JP6673281B2 - Light curing type anti-fog agent - Google Patents

Description

  The present invention relates to a photocurable antifogging agent.

The surfaces of substrates used for mirrors, glasses, and windows are fogged by humidity and temperature differences. Clouding is a phenomenon in which water in the air is dewed on the surface of a base material and countless fine water droplets are generated to diffusely reflect light. Since the visibility deteriorates due to the fogging of the base material, a method for improving the visibility is required.
Until now, various methods for imparting antifogging properties to a substrate have been studied, and it has been found that a method of forming a water film by hydrophilizing the substrate surface to prevent diffuse reflection is effective.

For example, Patent Literature 1 and Patent Literature 2 propose a method in which hydrophilic polyvinyl alcohol or polyethylene glycol is coated on a substrate surface to impart anti-fogging property.
Further, in Patent Document 3, a porous film of silica fine particles and a water-absorbing type anti-fogging agent using a water-absorbing resin have been developed, and development for improving water resistance has also been made.
In these antifogging agents, when light is applied to the antifogging agent portion, radicals are generated, and the bond between components may be destroyed to cause deterioration. In order to suppress such radicals, for example, Patent Document 4 proposes an antifogging agent in which a radical scavenger is separately added to suppress deterioration of components.

JP 2000-192019 A JP 2014-070120 A JP 2000-239045 A JP-A-2013-030803

However, the anti-fogging agents of Patent Literature 1 and Patent Literature 2 have a problem that the solubility in water is high even after the treatment with the anti-fogging agent, and the water resistance is not sufficient.
On the other hand, a water-absorbing type anti-fog agent as disclosed in Patent Document 3 in consideration of solubility in water has a limit in water absorption, and when the water absorption exceeds the limit water absorption, it tends to be cloudy rather than a short duration. is there. In addition, when water is absorbed, there is a problem that the hardness of the anti-fogging portion is reduced and the portion is easily worn.
Further, the anti-fogging agent of Patent Document 4 needs to mix a radical scavenger separately from the main component, and has a disadvantage that the number of steps is increased.

  The present invention has been made in view of the above circumstances, and when a substrate surface is treated, a photocuring type anti-fog effect capable of imparting an anti-fog effect having high water resistance, abrasion resistance, and light resistance to a portion to be processed. It is intended to provide a fogging agent.

  The present inventors have conducted intensive studies to achieve the above object, and as a result, a predetermined hindered amino group-containing organosilicon compound, a mixed oligomer of an acryl group-containing organosilicon compound and an alkoxysilane, a solvent, and a photopolymerization initiator By treating the substrate surface with a photocurable composition containing, imparting anti-fogging properties to the portion to be treated, furthermore, its anti-fogging effect has high water resistance and abrasion resistance, The present invention has been completed.

（式中、Ｒ¹は、水素原子、炭素数１〜８の１価炭化水素基、又は炭素数１〜８のアルコキシ基を表し、Ｒ²は、炭素原子の一部がヘテロ原子に置換されていてもよい、炭素数１〜８の２価炭化水素基を表し、Ｒ³及びＲ⁶は、互いに独立して、炭素数１〜８の１価炭化水素基を表し、Ｒ⁴は、水素原子又はメチル基を表し、Ｒ⁵は、炭素数１〜８の２価炭化水素基を表し、Ｒ⁷は、炭素数１〜８の１価炭化水素基、又は炭素原子の一部がヘテロ原子に置換されていてもよい、炭素数１〜８の２価炭化水素基を表し、ｎ及びｍは、０〜２の整数を表し、αは、１〜３の整数を表し、βは、（４−α）／２を満たす数を表し、ａは、０．５〜０．９、ｂは、０．００１〜０．５、ｃは、０〜０．３、かつ、ａ＋ｂ＋ｃ＝１を満たす数を表す。）
２． 前記混合オリゴマーが、０．００１〜５０質量％含まれる１の光硬化型防曇剤
を提供する。 That is, the present invention
1. A hindered amino group-containing organosilicon compound, an acryl group-containing organosilicon compound having a weight average molecular weight in terms of polystyrene of 2,000 to 5,000,000 as determined by gel permeation chromatography and represented by the following average composition formula (1): A mixed oligomer of alkoxysilane, a solvent, and a photocurable anti-fog agent, comprising a photopolymerization initiator,

(Wherein, R ¹ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, and R ² has a part of carbon atoms substituted by a hetero atom. May represent a divalent hydrocarbon group having 1 to 8 carbon atoms, R ³ and R ⁶ independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁴ represents hydrogen R ⁵ represents a divalent hydrocarbon group having 1 to 8 carbon atoms, R ⁷ represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a part of carbon atoms is a heteroatom; Represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be substituted, n and m represent an integer of 0 to 2, α represents an integer of 1 to 3, and β represents ( 4-α) / 2, a represents 0.5 to 0.9, b represents 0.001 to 0.5, c represents 0 to 0.3, and a + b + c = 1. Represents a number.)
2. The photo-curable anti-fogging agent according to claim 1, wherein the mixed oligomer is contained in an amount of 0.001 to 50% by mass.

Surface treatment of the substrate using the photocurable antifogging agent of the present invention, and curing by UV irradiation, not only imparts an antifogging effect to the portion to be treated, but also has high water resistance, abrasion resistance and Light resistance is also exhibited.
The antifogging agent of the present invention having such characteristics can be suitably used for a transparent substrate such as glass, a composite material containing the same, and the like.

1 is a ¹ H-NMR spectrum of the mixed oligomer obtained in Example 1. 3 is an IR spectrum of the mixed oligomer obtained in Example 1. 3 is a ¹ H-NMR spectrum of the mixed oligomer obtained in Example 2. 6 is an IR spectrum of the mixed oligomer obtained in Example 2. 4 is a ¹ H-NMR spectrum of the mixed oligomer obtained in Example 3. 6 is an IR spectrum of the mixed oligomer obtained in Example 3. 6 is a ¹ H-NMR spectrum of the mixed oligomer obtained in Example 4. 9 is an IR spectrum of the mixed oligomer obtained in Example 4. 9 is a ¹ H-NMR spectrum of the mixed oligomer obtained in Example 5. 9 is an IR spectrum of the mixed oligomer obtained in Example 5. 9 is a ¹ H-NMR spectrum of the mixed oligomer obtained in Example 6. 9 is an IR spectrum of the mixed oligomer obtained in Example 6. 9 is a ¹ H-NMR spectrum of the mixed oligomer obtained in Example 7. 9 is an IR spectrum of the mixed oligomer obtained in Example 7. 9 is a ¹ H-NMR spectrum of the mixed oligomer obtained in Example 8. 9 is an IR spectrum of the mixed oligomer obtained in Example 8. 9 is a ¹ H-NMR spectrum of the mixed oligomer obtained in Example 9. 9 is an IR spectrum of the mixed oligomer obtained in Example 9.

Hereinafter, the present invention will be described specifically.
The antifogging agent of the present invention has a weight average molecular weight of 2,000 to 5,000,000 in terms of polystyrene by gel permeation chromatography (hereinafter, also referred to as “GPC”) represented by the following average composition formula (1). And a mixed oligomer of a hindered amino group-containing organosilicon compound, an acryl group-containing organosilicon compound and an alkoxysilane, a solvent, and a photopolymerization initiator.

In the formula (1), R ¹ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, and R ² has a part of carbon atoms as a hetero atom. Represents an optionally substituted divalent hydrocarbon group having 1 to 8 carbon atoms, R ³ and R ⁶ independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁴ represents Represents a hydrogen atom or a methyl group, R ⁵ represents a divalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁷ represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a part of carbon atoms. Represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be substituted by a hetero atom.

Here, specific examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms for R ¹ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, linear alkyl groups such as n-heptyl group and n-octyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, isohexyl group, and isoheptyl group And a branched alkyl group such as an isooctyl group and a tert-octyl group; and a cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group. Among these, a monovalent hydrocarbon group having 1 to 3 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are more preferable.

  Specific examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentoxy group, an n-hexoxy group, an n-heptoxy group, and an n-oxytoxy group. Linear alkoxy groups such as isopropoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, isopentoxy group, neopentoxy group, isohexoxy group, isoheptoxy group, isooctoxy group, tert-octoxy group, etc. A branched alkoxy group. Among these, a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group, which are alkoxy groups having 1 to 3 carbon atoms, are preferred.

Examples of the divalent hydrocarbon group having 1 to 8 carbon atoms for R ² include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group. Chain alkylene group; branched alkylene group such as isoprene group, isobutene group, sec-butylene group, isopentene group, neopentene group, isohexene group, isoheptene group, isooctene group, tert-octene group; cyclopentane Examples include a cyclic alkylene group such as a diyl group and a cyclohexanediyl group, among which a divalent hydrocarbon group having 1 to 4 carbon atoms is preferable, and a methylene group, an ethylene group, a trimethylene group, and an isoprene group are more preferable. .
This divalent hydrocarbon group may have a part of its carbon atoms substituted with a hetero atom, and specific examples of the substituent include -NH-, -CO-, -S-, -O-,- COO -, - OOC-, and the like, as such substituted divalent hydrocarbon _{radical, -O- (CH 2) 3 -} , - NH- (CH 2) 3 -, - S- (CH _{2) 3 -, - OOC- (} CH 2) 3 - is preferable.

Specific examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms of R ³ and R ⁶ include the same substituents as those exemplified for R ¹ above. From the viewpoint of hydrolysis rate, a methyl group, An ethyl group and an n-propyl group are preferred.
Specific examples of the divalent hydrocarbon group having 1 to 8 carbon atoms for R ⁵ include those similar to the divalent hydrocarbon groups exemplified for R ² above.

Specific examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms for R ⁷ include the same substituents as those exemplified for R ¹ , and an aryl group having 6 to 8 carbon atoms such as a phenyl group. . On the other hand, specific examples of the divalent hydrocarbon group include linear alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group; Branched alkylene groups such as isoprene group, isobutene group, sec-butylene group, isopentene group, neopentene group, isohexene group, isoheptene group, isooctene group, tert-octene group; cyclobutenediyl group, cyclopentenediyl group , Cyclopentadienediyl, cyclohexenediyl, 1,3-cyclohexadienediyl, 1,4-cyclohexadienediyl, cycloheptenediyl, cycloheptatrienediyl, cyclooctenediyl, 1,5-cyclo Octadienediyl group, cyclooctate A cycloalkylenediyl group having 3 to 8 carbon atoms having one or two double bonds, such as an enediyl group; a cyclic alkylene group including a phenyl group, among others; From the viewpoint, a linear alkyl group or a phenyl group is desirable.
This divalent hydrocarbon group may have a part of its carbon atoms substituted with a hetero atom, and specific examples of the substituent include -NH-, -CO-, -S-, -O-,- COO -, - OOC-, and the like, as such substituted divalent hydrocarbon _{radical, -O- (CH 2) 3 -} , - NH- (CH 2) 3 -, - S- (CH _{2) 3 -, - OOC- (} CH 2) 3 - is preferable.

Further, in the formula (1), n and m represent an integer of 0 to 2, and preferably an integer of 0 to 1 for both.
α represents an integer of 1 to 3, preferably 1, and β is a number satisfying (4-α) / 2. When α is 1, 1.5 is preferable.
a represents a number of 0.5 to 0.9, and is preferably 0.7 to 0.9 from the viewpoint of further improving the anti-fogging effect.
b represents a number of 0.01 to 0.5, but is preferably 0.05 to 0.5 from the viewpoint of increasing the hardness of the anti-fogging treatment portion.
c represents a number of 0 to 0.3, and is preferably 0.05 to 0.3 from the viewpoint of water resistance.
Note that a, b, and c satisfy a + b + c = 1.

In the present invention, the weight average molecular weight of the mixed oligomer represented by the above average composition formula (1) in terms of polystyrene by GPC is from 2,000 to 5,000,000, but from 5,000 to 1,000,000. Is preferred.
The weight average molecular weight is measured by a static light scattering method. For example, using a molecular weight measurement system (ELSZ-2000, manufactured by Otsuka Electronics Co., Ltd.), the temperature is 25 ° C., and 0 to 10% by mass using a tetrahydrofuran solvent. The refractive index required for this analysis can be determined using a high-sensitivity suggestive refractometer (DRM-3000, manufactured by Otsuka Electronics Co., Ltd.).

  The content of the mixed oligomer in the photocurable antifogging agent of the present invention is not particularly limited, but from the viewpoint of facilitating uniform application of the antifogging agent, 0.001 to 50 with respect to the substrate. % Is preferable, and 0.01 to 50% by mass is more preferable.

The mixed oligomer of the hindered amino group-containing organosilicon compound represented by the above average composition formula (1), the acryl group-containing silicon compound and the alkoxysilane is a hindered amino group-containing organosilicon compound represented by the general formula (2) And an acrylic group-containing organosilicon compound represented by the general formula (3).
Further, in order to improve the water resistance of the anti-fog, an alkoxysilane represented by the general formula (4) may be added as necessary to carry out hydrolysis. In addition, the compounds represented by the general formulas (2), (3) and (4), which are raw materials, may remain.

In the formula (2), R ⁹ represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ^{1 to} R ³ and n have the same meaning as described above.
Specific examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms for R ⁹ include the same groups as those exemplified for R ¹ above. From the viewpoint of the hydrolysis rate, methyl, ethyl, n -A propyl group is preferred.
In the formula (3), R ¹⁰ represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ^{4 to} R ⁶ and m have the same meaning as described above.
Specific examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms for R ¹⁰ include the same groups as those exemplified for R ¹ above. From the viewpoint of the hydrolysis rate, methyl, ethyl, n -A propyl group is preferred.
In the formula (4), R ¹¹ represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁷ and α have the same meaning as described above.
Specific examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms for R ¹¹ include the same substituents as those exemplified for R ¹ above, and an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group , An ethyl group and an n-propyl group are more preferred.

Specific examples of the hindered amino group-containing organosilicon compound represented by the general formula (2) include trimethoxysilylmethoxy-2,2,6,6-tetramethylpiperidine, trimethoxysilylmethylamino-2,2,6 , 6-Tetramethyl-4-piperidine, trimethoxysilylmethoxy-1,2,2,6,6-pentamethyl-4-piperidine, trimethoxysilylmethoxy-2,2,6,6-tetraethyl-1 -Ethyl-4-piperidine, trimethoxysilylmethoxy-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, trimethoxysilylmethylamino-2,2,6,6-tetramethyl -4-propylpiperidine, trimethoxysilylmethoxy-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, trimethoxysilylmethyl Amino-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, trimethoxysilylmethoxy-2,2,6,6-tetramethyl-1-ethoxy-4-piperidine, Methoxysilylmethylamino-2,2,6,6-tetramethyl-1-ethoxy-4-piperidine, trimethoxysilylmethoxy-2,2,6,6-tetramethyl-1-propoxy-4-piperidine Lysine, trimethoxysilylmethylamino-2,2,6,6-tetramethyl-1-propoxy-4-piperidine, trimethoxysilylethoxy-2,2,6,6-tetramethylpiperidine, trimethoxysilylethyl Amino-2,2,6,6-tetramethylpiperidine, trimethoxysilylethoxy-1,2,2,6,6-pentamethyl-4-piperidine, trimethoxy Ruethylamino-1,2,2,6,6-pentamethyl-4-piperidine, trimethoxysilylethoxy-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, trimethoxysilylethylamino- 2,2,6,6-tetraethyl-1-ethyl-4-piperidine, trimethoxysilylethoxy-2,2,6,6-tetramethyl-4-propylpiperidine, trimethoxysilylethoxy-2,2 , 6,6-Tetramethyl-1-methoxy-4-piperidine, trimethoxysilylethyl-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, trimethoxysilylethoxy-2 , 2,6,6-tetramethyl-1-methoxy-4-piperidine,
Trimethoxysilylethylamino-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, trimethoxysilylethoxy-2,2,6,6-tetramethyl-1-propoxy-4-piぺ lysine, trimethoxysilylethylamino-2,2,6,6-tetramethyl-1-propoxy-4-piperidine, trimethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine, trimethoxysilyl Propylamino-2,2,6,6-tetramethylpiperidine, trimethoxysilylpropoxy-1,2,2,6,6-pentamethyl-4-piperidine, trimethoxysilylpropylamino-1,2,2,6 , 6-Pentamethyl 4-piperidine, trimethoxysilylpropoxy-1,2,2,6,6-pentamethyl 4-piperidine, trimeth Silicylpropylamino-1,2,2,6,6-pentamethyl-4-piperidine, trimethoxysilylpropoxy-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, trimethoxysilyl Propylamino-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, trimethoxysilylpropoxy-2,2,6,6-tetramethyl-1-propyl-4-piperidine, tripropyl Methoxysilylpropylamino-2,2,6,6-tetramethyl-1-propyl-4-piperidine, trimethoxysilylpropoxy-2,2,6,6-tetramethyl-1-methoxy-4-piperidine Lysine, trimethoxysilylpropylamino-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, trimethoxysilylpropylamino-2,2,6 6-tetramethyl-1-methoxy-4-piperidine, trimethoxysilylpropoxy-2,2,6,6-tetramethyl-1-propoxy-4-piperidine, trimethoxysilylpropylamino-2,2 , 6,6-tetramethyl-1-propoxy-4-piperidine, triethoxysilylmethoxy-2,2,6,6-tetramethylpiperidine, triethoxysilylmethylamino-2,2,6,6-tetramethylpiperidineぺ lysine, triethoxysilylmethoxy-1,2,2,6,6-pentamethyl-4-piperidine, triethoxysilylmethylamino-1,2,2,6,6-pentamethyl-4-piperidine, triethoxy Silylmethoxy-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, triethoxysilylmethylamino-2,2,6,6- Tetraethyl-1-ethyl-4-piperidine, triethoxysilylmethoxy-2,2,6,6-tetramethyl-1-propyl-4-piperidine, triethoxysilylmethylamino-2,2,6, 6-tetramethyl-1-propyl-4-piperidine, triethoxysilylmethoxy-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, triethoxysilylmethylamino-2,2 , 6,6-tetramethyl-1-methoxy-4-piperidine, triethoxysilylmethoxy-2,2,6,6-tetramethyl-1-ethoxy-4-piperidine, triethoxysilylmethylamino- 2,2,6,6-tetramethyl-1-ethoxy-4-piperidine, triethoxysilylmethoxy-2,2,6,6-tetramethyl-1-propoxy-4-piperidine , Triethoxysilylmethylamino-2,2,6,6-tetramethyl-1-propoxy-4-piperidine, triethoxysilylethoxy-2,2,6,6-tetramethylpiperidine, triethoxysilylethyl Amino-2,2,6,6-tetramethyl-4-piperidine, triethoxysilylethoxy-1,2,2,6,6-pentamethyl-4-piperidine, triethoxysilylethylamino-1,2 , 2,6,6-pentamethyl-4-piperidine, triethoxysilylethoxy-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, triethoxysilylethoxy-2,2,6, 6-tetramethyl-4-propylpiperidine, triethoxysilylethylamino-2,2,6,6-tetramethyl-4-propylpiperidine, triethoxy Silylethoxy-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, triethoxysilylethylamino-2,2,6,6-tetramethyl-1-methoxy-4-piperidine , Triethoxysilylethoxy-2,2,6,6-tetramethyl-1-ethoxy-4-piperidine, triethoxysilylethylamino-2,2,6,6-tetramethyl-1-ethoxy-4- Piperidine, triethoxysilylethoxy-2,2,6,6-tetramethyl-1-propoxy-4-piperidine, triethoxysilylethylamino-2,2,6,6-tetramethyl-1-propoxy -4-piperidine, triethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine, triethoxysilylpropylamino-2,2,6,6-tetramethylpiperidine Peridine, triethoxysilylpropoxy-1,2,2,6,6-pentamethyl-4-piperidine, triethoxysilylpropylamino-1,2,2,6,6-pentamethyl4-piperidine, triethoxy Silylpropoxy-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, triethoxysilylpropylamino-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, tri Ethoxysilylpropoxy-2,2,6,6-tetramethyl-1-propyl-4-piperidine, triethoxysilylpropylamino-2,2,6,6-tetramethyl-1-propyl-4-piperidine Lysine, triethoxysilylpropoxy-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, triethoxysilylpropylamino-2,2, , 6-Tetramethyl-1-methoxy-4-piperidine, triethoxysilylpropoxy-2,2,6,6-tetramethyl-1-ethoxy-4-piperidine, triethoxysilylpropylamino-2, 2,6,6-tetramethyl-1-ethoxy-4-piperidine, trimethoxysilylpropoxy-2,2,6,6-tetramethyl-1-propoxy-4-piperidine, trimethoxysilylpropylamino -2,2,6,6-tetramethyl-1-propoxy-4-piperidine, tripropoxysilylmethoxy-2,2,6,6-tetramethyl-4-piperidine, tripropoxysilylmethylamino- 2,2,6,6-tetramethyl-4-piperidine, tripropoxysilylmethoxy-1,2,2,6,6-pentamethyl-4-piperidine, tripro Xysilylmethylamino-1,2,2,6,6-pentamethyl-4-piperidine, tripropoxysilylmethoxy-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, tripropoxysilyl Methylamino-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, tripropoxysilylmethoxy-2,2,6,6-tetramethyl-1-propyl-4-piperidine, Propoxysilylmethylamino-2,2,6,6-tetramethyl-1-propyl-4-piperidine, tripropoxysilylmethylamino-2,2,6,6-tetramethyl-1-methoxy-4-piぺ lysine, tripropoxysilylmethoxy-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, tripropoxysilylmethoxy-2,2,6,6- Tetramethyl-1-ethoxy-4-piperidine, tripropoxysilylmethylamino-2,2,6,6-tetramethyl-1-ethoxy-4-piperidine, tripropoxysilylmethoxy-2,2,6 , 6-Tetramethyl-1-propoxy-4-piperidine, tripropoxysilylmethylamino-2,2,6,6-tetramethyl-1-propoxy-4-piperidine, triethoxysilylpropylamino-2 , 2,6,6-tetramethyl-4-piperidine, tripropoxysilylethoxy-1,2,2,6,6-pentamethyl-4-piperidine, tripropoxysilylethylamino-1,2,2, 6,6-pentamethyl 4-piperidine, tripropoxysilylethoxy-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, tripropoxy Silylethylamino-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, tripropoxysilylethoxy-2,2,6,6-tetramethyl-1-propyl-4-piperidine, Tripropoxysilylethylamino-2,2,6,6-tetramethyl-1-propyl-4-piperidine, tripropoxysilylethoxy-2,2,6,6-tetramethyl-1-methoxy-4-piぺ lysine, tripropoxysilylethylamino-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, tripropoxysilylethylamino-2,2,6,6-tetramethyl-1-ethoxy -4-piperidine, tripropoxysilylethoxy-2,2,6,6-tetramethyl-1-propoxy-4-piperidine, tripropoxysilylethylamino 2,2,6,6-tetramethyl-1-propoxy-4-piperidine, tripropoxysilylpropoxy-2,2,6,6-tetramethylpiperidine, tripropoxysilylpropylamino-2,2,6 6-tetramethyl-4-piperidine, tripropoxysilylpropoxy-1,2,2,6,6-pentamethyl 4-piperidine, tripropoxysilylpropylamino-1,2,2,6,6-pentamethyl 4-piperidine, tripropoxysilylpropoxy-2,2,6,6-tetramethyl-1-ethyl-4-piperidine, tripropoxysilylpropylamino-2,2,6,6-tetramethyl-1 -Ethyl-4-piperidine, tripropoxysilylpropoxy-2,2,6,6-tetramethyl-1-propyl-4-piperidine, tripropoxy Xixylylpropylsilyl-2,2,6,6-tetramethyl-1-propyl-4-piperidine, tripropoxysilylpropoxy-2,2,6,6-tetramethyl-1-methoxy-4-piperidine Lysine, tripropoxysilylpropylsilyl-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, tripropoxysilylpropoxy-2,2,6,6-tetramethyl-1-ethoxy-4 -Piperidine, tripropoxysilylpropylamino-2,2,6,6-tetramethyl-1-ethoxy-4-piperidine, tripropoxysilylpropoxy-2,2,6,6-tetramethyl-1- Propoxy-4-piperidine, tripropoxysilylpropylamino-2,2,6,6-tetramethyl-1-propoxy-4-piperidine, tripropoxy Silylmethoxy-2,2,6,6-tetramethylpiperidine, tripropoxysilylmethylamino-2,2,6,6-tetramethyl-4-piperidine, tripropoxysilylmethoxy-1,2,2,6 , 6-Pentamethyl-4-piperidine, tripropoxysilylmethylamino-1,2,2,6,6-pentamethyl-4-piperidine, tripropoxysilylmethoxy-2,2,6,6-tetraethyl-1- Ethyl-4-piperidine, tripropoxysilylmethylamino-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, tripropoxysilylmethoxy-2,2,6,6-tetramethyl- 1-propyl-4-piperidine, tripropoxysilylmethylamino-2,2,6,6-tetramethyl-1-propyl-4-piperidine, tripropyl Ropoxysilylmethoxy-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, tripropoxysilylmethylamino-2,2,6,6-tetramethyl-1-methoxy-4-piperidineぺ lysine, tripropoxysilylmethoxy-2,2,6,6-tetramethyl-1-ethoxy-4-piperidine, tripropoxysilylmethylamino-2,2,6,6-tetramethyl-1-ethoxy- 4-piperidine, tripropoxysilylmethoxy-2,2,6,6-tetramethyl-1-propoxy-4-piperidine, tripropoxysilylmethylamino-2,2,6,6-tetramethyl-1 -Propoxy-4-piperidine and the like.

  Specific examples of the acrylic group-containing organosilicon compound represented by the general formula (3) include 3-acryloxymethyltrimethoxysilane, 3-acryloxymethyldimethoxymethylsilane, 3-acryloxymethylmethoxydimethylsilane, and 3-acrylic acid. Roxymethyltriethoxysilane, 3-acryloxymethyldiethoxymethylsilane, 3-acryloxymethylethoxydimethylsilane, 3-acryloxymethyltripropoxysilane, 3-acryloxymethyldipropoxymethylsilane, 3-acryloxymethylpropoxy Dimethylsilane, 3-acryloxymethyldimethoxyethylsilane, 3-acryloxymethylmethoxydiethylsilane, 3-acryloxymethyldimethoxypropylsilane, 3-acryloxymethylmethoxydipropylsilane, -Acryloxymethyldiethoxyethylsilane, 3-acryloxymethylethoxydiethylsilane, 3-acryloxymethyldiethoxypropylsilane, 3-acryloxymethylethoxydipropylsilane, 3-acryloxymethyldipropoxypropylsilane, 3- Acryloxymethylpropoxydipropylsilane, 3-acryloxyethyltrimethoxysilane, 3-acryloxyethyldimethoxymethylsilane, 3-acryloxyethylmethoxydimethylsilane, 3-acryloxyethyltriethoxysilane, 3-acryloxyethyldi Ethoxymethylsilane, 3-acryloxyethylethoxydimethylsilane, 3-acryloxyethyltripropoxysilane, 3-acryloxyethyldipropoxymethylsilane, 3-acryloxye Lepropoxydimethylsilane, 3-acryloxyethyldimethoxyethylsilane, 3-acryloxyethylmethoxydiethylsilane, 3-acryloxyethyldimethoxypropylsilane, 3-acryloxyethylmethoxydipropylsilane, 3-acryloxyethyldiethoxyethyl Silane, 3-acryloxyethylethoxydiethylsilane, 3-acryloxyethyldimethoxypropylsilane, 3-acryloxyethylmethoxydipropylsilane, 3-acryloxyethyldiethoxypropylsilane, 3-acryloxyethylethoxydipropylsilane, 3-acryloxyethyldipropoxypropylsilane, 3-acryloxyethylpropoxydipropylsilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Rudimethoxymethylsilane, 3-acryloxypropylmethoxydimethylsilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyldiethoxymethylsilane, 3-acryloxypropylethoxydimethylsilane, 3-acryloxypropyltripropoxysilane , 3-acryloxypropyldipropoxymethylsilane, 3-acryloxypropylpropoxydimethylsilane, 3-acryloxypropyldimethoxyethylsilane, 3-acryloxypropylmethoxydiethylsilane, 3-acryloxypropyldimethoxypropylsilane, 3-acryl Roxypropylmethoxydipropylsilane, 3-acryloxypropyldiethoxyethylsilane, 3-acryloxypropylethoxydiethylsilane, 3-acryloxy Propyldimethoxypropylsilane, 3-acryloxypropylmethoxydipropylsilane, 3-acryloxypropyldiethoxypropylsilane, 3-acryloxypropylethoxydipropylsilane, 3-acryloxypropyldipropoxypropylsilane, 3-acryloxypropyl Propoxydipropylsilane, 3-methacryloxymethyltrimethoxysilane, 3-methacryloxymethyldimethoxymethylsilane, 3-methacryloxymethylmethoxydimethylsilane, 3-methacryloxymethyltriethoxysilane, 3-methacryloxymethyldiethoxymethylsilane 3-methacryloxymethylethoxydimethylsilane, 3-methacryloxymethyltripropoxysilane, 3-methacryloxymethyldipropoxymethylsilane, -Methacryloxymethylpropoxydimethylsilane, 3-methacryloxymethyldimethoxyethylsilane, 3-methacryloxymethylmethoxydiethylsilane, 3-methacryloxymethyldimethoxypropylsilane, 3-methacryloxymethylmethoxydipropylsilane, 3-methacryloxymethyl Diethoxyethylsilane, 3-methacryloxymethylethoxydiethylsilane, 3-methacryloxymethyldiethoxypropylsilane, 3-methacryloxymethylethoxydipropylsilane, 3-methacryloxymethyldipropoxypropylsilane, 3-methacryloxymethylpropoxy Dipropylsilane, 3-methacryloxyethyltrimethoxysilane, 3-methacryloxyethyldimethoxymethylsilane, 3-methacryloxyethylmethoxy Sidimethylsilane, 3-methacryloxyethyltriethoxysilane, 3-methacryloxyethyldiethoxymethylsilane, 3-methacryloxyethylethoxydimethylsilane, 3-methacryloxyethyltripropoxysilane, 3-methacryloxyethyldipropoxymethylsilane , 3-methacryloxyethylpropoxydimethylsilane, 3-methacryloxyethyldimethoxyethylsilane, 3-methacryloxyethylmethoxydiethylsilane, 3-methacryloxyethyldimethoxypropylsilane, 3-methacryloxyethylmethoxydipropylsilane, 3-methacryl Roxyethyldiethoxyethylsilane, 3-methacryloxyethylethoxydiethylsilane, 3-methacryloxyethyldimethoxypropylsilane, 3-methacryloxyie Methoxydipropylsilane, 3-methacryloxyethyldiethoxypropylsilane, 3-methacryloxyethylethoxydipropylsilane, 3-methacryloxyethyldipropoxypropylsilane, 3-methacryloxyethylpropoxydipropylsilane, 3-methacryloxy Propyltrimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropylmethoxydimethylsilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyldiethoxymethylsilane, 3-methacryloxypropylethoxydimethylsilane 3-methacryloxypropyltripropoxysilane, 3-methacryloxypropyldipropoxymethylsilane, 3-methacryloxypropylpropoxydim Silane, 3-methacryloxypropyldimethoxyethylsilane, 3-methacryloxypropylmethoxydiethylsilane, 3-methacryloxypropyldimethoxypropylsilane, 3-methacryloxypropylmethoxydipropylsilane, 3-methacryloxypropyldiethoxyethylsilane, 3 -Methacryloxypropylethoxydiethylsilane, 3-methacryloxypropyldimethoxypropylsilane, 3-methacryloxypropylmethoxydipropylsilane, 3-methacryloxypropyldiethoxypropylsilane, 3-methacryloxypropylethoxydipropylsilane, 3-methacrylic Roxypropyldipropoxypropylsilane, 3-methacryloxypropylpropoxydipropylsilane and the like can be mentioned.

  Specific examples of the alkoxysilane compound represented by the general formula (4) include tetramethoxysilane, trimethoxymethylsilane, dimethoxydimethylsilane, methoxytrimethylsilane, tetraethoxysilane, triethoxymethylsilane, diethoxydimethylsilane, and ethoxytrimethyl. Silane, tripropoxymethylsilane, dipropoxydimethylsilane, propoxytrimethylsilane, trimethoxyethylsilane, dimethoxydiethylsilane, methoxytriethylsilane, trimethoxypropylsilane, dimethoxydipropylsilane, methoxytripropylsilane, triethoxyethylsilane, diethoxyethylsilane Ethoxydiethylsilane, ethoxytriethylsilane, triethoxypropylsilane, diethoxydipropylsilane, ethoxytripropylsila , Tripropoxyethylsilane, dipropoxydiethylsilane, propoxytriethylsilane, tripropoxypropylsilane, dipropoxydipropylsilane, propoxytripropylsilane, phenyltrimethoxysilane, phenyldimethoxymethylsilane, phenylmethoxydimethylsilane, phenyldimethoxyethylsilane , Phenylmethoxydiethylsilane, phenyldipropoxymethylsilane, phenylpropoxydimethylsilane, phenyltriethoxysilane, phenyldiethoxydimethylsilane, phenylethoxytrimethylsilane, phenyldiethoxyethylsilane, phenylethoxydiethylsilane, phenyldiethoxypropylsilane, Phenylethoxydipropylsilane, phenyltripropoxysilane, phenyl Dipropoxymethyl silane, phenylpropoxy dimethylsilane, phenyl dipropoxy triethylsilane, phenylpropoxy diethyl silane, phenyl di propoxypropyl silane, phenyl propoxy dipropyl silane.

In producing the mixed oligomer of the hindered amino group-containing organosilicon compound, the acryl group-containing organosilicon compound and the alkoxysilane represented by the above average composition formula (1) in the present invention, the raw material is represented by the general formula (2). The order of co-hydrolysis of the hindered amino group-containing organosilicon compound, the acryl group-containing organosilicon compound represented by the general formula (3), and the alkoxysilane represented by the general formula (4) is not particularly limited. After mixing and hydrolyzing the two components, the remaining components may be mixed and further hydrolyzed, or all three components may be mixed and hydrolyzed simultaneously.
The amount of water used in the hydrolysis reaction is preferably 6 to 100 mol, more preferably 10 to 100 mol, and more preferably 10 to 100 mol, based on the total amount of the organosilicon compound or the organosilicon compound and the alkoxysilane used, from the viewpoint of the hydrolysis rate. -100 mol is even more preferred.
At the time of the hydrolysis reaction, an organic solvent described below may be used. In this case, the total amount of the raw material organosilicon compound or organosilicon compound and alkoxysilane is preferably 0.5 to 500% by mass relative to the organic solvent, -500 mass% is more preferable, and 10-500 mass% is even more preferable.
The reaction temperature of the hydrolysis reaction is not particularly limited, but is preferably from 0 to 120 ° C, more preferably from 60 to 120 ° C.
The reaction time is not particularly limited, but is preferably 1 to 15 hours, more preferably 1 to 10 hours.

When the reaction solution containing the mixed oligomer represented by the average composition formula (1) contains a solvent, the photocurable anti-fogging agent of the present invention is added to a photopolymerization initiator described later and applied to the substrate as it is. After removing the solvent of the reaction solution once at normal pressure or under pressure, a new solvent may be added to form a solution, to which a photopolymerization initiator described later may be added for use.
Specific examples of the solvent include polar solvents such as alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ketones such as acetone and methyl isobutyl ketone.
The content of the solvent in the photocurable antifogging agent is not particularly limited, but from the viewpoint of facilitating uniform application of the antifogging agent, is preferably 40 to 99% by mass based on the base material, 50-90 mass% is more preferable.

The photopolymerization initiator used in the photocurable antifogging agent of the present invention is not particularly limited, as long as it is appropriate from the viewpoint of compatibility with the mixed oligomer and the solvent and curability.
Specific examples of the photopolymerization initiator include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethylketal, 2,2-diethoxyacetophenone, 1-hydroxy Carbonyl compounds such as cyclohexylphenyl ketone, methylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis (2,4,6-trimethylben Phosphorus) compounds such as yl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide; 2-benzyl-2-dimethylamino-1- (4-morpholine (Linophenyl) butanone-1, camphorquinone, etc., and these may be used alone or in combination of two or more.
Among these, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis ( (2,6-Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide is preferred.
The content of the photopolymerization initiator in the photocurable antifogging agent is preferably 0.1 to 10% by mass based on the acrylic group-containing organosilicon compound from the viewpoint of maintaining the degree of curing and the antifogging effect. ~ 6 mass% is more preferred.

In the anti-fogging treatment using the photo-curing anti-fogging agent of the present invention, a photo-curing anti-fogging agent is applied to a substrate such as glass, and then dried and cured by UV irradiation.
The coating method is not particularly limited, and various known coating methods, for example, a brush coating method, a spray coating method, a wire bar method, a blade method, a roll coating method, a dipping method, and the like can be adopted.
The drying conditions are also arbitrary, and heating from room temperature to heating can be adopted, but drying under heating is preferred. The temperature at this time is not particularly limited as long as it does not adversely affect the substrate, but is usually about 50 to 150 ° C.
The method of curing the coating film can be carried out, for example, by irradiating ultraviolet rays (wavelength near 365 nm 3633) using an ultraviolet irradiation apparatus ELC-500 (manufactured by Electro Lite Corporation).

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

[1] Synthesis of hindered amino group-containing organosilicon compound [Synthesis Example 1]
A 500 mL four-necked flask equipped with a Dimroth cooling condenser, stirrer, thermometer, and dropping funnel was sufficiently purged with nitrogen. Next, 293.5 g of 4-allyloxy-2,2,6,6-tetramethylpiperidine and 975.5 mg of a platinum catalyst were charged, and the mixture was heated and stirred at 60 to 70 ° C. for 6 hours while slowly dropping 184.6 g of triethoxysilane. . After confirming the disappearance of the raw materials by gas chromatography, purification was performed by distillation to obtain triethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine.

[Synthesis Example 2]
A 1-L four-necked flask equipped with a Dimroth-type cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was sufficiently purged with nitrogen. Next, 572.5 g of pure water was charged, and 72.6 g of triethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine produced in Synthesis Example 1 was slowly added dropwise. After aging for 11 hours at 60 ° C. under normal pressure, the temperature was raised to 120 ° C. to extract by-produced ethanol. Thereafter, vacuum drying was performed to obtain a colorless solid hydrolyzed condensate. The weight average molecular weight was 2,000. 72.0 g of the obtained oligomer was dissolved in 72.0 g of water to obtain an aqueous solution of triethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine.

[2] Production of antifogging agent
[Example 1]
A 200 mL four-necked flask equipped with a Dimroth cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was sufficiently purged with nitrogen. Next, 54.0 g of the aqueous oligomer solution prepared in Synthesis Example 2 and 270.0 g of ethanol were charged, and 3.0 g of 3-acryloxypropyltrimethoxysilane was slowly added dropwise. The mixture was aged at 60 ° C. for 3 hours under normal pressure to obtain a mixed oligomer. A solution was obtained. The obtained mixed oligomer was measured for ¹ H-NMR spectrum and IR spectrum. The results are shown in FIGS. As a result of ¹ H-NMR and IR analysis, the obtained mixed oligomer had a weight average molecular weight of 100,000, and was confirmed to have a structure represented by the following average composition formula (5).

[Example 2]
A 200 mL four-necked flask equipped with a Dimroth cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was sufficiently purged with nitrogen. Next, 54.0 g of the aqueous oligomer solution prepared in Synthesis Example 2 and 270.0 g of ethanol were charged, and 3.0 g of 3-methacryloxypropyltrimethoxysilane was slowly dropped, and the mixture was aged at 60 ° C. for 3 hours under normal pressure to obtain a mixed oligomer. A solution was obtained. The obtained mixed oligomer was measured for ¹ H-NMR spectrum and IR spectrum. The results are shown in FIGS. As a result of ¹ H-NMR and IR analysis, the weight average molecular weight of the obtained mixed oligomer was 60,000, and it was confirmed that the mixed oligomer had a structure represented by the following average composition formula (6).

[Example 3]
A 200 mL four-necked flask equipped with a Dimroth cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was sufficiently purged with nitrogen. Next, 39.9 g of the aqueous oligomer solution prepared in Synthesis Example 2 and 90.0 g of ethanol were charged, and 17.0 g of 3-acryloxypropyltrimethoxysilane was slowly dropped, and the mixture was aged at 60 ° C. for 3.5 hours under normal pressure. A mixed oligomer solution was obtained. The obtained mixed oligomer was measured for ¹ H-NMR spectrum and IR spectrum. The results are shown in FIGS. As a result of ¹ H-NMR and IR analysis, it was confirmed that the obtained mixed oligomer had a weight average molecular weight of 400,000 and had a structure represented by the following average composition formula (7).

[Example 4]
A 200 mL four-necked flask equipped with a Dimroth cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was sufficiently purged with nitrogen. Next, 39.9 g of the aqueous oligomer solution prepared in Synthesis Example 2 and 90.0 g of ethanol were charged, and 17.0 g of 3-methacryloxypropyltrimethoxysilane was slowly dropped, and the mixture was aged at 60 ° C. for 3 hours under normal pressure to obtain a mixed oligomer. A solution was obtained. The obtained mixed oligomer was measured for ¹ H-NMR spectrum and IR spectrum. The results are shown in FIGS. As a result of ¹ H-NMR and IR analysis, the obtained mixed oligomer had a weight average molecular weight of 80,000, and was confirmed to have a structure represented by the following average composition formula (8).

[Example 5]
A 200 mL four-necked flask equipped with a Dimroth cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was sufficiently purged with nitrogen. Next, 3.5 g of a solution containing the oligomer of triethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine prepared in Example 1 and 3-acryloxypropyltrimethoxysilane at a mass ratio of 9: 1 was prepared. Then, 0.54 g of tetraethoxysilane was slowly dropped, and the mixture was aged at 25 to 30 ° C. for 10 hours under normal pressure to obtain a mixed oligomer solution. The obtained mixed oligomer was measured for ¹ H-NMR spectrum and IR spectrum. The results are shown in FIGS. As a result of ¹ H-NMR and IR analysis, it was confirmed that the obtained mixed oligomer had a weight average molecular weight of 300,000 and had a structure represented by the following average composition formula (9).

[Example 6]
A 200 mL four-necked flask equipped with a Dimroth cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was sufficiently purged with nitrogen. Next, 3.5 g of an oligomer solution containing the triethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine oligomer prepared in Example 3 and 3-acryloxypropyltrimethoxysilane at a mass ratio of 7: 3. Was added thereto, and 0.84 g of tetraethoxysilane was slowly added dropwise thereto, followed by aging under normal pressure at 25 to 30 ° C. for 12 hours to obtain a mixed oligomer solution. The obtained mixed oligomer was measured for ¹ H-NMR spectrum and IR spectrum. The results are shown in FIGS. As a result of ¹ H-NMR and IR analysis, the weight average molecular weight of the obtained mixed oligomer was 700,000, and it was confirmed that the mixed oligomer had a structure represented by the following average composition formula (10).

[Example 7]
A 200 mL four-necked flask equipped with a Dimroth cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was sufficiently purged with nitrogen. Next, 3.5 g of an oligomer solution containing the oligomer of triethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine and 3-acryloxypropyltrimethoxysilane prepared in Example 1 at a mass ratio of 9: 1. Was further slowly added dropwise with 0.62 g of hexyltriethoxysilane, and the mixture was aged at 25 to 30 ° C. for 12 hours under normal pressure to obtain a mixed oligomer solution. The obtained mixed oligomer was measured for ¹ H-NMR spectrum and IR spectrum. The results are shown in FIGS. As a result of ¹ H-NMR and IR analysis, it was confirmed that the obtained mixed oligomer had a weight average molecular weight of 50,000 and had a structure represented by the following average composition formula (11).

Example 8
A 200 mL four-necked flask equipped with a Dimroth cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was sufficiently purged with nitrogen. Next, an oligomer solution 3 containing the oligomer of triethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine and 3-acryloxypropyltrimethoxysilane prepared in Example 1-1 at a mass ratio of 9: 1. 0.5 g of octyltriethoxysilane was slowly added dropwise thereto, and the mixture was aged at 25 to 30 ° C. for 10 hours under normal pressure to obtain a mixed oligomer solution. The obtained mixed oligomer was measured for ¹ H-NMR spectrum and IR spectrum. The results are shown in FIGS. As a result of ¹ H-NMR and IR analysis, the obtained mixed oligomer had a weight average molecular weight of 40,000, and it was confirmed that the mixed oligomer had a structure represented by the following average composition formula (12).

[Example 9]
A 200 mL four-necked flask equipped with a Dimroth cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was sufficiently purged with nitrogen. Next, an oligomer solution 3 containing the oligomer of triethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine and 3-acryloxypropyltrimethoxysilane prepared in Example 1-1 at a mass ratio of 9: 1. Then, 0.61 g of phenyltriethoxysilane was slowly dropped, and the mixture was aged at 25 to 30 ° C. for 10 hours under normal pressure to obtain a mixed oligomer solution. The obtained mixed oligomer was measured for ¹ H-NMR spectrum and IR spectrum. The results are shown in FIGS. As a result of ¹ H-NMR and IR analysis, it was confirmed that the obtained mixed oligomer had a weight average molecular weight of 30,000 and had a structure represented by the following average composition formula (13).

(Evaluation of antifogging property)
The antifogging agents prepared in Examples 1 to 9 were evaluated for antifogging properties by the following method. Table 1 shows the results.
In each of the solutions obtained in Examples 1 to 9, the surface was washed well with water or acetone in advance, and a clean slide glass heated in an oven at 110 ° C. for 3 hours was immersed. Thereafter, photocuring was performed by UV irradiation.
Table 1 shows the appearance and the visual antifogging property of the obtained antifogging sample.
The appearance of the anti-fog sample was determined by visual inspection under a fluorescent lamp.
In addition, the visual antifogging property was evaluated by spraying breath on the antifogging sample, and the case where no visual fogging was observed on the entire surface of the slide glass subjected to antifogging treatment was regarded as “「 ”, and the visual fogging was 10 to 20 mass. % Is shown as “○”.

(Water resistance evaluation)
The water resistance was evaluated by the following method using the antifogging agents prepared in Examples 1 to 9 described above. The results are shown in Table 1.
The anti-fogging sample produced by the above method is immersed in water at 40 ° C., and the anti-fogging sample is pulled up every hour, and air is blown on the anti-fogging sample until the entire surface becomes cloudy (the anti-fogging property is not exhibited). Was taken as a measure of water resistance.

  As shown in Table 1, the oligomer using the hindered amino group-containing organosilicon compound and the acryl group-containing organosilicon compound exhibited excellent antifogging water resistance of 15 hours or more. Further, the compound that was co-hydrolyzed with the alkoxysilane maintained its antifogging property in water at 40 ° C. for about 50 hours.

Claims (2)

A hindered amino group-containing organosilicon compound, an acryl group-containing organosilicon compound having a weight average molecular weight in terms of polystyrene of 2,000 to 5,000,000 as determined by gel permeation chromatography and represented by the following average composition formula (1): A photocurable antifogging agent comprising a mixed oligomer of alkoxysilane, a solvent, and a photopolymerization initiator.

(Wherein, R ¹ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, and R ² has a part of carbon atoms substituted by a hetero atom. May represent a divalent hydrocarbon group having 1 to 8 carbon atoms, R ³ and R ⁶ independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁴ represents hydrogen R ⁵ represents a divalent hydrocarbon group having 1 to 8 carbon atoms, R ⁷ represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a part of carbon atoms is a heteroatom; Represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be substituted, n and m represent an integer of 0 to 2, α represents an integer of 1 to 3, and β represents ( 4-α) / 2, a represents 0.5 to 0.9, b represents 0.001 to 0.5, c represents 0 to 0.3, and a + b + c = 1. Represents a number.)   The photocurable antifogging agent according to claim 1, wherein the mixed oligomer is contained in an amount of 0.001 to 50% by mass.

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