WO2020138070A1

WO2020138070A1 - Adhesive composition for fixing movable component, optical component, electronic component, and electronic module

Info

Publication number: WO2020138070A1
Application number: PCT/JP2019/050585
Authority: WO
Inventors: 秀幸林
Original assignee: 積水化学工業株式会社
Priority date: 2018-12-26
Filing date: 2019-12-24
Publication date: 2020-07-02
Also published as: JPWO2020138070A1; JP7431720B2; TW202035624A

Abstract

A purpose of the present invention is to provide an adhesive composition for fixing movable components which has excellent adhesiveness to both metals and non-metals, can be cured at low temperatures, and can prevent the movable components from shifting from the original positions. Another purpose of the present invention is to provide an optical component, an electronic component, and an electronic module all obtained using the adhesive composition for fixing movable components. The adhesive composition for fixing movable components of the present invention comprises a poly(vinyl acetal) resin, a compound having an epoxy group and/or a (meth)acryloyl group, and a polymerizable hardener and gives cured objects having a 25°C storage modulus of 1.0 GPa or greater.

Description

Adhesive composition for fixing movable parts, optical parts, electronic parts, and electronic module

The present invention relates to an adhesive composition for fixing movable parts, which has excellent adhesiveness to both metals and non-metals, can be cured at a low temperature, and can prevent displacement of movable parts. Further, the present invention relates to an optical component, an electronic component, and an electronic module which use the adhesive composition for fixing a movable component.

An adhesive composition that is cured by light irradiation and/or heating is used to fix movable parts in a camera module or the like that uses CCD (charge-coupled device), CMOS (complementary metal oxide semiconductor), etc. as an image sensor. There is.
As such an adhesive composition, for example, Patent Document 1 discloses a silicone composition in which a specific silicone compound is combined, and Patent Document 2 discloses an aminoglycidyl ether and a phenolic compound having an alkenyl group. A liquid epoxy resin composition in which a curing agent and a thiol compound having a triazine skeleton are combined is disclosed. However, the conventional adhesive composition has a problem that it is easily peeled off by impact, vibration, or the like, or a position shift occurs when a movable part moves.

In recent years, development of movable parts using a non-metal material such as polyamide has progressed, and an adhesive composition having a high adhesive force to both metal and non-metal has been demanded. Further, in order to reduce damage to optical parts and electronic parts, there has been a demand for an adhesive composition that can be sufficiently cured by heating at a low temperature.

JP, 2011-057755, A JP, 2014-031461, A

The present invention provides an adhesive composition for fixing movable parts, which has excellent adhesion to both metal and non-metal, can be cured at low temperature, and can prevent displacement of movable parts. With the goal. Another object of the present invention is to provide an optical component, an electronic component, and an electronic module which use the adhesive composition for fixing a movable component.

The present invention contains a polyvinyl acetal resin, a compound having an epoxy group and/or a (meth)acryloyl group, and a polymerizable curing agent, and has a storage elastic modulus at 25° C. of 1.0 GPa or more. An adhesive composition for fixing parts.
The present invention is described in detail below.

The present inventor uses a polyvinyl acetal resin, a compound having an epoxy group and/or a (meth)acryloyl group, and a polymerizable curing agent in combination, and has a storage elastic modulus at 25° C. of 1.0 GPa. I considered how to make it above. As a result, it is possible to obtain an adhesive composition for fixing movable parts, which has excellent adhesiveness to both metals and non-metals, can be cured at a low temperature, and can prevent displacement of movable parts. The present invention has been completed and the present invention has been completed.
In addition, in this specification, the said "(meth)acryloyl" means acryloyl or methacryloyl.

The lower limit of the storage elastic modulus at 25° C. of the cured product of the adhesive composition for fixing a movable part of the present invention is 1.0 GPa. Since the cured product has a storage elastic modulus at 25° C. of 1.0 GPa or more, the adhesive composition for fixing a movable part of the present invention can prevent displacement of the movable part and has moisture resistance. Will also be excellent. The preferred lower limit of the storage elastic modulus at 25° C. of the cured product is 1.5 GPa, and the more preferred lower limit thereof is 2.0 GPa. There is no particular upper limit to the storage modulus at 25° C. of the cured product, but the practical upper limit is 8.0 GPa.
The storage elastic modulus can be measured using a dynamic viscoelasticity measuring device under the conditions of a test piece width of 5 mm, a thickness of 0.35 mm, a gripping width of 25 mm, a temperature rising rate of 10° C./min, and a frequency of 10 Hz. ..
As a cured product for measuring the storage elastic modulus, a cured product obtained by irradiating an adhesive composition for fixing a movable part with ultraviolet rays of 100 mW/cm ² for 30 seconds and then heating it at 80° C. for 1 hour is used. ..

In the adhesive composition for fixing a movable part of the present invention, a polyvinyl acetal resin, an epoxy group and/or a (meth)acryloyl group, which will be described later, may be used as a method for setting the storage elastic modulus at 25° C. of 1.0 GPa or more. A method of adjusting the type and content ratio of each constituent component such as the compound and the polymerizable curing agent is suitable.

The adhesive composition for fixing a movable part of the present invention contains a polyvinyl acetal resin.
By containing the polyvinyl acetal resin, the adhesiveness to both metal and non-metal and the effect of preventing the displacement of the movable parts are excellent.

The polyvinyl acetal resin is a structural unit having an acetal group represented by the following formula (1-1), a structural unit having a hydroxyl group represented by the following formula (1-2), and the following formula (1-3) Having a structural unit having an acetyl group represented by

In the above formula (1-1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, Examples thereof include tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and eicosyl group. Of these, a methyl group, an ethyl group and a propyl group are preferable.
Further, the adhesive composition for fixing a movable part of the present invention more preferably contains a polyvinyl butyral resin having a structural unit in which R ¹ is a propyl group in the formula (1-1).

In the polyvinyl acetal resin, the preferable lower limit of the content of the constituent unit having the acetal group (hereinafter, also referred to as "acetal group amount") is 60 mol%, and the preferable upper limit thereof is 90 mol%. When the amount of the acetal group is 60 mol% or more, the polyvinyl acetal resin can be sufficiently deposited in the synthesis step by the precipitation method. Further, when the amount of the acetal group is 90 mol% or less, the compatibility with the epoxy compound can be improved. The more preferable lower limit of the amount of the acetal group is 65 mol%, and the more preferable upper limit thereof is 85 mol%.

In the polyvinyl acetal resin, the content of the structural unit having a hydroxyl group (hereinafter, also referred to as “hydroxyl group amount”) has a preferable lower limit of 15 mol% and a preferable upper limit of 35 mol %. When the amount of the hydroxyl group is 15 mol% or more, the toughness of the polyvinyl acetal resin can be sufficiently increased, and the strength of the resulting crosslinked product becomes good. Further, when the amount of the hydroxyl group is 35 mol% or less, the polarity of the polyvinyl acetal resin does not become too high, and defects such as cracks in the resulting crosslinked product are suppressed and the releasability is improved. be able to. The more preferable lower limit of the amount of the hydroxyl group is 17 mol %, and the more preferable upper limit thereof is 30 mol %.

In the polyvinyl acetal resin, the preferable lower limit of the content of the constituent unit having the acetyl group (hereinafter, also referred to as "the amount of acetyl group") is 0.0001 mol%, and the preferable upper limit thereof is 15 mol%.

The preferred lower limit of the number average molecular weight (Mn) of the polyvinyl acetal resin is 5,000, and the preferred upper limit is 200,000. When the number average molecular weight (Mn) of the polyvinyl acetal resin is 5000 or more, an adhesive composition having a sufficient viscosity can be obtained. When the number average molecular weight (Mn) of the polyvinyl acetal resin is 200,000 or less, the coating property of the obtained adhesive composition for fixing a movable part can be improved, and the handling can be improved, and the adhesion can be improved. The power can be further improved. The more preferable lower limit of the number average molecular weight (Mn) of the polyvinyl acetal resin is 10,000, and the more preferable upper limit thereof is 100,000.

The polyvinyl acetal resin preferably contains a modified polyvinyl acetal resin having a structural unit having an imine structure and/or a structural unit having an acid-modified group.
By containing such a modified polyvinyl acetal resin, a crosslinked structure can be formed with a compound having an epoxy group and/or a (meth)acryloyl group described later. Therefore, the obtained cured product of the adhesive composition for fixing a movable part has high mechanical strength. Furthermore, when the curing shrinkage is moderated and used for bonding different materials, it is possible to suppress warpage and peeling of the bonded portion due to the difference in shrinkage ratio of each material.
In the present specification, the above “imine structure” means a structure having a C═N bond.

In the modified polyvinyl acetal resin, the imine structure or the acid-modified group may be directly bonded to carbon constituting the main chain of the modified polyvinyl acetal resin, or bonded via a linking group such as an alkylene group. May be.
The modified polyvinyl acetal resin preferably has a structural unit having the imine structure and/or a structural unit having an acid-modified group in its side chain.

Examples of the structural unit having the imine structure include structural units represented by the following formula (2).

In formula (2), R ² represents a single bond or an alkylene group, and R ³ represents a group having an imine structure.

In the above formula (2), when R ² is an alkylene group, the preferable lower limit of the carbon number of the alkylene group is 1, and the preferable upper limit thereof is 12. When the number of carbon atoms in the alkylene group exceeds 12, optimum strength may not be obtained. When R ² is an alkylene group, the more preferable upper limit of the carbon number of the alkylene group is 5.

In the above formula (2), when R ² is an alkylene group, the alkylene group may be a linear alkylene group, a branched alkylene group, or a cyclic alkylene group. May be.
Examples of the linear alkylene group include methylene group, ethylene group, n-propylene group, n-butylene group, pentamethylene group, hexamethylene group, octamethylene group, decamethylene group and the like.
Examples of the branched alkylene group include a methylmethylene group, a methylethylene group, a 1-methylpentylene group, and a 1,4-dimethylbutylene group.
Examples of the cyclic alkylene group include a cyclopropylene group, a cyclobutylene group, a cyclohexylene group, and the like.
Of these, a linear alkylene group is preferable, a methylene group, an ethylene group, an n-propylene group, and an n-butylene group are more preferable, and a methylene group and an ethylene group are further preferable.

In the above formula (2), examples of R ³ include a functional group represented by the following formula (3).

In the formula (3), R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ⁵ represents a hydrocarbon group having 1 to 18 carbon atoms.

Examples of the hydrocarbon group represented by R ⁴ and R ⁵ above include a saturated hydrocarbon group, an unsaturated hydrocarbon group, and an aromatic hydrocarbon group.
The hydrocarbon group may be a saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic hydrocarbon group alone, or may be a combination of two or more thereof. Good.

Examples of the saturated hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. And heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group and the like. Of these, a methyl group, an ethyl group, an n-propyl group, and an n-butyl group are preferable.
Examples of the aromatic hydrocarbon group include a phenyl group, a toluyl group, a xylyl group, a t-butylphenyl group and a benzyl group.

In the modified polyvinyl acetal resin, as the structural unit having the imine structure, R ² in the formula (2) is a single bond, and R ⁴ in the formula (3) is a hydrogen atom, a methyl group, or an ethyl group. And a structural unit in which R ⁵ in the above formula (3) is a methyl group or an ethyl group is preferred.

In the modified polyvinyl acetal resin, the preferable lower limit of the content of the constituent unit having an imine structure is 0.1 mol% and the preferable upper limit thereof is 20.0 mol%.
When the content of the constituent unit having the imine structure is 0.1 mol% or more, the viscosity stability with time of the obtained adhesive composition for fixing a movable part is improved. When the content of the structural unit having the imine structure is 20.0 mol% or less, acetalization can be sufficiently advanced. The more preferable lower limit of the content of the structural unit having the imine structure is 1.0 mol%, and the more preferable upper limit thereof is 15.0 mol%.
The content of the structural unit having the imine structure can be measured by, for example, ¹ H-NMR and ¹³ C-NMR.

Examples of the acid-modified group include a carboxyl group, a sulfonic acid group, a maleic acid group, a sulfinic acid group, a sulfenic acid group, a phosphoric acid group, a phosphonic acid group, and salts thereof.
When the modified polyvinyl acetal resin has the structural unit having the acid-modified group, the compatibility with a compound having an epoxy group and/or a (meth)acryloyl group described later is improved, and high mechanical strength is realized. be able to.

Examples of the structural unit having a carboxyl group include a structural unit represented by the following formula (4-1), a structural unit represented by the following formula (4-2), and a structural unit represented by the following formula (4-3). And the like.

In the above formula (4-1), R ⁶ represents a single bond or an alkylene group having 1 to 10 carbon atoms, and X ¹ represents a hydrogen atom, a metal atom or a methyl group.
R ⁶ is preferably a single bond or an alkylene group having 1 to 5 carbon atoms, and more preferably a single bond or an alkylene group having 1 to 3 carbon atoms.

Examples of the alkylene group having 1 to 10 carbon atoms include a linear alkylene group, a branched alkylene group and a cyclic alkylene group.
Examples of the linear alkylene group include methylene group, ethylene group, n-propylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group and decamethylene group.
Examples of the branched alkylene group include a methylmethylene group, a methylethylene group, a 1-methylpentylene group, and a 1,4-dimethylbutylene group.
Examples of the cyclic alkylene group include a cyclic alkylene group such as a cyclopropylene group, a cyclobutylene group, and a cyclohexylene group.
Among them, a methylene group, an ethylene group and an n-propylene group are preferable, and a methylene group and an ethylene group are more preferable.

Examples of the metal atom include sodium atom, lithium atom, potassium atom and the like. Of these, sodium atom is preferred.

In the above formula (4-2), R ⁷ and R ⁸ each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms, and X ² and X ³ each independently represent a hydrogen atom, Represents a metal atom or a methyl group.
Examples of the alkylene group having 1 to 10 carbon atoms include those similar to R ⁶ in the above formula (4-1).
Examples of the metal atom include those similar to X ¹ in the above formula (4-1).

In the formula (4-3), R ⁹ and R ¹⁰ each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms, and X ⁴ and X ⁵ each independently represent a hydrogen atom, Represents a metal atom or a methyl group.
Examples of the alkylene group having 1 to 10 carbon atoms include those similar to R ⁶ in the above formula (4-1).
Examples of the metal atom include those similar to X ¹ in the above formula (4-1).

In the modified polyvinyl acetal resin, the preferable lower limit of the content of the structural unit having an acid-modified group is 0.01 mol%, and the preferable upper limit thereof is 5.0 mol%. When the content of the structural unit having an acid-modified group is 0.01 mol% or more, it may be excellent in reactivity with a compound having an epoxy group and/or a (meth)acryloyl group described later. it can. When the content of the constituent unit having an acid-modified group is 5.0 mol% or less, the storage stability of the resulting adhesive composition for fixing movable parts can be improved. The more preferable lower limit of the content of the constituent unit having an acid-modified group is 0.05 mol%, and the more preferable upper limit thereof is 3.0 mol%. The content of the constituent unit having an acid-modified group can be measured by, for example, ¹ H-NMR and ¹³ C-NMR.

The modified polyvinyl acetal resin may further have a constitutional unit having an amino group or an amide structure. By having a constituent unit having the above amino group or the above amide structure, it becomes easier to form a crosslinked structure with a compound having an epoxy group and/or a (meth)acryloyl group described later.

The modified polyvinyl acetal resin preferably has the amino group or the amide structure in the side chain. The amino group or the amide structure may be directly bonded to carbon constituting the main chain of the modified polyvinyl acetal resin, or may be bonded via a linking group such as an alkylene group. Further, the amine from which the amino group is derived may be a primary amine or a secondary amine. Particularly, the above amino group is preferably —NH ₂ . Among them, the structural unit having an amino group preferably has a structure represented by the following formula (5).
Further, the constitutional unit having the amide structure is preferably a structure represented by the following formula (6).
In the present invention, the amide structure means a structure having —C(═O)—NH—.
In addition, having the amino group or the amide structure in the side chain means having the amino group or the amide structure in the graft chain of the modified polyvinyl acetal resin.

In formula (6), R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, and the like.

In the modified polyvinyl acetal resin, the lower limit of the content of the constituent unit having the amino group or the amide structure is preferably 0.1 mol %, and the upper limit thereof is preferably 20 mol %. When the content of the constituent unit having the amino group or the amide structure is 0.1 mol% or more, the additional property can be made sufficient. When the content of the constituent unit having the amino group or the amide structure is 20 mol% or less, the solubility does not increase excessively, and the modified polyvinyl acetal resin powder can be easily taken out by the precipitation method. The more preferable lower limit of the content of the constituent unit having the amino group or the amide structure is 0.5 mol %, and the more preferable upper limit thereof is 10 mol %.
The content of the constituent unit having an amino group or an amide structure can be measured by ¹ H-NMR and ¹³ C-NMR.
The preferable lower limit of the total content of the structural unit having the amino group or the amide structure and the structural unit having the imine structure is 0.1 mol%, and the preferable upper limit is 20 mol%. The more preferable lower limit of the total content of the structural unit having the amino group or the amide structure and the structural unit having the imine structure is 0.5 mol %, and the more preferable upper limit thereof is 10 mol %.

Examples of the method of producing the polyvinyl acetal resin include a method of acetalizing polyvinyl alcohol.
A known method can be used for the acetalization, and it is preferably performed in a water solvent, a mixed solvent of water and an organic solvent having compatibility with water, or an organic solvent.
Examples of the organic solvent compatible with water include alcohol organic solvents.
Examples of the organic solvent include alcohol organic solvents, aromatic organic solvents, aliphatic ester solvents, ketone solvents, lower paraffin solvents, ether solvents, amide solvents, amine solvents and the like.
Examples of the alcohol-based organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like.
Examples of the aromatic organic solvent include xylene, toluene, ethylbenzene, methyl benzoate and the like.
Examples of the aliphatic ester-based solvent include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetoacetate, ethyl acetoacetate and the like.
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, benzophenone, acetophenone and the like.
Examples of the lower paraffinic solvent include hexane, pentane, octane, cyclohexane, decane and the like.
Examples of the ether solvent include diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether and the like.
Examples of the amide-based solvent include N,N-dimethylformamide, N,N-dimethyltecetoamide, N-methylpyrrolidone, acetanilide and the like.
Examples of the amine solvent include ammonia, trimethylamine, triethylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, aniline, N-methylaniline, N,N-dimethylaniline, pyridine and the like.
These may be used alone or in a mixture of two or more kinds of solvents. Among them, ethanol, n-propanol, isopropanol, and tetrahydrofuran are preferable from the viewpoint of solubility in resin and easiness at the time of purification.

Examples of the aldehyde used for acetalization include an aliphatic aldehyde having a chain aliphatic group or a cyclic aliphatic group having 1 to 10 carbon atoms, an aromatic aldehyde, and the like.
Examples of the aliphatic aldehyde include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, 2-ethylhexylaldehyde, n-heptylaldehyde, Examples thereof include n-octeraldehyde, n-nonyl aldehyde, n-decyl aldehyde and amyl aldehyde.
Examples of the aromatic aldehyde include benzaldehyde, cinnamaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde and β-phenylpropionaldehyde. To be
These aldehydes may be used alone or in combination of two or more.
Among them, formaldehyde, acetaldehyde, butyraldehyde, 2-ethylhexyl aldehyde, n-n-, n-, etc. are excellent in acetalization reactivity, can bring a sufficient internal plasticizing effect to the resulting resin, and can impart good flexibility as a result. Nonyl aldehyde is preferable, and formaldehyde, acetaldehyde and butyraldehyde are more preferable.

The amount of the above-mentioned aldehyde added can be appropriately set according to the amount of the acetal group of the targeted modified polyvinyl acetal resin. Particularly, when it is 60 to 95 mol %, preferably 65 to 90 mol% with respect to 100 mol% of polyvinyl alcohol, the acetalization reaction is efficiently carried out and unreacted aldehyde is easily removed.

The acetalization is preferably performed in the presence of an acid catalyst.
Examples of the acid catalyst include mineral acid, carboxylic acid, sulfonic acid and the like.
Examples of the mineral acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and the like.
Examples of the carboxylic acid include formic acid, acetic acid, propionic acid and the like.
Examples of the sulfonic acid include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, paratoluenesulfonic acid and the like.
These acid catalysts may be used alone or in combination of two or more kinds. Of these, hydrochloric acid, nitric acid and sulfuric acid are preferable, and hydrochloric acid is particularly preferable.

As a method for producing a modified polyvinyl acetal resin having a structural unit having an acid-modified group, for example, after copolymerizing a monomer having an acid-modified group with vinyl acetate to obtain polyvinyl acetate, Examples thereof include a method of saponifying vinyl acetate to prepare polyvinyl alcohol, and acetalizing the polyvinyl alcohol by a conventionally known method. Alternatively, an unmodified polyvinyl alcohol may be acetalized by a conventionally known method to prepare a polyvinyl acetal resin, and the obtained polyvinyl acetal resin may be post-modified to introduce an acid-modified group.
That is, the modified polyvinyl acetal resin may be an acetalized product of polyvinyl alcohol having an acid-modified group, or may be an unmodified polyvinyl alcohol acetalized product into which an acid-modified group is introduced.

Examples of the monomer having an acid-modified group include monocarboxylic acid, dicarboxylic acid, carboxylic acid anhydride, and metal salts thereof.
Examples of the monocarboxylic acid include (meth)acrylic acid, crotonic acid, methacrylic acid, oleic acid and the like.
Examples of the dicarboxylic acid include methylene malonic acid, itaconic acid, 2-methylene glutaric acid, 2-methylene adipic acid, 2-methylene sebacic acid and the like.
Examples of the carboxylic acid anhydride include maleic anhydride and the like.

As a method for producing a modified polyvinyl acetal resin having a structural unit having the imine structure, for example, after copolymerizing a monomer having the imine structure and vinyl acetate to obtain polyvinyl acetate, Examples thereof include a method of saponifying vinyl acetate to prepare polyvinyl alcohol, and acetalizing the polyvinyl alcohol by a conventionally known method. Further, a method of introducing an imine structure by acetalizing polyvinyl alcohol having a structural unit having an amino group or an amide structure by a conventionally known method may be used. Furthermore, a modified polyvinyl alcohol having an imine structure is produced by post-modifying a polyvinyl alcohol having a constitutional unit having an amino group or an amide structure, and the obtained modified polyvinyl alcohol is acetalized by a conventionally known method. Good. In addition, an imine structure may be introduced by post-modifying an unmodified polyvinyl acetal resin.
That is, the modified polyvinyl acetal resin may be an acetalized product of polyvinyl alcohol having an amino group or an amide structure.
Among them, a method of introducing an imine structure by acetalizing polyvinyl alcohol having a constitutional unit having an amino group or an amide structure by a conventionally known method is preferable. When such a method is used, an imine structure can be obtained by adding an aldehyde used for acetalization and an acid catalyst in excess. For example, it is preferable to add 1.0% by weight or more of the acid catalyst.
As a method for confirming the constitutional unit having an amino group or an amide structure and the constitutional unit having an imine structure, for example, a method of confirming the spectrum of an amino group (around 1600 cm ⁻¹ ) using FT-IR, A method of confirming an imine structure spectrum (160 to 170 ppm) using ¹³ C-NMR and the like can be mentioned.

In the adhesive composition for fixing a movable part of the present invention, the preferable lower limit of the content of the polyvinyl acetal resin is 4.5% by weight, and the preferable upper limit thereof is 50% by weight. When the content of the polyvinyl acetal resin is 4.5% by weight or more, the obtained adhesive composition for fixing a movable part can exhibit high toughness. When the content of the polyvinyl acetal resin is 50% by weight or less, the obtained adhesive composition for fixing a movable part can exhibit high adhesiveness.
The more preferable lower limit of the content of the polyvinyl acetal resin is 9% by weight, the still more preferable lower limit thereof is 13% by weight, the more preferable upper limit thereof is 40% by weight, and the further preferable upper limit thereof is 30% by weight.

The adhesive composition for fixing a movable part of the present invention contains a compound having an epoxy group and/or a (meth)acryloyl group.
By containing the compound having an epoxy group and/or a (meth)acryloyl group, crosslinking can be achieved by applying energy by heating or the like, and high adhesiveness can be realized.

The compound having an epoxy group and/or a (meth)acryloyl group preferably has a bisphenol skeleton. Since the compound having an epoxy group and/or a (meth)acryloyl group has a bisphenol skeleton, the reliability when an electronic module or the like obtained by using a movable part is subjected to a high temperature test and/or a high temperature and high humidity test, etc. It will be excellent. Among them, a bisphenol A skeleton, a bisphenol F skeleton, or a bisphenol E skeleton is preferable, a bisphenol A skeleton or a bisphenol F skeleton is more preferable, and a bisphenol A skeleton is further preferable.

When the moving part fixing adhesive composition of the present invention is used for a conductive paste or the like, the moving part fixing adhesive composition of the present invention contains an epoxy group as a compound having an epoxy group and/or a (meth)acryloyl group. It is preferable to contain a compound having the compound (hereinafter, also referred to as “epoxy compound”).

Among the compounds having an epoxy group and/or a (meth)acryloyl group, the epoxy compound may be a monofunctional epoxy compound or a polyfunctional epoxy compound, and may be a monofunctional epoxy compound and a bifunctional epoxy compound. It is preferable to include an epoxy compound.

Examples of the monofunctional epoxy compound include aliphatic epoxy resins and aromatic epoxy resins.
Examples of the aliphatic epoxy resin include glycidyl ethers of aliphatic alcohols such as butyl glycidyl ether and lauryl glycidyl ether.
Examples of the aromatic epoxy resin include phenyl glycidyl ether and 4-t-butylphenyl glycidyl ether.
Of these, aromatic epoxy resins are preferable.

Among the above polyfunctional epoxy compounds, examples of the bifunctional epoxy compound include a bifunctional aromatic epoxy resin, a bifunctional alicyclic epoxy resin, a (poly)alkylene glycol diglycidyl ether, and a bifunctional glycidyl ester type. Epoxy resin, bifunctional glycidyl amine type epoxy resin, bifunctional heterocyclic epoxy resin, bifunctional diaryl sulfone type epoxy resin, hydroquinone type epoxy resin, bifunctional glycidyl group-containing hydantoin compound, bifunctional glycidyl group Examples thereof include siloxane and modified products thereof.
Examples of the bifunctional aromatic epoxy resin include phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alkylphenol type epoxy resin, resorcin type epoxy resin, and bifunctional. Naphthalene type epoxy resin, etc.
Examples of the bifunctional alicyclic epoxy resin include dicyclopentadiene dimethanol diglycidyl ether and the like.
Examples of the (poly)alkylene glycol diglycidyl ether include neopentyl glycol diglycidyl ether, butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and the like.
Examples of the bifunctional glycidyl ester type epoxy resin include diglycidyl phthalate, diglycidyl tetrahydrophthalate, dimer acid diglycidyl ester, and the like.
Examples of the bifunctional glycidyl amine type epoxy resin include diglycidyl aniline and diglycidyl toluidine.
Examples of the hydroquinone type epoxy resin include hydroquinone diglycidyl ether, 2,5-di-tert-butylhydroquinone diglycidyl ether, resorcin diglycidyl ether and the like.
Examples of the bifunctional glycidyl group-containing hydantoin compound include 1,3-diglycidyl-5,5-dialkylhydantoin and 1-glycidyl-3-(glycidoxyalkyl)-5,5-dialkylhydantoin. ..
Examples of the bifunctional glycidyl group-containing siloxane include 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane and α,β-bis(3-glycid Xypropyl)polydimethylsiloxane and the like.
These may be used alone or in combination of two or more.
Among them, a bifunctional alicyclic epoxy resin and (poly)alkylene glycol diglycidyl ether are preferable from the viewpoint of reactivity and workability.

Among the above polyfunctional epoxy compounds, examples of the trifunctional or higher functional epoxy compound include, for example, a trifunctional or higher functional aromatic epoxy resin, a trifunctional or higher alicyclic epoxy resin, a trifunctional or higher functional glycidyl ester type epoxy resin, Functional or higher glycidyl amine type epoxy resin, trifunctional or higher heterocyclic epoxy resin, trifunctional or higher diarylsulfone type epoxy resin, trifunctional or higher alkylene glycidyl ether compound, trifunctional or higher glycidyl group-containing hydantoin compound, 3 Examples thereof include functional glycidyl group-containing siloxanes and modified products thereof.
Examples of the trifunctional or higher functional aromatic epoxy resin include trifunctional or higher functional phenol novolac type epoxy resins.
Examples of the trifunctional or higher functional glycidylamine type epoxy resin include tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenylmethane, triglycidyl-m-aminophenylmethane, tetraglycidyl-m-xylylenediamine and the like. ..
Examples of the trifunctional or higher functional alkylene glycidyl ether compounds include glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and the like.
These may be used alone or in combination of two or more.

In the case where the epoxy compound contains a bifunctional aromatic epoxy resin and/or a trifunctional or higher functional aromatic epoxy resin (hereinafter, also referred to as “multifunctional aromatic epoxy resin”), The preferable upper limit of the content of the polyfunctional aromatic epoxy resin is 40% by weight. When the content of the polyfunctional aromatic epoxy resin is 40% by weight or less, the compatibility between the polyvinyl acetal resin and the epoxy compound is sufficiently improved, and the adhesive composition for fixing movable parts is gelled. This can be suppressed and the adhesiveness can be sufficiently improved. A more preferable upper limit of the content of the polyfunctional aromatic epoxy resin is 20% by weight. ――

When the adhesive composition for fixing movable parts of the present invention contains a polyfunctional aromatic epoxy resin, the preferable upper limit of the content of the polyfunctional aromatic epoxy resin in the adhesive composition for fixing movable parts of the present invention. Is 25% by weight.
When the content of the polyfunctional aromatic epoxy resin is 25% by weight or less, the compatibility between the polyvinyl acetal resin and the epoxy compound is sufficiently improved, and the adhesive composition for fixing a movable part gels. This can be suppressed and the adhesiveness can be sufficiently improved. A more preferable upper limit of the content of the polyfunctional aromatic epoxy resin is 5% by weight.

When the moving part fixing adhesive composition of the present invention contains a monofunctional epoxy compound, the content of the polyvinyl acetal resin and the monofunctional epoxy compound in the moving part fixing adhesive composition of the present invention The preferable lower limit of the ratio (content of polyvinyl acetal resin/content of monofunctional epoxy compound) is ⅕, and preferable upper limit is 1/1. The more preferable lower limit of the content of the polyvinyl acetal resin/the content of the monofunctional epoxy compound is 1/4, and the more preferable upper limit thereof is 1/2.

When the adhesive composition for fixing a movable part of the present invention contains a monofunctional epoxy compound, a preferable lower limit of the content of the monofunctional epoxy compound in the adhesive composition for fixing a movable part of the present invention is 40% by weight, A preferable upper limit is 70% by weight. When the content of the monofunctional epoxy compound is within this range, it becomes easy to adjust the tensile breaking strain and the upper yield point stress when the obtained adhesive composition for fixing a movable component is cured. The more preferable lower limit of the content of the monofunctional epoxy compound is 50% by weight, and the more preferable upper limit thereof is 60% by weight.

When the adhesive composition for fixing movable parts of the present invention contains a monofunctional epoxy compound and a bifunctional epoxy compound, the content of the monofunctional epoxy compound in the adhesive composition for fixing movable parts of the present invention and the above 2 A preferable lower limit of the ratio to the content of the functional epoxy compound (content of the monofunctional epoxy compound/content of the bifunctional epoxy compound) is 1/8.5, and a preferable upper limit is 7/1. The more preferable lower limit of the content of the monofunctional epoxy compound/2 of the content of the bifunctional epoxy compound is 1/4, and the more preferable upper limit thereof is 5/1.

In the epoxy compound, a preferable lower limit of the epoxy equivalent (molecular weight per epoxy group) is 100, and a preferable upper limit thereof is 600.

When the adhesive composition for fixing a movable part of the present invention contains a monofunctional epoxy compound and a bifunctional epoxy compound, the ratio of the epoxy equivalent of the monofunctional epoxy compound to the epoxy equivalent of the bifunctional epoxy compound (monofunctional epoxy compound The preferable lower limit of (epoxy equivalent of compound/epoxy equivalent of bifunctional epoxy compound) is 1/7, and the preferable upper limit is 5/1.

Regarding the molecular weight of the epoxy compound, a preferable lower limit is 100 and a preferable upper limit is 600.

When the adhesive composition for fixing a movable part of the present invention contains a monofunctional epoxy compound and a bifunctional epoxy compound, the ratio of the molecular weight of the monofunctional epoxy compound to the molecular weight of the bifunctional epoxy compound (monofunctional epoxy compound The preferable lower limit of (molecular weight/molecular weight of bifunctional epoxy compound) is 1/6, and the preferable upper limit is 2/1.

Among the compounds having an epoxy group and/or a (meth)acryloyl group, examples of the compound having a (meth)acryloyl group include (meth)acrylic acid ester compounds and epoxy (meth)acrylates.
Examples of the (meth)acrylic acid ester compound include tricyclodecane dimethanol di(meth)acrylate, isobornyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.
Examples of the epoxy (meth)acrylate include bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol E type epoxy (meth)acrylate, and caprolactone modified products thereof.
In the present specification, the “(meth)acrylate” means acrylate or methacrylate, and the “epoxy (meth)acrylate” means that all epoxy groups in an epoxy compound are reacted with (meth)acrylic acid. Represents the compound.

When the adhesive composition for fixing a movable part of the present invention is used at a site requiring a positioning step, the adhesive composition for fixing a movable part of the present invention is a compound having an epoxy group and/or a (meth)acryloyl group. It is preferable that the compound contains a compound having an epoxy group and a (meth)acryloyl group. Examples of the above-mentioned “positioning process” include an active alignment process in a camera module.

Among the compounds having an epoxy group and/or a (meth)acryloyl group, examples of the compound having an epoxy group and a (meth)acryloyl group include, for example, a (meth)acrylic acid ester having a glycidyl group and a partial (meth)acryl. Examples include modified epoxy compounds.
In the present specification, the above-mentioned “partial (meth)acrylic modified epoxy compound” is obtained by reacting a part of epoxy groups of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid. Means a compound.

Examples of the (meth)acrylic acid ester having a glycidyl group include glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate glycidyl ether, 2-hydroxypropyl (meth)acrylate glycidyl ether, and 3-hydroxypropyl (meth ) Acrylate glycidyl ether, 4-hydroxybutyl (meth)acrylate glycidyl ether, polyethylene glycol-polypropylene glycol (meth)acrylate glycidyl ether, and the like.

Examples of the partial (meth)acrylic modified epoxy compound include a partial (meth)acrylic modified bisphenol A type epoxy compound, a partial (meth)acrylic modified bisphenol F type epoxy compound, and a partial (meth)acrylic modified bisphenol E type epoxy compound. Is mentioned.

In the adhesive composition for fixing a movable part of the present invention, the preferable lower limit of the content of the compound having the epoxy group and/or the (meth)acryloyl group is 50% by weight, and the preferable upper limit is 95% by weight. A more preferable lower limit of the content of the compound having an epoxy group and/or a (meth)acryloyl group is 75% by weight, and a more preferable upper limit thereof is 85% by weight.

In the adhesive composition for fixing movable parts of the present invention, the ratio of the content of the polyvinyl acetal resin to the content of the compound having the epoxy group and/or the (meth)acryloyl group (content of polyvinyl acetal resin/epoxy The preferred lower limit of the content of the compound having a group and/or a (meth)acryloyl group) is 1/19, and the preferred upper limit is 1/1. The more preferable lower limit of the content of the polyvinyl acetal resin/the content of the compound having an epoxy group and/or the (meth)acryloyl group is 3/17, and the more preferable upper limit thereof is 1/3.

The movable part fixing adhesive composition of the present invention contains a polymerizable curing agent.
The polymerizable curing agent preferably has a melting point of 100° C. or lower. When the melting point of the polymerizable curing agent is 100° C. or less, the adhesive composition for fixing a movable part of the present invention is more excellent in curability by heating at a low temperature. The melting point of the polymerizable curing agent is more preferably 80°C or lower.

The polymerizable curing agent preferably contains an imidazole curing agent and/or a tertiary amine polymerization catalyst.

Examples of the imidazole-based curing agent include imidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-Phenyl-4-methylimidazole, 1-benzylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole and the like can be mentioned.

Examples of the tertiary amine-based polymerization catalyst include trimethylamine, triethylamine, N,N-dimethylpiperazine, triethylenediamine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl). Phenol, 1,8-diazabicyclo(5.4.0)-undecene-7, 1,5-diazabicyclo(4.3.0)-nonene-5 and the like can be mentioned.

Further, the above-mentioned polymerizable curing agent may be used in a state of being contained in microcapsules.
When the polymerizable curing agent is used in a state of being contained in microcapsules, the preferable upper limit of the melting temperature of the material forming the shell of the microcapsules is 100°C, and the more preferable upper limit is 80°C.

Regarding the content of the polymerizable curing agent, a preferable lower limit is 5 parts by weight and a preferable upper limit is 30 parts by weight with respect to 100 parts by weight in total of the compound having the polyvinyl acetal resin and the epoxy group and/or (meth)acryloyl group. It is a department. When the content of the polymerizable curing agent is within this range, the tensile rupture strain and the upper yield point stress of the resin composition after curing can be set within a suitable range. The more preferable lower limit of the content of the polymerizable curing agent is 7 parts by weight, and the more preferable upper limit thereof is 15 parts by weight.

The preferable lower limit of the content of the polymerizable curing agent in the adhesive composition for fixing a movable part of the present invention is 3% by weight, and the preferable upper limit is 30% by weight. The more preferable lower limit of the content of the polymerizable curing agent is 5% by weight, and the more preferable upper limit thereof is 10% by weight.

When the compound having the (meth)acryloyl group as the compound having the epoxy group and/or the (meth)acryloyl group, or the compound having the epoxy group and the (meth)acryloyl group is contained, for fixing the movable part of the present invention The adhesive composition preferably contains a radical polymerization initiator.

Examples of the radical polymerization initiator include a photoradical polymerization initiator that generates a radical upon irradiation with light and a thermal radical polymerization initiator that generates a radical upon heating.

Examples of the photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone compounds.
Specific examples of the photo-radical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 1,2-(dimethylamino) -2-((4-methylphenyl)methyl)-1-(4-(4-morpholinyl)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2 , 4,6-Trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)- 2-hydroxy-2-methyl-1-propan-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyloxime), 2,4,6-trimethylbenzoyl Examples thereof include diphenylphosphine oxide, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether.

Examples of the thermal radical polymerization initiator include those composed of azo compounds, organic peroxides and the like. Among them, an initiator composed of an azo compound (hereinafter, also referred to as “azo initiator”) is preferable.
Examples of the azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable.
Specific examples of the azo compound include polycondensates of 4,4′-azobis(4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis(4-cyanopentanoic acid) and terminals. Examples thereof include polycondensation products of polydimethylsiloxane having an amino group.

Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, and peroxydicarbonate.

The content of the radical polymerization initiator has a preferred lower limit of 0.1 parts by weight and a preferred upper limit of 100 parts by weight with respect to a total of 100 parts by weight of the polyvinyl acetal resin and the compound having an epoxy group and/or a (meth)acryloyl group. It is 20.0 parts by weight. When the content of the radical polymerization initiator is within this range, the obtained adhesive composition for fixing a movable part has excellent curability while maintaining excellent storage stability. The more preferable lower limit of the content of the radical polymerization initiator is 0.5 parts by weight, and the more preferable upper limit thereof is 10.0 parts by weight.

The adhesive composition for fixing a movable part of the present invention may contain a filler for the purpose of improving viscosity, further improving adhesiveness due to stress dispersion effect, improving linear expansion coefficient and the like.

An inorganic filler or an organic filler can be used as the filler.
Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide. , Calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like.

The preferable lower limit of the content of the filler in 100 parts by weight of the adhesive composition for fixing a movable part of the present invention is 0.1 part by weight, and the preferable upper limit is 70 parts by weight. When the content of the above-mentioned filler is in this range, it is possible to further exhibit the effect of improving the adhesiveness while suppressing the deterioration of the coating property and the like. The more preferable lower limit of the content of the filler is 5.0 parts by weight, and the more preferable upper limit thereof is 50 parts by weight.

The adhesive composition for fixing a movable part of the present invention may contain a silane coupling agent for the purpose of further improving the adhesiveness.

Preferred examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-(meth)acryloyloxypropyltrimethoxysilane. Used for.

The preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the adhesive composition for fixing a movable part of the present invention is 0.1 part by weight, and the preferable upper limit is 5.0 parts by weight. When the content of the silane coupling agent is in this range, the effect of improving the adhesiveness can be more exerted while suppressing the bleedout and the like obtained. The more preferable lower limit of the content of the silane coupling agent is 0.3 parts by weight, and the more preferable upper limit thereof is 3.0 parts by weight.

The movable component-fixing adhesive composition of the present invention may contain a viscosity modifier for the purpose of improving the wettability to an adherend in a short time and the shape retention.
Examples of the viscosity modifier include fumed silica and layered silicate.
The above viscosity modifier may be used alone or in combination of two or more kinds.

The preferable lower limit of the content of the viscosity adjusting agent in 100 parts by weight of the adhesive composition for fixing a movable part of the present invention is 0.5 part by weight, and the preferable upper limit is 20 parts by weight. When the content of the viscosity modifier is in this range, the effect of improving the wettability to the adherend in a short period of time and the shape-retaining property is improved. The more preferable lower limit of the content of the viscosity modifier is 1.0 part by weight, and the more preferable upper limit thereof is 10 parts by weight.

The movable part fixing adhesive composition of the present invention preferably contains conductive particles. By containing the above-mentioned conductive particles, the adhesive composition for fixing a movable part of the present invention can be suitably used for a conductive paste or the like.

As the conductive fine particles, metal balls, resin fine particles having a conductive metal layer formed on the surface thereof, or the like can be used. Above all, a resin fine particle having a conductive metal layer formed on the surface thereof is preferable because conductive connection can be made without damaging a transparent substrate or the like due to excellent elasticity of the resin fine particle.

The preferable lower limit of the content of the conductive fine particles in 100 parts by weight of the adhesive composition for fixing a movable part of the present invention is 0.1 part by weight, and the preferable upper limit is 20 parts by weight. When the content of the conductive fine particles is within this range, it is possible to further exhibit the effect of improving the conductivity while suppressing the deterioration of the coating property and the like. The more preferable lower limit of the content of the conductive particles is 1.0 part by weight, and the more preferable upper limit thereof is 15.0 parts by weight.

The adhesive composition for fixing a movable part of the present invention may further contain a cross-linking agent, an organic solvent, a plasticizer, a dispersant, etc. within a range that does not impair the object of the present invention.

Examples of the cross-linking agent include halohydrin compounds, halogen compounds, isocyanate compounds, bisacrylamide compounds, urea compounds, guanidine compounds, dicarboxylic acid compounds, unsaturated carboxylic acid compounds, unsaturated carboxylic acid ester compounds, and aldehyde compounds. ..
Examples of the halohydrin compound include epichlorohydrin, epibromohydrin and the like.
Examples of the halogen compound include 1,2-dichloroethane, 1,3-dichloropropane and the like.
Examples of the isocyanate compound include hexamethylene diisocyanate.
Examples of the bisacrylamide compound include N,N′-methylenebisacrylamide and N,N′-ethylenebisacrylamide.
Examples of the urea compound include urea and thiourea.
Examples of the guanidine compound include guanidine and diguanide.
Examples of the dicarboxylic acid compound include oxalic acid and adipic acid.
Examples of the unsaturated carboxylic acid compound include acrylic acid and methacrylic acid.
Examples of the unsaturated carboxylic acid ester compounds include methyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, isobutyl acrylate, butyl acrylate, 2-ethylhexyl methacrylate, isobutyl methacrylate, butyl methacrylate and the like. Are listed.
Examples of the aldehyde compound include glyoxal, glutaraldehyde, malonaldehyde, succinaldehyde, adipine aldehyde, phthalaldehyde, isophthalaldehyde, terephthalaldehyde and the like.
These may be used alone or in combination of two or more. Further, these cross-linking agents can be used by dissolving them in an organic solvent such as water or alcohol, if necessary.

Examples of the organic solvent include ketones, alcohols, aromatic hydrocarbons, esters, methylcellosolve, ethylcellosolve, butylcellosolve, terpineol, dihydroterpineol, butylcellosolve acetate, butylcarbitol acetate, Examples thereof include terpineol acetate and dihydroterpineol acetate.
Examples of the above-mentioned ketones include acetone, methyl ethyl ketone, dipropyl ketone, diisobutyl ketone and the like.
Examples of the alcohols include methanol, ethanol, isopropanol, butanol and the like.
Examples of the aromatic hydrocarbons include toluene and xylene.
Examples of the esters include methyl propionate, ethyl propionate, butyl propionate, methyl butanoate, ethyl butanoate, butyl butanoate, methyl pentanoate, ethyl pentanoate, butyl pentanoate, methyl hexanoate, hexanoic acid. Examples thereof include ethyl, butyl hexanoate, 2-ethylhexyl acetate, 2-ethylhexyl butyrate.

It is preferable that the adhesive composition for fixing a movable part of the present invention does not contain the organic solvent, but when the organic solvent is contained, the preferable upper limit of the content of the organic solvent is 10.0% by weight. When the content of the organic solvent is 10.0% by weight or less, the inhibition of curing can be made difficult to occur.

As a method for producing the adhesive composition for fixing a movable part of the present invention, for example, using a mixer, a polyvinyl acetal resin, a compound having an epoxy group and/or a (meth)acryloyl group, and a polymerizable curing agent are used. And a silane coupling agent or the like added as necessary, and the like.
Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.

The adhesive composition for fixing a movable part of the present invention may be used for fixing a metal part of a movable part, or may be used for fixing a non-metal part of a movable part.
Examples of the metal forming the metal part include copper and nickel.
Examples of the nonmetal forming the nonmetal part include polyamide, LCP (liquid crystal polymer), and ceramics.

Further, an optical component having a cured product of the adhesive composition for fixing a movable part of the present invention and an electronic component having a cured product of the adhesive composition for fixing a movable part of the present invention are also included in the present invention. Is.
Further, an electronic module having the optical component of the present invention or the electronic component of the present invention is also one aspect of the present invention.

According to the present invention, there is provided an adhesive composition for fixing movable parts, which has excellent adhesiveness to both metal and non-metal, can be cured at low temperature, and can prevent displacement of movable parts. can do. Further, according to the present invention, it is possible to provide an optical component, an electronic component, and an electronic module which use the adhesive composition for fixing a movable component.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

(Examples 1 to 30, Comparative Examples 1 to 15)
The materials were mixed in a mixer according to the compounding ratios shown in Tables 1 to 5 to obtain movable part fixing adhesive compositions of Examples 1 to 30 and Comparative Examples 1 to 15. As the mixer, ARE-310 (manufactured by Shinky Co.) was used.
Each of the obtained adhesive compositions for fixing movable parts was irradiated with ultraviolet rays (wavelength 365 nm) of 100 mW/cm ² for 30 seconds using a metal halide lamp, and then heated at 80° C. for 1 hour to obtain a cured product. ..
Using the dynamic viscoelasticity measuring device, the obtained cured product was stored at 25° C. under the conditions of a test piece width of 5.0 mm, a thickness of 0.35 mm, a gripping width of 25 mm, a heating rate of 10° C./min, and a frequency of 10 Hz. The elastic modulus was measured. The results are shown in Tables 1-5.

<Evaluation>
The following evaluations were carried out on the movable part fixing adhesive compositions obtained in the examples and comparative examples. The results are shown in Tables 6-10.

(Storage stability)
For each of the adhesive compositions for fixing movable parts obtained in Examples and Comparative Examples, the initial viscosity immediately after production and the viscosity when stored at 25° C. for 48 hours were measured and measured (after storage at 25° C. for 48 hours). Viscosity)/(initial viscosity) was derived as the viscosity change rate.
A viscosity change rate of 1.1 or less was “Excellent”, a viscosity of more than 1.1 and 1.2 or less was “◯”, and a viscosity change rate of more than 1.2 and 1.5 or less was “O”. The storage stability was evaluated as "B", and those exceeding 1.5 were evaluated as "X".
The viscosity of the sealant was measured using an E-type viscometer ("DV-III" manufactured by Brookfield Co., Ltd.) at a rotation speed of 1.0 rpm at 25°C.

(Reactivity)
Each of the adhesive compositions for fixing movable parts obtained in Examples and Comparative Examples was irradiated with ultraviolet rays (wavelength 365 nm) of 100 mW/cm ² for 30 seconds using a metal halide lamp, and then heated at 80° C. for 1 hour. A cured product was obtained.
For the adhesive composition for fixing movable parts before curing and the obtained cured product, the total peak area of the peak derived from the epoxy group and the peak derived from the (meth)acryloyl group was measured using an infrared spectroscopic device, and before and after curing. The change amount (reduction rate) of the total peak area was derived. As the infrared spectroscope, FTS3000 (manufactured by BIORAD) was used.
The reactivity was evaluated as "O" when the reduction rate of the total peak area was 80% or more and "X" when it was less than 80%.

(Adhesiveness)
Each of the base materials (length 100 mm, width 25 mm, thickness 2.0 mm) described in Tables 6 to 10 was coated with the adhesive composition for fixing movable parts obtained in Examples and Comparative Examples to obtain a silicon wafer substrate. (Length 2 mm, width 2 mm, thickness 0.7 mm) were stacked. Then, the adhesive composition for fixing movable parts was cured by heating at 100° C. for 1 hour or at 80° C. for 1 hour to obtain a test piece. The die shear strength of the obtained test piece was measured at 25° C. at a speed of 300 μm/s using a die shear tester. A bond tester DAGE4000 (manufactured by NORDSON DAGE) was used as the die shear tester.
When the die shear strength is 45 N or more, it is "⊚", when it is 40 N or more and less than 45 N, it is "○", when it is 20 N or more and less than 40 N, it is "△", and when it is less than 20 N, it is "x". Was evaluated as adhesiveness. In addition, those for which the die shear strength could not be measured were marked with "-".

According to the present invention, there is provided an adhesive composition for fixing movable parts, which has excellent adhesiveness to both metal and non-metal, can be cured at low temperature, and can prevent displacement of movable parts. can do. Further, according to the present invention, it is possible to provide an optical component, an electronic component, and an electronic module, which are obtained by using the adhesive composition for fixing a movable component.

Claims

Containing a polyvinyl acetal resin, a compound having an epoxy group and/or a (meth)acryloyl group, and a polymerizable curing agent,
An adhesive composition for fixing movable parts, characterized in that the cured product has a storage elastic modulus at 25° C. of 1.0 GPa or more.
The adhesive composition for fixing movable parts according to claim 1, wherein the polyvinyl acetal resin has a number average molecular weight of 5,000 or more and 200,000 or less.
The adhesive composition for fixing movable parts according to claim 1 or 2, which contains a compound having an epoxy group as the compound having an epoxy group and/or a (meth)acryloyl group.
The adhesive composition for fixing movable parts according to claim 1 or 2, containing a compound having an epoxy group and a (meth)acryloyl group as the compound having an epoxy group and/or a (meth)acryloyl group.
The adhesive composition for fixing movable parts according to claim 1, 2, 3 or 4, wherein the compound having an epoxy group and/or a (meth)acryloyl group has a bisphenol skeleton.
The adhesive composition for fixing movable parts according to claim 1, 2, 3, 4 or 5, wherein the polymerizable curing agent contains an imidazole curing agent and/or a tertiary amine polymerization catalyst.
The adhesive composition for fixing movable parts according to claim 1, 2, 3, 4, 5 or 6, which contains conductive particles.
The adhesive composition for fixing a movable part according to claim 1, 2, 3, 4, 5, 6 or 7, which is used for fixing a metal part of a movable part.
The adhesive composition for fixing a movable part according to claim 1, 2, 3, 4, 5, 6 or 7, which is used for fixing a non-metal part of a movable part.
An optical component comprising a cured product of the adhesive composition for fixing a movable component according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9.
An electronic component having a cured product of the adhesive composition for fixing a movable component according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9.
An electronic module comprising the optical component according to claim 10 or the electronic component according to claim 11.