JP2017160172A - Hindered amino group-containing organic silicon compound, composition containing the same, and method for producing hindered amino group-containing organic silicon compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hindered amino group-containing organic silicon compound which improves water resistance of a portion to be treated when an inorganic compound is treated, and can impart sustainable light resistance thereto, and to provide a composition containing the same.SOLUTION: A hindered amino group-containing organic silicon compound is represented by average composition formula (1) and has a weight average molecular weight in terms of polystyrene by gel permeation chromatography of 2,000-1,000,000. In formula (1), Rrepresents a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; Ris a divalent hydrocarbon group which has a part of carbon atoms that may be substituted with a hetero atom, is substituted or unsubstituted, and has 1 to 8 carbon atoms; Rand Reach independently represent a monovalent hydrocarbon group having 1 to 8 carbon atoms; n represents an integer of 0-2; m represents an integer of 0-3; and a and b are numbers satisfying a relationship of 1<a/b<100.SELECTED DRAWING: None

Description

  The present invention relates to a hindered amino group-containing organosilicon compound, a composition containing the same, and a method for producing a hindered amino group-containing organosilicon compound.

  It is well known that many polymers are deteriorated with time by the action of light. This deterioration is caused by the fact that ultraviolet rays contained in light cause radicals in the polymer and the bond chain of the compound is broken by radicals. In order not to cause deterioration, the generation of radicals is suppressed. Or it is necessary to invalidate radicals.

The hindered amino group-containing hydrocarbon compound has the property of scavenging and invalidating radicals, and is used as a light-proofing agent and an antifogging agent for preventing deterioration of the polymer.
However, this compound has a problem that when used for surface treatment of an organic-inorganic composite material, glass or the like, its adhesion to these is low.
In order to solve this problem, a hindered amino group-containing silicon compound that is bonded to an inorganic compound and has improved adhesion has been developed (see Patent Document 1). By using this hindered amino group-containing silicon compound, It is possible to prevent bleed out from the material and surface deterioration of the filler such as inorganic compounds.

On the other hand, the surface of transparent substrates widely used for mirrors, glasses, and windows has the problem that the field of view is blocked by cloudiness when used in places with high humidity, temperature differences, or humidity differences. is there. The reason that fogging is caused is that water adhering to the glass or plastic substrate surface forms water droplets due to surface tension, and the water droplets cause light scattering.
Various methods for applying antifogging properties to a substrate have been studied so far, and a method of coating hydrophilic polyvinyl alcohol or polyethylene glycol as an antifogging agent has been proposed (see Patent Document 2). There was a problem that water resistance was low.
In order to improve this, a water-absorbing type antifogging agent using a porous film of silica fine particles and a water-absorbing resin has also been developed, and development to improve the water resistance of the antifogging has been carried out (Patent Literature). 3).

International Publication No. 2012/105103 JP 2005-194471 A JP 2001-233638 A

However, the hindered amino group-containing silicon compound as in Patent Document 1 causes the dissociation of the Si—O bond due to its basicity as in the case of a normal aminosilane compound. Therefore, the water resistance was low, it was liberated from the inorganic compound, and the duration of light resistance was short.
Moreover, in the technique of patent document 3, there existed a problem that a coupling | bonding with a base material and adhesiveness were insufficient and sufficient durability was not acquired.
In addition, when these anti-fogging agents are used outdoors such as windows and car glass parts, the anti-fogging agents deteriorate due to oxygen and ultraviolet rays, causing yellowing and shortening the life of the anti-fogging effect. was there.

  The present invention has been made in view of the above circumstances, and when an inorganic compound is treated, the hindered amino group-containing organosilicon compound can improve the water resistance of the site to be treated and can impart a durable light resistance, And it aims at providing the composition containing this.

  As a result of intensive investigations to achieve the above object, the present inventors have found that when an inorganic compound is treated with a composition containing a predetermined hindered amino group-containing organosilicon compound, As a result, it was found that light resistance was imparted and that the imparted weather resistance was sustained, and the present invention was completed.

（式中、Ｒ¹は、水素原子、炭素数１〜８の１価炭化水素基、または炭素数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で置換されていてもよい、置換または非置換の炭素数１〜８の２価炭化水素基を表し、Ｒ³およびＲ⁵は、互いに独立して、炭素数１〜８の１価炭化水素基を表し、ｎは、０〜２の整数を表し、ｍは、０〜３の整数を表し、ａおよびｂは、１＜ａ／ｂ＜１００を満たす数である。）
２． １のヒンダードアミノ基含有有機ケイ素化合物および溶媒を含む組成物、
３． 前記ヒンダードアミノ基含有有機ケイ素化合物が、０．１〜５０質量％含まれる２の組成物、
４． アルコール含有量が１質量％以下である２または３の組成物、
５． 下記一般式（２）

（式中、Ｒ⁴は、炭素数１〜８の１価炭化水素基を表し、Ｒ¹〜Ｒ³、およびｎは、前記と同じ意味を表す。）
で示されるヒンダードアミノ基含有アルコキシシラン化合物および下記一般式（３）

（式中、Ｒ⁶は、炭素数１〜８の１価炭化水素基を表し、Ｒ⁵およびｍは、前記と同じ意味を表す。）
で示されるアルコキシシラン化合物を共加水分解反応させる１のヒンダードアミノ基含有有機ケイ素化合物の製造方法、
６． 前記式（２）および式（３）で示される各化合物中のケイ素原子合計１モルに対し、３〜１００倍モルの水を用いて共加水分解反応を行う５のヒンダードアミノ基含有有機ケイ素化合物の製造方法、
７． 前記共加水分解反応後、生成したアルコールおよび水を除去する５または６のヒンダードアミノ基含有有機ケイ素化合物の製造方法
を提供する。 That is, the present invention
1. A hindered amino group-containing organosilicon compound represented by the following average composition formula (1), wherein the polystyrene-reduced weight average molecular weight by gel permeation chromatography is 2,000 to 1,000,000,

(In the formula, 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 carbon atom partially substituted with a hetero atom. And represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, R ³ and R ⁵ independently of each other represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, n represents an integer of 0 to 2, m represents an integer of 0 to 3, and a and b are numbers satisfying 1 <a / b <100.)
2. A composition comprising one hindered amino group-containing organosilicon compound and a solvent,
3. 2 composition containing 0.1-50 mass% of said hindered amino group containing organosilicon compounds,
4). 2 or 3 composition whose alcohol content is 1 mass% or less,
5. The following general formula (2)

(In the formula, R ⁴ represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ^{1 to} R ³ and n represent the same meaning as described above.)
A hindered amino group-containing alkoxysilane compound represented by the following general formula (3):

(In the formula, R ⁶ represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁵ and m represent the same meaning as described above.)
A process for producing a hindered amino group-containing organosilicon compound, wherein the alkoxysilane compound represented by formula (1) is subjected to a cohydrolysis reaction;
6). 5 hindered amino group-containing organosilicons that perform a co-hydrolysis reaction using 3 to 100 times moles of water for a total of 1 mole of silicon atoms in each compound represented by formula (2) and formula (3) A method for producing the compound,
7). Provided is a method for producing a 5 or 6 hindered amino group-containing organosilicon compound that removes the alcohol and water produced after the cohydrolysis reaction.

By performing the surface treatment of the inorganic compound using the hindered amino group-containing organosilicon compound of the present invention, the water resistance of the treated surface is improved and the light resistance having high durability is exhibited.
The hindered amino group-containing organosilicon compound of the present invention having such properties can be suitably used as a transparent base material such as glass or an antifogging agent for a composite material containing the same.

It is a < ¹ > H-NMR spectrum figure of the hindered amino group containing organosilicon compound of Example 1-1. It is IR spectrum figure of the hindered amino group containing organosilicon compound of Example 1-1. It is a < ¹ > H-NMR spectrum figure of the hindered amino group containing organosilicon compound of Example 1-2. It is IR spectrum figure of the hindered amino group containing organosilicon compound of Example 1-2. It is a < ¹ > H-NMR spectrum figure of the hindered amino group containing organosilicon compound of Example 1-3. It is IR spectrum figure of the hindered amino group containing organosilicon compound of Example 1-3. It is a < ¹ > H-NMR spectrum figure of the hindered amino group containing organosilicon compound of Example 1-4. It is IR spectrum figure of the hindered amino group containing organosilicon compound of Example 1-4. It is a < ¹ > H-NMR spectrum figure of the hindered amino group containing organosilicon compound of Example 1-5. It is IR spectrum figure of the hindered amino group containing organosilicon compound of Example 1-5. It is a < ¹ > H-NMR spectrum figure of the hindered amino group containing organosilicon compound of Example 1-6. It is IR spectrum figure of the hindered amino group containing organosilicon compound of Example 1-6.

Hereinafter, the present invention will be specifically described.
The hindered amino group-containing organosilicon compound of the present invention is represented by the following average composition formula (1).

In 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 is a hetero atom in which some of the carbon atoms are heteroatoms. Represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms which may be substituted, and R ³ and R ⁵ independently of each other represent a monovalent hydrocarbon group having 1 to 8 carbon atoms. Represent.

Here, specific examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms of 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, n-heptyl group, linear alkyl group such as n-octyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, isohexyl group, isoheptyl group Branched alkyl groups such as isooctyl group and tert-octyl group; cyclic alkyl groups such as cyclopentyl group and cyclohexyl group, etc., among these, monovalent hydrocarbon groups having 1 to 3 carbon atoms. In particular, 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 methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group, n-hexoxy group, n-heptoxy group and n-octoxy 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-octyl group, etc. 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 preferable.

Examples of the substituted or unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms of R ² include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octane group. Linear alkylene groups such as methylene groups; branched structures such as isoprene groups, isobutene groups, sec-butylene groups, isopentene groups, neopentene groups, isohexene groups, isoheptene groups, isooctene groups, tert-octene groups Alkylene group; cyclic alkylene groups such as cyclopentanediyl group, cyclohexanediyl group and the like are mentioned. Among these, divalent hydrocarbon groups having 1 to 4 carbon atoms are preferable, and methylene group, ethylene group, trimethylene group, isoprene Groups are more preferred.
In this divalent hydrocarbon group, a part of the carbon atom thereof may be substituted with a hetero atom. Specific examples of the substituent include —NH—, —CO—, —S—, —O—, — COO—, —OOC— and the like can be mentioned. Examples of such a substituted divalent hydrocarbon group include —O— (CH ₂ ) ₃ —, —NH— (CH ₂ ) ₃ —, —S— (CH _{2) 3 -, - OOC- (} CH 2) 3 - is preferable.
In the divalent hydrocarbon group, at least a part of the hydrogen atoms may be substituted with a halogen atom such as a chlorine atom, a bromine atom or an iodine atom.

Specific examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms of R ³ and R ⁵ include the same groups as those exemplified for R ¹ above, but from the viewpoint of hydrolysis rate, a methyl group, ethyl Group, n-propyl group is preferred.

N represents an integer of 0 to 2, and an integer of 0 to 1 is preferable.
m represents an integer of 0 to 3, and an integer of 0 to 1 is preferable.
a / b is a number satisfying 1 <a / b <100, but a number satisfying 1 <a / b <10 is preferable.

In the present invention, the hindered amino group-containing organosilicon compound represented by the above average composition formula (1) has a polystyrene equivalent weight average molecular weight by GPC of 2,000 to 1,000,000, but 10,000. ~ 100,000 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.), a temperature of 25 ° C. and 0 to 10% by mass using a tetrahydrofuran solvent. A high sensitivity suggesting refractometer (manufactured by Otsuka Electronics Co., Ltd., DRM-3000) can be used as the refractive index necessary for this analysis.

  As a manufacturing method of the hindered amino group containing organosilicon compound shown by the said average composition formula (1) in this invention, for example, the hindered amino group containing alkoxysilane compound shown by General formula (2), and General formula (3) The method of co-hydrolyzing the alkoxysilane compound shown by this is mentioned.

（式中、Ｒ⁴およびＲ⁶は、炭素数１〜８の１価炭化水素基を表し、Ｒ¹〜Ｒ³、Ｒ⁵、ｍおよびｎは、上記と同じ意味を表す。）

(In the formula, R ⁴ and R ⁶ represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ^{1 to} R ³ , R ⁵ , m and n represent the same meaning as described above.)

Here, specific examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms of R ⁴ and R ⁶ include the same ones as described above, but 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 preferable.

Specific examples of the hindered amino group-containing organic alkoxysilane 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-tetra Methyl-4-propylpiperidine, trimethoxysilylmethoxy-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, trimethoxy Silylmethylamino-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, trimethoxysilylmethoxy-2,2,6,6-tetramethyl-1-ethoxy-4-piperidine , Trimethoxysilylmethylamino-2,2,6,6-tetramethyl-1-ethoxy-4-piperidine, trimethoxysilylmethoxy-2,2,6,6-tetramethyl-1-propoxy-4- Piperidine, trimethoxysilylmethylamino-2,2,6,6-tetramethyl-1-propoxy-4-piperidine, trimethoxysilylethoxy-2,2,6,6-tetramethylpiperidine, trimethoxy Silylethylamino-2,2,6,6-tetramethylpiperidine, trimethoxysilylethoxy-1,2,2,6,6-pentamethyl-4-piperidine, tri Toxisilylethylamino-1,2,2,6,6-pentamethyl-4-piperidine, trimethoxysilylethoxy-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, trimethoxysilyl Ethylamino-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, trimethoxysilyl Ethoxy-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, trimethoxysilylethylamino-2,2,6,6-tetramethyl-1-methoxy Ci-4-piperidine, trimethoxysilylethoxy-2,2,6,6-tetramethyl-1-propoxy-4-piperidine, trimethoxysilylethylamino-2,2,6,6-tetramethyl -1-propoxy-4-piperidine, trimethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine, trimethoxysilylpropylamino-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, trimethoxysilylpropylamino-1,2,2,6,6-pentamethyl-4-piperidine Trimethoxysilylpropoxy-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, trimethoxysilylpropylamino-2,2,6,6-tetraethyl-1-ethyl-4-piperidine , Trimethoxysilylpropoxy-2,2,6,6-tetramethyl-1-propyl-4-piperidine, trimethoxysilylpropylamino-2,2,6,6-tetramethyl-1-propyl-4- Piperidine, trimethoxysilylpropoxy-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, trimethoxysilylpropylamino-2,2,6,6-tetramethyl-1-methoxy -4-piperidine, trimethoxysilylpropylamino-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, trimethoxysilylpro Xy-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, triethoxysilylmethoxy-1,2,2,6,6- Pentamethyl 4-piperidine, triethoxysilylmethylamino-1,2,2,6,6-pentamethyl 4-piperidine, triethoxysilylmethoxy-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, triethoxysilyl Methoxy-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-pi Peridine, 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, Triethoxysilylethylamino-2,2,6,6-tetramethyl-4-piperidine, triethoxysilylethoxy-1,2,2,6,6-pentamethyl-4- Peridine, 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, triethoxysilylethoxy -2,2,6,6-tetramethyl-1-methoxy-4-piperidine, triethoxysilylethylamino-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, tri Ethoxysilylethoxy-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-pi Peridine, triethoxysilylethylamino-2,2,6,6-tetramethyl-1-propoxy-4-piperidine, triethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine, triethoxysilyl Propylamino-2,2,6,6-tetramethylpiperidine, triethoxysilylpropoxy-1,2,2,6,6-pentamethyl-4-piperidine, triethoxysilylpropylamino-1,2,2,6 , 6-pentamethyl-4-piperidine, triethoxysilylpropoxy-2,2,6,6-tetraethyl-1-ethyl-4-piperidine Triethoxysilylpropylamino-2,2,6,6-tetraethyl-1-ethyl-4-piperidine, triethoxysilylpropoxy-2,2,6,6-tetramethyl-1-propyl-4-pipe Lysine, triethoxysilylpropylamino-2,2,6,6-tetramethyl-1-propyl-4-piperidine, triethoxysilylpropoxy-2,2,6,6-tetramethyl-1-methoxy-4 -Piperidine, triethoxysilylpropylamino-2,2,6,6-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, trimethoxysilylop Poxy-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, 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, tri Propoxysilylmethoxy-2,2,6,6-tetramethyl-1-propyl-4-piperidine, tripropoxysilylmethylamino-2,2,6,6-tetramethyl-1-propyl-4-pipe Lysine, tripropoxysilylmethylamino-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, 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, tripropoxysilylethylamino-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-piperidine, 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, tripropoxy Silylpropoxy-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,
Tripropoxysilylpropylsilyl-2,2,6,6-tetramethyl-1-propyl-4-piperidine, tripropoxysilylpropoxy-2,2,6,6-tetramethyl-1-methoxy-4-pi Peridine, 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, Propoxysilylmethoxy-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-piperi , Tripropoxysilylmethoxy-2,2,6,6-tetramethyl-1-methoxy-4-piperidine, tripropoxysilylmethylamino-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 Examples include -1-propoxy-4-piperidine.

  Specific examples of the alkoxysilane compound represented by the general formula (3) include tetramethoxysilane, trimethoxymethylsilane, dimethoxydimethylsilane, methoxytrimethylsilane, tetraethoxysilane, triethoxymethylsilane, diethoxydimethylsilane, and ethoxytrimethyl. Silane, tripropoxymethylsilane, dipropoxydimethylsilane, propoxytrimethylsilane, trimethoxyethylsilane, dimethoxydiethylsilane, methoxytriethylsilane, trimethoxypropylsilane, dimethoxydipropylsilane, methoxytripropylsilane, triethoxyethylsilane, di 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.

The amount of water used for the cohydrolysis reaction is the total silicon of the hindered amino group-containing alkoxysilane compound represented by the general formula (2) and the alkoxysilane compound represented by the general formula (3) from the viewpoint of the cohydrolysis rate. 3-100 mol is preferable with respect to 1 mol of atoms, 50-100 mol is more preferable, and 70-100 mol is still more preferable.
Although the reaction temperature of a cohydrolysis reaction is not specifically limited, 0-120 degreeC is preferable and 60-120 degreeC is more preferable.
Although reaction time is not specifically limited, 1 to 20 hours are preferable and 1 to 14 hours are more preferable.
The alcohol and water produced after the cohydrolysis reaction are preferably removed by a method such as vaporization or separation under reduced pressure or normal pressure from the viewpoint of the stability of the compound.
The hindered amino group-containing organosilicon compound thus obtained can have any structure such as a random structure, a cage structure, and a ladder structure.

The composition of the present invention comprises a hindered amino group-containing organosilicon compound represented by the aforementioned average composition formula (1) and a solvent.
As a solvent, it can select from water, an organic solvent, and these mixed solvents suitably, and can use it.
Usable organic solvents include polar solvents such as alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ketones such as acetone and methyl isobutyl ketone.
The proportion of the hindered amino group-containing organosilicon compound represented by the average composition formula (1) in the composition is preferably 0.1 to 50% by mass, and preferably 1 to 30% by mass from the viewpoint of ease of application and the like. 1 to 15% by mass is even more preferable.
In addition, the alcohol content in the composition is preferably 1% by mass or less, and more preferably 0.5% by mass or less from the viewpoint of improving the finish when applied.

After apply | coating the composition of this invention demonstrated above to the inorganic substance surface as which an anti-fogging process of glass etc. is requested | required, it dries and performs an anti-fogging process.
The coating method is not particularly limited, and various known coating methods such as brush coating method, spray coating method, wire bar method, blade method, roll coating method, dipping method and the like can be employed.
Moreover, drying conditions are also arbitrary and heating from normal temperature can be adopted, but drying under heating is preferable. 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.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
The ¹ H-NMR spectrum was measured with 600 MHz and deuterated chloroform solvent, and the IR spectrum was measured with D-ATR.

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

[Synthesis Example 2]
A 500 mL four-necked flask equipped with a Dimroth type cooling condenser, a stirrer, a thermometer, and a 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 adding 158.0 g of dimethoxymethylsilane. . After confirming the disappearance of the raw materials by gas chromatography, purification was performed by distillation to obtain 443.7 g of dimethoxymethylsilylpropoxy-2,2,6,6-tetramethylpiperidine.

[Synthesis Example 3]
A 500 mL four-necked flask equipped with a Dimroth type cooling condenser, a stirrer, a thermometer, and a dropping funnel was sufficiently purged with nitrogen. Subsequently, 488.6 g of 4-allyloxy-1,2,2,6,6-pentamethylpiperidine and 1.5 g of a platinum catalyst were charged, and 4.5 g at 65 to 75 ° C. while slowly dropping 303.9 g of triethoxysilane. Stir for hours. After confirming the disappearance of the raw materials by gas chromatography, purification was performed by distillation to obtain triethoxysilylpropoxy-1,2,2,6,6-pentamethylpiperidine.

[2] Synthesis of hindered amino group-containing organosilicon compound [Example 1-1]

A 500 mL four-necked flask equipped with a Dimroth type cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was thoroughly purged with nitrogen. Next, 242.2 g of pure water was charged, and 35.0 g of triethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine produced in Synthesis Example 1 and 9.2 g of tetraethoxysilane were slowly added dropwise. After aging at 60 ° C. for 12 hours under normal pressure, the temperature was raised to 120 ° C., and by-produced alcohol was slowly extracted. Water and residual alcohol in the obtained aqueous solution were distilled off and dried to obtain a colorless solid. As a result of ¹ H-NMR and IR analysis, the structure of the following average composition formula (4) was confirmed. The weight average molecular weight was 18,050. ¹ H-NMR spectrum and IR spectrum are shown in FIGS.

[Example 1-2]

A 300 mL four-necked flask equipped with a Dimroth type cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was thoroughly purged with nitrogen. Next, 52.0 g of pure water was charged, and 7.5 g of triethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine produced in Synthesis Example 1 and 2.6 g of tetraethoxysilane were slowly added dropwise. After aging at 60 ° C. for 12 hours under normal pressure, the temperature was raised to 120 ° C., and by-produced alcohol was slowly extracted. Water and residual alcohol in the obtained aqueous solution were distilled off and dried to obtain a colorless solid. As a result of ¹ H-NMR and IR analysis, the structure of the average composition formula (5) was confirmed. The weight average molecular weight was 198,000. ¹ H-NMR spectrum and IR spectrum are shown in FIGS.

[Example 1-3]

A 300 mL four-necked flask equipped with a Dimroth type cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was thoroughly purged with nitrogen. Next, 52.0 g of pure water was charged, and 7.3 g of dimethoxymethylsilylpropoxy-2,2,6,6-tetramethylpiperidine produced in Synthesis Example 2 and 2.5 g of tetraethoxysilane were slowly added dropwise. After aging at 60 ° C. for 12 hours under normal pressure, the temperature was raised to 120 ° C., and alcohol produced as a by-product was slowly extracted. Water and residual alcohol in the obtained aqueous solution were distilled off and dried to obtain a colorless solid. As a result of ¹ H-NMR and IR analysis, the structure of the average composition formula (6) was confirmed. The weight average molecular weight was 39,000. ¹ H-NMR spectrum and IR spectrum are shown in FIGS.

[Example 1-4]

A 300 mL four-necked flask equipped with a Dimroth type cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was thoroughly purged with nitrogen. Next, 52.0 g of pure water was charged, and 7.3 g of triethoxysilylpropoxy-1,2,2,6,6-pentamethylpiperidine and 2.5 g of tetraethoxysilane produced in Synthesis Example 3 were slowly added dropwise. After aging at 60 ° C. for 12 hours under normal pressure, the temperature was raised to 120 ° C., and alcohol produced as a by-product was slowly extracted. Water and residual alcohol in the obtained aqueous solution were distilled off and dried to obtain a colorless solid. As a result of ¹ H-NMR and IR analysis, the structure of the average composition formula (7) was confirmed. The weight average molecular weight was 30,000. ¹ H-NMR spectrum and IR spectrum are shown in FIGS.

[Example 1-5]

A 200 mL four-necked flask equipped with a Dimroth type cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was thoroughly purged with nitrogen. Next, 72.5 g of pure water and 31.0 g of tetrahydrofuran were charged, and 15.2 g of triethoxysilylpropoxy-2,2,6,6-tetramethylpiperidine prepared in Synthesis Example 3 and 2.0 g of triethoxyoctylsilane were slowly added. It was dripped. After aging at 60 ° C. for 12 hours under normal pressure, the temperature was raised to 120 ° C., and alcohol produced as a by-product was slowly extracted. Water and residual alcohol were distilled off from the resulting solution and dried to obtain a colorless solid. As a result of ¹ H-NMR and IR analysis, the structure of the average composition formula (8) was confirmed. The weight average molecular weight was 39,000. ¹ H-NMR spectrum and IR spectrum are shown in FIGS.

[Example 1-6]

A 200 mL four-necked flask equipped with a Dimroth type cooling condenser, Dean Stark, stirrer, thermometer, and dropping funnel was thoroughly purged with nitrogen. Next, 63.5 g of pure water was charged, and 7.5 g of dimethoxymethylsilylpropoxy-2,2,6,6-tetramethylpiperidine produced in Synthesis Example 2 and 2.4 g of triethoxyoctylsilane were slowly added dropwise. After aging at 60 ° C. for 15 hours under normal pressure, the temperature was raised to 120 ° C., and the by-produced alcohol was slowly extracted. Water and residual alcohol were distilled off from the resulting solution and dried to obtain a white solid. As a result of ¹ H-NMR and IR analysis, the structure of the average composition formula (9) was confirmed. The weight average molecular weight was 38,000. ¹ H-NMR spectrum and IR spectrum are shown in FIGS.

[3] Preparation of composition
[Example 2-1]
14.0 g of the compound produced in Example 1-1 was dissolved in 280.0 g of water to obtain a colorless and transparent solution.

[Example 2-2]
14.0 g of the compound produced in Example 1-1 was dissolved in a mixed solution of 196.0 g of water and 84.0 g of tetrahydrofuran to obtain a colorless and transparent solution.

[Example 2-3]
2.5 g of the compound produced in Example 1-2 was dissolved in a mixed solution of 33.6 g of water and 14.4 g of ethanol to obtain a colorless and transparent solution.

[Example 2-4]
2.5 g of the compound produced in Example 1-2 was dissolved in a mixed solution of 33.6 g of water and 14.4 g of tetrahydrofuran to obtain a colorless and transparent solution.

[Example 2-5]
2.5 g of the compound produced in Example 1-3 was dissolved in a mixed solution of 33.6 g of water and 14.4 g of ethanol to obtain a colorless and transparent solution.

[Example 2-6]
2.5 g of the compound produced in Example 1-3 was dissolved in a mixed solution of 33.6 g of water and 14.4 g of tetrahydrofuran to obtain a colorless and transparent solution.

[Example 2-7]
2.5 g of the compound produced in Example 1-4 was dissolved in a mixed solution of 33.6 g of water and 14.4 g of ethanol to obtain a colorless and transparent solution.

[Example 2-8]
2.5 g of the compound produced in Example 1-4 was dissolved in a mixed solution of 33.6 g of water and 14.4 g of tetrahydrofuran to obtain a colorless and transparent solution.

[Example 2-9]
5.0 g of the compound prepared in Example 1-5 was dissolved in a mixed solution of 68.4 g of water and 28.8 g of tetrahydrofuran to obtain a colorless and transparent solution.

[Example 2-10]
5.0 g of the compound prepared in Example 1-6 was dissolved in a mixed solution of 11.2 g of water and 4.8 g of tetrahydrofuran to obtain a colorless and transparent solution.

[Anti-fogging evaluation]
Using the solutions prepared in Examples 2-1 to 2-10, the antifogging property when using a hindered amino group-containing organosilicon compound as an antifogging agent was evaluated by the following method. The results are shown in Table 1.
The surface was washed well with water and acetone in advance, and a clean glass slide heated in an oven at 110 ° C. for 3 hours was immersed in each solution prepared in Examples 2-1 to 2-10 at room temperature for 2 hours. Thereafter, the slide glass was pulled up, blown with nitrogen, and then heated in an oven at 110 ° C. for 2 hours to prepare an antifogging sample.
Table 1 shows the appearance and visual antifogging property of the obtained antifogging sample.
The appearance of the antifogging sample was determined by visual observation under a fluorescent lamp.
Further, the visual anti-fogging property is defined as “を” when no breath is observed on the entire surface of the slide glass surface subjected to the anti-fogging treatment by blowing breath on the anti-fogging sample, and the visual fogging is 10 to 20 mass. % Was seen as “◯”.

(Water resistance evaluation)
Using the solutions prepared in Examples 2-1 to 2-10, the water resistance when a hindered amino group-containing organosilicon compound was used as an antifogging agent was evaluated by the following method. The results are also shown in Table 1.
The anti-fog sample prepared by the above method is immersed in water at 40 ° C. or exposed to water vapor for about 20 hours, and the anti-fog sample is pulled up every 1 hour and blown on the anti-fog sample dried at 110 ° C. The time required for the entire surface to become cloudy (no longer exhibiting antifogging properties) was taken as a measure of water resistance.

  As shown in Table 1, it can be seen that all of the antifogging samples were confirmed to have an antifogging property by visual observation and the water resistance time was 10 hours or more.

Claims (7)

A hindered amino group-containing organosilicon compound represented by the following average composition formula (1) and having a polystyrene-reduced weight average molecular weight of 2,000 to 1,000,000 by gel permeation chromatography.

(In the formula, 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 carbon atom partially substituted with a hetero atom. And represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, R ³ and R ⁵ independently of each other represent a monovalent hydrocarbon group having 1 to 8 carbon atoms, n represents an integer of 0 to 2, m represents an integer of 0 to 3, and a and b are numbers satisfying 1 <a / b <100.)   A composition comprising the hindered amino group-containing organosilicon compound according to claim 1 and a solvent.   The composition according to claim 2, wherein the hindered amino group-containing organosilicon compound is contained in an amount of 0.1 to 50 mass%.   The composition according to claim 2 or 3, wherein the alcohol content is 1% by mass or less. The following general formula (2)

(In the formula, R ⁴ represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ^{1 to} R ³ and n represent the same meaning as described above.)
A hindered amino group-containing alkoxysilane compound represented by the following general formula (3):

(In the formula, R ⁶ represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ⁵ and m represent the same meaning as described above.)
The method for producing a hindered amino group-containing organosilicon compound according to claim 1, wherein the alkoxysilane compound represented by formula (1) is subjected to a cohydrolysis reaction.   The hindered amino group-containing organosilicon according to claim 5, wherein a cohydrolysis reaction is carried out using 3 to 100 mol of water with respect to 1 mol of silicon atoms in each compound represented by formula (2) and formula (3). Compound production method.   The method for producing a hindered amino group-containing organosilicon compound according to claim 5 or 6, wherein after the cohydrolysis reaction, the produced alcohol and water are removed.

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