JP2021109947A - Curable composition, cured product and method for producing curable composition - Google Patents

Abstract

To provide: a curable composition having excellent antifouling property and self-cleaning properties of a cured product; a cured product of the curable composition; and a method for producing the curable composition.SOLUTION: There is provided a curable composition which comprises a non-fluorine polymer having a reactive silicon group and a fluorine-containing polymer having the reactive silicon group, wherein the non-fluorine polymer is either one or both of an oxyalkylene polymer and a (meth)acrylic ester polymer and the fluorine-containing polymer is a polymer having either one or both of a repeating unit based on a (meth)acrylic acid ester having a polyfluoroalkyl group, a repeating unit based on a polymer having a hydrophilic group and a polymerizable unsaturated group, a repeating unit based on a polymer having the reactive silicon group and a polymerizable unsaturated group and a repeating unit based on a compound having the reactive silicon group and a sulfanyl group.SELECTED DRAWING: None

Description

The present invention relates to a curable composition, a cured product of the curable composition, and a method for producing the curable composition.

A curable composition containing a polymer having a reactive silicon group is used, for example, as a sealing material for joints of outer walls.
It is desirable that the outer wall of a building has excellent antifouling properties and is not easily soiled. Therefore, it is desirable to have a self-cleaning property in which the attached dirt is washed away by rainfall or the like.

Patent Document 1 describes a method of blending a fluorine-containing nonionic surfactant with a sealing material to make the surface after curing hydrophilic and imparting a self-cleaning effect by rainfall.
Patent Document 2 describes a method of mixing a specific fluorine copolymer with a sealing material to develop water and oil repellency and ease of wiping off dirt.

Japanese Unexamined Patent Publication No. 2008-291159 JP-A-2017-128725

In recent years, with the improvement of the self-cleaning property of the outer wall board, the sealing material is also required to be improved in the self-cleaning property so that the stains on the joints are less noticeable.
However, the sealing materials described in Patent Documents 1 and 2 do not always have sufficient self-cleaning properties.
An object of the present invention is to provide a curable composition having excellent antifouling property and self-cleaning property of the cured product, a cured product of the curable composition, and a method for producing the curable composition.

The present invention is the following [1] to [9].
[1] A curable composition containing a non-fluorinated polymer and a fluoropolymer, wherein the non-fluorinated polymer is an oxyalkylene polymer having a reactive silicon group represented by the following formula 1 and the following formula 1. One or both of the (meth) acrylic acid ester polymers having a reactive silicon group represented by, and the fluorine-containing polymer is a repeating unit based on the first monomer and a second simple substance. A polymer having one or both of a repeating unit based on a metric, a repeating unit based on a third monomer, and a unit based on compound a, wherein the first monomer is polyfluoro. It is a (meth) acrylic acid ester having an alkyl group, the second monomer is a monomer having a hydrophilic group and a polymerizable unsaturated group, and the third monomer is represented by the following formula 1. A curable composition which is a monomer having both a reactive silicon group and a polymerizable unsaturated group represented, and the compound a is a compound having both the reactive silicon group and the sulfanyl group.
−SiX _a R _3-a formula 1
In the above formula 1, R is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group, X represents a hydroxyl group or a hydrolyzable group, and a is 1-3. It indicates an integer, and when a is 1, R may be the same or different from each other, and when a is 2 or 3, X may be the same or different from each other.

[2] The curable composition according to [1], wherein the content of the fluorine-containing polymer with respect to 100 parts by mass of the non-fluorine polymer is 0.1 to 20 parts by mass.
[3] The curable composition according to [1] or [2], wherein the fluorine-containing polymer has a number average molecular weight of 3,000 to 20,000.
[4] The curable composition according to any one of [1] to [3], wherein the ratio of fluorine atoms to the fluorine-containing polymer is 5 to 35% by mass.
[5] The curable composition according to any one of [1] to [4], wherein the second monomer contains a monomer represented by the following formula 2.
R ²⁰ −Z ²¹ − (CH ₂ CH ₂ O) _n R ²² Equation 2
In the above formula 2, R ²⁰ is CH ₂ = CH _2- , CH ₂ = CH _{2 -CH 2-} O-, CH ₂ = CR ^21- C (= O) O- or CH ₂ = CR ^21- OC ( = O) −, R ²² represents a hydrogen atom or a methyl group, and Z ²¹ represents a single bond or an alkylene group having 1 to 10 carbon atoms. R ²¹ is a hydrogen atom, a chlorine atom, a fluorine atom, or a linear or branched alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 24.
[6] The curable composition according to any one of [1] to [5], wherein the ratio of fluorine atoms to the curable composition is 0.1 to 15% by mass.
[7] The curable composition according to any one of [1] to [6], which further contains an amine compound.
[8] A cured product of the curable composition according to any one of [1] to [7].
[9] The method for producing a curable composition according to any one of [1] to [7], wherein the first monomer, the second monomer, and the third monomer are used. A curable composition obtained by reacting one or both of the monomer of the above compound and the compound a to obtain the fluorine-containing polymer, and mixing the fluorine-containing polymer and the non-fluorine-containing polymer. Manufacturing method.

The curable composition of the present invention is excellent in antifouling property and self-cleaning property of the cured product.
The cured product of the present invention is excellent in antifouling property and self-cleaning property.
The method for producing a curable composition of the present invention can produce a curable composition having excellent antifouling property and self-cleaning property of the cured product.

Definitions of terms herein are as follows.
The numerical range represented by "~" means a numerical range in which the numerical values before and after ~ are the lower limit value and the upper limit value.
"Oxyalkylene polymer" means a polymer having a polyoxyalkylene chain formed from repeating units based on cyclic ether.
The "precursor polymer" is composed of a residue of an initiator, a polyoxyalkylene chain formed by ring-opening addition polymerization of cyclic ether, and a terminal group containing a terminal oxygen atom of the polyoxyalkylene chain, and has a terminal. It is a polymer in which at least a part of the group is a hydroxyl group.

The "(meth) acrylic acid alkyl ester polymer" is a weight having one or both of a polymer chain formed from a repeating unit based on an acrylic acid alkyl ester and a polymer chain formed from a repeating unit based on a methacrylate alkyl ester. Means coalescence.
"(Meta) acrylic acid" means one or both of acrylic acid and methacrylic acid.
"Ester moiety" means an atomic group bonded to an oxygen atom of an ester bond.

The "active hydrogen-containing group" is at least one group selected from the group consisting of a hydroxyl group, a carboxy group, an amino group, a monovalent group obtained by removing a hydrogen atom from a primary amine, a hydrazide group and a sulfanyl group.
The "active hydrogen" is a hydrogen atom based on the active hydrogen-containing group.
The "silylating agent" is a compound capable of introducing a reactive silicon group by reacting with an active hydrogen-containing group or an unsaturated group.

The "(meth) acrylic acid ester having a polyfluoroalkyl group" is a (meth) acrylic acid ester compound having a fluoroalkyl group at the ester moiety, and the ratio of fluorine atoms to the compound is 30% by mass or more. Is.
A "fluoroalkyl group" is a monovalent group in which at least one hydrogen atom in the alkyl group is replaced with a fluorine atom.

The "silylation rate" of an oxyalkylene polymer having a reactive silicon group is the reactive silicon group with respect to the total number of reactive silicon groups, active hydrogen-containing groups, and unsaturated groups contained in the terminal group of the polymer. Is the ratio of the number of. The value of the silylation rate can be measured by NMR analysis.

The number average molecular weight (hereinafter referred to as "Mn") and the mass average molecular weight (hereinafter referred to as "Mw") are polystyrene-equivalent molecular weights obtained by gel permeation chromatography (GPC) measurement. The molecular weight distribution is a value calculated from Mw and Mn, and is a ratio of Mw to Mn (hereinafter, referred to as “Mw / Mn”).

The "content of fluorine atoms in the curable composition, polymer, or monomer" means that, when the content of fluorine atoms in the monomer is known, each monomer in the production of the polymer is used. It can be calculated based on the charging ratio of the polymer and the blending ratio of the polymer in the curable composition. When measuring from the obtained curable composition or polymer, for example, the curable composition or polymer that has been heated and incinerated is subjected to an energy dispersion type X-ray (EDX) analysis method or F-Ka ray. A method of measuring intensity by a fluorescent X-ray analysis method, in which a curable composition or polymer is burned at 1000 ° C. or higher in an oxygen-filled quartz flask, and the obtained combustion gas is absorbed by a collecting liquid. After that, the oxygen combustion flask method in which fluorine ions are measured by ion chromatography or F electrode method, the quartz tube oxygen combustion gas collection method in which combustion is performed inside the quartz tube instead of burning in the quartz flask, and the combustion in the quartz flask. It can be measured by the potassium carbonate capsule method or the like in which the mixture is burned together with potassium carbonate powder at about 600 ° C. in a platinum container instead of being burned.

The curable composition of the present embodiment contains a non-fluorinated polymer and a fluorinated polymer. The non-fluorine polymer is a non-fluorine polymer having the following reactive silicon group (hereinafter, referred to as “polymer A”). The fluorine-containing polymer is a fluorine-containing polymer having the following reactive silicon group (hereinafter, referred to as “polymer B”). The amount of the polymer A contained in the curable composition may be two or more. The amount of the polymer B contained in the curable composition may be two or more.

<Reactive silicon group>
The reactive silicon group is represented by the following formula 1.
−SiX _a R _3-a formula 1
In the above formula 1, R represents a monovalent organic group having 1 to 20 carbon atoms. R does not contain a hydrolyzable group.
Examples of R include a hydrocarbon group, a halohydrocarbon group and a triorganosyloxy group.

As R, an alkyl group, a cycloalkyl group, an aryl group, a 1-chloroalkyl group and a triorganosyloxy group are preferable. At least one selected from the group consisting of a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, a 1-chloromethyl group, a trimethylsiloxy group, a triethylsiloxy group and a triphenylsiloxy group. Is more preferable. A methyl group or an ethyl group is preferable from the viewpoint of good curability of the polymer having a reactive silicon group and stability of the curable composition. A 1-chloromethyl group is preferable from the viewpoint of a high curing rate of the cured product. A methyl group is particularly preferred because it is readily available.

In the above formula 1, X represents a hydroxyl group or a hydrolyzable group.
Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a sulfanyl group and an alkenyloxy group.
As X, an alkoxy group is preferable because it has mild hydrolyzability and is easy to handle. The alkoxy group is preferably a methoxy group, an ethoxy group, or an isopropoxy group, and more preferably a methoxy group or an ethoxy group. When the alkoxy group is a methoxy group or an ethoxy group, a siloxane bond is rapidly formed, a crosslinked structure is easily formed in the cured product, and the physical property value of the cured product becomes better.

In the above formula 1, a represents an integer of 1 to 3. When a is 1, R may be the same or different from each other. When a is 2 or more, X may be the same or different from each other.
a is preferably 1 or 2, and a is more preferably 2.

Examples of the reactive silicon group represented by the above formula 1 include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, and a dimethoxymethylsilyl group. Examples thereof include a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a diisopropoxymethylsilyl group, a chloromethyldimethoxysilyl group, and a chloromethyldiethoxysilyl group. From the viewpoint of high activity and good curability, a trimethoxysilyl group, a triethoxysilyl group, a dimethoxymethylsilyl group and a diethoxymethylsilyl group are preferable, and a dimethoxymethylsilyl group and a trimethoxysilyl group are more preferable.

<Polymer A>
The polymer A is an oxyalkylene polymer having the reactive silicon group (hereinafter referred to as “polymer A1”) and a (meth) acrylic acid ester polymer having the reactive silicon group (hereinafter referred to as “polymer A2”). ”) Either one or both. The polymer A1 may be two or more kinds. The polymer A2 may be two or more kinds.

(Polymer A1)
The polymer A1 has an initiator residue, a polyoxyalkylene chain formed by ring-opening addition polymerization of a cyclic ether, and a terminal group containing a terminal oxygen atom of the polyoxyalkylene chain. The valence of the initiator residue, the number of polyoxyalkylene chains, and the number of end groups are equal.
Examples of the cyclic ether include alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide, and cyclic ethers other than alkylene oxides such as tetrahydrofuran. In particular, propylene oxide is preferable.
The polyoxyalkylene chain may be a copolymer chain having two or more kinds of oxyalkylene groups, and in that case, the copolymer chain may be a block copolymer chain or a random copolymer chain.
Examples of the polyoxyalkylene chain contained in the polymer A1 include a polyoxypropylene chain, a polyoxyethylene chain, a poly (oxy-2-ethylethylene) chain, a poly (oxy-1,2-dimethylethylene) chain, and a poly (oxytetra). Examples thereof include a methylene) chain, a poly (oxyethylene / oxypropylene) chain, and a poly (oxypropylene / oxy-2-ethylethylene) chain. As the polyoxyalkylene chain, a polyoxypropylene chain and a poly (oxyethylene / oxypropylene) chain are preferable, and a polyoxypropylene chain is particularly preferable.

From the viewpoint of curability of the cured product, the polymer A1 preferably has 0.5 to 1.0 of the reactive silicon groups on average at one terminal group, and 0.55 to 0.97. Is more preferable, and 0.65 to 0.95 is more preferable.

The Mn of the polymer A1 is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 3,000 to 40,000. When Mn is at least the lower limit of the above range, the amount of reactive silicon groups introduced per mass of the polymer A1 does not become too large, and it is preferable in that it is easy to achieve both elongation and durability. When it is not more than the upper limit value, the viscosity becomes sufficiently low and the workability is improved.
The molecular weight distribution of the polymer A1 is preferably 1.60 or less, more preferably 1.40 or less, further preferably 1.20 or less, particularly preferably 1.17 or less, and particularly preferably 1.15 or less. The molecular weight distribution of the polymer A1 is preferably 1.00 or more. When the molecular weight distribution is not more than the upper limit value, the extensibility of the cured product is likely to be improved.
The viscosity of the polymer A1 at 25 ° C. is preferably 0.1 to 70 Pa · s, more preferably 0.5 to 60 Pa · s, and even more preferably 1 to 55 Pa · s. If it is within the above range, workability is better.

The polymer A1 preferably has 2 to 8 end groups in one molecule, more preferably 2 to 6 ends, and even more preferably 2 or 3 ends.
The polymer A1 preferably contains a group that is either a reactive silicon group, an active hydrogen-containing group, or an unsaturated group as a terminal group.

The polymer A1 has two or three terminal groups in one molecule, and each terminal group is summed by averaging the groups which are either the reactive silicon group, the active hydrogen-containing group, or the unsaturated group. It is preferable to have more than 0 pieces and 4.0 pieces or less.
The polymer A1 preferably has an average of 0.5 to 3.5 groups, which are any of the reactive silicon groups, active hydrogen-containing groups, or unsaturated groups, in one molecule.

(Method for producing polymer A1)
The polymer A1 is obtained by introducing the reactive silicon group into the terminal group of the precursor polymer.
As a method of introducing the reactive silicon group into the terminal group of the precursor polymer, a method of directly converting the active hydrogen-containing group of the terminal group of the precursor polymer into a reactive silicon group, or one terminal group of the precursor polymer A method of converting the unsaturated group into a reactive silicon group after introducing one or two unsaturated groups is preferable.

The precursor polymer is preferably a polymer having a hydroxyl group as a terminal group, which is obtained by ring-opening addition polymerization of a cyclic ether to an initiator having a hydroxyl group.
As the initiator, an initiator having 2 to 8 hydroxyl groups is preferable, an initiator having 2 to 6 hydroxyl groups is more preferable, and an initiator having 2 or 3 hydroxyl groups is further preferable. Two or more types of initiators may be used in combination.

Examples of the initiator having two hydroxyl groups include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, and low molecular weight. Polyoxypropylene glycol can be exemplified.
Examples of the initiator having three or more hydroxyl groups include glycerin, trimethylolpropane, trimethylolethane, low molecular weight polyoxypropylene triol, pentaerythritol, sorbitol, and sucrose.

Conventionally known catalysts can be used as the ring-opening addition polymerization catalyst for ring-opening addition polymerization of cyclic ether as an initiator. For example, an alkali catalyst (KOH or the like), a transition metal compound-porphyrin complex catalyst (organic aluminum) can be used. Examples thereof include a complex obtained by reacting a compound with porphyrin), a composite metal cyanide complex catalyst, and a catalyst composed of a phosphazene compound.

A composite metal cyanide complex catalyst is preferable because the molecular weight distribution of the polymer A1 can be narrowed and a curable composition having a low viscosity can be easily obtained. As the composite metal cyanide complex catalyst, a conventionally known compound can be used, and a known method can also be adopted as a method for producing a polymer using the composite metal cyanide complex. For example, International Publication No. 2003/062301, International Publication No. 2004/067633, JP-A-2004-2697776, JP-A-2005-15786, International Publication No. 2013/065802, JP-A-2015-01162 The compounds and production methods disclosed in the publication can be used.

As a method of introducing one unsaturated group into one terminal group of the precursor polymer, the active hydrogen-containing group of the terminal group of the precursor polymer is allowed to act on an alkali metal salt and then has an unsaturated group. A method of reacting a halogenated hydrocarbon is preferable. As a method of introducing two unsaturated groups into one terminal group of the precursor polymer, the active hydrogen-containing group of the terminal group of the precursor polymer is allowed to act on an alkali metal salt and then has an unsaturated group. A method of reacting an epoxy compound and then a halogenated hydrocarbon compound having an unsaturated group is preferable.

As a method for converting an unsaturated group into a reactive silicon group, a method of reacting the unsaturated group with a silylating agent is preferable. As a method for directly converting the active hydrogen-containing group into the reactive silicon group, a method of reacting the active hydrogen-containing group with the silylating agent is preferable.
The silylating agent used in the method of converting an unsaturated group into a reactive silicon group has both a group capable of reacting with an unsaturated group to form a bond (for example, a sulfanyl group) and the reactive silicon group. Examples thereof include compounds and hydrosilane compounds (for example, HSiX _a R _3-a , where X, R and a are the same as in Formula 1 above). Specifically, for example, trimethoxysilane, triethoxysilane, triisopropoxysilane, tris (2-propenyloxy) silane, triacetoxysilane, methyldimethoxysilane, methyldiethoxysilane, ethyldimethoxysilane, methyldiisopropoxy. Examples thereof include silane, (α-chloromethyl) dimethoxysilane, and (α-chloromethyl) diethoxysilane. From the viewpoint of high activity and good curability, trimethoxysilane, triethoxysilane, methyldimethoxysilane and methyldiethoxysilane are preferable, and methyldimethoxysilane or trimethoxysilane is more preferable.

Examples of the silylating agent used in the method of directly converting an active hydrogen-containing group into a reactive silicon group include a group capable of reacting with an active hydrogen-containing group to form a bond (for example, an isocyanate group) and the reactive silicon group. A compound having both (for example, an isocyanate silane compound) can be exemplified. As the isocyanate silane compound, for example, the conventional isocyanate silane compound described in JP-A-2011-178955 can be used.

The method of introducing one unsaturated group into one terminal group of the precursor polymer, the method of converting an unsaturated group into a reactive silicon group, and the method of directly converting an active hydrogen-containing group into a reactive silicon group are , Conventionally known methods can be used, for example, JP-A-45-363319, JP-A-50-156599, JP-A-61-197631, JP-A-3-72527, JP-A-8-231707, Examples thereof include the methods proposed in JP-A-2011-178955, US Pat. No. 3,632,557, and US Pat. No. 4,960,844.

As a method for introducing two unsaturated groups into one terminal group of the precursor polymer, a known method can be used without particular limitation. For example, International Publication No. 2013/180203, International Publication No. 2014 / 192842, JP2015-105293, JP2015-105322, JP2015-105323, JP2015-105324, International Publication No. 2015/080067, International Publication No. 2015/105122 , 2015/111577, International Publication 2016/002907, 2016-216633, 2017-39782 can be used.

In the above-mentioned production method, the silylation rate is preferably more than 50 mol% and 100 mol% or less, more preferably 55 to 98 mol%, still more preferably 60 to 97 mol%. When the curable composition contains two or more kinds of polymers A1, the average silylation rate in the whole polymer A1 may be within the above range.

(Polymer A2)
The polymer A2 has one or both of a polymer chain formed from a repeating unit based on an acrylic acid alkyl ester and a polymer chain formed from a repeating unit based on a methacrylic acid alkyl ester.
The polymer A2 may have a repeating unit based on a monomer having an unsaturated group copolymerizable with the (meth) acrylic acid alkyl ester, in addition to the repeating unit based on the (meth) acrylic acid alkyl ester. ..
As the monomer constituting the polymer A2, for example, conventionally known monomers described in JP-A-3-14068, JP-A-6-21922, and JP-A-11-130931 are used. be able to.
The (meth) acrylic acid ester is preferably 50% by mass or more, more preferably 70% by mass or more, and may be 100% by mass with respect to all the monomers constituting the polymer A2.

The reactive silicon group in the polymer A2 may be introduced into the terminal group, the side chain, or both the terminal group and the side chain.

The average number of reactive silicon groups per molecule of the polymer A2 is more than 0.5, preferably 0.6 or more from the viewpoint of strength after curing. From the viewpoint of good elongation of the cured product, 4.0 or less is preferable, and 3.0 or less is more preferable.
The average number of reactive silicon groups per molecule of the polymer A2 is calculated by "concentration of reactive silicon groups in the polymer A2 [mol / g] x Mn of the polymer A2". The concentration [mol / g] of the reactive silicon group in the polymer A2 can be measured by NMR.

The Mn of the polymer A2 is preferably 500 to 100,000, more preferably 1,000 to 80,000, and even more preferably 2,000 to 50,000. When it is at least the lower limit value of the above range, the extensibility of the cured product is likely to be excellent, and when it is at least the upper limit value, the viscosity is likely to be low and the workability is likely to be excellent.
The molecular weight distribution of the (meth) acrylic acid ester polymer A2 is preferably 3.0 or less, more preferably 2.5 or less.

(Method for producing polymer A2)
The polymer A2 is obtained by polymerizing a (meth) acrylic acid ester with a monomer containing a reactive silicon group and a polymerizable unsaturated group. Examples of the monomer containing a reactive silicon group and a polymerizable unsaturated group include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, and tris (tris). 2-methoxyethoxy) vinylsilane, (meth) acrylate-3- (methyldimethoxyryl) propyl, (meth) acrylate-3- (trimethoxysilyl) propyl, (meth) acrylate-3- (triethoxysilyl) Propyl can be exemplified. These may be one kind, or two or more kinds may be used in combination.

When a monomer containing a reactive silicon group and a polymerizable unsaturated group and a (meth) acrylic acid ester are polymerized by a free radical polymerization method, a polymer A2 having a reactive silicon group in the side chain is obtained.
When the living radical polymerization method is used, a polymer A2 having a reactive silicon group as a terminal group can be obtained.

The polymer A2 can be polymerized by a conventionally known polymerization method described in JP-A-2006-257405, JP-A-2006-37076, JP-A-2008-45059 and the like. Conventionally known auxiliary materials such as an initiator required for polymerization can be used, and reaction conditions such as reaction temperature and reaction pressure can be appropriately selected.
Examples of the polymerization method include a polymerization method using a free radical polymerization initiator by solution polymerization, emulsion polymerization, suspension polymerization or bulk polymerization, and living radical polymerization. As the living radical polymerization method, a method using a cobalt porphyrin complex as shown in Journal of American Chemical Society (J. Am. Chem. Soc), 1994, Vol. 116, p. 7943, special feature. Transition metals using nitrooxide radicals as shown in Table 2003-570378, organic halides and halide sulfonyl compounds as shown in JP-A-11-130931 as initiators. Atom transfer radical polymerization (ATRP method) using a complex as a catalyst can be exemplified. The polymer obtained by living radical polymerization tends to have a narrow molecular weight distribution and a low viscosity.

When both the polymer A1 and the polymer A2 are contained, the ratio of the polymer A1 to the total of the polymer A1 and the polymer A2 is preferably 1 to 70% by mass, more preferably 5 to 65% by mass, and 10 to 10% by mass. 60% by mass is more preferable. If it is within the above range, the curability is likely to be excellent.

<Polymer B>
The polymer B is any one of a repeating unit based on the first monomer, a repeating unit based on the second monomer, a repeating unit based on the third monomer, and a unit based on the first compound. It is a polymer having one or both. The first monomer is a (meth) acrylic acid ester having a polyfluoroalkyl group (hereinafter referred to as “monomer b ¹ ”). The second monomer is a monomer having a hydrophilic group and a polymerizable unsaturated group (hereinafter, referred to as “monomer b ² ”). The third monomer is a monomer having the reactive silicon group and the polymerizable unsaturated group (hereinafter, referred to as “monomer b ³ ”). The first compound is the compound having a reactive silicon group and a sulfanil group (hereinafter, referred to as “compound a”). The polymer B may be two or more kinds.
Monomer b ¹ has no has a polyfluoroalkyl group, a hydrophilic group, and a reactive silicon group.
Monomer b ² has a hydrophilic group and does not have a polyfluoroalkyl group and a reactive silicon group.
Monomer b ³ has no has a reactive silicon group, a polyfluoroalkyl group, and a hydrophilic group.
Compound a has a reactive silicon group and a sulfanyl group, and does not have a polyfluoroalkyl group, a hydrophilic group, and a polymerizable unsaturated group.

The ratio of fluorine atoms to the polymer B is preferably 5 to 35% by mass, more preferably 10 to 30% by mass, still more preferably 15 to 25% by mass. When the proportion of fluorine atoms is not less than the lower limit of the above range, the surface tension of the curable composition is likely to decrease and is more excellent in antifouling property, and when it is not more than the upper limit value, the surface hydrophilicity of the curable composition is excellent. Excellent in self-cleaning property.

Monomer b ¹ is a (meth) acrylic acid ester having a fluoroalkyl group at the ester moiety. As the fluoroalkyl group, a polyfluoroalkyl group is preferable, and a linear polyfluoroalkyl group is more preferable.
The number of carbon atoms of the fluoroalkyl group is preferably 1 to 30, more preferably 1 to 26, further preferably 1 to 12, and 1 to 10 in that the surface tension is likely to be lowered and the antifouling property is improved. It is particularly preferable, and 1 to 8 are most preferable.
It is preferable that the polymer B ^{contains a repeating unit based on the monomer b 1} because the surface tension of the surface of the obtained cured product tends to be low.

The proportion of fluorine atoms to the monomer ^{b 1} is preferably 30 to 70 wt%, more preferably from 35 to 65 wt%, more preferably 40 to 60 wt%. When the proportion of fluorine atoms is not less than the lower limit of the above range, the surface tension of the curable composition is likely to decrease and is more excellent in antifouling property, and when it is not more than the upper limit value, the surface hydrophilicity of the curable composition is more excellent. Excellent in self-cleaning property.
In the monomer ^{b 1,} the ratio of the number of fluorine atoms to the total of hydrogen atoms and the number of fluorine atoms is preferably from 30% to 80%, more preferably 35-75%, more preferably 40 to 70%. When the ratio of the number of fluorine atoms is not less than the lower limit of the above range, the surface tension of the curable composition tends to decrease, which is more excellent in antifouling property, and when it is less than the upper limit, the surface hydrophilicity of the curable composition is more excellent. , Excellent in self-cleaning property.

The monomer b ¹ preferably contains a monomer represented by the following formula 3 from the viewpoint of reducing the surface tension of the curable composition.
CH ₂ = C (R ¹¹ ) -C (= O) O-Z ^11- R ¹² formula 3
In the above formula 3, R ¹¹ represents a hydrogen atom, a halogen atom or a methyl group, Z ¹¹ represents a single bond or a divalent organic group, and R ¹² represents a perfluoroalkyl group having 1 to 10 carbon atoms.

The carbon number of Z ¹¹ is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2.
The carbon number of R ¹² is preferably 1 to 10, more preferably 1 to 8, and even more preferably 4 to 6.
The total number of carbon atoms of Z ¹¹ and R ¹² is preferably 2 to 16, more preferably 2 to 14, further preferably 2 to 10, and most preferably 6 to 8.

The ^{divalent organic group Z 11} has -O-, -NH-, -CO-, -S-, -SO _2- , -CD ¹ = at the end between carbon atoms or ^{on the side bonded to R 12.} It is preferable to use an alkylene group and an alkenylene group which may have CD ^2- (where D ¹ and D ^{2 are independently hydrogen atoms or methyl groups, respectively).}
Examples of Z ¹¹ are single bond, −CH ₂ −, − (CH ₂ ) ₂ −, − (CH ₂ ) ₃ −, −CH ₂ CH (CH ₃ ) −, −CH (CH ₃ ) CH ₂ CH. _2- , _{-CH 2} -CH = CH-,-(CH ₂ ) _2- S-,-(CH ₂ ) ₂ -S- (CH ₂ ) ₂ -,-(CH ₂ ) _2- SO _2- (CH) ₂ ) ₂ − can be mentioned. In terms of stability of the monomer _{^{b 1, - (CH 2)}} 2 -, - (CH 2) 3 -, - CH (CH 3) CH 2 CH 2 - alkylene groups are preferred.

As the monomer represented by the above formula 3, R ¹¹ is a hydrogen atom, a halogen atom or a methyl group, Z ¹¹ is an alkylene group having 1 to 6 carbon atoms, and R ¹² is a perfluoroalkyl group having 1 to 10 carbon atoms. A certain monomer is preferable in that the surface of the cured product of the curable composition is more easily hydrophilic and the self-cleaning property is better. R ¹¹ is a hydrogen atom, a chlorine atom or a methyl group, and Z ¹¹ is the number of carbon atoms. More preferably, a monomer having 1 to 2 alkylene groups and R ¹² being a perfluoroalkyl group having 4 to 6 carbon atoms is preferable.

^{The monomer b 1} represented by the above formula 3 includes
CH ₂ = CH-C (= O) O- (CH ₂ ) ₂ (CF ₂ ) ₃ CF ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) O- (CH ₂ ) ₂ (CF ₂ ) ₃ CF ₃ ,
CH ₂ = CH-C (= O) O- (CH ₂ ) ₂ (CF ₂ ) ₅ CF ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) O- (CH ₂ ) ₂ (CF ₂ ) ₅ CF ₃ ,
CH ₂ = CH-C (= O) O- (CH ₂ ) ₃ (CF ₂ ) ₃ CF ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) O- (CH ₂ ) ₃ (CF ₂ ) ₃ CF ₃ ,
CH ₂ = CH-C (= O) O- (CH ₂ ) ₃ (CF ₂ ) ₅ CF ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) O- (CH ₂ ) ₃ (CF ₂ ) ₅ CF ₃ ,
CH ₂ = CH-C (= O) O- (CH ₂ CH (CH ₃ )) (CF ₂ ) ₃ CF ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) O- (CH ₂ CH (CH ₃ )) (CF ₂ ) ₃ CF ₃ ,
CH ₂ = CH-C (= O) O- (CH ₂ CH (CH ₃ )) (CF ₂ ) ₅ CF ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) O- (CH ₂ CH (CH ₃ )) (CF ₂ ) ₅ CF ₃ ,
CH ₂ = CCl-C (= O) O- (CH ₂ ) ₂ (CF ₂ ) ₃ CF ₃ ,
CH ₂ = CCl-C (= O) O- (CH ₂ ) ₂ (CF ₂ ) ₅ CF ₃ can be exemplified.

^{The monomer b 1} constituting the polymer B may be two or more kinds.
Against repeating units derived from monomer b ^1, repeating units based on a monomer represented by the formula 3 is preferably at least 80 mass%, more preferably at least 90 mass%. It may be 100% by mass.

The hydrophilic group of monomer b ² is an alkylene oxide group (-R'O-;R'is an alkylene group), an amino group, a hydroxy group, an acrylamide group (CH ₂ = CHCONH-), a carboxy group, and a phosphoric acid. It is preferably at least one selected from the group consisting of a group (-PO ₃ ^2- ), a sulfone group (-SO _{2 (OH)), and a quaternary ammonium salt.} The carbon number of R'is preferably 1 to 5, and more preferably 1 to 3.

^{The monomer b 2} preferably has an alkylene oxide chain represented by _{− (RO) v} − as a hydrophilic group in that the dispersion stability of the obtained polymer tends to be good. v represents an integer of 1 to 30.
When v is 2 or more, v (R'O) may be 1 type or 2 or more types. When there are two or more types of (R'O), the polymerization may be random polymerization or block polymerization.

The polymerizable unsaturated group of the monomer ^{b 2,} for _{example, CH 2 = CH-, CH 2} = CH-CH 2 -O-, CH 2 = CR 21 -C (= O) O-, CH 2 = CR ²¹ −OC (= O) − can be mentioned (where R ²¹ is a hydrogen atom, a chlorine atom, a fluorine atom or a linear or branched alkyl group having 1 to 3 carbon atoms). As the polymerizable unsaturated group of the monomer b ² _{, CH 2} = CH-, CH ₂ = CH-CH _2- O-, CH ₂ = CH-C (= O) O-, CH ₂ = C (CH). ₃ ) -OC (= O) O-, CH ₂ = CH-OC (= O _{)-and CH 2} = C (CH ₃ ) -OC (= O)-are preferred, and CH ₂ = CH-C (= O). ) O− and CH ₂ = C (CH ₃ ) −OC (= O) O− are more preferred.
It is preferable that the polymer B ^{contains a repeating unit based on the monomer b 2} in that the surface tension of the surface of the obtained cured product tends to be low.

The monomer b ² preferably contains a monomer represented by the following formula 2 in that good hydrophilicity of the obtained cured product can be easily obtained.
R ²⁰ −Z ²¹ − (CH ₂ CH ₂ O) _n R ²² Equation 2
In the above formula 2, R ²⁰ is CH ₂ = CH _2- , CH ₂ = CH _{2 -CH 2-} O-, CH ₂ = CR ^21- C (= O) O- or CH ₂ = CR ^21- OC ( = O) −, and R ²² represents a hydrogen atom or a methyl group. Z ²¹ represents a single bond or an alkylene group having 1 to 10 carbon atoms. R ²¹ is the same as above, and n represents an integer of 1 to 24.

The carbon number of Z ²¹ is preferably 0 to 10, more preferably 0 to 5, and even more preferably 0 to 3.
n is preferably 2 to 24, more preferably 4 to 9.

As the monomer represented by the above formula 2, R ²⁰ is CH ₂ = CR ^21- C (= O) O-, R ²¹ is a hydrogen atom or a methyl group, and Z ²¹ is an alkylene group having 0 to 10 carbon atoms. , N of 2 to 24 are preferable in terms of hydrophilicity, R ²⁰ is CH ₂ = CR ^21- C (= O) O-, R ²¹ is a hydrogen atom or a methyl group, and Z ²¹ is carbon. A monomer having an alkylene group of several to 3 and n of 4 to 9 is more preferable.

^{The monomer b 2} represented by the above formula 2 includes
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _2- H,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _5- H,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _10- H,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _24- H,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _2- H,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _5- H,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _8- H,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _23- H,
_{CH 2 = CH-C (=} O) -O- (CH 2 CH 2 O) 4 - (CH 2 CH 2 (CH 3) O) 3 -H,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _5- (CH ₂ CH ₂ (CH ₃ ) O) _2- H,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _2- CH ₃ ,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _4- CH ₃ ,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _9- CH ₃ ,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _13- CH ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _2- CH ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _4- CH ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _9- CH ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _13- CH ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) -O- (CH ₂ CH ₂ O) _23- CH ₃ ,
Can be exemplified.

^{As the monomer b 2} other than the monomer represented by the above formula 2,
_{CH 2 = CH-C (=} O) -O- (CH 2 CH 2 O) 4 - (CH 2 CH 2 (CH 3) O) 3 -CH 3,
CH ₂ = CH-C (= O) -O- (CH ₂ CH ₂ O) _5- (CH ₂ CH ₂ (CH ₃ ) O) _2- H,
CH ₂ = CH-C (= O) -OH,
CH ₂ = C (CH ₃ ) -C (= O) -OH,
CH ₂ = C (CH ₃ ) -C (= O) -CH _2- CH _2- NH ₃ ,
CH ₂ = CH-C (= O) -CH _2- CH _2- NH ₃ ,
CH ₂ = C (CH ₃ ) -C (= O) -N (CH ₃ ) ₂ ,
CH ₂ = CH-C (= O) -N (CH ₃ ) ₂ ,
CH ₂ = C (CH ₃ ) -C (= O) -N (CH ₂ CH ₂ OCH ₂ CH ₂ ),
CH ₂ = CH-C (= O) -N (CH ₂ CH ₂ OCH ₂ CH ₂ ),
_{CH 2 = CH-C (=} O) -NH- (CH 2) 3 -N + (CH 3) 3 · Cl -,
Can be exemplified.

^{The monomer b 2} constituting the polymer B may be of two or more types.
Against repeating units derived from monomer b ^2, repeating units based on a monomer represented by the formula 2 is preferably at least 80 mass%, more preferably at least 90 mass%. It may be 100% by mass.

The reactive silicon group represented by the formula 1 with the monomer b ³ and compound a, high activity. From the viewpoint of more excellent curability of the curable composition, a diethoxymethylsilyl group, a dimethoxymethylsilyl group, a diisopropoxymethylsilyl group, a trimethoxysilyl group, a triethoxysilyl group, and a triisopropoxysilyl group are preferable. More preferably, an ethoxymethylsilyl group, a dimethoxymethylsilyl group, and a trimethoxysilyl group.
Monomer ^{b 3} and compound a preferably has 0.5 or an average of the reactive silicon groups per molecule, more preferably has 0.7 to 1 or, 0.8 to 1 It is more preferable to have one.
By polymer B comprising units based on the repeating unit, or compound a derived from monomer b ^3, preferable in that easily hydrophilicity of the surface of the cured product obtained is maintained.

The monomer b ³ preferably contains the monomer represented by the following formula 4 in that the polymerizable property with the monomer b ¹ and the monomer b ^{2 is better.}
CH ₂ = C (R ³¹ ) -C (= O) O-Z ³¹ formula 4
In the formula 4, R ³¹ is the ^{same as R 11 in the} formula 3, and Z ³¹ represents a monovalent organic group having the reactive silicon group as a substituent.

Examples of the monovalent organic group having a reactive silicon group, which is Z ³¹ , include an alkyl group having a reactive silicon group, an alkoxy group, a cycloalkyl group, an alkenyl group, an aryl group, an α-chloroalkyl group and a triorganosyloxy group. An alkyl group and an alkoxy group are preferable, and an alkyl group is more preferable, in that the curable composition has better curability and stability. The alkyl group and the alkenyl group may be linear or branched.

Z ³¹ has a structure in which one or more hydrogen atoms in the organic group are substituted with the reactive silicon group. As the monomer represented by the above formula 4, a linear linear chain having 1 to 6 carbon atoms in which ^{R 31} is a hydrogen atom or a methyl group and Z ^{31 is a terminal hydrogen atom substituted with the reactive silicon group.} A monomer which is an alkyl group is preferable from the viewpoint of curability, and R ³¹ is a hydrogen atom or a methyl group, and Z ³¹ is a terminal hydrogen atom having 1 to 3 carbon atoms substituted with the reactive silicon group. A monomer which is a linear alkyl group of the above is more preferable.

As the monomer b ³ represented by the formula 4,
CH ₂ = CH-C (= O) O- (CH ₂ ) ^-r Si,
CH ₂ = C (CH ₃ ) -C (= O) O- (CH ₂ ) ^-r Si,
CH ₂ = CH-C (= O) O- (CH ₂ ) ₂ - ^r Si,
CH ₂ = C (CH ₃ ) -C (= O) O- (CH ₂ ) ₂ - ^r Si,
CH ₂ = CH-C (= O) O- (CH ₂ ) ₃ - ^r Si,
CH ₂ = C (CH ₃ ) -C (= O) O- (CH ₂ ) ₃ - ^r Si,
CH ₂ = CH-C (= O) O- (CH ₂ ) ₄ - ^r Si,
CH ₂ = C (CH ₃ ) -C (= O) O- (CH ₂ ) ₄ - ^r Si,
Can be exemplified.
In the formula, ^r Si represents a reactive silicon group.

^{The monomer b 3} constituting the polymer B may be of two or more types.
With respect to the total weight of repeating units derived from monomer b ^3, repeating units based on a monomer represented by the formula 4 is preferably at least 80 mass%, more preferably at least 90 mass%. It may be 100% by mass.

The compound a preferably contains the compound represented by the following formula 5 in that the introduction rate into the polymer B becomes better.
Z ^41- SH formula 5
Z ⁴¹ represents a monovalent organic group having the reactive silicon group as a substituent, and a preferred embodiment is the same as that ^{of Z 31 of the above formula 4.}

Examples of the compound a include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane, and 3-mercaptopropyldiethoxymethylsilane.

The polymer B may further contain a repeating unit based on a (meth) acrylic acid ester (hereinafter referred to as “monomer b ^{4”) having an alkyl group having 1 to 8 carbon atoms at the ester moiety.}
Polymer B by containing repeating units derived from monomer b ^4, the hydrophilic of the cured product surface obtained is improved.
Monomer b ⁴ has no polyfluoroalkyl group, a hydrophilic group and a reactive silicon group.

The monomer b ⁴ preferably contains the monomer represented by the following formula 6 in that compatibility with the polymer A can be easily obtained.
CH ₂ = C (R ⁵¹ ) -C (= O) OR ⁵² formula 6
In the formula 6, R ⁵¹ is the ^{same as R 11 in the} formula 3, and R ⁵² represents an alkyl group having 1 to 8 carbon atoms.
^{As the monomer b 4} represented by the formula 6, a monomer having an alkyl group having 2 to 8 carbon atoms is preferable as ^{R 52} in terms of compatibility with the polymer A, and the monomer b 4 has 2 to 8 carbon atoms. A monomer having an alkyl group of 6 is more preferable. The alkyl group may be linear or branched, and a linear alkyl group is preferable in terms of compatibility with the polymer A.

As the monomer ^{b 4} of the formula 6, (meth) acrylate, (meth) acrylate, (meth) propyl acrylate, (meth)-n-butyl acrylate, (meth) acrylic Examples thereof include isobutyl acid acid, -t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, and -2-ethylhexyl (meth) acrylate. Ethyl (meth) acrylate, propyl (meth) acrylate, -n-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, -2-ethylhexyl (meth) acrylate are preferred. Ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and hexyl (meth) acrylate are more preferred.

If polymer B comprises repeat units derived from monomer b ^4, the monomer b ⁴ may be two or more.

The polymer B may ^{be a repeating unit based on monomer b 1} , a repeating unit based on monomer b ² , a repeating unit based on monomer b ³ , a unit based on compound a, and a monomer, if necessary. b may contain other units other than the repeating units based on ^4.
The other unit is not particularly limited as long as it is a repeating unit based on the monomer forming a polymer with ^{the monomer b 1} , the monomer b ² , and the monomer b ^3. For example, repetition based on (meth) acrylate ester having an alkyl group having 9 to 24 carbon atoms such as lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate. Units, vinyl ethers such as vinyl chloride, vinylidene chloride, 4-hydroxybutyl vinyl ether, stearyl vinyl ether, chloromethyl vinyl ether, 2-chloroethyl vinyl ether, repeating units based on vinyl halides such as tetrafluoroethylene, vinyl acetate, vinyl butyrate, pival Vinyl esters such as vinyl acid acid, allyl esters such as allyl acetate and dially adipate, diallyl ethers, allyl ethers such as 1,3 diallyloxy-2-propanol, long chain alkyl vinyls such as vinyl laurate and vinyl stearate, and ethylene. , Propylene, 1,4-butadiene and other hydrocarbon olefin compounds.
The other repeating units are preferably less than 50% by mass, preferably less than 40% by mass, based on all the repeating units constituting the polymer B.

^{The ratio of the repeating unit based on the monomer b 1} to all the repeating units constituting the polymer B is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, still more preferably 20 to 50% by mass.
^{The ratio of the repeating unit based on the monomer b 2} to all the repeating units constituting the polymer B is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, still more preferably 20 to 50% by mass.
If polymer B comprises repeat units derived from monomer b ^3, the proportion of repeating units derived from monomers b ³ with respect to all repeating units constituting the polymer B is preferably 0.1 to 10 mass% , 0.2 to 8% by mass, more preferably 0.3 to 6% by mass.
When the polymer B contains a unit based on the compound a, the ratio of the unit based on the compound a to all the repeating units constituting the polymer B is preferably 0.1 to 5% by mass, preferably 0.2 to 4% by mass. Is more preferable, and 0.3 to 3% by mass is further preferable.
If polymer B comprises repeat units derived from monomer b ^4, the proportion of repeating units derived from monomers b ⁴ to all of the repeating units constituting the polymer B is preferably 1 to 40 wt%, 2 ~ 35% by mass is more preferable, and 5 to 30% by mass is further preferable.

^{A repeating unit based on monomer b 1} , a repeating unit based on monomer b ² , a repeating unit based on monomer b ³ , and a unit based on compound a for all the repeating units constituting the polymer B. The total ratio is preferably 50 to 95% by mass, more preferably 55 to 95% by mass, still more preferably 60 to 90% by mass.
If the polymer B ^{contains both a monomer b 3} based repeat unit and a compound a based repeat unit, the ratio of the compound a based unit to the ^{monomer b 3 based repeat unit (a / b 3} ) is , 0.1 to 50, more preferably 0.2 to 30, and even more preferably 0.5 to 20.

The Mn of the polymer B is preferably 3,000 to 20,000, more preferably 4000 to 15000, and even more preferably 4500 to 12000. Within the above range, the curable composition is excellent in transferability to the surface.
The molecular weight distribution of the polymer B is preferably 2.5 or less, more preferably 2.0 or less.

<Method for producing polymer B>
The polymer B is ^{obtained by polymerizing the monomer b 1} , the monomer b ^2, and any one or both of the monomer b ³ and the compound a in an organic solvent. When the polymer B contains a repeating unit based on the ^{monomer b 4 , a single amount of the monomer b 1} , the monomer b ² , one or both of the monomer b ³ and the compound a is used. a monomer component containing a body b ^4, obtained by polymerization in an organic solvent. Examples of the organic solvent include acetone, methyl ethyl ketone, methanol, ethanol, isobutanol, 2-propanol, ethyl acetate, butyl acetate, diisopropyl ether, tetrahydrofuran, hexane, toluene, N, N-dimethylformamide, acetonitrile and the like. Ethyl acetate, 2-propanol, and isobutanol are preferable because the solubility of the monomer is easily obtained and a good yield is easily obtained. The organic solvent may be a mixture of two or more kinds.

Examples of the initiator in the polymerization reaction include a peroxide polymerization initiator, an azo polymerization initiator, a redox polymerization initiator, a metal compound catalyst, and the like. Examples of the radical polymerization initiator include 2,2'-azobisisobutyro, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and benzoylper. Examples thereof include oxide, t-butyl peroxide, acetyl peroxide, diisopropyl peroxy dicarbonate and the like.
The polymerization temperature and polymerization time can be appropriately selected depending on the boiling point of the solvent used, the half-life temperature of the initiator, etc., but the polymerization temperature may be 20 to 200 ° C., preferably 50 to 150 ° C., and the polymerization time is several hours. ~ Dozens of hours are preferable.

If necessary, a chain transfer agent can be used in the polymerization reaction. Examples of the chain transfer agent include n-dodecyl mercaptan, n-octadecyl mercaptan, t-dodecyl mercaptan, α-methylstyrene, and α-methylstyrene dimer.

<Curable composition>
The curable composition is obtained by synthesizing the polymer A and the polymer B by the above methods, respectively, adding necessary components to the polymer A and the polymer B, and mixing them.
The proportion of the polymer A in the curable composition is preferably 5 to 60% by mass, more preferably 10 to 55% by mass, still more preferably 15 to 50% by mass. When the proportion of the polymer A is within the above range, the elongation characteristics of the curable composition become better.
The proportion of the polymer B in the curable composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, still more preferably 1 to 10% by mass. When the ratio of the polymer B is within the above range, the contamination of the curable composition after washing with water is more likely to be reduced.
The total ratio of the polymer A and the polymer B in the curable composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 15 to 60% by mass. When the total ratio of the polymer A and the polymer B is within the above range, the obtained cured product is excellent in antifouling property and self-cleaning property.
The content of the polymer B is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, still more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the polymer A. When the content of the polymer B is not less than the lower limit of the above range, the obtained cured product is excellent in antifouling property and self-cleaning property, and when it is not more than the upper limit value, the compatibility between the polymer A and the polymer B is excellent.
The ratio of fluorine atoms to the total mass of the curable composition is preferably 0.1 to 15% by mass, more preferably 0.2 to 12% by mass, still more preferably 0.3 to 10% by mass. When the content ratio of fluorine atoms is at least the lower limit of the above range, the surface tension of the curable composition tends to decrease, and the antifouling property is more excellent. When the content is at least the upper limit, the surface of the curable composition becomes hydrophilic. Excellent and superior in self-cleaning property.
The ratio of the number of reactive silicon groups contained in the polymer B to the number of reactive silicon groups contained in the polymer A in the curable composition is preferably 0.1 to 40%, more preferably 0.3 to 30%. It is preferable, and 0.5 to 20% is more preferable. Within the above range, the elongation characteristics of the curable composition are more excellent, and the maintenance of the stain resistance on the surface of the curable composition is improved.

The viscosity of the mixture of the polymer A and the polymer B at 25 ° C. is preferably 1.5 to 50 Pa · s, more preferably 2 to 35 Pa · s, still more preferably 4 to 40 Pa · s. When the viscosity of the mixture of the polymer A and the polymer B is at least the lower limit of the above range, dripping during work is unlikely to occur, and when it is at least the upper limit, the workability tends to be good.
Examples of the method of lowering the molecular weights of the polymer A and the polymer B include a method of lowering the molecular weight of the polymer B.
The viscosity was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: RE80 type) at a measurement temperature of 25 ° C. and a rotor No. It is a value obtained by measuring the viscosity under the condition of 4.

The amine compound contributes to the suppression of tack (stickiness) on the surface of the cured product.
The curable composition of the present invention exhibits good self-cleaning property even if it does not contain an amine compound, but when it contains an amine compound, the self-cleaning property is likely to be improved.
As the amine compound, for example, one or more selected from the group consisting of naturally occurring amine compounds having a freezing point of 34 ° C. or lower and amine compounds having a melting point of 35 ° C. or higher, which are described in JP-A-2008-291159, are used. be able to. As the naturally occurring amine compound having a freezing point of 34 ° C. or lower, an amine compound having an alkyl group and having an alkyl group chain length distribution of 8 to 16 carbon atoms is preferable. Specific examples include coconut amine (amine made from coconut oil), octyl amine, and lauryl amine. Examples of the amine compound having a melting point of 35 ° C. or higher include an amine compound having an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aliphatic hydrocarbon group having 18 to 24 carbon atoms, and examples thereof include stearylamine and phenylenediamine. Toluenediamine can be mentioned. From the viewpoint of heat resistance, an amine compound having a melting point of 35 ° C. or higher is preferable.
Further, a compound that produces an amine by hydrolysis (for example, a ketimine compound) may be used as the amine compound.

<Other ingredients>
The curable composition may contain other components other than the polymer A, the polymer B and the amine compound. Other components include polymer A, other polymers other than polymer B, fillers, plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, dehydrating agents, adhesive-imparting agents, and oxygen-curable compounds. , Photocurable compounds, curing catalysts (silanol condensation polymers), amine compounds can be exemplified.
Examples of the main chain skeleton of other polymers include saturated hydrocarbon-based polymers, polyester-based polymers, vinyl-based polymers other than polymer A2, polysulfide-based polymers, polyamide-based polymers, and polycarbonate-based polymers. Examples thereof include diallyl phthalate-based polymers. These polymers may have the reactive silicon group.
Other components include International Publication No. 2013/180203, International Publication No. 2014/192842, International Publication No. 2016/002907, JP-A-2014-88481, JP-A-2015-10162, JP-A-2015-105293. No., JP-A-2017-039728, JP-A-2017-214541 and the like can be used in combination without limitation.
Two or more kinds of each component may be used in combination.

Examples of the plasticizer include phthalates (diisonyl phthalate, etc.), epoxy plasticizers (4,5-epoxycyclohexane-1,2-dicarboxylic acid-di-2-ethylhexyl, etc.), and paraffin-based plasticizers having 6 to 18 carbon atoms. Examples thereof include hydrocarbons (n-dodecane and the like), acrylic plasticizers (solvent-free acrylic polymers and the like), and polyether plasticizers (oxyalkylene polymers and the like).
If a polymer plasticizer having Mn of 1,000 or more, Mw of 1,000 or more, or a molecular weight of 500 or more per hydroxyl group is used as a part or all of the plasticizer, the surface of the cured product is contaminated or the periphery is used. It is preferable in that effects such as reduction of contamination, improvement of drying property of the coating material on the cured product, reduction of contamination property of the coating surface, and improvement of weather resistance can be easily obtained.

The curable composition may be a one-component type in which all the compounding components are premixed, sealed and stored, and cured by the humidity in the air after construction, or at least a main component composition containing a component having a reactive silicon group and at least. A two-component type may be used in which the curing agent composition containing the curing catalyst is stored separately and the curing agent composition and the main agent composition are mixed before use. A one-component curable composition is preferred because it is easy to install.

The one-component curable composition preferably does not contain water. It is preferable to dehydrate and dry the compounding component containing water in advance, or to dehydrate by reducing the pressure during compounding and kneading.
In the two-component curable composition, the curing agent composition may contain water, and the main component composition is difficult to gel even if it contains a small amount of water, but from the viewpoint of storage stability, the ingredients are dehydrated and dried in advance. Is preferable.
A dehydrating agent may be added to the one-component curable composition or the two-component main composition in order to improve the storage stability.

The curable composition is used as a sealing material (for example, an elastic sealing material for construction, a sealing material for double glazing, a sealing material for rust prevention / waterproofing at the end of glass, a sealing material for the back surface of a solar cell, and a sealing material for buildings. Materials, sealing materials for ships, sealing materials for automobiles, sealing materials for roads), electrical insulating materials (insulating coating materials for electric wires / cables), and adhesives are suitable.
In particular, it is suitable for applications that require self-cleaning property, and examples thereof include a sealing material that is applied outdoors.

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

<Measurement method>
[Molecular weight of precursor polymer]
The hydroxyl group-equivalent molecular weight of the precursor polymer of the oxyalkylene polymer in the following example is calculated by calculating the hydroxyl value of the precursor polymer based on JIS K 1557 (2007), and "56,100 / (hydroxyl value) × (start). It is a value calculated as "the number of active hydrogens of the agent or the number of terminal groups of the precursor polymer)".

[Mn and molecular weight distribution]
Using HLC-8220GPC (product name of Tosoh Corporation), Mw, Mn and Mw / Mn were determined under the following conditions.
(GPC measurement conditions)
Model used: HLC-8220GPC (Tosoh product name),
Data processing device: SC-8020 (Tosoh product name),
Columns used: Two TSG gel SuperMultipore HZ 4000 (Tosoh product name) and two TSG gel Super Multipore HZ 2500 (Tosoh product name) were connected and used in series.
Column temperature: 40 ° C,
Detector: RI,
Solvent: tetrahydrofuran,
Flow velocity: 0.35 ml / min,
Sample concentration: 0.5% by mass,
Injection volume: 20 μl,
Standard sample for preparing a calibration curve: polystyrene ([Easical] PS-2 [Polystyrene Standards], Polymer Laboratories product name).

[Average number of reactive silicon groups in one molecule in polymer A1 (number of silyl groups)]
In a method in which an unsaturated group is introduced into an terminal group using allyl chloride and a silylating agent is reacted with the unsaturated group to introduce a reactive silicon group, the unsaturated group introduced into the terminal group is silylated. The charge equivalent (molar ratio) of the reactive silicon group of the agent was taken as the silylation rate.
In the reaction between the unsaturated group introduced using allyl chloride and the silylating agent, about 10% of the unsaturated groups do not react with the silylating agent due to a side reaction. Therefore, when less than 90 mol% of unsaturated groups are reacted with the silylating agent, the above charged equivalent is defined as the silylation rate.
The number of silyl groups was calculated based on the silylation rate.

[Average number of reactive silicon groups in one molecule in polymer A2 (number of silyl groups)]
The number of silyl groups in the polymer A2 was calculated by multiplying the concentration [mol / g] of the reactive silicon groups in the polymer calculated by ^{1 H-NMR by the Mn measured by the above GPC.}

[Content ratio of fluorine atoms]
The proportion of fluorine atoms in the polymer B and the proportion of fluorine atoms in the curable composition are determined by energy dispersive X-ray analysis (EDX) after heating 10 g of the polymer B at 600 ° C. for 1 hour to incinerate it. It was calculated from the strength of the fluorine atom obtained by (analysis).

[Contact angle]
The curable composition of each example was cast as a sealing material on a flexible board provided with a groove of about 3 mm (depth) x 30 mm (width), and left for 7 days in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%. Then, a cured product was obtained. At room temperature (25 ° C.), 1 μL of water was allowed to stand on the surface of the cured product, and the contact angles after 5 seconds and 60 seconds were measured. The measurement results under this condition are shown in the "normal" column in Table 4.
The cured product obtained above was further left to stand in an atmosphere of a temperature of 50 ° C. and a relative humidity of 65% for 3 days. At room temperature (25 ° C.), 1 μL of water was allowed to stand on the surface of the obtained cured product, and the contact angles after 5 seconds and 60 seconds were measured. The measurement results under this condition are shown in the column of "heat resistance" in Table 4.

[Curing material contamination]
The curable composition of each example was cast as a sealing material on a flexible board provided with a groove of about 3 mm (depth) x 30 mm (width), and left for 7 days in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%. To obtain a cured product. Red clay was sprinkled on the surface of the cured product, and the flexible board was dropped onto the floor from a height of 20 cm three times with the flexible board standing vertically, and excess red clay was shaken off to prepare a test piece. The value of Eab (after contamination) was measured using a color difference meter for the state in which the red soil of the obtained test piece was attached. Next, with the test piece standing vertically, 100 cc of water was sprayed on the surface sprinkled with red clay from a distance of 20 cm by spraying, and after leaving to dry, the state where the red clay had adhered was observed using an Eab using a color difference meter. The value (after washing with water) was measured.
When the value of Eab (after contamination) is 30 or less, it is evaluated that the antifouling property is good, and the judgment "○" is described in the table. When the value is more than 30 and 40 or less, it is evaluated as "Δ", and when the value is more than 40, it is evaluated as having poor antifouling property, and it is described as "x" in the table.
When the value of Eab (after washing with water) is 25 or less, it is evaluated that the self-cleaning property is good, and the judgment "◯" is described in the table. If the value is more than 25 and 35 or less, it is evaluated as "Δ", and if the value is more than 35, it is evaluated that the self-cleaning property is poor, and it is described as "x" in the table.

<Synthesis of polymer A and polymer B>
(Synthesis Example 1: Polymer A1)
Propylene oxide was polymerized using propylene glycol as an initiator and a zinc hexacyanocobaltate complex having a ligand of t-butyl alcohol as a catalyst to obtain a precursor polymer having a hydroxyl group equivalent molecular weight of 16,000. Next, a methanol solution of sodium methoxide in an amount of 1.05 mol equivalent with respect to the amount of hydroxyl groups of the precursor polymer was added to alcorate the precursor polymer. Next, methanol was distilled off by heating and depressurizing, and an excess amount of allyl chloride was added to the amount of hydroxyl groups of the precursor polymer to introduce an allyloxy group into the terminal group. Next, in the presence of chloroplatinic acid hexahydrate, 0.65 molar equivalent of methyldimethoxysilane was added as a silylating agent to the converted allyloxy group of the precursor polymer, and the reaction was carried out at 70 ° C. for 5 hours. Then, a polymer (polymer A1) in which an average of 0.65 dimethoxymethylsilyl groups were introduced into one terminal group as a reactive silicon group was obtained.
The Mn, Mw / Mn, and the number of silyl groups of the obtained polymer are shown in Table 1 (hereinafter, similarly shown).

(Synthesis Example 2: Polymer A2)
85 g of butyl acrylate as a monomer, 400 g of methoxypolyethylene glycol acrylate (Nichiyu Co., Ltd. product name: AME400, hereinafter referred to as "AME400", which contains about 9 mol of an oxyethylene group in one molecule), 3-methacryloyloxypropyl 15 g of dimethoxysilane (hereinafter referred to as "MPDMS") was used. 5 g of 2,2'-azobis-2-methylbutyronitrile (Fujifilm Wako Pure Chemical Industries, Ltd. product name: V-59, hereinafter referred to as "V-59") is added to a total mass of 500 g of the monomer. The mixed mixture was added dropwise to 500 g of isobutanol heated to 105 ° C. over 5 hours and then polymerized for 1 hour, and then isobutanol was removed under heating and reduced pressure to remove the (meth) acrylic acid ester polymer (meth) acrylic acid ester polymer (meth). Polymer A2) was obtained. Table 2 shows the composition of the monomer of the polymer A2 and the like.

(Synthesis Example 3: Polymer B1)
As a monomer, 97.5 g of butyl acrylate, 195 g of AME400, 195 g of 2-perfluorohexyl ethyl methacrylate (hereinafter referred to as "C6FMA"), 3-methacryloyloxypropyldiethoxysilane (hereinafter referred to as "MPDES"). 12.5 g was used. For a total mass of 500 g of the monomer, 5.9 g of the chain transfer agent n-dodecyl mercaptan (hereinafter referred to as "DoSH") and the initiator 2,2'-azobis-2,4-dimethylvalero A mixed solution containing 9.8 g of nitrile (Fuji Film Wako Junyaku Co., Ltd. product name: V-65, hereinafter referred to as "V-65") was added dropwise to 500 g of isobutanol heated to 80 ° C. over 2 hours. Then, the mixture was polymerized for 2 hours, and then isobutanol was removed under heating and reduced pressure to obtain a polymer B1.
The composition and the like of the monomer of the obtained polymer are shown in Table 2 (hereinafter, similarly shown).

(Synthesis example: Polymer B2)
As the monomer, 100 g of butyl acrylate, 200 g of AME, and 200 g of C6FMA were used. A mixed solution prepared by mixing 10 g of 3-mercaptopropyltrimethoxysilane (hereinafter referred to as "MCPTMS") and 15 g of V-65 with respect to a total mass of 500 g of the monomer was heated to 80 ° C. and 500 g of isobutanol. After dropping over 2 hours, the mixture was polymerized for 2 hours, and then isobutanol was removed under heating and reduced pressure to obtain polymer B2.

<Other ingredients>
The additives listed in Table 3 are as follows.
Whiten SB: Heavy calcium carbonate, product name of Shiraishi Kogyo Co., Ltd.
CCR: White glossy CCR Calcium carbonate, product name of Shiraishi Kogyo Co., Ltd.
R-820: Titanium oxide, Ishihara Sangyo Co., Ltd. product name.
Balloon 80GCA: Organic balloon, product name of Matsumoto Oil & Fats Co., Ltd.
UP-1110: ARUFON UP-1110, acrylic polymer with Mn = 1,500, product name of Toagosei Co., Ltd.
EL3020: An oxyalkylene polymer having two hydroxyl groups per molecule and a molecular weight conversion equivalent to 2000, Excelol 3020, a product name of Asahi Glass Co., Ltd.
DINP: Diisononyl phthalate.
N-12D: n-dodecane, purity 98.0%, cactus normal paraffin N-12D, JXTG Energy Co., Ltd. product.
Sansosizer EPS: 4,5-epoxycyclohexane-1,2-dicarboxylic acid-di-2-ethylhexyl, product name of Shin Nihon Rikasha.
IRGANOX1135: Hindered phenolic antioxidant, BASF product name.
TINUVIN326: Benzotriazole-based UV absorber, product name of BASF.
TINUVIN765: A hindered amine-based light stabilizer containing a tertiary amine, a product name of BASF.
LA-63P: ADEKA STAB LA-63P, ADEKA product name.
KBM-1003: Vinyl trimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.
KBM-403: 3-glycidyloxypropyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.
KBM-603: 3- (2-aminoethylamino) propyltrimethoxysilane, product name of Shin-Etsu Chemical Co., Ltd.
Laurylamine: Reagent, manufactured by Junsei Chemical Co., Ltd.
Farmin CS: Coconut amine, Kao product name.
EH-235R-2: Ketimine compound, ADEKA product name.
Tung oil: Air oxidative curable compound, manufactured by Kimura.
M-309: Aronix M-309, Toagosei product name.
U-220H: Tin catalyst, product name of Nitto Kaseisha.

<Manufacturing of curable composition>
Examples 1 to 3 and Examples 6 to 29 are Examples, and Examples 4 and 5 are Comparative Examples.

(Examples 1 to 5)
A curable composition was produced by mixing polymer A and polymer B having the formulations shown in Table 4 (unit: parts by mass) and additive 1 having the formulations shown in Table 3. The composition shown in Table 3 is a value (unit: parts by mass) with respect to a total of 100 parts by mass of the polymer A and the polymer B.
With respect to the cured product of the obtained curable composition, the contact angle and the contaminating property of the cured product were evaluated by the above-mentioned method. The results are shown in Table 4.

In Examples 1 to 3, the Eab value after contamination and after washing with water was low, and the antifouling property and self-cleaning property were good.

(Examples 6 to 29)
In Examples 1 to 3, the additives were changed to Additives 2 to 9 in Table 3 to produce curable compositions, respectively, which were evaluated in the same manner as described above. Examples 6 to 8 are examples in which the additive 2 is added, Examples 9 to 11 are examples in which the additive 3 is added, Examples 12 to 14 are examples in which the additive 4 is added, and Examples 15 to 17 are examples in which the additive 4 is added. Examples are examples in which the additive 5 is added, Examples 18 to 20 are examples in which the additive 6 is added, Examples 21 to 23 are examples in which the additive 7 is added, and Examples 24 to 26 are examples in which the additive 8 is added. Examples 27 to 29 are examples in which the additive 9 is added. In all cases, the Eab value after contamination and after washing with water was low, and the antifouling property and self-cleaning were good.

Claims (9)

A curable composition containing a non-fluorine polymer and a fluorine-containing polymer.
The non-fluorine polymer is either an oxyalkylene polymer having a reactive silicon group represented by the following formula 1 or a (meth) acrylic acid ester polymer having a reactive silicon group represented by the following formula 1. Or both
The fluorine-containing polymer is any one of a repeating unit based on the first monomer, a repeating unit based on the second monomer, a repeating unit based on the third monomer, and a unit based on compound a. A polymer having one or both,
The first monomer is a (meth) acrylic acid ester having a polyfluoroalkyl group.
The second monomer is a monomer having a hydrophilic group and a polymerizable unsaturated group.
The third monomer is a monomer having both a reactive silicon group and a polymerizable unsaturated group represented by the following formula 1.
A curable composition in which compound a is a compound having both a reactive silicon group and a sulfanil group.
−SiX _a R _3-a formula 1
In the above formula 1, R is a monovalent organic group having 1 to 20 carbon atoms and represents an organic group other than a hydrolyzable group, X represents a hydroxyl group or a hydrolyzable group, and a is 1 to 3 It indicates an integer, and when a is 1, R may be the same or different from each other, and when a is 2 or 3, X may be the same or different from each other. The curable composition according to claim 1, wherein the content of the fluorine-containing polymer with respect to 100 parts by mass of the non-fluorine polymer is 0.1 to 20 parts by mass. The curable composition according to claim 1 or 2, wherein the fluorine-containing polymer has a number average molecular weight of 3,000 to 20,000. The curable composition according to any one of claims 1 to 3, wherein the ratio of fluorine atoms to the fluorine-containing polymer is 5 to 35% by mass. The curable composition according to any one of claims 1 to 4, wherein the second monomer contains a monomer represented by the following formula 2.
R ²⁰ −Z ²¹ − (CH ₂ CH ₂ O) _n R ²² Equation 2
In the above formula 2, R ²⁰ is CH ₂ = CH _2- , CH ₂ = CH _{2 -CH 2-} O-, CH ₂ = CR ^21- C (= O) O- or CH ₂ = CR ^21- OC ( = O) −, R ²² represents a hydrogen atom or a methyl group, and Z ²¹ represents a single bond or an alkylene group having 1 to 10 carbon atoms. R ²¹ is a hydrogen atom, a chlorine atom, a fluorine atom, or a linear or branched alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 24. The curable composition according to any one of claims 1 to 5, wherein the ratio of fluorine atoms to the curable composition is 0.1 to 15% by mass. The curable composition according to any one of claims 1 to 6, further containing an amine compound. A cured product of the curable composition according to any one of claims 1 to 7. The method for producing a curable composition according to any one of claims 1 to 7.
The first monomer, the second monomer, one or both of the third monomer and the compound a were reacted to obtain the fluorine-containing polymer.
A method for producing a curable composition, in which the fluorine-containing polymer and the non-fluorine polymer are mixed.