JPWO2018030435A1 - Adhesive composition, cured product, electronic component and assembly component - Google Patents

Abstract

An object of the present invention is to provide an adhesive composition which has excellent adhesion and which can be easily reworked at low temperatures. Another object of the present invention is to provide a cured product of the adhesive composition, and an electronic component and an assembled part having the cured product of the adhesive composition. The present invention is an adhesive composition containing a moisture-curable resin and a wax.

Description

The present invention relates to an adhesive composition having excellent adhesion and easy rework at low temperatures. The present invention also relates to a cured product of the adhesive composition, and an electronic component and an assembled part having the cured product of the adhesive composition.

BACKGROUND ART In recent years, liquid crystal display elements, organic EL display elements, and the like have been widely used as display elements having features such as thinness, light weight, and low power consumption. In these display elements, a photocurable resin composition is usually used for sealing of a liquid crystal or a light emitting layer, adhesion of various members such as a substrate, an optical film, a protective film and the like. In addition, in the modern world in which mobile devices with various display elements such as mobile phones and portable game machines are in widespread use, miniaturization of the display elements is the most demanded issue.
However, as the display element is miniaturized, the photocurable resin composition may be applied to the part where light does not reach sufficiently, and as a result, the photocurable resin composition applied to the part where light does not reach There is a problem that curing becomes insufficient. Therefore, a photo-thermosetting resin composition is used as a resin composition that can be sufficiently cured even when applied to a portion to which light does not reach, and it is also practiced to use photocuring and thermosetting together. There was a possibility that the elements and the like were adversely affected by the heating.

In recent years, high integration and miniaturization are required for electronic components such as semiconductor chips, and for example, bonding of a plurality of thin semiconductor chips via an adhesive layer to form a laminate of semiconductor chips It has been done. For example, a method of laminating an adhesive on one of the semiconductor chips, laminating the other semiconductor chip through the adhesive, and then curing the adhesive. It is manufactured by a method of filling an adhesive between semiconductor chips held at intervals and thereafter curing the adhesive.
As an adhesive used for adhesion | attachment of such an electronic component, the thermosetting type adhesive containing the epoxy compound which is a number average molecular weight 600-1000 is disclosed by patent document 1, for example. However, a thermosetting adhesive as disclosed in Patent Document 1 is not suitable for bonding of electronic parts that can be damaged by heat.

As a method of curing a resin composition without heating at a high temperature, a method using a moisture curable resin composition has been studied. For example, Patent Document 2 discloses a moisture-curable resin composition which is crosslinked and cured by reacting an isocyanate group in the resin with moisture (water) in air or an adherend. However, a thermosetting adhesive as disclosed in Patent Document 1 is not suitable for bonding of electronic parts that can be damaged by heat. In addition, it is difficult to obtain a highly reliable adhesive, because a thermosetting adhesive is likely to deteriorate its adhesive properties when a large load is applied for a long time.

JP 2000-178342 A JP 2002-212534 A

At present, the inventors obtained an idea of a new type of moisture-curable resin composition having reworkability, but the moisture-curable resin composition as described above has adhesiveness and reworkability (removability It is difficult to make it compatible with In particular, since rework under high temperature conditions has a problem of damaging the electronic parts etc., it is cured without requiring heating at high temperature at the time of fixing and has excellent adhesion and at low temperature conditions during rework. It was necessary to study a resin composition that could be easily peeled off by heating.
An object of the present invention is to provide an adhesive composition which has excellent adhesion and which can be easily reworked at a low temperature. The present invention also provides a cured product of the adhesive composition, and an electronic component and an assembled part having the cured product of the adhesive composition.

The present invention is an adhesive composition containing a moisture-curable resin and a wax.
The present invention will be described in detail below.

The present inventors have found that by blending a wax with a moisture-curable resin composition, it is possible to obtain an adhesive composition that is excellent in adhesion and easy to be reworked at low temperatures, and the present invention has been completed. It came to

The adhesive composition of the present invention contains a wax.
By containing the above-mentioned wax, the adhesive composition of the present invention becomes excellent in rework property because the cured product is softened by heating at the time of rework and the adhesive strength is significantly reduced.
In the present specification, the above-mentioned “wax” means an organic substance which is solid at 23 ° C. and becomes a liquid by heating.

The preferable lower limit of the melting point of the above wax is 50 ° C., and the preferable upper limit is 140 ° C. When the melting point of the above-mentioned wax is in this range, the adhesive composition obtained becomes excellent due to the effect of achieving both the adhesiveness and the reworkability. A more preferable lower limit of the melting point of the wax is 70 ° C., and a more preferable upper limit is 110 ° C.
The melting point of the above-mentioned wax is taken as the temperature which shows the peak top of heat absorption in the graph obtained by differential scanning calorimetry.

When the above-mentioned wax is present in the adhesive composition of the present invention as fine particles (hereinafter also referred to as "wax fine particles"), the contact area between the resin and the wax becomes large, and the obtained adhesive composition has reworkability It is preferable because it is more excellent.
The smaller the particle diameter of the wax particles, the better, and the preferred upper limit is 300 μm. By the particle diameter of the said wax microparticles | fine-particles being 300 micrometers or less, the adhesive composition obtained becomes what is excellent by rework property. The upper limit of the particle diameter of the wax fine particles is more preferably 250 μm, still more preferably 100 μm, still more preferably 50 μm, and particularly preferably 10 μm.
There is no particular lower limit of the particle diameter of the wax fine particles, but the substantial lower limit is 0.1 μm.
The particle diameter of the above-mentioned wax particles is, for example, a scanning electron microscope, a laser microscope, a laser diffraction particle size distribution measuring device, a disk centrifugal particle size distribution measuring device, a number counting type when measuring wax particles as a raw material. It can measure with a particle size distribution measuring device etc. When the wax fine particles present in the adhesive composition of the present invention are measured, they can be measured by a scanning electron microscope, a transmission electron microscope, a laser microscope or the like. As a preferable measurement method, a method using a "laser diffraction type particle size distribution measuring apparatus" is used to measure wax particles as a raw material, and a method to measure wax particles present in the adhesive composition of the present invention is used. It is a method of using a scanning electron microscope.

Specifically, examples of the wax include olefin waxes such as polypropylene wax, polyethylene wax, microcrystalline wax, polyethylene oxide wax or paraffin wax, and aliphatics such as carnauba wax, sasol wax, montanic acid ester wax, etc. Ester-based wax, deacidified carnauba wax, saturated aliphatic acid-based wax such as baltic acid, stearic acid, montanic acid, unsaturated aliphatic acid-based wax such as plasicic acid, eleostearic acid, valinaric acid, Saturated alcohol wax such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol, melicyl alcohol or aliphatic alcohol wax, polyvalent alcohol such as sorbitol Wax, saturated fatty acid amide wax such as linoleic acid amide, oleic acid amide and lauric acid amide, methylenebisstearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bisstearic acid amide And unsaturated fatty acid amides such as ethylene fatty acid bisamide wax, ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipic acid amide, N, N'-dioleyl sebacic acid amide, etc. Wax, aromatic bisamide-based wax such as m-xylene bis-stearic acid amide, N, N'-distearyl isophthalic acid amide, graft-modified wax obtained by graft-polymerizing vinyl-based monomer such as styrene onto polyolefin, behenic acid Monoglyceride Partial ester wax in which fatty acid and polyhydric alcohol are reacted, methyl ester wax having hydroxyl group obtained by hydrogenating vegetable oil and fat, and ethylene / vinyl acetate copolymer wax having a high content ratio of ethylene component And long-chain alkyl acrylate waxes such as saturated stearyl acrylate wax such as acrylic acid, and aromatic acrylate waxes such as benzyl acrylate wax. Among them, paraffin wax and Sazole wax are preferable.

Among the above-mentioned waxes, commercially available ones are, for example, HS Christa-6100, HS Christa-7100 (all manufactured by Toyokuni Oil Co., Ltd.), H1, H1N6, C105, H105, C80, SPRAY30, SPRAY105, (all are Sasol) Company company), ParaffinWax-155, ParaffinWax-150, ParaffinWax-145, ParaffinWax-140, HNP-3, HNP-9, HNP-51, SP-0165, Hi-Mic-2095, Hi-Mic-1090, Hi- Mic-1080, Hi-Mic-1070, NPS-6010, FT115, SX105, FNP-0090 (all are Nippon Seiwa Co., Ltd. make) etc. are mentioned.

The preferable lower limit of the content of the wax in 100 parts by weight of the adhesive composition of the present invention is 1 part by weight, and the preferable upper limit is 50 parts by weight. When the content of the wax is in this range, the obtained adhesive composition becomes excellent due to the effect of achieving both adhesiveness and reworkability. The lower limit of the content of the wax is preferably 3 parts by weight, more preferably 40 parts by weight, still more preferably 5 parts by weight, and still more preferably 30 parts by weight.

The adhesive composition of the present invention contains a moisture-curable resin.
Examples of the moisture-curable resin include a moisture-curable urethane resin, a hydrolyzable silyl group-containing resin, and the like. Among them, a moisture-curable urethane resin is preferable.
The moisture-curable urethane resin has a urethane bond and an isocyanate group, and the isocyanate group in the molecule reacts with the moisture in the air or in the adherend to be cured.

The moisture-curable urethane resin may have only one isocyanate group in one molecule, or may have two or more isocyanate groups. Among them, it is preferable to have an isocyanate group at both ends of the main chain of the molecule.

The moisture-curable urethane resin can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule.

The reaction between the polyol compound and the polyisocyanate compound is usually carried out by the molar ratio of hydroxyl group (OH) in the polyol compound to isocyanate group (NCO) in the polyisocyanate compound [NCO] / [OH] = 2.0-2 It takes place in the range of .5.

As a polyol compound used as a raw material of the above-mentioned moisture hardening type urethane resin, a well-known polyol compound usually used for manufacture of polyurethane can be used, for example, polyester polyol, polyether polyol, polyalkylene polyol, polycarbonate polyol Etc. These polyol compounds may be used alone or in combination of two or more.

As said polyester polyol, the polyester polyol obtained by reaction of polyhydric carboxylic acid and a polyol, the poly- (epsilon) -caprolactone polyol etc. which are obtained by ring-opening-polymerizing (epsilon) -caprolactone etc. are mentioned, for example.

Examples of the polyvalent carboxylic acid as a raw material of the polyester polyol include terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberin Acids, azelaic acids, sebacic acids, decamethylene dicarboxylic acids, dodecamethylene dicarboxylic acids and the like can be mentioned.

As said polyol used as the raw material of said polyester polyol, ethylene glycol, propylene glycol, 1, 3- propanediol, 1, 4- butanediol, neopentyl glycol, 1, 5- pentanediol, 1, 6- hexane, for example Diol, diethylene glycol, cyclohexanediol and the like can be mentioned.

Examples of the polyether polyols include ethylene glycol, propylene glycol, ring-opening polymers of tetrahydrofuran, ring-opening polymers of 3-methyltetrahydrofuran, and random copolymers or block copolymers of these or their derivatives, bisphenol Type polyoxyalkylene modified products and the like.

The bisphenol type polyoxyalkylene modified substance is a polyether polyol obtained by subjecting an active hydrogen portion of a bisphenol type molecular skeleton to an addition reaction of an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) It may be a random copolymer or a block copolymer. It is preferable that the said bisphenol type polyoxyalkylene modified body is 1 type or 2 types or more of alkylene oxides being added to the both terminal of bisphenol type molecular frame. It does not specifically limit as a bisphenol type, A-type, F-type, S-type etc. are mentioned, Preferably it is bisphenol A-type.

As said polyalkylene polyol, a polybutadiene polyol, a hydrogenated polybutadiene polyol, a hydrogenated polyisoprene polyol etc. are mentioned, for example.

Examples of the polycarbonate polyol include polyhexamethylene carbonate polyol and polycyclohexane dimethylene carbonate polyol.

As a polyisocyanate compound used as a raw material of the said moisture hardening type urethane resin, an aromatic polyisocyanate compound and an aliphatic polyisocyanate compound are used suitably.
Examples of the aromatic polyisocyanate compound include diphenylmethane diisocyanate, liquid modified products of diphenylmethane diisocyanate, polymeric MDI, tolylene diisocyanate, naphthalene-1,5-diisocyanate and the like.
Examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and cyclohexane. Diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate and the like can be mentioned.
Among the above polyisocyanate compounds, diphenylmethane diisocyanate and modified products thereof are preferable in view of low vapor pressure, low toxicity and ease of handling.
The said polyisocyanate compound may be used independently, and may be used in combination of 2 or more type.

Moreover, it is preferable that the said moisture hardening type urethane resin is a thing obtained using the polyol compound which has a structure represented by following formula (1). By using a polyol compound having a structure represented by the following formula (1), it is possible to obtain a composition having excellent adhesiveness and a cured product which is flexible and has a good elongation, and is in phase with a radical polymerizable compound described later. It becomes excellent in solubility.
Among them, those using a polyether polyol comprising a ring opening polymerization compound of propylene glycol, a tetrahydrofuran (THF) compound, or a ring opening polymerization compound of a tetrahydrofuran compound having a substituent such as a methyl group are preferable.

In formula (1), R represents a hydrogen atom, a methyl group or an ethyl group, l is an integer of 0 to 5, m is an integer of 1 to 500, and n is an integer of 1 to 10. . l is preferably 0 to 4, m is preferably 50 to 200, and n is preferably 1 to 5.
The case where l is 0 means that the carbon bonded to R is directly bonded to oxygen.

The hydrolyzable silyl group-containing resin is cured by the reaction of the hydrolyzable silyl group in the molecule with the moisture in the air or the adherend.
The hydrolyzable silyl group-containing resin may have only one hydrolyzable silyl group in one molecule, or may have two or more hydrolyzable silyl groups. Among them, it is preferable to have hydrolyzable silyl groups at both ends of the main chain of the molecule.

The hydrolyzable silyl group is represented by the following formula (2).

In formula (2), R ¹ is each independently an optionally substituted alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms, an aryl group, 7 to 20 carbon atoms, or an aralkyl group Or —OSiR ² ₃ (wherein R ² is each independently a hydrocarbon group having 1 to 20 carbon atoms). Moreover, in Formula (2), X is a hydroxy group or a hydrolysable group each independently. Furthermore, in Formula (2), a is an integer of 1 to 3.

The hydrolyzable group is not particularly limited, and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an alkenyloxy group, an aryloxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an acid amide group, an aminooxy group, A mercapto group etc. are mentioned. Among them, a halogen atom, an alkoxy group, an alkenyloxy group and an acyloxy group are preferable because of high activity, and an alkoxy group such as a methoxy group and an ethoxy group is more preferable, since a hydrolyzability is mild and easy to handle. And ethoxy groups are more preferred. Further, from the viewpoint of safety, an ethoxy group and an isopropenoxy group are preferable in which the compounds to be eliminated by the reaction are ethanol and acetone, respectively.

The hydroxy group or the hydrolyzable group can be bonded to one silicon atom in the range of 1 to 3. When two or more of the hydroxy group or the hydrolyzable group are bonded to one silicon atom, those groups may be identical or different.

From the viewpoint of curability, a in the above formula (2) is preferably 2 or 3, and particularly preferably 3. Further, in terms of storage stability, a is preferably 2.

Further, R ¹ in the above formula (2) is, for example, an alkyl group such as methyl group or ethyl group, a cycloalkyl group such as cyclohexyl group, an aryl group such as phenyl group, an aralkyl group such as benzyl group, a trimethylsiloxy group , Chloromethyl group, methoxymethyl group and the like. Among them, methyl group is preferable.

As the hydrolyzable silyl group, for example, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, tris (2-propenyloxy) silyl group, triacetoxysilyl group, (chloromethyl) dimethoxysilyl group, Chloromethyl) diethoxysilyl group, (dichloromethyl) dimethoxysilyl group, (1-chloroethyl) dimethoxysilyl group, (1-chloropropyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group Group, (ethoxymethyl) dimethoxysilyl group, (1-methoxyethyl) dimethoxysilyl group, (aminomethyl) dimethoxysilyl group, (N, N-dimethylaminomethyl) dimethoxysilyl group, (N, N-diethylaminomethyl) dimethoxy group Silyl group, (N N- diethylaminomethyl) diethoxysilyl group, (N- (2-aminoethyl) aminomethyl) dimethoxy silyl group, (acetoxymethyl) dimethoxy silyl group, and (acetoxymethyl) diethoxysilyl group.

As the hydrolyzable silyl group-containing resin, for example, a hydrolyzable silyl group-containing (meth) acrylic resin, an organic polymer having a hydrolyzable silyl group at a molecular chain terminal or a molecular chain terminal site, a hydrolyzable silyl group Containing polyurethane resin etc. are mentioned.

The hydrolyzable silyl group-containing (meth) acrylic resin preferably has a repeating structural unit derived from a hydrolyzable silyl group-containing (meth) acrylic acid ester and a (meth) acrylic acid alkyl ester in the main chain.

Examples of the hydrolyzable silyl group-containing (meth) acrylic acid ester include 3- (trimethoxysilyl) propyl (meth) acrylate, 3- (triethoxysilyl) propyl (meth) acrylate, and (meth) acrylic acid. 3- (Methyldimethoxysilyl) propyl acid, 2- (trimethoxysilyl) ethyl (meth) acrylate, 2- (triethoxysilyl) ethyl (meth) acrylate, 2- (methyldimethoxysilyl) acrylic acid Ethyl, trimethoxysilylmethyl (meth) acrylate, triethoxysilylmethyl (meth) acrylate, (meth) acrylic acid (methyldimethoxysilyl) methyl and the like can be mentioned.

Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- (meth) acrylate Butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n- (meth) acrylate Heptyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, (meth) Examples include stearyl acrylate and the like.

Specifically as a method of manufacturing the said hydrolysable silyl group containing (meth) acrylic resin, the hydrolysable silicon group containing (meth) acrylic acid ester system described in, for example, WO 2016/035718 The synthesis method of a polymer etc. are mentioned.

The organic polymer having a hydrolyzable silyl group at the molecular chain terminal or at the molecular chain terminal site has a hydrolyzable silyl group at least either of the terminal of the main chain and the terminal of the side chain.
The skeleton structure of the main chain is not particularly limited, and examples thereof include saturated hydrocarbon polymers, polyoxyalkylene polymers, (meth) acrylic acid ester polymers and the like.

Examples of the polyoxyalkylene polymer include a polyoxyethylene structure, a polyoxypropylene structure, a polyoxybutylene structure, a polyoxytetramethylene structure, a polyoxyethylene-polyoxypropylene copolymer structure, a polyoxypropylene-poly. The polymer etc. which have an oxybutylene copolymer structure are mentioned.

Specific examples of the method for producing an organic polymer having a hydrolyzable silyl group at the molecular chain terminal or at the molecular chain terminal site include the molecular chain terminal or the molecular chain terminal or the molecular chain terminal described in WO 2016/035718. The synthesis method of the organic polymer which has a crosslinkable silyl group only in the molecular chain terminal part is mentioned. Moreover, as another method for producing an organic polymer having a hydrolyzable silyl group at the molecular chain terminal or at the molecular chain terminal position, for example, a reactive silicon group-containing compound described in WO 2012/117902 The synthesis method of a polyoxyalkylene type polymer etc. are mentioned.

As a method for producing the hydrolyzable silyl group-containing polyurethane resin, for example, when producing a polyurethane resin by reacting a polyol compound and a polyisocyanate compound, a silyl group-containing compound such as a silane coupling agent is further added. The method of making it react etc. are mentioned. Specifically, for example, a synthesis method of a urethane oligomer having a hydrolyzable silyl group described in JP-A-2017-48345 can be mentioned.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxy-ethoxy) silane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, and γ-glycidoxy. Propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -Γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-isocyanate propyl Trimethoxysilane, 3-isocyanate propyl triethoxysilane, and the like. Among these, γ-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane are preferable. These silane coupling agents may be used alone or in combination of two or more.

Furthermore, the moisture-curable resin may have a radically polymerizable functional group.
As a radically polymerizable functional group which the said moisture-curable resin may have, the group which has an unsaturated double bond is preferable, and the (meth) acryloyl group is more preferable especially from the reactive surface.
The moisture-curable resin having a radically polymerizable functional group is not included in the radically polymerizable compound described later, and is treated as a moisture-curable resin.

The weight average molecular weight of the moisture-curable resin is not particularly limited, but a preferable lower limit is 800 and a preferable upper limit is 10,000. When the weight-average molecular weight of the moisture-curable resin is in this range, the resulting adhesive composition will be more excellent in flexibility without becoming too high in crosslinking density during curing, and will be more excellent in coating properties . The lower limit of the weight average molecular weight of the moisture-curable resin is more preferably 2,000, more preferably 8,000, still more preferably 2,500, still more preferably 6,000.
In the present specification, the weight average molecular weight is a value determined by gel permeation chromatography (GPC) and converted to polystyrene. As a column at the time of measuring the weight average molecular weight by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Denko) etc. are mentioned, for example. Moreover, tetrahydrofuran etc. are mentioned as a solvent used by GPC.

The preferable lower limit of the content of the moisture-curable resin in 100 parts by weight of the adhesive composition of the present invention is 20 parts by weight, and the preferable upper limit is 90 parts by weight. When the content of the moisture-curable resin is in this range, the resulting adhesive composition is excellent in moisture curability while maintaining excellent weather resistance and flexibility of a cured product. A more preferable lower limit of the content of the moisture-curable resin is 30 parts by weight, and a more preferable upper limit is 70 parts by weight.

The inventors of the present invention have attempted to increase the amount of wax per unit area in contact with the adherend in order to further improve the effect of achieving both adhesion and reworkability. It was examined to thicken the adhesive layer containing the agent composition. FIG. 1 is a schematic view showing the adhesion state of an adherend with the adhesive composition of the present invention when (a) the thickness of the adhesive layer is small and (b) when it is large.
As shown in FIG. 1, as the thickness 3 of the adhesive layer comprising the adhesive composition 2 for adhering the adherend 1 increases, the amount of wax 5 present in the adhesive composition 2 per unit area 4 increases. Become. Therefore, the effect which makes adhesiveness and rework property compatible is further improved by making thickness 3 of adhesion layer into big thickness in the limit which can maintain adhesiveness. In this case, in order to maintain the thickness 3 of the adhesive layer, it is preferable to perform photocuring as a pretreatment. Then, in order to develop photocurability, it is preferable that the adhesive composition of this invention contains a radically polymerizable compound and a radical photopolymerization initiator. That is, by containing the radically polymerizable compound and the radical photopolymerization initiator, the photocurability and the moisture curability are secured, and it is more effective to achieve both the adhesiveness and the reworkability. Such an adhesive composition of the present invention can be suitably used particularly for a sealing agent for a display element or an adhesive used for housing connection of a narrow frame design.

The radically polymerizable compound is not particularly limited as long as it is a radically polymerizable compound having photopolymerizability, and a compound having a radically polymerizable functional group in the molecule. Among them, a compound having an unsaturated double bond as a radically polymerizable functional group is preferable, and a compound having a (meth) acryloyl group (hereinafter, also referred to as “(meth) acrylic compound”) is particularly preferable from the viewpoint of reactivity. It is suitable.
In the present specification, the above "(meth) acryloyl" means acryloyl or methacryloyl, and the above "(meth) acryl" means acrylic or methacryl.

As said (meth) acrylic compound, a (meth) acrylic acid ester compound, an epoxy (meth) acrylate, urethane (meth) acrylate etc. are mentioned, for example.
In the present specification, the above "(meth) acrylate" means acrylate or methacrylate. Moreover, the said urethane (meth) acrylate does not have a residual isocyanate group.

As a monofunctional thing among the said (meth) acrylic acid ester compounds, phthalimide acrylates, such as N- acryloyl oxyethyl hexahydro phthalimide, various imide (meth) acrylates, a methyl (meth) acrylate, an ethyl (meth), for example Acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate , Isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, methoxy ethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate Ethyl carbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) Acrylate, phenoxy polyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl ( Meta) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) Examples thereof include acryloyloxyethyl-2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate and the like.

Moreover, as a bifunctional thing among the said (meth) acrylic acid ester compounds, a 1, 3- butanediol di (meth) acrylate, a 1, 4- butanediol di (meth) acrylate, 1, 6- hexane, for example is mentioned. Diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) ) Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, poly Lopylene glycol di (meth) acrylate, ethylene oxide added bisphenol A di (meth) acrylate, propylene oxide added bisphenol A di (meth) acrylate, ethylene oxide added bisphenol F di (meth) acrylate, dimethylol dicyclopentadienyl di (meth) Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol Di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol (Meth) acrylate.

Moreover, as a thing of trifunctional or more among the said (meth) acrylic acid ester compounds, for example, trimethylol propane tri (meth) acrylate, ethylene oxide addition trimethylol propane tri (meth) acrylate, propylene oxide addition trimethylol propane tri ( Meta) acrylate, caprolactone modified with trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide-added isocyanurate tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide added glycerin tri (meth) acrylate, Tris (meth) acryloyl oxyethyl phosphate, ditrimethylol propane tetra (meth) acrylate, pentaerythritol tetra Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.

As said epoxy (meth) acrylate, what is obtained by making an epoxy compound and (meth) acrylic acid react in presence of a basic catalyst according to a conventional method etc. are mentioned, for example.

As an epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meta) acrylate, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, 2,2'-diallyl bisphenol A epoxy resin Hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol Novolac epoxy resin, ortho cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphth Ren phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compounds, bisphenol A type episulfide resins.

Among the above epoxy (meth) acrylates, commercially available ones include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3702, EBECRYL3800, EBECRYL L 40 40.degree. ), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all from Shin-Nakamura Chemical Co., Ltd.), epoxy ester M-600A, epoxy ester 40 EM, epoxy ester 70 PA, Epoxy ester 200 PA, epoxy ester 80 MF , Epoxy ester 3002 M, epoxy ester 3002 A, epoxy ester 1600 A, epoxy ester 3000 M, epoxy ester 3000 A, epoxy ester 200 EA, epoxy ester 400 EA (all from Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Denacol acrylate DA-314 And Denacol acrylate DA-911 (all of which are manufactured by Nagase ChemteX).

The urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin-based compound.

Examples of the isocyanate compound include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), and hydrogenation. MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethyl xylylene An isocyanate, 1,6, 11-undecane triisocyanate etc. are mentioned.

Moreover, as the above-mentioned isocyanate compound, a chain-extended isocyanate compound obtained by the reaction of a polyol and an excess of an isocyanate compound can also be used.
Examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and the like.

Examples of the (meth) acrylic acid derivative having a hydroxyl group include dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol and polyethylene glycol. Mono- (meth) acrylates of trihydric alcohols such as trimethylol ethane, trimethylol propane, and glycerol, or mono- (meth) acrylates or di (meth) acrylates of trihydric alcohols such as glycerin, and epoxy (meth) And the like.

Among the above urethane (meth) acrylates, commercially available ones are, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8411, EBECRYL8413, EBECRYL 8104, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL 1290, EBECRYL5129, EBECRYL4842, EBECRYL 4827, EBECRYLL 7300h Echyl ), Art resin UN-9000H, Art resin UN-9000A, Art resin UN-7100, Art resin UN-1255, Art resin UN-330, Art resin UN-3320 HB, Art resin UN-1200TPK, Art resin SH-500 B ( All are Negami Industrial Co., Ltd.), U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6LPA, U-6HA, U-10H, U-15HA, U-122A, U- 122P, U-108, U-108A, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4100, UA-4000, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A (all are new Nakamura Manabu Industries, Ltd.), AI-600, AH-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all manufactured by Kyoeisha Chemical Co., Ltd.).

In addition, other radically polymerizable compounds other than those described above can also be used appropriately.
Examples of the other radically polymerizable compounds include N, N-dimethyl (meth) acrylamide, N- (meth) acryloyl morpholine, N-hydroxyethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N -(Meth) acrylamide compounds such as isopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, styrene, α-methylstyrene, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, etc. Vinyl compounds and the like can be mentioned.

It is preferable that the said radically polymerizable compound contains a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound from a viewpoint of adjusting curability. By containing the said monofunctional radically polymerizable compound and the said polyfunctional radically polymerizable compound, the adhesive composition obtained becomes what is excellent by curability and tackiness. Among them, urethane (meth) acrylate is preferably used in combination with the monofunctional radically polymerizable compound as the polyfunctional radically polymerizable compound. Moreover, it is preferable that it is bifunctional or trifunctional, and, as for the said polyfunctional radically polymerizable compound, it is more preferable that it is bifunctional.

When the radically polymerizable compound contains the monofunctional radically polymerizable compound and the polyfunctional radically polymerizable compound, the content of the polyfunctional radically polymerizable compound is the same as that of the monofunctional radically polymerizable compound and the polybasic radically polymerizable compound. The preferable lower limit is 2 parts by weight and the preferable upper limit is 45 parts by weight with respect to 100 parts by weight in total with the functional radically polymerizable compound. When the content of the above-mentioned polyfunctional radically polymerizable compound is in this range, the resulting adhesive composition is more excellent in curability and tackiness. A more preferable lower limit of the content of the polyfunctional radically polymerizable compound is 5 parts by weight, and a more preferable upper limit is 35 parts by weight.

The preferable lower limit of the content of the radically polymerizable compound in 100 parts by weight of the adhesive composition of the present invention is 10 parts by weight, and the preferable upper limit is 80 parts by weight. When the content of the radically polymerizable compound is in this range, the obtained adhesive composition is excellent in both of the photocurability and the moisture curability. The more preferable lower limit of the content of the radically polymerizable compound is 30 parts by weight, and the more preferable upper limit is 60 parts by weight.

Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acyl phosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone and the like.

Among the above photo radical polymerization initiators, commercially available ones are IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 784, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, Lucirin TPO (all manufactured by BASF Co., Ltd.), benzoin methyl ether And benzoin ethyl ether and benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.).

The preferable lower limit of the content of the photo radical polymerization initiator is 0.01 parts by weight and the preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the radical polymerizable compound. When the content of the photo radical polymerization initiator is in this range, the resulting adhesive composition is more excellent in photocurability and storage stability. A more preferable lower limit of the content of the photo radical polymerization initiator is 0.1 parts by weight, and a more preferable upper limit is 5 parts by weight.

The adhesive composition of the present invention preferably contains a filler.
By containing the above-mentioned filler, the adhesive composition of the present invention has suitable thixotropy, and the shape after application can be sufficiently maintained.

The preferable lower limit of the primary particle diameter of the filler is 1 nm, and the preferable upper limit is 50 nm. By the primary particle diameter of the said filler being this range, the adhesive composition obtained becomes what is excellent by the coating property and the shape retentivity after application. A more preferable lower limit of the primary particle diameter of the filler is 5 nm, a more preferable upper limit is 30 nm, a still more preferable lower limit is 10 nm, and a still more preferable upper limit is 20 nm.
The primary particle diameter of the above-mentioned filler can be measured by dispersing the above-mentioned filler in a solvent (water, organic solvent, etc.) using NICOMP 380 ZLS (manufactured by PARTICLE SIZING SYSTEMS).
The filler may be present as secondary particles (a collection of a plurality of primary particles) in the adhesive composition of the present invention, and the preferred lower limit of the particle diameter of such secondary particles is 5 nm. The upper limit is preferably 500 nm, more preferably 10 nm, and still more preferably 100 nm. The particle diameter of the secondary particles of the filler can be measured by observing the adhesive composition of the present invention or the cured product thereof using a transmission electron microscope (TEM).

The filler is preferably an inorganic filler, and examples thereof include silica, talc, titanium oxide, zinc oxide, calcium carbonate and the like. Among them, silica is preferable because the adhesive composition to be obtained is excellent in ultraviolet ray permeability. These fillers may be used alone or in combination of two or more.

The filler is preferably subjected to hydrophobic surface treatment. By the said hydrophobic surface treatment, the adhesive composition obtained becomes what is excellent by the shape-retaining property after application | coating.
Examples of the hydrophobic surface treatment include silylation treatment, alkylation treatment, epoxidation treatment and the like. Among them, silylation treatment is preferable, and trimethylsilylation treatment is more preferable, because it is excellent in the effect of improving shape retention.

As a method of hydrophobic-surface-treating the said filler, the method of processing the surface of a filler, etc. are mentioned using surface treating agents, such as a silane coupling agent, for example.
Specifically, for example, the above-mentioned trimethylsilylation-treated silica is a method of synthesizing silica by a sol-gel method and spraying hexamethyldisilazane in a state in which silica is made to flow, or in an organic solvent such as alcohol or toluene. After adding silica, hexamethyldisilazane and water, it can be produced by a method such as evaporating and drying water and an organic solvent with an evaporator.

The preferable lower limit of the content of the filler in 100 parts by weight of the adhesive composition of the present invention is 1 part by weight, and the preferable upper limit is 20 parts by weight. When the content of the above-mentioned filler is in this range, the adhesive composition obtained is excellent in the coating property and the shape retention after coating. The lower limit of the content of the filler is preferably 2 parts by weight, more preferably 15 parts by weight, still more preferably 3 parts by weight, still more preferably 10 parts by weight, particularly preferably 4 parts by weight. .

The adhesive composition of the present invention may contain a light shielding agent.
By containing the light shielding agent, the adhesive composition of the present invention is excellent in the light shielding property, and for example, when used in a display element, light leakage can be prevented. Moreover, the display element manufactured using the adhesive composition of this invention which mix | blended the said light shielding agent does not have the leak of light, and since the adhesive composition has sufficient light shielding property, it is excellent. Image display quality.
In the present specification, the above-mentioned "light shielding agent" means a material having the ability to hardly transmit light in the visible light region.

Examples of the light shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black and the like. Further, the light shielding agent does not have to have a black color, and as long as it is a material having the ability to hardly transmit light in the visible light region, the materials mentioned as fillers, such as silica, talc, titanium oxide, etc. It is contained in the said light-shielding agent. Among them, titanium black is preferred.

The above-mentioned titanium black is a substance whose transmittance to light in the vicinity of the ultraviolet region, particularly to light having a wavelength of 370 to 450 nm is higher than the average transmittance to light having a wavelength of 300 to 800 nm.
That is, while the titanium black sufficiently imparts a light shielding property to the adhesive composition of the present invention by sufficiently shielding light having a wavelength in the visible light region, it has a light shielding property of transmitting light having a wavelength near the ultraviolet region. It is an agent. Therefore, the photocurability of the adhesive composition of the present invention can be obtained by using, as the photoradical polymerization initiator, one capable of initiating a reaction by light of a wavelength (370 to 450 nm) at which the transmittance of the titanium black becomes high. It can be increased more. On the other hand, as the light shielding agent contained in the adhesive composition of the present invention, a substance having a high insulating property is preferable, and titanium black is also preferable as a light shielding agent having a high insulating property.
The titanium black preferably has an optical density (OD value) of 3 or more, and more preferably 4 or more. The titanium black preferably has a degree of blackness (L value) of 9 or more, more preferably 11 or more. The higher the light shielding property of the titanium black, the better. There is no particular upper limit to the OD value of the titanium black, but it is usually 5 or less.

The above-mentioned titanium black exhibits sufficient effects even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide Surface-treated titanium black, such as those coated with an inorganic component such as magnesium oxide, can also be used. Especially, what is processed by the organic component is preferable at the point which can improve insulation more.

Among the titanium blacks, commercially available ones include 12S, 13M, 13M-C, 13R-N (all manufactured by Mitsubishi Materials Corporation), Tilac D (manufactured by Akao Kasei Co., Ltd.), and the like.

The lower limit of the specific surface area of the titanium black is preferably 5 m ² / g, preferably 40 m ² / g, more preferably 10 m ² / g, and still more preferably 25 m ² / g.
In addition, a preferable lower limit of the sheet resistance of the above-mentioned titanium black is 10 ⁹ Ω / □ when it is mixed with a resin (70% blending), and a more preferable lower limit is 10 ¹¹ Ω / □.

In the adhesive composition of the present invention, the primary particle diameter of the light shielding agent is appropriately selected according to the application, such as the distance between the substrates of the display element or less, but the lower limit is preferably 30 nm and the upper limit is preferably 500 nm. When the primary particle diameter of the light shielding agent is in this range, the adhesive composition obtained is excellent in the coating property on the substrate and the workability without the viscosity and the thixotropy largely increasing. The more preferable lower limit of the primary particle diameter of the light shielding agent is 50 nm, and the more preferable upper limit is 200 nm.
The primary particle diameter of the light shielding agent can be measured in the same manner as the primary particle diameter of the filler.

The preferable lower limit of the content of the light shielding agent in 100 parts by weight of the adhesive composition of the present invention is 0.05 parts by weight, and the preferable upper limit is 10 parts by weight. When the content of the light shielding agent is in this range, the obtained adhesive composition is excellent in light shielding property while maintaining excellent drawability, adhesiveness to a substrate etc., and strength after curing. Become. A more preferable lower limit of the content of the light shielding agent is 0.1 parts by weight, a more preferable upper limit is 2 parts by weight, and a still more preferable upper limit is 1 part by weight.

The adhesive composition of the present invention may further contain, if necessary, additives such as a colorant, an ionic liquid, a solvent, metal-containing particles, a reactive diluent and the like.

As a method for producing the adhesive composition of the present invention, for example, a moisture curable resin, a wax, and a mixer using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a 3-roll mill. Examples thereof include a method of mixing a radically polymerizable compound to be added as necessary, and a radical photopolymerization initiator and additives.

The adhesive composition of the present invention preferably contains a water content of 100 ppm or less. When the water content is 100 ppm or less, the reaction between the moisture-curable resin and water during storage can be suppressed, and the adhesive composition can be more excellent in storage stability. The water content is more preferably 80 ppm or less.
The water content can be measured by a Karl-Fisher water measuring apparatus.

In the adhesive composition of the present invention, the preferable lower limit of the viscosity measured under the conditions of 25 ° C. and 1 rpm using a cone-plate viscometer is 50 Pa · s, and the preferable upper limit is 1000 Pa · s. When the viscosity is in this range, the workability at the time of applying the adhesive composition to an adherend such as a substrate is excellent. A more preferable lower limit of the viscosity is 80 Pa · s, a more preferable upper limit is 500 Pa · s, and a further preferable upper limit is 400 Pa · s.
In addition, when the viscosity of the adhesive composition of this invention is too high, applicability | paintability can be improved by heating at the time of application | coating.

The preferable lower limit of the thixotropic index of the adhesive composition of the present invention is 1.3, and the preferable upper limit is 5.0. When the thixotropic index is in this range, the workability at the time of applying the adhesive composition to an adherend such as a substrate is more excellent. The more preferable lower limit of the thixotropic index is 1.5, and the more preferable upper limit is 4.0.
In the present specification, the above-mentioned thixotropic index is a viscosity measured at 25 ° C. and 1 rpm using a cone and plate viscometer, and was measured at 25 ° C. and 10 rpm using a cone and plate viscometer It means the value divided by the viscosity.

In the adhesive composition of the present invention, the optical density (OD value) of a 1 mm thick cured product after curing is preferably 1 or more. When the OD value is 1 or more, the light shielding property is excellent, and when used in a display element, light leakage can be prevented, and high contrast can be obtained. The OD value is more preferably 1.5 or more.
The higher the OD value, the better. However, if too much a light shielding agent is blended to increase the OD value, workability is reduced due to thickening, etc., to balance the compounding amount of the light shielding agent The preferable upper limit of the OD value of the cured product is 4.
The OD value after curing of the adhesive composition can be measured using an optical densitometer.

The adhesive composition of the present invention can be easily peeled off by heating during rework after curing.
The preferable lower limit of the heating temperature at the time of rework is 60 ° C., and the preferable upper limit is 120 ° C. When the heating temperature is in this range, it can be easily peeled off without damaging the electronic parts and the like. The more preferable lower limit of the heating temperature at the time of rework is 75 ° C., and the more preferable upper limit is 110 ° C.

The cured product of the adhesive composition of the present invention is also one of the present invention.
When the adhesive composition of the present invention before curing contains a moisture-curable urethane resin, the cured product of the present invention has a urea bond and / or a urethane bond. The components contained in the cured product of the present invention are the components contained in the adhesive composition of the present invention and the components obtained by changing the components upon curing of the adhesive composition of the present invention.

The cured product of the present invention is suitable because when the above-mentioned wax is present as the above-described wax fine particles in the cured product, the contact area between the resin and the wax is increased, and the reworkability is excellent.
The smaller the particle diameter of the wax fine particles in the cured product, the better, and the preferred upper limit is 300 μm. By the particle diameter of the said wax particle | grain being 300 micrometers or less, it becomes what is excellent by rework property. The upper limit of the particle diameter of the wax fine particles in the cured product is preferably 250 μm, more preferably 100 μm, still more preferably 50 μm, and particularly preferably 10 μm.
The lower limit of the particle diameter of the wax fine particles in the cured product is not particularly limited, but the substantial lower limit is 0.1 μm.
The particle diameter of the wax fine particles in the cured product can be measured by observing the cut surface of the cured product using a scanning electron microscope, a transmission electron microscope, a laser microscope or the like. As a preferable measurement method, a cross section of the cured product is exposed using a cryomicrotome, the cross section is observed using a scanning electron microscope, and the particle sizes of 50 randomly selected particles are measured, and the average value is measured. There is a method of calculating

The temperature of 10 ° C. at which the change rate of the storage elastic modulus ((storage elastic modulus at high temperature side) / (storage elastic modulus at low temperature side) is the largest among the temperatures of 60 ° C. to 130 ° C. It is preferable that the change rate of the storage elastic modulus in the above is 0.6 or less. When the rate of change of the storage elastic modulus is 0.6 or less, the cured product of the present invention is excellent in adhesion stability at the time of adhesion and at the time of rework, because the adhesion is reduced, it becomes more excellent in rework workability. A more preferable upper limit of the rate of change of the storage elastic modulus is 0.55, and a still more preferable upper limit is 0.45.

The cured product of the present invention has an energy amount per unit time at the peak top of the endotherm of the cured product in differential scanning calorimetry A, and an energy amount per unit time of the moisture curable resin at the measurement temperature of A, Assuming that the energy amount per unit time of the wax at the measurement temperature of A is C, and the content of the wax in the cured product is X wt%, it is preferable to satisfy the following formula.
(A−B) / (C × X / 100) ≧ 50
By satisfy | filling the said Formula, the hardened | cured material of this invention becomes what is excellent by rework property.
The more preferable lower limit of (A−B) / (C × X / 100) is 60, and the still more preferable lower limit is 70.

An electronic component having a cured product of the adhesive composition of the present invention is also one of the present invention. The adhesive composition of the present invention exhibits the above-described excellent effects particularly in an electronic component that requires miniaturization. In the electronic component of the present invention, the adhesive composition of the present invention is mainly used for adhesion of adherends.

As adherends that can be adhered using the adhesive composition of the present invention, various adherends such as metal, glass, plastic and the like can be mentioned.
Examples of the shape of the adherend include a film, a sheet, a plate, a panel, a tray, a rod (rod), a box, and a housing.

As said metal, steel, stainless steel, aluminum, copper, nickel, chromium, or its alloy etc. are mentioned, for example.
As said glass, an alkali glass, an alkali free glass, quartz glass etc. are mentioned, for example.
Examples of the plastic include polyolefin resins such as high density polyethylene, ultra high molecular weight polyethylene, isotactic polypropylene, syndiotactic polypropylene, ethylene propylene copolymer resin, nylon 6 (N 6), nylon 66 (N 66), Nylon 46 (N46), nylon 11 (N11), nylon 12 (N12), nylon 610 (N610), nylon 612 (N612), nylon 6/66 copolymer (N6 / 66), nylon 6/66/610 Polymer (N6 / 66/610), Nylon MXD6 (MXD6), Nylon 6T, Nylon 6 / 6T copolymer, Nylon 66 / PP copolymer, Polyamide resin such as nylon 66 / PPS copolymer, Polybutylene Terephthalate (PBT), polyethylene Rephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimido diacid / polybutylene terephthalate copolymer, etc. Aromatic polyester resins, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene copolymer, etc. Resin, polycarbonate, polymethyl methacrylate (PMMA), polymethacrylate resin such as polyethyl methacrylate, ethylene / vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), vinyl alcohol Polyvinyl resins such as ethylene / ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, etc. .

In addition, as the adherend, a composite material having a metal plating layer on the surface can also be mentioned, and as a base material for plating of the composite material, for example, the above-mentioned metals, glass, plastics and the like can be mentioned.
Furthermore, as the adherend, materials in which a passivation film is formed by passivating the metal surface can also be mentioned, and as the passivation treatment, for example, heat treatment, anodizing treatment, etc. can be mentioned. . In particular, in the case of an aluminum alloy or the like in which the international aluminum alloy name is a material of the 6000th series, the adhesiveness can be improved by performing a sulfuric acid alumite treatment or a phosphoric acid alumite treatment as the passivation treatment.

In addition, it has a first substrate, a second substrate, and a cured product of the adhesive composition of the present invention, and at least a portion of the first substrate corresponds to at least a portion of the second substrate and the above. Assembly parts joined via a cured body of adhesive composition are also part of the invention.
Each of the first substrate and the second substrate preferably has at least one electronic component.

ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition which is excellent in adhesiveness and can be easily reworked in low temperature can be provided. Further, according to the present invention, it is possible to provide a cured product of the adhesive composition, and an electronic component and an assembled part having the cured product of the adhesive composition.

It is a schematic diagram which shows the adhesion state of the to-be-adhered body by the adhesive composition of this invention in, when the thickness of an adhesive layer is small (a) and (b) large. (A) is a schematic diagram which shows the case where the sample for rework property evaluation is seen from the top, (b) is a schematic diagram which shows the case where the sample for rework property evaluation is seen from the side.

EXAMPLES The present invention will be described in more detail by way of the following examples, but the present invention is not limited to these examples.

Synthesis Example 1 (Preparation of Moisture-Curable Urethane Resin)
In a 500 mL separable flask, 100 parts by weight of polytetramethylene ether glycol ("PTMG-2000" manufactured by Mitsubishi Chemical Corporation) and 0.01 parts by weight of dibutyltin dilaurate as a polyol compound are placed under vacuum (20 mmHg) Below, it stirred for 30 minutes at 100 degreeC, and mixed. Thereafter, under normal pressure, 26.5 parts by weight of diphenylmethane diisocyanate ("Pure MDI", manufactured by Nippon Soda Co., Ltd.) is added as a polyisocyanate compound, and the mixture is reacted by stirring at 80 ° C for 3 hours to react. Molecular weight 2700) was obtained.

(Examples 1 to 6, Comparative Example 1)
According to the compounding ratio described in Table 1, each material was stirred by a planetary stirrer ("Awatori Neritaro" manufactured by Shinky Co., Ltd.), and then uniformly mixed by three ceramic rolls to obtain Example 1 The adhesive composition of -6 and the comparative example 1 was obtained.

<Evaluation>
The following evaluation was performed about each adhesive composition obtained by the Example and the comparative example. The results are shown in Table 1.

(Reworkability)
Each adhesive composition obtained in Examples and Comparative Examples was applied to a polycarbonate substrate with a width of about 2 mm using a dispensing device. Thereafter, the adhesive composition is irradiated with ultraviolet light at 1000 mJ / cm ² using a UV-LED (wavelength 365 nm), a glass plate is attached to a polycarbonate substrate, a 20 g weight is placed, and moisture curing is performed by standing overnight. The sample for evaluation of reworkability was obtained.
FIG. 2 is a schematic view showing the reworkability evaluation sample viewed from above (FIG. 2A) and a schematic view showing the reworkability evaluation sample viewed from the side (FIG. 2B) showed that.
The prepared samples for evaluation of reworkability are stretched at a speed of 5 mm / sec in a shear direction at 25 ° C. and 100 ° C. using a tensile tester (“Ez-Graph” manufactured by Shimadzu Corporation), polycarbonate substrate and glass plate The strength (adhesion strength) when peeling off was measured. As a result, when the ratio of the adhesive strength at 100 ° C. to the adhesive strength at 25 ° C. ((adhesive strength at 100 ° C.) / (Adhesive strength at 25 ° C.)) is 0.3 or less, “を” If more than 0.3 and 0.5 or less, "○" If more than 0.5 and 0.7 or less, "△", if over 0.7 as "X" rework The sex was evaluated.

(Rate of change of storage modulus)
Each adhesive composition obtained in Examples and Comparative Examples is cast into a Teflon (registered trademark) type having a width of 3 mm, a length of 30 mm, and a thickness of 1 mm, and UV light of 1000 mJ / using a UV-LED (wavelength 365 nm). After photocuring by cm ² irradiation, it was allowed to stand for 3 days to allow moisture curing to obtain a cured product.
The obtained cured product was stretched using a dynamic viscoelasticity measuring apparatus ("DVA-200" manufactured by IT Measurement & Control Co., Ltd.), deformation mode: set strain: 1%, measurement frequency: 1 Hz, temperature rising rate: Dynamic viscoelasticity was measured in the range of 40 ° C. to 150 ° C. under the condition of 5 ° C./min, and the storage elastic modulus at each temperature was determined. About the obtained storage elastic modulus, the change rate of the storage elastic modulus at a temperature interval of 10 ° C. at which the change amount of the storage elastic modulus is the largest among the temperatures of 60 ° C. or more and 130 ° C. or less was calculated by the following equation.
Storage elastic modulus change ratio = (high temperature side storage elastic modulus) / (low temperature side storage elastic modulus)

(Influence of wax in heat measurement)
A differential scanning calorimeter (TA Instruments, Inc.) is used for a cured product of each adhesive composition obtained in the same manner as the above “(rate of change of storage elastic modulus)” and a single wax used for each adhesive composition. Calorie change accompanying temperature change was measured using a product, "DSC Q100". The amount of energy per unit time at the peak endothermic peak of the cured product is A, the amount of energy per unit time of the moisture curable resin at the measurement temperature of A, the amount of energy per unit time of the moisture curable resin at the measurement temperature of A, per unit time of wax Assuming that the amount of energy is C and the content of wax in the cured product is X wt%, the degree of influence of the wax in heat measurement is calculated by the following equation.
Degree of influence of wax in calorimetry measurement = (A-B) / (C x X / 100)
In addition, the measurement of the said calorie | heat amount change was implemented on the following measurement conditions, and made the obtained measured value A, B, and C, respectively.
<Measurement conditions>
Atmosphere: Nitrogen (flow rate 40 mL / min)
Heating rate: 10 ° C / min
Sample amount: 10 mg
In addition, since the adhesive composition obtained by the comparative example 1 is a thing which does not contain a wax, this evaluation was not performed.

ADVANTAGE OF THE INVENTION According to this invention, the adhesive composition which is excellent in adhesiveness and can be easily reworked in low temperature can be provided. Further, according to the present invention, it is possible to provide a cured product of the adhesive composition, and an electronic component and an assembled part having the cured product of the adhesive composition.

1 adherend 2 adhesive composition 3 thickness of adhesive layer 4 unit area 5 wax 6 polycarbonate substrate 7 adhesive composition 8 glass plate

Claims (13)

An adhesive composition comprising a moisture-curable resin and a wax. The adhesive composition according to claim 1, wherein the wax has a melting point of 50 ° C to 140 ° C. The adhesive composition according to claim 1 or 2, wherein a content of the wax in 100 parts by weight of the adhesive composition is 1 part by weight or more and 50 parts by weight or less. 4. Adhesive composition according to claim 1, 2 or 3, characterized in that the wax is present in particulate form in the adhesive composition. The adhesive composition according to claim 4, wherein a particle diameter of the fine particles is 300 μm or less. The adhesive composition according to any one of claims 1, 2, 3, 4 and 5, wherein the moisture-curable resin is a moisture-curable urethane resin. The adhesive composition according to any one of claims 1, 2, 3, 4, 5 or 6, comprising a radically polymerizable compound and a radical photopolymerization initiator. A cured product of the adhesive composition according to claim 4, 5, 6, or 7.
A particle size of the fine particles in the cured product is 300 μm or less. A cured product of the adhesive composition according to claim 1, 2, 3, 4, 5, 6, or 7.
The change in storage modulus at a temperature interval of 10 ° C. at which the rate of change in storage modulus ((storage modulus at high temperature side) / (storage modulus at low temperature side) is largest among temperatures of 60 ° C. or more and 130 ° C. or less A cured product characterized in that the ratio is 0.6 or less. A cured product of the adhesive composition according to claim 1, 2, 3, 4, 5, 6, or 7.
The amount of energy per unit time at the peak top of the endotherm of the cured product in differential scanning calorimetry A, the amount of energy per unit time of the moisture curable resin at the measurement temperature of A, the wax at the temperature of B, A A cured product characterized by satisfying the following formula, where the energy amount per unit time is C, and the content of wax in the cured product is X wt%.
(A−B) / (C × X / 100) ≧ 50 An electronic component comprising the cured product of the adhesive composition according to any one of claims 1, 2, 3, 4, 5, 6 or 7. 8. A cured product of the adhesive composition according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the first substrate, the second substrate, and
At least a portion of the first substrate is bonded to at least a portion of the second substrate via a cured body of the adhesive composition. The assembly of claim 12, wherein the first substrate and the second substrate each have at least one electronic component.

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