Article and method for manufacturing the same

Abstract

To provide an article having improved adhesive strength between a base material and a cured matter.SOLUTION: An article according to one aspect of the invention includes a base material and a curable composition. At least a part of an adhesive surface where the curable composition and the base material are in contact is subjected to plasma processing. The curable composition includes: a component A that is an isobutylene-based polymer having 1.2 pieces or more of (meth)acryloyl groups per molecule on average; and a component B that is a radical polymerization initiator.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an article comprising a curable composition or a cured product and a substrate. The present invention also relates to a method for making the article. [Background technology]

[0002] Conventionally, curable compositions containing isobutylene polymers having (meth)acryloyl groups have been used in applications such as sealing materials and adhesives. Examples of documents disclosing such curable compositions include Patent Documents 1 and 2. Furthermore, Patent Document 3 is an example of a document disclosing a method for producing an isobutylene polymer having a (meth)acryloyl group. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-216782 [Patent Document 2] International Publication No. 2013 / 047314 [Patent Document 3] International Publication No. 2017 / 047335 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the above-mentioned conventional techniques leave room for further improvement in the adhesive strength between the substrate and the cured product.

[0005] An object of one aspect of the present invention is to provide an article having improved adhesive strength between a substrate and a cured product. [Means for solving the problem]

[0006] An article according to one aspect of the present invention is an article comprising a substrate and a curable composition, the curable composition is in contact with the substrate at an adhesive surface of the substrate, At least a portion of the adhesive surface is plasma treated; The curable composition includes the following components A and B: Component A: an isobutylene polymer having an average of 1.2 or more (meth)acryloyl groups per molecule; Component B: Radical polymerization initiator.

[0007] An article according to another aspect of the present invention is an article comprising a substrate and a cured product, the cured product is in contact with the substrate at an adhesive surface of the substrate, At least a portion of the adhesive surface is plasma treated; The cured product is obtained by curing a curable composition containing the following components A and B: Component A: an isobutylene polymer having an average of 1.2 or more (meth)acryloyl groups per molecule; Component B: Radical polymerization initiator.

[0008] A method for manufacturing an article according to one aspect of the present invention includes the following steps: Step 2a: applying a curable composition to an adhesive surface of a substrate; At least a portion of the adhesive surface is plasma treated; The curable composition includes the following components A and B: Component A: an isobutylene polymer having an average of 1.2 or more (meth)acryloyl groups per molecule; Component B: Radical polymerization initiator.

[0009] Another aspect of the present invention provides a method for manufacturing an article, the method comprising the steps of: Step 2b: curing the curable composition applied to the adhesive surface of the substrate; At least a portion of the adhesive surface is plasma treated; The curable composition includes the following components A and B: Component A: an isobutylene polymer having an average of 1.2 or more (meth)acryloyl groups per molecule; Component B: Radical polymerization initiator. [Effects of the Invention]

[0010] According to one aspect of the present invention, an article is provided in which the adhesive strength between a substrate and a cured product is improved. DETAILED DESCRIPTION OF THE INVENTION

[0011] However, the present invention is not limited to the following embodiments and various modifications may be made within the scope of the claims. Embodiments that combine technical means described in different embodiments are also included in the technical scope of the present invention.

[0012] Unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more and B or less." In this specification, "(meth)acrylic" means "acrylic and / or methacrylic." In this specification, "(meth)acryloyl" means "acryloyl and / or methacryloyl."

[0013] [1. Goods] One aspect of the present invention is an article comprising a substrate and a curable composition. In this aspect, the curable composition is uncured. In this aspect, the substrate side of the surface where the substrate and the curable composition are in contact is referred to as the adhesive surface. At least a portion of the adhesive surface is plasma-treated. Such an article can be obtained, for example, by applying the curable composition to the adhesive surface of the substrate.

[0014] Another aspect of the present invention is an article comprising a substrate and a cured product. In this aspect, the cured product is obtained by curing a curable composition. In this aspect, the surface of the substrate where the substrate and the cured product contact each other is referred to as the adhesive surface. At least a portion of the adhesive surface is plasma-treated. Such an article can be obtained, for example, by applying a curable composition to the adhesive surface of the substrate and then curing the curable composition.

[0015] 1.1. Components of the Curable Composition The curable composition contains Component A: an isobutylene polymer having an average of 1.2 or more (meth)acryloyl groups per molecule, and Component B: a radical polymerization initiator. The curable composition may optionally contain Component C: a plasticizer and / or Component D: a vinyl monomer. The curable composition may contain other components in addition to those described above. Each of these components may be contained alone or in combination of two or more. Each component will be described in detail below.

[0016] [1.1.1. Component A: Isobutylene polymer having an average of 1.2 or more (meth)acryloyl groups per molecule] Component A is an isobutylene polymer. This isobutylene polymer has (meth)acryloyl groups, the number of which is 1.2 or more on average per molecule.

[0017] The isobutylene polymer is a polymer mainly composed of units derived from isobutylene. The proportion of the isobutylene-derived units in the total weight of the isobutylene polymer is preferably 50% by weight or more, more preferably 70% by weight or more, and even more preferably 90% by weight or more.

[0018] Component A may contain units derived from a monomer other than isobutylene. Examples of such monomers include aliphatic olefins (such as 1-butene); aromatic vinyls (such as styrene, methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and α-methylstyrene); dienes (such as 1,3-butadiene and isoprene); vinyl ethers (such as butyl vinyl ether); silanes (such as vinyltrimethylsilane and allyltrimethylsilane); terpenes (such as α-pinene, β-pinene, and limonene); vinylcarbazole; and acenaphthylene. In terms of ease of copolymerization with isobutylene and favorable physical properties of the resulting copolymer, the comonomer used is preferably one or more selected from the group consisting of 1-butene, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, 1,3-butadiene, isoprene, α-pinene, β-pinene, and limonene.

[0019] The lower limit of the number of (meth)acryloyl groups contained in Component A is, on average, 1.2 or more, preferably 1.5 or more, and more preferably 1.7 or more per molecule. The upper limit of the number of (meth)acryloyl groups contained in Component A can be, on average, 10.0 or less, 8.0 or less, 6.0 or less, 4.0 or less, or 2.0 or less per molecule. The average number of (meth)acryloyl groups contained in Component A per molecule is 1 Calculated from HNMR spectrum.

[0020] In Component A, the (meth)acryloyl group may be located at the end of the main chain, or in the middle of the main chain, or at both of these locations. When located in the middle of the main chain, the (meth)acryloyl group is included as a side chain in Component A. In one embodiment, the (meth)acryloyl group is located only at the end of the main chain of Component A.

[0021] The (meth)acryloyl group contained in Component A is preferably represented by the following general formula (1). [ka]

[0022] R 1 represents a hydrogen atom or a methyl group. 1 When R is a hydrogen atom, formula (1) is an acryloyl group. 1 is a methyl group, then formula (1) is a methacryloyl group.

[0023] R 2 is a divalent saturated hydrocarbon group having 2 to 6 carbon atoms and containing no heteroatoms. 2 Examples of R include alkylene groups (methylene, propylene, butylene, pentylene, hexylene, etc.). From the standpoint of raw material availability and reactivity, R 2 is preferably a butylene group or a pentylene group.

[0024] R 3 ~R 6 are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group. Specific examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, a nonyl group, and a decanyl group. Specific examples of alkoxy groups include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. From the viewpoint of reactivity, R 3 ~R 6 are preferably each independently selected from the group consisting of a hydrogen atom, a methyl group, and a methoxy group. 3 ~R 6 are more preferably all hydrogen atoms.

[0025] The lower limit of the number average molecular weight (Mn) of component A is preferably 200 or more, more preferably 300 or more, and even more preferably 1,000 or more. The upper limit of the number average molecular weight (Mn) of component A is preferably 500,000 or less, more preferably 150,000 or less, and even more preferably 50,000 or less. The lower limit of the weight average molecular weight (Mw) of component A is preferably 200 or more, more preferably 300 or more, and even more preferably 1,000 or more. The upper limit of the weight average molecular weight (Mw) of component A is preferably 750,000 or less, more preferably 230,000 or less, and even more preferably 75,000 or less. If the molecular weight of component A is within the above range, a cured product with sufficient strength is easily obtained. The number average molecular weight and weight average molecular weight of component A are determined by standard polystyrene conversion using size exclusion chromatography (SEC).

[0026] The molecular weight distribution (Mw / Mn) of Component A is preferably 1.8 or less, more preferably 1.5 or less, and even more preferably 1.3 or less. The lower limit of the molecular weight distribution of Component A can be 1.0 or more. When the molecular weight distribution of Component A is within the above range, a curable composition with high workability is easily obtained.

[0027] [1.1.1.1. Manufacturing method of component A] Component A can be produced by a known method, for example as follows (see Production Example 1 for a more specific example). 1. Living cationic polymerization of isobutylene occurs in the presence of a polymerization initiator, a Lewis acid catalyst, and an electron donor component, resulting in the formation of an isobutylene polymer backbone. 2. (Meth)acryloyl groups are introduced to the ends of the main chain using a (meth)acrylate phenoxyalkyl compound, etc. The number of (meth)acryloyl groups introduced to the main chain can be adjusted by changing the amount of (meth)acrylate phenoxyalkyl compound added to the polymerization system.

[0028] Examples of polymerization initiators include cumyl chloride, p-dicumyl chloride, tert-butyl chloride, and 2-chloro-2,4,4-trimethylpentane. Examples of Lewis acid catalysts include titanium tetrachloride. Examples of electron donor components include nitrogen-containing compounds (2-methylpyridine, 2,6-lutidine, triethylamine, etc.).

[0029] The polymerization solvent in the above production method is preferably one or more selected from the group consisting of methyl chloride, butyl chloride, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, and toluene. These solvents are easily available, dissolve the raw materials and the polymer well, and are inexpensive.

[0030] The reaction temperature in the above production method is preferably low (for example, −70° C.).

[0031] ((Meth)acrylate phenoxyalkyl compounds) The phenoxyalkyl (meth)acrylate compound may be a commercially available product and used as is, or may be synthesized by a known method.

[0032] One example of a method for synthesizing a phenoxyalkyl (meth)acrylate compound is to react a compound represented by the following general formula (2), which is an alcohol compound, with a compound represented by the following general formula (3).The phenoxyalkyl (meth)acrylate compound obtained in this way can be used to introduce a (meth)acryloyl group represented by general formula (1). [ka]

[0033] In general formulas (2) and (3), R 1 ~R 6 is as defined above. X is a chlorine atom, a bromine atom or an iodine atom.

[0034] When reacting a compound represented by general formula (2) with a compound represented by general formula (3), a base may be added to the reaction system. This captures the generated HX (hydrogen chloride, hydrogen bromide, or hydrogen iodide) and promotes the reaction. Examples of bases include amine compounds and metal salts. Specific examples of amine compounds include nitrogen-containing compounds such as ammonia, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-i-propylamine, tri-i-propylamine, di-n-butylamine, tri-n-butylamine, di-i-butylamine, tri-i-butylamine, pyridine, α-picoline, β-picoline, aniline, methylaniline, dimethylaniline, and N,N-dimethylaniline. Examples of metal salts include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, lithium hydride, sodium hydride, potassium hydride, butyllithium, and lithium diisopropylamide.

[0035] The system in which the compound represented by general formula (2) and the compound represented by general formula (3) are reacted may be a solvent system or a solvent-free system. The solvent used in the solvent system is preferably a dehydrated solvent.

[0036] Examples of solvents include halogenated hydrocarbons (methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride, n-butyl chloride, etc.); aromatic hydrocarbons (benzene, toluene, xylene, etc.); aliphatic hydrocarbons (pentane, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc.); ethers (diethyl ether, dibutyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, etc.); esters (ethyl acetate, etc.); and other solvents (acetone, dimethylformamide, acetonitrile, pyridine, triethylamine, etc.).

[0037] The reaction temperature when reacting the compound represented by general formula (2) with the compound represented by general formula (3) is usually −70° C. to 200° C., and preferably 0° C. to 100° C. The reaction time is usually 1 minute to 24 hours.

[0038] Another example of a method for synthesizing a phenoxyalkyl (meth)acrylate compound is a method of reacting a compound represented by the following general formula (4) having a phenoxy group and a halogen group with a compound represented by the following general formula (5). [ka]

[0039] In general formulas (4) and (5), R 1 ~R 6 is as defined above. X is a chlorine atom, a bromine atom or an iodine atom.

[0040] When reacting a compound represented by general formula (4) with a compound represented by general formula (5), a base may be added to the reaction system. This captures the generated HX (hydrogen chloride, hydrogen bromide, or hydrogen iodide) and promotes the reaction. Examples of the base include amine compounds and metal salts. Specific examples of amine compounds include nitrogen-containing compounds such as ammonia, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-i-propylamine, tri-i-propylamine, di-n-butylamine, tri-n-butylamine, di-i-butylamine, tri-i-butylamine, pyridine, α-picoline, β-picoline, aniline, methylaniline, dimethylaniline, and N,N-dimethylaniline. Examples of metal salts include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, lithium hydride, sodium hydride, potassium hydride, butyllithium, and lithium diisopropylamide.

[0041] Prior to reacting the compound represented by general formula (4) with the compound represented by general formula (5), the compound represented by general formula (5) may be reacted with the above-mentioned base. In this case, the resulting neutralized product is reacted with the compound represented by general formula (4).

[0042] When reacting the compound represented by general formula (4) with the compound represented by general formula (5), a phase transfer catalyst may be added to the reaction system to promote the reaction. Examples of the phase transfer catalyst include tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium bromide.

[0043] The system in which the compound represented by general formula (4) and the compound represented by general formula (5) are reacted may be a solvent system or a solvent-free system. The solvent used in the solvent system is preferably a dehydrated solvent.

[0044] Examples of solvents include halogenated hydrocarbons (methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride, n-butyl chloride, etc.); aromatic hydrocarbons (benzene, toluene, xylene, etc.); aliphatic hydrocarbons (pentane, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc.); ethers (diethyl ether, dibutyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, etc.); esters (ethyl acetate, etc.); and other solvents (acetone, dimethylformamide, acetonitrile, pyridine, triethylamine, etc.).

[0045] The reaction temperature when reacting the compound represented by general formula (4) with the compound represented by general formula (5) is usually −70° C. to 200° C., and preferably 0° C. to 100° C. The reaction time is usually 1 minute to 24 hours.

[0046] The compound represented by general formula (4) may be a commercially available product and used as is, or may be synthesized by a known method.

[0047] An example of a method for synthesizing the compound represented by general formula (4) is a method of reacting a compound represented by the following general formula (6) with a compound represented by the following general formula (7). [ka]

[0048] In general formulas (6) and (7), R 2 ~R 6 The definition of is as described above. X and Y are chlorine atoms, bromine atoms, or iodine atoms. X and Y may be the same or different.

[0049] When the compound represented by general formula (6) is reacted with the compound represented by general formula (7), an alkali metal halide may be added to the reaction system to promote the reaction. Examples of alkali metal halides include sodium iodide and potassium iodide.

[0050] When reacting a compound represented by general formula (6) with a compound represented by general formula (7), a base may be added to the reaction system to promote the reaction. Examples of the base include metal salts. Specific examples of metal salts include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, lithium hydride, potassium hydride, sodium hydride, butyllithium, and lithium diisopropylamide.

[0051] The system in which the compound represented by general formula (6) and the compound represented by general formula (7) are reacted may be a solvent system or a solvent-free system. The solvent used in the solvent system is preferably a dehydrated solvent.

[0052] Examples of solvents include halogenated hydrocarbons (methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride, n-butyl chloride, etc.); aromatic hydrocarbons (benzene, toluene, xylene, etc.); aliphatic hydrocarbons (pentane, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc.); ethers (diethyl ether, dibutyl ether, diisopropyl ether, tetrahydrofuran, dimethoxyethane, dioxane, etc.); esters (ethyl acetate, etc.); and other solvents (acetone, dimethylformamide, acetonitrile, pyridine, triethylamine, etc.).

[0053] The reaction temperature when reacting the compound represented by general formula (6) with the compound represented by general formula (7) is usually −70° C. to 200° C., and preferably 0° C. to 100° C. The reaction time is usually 1 minute to 24 hours.

[0054] The phenoxyalkyl (meth)acrylate compound used in the synthesis of component A may be purified as appropriate. The purification method is not particularly limited, and known methods can be used. Examples of purification methods include washing with water (the water may be acidic, alkaline, or neutral) and using an adsorbent.

[0055] Other examples of methods for producing component A include the following. 1. A monomer having both a cationically polymerizable functional group and a (meth)acryloyl group is prepared. 2. The above monomer and isobutylene are copolymerized to obtain an isobutylene polymer having a (meth)acryloyl group as a side chain.

[0056] [1.1.2. Component B: Radical Polymerization Initiator] Component B is a radical polymerization initiator. Examples of the radical polymerization initiator include a thermal radical polymerization initiator and a photoradical polymerization initiator.

[0057] In one embodiment, component B is a photoradical polymerization initiator. A photopolymerization initiator is a compound that generates an active species (such as a radical species) that initiates polymerization of a monomer when irradiated with active energy rays. In this specification, the term "active energy rays" generally refers to light rays in a broad sense. Examples of active energy rays include radiation (such as α rays and β rays), electromagnetic waves (such as γ rays and X-rays), electron beams (EB), ultraviolet rays (wavelength: 100 to 400 nm), and visible light (wavelength: 400 to 800 nm). In one embodiment, the active energy rays are ultraviolet rays.

[0058] Examples of the photoradical polymerization initiator include those described in International Publication No. 2013 / 047314 and Japanese Patent Application Laid-Open No. 2013-216782. Among these, compounds having a hydroxyl group and a phenyl ketone structure, compounds having a benzophenone structure, and compounds having an acylphosphine oxide structure are preferably used.

[0059] Examples of compounds having a hydroxyl group and a phenyl ketone structure include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanon-1-one, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one.

[0060] Examples of compounds having a benzophenone structure include benzophenone, 3-methoxybenzophenone, 4-methylbenzophenone, 4,4'-bis(diethylamino)benzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, and 4-chloro-4'-benzylbenzophenone.

[0061] Examples of compounds having an acylphosphine oxide structure include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

[0062] The photoradical polymerization initiator may be used in combination with other compounds. Examples of such combinations include the following: Combination with amines (diethanolmethylamine, dimethylethanolamine, triethanolamine, etc.) Combinations with amines and iodonium salts (e.g., phenyliodonium chloride) Combination with amines and dyes (e.g., methylene blue)

[0063] 1.1.3. Component C: Plasticizer Component C is a plasticizer. Component C is an optional component, so it may or may not be included in the curable composition. Examples of component C include polybutene oil and process oil.

[0064] Polybutene oil is a polymer obtained by polymerizing n-butene (1-butene and 2-butene) and isobutene (2-methylpropene). Among these, a copolymer with isobutene as the main monomer and n-butene as the comonomer is preferably used. Commercially available polybutenes may be used. Examples of commercially available products include Nippon Oil Polybutene (ENEOS Corporation); NOF Polybutene, Eumat (all NOF Corporation); and Oppanol (BASF SE).

[0065] Examples of process oils include paraffin oil, naphthenic oil, and aromatic oil. Among these, paraffin oil is preferred. Paraffin oil refers to an oil solution whose main component is paraffin (chain hydrocarbon). Examples of paraffin include n-paraffin and isoparaffin. Examples of n-paraffin include butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, and eicosane. Examples of isoparaffins include isobutane, isopentane, neopentane, isohexane, isopentane, neohexane, 2,3-dimethylbutane, methylhexanes, 3-ethylpentane, dimethylpentanes, 2,2,3-trimethylbutane, 3-methylheptane, dimethylhexanes, trimethylpentanes, isononane, 2-methylnonane, isodecane, isoundecane, isododecane, isotridecane, isotetradecane, isopentadecane, isooctadecane, isonadecane, isoeicosane, and 4-ethyl-5-methyloctane.

[0066] [1.1.4. Component D: Vinyl Monomer] Component D is a vinyl-based monomer. The vinyl-based monomer refers to a compound having a polymerizable vinyl group.

[0067] In one embodiment, component D is a (meth)acrylic monomer and / or an aromatic vinyl monomer. The (meth)acrylic monomer refers to a compound having a (meth)acryloyl group (the (meth)acryloyl group contains a polymerizable vinyl group). The aromatic vinyl monomer refers to a compound having an aromatic ring and a polymerizable vinyl group. In one embodiment, the aromatic vinyl monomer is a styrene monomer.

[0068] There is no particular limitation on the number of polymerizable vinyl groups contained in Component D. For example, the number of polymerizable vinyl groups contained in Component D is 5 or less, 4 or less, 3 or less, 2 or less, or 1.

[0069] The molecular weight of Component D is preferably 5,000 or less, more preferably 1,500 or less, and even more preferably 500 or less. The number of carbon atoms in Component D is preferably 400 or less, more preferably 120 or less, and even more preferably 40 or less.

[0070] Examples of (meth)acrylic monomers include (meth)acrylic acid esters, (meth)acryloyl group-containing alicyclic compounds, (meth)acrylamide, and (meth)acrylonitrile. Among these, (meth)acrylic acid esters are preferred. (Meth)acrylic acid esters are those represented by the general formula "CH2=C(R 1 )COOR 2 " is a compound represented by the formula: 1 is a hydrogen atom or a methyl group. 2 is, for example, a hydrocarbon group which may have a heteroatom (such as a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, or a halogen atom). 2 The number of carbon atoms contained in R may be 50 or less, 40 or less, 30 or less, 20 or less, or 15 or less. 2The number of heteroatoms contained in R may be 10 or less, 8 or less, 5 or less, 4 or less, 3 or less, 2 or less, or 1 or less. 2 is composed only of carbon and hydrogen atoms.

[0071] Specific examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, and n-hexyl (meth)acrylate. Butyl, (meth)acrylate-n-octyl, (meth)acrylate 2-ethylhexyl, (meth)acrylate isooctyl, (meth)acrylate nonyl, (meth)acrylate isononyl, (meth)acrylate decyl, (meth)acrylate isodecyl, (meth)acrylate undecyl, (meth)acrylate dodecyl, (meth)acrylate tridecyl, (meth)acrylate tetradecyl, (meth)acrylate pentadecyl, (meth)acrylate hexadecyl, (meth)acrylate Heptadecyl acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, oleyl (meth)acrylate, behenyl (meth)acrylate, 2-decyltetradecanyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, tolyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 1-methyladamantyl (meth)acrylate, 1-ethyladamantyl (meth)acrylate, and benzyl (meth)acrylate.

[0072] Specific examples of aromatic vinyl monomers include styrene, vinyl ketone, α-methylstyrene, p-methylstyrene, and chlorostyrene.

[0073] In one embodiment, component D further comprises, in addition to the polymerizable vinyl group, one or more functional groups selected from the group consisting of a carboxyl group and its alkali metal salts, a phosphate group and its alkali metal salts, a hydroxyl group and its alkali metal salts, an amino group, and an epoxy group. In one embodiment, the curable composition does not comprise a component D having these specific functional groups.

[0074] Alkali metals are elements from Group 1 of the periodic table excluding hydrogen. In one embodiment, the alkali metals are sodium and / or potassium.

[0075] When component D is an alkali metal salt, the number of alkali metal ions contained in component D may be one or more. When component D contains more than one alkali metal ion, the types of these alkali metal ions may be the same or different. When component D is an alkali metal salt, component D may contain a cation other than an alkali metal ion.

[0076] Examples of component D having a carboxyl group include (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, and mono(2-(meth)acryloyloxyethyl) succinate (all of which are (meth)acryloyl-based monomers); 4-vinylbenzoic acid, 2-vinylbenzoic acid, and cinnamic acid (all of which are aromatic vinyl-based monomers). Examples of component D having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy-1-methylethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 3-hydroxy-1-adamantyl (meth)acrylate (all of which are (meth)acryloyl-based monomers); and 4-vinylphenol and 2-methoxy-4-vinylphenol (all of which are aromatic vinyl-based monomers). Examples of component D having a phosphoric acid group include 2-(meth)acryloyloxyethyl phosphate ester (all (meth)acryloyl-based monomers). The alkali metal salts of component D described above are also included in the examples of component D. Examples of component D having an amino group include 2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl (meth)acrylate, and quaternized 2-dimethylaminoethyl (meth)acrylate (all (meth)acryloyl-based monomers); 4-aminostyrene, and 4-dimethylaminostyrene (all aromatic vinyl-based monomers). Examples of component D having an epoxy group include glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether (all (meth)acryloyl-based monomers).

[0077] Examples of vinyl monomers that are not (meth)acrylic monomers or aromatic vinyl monomers include fluorine-containing vinyl monomers (perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc.); silicon-containing vinyl monomers (vinyltrimethoxysilane, vinyltriethoxysilane, etc.); vinyl ester monomers (vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, etc.); vinyl chloride, vinylidene chloride, vinyl iodide, vinyl bromide, vinylidene bromide, allyl chloride, allyl alcohol, vinyl ether, and methyl vinyl ketone.

[0078] [1.1.5. Other Ingredients] The curable composition may contain other components in addition to the above-mentioned components A to D. Examples of such other components include additives (fillers, plasticizers, antioxidants, UV absorbers, flame retardants, antistatic agents, pigments, etc.), elastomers ((meth)acryloyl group-containing oligomers, styrene-based block copolymers, etc.) that adjust the rubber properties of the cured product, thiol compounds, tertiary amine compounds, and adhesion promoters.

[0079] (additives) Examples of additives include those described in International Publication No. 2013 / 047314 and Japanese Patent Application Laid-Open No. 2013-216782. The contents of the filler and plasticizer are each preferably 0.1 to 500 parts by weight, and more preferably 1.0 to 300 parts by weight, based on 100 parts by weight of Component A. The contents of the antioxidant, UV absorber, flame retardant, antistatic agent, and pigment are each preferably 0.01 to 20.0 parts by weight, and more preferably 0.10 to 10.0 parts by weight, based on 100 parts by weight of Component A. When the additive contents are within the above ranges, a good balance between the effect of adding the additive and the cost is achieved.

[0080] ((Meth)acryloyl group-containing oligomer) Examples of (meth)acryloyl group-containing oligomers include compounds having a main chain made of an oligomer and a (meth)acryloyl group. In one embodiment, the main chain of the (meth)acryloyl group-containing oligomer does not contain a unit derived from isobutylene. In one embodiment, the (meth)acryloyl group-containing oligomer has an average of one or more (meth)acryloyl groups per molecule.

[0081] Examples of the main chain structure of the (meth)acryloyl group-containing oligomer include polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, polyether, polyester, polycarbonate, polyacrylate, polymers of epoxy compounds, castor oil, and silicone polymers. Among these, polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, polyacrylate, polymers of epoxy compounds, and castor oil are preferred. These main chain structures have excellent compatibility with other components contained in the curable composition.

[0082] The number-average molecular weight of the (meth)acryloyl group-containing oligomer is preferably 200 to 500,000, more preferably 1,000 to 100,000. A (meth)acryloyl group-containing oligomer having a number-average molecular weight within the above range is easily available and has good compatibility with other components of the curable composition. In addition, the resulting curable composition is easy to handle.

[0083] The content of the (meth)acryloyl group-containing oligomer is preferably 0.1 to 1000 parts by weight, and more preferably 1.0 to 300 parts by weight, relative to 100 parts by weight of the content of Component A. When the content is within the above range, the compatibility with other components of the curable composition is good, and the viscosity of the obtained curable composition is also appropriate.

[0084] (styrene-based block copolymer) Examples of styrene-based block copolymers include styrene-butadiene copolymer (SBS), styrene-isoprene copolymer (SIS), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-isobutylene-styrene copolymer (SIBS), acrylonitrile-styrene copolymer (AS), and styrene-butadiene-acrylonitrile copolymer (ABS). Among these, styrene-butadiene copolymer (SBS), styrene-isoprene copolymer (SIS), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), and styrene-isobutylene-styrene copolymer (SIBS) are preferred. These styrene-based block copolymers have excellent compatibility with other components contained in the curable composition and impart favorable rubber physical properties to the resulting cured product.

[0085] The number average molecular weight of the styrene-based block copolymer is preferably 10,000 to 500,000, more preferably 50,000 to 300,000. When the number average molecular weight is within the above range, the compatibility with other components of the curable composition is good, and the viscosity of the obtained curable composition is also appropriate.

[0086] The content of the styrene-based block copolymer is preferably 0.1 to 1000 parts by weight, and more preferably 1.0 to 300 parts by weight, relative to 100 parts by weight of the content of component A. When the content is within the above range, a cured product having a good balance of adhesion and durability can be obtained.

[0087] (Thiol compounds) The inclusion of a thiol compound in a curable composition increases the number of crosslinking points, thereby improving curability and improving the hardness and strength of the cured product. Alternatively, the reduction of crosslinking points through chain transfer can improve the flexibility and adhesiveness of the cured product.

[0088] Examples of thiol compounds include decanethiol, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), ethylene glycol bis(3-mercaptoglycolate), butanediol bis(3-mercaptoglycolate), trimethylolpropane tris(3-mercaptoglycolate), pentaerythritol tetrakis(3 -mercaptoglycolate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0089] The content of the thiol compound is preferably 0.1 to 100 parts by weight, and more preferably 0.50 to 30 parts by weight, relative to 100 parts by weight of the content of component A. When the content is within the above range, the curability and handleability of the curable composition are good.

[0090] (Tertiary amine compounds) When the curable composition contains a tertiary amine compound, the photocurability is improved.

[0091] Examples of tertiary amine compounds include trimethylamine, triethylamine, tributylamine, N,N'-diethanolamine, N,N'-dimethyl-p-toluidine, N,N'-dimethyl-aniline, N-methyl-diethanolamine, N-methyl-dimethanolamine, N,N'-dimethylamino-acetophenone, N,N'-dimethylaminobenzophenone, N,N'-diethylamino-benzophenone, and triisopropanolamine.

[0092] The content of the tertiary amine compound is preferably 0.1 to 100 parts by weight, and more preferably 0.50 to 30 parts by weight, relative to 100 parts by weight of the content of component A. When the content is within the above range, the curable composition has excellent curability.

[0093] (adhesion imparting agent) When the curable composition contains an adhesion promoter, the adhesiveness of the cured product is improved.

[0094] Examples of adhesion promoters include 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, (meth)acryloxyoctyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-chloropropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, hydroxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltriethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 2-hydroxyethyl (meth)acrylate phosphate ester, methacryloxyoxyethyl acid phosphate monoethylamine half salt, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate.Among these, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, Particularly preferred are silane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 2-hydroxyethyl(meth)acrylate phosphate ester, 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, and 4-hydroxybutyl(meth)acrylate.

[0095] The content of the adhesion promoter is preferably 0.01 to 20.0 parts by weight, and more preferably 0.1 to 10.0 parts by weight, relative to 100 parts by weight of the content of component A. If the content is within the above range, a good balance between curability and adhesion will be achieved.

[0096] [1.2. Composition of Curable Composition] The lower limit of the content of component B is preferably 0.001 part by weight or more, more preferably 0.005 part by weight or more, even more preferably 0.01 part by weight or more, and particularly preferably 0.05 part by weight or more, relative to 100 parts by weight of the content of component A. The upper limit of the content of component B is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, even more preferably 3 parts by weight or less, and particularly preferably 1 part by weight or less, relative to 100 parts by weight of the content of component A.

[0097] The lower limit of the content of component C is preferably more than 0 parts by weight, more preferably 3 parts by weight or more, and even more preferably 5 parts by weight or more, relative to 100 parts by weight of the content of component A. The upper limit of the content of component C is preferably 100 parts by weight or less, more preferably 80 parts by weight or less, even more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight or less, relative to 100 parts by weight of the content of component A.

[0098] The lower limit of the content of component D is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and even more preferably 5 parts by weight or more, relative to 100 parts by weight of the content of component A. The upper limit of the content of component D is preferably 150 parts by weight or less, more preferably 100 parts by weight or less, and even more preferably 80 parts by weight or less, relative to 100 parts by weight of the content of component A.

[0099] [1.3. Cured product] The cured product is obtained by curing the above-mentioned curable composition, which can be cured, for example, by irradiation with UV light.

[0100] The cured product can be used for a variety of applications. Examples include sealing materials, pressure-sensitive adhesives, sealing materials, gasket materials, adhesives, coating materials, covering materials, resist materials, vibration-proofing materials, vibration-damping materials, shock-absorbing materials, buffer materials, electrical insulating materials, foams, paints, inks, casting agents, potting agents, molding materials, underfill materials, die-bonding materials, and fillers. Specific examples of parts in which the cured product can be used include electrical and electronic components (LEDs, batteries, fuel cells, secondary batteries, sensors, semiconductors, circuit boards, displays, home appliances, optical communications and optical circuits, optical recording, magnetic recording, etc.), pharmaceuticals and medical products, automotive and marine parts, building components, and acoustic components. The cured product can be in the form of, for example, a sheet (film), a tape, or a molded product (packing, O-rings, belts, tubes, valves, hoses, etc.).

[0101] [1.4. Base material] The substrate, together with the curable composition or the cured product, constitutes an article according to one embodiment of the present invention. The substrate is in contact with the curable composition or the cured product at an adhesive surface. At least a portion of the adhesive surface is plasma-treated.

[0102] In one embodiment, at least a portion of the bonding surface is made of a metal. Examples of metals include iron, aluminum, iron-based alloys (steel, cast iron, stainless steel, etc.), and aluminum-based alloys. The curable composition having the above-described composition has improved adhesion to plasma-treated metals (particularly plasma-treated aluminum alloys or stainless steel). Therefore, it is preferred that at least a portion of the bonding surface is made of a plasma-treated aluminum alloy or stainless steel.

[0103] In one embodiment, the first substrate and the second substrate are bonded via a curable composition or a cured product. At least a portion of the bonding surface of the first substrate and / or the bonding surface of the second substrate is plasma-treated. Preferably, at least a portion of the bonding surface of the first substrate and / or the bonding surface of the second substrate is metal.

[0104] 2. Manufacturing method of the article One aspect of the present invention is a method for manufacturing an article comprising a substrate and a curable composition. In this aspect, the curable composition is uncured. The method includes applying the curable composition to an adhesive surface, at least a portion of which has been plasma-treated.

[0105] One aspect of the present invention is a method for producing an article comprising a substrate and a cured product. In this aspect, the cured product is obtained by curing a curable composition. This production method includes a step of curing the curable composition applied to an adhesive surface. At this time, at least a portion of the adhesive surface is plasma-treated. This production method may also include a step of applying the curable composition to the adhesive surface.

[0106] [2.1. Plasma treatment] In one embodiment, at least a portion of the adhesive surface is plasma-treated. The plasma-treated adhesive surface has fine scratches and generates many hydrophilic functional groups, thereby improving the adhesive strength between the cured product and the substrate interface. Specific plasma treatment methods are well known in the art and can be appropriately selected by those skilled in the art.

[0107] As an example, the plasma treatment conditions may satisfy one or more of the following: Irradiation distance: 1mm or more, 2mm or more, or 3mm or more; 100mm or less, 80mm or less, or 50mm or less Irradiation travel speed: 1mm / sec or more, 10mm / sec or more, or 30mm / sec or more; 1000mm / sec or less, 800mm / sec or less, or 600mm / sec or less

[0108] [2.2. Application and curing of curable composition] Known techniques can be used to apply the curable composition to a substrate. The amount of the curable composition to be applied (weight per unit area, etc.) can be determined appropriately by those skilled in the art. The dimensions (thickness, etc.) of the cured product obtained by curing the curable composition can also be determined appropriately by those skilled in the art.

[0109] Known techniques can be used to cure the curable composition. Typically, the curable composition is cured by irradiating it with active energy rays (such as ultraviolet rays). The irradiation dose and irradiation time of the active energy rays may be appropriately determined by those skilled in the art.

[0110] [3. Summary] <1> An article comprising a substrate and a curable composition, the curable composition is in contact with the substrate at an adhesive surface of the substrate, At least a portion of the adhesive surface is plasma treated; The curable composition comprises the following component A and component B: Component A: an isobutylene polymer having an average of 1.2 or more (meth)acryloyl groups per molecule; Component B: Radical polymerization initiator. <2> An article comprising a substrate and a cured product, the cured product is in contact with the substrate at an adhesive surface of the substrate, At least a portion of the adhesive surface is plasma treated; The cured product is obtained by curing a curable composition containing the following components A and B: Component A: an isobutylene polymer having an average of 1.2 or more (meth)acryloyl groups per molecule; Component B: Radical polymerization initiator. <3> At least a portion of the adhesive surface is metal. <1> or <2> The article described in <4> At least a portion of the adhesive surface is aluminum, an aluminum-based alloy, iron, an iron-based alloy, or a combination thereof. <1> ~ <3> An article according to any one of the preceding items. <5> The curable composition further contains the following component C and / or component D: <1> ~ <4> Any of the following: Component C: Plasticizer; Component D: vinyl monomer. <6> The component D is polybutene oil and / or paraffin oil. <5> The article described in <7> 1. A method for manufacturing an article, comprising the steps of: Step 2a: applying a curable composition to an adhesive surface of a substrate; At least a portion of the adhesive surface is plasma treated; The curable composition includes the following component A and component B. Component A: an isobutylene polymer having an average of 1.2 or more (meth)acryloyl groups per molecule; Component B: Radical polymerization initiator. <8> 1. A method for manufacturing an article, comprising the steps of: Step 2b: curing the curable composition applied to the adhesive surface of the substrate; At least a portion of the adhesive surface is plasma treated; The curable composition includes the following component A and component B. Component A: an isobutylene polymer having an average of 1.2 or more (meth)acryloyl groups per molecule; Component B: Radical polymerization initiator. <9> The method further comprises the steps of: <7> or <8> 1. A method for producing a semiconductor device according to claim 1, wherein the method comprises: Step 1: Plasma treating the substrate; The manufacturing method, wherein the plasma treatment satisfies one or more of the following conditions: ·Irradiation distance: 1~100mm Irradiation movement speed: 1~1000mm / sec

[0111] In one embodiment, <2> The goods related to <1> The article may be obtained by curing the curable composition according to the above.

[0112] In one embodiment, <8> The manufacturing method according to the present invention comprises the steps of: <7> The method may include step 2a described in the above. [Example]

[0113] [Measurement method] (1)Molecular weight The number average molecular weight (Mn) of the isobutylene polymer was measured by a standard polystyrene conversion method using size exclusion chromatography (SEC). The specifications of SEC are as follows: SEC system: LCModule1 (Waters) Stationary phase: Shodex GPCK-804 (polystyrene cross-linked gel packed column, Showa Denko K.K.) Mobile phase: chloroform

[0114] (2) Number of (meth)acryloyl groups The average number of (meth)acryloyl groups introduced per molecule of the isobutylene polymer was determined by the following procedure. The number average molecular weight (Mn) of the isobutylene polymer was measured by the method described in 1.(1). 2. Isobutylene polymer 1 HNMR was measured. First, the area of the peaks assigned to the two methyl groups in the isobutylene skeleton was used as the reference area. Specifically, the integral value of the peak near 1.3 ppm was set to satisfy the following formula: Integration value of the peak near 1.3 ppm = (Mn / 56.11) x 6 3. The peaks appearing around 5.8 to 5.9 ppm, around 6.1 to 6.2 ppm, and around 6.4 ppm were determined to be peaks derived from (meth)acryloyl groups. The integral value of each peak was calculated as a relative value to the reference area, and the average of the three integral values was calculated. The obtained average value was determined to be the average number of (meth)acryloyl groups introduced per molecule of the isobutylene polymer.

[0115] (3) Peel test This was carried out according to the following procedure. 1. A first substrate, a second substrate, and a curable composition were prepared. The material of the first substrate was stainless steel (SUS304) or aluminum-based alloy (A2024). The dimensions of the first substrate were length: 25 mm x width: 100 mm x thickness: 2 mm (stainless steel) and length: 25 mm x width: 100 mm x thickness: 1.6 mm (aluminum-based alloy). The second substrate was glass. The dimensions of the second substrate were length: 25 mm x width: 100 mm x thickness: 5 mm. The curable composition was one prepared in the examples or comparative examples. 2. In the examples, the surface of the first substrate was plasma-treated. For the plasma treatment, an atmospheric pressure plasma surface treatment device (Laboratory system with rotating nozzle RD1004 and 3-axis robot, Nippon Plasmatreat Inc.) was used. The treatment conditions were as follows. In the comparative examples, no plasma treatment was performed. Voltage: 280V Distance between nozzle and first substrate: 5mm Nozzle scanning speed: 100mm / sec 3. The first and second substrates were bonded together via their adhesive surfaces so that only their edges overlapped. The dimensions of the adhesive surface were 25 mm long x 10 mm wide. The thickness of the curable composition applied to the adhesive surface was 1 mm. 4. The curable composition was cured by irradiating it with ultraviolet light. The irradiation conditions were: peak irradiance: 500 mW / cm 2 Ultra, cumulative light intensity 5000mJ / cm 2 An electrodeless UV lamp bulb (LH6 (H-bulb), Heraeus) was used for ultraviolet irradiation. 5. The first substrate and the second substrate were pulled so that the directions of the forces applied to them were 180° apart, and the stress at which the two substrates peeled was measured. An AGS-J (Shimadzu Corporation) was used for the measurements. The peeled surface was also observed to determine whether interfacial failure (AF) or cohesive failure (CF) occurred.

[0116] 〔material〕 The materials used in the examples and comparative examples are as follows. ●Ingredient A Isobutylene polymer having (meth)acryloyl groups: obtained in Production Example 1 ●Ingredient B Photoradical polymerization initiator: the product obtained in Production Example 2 ●Component C Plasticizers (Nippon Oil Polybutene HV-100, ENEOS Corporation, Polybutene Oil) ●Component D Monomer D1: Lauryl acrylate Monomer D2: Acrylic acid Monomer D3: 2-dimethylaminoethyl acrylate Monomer D4: Ester of phosphoric acid and 2-hydroxyethyl methacrylate (Light Ester P-1M, Kyoeisha Chemical Co., Ltd.) Monomer D5: 4-hydroxybutyl acrylate ●Other Antioxidant (hindered phenol, Adekastab AO-50, ADEKA Corporation)

[0117] [Production Example 1: Production of isobutylene polymer] An isobutylene polymer having an acryloyl group introduced at the molecular end was produced by the following procedure. 1. The atmosphere inside a 1 L separable flask was replaced with nitrogen. 2. 44 mL of n-hexane and 395 mL of butyl chloride were charged and cooled to -70°C with stirring under a nitrogen atmosphere. n-Hexane and butyl chloride were dried over molecular sieves before use. 3. 159 mL of isobutylene (1.68 mol), 1.86 g of p-dicumyl chloride (0.0081 mol), and 0.302 g of 2,6-lutidine (0.00282 mol) were added to a vessel. 4. After the reaction mixture was cooled to -70°C, 0.88 mL of titanium tetrachloride (0.0080 mol) was added to initiate the polymerization. 5. When the remaining amount of isobutylene was below 0.5% of the amount charged, 4.08 g of 4-phenoxybutyl acrylate and 5.29 mL of titanium tetrachloride were added to the vessel. The remaining amount of isobutylene was measured by gas chromatography. 6. The mixture was stirred at -70°C for 1 hour. 7. 580 g of purified water, 22 g of 48% aqueous sodium hydroxide solution, 10 mL of n-hexane, and 87 mL of butyl chloride were added to the vessel to stop the reaction. 8. The resulting polymerization solution was washed twice with 145 mL of pure water. 9. 8.3 g of powdered activated carbon (Taiko A, Futamura Chemical Co., Ltd.) was added to the washed polymerization solution, and the mixture was stirred for 30 minutes, and then filtered through a filter with 1 μm openings. 10. To the obtained filtrate, 0.17 g of 4-methoxyphenol was added, and the solvent was distilled off under reduced pressure at 120° C. In this way, an isobutylene polymer having an acryloyl group introduced at the molecular terminal was obtained.

[0118] The isobutylene polymer had a number average molecular weight (Mn) of 15,200. The number of acryloyl groups introduced into the terminals of the isobutylene polymer was 1.88 on average per molecule.

[0119] [Production Example 2: Preparation of photopolymerization initiator] A photopolymerization initiator was prepared according to the following procedure. 1. 20 g of 2-hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCUR1173, BASF Japan Ltd.) and 10 g of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IRGACURE819, BASF Japan Ltd.) were weighed out. 2. While heated to 80°C, the components were mixed with a spatula for 5 minutes to obtain a photopolymerization initiator.

[0120] [Examples 1 to 9, Comparative Examples 1 to 9] A curable composition was obtained by the following procedure. 1. The components listed in Table 1 were prepared (unit: parts by weight). 2. All ingredients except for ingredient B were heated to 90°C and mixed by hand with a spatula for 5 minutes. 3. Component B was further added and mixed by hand for 2 minutes. 4. The curable composition was degassed under vacuum for 7 minutes using a rotation-revolution mixer, Awatori Rentaro ARE-310 (Thinky Corporation).

[0121] [result] The results are shown in Table 1. JPEG2025121275000005.jpg252112

[0122] As can be seen from Table 1, by treating the substrate with plasma, adhesion was improved regardless of the composition of the curable composition. Furthermore, by incorporating a monomer having a carboxyl group or an amino group as component B, adhesion to the substrate was further improved. These results suggest that the article according to one embodiment of the present invention has improved adhesion between the substrate (particularly a metal substrate) and the cured product. [Industrial Applicability]

[0123] The present invention can be used for bonding substrates together, etc.

Claims

1. An article comprising a substrate and a curable composition, the curable composition is in contact with the substrate at an adhesive surface of the substrate, At least a portion of the adhesive surface is plasma treated; The curable composition comprises the following component A and component B: Component A: an isobutylene polymer having an average of 1.2 or more (meth)acryloyl groups per molecule; Component B: Radical polymerization initiator.

2. An article comprising a substrate and a cured product, the cured product is in contact with the substrate at an adhesive surface of the substrate, At least a portion of the adhesive surface is plasma treated; The cured product is obtained by curing a curable composition containing the following components A and B: Component A: an isobutylene polymer having an average of 1.2 or more (meth)acryloyl groups per molecule; Component B: Radical polymerization initiator.

3. 3. The article of claim 1 or 2, wherein at least a portion of the adhesive surface is metal.

4. 3. The article of claim 1 or 2, wherein at least a portion of the adhesive surface is aluminum, an aluminum-based alloy, iron, an iron-based alloy, or a combination thereof.

5. The article of claim 1 or 2, wherein the curable composition further comprises the following component C and / or component D: Component C: plasticizer; Component D: vinyl monomer.

6. 6. The article of claim 5, wherein component D is polybutene oil and / or paraffin oil.

7. 1. A method for manufacturing an article, comprising the steps of: Step 2a: applying a curable composition to the adhesive surface of the substrate; At least a portion of the adhesive surface is plasma treated; The curable composition includes the following component A and component B. Component A: an isobutylene polymer having an average of 1.2 or more (meth)acryloyl groups per molecule; Component B: Radical polymerization initiator.

8. 1. A method for manufacturing an article, comprising the steps of: Step 2b: curing the curable composition applied to the adhesive surface of the substrate; At least a portion of the adhesive surface is plasma treated; The curable composition includes the following component A and component B. Component A: an isobutylene polymer having an average of 1.2 or more (meth)acryloyl groups per molecule; Component B: Radical polymerization initiator.

9. 9. The method of claim 7 or 8, further comprising the steps of: Step 1: Plasma treating the substrate; The manufacturing method, wherein the plasma treatment satisfies one or more of the following conditions: ・Irradiation distance: 1-100mm Irradiation movement speed: 1 to 1000 mm / sec

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