Composition containing surface treatment component or curing promotion component

Abstract

The present invention relates to a composition comprising a surface treatment component or a curing promoting component. The present invention relates to a composition comprising: a component (A-1): a surface treatment component or a component (A-2): a curing accelerator component, a component (B): a benzo # imgabs0 # azole-based fluorescence sensitizer, and a component (C): a solvent.

Description

Technical Field

[0001] The present invention relates to a composition comprising a surface treatment component or a curing accelerating component. Background Art

[0002] For the purpose of improving visual recognition, the coating composition comprising luminescent material disclosed in known patent documentation 1. These coating compositions are coatings, comprising resin, polymer. If the composition is applied to substrate, then by ensuring a certain degree of film thickness, thereby visual recognition is manifested. In addition, if more fillers etc. are added in the composition with materials of shielding property, visual recognition is correspondingly improved. However, even if various compositions obtained by dissolving only a small amount of surface treatment component or curing accelerating component in solvent are applied to substrate, it is also difficult to confirm the coating area by visual inspection.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application No. 2018-505265 Summary of the invention

[0006] Problems to be solved by the invention

[0007] Conventionally, when a composition containing a surface treatment component or a curing accelerating component is applied to a substrate, there is a problem that if the composition is transparent, the visibility in a wet state is low, and the visibility in a dry state after the solvent has dried is even lower.

[0008] Means for solving problems

[0009] The present inventors have conducted intensive studies to achieve the above object and, as a result, have found that a composition containing a surface treatment component or a curing accelerating component can solve the above problems, thereby completing the present invention.

[0010] Next, the gist of the present invention will be described.

[0011] The first embodiment of the present invention is a composition comprising the following (A-1) component, (B) component, and (C) component.

[0012] (A-1) Ingredients: surface treatment ingredients,

[0013] (B) Component: Benzo Azole fluorescent sensitizer,

[0014] (C) Ingredient: Solvent

[0015] The second embodiment of the present invention is a composition comprising the following (A-2) component, (B) component, and (C) component.

[0016] (A-2) component: a curing accelerating component,

[0017] (B) Component: Benzo Azole fluorescent sensitizer,

[0018] (C) Ingredient: Solvent

[0019] A third aspect of the present invention is the composition according to the first aspect, wherein the component (A-1) is at least one selected from the group consisting of benzophenone and benzophenone derivatives.

[0020] A fourth embodiment of the present invention is the composition according to the second embodiment, wherein the component (A-2) is at least one selected from the group consisting of metal complexes, inclusion compounds, water, hydrazine compounds, thiol compounds, aldehyde compounds, amine compounds, and metal catalysts.

[0021] A fifth embodiment of the present invention is the composition according to the first or second embodiment, which does not contain a curable resin, a polymer, an oligomer, an elastomer, a rubber, a thermoplastic resin, and a filler.

[0022] The sixth embodiment of the present invention is a method for treating a surface of a substrate, comprising applying the composition according to the first embodiment to a substrate and irradiating the composition with active energy rays.

[0023] A seventh embodiment of the present invention is a method for coating a composition, comprising coating the composition according to the first or second embodiment on a substrate, wherein the thickness of the coating film obtained by the coating is 10 μm or less in a wet state.

[0024] An eighth embodiment of the present invention is a method for confirming a coating area, wherein the composition according to the first or second embodiment is applied to a substrate, and a black light is used to confirm the area where the composition is applied.

[0025] A ninth embodiment of the present invention is a method for confirming a coated area, wherein the composition according to the first or second embodiment is applied to a substrate, the component (C) is dried, and the area where the composition is applied is confirmed using a black light.

[0026] The tenth embodiment of the present invention is a method for bonding substrates, wherein a first substrate and a second substrate are prepared, the composition described in the first or second embodiment is applied to the first substrate, and the second substrate and the first substrate are bonded using a curable resin composition.

[0027] The eleventh embodiment of the present invention is a method for bonding substrates, wherein a first substrate and a second substrate are prepared, the composition described in the first or second embodiment is applied to the first substrate, the (C) component is dried, and the second substrate is bonded to the first substrate using a curable resin composition.

[0028] Effects of the Invention

[0029] In the present invention, when the composition is applied to a substrate, if the composition is transparent, traces of the application of the composition can be easily confirmed visually using a black light, regardless of whether the composition is in a wet state or in a dry state where the solvent has dried. DETAILED DESCRIPTION

[0030] Next, the details of the present invention are described. The component (A-1) that can be used in the present invention is a surface treatment component. The component (A-2) that can be used in the present invention is a curing accelerating component. The so-called surface treatment component is used to modify the surface of the substrate by heating and irradiation with active energy rays, so that the adhesion of the curable resin composition described later is improved. In addition, the so-called curing accelerating component is used to make the component that improves the curability of the curable resin composition remain on the surface of the substrate, so as to improve the curability and rapid curing of the curable resin composition.

[0031] As specific examples of surface treatment components that can be used as (A-1) components, benzophenone and benzophenone derivatives can be cited. Here, derivatives refer to compounds obtained by replacing hydrogen on the basic skeleton with substituents. Although the clear reason is not clear, it is speculated that benzophenone and benzophenone derivatives become triplet excited states on the surface of the substrate by irradiation with active energy rays such as ultraviolet rays, and hydrogen abstraction reaction occurs, thereby modifying the surface of the substrate. As a result, a significant effect of improving the adhesion of the curable resin composition described later is shown.

[0032] The active energy rays referred to in the present invention include all light in a broad sense, such as radiation such as α-rays and β-rays, electromagnetic waves such as γ-rays and X-rays, electron beams (EB), ultraviolet rays (UV) with a wavelength of about 100 to 400 nm, and visible light with a wavelength of about 400 to 800 nm, preferably ultraviolet rays.

[0033] Specific examples of benzophenone and benzophenone derivatives include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 2-ethylbenzophenone, 3-ethylbenzophenone, 4-methylbenzophenone, 4-ethylbenzophenone, 4-bromobenzophenone, 4-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4-chloro-4'-benzylbenzophenone, 4,4'-dimethoxybenzophenone, 3-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4-cyanobenzophenone, 4-methylbenzophenone, Acryloyloxybenzophenone, 4-benzoylbenzoic acid, 2,2,4,4-tetramethylbenzophenone, 4,4-dimethylbenzophenone, 4-dimethylaminobenzophenone, 2,4-dihydroxybenzophenone, 3,3,4,4-benzophenonetetracarboxylic dianhydride, 4-(dimethylamino)benzophenone, 2,4-dimethoxy-4'-hydroxybenzophenone, xanthone, 3-hydroxyxanthene-9-one, 9-hydroxyxanthene, thioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthene-9-one, anthraquinone-2-sulfonate sodium monohydrate, etc., but are not limited to these.

[0034] The curable resin composition used for bonding purposes after the substrate is surface-treated with the component (A-1) may contain various curable resins. Specific examples of curable resins include: epoxy resin compositions containing epoxy compounds; (meth)acrylate / salt compositions containing (meth)acrylate / salt compounds; curable resin compositions containing cyanoacrylate / salt compounds; urethane resin compositions; addition reaction type silicone resin compositions containing a resin containing a vinyl siloxane group and a polyorganosiloxane as the main skeleton and a resin containing a hydrogen siloxane group in the composition; condensation reaction type silicone resin compositions containing a resin containing a hydrolyzable silyl group and a polyorganosiloxane as the main skeleton; addition reaction type modified silicone compositions containing a resin containing a vinyl siloxane group and a resin containing a hydrogen siloxane group and a main skeleton other than a polyorganosiloxane in the composition; condensation reaction type modified silicone compositions containing a resin containing a hydrolyzable silyl group and a main skeleton other than a polyorganosiloxane, etc., but are not limited to these. In addition, the curable resin composition may be a one-component type containing all the components, or a two-component type with a main agent and a curing agent separated. As the curing form of the curable resin composition, various forms such as thermosetting, photocuring, anaerobic curing, and moisture curing can also be used.

[0035] The curing accelerating component that can be used as the (A-2) component can be used in various curable resin compositions. The curing accelerating component has the effect of promoting curing in the area in contact with the curable resin composition, and there is an inherent (A-2) component for each curable resin composition. As a specific curable resin composition, as described above, but not limited to these. In particular, the curing accelerating component is used for a curable resin composition with anaerobic curability containing a (meth)acrylate / salt compound, a curable resin composition containing a cyanoacrylate / salt compound, a curable resin composition containing a vinylsiloxane group-containing resin and a hydrogensiloxane group-containing resin in the composition and obtained by an addition reaction, etc., but the curable resin composition used is not limited to these.

[0036] As the (A-2) component preferably used for the curable resin composition having anaerobic curability containing a (meth)acrylate compound, there can be mentioned an organic metal complex that promotes anaerobic curability, an amine compound that promotes anaerobic curability, a thiol compound that promotes anaerobic curability, etc. In order to exhibit anaerobic curability, saccharin, etc. may be contained in the curable resin composition.

[0037] As the organic metal complex, a metal chelate complex is preferably used. For example, iron pentanedione, cobalt pentanedione, copper pentanedione, copper propylenediamine, copper ethylenediamine, iron naphthenate, nickel naphthenate, cobalt naphthenate, copper naphthenate, copper octoate, copper 2-ethylhexanoate, iron hexanoate, iron propionate, vanadium acetylacetonate, etc. can be cited, but it is not limited to these. In particular, organic copper complexes and organic iron complexes are preferred.

[0038] As an amine compound preferably used for an anaerobic curable curable resin composition containing a (meth)acrylate compound, a hydrazine compound can be mentioned in particular. As the hydrazine compound, for example, 1-acetyl-2-phenylhydrazine, 1-acetyl-2 (p-tolyl) hydrazine, 1-benzoyl-2-phenylhydrazine, 1-(1',1',1'-trifluoro)acetyl-2-phenylhydrazine, 1,5-diphenyl-carbohydrazide, 1-formyl-2-phenylhydrazine, 1-acetyl-2-(p-bromophenyl) hydrazine, 1-acetyl-2-(p-nitrophenyl) hydrazine, 1-acetyl-2-(2'-phenylethylhydrazine), ethyl carbazate, p-nitrophenylhydrazine, p-trisulfonylhydrazide, etc. can be mentioned, but it is not limited to these.

[0039] Examples of amine compounds other than hydrazine compounds include secondary heterocyclic amines such as 2-ethylhexylamine, 1,2,3,4-tetrahydroquinone, and 1,2,3,4-tetrahydroquinaldine; tertiary heterocyclic amines such as quinoline, methylquinoline, quinaldine, and quinoxalinephenazine; aromatic tertiary amines such as N,N-dimethyl-p-toluidine, N,N-dimethylanisidine, and N,N-dimethylaniline; 1,2,4-triazole, Azoles, Examples of the azole compounds include, but are not limited to, oxadiazole, thiadiazole, benzotriazole, hydroxybenzotriazole, 1,2,3-benzothiadiazole, and 3-mercaptobenzotriazole.

[0040] Examples of the thiol compound include, but are not limited to, linear thiols such as n-dodecyl mercaptan, ethyl mercaptan, and butyl mercaptan. However, amine compounds are not included.

[0041] The component (A-2) preferably used for the curable resin composition containing the cyanoacrylate compound includes aldehyde compounds, amine compounds, inclusion compounds, and water. The component (A-2) may be a compound that can become a desired anion species when the cyanoacrylate is cured, or a compound that introduces moisture from the outside air.

[0042] Specific examples of aldehyde compounds include benzaldehyde, dimethylaminobenzaldehyde, diethylaminobenzaldehyde, p-dimethylbenzaldehyde, aminobenzaldehyde, terephthalaldehyde, and aldehyde aniline compounds. In addition, specific examples of aldehyde aniline compounds include compounds generated by a dehydration condensation reaction of an aldehyde and aniline, and specifically, acetaldehyde aniline, propionaldehyde aniline, butyraldehyde aniline, valeraldehyde aniline, hexylaldehyde aniline, valeraldehyde aniline, etc., but are not limited to these.

[0043] Specific examples of amine compounds preferably used for the curable resin composition containing a cyanoacrylate compound include dimethylaminopropanol, diethylaminopropanol, diethylaminopentanol, dimethylaminohexanol, 2-dimethylamino-2-methylpropanol, and the like. In addition, amine compounds represented by the general formula R(NH2)2 (wherein R is C n H 2n , n=1 to 10), specifically, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, etc. In addition, diethylenetriamine, triethylenetetramine, N-methyldiethanolamine, etc. can also be used, but it is not limited to these.

[0044] Examples of the inclusion compound include polyethylene glycol derivatives, crown ethers and their derivatives, calixarene derivatives, thiacalixarene derivatives, and the like, but are not limited thereto.

[0045] As water, alkaline electrolyzed water, ion exchange water, etc. can be used, but it is not limited to these.

[0046] The component (A-2) preferably used for the curable resin composition obtained by addition reaction of the vinylsiloxane group-containing resin and the hydrogensiloxane group-containing resin in the composition is not limited as long as it is a metal catalyst that promotes the addition reaction.

[0047] As a metal catalyst promoting the addition reaction, from the perspective of price and variety, platinum-based metal catalysts and / or rhodium-based metal catalysts are preferred. As a specific example of a platinum-based metal catalyst, in a 0-valent platinum complex, divinyltetramethyldisiloxane platinum complex and tetravinyltetramethyltetracyclosiloxane platinum complex can be cited, in a 2-valent platinum complex, dichlorobistriphenylphosphine palladium complex can be cited, and in a 4-valent platinum complex, chloroplatinic acid can be cited, but it is not limited to this. As a specific example of a rhodium-based metal catalyst, in a 1-valent rhodium complex, chlorotristriphenylphosphite-rhodium complex can be cited, in a 2-valent rhodium complex, tetraacetic acid dirhodium complex can be cited, and in a 3-valent rhodium complex, triacetylacetone rhodium complex can be cited, but it is not limited to this. In addition, two or more metal catalysts can be mixed and used.

[0048] As the skeleton of the main agent of the resin containing vinyl siloxane, dimethyl siloxane skeleton, polyisobutylene skeleton, polyisoprene skeleton, polybutadiene skeleton, etc. can be cited. As the resin containing vinyl siloxane, hydrogenated types of these resins having carbon-carbon double bonds in the skeleton can be cited. Hydrogenation is also called hydrogenation, which is a reduction reaction in which hydrogen atoms are added to a compound using hydrogen as a reducing agent to make the unsaturated bonds present in the molecule become saturated bonds. On the other hand, the resin containing hydrogen siloxane is a so-called crosslinking agent, which is a compound having more than one hydrogen siloxane group in one molecule. The compound is preferably a compound having more than two hydrogen siloxane groups in one molecule, and is particularly preferably a compound having compatibility with the resin containing vinyl siloxane.

[0049] The component (B) that can be used in the present invention is benzo Azole-based fluorescent sensitizer. However, it does not include component (A-1) and component (A-2). When the composition of the present invention is applied to a substrate, the presence of component (B) enables the area coated with the composition to be visually identified using a black light. Azole-based fluorescence sensitizers include benzo Azoles and benzo Azole derivatives. Azole derivatives, including compounds in which hydrogen or the like of the basic skeleton is replaced by a substituent, compounds having multiple benzophenones in one molecule Polymers of azole skeletons. However, those that do not show fluorescence sensitization effect are not included.

[0050] [Chemical formula 1]

[0051]

[0052] Specific examples of the component (B) include benzophenone Azoles, 1,4-bis(2-benzo oxazolidinyl)naphthalene, 2,5-bis(5-tert-butyl-2-benzo oxazolyl)thiophene, etc., but not limited to these. In addition, the (B) component may be used alone or in combination of two or more.

[0053] Examples of the component (B) include Nikkafluor SC200 manufactured by Nippon Chemical Industry Co., Ltd., and Tinopal OB CO and Tinopal OB of the Tinopal (registered trademark) series manufactured by BASF, but are not limited thereto.

[0054] The component (C) that can be used in the present invention is a solvent. The component (C) can be used as long as it is a solvent that dissolves the component (A-1), the component (A-2) and the component (B). In particular, solvents with low polarity and high volatility are preferred. The boiling point of the component (C) is preferably below 100°C, and in particular, below 80°C. Specific examples of the component (C) include hydrocarbon solvents such as n-hexane and cyclohexane; aromatic solvents such as toluene; ketone solvents such as acetone; ester solvents such as ethyl acetate, butyl acetate, propyl acetate; and fluorine-based solvents such as hydrochlorofluoroolefins, hydrofluoroethers, and hydrofluorocarbons, but are not limited to these. In order to adjust the leveling and viscosity of the composition, the concentrations of the components (A-1), (A-2) and (B) in the composition can be adjusted.

[0055] Relative to 100 parts by mass of component (C), it is preferred to contain 0.1 to 10 parts by mass of component (A-1) or component (A-2). If the content of component (A-1) or component (A-2) is 0.1 parts by mass or more, surface modification is easy to carry out when a surface treatment component is used, and curing acceleration is easy to carry out when a curing accelerator is used. If the content of component (A-1) or component (A-2) is 10 parts by mass or less, component (A-1) or component (A-2) is uniformly attached to the substrate without deviation.

[0056] The component (B) is preferably contained in an amount of 0.01 to 5.0 parts by mass relative to 100 parts by mass of the component (C). If the content of the component (B) is 0.01 parts by mass or more, the visual recognition under a black light is improved, and if the content of the component (B) is 5.0 parts by mass or less, the effects of the components (A-1) and (A-2) are not impaired.

[0057] In the composition of the present invention, within the range that does not impair the characteristics of the present invention, colorants such as pigments and dyes (excluding component (B)); inorganic fillers such as metal powder, calcium carbonate, talc, silicon dioxide, aluminum oxide, aluminum hydroxide; additives such as flame retardants, organic fillers, plasticizers, antioxidants, defoamers, coupling agents, leveling agents, and rheology control agents can be appropriately formulated. By adding them, a composition and a cured product thereof having excellent resin strength, workability, and storage properties are obtained. However, since the effects of the surface treatment of the present invention and the effects of curing promotion are hindered, it is most preferred that the composition does not contain curable resins, polymers, oligomers, elastomers, rubbers, thermoplastic resins, and fillers.

[0058] As described above, in the method for treating a substrate surface of the present invention, the method for applying a composition of the present invention, and the method for confirming a coated area of ​​the present invention, the composition is applied to a substrate.

[0059] As the substrate, plastics, metals, coated steel plates, etc. can be cited, but are not limited to these. When at least one selected from the group consisting of benzophenone and benzophenone derivatives is used as the (A-1) component, it is particularly effective for polyolefins such as polypropylene, which are difficult-to-bond substrates.

[0060] When the composition of the present invention is applied to a substrate, in order to show the adhesion of the curable resin composition, the thickness of the coating obtained by the coating in a wet state is preferably 10 μm or less. The composition can also be applied by a cotton swab, spray, etc., and the composition is intentionally spread on the surface of the substrate. In addition, after applying the composition, the composition can also be intentionally dried to form a dry coating. In particular, when at least one of the group consisting of benzophenone and benzophenone derivatives selected from the component (A-1) is used, it is preferred that after the composition is applied to the substrate, the component (C) is dried and then irradiated with active energy rays with a cumulative light amount. As the drying temperature, it is preferably 10 to 40°C, and as the drying time, it is preferably 1 second to 10 minutes.

[0061] As a method for confirming the area coated with the composition after the composition is applied to the substrate, a black light is used for confirmation. As a black light, a portable UV lamp SLUV-4 manufactured by AS ONE Co., Ltd. can be used, but it is not limited to these. In the present invention, by irradiating the area coated with the composition with a black light, the coating film looks whitish and floats. In addition, in the undried state or dry state of the (C) component, the area coated with the composition can be confirmed.

[0062] In addition, in the bonding method of the substrate of the present invention, a first substrate and a second substrate are prepared, the composition is applied to the first substrate, and the second substrate is bonded to the first substrate using a curable resin composition. The specific examples of the first substrate and the second substrate are the same as the specific examples of the above-mentioned substrate. The first substrate and the second substrate can use the same substrate or different substrates. In addition, after the composition is applied to the first substrate, the (C) component can be dried at the above-mentioned temperature and time.

[0063] The second substrate and the first substrate are bonded together by a curable resin composition. Depending on the components of the curable resin composition, the bonding and curing may be performed by leaving the composition at room temperature, or by heating the composition in a hot air drying furnace or the like.

[0064] Example

[0065] Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Hereinafter, the composition containing the surface treatment component or the curing accelerating component is also simply referred to as a composition.

[0066] [Examples 1 to 8, Reference Examples 1 and 2, Comparative Examples 1 to 3]

[0067] To prepare the composition, prepare the following ingredients.

[0068] (A-1) Component: Surface treatment component

[0069] ・Benzophenone (reagent)

[0070] (A-2) Component: Curing-accelerating component of curable resin

[0071] ・Copper 2-ethylhexanoate (reagent)

[0072] (B) Component: Benzo Azole fluorescent sensitizer

[0073] ・Benzo Azole fluorescent brightener (Nikkafluor SC200, manufactured by Nippon Chemical Industry Co., Ltd.)

[0074] ・1,4-Bis(2-benzo (oxazolyl)naphthalene (fluorescent brightener) (Tinopal (registered trademark) OB CO, manufactured by BASF)

[0075] ・2,5-bis(5-tert-butyl-2-benzo (Azolyl)thiophene (Tinopal (registered trademark) OB, manufactured by BASF)

[0076] (B') component: the following compounds not belonging to (B) component

[0077] ・Coumarin-based fluorescent whitening agent (Nikkafluor MCT, manufactured by Nippon Chemical Industry Co., Ltd.)

[0078] ・Fluorescent dye (Kayaset Flavine FG, manufactured by Nippon Kayaku Co., Ltd.)

[0079] ・Fluorescent brightener (Kayalight OS, manufactured by Nippon Kayaku Co., Ltd.)

[0080] (C) Ingredient: Solvent

[0081] ・Acetone (reagent)

[0082] ・n-Hexane (reagent)

[0083] Other ingredients

[0084] ・3-Methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0085] To prepare the compositions of Examples 1 to 5, Reference Example 1, and Comparative Examples 1 to 3, weigh component (C) into a container, weigh component (A-1) and place it in the container, and stir for 10 minutes until component (A-1) is dissolved. Weigh component (B) or component (B') and place it in a container, and stir for 30 minutes. If component (C) evaporates, add the volatile portion. The detailed preparation amounts are shown in Table 1, and the values ​​are expressed in parts by mass.

[0086] In addition, in Reference Example 1, the (B) component and the (B′) component were not used.

[0087]

[0088] The compositions of Examples 1 to 5, Reference Example 1, and Comparative Examples 1 to 3 were subjected to the solubility confirmation, appearance confirmation, fluorescence confirmation 1, and tensile shear adhesive strength measurement 1 described below. The results are summarized in Table 2.

[0089] [Solubility confirmation]

[0090] The composition was prepared and allowed to stand at 25°C for 10 minutes. The bottom of the colorless and transparent container was visually checked and the results were recorded in the "Solubility" row of Table 2 according to the following evaluation criteria. In order to ensure that there is no deviation between the components (A-1) and (B), the result of "A" is preferred. In the following appearance confirmation, fluorescence confirmation 1 and fluorescence confirmation 2, the expression "supernatant" is used even if the evaluation criteria is "A".

[0091] Evaluation Benchmarks

[0092] A: No residue (completely dissolved).

[0093] B: There is some residue (dissolved residue).

[0094] C: There is a large amount of residue (not dissolved at all).

[0095] [Appearance confirmation]

[0096] The prepared composition was left standing at 25°C for 10 minutes, and the supernatant liquid as the liquid portion of the container was visually checked. The results are recorded in the "Appearance" row of Table 2. In order to ensure that there is no difference between the (A-1) component and the (B) component, the supernatant liquid is preferably transparent.

[0097] [Fluorescence confirmation 1]

[0098] The supernatant obtained by the appearance check was applied to a polypropylene plate as a substrate with a cotton swab and allowed to stand for 30 seconds in an atmosphere of 25°C. Then, a conveyor-type ultraviolet irradiator using a high-pressure mercury lamp was used to irradiate at 30 kJ / m 2 The coated surface was irradiated with a cumulative light amount of 1000 nm and allowed to stand for 1 minute. Then, a black light was shone on the polypropylene plate and visually confirmed. The results were recorded in the "Fluorescence 1" row of Table 2 according to the following evaluation criteria. In order to reliably determine that the supernatant was applied by visual inspection, a result of "A" is preferred.

[0099] Evaluation Benchmarks

[0100] A: Glowing.

[0101] C: No light.

[0102] [Tensile shear bond strength measurement 1]

[0103] As a substrate, two polypropylene plates of 25 mm in width, 2.0 mm in thickness, and 100 mm in length were prepared, and the composition was applied to the surface of the substrate using a cotton swab, and then allowed to stand for 30 seconds in an atmosphere of 25°C. Then, a conveyor-type ultraviolet irradiator using a high-pressure mercury lamp was used to irradiate at 30 kJ / m 2The coating surface is irradiated with a cumulative light amount of to perform surface modification. As a curable resin composition, a two-component epoxy resin composition is used. The main agent is bisphenol A type epoxy resin, and the curing agent is triethylenetetramine. The main agent and the curing agent are mixed at a ratio of 100:13. The mixture of the main agent and the curing agent is used within 10 minutes after mixing. The curable resin composition is applied to the surface modified surface of a substrate that has completed surface modification, and the surface modified surface of another substrate that has completed surface modification is bonded to form a bonding surface of 25mm in width × 10mm in length, and fixed with a clamp. Then, it is placed in a hot air drying furnace at 100°C for 1 hour to prepare a test piece. The test piece is taken out after being placed, and after confirming that it has returned to room temperature, the two ends of the test piece are fixed with the chuck of the tensile testing machine, and the measurement is performed at a speed of 10mm / min in the shear direction. The "shear adhesion 1 (MPa)" is calculated from the maximum strength and the bonding area. In order to reliably perform surface modification, it is preferred that the shear adhesion is 3.0MPa or more. Incidentally, when the shear adhesive strength was measured using a two-component epoxy resin composition without surface modification of the polypropylene plate, the shear adhesive strength was 0.4 MPa.

[0104]

[0105] Table 2 shows the results of the verification of the composition containing the surface treatment component, which modifies the surface of the substrate by heating and irradiation with active energy rays. The azole-based fluorescent sensitizer was confirmed to have good solubility in both solvents, acetone and n-hexane, and to exhibit fluorescence. On the other hand, in Comparative Examples 1 to 3 using component (B'), although the solubility was good, no fluorescence was exhibited. In Reference Example 1, which did not contain component (B) and component (B'), no fluorescence was exhibited.

[0106] To prepare the compositions of Examples 6 to 8 and Reference Example 2, weigh component (C) into a container, weigh component (A-2) and other components and put them into the container, and stir for 10 minutes until component (A-2) is dissolved. Weigh component (B) and put it into a container, and stir for 30 minutes. In the case that component (C) volatilizes, add the volatile part. The detailed preparation amounts are shown in Table 3, and the values ​​are expressed in parts by mass.

[0107] In addition, in Reference Example 2, the (B) component and the (B′) component were not used.

[0108]

[0109] The compositions of Examples 6 to 8 and Reference Example 2 were subjected to the solubility confirmation, appearance confirmation, fluorescence confirmation 2, and tensile shear adhesive strength measurement 2 described below, and the results are summarized in Table 4. The solubility confirmation and appearance confirmation were performed using the same methods as described above. The fluorescence confirmation 2 and tensile shear adhesive strength measurement 2 were performed as follows.

[0110] [Fluorescence confirmation 2]

[0111] The supernatant obtained by the appearance check was applied to a polypropylene plate as a substrate with a cotton swab and left at 25°C for 1 minute. The polypropylene plate was then irradiated with a black light and visually checked. The results were recorded in the "Fluorescence 2" row of Table 4 according to the following evaluation criteria. In order to reliably determine that the supernatant was applied by visual inspection, a result of "A" is preferred.

[0112] Evaluation Benchmarks

[0113] A: Glow

[0114] C: No light

[0115] [Tensile shear bond strength measurement 2]

[0116] As a substrate, prepare 2 SPCC (Steel Plate Cold Commercial) plates with a width of 25 mm × a thickness of 1.6 mm × a length of 100 mm, apply the composition to the surface of the bonding area of ​​the substrate with a cotton swab, and let it stand for 30 seconds in an atmosphere of 25°C. As a curable resin composition, "ThreeBond 1357K manufactured by ThreeBond Co., Ltd." is used as a one-component anaerobic curing composition. The curable resin composition is applied to the bonding area of ​​one substrate, and the bonding area of ​​the other substrate is bonded in a manner to form a bonding surface with a width of 25 mm × a length of 10 mm, and fixed with a clamp. Place it in an atmosphere of 25°C for 1 hour to make a test piece. Fix both sides of the test piece with the chuck of a tensile testing machine, measure it at a speed of 10 mm / minute in the shear direction, and calculate the "shear bonding force 2 (MPa)" from the maximum strength and the bonding area. If the curing promotion is carried out reliably, it is preferred that the shear bonding force is 3.0 MPa or more.

[0117]

[0118] Table 4 shows the results of the verification of the composition containing the curing accelerating component. In Examples 6 to 8, benzophenone was added as the component (B). The azole-based fluorescence sensitizer was confirmed to have good solubility in acetone and to exhibit fluorescence. Reference Example 2, which did not contain the component (B) and the component (B'), did not exhibit fluorescence.

[0119] Although the present invention is described in detail with reference to specific embodiments, it is obvious to those skilled in the art that various changes and modifications can be made without departing from the subject matter and scope of the present invention. This application is based on Japanese patent application (Japanese Patent Application No. 2023-122864) filed on July 27, 2023, the contents of which are incorporated herein by reference.

[0120] Industrial Applicability

[0121] If the composition is opaque in a wet state, the appearance is poor when applied to an adherend. In addition, when a large amount of the composition is applied, if it cannot be visually recognized, it will cause obstacles in operation. As for the composition related to the present invention, the composition itself is transparent, and even if a small amount of coating is applied, it can be easily visually recognized using a black light, so it is a surface treatment agent for an adherend with good operability and a curing accelerator for a curable resin composition.

Claims

1. A composition comprising the following components (A-1), (B) and (C), (A-1) Components: Surface treatment components, (B) Component: Benzo Azole fluorescent sensitizer, (C) Component: solvent.

2. A composition comprising the following components (A-2), (B) and (C), (A-2) component: a curing accelerating component, (B) Component: Benzo Azole fluorescent sensitizer, (C) Component: solvent.

3. The composition according to claim 1, wherein The component (A-1) is at least one selected from the group consisting of benzophenone and benzophenone derivatives.

4. The composition according to claim 2, wherein The component (A-2) is at least one selected from the group consisting of an organic metal complex, a clathrate, water, a hydrazine compound, a thiol compound, an aldehyde compound, an amine compound, and a metal catalyst.

5. The composition according to claim 1 or 2, which does not contain a curable resin, a polymer, an oligomer, an elastomer, a rubber, a thermoplastic resin and a filler.

6. A method for treating a substrate surface, wherein: The composition according to claim 1 is applied to a substrate, and the composition is irradiated with active energy rays.

7. A method for coating a composition, comprising coating the composition according to claim 1 or 2 on a substrate, wherein The thickness of the coating film obtained by this coating is 10 μm or less in a wet state.

8. A method for confirming a coating area, wherein: The composition according to claim 1 or 2 is applied to a substrate, and the area where the composition is applied is confirmed using a black light.

9. A method for confirming a coating area, wherein: The composition according to claim 1 or 2 is applied to a substrate, the component (C) is dried, and the area where the composition is applied is confirmed using a black light.

10. A method for bonding substrates, wherein: preparing a first substrate and a second substrate, applying the composition according to claim 1 or 2 to the first substrate, The second substrate and the first substrate are bonded together using a curable resin composition.

11. A method for bonding substrates, wherein: preparing a first substrate and a second substrate, applying the composition according to claim 1 or 2 to the first substrate, Drying the component (C), The second substrate and the first substrate are bonded together using a curable resin composition.

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