Photocurable resin composition and its uses

Abstract

To provide a photocurable resin composition to be used for forming a coating film which has excellent antifogging properties and can maintain the antifogging properties over a long period of time..SOLUTION: The photocurable resin composition contains a polymer containing a structural unit represented by formula (NB) and a maleic anhydride structural unit, a photoradical polymerization initiator, and a reactive surfactant. (In the formula (NB), R1, R2, R3 and R4 are each independently a hydrogen atom or a C1-30 organic group; and a1 is 0, 1 or 2.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photocurable resin composition and its use. More specifically, the present invention relates to a photocurable resin composition used as an anti-fog coating material and an article coated with the anti-fog coating material. [Background technology]

[0002] Resin molded bodies are widely used as an alternative to glass plates from the viewpoints of weight reduction and moldability. Applications include a wide range of fields, such as automobile parts, home appliance parts, housings, containers, films, and sheets. In particular, transparent plastics are used in various windows, optical lenses, mirrors, glasses, goggles, soundproofing walls, traffic light lenses, headlight lenses, convex mirrors, windshields, nameplates, and the like. However, when one side of a resin substrate such as plastic falls below the dew point temperature due to the temperature and humidity difference with the outside air, or when a sudden change in temperature and humidity occurs, condensation occurs on the substrate surface, and fine water droplets adhere to the surface, scattering transmitted light. In such cases, the transparency of the resin molded body is impaired, and so-called fogging occurs.

[0003] A known method for preventing the occurrence of the above-mentioned fogging (anti-fogging) is to apply a solution containing a hydrophilic resin and a surfactant to the surface of the substrate to form a coating film (dried coating film or hardened coating film).

[0004] In this method, the surfactant contained in the coating film reduces the contact angle of the attached water droplets, and the moisture attached to the substrate surface does not form water droplets but a water film, which prevents light from being scattered, thereby exerting an anti-fogging effect. In addition, in this method, the surfactant quickly reduces the contact angle of the water droplets, so the anti-fogging effect can be exerted quickly.

[0005] However, when the above coating film is actually used (for example, when it is used for a long period of time or when the coating film surface is wiped with water), the surfactant inside the coating film easily flows out, and the anti-fogging property is reduced. On the other hand, although the durability of the anti-fogging property can be improved somewhat by adding a large amount of surfactant, it is not possible to improve it significantly, and there is also a problem that the coating film becomes easily damaged and the appearance of the coating film is deteriorated.

[0006] In order to prevent such outflow of the surfactant, a method of using a surfactant that is poorly soluble in water (Patent Document 1) has been reported. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2015-86370 A Summary of the Invention [Problem to be solved by the invention]

[0008] However, even with the technology of Patent Document 1, it was not possible to completely prevent the outflow of the surfactant, and there was room for improvement in terms of suppressing the outflow of the surfactant and maintaining anti-fogging properties over a long period of time. [Means for solving the problem]

[0009] The present invention has been made in consideration of the above problems, and has been completed based on the discovery that a coating film obtained from a polymer containing a specific structural unit having a hydrophilic group has excellent anti-fogging properties and can maintain the anti-fogging properties for a long period of time.

[0010] According to the present invention, A polymer including a structural unit represented by formula (NB) and a structural unit represented by formula (1); A photoradical polymerization initiator; and a reactive surfactant.

[0011] [ka] (In formula (NB), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1 or 2.

[0012] [ka] (In formula (1), R p is a group having two or more (meth)acryloyl groups.

[0013] Further, according to the present invention, A substrate made of a thermoplastic resin; A coating film formed on at least a portion of the surface of the substrate, An article is provided, in which the coating film is a cured film of the above-mentioned photocurable resin composition.

[0014] Furthermore, according to the present invention, applying the photocurable resin composition to a substrate to form a coating film of the photocurable resin composition on the substrate; and curing the coating film by irradiating the coating film with light to obtain a cured film. Effect of the Invention

[0015] According to the present invention, there are provided a photocurable resin composition used for forming a coating film having excellent anti-fogging properties and capable of maintaining the anti-fogging properties for a long period of time, an article obtained by coating the photocurable resin composition, and a method for producing a cured resin film using the photocurable resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Hereinafter, the embodiments of the present invention will be described. In this specification, the expression "a to b" in the explanation of a numerical range means "a or more and b or less" unless otherwise specified. For example, "5 to 90% by mass" means "5% by mass or more and 90% by mass or less."

[0017] In the description of groups (atomic groups) in this specification, when a description is made without specifying whether the group is substituted or unsubstituted, the description includes both groups having no substituents and groups having a substituent. For example, an "alkyl group" includes not only an alkyl group having no substituents (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[0018] In this specification, the term "(meth)acrylic" refers to a concept that includes both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In particular, the term "(meth)acryloyl group" in this specification represents a concept that encompasses an acryloyl group represented by -C(=O)-CH=CH2 and a methacryloyl group represented by -C(=O)-C(CH3)=CH2.

[0019] [Photocurable resin composition] The photocurable resin composition of the present invention (sometimes referred to as the "resin composition" in the present specification) has the following properties: A polymer including a structural unit represented by formula (NB) and a structural unit represented by formula (1); A photoradical polymerization initiator; and a reactive surfactant.

[0020] [ka]

[0021] In formula (NB), R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms; a1 is 0, 1 or 2.

[0022] [ka]

[0023] In formula (1), R p is a group having two or more (meth)acryloyl groups.

[0024] The resin composition of this embodiment contains a polymer (referred to as "polymer (P)" in this specification) containing a structural unit represented by formula (NB) and a structural unit represented by formula (1), and this polymer (P) has two or more (meth)acryloyl groups in its side chain. The thermosetting resin composition of this embodiment contains, in addition to the polymer (P), a photoradical polymerization initiator and a reactive surfactant, and this reactive surfactant crosslinks with the (meth)acryloyl group of the polymer (P) and the thiol group of the sensitizer by the action of the photoradical polymerization initiator activated by light irradiation to generate a crosslinked structure. The generated crosslinked structure is water-insoluble. In addition, since the reactive surfactant has a hydrophilic functional group, the generated crosslinked structure has a hydrophilic functional group derived from this reactive surfactant.

[0025] When the crosslinked structure is applied to the surface of a substrate, it forms a coating film on the surface of the substrate. Since the crosslinked structure has a hydrophilic functional group derived from the reactive surfactant, the resulting coating film has hydrophilicity, and therefore, when water (water vapor) adheres to the coating film, the water does not become water droplets but forms a water film. As a result, the substrate to which the coating film is applied exhibits anti-fogging properties. Furthermore, since the crosslinked structure has a three-dimensional network structure and is water-insoluble, even when the resulting coating film is exposed to water, it does not dissolve in water or desorb. Furthermore, the crosslinked structure has a structure in which a hydrophilic group derived from a reactive surfactant is covalently bonded to the main chain. Therefore, even when the coating film made of the crosslinked structure is exposed to water, the hydrophilic group derived from the reactive surfactant does not desorb from the crosslinked structure. Therefore, the coating film made of the crosslinked structure has excellent anti-fogging properties.

[0026] Each component contained in the thermosetting resin composition of the present embodiment will be described below.

[0027] (Polymer (P))

[0028] The polymer (P) used in the resin composition of the present embodiment contains a structural unit represented by formula (NB) and a structural unit represented by formula (1).

[0029] [ka]

[0030] In formula (NB), R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or an organic group having 1 to 30 carbon atoms; a1 is 0, 1 or 2.

[0031] [ka]

[0032] In formula (1), R p is a group having two or more (meth)acryloyl groups.

[0033] The polymer (P) used in the resin composition of this embodiment contains a structural unit represented by formula (1). In other words, the polymer (P) contains a structural unit having two or more (meth)acryloyl groups. This gives the polymer (P) excellent sensitivity, and the polymer (P) can undergo a crosslinking reaction with a reactive surfactant by light irradiation treatment. The polymer (P) also contains a structural unit represented by formula (NB). The structural unit (NB) is chemically robust. Therefore, the polymer (P) containing this structural unit as an essential component has excellent durability and weather resistance.

[0034] The proportion of the structural unit represented by formula (NB) in all structural units of the polymer P is preferably from 10 to 90 mol %, more preferably from 30 to 70 mol %, and further preferably from 40 to 60 mol %.

[0035] The proportion of the structural unit represented by formula (1) in all structural units of the polymer P is preferably from 3 to 40 mol %, more preferably from 3 to 30 mol %.

[0036] In one embodiment, the polymer (P) may contain a structural unit represented by formula (2) in addition to the structural unit (NB) and the structural unit (1).

[0037] [ka]

[0038] In formula (2), R s is a group having one (meth)acryloyl group. When the polymer (P) contains a structural unit represented by formula (2), the proportion of the structural unit represented by formula (2) in all structural units of the polymer (P) is preferably 5 to 30 mol %, more preferably 10 to 25 mol %. The unit represented by formula (2) has one (meth)acryloyl group, and the polymer (P) having such a structural unit has excellent sensitivity to light irradiation treatment and excellent crosslinking reactivity with reactive surfactants.

[0039] In one embodiment, the polymer (P) may contain a structural unit represented by formula (MA) in addition to the above structural units. When the polymer (P) contains a structural unit represented by formula (MA), the structural unit represented by formula (MA) preferably accounts for 10 to 30 mol %, more preferably 15 to 25 mol %, of all structural units of the polymer (P).

[0040] [ka]

[0041] In the structural unit represented by the formula (NB) constituting the polymer (P), R 1 ~R 4 Examples of the organic group having 1 to 30 carbon atoms that can constitute the above group include substituted or unsubstituted, linear or branched alkyl groups having 1 to 30 carbon atoms, and more specific examples thereof include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxyl groups.

[0042] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. The alkynyl group includes, for example, an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group, a neopentyloxy group, and an n-hexyloxy group. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

[0043] In the structural unit represented by the formula (NB), R 1, R 2 , R 3 and R 4 is preferably hydrogen or an alkyl group, and more preferably hydrogen. In addition, R 1 , R 2 , R 3 and R 4 The hydrogen atoms in the organic group having 1 to 30 carbon atoms may be substituted with any atomic group. For example, they may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, or the like. More specifically, R 1 , R 2 , R 3 and R 4 As the organic group having 1 to 30 carbon atoms, a fluorinated alkyl group or the like may be selected. In the structural unit represented by formula (NB), a1 is preferably 0 or 1, and more preferably 0.

[0044] In the structural unit represented by formula (1) constituting the polymer (P), R p R is a group containing two or more (meth)acryloyl groups, preferably a group containing 2 to 6 (meth)acryloyl groups, and more preferably a group containing 3 to 5 (meth)acryloyl groups. p By optimizing the number of (meth)acryloyl groups contained in, the crosslinking reactivity of the polymer (P) containing the same can be further increased, and the durability of the crosslinked structure obtained by the crosslinking reaction between the polymer (P), the crosslinking agent, and the reactive surfactant can be improved.

[0045] R in formula (1) p is preferably a group represented by formula (1b), a group represented by formula (1c), or a group represented by formula (1d). By using such a group, it is easy to obtain the above-mentioned various effects.

[0046] [ka]

[0047] In formula (1b), k is 2 or 3; R is a hydrogen atom or a methyl group, and multiple R may be the same or different. X 1 is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are multiple X 1 may be the same or different, X 1 ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X 2 is a k+1 valent organic group having 1 to 12 carbon atoms. From the viewpoint of crosslinking reactivity, R is preferably a hydrogen atom. Although k may be 2 or 3, it is preferably 3 from the viewpoints of availability of raw materials and further improvement of crosslinking reactivity.

[0048] X 1 When is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched. X 1 When X is an alkylene group having 1 to 6 carbon atoms, 1 is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH2- (methylene group).

[0049] X 1 When is a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), the alkylene group having 1 to 6 carbon atoms of X may be linear or branched. The alkylene group having 1 to 6 carbon atoms for X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH2-CH2- (ethylene group) or -CH2-CH(CH3)-.

[0050] X 1When X′ is an alkylene group having 1 to 6 carbon atoms, specific embodiments thereof are 1 is the same as: X 1 When X′ is a group represented by —X′-Z′-, specific embodiments of X′ are the same as those of X described above.

[0051] X 2 The k+1 valent organic group having 1 to 12 carbon atoms may be any group obtained by removing k+1 hydrogen atoms from any organic compound. Here, the any organic compound is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less. X 2 is, for example, a group in which k+1 hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group in which k+1 hydrogen atoms have been removed from a linear hydrocarbon having 1 to 3 carbon atoms. The hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxyl group). In addition, the hydrocarbon is preferably a saturated hydrocarbon.

[0052] [ka]

[0053] In formula (1c), k, R, X 1 and X 2 are R, k, and X in formula (1b), respectively. 1 and X 2 and R may be the same or different from each other, and X 1 may be the same or different, X 3 is a divalent organic group having 1 to 6 carbon atoms, X 4 and X 5 each independently represents a single bond or a divalent organic group having 1 to 6 carbon atoms, X 6 is a divalent organic group having 1 to 6 carbon atoms.

[0054] R, k, X 1 and X 2 Specific embodiments, preferred embodiments, etc. of are the same as those explained for general formula (1b). X 3 and X 6 Examples of the divalent organic group having 1 to 6 carbon atoms include a group in which two hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 6 carbon atoms. The hydrocarbon may contain an oxygen atom (for example, an ether bond or a hydroxyl group). The hydrocarbon is preferably a saturated hydrocarbon. X 4 and X 5 The divalent organic group having 1 to 6 carbon atoms may be a linear or branched alkylene group. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

[0055] [ka]

[0056] In formula (1d), n is an integer from 2 to 5, R is independently a hydrogen atom or a methyl group.

[0057] In the structural unit represented by formula (2), R S is, for example, a group represented by the following formula (2a).

[0058] [ka]

[0059] In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. X 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10. In formula (2a), X 10is a divalent organic group, and R is a hydrogen atom or a methyl group. X 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10. X 10 As the divalent organic group, for example, an alkylene group is preferable. A part of -CH2- in this alkylene group may be an ether group (-O-). The alkylene group may be linear or branched, but is more preferably linear.

[0060] X 10 The divalent organic group X is more preferably a linear alkylene group having a total of 3 to 6 carbon atoms. 10 The number of carbon atoms (X 10 By appropriately selecting the chain length of the structural unit represented by formula (2), the structural unit represented by formula (2) can be more easily involved in the crosslinking reaction, thereby increasing the crosslinking reactivity.

[0061] X 10 The divalent organic group (for example, an alkylene group) may be substituted with any substituent, such as an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. Also, X 10 The divalent organic group may be any group other than an alkylene group, for example, a divalent group formed by linking one or more groups selected from an alkylene group, a cycloalkylene group, an arylene group, an ether group, a carbonyl group, a carboxy group, and the like.

[0062] The content (ratio) of each structural unit contained in the polymer (P) can be determined by the amount (molar amount) of the raw materials used in synthesizing the polymer, the amount of the raw materials remaining after synthesis, and various spectra (e.g., IR spectrum, 1 H-NMR spectrum, 13 It can be estimated / calculated from the presence and peak area of ​​the C-NMR spectrum.

[0063] The weight average molecular weight Mw of the polymer (P) is, for example, 1000 to 22000, preferably 2000 to 20000, more preferably 3000 to 18000, and further preferably 3000 to 16000. By appropriately adjusting the weight average molecular weight, the properties of the crosslinked structure obtained from the polymer (P) can be controlled.

[0064] The dispersity of the polymer (P) (weight average molecular weight Mw / number average molecular weight Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and even more preferably 1.0 to 2.0. By appropriately adjusting the dispersity, the physical properties of the polymer (P) can be made uniform, which is preferable. These values ​​can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

[0065] The polymer (P) can be produced (synthesized) by a method known in the art to which the present invention pertains. The polymer (P) can be, for example, Step (I): preparing a raw material polymer containing a structural unit represented by formula (NB) and a structural unit represented by formula (MA); Step (II): A step of reacting the raw polymer obtained in step (I) with a compound having a hydroxyl group and two or more (meth)acryloyl groups (polyfunctional (meth)acrylic monomer) and / or a compound having a hydroxyl group and one (meth)acryloyl group (monofunctional (meth)acrylic monomer) in the presence of a basic catalyst to prepare a polymer (P) containing a structural unit represented by formula (NB), and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further containing a structural unit represented by formula (MA).

[0066] (Photoradical polymerization initiator) As the photoradical polymerization initiator used in the resin composition of the present embodiment, a known compound can be used, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-Methylpropan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone and other alkylphenone compounds; benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone and other benzoin methyl ether benzoin compounds such as benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine. halomethylated triazine compounds such as 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine, etc.; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole, etc.;Biimidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; 1-[4-(phenylthio)phenyl]-1,2-octanedione (O-benzoylthio) oxime), 1-(9-ethyl-9H-carbazol-3-yl)ethanone (O-acetyloxime), and other oxime ester compounds; bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, and other titanocene compounds; benzoic acid ester compounds, such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds, such as 9-phenylacridine. The photoradical polymerization initiator may be used alone or in combination of two or more kinds.; Among these, from the viewpoint of availability, oxime ester compounds such as 1-[4-(phenylthio)phenyl]-1,2-octanedione (O-benzoyloxime) and 1-(9-ethyl-9H-carbazol-3-yl)ethanone (O-acetyloxime) are preferably used. The photoradical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, relative to 100 parts by mass of the polymer (P).

[0067] (Reactive surfactant) The resin composition of this embodiment contains a reactive surfactant. The reactive surfactant refers to a surfactant capable of polymerizing with the (meth)acryloyl group of the polymer (P), specifically, a surfactant having a reactive functional group capable of polymerizing with the ethylenically unsaturated bond of the (meth)acryloyl group. Here, examples of the reactive functional group include a vinyl group, an allyl group, and a (meth)acryloyl group, and preferably a vinyl group. When the resin composition of this embodiment is irradiated with light, the (meth)acryloyl group of the polymer (P) and the reactive functional group of the reactive surfactant undergo a polymerization reaction due to the action of the photoradical initiator contained therein, thereby generating a crosslinked structure.

[0068] Examples of reactive surfactants that can be used include polyoxyethylene alkyl ether sulfates (commercially available products include Aqualon KH-05, KH-10, and KH-20 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Adeka Reasoap SR-10N and SR-20N manufactured by ADEKA Corporation, and Latemul PD-104 manufactured by Kao Corporation), polyoxyalkylene styrenated phenyl ether sulfates (commercially available products include Aqualon AR-10 and AR-20 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), sulfosuccinates (commercially available products include Latemul S-120, S-120A, S-180P, and S-180A manufactured by Kao Corporation, and Eleminol JS-2 manufactured by Sanyo Chemical Industries, Ltd.), polyoxyethylene alkyl phenyl ether sulfates, and polyoxyethylene alkyl phenyl ether sulfates. anionic reactive surfactants such as oxyethylene alkylphenyl ester sulfates (commercially available products include, for example, Aqualon HS-10, HS-20, HS-30, BC-10, and BC-20 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., and Adeka Reasoap SDX-222, SDX-223, SDX-232, SDX-233, SDX-259, SE-10N, and SE-20N manufactured by ADEKA Corporation), (meth)acrylate sulfates (commercially available products include, for example, Antox MS-60 and MS-2N manufactured by Nippon Nyukazai Co., Ltd., and Eleminol RS-30 manufactured by Sanyo Chemical Industries, Ltd.), and phosphates (commercially available products include, for example, H-3330PL manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., and Adeka Reasoap PP-70 manufactured by ADEKA Corporation); and Examples of the nonionic reactive surfactants include polyoxyethylene alkyl ether surfactants (commercially available products include ADEKA REASOAP ER-10, ER-20, ER-30, and ER-40 manufactured by ADEKA CORPORATION, and LATEMURU PD-420, PD-430, and PD-450 manufactured by Kao Corporation), polyoxyalkylene styrenated phenyl ether surfactants (commercially available products include AQUALON AN-10 and AN-20 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene alkyl phenyl ether surfactants or alkyl phenyl ester surfactants (commercially available products include AQUALON RN-10, RN-20, RN-30, and RN-50 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., and ADEKA REASOAP NE-10, NE-20, NE-30, and NE-40 manufactured by ADEKA CORPORATION), and (meth)acrylate sulfate surfactants (commercially available products include RMA-564, RMA-568, and RMA-1114 manufactured by Nippon Nyukazai Co., Ltd.).

[0069] The reactive surfactant of the present embodiment is particularly preferably an anionic surfactant represented by the following formula (sf1) or a nonionic surfactant represented by the following formula (sf2).

[0070] [ka]

[0071] In formula (sf1), q is an integer of 8 to 35, and preferably an integer of 8 to 20. R in formula (sf1) is an alkyl group having 1 to 20 carbon atoms, and preferably an alkyl group having 1 to 15 carbon atoms.

[0072] [ka]

[0073] In formula (sf2), r is an integer of 8 to 35, and preferably an integer of 8 to 20. R in formula (sf2) is an alkyl group having 1 to 20 carbon atoms, and preferably an alkyl group having 1 to 15 carbon atoms.

[0074] The amount of the reactive surfactant is, for example, 1 to 40 parts by mass, preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the polymer (P). By blending the polymer (P) and the reactive surfactant in the above-mentioned ranges in the resin composition, the crosslinked structure formed by the crosslinking reaction between them has a sufficiently high molecular weight to exhibit water resistance and has a sufficient hydrophilic functional group to exhibit anti-fogging properties.

[0075] (sensitizer) In one embodiment, the resin composition of the present invention may contain a sensitizer, and a compound containing at least two thiol groups is used as the sensitizer. Examples of compounds used as the sensitizer include the following formulas (s-1) to (s-20). These sensitizers may be used alone or in combination of two or more.

[0076] [ka]

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[0096] When the resin composition of the present embodiment contains a sensitizer, the amount thereof is, for example, 1 to 30 mass %, or preferably 5 to 20 mass %, based on the total solid content of the resin composition.

[0097] (Crosslinking agent) In one embodiment, the resin composition may contain a crosslinking agent, and as the crosslinking agent, a compound having at least two (meth)acryloyl groups (referred to as a "polyfunctional (meth)acrylic compound" in this specification) is used. Note that the polyfunctional (meth)acrylic compound as the crosslinking agent does not correspond to the above polymer (P). By photocuring the resin composition, an acrylic curing reaction between the above polymer (P), the reactive surfactant, and the crosslinking agent proceeds to generate a crosslinked structure. There is no particular upper limit to the number of functions (the number of polymerizable double bonds) per molecule of the crosslinking agent, but it is, for example, 8 or less, preferably 6 or less.

[0098] Specific examples of the crosslinking agent include the following: Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide adduct trimethylolpropane tri(meth)acrylate, ethylene oxide adduct Polyfunctional (meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate, and ε-caprolactone-added dipentaerythritol hexa(meth)acrylate.

[0099] Polyfunctional vinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexavinyl ether.

[0100] Vinyl ether group-containing (meth)acrylic acid esters such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate.

[0101] Polyfunctional allyl ethers such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether.

[0102] Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate. Polyfunctional (meth)acryloyl group-containing isocyanurates such as tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, and alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate. Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate. Polyfunctional urethane (meth)acrylates obtained by reacting polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Polyfunctional aromatic vinyls such as divinylbenzene.

[0103] Among these, trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and glycerin tri(meth)acrylate, tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate, and hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate are preferred.

[0104] When a crosslinking agent is used, the blending amount thereof is, for example, 10 to 60 parts by mass, preferably 10 to 50 parts by mass, and more preferably 15 to 45 parts by mass, relative to 100 parts by mass of the polymer (P).

[0105] (Adhesion aid) In one embodiment, the resin composition of the present invention may contain an adhesion aid. The adhesion aid is used to improve the adhesion between a coating film made of the resin composition and a substrate to which it is applied. As the adhesion aid, a silane coupling agent is preferably used. Examples of the silane coupling agent include vinyl silanes such as vinyl trimethoxy silane and vinyl triethoxy silane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyl trimethoxy silane, 3-glycidyloxypropyl trimethoxy silane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl methyl diethoxy silane, and 3-glycidoxypropyl triethoxy silane; styryl silanes such as p-styryl trimethoxy silane; methacryl silanes such as 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, and 3-methacryloxypropyl triethoxy silane; methacryl silanes such as methacryl ... Examples of suitable silane coupling agents include acrylic silanes such as 3-(trimethoxysilyl)propyl acid and 3-acryloxypropyltrimethoxysilane; amino silanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine and N-phenyl-γ-aminopropyltrimethoxysilane; isocyanurate silanes; alkyl silanes; ureido silanes such as 3-ureidopropyltrialkoxysilane; mercapto silanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; and isocyanate silanes such as 3-isocyanatepropyltriethoxysilane. The silane coupling agents may be used alone or in combination of two or more.

[0106] When an adhesion aid is used, the blending amount thereof is, for example, 0.01 to 5 mass %, preferably 0.1 to 4 mass %, and more preferably 1 to 3 mass %, based on the total solid content of the resin composition.

[0107] (solvent) The resin composition of the present embodiment typically contains a solvent. As the solvent, an organic solvent is preferably used. Specifically, one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, etc. can be used.

[0108] Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl-n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or mixtures thereof.

[0109] [Production of photocurable resin composition] The thermosetting resin composition of the present embodiment is provided as a liquid or varnish-like resin composition by dissolving or dispersing the above-mentioned polymer (P1), photoradical polymerization initiator, and reactive surfactant, and, if necessary, the above-mentioned adhesion aid and sensitizer, in the above-mentioned solvent.

[0110] The amount of the solvent used is not particularly limited, but is used in an amount such that the concentration of the non-volatile components (solid content) becomes, for example, 10 to 50% by mass, and preferably 15 to 40% by mass.

[0111] The resin composition of the present embodiment may contain other components such as surfactants, ultraviolet absorbers, antioxidants, matting agents, defoamers, and leveling agents, as necessary. When the resin composition of the present embodiment contains a surfactant, the amount of the surfactant is, for example, 5% by mass or less, preferably 3% by mass or less, and more preferably no surfactant, based on the total solid content of the resin composition. Here, the "surfactant" refers to a surfactant that is not introduced into the photocured product of the resin composition of the present embodiment and is separately blended, different from the above-mentioned "reactive surfactant". Since the resin composition of the present embodiment does not contain a surfactant, there is no problem of surfactant bleeding out when the coating film is exposed to water. Therefore, a coating film with excellent appearance can be obtained.

[0112] The coating film obtained from the resin composition of this embodiment has excellent anti-fogging properties. In this embodiment, the anti-fogging properties can be evaluated using the contact angle of the coating film with water as an index. The coating film obtained from the resin composition of this embodiment has high hydrophilicity, and therefore acts to lower the contact angle of the attached water droplets and form a water film. The water film formed on the coating film does not cause light scattering, and as a result, an anti-fogging effect is obtained. The contact angle of the coating film obtained from the resin composition of this embodiment with water is 60° or less, preferably 50° or less, more preferably 40° or less, even more preferably 30° or less, and even more preferably 20° or less. The contact angle can be measured by applying the resin composition of this embodiment to a substrate, heating it at 120°C to obtain a coating film, and measuring the coating film using a commercially available device such as "CA-Z" manufactured by Kyowa Interface Science Co., Ltd.

[0113] The coating film obtained from the resin composition of this embodiment is water-insoluble, and even when exposed to water, its performance, shape, and appearance are hardly or not changed. In this embodiment, being water-insoluble means that when the resin composition is applied to a substrate and dried at 120°C until a constant weight is reached to obtain a coating film, and the obtained coating film is dissolved in 100 g of water at 25°C until saturation is reached, the amount of dissolution is 10 g or less.

[0114] [Application] The photocurable resin composition of the present embodiment is applied to a substrate by a coating method commonly used in the art, dried as necessary, and then subjected to a light irradiation treatment, whereby a coating film (cured resin film) having anti-fogging properties can be formed on the surface of the substrate.

[0115] The substrate is not particularly limited, and known resin substrates (members) can be used. Examples of resin substrates (members) include polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, and polyamide resin. These substrates may be appropriately subjected to surface functionalization treatments such as hard coat treatment, anti-reflection treatment, transparent conductive treatment, electromagnetic wave shielding treatment, and gas barrier treatment depending on the purpose.

[0116] The method for applying the resin composition to the substrate may be a known method such as bar coater coating, brush coating, flow coating, dip coating, spray coating, spin coating, flow coating, etc. Preferably, the resin composition of the present embodiment is applied by spray coating using a spray coater.

[0117] The resin composition applied onto the substrate is typically dried by heating using a hot plate, hot air, an oven, etc. The heating temperature is usually 80 to 140° C., and preferably 90 to 120° C. The heating time is usually 30 to 600 seconds, and preferably about 30 to 300 seconds.

[0118] Subsequently, the coating film obtained by drying the resin composition is irradiated with active light rays to obtain a cured resin film by a crosslinking (curing) reaction. Examples of actinic rays include X-rays, electron beams, ultraviolet rays, and visible rays. In terms of wavelength, light of 200 to 500 nm is preferred. In terms of pattern resolution and ease of handling, the light source is preferably g-ray, h-ray, or i-ray from a mercury lamp, and particularly preferably i-ray. Two or more light rays may be mixed and used. As the exposure device, a contact aligner, a mirror projection, or a stepper is preferred. The amount of light for exposure may be appropriately adjusted depending on the amount of photosensitizer in the photosensitive resin film, but is, for example, 100 to 500 mJ / cm 2 That's about it.

[0119] After the light irradiation, the photosensitive resin film may be heated again (post-exposure bake) if necessary. The temperature is, for example, 70 to 150° C., and preferably 90 to 120° C. The time is, for example, 30 to 600 seconds, and preferably 30 to 300 seconds. Post-exposure bake promotes the reaction by the radicals generated from the photoradical polymerization initiator, and further promotes the curing reaction.

[0120] The thickness of the coating film obtained by coating and photocuring the resin composition of the present embodiment is preferably 0.5 μm or more, more preferably 1.0 μm or more, from the viewpoint of improving antifogging properties, and is preferably 20 μm or less, more preferably 10 μm or less, from the viewpoint of improving smoothness of the coating film.

[0121] Substrates coated with the resin composition of the present embodiment can be used for, for example, furniture, household goods, storage or stockpiling items, building materials such as walls or roofs, toys or play equipment, hobby items such as pachinko faces, medical supplies, welfare products, office automation equipment, audio-visual equipment, battery-powered electrical equipment, electrical or electronic products, lighting equipment, marine parts, body parts for aircraft structures, vehicle parts, and optical parts, and are particularly preferably used for vehicle applications and optical applications.

[0122] In vehicle applications, the film is suitable for interior and exterior components, and can be used in particular for components where LED light sources are expected, such as headlight covers, meter covers, or tail lamp covers. Examples of optical applications include transparent substrates used in solar cells. In addition, in the fields of optical communication systems, optical switching systems, and optical measurement systems, the material can be used for waveguides, optical fibers, optical fiber coating materials, LED lenses, LED lens (cap) covers, covers for various LEDs and EL lighting, etc. Particularly preferably, the material can be used for optical fibers, LED lenses, LED lens (cap) covers, covers for various LEDs and EL lighting, etc.

[0123] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can also be adopted. EXAMPLES

[0124] EXAMPLES Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these.

[0125] The compounds used in the examples may be indicated by the following abbreviations or trade names. ·MA: Maleic anhydride ·NB: 2-Norbornene MEK: Methyl ethyl ketone 4-HBA: 4-Hydroxybutyl acrylate A-TMM-3LM-N: A mixture of the following two compounds. The amount of the compound on the left in the mixture based on gas chromatography is approximately 57% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0126] [ka]

[0127] (Preparation Example 1: Preparation of Polymer (P1)) In a suitable sized reaction vessel equipped with a stirrer and a condenser, 353.02g (3.6mol) of maleic anhydride, 338.94g (3.6mol) of 2-norbornene, and 41.45g (0.180mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed out and dissolved in a mixed solvent of 578.98g of methyl ethyl ketone and 113.0g of toluene to prepare a solution. Nitrogen was bubbled through this solution for 30 minutes to remove oxygen, and then the solution was heated at 63° C. for 9.5 hours with stirring to polymerize maleic anhydride and 2-norbornene, producing a polymerized solution. The polymerization solution obtained above was diluted with 712.92 g of methyl ethyl ketone, and then added dropwise to 8519.9 g of methanol to precipitate a white solid. The obtained white solid was vacuum-dried at a temperature of 120° C. to obtain 550.4 g of a polymer (p1) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. The resulting polymer (p1) was subjected to GPC measurement, and as a result, the weight average molecular weight Mw was 11,600, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.79.

[0128] Next, the MA-derived structural units of polymer (p1) were ring-opened with a trifunctional (meth)acrylic compound (A-TMM-3LM-N) and a monofunctional (meth)acrylic compound (4-HBA) to prepare polymer (P1). Specifically, 150.45g of MEK was added to 90g of polymer (p1) (0.468 mol in terms of MA) to prepare a solution. Next, 87.18g of A-TMM-3LM-N was added to this solution, and then 27.00g (0.267 mol) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. After that, 84.41g (0.585 mol) of 4-HBA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. The reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase. The polymer was then purified as follows: The polymer was reprecipitated with an excess amount of toluene. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. After washing twice, the polymer powder was washed with an excess amount of water three times. The resulting reaction product was dried at 40°C for 16 hours. As a result, a polymer (P1) was obtained in which the structural units derived from maleic anhydride in the polymer (p1) were ring-opened with A-TMM-3LM-N and 4-HBA. By GPC measurement of the polymer (P1), it was confirmed that the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used disappeared. This confirmed that the obtained polymer P1 did not contain any unreacted (meth)acrylic compound or any (meth)acrylic compound without a hydroxyl group. In addition, the weight average molecular weight Mw of the obtained polymer (P1) was 14,100, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 1.69. 1 H-NMR measurement confirmed that the polymer (P1) had a structure in which the ring was opened with A-TMM-3LM-N and 4-HBA.

[0129] [Preparation of photocurable resin composition] (Examples 1 to 9, Comparative Example 1) Each component shown in Table 1 was dissolved in propylene glycol monomethyl ether (PGME) in the amount shown in Table 1 to prepare a resin composition having a solid content concentration of 22 mass %.

[0130] Details of each component listed in Table 1 are shown below. (Polymer (P)) Polymer (P1): Polymer (P1) obtained in Preparation Example 1 above (Photoradical polymerization initiator) Photoradical polymerization initiator 1: 1-[4-(phenylthio)phenyl]-1,2-octanedione (O-benzoyloxime) (BASF, Irgacure OXE01) (Reactive surfactant) Reactive surfactant 1: A compound of the following formula (SR-10) (R in formula (SR-10) is a hydrocarbon group, manufactured by ADEKA Corporation, product name ADEKA Reasoap SR-10)

[0131] [ka]

[0132] Reactive surfactant 2: a compound of the following formula (ER-10) (R in formula (ER-10) is a hydrocarbon group, manufactured by ADEKA Corporation, product name ADEKA REASOAP ER-10)

[0133] [ka]

[0134] (Crosslinking agent) Crosslinking agent 1: Ethoxylated glycerin triacrylate (A-GLY-3E, manufactured by Shin-Nakamura Chemical Co., Ltd.) Crosslinking agent 2: Dipentaerythritol polyacrylate (A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) (sensitizer) Sensitizer 1: pentaerythritol tetrakis(3-mercaptopropionate), a thiol group-containing compound of the above formula (s-2) (manufactured by SC Organic Chemical Co., Ltd.) (Adhesion aid) Adhesion aid 1: 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-403)

[0135] [Preparation of coating film and performance evaluation] The obtained resin composition was applied to a polycarbonate plate by spin coating at 2100 rpm. Then, it was baked on a hot plate at 100°C for 120 seconds to dry and remove the PGME, obtaining a coating film with a thickness of 2.0 μm. This coating film was then irradiated with 100 mJ / cm using a g+h+i line mask aligner (PLA-501F) manufactured by Canon Inc. 2 The coating was irradiated with g+h+i rays at an exposure dose of 100 to obtain a photocured film (coating film) of the resin composition. The polycarbonate plates coated with the coating film obtained above were used as test pieces and evaluated for the following items.

[0136] (Anti-fogging evaluation - Presence or absence of fogging due to exhalation) The test piece was blew on the coating surface several times and visually inspected for cloudiness. The results are shown in Table 1 using the following notation. 〇: Does not fog up △: Cloudiness disappears in an instant ×: Cloudy

[0137] (Anti-fogging evaluation - 80℃ steam test) The test piece was placed in a 80°C hot water bath so that the coating surface of the test piece was exposed to steam for 10 seconds. Immediately after the steam exposure, it was visually confirmed whether a water film was formed. The results are shown in Table 1 according to the following evaluation criteria. ◎: Creates a clean water film 〇: A water film is formed, but rippling is observed. ×: Water droplets are formed or the surface becomes cloudy.

[0138] (Evaluation of anti-fogging maintenance - repeated 80℃ steam test) The test piece was placed in a 80°C hot water bath so that the coating surface of the test piece was exposed to steam for 10 seconds, and then tilted and dried. This process was repeated 50 times, and it was visually confirmed whether a water film was formed immediately after the steam exposure. The results are shown in Table 1 according to the following evaluation criteria. ◎: Creates a clean water film 〇: A water film is formed, but rippling is observed. ×: Water droplets are formed or the surface becomes cloudy.

[0139] [Table 1]

[0140] All of the coating films obtained from the resin compositions of the Examples were excellent in anti-fogging properties and also in maintaining the anti-fogging properties.

Claims

1. A polymer including a structural unit represented by formula (NB) and a structural unit represented by formula (1); A photoradical polymerization initiator; A reactive surfactant, Photocurable resin composition. 【Chemistry 1】 (In formula (NB), R １ , R ２ , R ３ and R ４ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms; １ is 0, 1 or 2.) 【Chemistry 2】 (In formula (1), R ｐ is a group having two or more (meth)acryloyl groups.

2. 2. The photocurable resin composition according to claim 1, wherein the reactive surfactant is at least one selected from an anionic reactive surfactant and a nonionic reactive surfactant.

3. The photocurable resin composition according to claim 1 or 2, wherein the polymer further comprises a structural unit represented by formula (2). 【Chemistry 3】 (In formula (2), R ｓ is a group having one (meth)acryloyl group.

4. The photocurable resin composition according to claim 1 , wherein the polymer further comprises a structural unit represented by formula (MA). 【Chemistry 4】

5. Further comprising a cross-linking agent, The photocurable resin composition according to claim 1 , wherein the crosslinking agent is a compound having two or more (meth)acryloyl groups.

6. Further comprising a sensitizer, 6. The photocurable resin composition according to claim 1, wherein the sensitizer is a compound containing at least two thiol groups.

7. The photocurable resin composition according to claim 1 , further comprising an adhesion aid.

8. The photocurable resin composition according to claim 1 , further comprising a solvent.

9. A substrate made of a thermoplastic resin; A coating film formed on at least a portion of the surface of the substrate, An article, wherein the coating film is a cured resin film of the photocurable resin composition according to claim 1 .

10. The article according to claim 9, which is a vehicle component.

11. The article of claim 10 , wherein the vehicle component is a headlight cover, a meter cover, or a tail lamp cover.

12. A step of applying the photocurable resin composition according to any one of claims 1 to 8 onto a substrate to form a coating film of the photocurable resin composition on the substrate; a step of curing the coating film by irradiating the coating film with light to obtain a cured resin film; A method for producing a cured resin film, comprising:

13. The method for producing a cured film according to claim 12, wherein the step of applying the photocurable resin composition to a substrate is carried out by spray coating.

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