Adhesive kit, film, adhesive body and method for separating adhesive bodies

Abstract

The present invention discloses an adhesive kit. The adhesive kit comprises: a main agent containing a compound having two or more isocyanate groups; and a curing agent containing a compound having two or more hydroxyl groups. At least one of the compound having two or more isocyanate groups and the compound having two or more hydroxyl groups has a disulfide bond in the molecule. At least one of the main agent and the curing agent further contains a curing catalyst. At least one of the main agent and the curing agent further contains a photo-free radical generator.

Description

Technical Field

[0001] The present invention relates to an adhesive kit, a film, an adhesive body and a method for separating an adherend. Background Art

[0002] Compositions that exhibit photofusibility and melt by light irradiation are used in various applications. For example, Patent Document 1 discloses an image forming apparatus including a recording member having a composition that exhibits photofusibility.

[0003] Previous technical literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 11-190883 Summary of the invention

[0006] Technical issues to be solved by the invention

[0007] A main object of the present invention is to provide an adhesive kit capable of obtaining a cured product of an adhesive composition exhibiting photofusibility.

[0008] Means for solving technical problems

[0009] One aspect of the present invention relates to an adhesive kit. The adhesive kit comprises: a main agent, containing a compound having two or more isocyanate groups; and a curing agent, containing a compound having two or more hydroxyl groups. At least one of the compound having two or more isocyanate groups and the compound having two or more hydroxyl groups has a disulfide bond in the molecule. At least one of the main agent and the curing agent also contains a curing catalyst. At least one of the main agent and the curing agent also contains a photoradical generator. According to this adhesive kit, by mixing the main agent and the curing agent, an adhesive composition containing the main agent and the curing agent can be obtained, and by further curing the adhesive composition, a cured product of the adhesive composition can be obtained. Here, it can be inferred that the formation of the cured product of the adhesive composition is manifested in the following manner, that is, the isocyanate group in the compound having two or more isocyanate groups of the main agent in the adhesive composition reacts with the hydroxyl group in the compound having two or more hydroxyl groups of the curing agent to form a high molecular weight.

[0010] The cured product of the adhesive composition shows photofusibility based on the irradiation of light. Regarding the reason for showing such photofusibility, the inventors of the present invention and others believe as follows. The cured product of the adhesive composition is a reaction product of a compound having an isocyanate group and a compound having a hydroxyl group, and is formed by reacting a compound having an isocyanate group with a compound having a hydroxyl group and high molecular weight (polymerization). Therefore, the cured product of the adhesive composition can include a polymer, which includes a monomer unit having an isocyanate group and a monomer unit having a hydroxyl group. At this time, since at least one of the compound having an isocyanate group (monomer unit) and the compound having a hydroxyl group (monomer unit) has a disulfide bond in the molecule, the polymer has a disulfide bond in the molecule. Here, when the cured product of the adhesive composition is irradiated with light, the disulfide bond in the polymer is decomposed (cleaved) to generate thiol radicals. At this time, it is believed that if there is a photo radical generator in the cured product of the adhesive composition, the thiol radical reacts with the photo radical generator, and the cured product of the adhesive composition is low molecular weight, so that the cured product of the adhesive composition melts. This reaction can be said to be an irreversible reaction. In addition, the following reaction mechanism can also be considered: the photoinduced free radicals generated by the photoradical generator directly react with the disulfide bond, resulting in the formation of a photoinduced free radical-thioether bond and the generation of a thiol free radical, and the thiol free radical reacts with other photoinduced free radicals, that is, the compound having a disulfide bond itself does not undergo a cleavage step to reduce the molecular weight.

[0011] One form of the curing catalyst is a tin-based curing catalyst. When a tin-based curing catalyst is used as a curing catalyst, the time until the adhesive composition is cured can be further extended. By extending the curing time of the adhesive composition, the usable time can be longer, thereby further improving operability. Another form of the curing catalyst is a zirconium-based curing catalyst. When a zirconium-based curing catalyst is used as a curing catalyst, an adhesive composition showing higher bonding force can be prepared.

[0012] Another aspect of the present invention relates to a film. One aspect of the film contains a cured product of an adhesive composition comprising a main agent and a curing agent in the above-mentioned adhesive set. Another aspect of the film contains: a polymer comprising a monomer unit having two or more isocyanate groups and a monomer unit having two or more hydroxyl groups; and a photoradical generator. In another aspect of the film, at least one of the monomer unit having two or more isocyanate groups and the monomer unit having two or more hydroxyl groups has a disulfide bond in the molecule.

[0013] These films contain a cured product of an adhesive composition containing a main agent and a curing agent, or a polymer containing a monomer unit having two or more isocyanate groups and a monomer unit having two or more hydroxyl groups. At this time, at least one of the compound (monomer unit) having an isocyanate group and the compound (monomer unit) having a hydroxyl group has a disulfide bond in the molecule. Furthermore, these films contain a photoradical generator. Therefore, these films can become films that show photofusibility by irradiation with light.

[0014] Another aspect of the present invention relates to an adhesive body. The adhesive body comprises: a first adherend; a second adherend; and an adhesive layer for bonding the first adherend and the second adherend to each other. The adhesive layer contains a cured product of an adhesive composition comprising a main agent and a curing agent in the adhesive set.

[0015] Another aspect of the present invention relates to a method for separating an adherend from an adhesive body, wherein the method comprises the step of irradiating an adhesive layer of the adhesive body with light to separate a first adherend from a second adherend.

[0016] Effects of the Invention

[0017] According to the present invention, there is provided an adhesive kit capable of obtaining a cured product of an adhesive composition exhibiting light melting properties. Several types of adhesive kits can extend the time until the adhesive composition is cured. Furthermore, several types of adhesive kits can prepare an adhesive composition exhibiting higher adhesive force. Furthermore, according to the present invention, there is provided an adhesive body using such an adhesive kit and a method for separating an adherend from the adhesive body. DETAILED DESCRIPTION

[0018] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

[0019] In this specification, the numerical range indicated by "~" indicates a range including the numerical values ​​recorded before and after "~" as the minimum and maximum values, respectively. In the numerical range recorded in stages in this specification, the upper limit or lower limit of the numerical range of a certain stage can be replaced by the upper limit or lower limit of the numerical range of another stage. Moreover, in the numerical range recorded in this specification, the upper limit or lower limit of the numerical range can be replaced by the value shown in the embodiment. Moreover, the upper limit and lower limit recorded individually can be combined arbitrarily. Moreover, in this specification, "(meth)acrylate" refers to at least one of acrylate and its corresponding methacrylate. The same is true in other similar expressions such as "(meth)acryloyl". Moreover, "A or B" can include either A and B, or both. Moreover, with respect to the materials exemplified below, unless otherwise specified, one can be used alone, or two or more can be used in combination. With respect to the content of each component in the composition, when there are multiple substances equivalent to each component in the composition, unless otherwise specified, it refers to the total amount of the multiple substances present in the composition.

[0020] [Adhesive Set]

[0021] An adhesive set of one embodiment comprises: a main agent containing a compound having two or more isocyanate groups; and a curing agent containing a compound having two or more hydroxyl groups. The adhesive set of this embodiment can obtain an adhesive composition containing the main agent and the curing agent by mixing the main agent and the curing agent, and can obtain a cured product of the adhesive composition by further curing the adhesive composition.

[0022] The main agent contains a compound having two or more isocyanate groups (hereinafter, sometimes referred to as "(A) component".). The curing agent contains a compound having two or more hydroxyl groups (hereinafter, sometimes referred to as "(B) component".). From the perspective of exhibiting photofusibility, at least one of the (A) component and the (B) component has a disulfide bond in the molecule. At least one of the main agent and the curing agent also contains a curing catalyst (hereinafter, sometimes referred to as "(C) component".). At least one of the main agent and the curing agent also contains a photoradical generator (hereinafter, sometimes referred to as "(D) component".). At least one of the main agent and the curing agent also contains any one of a sensitizer, etc. The following describes each component.

[0023] Component (A): Compound having two or more isocyanate groups

[0024] The component (A) may be a compound having two or more isocyanate groups and having a disulfide bond (hereinafter, sometimes referred to as "component (A1)"). Or a compound having two or more isocyanate groups and not having a disulfide bond (hereinafter, sometimes referred to as "component (A2)").

[0025] The component (A1) is not particularly limited as long as it has two or more isocyanate groups and a disulfide bond, but the component (A1) is reduced in molecular weight by light irradiation, and thus may be a high molecular weight component of a polymer or oligomer. The component (A1) may be used alone or in combination of two or more. The component (A1) preferably has a plurality of (two or more) disulfide bonds in the molecule.

[0026] The component (A1) may be, for example, a copolymer obtained by reacting a compound having a disulfide bond and a functional group (hereinafter, sometimes referred to as the "component (A1-a)") with a compound having an isocyanate group and a substituent capable of reacting with the functional group (hereinafter, sometimes referred to as the "component (A1-b)"), in other words, a reactant of the component (A1-a) and the component (A1-b), that is, a copolymer containing monomer units of the component (A1-a) and monomer units of the component (A1-b).

[0027] As long as the component (A1-a) is a compound having a disulfide bond and a functional group, it can be used without particular limitation. Here, as the functional group in the component (A1-a), for example, a thiol group, a carboxyl group, an amino group, etc. can be cited. The functional group in the component (A1-a), for example, can be at least one selected from the group consisting of a thiol group and a carboxyl group. From the viewpoint of high molecular weight, the number of functional groups of the component (A1-a) can be more than 2. On the other hand, the lower the crosslinking degree of the component (A), the easier it is to melt the cured product of the adhesive composition when it is irradiated with light, so as the component (A1-a), it is preferred to use a compound having a functional group number of 2. When using a plurality of compounds having different functional group numbers, it is preferred to increase the proportion of compounds having a functional group number of 2.

[0028] Examples of the component (A1-a) include Thiokol LP series (dithiol having a disulfide bond, manufactured by Toray Fine Chemicals Co., Ltd.), 3,3'-dithiodipropionic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), etc. These components (A1-a) may be used alone or in combination of two or more.

[0029] As long as the component (A1-b) is a compound having an isocyanate group and a substituent capable of reacting with a functional group, it can be used without particular limitation. Here, as the substituent in the component (A1-b), for example, an isocyanate group, a (meth)acryloyl group, an aldehyde group, etc. can be cited. The substituent in the component (A1-b) can be, for example, an isocyanate group. Regarding the component (A1-b), from the viewpoint of reacting with the functional group of the component (A1-a) to generate a compound having an isocyanate group, the component (A1-b) can be a compound having 1 isocyanate group and 1 substituent group, or can be a compound having 2 isocyanate groups.

[0030] As the component (A1-b), for example, aromatic polyisocyanates such as diphenylmethane diisocyanate, dimethyl diphenylmethane diisocyanate, toluene diisocyanate, meta-xylylene diisocyanate, p-phenylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc. can be mentioned. These (A1-b) components can be used alone or in combination of two or more.

[0031] A preferred combination of the component (A1-a) and the component (A1-b) may be, for example, a combination of a compound having a disulfide bond and two thiol groups and a compound having two isocyanate groups.

[0032] When reacting the components (A1-a) and (A1-b) to obtain a copolymer as the component (A1), the reaction ratio of these components can be appropriately adjusted according to the functional group equivalent of the component (A1-a) and the substituent equivalent of the component (A1-b) so that the obtained component (A1) has two or more isocyanate groups. The reaction of the components (A1-a) and (A1-b) can be carried out while heating. The reaction temperature can be, for example, 0 to 200° C., and the reaction time can be, for example, 0.1 to 240 hours.

[0033] When reacting the components (A1-a) and (A1-b), a curing catalyst (hereinafter sometimes referred to as "component (A1-c)") may be used as needed. The component (A1-c) can be arbitrarily selected in accordance with the type of functional group of the component (A1-a) and the type of substituent of the component (A1-b). When reacting a compound having a thiol group as a functional group as the component (A1-a) and a compound having an isocyanate group as a substituent as the component (A1-b), the component (A1-c) may be, for example, a tin-based curing catalyst or an amine-based curing catalyst.

[0034] Tin-based curing catalysts may be, for example, tin compounds having tin and an organic group (alkyl, carboxylate, etc.). Examples of tin-based curing catalysts include dibutyltin dilaurate, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, bis(tributyltin) sulfide, bis(tributyltin) oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate, etc.

[0035] Amine curing catalysts may be, for example, (tertiary) amine compounds, imidazole compounds, etc. Examples of amine curing catalysts include triethylamine, triethylenediamine (TEDA), 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), and 1-isobutyl-2-methylimidazole (IBM).

[0036] The content of the component (A1-c) may be 0.005 to 10% by mass, 0.01 to 5% by mass, or 0.02 to 3% by mass based on the total of the components (A1-a) and (A1-b).

[0037] The molecular weight or weight average molecular weight of the component (A1) may be 200 to 10,000,000, 1,000 to 2,000,000, or 2,500 to 1,000,000. The weight average molecular weight is a polystyrene conversion value obtained by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

[0038] As long as the component (A2) has two or more isocyanate groups and does not have a disulfide bond, it can be used without particular limitation. The component (A2) can be exemplified by the same compound as the compound in the component (A1-b). The component (A2) can be a polymer of a compound having two or more isocyanate groups. As such a polymer, for example, polymers of aliphatic diisocyanates such as hexamethylene diisocyanate (HDI); polymers of aromatic diisocyanates such as diphenylmethane diisocyanate (MDI), etc. can be cited. The polymer of aliphatic diisocyanates can be, for example, a trimer of aliphatic diisocyanates (adducts of isocyanurate, biuret or trimethylolpropane (TMP)).

[0039] For example, based on the total amount of the main agent and the curing agent, the content of component (A) can be more than 0.5 mass%, more than 1 mass%, more than 5 mass% or more than 10 mass%, or it can be less than 80 mass%, less than 70 mass%, less than 60 mass% or less than 55 mass%.

[0040] Component (B): Compound having two or more hydroxyl groups

[0041] The component (B) may be a compound having two or more hydroxyl groups and having a disulfide bond (hereinafter, sometimes referred to as "component (B1)"). Or a compound having two or more hydroxyl groups and not having a disulfide bond (hereinafter, sometimes referred to as "component (B2)").

[0042] There are no particular limitations on the component (B1) as long as it has two or more hydroxyl groups and a disulfide bond. However, the component (B1) is reduced in molecular weight by light irradiation, and thus may be a high molecular weight component of a polymer or oligomer. The component (B1) may be used alone or in combination of two or more. The component (B1) preferably has a plurality of (two or more) disulfide bonds in the molecule.

[0043] The component (B1) may be, for example, a copolymer obtained by reacting a compound having a disulfide bond and a functional group (hereinafter, sometimes referred to as the "component (B1-a)") with a compound having a hydroxyl group and a substituent capable of reacting with the functional group (hereinafter, sometimes referred to as the "component (B1-b)"), in other words, a reactant of the component (B1-a) and the component (B1-b), that is, a copolymer containing monomer units of the component (B1-a) and monomer units of the component (B1-b).

[0044] Examples of the component (B1-a) include the compounds exemplified as the component (A1-a).

[0045] As long as the component (B1-b) is a compound having a hydroxyl group and a substituent capable of reacting with a functional group, it can be used without particular limitation. Here, as the substituent in the component (B1-b), for example, a group containing a cyclic ether (for example, a glycidyl group, etc.), a (meth)acryloyl group, an aldehyde group, etc. can be cited. The substituent in the component (B1-b) can be, for example, a (meth)acryloyl group. Regarding the component (B1-b), from the viewpoint of reacting with the functional group of the component (B1-a) to generate a compound having a hydroxyl group, the component (B1-b) can be a compound having 1 hydroxyl group and 1 substituent group, or a compound having 1 hydroxyl group and 1 (meth)acryloyl group.

[0046] Examples of the component (B1-b) include (meth)acrylates having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 1-hydroxybutyl (meth)acrylate. These components (B1-b) may be used alone or in combination of two or more.

[0047] A preferred combination of the component (B1-a) and the component (B1-b) may be, for example, a combination of a compound having a disulfide bond and two thiol groups and a compound having one hydroxyl group and one (meth)acryloyl group.

[0048] When the component (B1-a) and the component (B1-b) are reacted to obtain a copolymer as the component (B1), the reaction ratio of these components can be appropriately adjusted according to the functional group equivalent of the component (B1-a) and the substituent equivalent of the component (B1-b) so that the obtained component (B1) has two or more hydroxyl groups. The reaction of the component (B1-a) and the component (B1-b) can be carried out while heating. The reaction temperature can be, for example, 0 to 200° C., and the reaction time can be, for example, 0.1 to 240 hours.

[0049] When reacting component (B1-a) with component (B1-b), a curing catalyst (hereinafter sometimes referred to as "component (B1-c)") can be used as needed. Component (B1-c) can be arbitrarily selected corresponding to the type of functional group of component (B1-a) and the type of substituent of component (B1-b). When reacting a compound having a thiol group as a functional group as component (B1-a) with a compound having a (meth)acryloyl group as a substituent as component (B1-b), component (B1-c) can be, for example, a tin-based curing catalyst or an amine-based curing catalyst. Examples of tin-based curing catalysts and amine-based curing catalysts include the same curing catalysts as the tin-based curing catalysts and amine-based curing catalysts in component (A1-c).

[0050] The content of the component (B1-c) may be 0.005 to 10% by mass, 0.01 to 5% by mass, or 0.02 to 3% by mass based on the total of the components (B1-a) and (B1-b).

[0051] The molecular weight or weight average molecular weight of the component (B1) may be 200 to 10,000,000, 1,000 to 2,000,000, or 2,500 to 1,000,000. The weight average molecular weight is a polystyrene conversion value obtained by gel permeation chromatography (GPC) using a calibration curve based on standard polystyrene.

[0052] As long as the component (B2) has two or more hydroxyl groups and does not have a disulfide bond, it can be used without particular limitation. Examples of the component (B2) include polyester polyols, polyether polyols, polypropionate polyols, polycarbonate polyols, polysiloxane polyols, polyisoprene polyols, polyolefin polyols, and the like. The component (B2) may be used alone or in combination of two or more.

[0053] Based on the total amount of the main agent and the curing agent, the content of component (B) can be, for example, more than 20 mass %, more than 25 mass %, more than 30 mass % or more than 35 mass %, or less than 95 mass %, less than 92 mass %, less than 90 mass % or less than 88 mass %.

[0054] From the viewpoint of developing photofusability, at least one of the components (A) and (B) contains a compound having a disulfide bond in the molecule. That is, the adhesive kit contains at least one compound selected from the group consisting of the component (A1) as the component (A) and the component (B1) as the component (B). Based on the total amount of the main agent and the curing agent, the content (total amount) of the components (A1) and (B1) may be 50% by mass or more, 60% by mass or more, 70% by mass or more, or 75% by mass or less, or 99% by mass or less, 98% by mass or less, 97% by mass or less, or 96% by mass or less.

[0055] (C) Component: Curing Catalyst

[0056] The component (C) is a catalyst for promoting the reaction between the components (A) and (B). The component (C) only needs to be contained in at least one of the main agent and the curing agent, but from the viewpoint of curing stability and storage stability, it is preferably contained in the curing agent. As the component (C), for example, tin-based curing catalysts, amine-based curing catalysts, zirconium-based curing catalysts, etc. can be cited. The component (C) can be used alone or in combination of two or more.

[0057] Tin-based curing catalysts can be exemplified by the same curing catalysts as those in component (A1-c). As component (C), by using a tin-based curing catalyst, the curing time of the adhesive composition can be extended. By extending the curing time of the adhesive composition, the usable time can be extended, thereby further improving operability.

[0058] Examples of the amine-based curing catalyst include the same ones as those in the component (A1-c).

[0059] The zirconium-based curing catalyst may be, for example, a zirconium compound having zirconium and an organic group (alkyl, carboxylate, etc.). Examples of the zirconium-based curing catalyst include tetra-n-propyl zirconate, tetra-n-butyl zirconate, zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium dibutoxybis(ethyl acetylacetate), and zirconium octanoate compounds. By using a zirconium-based curing catalyst as component (C), an adhesive composition exhibiting higher adhesive strength can be prepared.

[0060] Based on the total amount of the main agent and the curing agent, the content of component (C) may be 0.001 mass %, 0.01 mass %, 0.05 mass % or 0.1 mass %, or less than 10 mass %, 5 mass %, 3 mass % or less than 1 mass %.

[0061] (D) Ingredient: Photoradical Generator

[0062] The component (D) may be a component that reacts with thiol radicals generated when the cured product of the adhesive composition is irradiated with light or a component that generates photoinduced radicals. The component (D) may be contained in at least one of the main agent and the curing agent, but is preferably contained in the main agent from the viewpoint of curing stability and storage stability.

[0063] Examples of the photoradical generator include intramolecular cleavage-type photoradical polymerization initiators and dehydrogenation-type photoradical polymerization initiators. Examples of the intramolecular cleavage-type photoradical polymerization initiators include benzyl ketal-based photoradical polymerization initiators; α-hydroxyacetophenone-based photoradical polymerization initiators; benzoin-based photoradical polymerization initiators; aminoacetophenone-based photoradical polymerization initiators; oxime-based photoradical polymerization initiators; acylphosphine oxide-based photoradical polymerization initiators; titanocene-based photoradical polymerization initiators; thiobenzoic acid S-phenyl polymerization initiators; and high molecular weight derivatives thereof. Examples of the dehydrogenation-type photoradical polymerization initiators include benzophenone-based photoradical initiators, thioxanthone-based photoradical polymerization initiators, and anthraquinone-based photoradical polymerization initiators.

[0064] Based on the total amount of the main agent and the curing agent, the content of component (D) can be more than 0.1 mass%, more than 1 mass%, more than 3 mass% or more than 5 mass%, or less than 50 mass%, less than 40 mass%, less than 30 mass% or less than 20 mass%.

[0065] At least one of the main agent and the curing agent may further contain a sensitizer or the like.

[0066] The sensitizer is not particularly limited, and a known triplet sensitizer can be used. Examples of the sensitizer include benzoic acid-based photosensitizers and amine-based photosensitizers. The sensitizer may be used alone or in combination of two or more.

[0067] The content of the sensitizer may be 0.1 to 10% by mass, 0.5 to 8% by mass, or 1 to 5% by mass, based on the total amount of the main agent and the curing agent.

[0068] At least one of the main agent and the curing agent may contain, in addition to the above-mentioned (A) to (D) components and the sensitizer, other components such as a coupling agent or other adhesion enhancer, a polymerization inhibitor, a light stabilizer, a defoamer, a filler, a chain transfer agent, a thixotropic agent, a flame retardant, a mold release agent, a surfactant, a lubricant, an antistatic agent, and other additives. These additives can use known additives. Based on the total amount of the main agent and the curing agent, the content (total amount) of the other components may be 0.01 to 20% by mass or 0.1 to 10% by mass.

[0069] When the main agent and the curing agent are mixed, the equivalent ratio (molar ratio) of the isocyanate group of the component (A) to the hydroxyl group of the component (B) (NCO group / OH group) may be, for example, 0.76 to 1.3.

[0070] The adhesive kit of this embodiment can prepare an adhesive composition by mixing a main agent and a curing agent. The temperature and time when mixing the main agent and the curing agent can be, for example, 10 to 35° C. and 0.1 to 60 minutes.

[0071] Examples of a method for mixing the main agent and the curing agent include a method of manually mixing using a spatula, a method of mixing by hand using a conventional caulking gun, a method of mixing using a pump (e.g., a gear pump, a plunger pump, etc.) and a throttle valve for conveying raw materials and having a quantitative function, a method of mixing using a mechanical rotary mixer, a static mixer, and the like, and the like.

[0072] The prepared adhesive composition can be cured to form a cured product of the adhesive composition, and can function as an adhesive layer for bonding adherends to each other. The conditions for curing the adhesive composition (curing conditions) can be, for example, 10 to 35° C., 30 to 60% RH (relative humidity), and 0.1 to 7 days.

[0073] The cured product of the adhesive composition has the following properties, that is, by light irradiation, the disulfide bond (-SS-) in the cured product is broken, and the compound with the disulfide bond is low-molecular and melted. By utilizing this property, the cured product of the adhesive composition can be applied to the purpose of the photoresist of the photolithography method, for example. The cured products of these adhesive compositions can be patterned by light irradiation (exposure), and then, after light irradiation (exposure), for example, it can be developed by washing with water. The cured product of the adhesive composition can be suitably used for the formation of patterned films. In addition, the adhesive composition comprising a main agent and a curing agent has adhesion, and the cured product of the adhesive composition has light melting properties based on light irradiation. Therefore, the adhesive composition can also be used as an adhesive with repairability.

[0074] The light used in the light irradiation is not particularly limited, and may be, for example, ultraviolet light or visible light. The wavelength of the light used in the light irradiation may be 150 to 830 nm. The light irradiation may be performed using, for example, a light irradiation device at an irradiation dose of 100 mJ / cm 2 The above conditions are carried out. In addition, the irradiation amount refers to the product of the illuminance and the irradiation time (seconds). In addition, as a light source for ultraviolet light or visible light irradiation, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an LED lamp, etc. can be cited. The cured product of the adhesive composition can be irradiated with light directly or through glass.

[0075] The cured product of the adhesive composition may be irradiated with light while being heated. The heating conditions may be, for example, 40 to 200°C.

[0076] [membrane]

[0077] The film of one embodiment is a film containing a cured product of an adhesive composition including a main agent and a curing agent in the above-mentioned adhesive set. The film can also be referred to as a film containing: a polymer including a monomer unit having two or more isocyanate groups and a monomer unit having two or more hydroxyl groups; and a photo radical generator, wherein at least one of the monomer unit having two or more isocyanate groups and the monomer unit having two or more hydroxyl groups includes a monomer unit having a disulfide bond in the molecule.

[0078] The film can be obtained, for example, by forming an adhesive composition containing a main agent and a curing agent into a film to prepare an adhesive film, and aging (curing) the obtained adhesive film under the same conditions as above. Here, the adhesive film contains a cured product of the adhesive composition containing the main agent and the curing agent in the above-mentioned adhesive set.

[0079] The thickness of the film is not particularly limited, and may be, for example, 5 to 300 μm, 20 to 200 μm, or 60 to 180 μm.

[0080] [Adhesive body]

[0081] An adhesive body according to one embodiment comprises: a first adherend; a second adherend; and an adhesive layer for bonding the first adherend and the second adherend to each other. The adhesive layer contains a cured product of the adhesive composition comprising a base agent and a curing agent in the adhesive set described above.

[0082] Examples of the first adherend and the second adherend include plastics such as polyolefin resins, polyamide resins, ABS (acrylonitrile-butadiene-styrene) resins, PC (polycarbonate) resins, PET (polyethylene terephthalate) resins, PPS (polyphenylene sulfide) resins, and acrylic resins; inorganic materials such as steel, stainless steel, metals (aluminum, copper, nickel, chromium, etc.) or alloys of these metals, glass, and silicon wafers; wood; rubber, etc. Furthermore, examples of the first adherend and the second adherend include materials obtained by combining the above-mentioned plastics with the above-mentioned inorganic materials.

[0083] The adhesive body can be obtained by the following method: the method comprises the step of bonding the first adhesive body and the second adhesive body via an adhesive composition containing a main agent and a curing agent. The temperature and time when mixing the main agent and the curing agent in the adhesive set, the conditions for curing the adhesive composition, etc. can be the same as above.

[0084] [Method for separating adherends]

[0085] A method for separating adherends according to one embodiment includes the following steps: irradiating an adhesive layer of an adhesive body with light to separate a first adherend from a second adherend. Since the adhesive layer contains a cured product of an adhesive composition including a main agent and a curing agent in the adhesive set described above, the cured product of the adhesive composition can be melted by irradiating light, making it easy to separate the adherends from each other.

[0086] In the method for separating an adherend, the type of light, light source, etc. when irradiating light may be the same as those described above.

[0087] Example

[0088] The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

[0089] [Preparation of raw materials]

[0090] (Synthesis of raw materials)

[0091] Production Example 1: Compound having two or more isocyanate groups and having a disulfide bond

[0092] 400 g of Thiokol LP-55 was added to the flask, and nitrogen was added, stirred and heated to 95°C within 15 minutes. Dehydration was carried out by maintaining 95°C and reducing pressure (gauge pressure 0.1 MPa), and stirring for 2 hours and 15 minutes. After dehydration, it was cooled to room temperature (25°C). Under a nitrogen atmosphere, at room temperature (25°C), 36.6 g of HDI (hexamethylene diisocyanate, manufactured by TOSOH CORPORATION) was added to the flask, followed by 138 mg of triethylamine as a catalyst, and stirring of the mixed solution was started. After the catalyst was added, the temperature of the mixed solution rose to 40°C due to the heat of reaction. The reaction tracked the reduction rate of the isocyanate group of HDI by measuring the infrared absorption spectrum, and stirring was stopped after 3 hours when the prescribed reduction rate was reached. The reactant after stopping stirring was used as a compound having more than two hydroxyl groups and a disulfide bond in Preparation Example 1. The NCO content (%) of the compound of Production Example 1 was measured and found to be 2.16% (theoretical value: 2.09%).

[0093] Production Example 2: Compounds having two or more hydroxyl groups and a disulfide bond

[0094] 367.8 g of Thiokol LP-55 (dithiol having a disulfide bond, manufactured by Toray Fine Chemicals Co., Ltd.) and 23.2 g of HEA (hydroxyethyl acrylate, manufactured by Nippon Shokubai Co., Ltd.) were added to the flask. The mixture was stirred and heated, and DBU (1,8-diazabicyclo[5.4.0]undecene-7, manufactured by San-Apro Ltd.) was added. Thereafter, the temperature was raised to 90°C, and stirred at 90°C for 4 hours and 15 minutes. The stirred reaction product was used as a compound having two or more hydroxyl groups and a disulfide bond of Production Example 2. The hydroxyl value of the compound of Production Example 2 was measured and found to be 25.7 mg / KOHg (theoretical value: 28.7 mg / KOHg).

[0095] (Preparation of raw materials)

[0096] (A) Compounds having two or more isocyanate groups

[0097] (A1) Compounds having two or more isocyanate groups and having a disulfide bond

[0098] A1-1: Compound of Preparation Example 1

[0099] (A2) Compounds having two or more isocyanate groups and no disulfide bond

[0100] A2-1: HDI (hexamethylene diisocyanate, manufactured by TOSOH CORPORATION)

[0101] A2-2: Sumidur N3300 (hexamethylene diisocyanate type isocyanurate, manufactured by Sumika CovestroUrethane Co., Ltd.)

[0102] (B) Compounds having two or more hydroxyl groups

[0103] (B1) Compounds having two or more hydroxyl groups and having a disulfide bond

[0104] B1-1: Compound of Production Example 2

[0105] (C) Curing Catalyst

[0106] (C1) Amine curing catalyst

[0107] C1-1: DBU (1,8-diazabicyclo[5.4.0]undecene-7, manufactured by San-Apro Ltd.)

[0108] C1-2: TEDA L-33 (triethylenediamine (TEDA) in dipropylene glycol solution (33% by mass: triethylenediamine, 67% by mass: dipropylene glycol), manufactured by TOSOH CORPORATION)

[0109] C1-3: Texnol IBM-12 (1-isobutyl-2-methylimidazole, manufactured by Nippon Nyukazai Co., Ltd.)

[0110] (C2) Tin-based curing catalyst

[0111] C2-1: L101-1 (dibutyltin dilaurate, manufactured by Tokyo Fine Chemical Co., Ltd.)

[0112] (C3) Zirconium-based curing catalyst

[0113] C3-1: ZC-162 (zirconium tetraacetylacetonate, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0114] (D) Photoradical Generator

[0115] D-1: Omnirad 651 (benzyl ketal, manufactured by IGM Resins BV)

[0116] (Examples 1-1 to 1-6, Examples 2-1 to 2-4 and Examples 3-1 to 3-10)

[0117] [Adhesive kit production]

[0118] (Main agent)

[0119] The components (A) and (D) were stirred at 2000 rpm for 90 seconds using a rotation-revolution stirring device (Awatori Rentaro stirring degassing machine AR-250, manufactured by THINKY CORPORATION) in the types and proportions (unit: parts by mass) shown in Tables 1, 2, and 3, and then heated at 70° C. for 30 minutes. After cooling, the mixture was further stirred at 2000 rpm for 90 seconds to obtain a curing agent.

[0120] (Curing agent)

[0121] The (B) component and the (C) component were mixed in the types and proportions (unit: parts by mass) shown in Tables 1, 2, and 3 to obtain a curing agent.

[0122] [Confirmation of curability of adhesive composition]

[0123] The prepared main agent and the prepared curing agent were stirred for 1 minute using a spatula, and then left at room temperature (25° C.) for 24 hours or more to visually check whether curability was developed.

[0124] [Confirmation of Photofusibility of Cured Adhesive Composition]

[0125] The prepared main agent and the prepared curing agent were stirred for 1 minute using a spatula, and then placed at room temperature (25°C) for more than 24 hours to obtain a cured product of the adhesive composition. A photofusibility test was performed using the cured product of the obtained adhesive composition. In addition, regarding the photofusibility test, in order to eliminate the influence of oxygen, the cured product of the adhesive composition was clamped with a glass slide and then irradiated with light. More specifically, 0.02 g of the cured product of the adhesive composition was placed on a glass slide and then clamped with another glass slide to obtain a test sample. The cured product of the adhesive composition of the test sample was irradiated with light using an LED (365 nm, illumination: 600 mW / cm 2 ) for 80 seconds (total light intensity: about 48000mJ / cm 2 ). After irradiation, the slide glass was peeled off and the presence of liquid components was confirmed with the naked eye. Observation of liquid components means that the photofusible properties are present. The results are shown in Tables 1, 2, and 3.

[0126]

[0127]

[0128] As shown in Table 1, Table 2 and Table 3, it can be seen that by using the adhesive kits of Examples 1-1 to 1-6, Examples 2-1 to 2-4 and Examples 3-1 to 3-10, a cured product of the adhesive composition can be produced. In addition, as shown in Table 1, Table 2 and Table 3, it can be seen that the cured product of the adhesive composition exhibits photofusibility. From these results, it was confirmed that the adhesive kit of the present invention can obtain a cured product of the adhesive composition exhibiting photofusibility.

[0129] [Evaluation of curing time]

[0130] The curing time was evaluated using the adhesive sets of Examples 1-4 and 2-2 to 2-4. The prepared main agent and the prepared curing agent were stirred with a spatula for 1 minute, and then placed at room temperature (25°C), and the adhesive composition was lifted with a spatula every 5 minutes. The adhesive set composition was judged as "cured" when it was not lifted, and the curability of the adhesive composition was evaluated using the time at this time as the curing time. The results are shown in Table 4.

[0131] [Table 4]

[0132]

[0133] As shown in Table 4, it can be seen that when the adhesive sets of Examples 2-2 to 2-4 in which the curing catalyst is a tin-based curing catalyst are used, the curing time when the cured product of the adhesive composition is produced is longer than when the adhesive set of Example 1-4 in which the curing catalyst is not a tin-based curing catalyst is used.

[0134] [Evaluation of Adhesive Strength of Adhesive Composition]

[0135] Using the adhesive kits of Examples 1-4, 3-2, 3-4 and 3-5, the adhesive force of the adhesive composition was evaluated. The adhesive force of the adhesive composition was evaluated by measuring the 90° peel strength. The adhesive composition obtained by stirring the prepared main agent and the prepared curing agent for 1 minute using a spatula was arranged on a glass substrate with 150μm spacers at both ends. Then, a PET film was covered on the configured adhesive composition and applied to the entire glass substrate using a ruler to obtain a measurement laminate consisting of a glass substrate, an adhesive composition layer (thickness: 150μm) and a PET film. At this time, the width of the adhesive composition layer of the measurement laminate was set to 25mm. Using a tensile tester (manufactured by SHIMADZU CORPORATION, Autograph "AGS-1000"), the PET film was stretched from the measurement sample, and the peel strength of the adhesive composition layer relative to the glass substrate was measured. The measurement conditions were set to a stretching angle of 90° and a stretching speed of 300mm / min. The results are shown in Table 5.

[0136] [Table 5]

[0137]

[0138] As shown in Table 5, it can be seen that when the adhesive sets of Examples 3-2, 3-4 and 3-5 using a zirconium-based curing catalyst are used, the adhesive strength of the adhesive composition is higher than when the adhesive set of Example 1-4 using a non-tin-based curing catalyst is used.

[0139] Industrial Applicability

[0140] According to the present invention, there is provided an adhesive kit capable of obtaining a cured product of an adhesive composition exhibiting light melting properties. Several types of adhesive kits can extend the time until the adhesive composition is cured. Furthermore, several types of adhesive kits can prepare an adhesive composition exhibiting higher adhesive force. Furthermore, according to the present invention, there is provided an adhesive body using such an adhesive kit and a method for separating an adherend from the adhesive body.

Claims

1. An adhesive kit comprising: A main agent containing a compound having two or more isocyanate groups; and A curing agent comprising a compound having two or more hydroxyl groups, At least one of the compound having two or more isocyanate groups and the compound having two or more hydroxyl groups has a disulfide bond in the molecule, At least one of the main agent and the curing agent further contains a curing catalyst, At least one of the main agent and the curing agent further contains a photo-radical generator. The curing catalyst is a zirconium-based curing catalyst. 2 . A film comprising a cured product of an adhesive composition comprising the main agent and the curing agent in the adhesive kit according to claim 1 .

3. An adhesive body, comprising: The first bonded body; a second adherend; and an adhesive layer for bonding the first adherend and the second adherend to each other, The adhesive layer contains a cured product of the adhesive composition comprising the main agent and the curing agent in the adhesive set according to claim 1 .

4. A method for separating an adherend, which is a method for separating an adherend from the adherend according to claim 3, the method comprising the following steps: The adhesive layer of the adhesive body is irradiated with light to separate the first adherend from the second adherend.

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