KR102687767B1 - Method for manufacturing curable film-like adhesives and devices - Google Patents

Abstract

The present invention constitutes a sensor device comprising a compound having a cyclic ether group, a polymer component, and a curing agent containing an imidazole compound having a reaction activation temperature of 125°C or lower and a thermal cationic polymerization initiator having a reaction activation temperature of 160°C or lower. A curable film adhesive used in a member, and a process of curing the curable film adhesive by attaching the curable film adhesive to a member including a module and heating it to a temperature in the range of 80 to 110 ° C. A method of manufacturing a device, including: According to the present invention, a curable film-like adhesive used in a member constituting a sensor device provides a cured product that can be cured at low temperature and has excellent transparency, and can be cured at low temperature and also has transparency. A method of manufacturing a device using a curable film-like adhesive that provides an excellent cured product is provided.

Description

Method for manufacturing curable film-like adhesives and devices

The present invention includes a curable film adhesive used in a member constituting a sensor device that can be cured at low temperature and provides a cured product with excellent transparency, and a process for curing this curable film adhesive. , relates to a method of manufacturing a device.

Various sensors are built into portable electronic devices such as portable personal computers and smart phones. For example, many portable electronic devices have a built-in luminance sensor for detecting the amount of external light (environmental light) and a proximity sensor (sensor chip) for detecting the detection target in a non-contact state.

Additionally, in recent years, thin sensor modules that adhere optical components (protective layers) directly onto the sensor chip are also being studied.

For example, in Patent Document 1, (i) a sensor chip having a surface having a sensor area on which a plurality of pixels is formed is mounted face-up on the upper surface of a wiring board, and then the sensor chip is placed face-up at a plurality of points on the surface of the sensor chip. A process of forming a plurality of first spacers having adhesive properties on the surface of the sensor chip by placing a first adhesive material on the surface and curing the first adhesive material, (ii) disposing a second adhesive material in the form of paste on the surface of the sensor chip, Then, a process of placing a first optical component having a light-shielding layer on which a plurality of optical regions is formed on the surface of the sensor chip via a plurality of first spacers and a second adhesive material while applying a load to the first optical component, and, (iii) thereafter curing the second adhesive in a state without applying a load to the first optical component, thereby fixing the first optical component.

In addition, in this document, an ultraviolet curing adhesive is applied on a sensor chip, an optical component is placed on it, the adhesive is cured by irradiating ultraviolet rays while the optical component is held by a bonding tool, and the adhesive is cured on the sensor chip. A method for gluing optical components is also described.

Additionally, this document also describes that the adhesive used must have light transparency.

Japanese Patent Publication No. 2015-38991

Methods for curing the adhesive applied on the sensor chip include a method of curing the adhesive by heating it (heat curing method) and a method of curing the adhesive by irradiating light (photo curing method).

Sensor chips and optical components are easily affected by heat. Therefore, when employing a heat curing method, it is desirable to cure the adhesive at the lowest possible temperature from the viewpoint of avoiding the influence of heating on the sensor chip or optical components.

However, heat treatment at low temperatures has the problem that it is difficult to sufficiently cure the adhesive.

The present invention has been made in view of this viewpoint, and provides a cured product that can be cured at low temperature and has excellent transparency, a curable film-like adhesive used in a member constituting a sensor device, and the curable film-like adhesive. The purpose is to provide a method of manufacturing a device using an adhesive.

As a result of intensive studies to solve the above problems, the present inventors have found a compound containing a cyclic ether group, a polymer component, and an imidazole compound with a reaction activation temperature of 125 ° C. or lower or a thermal cation polymerization initiator with a reaction activation temperature of 160 ° C. or lower. It has been found that a curable film-like adhesive containing a curing agent can be cured at low temperatures and provides a cured product with excellent transparency, and can be suitably used for adhesion of parts constituting various devices such as sensor devices. This led to completion of the present invention.

In this way, according to the present invention, a method of manufacturing the curable film adhesive of [1] to [7] below and the device of [8] is provided.

[1] Contains a compound having a cyclic ether group, a polymer component, and a curing agent containing at least one selected from the group consisting of an imidazole compound with a reaction activation temperature of 125°C or lower and a thermal cationic polymerization initiator with a reaction activation temperature of 160°C or lower, , a curable film-like adhesive used for members constituting a sensor device.

[2] The curable film form according to [1], wherein at least one reaction activation temperature selected from the imidazole compound having a reaction activation temperature of 125°C or lower and a thermal cationic polymerization initiator having a reaction activation temperature of 160°C or lower is 100°C or higher. glue.

[3] The curable film adhesive according to any one of [1] or [2], wherein the sensor device is an optical sensor device, and the total light transmittance after curing of the curable film adhesive is 80% or more.

[4] The curing agent contains as a main component at least one type selected from an imidazole-based compound having a reaction activation temperature of 125°C or lower and a thermal cationic polymerization initiator having a reaction activation temperature of 160°C or lower, [1] to [3] ] The curable film-like adhesive according to any one of the above.

[5] The curable film adhesive according to any one of [1] to [4], wherein the curing agent contains a thermal cation polymerization initiator having a reaction activation temperature of 160°C or lower.

[6] The curable film adhesive according to any one of [1] to [5], wherein the polymer component contains an acid-modified polyolefin resin.

[7] The curable film adhesive according to any one of [1] to [6], wherein the cyclic ether compound is an aliphatic compound.

[8] A curable film containing a cyclic ether compound, a polymer component, and a curing agent containing at least one selected from the group consisting of an imidazole compound having a reaction activation temperature of 125°C or lower and a thermal cationic polymerization initiator having a reaction activation temperature of 160°C or lower. A method of manufacturing a device, comprising a step of curing the curable film adhesive by attaching the adhesive to a member including a module and heating it to a temperature in the range of 80 to 110°C.

According to the present invention, a curable film adhesive used in a member constituting a sensor device can be cured at a low temperature and provides a cured product with excellent transparency, and the manufacture of a device using the curable film adhesive. A method is provided.

Hereinafter, the present invention will be described in detail by dividing it into 1) a curable film-like adhesive, and 2) a device manufacturing method.

1) Curable film adhesive

The present invention contains a curing agent containing a compound having a cyclic ether group, a polymer component, and at least one selected from the group consisting of an imidazole compound with a reaction activation temperature of 125°C or lower and a thermal cationic polymerization initiator with a reaction activation temperature of 160°C or lower. It is a curable film-like adhesive used for members constituting sensor devices.

Here, “curability” refers to the physical property of curing by heating to a predetermined temperature to provide a cured product.

“Film-like” means that the adhesive of the present invention has a film shape or sheet shape. The film adhesive of the present invention may be in a strip form (label shape) or in a long form (a shape that can be wound into a roll).

[Compounds having a cyclic ether group]

The curable film adhesive of the present invention contains a compound having a cyclic ether group.

Since the compound having a cyclic ether group has excellent compatibility with the polymer component described later, by using it, a film-like adhesive with excellent film-forming properties and sheet processability in a room temperature environment can be obtained.

In addition, in this specification, a room temperature environment refers to an environment of 20°C ± 15°C (5 to 35°C) (JIS Z 8703).

A compound having a cyclic ether group refers to a compound having at least one cyclic ether group in the molecule.

Examples of the cyclic ether group include oxirane group (epoxy group), oxetane group (oxetanyl group), tetrahydrofuryl group, and tetrahydropyranyl group.

Among these, from the viewpoint of obtaining a film adhesive with better film forming properties and sheet processability under a room temperature environment and a cured product of the film adhesive with better adhesive strength, compounds having an oxirane group or an oxetane group are preferred. Preferred, and compounds having two or more oxirane groups or oxetane groups in the molecule are particularly preferred.

In addition, in the present invention, the phenoxy resin described later is not contained.

Compounds having an oxirane group in the molecule include aliphatic epoxy compounds (excluding alicyclic epoxy compounds), alicyclic epoxy compounds, and aromatic epoxy compounds.

Examples of the aliphatic epoxy compound include monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols and glycidyl esters of alkyl carboxylic acids;

Polyfunctional epoxy compounds such as polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, and epoxy compounds having a triazine skeleton can be mentioned.

Representative compounds of these aliphatic epoxy compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, and 1,4-butanediol diglycidyl. Ether, neopentyl glycol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol. Glycidyl ether of polyhydric alcohol such as glycidyl ether, diglycidyl ether of polypropylene glycol, dicyclopentadienedimethanol diglycidyl ether, or aliphatic polyhydric alcohol such as propylene glycol, trimethylolpropane, and glycerin. polyglycidyl ethers of polyether polyols obtained by adding one or more types of alkylene oxides, diglycidyl esters of long aliphatic dibasic acids;

Monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, and epoxidized polybutadiene;

2,4,6-tri(glycidyloxy)-1,3,5-triazine, etc. can be mentioned.

Moreover, as an aliphatic epoxy compound, a commercial item can also be used. Commercially available products include Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, and Denacol EX- 321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 (above, manufactured by Nagase Chemtex Corporation);

Eporite M-1230, Eporite 40E, Eporite 100E, Eporite 200E, Eporite 400E, Eporite 70P, Eporite 200P, Eporite 400P, Eporite 1500NP, Eporite 1600, Eporite 80MF, Eporite 100MF ( Above, manufactured by Kyoeisha Chemical Co., Ltd.);

Adeka Glycyrol ED-503, Adeka Glycyrol ED-503G, Adeka Glycyrol ED-506, Adeka Glycyrol ED-523T, Adeka Resin EP-4088S, Adeka Resin EP-4088L, Adeka Resin EP-4080E (above, manufactured by ADEKA);

Examples include TEPIC-FL, TEPIC-PAS, and TEPIC-UC (manufactured by Nissan Chemical Co., Ltd.).

Examples of the alicyclic epoxy compound include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic structure, or cyclohexene oxide obtained by epoxidizing a compound containing a cyclohexene ring or a cyclopentene ring with an oxidizing agent. and cyclopentene oxide-containing compounds.

Representative compounds of these alicyclic epoxy compounds include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 3,4-epoxy-1-methyl. Cyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy -3-Methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate , bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), propane-2,2-diyl- Bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), Dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene Dioxide, etc. can be mentioned.

Moreover, as an alicyclic epoxy compound, a commercial item can also be used. Commercially available products include Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000 (manufactured by Daicel Corporation), YX8000, and YX8034 (manufactured by Mitsubishi Chemical Corporation).

Examples of the aromatic epoxy compound include phenols having at least one aromatic ring, such as phenol, cresol, and butylphenol, or mono/polyglycidyl etherified products of alkylene oxide adducts thereof.

Representative examples of these aromatic epoxy compounds include bisphenol A, bisphenol F, or glycidyl ether products of compounds obtained by adding alkylene oxide to these compounds, and epoxy novolak resins;

Mono/polyglycidyl etherified products of aromatic compounds having two or more phenolic hydroxyl groups, such as resorcinol, hydroquinone, and catechol;

Glycidyl etherified products of aromatic compounds having two or more alcoholic hydroxyl groups, such as phenyl dimethanol, phenyldiethanol, and phenyldibutanol;

Examples include glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, and trimellitic acid, glycidyl esters of benzoic acid, styrene oxide, or epoxidized products of divinylbenzene.

Moreover, as an aromatic epoxy compound, a commercial item can also be used. Commercially available products include Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncote EX-1020, Oncote EX- 1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (above, manufactured by Nagase Chemtex Co., Ltd.); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (above, manufactured by Osaka Gas Chemical Co., Ltd.); HP4032, HP4032D, HP4700 (above, manufactured by DIC); ESN-475V (above, manufactured by Nittetsu Chemical & Materials Co., Ltd.); JER (formerly Epicoat) YX8800, YL980 (above, manufactured by Mitsubishi Chemical Corporation); Maproof G-0105SA, Maproof G-0130SP (above, manufactured by Nichiyu Co., Ltd.); Epiclon N-665, Epiclon HP-7200 (above, manufactured by DIC); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (above, manufactured by ADEKA); TECHMORE VG-3101L (above, manufactured by Printec) etc. can be mentioned.

Compounds having an oxetane group in the molecule include 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene. , 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3 -ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, 1, Bifunctional aliphatic oxetane compounds such as 4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, 3-ethyl-3- [(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxylmethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxylmethyl)oxetane, 3-ethyl-3-(hydroxyl and monofunctional oxetane compounds such as methyl)oxetane and 3-ethyl-3-(chloromethyl)oxetane.

As a compound having an oxetane group in the molecule, a commercial product can also be used. Commercially available products include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinyl ether (above, manufactured by Maruzen Petrochemical Co., Ltd.); Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (above, manufactured by Toa Synthetic Company); Eternacall OXBP, OXTP (above, manufactured by Ube Industries), etc.

Among these compounds having a cyclic ether group, compounds (aliphatic compounds) that do not have an aromatic ring, such as aliphatic epoxy compounds (excluding alicyclic epoxy compounds) and alicyclic epoxy compounds, can suppress coloring of the film adhesive. , it is preferable because it can be preferably used as an optical sensor device.

The molecular weight of the compound having a cyclic ether group is usually 700 to 5,000, preferably 1,200 to 4,000.

The cyclic ether equivalent weight of the compound having a cyclic ether group is preferably 100 g/eq or more and 500 g/eq or less, more preferably 150 g/eq or more and 300 g/eq or less.

By using a compound having a cyclic ether group whose cyclic ether equivalent weight is within the above range, a curable film adhesive with strong adhesive strength and excellent curability can be efficiently produced.

These compounds having a cyclic ether group can be used individually or in combination of two or more types.

In addition, the cyclic ether equivalent in the present invention means the value obtained by dividing the molecular weight by the number of cyclic ether groups.

From the viewpoint of making it easy to obtain a film adhesive having excellent sheet shape retention and sheet processability while increasing the elastic modulus of the film adhesive after curing, the content of the compound having a cyclic ether group in the film adhesive is preferably It is 5-80 mass %, More preferably, it is 10-75 mass %.

[Polymer component]

The curable film adhesive of the present invention contains a polymer component in addition to the compound having the cyclic ether group.

By containing the polymer component, a film adhesive with better sheet processability and a cured product of the film adhesive with better adhesive strength can be obtained. Additionally, by containing a polymer component, a film-like adhesive of a desired thickness can be efficiently manufactured.

The polymer component is added for the main purpose of providing sheet shape retention to the film adhesive.

In order to achieve the above object, the weight average molecular weight (Mw) of the polymer component is usually 20,000 or more, and is preferably 20,000 to 3,000,000. Moreover, the number average molecular weight (Mn) of the polymer component is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer component can be obtained as standard polystyrene conversion values by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

The content of the polymer component in the film adhesive is preferably 15 to 90 mass%, more preferably 20 to 85 mass%. By keeping the content of the polymer component within the above range, it is easy to adjust the amount of the cyclic ether compound to be blended while maintaining the sheet shape of the film adhesive.

As the polymer component, polyolefin resin, modified polyolefin resin, acrylic polymer, polyester resin, phenoxy resin, polycarbonate, polyether resin, polyurethane resin, polysiloxane, rubber polymer, etc. can be used. These polymer components can be used individually or in combination of two or more types.

Among these, from the viewpoint of compatibility with compounds having a cyclic ether group, polyolefin resins, modified polyolefin resins, acrylic polymers, polyester resins, and phenoxy resins are preferable.

(polyolefin resin)

Polyolefin resin is a polymer containing repeating units derived from olefin monomers. The polyolefin resin may be a polymer composed only of repeating units derived from olefinic monomers, or may be a polymer composed of repeating units derived from olefinic monomers and repeating units derived from monomers copolymerizable with olefinic monomers.

As the olefinic monomer, α-olefins having 2 to 8 carbon atoms are preferable, ethylene, propylene, 1-butene, isobutylene, or 1-hexene are more preferable, and ethylene or propylene is still more preferable.

These olefinic monomers can be used individually or in combination of two or more types.

Monomers that can be copolymerized with olefin monomers include vinyl acetate, (meth)acrylic acid ester, and styrene. Here, “(meth)acrylic acid” represents acrylic acid or methacrylic acid (the same applies hereinafter).

The monomers copolymerizable with these olefinic monomers can be used individually or in combination of two or more types.

Polyolefin resins include very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), and ethylene-propylene. Copolymers, olefin elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, etc. are mentioned.

(Modified polyolefin resin)

Modified polyolefin-based resin is a polyolefin-based resin into which a functional group is introduced, obtained by using a polyolefin-based resin as a precursor and subjecting it to a modification treatment using a denaturing agent.

The modifier used in the modification treatment of polyolefin resin is a compound having a functional group in the molecule.

Modified polyolefin-based resin is preferably used as a polymer component because it promotes the thermal reaction of the cyclic ether compound and improves the curability of the film adhesive at low temperatures.

Functional groups include carboxyl group, carboxylic acid anhydride group, carboxylic acid ester group, hydroxyl group, epoxy group, amide group, ammonium group, nitrile group, amino group, imide group, isocyanate group, acetyl group, thiol group, ether group, and thioether group. , sulfone group, phosphone group, nitro group, urethane group, alkoxysilyl group, silanol group, halogen atom, etc. Among these, a carboxyl group, carboxylic acid anhydride group, carboxylic acid ester group, hydroxyl group, ammonium group, amino group, imide group, isocyanate group, and alkoxysilyl group are preferable, and carboxyl group, carboxylic acid anhydride group, and alkoxysilyl group are more preferable, From the viewpoint of improving the curability of the film adhesive at low temperatures, a carboxyl group and a carboxylic acid anhydride group are particularly preferable.

A compound having a functional group may have two or more types of functional groups in the molecule.

Modified polyolefin-based resins include acid-modified polyolefin-based resins and silane-modified polyolefin-based resins. From the viewpoint of making it easier to obtain the effect of improving the curability at low temperatures of the film adhesive of the present invention, it is preferable to use an acid-modified polyolefin-based resin as the modified polyolefin-based resin. Additionally, when the curing agent of the present invention contains an imidazole compound with a reaction activation temperature of 125°C or lower, it is preferable to use an acid-modified polyolefin resin as the polymer component in order to further improve curing properties at low temperatures.

Acid-modified polyolefin-based resin refers to polyolefin-based resin graft-modified with acid. For example, there is a polyolefin resin in which an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride is reacted to introduce a carboxyl group or a carboxylic acid anhydride group (graft modification).

Examples of the unsaturated carboxylic acid and unsaturated carboxylic acid anhydride reacted with the polyolefin resin include unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, and aconitic acid; Unsaturated carboxylic acid anhydrides such as maleic acid anhydride, itaconic anhydride, glutaconic acid anhydride, citraconic acid anhydride, aconitic acid anhydride, norbornenedicarboxylic anhydride, and tetrahydrophthalic anhydride; can be mentioned.

These can be used individually or in combination of two or more types. Among these, maleic anhydride is preferable because it is easy to obtain a film adhesive with better sheet processability and a cured product of the film adhesive with better adhesive strength.

The amount of unsaturated carboxylic acid (or unsaturated carboxylic acid anhydride) reacted with the polyolefin resin is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, with respect to 100 parts by mass of the polyolefin resin. Preferably it is 0.2 to 1 part by mass. The curable film adhesive containing the acid-modified polyolefin resin obtained in this way makes it easy to obtain a cured product with superior adhesive strength.

As the acid-modified polyolefin-based resin, a commercial item can also be used. Commercially available products include, for example, Admer (registered trademark) (manufactured by Mitsui Chemicals, Inc.), Unistol (registered trademark) (manufactured by Mitsui Chemicals, Inc.), BondyRam (manufactured by Polyram, Inc.), orevac (registered trademark) (manufactured by ARKEMA, Inc.), Modic (registered trademark) (manufactured by Mitsubishi Chemical Corporation), etc. can be mentioned.

Silane-modified polyolefin-based resin refers to a polyolefin resin graft-modified with an unsaturated silane compound. Silane-modified polyolefin-based resin has a structure in which an unsaturated silane compound as a side chain is graft-copolymerized to a polyolefin resin as the main chain. Examples include silane-modified polyethylene resin and silane-modified ethylene-vinyl acetate copolymer, and silane-modified polyethylene resins such as silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene are preferred.

As an unsaturated silane compound reacted with the polyolefin resin, a vinyl silane compound is preferable. Vinyl silane compounds include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tripropoxy silane, vinyl triisopropoxy silane, vinyl tributoxy silane, vinyl tripentyloxy silane, vinyl triphenoxy silane, and vinyl silane. Tribenzyloxysilane, vinyltrimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, vinyltricarboxysilane, etc. are mentioned.

These can be used individually or in combination of two or more types.

In addition, the conditions for graft polymerizing an unsaturated silane compound to the polyolefin resin as the main chain may be a conventional method of known graft polymerization.

The amount of the unsaturated silane compound reacted with the polyolefin resin is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the polyolefin resin. The curable film adhesive containing the silane-modified polyolefin resin obtained in this way makes it easy to obtain a cured product with superior adhesive strength.

As the silane-modified polyolefin-based resin, a commercial product can also be used. Commercially available products include, for example, Linclon (registered trademark) (manufactured by Mitsubishi Chemical Corporation). Among these, low-density polyethylene-based Linclon, linear low-density polyethylene-based Linclon, ultra-low-density polyethylene-based Linclon, and ethylene-vinyl acetate copolymer-based Linclon can be preferably used.

Modified polyolefin resin can be used individually or in combination of two or more types.

(Acrylic polymer)

An acrylic polymer is a polymer that contains a repeating unit derived from (meth)acrylic acid ester in its molecule. The proportion of repeating units derived from (meth)acrylic acid ester in the acrylic polymer is usually 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, with respect to all repeating units. Typically, it is 70% by mass or more. Additionally, the ratio of repeating units contained in the acrylic polymer usually corresponds to the ratio (injection ratio) of monomers that can form each repeating unit among all monomers used for polymerization of the acrylic polymer.

(meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, etc. Alkyl (meth)acrylate having a value of 1 to 18; Cycloalkyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl ( (meth)acrylate having a cyclic skeleton such as meth)acrylate and imide (meth)acrylate; (meth)acrylic acid esters having a hydroxyl group such as 2-hydroxylethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; (meth)acrylic acid esters having an amide group such as N-methylol (meth)acrylamide; (meth)acrylic acid esters having an amino group such as monoethylamino (meth)acrylate; etc. can be mentioned.

Here, (meth)acrylic means including both acrylic and methacrylic.

Moreover, as a monomer constituting the acrylic polymer, in addition to (meth)acrylic acid ester, monomers having a carboxyl group such as (meth)acrylic acid, maleic acid, fumaric acid, and itaconic acid; Vinyl compounds such as vinyl acetate and styrene; Ethylene, α-olefin, etc. may be used.

The acrylic polymer may be crosslinked. Crosslinking is carried out by adding a crosslinking agent to a composition where the acrylic polymer before crosslinking has a crosslinkable functional group such as a hydroxyl group and reacting the crosslinkable functional group with the functional group of the crosslinking agent. By crosslinking the acrylic polymer, it becomes possible to control the initial adhesion and cohesion of the film adhesive.

(polyester resin)

Polyester resin is a polycondensate of polyhydric carboxylic acid (dicarboxylic acid) and polyalcohol (diol).

Examples of polyester resins include polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, and polylactic acid.

(phenoxy resin)

Phenoxy resins are high molecular weight thermoplastic condensation products of bisphenol A and epichlorohydrin and their derivatives.

The phenoxy resin is not particularly limited and includes bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, and norbornene. and those having one or more types of skeletons selected from the skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton.

When the curing agent of the present invention contains a thermal cation polymerization initiator with a reaction activation temperature of 160° C. or lower, the polymer component may include polyolefin resin, acrylic polymer, polyester resin, phenoxy resin, polycarbonate, polyether resin, poly It is preferable to use unmodified polymer components such as urethane resin, polysiloxane, and rubber polymer. When the curing agent of the present invention contains a thermal cation polymerization initiator with a reaction activation temperature of 160°C or lower, it becomes easy to provide sufficient curability at low temperatures to the curable film adhesive. Therefore, there is little need to improve the curability of the film adhesive by using a modified polyolefin resin or the like, and rather, the storage stability of the film adhesive can be improved by using a non-modified polymer component.

[Hardener]

The curable film adhesive of the present invention, in addition to the compound and polymer component having a cyclic ether group, contains at least one selected from the group consisting of an imidazole compound with a reaction activation temperature of 125°C or lower and a thermal cationic polymerization initiator with a reaction activation temperature of 160°C or lower. Contains a hardener containing species.

The curing agent is used for the purpose of adjusting the reaction temperature and reaction speed of heat curing of the film adhesive.

The curing agent used in the present invention contains at least one selected from the group consisting of an imidazole compound with a reaction activation temperature of 125°C or lower and a thermal cation polymerization initiator with a reaction activation temperature of 160°C. By using these compounds as curing agents, the curable film adhesive can be sufficiently cured at low temperatures. That is, by using these compounds as a curing agent, it is possible to bond members constituting the sensor device to each other, or to members constituting the sensor device and other members, without causing heat damage to the sensor device.

Here, the “reaction activation temperature” means that when the compound used in the curing agent and a general-purpose liquid bisphenol A type epoxy resin are mixed and heated, the peak of curing heat generation is confirmed at the lowest temperature by differential scanning calorimetry (DSC). This is the temperature. About the imidazole compound, liquid bisphenol A type epoxy resin and the imidazole compound are mixed and measured. In addition, the thermal cation polymerization initiator is measured by mixing liquid bisphenol A type epoxy resin, thermal cation polymerization initiator, and γ-butyrolactone. More specifically, the “reaction activation temperature” can be measured by the method described in the Examples.

At least one selected from the imidazole compound and thermal cation polymerization initiator used in the curing agent of the present invention preferably has a reaction activation temperature of 100°C or higher. If the reaction activation temperature of the curing agent is high to a certain degree, it is possible to suppress thermal curing due to heat generated during film forming of the film adhesive (drying of the coating film, hot melt).

At least one type selected from the imidazole compound and thermal cation polymerization initiator used in the curing agent of the present invention can be widely used as long as the reaction activation temperature is 125°C or lower or 160°C or lower. In addition, the curing agent preferably contains at least one type selected as a main component from an imidazole-based compound with a reaction activation temperature of 125°C or lower and a thermal cationic polymerization initiator with a reaction activation temperature of 160°C or lower. That is, the content of “at least one type selected from imidazole-based compounds with a reaction activation temperature of 125°C or lower and thermal cation polymerization initiators with a reaction activation temperature of 160°C or lower” relative to the total curing agent is preferably 70% by mass or more, More preferably, it is 90 mass% or more. In this way, by reducing the amount of compounds other than the imidazole compound or thermal cation polymerization initiator used as a curing agent, it is possible to improve the curability of the film adhesive at low temperatures and increase the total light transmittance after curing of the film adhesive. It becomes easier.

Imidazole-based compounds with a reaction activation temperature of 125°C or lower include commercially available products such as C17Z, 2E4MZ, 2PZ, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, 2E4MZ-CN, and 2PZ-OK (manufactured by Shikoku Chemical Company). I can hear it. When measuring the reaction activation temperature of an imidazole-based compound, it is preferable to measure by mixing 100 parts by mass of the liquid bisphenol A type epoxy resin and 5 parts by mass of the imidazole compound.

A thermal cationic polymerization initiator is a compound that can generate cationic species that initiate polymerization by heating. The thermal cation polymerization initiator is not particularly limited and is appropriately selected depending on curing conditions and the type of cation polymerizable compound.

The thermal cationic polymerization initiator used for curing can be widely used as long as the reaction activation temperature is 160°C or lower. Examples include sulfonium salt-based compounds, quaternary ammonium salt-based compounds, phosphonium salt-based compounds, diazonium salt-based compounds, and iodonium salt-based compounds. Among these, from the viewpoint of being able to cure the sealing sheet at low temperature, sulfonium salt-based compounds or quaternary ammonium salt-based compounds are preferable, and sulfonium salt-based compounds are more preferable. Moreover, among sulfonium salt-based compounds, it is preferable that the counter anion is tetrakis(pentafluorophenyl)borate anion from the viewpoint of being able to reduce the amount of the thermal cation polymerization initiator used.

As a sulfonium salt-based compound, commercially available products include San-Aid SI-300, San-Aid SI-360, San-Aid SI-B2A, San-Aid SI-B7, San-Aid SI-B3A, and San-Aid SI-B3 (above, SanShin Chemical Co., Ltd.) manufacturing), etc. When measuring the reaction activation temperature of a sulfonium salt-based compound, when the counter anion is tetrakis(pentafluorophenyl)borate anion, 100 parts by mass of liquid bisphenol A type epoxy resin and 0.1 part by mass of thermal cation polymerization initiator. , and 0.1 parts by mass of γ-butyrolactone are preferably mixed for measurement. In addition, when the counter anion is hexafluorophosphate anion, measurement is performed by mixing 100 parts by mass of liquid bisphenol A type epoxy resin, 2 parts by mass of thermal cationic polymerization initiator, and 2 parts by mass of γ-butyrolactone. desirable. Additionally, as the liquid bisphenol A type epoxy resin, it is preferable to use jER828 manufactured by Mitsubishi Chemical Corporation, and the temperature increase rate in the DSC measurement is preferably 10°C/min.

The curing agent of the present invention preferably contains a thermal cationic polymerization initiator with a reaction activation temperature of 160°C or lower. The thermal cationic polymerization initiator has a narrower temperature range at which heat generation occurs near the reaction activation temperature than the imidazole compound. Therefore, while obtaining sufficient curing properties of the film adhesive at low temperatures, the reaction with the compound having a cyclic ether group does not proceed well at a temperature lower than the temperature at which the film adhesive is cured, resulting in a film adhesive having excellent storage stability. It has the advantage of being easy to obtain.

The content of at least one kind selected from an imidazole compound having a reaction activation temperature of 125°C or lower and a thermal cation polymerization initiator having a reaction activation temperature of 160°C or lower is 0.05 to 10 parts by mass based on 100 parts by mass of the compound having the cyclic ether group. It is more preferable that it is 0.1 to 8 parts by mass.

The curable film adhesive of the present invention comprises a compound having a cyclic ether group, a polymer component, and at least one selected from the group consisting of an imidazole compound with a reaction activation temperature of 125°C or lower and a thermal cationic polymerization initiator with a reaction activation temperature of 160°C or lower. In addition to the curing agent contained, other components may be contained. Other components include silane coupling agents, tackifiers, etc.

Silane coupling agents include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, Silane coupling agents having a (meth)acryloyl group such as 3-acryloxypropyltrimethoxysilane; Silane coupling agents having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trichlorovinylsilane, and vinyltris(2-methoxyethoxy)silane;

2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, Silane coupling agents having an epoxy group such as 8-glycidoxyoctyltrimethoxysilane; Silane coupling agents having a styryl group such as p-styryltrimethoxysilane and p-styryltriethoxysilane; N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltri Ethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl·butylidene)propylamine, N-phenyl-3 -Aminopropyltrimethoxysilane, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, etc. Silane coupling agent having an amino group;

Silane coupling agents having a ureide group such as 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane; Silane coupling agents having halogen atoms such as 3-chloropropyltrimethoxysilane and 3-chloropropyltriethoxysilane; Silane coupling agents having a mercapto group such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; Silane coupling agents having a sulfide group such as bis(trimethoxysilylpropyl)tetrasulfide and bis(triethoxysilylpropyl)tetrasulfide; Silane coupling agents having an isocyanate group such as 3-isocyanate propyltrimethoxysilane and 3-isocyanate propyltriethoxysilane; Silane coupling agents having an allyl group such as allyltrichlorosilane, allyltriethoxysilane, and allyltrimethoxysilane; Silane coupling agents having hydroxyl groups such as 3-hydroxypropyltrimethoxysilane and 3-hydroxypropyltriethoxysilane; etc. can be mentioned.

These silane coupling agents can be used individually or in combination of two or more types.

When the curable film adhesive of the present invention contains a silane coupling agent, the content is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, based on 100 parts by mass of the compound having the cyclic ether group. It is wealth.

By setting the content of the silane coupling agent within the above range, it becomes easy to obtain a cured film-like adhesive having superior adhesive strength under room temperature and high temperature environments.

In addition, in this specification, a high temperature environment refers to an environment of 40 to 80°C.

Examples of the tackifier include rosin-based resins such as rosin resin, rosin ester resin, and rosin-modified phenol resin; Hydrogenated rosin-based resin obtained by hydrogenating these rosin-based resins; Terpene resins such as terpene resins, aromatic modified terpene resins, and terpene phenol resins; Hydrogenated terpene-based resin obtained by hydrogenating these terpene-based resins; α-methylstyrene single polymerization resin, α-methylstyrene/styrene copolymerization resin, styrene monomer/aliphatic monomer copolymerization resin, styrene monomer/α-methylstyrene/aliphatic monomer copolymerization resin, styrene monomer single Styrene-based resins such as polymerized resins and styrene-based monomer/aromatic monomer copolymerized resins; Hydrogenated styrene-based resin obtained by hydrogenating these styrene-based resins; C9-based petroleum resin obtained by copolymerizing C9 fractions such as indene and vinyl toluene produced by thermal decomposition of petroleum naphtha, and petroleum resin obtained by hydrogenating this C9-based petroleum resin; etc. can be mentioned.

Among these, styrene-based resin is preferable, and styrene-based monomer/aliphatic monomer copolymer resin is more preferable.

These tackifiers can be used individually or in combination of two or more types.

When the curable film adhesive of the present invention contains a tackifier, the content of the tackifier is preferably 1 to 200 parts by mass, more preferably 10 parts by mass, based on 100 parts by mass of the compound having the cyclic ether group. ~150 parts by mass.

By setting the content of the tackifier within the above range, it becomes easy to obtain a curable film-like adhesive with more excellent film-forming properties in a room temperature environment.

Additionally, the curable film adhesive of the present invention may contain components other than the silane coupling agent and tackifier as long as they do not impair the effects of the present invention.

Examples of the other ingredients include antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, and coloring pigments. These contents may be determined appropriately according to the purpose.

(Method for producing curable film adhesive)

The curable film adhesive of the present invention is obtained by forming into a film an adhesive composition obtained by mixing each of the above components in an appropriate ratio.

When mixing the above components, each component may be diluted with a solvent in advance, or the solvent may be added during mixing. Additionally, when using the adhesive composition, you may dilute it with a solvent.

The above mixing and kneading can be performed by using a normal stirrer, a shaker, a three-roller, a disperser such as a ball mill, and combining them appropriately.

The organic solvent for preparing the adhesive composition is not limited as long as it can uniformly dissolve, knead, or disperse the components, and conventionally known solvents can be used.

Examples of such solvents include aliphatic hydrocarbon-based solvents such as n-hexane and n-heptane; Aromatic hydrocarbon-based solvents such as toluene and xylene; Halogenated hydrocarbon solvents such as dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, and monochlorobenzene; Alcohol-based solvents such as methanol, ethanol, propanol, butanol, and propylene glycol monomethyl ether; Ketone-based solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone; Ester solvents such as ethyl acetate and butyl acetate; Cellosolve-based solvents such as ethyl cellosolve; Ether-based solvents such as 1,3-dioxolane; etc. can be mentioned.

These solvents can be used individually or in combination of two or more types. The solvent content can be appropriately determined in consideration of coating properties, film thickness, etc.

A layer of the adhesive composition is formed by applying the obtained adhesive composition on the release film. Next, by removing the solvent from the layer of the adhesive composition by heat drying, a film-like adhesive with a peeling film attached can be obtained.

Peeling films include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, and polybutylene terephthalate. Phthalate film, polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene/(meth)acrylic acid copolymer film, ethylene/(meth)acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film. , fluororesin films, etc. are used. These crosslinked films are also used. Furthermore, these laminated films may be used. Additionally, films colored with these can be used.

In addition, it is preferable that the surface of the release film on which the adhesive composition layer is laminated is subjected to a release treatment from the viewpoint of workability.

The method of coating the adhesive composition on the release film is not particularly limited, and a conventionally known coating method can be adopted. For example, spin coat method, spray coat method, bar coat method, knife coat method, roll coat method, blade coat method, die coat method, gravure coat method, etc.

The method of drying the coating film is not particularly limited, and a known method for drying the coating film of the resin composition can be used.

The heating and drying temperature is not particularly limited as long as the solvent used is sufficiently volatilized and the layer of the curable film adhesive is not hardened, but is usually 80 to 100°C, and the heating time is usually tens of seconds to tens of minutes. .

Alternatively, if desired, a protective film may be additionally laminated on the layer of the curable film-like adhesive of the curable film-like adhesive with a release film attached, and stored and transported as a film-like adhesive with a protective film and a release film. do.

As a protective film, the same thing as the said peeling film can be used. In addition, a peeling treatment may be performed on the surface of the protective film on the side where it is laminated with the layer of the curable film-like adhesive.

In addition, the release film and the protective film are peeled and removed when using the curable film-like adhesive.

In addition, the curable film adhesive of the present invention may be obtained by molding the adhesive composition (does not contain a solvent) into a film (a so-called hot melt adhesive may be used). In this case, the film adhesive may be one in which release films are laminated on both surfaces. In addition, in the present invention, the curable film-like adhesive of the present invention formed into a film during the manufacturing process may hereinafter be referred to as an “adhesive layer.”

The thickness of the curable film adhesive of the present invention is not particularly limited, but is preferably 3 to 300 μm, more preferably 5 to 250 μm, and particularly preferably 7 to 200 μm.

The curable film adhesive of the present invention is used for members constituting a sensor device.

Here, “used in the members constituting the sensor device” means “the curable film adhesive of the present invention is used as an adhesive to bond members constituting the sensor device, or members constituting the sensor device and other members.” It means “to become.”

Sensor device is generally a general term for devices that detect absolute values or changes in physical quantities such as intensity, temperature, pressure, flow rate, and pH of light waves or radiation. For example, optical sensor devices such as photoelectronics, infrared sensors, visible light sensors, ultraviolet (UV) sensors, illuminance sensors, radiation detection sensors, and color sensors; Temperature sensor devices such as analog temperature sensors, digital temperature sensors, and thermocouples; Magnetic sensor, encoder, accessories, position sensor, proximity sensor, acceleration sensor, level sensor, image sensor, motion sensor, humidity sensor, gas sensor, flow sensor, gyroscope, vibration sensor, shock sensor, leak sensor, piezo sensor, alcohol Other sensor devices such as sensors and speed rotation sensors; can be mentioned.

Among these, the curable film adhesive of the present invention is particularly preferable in the case of an optical sensor device because it can be cured at low temperature and can provide a cured product with excellent transparency.

When the curable film adhesive of the present invention is used for a member constituting an optical sensor device, the total light transmittance after curing of the curable film adhesive is preferably 80% or more, and more preferably 90% or more. .

When the sensor device is an optical sensor device, it is preferable that the total light transmittance after curing of the film adhesive is high because the introduction of light is not hindered by the film adhesive even if the film adhesive is placed between the light receiving element and the light incident portion. do.

When using the curable film adhesive of the present invention to bond members constituting a sensor device, for example, a film of the present invention cut to an appropriate size is applied to the adhesive surface of one of the members constituting the sensor device. The upper adhesives are bonded together, the adhesive surfaces of the members constituting the sensor device on the other are overlapped, the adhesive is heated to a predetermined temperature, the adhesive is cured, and the members constituting the sensor device are bonded together. You can do it.

In addition, when bonding a member constituting the sensor device and another member, the film adhesive of the present invention cut to an appropriate size is bonded to the adhesive surface of the member constituting the sensor device (or other member), and then bonded thereto, The adhesive surfaces of other members (or members constituting the sensor device) are overlapped, the adhesive is heated to a predetermined temperature, the adhesive is cured, and the member constituting the sensor device and the other member can be bonded.

When heating the curable film adhesive to a predetermined temperature, the heating temperature is preferably 80 to 125°C, and more preferably 80 to 110°C.

Since the curable film adhesive of the present invention contains a curing agent containing at least one selected from the group consisting of an imidazole compound with a reaction activation temperature of 125°C or lower and a thermal cationic polymerization initiator with a reaction activation temperature of 160°C or lower, low temperature heating The curing reaction can sufficiently proceed. Accordingly, members constituting various devices that are easily affected by heat can be bonded without adversely affecting heat.

2) Device manufacturing method

The method for producing the device of the present invention is a curable film containing a cyclic ether compound, a polymer component, and a curing agent containing an imidazole compound with a reaction activation temperature of 125 ° C. or lower and a thermal cationic polymerization initiator with a reaction activation temperature of 160 ° C. or lower. The curable film adhesive is cured by attaching the upper adhesive (hereinafter, sometimes referred to as “film adhesive (A)”) to a member containing the module and heating it to a temperature in the range of 80 to 110 ° C. It includes processes.

The curing agent containing a cyclic ether compound, a polymer component, and an imidazole compound with a reaction activation temperature of 125°C or lower and a thermal cation polymerization initiator with a reaction activation temperature of 160°C or lower includes the above “compound, polymer component having a cyclic ether group, and a curing agent containing an imidazole compound with a reaction activation temperature of 125°C or lower and a thermal cation polymerization initiator with a reaction activation temperature of 160°C or lower. The same thing as what is described can be used.

In the device manufacturing method of the present invention, for example, when members including modules are bonded to each other, a film-like adhesive (A) cut to an appropriate size is applied to the adhesive surface of one of the members including the module. It includes a process of bonding the members including the module to each other by overlapping the adhesive surface of the member including the other module and heating the film adhesive (A) to a predetermined temperature and hardening it.

Additionally, when bonding a member containing a module to another member, a film-like adhesive (A) cut to an appropriate size is bonded to the adhesive surface of the member containing the module (or another member), and the other member is attached thereto. It includes the process of overlapping the adhesive surfaces of (or members including modules), heating and curing the film-like adhesive (A) to a predetermined temperature, and bonding the members constituting the sensor device to each other.

The heating temperature when heating and curing the film adhesive (A) to a predetermined temperature is 80 to 110°C from the viewpoint of reducing the adverse effects of heat on the module.

Since the film adhesive (A) contains a curing agent containing at least one selected from the group consisting of an imidazole compound with a reaction activation temperature of 125°C or lower and a thermal cationic polymerization initiator with a reaction activation temperature of 160°C or lower, it can be used by low-temperature heating. By sufficiently advancing the curing reaction, members including modules can be bonded.

Example

Hereinafter, the present invention will be described in more detail through examples. However, the present invention is not limited to the following examples.

Parts and % in each example are based on mass, unless otherwise specified. The reaction activation temperature for the imidazole compound was obtained by mixing 100 parts by mass of a liquid bisphenol A type epoxy resin and 5 parts by mass of an imidazole compound and performing DSC measurement. In addition, as for the thermal cation polymerization initiator, 100 parts by mass of liquid bisphenol A type epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation), 0.1 part by mass of thermal cationic polymerization initiator, and 0.1 part by mass of γ-butyrolactone were mixed, and the temperature increase rate was adjusted. It was obtained by DSC measurement at 10 °C/min.

[Example 1]

100 parts of acid-modified polyolefin resin (acid-modified α-olefin polymer, manufactured by Mitsui Chemicals, brand name: Unistol H-200, weight average molecular weight: 52,000), polyfunctional epoxy compound (1) (hydrogenated bisphenol A type epoxy resin, Manufactured by Mitsubishi Chemical Corporation, brand name: YX8000, epoxy equivalent: 205 g/eq) 25 parts, curing agent (manufactured by Shikoku Chemical Company, brand name: Qazole 2E4MZ, 2-ethyl-4-methylimidazole, reaction activation temperature: 107°C ) 0.25 part and 0.1 part of silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., brand name: KBM6803) were dissolved in methyl ethyl ketone to prepare adhesive composition 1 with a solid content concentration of 20%.

This adhesive composition 1 was applied on the peeling surface of a release film (product name: SP-PET382150, manufactured by Lintech Co., Ltd.), and the obtained coating film was dried at 100°C for 2 minutes to form an adhesive layer with a thickness of 10 μm. On top of this, the peeled surfaces of another release film (product name: SP-PET381031, manufactured by Lintec) were bonded together to obtain curable film-like adhesive 1 with a release film attached.

[Example 2]

100 parts of acid-modified polyolefin resin (acid-modified α-olefin polymer, manufactured by Mitsui Chemicals, brand name: Unistol H-200, weight average molecular weight: 52,000), polyfunctional epoxy compound (1) (bisphenol A diglycidyl ether, Manufactured by Mitsubishi Chemical, brand name: YL980, epoxy equivalent weight 180 to 190 g/eq, molecular weight: 2,400) 100 parts, tackifier (styrene-based monomer aliphatic monomer copolymer, softening point 95°C, manufactured by Mitsui Chemicals, brand name: FTR6100) 50 parts, and 1 part of the curing agent (manufactured by Shikoku Chemical Company, brand name: Qazole 2E4MZ, 2-ethyl-4-methylimidazole, reaction activation temperature: 107°C) were dissolved in methyl ethyl ketone, and the solid content concentration was 30%. Adhesive composition 2 was prepared. This adhesive composition 2 was applied on the peeling surface of a release film (manufactured by Lintec, brand name: SP-PET382150), and the obtained coating film was dried at 100°C for 2 minutes to form an adhesive layer with a thickness of 12 μm. On top of this, the peeled surfaces of another release film (manufactured by Lintec, brand name: SP-PET381031) were bonded together to obtain curable film-like adhesive 2 with a release film attached.

[Example 3]

As a binder component, 100 parts of phenoxy resin (manufactured by Mitsubishi Chemical Corporation, brand name: YX7200B35, weight average molecular weight: 30,000), a compound having a cyclic ether group (hydrogenated bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, brand name: YX8034) 250 parts, and 0.2 parts of thermal cationic polymerization initiator (manufactured by Sanshin Chemical Industries, Ltd., brand name: SAN-AID SI-B3, reaction activation temperature: 140°C), 2 parts, silane coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., brand name: KBM4803) This part was dissolved in methyl ethyl ketone to prepare a coating liquid with a solid content concentration of 35%.

This coating liquid was applied on the peeling treated surface of a release film (manufactured by Lintec, brand name: SP-PET382150), and the obtained coating film was dried at 100°C for 2 minutes to form an adhesive layer with a thickness of 10 μm, and then applied on top of this coating liquid. , the peeled surfaces of another release film (manufactured by Lintec, brand name: SP-PET381031) were bonded together to obtain curable film-like adhesive 3 with a release film attached.

[Comparative Example 1]

The procedure was carried out except that the imidazole-based curing catalyst was changed to 1-(2-cyanoethyl)-2-undecylimidazole (manufactured by Shikoku Chemical Company, brand name: C11Z-CN, reaction activation temperature: 146°C). In the same manner as in Example 1, adhesive composition 4 was prepared, and curable film-like adhesive 4 with a release film was obtained.

[Comparative Example 2]

Acrylic resin: Acrylic resin obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass) (weight average molecular weight (Mw) 600,000): for 100 parts by mass, epoxy resin ( Product name “CNA-147” manufactured by Nippon Explosives Co., Ltd.): 15 parts by mass, phenol resin (product name “Millex "Manufactured by Admatex Co., Ltd.): 90 parts by mass, cross-linking agent (brand name "BHS8515" manufactured by Toyochem Co., Ltd.): 1 part by mass is dissolved or dispersed in methyl ethyl ketone and stirred at 23°C to obtain a solid content concentration of 20 mass%. An adhesive composition was obtained.

The obtained adhesive composition was applied to the peeling surface of a polyethylene terephthalate film (thickness 38 µm) on one side of which was peeled by silicone treatment, and dried at 100°C for 2 minutes to form a film with a thickness of 10 µm. Adhesive 5 was obtained.

[Measurement of gel fraction]

The film adhesives 1 to 5 with release films obtained in the examples and comparative examples were placed in an environment at 100°C for 2 hours, and a curing step of the film adhesive was performed. The release film was removed from the film-like adhesive to which the release film was attached after the curing process, and the adhesive was immersed in toluene at 25°C for 24 hours, and the gel fraction was calculated from the difference between the weight before immersion and the dried weight after immersion.

[Measurement of total light transmittance]

The release film on one side was peeled from the film adhesives 1 to 5 with release films obtained in the examples and comparative examples, and the exposed surface of the film adhesive was affixed to a glass plate. A curing process was performed on the glass plate on which the film adhesive was affixed under the same conditions as the measurement of the gel fraction, and the total light transmittance of the film adhesive after the curing process was measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "NDH2000"). Measurement was made according to JIS K7136:2000.

The measurement results of the main component, gel fraction, and total light transmittance of the curing agent used in Examples 1 to 3 and Comparative Examples 1 and 2 are summarized in Table 1.

From Table 1, it can be seen that according to the film adhesives of Examples 1 to 3, the gel fraction is high, the curing reaction sufficiently proceeds even at low temperature (100 ° C.), and a cured product with excellent transparency is obtained. . On the other hand, the film adhesives of Comparative Examples 1 and 2 provide cured products with excellent transparency, but the gel fraction is low, suggesting that the curing reaction is not sufficiently progressing.

Claims (8)

Containing a compound having a cyclic ether group, a polymer component, and a curing agent containing at least one selected from the group consisting of an imidazole compound having a reaction activation temperature of 125°C or lower and a thermal cationic polymerization initiator having a reaction activation temperature of 160°C or lower, the polymer A curable film-like adhesive containing an acid-modified polyolefin resin as a component and used for members constituting a sensor device. According to claim 1,
A curable film-like adhesive having a reaction activation temperature of at least 1 type selected from the imidazole compound having a reaction activation temperature of 125°C or lower and a thermal cation polymerization initiator having a reaction activation temperature of 160°C or lower. According to claim 1,
A curable film adhesive, wherein the sensor device is an optical sensor device, and the total light transmittance of the curable film adhesive after curing is 80% or more. The method according to any one of claims 1 to 3,
A curable film-like adhesive, wherein the curing agent is mainly composed of at least one selected from an imidazole-based compound having a reaction activation temperature of 125°C or lower and a thermal cationic polymerization initiator having a reaction activation temperature of 160°C or lower. The method according to any one of claims 1 to 3,
A curable film-like adhesive, wherein the curing agent contains a thermal cationic polymerization initiator having a reaction activation temperature of 160° C. or lower. The method according to any one of claims 1 to 3,
A curable film-like adhesive, wherein the cyclic ether compound is an aliphatic compound. It contains a cyclic ether compound, a polymer component, and a curing agent containing at least one selected from the group consisting of an imidazole compound having a reaction activation temperature of 125°C or lower and a thermal cation polymerization initiator having a reaction activation temperature of 160°C or lower, wherein the polymer component is A curable film-like adhesive containing an acid-modified polyolefin-based resin is attached to a member including a module and heated to a temperature in the range of 80 to 110° C., thereby curing the curable film-like adhesive. Method of manufacturing the device. delete