Curable composition, undercoat layer, laminate, and display device

Abstract

The purpose of the present invention is to provide a curable composition which is capable of forming a layer that exhibits excellent adhesion to a substrate and a hard coat layer and exhibits high surface hardness when a hard coat layer is laminated. The curable composition according to the present disclosure is characterized by containing, as a curable compound, a first epoxy compound, which is an organosiloxane containing two or more alicyclic epoxy groups, a second epoxy compound, a polyorganosiloxane having a silanol group, and a third epoxy compound or an oxetane compound. In addition, the curable composition of the present disclosure preferably contains the first epoxy compound, the second epoxy compound, the polyorganosiloxane having a silanol group, and the oxetane compound.

Description

Technical Field

[0001] The present disclosure relates to a curable composition, an undercoat for a cured product containing the curable composition, a laminate, and a display device. Background Art

[0002] The following configuration is known: on the surface of an article (substrate) that emphasizes transparency or aesthetics, such as a display of a television, a personal computer, a smartphone, or a film for a display thereof, a hard coat is provided for the purpose of improving scratch resistance (i.e., the property of preventing damage caused by scratching or scribing).

[0003] In particular, in order to exhibit the adhesion between the substrate and the hard coat, a configuration in which an undercoat (interlayer adhesion layer) is provided between the substrate and the hard coat is known (for example, Patent Document 1).

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2003-55601 Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] However, even when an undercoat is used, there continues to be a problem of insufficient adhesion between the undercoat and a hard coat having a specific composition.

[0009] In addition, if the adhesion to the substrate and the hard coat is improved, the surface hardness is likely to deteriorate when the hard coat is laminated, and it is difficult to balance the adhesion to the substrate and the hard coat and the high surface hardness.

[0010] The present disclosure solves the above problems, and an object thereof is to provide a curable composition capable of forming a layer having excellent adhesion to a substrate and a hard coat and exhibiting high surface hardness when the hard coat is laminated.

[0011] Solution to the Problem

[0012] The inventors of the present disclosure have found that, according to the following curable composition, the adhesion to a substrate and a hard coat is excellent, and high surface hardness is exhibited when the hard coat is laminated. The curable composition contains, as a curable compound: a first epoxy compound that is an organosiloxane containing two or more alicyclic epoxy groups, a second epoxy compound, a polyorganosiloxane having a silanol group, and a third epoxy compound or an oxetane compound. The present disclosure has been completed based on these findings.

[0013] That is, the present disclosure provides a curable composition containing the following compounds as curable compounds: a first epoxy compound which is an organosiloxane containing two or more alicyclic epoxy groups, a second epoxy compound, a polyorganosiloxane having a silanol group, and a third epoxy compound or an oxetane compound.

[0014] Preferably, the above curable composition contains the above first epoxy compound, the above second epoxy compound, the above polyorganosiloxane having a silanol group, and the above oxetane compound.

[0015] Preferably, in the above curable composition, the content of the above first epoxy compound is 30% by mass to 70% by mass relative to the total amount of the above curable compounds.

[0016] Preferably, in the above curable composition, the content of the above second epoxy compound is 20% by mass to 60% by mass relative to the total amount of the above curable compounds.

[0017] Preferably, in the above curable composition, the content of the above oxetane compound is 5% by mass to 25% by mass relative to the total amount of the above curable compounds.

[0018] Preferably, in the above curable composition, the content of the above polyorganosiloxane having a silanol group is 1% by mass to 15% by mass relative to the total amount of the above curable compounds.

[0019] Preferably, the above curable composition does not contain highly toxic substances.

[0020] Preferably, the above curable composition does not contain compounds conforming to PFAS.

[0021] In addition, the present disclosure provides a primer coat containing a cured product of the above curable composition.

[0022] Preferably, the thickness of the above primer coat is 0.1 μm to 20 μm.

[0023] In addition, the present disclosure provides a laminate which sequentially laminates a substrate, the above primer coat formed on at least one surface of the above substrate, and a hard coat.

[0024] Preferably, the above substrate of the above laminate is a glass substrate.

[0025] Preferably, the above hard coat of the above laminate contains a curable polyorganosilsesquioxane resin as a curable resin.

[0026] Preferably, the pencil hardness of the surface of the above hard coat of the above laminate is 3H or more.

[0027] Preferably, in the above laminate, 100 f squares are formed in a grid pattern on the surface of the above hard coat at intervals of 1 mm, a tape is adhered, and when peeled off in the 90° direction, 90 or more squares remain.

[0028] Preferably, the above hard coat of the above laminate does not contain a compound conforming to PFAS.

[0029] In addition, the present disclosure provides an image display device including the above laminate.

[0030] Advantages of the Invention

[0031] The curable composition of the present disclosure can form a layer having excellent adhesion to a substrate and a hard coat and exhibiting high surface hardness when laminating the hard coat. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 is a diagram showing an embodiment of a polyorganosiloxane having a silanol group 29 Si-NMR spectrum. DETAILED DESCRIPTION

[0033] In the present disclosure, “(meth)acryloyl” means “acryloyl and / or methacryloyl”. “(meth)acrylate” means “acrylate and / or methacrylate”.

[0034] [Curable Composition]

[0035] The curable composition of the present disclosure contains, as a curable compound: a first epoxy compound which is an organosiloxane having two or more alicyclic epoxy groups, a second epoxy compound, a polyorganosiloxane having a silanol group, and a third epoxy compound or an oxetane compound.

[0036] In addition, the above curable composition may be a photocurable composition, a thermosetting composition, or a curable composition having both photocurability and thermosetting properties. Among them, the above curable composition is preferably a photocurable composition.

[0037] [Organosiloxane having two or more alicyclic epoxy groups (first epoxy compound)]

[0038] The above-mentioned curable composition contains the above-mentioned first epoxy compound which is an organosiloxane having two or more alicyclic epoxy groups. The above-mentioned first epoxy compound is a compound having two or more alicyclic epoxy groups in the molecule and at least having a siloxane skeleton composed of siloxane bonds (Si-O-Si). The siloxane skeleton includes: a cyclic siloxane skeleton, a linear or branched organosilicon (linear or branched polysiloxane), a cage-type or ladder-type polysilsesquioxane, etc. In the present disclosure, among them, from the viewpoint of achieving both ease of coating on a substrate and adhesion, a compound having a cyclic siloxane skeleton is preferred. It should be noted that the above-mentioned first epoxy compound may be used alone or in combination of two or more.

[0039] In addition, when the above-mentioned first epoxy compound has a cyclic siloxane skeleton, the number of Si-O units forming the siloxane ring (equal to the number of silicon atoms forming the siloxane ring) is preferably 2 to 12, more preferably 4 to 8.

[0040] It should be noted that the existence rate of the silanol group in the above-mentioned first epoxy compound is preferably less than 5%, more preferably 1% or less, and further preferably 0%. That is, the above-mentioned first epoxy compound preferably does not contain a silanol group. It should be noted that the existence rate of the silanol group can be measured by the same method as that for measuring the following polyorganosiloxane having a silanol group.

[0041] The number average molecular weight (Mn) of the above-mentioned first epoxy compound in terms of standard polystyrene obtained by gel permeation chromatography is not particularly limited. For example, it is preferably 200 to less than 3000, more preferably 300 to 2000, and further preferably 400 to 800.

[0042] In addition, the alicyclic epoxy group of the above-mentioned first epoxy compound refers to a cyclic olefin group epoxidized in the molecule. The "epoxidized cyclic olefin group" refers to a group (monovalent group) formed by removing one hydrogen atom from a structure in which at least one of the carbon-carbon unsaturated bonds of a cyclic olefin (a cyclic aliphatic hydrocarbon in which at least one of the carbon-carbon bonds forming the ring is a carbon-carbon unsaturated bond) is epoxidized. That is, the epoxidized cyclic olefin group is a group containing an aliphatic hydrocarbon ring structure and an epoxy group, and the above-mentioned epoxy group is an epoxy group composed of two adjacent carbon atoms and an oxygen atom constituting the above-mentioned aliphatic hydrocarbon ring.

[0043] As the cycloalkenyl group (in the form before epoxidation) in the above epoxidized cycloalkenyl group, examples include: cycloalkenyl groups such as cyclopropenyl (e.g., 2-cyclopropen-1-yl, etc.), cyclobutenyl (e.g., 2-cyclobuten-1-yl, etc.), cyclopentenyl (e.g., 2-cyclopenten-1-yl, 3-cyclopenten-1-yl, etc.), cyclohexenyl (e.g., 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, etc.); cyclodienyl groups such as 2,4-cyclopentadien-1-yl, 2,4-cyclohexadien-1-yl, 2,5-cyclohexadien-1-yl; polycyclic groups such as dicyclopentenyl, dicyclohexenyl, norbornenyl, etc.

[0044] It should be noted that one or more substituents may be bonded to the aliphatic hydrocarbon ring forming the cycloalkenyl group in the above epoxidized cycloalkenyl group. As the above substituents, for example, substituents having 0 to 20 carbon atoms (more preferably 0 to 10 carbon atoms) can be cited. More specifically, examples include: halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydroxyl group; alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy (preferably C 1-6 alkoxy, more preferably C 1-4 alkoxy); alkenyloxy groups such as allyloxy (preferably C 2-6 alkenyloxy, more preferably C 2-4 alkenyloxy); aryloxy groups optionally having C 1-4 alkyl, C 2-4 alkenyl, halogen atom, C 1-4 alkoxy and other substituents on the aromatic ring, such as phenoxy, tolyloxy, naphthyloxy (preferably C 6-14 aryloxy); aralkyloxy groups such as benzyloxy, phenethyloxy (preferably C 7-18 aralkyloxy); acyloxy groups such as acetoxy, propionyloxy, (meth)acryloxy, benzoyloxy (preferably C 1-12 acyloxy); mercapto group; alkylthio groups such as methylthio, ethylthio (preferably C 1-6 alkylthio, more preferably C 1-4 alkylthio); alkenylthio groups such as allylthio (preferably C 2-6 alkenylthio, more preferably C 2-4 alkenylthio); arylthio groups optionally having C 1-4 alkyl, C 2-4 alkenyl, halogen atom, C 1-4 alkoxy and other substituents on the aromatic ring, such as phenylthio, tolylthio, naphthylthio (preferably C 6-14 arylthio); aralkylthio groups such as benzylthio, phenethylthio (preferably C 7-18 aralkylthio); carboxyl group; alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl (preferably C 1-6(alkoxy-carbonyl); aryloxy-carbonyl such as phenoxy-carbonyl, tolyloxy-carbonyl, naphthyloxy-carbonyl (preferably C 6-14 (aryloxy-carbonyl); aralkyloxy-carbonyl such as benzyloxy-carbonyl (preferably C 7-18 (aralkyloxy-carbonyl); amino; mono- or dialkylamino such as methylamino, ethylamino, dimethylamino, diethylamino (preferably mono- or di-C 1-6 alkylamino); acylamino such as acetylamino, propionylamino, benzoylamino (preferably C 1-11 acylamino); a group containing an oxetanyl group such as ethyloxetanyloxy; acyl groups such as acetyl, propionyl, benzoyl; oxo group; a group formed by bonding two or more of these groups via C 1-6 alkylene bond, etc.

[0045] Among them, as the above cyclic olefin group, a cyclic olefin group having 5 to 12 carbon atoms is preferred, a cycloalkenyl group having 5 to 12 carbon atoms is more preferred, and a cyclohexenyl group is further preferred. That is, as the above epoxidized cyclic olefin group, a group formed by epoxidizing a cyclic olefin group having 5 to 12 carbon atoms is preferred, a group formed by epoxidizing a cycloalkenyl group having 5 to 12 carbon atoms is more preferred, and a group formed by epoxidizing a cyclohexenyl group (epoxycyclohexyl) is further preferred. It should be noted that the above first epoxide may have one kind of epoxidized cyclic olefin group or two or more kinds of epoxidized cyclic olefin groups.

[0046] The number of epoxidized cyclic olefin groups in the above first epoxide in the molecule only needs to be 2 or more, and there is no particular limitation. It is preferably 2 to 6, more preferably 3 to 5, and further preferably 4.

[0047] As the above-mentioned first epoxy compound, for example, the following can be cited: 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8,8-hexamethyl-cyclotetrasiloxane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,2,4,6,6,8-hexamethyl-cyclotetrasiloxane, 2,4-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6,8-dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 4,8-bis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,8-tris[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8-pentamethyl-cyclotetrasiloxane, 2,4,8-tris[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6-propyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,6,8-tetrakis[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,8-tetramethyl-cyclotetrasiloxane, epoxy group-containing sesquisiloxane, etc.

[0048] The content of the above-mentioned first epoxy compound in the curable composition of the present disclosure is preferably 30% by mass to 70% by mass, more preferably 35% by mass to 65% by mass, and still more preferably 40% by mass to 60% by mass, relative to the total amount (100% by mass) of the curable compounds. By being within the above range, the curable composition can be easily coated on the substrate, and further, the adhesion of the coated substrate is excellent.

[0049] <Second epoxy compound>

[0050] The above-mentioned curable composition contains other epoxy compounds (hereinafter, sometimes referred to as "second epoxy compounds") other than the above-mentioned first epoxy compound and the polyorganosiloxane having a silanol group described later. By containing the above-mentioned second epoxy compound, the curable composition can be easily coated on the substrate.

[0051] As the above-mentioned second epoxy compound, the following can be cited: alicyclic epoxy compounds, aliphatic epoxy compounds, aromatic epoxy compounds, etc. other than the above-mentioned first epoxy compound. From the viewpoint of facilitating the coating on the substrate when combined with the above-mentioned first epoxy compound, the above-mentioned second epoxy compound is preferably an alicyclic epoxy compound.

[0052] As the above-mentioned other alicyclic epoxy compounds, for example, the compound represented by the following formula (a1) can be cited.

[0053] [Chemical formula 1]

[0054] R-X—R (a1)

[0055] In the above formula (a1), examples of R include the same groups as the above epoxidized cyclic olefin groups. The two Rs are optionally the same or different. X represents a single bond or a linking group (a divalent group having more than one atom; excluding groups containing a siloxane bond). Examples of the above linking group include: a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group formed by linking a plurality of them. Examples of the above divalent hydrocarbon group include: a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a group formed by bonding a plurality of them. Examples of the above divalent aliphatic hydrocarbon group include: a straight-chain or branched alkylene group such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene (for example, an alkylene group having 1 to 6 carbon atoms). In addition, examples of the divalent alicyclic hydrocarbon group include: a divalent cycloalkyl group such as 1,2-cyclopentylene, 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene. Examples of the compound represented by the above formula (a1) include a compound in which both Rs are epoxycyclohexyl groups (especially a compound in which the 4-position carbon atoms of two epoxycyclohexyl groups (assuming the positions of the two carbon atoms forming the epoxy group are the 1st and 2nd positions) are connected by a single bond or a divalent hydrocarbon group).

[0056] Specific examples of the alicyclic epoxy compound represented by the above formula (a1) include: (3,4,3',4'-diepoxy)bicyclohexane, bis(3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexan-1-yl)propane, 1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, bis(3,4-epoxycyclohexylmethyl) ether, 3',4'-epoxycyclohexylmethyl, 3,4-epoxycyclohexane carboxylate, etc.

[0057] In addition, among the above other alicyclic epoxy compounds, there are also compounds represented by the following formula (b1), etc., compounds in which an epoxy group is directly bonded to an alicyclic ring by a single bond, hydrogenated aromatic glycidyl ether-based epoxy compounds, etc.

[0058] [Chemical formula 2]

[0059]

[0060] In formula (b1), R i is a group obtained by removing q -OHs from a q-valent alcohol, and p and q each represent a natural number. As the q-valent alcohol [R i (OH) q, polyhydric alcohols such as 2,2-bis(hydroxymethyl)-1-butanol (alcohols having 1 to 15 carbon atoms, etc.) can be cited. q is preferably 1 to 6, and p is preferably 1 to 30. When q is 2 or more, p in the groups within two or more () (inside the parentheses) can be the same or different. As the above compound, specifically, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, trade name "EHPE3150" (manufactured by DAICEL Corporation), etc. can be cited.

[0061] As the above hydrogenated aromatic glycidyl ether-based epoxy compound, for example, the following can be cited: compounds obtained by hydrogenating bisphenol A type epoxy compounds such as 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane, 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane, and their polymers (hydrogenated bisphenol A type epoxy compounds); compounds obtained by hydrogenating bisphenol F type epoxy compounds such as bis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane, and their polymers (hydrogenated bisphenol F type epoxy compounds); hydrogenated biphenol type epoxy compounds; hydrogenated phenol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compound of bisphenol A; hydrogenated naphthalene type epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from triphenylmethane, etc.

[0062] As the above aliphatic epoxy compound, for example, the following can be cited: glycidyl ethers of q-valent alcohols having no cyclic structure (q is a natural number); glycidyl esters of monovalent or polyvalent carboxylic acids [such as acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.]; epoxides of oils and fats having double bonds such as epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil; epoxides of polyolefins (including polydienes) such as epoxidized polybutadiene, etc.

[0063] As the above q-valent alcohol having no cyclic structure, for example, the following can be cited: monovalent alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol; divalent alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol; polyhydric alcohols having three or more valences such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, etc. In addition, q-valent alcohols can include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, etc.

[0064] As the above-mentioned aromatic epoxy compound, for example, there can be mentioned: Epoxy-Bis type glycidyl ether type epoxy resins obtained by the condensation reaction of bisphenols [for example, bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene, etc.] and epihalohydrin; high molecular weight Epoxy-Bis type glycidyl ether type epoxy resins obtained by further addition reaction of these Epoxy-Bis type glycidyl ether type epoxy resins with the above-mentioned bisphenols; linear novolac / alkyl type glycidyl ether type epoxy resins obtained by the condensation reaction of phenols [for example, phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, etc.] and aldehydes [for example, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.] to obtain polyols, and further subjecting the polyols to a condensation reaction with epihalohydrin; epoxy compounds in which two phenolic skeletons are bonded to the 9-position of the fluorene ring, and glycidyl groups are directly or via an alkyleneoxy group bonded to the oxygen atoms after removing hydrogen atoms from the hydroxyl groups of these phenolic skeletons, etc.

[0065] The content of the second epoxy compound in the curable composition of the present disclosure is preferably 20% by mass to 60% by mass, more preferably 25% by mass to 55% by mass, and still more preferably 30% by mass to 50% based on the total amount (100% by mass) of the curable compounds. By being within the above range, the curable composition can be easily coated on the substrate.

[0066] <Polyorganosiloxane having a silanol group>

[0067] In addition to the above-mentioned first epoxy compound and second epoxy compound, the above-mentioned curable composition further contains a polyorganosiloxane having a silanol group. It is presumed that the silanol group contained in the above-mentioned polyorganosiloxane having a silanol group interacts with the substrate and the hard coat, thereby improving the adhesion. In addition, specifically, the above-mentioned polyorganosiloxane having a silanol group is preferably a compound having a different silanol group occupancy or number average molecular weight from the above-mentioned first epoxy compound, and more preferably a compound having a different silanol group occupancy and number average molecular weight from the above-mentioned first epoxy compound. As the above-mentioned polyorganosiloxane having a silanol group, only one kind can be used, or two or more kinds can be used.

[0068] The number average molecular weight (Mn) in terms of standard polystyrene obtained by gel permeation chromatography of the above-mentioned polyorganosiloxane having a silanol group is not particularly limited, and is preferably 1000 to 20000, more preferably 1500 to 15000, and still more preferably 2000 to 10000, for example.

[0069] As the structural unit contained in the above-mentioned polyorganosiloxane having a silanol group, there can be mentioned the structural unit (M unit) represented by [R3SiO 1 / 2 , and [R2SiO2 / 2 ] shown in the structural unit (D unit), [RSiO 3 / 2 ] and the structural unit (T unit) shown in [SiO 4 / 2 ] The structural unit (Q unit) shown in FIG. Among them, it is preferred to contain the above-mentioned T unit.

[0070] The ratio (total amount) of the T unit relative to the total amount of the siloxane structural units in the polyorganosiloxane having a silanol group [all siloxane structural units; the total amount of M units, D units, T units, and Q units] (100 mol%) is not particularly limited, but is preferably 70 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more. By setting the above ratio to 70 mol% or more, the adhesion of the curable composition can be easily improved. The upper limit is not particularly limited and may be 100 mol%. It should be noted that the ratio of each siloxane structural unit in the polyorganosilsesquioxane of the present disclosure can be calculated, for example, by the composition of the raw materials, NMR spectrum measurement described later, and the like.

[0071] The silanol group content of the polyorganosiloxane having silanol groups is preferably 5% or more, more preferably 10% or more, further preferably 15% or more, and particularly preferably 20% or more. A silanol group content of 5% or more facilitates adhesion to the substrate. The upper limit is not particularly limited and may be 50% or less.

[0072] In addition, the abundance ratio of the said silanol group can be measured by the following method.

[0073] Figure 1 One embodiment of polyorganosiloxane having a silanol group is represented by 29 Spectrum obtained by Si-NMR measurement. The obtained spectrum was subjected to waveform separation, and the peak observed between the chemical shift of -47ppm and -53ppm was identified as originating from the T1 structure, the peak observed between -54ppm and -60ppm was identified as originating from the T2 structure, and the peak observed between -64ppm and -70ppm was identified as originating from the T3 structure. It should be noted that the T1 body, T2 body, and T3 body are defined according to the number of silicon atoms bonded via oxygen atoms. At this time, the ratio (%) of the area value of each peak of T1 to T3 body relative to the total area value of each peak (100%) is the content ratio (mol %) of each structure (T1 to T3 body) in the polyorganosiloxane having a silanol group as the measurement object. Then, using this value and the content ratio of hydroxyl groups relative to the total molar number of oxygen atoms and hydroxyl groups in each structure of T1 to T3 body, the presence rate (%) of all silanol groups can be calculated according to the following formula.

[0074] Percentage of silanol groups present (%) = (T1 × 2 / 3 + T2 × 1 / 3 + T3 × 0 / 3)

[0075] In the above formula, T1, T2, and T3 respectively represent the ratio (%) of the peak area of the structure derived from each silicon atom to the total peak area (100%) of the structure derived from silicon atoms, as determined by 29 Si-NMR measurement, that is, the content ratio of each structure obtained from the above NMR measurement results.

[0076] Similarly, for the D unit, the spectrum obtained by 29 Si-NMR measurement is subjected to waveform separation and identified as derived from the D1 body structure and the D2 body structure. The D1 body and D2 body are defined according to the number of silicon atoms bonded via oxygen atoms. In addition, the percentage of the total silanol groups present (%) can be calculated according to the following formula by the same method as in the case of the above T unit.

[0077] Percentage of silanol groups present (%) = (D1 × 1 / 2 + D2 × 0 / 2)

[0078] Similarly, for the Q unit, the spectrum obtained by 29 Si-NMR measurement is subjected to waveform separation and identified as derived from the Q1 body structure, the Q2 body structure, the Q3 body structure, and the Q4 body structure. The Q1 body, Q2 body, Q3 body, and Q4 body are defined according to the number of silicon atoms bonded via oxygen atoms. In addition, the percentage of the total silanol groups present (%) can be calculated according to the following formula by the same method as in the case of the above T unit.

[0079] Percentage of silanol groups present (%) = (Q1 × 3 / 4 + Q2 × 2 / 4 + Q3 × 1 / 4 + Q4 × 0 / 4)

[0080] By measuring the amount of silanol groups present in the above T unit, D unit, and Q unit and adding them together, the percentage of silanol groups present in the above polyorganosiloxane having silanol groups can be calculated.

[0081] For the above polyorganosiloxane having silanol groups 29 The Si-NMR spectrum can be measured, for example, by the following apparatus and conditions.

[0082] Measuring apparatus: Trade name "JNM-ECA500 NMR" (manufactured by JEOL Ltd.).

[0083] Solvent: Deuterochloroform.

[0084] Number of accumulations: 10,000 times.

[0085] Measurement temperature: 25 °C.

[0086] In addition, when the polyorganosiloxane having a silanol group contains T units, as the content ratio of the above-mentioned T1 body, relative to the total of the above-mentioned T1 to T3 bodies (100%), it is preferably 5% or more, more preferably 10% or more. By making the content ratio of the T1 body 5% or more, the ratio of the silanol group can be easily made sufficient. There is no particular limitation on the upper limit, and it can be 50% or less, or 30% or less.

[0087] In addition, when the polyorganosiloxane having a silanol group contains T units, as the content ratio of the above-mentioned T2 body, relative to the total of the above-mentioned T1 to T3 bodies (100%), it is preferably 30% or more, more preferably 40% or more, and further preferably 50% or more. By making the content ratio of the T2 body 30% or more, the ratio of the silanol group can be easily made sufficient. There is no particular limitation on the upper limit, and it can be 80% or less, or 70% or less.

[0088] In addition, when the polyorganosiloxane having a silanol group contains T units, as the content ratio of the above-mentioned T3 body, relative to the total of the above-mentioned T1 to T3 bodies (100%), it is preferably 40% or less, more preferably 30% or less. There is no particular limitation on the lower limit, and it can be 5% or more, or 10% or more.

[0089] The above-mentioned polyorganosiloxane having a silanol group preferably contains an active energy ray curable functional group. Examples of the above-mentioned active energy ray curable functional group include a photo cationic polymerizable functional group, a photo radical polymerizable functional group, etc. Among them, as the above-mentioned photo cationic polymerizable functional group, an epoxy group is preferably included. In addition, examples of the above-mentioned epoxy group include the same groups as the epoxy groups exemplified for the above-mentioned first epoxy compound and the above-mentioned second epoxy compound, and a glycidyl ether group and a group exemplified as an aromatic epoxy compound are particularly preferably included.

[0090] As the content of the above-mentioned polyorganosiloxane having a silanol group, relative to the total amount of the curable compound (100% by mass), it is preferably 1% by mass to 15% by mass, more preferably 2% by mass to 10% by mass. If the content of the polyorganosiloxane having a silanol group is 1% by mass or more, the amount of the silanol group is sufficient and the adhesiveness is easily exhibited. In addition, by making the content of the polyorganosiloxane having a silanol group 15% by mass or less, the storage stability is excellent.

[0091] <Oxetane compound>

[0092] As an embodiment of the curable composition of the present disclosure, in addition to the above-mentioned first epoxy compound, the above-mentioned second epoxy compound, and the above-mentioned polysiloxane having a silanol group, an oxetane compound is further contained. The above-mentioned oxetane compound is a compound having at least one or more oxetanyl groups as a cationically polymerizable group in one molecule, and may also be a compound containing two or more oxetanyl groups. It should be noted that one kind of the above-mentioned oxetane compound may be used, or two or more kinds may be used. By containing the above-mentioned oxetane compound, there is a tendency that the curable composition can exhibit adhesion to the substrate.

[0093] Examples of the above-mentioned oxetane compound include: trimethylene oxide, 3,3-bis(ethenyloxymethyl)oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, 3,3-bis(chloromethyl)oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, bis{[1-ethyl(3-oxetanyl)]methyl}ether, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]bicyclohexane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]cyclohexane, 3-{ethyl-[ethyl(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, and the like.

[0094] As the content of the above-mentioned oxetane compound, relative to the total amount (100% by mass) of the curable compound, it is preferably 5% by mass to 25% by mass, more preferably 10% by mass to 20% by mass. If the content of the oxetane compound is within the above range, it is easy to exhibit adhesion to the substrate.

[0095] It should be noted that in the above-mentioned curable composition, the third epoxy compound and the fourth epoxy compound described later may also be contained together with the above-mentioned oxetane compound.

[0096] <Third epoxy compound>

[0097] In addition, as another embodiment of the curable composition of the present disclosure, in addition to the above-mentioned first epoxy compound, second epoxy compound, and the above-mentioned polyorganosiloxane having a silanol group, a third epoxy compound is preferably contained. The third epoxy compound does not conform to the above-mentioned first epoxy compound and the above-mentioned polyorganosiloxane having a silanol group and is a component different from the above-mentioned second epoxy compound. It should be noted that in the above-mentioned curable composition, the epoxy compound with a higher content is used as the second epoxy compound, and the epoxy compound with a lower content is used as the third epoxy compound.

[0098] As the above-mentioned third epoxy compound, an epoxy compound that does not conform to the above-mentioned first epoxy compound and the above-mentioned polyorganosiloxane having a silanol group and is other than the epoxy compound used as the above-mentioned second epoxy compound can be cited. Specifically, the epoxy compounds exemplified as the above-mentioned second epoxy compound can be used.

[0099] As the above-mentioned third epoxy compound, particularly when an alicyclic epoxy compound is used as the second epoxy compound, an aliphatic epoxy compound is preferably contained as the third epoxy compound. By containing the above-mentioned aliphatic epoxy compound as the third epoxy compound, the adhesion to the substrate can be easily exhibited. It should be noted that as the above-mentioned aliphatic epoxy compound, the substances exemplified as the aliphatic epoxy compound of the above-mentioned second epoxy compound can be used.

[0100] When the above-mentioned third epoxy compound is contained, the content of the third epoxy compound is preferably 5% by mass to 25% by mass, more preferably 7% by mass to 20% by mass, based on the total amount (100% by mass) of the curable compound. If the content of the third epoxy compound is within the above range, the adhesion to the substrate can be easily exhibited.

[0101] In addition, the above-mentioned curable composition may further contain an epoxy compound (hereinafter referred to as "fourth epoxy compound") other than the above-mentioned first to third epoxy compounds and the above-mentioned polyorganosiloxane having a silanol group. As the above-mentioned fourth epoxy compound, an epoxy compound that does not conform to the above-mentioned first epoxy compound and is other than the epoxy compounds used as the above-mentioned second and third epoxy compounds can be used. That is, as the above-mentioned fourth epoxy compound, an epoxy compound other than the epoxy compounds used as the second and third epoxy compounds among the epoxy compounds exemplified as the above-mentioned second epoxy compound can be used. It should be noted that in the above-mentioned curable composition, the above-mentioned fourth epoxy compound is an epoxy compound with a lower content than the above-mentioned second epoxy compound and the above-mentioned third epoxy compound. One kind of the above-mentioned fourth epoxy compound can be used, or two or more kinds can be used.

[0102] In addition, when the above curable composition is a thermosetting composition, a thermosetting resin may also be contained. Examples of the above thermosetting resin include: phenolic resin, melamine resin, urea resin, silicone resin, epoxy resin, unsaturated polyester, vinyl ester resin, polyurethane, etc. The above thermosetting resin may be used alone or in combination of two or more.

[0103] Preferably, the above curable composition further contains a curing agent. As the above curing agent, known or conventional thermal polymerization initiators and photoinitiators can be used, and photoinitiators are preferably used. Among them, as the above photoinitiator, a photo cationic polymerization initiator can be preferably used. The above curing agent may be used singly or in combination of two or more.

[0104] As the above photo cationic polymerization initiator, known or conventional photo cationic polymerization initiators can be used. For example, there can be mentioned: sulfonium salts (salts formed by sulfonium ions and anions), iodonium salts (salts formed by iodonium ions and anions), selenonium salts (salts formed by selenonium ions and anions), ammonium salts (salts formed by ammonium ions and anions), phosphonium salts (salts formed by phosphonium ions and anions), salts formed by transition metal complex ions and anions, etc.

[0105] Examples of the above sulfonium salts include: triaryl sulfonium salts such as triphenyl sulfonium salt, tri-p-tolyl sulfonium salt, tri-o-tolyl sulfonium salt, tris(4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenyl sulfonium salt, 2-naphthyldiphenyl sulfonium salt, tris(4-fluorophenyl) sulfonium salt, tri-1-naphthyl sulfonium salt, tri-2-naphthyl sulfonium salt, tris(4-hydroxyphenyl) sulfonium salt, diphenyl[4-(phenylthio)phenyl] sulfonium salt, 4-(p-tolylthio)phenyl di-(p-phenyl) sulfonium salt; diaryl sulfonium salts such as diphenyl benzoylmethyl sulfonium salt, diphenyl 4-nitrobenzoylmethyl sulfonium salt, diphenyl benzyl sulfonium salt, diphenyl methyl sulfonium salt; monoaryl sulfonium salts such as phenyl methyl benzyl sulfonium salt, 4-hydroxyphenyl methyl benzyl sulfonium salt, 4-methoxyphenyl methyl benzyl sulfonium salt; trialkyl sulfonium salts such as dimethyl benzoylmethyl sulfonium salt, benzoylmethyl tetrahydrothiophenium salt, dimethyl benzyl sulfonium salt, etc.

[0106] Examples of the above diphenyl[4-(phenylthio)phenyl] sulfonium salt include diphenyl[4-(phenylthio)phenyl] sulfonium tetrakis(pentafluorophenyl) borate, diphenyl[4-(phenylthio)phenyl] sulfonium hexafluorophosphate, etc. In addition, commercially available products such as the trade name "CPI-100P" (manufactured by San-Apro Co., diphenyl[4-(phenylthio)phenyl] sulfonium hexafluorophosphate 50% propylene carbonate solution) can also be used.

[0107] As the above-mentioned iodonium salts, for example, the following can be cited: trade name "RHODORSIL PHOTOINITIATOR 2074" (manufactured by Rhodia Japan Co., Ltd., tetra(pentafluorophenyl)borate = [(1-methylethyl)phenyl](methylphenyl)iodonium), trade name "WPI-124" (manufactured by Wako Pure Chemical Industries, Ltd.), diphenyliodonium salts, ditolyl iodonium salts, bis(4-dodecylphenyl)iodonium salts, bis(4-methoxyphenyl)iodonium salts, etc.

[0108] As the above-mentioned selenonium salts, for example, the following can be cited: triarylselenonium salts such as triphenylselenonium salts, tritolylselenonium salts, tri(o-tolyl)selenonium salts, tris(4-methoxyphenyl)selenonium salts, 1-naphthyldiphenylselenium salts; diarylselenonium salts such as diphenylbenzoylmethylselenonium salts, diphenylbenzylselenonium salts, diphenylmethylselenonium salts; monoarylselenonium salts such as phenylmethylbenzylselenonium salts; trialkylselenonium salts such as dimethylbenzoylmethylselenium salts, etc.

[0109] As the above-mentioned ammonium salts, for example, the following can be cited: tetraalkylammonium salts such as tetramethylammonium salts, ethyltrimethylammonium salts, diethyldimethylammonium salts, triethylmethylammonium salts, tetraethylammonium salts, trimethyl(n-propyl)ammonium salts, trimethyl(n-butyl)ammonium salts; pyrrolonium salts such as N,N-dimethylpyrrolonium salts, N-ethyl-N-methylpyrrolonium salts; imidazolinium salts such as N,N'-dimethylimidazolinium salts, N,N'-diethylimidazolinium salts; tetrahydropyrimidinium salts such as N,N'-dimethyltetrahydropyrimidinium salts, N,N'-diethyltetrahydropyrimidinium salts; morpholinium salts such as N,N-dimethylmorpholinium salts, N,N-diethylmorpholinium salts; piperidinium salts such as N,N-dimethylpiperidinium salts, N,N-diethylpiperidinium salts; pyridinium salts such as N-methylpyridinium salts, N-ethylpyridinium salts; imidazolium salts such as N,N'-dimethylimidazolium salts; quinolinium salts such as N-methylquinolinium salts; isoquinolinium salts such as N-methylisoquinolinium salts; thiazolium salts such as benzylbenzothiazolium salts; acridinium salts such as benzylacridinium salts, etc.

[0110] As the above-mentioned phosphonium salts, for example, the following can be cited: tetraarylphosphonium salts such as tetraphenylphosphonium salts, tetratolylphosphonium salts, tetra(2-methoxyphenyl)phosphonium salts; triarylphosphonium salts such as triphenylbenzylphosphonium salts; tetraalkylphosphonium salts such as triethylbenzylphosphonium salts, tributylbenzylphosphonium salts, tetraethylphosphonium salts, tetrabutylphosphonium salts, triethylbenzoylmethylphosphonium salts, etc.

[0111] As the above-mentioned transition metal complex ionic salts, for example, the following can be cited: (η 5 -cyclopentadienyl)(η 6 -toluene)Cr + 、(η 5 -cyclopentadienyl)(η 6 -xylene)Cr +Salts of chromium complex cations; (η 5 -cyclopentadienyl)(η 6 -toluene)Fe + 、(η 5 -cyclopentadienyl)(η 6 -xylene)Fe + and salts of iron complex cations such as etc.

[0112] As anions constituting the above salts, for example, PF6 - 、BF4 - 、(C6F5)4B - 、(C6F5)4Ga - 、sulfonic acid anions, perhalic acid ions, halogenated sulfonic acid ions, sulfate ions, carbonate ions, aluminate ions, carboxylic acid ions, arylborate ions, thiocyanate ions, nitrate ions, etc.

[0113] The amount (mixing amount) of the above curing agent used is preferably 0.01 part by mass to 15 parts by mass, more preferably 0.03 part by mass to 10 parts by mass, still more preferably 0.05 part by mass to 10 parts by mass, and particularly preferably 0.1 part by mass to 5 parts by mass, relative to the total amount (100 parts by mass) of the curable compounds contained in the above curable composition. By using the curing agent within the above range, a cured product with excellent adhesion to the substrate can be obtained.

[0114] Preferably, the above curable composition further contains an antioxidant. As the above antioxidant, known or conventional antioxidants can be used. One kind of the above antioxidant can be used, or two or more kinds can be used.

[0115] As the antioxidant, known or conventional antioxidants can be used, and there is no particular limitation. For example, phenolic antioxidants (phenolic compounds), hindered amine antioxidants (hindered amine compounds), phosphorus antioxidants (phosphorus compounds), sulfur antioxidants (sulfur compounds), etc. can be cited.

[0116] As the above-mentioned phenolic antioxidants, for example, the following can be cited: monophenols such as 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethylphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, etc.; bisphenols such as 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy}ethyl] 2,4,8,10-tetraoxaspiro[5.5]undecane, etc.; polymeric phenols such as 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetra[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate]methane, bis[3,3'-bis(4'-hydroxy-3'-tert-butylphenyl)butyric acid] ethylene glycol ester, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-s-triazine-2,4,6-(1H, 3H, 5H)trione, tocopherol, etc.

[0117] As the above-mentioned hindered amine antioxidants, for example, the following can be cited: bis(1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl] malonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, etc.

[0118] As the above-mentioned phosphorus antioxidants, for example, the following can be cited: phosphite esters such as triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, cyclopentanetetraylbis(octadecyl) phosphite, cyclopentanetetraylbis(2,4-di-tert-butylphenyl) phosphite, cyclopentanetetraylbis(2,4-di-tert-butyl-4-methylphenyl) phosphite, bis[2-tert-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl] hydrogen phosphite, etc.; oxaphosphaphenanthrene oxides such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.

[0119] As the above-mentioned sulfur-based antioxidant, for example, dodecyl mercaptan, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, etc. can be cited.

[0120] Among them, as the antioxidant, phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred, and phenolic antioxidants are particularly preferred.

[0121] The usage amount (mixing amount) of the above-mentioned antioxidant is preferably 0.01 parts by mass to 15 parts by mass, more preferably 0.03 parts by mass to 10 parts by mass, further preferably 0.05 parts by mass to 10 parts by mass, and particularly preferably 0.1 parts by mass to 5 parts by mass with respect to the total amount (100 parts by mass) of the curable compound.

[0122] <Other Compounds>

[0123] The curable composition of the present disclosure may further contain other compounds in addition to the above-mentioned compounds. As the above-mentioned other compounds, for example, solvents, metal oxide particles, rubber particles, silicone-based defoamers, silane coupling agents, fillers, plasticizers, antistatic agents, flame retardants, colorants, ultraviolet absorbers, ion adsorbents, pigments, mold release agents, etc. can be cited. The content (mixing amount) of these various additives is preferably set to 5% by mass or less of the total amount (100% by mass) of the curable composition.

[0124] In addition, the above-mentioned curable composition preferably does not contain PFAS-compliant compounds. By having the above-mentioned constitution, PFAS-compliant compounds can be not used, which is suitable for environmental regulations and has excellent safety. It should be noted that in the present disclosure, "PFAS-compliant compounds" is a general term for perfluoroalkyl compounds and polyfluoroalkyl compounds.

[0125] In addition, the content of highly toxic substances in the above-mentioned curable composition is preferably 1000 mass ppm or less, and more preferably 0 mass ppm with respect to the total amount (100% by mass) of the curable composition. That is, it is preferred that the above-mentioned curable composition does not contain highly toxic substances. As the above-mentioned highly toxic substances, specifically, antimony compounds can be cited.

[0126] [Base Coating]

[0127] As an embodiment of the present disclosure, a base coating containing a cured product of the above-mentioned curable composition can be cited. The above-mentioned base coating can be obtained, for example, by coating at least one surface of a substrate with the above-mentioned curable composition and curing it.

[0128] As the above-mentioned base material, it can be a single layer or multiple layers composed of the same or different materials. In addition, as the above-mentioned base material, a resin base material, a glass base material, a metal base material, etc. can be used, and from the viewpoint of adhesion to the above-mentioned undercoat, a glass base material is preferred.

[0129] As a method for forming the above-mentioned undercoat, a common coating method can be used. For example, known methods such as dipping method, roll coating method, gravure coating method, reverse coating method, air knife coating method, comma coating method, die coating method, screen printing method, spraying method, inkjet coating method, spin coating method, intaglio offset printing method, organic vapor deposition method, etc. can be used. As the curing treatment, in the case where the above-mentioned curable composition is a photocurable composition, for example, light irradiation using a mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, sunlight, electron beam source, laser light source, LED light source, etc. can be cited. It is preferably irradiated within a range of, for example, 300 mJ / cm 2 ~10000 mJ / cm 2 The irradiation is carried out within the range. In the case where the above-mentioned curable composition is a thermosetting composition, the treatment can be carried out under the conditions of a heating temperature of 50°C to 200°C and a heating time of 5 minutes to 120 minutes. In addition, the heating temperature can be constant or can change stepwise. In addition, a transfer method such as adhesive material transfer, heat transfer, UV transfer, etc. can also be used to transfer a film pre-coated on another substrate by the above-mentioned forming method to the substrate.

[0130] Preferably, in the case where the above-mentioned curable composition is a photocurable composition, after the light irradiation is completed, an annealing treatment is further carried out to remove internal strain, for example, it is preferably heated at a temperature of 100°C to 200°C for about 30 minutes to 1 hour.

[0131] In addition, when visually confirming the appearance of the above-mentioned undercoat after curing, it is preferred that the coating can be carried out on the substrate without depressions, and more preferably, the coating can be uniformly carried out on the surface of the undercoat without roughness.

[0132] The thickness of the above-mentioned undercoat is preferably 0.1 μm to 20 μm, and more preferably 1 μm to 15 μm. By making the thickness of the undercoat 0.1 μm or more, the adhesion to the substrate and the hard coat can be easily exhibited. In addition, by making the thickness of the undercoat 20 μm or less, when laminating the hard coat, it is easy to improve the surface hardness of the hard coat surface.

[0133] [Laminate]

[0134] As an embodiment of the present disclosure, a laminate including the above-described substrate, the above-described undercoat layer, and the hard coat layer can be cited. The above laminate can be produced by further forming a hard coat layer on the undercoat layer formed on the above substrate. It should be noted that in the above laminate, the above laminate structure may be formed only on one surface (single surface) of the above substrate, or may be formed on both surfaces (both sides) of the above substrate. In addition, the above laminate may also have layers other than the undercoat layer and the hard coat layer. From the viewpoint of exhibiting the adhesiveness of the laminate, it is preferable to laminate the substrate, the undercoat layer, and the hard coat layer in this order.

[0135] The above hard coat layer preferably contains a curable resin. As the above curable resin, a cured product of a polyorganosilsesquioxane having a structural unit represented by the following formula (1) (hereinafter, sometimes referred to as "the polyorganosilsesquioxane of the present disclosure"), that is, a curable polyorganosilsesquioxane resin is preferably included. In other words, the curable composition (hereinafter, sometimes referred to as "hard coat agent") for forming the above hard coat layer preferably contains a polyorganosilsesquioxane having a structural unit represented by the following formula (1). As described later, the above hard coat agent may also contain other components such as a curing agent (especially a photo cationic polymerization initiator, a photo radical polymerization initiator), an antioxidant, etc.

[0136] [Chemical formula 3]

[0137] [R 1 SiO 3 / 2 (1)

[0138] [In formula (1), R 1 represents a group containing an active energy ray curable functional group.]

[0139] The polyorganosilsesquioxane of the present disclosure is characterized by having the structural unit represented by the above formula (1). In addition, the polyorganosilsesquioxane of the present disclosure preferably has a structural unit represented by the following formula (I) (sometimes referred to as "T3 body") and a structural unit represented by the following formula (II) (sometimes referred to as "T2 body"). Furthermore, the polyorganosilsesquioxane of the present disclosure preferably has a structural unit represented by formula (4) described later.

[0140] [Chemical formula 4]

[0141] [R a SiO 3 / 2 (I)

[0142] [Chemical formula 5]

[0143] [R b SiO 2 / 2 (OR c )] (II)

[0144] The structural unit represented by the above formula (1) is usually a 3 / 2 silsesquioxane structural unit (T unit) represented by ]. It should be noted that in the above formula, R represents a hydrogen atom or a monovalent organic group, and the same applies hereinafter. The structural unit represented by the above formula (1) is formed by hydrolysis and condensation reactions of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, the compound represented by the following formula (a)).

[0145] R in formula (1) 1 represents a group (monovalent group) containing an energy ray curable functional group. That is, the polyorganosilsesquioxane of the present disclosure is a cationic photo-curable compound (cationic photopolymerizable compound) or a free radical photo-curable compound (free radical photopolymerizable compound) having at least an energy ray curable functional group in the molecule.

[0146] As the "cationic photopolymerizable functional group" in the group containing the energy ray curable functional group, there is no particular limitation as long as it has cationic photopolymerizability, and examples thereof include an epoxy group, an oxetanyl group, a vinyl ether group, a vinylphenyl group, etc. As the "free radical photopolymerizable functional group" in the group containing the energy ray curable functional group, there is no particular limitation as long as it has free radical photopolymerizability, and examples thereof include a (meth)acryloyloxy group, a (meth)acrylamide group, a vinyl group, a vinylthio group, etc. As the energy ray curable functional group, from the viewpoint of the surface hardness of the cured product (coating film), an epoxy group, a (meth)acryloyloxy group, etc. are preferred, and an epoxy group is particularly preferred.

[0147] As the group containing the above epoxy group, known or conventional groups having an ethylene oxide ring can be cited, and there is no particular limitation. From the viewpoints of the curability of the hard coat agent, the scratch resistance and toughness of the cured product (coating film), the group represented by the following formula (1a), the group represented by the following formula (1b), the group represented by the following formula (1c), and the group represented by the following formula (1d) are preferred, and the group represented by the following formula (1a) and the group represented by the following formula (1c) are more preferred, and the group represented by the following formula (1a) is further preferred.

[0148] [Chemical formula 6]

[0149]

[0150] [Chemical formula 7]

[0151]

[0152] [Chemical formula 8]

[0153]

[0154] [Chemical Formula 9]

[0155]

[0156] In the above formula (1a), R 1a represents a linear or branched alkylene group. Examples of the linear or branched alkylene group include linear or branched alkylene groups having 1 to 10 carbon atoms such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and decamethylene. Among them, as R 1a , from the viewpoints of the abrasion resistance and toughness of the cured product (coating film), a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferred, an ethylene group, trimethylene group, or propylene group is more preferred, and an ethylene group or trimethylene group is further preferred.

[0157] In the above formula (1b), R 1b represents a linear or branched alkylene group, and the same groups as those of R 1a can be exemplified. Among them, as R 1b , from the viewpoints of the abrasion resistance and toughness of the cured product (coating film), a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferred, an ethylene group, trimethylene group, or propylene group is more preferred, and an ethylene group or trimethylene group is further preferred.

[0158] In the above formula (1c), R 1c represents a linear or branched alkylene group, and the same groups as those of R 1a can be exemplified. Among them, as R 1c , from the viewpoints of the abrasion resistance and toughness of the cured product (coating film), a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferred, an ethylene group, trimethylene group, or propylene group is more preferred, and an ethylene group or trimethylene group is further preferred.

[0159] In the above formula (1d), R 1d represents a linear or branched alkylene group, and the same groups as those of R 1a can be exemplified. Among them, as R 1d , from the viewpoints of the abrasion resistance and toughness of the cured product (coating film), a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferred, an ethylene group, trimethylene group, or propylene group is more preferred, and an ethylene group or trimethylene group is further preferred.

[0160] As R 1 in the formula (1), from the viewpoints of the abrasion resistance and toughness of the cured product (coating film), the one represented by the above formula (1a) and R1a A group that is ethylene group [wherein, 2-(3',4'-epoxycyclohexyl)ethyl].

[0161] As the group containing the above oxetanyl group, known or conventional groups having an oxetane ring can be cited, and there is no particular limitation. For example, the oxetanyl group itself, a group in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms) is substituted with an oxetanyl group can be cited. From the viewpoints of the curability of the above hard coat agent, the abrasion resistance and toughness of the cured product (coating film), 3-oxetanyl, oxetane-3-ylmethyl, 3-ethyloxetane-3-ylmethyl, 2-(oxetane-3-yl)ethyl, 2-(3-ethyloxetane-3-yl)ethyl, 3-(oxetane-3-ylmethoxy)propyl, 3-(3-ethyloxetane-3-ylmethoxy)propyl, etc. are preferred.

[0162] As the group containing the above vinyl ether group, known or conventional groups having a vinyl ether group can be cited, and there is no particular limitation. For example, the vinyl ether group itself, a group in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms) is substituted with a vinyl ether group can be cited. From the viewpoints of the curability of the above hard coat agent, the abrasion resistance and toughness of the cured product (coating film), vinyloxymethyl, 2-(vinyloxy)ethyl, 3-(vinyloxy)propyl, etc. are preferred.

[0163] As the group containing the above vinylphenyl group, known or conventional groups having a vinylphenyl group can be cited, and there is no particular limitation. For example, the vinylphenyl group itself, a group in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms) is substituted with a vinylphenyl group can be cited. From the viewpoints of the curability of the above hard coat agent, the abrasion resistance and toughness of the cured product (coating film), 4-vinylphenyl, 3-vinylphenyl, 2-vinylphenyl, etc. are preferred.

[0164] Examples of the group containing the above (meth)acryloyloxy group include known or commonly used groups having a (meth)acryloyloxy group, and there is no particular limitation. For example, there can be mentioned: (meth)acryloyloxy itself, a group in which a hydrogen atom of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms) (usually one or more, preferably one hydrogen atom) is substituted with a (meth)acryloyloxy group. From the viewpoints of the curability of the above hard coat agent (coating film), the abrasion resistance and toughness of the cured product (coating film), 2-((meth)acryloyloxy)ethyl, 3-((meth)acryloyloxy)propyl, etc. are preferred.

[0165] Examples of the group containing the above (meth)acrylamide group include known or commonly used groups having a (meth)acrylamide group, and there is no particular limitation. For example, there can be mentioned: (meth)acrylamide itself, a group in which a hydrogen atom of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms) (usually one or more, preferably one hydrogen atom) is substituted with a (meth)acrylamide group. From the viewpoints of the curability of the above hard coat agent, the abrasion resistance and toughness of the cured product (coating film), 2-((meth)acrylamide)ethyl, 3-((meth)acrylamide)propyl, etc. are preferred.

[0166] Examples of the group containing the above vinyl group include known or commonly used groups having a vinyl group, and there is no particular limitation. For example, there can be mentioned: vinyl itself, a group in which a hydrogen atom of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms) (usually one or more, preferably one hydrogen atom) is substituted with a vinyl group. From the viewpoints of the curability of the above hard coat agent, the abrasion resistance and toughness of the cured product (coating film), vinyl, vinylmethyl, 2-vinylethyl, 3-vinylpropyl, etc. are preferred.

[0167] Examples of the group containing the above vinylthio group include known or commonly used groups having a vinylthio group, and there is no particular limitation. For example, there can be mentioned: vinylthio itself, a group in which a hydrogen atom of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms) (usually one or more, preferably one hydrogen atom) is substituted with a vinylthio group. From the viewpoints of the curability of the above hard coat agent, the abrasion resistance and toughness of the cured product (coating film), vinylthiomethyl, 2-(vinylthio)ethyl, 3-(vinylthio)propyl, etc. are preferred.

[0168] As R in formula (1) 1 , from the viewpoints of the abrasion resistance and toughness of the cured product (coating film), a group containing an epoxy group and a group containing a (meth)acryloyloxy group are preferred, and particularly preferred is the one represented by the above formula (1a) and R 1aGroups that are ethylene groups [wherein, 2-(3',4'-epoxycyclohexyl)ethyl], 3-(acryloyloxy)propyl, 3-(methacryloyloxy)propyl.

[0169] The polyorganosilsesquioxane of the present disclosure may have only one structural unit represented by the above formula (1), or may have two or more structural units represented by the above formula (1).

[0170] In addition to having the structural unit represented by the above formula (1), the polyorganosilsesquioxane of the present disclosure may also have a structural unit represented by the following formula (2) as a sesquisiloxane structural unit [RSiO 3 / 2 .

[0171] [Chemical formula 10]

[0172] [R 2 SiO 3 / 2 (2)

[0173] The structural unit represented by the above formula (2) is usually a sesquisiloxane structural unit (T unit) represented by [RSiO 3 / 2 . That is, the structural unit represented by the above formula (2) is formed by hydrolysis and condensation reactions of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, the compound represented by formula (b) described later).

[0174] R in the above formula (2) 2 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. As the above aryl group, for example, phenyl, tolyl, naphthyl, etc. can be cited. As the above aralkyl group, for example, benzyl, phenethyl, etc. can be cited. As the above cycloalkyl group, for example, cyclobutyl, cyclopentyl, cyclohexyl, etc. can be cited. As the above alkyl group, for example, straight-chain or branched alkyl groups such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, etc. can be cited. As the above alkenyl group, for example, straight-chain or branched alkenyl groups such as vinyl, allyl, isopropenyl, etc. can be cited.

[0175] As the above substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, substituted alkyl group, substituted alkenyl group, groups in which at least one of the hydrogen atoms or a part or all of the main chain skeleton of the above aryl group, aralkyl group, cycloalkyl group, alkyl group, alkenyl group is substituted by a group selected from the group consisting of an ether group, an ester group, a carbonyl group, a siloxanyl group, a halogen atom (fluorine atom, etc.), an acryloyl group, a methacryloyl group, a mercapto group, an amino group, and a hydroxyl group can be cited.

[0176] Among them, as R 2, preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, and further preferably a phenyl group.

[0177] The ratios of the above-mentioned various sesquisiloxane structural units (the structural unit represented by formula (1) and the structural unit represented by formula (2)) in the polyorganosilsesquioxane of the present disclosure can be appropriately adjusted according to the composition of the raw materials (hydrolyzable trifunctional silanes) used to form these structural units.

[0178] In addition, the polyorganosilsesquioxane of the present disclosure may also have at least one siloxane structural unit selected from the group consisting of sesquisiloxane structural units other than the structural unit represented by the above formula (1) and the structural unit represented by the above formula (2) [RSiO 3 / 2 , M unit, D unit, and Q unit. It should be noted that, as sesquisiloxane structural units other than the structural unit represented by the above formula (1) and the structural unit represented by the above formula (2), for example, the structural unit represented by the following formula (3) can be cited.

[0179] [Chemical formula 11]

[0180] [HSiO 3 / 2 (3)

[0181] When the polyorganosilsesquioxane of the present disclosure has the structural unit (T3 body) represented by the above formula (I) and the structural unit (T2 body) represented by the above formula (II), the ratio [T3 body / T2 body] is not particularly limited and can be appropriately selected, for example, from the range of 5 or more (for example, 5 or more and 500 or less). The lower limit value of the above ratio [T3 body / T2 body] is preferably 20, more preferably 21, more preferably 23, and further preferably 25. By setting the above ratio [T3 body / T2 body] to 5 or more, there is a tendency for the surface hardness, scratch resistance, and toughness of the cured product (coating film) to increase. On the other hand, the upper limit value of the above ratio [T3 body / T2 body] is preferably 500, more preferably 100, more preferably 50, and further preferably 40. By setting the above ratio [T3 body / T2 body] to 500 or less, the compatibility with other components in the hard coat agent is improved, and the viscosity is also suppressed, so the treatment becomes easy and it is easy to coat as a hard coat agent.

[0182] It should be noted that if the structural unit shown in the above formula (I) is described in more detail, it is represented by the following formula (I'). In addition, if the structural unit shown in the above formula (II) is described in more detail, it is represented by the following formula (II'). Among the three oxygen atoms bonded to the silicon atom shown in the structure shown in the following formula (I'), each is bonded to another silicon atom (a silicon atom not shown in formula (I')). On the other hand, the two oxygen atoms above and below the silicon atom shown in the structure shown in the following formula (II') are each bonded to another silicon atom (a silicon atom not shown in formula (II')). That is, the above T3 body and T2 body are both structural units (T units) formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound.

[0183] [Chemical formula 12]

[0184]

[0185] [Chemical formula 13]

[0186]

[0187] R in the above formula (I) a (R in formula (I') a is the same) and R in formula (II) b (R in formula (II') b is the same) each represent a group containing an active energy ray curable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom. As specific examples of R a and R b , the same groups as R 1 in the above formula (1) and R 2 in the above formula (2) can be exemplified. It should be noted that R a in formula (I) and R b in formula (II) respectively originate from the groups bonded to the silicon atom in the hydrolyzable trifunctional silane compound used as the raw material of the polyorganosilsesquioxane of the present disclosure (groups other than alkoxy groups and halogen atoms; for example, R 1 , R 2 , hydrogen atom, etc. in the following formulas (a) to (c)).

[0188] R in the above formula (II) c (R in formula (II') calso represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include linear or branched alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, and isobutyl. R in formula (II) c The alkyl group in is usually derived from the alkoxy group in the hydrolyzable silane compound used as a raw material for the polyorganosilsesquioxane of the present disclosure (for example, as the alkoxy group of X 1 to X 3 etc.).

[0189] The above ratio [T3 body / T2 body] in the polyorganosilsesquioxane of the present disclosure can be determined, for example, by 29 Si-NMR spectroscopy. In the 29 Si-NMR spectrum, the silicon atoms in the structural unit (T3 body) represented by the above formula (I) and the silicon atoms in the structural unit (T2 body) represented by the above formula (II) show signals (peaks) at different positions (chemical shifts). Therefore, the above ratio [T3 body / T2 body] can be determined by calculating the integral ratio of these respective peaks. Specifically, for example, when the polyorganosilsesquioxane of the present disclosure has a structural unit represented by the above formula (1) and R 1 is 2-(3',4'-epoxycyclohexyl)ethyl, the signal of the silicon atom in the structure (T3 body) represented by the above formula (I) appears at -62 ppm to -72 ppm, and the signal of the silicon atom in the structure (T2 body) represented by the above formula (II) appears at -55 ppm to -60 ppm. Therefore, in this case, the above ratio [T3 body / T2 body] can be determined by calculating the integral ratio of the signal (T3 body) at -62 ppm to -72 ppm and the signal (T2 body) at -55 ppm to -60 ppm. When R 1 is a group containing a radically curable functional group other than 2-(3',4'-epoxycyclohexyl)ethyl, [T3 body / T2 body] can be determined in the same manner. The 29 Si-NMR spectrum of the polyorganosilsesquioxane of the present disclosure can be measured under the same conditions as the measurement of the polysiloxane having a silanol group described above.

[0190] The case where the above ratio [T3 body / T2 body] of the polyorganosilsesquioxane of the present disclosure is within the above range (for example, 5 or more and 500 or less) means that a certain amount of T2 body is present relative to the T3 body in the polyorganosilsesquioxane of the present disclosure. Examples of such T2 body include a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), etc. R in the following formula (4) 1 and R in the following formula (5) 2 are respectively the same as R in the above formula (1)1 is the same as R in the above formula (2). 2 R in the following formulas (4) to (6) c is the same as R in formula (II) c and represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0191] [Chemical formula 14]

[0192] [R 1 SiO 2 / 2 (OR c )] (4)

[0193] [Chemical formula 15]

[0194] [R 2 SiO 2 / 2 (OR c )] (5)

[0195] [Chemical formula 16]

[0196] [HSiO 2 / 2 (OR c )] (6)

[0197] The polyorganosilsesquioxane of the present disclosure may have any one of a cage-type, an incomplete cage-type, a ladder-type, and a random-type sesquioxane structure, or may have two or more of these sesquioxane structures in combination.

[0198] When the polyorganosilsesquioxane of the present disclosure has a structural unit represented by the above formula (4), the ratio (total amount) of the structural unit represented by the above formula (1) and the structural unit represented by the above formula (4) with respect to the total amount of siloxane structural units [total siloxane structural units; the total amount of M units, D units, T units, and Q units] (100 mol%) is not particularly limited, and is preferably 55 mol% to 100 mol%, more preferably 65 mol% to 100 mol%, and further preferably 80 mol% to 99 mol%. By setting the above ratio to 55 mol% or more, the curability of the hard coat agent is improved, and in addition, the abrasion resistance and toughness of the cured product (coating film) are significantly increased. It should be noted that the ratio of each siloxane structural unit in the polyorganosilsesquioxane of the present disclosure can be calculated, for example, from the composition of the raw materials and NMR spectrum measurement.

[0199] The ratio (total amount) of the structural unit represented by the above formula (2) and the structural unit represented by the above formula (5) relative to the total amount of the siloxane structural units [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%) in the polyorganosilsesquioxane of the present disclosure is not particularly limited, preferably 0 mol% to 70 mol%, more preferably 0 mol% to 60 mol%, further preferably 0 mol% to 40 mol%, and particularly preferably 1 mol% to 15 mol%. By setting the above ratio to 70 mol% or less, the ratio of the structural unit represented by the above formula (1) and the structural unit represented by the above formula (4) can be relatively increased, and thus there is a tendency that the curability of the hard coat agent is improved and the abrasion resistance and toughness of the cured product (coating film) become higher.

[0200] The ratio (total amount) of the structural unit represented by the above formula (1), the structural unit represented by the above formula (2), the structural unit represented by the above formula (4), and the structural unit represented by the above formula (5) relative to the total amount of the siloxane structural units [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%) in the polyorganosilsesquioxane of the present disclosure is not particularly limited, preferably 60 mol% to 100 mol%, more preferably 70 mol% to 100 mol%, and further preferably 80 mol% to 100 mol%. By setting the above ratio to 60 mol% or more, there is a tendency that the abrasion resistance and toughness of the cured product (coating film) become higher.

[0201] The number average molecular weight (Mn) in terms of standard polystyrene obtained by gel permeation chromatography of the polyorganosilsesquioxane of the present disclosure is not particularly limited and can be appropriately selected, for example, from the range of 1000 to 50000. The lower limit value of the number average molecular weight is preferably 1500, more preferably 1800, and further preferably 2000. By setting the number average molecular weight to 1000 or more, there is a tendency that the abrasion resistance and toughness of the cured product (coating film) are further improved. On the other hand, the upper limit value of the number average molecular weight is preferably 50000, more preferably 10000, and further preferably 8000. By setting the number average molecular weight to 50000 or less (for example, 3000 or less), there is a tendency that the compatibility with other components in the hard coat agent is improved and the abrasion resistance and toughness of the cured product (coating film) are further improved.

[0202] The polydispersity (Mw / Mn) in terms of standard polystyrene conversion obtained by gel permeation chromatography of the polyorganosilsesquioxane of the present disclosure is not particularly limited and can be appropriately selected from the range of 1.0 to 4.0. The lower limit value of the polydispersity is preferably 1.0, more preferably 1.1, and further preferably 1.2. By setting the polydispersity to 1.1 or more, the hard coat agent tends to be in a liquid state and the operability is improved. On the other hand, the upper limit value of the polydispersity is preferably 4.0, more preferably 3.0, and further preferably 2.5. By setting the polydispersity to 4.0 or less, the abrasion resistance and toughness of the cured product (coating film) tend to be higher.

[0203] It should be noted that the number average molecular weight and polydispersity of the polyorganosilsesquioxane of the present disclosure can be measured by the following apparatus and conditions.

[0204] Measuring apparatus: Trade name "LC-20AD" (manufactured by Shimadzu Corporation).

[0205] Chromatographic columns: Shodex KF-801×2 columns, KF-802, and KF-803 (manufactured by Showa Denko K.K.).

[0206] Measuring temperature: 40°C.

[0207] Eluent: THF, sample concentration 0.1 mass% to 0.2 mass%.

[0208] Flow rate: 1 mL / minute.

[0209] Detector: UV-VIS detector (trade name "SPD-20A", manufactured by Shimadzu Corporation).

[0210] Molecular weight: In terms of standard polystyrene conversion.

[0211] The temperature (T at which the polyorganosilsesquioxane of the present disclosure loses 5% of its weight in an air atmosphere d5)There is no particular limitation, preferably 330 °C or higher (for example, 330 °C to 450 °C), more preferably 340 °C or higher, and further preferably 350 °C or higher. By making the temperature at which the weight loss is 5% 330 °C or higher, there is a tendency for the abrasion resistance and toughness of the cured product (coating film) to be further improved. In particular, by making the above ratio [T3 body / T2 body] of the polyorganosilsesquioxane of the present disclosure 5 or more and 500 or less, the number average molecular weight 1000 to 50000, and the molecular weight dispersity 1.0 to 4.0, the temperature at which its weight loss is 5% is controlled to 330 °C or higher. It should be noted that the temperature at which the weight loss is 5% is the temperature at the time point when the weight before heating is reduced by 5% when heating is performed at a fixed heating rate, and is an index of heat resistance. The above temperature at which the weight loss is 5% can be measured by TGA (thermogravimetric analysis) under an air atmosphere and at a heating rate of 5 °C / minute.

[0212] In addition, the existence rate of the silanol group in the polyorganosilsesquioxane of the present disclosure measured by the same method as above is preferably 0.1% to 5%, more preferably 0.5% to 4%, and further preferably 1% to 3%. By making the existence rate of the silanol group in the polyorganosilsesquioxane of the present disclosure 0.1% or more, the adhesion to the undercoat is likely to be exhibited.

[0213] The polyorganosilsesquioxane of the present disclosure can be produced by a known or conventional method for producing polysiloxanes, and there is no particular limitation. For example, it can be produced by a method of hydrolyzing and condensing one or two or more hydrolyzable silane compounds.

[0214] Since the polyorganosilsesquioxane of the present disclosure has the above configuration, the hard coat containing the above polyorganosilsesquioxane has excellent abrasion resistance and toughness.

[0215] In the above hard coat agent, one kind of the polyorganosilsesquioxane of the present disclosure can be used alone, or two or more kinds can be used. That is, the above hard coat can contain one kind alone, or can contain two or more kinds of the polyorganosilsesquioxane of the present disclosure.

[0216] The content (mixing amount) of the curable polyorganosilsesquioxane resin in the above hard coat is not particularly limited, and is preferably 70% by mass or more and less than 100% by mass, more preferably 80% by mass to 99.8% by mass, and further preferably 90% by mass to 99.5% by mass with respect to the total amount of the hard coat (the total amount of the hard coat agent excluding the solvent; 100% by mass). By making the content of the curable polyorganosilsesquioxane resin 70% by mass or more, there is a tendency for the abrasion resistance and toughness of the cured product (coating film) to be further improved. On the other hand, by making the content of the curable polyorganosilsesquioxane resin less than 100% by mass, a curing agent can be contained, and there is a tendency for more efficient curing.

[0217] The ratio of the polyorganosilsesquioxane of the present disclosure to the total amount (100% by mass) of the photo cationic curable compound and the photo radical curable compound contained in the above-mentioned hard coat agent is not particularly limited, preferably 70% by mass to 100% by mass, more preferably 75% by mass to 98% by mass, and still more preferably 80% by mass to 95% by mass. By setting the ratio of the polyorganosilsesquioxane of the present disclosure to 70% by mass or more, there is a tendency for the scratch resistance and toughness of the cured product (coating film) to be further improved. It should be noted that in the case of containing only any one of the above-mentioned photo cationic curable compound and the above-mentioned photo radical curable compound, it represents the ratio to its total amount.

[0218] In order to promote the curing reaction by irradiation with active energy rays, the above-mentioned hard coat agent preferably further contains a curing agent. Among them, in terms of further shortening the curing time until it becomes non-tacky, it is particularly preferable to contain a photo cationic polymerization initiator and / or a photo radical polymerization initiator as the curing agent.

[0219] As the above-mentioned photo cationic polymerization initiator, the same substances as those disclosed in the above-mentioned curable composition can be used.

[0220] The above-mentioned photo radical polymerization initiator is a compound that can initiate or promote the photo radical polymerization reaction of photo radical curable compounds such as the polyorganosilsesquioxane of the present disclosure. As the above-mentioned photo radical polymerization initiator, for example, alkyl phenyl ketone-based photo radical polymerization initiators, acylphosphine oxide-based photo radical polymerization initiators, oxime ester-based photo radical polymerization initiators, α-hydroxy ketone-based photo radical polymerization initiators, etc. can be cited.

[0221] It should be noted that in the above-mentioned hard coat agent, the above-mentioned curing agent can be used alone or in combination of two or more.

[0222] The content (blending amount) of the above-mentioned curing agent in the above-mentioned hard coat agent is not particularly limited, and is preferably 0.01 part by mass to 10.0 parts by mass, more preferably 0.05 part by mass to 5.0 parts by mass, and still more preferably 0.1 part by mass to 3.0 parts by mass with respect to the total amount (100 parts by mass; total amount of active energy ray curable compounds) of the polyorganosilsesquioxane of the present disclosure and other active energy ray curable compounds described later. By setting the content of the curing agent to 0.01 part by mass or more, the curing reaction can be effectively and sufficiently carried out, and there is a tendency for the scratch resistance and toughness of the cured product (coating film) to be further improved. On the other hand, by setting the content of the curing agent to 5.0 parts by mass or less, there is a tendency for the storage stability of the hard coat agent to be further improved, or the coloring of the cured product (coating film) to be suppressed.

[0223] The above-mentioned hard coat agent may further contain a radiation curable compound (sometimes referred to as "other radiation curable compound") other than the polyorganosilsesquioxane of the present disclosure. As the other radiation curable compound, a photo cationic curable compound (sometimes referred to as "other photo cationic curable compound") and / or a photo radical curable compound (sometimes referred to as "other photo radical curable compound") other than the polyorganosilsesquioxane of the present disclosure can be cited.

[0224] As the other photo cationic curable compound, a known or commonly used photo cationic curable compound can be used, and there is no particular limitation. For example, epoxy compounds, oxetane compounds, vinyl ether compounds, etc. other than the polyorganosilsesquioxane of the present disclosure can be cited. It should be noted that in the above-mentioned hard coat agent, the other photo cationic curable compound can be used alone or in combination of two or more.

[0225] As the above-mentioned epoxy compound and the above-mentioned oxetane compound, the same substances as those described in the above-mentioned curable composition can be exemplified.

[0226] In the above-mentioned hard coat agent, it is preferable to use an epoxy compound as the other photo cationic curable compound in combination with the polyorganosilsesquioxane of the present disclosure.

[0227] As the other photo radical curable compound, a known or commonly used photo radical curable compound can be used, and there is no particular limitation. For example, a compound having one or more (meth)acryloyl groups, (meth)acryloyloxy groups, (meth)acrylamino groups, vinyl ether groups, vinyl aryl groups, vinyloxycarbonyl groups, etc. in one molecule other than the polyorganosilsesquioxane of the present disclosure can be cited. It should be noted that in the above-mentioned hard coat agent, the other photo radical curable compound can be used alone or in combination of two or more.

[0228] When the above hard coat agent contains other active energy ray curable compounds, their content (mixing amount) is not particularly limited. Relative to the total amount (100% by mass; total amount of active energy ray curable compounds) of the polyorganosilsesquioxane of the present disclosure and other active energy ray curable compounds, it is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and still more preferably 7% by mass to 30% by mass. By setting the content of other active energy ray curable compounds to 50% by mass or less, there is a tendency for the abrasion resistance and toughness of the cured product (coating film) to be further improved. On the other hand, by setting the content of other active energy ray curable compounds to 3% by mass or more, it is sometimes possible to impart desired properties to the hard coat agent and the cured product (coating film) (for example, rapid curability and viscosity adjustment of the hard coat agent).

[0229] The above hard coat agent preferably contains a compound having one or more thermal polymerization functional groups and one or more photopolymerization functional groups in one molecule (hereinafter, sometimes referred to as "compound A"). By making the hard coat agent contain the polyorganosilsesquioxane of the present disclosure and compound A together, it is possible to effectively

[0230] increase the crosslinking density when forming a cured product, and it is easy to impart high surface hardness to the cured product (coating film).

[0231] The "thermal polymerization functional group" possessed by compound A is not particularly limited as long as it imparts polymerizability to compound A by heat, and examples thereof include: hydroxyl group, epoxy group, oxetanyl group, vinyl ether group, etc. From the viewpoint of the surface hardness of the coating film of the present disclosure, hydroxyl group and epoxy group are preferred.

[0232] When compound A has two or more thermal polymerization functional groups, these thermal polymerization functional groups may be the same or different respectively.

[0233] The "photopolymerization functional group" possessed by compound A is not particularly limited as long as it imparts polymerizability to compound A by light (for example, ultraviolet light), and examples thereof include (meth)acryloyl group, vinyl group, etc. From the viewpoint of the surface hardness of the coating film of the present disclosure, (meth)acryloyl group is preferred.

[0234] When compound A has two or more photopolymerization functional groups, these photopolymerization functional groups may be the same or different respectively.

[0235] When compound A has two or more photopolymerization functional groups, these photopolymerization functional groups may be the same or different respectively.

[0236] For example, (meth)acryloyl group, vinyl group, etc., and from the viewpoint of the surface hardness of the coating film of the present disclosure, (meth)acryloyl group is preferred.

[0237] When compound A has two or more photopolymerization functional groups, these photopolymerization functional groups may be the same or different respectively.

[0238] When compound A has two or more photopolymerization functional groups, these photopolymerization functional groups may be the same or different respectively.

[0239] When compound A has two or more photopolymerization functional groups, these photopolymerization functional groups may be the same or different respectively.

[0240] The number of thermopolymerizable functional groups in Compound A within one molecule only needs to be 1 or more, and there is no particular limitation. For example, it is preferably 1 to 5, more preferably 1 to 3, and further preferably 1 or 2.

[0241] That's all, and there is no particular limitation. For example, it is preferably 1 to 5, more preferably 1 to 3, and further preferably 1 or 2.

[0242] In addition, the number of photopolymerizable functional groups in Compound A within one molecule only needs to be 1 or more, and there is no particular limitation. For example, it is preferably 1 to 5, more preferably 1 to 3, and further preferably 1 or 2.

[0243] That's all, and there is no particular limitation. For example, it is preferably 1 to 5, more preferably 1 to 3, and further preferably 1 or 2.

[0244] The functional group equivalent of the thermopolymerizable functional group of Compound A is not particularly limited, and is preferably 50 to

[0245] 500, more preferably 80 to 480, and further preferably 120 to 450. If the above functional group equivalent is less than

[0246] 50, the cured product (coating film) may sometimes be insufficient. On the other hand, if the above functional group equivalent exceeds

[0247] 500, the surface hardness of the cured product (coating film) may sometimes decrease. It should be noted that the functional group equivalent of the thermopolymerizable functional group of Compound A

[0248] can be calculated by the following formula.

[0249] [Functional group equivalent of thermopolymerizable functional group] = [Molecular weight of Compound A] / [Number of thermopolymerizable functional groups possessed by Compound A]

[0250] The functional group equivalent of the photopolymerizable functional group of Compound A is not particularly limited, and is preferably 50 to

[0251] 500, more preferably 80 to 480, and further preferably 120 to 450. If the above functional group equivalent is less than

[0252] 50, the cured product (coating film) may sometimes be insufficient. On the other hand, if the above functional group equivalent exceeds

[0253] 500, the surface hardness of the cured product (coating film) may sometimes decrease. It should be noted that the functional group equivalent of the photopolymerizable functional group of Compound A

[0254] can be calculated by the following formula.

[0255] [Functional group equivalent of photopolymerizable functional group] = [Molecular weight of Compound A] / [Number of photopolymerizable functional groups possessed by Compound A]

[0256] As compound A, specifically, for example, the following can be cited: 3,4-epoxycyclohexylmethyl (meth)acrylate

[0257] hexylmethyl ester, glycidyl (meth)acrylate, dipropylene glycol diglycidyl ether di(meth)acrylate (a compound obtained by reacting two epoxy groups of dipropylene glycol diglycidyl ether with (meth)acrylic acid)

[0258] (compound obtained by reacting two epoxy groups of dipropylene glycol diglycidyl ether with (meth)acrylic acid), dipropylene glycol diglycidyl ether mono(meth)acrylate (a compound obtained by reacting one epoxy group of dipropylene glycol diglycidyl ether with (meth)acrylic acid), bisphenol A epoxy

[0259] di(meth)acrylate (a compound obtained by reacting two epoxy groups of bisphenol A diglycidyl ether with (meth)acrylic acid), bisphenol A epoxy mono(meth)acrylate (a compound obtained by reacting (meth)acrylic acid or its derivative with one epoxy group of bisphenol A diglycidyl ether)

[0260] compound), bisphenol F epoxy di(meth)acrylate, bisphenol F epoxy mono(meth)acrylate, bisphenol S epoxy

[0261] di(meth)acrylate, bisphenol S epoxy mono(meth)acrylate, etc., compounds having an epoxy group and / or a hydroxyl group and a (meth)acryloyl group in one molecule; 3-oxetanylmethyl (meth)acrylate,

[0262] 3-methyl-3-oxetanylmethyl (meth)acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, 3-butyl-3-oxetanylmethyl (meth)acrylate, 3-hexyl-3-oxetanylmethyl (meth)acrylate, etc., compounds having an oxetanyl group and a (meth)acryloyl group in one molecule; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate,

[0263] compound), etc.

[0264] compounds having an oxetanyl group and a (meth)acryloyl group in one molecule; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate,

[0265] compounds having an oxetanyl group and a (meth)acryloyl group in one molecule; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate,

[0266] compounds having an oxetanyl group and a (meth)acryloyl group in one molecule; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate,

[0267] 3-methyl-3-oxetanylmethyl (meth)acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, 3-butyl-3-oxetanylmethyl (meth)acrylate, 3-hexyl-3-oxetanylmethyl (meth)acrylate, etc., compounds having an oxetanyl group and a (meth)acryloyl group in one molecule; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate,

[0268] 3-butyl-3-oxetanylmethyl (meth)acrylate, 3-hexyl-3-oxetanylmethyl (meth)acrylate, etc., compounds having an oxetanyl group and a (meth)acryloyl group in one molecule; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate,

[0269] compounds having an oxetanyl group and a (meth)acryloyl group in one molecule; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate,

[0270] compounds having an oxetanyl group and a (meth)acryloyl group in one molecule; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate,

[0271] 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate,

[0272] 4-Vinyloxybutyl (meth)acrylate, 1-Methyl-3-vinyloxypropyl (meth)acrylate, 1-Vinyloxymethylpropyl (meth)acrylate, 2-Methyl-3-vinyloxypropyl (meth)acrylate, 1,1-Dimethyl-2-vinyloxyethyl (meth)acrylate, 3-Vinyloxybutyl (meth)acrylate, 1-Methyl-2-vinyloxypropyl (meth)acrylate, 2-Vinyloxybutyl (meth)acrylate, 4-Vinyloxycyclohexyl (meth)acrylate, 6-Vinyloxyhexyl (meth)acrylate, 4-Vinyloxymethylcyclohexylmethyl (meth)acrylate, 3-Vinyloxymethylcyclohexylmethyl (meth)acrylate, 2-Vinyloxycyclohexylmethyl (meth)acrylate, p-Vinyloxymethylphenylmethyl (meth)acrylate

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279] ​​​​​​esters, m-vinyl-oxymethylphenyl (meth)acrylate, o-vinyl-oxymethylphenyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyisopropoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxy)propyl (meth)acrylate, 2-(vinyloxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyisopropoxy)propyl (meth)acrylate, 2-(vinyloxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyisopropoxy)ethyl (meth)acrylate, 2-(vinyloxyisopropoxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyisopropoxyisopropoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxy)propyl (meth)acrylate, 2-(vinyloxyethoxyisopropoxy)propyl (meth)acrylate, 2-(vinyloxyisopropoxyethoxy)propyl (meth)acrylate, 2-(vinyloxyisopropoxyisopropoxy)propyl (meth)acrylate, 2-(vinyloxyethoxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyisopropoxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyisopropoxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxyethoxyethoxyethoxy)ethyl (meth)acrylate, polyethylene glycol mono vinyl ether (meth)acrylate, polypropylene glycol mono vinyl ether (meth)acrylate and other compounds having an ethylene ether group and a (meth)acryloyl group in one molecule, etc.

[0280] From the viewpoint of the surface hardness of the cured product (coating film), as Compound A, a compound having an epoxy group and / or a hydroxyl group as a thermopolymerizable functional group and a (meth)acryloyl group as a photopolymerizable functional group in one molecule is preferred. Specifically, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, tripropylene glycol diglycidyl ether hemis (meth)acrylate, bisphenol A epoxy hemis (meth)acrylate, bisphenol F epoxy hemis (meth)acrylate, bisphenol S epoxy hemis (meth)acrylate, etc. are preferred.

[0281] It should be noted that in the above-mentioned hard coating agent, one type of compound A can be used alone, or two or more types can be used. Compound A can be produced by a known method. For example, it can be obtained by reacting a part of the above-mentioned thermopolymerizable functional groups (such as epoxy groups, hydroxyl groups) of a compound having two or more thermopolymerizable functional groups in one molecule with a carboxylic acid (such as acrylic acid, methacrylic acid, etc.) or a derivative having a photopolymerizable functional group.

[0282] The content (mixing amount) of the above-mentioned compound A in the above-mentioned hard coating agent is not particularly limited. Based on the solid content, relative to 100 parts by mass of the total amount of the polyorganosilsesquioxane and other active energy ray curable compounds (total amount of active energy ray curable compounds) of the present disclosure, it is preferably 1.0 part by mass to 100 parts by mass, more preferably 1.3 parts by mass to 75 parts by mass, and further preferably 1.5 parts by mass to 50 parts by mass. By setting the content of compound A to 1 part by mass or more, there is a tendency for the cured product (coating film) to be further improved. On the other hand, by setting the content of compound A to 100 parts by mass or less, there is a tendency to maintain the surface hardness of the cured product (coating film).

[0283] The above-mentioned hard coating agent preferably contains a surface conditioner. As the above-mentioned surface conditioner, a known or conventional compound added for the purpose of defoaming, leveling, anti-foaming, etc. can be used. As the above-mentioned defoaming agent, leveling agent, anti-foaming agent, for example, a water-based or non-aqueous compound mainly composed of polymers such as butadiene, acrylic acid, and olefins, or containing a main component selected from main components such as organosilicon and fluorine-modified organosilicon can be used. Among them, as the water-based or non-aqueous compound containing a main component selected from the above-mentioned organosilicon-based main components, a free radical curable polyorganosiloxane is preferably included. By using the above-mentioned free radical curable polyorganosiloxane, the smoothness of the hard coating surface is improved, the sebum adhesion resistance is excellent, and the surface is not easily stained with fingerprints. In addition, the free radical curable polyorganosiloxane is preferably not a compound conforming to PFAS. In this case, although it is not included in the compound conforming to PFAS, it still exhibits the above-mentioned effects. Since the above-mentioned free radical curable polyorganosiloxane has free radical curability, it also conforms to the above-mentioned curable compound. The above-mentioned free radical curable polyorganosiloxane can be used alone or in combination of two or more.

[0284] The above-mentioned free radical curable polyorganosiloxane has a free radical polymerizable functional group in the molecule. As the free radical curable functional group, a photo free radical polymerizable functional group can be cited.

[0285] As the above-mentioned photo free radical polymerizable functional group, for example, (meth)acryloyl group, (meth)acrylamide group, vinyl group, vinyl thio group, etc. can be cited. Among them, the (meth)acryloyl group is preferred.

[0286] As the polyorganosiloxane in the above radical-curable polyorganosiloxane, from the viewpoint of further exerting the effect as a leveling agent, a linear polyorganosiloxane is preferred.

[0287] The content (mixing amount) of the above surface conditioner in the above hard coat agent is not particularly limited. As a solid component, it is, for example, 0.01 parts by mass to 15 parts by mass, preferably 0.05 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass, and further preferably 0.2 parts by mass to 3 parts by mass with respect to 100 parts by mass of the total amount of the polyorganosilsesquioxane and other active energy ray-curable compounds of the present disclosure (the total amount of the active energy ray-curable compounds). By setting the content of the surface conditioner to 0.01 parts by mass or more, there is a tendency for the leveling property of the cured product (coating film) to be further improved.

[0288] The above hard coat agent preferably contains an antioxidant. By making the above hard coat agent contain an antioxidant, there is a tendency for the surface hardness of the cured product (coating film) to be further improved. As the above antioxidant, only one kind can be used, or two or more kinds can be used.

[0289] As the above antioxidant, the same antioxidants as those exemplified in the above photocurable compounds can be used.

[0290] When the above hard coat agent contains an antioxidant, its content (mixing amount) is not particularly limited, and it is preferably 0.05 parts by mass to 5 parts by mass, more preferably 0.1 parts by mass to 3 parts by mass with respect to the total amount (100 parts by mass) of the active energy ray-curable compounds contained in the hard coat agent. If the content of the antioxidant is 0.05 parts by mass or more, the storage stability of the cured product (coating film) is likely to be sufficient. On the other hand, when the content of the antioxidant is 5 parts by mass or less, coloring of the cured product (coating film) can be suppressed.

[0291] The above hard coat agent may preferably further contain a solvent. As the solvent, there is no particular limitation as long as it can dissolve the polyorganosilsesquioxane of the present disclosure and additives used as needed and does not hinder polymerization. As the above solvent, only one kind can be used, or two or more kinds can be used.

[0292] The solvent is preferably a solvent that can impart fluidity suitable for coating on the hard coat and can be easily removed by heating at a temperature that can inhibit the progress of polymerization. It is preferably one or more solvents having a boiling point (under one atmosphere) of 170 °C or lower (for example, aromatic solvents such as toluene, xylene, and mesitylene, esters such as butyl acetate, ketones such as methyl isobutyl ketone and cyclohexanone, ethers such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, etc.).

[0293] From the viewpoint of excellent coatability, the solvent is preferably used in a range where the concentration of the non-volatile components contained in the hard coat agent is, for example, about 5% by mass to 100% by mass, preferably 10% by mass to 80% by mass, and particularly preferably 20% by mass to 70% by mass. However, the addition amount should be selected as the optimal addition amount to adjust the viscosity to achieve an appropriate film thickness, and is not limited to the above range. That is, if the amount of the solvent used is excessive, the viscosity of the hard coat agent decreases, and there is a tendency that it is difficult to form a coating film with an appropriate film thickness. On the other hand, if the amount of the solvent used is too small, the viscosity of the hard coat agent becomes too high, and there is a tendency that it is difficult to uniformly coat the glass substitute substrate.

[0294] The above hard coat agent may further contain the following conventional additives as other optional components: inorganic fillers such as precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride, etc.; inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, and organosilazanes; organic resin fine powders such as silicone resins, epoxy resins, and fluororesins; fillers such as conductive metal powders of silver, copper, etc., curing aids, stabilizers (light stabilizers, heat stabilizers, heavy metal passivators, etc.), ultraviolet absorbers (triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, oxybenzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers), flame retardants (phosphorus-based flame retardants, halogen-based flame retardants, inorganic-based flame retardants, etc.), flame retardant aids, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents (silane coupling agents, etc.), lubricants, waxes, plasticizers, mold release agents, impact resistance improvers, hue improvers, clarifying agents, rheology modifiers (flowability improvers, etc.), processability improvers, colorants (dyes, pigments, etc.), antistatic agents, dispersants, surface modifiers (slip agents, etc.), matting agents, defoaming agents, foam suppressants, degassing agents, antibacterial agents, preservatives, viscosity modifiers, tackifiers, photosensitizers, foaming agents, etc. These additives can be used alone or in combination of two or more.

[0295] In addition, the above hard coat agent preferably does not contain compounds conforming to PFAS. That is, the above hard coat containing the above hard coat agent preferably does not contain compounds conforming to PFAS. By having the above constitution, it is possible not to use compounds conforming to PFAS, which is suitable for environmental regulations and has excellent safety.

[0296] The above-mentioned hard coating agent is not particularly limited and can be prepared by stirring / mixing the above-mentioned respective components at room temperature or by heating as needed. It should be noted that the above-mentioned hard coating agent can be used as a one-component composition in which the respective components are pre-mixed and directly used, or can be used as a multi-component (e.g., two-component) composition in which two or more components stored separately are mixed at a specified ratio before use.

[0297] The above-mentioned hard coating agent is not particularly limited and is preferably a liquid at normal temperature (about 25°C). More specifically, for the above-mentioned hard coating agent, as the viscosity of a liquid diluted to 20% with a solvent [in particular, a hard coating agent solution in which the proportion of methyl isobutyl ketone is 20% by mass] at 25°C, it is preferably 300 mPa·s to 20000 mPa·s, more preferably 500 mPa·s to 10000 mPa·s, and further preferably 1000 mPa·s to 8000 mPa·s. By setting the above viscosity to 300 mPa·s or more, there is a tendency for the cured product (coating film) to be further improved. On the other hand, by setting the above viscosity to 20000 mPa·s or less, there is a tendency for the preparation and operation of the hard coating agent to become easy and for bubbles to be less likely to remain in the cured product (coating film). It should be noted that the viscosity of the above-mentioned hard coating agent is measured using a viscometer (trade name "MCR301", manufactured by Anton-Paar) under the conditions of a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature of 25°C.

[0298] The prepared above-mentioned hard coating agent is coated on the above-mentioned base coating by a known or conventional method and cured, whereby a laminate having a three-layer structure of a substrate, a base coating, and a hard coating can be produced.

[0299] As the method for coating and curing the above-mentioned hard coating, it can be carried out by the same method as the method exemplified in the above-mentioned base coating. It should be noted that when ultraviolet rays are irradiated during the curing of the hard coating, for example, the cumulative irradiation amount is preferably set to 1 mJ / cm 2 ~5000 mJ / cm 2 or so.

[0300] As specific curing conditions, there is no particular limitation. For example, for the above-mentioned hard coating agent, first, heat treatment (pre-baking) is preferably carried out at 60°C or higher, more preferably 120°C or higher, and further preferably 150°C or higher for preferably 10 seconds or more, more preferably 30 seconds or more, and further preferably 60 seconds or more. Then, ultraviolet rays are irradiated (irradiation conditions (irradiation amount): preferably 300 mJ / cm 2 or more; irradiation intensity: 100 mW / cm 2Thereafter, finally, heat treatment (aging) is preferably performed at 120°C or higher for 0.5 hours or longer, whereby the above-mentioned hard coat agent can be cured. However, the curing conditions are not limited to this range, and the pre-baking temperature, time, and aging temperature can be appropriately selected according to the solvent used. In addition, the ultraviolet irradiation conditions can also be appropriately selected according to the curing agent used.

[0301] As described above, the above-mentioned hard coat agent can form a hard coat layer having high scratch resistance, surface hardness, and toughness through coating and curing. The laminate thus produced has excellent adhesion, and the surface hardness of the hard coat layer can be improved.

[0302] The thickness of the above-mentioned hard coat layer is preferably 0.5 μm to 50 μm, more preferably 1 μm to 4 μm, and particularly preferably 3 μm to 30 μm. By making the thickness of the above-mentioned hard coat layer 0.5 μm or more, it is easy to improve the surface hardness.

[0303] It is preferable that the surface of the hard coat layer of the above-mentioned laminate is not confirmed to be sticky by finger touch.

[0304] The pencil hardness of the surface of the hard coat layer of the above-mentioned laminate is preferably 3H or higher, more preferably 4H or higher. It should be noted that the pencil hardness can be evaluated according to the method described in JIS K5600-5-4 (750 g load). By making the above-mentioned pencil hardness 3H or higher, there is a tendency that the above-mentioned laminate has sufficient surface hardness and excellent scratch resistance.

[0305] In addition, for the above-mentioned laminate, according to JIS K5600-5-6, cut with a cutter at intervals of 1 mm from the hard coat layer side to make 100 squares in a grid pattern, stick a tape, peel it off along the 90° direction, and visually confirm whether the surface of the coating adheres to the tape and then peels off. At this time, it is preferably 90 or more remaining, more preferably 95 or more remaining, and particularly preferably 100 remaining. By having 90 or more remaining on the laminate, it can be confirmed that the hard coat layer and the undercoat layer exhibit sufficient adhesion.

[0306] [Display device]

[0307] As an embodiment of the present disclosure, a display device including the above-mentioned laminate can be cited. In the above-mentioned display device, the above-mentioned laminate is arranged such that, for example, the hard coat layer constitutes the surface on the visible side. The above-mentioned display device is not particularly limited, and examples thereof include display devices such as an organic EL display device, an inorganic EL display device, and a liquid crystal display device. Since the surface of the hard coat layer of the above-mentioned display device has sufficient surface hardness, damage is not easily generated on the surface. In addition, the above-mentioned display device can also be used as a flexible display that can be bent or wound.

[0308] The various solutions disclosed in this specification can also be combined with any other features disclosed in this specification. In addition, each component and the combination of components in each embodiment are examples, and appropriate addition, omission, and other changes of components can be made without departing from the gist of the present disclosure. The present disclosure is not limited by the embodiments but only by the claims.

[0309] Example

[0310] Hereinafter, one embodiment of the present disclosure will be described in more detail based on examples.

[0311] Production Example 1

[0312] (Production of polyorganosilsesquioxane)

[0313] Into a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirring device, a reflux condenser, and a nitrogen inlet tube, 277.2 mmol (68.30 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3.0 mmol (0.56 g) of phenyltrimethoxysilane, and 275.4 g of acetone were charged under a nitrogen stream, and the temperature was raised to 50°C. To the mixture thus obtained, 7.74 g of a 5% potassium carbonate aqueous solution (2.8 mmol as potassium carbonate) was added over 5 minutes, and then 2800.0 mmol (50.40 g) of water was added over 20 minutes. It should be noted that no significant temperature rise occurred during the addition. Thereafter, the temperature was maintained at 50°C, and a polycondensation reaction was carried out for 5 hours under a nitrogen stream.

[0314] Thereafter, while cooling the reaction solution, 137.70 g of methyl isobutyl ketone and 100.60 g of 5% brine were added. The solution was transferred to a 1 L separatory funnel, and 137.70 g of methyl isobutyl ketone was added again for washing with water. After liquid separation, the aqueous layer was drawn off, and washing with water was carried out until the lower layer liquid became neutral. After separating the upper layer liquid, the solvent was distilled off from the upper layer liquid under the conditions of 1 mmHg and 50°C to obtain 75.18 g of a colorless, transparent, and liquid product (epoxy group-containing low molecular weight polyorganosilsesquioxane: the sesquioxane of Production Example 1) containing 23% by mass of methyl isobutyl ketone.

[0315] It should be noted that the product was analyzed, and as a result, the number average molecular weight was 2235, and the molecular weight dispersity was 1.54. The ratio [T3 body / T2 body] of the T2 body to the T3 body calculated from the 29 Si-NMR spectrum of the above product was 11.9. The obtained epoxy group-containing low molecular weight polyorganosilsesquioxane was confirmed by 1 H-NMR, 29 Si-NMR.

[0316] Note that the molecular weight of the product was measured under the following conditions: Pump: Shimadzu LC-20AD, Detector: Shodex RI-504, Column: Shodex GPC KF-602, KF-603, Guard column: Shodex GPC KF-G, Solvent: THF, Measurement conditions: 40 °C. In addition, the ratio of T2 form to T3 form [T3 form / T2 form] in the product was measured by 29 Si-NMR spectroscopy using JEOL ECA500 (500 MHz).

[0317] (Preparation of Hard Coating Agent)

[0318] Each material was mixed with the silsesquioxane of Production Example 1 so as to have the composition ratios described in Table 1, thereby preparing a hard coating agent. Note that the content ratios shown in Table 1 are the mixing ratios of the respective components. For the silsesquioxane of Production Example 1 (active ingredient: 77% by mass) and RS-57 (active ingredient: 20% by mass), the values are those of the solutions, and for the other respective components, the values are those of the active ingredients.

[0319] [Table 1]

[0320] Table 1

[0321]

[0322] Each of the components shown in Table 1 will be described in detail below.

[0323] 200PA-E5: Trade name “Epoxy Ester 200PA-E5”, manufactured by Kyoeisha Chemical Co., Ltd. (a compound having one or more thermopolymerizable functional groups and one or more photopolymerizable functional groups in one molecule).

[0324] Epolight 1600N: Trade name “Epolight 1600N”, manufactured by Kyoeisha Chemical Co., Ltd. (other photocationic curable composition).

[0325] RS-57: Trade name “MEGAFAC RS-57”, manufactured by DIC Corporation (surface conditioner).

[0326] Omnirad127: Trade name “Omnirad127”, manufactured by IGM Resins B.V. (photo radical polymerization initiator).

[0327] CPI-310FG: Trade name “CPI-310FG”, manufactured by San-Apro Ltd. (photo cationic polymerization initiator).

[0328] ADK STAB AO-02: Product name "ADK STAB AO-02", manufactured by ADEKA Corporation (antioxidant).

[0329] MIBK: Methyl isobutyl ketone (solvent).

[0330] MEK: Methyl ethyl ketone (solvent).

[0331] Examples 1 to 6, Comparative Examples 1 to 5

[0332] [[ID=1 2]]Prepare a mixed solution with the formulation shown in Table 2 and use it as the curable composition. Apply the curable composition obtained above to the surface of a glass substrate (slide) using a wire bar #12 so that the cured thickness becomes 10 μm. Then, irradiate ultraviolet rays using an LED lamp with an illuminance of 3000 mJ / cm 2 Then, perform heat treatment in an oven at 150 °C for 30 minutes to produce a bottom coat.

[0333] Each component described in Table 2 will be described in detail below.

[0334] KR-470: Product name "KR-470", manufactured by Shin-Etsu Chemical Co., Ltd. (organosiloxane containing two or more alicyclic epoxy groups, number average molecular weight: 740).

[0335] A-1: 3',4'-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (alicyclic epoxy compound).

[0336] A-2: 3,4,3',4'-Diepoxy bicyclohexane (alicyclic epoxy compound).

[0337] YX7400N: Product name "YX7400N", manufactured by Mitsubishi Chemical Corporation (aliphatic epoxy compound).

[0338] OXT-101: Product name "OXT-101", manufactured by Toagosei Co., Ltd. (oxetane compound).

[0339] SQ502-8: Product name "Compoceran SQ502-8", manufactured by Arakawa Chemical Industries, Ltd. (polyorganosiloxane with a silanol group, containing 25% of T1, 63% of T2, and 12% of T3).

[0340] E103-D: Product name "Compoceran E103-D", manufactured by Arakawa Chemical Industries, Ltd. (polyorganosiloxane with a silanol group).

[0341] CPI-101A: Trade name "CPI-101A", manufactured by SAN-APRO (photoinitiator).

[0342] CPI-100P: Trade name "CPI-100P", manufactured by SAN-APRO (photoinitiator).

[0343] PEP-36: Trade name "ADK STAB PEP-36", manufactured by ADEKA (antioxidant).

[0344] GA-80: Trade name "Sumilizer GA-80", manufactured by Sumitomo Chemical (antioxidant).

[0345] On the above-mentioned undercoat, a hard coat agent produced in Production Example 1 was further coated using a wire bar #24 so that the thickness of the cured hard coat became 20 μm, and then it was placed in an oven at 80 °C for 1 minute and in an oven at 120 °C for 2 minutes. Next, using a high-pressure mercury lamp, ultraviolet rays were irradiated at an illuminance of 300 mJ / cm 2 . Then, the hard coat agent was cured by heat treatment in an oven at 120 °C for 60 minutes to produce the laminates of Examples 1 to 6 and Comparative Examples 1 to 5.

[0346] [Evaluation]

[0347] The following evaluations were performed on the laminates of Examples 1 to 6 and Comparative Examples 1 to 5, and the results are shown in Table 2.

[0348] (1) Viscosity after curing

[0349] By touching the surfaces of the laminates of Examples 1 to 6 and Comparative Examples 1 to 5 with a finger, the viscosity was confirmed. When it was sticky, it was designated as Δ, and when it was non-sticky, it was designated as 〇.

[0350] (2) Adhesion test

[0351] For the hard coat surfaces of the laminates of Examples 1 to 6 and Comparative Examples 1 to 5, according to JIS K5600-5-6, 100 squares in a grid pattern were cut with a cutter at intervals of 1 mm, and a tape was pasted. Then, it was peeled off along the 90° direction, and it was visually confirmed whether the surface of the coating adhered to the tape after peeling. When 100 were adhered, it was designated as ◎, when more than 90 were adhered, it was designated as 〇, and when less than 90 were adhered, it was designated as ×.

[0352] (3) Pencil hardness

[0353] According to JIS K5600-5-4 (750 g load), the pencil hardness of the hard coat surfaces of the laminates of Examples 1 to 6 and Comparative Examples 1 to 5 was measured.

[0354] [Table 2]

[0355] Table 2

[0356]

[0357] As shown in Table 2, it was confirmed that the curable composition of the present disclosure forms a hard coat having sufficient adhesion and excellent surface hardness by including a first epoxy compound, which is an organosiloxane containing two or more alicyclic epoxy groups, a second epoxy compound, a polyorganosiloxane having a silanol group, and a third epoxy compound or an oxetane compound (Examples 1 to 6). On the other hand, in the case where the polyorganosiloxane having a silanol group is not included, the adhesion deteriorates (Comparative Examples 1 and 2), and in the case where the composition is changed to improve the adhesion without including the polyorganosiloxane having a silanol group, the surface hardness deteriorates (Comparative Examples 3 to 5).

[0358] Hereinafter, modifications of the invention of the present disclosure will be described.

[0359] [Supplementary Note 1]

[0360] A curable composition comprising the following compounds as curable compounds: a first epoxy compound, which is an organosiloxane containing two or more alicyclic epoxy groups, a second epoxy compound, a polyorganosiloxane having a silanol group, and a third epoxy compound or an oxetane compound.

[0361] [Supplementary Note 2]

[0362] The curable composition according to Supplementary Note 1, wherein the first epoxy compound, the second epoxy compound, the polyorganosiloxane having a silanol group, and the oxetane compound are included.

[0363] [Supplementary Note 3]

[0364] The curable composition according to Supplementary Note 1 or 2, wherein the content of the first epoxy compound is 30% by mass to 70% by mass based on the total amount of the curable compounds.

[0365] [Supplementary Note 4]

[0366] The curable composition according to any one of Supplementary Notes 1 to 3, wherein the content of the second epoxy compound is 20% by mass to 60% by mass based on the total amount of the curable compounds.

[0367] [Supplementary Note 5]

[0368] The curable composition according to any one of Supplementary Notes 1 to 4, wherein the content of the oxetane compound is 5% by mass to 25% by mass relative to the total amount of the curable compounds.

[0369] [Supplementary Note 6]

[0370] The curable composition according to any one of Supplementary Notes 1 to 5, wherein the content of the polysiloxane having a silanol group is 1% by mass to 15% by mass relative to the total amount of the curable compounds.

[0371] [Supplementary Note 7]

[0372] The curable composition according to any one of Supplementary Notes 1 to 6, which does not contain highly toxic substances.

[0373] [Supplementary Note 8]

[0374] The curable composition according to any one of Supplementary Notes 1 to 7, which does not contain compounds conforming to PFAS.

[0375] [Supplementary Note 9]

[0376] An undercoat, which contains a cured product of the curable composition according to any one of Supplementary Notes 1 to 8.

[0377] [Supplementary Note 10]

[0378] The undercoat according to Supplementary Note 9, wherein the thickness of the undercoat is 0.1 μm to 20 μm.

[0379] [Supplementary Note 11]

[0380] A laminate, which is sequentially laminated with a substrate, an undercoat formed on at least one surface of the substrate according to Supplementary Note 9 or 10, and a hard coat.

[0381] [Supplementary Note 12]

[0382] The laminate according to Supplementary Note 11, wherein the substrate is a glass substrate.

[0383] [Supplementary Note 13]

[0384] The laminate according to Supplementary Note 11 or 12, wherein the hard coat contains a curable polyorganosilsesquioxane resin as a curable resin.

[0385] [Supplementary Note 14]

[0386] The laminate according to any one of Supplementary Notes 11 to 13, wherein the pencil hardness of the surface of the hard coat is 3H or more.

[0387] [Supplementary Note 15]

[0388] The laminate according to any one of Attachments 11 to 14, wherein 100 squares are formed in a lattice pattern on the surface of the hard coat at intervals of 1 mm, a tape is adhered, and when peeled off in the 90° direction, 90 or more squares remain.

[0389] [Attachment 16]

[0390] The laminate according to any one of Attachments 11 to 15, wherein the hard coat does not contain a compound conforming to PFAS.

[0391] [Attachment 17]

[0392] A display device including the laminate according to any one of Attachments 11 to 16.

Claims

1. A curable composition comprising the following compounds as curable compounds: a first epoxy compound which is an organosiloxane containing two or more alicyclic epoxy groups, a second epoxy compound, a polyorganosiloxane having a silanol group, and a third epoxy compound or an oxetane compound.

2. The curable composition according to claim 1, wherein it contains the first epoxy compound, the second epoxy compound, the polyorganosiloxane having a silanol group, and the oxetane compound.

3. The curable composition according to claim 1 or 2, wherein the content of the first epoxy compound is 30% by mass to 70% by mass relative to the total amount of the curable compounds.

4. The curable composition according to claim 1 or 2, wherein the content of the second epoxy compound is 20% by mass to 60% by mass relative to the total amount of the curable compounds.

5. The curable composition according to claim 1 or 2, wherein the content of the oxetane compound is 5% by mass to 25% by mass relative to the total amount of the curable compounds.

6. The curable composition according to claim 1 or 2, wherein the content of the polyorganosiloxane having a silanol group is 1% by mass to 15% by mass relative to the total amount of the curable compounds.

7. The curable composition according to claim 1 or 2, wherein it does not contain highly toxic substances.

8. The curable composition according to claim 1 or 2, wherein it does not contain PFAS-compliant compounds.

9. A primer coat comprising a cured product of the curable composition according to claim 1 or 2.

10. The primer coat according to claim 9, wherein the thickness of the primer coat is 0.1 μm to 20 μm.

11. A laminate having a substrate, a primer coat according to claim 9 formed on at least one surface of the substrate, and a hard coat laminated in this order.

12. The laminate according to claim 11, wherein the substrate is a glass substrate.

13. The laminate according to claim 11, wherein the hard coat contains a curable polyorganosilsesquioxane resin as a curable resin.

14. The laminate according to claim 11, wherein the pencil hardness of the surface of the hard coat is 3H or more.

15. The laminate according to claim 11, wherein 100 squares are formed in a grid pattern at 1 mm intervals on the surface of the hard coat, a tape is adhered, and when peeled off in the 90° direction, 90 or more squares remain.

16. The laminate according to claim 11, wherein the hard coat does not contain PFAS-compliant compounds.

17. A display device comprising the laminate according to claim 11.

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