KR20210037604A - Method for manufacturing curable film-like adhesive and device - 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 less and a thermal cation polymerization initiator having a reaction activation temperature of 160°C or less The curable film-like adhesive used for the member to be used, and the curable film-like adhesive are affixed to a member including a module and heated to a temperature in the range of 80 to 110°C to cure the curable film-like adhesive. It is a method of manufacturing a device to include. According to the present invention, a curable film-like adhesive used for a member constituting a sensor device, which can be cured at a low temperature and provides a cured product having excellent transparency, and can be cured at a 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 adhesive and device

The present invention includes a curable film-like adhesive used for a member constituting a sensor device, which can be cured at a low temperature and provides a cured product having excellent transparency, and a step of curing the curable film-like adhesive. , To a method of manufacturing a device.

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

In addition, in recent years, a thin sensor module in which an optical component (protective layer) is directly adhered onto a sensor chip is also being studied.

For example, in Patent Document 1, (i) a sensor chip having a surface having a sensor region in which a plurality of pixels are formed is mounted on the upper surface of a wiring board by face-up, and then a plurality of points on the surface of the sensor chip A step of forming a plurality of first spacers having adhesiveness on the surface of the sensor chip by disposing the first adhesive material and curing the first adhesive material on the surface of the sensor chip, (ii) disposing a pasty second adhesive material on the surface of the sensor chip, Then, a step of disposing 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 through a plurality of first spacers and a second adhesive material while applying a load to the first optical component, And (iii) thereafter, a method of manufacturing a semiconductor device having a step of fixing the first optical component by curing the second adhesive material in a state where no load is applied to the first optical component.

Further, in this document, an ultraviolet curable adhesive is applied on the sensor chip, an optical component is placed thereon, and the adhesive is irradiated with ultraviolet rays while holding the optical component with a bonding tool to cure the adhesive. Methods for bonding optical components are also described.

Further, in this document, it is also described that it is necessary for the adhesive material to be used to have light-transmitting properties.

Japanese Unexamined Patent Publication No. 2015-38991

As a method of curing an adhesive (adhesive) applied on a sensor chip, a method of curing by heating an adhesive (heat curing method) and a method of curing the adhesive by irradiating light (photocuring method) are known.

Sensor chips and optical components are susceptible to heat. Therefore, in the case of employing the heat curing method, it is preferable to cure the adhesive at a low temperature as much as possible from the viewpoint of avoiding the influence of heating on the sensor chip or the optical component.

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

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

The inventors of the present invention have studied intensively in order to solve the above problems, as a result of containing a compound having a cyclic ether group, a polymer component, and an imidazole compound having a reaction activation temperature of 125°C or less or a thermal cation polymerization initiator having a reaction activation temperature of 160°C or less. It is known that a curable film-like adhesive containing a curing agent that can be cured at low temperatures and provides a cured product with excellent transparency, and can be preferably used for bonding parts constituting various devices such as sensor devices. And came to complete the present invention.

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

[1] A curing agent containing a compound having a cyclic ether group, a polymer component, and at least one selected from an imidazole compound having a reaction activation temperature of 125°C or less and a thermal cation polymerization initiator having a reaction activation temperature of 160°C or less, , Curable film-like adhesive used for a member constituting a sensor device.

[2] The curable film phase according to [1], wherein at least one reaction activation temperature selected from an imidazole compound having a reaction activation temperature of 125°C or less and a thermal cation polymerization initiator having a reaction activation temperature of 160°C or less is 100°C or more. glue.

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

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

[5] The curable film-like 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 less.

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

[7] The curable film-like 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 an imidazole compound having a reaction activation temperature of 125°C or less and a thermal cation polymerization initiator having a reaction activation temperature of 160°C or less A device manufacturing method comprising a step of affixing an upper adhesive to a member including a module and heating to a temperature in the range of 80 to 110°C to cure the curable film adhesive.

According to the present invention, it is possible to cure at a low temperature and provides a cured product having excellent transparency, a curable film-like adhesive used for a member constituting a sensor device, and a device using the curable film-like adhesive A method is provided.

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

1) Curable film-like adhesive

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

Here, "curability" refers to physical properties that are cured by heating to a predetermined temperature to provide a cured product.

The "film form" means that the adhesive of the present invention has a film shape or a sheet shape. The film-like adhesive of the present invention may be in the form of a strip (label), or may be in the form of an elongate (shape that can be wound up in a roll form).

[Compound having a cyclic ether group]

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

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

In addition, in this specification, under normal temperature environment, it is under the environment of 20 degreeC±15 degreeC (5 to 35 degreeC) (JIS Z 8703).

The compound having a cyclic ether group refers to a compound having at least one or more cyclic ether groups in the molecule.

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

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

In addition, in this invention, it is assumed that a phenoxy resin mentioned later is not contained.

Examples of the compound 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 ether products of aliphatic alcohols and glycidyl esters of alkyl carboxylic acids;

And polyfunctional epoxy compounds such as polyglycidyl ether products of aliphatic polyhydric alcohols or their alkylene oxide adducts, polyglycidyl esters of aliphatic long-chain polybasic acids, and epoxy compounds having a triazine skeleton.

Representative compounds of these aliphatic epoxy compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12 to 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, di of polyethylene glycol Glycidyl ether of polyhydric alcohols such as glycidyl ether, diglycidyl ether of polypropylene glycol, dicyclopentadiene dimethanol diglycidyl ether, or aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin A polyglycidyl ether product of a polyether polyol obtained by adding one or two or more kinds of alkylene oxides to an aliphatic long-chain dibasic acid diglycidyl ester;

Monoglycidyl ether of aliphatic higher alcohol and glycidyl ester of higher fatty acid, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized polybutadiene;

2,4,6-tri(glycidyloxy)-1,3,5-triazine, etc. are 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, 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);

Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF ( As mentioned above, Kyoeisha Chemical Co., Ltd. make);

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

TEPIC-FL, TEPIC-PAS, TEPIC-UC (above, manufactured by Nissan Chemical Corporation), etc. are mentioned.

As an alicyclic epoxy compound, a polyglycidyl ether product of a polyhydric alcohol having at least one or more alicyclic structures, or a cyclohexene oxide obtained by epoxidating a compound containing a cyclohexene ring or a cyclopentene ring with an oxidizing agent, or 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, dicyclopentadienediepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), Dioctyl epoxy hexahydrophthalate, di-2-ethylhexyl epoxy hexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene Dioxide, etc. are mentioned.

Moreover, as an alicyclic epoxy compound, a commercial item can also be used. As a commercial item, Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000 (above, made by Daicel Corporation), YX8000, YX8034 (above, manufactured by Mitsubishi Chemical Corporation), etc. are mentioned.

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

Typical compounds of these aromatic epoxy compounds include glycidyl ether products or epoxy novolac resins of bisphenol A, bisphenol F, or a compound to which an alkylene oxide is further added;

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

A glycidyl ether product of an aromatic compound having two or more alcoholic hydroxyl groups such as phenyl dimethanol, phenyl diethanol and phenyl dibutanol;

And 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, epoxidation products of styrene oxide or divinylbenzene, and the like.

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, Oncoat EX-1020, Oncoat EX- 1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (above, manufactured by Nagase Chemtex); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (above, manufactured by Osaka Gas Chemical); HP4032, HP4032D, HP4700 (above, manufactured by DIC Corporation); ESN-475V (above, manufactured by Nittetsu Chemical & Material Co., Ltd.); JER (formerly Epicoat) YX8800, YL980 (above, manufactured by Mitsubishi Chemical); 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, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (above, manufactured by Nippon Explosives); 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), and the like.

As a compound having an oxetane group in the molecule, 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 glycolbis(3 -Ethyl-3-oxetanylmethyl)ether, triethylene glycolbis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycolbis(3-ethyl-3-oxetanylmethyl)ether, 1, 2-functional aliphatic oxetane compounds such as 4-bis(3-ethyl-3-oxetanylmethoxy)butane and 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, 3-ethyl-3- [(Phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxylmethyl)oxetane, 3-ethyl-3-(hydroxy 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 item can also be used. As a commercial item, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (above, Maruzen Petrochemical company make); Aaron oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (above, manufactured by Toa Synthetic Corporation); Eternal call OXBP, OXTP (above, manufactured by Ube Hungsan Co., Ltd.), and the like.

Among the compounds having a cyclic ether group, compounds having no aromatic rings (aliphatic compounds) such as aliphatic epoxy compounds (excluding alicyclic epoxy compounds) and alicyclic epoxy compounds (aliphatic compounds) can suppress the coloring of the film-like adhesive. , It is preferable because it can be preferably used as an optical sensor device application.

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

By using a compound having a cyclic ether group having a cyclic ether equivalent in the above range, a curable film-like adhesive having strong adhesive strength and excellent curability can be efficiently produced.

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

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

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

[Polymer component]

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

By containing the polymer component, it is possible to obtain a film adhesive having better sheet processability and a cured product of a film adhesive having more excellent adhesive strength. In addition, by containing a polymer component, a film-like adhesive having a desired thickness can be efficiently produced.

The polymer component is added for the purpose of imparting sheet-like retention to the film-like adhesive.

In order to achieve the above object, the weight average molecular weight (Mw) of the polymer component is usually 20,000 or more, preferably 20,000 to 3,000,000. Moreover, the number average molecular weight (Mn) of a polymer component becomes like this. Preferably it is 10,000 to 2,000,000, More preferably, it is 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 rate of the polymer component in the film adhesive is preferably 15 to 90% by mass, more preferably 20 to 85% by mass. By making the content of the polymer component within the above range, it is easy to adjust the blending amount of the cyclic ether compound while maintaining the sheet shape of the film-like adhesive.

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

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

(Polyolefin resin)

The polyolefin-based resin is a polymer containing a repeating unit derived from an olefin-based monomer. The polyolefin resin may be a polymer composed of only repeating units derived from an olefinic monomer, or may be a polymer composed of repeating units derived from an olefinic monomer and a repeating unit derived from a monomer copolymerizable with the olefinic monomer.

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

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

As a monomer copolymerizable with an olefinic monomer, vinyl acetate, (meth)acrylic acid ester, styrene, etc. are mentioned. Here, "(meth)acrylic acid" represents acrylic acid or methacrylic acid (the same applies hereinafter).

These olefinic monomers and copolymerizable monomers can be used alone or in combination of two or more.

Polyolefin resins include ultra low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), ethylene-propylene. Copolymers, olefinic elastomers (TPO), ethylene-vinyl acetate copolymers (EVA), ethylene-(meth)acrylic acid copolymers, and ethylene-(meth)acrylic acid ester copolymers.

(Modified polyolefin resin)

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

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

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

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

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

Examples of the modified polyolefin-based resin include acid-modified polyolefin-based resins and silane-modified polyolefin-based resins. It is preferable to use an acid-modified polyolefin-based resin as the modified polyolefin-based resin from the viewpoint of facilitating obtaining the effect of improving the curability at low temperatures of the film-like adhesive of the present invention. In addition, when the curing agent of the present invention contains an imidazole compound having a reaction activation temperature of 125° C. or lower, it is preferable to use an acid-modified polyolefin-based resin as a polymer component in order to further improve curability at low temperatures.

The acid-modified polyolefin-based resin refers to a polyolefin-based resin graft-modified with an acid. For example, what made a polyolefin resin react with an unsaturated carboxylic acid or an unsaturated carboxylic anhydride, and introduced a carboxyl group or a carboxylic anhydride group (graft modification) is mentioned.

Examples of the unsaturated carboxylic acid and unsaturated carboxylic 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 anhydrides such as maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornenedicarboxylic anhydride, and tetrahydrophthalic anhydride; Can be mentioned.

These can be used alone or in combination of two or more. Among these, maleic anhydride is preferable because a film adhesive having more excellent sheet workability and a cured product of a film adhesive having more excellent adhesive strength can be easily obtained.

The amount of the unsaturated carboxylic acid (or unsaturated carboxylic anhydride) reacted with the polyolefin resin is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, furthermore, based on 100 parts by mass of the polyolefin resin. Preferably it is 0.2 to 1 mass part. The curable film-like adhesive containing the acid-modified polyolefin-based resin thus obtained becomes easy to obtain a cured product having more excellent adhesive strength.

As the acid-modified polyolefin resin, a commercial item can also be used. As a commercial item, for example, Admer (registered trademark) (manufactured by Mitsui Chemicals), Unistol (registered trademark) (manufactured by Mitsui Chemicals), BondyRam (manufactured by Polyram), orevac (registered trademark) (manufactured by ARKEMA), Modic (registered trademark) (manufactured by Mitsubishi Chemical), and the like.

The silane-modified polyolefin-based resin refers to a polyolefin resin that has been graft-modified with an unsaturated silane compound. The silane-modified polyolefin resin has a structure in which an unsaturated silane compound as a side chain is graft-copolymerized with a polyolefin resin as a main chain. For example, a silane-modified polyethylene resin and a silane-modified ethylene-vinyl acetate copolymer are mentioned, 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 the unsaturated silane compound reacted with the polyolefin resin, a vinyl silane compound is preferable. As a vinylsilane compound, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tripropoxysilane, vinyl triisopropoxysilane, vinyl tributoxysilane, vinyl tripentyloxysilane, vinyl triphenoxysilane, vinyl Tribenzyloxysilane, vinyltrimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, vinyltricarboxysilane, and the like.

These can be used alone or in combination of two or more.

In addition, conditions in the case of graft polymerization of the unsaturated silane compound to the polyolefin resin as the main chain may employ a known conventional method of 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 still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the polyolefin resin. The curable film-like adhesive containing the silane-modified polyolefin-based resin thus obtained becomes easy to obtain a cured product having more excellent adhesive strength.

As the silane-modified polyolefin-based resin, a commercial item can also be used. As a commercial item, Linclone (registered trademark) (manufactured by Mitsubishi Chemical Corporation), etc. are mentioned, for example. Among these, a low-density polyethylene-based linclone, a linear low-density polyethylene-based linclone, an ultra-low-density polyethylene-based linclone, and an ethylene-vinyl acetate copolymer-based linclone can be preferably used.

Modified polyolefin resins can be used alone or in combination of two or more.

(Acrylic polymer)

The acrylic polymer is a polymer containing a repeating unit derived from a (meth)acrylic acid ester in a molecule. The proportion of the repeating unit derived from the (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, particularly preferably based on all repeating units. It is 70% by mass or more. In addition, the ratio of the repeating units contained in the acrylic polymer generally corresponds to the ratio (injection ratio) of the monomers capable of forming each repeating unit in all the monomers used for polymerization of the acrylic polymer.

As the (meth)acrylic acid ester, the number of carbon atoms in an alkyl group such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate Alkyl (meth)acrylate having 1 to 18; Cycloalkyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl ( (Meth)acrylates having a cyclic skeleton such as meth)acrylate and imide (meth)acrylate; (Meth)acrylic acid ester having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; (Meth)acrylic acid ester having an amide group such as N-methylol (meth)acrylamide; (Meth)acrylic acid ester having an amino group such as monoethylamino (meth)acrylate; And the like.

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

Further, as a monomer constituting the acrylic polymer, in addition to the (meth)acrylic acid ester, a monomer 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, or the like may be used.

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

(Polyester resin)

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

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

(Phenoxy resin)

Phenoxy resin is a high molecular weight thermoplastic condensation product of bisphenol A and epichlorohydrin and derivatives thereof.

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

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

[Hardener]

The curable film-like adhesive of the present invention, in addition to the compound and polymer component having a cyclic ether group, is at least one selected from an imidazole compound having a reaction activation temperature of 125° C. or less and a thermal cation polymerization initiator having a reaction activation temperature of 160° C. or less. It contains a species-containing curing agent.

The curing agent is used for the purpose of adjusting the reaction temperature and reaction rate of thermal curing of the film-like adhesive.

The curing agent used in the present invention contains at least one selected from an imidazole compound having a reaction activation temperature of 125°C or less and a thermal cation polymerization initiator having a reaction activation temperature of 160°C. By using these compounds as a curing agent, the curable film-like adhesive can be sufficiently cured at a low temperature. That is, by using these compounds as a curing agent, members constituting the sensor device or members constituting the sensor device and other members can be bonded to each other without imparting heat damage to the sensor device.

Here, ``reaction activation temperature'' means when the compound used for the curing agent and the general liquid bisphenol A type epoxy resin are mixed and heated, the peak of curing exotherm is confirmed at the lowest temperature by a differential scanning calorimeter (DSC). Is the temperature. About the imidazole compound, the liquid bisphenol A type epoxy resin and the imidazole compound are mixed and measured. In addition, about the thermal cation polymerization initiator, a liquid bisphenol A type epoxy resin, a thermal cation polymerization initiator, and γ-butyrolactone are mixed and measured. More specifically, the "reaction activation temperature" can be measured by the method described in Examples.

It is preferable that the reaction activation temperature of at least one selected from the imidazole compound and the thermal cation polymerization initiator used in the curing agent of the present invention is 100°C or higher. If the reaction activation temperature of the curing agent is high to some extent, it is possible to suppress the progress of thermal curing due to the heat of (drying of the coating film, hot melt) during film formation of the film-like adhesive.

At least one selected from the imidazole compound and the 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 less or 160°C or less. In addition, the curing agent preferably contains, as a main component, at least one selected from an imidazole-based compound having a reaction activation temperature of 125°C or less and a thermal cation polymerization initiator having a reaction activation temperature of 160°C or less. That is, the content of the entire curing agent of "at least one selected from an imidazole-based compound having a reaction activation temperature of 125°C or less and a thermal cation polymerization initiator having a reaction activation temperature of 160°C or less" is preferably 70% by mass or more, More preferably, it is 90 mass% or more. In this way, by reducing the amount of the imidazole compound used as a curing agent or a compound other than the thermal cation polymerization initiator, it is possible to increase the total light transmittance after curing of the film adhesive while improving the curability at low temperature of the film adhesive. It becomes easier.

As an imidazole-based compound having a reaction activation temperature of 125°C or less, commercially available products include C17Z, 2E4MZ, 2PZ, 2P4MZ, 1B2MZ, 1B2PZ, 2MZ-CN, 2E4MZ-CN, 2PZ-OK (above, manufactured by Shikoku Chemical Co., Ltd.). Can be lifted. When measuring the reaction activation temperature of the imidazole-based compound, it is preferable to mix and measure 100 parts by mass of the liquid bisphenol A epoxy resin and 5 parts by mass of the imidazole compound.

The thermal cation polymerization initiator is a compound capable of generating a cation species that initiates polymerization by heating. The thermal cation polymerization initiator is not particularly limited, and is appropriately selected depending on the curing conditions and the kind of the cation polymerizable compound.

Thermal cation polymerization initiators, as long as the reaction activation temperature is 160°C or less, can be widely used for curing. For example, a sulfonium salt-based compound, a quaternary ammonium salt-based compound, a phosphonium salt-based compound, a diazonium salt-based compound, an iodonium salt-based compound, and the like can be mentioned. Among these, from the viewpoint of curing the sealing sheet at a low temperature, a sulfonium salt compound or a quaternary ammonium salt compound is preferable, and a sulfonium salt compound is more preferable. In addition, among sulfonium salt compounds, it is preferable that the counter anion is tetrakis(pentafluorophenyl) borate anion from the viewpoint of reducing the amount of the thermal cation polymerization initiator used.

As a sulfonium salt compound, as a commercial product, San-Aid SI-300, San-Aid SI-360, San-Aid SI-B2A, San-Aid SI-B7, San-Aid SI-B3A, San-Aid SI-B3 (above, Sanshin Chemical Co., Ltd. Manufacturing) and the like. When measuring the reaction activation temperature of the sulfonium salt compound, when the counter anion is tetrakis (pentafluorophenyl) borate anion, 100 parts by mass of liquid bisphenol A epoxy resin, 0.1 parts by mass of thermal cation polymerization initiator , And 0.1 parts by mass of γ-butyrolactone are mixed and measured. In addition, when the counter anion is a hexafluorophosphate anion, it is measured by mixing 100 parts by mass of a liquid bisphenol A type epoxy resin, 2 parts by mass of a thermal cation polymerization initiator, and 2 parts by mass of γ-butyrolactone. desirable. Further, as the liquid bisphenol A type epoxy resin, it is preferable to use jER828 manufactured by Mitsubishi Chemical, and the temperature increase rate in DSC measurement is preferably 10°C/min.

It is preferable that the curing agent of the present invention contains a thermal cation polymerization initiator having a reaction activation temperature of 160°C or less. The thermal cation polymerization initiator has a narrower range of temperature at which heat generation occurs near the reaction activation temperature than the imidazole compound. Therefore, while obtaining sufficient curability 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. There is an advantage that it is easy to obtain.

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

The curable film adhesive of the present invention comprises at least one selected from a compound having a cyclic ether group, a polymer component, an imidazole compound having a reaction activation temperature of 125°C or less, and a thermal cation polymerization initiator having a reaction activation temperature of 160°C or less. In addition to the curing agent to be contained, other components may be contained. As another component, a silane coupling agent, a tackifier, etc. are mentioned.

As the silane coupling agent, 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 vinyl trimethoxy silane, vinyl triethoxy silane, dimethoxy methyl vinyl silane, diethoxy methyl vinyl silane, trichloro vinyl silane, and vinyl tris (2-methoxyethoxy) silane;

2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, Silane coupling agents having an epoxy group such as 8-glycidoxyoctyl trimethoxysilane; silane coupling agents having a styryl group such as p-styryl trimethoxysilane and p-styryl triethoxysilane; 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-dimethylbutylidene)propylamine, N-phenyl-3 -Aminopropyltrimethoxysilane, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, etc. A silane coupling agent having an amino group;

A silane coupling agent having a ureide group such as 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane; Silane coupling agents having a halogen atom 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; A silane coupling agent having an isocyanate group such as 3-isocyanate propyl trimethoxysilane and 3-isocyanate propyl triethoxysilane; Silane coupling agents having an allyl group such as allyl trichlorosilane, allyl triethoxysilane, and allyl trimethoxysilane; Silane coupling agents having a hydroxyl group such as 3-hydroxypropyltrimethoxysilane and 3-hydroxypropyltriethoxysilane; And the like.

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

When the curable film-like 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 a cyclic ether group. It's wealth.

By setting the content of the silane coupling agent in the above range, it becomes easy to obtain a cured product of a film-like adhesive having more excellent adhesive strength in a normal temperature and high temperature environment.

In addition, in this specification, the high-temperature environment is under the environment of 40-80 degreeC.

Examples of the tackifier include rosin resins such as rosin resins, rosin ester resins, and rosin-modified phenol resins; Hydrogenated rosin-type resin obtained by hydrogenating these rosin-type resins; Terpene resins such as terpene resins, aromatic modified terpene resins, and terpenephenol resins; Hydrogenated terpene-type resin which hydrogenated these terpene-type resins; α-methylstyrene single polymer resin, α-methylstyrene/styrene copolymer resin, styrene monomer/aliphatic monomer copolymer resin, styrene monomer/α-methylstyrene/aliphatic monomer copolymer resin, styrene monomer single Styrene-based resins, such as a polymerization-based resin and a styrene-based monomer/aromatic-based monomer copolymerized resin; Hydrogenated styrene resin obtained by hydrogenating these styrene 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 the C9-based petroleum resin; And the like.

Among these, a styrenic resin is preferable, and a styrenic monomer/aliphatic monomer copolymer resin is more preferable.

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

When the curable film-like 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 a cyclic ether group. It is-150 parts by mass.

By setting the content of the tackifier in the above range, it becomes easier to obtain a curable film-like adhesive that is more excellent in film-forming properties in a normal temperature environment.

Moreover, the curable film-like adhesive of this invention may contain other components other than the said silane coupling agent and tackifier, as long as the effect of this invention is not impaired.

Examples of the other components include antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, and colored pigments. The content of these may be appropriately determined according to the purpose.

(Method of manufacturing curable film adhesive)

The curable film-like adhesive of the present invention is obtained by forming a film of 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 a solvent may be added at the time of mixing. Moreover, when using the adhesive composition, you may dilute with a solvent.

The above mixing and kneading can be performed by using a conventional stirrer, a threshing machine, a three-roller, or a dispersing machine such as a ball mill, and appropriately combining these.

The organic solvent for preparing the adhesive composition is not limited as long as it is capable of uniformly dissolving, kneading or dispersing each of the components, and a conventionally known one can be used.

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

These solvents can be used alone or in combination of two or more. The content of the solvent can be appropriately determined in consideration of coating properties, film thickness, and the like.

The obtained adhesive composition is applied on a release film to form a layer of the adhesive composition. Subsequently, by removing the solvent from the layer of the adhesive composition by heat drying, a film adhesive with a release film can be obtained.

As a release film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polyethylene naphthalate film, a polybutylene tere 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 , A film such as a fluororesin film is used. Moreover, these crosslinked films are also used. Furthermore, these laminated films may be used. Moreover, a film etc. which colored these can be used.

Moreover, it is preferable that peeling treatment is performed on the surface of the side where the layer of the adhesive composition of a peeling film is laminated|stacked from a workability viewpoint.

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

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

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

In addition, if desired, a protective film may be further laminated on the layer of the curable film-like adhesive of the curable film-like adhesive with the release film attached thereto, so that the protective film and the release film may be preserved and transported as a film-like adhesive with a release film attached thereto. do.

As a protective film, the same thing as the said peeling film can be used. Moreover, a peeling treatment may be applied to the layer of the curable film-like adhesive of the protective film and the side to be laminated.

In addition, the peeling film and the protective film are peeled off in use of a curable film-like adhesive.

Moreover, the curable film-like adhesive of this invention may be obtained by molding the said adhesive composition (it does not contain a solvent) into a film (so-called hot melt adhesive may be sufficient). In this case, the film-like adhesive may be made by laminating a release film on both surfaces thereof. In addition, in the present invention, the curable film-like adhesive of the present invention formed into a film during the manufacturing process may be referred to as "adhesive layer" hereinafter.

The thickness of the curable film-like 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-like adhesive of the present invention is used for a member constituting a sensor device.

Here, "used for the member constituting the sensor device" means "the curable film-like adhesive of the present invention is used as an adhesive for bonding members constituting the sensor device to each other, or to a member constituting the sensor device and other members. It means to become”.

In general, a sensor device is a generic term for a device that detects an absolute value or change in physical quantities such as intensity, temperature, pressure, flow rate, and pH of light waves or radiation. For example, optical sensor devices such as photoelectron, infrared sensor, visible light sensor, ultraviolet (UV) sensor, illuminance sensor, radiation detection sensor, and color sensor; Temperature sensor devices, such as an analog temperature sensor, a digital temperature sensor, and a thermocouple; Magnetic sensor, encoder, accessory, 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 a sensor and a speed rotation sensor; Can be mentioned.

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

When the curable film-like 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-like adhesive is preferably 80% or more, and more preferably 90% or more. .

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

When bonding members constituting a sensor device using the curable film-like adhesive of the present invention, for example, the film of the present invention cut to an appropriate size on the adhesive surface of the member constituting one sensor device The upper adhesive is bonded, the adhesive surface of the member constituting the other sensor device is superimposed thereon, the adhesive is heated to a predetermined temperature, the adhesive is cured, and the members constituting the sensor device are bonded together. I can make it.

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

The heating temperature in heating the curable film-like adhesive to a predetermined temperature is preferably 80 to 125°C, more preferably 80 to 110°C.

Since the curable film-like adhesive of the present invention contains a curing agent containing at least one selected from an imidazole compound having a reaction activation temperature of 125°C or less and a thermal cation polymerization initiator having a reaction activation temperature of 160°C or less, low-temperature heating It is possible to sufficiently advance the curing reaction. Therefore, members constituting various devices that are susceptible to heat can be bonded without adversely affecting heat.

2) Device manufacturing method

The device manufacturing method of the present invention is a curable film containing a cyclic ether compound, a polymer component, and an imidazole compound having a reaction activation temperature of 125°C or less, and a curing agent containing a thermal cation polymerization initiator having a reaction activation temperature of 160°C or less. The upper adhesive (hereinafter, this may be referred to as "film adhesive (A)") is affixed to the member including the module and heated to a temperature in the range of 80 to 110°C to cure the curable film adhesive. It includes the process.

A curing agent containing a cyclic ether compound, a polymer component, and an imidazole compound having a reaction activation temperature of 125° C. or less and a thermal cation polymerization initiator having a reaction activation temperature of 160° C. or less, includes the above ``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 less and a thermal cation polymerization initiator having a reaction activation temperature of 160°C or less. It is possible to use the same ones as described above.

In the device manufacturing method of the present invention, for example, in the case of bonding members including modules to each other, a film-like adhesive (A) cut to an appropriate size is applied to the bonding surface of the member including one module. It includes a step of bonding the members including the modules together, by superimposing the adhesive surface of the member including the other module thereon, heating the film-like adhesive (A) to a predetermined temperature, and curing it.

In addition, in the case of bonding a member including a module to another member, a film-like adhesive (A) cut to an appropriate size is bonded to the bonding surface of the member (or other member) including the module, and thereto, the other member It includes a step of overlapping the adhesive surfaces of (or a member including a module), heating the film-like adhesive (A) to a predetermined temperature, curing, and bonding members constituting the sensor device to each other.

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

Since the film-like adhesive (A) contains a curing agent containing at least one selected from an imidazole compound having a reaction activation temperature of 125°C or less and a thermal cation polymerization initiator having a reaction activation temperature of 160°C or less, a low-temperature heating furnace By sufficiently advancing the curing reaction, the member including the module can be adhered.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples at all.

Unless otherwise stated, parts and% in each example are based on mass. The reaction activation temperature was obtained by mixing 100 parts by mass of a liquid bisphenol A epoxy resin and 5 parts by mass of an imidazole compound with respect to the imidazole compound, and performing DSC measurement. In addition, with respect to the thermal cation polymerization initiator, 100 parts by mass of a liquid bisphenol A epoxy resin (manufactured by Mitsubishi Chemical, jER828), 0.1 parts by mass of a thermal cation polymerization initiator, and 0.1 parts by mass of γ-butyrolactone are mixed, and the temperature rise rate It was obtained by performing DSC measurement at 10°C/min.

[Example 1]

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

This adhesive composition 1 was coated 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 having a thickness of 10 μm, On it, the peeling-treated surface of another peeling film (manufactured by Lintec, brand name: SP-PET381031) was bonded to each other to obtain a curable film-like adhesive 1 with a peeling film attached thereto.

[Example 2]

Acid-modified polyolefin resin (acid-modified α-olefin polymer, manufactured by Mitsui Chemicals, brand name: Unistol H-200, weight average molecular weight: 52,000) 100 parts, polyfunctional epoxy compound (1) (bisphenol A diglycidyl ether, Mitsubishi Chemical, brand name: YL980, epoxy equivalent 180-190 g/eq, molecular weight: 2,400) 100 parts, tackifier (styrene monomer aliphatic monomer copolymer, softening point 95°C, manufactured by Mitsui Chemical, brand name: FTR6100) 50 parts, and 1 part of a curing agent (manufactured by Shikoku Chemical Co., Ltd., trade name: cuazole 2E4MZ, 2-ethyl-4-methylimidazole, reaction activation temperature: 107° C.) were dissolved in methyl ethyl ketone, and a solid content concentration of 30% Adhesive composition 2 was prepared. This adhesive composition 2 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 having a thickness of 12 μm, and the Above, the peeling-treated surface of another peeling film (manufactured by Lintec, brand name: SP-PET381031) was bonded to each other to obtain a curable film-like adhesive 2 with a peeling film.

[Example 3]

As a binder component, 100 parts of a phenoxy resin (manufactured by Mitsubishi Chemical, 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, brand name: YX8034) 250 parts, and thermal cation polymerization initiator (manufactured by Sanshin Chemical Industries, Ltd., trade name: SAN-AID SI-B3, reaction activation temperature: 140°C) 2 parts, silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., brand name: KBM4803) 0.2 Part was dissolved in methyl ethyl ketone to prepare a coating liquid having a solid content concentration of 35%.

This coating solution 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 having a thickness of 10 μm, and thereon , The peeling-treated surface of the other one peeling film (manufactured by Lintec, brand name: SP-PET381031) was bonded to each other to obtain a curable film-like adhesive 3 with a peeling film.

[Comparative Example 1]

Except for changing the imidazole-based curing catalyst to 1-(2-cyanoethyl)-2-undecylimidazole (manufactured by Shikoku Chemical Co., Ltd., trade name: C11Z-CN, reaction activation temperature: 146°C) In the same manner as in Example 1, an adhesive composition 4 was prepared, and a 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 acrylate-2-hydroxyethyl (15 parts by mass) (weight average molecular weight (Mw) 600,000): per 100 parts by mass, epoxy resin ( Brand name "CNA-147" manufactured by Nippon Explosives Co., Ltd.): 15 parts by mass, phenol resin (brand name "Millex XLC-4L" manufactured by Mitsui Chemical Co., Ltd.): 12 parts by mass, spherical silica (average particle diameter of 0.05 µm, brand name "YA050C-SV2" "Admatex Co., Ltd. product): 90 parts by mass, crosslinking 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., so that the solid content concentration becomes 20% by mass. The adhesive composition was obtained.

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

[Measurement of gel fraction]

The film-like adhesives 1 to 5 with release films obtained in Examples and Comparative Examples were placed in an environment of 100° C. for 2 hours, and a curing step of the film-like adhesive was performed. The release film was removed from the film-like adhesive with the release film after the curing step, 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 weight dried 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 Examples and Comparative Examples, and the surface of the exposed film adhesive was affixed to a glass plate. A curing process was performed on the glass plate to which the film-like adhesive was affixed under the same conditions as the measurement of the gel fraction, and the total light transmittance of the film-like adhesive after the curing process was measured using a haze meter (manufactured by Nippon Electric Co., Ltd., product name ``NDH2000''), It measured according to JIS K7136:2000.

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

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

Claims (8)

A sensor device comprising a compound having a cyclic ether group, a polymer component, and a curing agent containing at least one selected from an imidazole compound having a reaction activation temperature of 125°C or less and a thermal cation polymerization initiator having a reaction activation temperature of 160°C or less A curable film-like adhesive used for a member constituting a. The method of claim 1,
At least one reaction activation temperature selected from an imidazole compound having a reaction activation temperature of 125° C. or less and a thermal cation polymerization initiator having a reaction activation temperature of 160° C. or less is 100° C. or more. The method according to claim 1 or 2,
The above-described sensor device is an optical sensor device, and the curable film-like adhesive has a total light transmittance of 80% or more after curing of the curable film-like adhesive. The method according to any one of claims 1 to 3,
The curable film-like adhesive comprising, as a main component, at least one selected from an imidazole-based compound having a reaction activation temperature of 125° C. or less and a thermal cation polymerization initiator having a reaction activation temperature of 160° C. or less. The method according to any one of claims 1 to 4,
The curable film-like adhesive, wherein the curing agent contains a thermal cationic polymerization initiator having a reaction activation temperature of 160° C. or less. The method according to any one of claims 1 to 5,
The curable film-like adhesive, wherein the polymer component contains an acid-modified polyolefin-based resin. The method according to any one of claims 1 to 6,
The curable film-like adhesive, wherein the cyclic ether compound is an aliphatic compound. A curable film-like adhesive containing a cyclic ether compound, a polymer component, and a curing agent containing at least one selected from an imidazole compound having a reaction activation temperature of 125° C. or less, and a thermal cation polymerization initiator having a reaction activation temperature of 160° C. or less. And a step of curing a curable film-like adhesive by attaching to a member including a module and heating at a temperature in the range of 80 to 110°C.