JPH05311149A - Surface-treating agent - Google Patents

Abstract

PURPOSE:To provide the agent containing a specific fluoroalkyl-containing polymer as an active component and capable of imparting various excellent properties such as water and oil repellency, stain-proofness and chemical resistance to the surface of various organic and inorganic materials such as optical lens and paint. CONSTITUTION:The agent contains an organic component selected from a polymer containing fluoroalkyl group, having a molecular weight of 500-1,000,000 and expressed by formula I [Z1 is H or methyl; Z2 and Z3 are 1-10C alkyl, alkoxy, etc.; R1 and R3 are H, halogen, etc.; R2 and R4 are H, cyano, etc.; RF is (CF2)nX or group of formula II (X is F, Cl, etc.; (n1) is 1-10; (n2) is 0-8); (m1) is 1-1,000; (m2) and (m3) are 0-3,000; (m9) is O or 1; Z1 is H when (m9) is 0], its hydrolyzed product, its hydrolytic condensation product and their mixture. The polymer of formula I is preferably produced by reacting a difluoroalkanoyl peroxide of formula III with polymerizable components of formula IV and/or formula V. The compound of formula III is preferably diperfluorobutyryl peroxide, etc., and the compound of formula IV is preferably vinyl chloride, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment agent utilizing a specific fluoroalkyl group-containing polymer.

[0002]

2. Description of the Related Art A compound containing a fluoroalkyl group in an organic compound has been attracting attention because it exhibits useful properties such as weather resistance, water and oil repellency, and physiological activity. In particular, a fluoroalkyl group-containing polymer in which a fluoroalkyl group is introduced into an organic compound has low surface tension, low refractivity, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, releasability, and resistance. Because it has excellent properties such as chemical properties, in various fields, for example, surfaces for imparting water and oil repellency and stain resistance to the surfaces of optical lenses, eyeglass lenses, glass equipment, paints, etc. It is useful in the fields of treatment agents, biomaterials, pharmaceuticals, raw materials for agricultural chemicals, and materials that impart releasability.

However, conventional fluoroalkyl group-containing polymers are those in which a fluoroalkyl group is introduced into acrylic acid or methacrylic acid through an ester bond or an amino bond (for example, a fluoroalkyl group is introduced through an amino bond. Fluorine-containing epoxy compound;
J. Fluorine Chem., 55 , 1 (1991)), and generally has a problem that it has drawbacks such as low weather resistance.

In an acrylic resin coating material containing a fluoroalkyl group, the fluoroalkyl group is introduced by an ester bond, so that the fluoroalkyl group is easily released by hydrolysis and the water and oil repellency is deteriorated. There is also a problem that the stain resistance is insufficient. Further, a fluororesin coating using chlorotrifluoroethylene developed for the purpose of improving weather resistance (Organic Synthetic Chemistry, 42 , 841 (1992)) has weather resistance but low water and oil repellency. Moreover, there is a drawback that the stain resistance is insufficient.

A fluororesin having a fluoroalkyl group such as a fluoroacrylate polymer in which a fluoroalkyl group is introduced by an ester bond forms a film on the surface of the equipment to protect the equipment, make it beautiful, have water and oil repellency, and have insulation properties. It is often used as a surface treatment agent that imparts properties such as releasability and antifouling property.

However, the above-mentioned fluororesins have problems such as poor adhesion to inorganic materials such as metals, glass and cement, various plastics, and organic materials such as base materials.
Further, since the fluoroalkyl group is introduced into the molecule through an ester bond, there is a problem that the stability against acid or alkali is poor.

On the other hand, a fluoroalkyl group-containing silicone compound has been proposed in Japanese Patent Application Laid-Open No. 59-10280 to improve the adhesion, but sufficient adhesion has not been obtained yet. Further, there is a drawback that the water and oil repellency is lowered.

More recently, SR processing agents, antifogging agents,
In a fluorine compound used for a surfactant and various surface treatment agents, etc., a surface treatment agent having an amphipathic property showing water repellency together with a fluoroalkyl group showing water and oil repellency in the same molecule is considered to be useful. The current situation is that it is attracting attention and its development is strongly desired.

Therefore, the fluoroalkyl group is directly carbon-
There is a strong demand for the development of a material that is bonded by a carbon bond and that has high weather resistance and high water and oil repellency.

[0010]

The object of the present invention is to provide water and oil repellency, stain resistance, chemical resistance, etc. on the surfaces of various inorganic and organic materials such as optical lenses, spectacle lenses, glass appliances, paints and the like. Another object of the present invention is to provide a surface treatment agent having excellent properties.

[0011]

According to the present invention, a fluoroalkyl group-containing polymer having a molecular weight of 500 to 1,000,000 represented by the following general formula (2) (hereinafter referred to as polymer A), its hydrolyzate, and its hydrolyzate Provided is a surface treatment agent containing as an active ingredient a component selected from the group consisting of decomposition condensates and mixtures thereof.

[0012]

[Chemical 2]

The present invention will be described in more detail below.

The surface treating agent of the present invention is characterized by using a component selected from the group consisting of a specific fluoroalkyl group-containing polymer, a hydrolyzate thereof, a hydrolyzed condensate thereof and a mixture thereof as an active ingredient. And

The specific fluoroalkyl group-containing polymer used as an active ingredient in the surface treating agent of the present invention is the polymer A represented by the general formula 2. Polymer A
In the case where Z ₂ and Z ₃ have 11 or more carbon atoms, R ₁ and R _{3 each} have 6 or more carbon atoms, and m ₁ exceeds 1000, m ₂ and m ₃
Is more than 3000, and m ₉ is 2 or more, the production is difficult. When n ₁ exceeds 10, or n ₂ exceeds 8, the solubility in the solvent decreases.

Further, the average molecular weight of the polymer A is 500.
Is about 1,000,000, and it is particularly preferably 500 to 10,000 in order to make the characteristics of the fluoroalkyl group manifest more remarkably. When the average molecular weight is out of the above range, the production is difficult.

In the polymer A, RF is-(CF
₂ ) n ₁ X or the following general formula 3.

[0018]

[Chemical 3]

Specific examples of the above-mentioned-(CF ₂ ) n ₁ X include F ₃ C-, F (CF ₂ ) _2- , F (CF ₂ ) _3- , F
(CF ₂ ) ₄ −, F (CF ₂ ) ₅ −, F (CF ₂ ) ₆ −, F
(CF ₂ ) ₇ −, F (CF ₂ ) ₈ −, F (CF ₂ ) ₉ −, F
(CF ₂ ) ₁₀ −, HCF ₂ −, H (CF ₂ ) ₂ −, H (CF
_{2) 3 -, H (CF} 2) 4 -, H (CF 2) 5 -, H (C
F ₂ ) ₆ −, H (CF ₂ ) ₇ −, H (CF ₂ ) ₈ −, H (CF
_{2) 9 -, H (CF} 2) 10 -, ClCF 2 -, Cl (C
_{F 2) 2 -, Cl (} CF 2) 3 -, Cl (CF 2) 4 -, Cl
(CF ₂ ) ₅ −, Cl (CF ₂ ) ₆ −, Cl (CF ₂ ) ₇ −,
_{Cl (CF 2) 8 -,} Cl (CF 2) 9 -, Cl (CF 2)
_10- , and when the general formula 3 is specifically listed, the following chemical formulas 4 to 12 are given.

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

[Chemical 8]

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical formula 12]

Preferred examples of the polymer A include those represented by the following formulas 13 to 98 (in the formula,
m ₁ is an integer of ₁ to 1000, m ₂ and m ₃ are 0 to 3000
, And m ₄ is an integer of 1 to 20).

[0030]

[Chemical 13]

[0031]

[Chemical 14]

[0032]

[Chemical 15]

[0033]

[Chemical 16]

[0034]

[Chemical 17]

[0035]

[Chemical 18]

[0036]

[Chemical 19]

[0037]

[Chemical 20]

[0038]

[Chemical 21]

[0039]

[Chemical formula 22]

[0040]

[Chemical formula 23]

[0041]

[Chemical formula 24]

[0042]

[Chemical 25]

[0043]

[Chemical formula 26]

[0044]

[Chemical 27]

[0045]

[Chemical 28]

[0046]

[Chemical 29]

[0047]

[Chemical 30]

[0048]

[Chemical 31]

[0049]

[Chemical 32]

[0050]

[Chemical 33]

[0051]

[Chemical 34]

[0052]

[Chemical 35]

[0053]

[Chemical 36]

[0054]

[Chemical 37]

[0055]

[Chemical 38]

[0056]

[Chemical Formula 39]

[0057]

[Chemical 40]

[0058]

[Chemical 41]

[0059]

[Chemical 42]

[0060]

[Chemical 43]

[0061]

[Chemical 44]

[0062]

[Chemical 45]

[0063]

[Chemical 46]

[0064]

[Chemical 47]

[0065]

[Chemical 48]

[0066]

[Chemical 49]

[0067]

[Chemical 50]

[0068]

[Chemical 51]

[0069]

[Chemical 52]

[0070]

[Chemical 53]

[0071]

[Chemical 54]

[0072]

[Chemical 55]

[0073]

[Chemical 56]

[0074]

[Chemical 57]

[0075]

[Chemical 58]

[0076]

[Chemical 59]

[0077]

[Chemical 60]

[0078]

[Chemical formula 61]

[0079]

[Chemical formula 62]

[0080]

[Chemical 63]

[0081]

[Chemical 64]

[0082]

[Chemical 65]

[0083]

[Chemical 66]

[0084]

[Chemical 67]

[0085]

[Chemical 68]

[0086]

[Chemical 69]

[0087]

[Chemical 70]

[0088]

[Chemical 71]

[0089]

[Chemical 72]

[0090]

[Chemical 73]

[0091]

[Chemical 74]

[0092]

[Chemical 75]

[0093]

[Chemical 76]

[0094]

[Chemical 77]

[0095]

[Chemical 78]

[0096]

[Chemical 79]

[0097]

[Chemical 80]

[0098]

[Chemical 81]

[0099]

[Chemical formula 82]

[0100]

[Chemical 83]

[0101]

[Chemical 84]

[0102]

[Chemical 85]

[0103]

[Chemical formula 86]

[0104]

[Chemical 87]

[0105]

[Chemical 88]

[0106]

[Chemical 89]

[0107]

[Chemical 90]

[0108]

[Chemical Formula 91]

[0109]

[Chemical Formula 92]

[0110]

[Chemical formula 93]

[0111]

[Chemical 94]

[0112]

[Chemical 95]

[0113]

[Chemical 96]

[0114]

[Chemical 97]

[0115]

[Chemical 98]

In the present invention, to prepare the polymer A, difluoroalkanoyl peroxide represented by the following general formula 99 (hereinafter referred to as difluoroalkanoyl 1) is used.
And a polymerizable component A represented by the following general formula 100 and / or a polymerizable component B represented by the following general formula 101 can be obtained.

[0117]

[Chemical 99]

[0118]

[Chemical 100]

[0119]

[Chemical 101]

In the above difluoroalkanoyl 1,
When n ₁ is 11 or more or n ₂ is 9 or more, the solubility of the difluoroalkanoyl 1 is lowered when the reaction is carried out in the presence of a solvent, and therefore it cannot be used.

Further, R in the difluoroalkanoyl 1 is
F is the same as RF specifically listed in the polymer A, and specific examples of the difluoroalkanoyl 1 include diperfluoro-2-methyl-3-peroxide.
Oxahexanoyl, diperfluoro-2,5-peroxide
Dimethyl-3,6-dioxanonanoyl, diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide, diperfluorobutyryl peroxide,
Preferable examples include diperfluoroheptanoyl peroxide and the like.

Specific examples of the polymerizable component A include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, acrylonitrile, vinyl acetate, vinyl propionate, vinyl butyrate, (meth) acrylic acid,
Methyl (meth) acrylate, (meth) acrylic acid-t-
Butyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid-2-ethylhexyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, CH ₂ = CHCO ₂ CHCH ₃ OC ₂ H ₅ , CH ₂ = CCH ₃ CO ₂
CHCH ₃ OC ₂ H ₅ , CH ₂ = CHCO ₂ CHCH ₃ OCH ₂ CH (CH ₃ ) ₂ , CH ₂ = CCH ₃ CO
₂ CHCH ₃ OCH ₂ CH (CH ₃ ) ₂ , CH ₂ = CHCO ₂ CHCH ₃ OCH ₂ C (C ₂ H ₅ ) H (C
H ₂ ) ₃ CH ₃ , CH ₂ = CCH ₃ CO ₂ CHCH ₃ OCH ₂ C (C ₂ H ₅ ) H (CH ₂ ) ₃ CH ₃ , CH
₂ = CHCO ₂ CH ₂ CH ₂ O (CO (CH ₂ ) ₅ O) uH, CH ₂ = CCH ₃ CO ₂ CH ₂ CH ₂ O (CO
(CH ₂ ) ₅ O) uH, CH ₂ = CCH ₃ CO ₂ (CH ₂ CH ₂ O) m ₄ H (m ₄ ≠ 1), CH ₂ = C
CH ₃ CO ₂ (CH ₂ CH ₂ O) m ₄ CH ₃ , CH ₂ = CCH ₃ CO ₂ (CH ₂ CH ₂ O) m ₄ (CH ₂ CH
(CH ₃ ) O) m ₅ H, CH ₂ = CCH ₃ CO ₂ (CH ₂ CH ₂ O) m ₄ (CH ₂ CH (CH ₃ ) O) m ₅ C
H ₃ , CH ₂ = CCH ₃ CO ₂ (CH ₂ CH ₂ O) m ₄ (CH ₂ CH ₂ (CH ₂ ) ₂ O) m ₅ H, CH ₂ =
CCH ₃ CO ₂ (CH ₂ CH ₂ O) m ₄ (CH ₂ CH ₂ (CH ₂ ) ₂ O) m ₅ CH ₃ , CH ₂ = CCH ₃ CO
₂ (CH ₂ CH (CH ₃ ) O) m ₄ (CH ₂ CH ₂ CH ₂ O) m ₆ H, CH ₂ = CCH ₃ CO ₂ (CH ₂ CH
(CH ₃ ) O) m ₄ (CH ₂ CH ₂ CH ₂ O) m ₆ CH ₃ , CH ₂ = CCH ₃ CO ₂ (CH ₂ CH (CH ₃ )
O) m ₄ H, CH ₂ = CCH ₃ CO ₂ (CH ₂ CH (CH ₃ ) O) m ₄ CH ₃ , CH ₂ = CHCO ₂ (CH
₂ CH ₂ O) m ₄ H (m ₄ ≠ 1), CH ₂ = CCHCO ₂ (CH ₂ CH ₂ O) m ₄ CH ₃ , CH ₂ = C
HCO ₂ (CH ₂ CH ₂ O) m ₄ (CH ₂ CH (CH ₃ ) O) m ₅ H, CH ₂ = CHCO ₂ (CH ₂ CH
₂ O) m ₄ (CH ₂ CH (CH ₃ ) O) m ₅ CH ₃ , CH ₂ = CHCO ₂ (CH ₂ CH ₂ O) m ₄ (CH ₂ C
H ₂ (CH ₂ ) ₂ O) m ₆ H, CH ₂ = CHCO ₂ (CH ₂ CH ₂ O) m ₄ (CH ₂ CH ₂ (CH ₂ ) ₂ O)
m ₆ CH ₃ , CH ₂ = CHCO ₂ (CH ₂ CH (CH ₃ ) O) m ₄ (CH ₂ CH ₂ CH ₂ O) m ₆ H, CH
₂ = CHCO ₂ (CH ₂ CH (CH ₃ ) O) m ₄ (CH ₂ CH ₂ CH ₂ O) m ₆ CH ₃ , CH ₂ = CHCO ₂
(CH ₂ CH (CH ₃ ) O) m ₄ H, CH ₂ = CHCO ₂ (CH ₂ CH (CH ₃ ) O) m ₄ CH ₃ , glycidyl (meth) acrylate, 2- (glycidyloxy) ethyl methacrylate, 6 -(Meth) acroyloxymethyl-7-oxybicyclo [4.1.0] heptane, methyl 6- (meth) acryloyloxyhexanoate-
7-oxybicyclo [4.1.0] heptane and the like can be preferably mentioned (provided that m ₄ is an integer of 1 to 20, m ₅ and m ₆ are integers of 1 to 20, and u is 1-5
, An integer of ₄ ), when used alone or m ₄ ,
It is possible to use a mixture in which m ₅ , m ₆ and u are in the above-mentioned integer ranges, and further a mixture thereof.

In the polymerizable component B, when Z ₂ and Z ₃ have 11 or more carbon atoms, it is difficult to produce.

Specific examples of the polymerizable component B include trimethoxyvinylsilane, triethoxyvinylsilane, diacetyloxymethylvinylsilane, diethoxymethylvinylsilane, triacetyloxyvinylsilane, triisopropoxyvinylsilane, trimethylvinylsilane, and tri-vinylsilane. t-butoxyvinylsilane, ethoxydiethylvinylsilane, diethylmethylvinylsilane, 3-methacryloxypropyltrimethoxysilane,
3-methacryloxypropyltriethoxysilane, 3-
Methacryloxypropyldiacetyloxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane, 3-methacryloxypropyltriacetyloxysilane, 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropyltrimethylsilane, 3-methacryloxy Propyltri-t-butoxysilane, 3-methacryloxypropylethoxydiethylsilane, 3-methacryloxypropyldiethylmethylsilane, 3-acryloxypropyltrimethoxysilane, 3
-Acryloxypropyltriethoxysilane, 3-acryloxypropyldiacetyloxymethylsilane, 3-
Acryloxypropyldiethoxymethylsilane, 3-acryloxypropyltriacetyloxysilane, 3-acryloxypropyltriisopropoxysilane, 3-acryloxypropyltrimethylsilane, 3-acryloxypropyltri-t-butoxysilane, 3- Preferable examples include acryloxypropylethoxydiethylsilane and 3-acryloxypropyldiethylmethylsilane.

When the difluoroalkanoyl 1 is reacted with the polymerizable component A and / or the polymerizable component B, the molar ratio of the charge is as follows: fluoroalkanoyl 2: polymerizable component A and / or B is 1: 0.1. The range is preferably from 5,000 to 5,000, more preferably from 1: 0.5 to 1,000. When the charged molar ratio of the polymerizable components A and / or B is less than 0.1, a large amount of products resulting from the self-decomposition of peroxide is produced, which is not industrially preferable, and exceeds 5000. In this case, the yield of the target polymer A is lowered, which is not preferable. When a mixture of the polymerizable component A and the polymerizable component B is used as the polymerizable component, the charging molar ratio of the polymerizable component A and the polymerizable component B is not particularly limited, but is 1: 0. 0
It is desirable to set it in the range of 1 to 100. Further, the molecular weight of the polymer A obtained by adjusting the charged molar ratio of the difluoroalkanoyl 1 can be adjusted. That is, if the charged molar ratio of the difluoroalkanoyl 1 is high, a polymer having a low molecular weight can be obtained, and if the charged molar ratio of the difluoroalkanoyl 1 is low, a polymer having a high molecular weight can be obtained.

The reaction of the difluoroalkanoyl 1 with the polymerizable components A and / or B can be carried out under normal pressure, and the reaction temperature is preferably -20 to +.
150 ° C, particularly preferably 0 to 100 ° C.
When the reaction temperature is lower than -20 ° C, the reaction takes a long time, and when it is higher than + 150 ° C, the pressure during the reaction becomes high and the reaction operation becomes difficult, which is not preferable. Furthermore, the reaction time is preferably in the range of 30 minutes to 20 hours, and industrially particularly preferably in the range of 1 to 10 hours.

Under the various reaction conditions, the difluoroalkanoyl 1 and the polymerizable component A and / or B are mixed.
The desired polymer A can be directly obtained by a one-step reaction by reacting with, but it is preferable to use a solvent in order to carry out the handling and reaction of the difluoroalkanoyl 1 more smoothly. As the solvent, a halogenated aliphatic solvent is particularly preferable, and specific examples thereof include methylene chloride, chloroform and 2-chloro-.
1,2-dibromo-1,1,2-trifluoroethane,
1,2-dibromohexafluoropropane, 1,2-dibromotetrafluoroethane, 1,1-difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,
3,3-trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,1-trichloropentafluoropropane, 1,1,2-trichlorotrifluoroethane, 1,1,1,2 , 2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane and the like can be used, and industrially, 1,1,1 , 2,2-Pentafluoro-3,3-dichloropropane, 1,1,2,
2,3-pentafluoro-1,3-dichloropropane,
Preference is given to 1,1,2-trichlorotrifluoroethane. When the solvent is used, the concentration of the difluoroalkanoyl 1 in the solvent is preferably 0.5 to 30% by weight based on the whole solution.

The product obtained is, in addition to the polymer A,
A product in which only one terminal in the general formula 2 is an RF group may also be produced as a mixed product, but depending on the application, such a mixed product may be produced without the purification step shown below. The thing can also be used as it is.

The reaction product thus obtained can be purified by a known method such as a reprecipitation method.

The hydrolyzate and hydrolyzed condensate of the polymer A, which can be used as an active ingredient in the surface treatment agent of the present invention, are obtained by adding the polymer A to a fluorochlorinated hydrocarbon containing water, or It can be obtained by dissolving in a mixed solvent of a fluorinated aromatic hydrocarbon and an alkyl alcohol, an alkyl alcohol solvent containing water, or an alcohol solvent, followed by hydrolysis or hydrolysis condensation. Examples of the fluorinated hydrocarbon solvent include 1,1,2-trichlorotrifluoroethane and 1,2-difluorotetrachloroethane, and examples of the fluorinated aromatic hydrocarbon solvent include benzotrifluoride and hexafluoro. Examples thereof include xylene, and examples of the alkyl alcohol solvent include ethanol, isopropanol, butanol and the like. The mixing ratio of the mixed solvent is not particularly limited as long as it can dissolve the polymer A, and the content of water is 1 to 30% by weight based on the mixed solvent or the solvent. Is preferred. The condensation temperature is preferably room temperature to 200 ° C., and the condensation time is preferably 30 minutes to 24 hours. That is, in order to use the surface treatment agent of the present invention, the active ingredient can be diluted with the solvent and used, and even if only the polymer A is used as the active ingredient, part or all of the active ingredient can be used. It can be a hydrolyzate or a hydrolyzed condensate.

The concentration of the active ingredient in the solution is 0.00
It is preferably in the range of 5 to 20% by weight. When the concentration is less than 0.005% by weight, the film formed by the surface treatment agent has a small film thickness and water and oil repellency deteriorates. When it exceeds 20% by weight, the film has a large film thickness but water and water repellency. The oiliness is not improved, the uniformity of the surface is lowered, and peeling easily occurs, which is not preferable.

Further, the surface treating agent of the present invention may further contain additives such as a surfactant and a leveling agent.

As the treatment method when the surface treatment agent of the present invention is used, known coating methods such as brush coating, spraying method, roll coating method, spin coating method and dip coating method are used. be able to. Further, the treatment temperature may be room temperature, but the temperature condition may be set to an arbitrary condition for the purpose of controlling the film formation rate. Furthermore, the film thickness of the film formed by the surface treatment agent of the present invention is preferably in the range of several Å to several tens of μ,
The film thickness can be adjusted to an arbitrary value depending on the processing temperature, the rotation speed in the spin coat method, the pulling speed in the dip coat method, and the like.

[0134]

The surface treating agent of the present invention is excellent in water and oil repellency, adhesion to a substrate, low surface adhesion, surface lubricity and the like. In addition, since the fluoroalkyl group is introduced as an active ingredient by a carbon-carbon bond instead of an ester bond, the characteristics resulting from the fluoroalkyl group can be stably expressed for a long period of time. Therefore, textiles, clothing, furniture, drapes, rugs, paper bags, cardboard containers, trunks, handbags, shoes, jackets, raincoats, tents, carpets, wood and asbestos wall coatings, bricks, concrete, Surface treatment agents for floors, wall tiles, glass, stone, wood, plasters, wallpaper and outer wall materials, bath wall materials, etc., surface treatment agents for painted or unpainted metal such as appliances and automobile bodies, iron, stainless steel , A surface treatment agent with good adhesion to duralumin, polyester resin, urethane resin, ABS resin, vinyl chloride resin, epoxy resin, phenol resin, etc. for the purpose of contributing to water and oil repellency and low adhesion to the surface. Surface treatment agent to facilitate mold release of plastics,
Surface treatment agent having anti-icing action for airplanes, surface treatment agent having frying pan anti-sticking action, and further surface solid lubricant for magnetic materials such as magnetic tape, floppy disk, hard disk, cosmetics It can be widely used as a surface treatment agent for materials, an agrochemical aid such as an emulsifier, a dispersant, a surface treatment agent for medical materials, etc., and is water and oil repellent, antifouling,
It is useful as a surface treatment agent that imparts non-adhesiveness, lubricity, interface characteristics, and the like.

Furthermore, since the surface treating agent of the present invention contains a compound containing a fluoroalkyl group and an alkylene oxide group or a hydroxyl group and an alkylene oxide group as an active ingredient, it has water-repellent and hydrophilic amphiphilic performance. It is useful as a material, and is also useful as an antifogging agent, an SR processing agent that imparts water repellency and oil repellency in air, and hydrophilicity in water, and particularly has excellent adhesion to a substrate.

[0136]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0137]

Example 1 Methyl methacrylate 30.0 g (300 m
mol), diperfluoro-2,5-dimethyl-peroxide
1,1,2-Trichlorotrifluoroethane solution 1 containing 3,6-dioxanonanoyl (9.9 g, 10 mmol)
50 g was added, and the reaction was carried out at 30 ° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solvent was removed, and then reprecipitation was carried out in a chloroform-methanol system, followed by drying under vacuum to obtain 36.1 g of a product. The product thus obtained was analyzed and found to be a fluoroalkyl group-containing polymer represented by the structural formula 102 below. The obtained polymer was dissolved in chloroform to form a film on a glass substrate, and the contact angle of the obtained film was measured. The results are shown in Table 1.

[0138]

[Chemical 102]

[0139]

Example 2 Diperfluoro-2-methyl-3-oxahexanoyl peroxide was added to diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide (1.32 g).
(2.0 mmol) and the charged molar ratio of methyl methacrylate was 6.0 g (60 mmol), the reaction was carried out in the same manner as in Example 1 to obtain the polymer represented by the structural formula 103 below. 0 g was obtained. Further, the contact angle was measured in the same manner as in Example 1. The results are shown in Table 1.

[0140]

[Chemical 103]

[0141]

EXAMPLE 3 Diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was replaced with diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl 13. The reaction was carried out in the same manner as in Example 1 except that the amount was 22 g (10 mmol).
A yield of 40.5 g of a polymer represented by Further, the contact angle was measured in the same manner as in Example 1. The results are shown in Table 1.

[0142]

[Chemical 104]

[0143]

Example 4 Reaction was carried out in the same manner as in Example 1 except that diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was replaced with 7.3 g (10 mmol) of diperfluoroheptanoyl peroxide. The yield was 34.2 g of a polymer represented by the following structural formula 105. Example 1
The contact angle was measured in the same manner as in. The results are shown in Table 1.

[0144]

[Chemical 105]

[0145]

Example 5 Example 1 was repeated except that diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was replaced with 4.3 g (10 mmol) of diperfluorobutyryl peroxide.
The reaction was carried out in the same manner as in, to obtain 31.1 g of a polymer represented by the following structural formula 106. Further, the contact angle was measured in the same manner as in Example 1. The results are shown in Table 1.

[0146]

[Chemical formula 106]

[0147]

[Example 6] Methyl methacrylate was set to 62.5 g (480 mmol) of 2-hydroxyethyl methacrylate, and the charged amount of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was 238 g (240 mmo).
The reaction was carried out in the same manner as in Example 1 except that 1), and 85 g of a white powder, which is a high-polymerization polymer of the polymer represented by the structural formula 107 below, and a colorless polymer, which was a low-polymerization polymer. 215 g of liquid substance were obtained. Further, the contact angle was measured in the same manner as in Example 1 using the high degree of polymerization polymer. The results are shown in Table 1.

[0148]

[Chemical formula 107]

[0149]

Example 7 Diperfluoro-2-methyl-3-oxahexanoyl peroxide was added to 158 g (24 g) of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide.
0 mmol), and the reaction was performed in the same manner as in Example 1 except that methyl methacrylate was changed to 62.5 g (480 mmol) of 2-hydroxyethyl methacrylate, and a high degree of polymerization of a polymer represented by the following structural formula 108 was obtained. As a result, 45 g of a white powder which is a substance and 144 g of a colorless liquid substance which is a low-polymerization degree polymer are obtained. In addition, by using a high degree of polymerization polymer,
The contact angle was measured in the same manner as in Example 1. The results are shown in Table 1.

[0150]

[Chemical 108]

[0151]

Example 8 Diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was converted into diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl 13. High polymerization of the polymer represented by the following structural formula 109 was carried out in the same manner as in Example 1 except that 22 g (10 mmol) and 2-hydroxyethyl methacrylate 3.9 g (30 mmol) were used as the methyl methacrylate. 4.1 g of a white powder, which is a low-polymerization polymer, and 10.0 g of a colorless liquid substance, which is a low-polymerization polymer, are obtained.
Further, the contact angle was measured in the same manner as in Example 1 using the high degree of polymerization polymer. The results are shown in Table 1.

[0152]

[Chemical 109]

[0153]

Example 9 Methyl methacrylate was added to acrylic acid 8.7.
g (120 mmol) and diperfluoro-2,5 peroxide
High-polymerization of the polymer represented by the following structural formula 110 was carried out in the same manner as in Example 1 except that the charged amount of dimethyl-3,6-dioxanonanoyl was 49.5 g (50 mmol). 18.2 g of a white powder which is a high-polymerization product and 30.0 g of a colorless liquid substance which is a low-polymerization polymer are obtained. Further, the contact angle was measured in the same manner as in Example 1 using the high degree of polymerization polymer. The results are shown in Table 1.

[0154]

[Chemical 110]

[0155]

Example 10 Diperfluoro-2-methyl-3-oxahexanoyl peroxide (155 g, 2) was added to diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide.
To 36 mmol) and 40.8 g (566 mmol) of acrylic acid as the methyl methacrylate, the reaction was carried out in the same manner as in Example 1 and was a high degree of polymerization polymer of the following structural formula 111. 78.6g of white powder
And 60.1 g of a colorless liquid substance which is a low degree of polymerization polymer
Obtained. Further, the contact angle was measured in the same manner as in Example 1 using the high degree of polymerization polymer. The results are shown in Table 1.

[0156]

[Chemical 111]

[0157]

Example 11 Diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was converted into diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide. 0 g (6.8 mmol), and methyl methacrylate was 1.22 g (16.9 mmo)
The reaction was carried out in the same manner as in Example 1 except that the above was changed to l), and 1.9 g of a white powder, which is a high-polymerization polymer of the polymer represented by the structural formula 112 below, and a low-polymerization polymer. 7.0 g of a colorless liquid substance was obtained. Further, the contact angle was measured in the same manner as in Example 1 using the high degree of polymerization polymer. The results are shown in Table 1.

[0158]

[Chemical 112]

[0159]

Example 12 2.5 g of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was charged.
(3.8 mmol), and methyl methacrylate was replaced by 1.20 g (12 mmol) of methyl methacrylate and 1.5 g (12 mmol) of 2-hydroxyethyl methacrylate, the reaction was carried out in the same manner as in Example 1, and the following structural formula The yield of the polymer represented by Chemical formula 113 was 2.5 g. Further, the contact angle was measured in the same manner as in Example 1. The results are shown in Table 1.
Shown in.

[0160]

[Chemical 113]

[0161]

EXAMPLE 13 Diperfluoro-2-methyl-3-oxahexanoyl peroxide (1.32 g) was added to diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide.
(2.0 mmol) and the amount of methyl methacrylate charged was 4.0 g (40 mmol), the reaction was carried out in the same manner as in Example 1 to obtain the polymer represented by the following structural formula 114 in a yield of 4. 4 g was obtained. Further, the contact angle was measured in the same manner as in Example 1. The results are shown in Table 1.

[0162]

[Chemical 114]

[0163]

Example 14 Diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was added to diperfluoro-2-methyl-3-oxahexanoyl peroxide 0.7 g.
(1.0 mmol) and methyl methacrylate is CH ₂ =
_{CCH 3 CO 2 CHCH 3 OC 2} H 5 1.6g (10mmol)
The reaction was performed in the same manner as in Example 1 except that the above-mentioned reaction was carried out to obtain 0.9 g of a polymer represented by the following structural formula 115. Further, the contact angle was measured in the same manner as in Example 1. The results are shown in Table 1.
Shown in.

[0164]

[Chemical 115]

[0165]

Example 15 1.0 g of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was charged.
(1 mmol) and methyl methacrylate is CH ₂ =
CCH ₃ CO ₂ CHCH ₃ OC ₂ H ₅ 1.6 g (10 mmo
The reaction was performed in the same manner as in Example 1 except that the above was changed to l), and 0.5 g of a polymer represented by the following structural formula 116 was obtained. Further, the contact angle was measured in the same manner as in Example 1. The results are shown in Table 1.

[0166]

[Chemical formula 116]

[0167]

Example 16 Diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was added to diperfluoro-2-methyl-3-oxahexanoyl peroxide 0.7 g.
(1.0 mmol) and methyl methacrylate is CH ₂ =
CCH ₃ CO ₂ CHCH ₃ OCH ₂ CH (CH ₃ ) ₂ 1.9 g
(10 mmol) except that the reaction was carried out in the same manner as in Example 1 to obtain a polymer represented by the following structural formula 117 in a yield of 0.1.
9 g were obtained. Further, the contact angle was measured in the same manner as in Example 1. The results are shown in Table 1.

[0168]

[Chemical 117]

[0169]

Example 17 1.0 g of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was charged.
(1 mmol) and methyl methacrylate is CH ₂ =
CCH ₃ CO ₂ CHCH ₃ OCH ₂ CH (CH ₃ ) ₂ 1.9 g
(10 mmol) except that the reaction was carried out in the same manner as in Example 1 to obtain a polymer represented by the following structural formula 118 in a yield of 0.
8 g was obtained. Further, the contact angle was measured in the same manner as in Example 1. The results are shown in Table 1.

[0170]

[Chemical 118]

[0171]

Example 18 Diperfluoro-2-methyl-3-oxahexanoyl peroxide (0.7 g) was added to diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide.
(1.0 mmol) and methyl methacrylate is CH ₂ =
_{CCH 3 CO 2 CHCH 3 OCH 2} CH (C 2 H 5) (CH 2) 3 C
The reaction was performed in the same manner as in Example 1 except that 2.4 g (10 mmol) of H ₃ was used to obtain 2.0 g of a polymer represented by the following structural formula 119. Further, the contact angle was measured in the same manner as in Example 1. The results are shown in Table 1.

[0172]

[Chemical 119]

[0173]

Example 19 1.0 g of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was charged.
(1 mmol) and methyl methacrylate is CH ₂ =
_{CCH 3 CO 2 CHCH 3 OCH 2} CH (C 2 H 5) (CH 2) 3 C
The reaction was performed in the same manner as in Example 1 except that H _{3 was changed to} 2.4 g (10 mmol) to obtain 1.9 g of a polymer represented by the following structural formula 120. Further, the contact angle was measured in the same manner as in Example 1. The results are shown in Table 1.

[0174]

[Chemical 120]

[0175]

EXAMPLE 20 Diperfluoro-2-methyl-3-oxahexanoyl peroxide (0.7 g) was added to diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide.
(1.0 mmol), methyl methacrylate was 1.0 g (10 mmol) of methyl methacrylate and CH ₂ = CCH ₃
The reaction was performed in the same manner as in Example 1 except that a mixture of 1.6 g (10 mmol) of CO ₂ CHCH ₃ OC ₂ H ₅ was used to obtain 1.8 g of a polymer represented by the following structural formula 121. Further, the contact angle was measured in the same manner as in Example 1. The results are shown in Table 1.
Shown in.

[0176]

[Chemical 121]

[0177]

[Example 21] A charged amount of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was 1.0 g.
(1 mmol), methylmethacrylate 1.0 g (10 mmol) and CH ₂ = CCH ₃
The reaction was performed in the same manner as in Example 1 except that a mixture of 1.6 g (10 mmol) of CO ₂ CHCH ₃ OC ₂ H ₅ was used to obtain 2.0 g of a polymer represented by the following structural formula 122. Further, the contact angle was measured in the same manner as in Example 1. The results are shown in Table 1.
Shown in.

[0178]

[Chemical formula 122]

[0179]

Comparative Example 1 Polymethylmethacrylate (Wako Pure Chemical Industries, Ltd.
The contact angle was measured in the same manner as in Example 1 except that the product manufactured by Co., Ltd. was used. The results are shown in Table 1.

[0180]

[Table 1]

[0181]

Example 22 Methyl methacrylate 1.5 g (15 mmo
l) and 2.2 g (15 mmol) of trimethoxyvinylsilane
And diperfluoro-2,5-dimethyl-3,6 peroxide
Containing dioxanonanoyl (5.0 g, 5 mmol)
150 g of 1,2-trichlorotrifluoroethane solution was added, and the reaction was carried out at 30 ° C. for 5 hours under a nitrogen atmosphere. After the reaction was completed, the reaction solvent was removed, and the residue was dried under vacuum to obtain 6.9 g of product. As a result of analyzing the obtained product, it was a polymer represented by the following structural formula 123. Also, acetic acid was added to the obtained polymer to obtain p
It was dissolved in a 95 wt% ethanol aqueous solution adjusted to H5.5 to prepare a 2 wt% solution. Then, using the obtained solution, a film is formed on a glass substrate by a dip coating method, and after heat treatment at 120 ° C. for 10 minutes,
The contact angle was measured. The results are shown in Table 2.

[0182]

[Chemical 123]

[0183]

Example 23: Diperfluoro-2-methyl-3-oxahexanoyl peroxide (3.2 g) was added to diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide.
The reaction was carried out in the same manner as in Example 22 except that (5.0 mmol) was obtained to obtain 5.2 g of a polymer represented by the following structural formula 124. Further, the contact angle was measured in the same manner as in Example 22. The results are shown in Table 2.

[0184]

[Chemical formula 124]

[0185]

Example 24 Diperfluoro-2-methyl-3-oxahexanoyl peroxide was added to diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide to give 3.2 g (5.0
mmol), and the charged amount of methyl methacrylate is 0.5
Example 2 except that the charged amount of g (5 mmol) and trimethoxyvinylsilane was 0.74 g (5 mmol).
The reaction was carried out in the same manner as in 2 to obtain 4.2 g of a polymer represented by the following structural formula 125. Further, the contact angle was measured in the same manner as in Example 22. The results are shown in Table 2.

[0186]

[Chemical 125]

[0187]

Example 25 Diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was replaced with diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide. 6 g (5 mmol), methylmethacrylate charge 0.5 g (5 mmol), trimethoxyvinylsilane charge 0.74 g (5 mmo)
The reaction was performed in the same manner as in Example 22 except that the above was changed to 1), and the yield of the polymer represented by the following structural formula 126 was 7.
5 g was obtained. Further, the contact angle was measured in the same manner as in Example 22. The results are shown in Table 2.

[0188]

[Chemical formula 126]

[0189]

Example 26 Diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was changed to 3.7 g (5 mmol) of diperfluoroheptanoyl peroxide, and the charged amount of methyl methacrylate was 0.5 g (5 mmol). ), The amount of trimethoxyvinylsilane charged is 0.74 g (5 mmo
The reaction was performed in the same manner as in Example 22 except that the above was changed to 1), and the yield of the polymer represented by the following structural formula 127 was 4.
8 g was obtained. Further, the contact angle was measured in the same manner as in Example 22. The results are shown in Table 2.

[0190]

[Chemical 127]

[0191]

[Example 27] A charged amount of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was 2.5 g.
Example 2 except that the amount of methyl methacrylate was 0.75 g (7.5 mmol), and that trimethoxyvinylsilane was 3.72 g (15 mmol) of 3-methacryloxypropyltrimethoxysilane.
The reaction was carried out in the same manner as in 2 to obtain 6.2 g of a polymer represented by the following structural formula 128. Further, the contact angle was measured in the same manner as in Example 22. The results are shown in Table 2.

[0192]

[Chemical 128]

[0193]

Example 28 Diperfluoro-2-methyl-3-oxahexanoyl peroxide (1.65 g) was used as diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide.
Example 22 except that the charged amount of methyl methacrylate was 0.75 g (7.5 mmol), and the amount of trimethoxyvinylsilane was 3-methacryloxypropyltrimethoxysilane 3.72 g (15 mmol). Reaction is carried out in the same manner as
Yield 5.0 g of the polymer represented by Example 2
The contact angle was measured in the same manner as in 2. The results are shown in Table 2.

[0194]

[Chemical formula 129]

[0195]

[Example 29] A charged amount of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was 5.0 g.
(5 mmol), methyl methacrylate to 2.0 g (15 mmol) of 2-hydroxyethyl methacrylate, and a charged amount of trimethoxyvinylsilane of 2.2 g (15 m).
mol), and the reaction was carried out in the same manner as in Example 22 to obtain 5.9 g of a polymer represented by the following structural formula 130. Further, the contact angle was measured in the same manner as in Example 22. The results are shown in Table 2.

[0196]

[Chemical 130]

[0197]

EXAMPLE 30 Diperfluoro-2-methyl-3-oxahexanoyl peroxide was added to diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide in an amount of 3.3 g (5 m).
to 2.0 g (15 mmol) of 2-hydroxyethyl methacrylate and 2.2 g (15 mmol) of trimethoxyvinylsilane.
Except that the reaction was performed in the same manner as in Example 22,
The yield of the polymer represented by the following structural formula 131 is 5.1 g.
Obtained. Further, the contact angle was measured in the same manner as in Example 22.
The results are shown in Table 2.

[0198]

[Chemical 131]

[0199]

Example 31 Diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was converted into diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide. To 61 g (5 mmol), methyl methacrylate was added to 2-hydroxyethyl methacrylate.2.
The reaction was performed in the same manner as in Example 22 except that the amount of trimethoxyvinylsilane charged was 0 g (15 mmol) and 2.2 g (15 mmol), and the yield of the polymer represented by the structural formula 132 was 7.1 g. Obtained. Example 22
The contact angle was measured in the same manner as in. The results are shown in Table 2.

[0200]

[Chemical 132]

[0201]

Example 32 A charged amount of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was 5.0 g.
(5 mmol), methyl methacrylate was 2.0 g (15 mmol) of 2-hydroxyethyl methacrylate, and trimethoxyvinylsilane was 3.7 g (15 mmol) of 3-methacryloxypropyltrimethoxysilane. The reaction was conducted to obtain 5.8 g of a polymer represented by the following structural formula 133. Further, the contact angle was measured in the same manner as in Example 22. The results are shown in Table 2.

[0202]

[Chemical 133]

[0203]

Example 33 Diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was replaced with diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide. To 61 g (5 mmol), methyl methacrylate was added to 2-hydroxyethyl methacrylate.2.
To 0 g (15 mmol) of trimethoxyvinylsilane was added 3-
Methacryloxypropyltrimethoxysilane 3.7g
The reaction was carried out in the same manner as in Example 22 except that (15 mmol) was obtained to obtain 6.9 g of a polymer represented by the following structural formula 134. Further, the contact angle was measured in the same manner as in Example 22. The results are shown in Table 2.

[0204]

[Chemical 134]

[0205]

Comparative Example 2 The contact angle of an untreated glass plate was measured in the same manner as in Example 22. The results are shown in Table 2.

[0206]

[Table 2]

[0207]

Example 34 CH ₂ ═C (CH ₃ ) CO ₂ (CH ₂ CH ₂ O) ₂
To 1.74 g (10 mmol) of H, diperfluoro peroxide
2,5-Dimethyl-3,6-dioxanonanoyl 9.
80 g of a 1,1,2-trichlorotrifluoroethane solution containing 9 g (10 mmol) was added, and under a nitrogen atmosphere, 30 ° C.
The reaction was carried out for 7 hours. After the reaction was completed, the white powder component was filtered, dried under vacuum and purified to obtain a white powder product in a yield of 1.0 g. Then, the reaction solvent in the filtrate was removed and dried under vacuum to obtain a colorless liquid product in a yield of 10.8 g. As a result of analysis of the obtained product, it was found to be a fluoroalkyl group-containing polymer represented by the structural formula 135 below. Then, the obtained polymer was dissolved in chloroform to prepare a 5 wt% solution, a film was formed on a glass substrate by a bar coater, and the contact angle of the obtained film with water and dodecane was measured. The results are shown in Table 3.

[0208]

[Chemical 135]

[0209]

Example 35 Example 34 except that diperfluoro-2-methyl-3-oxahexanoyl peroxide was used in place of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide. The reaction was carried out in the same manner as in (1) to give a white powder product in an amount of 0.9 g and a colorless liquid product in an amount of 9.9 g. The obtained product has the following structural formula 1.
It was a polymer represented by 36. Next, a film was prepared in the same manner as in Example 34, and the contact angle was measured. The results are shown in Table 3.
Shown in.

[0210]

[Chemical 136]

[0211]

Example 36 Diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide instead of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide The reaction was performed in the same manner as in Example 34 except that the above was used to give a white powder product in an amount of 1.3 g.
A colorless liquid product was obtained in a yield of 12.1 g. The obtained product was a polymer represented by the structural formula 137 below. Next, a film was prepared in the same manner as in Example 34, and the contact angle was measured. The results are shown in Table 3.

[0212]

[Chemical 137]

[0213]

Example 37 The reaction was carried out in the same manner as in Example 34 except that diperfluoroheptanoyl peroxide was used instead of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide. Yield 0.8 as a white powder product.
Yield 9.1 g of colorless liquid product. The obtained product was a polymer represented by the structural formula 138 below.
Next, a film was prepared in the same manner as in Example 34, and the contact angle was measured. The results are shown in Table 3.

[0214]

[Chemical 138]

[0215]

Example 38 Similar to Example 34 except that 4.3 g (10 mmol) of diperfluorobutyryl peroxide was used instead of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide. The reaction was carried out to obtain a white powder product in an amount of 0.6 g and a colorless liquid product in an amount of 8.7 g. The obtained product was a polymer represented by the structural formula 139 below. Next, a film was prepared in the same manner as in Example 34, and the contact angle was measured. The results are shown in Table 3.

[0216]

[Chemical 139]

[0217]

Example 39 CH ₂ = C (CH ₃ ) CO ₂ (CH ₂ CH ₂ O) ₂
Instead of 1.74 g (10 mmol) H ₂ , CH ₂ ═C (CH ₃ )
The reaction was carried out in the same manner as in Example 34 except that 4.38 g (10 mmol) of CO ₂ (CH ₂ CH ₂ O) m ₄ H was used, yielding 2.1 g of a white powder product and a colorless liquid product. Yield 1
2.1 g was obtained. The obtained product was a polymer represented by the structural formula 140 below. However, since m ₄ represents 7 to 9, the average molecular weight was m ₄ = 8. Next, a film was prepared in the same manner as in Example 34, and the contact angle was measured. The results are shown in Table 3.

[0218]

[Chemical 140]

[0219]

Example 40 CH ₂ ═C (CH ₃ ) CO ₂ (CH ₂ CH ₂ O) ₂
Instead of 1.74 g (10 mmol) H ₂ , CH ₂ ═C (CH ₃ )
_{CO 2 (CH 2 CH 2 O} ) 10 - (CH 2 CH 2 CH 2 CH 2 O) 5 H
The reaction was performed in the same manner as in Example 34 except that 8.86 g (10 mmol) was used, to give a white powder product in a yield of 3.1.
Yield 13.9 g of colorless liquid product. The obtained product was a polymer represented by the following structural formula 141.
Next, a film was prepared in the same manner as in Example 34, and the contact angle was measured. The results are shown in Table 3.

[0220]

[Chemical 141]

[0221]

EXAMPLE 41 CH ₂ ═C (CH ₃ ) CO ₂ (CH ₂ CH ₂ O) ₂
Diperfluoro peroxide was dissolved in 1.74 g (10 mmol) of H and 1.48 g (10 mmol) of trimethoxyvinylsilane.
2,5-Dimethyl-3,6-dioxanonanoyl 9.
80 g of a 1,1,2-trichlorotrifluoroethane solution containing 9 g (10 mmol) was added, and the reaction was carried out at 30 ° C. for 7 hours under a nitrogen atmosphere. After the reaction was completed, the white powder component was filtered, dried under vacuum, and purified to obtain a white powder product in a yield of 0.4 g. Then, the reaction solvent in the filtrate was removed and dried under vacuum to obtain a colorless liquid product in a yield of 12.3 g. The obtained product has the following structural formula 1.
It was a polymer represented by 42. Next, a film was prepared in the same manner as in Example 34, and the contact angle was measured. The results are shown in Table 3.
Shown in.

[0222]

[Chemical 142]

[0223]

EXAMPLE 42 Diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide instead of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide The reaction was performed in the same manner as in Example 41 except that the above was used to give 0.7 g of a white powder product.
And 13.9 g of a colorless liquid product were obtained. The obtained product was a polymer represented by the structural formula 143 below. Next, a film was prepared in the same manner as in Example 34, and the contact angle was measured. The results are shown in Table 3.

[0224]

[Chemical 143]

[0225]

Example 43 3 instead of trimethoxyvinylsilane
-A reaction was performed in the same manner as in Example 41 except that methacryloxypropyltrimethoxysilane was used, to give 0.6 g of a white powder product and 1 g of a colorless liquid product.
2.9 g was obtained. The obtained product was a polymer represented by the following structural formula 144. Next, a film was prepared in the same manner as in Example 34, and the contact angle was measured. The results are shown in Table 3.

[0226]

[Chemical 144]

[0227]

Comparative Example 3 The contact angle of the untreated glass plate was measured in the same manner as in Example 34. The results are shown in Table 3.

[0228]

[Table 3]

[0229]

[Example 44] 1.42 g of glycidyl methacrylate
(10 mmol) and trimethoxyvinylsilane 2.96 g
(20 mmol), diperfluoro-2-methyl-peroxide
66 g of a 1,1,2-trichlorotrifluoroethane solution containing 6.6 g (10 mmol) of 3-oxahexanoyl
Was added and reacted at 40 ° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, the solvent was removed under reduced pressure, and the product was dried under vacuum to yield a colorless transparent liquid product.
8 g was obtained. As a result of analyzing the obtained product, it was a polymer represented by the following structural formula 145. Then, acetic acid was added to the obtained polymer to adjust the pH to 5.5, and then 75
A 1 wt% solution of the polymer was prepared by dissolving in a wt% ethanol aqueous solution. Next, the obtained solution is formed into a film on a glass substrate by a dip coating method, and the temperature is 120 ° C.
After heat treatment for 10 minutes, the contact angle was measured.
The results are shown in Table 4.

[0230]

[Chemical 145]

[0231]

Example 45 Diperfluoro-2-methyl-3 peroxide
-A reaction was performed in the same manner as in Example 44 except that oxahexanoyl was replaced with diperfluoroheptanoyl peroxide, and the yield of the polymer represented by the following structural formula 146 was obtained.
Obtained 6 g. Next, a solution containing the polymer obtained in the same manner as in Example 44 was prepared, and the contact angle was measured. The results are shown in Table 4.

[0232]

[Chemical formula 146]

[0233]

Example 46 1.86 g (10 m of glycidyl methacrylate was added to 2- (glycidyloxy) ethyl methacrylate)
mol), and the reaction was carried out in the same manner as in Example 44 to obtain 8.0 g of a polymer represented by the following structural formula 147. Next, a solution containing the polymer obtained in the same manner as in Example 44 was prepared, and the contact angle was measured. The results are shown in Table 4.

[0234]

[Chemical 147]

[0235]

[Example 47] The reaction was performed in the same manner as in Example 44 except that 2-methylglycidyl methacrylate was changed to 1.56 g (10 mmol) to give a polymer represented by the following structural formula 148 in a yield of 7.5 g. Obtained.
Next, a solution containing the polymer obtained in the same manner as in Example 44 was prepared, and the contact angle was measured. The results are shown in Table 4.

[0236]

[Chemical 148]

[0237]

Example 48 2.48 g (10 mm) of trimethacryloxypropylsilane was added to trimethacryloxypropyltrimethoxysilane.
except that the reaction was conducted in the same manner as in Example 44 except that the polymer represented by the following structural formula 149 was obtained in a yield of 7.
2g was obtained. Next, a solution containing the polymer obtained in the same manner as in Example 44 was prepared, and the contact angle was measured. The results are shown in Table 4.

[0238]

[Chemical 149]

[0239]

Example 49 A mixture of 42.6 g (300 mmol) of glycidyl methacrylate and 42.6 g (300 mmol) of butyl methacrylate was used as glycidyl methacrylate, and perfluoro-2-methyl-3-oxahexanone peroxide was converted to perfluoro-2,5-peroxide. Dimethyl-
The reaction was carried out in the same manner as in Example 44 except that 1,1,2-trichlorotrifluoroethane containing 79.8 g (20 mmol) of 3,6-dioxanonanoyl was used, and represented by the following structural formula 150. 3.0 g of a polymer was obtained as a colorless transparent liquid. Next, a solution containing the polymer obtained in the same manner as in Example 44 was prepared, and the contact angle was measured. The results are shown in Table 4.

[0240]

[Chemical 150]

[0241]

Example 50 The reaction was carried out in the same manner as in Example 44 except that glycidyl methacrylate was a mixture of 42.6 g (300 mmol) of glycidyl methacrylate and 59.4 g (300 mmol) of 2-ethylhexyl methacrylate, and the following structural formula 151 was used. 107.4 g of a polymer represented by the above formula was obtained as a colorless transparent liquid substance. Next, a solution containing the polymer obtained in the same manner as in Example 44 was prepared, and the contact angle was measured. The results are shown in Table 4.

[0242]

[Chemical 151]

[0243]

Example 51 Glycidyl methacrylate was replaced with methyl 6-methacryloyloxyhexanoate-7-oxabicyclo [4.1.0] heptane 3.1 g (10 mmol),
Diperfluoro-2-methyl-3-oxanonanoyl peroxide was converted into diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide 13.2 g (1
The reaction was performed in the same manner as in Example 44 except that the amount of the polymer was changed to 0 mmol) to obtain 9.6 g of a polymer represented by the following structural formula 152. Next, a solution containing the polymer obtained in the same manner as in Example 44 was prepared, and the contact angle was measured. The results are shown in Table 4.

[0244]

[Chemical 152]

[0245]

[Embodiment 52] Trimethoxyvinylsilane was added to 3-methacryloxypropyltrimethoxysilane (2.48 g, 10 mm).
except that the reaction was performed in the same manner as in Example 44, except that the polymer represented by the following structural formula 153 was obtained.
0 g was obtained. Next, a solution containing the polymer obtained in the same manner as in Example 44 was prepared, and the contact angle was measured. The results are shown in Table 4.

[0246]

[Chemical 153]

[0247]

Example 53 Glycidyl methacrylate and trimethoxyvinylsilane were added to 9.8 g (50 mm) of methacryloyloxymethyl-7-oxabicyclo [4.1.0] heptane.
ol) and 2-ethylhexyl methacrylate 39.2 g
Instead of (200 mmol), diperfluoro-2-methyl-3-oxahexanoyl peroxide was replaced with 9.9 g (10 mmol) of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide. Was reacted in the same manner as in Example 44 to obtain 43 g of a polymer represented by the following structural formula 154. Next, a solution containing the polymer obtained in the same manner as in Example 44 was prepared, and the contact angle was measured. The results are shown in Table 4.

[0248]

[Chemical 154]

[0249]

[Table 4]

Claims (1)

[Claims] 1. A molecular weight of 50 represented by the following general formula 1.
0 to 1,000,000 fluoroalkyl group-containing polymers,
A surface treating agent comprising as an active ingredient a component selected from the group consisting of a hydrolyzate thereof, a hydrolyzed condensate thereof and a mixture thereof. [Chemical 1]