion degree (weight average molecular weight/number average molecular weight) is 1.0 to 3.0.

[R ¹ SiO _3/2 ] (1) In formula (1), R ¹ represents an epoxy group-containing group.

[R ^a SiO _3/2 ] (I) In formula (I), R ^a represents an epoxy-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted ring Alkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom.

[R ^b SiO _2/2 (OR ^c )] (II) In formula (II), R ^b represents an epoxy group-containing group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or Unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[R ¹ SiO _2/2 (OR ^c )] (4) In formula (4), R ¹ is the same as in formula (1). R ^c is the same as in formula (II).

In addition, the present invention provides the aforementioned hardened product, wherein the R ¹ is one or more groups selected from the group consisting of groups represented by the following formulas (1a) to (1d).

式中，R^1a，R^1b，R^1c，R^1d相同或相異且表示直鏈或分支鏈狀之伸烷基。

In the formula, R ^1a , R ^1b , R ^1c and R ^{1d are the} same or different and represent straight-chain or branched-chain alkylene.

Furthermore, the present invention provides the aforementioned hardened product, wherein the epoxy-modified polyorganosilsesquioxane system further contains a structural unit represented by the following formula (2).

[R ² SiO _3/2 ] (2) In formula (2), R ² represents substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted Alkyl, or substituted or unsubstituted alkenyl.

In addition, the present invention provides the aforementioned hardened product, wherein R ² is a substituted or unsubstituted aryl group.

Furthermore, the present invention provides the aforementioned cured product, wherein the curable composition further contains a polymerization initiator.

In addition, the present invention provides the aforementioned cured product, wherein the curable composition further contains a polymerization stabilizer.

Furthermore, the present invention provides the aforementioned hardened product, wherein the hardenable composition system further contains a silane coupling agent.

In addition, the present invention provides a method for producing a cured product by performing a heat treatment in which the curing temperature is changed stepwise on a curable composition containing a compound having a polymerizable group, wherein the first stage of the heat treatment is completed The degree of curing is 85% or less, and the degree of curing exceeds 85% by the heat treatment after the second stage.

In addition, the present invention provides a laminate, which is composed of three or more layers, and has two layers to be adhered, and an adhesion layer between the adhered layers, wherein the adhesion layer is the layer of the cured product.

Furthermore, the present invention provides a device having the aforementioned product Layers.

That is, the present invention relates to the following.

[1] A hardened product obtained by subjecting a hardenable composition containing a compound having a polymerizable group to a heat treatment in which the hardening temperature is changed in stages, and the degree of hardening at the end of the first heat treatment is 85% or less, by The heat treatment after the second stage makes the degree of hardening exceed 85%.

[2] The cured product as described in [1], wherein the polymerizable group in the compound having a polymerizable group is composed of an epoxy group, an oxetanyl group, a vinyl ether group, and a vinyl phenyl group Choose more than one type of base.

[3] The hardened product as described in [1], wherein the compound having a polymerizable group is an epoxy-modified polyorganosilsesquioxane, and the epoxy-modified polyorganosilsesquioxane system has: The structural unit represented by the following formula (1), and the molar ratio of the structural unit represented by the following formula (I) and the structural unit represented by the following formula (II) [the structural unit represented by the formula (I) /The structural unit represented by formula (II)] is 5 or more; the structural unit represented by the above formula (1) and the following formula (4) with respect to the total amount of siloxane constituent units (100 mol %) The ratio of the constituent units is 55 to 100 mol%, the number average molecular weight is 1000 to 3000, and the molecular weight dispersion degree (weight average molecular weight/number average molecular weight) is 1.0 to 3.0. [R ¹ SiO _3/2 ] (1) In formula (1), R ¹ represents an epoxy group-containing group. [R ^a SiO _3/2 ] (I) In formula (I), R ^a represents an epoxy-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted ring Alkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom. [R ^b SiO _2/2 (OR ^c )] (II) In formula (II), R ^b represents an epoxy group-containing group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or Unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. [R ¹ SiO _2/2 (OR ^c )] (4) In formula (4), R ¹ is the same as in formula (1). R ^c is the same as in formula (II).

式中，R^1a、R^1b、R^1c、R^1d係相同或相異且表示直鏈或分支鏈狀之伸烷基。 [4] The cured product according to [3], wherein the above R ¹ is one or more groups selected from the group consisting of groups represented by the following formulas (1a) to (1d).

In the formula, R ^1a , R ^1b , R ^1c and R ^1d are the same or different and represent a straight-chain or branched-chain alkylene group.

[5] The cured product according to [3] or [4], wherein the epoxy-modified polyorganosilsesquioxane system further has a structural unit represented by the following formula (2). [R ² SiO _3/2 ] (2) In formula (2), R ² represents substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted Alkyl, or substituted or unsubstituted alkenyl.

[6] The hardened product according to [5], wherein the above R ² is a substituted or unsubstituted aryl group.

[7] The hardened product as described in [5] or [6], wherein, relative to the total amount (100 mol %) of the siloxane constituent units in the epoxy-modified polyorganosilsesquioxane, the above The ratio (total amount) of the structural unit represented by the formula (1), the structural unit represented by the above formula (2), the structural unit represented by the above formula (4), and the structural unit represented by the following formula (5) 60 to 100 mol%. [R ² SiO _2/2 (OR ^c )] (5) In formula (5), R ² represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, Substituted or unsubstituted alkyl, or substituted or unsubstituted alkenyl. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[8] The cured product according to any one of [3] to [7], wherein the polymerizable compound in the curable composition is the total amount (100% by weight) of the curable composition excluding the solvent The content (compounding amount) is 70% by weight or more and less than 100% by weight, and the proportion of epoxy-modified polyorganosilsesquioxane is 70% by weight or more of the total polymerizable compound (100% by weight).

[9] The cured product according to any one of [1] to [8], wherein the curable composition further contains a polymerization initiator.

[10] The cured product according to any one of [1] to [9], wherein the curable composition further contains a polymerization stabilizer.

[11] The hardened product as described in any one of [1] to [10], wherein the hardening group The adult system further contains a silane coupling agent.

[12] The cured product according to any one of [1] to [11], wherein the thermal decomposition temperature is 200° C. or higher.

[13] A method for manufacturing a hardened product, which is to perform a heat treatment in which the hardening composition containing a compound having a polymerizable group is changed stepwise to a curing temperature to produce a hardened product, and the degree of curing at the end of the first stage of the heat treatment is Below 85%, the degree of hardening exceeds 85% by heat treatment after the second stage.

[14] The method for producing a hardened product as described in [13], wherein the compound having a polymerizable group contains epoxy-modified polyorganosilicon silsesquioxane, and the epoxy-modified polyorganosilicon silsesquioxane Alkanes: having a structural unit represented by the following formula (1), a molar ratio of a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II) [represented by the formula (I) The constitutional unit/the constitutional unit represented by formula (II)] is 5 or more, and the constitutional unit represented by the above formula (1) and the following formula (1) with respect to the total amount (100 mole %) of siloxane constituent units 4) The ratio of the constituent units shown is 55 to 100 mol%, the number average molecular weight is 1000 to 3000, and the molecular weight dispersion degree (weight average molecular weight/number average molecular weight) is 1.0 to 3.0. [R ¹ SiO _3/2 ] (1) In formula (1), R ¹ represents an epoxy group-containing group. [R ^a SiO _3/2 ] (I) In formula (I), R ^a represents an epoxy-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted ring Alkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom. [R ^b SiO _2/2 (OR ^c )] (II) In formula (II), R ^b represents an epoxy group-containing group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or Unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. [R ¹ SiO _2/2 (OR ^c )] (4) In formula (4), R ¹ is the same as in formula (1). R ^c is the same as in formula (II).

[15] The method for producing a cured product as described in [13] or [14], wherein the first-stage heat treatment is performed for 5 minutes or more.

[16] The method for producing a cured product as described in [15], wherein the heating temperature in the first-stage heating treatment is 90° C. or more and less than 150° C.

[17] The method for producing a cured product according to any one of [13] to [16], wherein the heating temperature in the heat treatment after the second stage is 150 to 200°C.

[18] The method for producing a hardened product according to any one of [13] to [17], wherein the heating time in the heat treatment after the second stage is 5 to 120 minutes.

[19] The method for manufacturing a hardened product as described in any one of [13] to [18], wherein the heat treatment time of the first stage and the second stage is totaled (when the third stage and later are performed, the third stage is also added) The time required for the subsequent heat treatment) is 0.5 to 2 hours.

[20] A laminate consisting of three or more layers and having two layers to be bonded, and a bonding layer between the bonded layers, wherein the bonding layer is any one of [1] to [12] The hardened layer described in the item.

[21] An apparatus having the laminate as described in [20].

If the adhesive layer in the laminate is cracked or peeled, it will cause the adhesive layer to be peeled off and the wiring will be destroyed. As a result, it will cause the failure of the device equipped with the laminate, but the hardened material of the present invention has heat resistance and resistance The crackability, adhesion to the adherend, and adhesion are excellent, so even if the hot and cold shocks are applied, the adhesive layer will not be cracked or peeled, and a device with trustworthiness can be formed. In addition, when the laminate of the present invention is a three-dimensional laminate of a semiconductor wafer, it is higher in volume and power-saving than conventional semiconductors. Therefore, if the laminate of the present invention is used, a smaller and high-performance electronic device can be provided.

Fig. 1 is an explanatory diagram showing a method of evaluating the heat resistance of a cured product (schematic diagram of thermogravimetric analysis results).

[Hardening composition]

The curable composition in the present invention contains at least a compound having a polymerizable group (hereinafter referred to as "polymerizable compound"). The curable composition system in the present invention may further contain other components such as a polymerization initiator, a polymerization stabilizer, a surface modifier, or a surface modifier.

(Compound with a polymerizable group)

The polymerizable group in the compound having a polymerizable group may be any group that can be polymerized by heat treatment to form a cured product, and includes, for example, a cationic polymerizable group and a radical polymerizable group. In the present invention, among them, one or more groups selected from the group consisting of an epoxy group, an oxetanyl group, a vinyl ether group, and a vinyl phenyl group are preferred.

That is, the polymerizable compound in the present invention is preferably a compound having an epoxy group (hereinafter referred to as an "epoxy compound") and a compound having an oxetanyl group (hereinafter referred to as an "oxetane compound" ”), a compound having a vinyl ether group (hereinafter referred to as a “vinyl ether compound”), and a compound having a vinyl phenyl group (hereinafter referred to as a “vinyl phenyl compound”) selected from more than one type of compound .

(Epoxy compound)

The epoxy compound may be a known or conventional compound having one or more epoxy groups (ethylene oxide ring) in the molecule, and is not particularly limited, but examples thereof include epoxy-modified silicone compounds and alicyclic rings. Oxygen compounds (alicyclic epoxy resin), aromatic epoxy compounds (aromatic epoxy resin), aliphatic epoxy compounds (aliphatic epoxy resin), etc.

<Epoxy-modified silicone compound>

Examples of the epoxy-modified silicone compound include epoxy-modified polysiloxane, epoxy-modified polyorganosilsesquioxane, and the like. These can be used alone or in combination of two or more.

The epoxy-modified polysiloxane is a compound in which an epoxy group (for example, epoxypropyl group, alicyclic epoxy group, etc.) is introduced into at least one of the terminal and side chain of the dimethyl polysiloxane skeleton.

The epoxy-modified polyorganosilsesquioxane system has a silsesquioxane structure and an epoxy-bonded polysiloxane compound bonded thereto. The silsesquioxane structure includes a random structure, Cage-type structure and ladder-type structure.

The better epoxy-modified polyorganosilicon silsesquioxane system can The following compounds are exemplified, the compound having a structural unit represented by the following formula (1), a structural unit represented by the following formula (I) (hereinafter referred to as "T3 body") and a compound represented by the following formula (II) The molar ratio of the structural unit (hereinafter referred to as "T2 body") [the structural unit represented by formula (I)/the structural unit represented by formula (II); hereinafter described as "T3 body/T2 body"] is 5 or more , The ratio (total amount) of the structural unit shown in the above formula (1) and the structural unit shown in the following formula (4) with respect to the total amount (100 mole %) of the siloxane structural units is 55 to 100 Molar %, the number average molecular weight is 1000 to 3000, and the molecular weight dispersion degree (weight average molecular weight/number average molecular weight) is 1.0 to 3.0.

[R ¹ SiO _3/2 ] (1) In formula (1), R ¹ represents an epoxy group-containing group.

[R ^a SiO _3/2 ] (I) In formula (I), R ^a represents an epoxy-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted ring Alkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom.

[R ^b SiO _2/2 (OR ^c )] (II) In formula (II), R ^b represents an epoxy group-containing group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or Unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[R ¹ SiO _2/2 (OR ^c )] (4) In formula (4), R ¹ is the same as in formula (1), and R ^c is the same as in formula (II).

If the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I′). In addition, if the structural unit represented by the above formula (II) is described in more detail, it is represented by the following formula (II′). The three oxygen atoms bonded to the silicon atom shown in the structure shown in the following formula (I') are respectively bonded to other silicon atoms (silicon atoms not represented by the formula (I')). In addition, the two oxygen atoms located above and below the silicon atoms shown in the structure represented by the following formula (II') are also bonded to other silicon atoms (silicon atoms not represented by the formula (II')), respectively. That is, the T3 body and the T2 body are generally the structural units (ie, T units) represented by [RSiO _3/2 ], and are formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound. In addition, R in the above formula represents a hydrogen atom or a monovalent organic group, and the same applies hereinafter.

In the above formula (I) R ^a (formula (I 'in the middle of) R ^a are also the same) and formula (II) R ^b (formula (II' of the) R ^b are also the same) respectively comprising an epoxy-based Radical, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom. Specific examples of R ^a and R ^b can be the same as R ¹ in formula (1) and R ² in formula (2) described later. Further, in the middle of the formula (I) R ^a and formula (II) R ^b lines were derived from an epoxy group is used as the modified polyethylene bonded hydrolyzable organic silicon material of the silsesquioxane compound of trifunctional Silane Groups based on silicon atoms (groups other than alkoxy groups and halogen atoms; for example, R ¹ , R ² , and hydrogen atoms in formulae (a) to (c) described later).

In the above formula (II) (OR ^c) group (in the formula (II ') (OR ^c) are also the same yl) system represents a hydroxyl group or an alkoxy group having a carbon number of 1-4. Examples of the alkoxy group having 1 to 4 carbon atoms include alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy groups. The (OR ^c ) group in formula (II) is generally derived from the alkoxy group in the hydrolyzable silane compound used as the raw material of the epoxy-modified polyorganosilsesquioxane (for example, as X ¹ to X described later) ³ alkoxy, etc.).

The structural unit represented by the above formula (1) is a T unit (especially T3 body), which is formed by hydrolysis and condensation reaction of a corresponding hydrolyzable trifunctional silane compound (for example, a compound represented by formula (a) described later) .

R ¹ in formula (1) represents an epoxy group-containing group (monovalent group). The epoxy group-containing group may be a known or conventional group having an ethylene oxide ring, and it is not particularly limited, but it is preferably from the viewpoint of the curability of the curable composition and the heat resistance of the cured product One or more groups selected from the group consisting of the groups represented by the following formulas (1a) to (1d), of which the group represented by the following formula (1a) or (1c) is more preferred, particularly preferred It is a base represented by the following formula (1a).

In the formula, R ^1a , R ^1b , R ^1c and R ^1d are the same or different and represent a straight-chain or branched-chain alkylene group, and examples include methylene, methylmethylene and dimethylmethylene Straight or branched chain alkylene groups with 1 to 10 carbon atoms, such as alkyl, ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decamethylene, etc. .

Among them, R ^1a , R ^1b , R ^1c and R ^{1d are} preferably straight-chain alkylene having 1 to 4 carbon atoms, branched chain alkylene having 3 or 4 carbon atoms, and more preferably ethylidene or trialkylene Methyl and propyl, and more preferably ethyl and trimethylene.

R ¹ in formula (1) is particularly preferably a group represented by the above formula (1a) and R ^1a is an ethylidene group [for example, 2-(3′,4′-epoxycyclohexyl)ethyl].

The epoxy-modified polyorganosilsesquioxane may have only one type of structural unit represented by the above formula (1), or may have two or more types of structural units represented by the above formula (1).

Epoxy-modified polyorganosilicon silsesquioxane, as T The unit (especially the T3 body) may have the following formula (2) in addition to the structural unit represented by the above formula (1)

[R ² SiO _3/2 ] The structural unit shown in (2). The structural unit represented by the above formula (2) is formed by the hydrolysis and condensation reaction of a corresponding hydrolyzable trifunctional silane compound (for example, a compound represented by the formula (b) described later).

R ² in the above formula (2) represents substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, or substituted or unsubstituted Alkenyl. Examples of the aryl group include phenyl, tolyl, and naphthyl. Examples of the aralkyl group include benzyl and phenethyl. Examples of the cycloalkyl group include cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkyl group include straight-chain or branched-chain alkyl groups such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, second butyl, third butyl, and isopentyl groups. . The above-mentioned alkenyl group may be straight-chain or branched-chain alkenyl groups such as vinyl, allyl, and isopropenyl.

Examples of the substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, substituted alkyl group, and substituted alkenyl group include the hydrogen atom or main group in the aryl group, aralkyl group, cycloalkyl group, alkyl group, and alkenyl group. Part or all of the chain skeleton is composed of ether groups, ester groups, carbonyl groups, siloxyalkyl groups, halogen atoms (fluorine atoms, etc.), acryl groups, methacryl groups, mercapto groups, amine groups, and hydroxyl groups (hydroxyl groups). At least one substituted group selected in groups.

Among them, R ^{2 is} preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, and still more preferably a phenyl group.

In the epoxy-modified polyorganosilicon silsesquioxane, the ratio of the structural unit represented by formula (1) and the structural unit represented by formula (2) can be used to form the raw materials (hydrolyzability) of these structural units The composition of trifunctional silane) can be adjusted appropriately.

In the epoxy-modified polyorganosilsesquioxane, as the T unit (especially the T3 body), in addition to the structural unit represented by the above formula (1) and the structural unit represented by the formula (2), it may have, for example The structural unit represented by the following formula (3).

[HSiO _3/2 ] (3)

The above ratio [T3 body/T2 body] of epoxy-modified polyorganosilsesquioxane is 5 or more, which means that there is a certain amount of T2 body relative to T3 body. Examples of such a T2 body include a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), and a structural unit represented by the following formula (6).

[R ¹ SiO _2/2 (OR ^c )] (4)

[R ² SiO _2/2 (OR ^c )] (5)

[HSiO _2/2 (OR ^c )] (6) The above R ¹ , R ² , and (OR ^c ) are the same as described above.

In epoxy-modified polyorganosilsesquioxane, the ratio of the structural unit (T3 body) represented by the above formula (I) to the structural unit (T2 body) represented by the above formula (II) [T3 body/T2 As described above, the system is 5 or more, preferably 5 to 18, more preferably 6 to 16, and even more preferably 7 to 14. By setting the above ratio [T3 body/T2 body] to 5 or more, the adhesion of the hardened product can be significantly improved.

In the epoxy-modified polyorganosilsesquioxane, the above ratio [T3 body/T2 body] system can be obtained by ²⁹ Si-NMR spectrometry, for example. ^{29 In the} Si-NMR spectrum, the silicon atom in the structural unit (T3 body) represented by the above formula (I) and the silicon atom in the structural unit (T2 body) represented by the above formula (II) are at different positions (chemical Displacement) shows the signal (peak), and the above ratio [T3 body/T2 body] is obtained by calculating the integral ratio of individual peaks. For example, when the epoxy-modified polyorganosilsesquioxane has the structural unit represented by the above formula (1) and R ¹ is 2-(3′,4′-epoxycyclohexyl)ethyl, the above formula ( The signal of the silicon atom in the structure (T3 body) shown in I) appears from -64 to -70 ppm, and the signal of the silicon atom in the structure (T2 body) shown in the above formula (II) appears in -54 to -60 ppm. Therefore, by calculating the integral ratio of the signal of -64 to -70 ppm (T3 body) and the signal of -54 to -60 ppm (T2 body) at this time, the above ratio [T3 body/T2 body] can be obtained.

In addition, for example, the ²⁹ Si-NMR spectrum of the epoxy-modified polyorganosilsesquioxane can be measured by the following equipment and conditions.

Measuring device: Trade name "JNM-ECA500NMR" (manufactured by JEOL Ltd.).

Solvent: heavy chloroform.

Cumulative times: 1800 times.

Measurement temperature: 25°C.

In general, the complete cage silsesquioxane is a polyorganosilsesquioxane composed of only T3 body, and there is no T2 body in the molecule. That is to say, the epoxy-modified polyorganosilsesquioxane system having the above ratio [T3 body/T2 body] of 5 or more has an incomplete cage-type silsesquioxane structure.

It can be confirmed from the FT-IR spectrum that there are no intrinsic absorption peaks near 1050cm ^-1 and 1150cm ^-1 respectively, and there is an intrinsic absorption peak near 1100cm ^-1 , and it is confirmed that the epoxy-modified polyorganosilsesquioxane has Cage type (especially incomplete cage type) silsesquioxane structure [Reference: RHRaney, M. Itoh, A. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. For this reason, it is generally recognized as having a ladder-type silsesquioxane structure when the FT-IR spectrum has inherent absorption peaks near 1050 cm ^-1 and 1150 cm ^-1 , respectively. In addition, for example, the FT-IR spectrum of epoxy-modified polyorganosilsesquioxane can be measured by the following equipment and conditions.

Measuring device: Trade name "FT-720" (Horiba Manufacturing Co., Ltd.).

Measurement method: penetration method.

Decomposition energy: 4cm ^-1 .

Measurement wavenumber domain: 400 to 4000 cm ^-1 .

Cumulative times: 16 times.

The epoxy-modified polyorganosilicon silsesquioxane may have, in addition to the T unit described above, for example, a structural unit represented by [R ₃ SiO _1/2 ] (that is, an M unit) or [R ₂ SiO] At least one type of siloxane constituent unit selected from the group consisting of the constituent unit (that is, D unit) and the constituent unit (that is, Q unit) shown in [SiO ₂ ].

Relative to the total amount of siloxane constituent units in epoxy-modified polyorganosilicon silsesquioxane [total siloxane constituent units; total amount of M units, D units, T units, and Q units] (100 Mo Ear %), the ratio (total amount) of the structural unit shown in the above formula (1) and the structural unit shown in the above formula (4) is 55 to 100 mole% as described above, preferably 65 to 100 mole Ear %, more preferably 80 to 99 mole %. By making the above ratio 55 mol% or more, While the hardenability of the hardenable composition can be improved, the adherence of the hardened object can be significantly improved. In addition, the ratio of each siloxane constituent unit in the epoxy-modified polyorganosilsesquioxane can be calculated from, for example, the raw material composition, NMR spectrum measurement, and the like.

Relative to the total amount of siloxane constituent units in epoxy-modified polyorganosilicon silsesquioxane [total siloxane constituent units; total amount of M units, D units, T units, and Q units] (100 Mo Ear%), the ratio (total amount) of the structural unit represented by the above formula (2) and the structural unit represented by the above formula (5) is not particularly limited, but it is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, more preferably 0 to 40 mol%, particularly preferably 1 to 15 mol%. By setting the above ratio to 70 mol% or less, the ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (4) can be relatively large, so the curability of the curable composition is improved Moreover, the tendency of the adhesiveness of the hardened material is further improved.

Relative to the total amount of siloxane constituent units in epoxy-modified polyorganosilicon silsesquioxane [total siloxane constituent units; total amount of M units, D units, T units, and Q units] (100 Mo Ear %), the proportion of the constituent unit shown in the above formula (1), the constituent unit shown in the above formula (2), the constituent unit shown in the above formula (4), and the constituent unit shown in the above formula (5) (Total amount) is not particularly limited, but it is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and still more preferably 80 to 100 mol%. By setting the above ratio to 60 mol% or more, there is a tendency to further improve the adhesion of the hardened product.

The epoxy-modified polyorganosilicon silsesquioxane has a molecular weight dispersion (Mw/Mn) in terms of standard polystyrene measured by GPC of 1.0 to 3.0 as described above, preferably 1.1 to 2.0, more preferably 1.2 to 1.9, special Good is 1.45 to 1.80. By making the molecular weight dispersion degree 3.0 or less, the adhesiveness of the cured product can be further improved. On the other hand, by setting the molecular weight dispersion degree to 1.0 or more (preferably 1.1 or more), there is a tendency to easily form a liquid state and improve workability.

The number-average molecular weight (Mn) of the epoxy-modified polyorganosilsesquioxane measured by GPC in terms of standard polystyrene is 1000 to 3000 as described above, preferably 1000 to 2800, more preferably 1000 to 2600. By setting the number average molecular weight to 1,000 or more, the heat resistance and adhesiveness of the cured product can be further improved. On the other hand, by setting the number average molecular weight to 3000 or less, the compatibility with other components in the curable composition can be improved, and the heat resistance of the cured product can be further improved.

In addition, the number average molecular weight and molecular weight dispersion of the epoxy-modified polyorganosilsesquioxane can be measured by the method described in the examples.

For example, epoxy-modified polyorganosilsesquioxane can be produced by the method of hydrolyzing and condensing one or more hydrolyzable silane compounds. However, as the aforementioned hydrolyzable silane compound, it is necessary to use a hydrolyzable trifunctional silane compound (compound represented by the following formula (a)) used to form the structural unit represented by the above formula (1) as a necessary hydrolyzability Silane compounds.

More specifically, for example, the compound represented by the following formula (a) used to form the hydrolyzable silane compound of the T unit, and the compound represented by the following formula (b) if necessary, the following formula (c) The method of hydrolysis and condensation of the compound shown to produce epoxy-modified polyorganosilsesquioxane.

R ¹ Si(X ¹ ) ₃ (a)

R ² Si(X ² ) ₃ (b)

HSi(X ³ ) ₃ (c)

The compound represented by the above formula (a) is a compound forming the structural unit represented by the formula (1) and the structural unit represented by the formula (4) in the epoxy-modified polyorganosilsesquioxane. In the formula (a) R ¹ group corresponding the above formula (1), (4) R ^1.

X ¹ in the above formula (a) represents an alkoxy group or a halogen atom. The alkoxy group in X ¹ may be the same as the alkoxy group having 1 to 4 carbon atoms in the (OR ^c ) group. In addition, the halogen atom in X ¹ may be a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or the like. X ¹ is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. In addition, the three X ^1s may be the same or different.

The compound represented by the above formula (b) is a compound that forms the structural unit represented by the formula (2) and the structural unit represented by the formula (5) in the epoxy-modified polyorganosilsesquioxane. In the formula (b) R ² lines corresponding to the above formula (2), (5) R ^2.

X ² in the above formula (b) represents an alkoxy group or a halogen atom. Specific examples of X ² include those exemplified by X ¹ . Among them, X ^{2 is} preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. In addition, the three X ² may be the same or different.

The compound represented by the above formula (c) is a compound forming the structural unit represented by the formula (3) and the structural unit represented by the formula (6) in the epoxy-modified polyorganosilsesquioxane. X ³ in the above formula (c) represents an alkoxy group or a halogen atom. Specific examples of X ³ include those exemplified by X ¹ . Among them, X ^{3 is} preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. In addition, the three X ³ may be the same or different.

As the hydrolyzable silane compound, hydrolyzable silane compounds other than the compounds represented by the above formulas (a) to (c) may be used in combination. Examples include hydrolyzable trifunctional silane compounds other than the compounds represented by the above formulas (a) to (c), hydrolyzable monofunctional silane compounds forming M units, hydrolyzable difunctional silane compounds forming D units, and Q units forming The hydrolyzable tetrafunctional silane compound, etc.

The use amount and composition of the above hydrolyzable silane compound can be adjusted appropriately according to the required structure of epoxy-modified polyorganosilsesquioxane. For example, the amount of the compound represented by the above formula (a) is not particularly limited, but it is preferably 55 to 100 mol% relative to the total amount of hydrolyzable silane compounds used (100 mol%), more preferably 65 to 100 mol%, and more preferably 80 to 99 mol%.

In addition, the amount of the compound represented by the above formula (b) is not particularly limited, but it is preferably 0 to 70 mol% relative to the total amount of hydrolyzable silane compounds used (100 mol%), more preferably 0 to 60 mol%, more preferably 0 to 40 mol%, particularly preferably 1 to 15 mol%.

In addition, the ratio (ratio of the total amount) of the compound represented by the formula (a) to the compound represented by the formula (b) with respect to the total amount (100 mole %) of the hydrolyzable silane compound used is not particularly limited, However, it is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and still more preferably 80 to 100 mol%.

Furthermore, when two or more of the above hydrolyzable silane compounds are used in combination, the hydrolysis and condensation reactions of these hydrolyzable silane compounds may be performed simultaneously or sequentially. When the above reaction is carried out one by one, the order of carrying out the reaction is not particularly limited.

烷等醚；丙酮、甲基乙酮、甲基異丁酮等酮；乙酸甲酯、乙酸乙酯、乙酸異丙酯、乙酸丁酯等酯；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺；乙腈、丙腈、苯甲腈等腈；甲醇、乙醇、異丙醇、丁醇等醇等。上述溶劑中較佳為酮、醚。又，溶劑可單獨使用1種或組合2種以上使用。 The hydrolysis and condensation reaction of the above hydrolyzable silane compound may be carried out in the presence of a solvent or in the absence. Among them, it is preferably carried out in the presence of a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; diethyl ether, dimethoxyethane, tetrahydrofuran,

Ethers such as alkane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate and other esters; N,N-dimethylformamide, N , N-dimethylacetamide and other amides; acetonitrile, propionitrile, benzonitrile and other nitriles; methanol, ethanol, isopropanol, butanol and other alcohols. Among the above solvents, ketones and ethers are preferred. In addition, one type of solvent may be used alone or two or more types may be used in combination.

The amount of the solvent used is not particularly limited, and it can be appropriately adjusted according to the required reaction time, etc. within a range of 0 to 2000 parts by weight with respect to the total amount of 100 parts by weight of the hydrolyzable silane compound.

The hydrolysis and condensation reaction of the hydrolyzable silane compound is preferably carried out in the presence of a catalyst and water. The above catalyst may be an acid catalyst or an alkali catalyst. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; phosphate esters; carboxylic acids such as acetic acid, formic acid, and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid. Acid; solid acid such as activated clay; Lewis acid such as ferric chloride. Examples of the alkali catalyst include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; hydroxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide; Lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate and other alkali metal carbonates; magnesium carbonate and other alkaline earth metal carbonates; lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate and other alkali metal bicarbonates ; Lithium acetate, sodium acetate, Organic acid salts of alkali metals such as potassium acetate and cesium acetate (such as acetate); Organic acid salts of alkaline earth metals such as magnesium acetate (such as acetate); lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide , Alkali metal alkoxides such as potassium ethoxide, potassium tributoxide, etc.; benzene oxides of alkali metals such as sodium phenoxide; triethylamine, N-methylpiperidine, 1,8-diazabicyclo[5.4 .0] Undecane-7-ene, 1,5-diazabicyclo[4.3.0]nonane-5-ene and other amines (level 3 amine, etc.); pyridine, 2,2'-bipyridine, 1,10-Porphyrin and other nitrogen-containing aromatic heterocyclic compounds. In addition, the catalyst can be used alone or in combination of two or more. In addition, the catalyst can be used in a state where it is dissolved or dispersed in water, a solvent, or the like.

The amount of the catalyst used is not particularly limited, and can be appropriately adjusted within a range of 0.002 to 0.200 mol relative to 1 mol of the total amount of hydrolyzable silane compounds.

In the above hydrolysis and condensation reaction, the amount of water used is not particularly limited, and can be appropriately adjusted within a range of 0.5 to 20 moles relative to 1 mole of the total amount of hydrolyzable silane compounds.

The method of adding the above water is not particularly limited, and the total amount of water used (total use amount) may be added at a time, or may be added sequentially. When adding one by one, it can be added continuously or at intervals.

As the reaction conditions for the hydrolysis and condensation reaction of the above hydrolyzable silane compound, it is particularly important to select a reaction in which the above ratio [T3 body/T2 body] in the epoxy-modified polyorganosilsesquioxane becomes 5 or more condition. The reaction temperature of the above hydrolysis and condensation reaction is not particularly limited, but it is preferably 40 to 100°C, more preferably 45 to 80°C. By controlling the reaction temperature in the above range, it is possible to more efficiently convert the above ratio [T3 body /T2 body] tends to be controlled at 5 or more. In addition, the reaction time of the above-mentioned hydrolysis and condensation reaction is not particularly limited, but it is preferably 0.1 to 10 hours, and more preferably 1.5 to 8 hours. In addition, the above-mentioned hydrolysis and condensation reactions may be carried out under normal pressure, or may be carried out under pressure or under reduced pressure. The environment during the hydrolysis and condensation reaction is not particularly limited. For example, it may be any of an inert gas environment such as a nitrogen environment and an argon environment, and the presence of oxygen such as air. However, it is preferably an inert gas environment. .

Through the hydrolysis and condensation reaction of the above hydrolyzable silane compound, epoxy-modified polyorganosilsesquioxane can be obtained. After the completion of the above hydrolysis and condensation reaction, in order to suppress the ring opening of the epoxy group, it is preferable to neutralize the catalyst. In addition, the obtained epoxy-modified polyorganosilsesquioxane can be washed, washed, pickled, washed with alkali, filtered, concentrated, distilled, extracted, crystallized, recrystallized, column chromatography, etc. Separation means, or a combination of these separation means, etc., and separation purification.

<alicyclic epoxy compound>

Examples of the alicyclic epoxy compound include known or conventional compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, which are not particularly limited, but include, for example, the following compounds.

(1) The molecule has an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting an alicyclic ring (referred to as "alicyclic epoxy group" in this specification. The alicyclic epoxy group includes, for example, an oxidized ring Compounds such as hexenyl.

(2) A compound in which an epoxy group is directly bonded to an alicyclic ring by a single bond.

(3) Compounds having alicyclic and glycidyl ether groups in the molecule (epoxypropyl ether type epoxy compounds).

Examples of the compound (1) having an alicyclic epoxy group in the molecule include compounds represented by the following formula (i).

In the above formula (i), Y represents a single bond or a linking group (a divalent group having 1 or more atoms). Examples of the above-mentioned linking group include a divalent hydrocarbon group, an alkenyl group in which a part or all of a carbon-carbon double bond is partially epoxy-based, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and the like Plural connected bases, etc.

Examples of the divalent hydrocarbon group include straight-chain or branched chain alkylene groups having 1 to 18 carbon atoms, and divalent alicyclic hydrocarbon groups having 3 to 18 carbon atoms. Examples of the straight-chain or branched-chain alkylene group having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylidene, propylidene and trimethylene groups. Examples of the divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms include 1,2-cyclopentyl, 1,3-cyclopentyl, cyclopentylene, 1,2-cyclohexyl, 1,3-cyclohexyl, Cycloalkylene (including cycloalkylene) such as 1,4-cyclohexylene and cyclohexylene, etc.

The alkenyl group in the alkenyl group in which a part or all of the above carbon-carbon double bond is partially or fully epoxylated (hereinafter referred to as "epoxylated alkenyl group") includes, for example, vinylidene group, propenyl group, Straight-chain or branched carbon number 2 to 8 such as 1-butenyl, 2-butenyl, butadienyl, pentenyl, hexenyl, heptenyl, octenyl, etc. Chain-like alkenyl and so on. Especially preferably, the above-mentioned epoxy-based alkenyl group is an alkenyl group in which all the carbon-carbon double bonds are epoxy-based, more preferably the carbon number of the carbon-carbon double bonds is all epoxy-based in the range of 2 to 4. Diene base.

Representative examples of the alicyclic epoxy compound represented by the above formula (i) include (3,4,3',4'-diepoxy)dicyclohexyl, bis(3,4-epoxycyclohexylmethyl Group) ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexane -1-yl)propane, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, compounds represented by the following formulas (i-1) to (i-10), etc. In addition, R′ in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and among them, methylene, ethylidene, propylidene, isopropylidene, etc. are preferred. 3 straight chain or branched chain alkylene. In addition, n ¹ to n ⁸ in the following formulas (i-5), (i-7), (i-9), and (i-10) each represent an integer of 1 to 30.

Examples of the compound in which (2) the epoxy group is directly bonded to the alicyclic ring by a single bond include compounds represented by the following formula (ii).

In formula (ii), R” is a group (p-valent organic group) in which p hydroxyl groups (-OH) are removed from the structural formula of p-alcohol, p and n represent natural numbers, respectively. p-valent alcohol [R” ( OH) _p ] include polyhydric alcohols such as 2,2-bis(hydroxymethyl)-1-butanol (alcohols having 1 to 15 carbon atoms) and the like. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in the base within each [] (inside the parenthesis) may be the same or different. The compound represented by the above formula (ii) specifically includes 1,2-epoxy-4-(2-oxiranyl) of 2,2-bis(hydroxymethyl)-1-butanol Cyclohexane adduct [for example, trade name "EHPE3150" (made by Daicel Corporation), etc.], etc.

Examples of the compound (3) having alicyclic and glycidyl ether groups in the molecule include glycidyl ethers of alicyclic alcohols (especially alicyclic polyols). More specifically, for example, 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane, 2,2-bis[3,5-dimethyl-4-(2, 3-epoxypropoxy)cyclohexyl]propane and other compounds that hydrogenate bisphenol A epoxy compound (hydrogenated bisphenol A epoxy compound); bis[o,o-(2,3-epoxypropoxy Yl)cyclohexyl]methane, bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl]methane , Bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane and other compounds that hydrogenate bisphenol F-type epoxy compounds (hydrogenated bisphenol F-type epoxy compounds) ; Hydrogenated biphenyl epoxy compound; Hydrogenated phenol novolac epoxy compound; Hydrogenated cresol novolac epoxy compound; Bisphenol A hydrogenated cresol novolac epoxy compound; Hydrogenated naphthalene epoxy compound; Hydrogenated epoxy compounds obtained from triphenol methane; hydrogenated aromatic epoxy compounds described below, etc.

<aromatic epoxy compound>

Examples of the above-mentioned aromatic epoxy compound include Epi-Bis-type propylene oxide obtained by condensation reaction of bisphenols [for example, bisphenol A, bisphenol F, bisphenol S, stilbene, etc.] with epichlorohydrin. Ether based epoxy resin; high molecular weight Epi-Bis epoxy propyl ether ring obtained by further addition reaction of these Epi-Bis epoxy propyl ether epoxy resin with the above bisphenols Oxygen resin; combining phenols [such as phenol, cresol, phenol, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, etc.] with aldehydes [such as formaldehyde, acetaldehyde, benzaldehyde , Hydroxybenzaldehyde, salicylaldehyde, etc.] Polyols obtained by condensation reaction, and then novolak/alkyl epoxypropyl ether type epoxy resin obtained by condensation reaction with epichlorohydrin; Two phenol skeletons are bonded to the site, and an epoxy compound, such as an epoxy group, is directly or through an alkoxy group bonded to an oxygen atom on which a hydrogen atom is removed from the hydroxyl group of the phenol skeleton.

<aliphatic epoxy compound>

Examples of the above-mentioned aliphatic epoxy compound include epoxypropyl ethers of alcohols having no q-valent cyclic structure (q is a natural number); monovalent or polyvalent carboxylic acids [e.g. acetic acid, propionic acid, butyric acid, stearic acid Acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.] epoxypropyl ester; epoxy-based linseed oil, epoxy-based soybean oil, epoxy-based castor oil, etc. The epoxy compound of the oil and fat of the bond; the epoxy compound of the polyolefin (containing polyalkylene) containing epoxy group polybutadiene, etc. Moreover, the alcohol which does not have a q-valent cyclic structure includes, for example, monohydric alcohols such as methanol, ethanol, 1-propanol, isopropanol, and 1-butanol; ethylene glycol, 1,2-propanediol, 1, 3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol Alcohol, polypropylene glycol and other diols; glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, neopentyl alcohol, dipentaerythritol, sorbitol, etc., with a trivalent or higher Of polyols, etc. Furthermore, the q-valent alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like.

(Oxetane compound)

The oxetane compound may be a known or conventional compound having one or more oxetane rings in the molecule, and is not particularly limited, but it may be, for example, 3,3-bis(ethyleneoxymethyl) Oxetane, 3-ethyl-3-(hydroxyl Methyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-[(phenoxy)methyl]oxy Heterocyclobutane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, 3,3-bis(chloro Methyl)oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, bis{[1-ethyl(3-oxetanyl )]Methyl}ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]bicyclohexane, 1,4-bis[(3-ethyl -3-oxetanyl)methoxymethyl]cyclohexane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3 -Ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl)}oxetane, xylene dioxetane, 3-ethyl -3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, oxetanyl silsesquioxane, phenol novolak oxetane, etc.

(Vinyl ether compound)

The vinyl ether compound may be a known or conventional compound having one or more vinyl ether groups in the molecule, and is not particularly limited, but examples thereof include 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether) and 3-hydroxypropyl Vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl Vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4 -Hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinyl ether, 1,8-octanediol divinyl ether, 1,4-cyclohexane Dimethanol monovinyl ether, 1,4-cyclohexane dimethanol divinyl ether, 1,3-cyclohexane dimethanol monovinyl ether, 1,3-cyclohexane dimethanol divinyl ether, 1,2-cyclo Hexane dimethanol monovinyl ether, 1,2-cyclohexane dimethanol divinyl ether, p-xylene glycol monovinyl ether, P-xylene glycol divinyl ether, m-xylene glycol monovinyl ether, m-xylene glycol divinyl ether, o-xylene glycol monovinyl ether, o-xylene glycol divinyl ether, ethylene glycol divinyl ether Ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol monovinyl ether, tetraethylene glycol divinyl ether, Pentaethylene glycol monovinyl ether, pentaethylene glycol divinyl ether, oligomeric polyethylene glycol monovinyl ether, oligomeric polyethylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol divinyl ether, Dipropylene glycol monovinyl ether, dipropylene glycol divinyl ether, tripropylene glycol monovinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol monovinyl ether, tetrapropylene glycol divinyl ether, pentapropylene glycol monovinyl ether, pentapropylene glycol divinyl ether, oligomer Propylene glycol monovinyl ether, oligomeric propylene glycol divinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol divinyl ether, isosorbide divinyl ether, oxanor camphenene divinyl ether, phenyl vinyl ether, n-butyl vinyl ether , Isobutyl vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, trimethylol propane di Vinyl ether, trimethylolpropane trivinyl ether, bisphenol A divinyl ether, bisphenol F divinyl ether, hydroxyoxorane camphane methanol divinyl ether, 1,4-cyclohexanediol divinyl ether, Neopentaerythritol triethylene ether, neopentaerythritol tetraethylene ether, dipentaerythritol pentaethylene ether, dipentaerythritol hexaethylene ether, etc.

(Vinyl phenyl compound)

Examples of the vinyl phenyl compound include styrene, divinylbenzene, methoxystyrene, ethoxystyrene, hydroxystyrene, vinylnaphthalene, vinylanthracene, 4-vinylphenyl acetate, (4-vinylphenyl ) Dihydroxyborane, 4-vinylphenylboronic acid, 4-vinylphenylborane acid, 4-vinylphenylboronic acid, p-ethylene Phenylboronic acid, N-(4-vinylphenyl)maleimide, etc.; and derivatives thereof.

In the present invention, the content (compounding amount) of the polymerizable compound in the curable composition is not particularly limited, but the total amount (100% by weight) of the curable composition excluding the solvent is 70% by weight or more, which is It is preferably less than 100% by weight, more preferably 80 to 99.8% by weight, and still more preferably 90 to 99.5% by weight. When the content of the polymerizable compound is 70% by weight or more, the heat resistance of the cured product tends to be further improved.

In addition, in the present invention, the curable composition preferably contains an epoxy-modified polyorganosilsesquioxane as a polymerizable compound in that it can form a cured product excellent in heat resistance and crack resistance. The proportion of epoxy-modified polyorganosilsesquioxane is preferably 70% by weight or more (for example, 70 to 100% by weight) of the total amount of polymerizable compounds (100% by weight) contained in the hardenable composition, more preferably It is 75% by weight or more, and more preferably 80% by weight or more.

(Polymerization initiator)

The polymerization initiator includes a cationic polymerization initiator and an anionic polymerization initiator. The cationic polymerization initiator is a compound that generates cationic species by heating and starts the hardening reaction of the polymerizable compound, and the anionic polymerization initiator is a compound that generates anionic species by heating and starts the hardening reaction of the polymerizable compound. If the curable composition in the present invention contains a polymerization initiator, the curing time until it becomes non-sticky can be shortened. In addition, the polymerization initiator may be used alone or in combination of two or more.

In the present invention, in order to obtain an adhesive layer having the following characteristics, it is preferable to include a polymerization start having the following hardening characteristics Agent: By heating and drying, the adhesive layer can be quickly formed without the hardening reaction, and it does not have adhesiveness at less than 50°C, and exhibits adhesiveness by heating at a temperature that can suppress damage to the adhesive body. , And then quickly hardened until it became non-sticky.

That is, in the case of a cationic polymerization initiator, it is preferable to use the following polymerization initiator, which is made of 3,4-epoxycyclohexylmethyl (3,4-epoxy) Cyclohexane carboxylate [e.g. trade name "CELLOXIDE 2021P" (made by Daicel Co., Ltd.)] 100 parts by weight of a composition obtained by adding 1 part by weight of a cationic polymerization initiator at 130°C has a heat curing time of 3.5 minutes or more (e.g. 3.5 to 7.0 minutes, preferably 4.5 to 6.0 minutes).

Moreover, in the case of an anionic polymerization initiator, it is preferable to use the following polymerization initiator which added 1 weight part of anionic polymerization initiators to 100 weight part of p-bisphenol A diglycidyl ether. The obtained composition had a heat curing time at 130°C of 3.5 minutes or more.

In addition, the thermal hardening time in the present invention is obtained by a method according to JIS K5909 (1994), and the aforementioned composition is heated on a hot plate until it becomes rubber-like (more specifically, hardening is performed until the needle does not Time until drawing). If a polymerization initiator with a heat hardening time lower than the above range is used, cationic species will be generated when the cationic polymerization initiator is used during heating and drying, and anionic species will be generated when the anionic polymerization initiator is used, and then even at room temperature It also slowly polymerizes, so it is difficult to form an adhesive layer with preservation stability.

The above cationic polymerization initiators include heat-absorbing sun The ion part and the anion part which becomes the source of acid generation. Examples of the cationic polymerization initiator include aryl alkoxide salts, aryl gallium salts, aromatic hydrocarbon-ion complexes, quaternary ammonium salts, aluminum chelate compounds, and boron trifluoride amine complexes. In the present invention, among them, aryl alkanoate is preferred in terms of hardening rate.

Examples of the cationic part in the aryl carbomer salt include (4-hydroxyphenyl) methylbenzyl carbamide ion, triphenyl carbamide ion, diphenyl[4-(phenylthio)phenyl] carbamide ion, 4 -(4-biphenylthio) phenyl-4-biphenylphenyl amide ions, tri-p-tolyl amide ions and other aryl amide ions (especially triaryl amide ions).

Aryl sulfonium anion portion salts may be, for example, _{^{SbF 6 -, PF 6 -,}} BF 4 -, (CF 3 CF 2) 3 PF 3 -, (CF 3 CF 2 CF 2) 3 PF 3 -, (C 6 F ^{_{5) 4 B -, (C}} 6 F 5) 4 Ga -, sulfonic acid anion (trifluoromethanesulfonic acid anion, pentafluoroethane sulfonic acid anion, nonafluorobutanesulfonic acid anion, methanesulfonic acid anion, benzenesulfonic acid anions, toluenesulfonic acid anions, _{etc.), (CF 3 SO 2)} 3 C -, (CF 3 SO 2) 2 N -, perhalogen acid ion, a sulfonic acid halide ion, sulfate ion, carbonate ion, aluminate ion , Hexafluorobismuth acid ion, carboxylic acid ion, aryl boric acid ion, thiocyanate ion, nitric acid ion, etc.

Examples of the cationic polymerization initiators include trade names "SP-66" and "SP-77" (above manufactured by ADEKA Corporation); trade names "SANEID SI-60L", "SANEID SI-80L", and "SANEID" "SI-100L", "SANEID SI-150L" (above are manufactured by Sanxin Chemical Industry Co., Ltd.) and other commercial products.

、2-苯基咪唑啉、2,3-二氫-1H-吡咯并[1,2-a]苯并咪唑、1-氰基乙基-2-甲基咪唑、1-氫基乙基-2-十一烷基咪唑等。又，前述3級胺包括例如三(二甲基胺基甲基)酚、苄基二甲胺、DBU(1,8-二氮雜雙環[5.4.0]十一烯-7)等。 Examples of the anionic polymerization initiator include primary amines, secondary amines, tertiary amines, imidazoles, and boron trifluoride-amine complexes. The aforementioned imidazoles include, for example, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2,4-diamine Yl-6-[2-methylimidazolyl-(1)]ethyl-s-tri

, 2-phenylimidazoline, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-cyanoethyl-2-methylimidazole, 1-hydroethyl- 2-undecyl imidazole, etc. In addition, the aforementioned tertiary amine includes, for example, tris(dimethylaminomethyl)phenol, benzyldimethylamine, DBU (1,8-diazabicyclo[5.4.0]undecene-7), and the like.

In the present invention, it is preferable to use a cationic polymerization initiator (in particular, a thermal cationic polymerization initiator, and most preferably an aryl alkoxide salt) in terms of the hardening rate.

The content (compounding amount) of the polymerization initiator is not particularly limited, but it is preferably 0.01 to 3.0 parts by weight, more preferably 0.05 to 100 parts by weight with respect to 100 parts by weight of the polymerizable compound contained in the curable composition in the present invention. 2.0 parts by weight, more preferably 0.1 to 1.0 parts by weight, particularly preferably 0.3 to 0.8 parts by weight. By setting the content of the polymerization initiator to be 0.01 parts by weight or more, the curing reaction can be efficiently performed, and there is a tendency to further improve the heat resistance and adhesiveness of the cured product. On the other hand, by setting the content of the polymerization initiator to 3.0 parts by weight or less, there is a tendency to further improve the storage property of the curable composition and suppress the coloration of the cured product.

(Polymer stabilizer)

The polymerization stabilizer is a compound that inhibits the progress of cationic polymerization by capturing cations. The cation trapping energy of the polymerization stabilizer is saturated and lost by heating. When the curable composition in the present invention contains a cationic polymerization initiator, it is possible to suppress the progress of polymerization for a long time after coating, drying and forming an adhesive layer, and excellent adhesion can be exhibited by heating when the adhesiveness is required It is preferable to contain a cationic polymerization initiator and a polymerization stabilizer in terms of the number of adhesive layers having excellent properties and excellent storage stability.

-2,4-二基][(2,2,6,6-四甲基-4-哌啶基)亞胺基]六亞甲基[(2,2,6,6-四甲基-4-哌啶基)亞胺基])、四(2,2,6,6-四甲基-4-哌啶基)丁烷-1,2,3,4-四羧酸酯、2,2,6,6-四甲基-4-哌啶基苯甲酸酯、(混合2,2,6,6-四甲基-4-哌啶基/三癸基)-1,2,3,4-丁烷四羧酸酯、3,9-雙(2,3-二第三丁基-4-甲基苯氧基)-2,4,8,10-四氧雜-3,9-二磷雜螺[5.5]十一烷、混合(2,2,6,6-四甲基-4-哌啶基/β,β,β’,β’-四甲基-3-9-[2,4,8,10-四氧雜螺[5.5]十一烷]二乙基)-1,2,3,4-丁烷四羧酸酯、聚([6-N-嗎啉基-1,3,5-三

-2,4-二基][(2,2,6,6-四甲基-4-哌啶基)亞胺基]六亞甲基[(2,2,6,6-四甲基-4-哌啶基)亞胺基])、[N-(2,2,6,6-四甲基-4-哌啶基)-2-甲基-2-(2,2,6,6-四甲基-4-哌啶基)亞胺基]丙醯胺、商品名「LA-77」、「LA-67」、「LA-57」(以上為ADEKA製)、商品名「TINUVIN123」、「TINUVIN152」(以上為CibaJapan股份有限公司製)等受阻胺系化合物；(4-羥基苯基)二甲基鋶甲基亞硫酸酯(SANEIDSI助劑、三新化學工業股份有限公司製)等鋶硫酸鹽系化合物、商品名「PEP-36」(ADEKA股份有限公司製)等亞磷酸酯系化合物等。該等可單獨使用1種或組合2種以上使用。 Examples of the aforementioned polymerization stabilizer include bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and poly((6-(1,1,3,3-tetramethylbutane Group) imino-1,3,5-tri

-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl- 4-piperidinyl)imino]), tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)butane-1,2,3,4-tetracarboxylate, 2, 2,6,6-tetramethyl-4-piperidinyl benzoate, (mixed 2,2,6,6-tetramethyl-4-piperidinyl/tridecyl)-1,2,3 ,4-butane tetracarboxylate, 3,9-bis(2,3-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9 -Diphosphaspiro[5.5]undecane, mixed (2,2,6,6-tetramethyl-4-piperidinyl/β,β,β',β'-tetramethyl-3-9- [2,4,8,10-tetraoxaspiro[5.5]undecane]diethyl)-1,2,3,4-butane tetracarboxylate, poly([6-N-morpholinyl -1,3,5-three

-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl- 4-piperidinyl)imino]), [N-(2,2,6,6-tetramethyl-4-piperidinyl)-2-methyl-2-(2,2,6,6 -Tetramethyl-4-piperidinyl)imino] acrylamide, trade names "LA-77", "LA-67", "LA-57" (above manufactured by ADEKA), trade name "TINUVIN123" , "TINUVIN152" (above is made by CibaJapan Co., Ltd.) and other hindered amine compounds; (4-hydroxyphenyl) dimethyl carbamoyl sulfite (SANEIDSI additives, manufactured by Sanshin Chemical Industry Co., Ltd.), etc. Phosphite-based compounds such as akura sulfate-based compounds and trade name "PEP-36" (made by ADEKA Corporation). These can be used alone or in combination of two or more.

The amount of polymerization stabilizer used relative to cationic polymerization The 100 parts by weight of the starting agent is, for example, 1 part by weight or more, preferably 3 to 20 parts by weight, particularly preferably 5 to 15 parts by weight.

The hardening composition in the present invention may optionally contain one or more kinds of precipitated silica, wet silica, atomized silica, fired silica, titanium oxide, alumina, glass, quartz , Aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride and other inorganic fillers; the fillers are organic halogenated silane, organic alkoxysilane, organic silicon Inorganic fillers treated with organosilicon compounds such as azones; fine powders of organic resins such as polysiloxane resins, epoxy resins, fluororesins; fillers, hardening aids, solvents (organic solvents) of conductive metal powders such as silver and copper Etc.), stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, thermal stabilizers, heavy metal deactivators, etc.), flame retardants (phosphorus flame retardants, halogen flame retardants, inorganic flame retardants) Agents), flame retardant additives, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents (silane coupling agents, etc.), slip agents, waxes, plasticizers, mold release agents, impact modifiers, hue Improvers, clearing agents, rheology modifiers (fluidity modifiers, etc.), processability modifiers, colorants (dyes, pigments, etc.), antistatic agents, dispersants, surface modifiers (leveling agents, pinholes) Preventive agents, etc.), surface modifiers (slip agents, etc.), matting agents, defoaming agents, foam inhibitors, defoamers, foaming agents, antibacterial agents, preservatives, viscosity modifiers, tackifiers, etc. additive.

The curable composition in the present invention is not particularly limited, but it can be prepared by stirring and mixing the above-mentioned components while heating at room temperature or heating as necessary. In addition, the curable composition in the present invention may be used as a one-component composition in which each component is mixed in advance and used directly, or may be used For example, it is used as a multi-liquid system (for example, two-liquid system) composition in which two or more components stored separately are mixed and used in a specific ratio before use.

The curable composition in the present invention is not particularly limited, but it is preferably liquid at normal temperature (about 25°C). When coating by spin coating, the viscosity of the curable composition is preferably adjusted according to the thickness of the coating film, and when the coating thickness is 0.1 to 50 μm, it is preferably 1 to 5000 mPa. s. The viscosity can form a coating film with a uniform film thickness on a substrate such as a silicon wafer. In addition, the viscosity of the hardenable composition is measured using a viscometer (trade name "MCR301", manufactured by Anton-Paar) under a condition of a swing angle of 5%, a frequency of 0.1 to 100 (1/s), and a temperature of 25°C .

[Hardened]

The cured product of the present invention is obtained by subjecting the above-mentioned curable composition to a heat treatment in which the curing temperature is changed step by step, and the curing degree at the end of the first-stage heat treatment is 85% or less (for example, 50 to 85%, more preferably 55 To 85%, and more preferably 60 to 80%), the heat treatment after the second stage makes the degree of hardening exceed 85% (preferably 90% or more, particularly preferably 95% or more. Also, the upper limit of the degree of hardening Is 100%). In addition, the degree of hardening at the end of the first-stage heat treatment can be calculated by DSC by measuring the calorific value of the sample at the end of the first-stage heat treatment and the calorific value of the sample before the heat treatment, and the following formula can be calculated.

Hardness (%)=[1-(heat value at the end of the first stage of heat treatment/heat value before the heat treatment)]×100.

That is, the method for manufacturing a hardened product of the present invention is to perform a heat treatment in which the hardening temperature of the compound containing a polymerizable group is changed step by step to produce a hardened product, and the first stage of heating At the end of the treatment, the degree of hardening is less than 85% (for example, 50 to 85%, more preferably 55 to 85%, and still more preferably 60 to 80%), and the degree of hardening exceeds 85 by heat treatment after the second stage % (Preferably 90% or more, particularly preferably 95% or more. The upper limit of the degree of hardening is 100%). By controlling the degree of hardening at the end of the heat treatment in the first stage to be 85% or less, it is possible to form a stress-relieving structure and improve the crack resistance of the resulting hardened product.

The degree of hardening can be controlled by adjusting the heating temperature and heating time. In the present invention, in terms of obtaining a hardened product having more excellent crack resistance, it is preferable to spend until the hardening degree reaches 50 to 85% (preferably 55 to 85%, more preferably 60 to 80%) Slow curing for a certain period of time, preferably the first-stage heat treatment takes, for example, 5 minutes or more (preferably 5 to 120 minutes, more preferably 10 to 60 minutes, and most preferably 30 to 60 minutes).

Even if the heat treatment is performed for more than 5 minutes, the heating temperature in the first-stage heating treatment may be a temperature at which the curing degree at the end of the first-stage heating treatment does not exceed 85%, and the curable composition contains epoxy-based modification When polyorganosilicon silsesquioxane is used as the polymerizable compound, it is, for example, 90°C or more and less than 150°C, preferably 100 to 140°C, and particularly preferably 110 to 140°C. If the first-stage heat treatment is performed at a temperature in the above range, a hardened product excellent in crack resistance can be produced with good workability. On the other hand, if the first-stage heat treatment is performed at a temperature exceeding 150° C., the curing will not proceed slowly, and the crack resistance of the resulting cured product tends to decrease. In addition, since the curing progresses too fast, it is difficult to terminate the heat treatment in the first stage at a stage where the degree of curing is 85% or less. If the first-stage heat treatment is performed at a temperature less than 90°C, the curing will take too much time and the workability will be reduced. to.

The heating temperature in the heat treatment after the second stage is, for example, 150 to 200°C, preferably 160 to 190°C, and particularly preferably 160 to 180°C. The heating time is, for example, 5 to 120 minutes, preferably 10 to 60 minutes. If the heat treatment temperature after the second stage is lower than 150°C, it is difficult to increase the degree of curing of the resulting cured product to 100%, and there is a tendency for heat resistance, crack resistance, adhesion to the adherend, and adhesion to decrease . Moreover, even if the degree of hardening can be increased to close to 100%, the hardening system takes too much time and the workability is reduced, which is not good. On the other hand, if the heat treatment temperature after the second stage is higher than 200°C, the adherend may deteriorate due to heat.

In addition, the heat treatment in each stage may be performed by changing the temperature stepwise within the above range, or may be fixed at a specific temperature within the above range to perform the heat treatment. In addition, the heat treatment of the present invention may be performed in two or more stages, and may be two or more stages in three or more stages.

In addition, the total time taken for the heat treatment in the first stage and the second stage (when performing the heat treatment after the third stage, the total time required for the heat treatment after the third stage) is, for example, about 0.5 to 2 hours, preferably 0.75 to 1.5 hours.

The hardened system of the present invention obtained by the above-mentioned manufacturing method is excellent in crack resistance, and even if cold or hot shock is applied, the occurrence of cracks can be suppressed.

Furthermore, the cured product of the present invention obtained by the above production method is excellent in heat resistance, and the thermal decomposition temperature is, for example, 200°C or higher (for example, 200 to 500°C), preferably 260°C or higher. In addition, the thermal decomposition temperature was obtained by the method described in the examples.

The shape of the cured product of the present invention can be appropriately adjusted according to the application, and is not particularly limited, but examples thereof include a sheet shape, a film shape, a belt shape, and a plate shape. The thickness of the hardened material is not particularly limited.

The hardened system of the present invention has heat resistance, crack resistance, excellent adhesion to an object, and adhesion. Therefore, when the curable composition of the present invention is used as an adhesive, especially as a thermosetting adhesive, the cured product of the present invention obtained by curing it has heat resistance, crack resistance, and resistance to an object Adhesive materials with excellent adhesion and adhesion can be used for the purpose of joining the required adherends.

[Laminate]

The laminate of the present invention is composed of three or more layers, and has two layers to be adhered, and an adhesion layer between the adhered layers, and the adhesion layer is the layer of the hardened material.

The laminate of the present invention is not particularly limited, but, for example, the adhesive layer can be formed by coating the curable composition of the present invention on an adhered layer and drying if necessary, or the curable composition of the present invention can be previously formed The adhesive layer applied to the surface of the release paper, etc. and dried if necessary, is bonded to a layer to be adhered, and then, another layer to be adhered is adhered to the layer of adhesive, and then the heat treatment as described above is carried out to The agent layer is hardened to obtain the laminate of the present invention. However, the manufacturing method of the laminate of the present invention is not limited to the above method.

The coating method of the curable composition is not particularly limited, and a well-known and usual method can be used. In addition, the means and conditions for drying are not particularly limited, and conditions can be appropriately set to remove volatile components such as solvents as much as possible, and Use well-known methods. In particular, when the curable composition contains a polymerization initiator obtained by adding 1 part by weight to 100 parts by weight of CELLOXIDE 2021P (made by Daicel Co., Ltd.), the thermal curing time at 130° C. is 3.5 minutes or more. The heating and drying suppress the progress of the hardening reaction, and can quickly remove volatile components such as solvents, and the system is excellent in workability. In addition, the resulting adhesive layer does not have adhesiveness below 50°C, and exhibits adhesiveness by heating at a temperature that can suppress damage to the adherend.

The adhered system forming the adhered layer in the laminate of the present invention is not particularly limited, and examples thereof include plastic substrates, metal substrates, ceramic substrates, semiconductor substrates (including semiconductor wafers, semiconductor wafers, etc.), glass substrates Materials, paper substrates, wood substrates, substrates with painted surfaces, etc. In addition, the laminate of the present invention may have only two layers to be adhered, or may have three or more layers. In addition, the thickness of the layer to be adhered is not particularly limited, and can be appropriately selected, for example, in the range of 1 to 100,000 μm. The layer to be adhered may not have a strict layered form.

The laminate of the present invention may have only one subsequent layer, or may have two or more layers. In addition, the thickness of the adhesive layer is not particularly limited, for example, it can be appropriately selected within the range of 0.1 to 10000 μm.

The laminate of the present invention may have other layers (for example, an intermediate layer, an undercoat layer, and other adhesive layers) in addition to the adhered layer and the adhesive layer.

The laminate of the present invention has a structure in which an adhesive layer and an adherend are excellent in heat resistance, crack resistance, adhesion to an adherend, and adhesion. Therefore, the layered product of the present invention can prevent Cracking and peeling will cause the adherend to peel off and the line will be destroyed, which can improve the reliability of the device with laminates. In addition, when the laminate of the present invention is a three-dimensional laminate of semiconductor wafers, it is higher in volume and power-saving than conventional semiconductors. Therefore, if the laminate of the present invention is used, a more compact and high-performance electronic device can be provided .

The laminate of the present invention includes, for example, a microprocessor, a semiconductor memory, an IC for power supply, an IC for communication, a semiconductor sensor, a MEMS, a semiconductor combining these, and the like. These systems can be used for high-performance servers, workstations, automotive computers, personal computers, communication equipment, photo equipment, image display devices, etc.

Therefore, the device of the present invention having the aforementioned laminate (or having the laminate) can be exemplified by a server, a workstation, a car computer, a personal computer, a communication device, a photographing device, an image display device, and the like.

(Example)

The present invention will be described in more detail based on examples below, but the present invention is not limited to these examples.

The number average molecular weight and molecular weight dispersion of the product were obtained by GPC analysis under the following conditions.

Alliance HPLC system 2695 (manufactured by Waters).

Refractive Index Detector 2414 (made by Waters).

Column: Tskgel GMH _HR- M×2 (manufactured by TOSOH Co., Ltd.).

Protection column: Tskgel guard column H _HR L (manufactured by TOSOH Corporation).

Column oven: COLUMN HEATER U-620 (manufactured by Sugai).

Solvent: THF.

Measurement conditions: 40°C.

Molecular weight: Standard polystyrene conversion.

The ratio of the T2 body to the T3 body in the product [T3 body/T2 body] was measured by ²⁹ Si-NMR spectrum measurement of JEOL ECA500 (500 MHz).

Modulation example 1

(Modified epoxy-modified polyorganosilicon silsesquioxane)

In a 300 mL flask (reaction vessel) equipped with a thermometer, a stirring device, a reflux cooler, and a nitrogen introduction tube, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 161.5 mmol ( 39.79g), phenyltrimethoxysilane 9mmol (1.69g), and acetone 165.9g, warmed to 50 ℃. After the mixture thus obtained took 1700 mmol (30.60 g) of water in 20 minutes, 4.70 g of 5% potassium carbonate aqueous solution (1.7 mmol of potassium carbonate) was added in 5 minutes. In addition, there was no significant temperature rise during dripping. Thereafter, the temperature was maintained at 50°C and the polycondensation reaction was carried out under a nitrogen flow for 4 hours.

The product in the reaction solution after the polycondensation reaction was analyzed. The number average molecular weight was 1900, and the molecular weight dispersion degree was 1.5. The ratio of T2 body to T3 body [T3 body/T2 body] calculated from the ²⁹ Si-NMR spectrum of the above product was 10.3.

After adding methyl isobutyl ketone and saline and heating and stirring, the reaction solution was cooled and washed with water until the lower layer liquid became neutral. After the upper layer liquid was separated, the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 40°C. Until the amount of the solvent becomes 25% by weight, a colorless and transparent liquid product (epoxy-modified polyorganosilsesquioxane) is obtained.

(Modulated hardenable composition)

100 parts by weight of epoxy-modified polyorganosilicon silsesquioxane obtained by mixing, 50 parts by weight of propylene glycol monomethyl ether acetate, antimony-based monium salt (trade name "SI-150L", manufactured by Sanshin Chemical Industry Co., Ltd.) ; For a composition obtained by adding 1 weight part to 100 weight parts of CELLOXIDE 2021P (made by Daicel Co., Ltd.), heat hardening time at 130° C.: 5.4 minutes) 0.45 weight parts (solid content conversion), (4-hydroxyphenyl ) Dimethyl carbamoyl sulfite (trade name "SANEID SI Auxiliary", manufactured by Sanshin Chemical Industry Co., Ltd.) 0.05 parts by weight to obtain a hardenable composition.

Example 1

Apply a silane coupling agent (trade name "KBE403", manufactured by Shin-Etsu Chemical Co., Ltd., below) on a silicon plate (size: 2cm x 5cm, made by SUMCO Corporation, cutting a silicon wafer with a diameter of 100mm) by spin coating It is called "KBE403") and heated at 120°C for 5 minutes to obtain a silicon plate with a silane coupling agent layer.

The surface of the silane coupling agent layer of the silicon plate with the silane coupling agent layer was spin-coated to apply the curable composition obtained in Preparation Example 1, heated at 80°C for 4 minutes, and then heated at 100°C for 2 minutes to remove residual solvent, and Obtain a silicon plate with an adhesive layer [adhesive layer/silane coupling agent layer/silicon plate]. The thickness of the adhesive layer is 5 to 6 μm.

Using the adhesive layer of the obtained silicon plate with an adhesive layer as a sample, it was heated at 130° C. for 30 minutes and then at 170° C. for 30 minutes to obtain a hardened product. After the curing reaction of the first stage (after heating at 130°C for 30 minutes), the curing degree of the adhesive layer is 80%. Also, the addition of the first stage The degree of hardening at the end of the heat treatment was measured by DSC to measure the calorific value of the sample at the end of the first-stage heating treatment and the calorific value of the sample before the heat treatment, and was calculated by the following formula. In the following examples and comparative examples, the degree of hardening was calculated by the same method.

Hardness (%)=[1-(heat value at the end of the first stage of heat treatment/heat value before the heat treatment)]×100.

The heat resistance, crack resistance, and adhesion of the resulting cured product were evaluated by the following methods.

(Heat resistance)

A thermoanalyzer (trade name "TG-DTA6300", manufactured by Seiko Electronics Co., Ltd.) was used for the hardened material, thermogravimetric analysis was performed under a nitrogen environment at a temperature increase rate of 10°C/min, and the thermal decomposition temperature (T) was measured The result was 260°C or higher, and it was found that it was excellent in heat resistance.

Also, as shown in Figure 1, the thermal decomposition temperature (T) is the inverse of the tangent when there is no initial weight loss or gradual decrease (the range shown in A in the figure) and when there is a sudden weight loss (the range shown in B in the figure) The temperature at which the tangent of the point crosses.

(Crack resistance)

The hardened product was heated and cooled at 250°C for 30 minutes and then quenched to room temperature. The non-cracked portion accounted for more than 60% of the hardened product, which was confirmed to be excellent in crack resistance.

(Adhesion)

A checkerboard tape test (according to JIS K5400-8.5) was performed to evaluate the adhesion of the cured product to the silicon plate. As a result, peeling from the silicon plate was not observed, and it was confirmed that the adhesiveness was excellent.

Example 2

The adhesive layer of the silicon plate with the adhesive layer obtained by the same method as in Example 1 was used as a sample, and it was heated at 120° C. for 30 minutes and then at 170° C. for 30 minutes to obtain a hardened product. After the end of the first stage hardening reaction (after heating at 120°C for 30 minutes), the degree of hardening of the adhesive layer is 60%.

The heat resistance, crack resistance, and adhesion of the resulting cured product were evaluated in the same manner as in Example 1.

(Heat resistance)

The thermal decomposition temperature (T) is 260°C or higher, and it is understood that the heat resistance is excellent.

(Crack resistance)

The non-cracked portion accounts for more than 60% of the hardened product, and it is confirmed that the crack resistance is excellent.

(Adhesion)

No peeling from the silicon plate was observed, and it was confirmed that the adhesion was excellent.

Comparative example 1

The adhesive layer of the silicon plate with an adhesive layer obtained by the same method as in Example 1 was used as a sample, and it was heated at 150° C. for 30 minutes and then at 170° C. for 30 minutes to obtain a hardened product. After the hardening reaction in the first stage (after heating at 150°C for 30 minutes), the curing degree of the adhesive layer is 95%.

When the crack resistance of the obtained cured product was evaluated in the same manner as in Example 1, the entire cured product was severely cracked.

Example 3

Apply a silane coupling agent (trade name "KBE403", manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as "KBE403") on a glass plate (4-inch, manufactured by SCHOTT Japan Co., Ltd.) by spin coating, and heat at 120°C for 5 Minutes to obtain a glass plate with a silane coupling agent layer. On the silane coupling agent layer of the obtained glass plate with silane coupling agent layer, the silicon board with adhesive layer obtained by the same method as in Example 1 was bonded under reduced pressure [adhesive layer/silane coupling agent layer/silicon The adhesive layer of the board] is heated to 60°C while applying a pressure of 200g/cm ² and bonding, then heated at 130°C for 30 minutes and then at 170°C for 30 minutes to obtain a laminate [glass plate/silane Coupling agent layer/adhesive layer/silane coupling agent layer/silicon plate]. In addition, the curing degree of the adhesive layer after the curing reaction in the first stage (after heating at 130°C for 30 minutes) was 80%.

The adhesion of the resulting laminate was evaluated by the following method.

(Adequacy)

When a razor blade (trade name "Single-face Blade Shaving Blade", manufactured by Nissin EM Co., Ltd.) was inserted at the adhesive interface of the laminate, peeling of the interface did not occur, and it was confirmed that the adhesiveness of the adhesive layer system was excellent.

Example 4

On the silane coupling agent layer of the glass plate with the silane coupling agent layer obtained by the same method as in Example 3, the silicon plate with the adhesive layer obtained by the same method as in Example 3 was bonded under reduced pressure [Next Adhesive layer/silane coupling agent layer/silicon plate], apply 200g/cm ² of pressure while heating to 60°C and apply the pressure, then heat at 120°C for 30 minutes, then 170°C for 30 minutes. This obtained a laminate [glass plate/silane coupling agent layer/adhesion layer/silane coupling agent layer/silicon plate]. Moreover, the curing degree of the adhesive layer after the curing reaction of the first stage (after heating at 120°C for 30 minutes) was 60%.

When the adhesiveness of the resulting laminate was evaluated in the same manner as in Example 3, peeling of the interface did not occur, and it was confirmed that the adhesiveness of the adhesive layer system was excellent.

[Industry availability]

The hardened system of the present invention has heat resistance, crack resistance, excellent adhesion to an object, and adhesion. Therefore, when the curable composition of the present invention is used as an adhesive, especially when it is used as a thermosetting adhesive, the cured product of the present invention obtained by curing it has heat resistance, crack resistance, Adhesive materials with excellent adhesion and adhesion of the body can be used for the purpose of joining the required adherend bodies.

Since the figure in this case is an explanatory diagram of the heat resistance evaluation method of the hardened product, it is not a representative figure in this case. Therefore, there is no designated representative figure in this case.

Claims (12)

A hardened product obtained by subjecting a hardenable composition to heat treatment in which the hardening temperature is changed in stages. The hardenable composition contains: epoxy-modified polyorganosilsesquioxane; and a thermal cationic polymerization initiator and/or Or thermal anionic polymerization initiator, the degree of curing at the end of the first stage of heat treatment is 85% or less, and the degree of curing exceeds 85% by the heat treatment after the second stage. The hardened product as described in item 1 of the patent application range, wherein the hardenable composition contains a thermal cationic polymerization initiator. The cured product as described in item 2 of the patent application range, wherein the curable composition further contains a polymerization stabilizer, which inhibits cationic polymerization by trapping cations. The hardened product according to any one of items 1 to 3 of the patent application scope, wherein the first-stage heat treatment is performed at 90°C or more in 10 to 120 minutes. The hardened product as described in any one of claims 1 to 3, wherein the epoxy-modified polyorganosilsesquioxane is an epoxy-modified polyorganosilsesquioxane, and the epoxy group Modified polyorganosilicon silsesquioxane system: It has a structural unit represented by the following formula (1), and a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II) The ear ratio [the structural unit shown in formula (I)/the structural unit shown in formula (II)] is 5 or more; it is shown in the above formula (1) with respect to the total amount of siloxane constituent units (100 mole %) The ratio of the constituent unit and the constituent unit represented by the following formula (4) is 55 to 100 mol %, the number average molecular weight is 1000 to 3000, and the molecular weight dispersion degree (weight average molecular weight/number average molecular weight) is 1.0 to 3.0; [R ¹ SiO _3/2 ] (1) In formula (1), R ¹ represents an epoxy group-containing group; [R ^a SiO _3/2 ] (I) In formula (I), R ^a represents an epoxy group Radical, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom; [R ^b SiO _2/2 (OR ^c )] (II) In formula (II), R ^b represents an epoxy group-containing group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or Unsubstituted cycloalkyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, or hydrogen atom, R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; [R ¹ SiO _2/2 ( OR ^c )] (4) In formula (4), R ¹ is the same as in formula (1), and R ^c is the same as in formula (II). The hardened product as described in item 5 of the patent application scope, wherein the above R ¹ is one or more groups selected from the group consisting of groups represented by the following formulas (1a) to (1d);

In the formula, R ^1a , R ^1b , R ^1c and R ^1d are the same or different and represent straight-chain or branched-chain alkylene. The hardened product as described in item 5 of the patent application scope, wherein the epoxy-modified polyorganosilsesquioxane system further has a structural unit represented by the following formula (2); [R ² SiO _3/2 ] ( 2) In formula (2), R ² represents substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkyl, or substituted or unsubstituted Alkenyl. The hardened product as described in item 7 of the patent application, wherein R ² is a substituted or unsubstituted aryl group. The hardened product as described in any one of claims 1 to 3, wherein the hardenable composition further contains a silane coupling agent. A method of manufacturing a hardened product, which is the implementation stage of a hardenable composition Heat treatment to change the hardening temperature to produce a hardened product, the hardenable composition contains: epoxy-modified polyorganosilsesquioxane; and thermal cationic polymerization initiator and/or thermal anionic polymerization initiator, wherein At the end of the first stage of heat treatment, the degree of curing is 85% or less, and the degree of curing exceeds 85% by the heat treatment after the second stage. A laminate consisting of more than 3 layers and having 2 layers to be bonded, and the bonding layer between the bonded layers; wherein, the bonding layer is any one of items 1 to 9 of the patent application The hardened layer. An electronic device with a laminate as described in item 11 of the patent scope.

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