JP2023149215A - Polymerizable composition, polymer, polymer composition, surface treating agent, article and method for producing article - Google Patents

Abstract

To provide a polymerizable composition, a polymer and a polymer composition or the like suitable as a surface treating agent capable of forming a surface treatment layer having excellent slipperiness and antifouling properties to a base material.SOLUTION: There is provided a polymerizable composition which comprises: a polymerizable compound A having a bivalent or higher linking group, two or more polyalkylene oxide chains bonded to the bivalent or higher linking group and polymerizable group; and at least one polymerizable compound B selected from the group consisting of a polymerizable compound B1 having an organopolysiloxane structure and a polymerizable group and a polymerizable compound B2 having a linear alkyl group having 12 to 30 carbon atoms and a polymerizable group and comprises at least a polymerizable compound having a reactive silyl group. There is also provided its application.SELECTED DRAWING: None

Description

The present disclosure relates to polymerizable compositions, polymers, polymer compositions, surface treatment agents, articles, and methods of manufacturing articles.

In recent years, in order to improve performance such as appearance and visibility, there has been a demand for technology that makes it difficult for fingerprints to form on the surface of articles and technology that makes it easier to remove dirt. As a specific method, a method is known in which the surface of an article is subjected to surface treatment using a surface treatment agent.

For example, Patent Document 1 describes a specific organosilicon compound and/or its partially hydrolyzed condensate, water in an amount greater than the amount that can theoretically hydrolyze and condense it 100%, a vinyl group-containing alkoxysilane, a vinyl group-containing polysiloxane. A curable composition comprising a methacrylic ester and/or acrylic ester having a hydroxyl group, and a silicone-modified acrylic copolymer obtained by copolymerizing the methacrylic ester and/or acrylic ester. Are listed. Patent Document 2 describes a compound having an alkoxysilyl group (component (A)) and a compound having a urethane (meth)acrylate and/or isocyanurate group having two or more (meth)acryloyl groups in one molecule. Contains a functional (meth)acrylate (component (B)), the content of component (A) is more than 10% by weight based on the total solid content of the curable resin composition, and component (A) and component ( Curable resin compositions are described in which the amount of B) is 10 to 80% by weight relative to the total amount.

Japanese Patent Application Publication No. 9-111185 Japanese Patent Application Publication No. 2015-187205

On the other hand, compositions used as surface treatment agents and the like are required to be further improved in terms of water repellency and abrasion resistance.

The present disclosure has been made in view of the above circumstances, and the problem to be solved by an embodiment of the present invention is to form a surface treatment layer with excellent slipperiness and antifouling properties on a base material. An object of the present invention is to provide a polymerizable composition, a polymer, and a polymer composition useful as a surface treatment agent.
The problem to be solved by an embodiment of the present invention is to provide a surface treatment agent that can form a surface treatment layer with excellent slipperiness and antifouling properties on a base material.
An object of an embodiment of the present invention is to provide an article having a surface-treated layer with excellent slip properties and antifouling properties, and a method for manufacturing the same.

The present disclosure includes the following aspects.
<1>
A polymerizable compound A having a linking group with a valence of 2 or more, 2 or more polyalkylene oxide chains bonded to a linking group with a valence of 2 or more, and a polymerizable group;
At least one member selected from the group consisting of a polymerizable compound B1 having an organopolysiloxane structure and a polymerizable group, and a polymerizable compound B2 having a linear alkyl group having 12 to 30 carbon atoms and a polymerizable group. A polymerizable compound B,
A polymerizable composition containing at least a polymerizable compound having a reactive silyl group.
<2>
The polymerizable composition according to <1>, wherein the polymerizable compound A has a reactive silyl group.
<3>
The polymerizable composition according to <1> or <2>, further comprising a polymerizable compound C having a reactive silyl group.
<4>
The polymerizable composition according to any one of <1> to <3>, wherein the divalent or higher-valent linking group is a trivalent or higher-valent linking group.
<5>
The polymerizable composition according to <4>, wherein the trivalent or higher-valent linking group is a group obtained by removing a hydrogen atom from a hydroxyl group of a sugar alcohol.
<6>
The polymerizable composition according to any one of <1> to <5>, wherein the polyalkylene oxide chain is a polyethylene oxide chain.
<7>
The polymerizable composition according to <6>, wherein the polyethylene oxide chain has a repeating number of 3 to 15.
<8>
The polymerizable composition according to any one of <1> to <7>, wherein the mass ratio of the content of polymerizable compound A to the content of polymerizable compound B is 1.5 to 5.
<9>
The polymerizable composition according to any one of <1> to <8>, further comprising a liquid medium.
<10>
A surface treatment agent comprising the polymerizable composition according to any one of <1> to <9>.
<11>
A polymer obtained by a polymerization reaction of the polymerizable composition according to any one of <1> to <8>.
<12>
A polymer composition comprising the polymer according to <11> and a liquid medium.
<13>
A surface treatment agent containing the polymer according to <11>.
<14>
The surface treatment agent according to <13>, further comprising a liquid medium.
<15>
Manufacturing an article by subjecting a base material to surface treatment using the surface treatment agent described in <10>, <13>, or <14> to manufacture an article with a surface treatment layer formed on the base material. Method.
<16>
An article comprising a base material and a surface treatment layer disposed on the base material and surface treated with the surface treatment agent described in <10>, <13> or <14>.
<17>
The article according to <16>, which is an optical member.
<18>
The article according to <16>, which is a display or a touch panel.

According to one embodiment of the present invention, a polymerizable composition, a polymer, and a polymer composition useful as a surface treatment agent capable of forming a surface treatment layer with excellent slip properties and antifouling properties on a substrate. things are provided.
According to one embodiment of the present invention, a surface treatment agent capable of forming a surface treatment layer with excellent slip properties and antifouling properties on a base material is provided.
According to one embodiment of the present invention, an article having a surface-treated layer with excellent slip properties and antifouling properties, and a method for manufacturing the article are provided.

In the present disclosure, numerical ranges indicated using "~" include the numerical values written before and after "~" as minimum and maximum values, respectively.
In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. . Further, in the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with the value shown in the Examples.
In the present disclosure, the term "surface treated layer" refers to a layer formed on the surface of a base material by surface treatment.
In the present disclosure, a "polymerizable compound" means a compound having a polymerizable group.

[Polymerizable composition]
The polymerizable composition of the present disclosure comprises a polymerizable compound A having a linking group with a valence of 2 or more, 2 or more polyalkylene oxide chains bonded to the linking group with a valence of 2 or more, and a polymerizable group; At least one kind selected from the group consisting of a polymerizable compound B1 having a polysiloxane structure and a polymerizable group, and a polymerizable compound B2 having a linear alkyl group having 12 to 30 carbon atoms and a polymerizable group. and a polymerizable compound B, and includes at least a polymerizable compound having a reactive silyl group.

When the polymerizable composition of the present disclosure is used as a surface treatment agent, a surface treatment layer with excellent slip properties and antifouling properties can be formed by performing a polymerization reaction after surface treatment. Further, when the polymer obtained by the polymerization reaction of the polymerizable composition of the present disclosure is used as a surface treatment agent, a surface treatment layer with excellent slip properties and antifouling properties can be formed. Although the reason for this is not certain, it is assumed as follows.
In the polymerizable composition of the present disclosure, the polymerizable compound A has two or more polyalkylene oxide chains bonded to a divalent or higher-valent linking group, and has excellent hydrophilicity. Further, the polymerizable compound B has at least one type selected from the group consisting of an organopolysiloxane structure and a linear alkyl group having 12 to 30 carbon atoms, and has excellent hydrophobicity. Since the polymer obtained by the polymerization reaction of the polymerizable composition of the present disclosure contains a hydrophilic portion and a hydrophobic portion, it is considered to have excellent slip properties and antifouling properties.

The compositions described in Patent Document 1 and Patent Document 2 are polymerizable compounds having a divalent or higher valence linking group, two or more polyalkylene oxide chains bonded to the divalent or higher linking group, and a polymerizable group. Since it does not contain any compounds, it is thought that when used as a surface treatment agent, the slipperiness and antifouling properties of the surface treatment layer are insufficient.

Hereinafter, the polymerizable composition of the present disclosure will be explained in detail.

The polymerizable composition of the present disclosure includes a polymerizable compound A and a polymerizable compound B, and includes at least a polymerizable compound having a reactive silyl group.

In the polymerizable composition of the present disclosure, the number of polymerizable compounds having a reactive silyl group may be one, or two or more.

In the polymerizable composition of the present disclosure, in addition to polymerizable compound A and polymerizable compound B, a polymerizable compound having a reactive silyl group may be included. Furthermore, in the polymerizable composition of the present disclosure, at least one of the polymerizable compound A and the polymerizable compound B may be a polymerizable compound having a reactive silyl group. That is, at least one of the polymerizable compound A and the polymerizable compound B may have a reactive silyl group.

Specific embodiments of the polymerizable composition of the present disclosure include the following embodiments.

Aspect 1: A polymerizable composition containing a polymerizable compound A having a reactive silyl group and a polymerizable compound B having no reactive silyl group.
Aspect 2: A polymerizable composition containing a polymerizable compound A that does not have a reactive silyl group and a polymerizable compound B that has a reactive silyl group.
Aspect 3: A polymerizable composition containing a polymerizable compound A having a reactive silyl group and a polymerizable compound B having a reactive silyl group.
Aspect 4: A polymerizable composition containing a polymerizable compound A that does not have a reactive silyl group, a polymerizable compound B that does not have a reactive silyl group, and a polymerizable compound C that has a reactive silyl group.
Aspect 5: Polymerizable composition comprising a polymerizable compound A having a reactive silyl group, a polymerizable compound B not having a reactive silyl group, and a polymerizable compound C having a reactive silyl group Aspect 6: Reaction A polymerizable composition comprising a polymerizable compound A having no reactive silyl group, a polymerizable compound B having a reactive silyl group, and a polymerizable compound C having a reactive silyl group.
Aspect 7: A polymerizable composition comprising a polymerizable compound A having a reactive silyl group, a polymerizable compound B having a reactive silyl group, and a polymerizable compound C having a reactive silyl group.

In addition, the polymerizable compound C having a reactive silyl group means a polymerizable compound having a reactive silyl group and falling under neither the polymerizable compound A nor the polymerizable compound B. That is, the polymerizable compound C having a reactive silyl group has a reactive silyl group and has two or more polyalkylene oxide chains bonded to a divalent or higher linking group, an organopolysiloxane structure, and a carbon number of 12 It is a polymerizable compound that does not contain at least one kind selected from the group consisting of ~30 linear alkyl groups.
Hereinafter, "polymerizable compound C having a reactive silyl group" will also be simply referred to as "polymerizable compound C."

Among these, from the viewpoint of forming a surface treatment layer with excellent slip properties and antifouling properties, an embodiment in which the polymerizable compound A has a reactive silyl group is preferable for the polymerizable composition of the present disclosure. Moreover, from the viewpoint of forming a surface treatment layer with excellent slip properties and antifouling properties, it is preferable that the polymerizable composition of the present disclosure further contains a polymerizable compound C having a reactive silyl group.

In particular, the polymerizable composition of the present disclosure is preferably the polymerizable composition shown in Aspect 1 or Aspect 4 above.

A reactive silyl group means a group in which a reactive group is bonded to a Si atom (silicon atom). The reactive group is preferably a hydrolyzable group or a hydroxyl group.

Hydrolyzable means a group that becomes a hydroxyl group through a hydrolysis reaction. That is, the hydrolyzable silyl group represented by Si-L becomes a silanol group represented by Si-OH through a hydrolysis reaction. The silanol groups further react among themselves to form Si--O--Si bonds. Further, the silanol group can undergo a dehydration condensation reaction with a silanol group derived from an oxide present on the surface of the base material to form a Si--O--Si bond. Examples of the hydrolyzable group include an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an acyloxy group, and an isocyanato group (-NCO). The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms. However, the aryl group of the aryloxy group includes a heteroaryl group. The halogen atom is preferably a chlorine atom. The acyl group is preferably an acyl group having 1 to 6 carbon atoms. The acyloxy group is preferably an acyloxy group having 1 to 6 carbon atoms.

From the viewpoint of easy production of a uniform film and excellent durability, the reactive silyl group is preferably an alkoxysilyl group or a trichlorosilyl group. From the viewpoint of ease of handling by-products generated in the reaction with the base material, the reactive silyl group is more preferably an alkoxysilyl group. Among these, the alkoxysilyl group is preferably a dialkoxysilyl group or a trialkoxysilyl group, and more preferably a trialkoxysilyl group.

The number of reactive silyl groups contained in the polymerizable compound having reactive silyl groups is 1 or more, and from the viewpoint of further improving the abrasion resistance of the surface treatment layer, the number is preferably 1 to 18, and more preferably 1 to 12. Preferably, 1 to 8 are more preferable.

When the polymerizable compound A has a reactive silyl group, the number of reactive silyl groups contained in the polymerizable compound A is 1 or more, and from the viewpoint of further improving the abrasion resistance of the surface treatment layer, the number is 2 to 12. is preferable, 2 to 10 is more preferable, and 2 to 8 is even more preferable.

When the polymerizable composition of the present disclosure contains the polymerizable compound C, the number of reactive silyl groups contained in the polymerizable compound C is 1 or more, and from the viewpoint of further improving the abrasion resistance of the surface treatment layer, 1 to 8 are preferred, 1 to 6 are more preferred, and 1 to 3 are even more preferred.

As the reactive silyl group, a group represented by the following formula A is preferable.

-Si(R ¹ ) _n L _3-n ... (A)
R ¹ is each independently a hydrocarbon group, L is each independently a hydrolyzable group or a hydroxyl group, and n is an integer from 0 to 2.

When there is a plurality of reactive silyl groups in one molecule, the plurality of reactive silyl groups may be the same or different from each other. From the viewpoint of easy availability of raw materials and ease of manufacturing the compound, it is preferable that the plurality of reactive silyl groups are the same.

Each R ¹ is independently a hydrocarbon group, preferably a saturated hydrocarbon group. The number of carbon atoms in R ¹ is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2.

As the hydrolyzable group, those mentioned above are preferred.

Among these, L is preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom from the viewpoint of ease of manufacturing the compound. L is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an ethoxy group or a methoxy group, since there is less outgassing during coating and the storage stability of the compound is better.

n is an integer of 0 to 2, preferably 0 or 1, and more preferably 0. The presence of a plurality of L's makes the adhesion of the surface treatment layer to the base material stronger.
When n is 1 or less, the plurality of L's present in one molecule may be the same or different from each other. From the viewpoint of ease of obtaining raw materials and ease of manufacturing the compound, it is preferable that the plurality of L's are the same. When n is 2, a plurality of R ^1s present in one molecule may be the same or different from each other. From the viewpoint of easy availability of raw materials and ease of manufacturing the compound, it is preferable that a plurality of R ¹ 's are the same.

<Polymerizable compound A>
The polymerizable composition of the present disclosure includes a polymerizable compound A having a divalent or higher-valent linking group, two or more polyalkylene oxide chains bonded to the divalent or higher-valent linking group, and a polymerizable group. Hereinafter, the divalent or higher-valent linking group contained in the polymerizable compound A will be described as a "linking group T."

Polymerizable compound A is a compound in which a polyalkylene oxide chain is bonded to the linking group T and a polymerizable group is directly bonded to the polyalkylene oxide chain, from the viewpoint of forming a surface treatment layer with excellent slip properties and antifouling properties. Alternatively, it is preferably a compound in which a polyalkylene oxide chain and a polymerizable group are bonded via a linking group (different from the above linking group T).

The number of polymerizable compounds A contained in the polymerizable composition of the present disclosure may be one, or two or more.

The linking group T contained in the polymerizable compound A is a linking group with a valence of 2 or more, and is preferably a linking group with a valence of 3 or more from the viewpoint of forming a surface treatment layer with excellent slip properties and antifouling properties. Although the upper limit of the valence of the linking group T is not particularly limited, it is preferably 8 from the viewpoint of easy availability of raw materials.

The linking group T included in the polymerizable compound A is not particularly limited, but is preferably a polyhydric alcohol residue from the viewpoint of ease of bonding with a polyalkylene oxide chain.

In the present disclosure, a polyhydric alcohol residue refers to a group obtained by removing hydrogen atoms from all hydroxyl groups contained in a polyhydric alcohol. Similarly, regarding specific examples of polyhydric alcohol residues, it means a group obtained by removing hydrogen atoms from all hydroxyl groups included in the specific examples of polyhydric alcohol residues.
For example, a glycerin residue is represented by -OCH ₂ -CH(-O-)-CH ₂ O-.

Among these, the polyhydric alcohol residue is more preferably a sugar alcohol residue from the viewpoint of forming a surface treatment layer with excellent slip properties and antifouling properties.

Examples of sugar alcohols include C ₃ H ₅ (OH) ₃ (glycerin), C ₄ H ₆ (OH) ₄ (erythritol, D-threitol, L-threitol), C ₅ H ₇ (OH) ₅ ( xylitol, D-arabinitol, L-arabinitol, ribitol), C ₆ H ₈ (OH) ₆ (sorbitol, mannitol, D-iditol, galactitol), C ₇ H ₉ (OH) ₇ (boremitol, perseitol), and C ₈ H ₁₀ (OH) ₈ (D-erythro-D-galacto-octitol). Examples of sugar alcohol residues include groups obtained by removing hydrogen atoms from all hydroxyl groups contained in the sugar alcohol.

Among these, the sugar alcohol residue is preferably a glycerin residue, an erythritol residue, a xylitol residue, or a sorbitol residue.

The polyalkylene oxide chain contained in the polymerizable compound A is bonded to the linking group T. Moreover, the number of polyalkylene oxide chains contained in the polymerizable compound A is 2 or more.

For example, when the linking group T included in the polymerizable compound A is a divalent linking group, a polyalkylene oxide chain is bonded to each of the two bonds in the linking group T. In this case, since the polymerizable group cannot be bonded to the linking group T, the polymerizable group is attached to the end of the polyalkylene oxide chain opposite to the side bonded to the linking group T, either directly or through another linking group. are combined.

For example, when the linking group T included in the polymerizable compound A is a trivalent or higher-valent linking group, a polyalkylene oxide chain is bonded to each of two or more bonds among the three or more bonds in the linking group T. ing. That is, when the linking group T included in the polymerizable compound A is a trivalent or higher valent linking group, a polyalkylene oxide chain may be bonded to each of all the bonds in the linking group T, and one A polyalkylene oxide chain may be bonded to each bond (however, two or more bonds) of the moiety.

Among these, from the viewpoint of forming a surface-treated layer with excellent slip properties and antifouling properties, it is preferable that a polyalkylene oxide chain is bonded to each of all the bonds in the linking group T.

The two or more polyalkylene oxide chains may be the same or different from each other. From the viewpoint of ease of synthesis, two or more polyalkylene oxide chains are preferably the same.

The polyalkylene oxide chain is represented by the following formula B.
(XO) _m ...(B)

In formula B, each X independently represents an alkylene group.

The number of carbon atoms in the alkylene group is preferably 1 to 6, more preferably 2 to 4, from the viewpoint of improving the water repellency and abrasion resistance of the surface treatment layer.
The alkylene group may be linear, branched, or cyclic.

Specific examples of (XO) include -CH ₂ O-, -C ₂ H ₄ O-, -C ₃ H ₆ O-, -C ₄ H ₈ O-, -C ₅ H ₁₀ O-, -C ₆ H ₁₂ O-, -CH(CH ₃ )CH ₂ O-, -CH(CH ₃ )CH ₂ CH ₂ O-, -cycloC ₄ H ₆ -O-, -cycloC ₅ H ₈ -O-, and -cycloC ₆ H ₁₀ -O- is mentioned.
Here, -cycloC ₄ H ₆ - means a cyclobutanediyl group. Examples of the cyclobutanediyl group include a cyclobutane-1,2-diyl group and a cyclobutane-1,3-diyl group. -cycloC ₅ H ₈ - means a cyclopentanediyl group. Examples of the cyclopentanediyl group include a cyclopentane-1,2-diyl group and a cyclopentane-1,3-diyl group. -cycloC ₆ H ₁₀ - means a cyclohexanediyl group. Examples of the cyclohexanediyl group include a cyclohexane-1,2-diyl group, a cyclohexane-1,3-diyl group, and a cyclohexane-1,4-diyl group.

The repeating number m of (XO) is an integer of 2 or more, more preferably an integer of 2 to 200, even more preferably an integer of 5 to 150, particularly preferably an integer of 5 to 100, most preferably an integer of 7 to 50. preferable. In each of the two or more polyalkylene oxide chains, the repeating number m of (XO) is preferably within the above range.

(XO) _m may contain two or more types of (XO).
The bonding order of two or more types of (XO) is not limited, and may be arranged randomly, alternately, or in blocks.
Containing two or more types of (XO) means that there are two or more types of (XO) with different numbers of carbon atoms in the compound, and even if the number of carbon atoms is the same, there is a difference in the presence or absence of a side chain or the presence or absence of a side chain. This refers to the presence of two or more types of (XO) that differ in type (for example, number of side chains, number of carbon atoms in side chains, etc.).
Regarding the arrangement of two or more types of (XO), for example, the structure represented by {(CH ₂ O) _m21 (C ₂ H ₄ O) _m22 } has m21 (CH ₂ O) and m22 ( C ₂ H ₄ O) are randomly arranged. Furthermore, the structure represented by (C ₂ H ₄ O-C ₃ H ₆ O) _m25 has m25 (C ₂ H ₄ O) and m25 (C ₃ H ₆ O) arranged alternately. represents that

Among them, (XO) _m is [(CH ₂ O) _m11 (C ₂ H ₄ O) _{m 12} (OC ₃ H ₆ ) _{m 13} (OC ₄ H ₈ ) _{m 14} (C ₅ H ₁₀ O) _{m 15}・(C ₆ H ₁₂ O) _m16 (cycloC ₄ H ₆ -O) _m17 (cycloC ₅ H ₈ -O) _m18 (cycloC ₆ H ₁₀ -O) _m19 ] is preferred.
m11, m12, m13, m14, m15, m16, m17, m18 and m19 are each independently an integer of 0 or more, preferably 100 or less.
m11 + m12 + m13 + m14 + m15 + m16 + m17 + m18 + m19 is an integer of 2 or more, more preferably an integer of 2 to 200, more preferably an integer of 5 to 150, even more preferably an integer of 5 to 100, particularly preferably an integer of 7 to 50.

m12 is preferably an integer of 2 or more, particularly preferably an integer of 2 to 200.
In addition, C ₃ H ₆ , C ₄ H ₈ , C ₅ H ₁₀ , and C ₆ H ₁₂ may be linear or branched, but the wear resistance of the surface treatment layer From the viewpoint of improving the properties, a straight chain is preferable.

Note that the above formula represents the type and number of units, but does not represent the arrangement of the units. That is, m11 to m19 represent the number of units; for example, (CH ₂ O) _m11 does not represent a block containing m11 consecutive (CH ₂ O) units. Similarly, the order in which (CH ₂ O) to (cycloC ₆ H ₁₀ -O) are written does not indicate that they are arranged in the order in which they are written.
In the above formula, when two or more of m11 to m19 are not 0 (that is, when (XO) _m is composed of two or more types of units), the arrangement of different units can be random arrangement, alternating arrangement, block arrangement, Any combination of these sequences may be used.

(XO) _m preferably has the following structure.
(C ₂ H ₄ O) _m21 ,
(C ₃ H ₆ O) _m22 ,
(C ₂ H ₄ O) _m23 (C ₃ H ₆ O) _m24 ,
(C ₂ H ₄ O-C ₃ H ₆ O) _m25 .
However, m21 is an integer of 2 or more, m22 is an integer of 2 or more, m23 and m24 are each independently an integer of 1 or more, m25 is an integer of 1 or more, and m26 and m27 are each an integer of 1 or more. independently an integer greater than or equal to 1;

Among them, from the viewpoint of forming a surface treatment layer with excellent slip properties and antifouling properties, it is more preferable that (XO) _m has a structure of (C ₂ H ₄ O) _m21 . That is, the polyalkylene oxide chain is more preferably a polyethylene oxide chain. More preferably, both of the two or more polyalkylene oxide chains are polyethylene oxide chains.

From the viewpoint of forming a surface treatment layer with excellent slip properties and antifouling properties, the polyethylene oxide chain preferably has a repeating number of 3 to 15, more preferably 7 to 12.

The polymerizable group contained in the polymerizable compound A may be a cationically polymerizable group or a radically polymerizable group. From the viewpoint of excellent curability, the polymerizable group is preferably a radically polymerizable group. Moreover, from the viewpoint of excellent curability, the radically polymerizable group is preferably an ethylenically unsaturated group, and more preferably a (meth)acryloyl group.

The number of polymerizable groups contained in the polymerizable compound A may be only one, or two or more.

Specifically, as the polymerizable compound A having no reactive silyl group, a compound represented by the following formula 1 is preferable.

T-(A-R-B) _k (1)
In formula 1, T is the above linking group T, A is each independently a polyalkylene oxide chain, R is a single bond or a linking group, B is a polymerizable group, and k is 2 or more is an integer.

Preferred embodiments of the linking group T, polyalkylene oxide chain, and polymerizable group in Formula 1 are as described above.

In Formula 1, k is preferably an integer of 3 or more from the viewpoint of forming a surface treated layer with excellent slip properties and antifouling properties. The upper limit of k is not particularly limited, but is preferably 8 from the viewpoint of forming a surface treated layer with excellent smoothness.

In formula 1, from the viewpoint of ease of synthesis, the terminal of the connecting group represented by R on the side connected to A is preferably -CO-NH-.

In addition, when the polymerizable compound A has a reactive silyl group, the bonding position of the reactive silyl group contained in the polymerizable compound A is not particularly limited, but from the viewpoint of forming a surface treatment layer with excellent slip properties and antifouling properties. Therefore, it is preferable that the reactive silyl group is directly bonded to the polyalkylene oxide chain or bonded to the polyalkylene oxide chain via a linking group (different from the above linking group T).

Specifically, as the polymerizable compound A having a reactive silyl group, a compound represented by the following formula 2 is preferable.

T-(A ¹¹ -R ¹¹ -B) _k1 (A ¹² -R ¹² -G) _k2 (2)
In formula 2, T is the above linking group T, A ¹¹ and A ¹² are each independently a polyalkylene oxide chain, R ¹¹ and R ¹² are each independently a single bond or a linking group, and B is a polymerizable group, G is a reactive silyl group, and k1 and k2 are each independently an integer of 1 or more.
In addition, in Formula 2, A ¹¹ and A ¹² are each bonded to T.

Preferred embodiments of the linking group T, polyalkylene oxide chain, polymerizable group, and reactive silyl group in Formula 2 are as described above.

In formula 2, k1 is preferably an integer of 1 to 6 from the viewpoint of forming a surface-treated layer with excellent polymerizability and smoothness.
In Formula 2, k2 is an integer of 1 or more from the viewpoint of forming a surface treated layer with excellent slip properties and antifouling properties. The upper limit of k2 is not particularly limited, but is preferably 7 from the viewpoint of forming a surface treated layer with excellent smoothness.
In Formula 2, k1+k2 is preferably an integer of 2 or more from the viewpoint of forming a surface treated layer with excellent slip properties and antifouling properties. The upper limit of k1+k2 is not particularly limited, but is preferably 8 from the viewpoint of forming a surface treated layer with excellent smoothness.

In Formula 2, the connecting group represented by R ¹¹ is preferably -CO-NH- at the end connected to A ¹¹ from the viewpoint of ease of synthesis. From the viewpoint of ease of synthesis, the linking group represented by R ¹² preferably has a -CO-NH- terminal on the side connected to A ¹² .

In formula 2, the polyalkylene oxide chains represented by A ¹¹ and A ¹² may be the same or different, but from the viewpoint of ease of synthesis, they are preferably the same.

Polymerizable compound A having no reactive silyl group can be produced, for example, by the following method.

First, an alkylene oxide adduct of a polyhydric alcohol is prepared. The alkylene oxide adduct of polyhydric alcohol may be a commercially available product, or may be produced by ring-opening polymerization of alkylene oxide to polyhydric alcohol.

Next, the alkylene oxide adduct of polyhydric alcohol is reacted with, for example, a compound having a functional group that can react with a hydroxyl group and a polymerizable group. Thereby, polymerizable compound A is obtained.

Examples of the compound having a functional group capable of reacting with a hydroxyl group and a polymerizable group include a compound having an isocyanate group and a polymerizable group, and a compound having an epoxy group and a polymerizable group.

Examples of compounds having an isocyanate group and a polymerizable group include 2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate, and 2-(2- Methacryloyloxyethyloxy)ethyl isocyanate is mentioned.

Examples of compounds having an epoxy group and a polymerizable group include glycidyl (meth)acrylate, epoxycyclohexyl (meth)acrylate, 1,3-butadiene monoepoxide, and 1,2-epoxy-4-vinylcyclohexane. .

Moreover, polymerizable compound A can be obtained by reacting an alkylene oxide adduct of a polyhydric alcohol with (meth)acrylic acid, (meth)acrylic acid chloride, or (meth)acrylic acid anhydride. .

Furthermore, a polymerizable compound A can be obtained by reacting an alkylene oxide adduct of a polyhydric alcohol with a diisocyanate and then reacting it with a compound having a hydroxyl group and a polymerizable group.

Examples of the diisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, and octamethylene. Aliphatic diisocyanates such as diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate;
m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, toridine diisocyanate, 1,4-naphthalene diisocyanate, 1,5 - Aromatic diisocyanates such as naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, metaxylylene diisocyanate, paraxylylene diisocyanate, tetramethylxylylene diisocyanate;
Examples include alicyclic diisocyanates such as hydrogenated xylylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane 4,4'-diisocyanate.

Examples of compounds having a hydroxyl group and a polymerizable group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, -hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

When producing a polymerizable compound A having a reactive silyl group, for example, a compound having a functional group that can react with a hydroxyl group and a reactive silyl group is reacted with an alkylene oxide adduct of a polyhydric alcohol. Then, a compound having a functional group capable of reacting with a hydroxyl group and a polymerizable group is reacted. A polymerizable compound A having a reactive silyl group can be obtained by controlling the amount of the compound having a functional group capable of reacting with a hydroxyl group and a reactive silyl group added to the alkylene oxide adduct of a polyhydric alcohol.

Examples of compounds having a functional group capable of reacting with a hydroxyl group and a reactive silyl group include 2-isocyanatoethyltrimethoxysilane, 2-isocyanatoethyltriethoxysilane, 2-isocyanatoethyldimethoxymonomethylsilane, -isocyanatoethylmonomethoxydimethylsilane, 2-isocyanatoethyldiethoxymonoethylsilane, 2-isocyanatoethylmonoethoxydiethylsilane,
3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyldimethoxymonomethylsilane, 3-isocyanatopropylmonomethoxydimethylsilane, 3-isocyanatopropyldiethoxymonoethylsilane, 3- isocyanatopropylmonoethoxydiethylsilane,
4-isocyanatobutyltrimethoxysilane, 4-isocyanatobutyltriethoxysilane, 4-isocyanatobutyldimethoxymonomethylsilane, 4-isocyanatobutylmonomethoxydimethylsilane, 4-isocyanatobutyldiethoxymonoethylsilane, and 4-isocyanatobutyltrimethoxysilane. -isocyanatobutylmonoethoxydiethylsilane.

The proportion of polymerizable compound A in all polymerizable compounds contained in the polymerizable composition of the present disclosure is preferably 50% to 85% by mass, more preferably 60% to 75% by mass.

Note that all the polymerizable compounds contained in the polymerizable composition of the present disclosure mean all compounds having a polymerizable group, and include polymerizable compound A and polymerizable compound B, and in some cases, polymerizable compound A. and polymerizable compounds other than polymerizable compound B (for example, polymerizable compound C).

<Polymerizable compound B>
The polymerizable composition of the present disclosure comprises a polymerizable compound B1 having an organopolysiloxane structure and a polymerizable group, and a polymerizable compound B2 having a linear alkyl group having 12 to 30 carbon atoms and a polymerizable group. It contains at least one kind of polymerizable compound B selected from the group consisting of:

The number of polymerizable compounds B1 and B2 contained in the polymerizable composition of the present disclosure may be one, or two or more.

The polymerizable group contained in the polymerizable compound B1 may be a cationically polymerizable group or a radically polymerizable group. From the viewpoint of excellent curability, the polymerizable group is preferably a radically polymerizable group. Moreover, from the viewpoint of excellent curability, the radically polymerizable group is preferably an ethylenically unsaturated group, and more preferably a (meth)acryloyl group.

The number of polymerizable groups contained in the polymerizable compound B1 may be only one, or may be two or more.

Examples of the organopolysiloxane structure contained in the polymerizable compound B1 include structures represented by the following formulas P1 to P3.

In formulas P1 to P3, R ³ is each independently a hydrocarbon group.
In formula P1, s1 is an integer of 1 or more.
In formula P2, s2 and s3 are each independently an integer of 1 or more.
In formula P3, s4 is an integer from 1 to 3.

Examples of the hydrocarbon group represented by R ³ include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Among these, the hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. The alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, but a linear alkyl group is preferable, and a methyl group, ethyl group, n-propyl group, or n -butyl group is more preferred, and methyl group is even more preferred.

s1 is an integer of 1 or more, preferably from 5 to 250, more preferably from 10 to 200.

s2 is an integer of 1 or more, preferably from 2 to 5, more preferably from 2 to 3.

s3 is an integer of 1 or more, preferably from 5 to 250, more preferably from 10 to 200.

s4 is an integer from 1 to 3, preferably from 1 to 2.

Among these, from the viewpoint of forming a surface treatment layer with excellent slipperiness and antifouling properties, the organopolysiloxane structure is preferably a structure represented by formula P1.

Examples of the polymerizable compound B1 include polydimethylsiloxane having a methacryloyl group at one end (product name "X-22-174BX", manufactured by Shin-Etsu Chemical Co., Ltd., number of repeating units: 29.1), and a methacryloyl group at both ends. Examples include polydimethylsiloxanes (product names: "Siraplane FM-7711", "Silaprane FM-7721", "Silaprane FM-7725", manufactured by JNC Corporation).

In addition, when the polymerizable compound B1 has a reactive silyl group, the bonding position of the reactive silyl group contained in the polymerizable compound B1 is not particularly limited, but the reactive silyl group is bonded to one end of the organopolysiloxane structure. However, it is preferable that a polymerizable group is bonded to the other end.

Examples of the polymerizable compound B1 having a reactive silyl group include polydimethylsiloxane having a methacryloyl group at one end and an alkoxylyl group at the other end.

The polymerizable group contained in the polymerizable compound B2 may be a cationically polymerizable group or a radically polymerizable group. From the viewpoint of curability, the polymerizable group is preferably a radically polymerizable group. Further, from the viewpoint of curability, the radically polymerizable group is preferably an ethylenically unsaturated group, and more preferably a (meth)acryloyl group.

The number of polymerizable groups contained in the polymerizable compound B2 may be only one, or may be two or more.

The linear alkyl group contained in the polymerizable compound B2 has 12 to 30 carbon atoms, preferably 14 to 28 carbon atoms, and more preferably 16 to 26 carbon atoms.

Examples of the polymerizable compound B2 include dodecyl (meth)acrylate [also known as lauryl (meth)acrylate], tetradecyl (meth)acrylate [also known as myristyl (meth)acrylate], hexadecyl (meth)acrylate, and octadecyl (meth)acrylate. [Also known as: stearyl (meth)acrylate], eicosyl (meth)acrylate, and docosyl (meth)acrylate [also known as: behenyl (meth)acrylate].

The proportion of polymerizable compound B in all polymerizable compounds contained in the polymerizable composition of the present disclosure is preferably 15 to 50% by mass, more preferably 25 to 40% by mass.

From the viewpoint of forming a surface treatment layer with excellent slip properties and antifouling properties, the mass ratio of the content of polymerizable compound A to the content of polymerizable compound B is preferably 1.5 to 5, and 1. More preferably, it is 8 to 3.2.

<Polymerizable compound C>
When the polymerizable composition of the present disclosure includes a polymerizable compound C, the polymerizable group contained in the polymerizable compound C may be a cationically polymerizable group or a radically polymerizable group. From the viewpoint of excellent curability, the polymerizable group is preferably a radically polymerizable group. Moreover, from the viewpoint of excellent curability, the radically polymerizable group is preferably an ethylenically unsaturated group, and more preferably a (meth)acryloyl group.

Specifically, as the polymerizable compound C, a compound represented by the following formula 3 is preferable.

(B ¹ ) _k3 −R ² −(G ¹ ) _k4 (1)
In formula 1, B ¹ is each independently a polymerizable group, G ¹ is each independently a reactive silyl group, R ² is a single bond or a (k3+k4)-valent linking group, and k ³ and k ⁴ are each independently an integer of 1 or more.

Preferred embodiments of the polymerizable group and the reactive silyl group in Formula 3 are as described above.

In Formula 3, k3 is preferably an integer of 1 to 6, more preferably an integer of 1 to 2.
In Formula 3, k4 is preferably an integer of 1 to 6, more preferably an integer of 1 to 2.
In Formula 3, k3+k4 is preferably an integer of 2 to 12, more preferably an integer of 2 to 4.

In formula 3, the (k3+k4)-valent linking group represented by R ² is preferably a divalent linking group from the viewpoint of easy availability. The divalent linking group is preferably a divalent hydrocarbon group, more preferably an alkylene group, and even more preferably an alkylene group having 1 to 6 carbon atoms.

Examples of the polymerizable compound C include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl Examples include diethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

Among them, from the viewpoint of excellent curability, polymerizable compounds C include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxy. Silane or 3-acryloxypropyltrimethoxysilane is preferable, and 3-methacryloxypropyltrimethoxysilane is more preferable.

When the polymerizable composition of the present disclosure includes a polymerizable compound C, the proportion of the polymerizable compound C in all polymerizable compounds contained in the polymerizable composition of the present disclosure is 1% by mass to 10% by mass. is preferable, and 2% by weight to 8% by weight is more preferable.

The polymerizable composition of the present disclosure contains a polymerizable compound A and a polymerizable compound B, and only needs to contain a polymerizable compound having a reactive silyl group, and other than the polymerizable compound A and the polymerizable compound B. It may contain ingredients.

Preferably, the polymerizable composition of the present disclosure further includes a liquid medium. When containing a liquid medium, the polymerizable composition of the present disclosure only needs to be liquid, and may be a solution or a dispersion.

The total content of all polymerizable compounds contained in the polymerizable composition of the present disclosure is preferably 0.01 to 60% by mass, and 0.1 to 40% by mass, based on the total amount of the polymerizable composition of the present disclosure. % is more preferable, and 1 to 20% by mass is even more preferable.

Examples of liquid media include water and organic solvents. Among these, the liquid medium is preferably an organic solvent.

When the liquid medium is water, it is preferable that the polymerizable compound is dispersed with a surfactant. As the surfactant, a surfactant containing no fluorine atoms is preferred. Specifically, the surfactant is preferably an anionic surfactant, a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant that does not contain a fluorine atom.

Examples of organic solvents include compounds consisting only of hydrogen atoms and carbon atoms, and compounds consisting only of hydrogen atoms, carbon atoms, and oxygen atoms. Specifically, examples include hydrocarbon-based organic solvents, ketone-based organic solvents, and ethers. Examples include organic solvents based on organic solvents, organic solvents based on esters, organic solvents based on glycol, and organic solvents based on alcohol.

Specific examples of hydrocarbon organic solvents include hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene.
Specific examples of ketone organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
Specific examples of ether organic solvents include diethyl ether and tetrahydrofuran.
Specific examples of ester organic solvents include ethyl acetate and butyl acetate.
Specific examples of glycol organic solvents include ethylene glycol, ethylene glycol dimethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene Examples include glycol monobutyl ether acetate, diethylene glycol, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether pentane, dipropylene glycol, dipropylene glycol monomethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and tripropylene glycol.
Specific examples of alcoholic organic solvents include methanol, ethanol, 1-propanol, isopropyl alcohol, n-butanol, diacetone alcohol, and 3-methoxy-3-methyl-1-butanol.

Furthermore, examples of the organic solvent include halogenated organic solvents, nitrogen-containing compounds, and sulfur-containing compounds.
Specific examples of halogenated organic solvents include dichloromethane, chloroform, carbon tetrachloride, and dichloroethane.
Specific examples of nitrogen-containing compounds include nitrobenzene, acetonitrile, benzonitrile, dimethylformamide, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide.
Specific examples of sulfur-containing compounds include carbon disulfide and dimethyl sulfoxide.

The content of the liquid medium is preferably 40 to 99.99% by mass, more preferably 60 to 99.9% by mass, and even more preferably 80 to 99% by mass, based on the total amount of the polymerizable composition of the present disclosure.

It is preferable that the polymerizable composition of the present disclosure further contains a polymerization initiator. The type of polymerization initiator is not particularly limited, and examples thereof include known polymerization initiators.

The content of the polymerization initiator is preferably 0.1 to 10% by mass, and 0.2 to 5% by mass, based on the total content of all polymerizable compounds contained in the polymerizable composition of the present disclosure. % is more preferable.

In addition to the above-mentioned components, the polymerizable composition of the present disclosure may contain other components as long as the effects of the present disclosure are not impaired.
Other components include, for example, a polymerizable compound that does not have a reactive silyl group (excluding polymerizable compound A and polymerizable compound B), an acid catalyst that promotes the hydrolysis and condensation reaction of the reactive silyl group, Basic catalyst, non-fluorinated polymer, crosslinking agent, penetrating agent, antifoaming agent, film forming aid, insect repellent, fungicide, preservative, flame retardant, antistatic agent, anti-wrinkle agent, softener, pH Known additives such as regulators may be used.

Further, other components include metal compounds having a hydrolyzable group (hereinafter, metal compounds having a hydrolyzable group are also referred to as "specific metal compounds"). When the composition of the present disclosure contains a specific metal compound, the slipperiness and antifouling properties of the surface treatment layer can be further improved. Specific metal compounds include the following formulas (M1) and (M2).

M(X ^b1 ) _m1 (X ^b2 ) _m2 (X ^b3 ) _m3 ...(M1)
Si(X ^b4 )(X ^b5 ) ₃ ...(M2)

In formula (M1),
M represents a trivalent or tetravalent metal atom.
Each of X ^b1 independently represents a hydrolyzable group.
Each of X ^b2 independently represents a siloxane skeleton-containing group.
Each of X ^b3 independently represents a hydrocarbon chain-containing group.
m1 is an integer from 2 to 4,
m2 and m3 are each independently an integer of 0 to 2,
When M is a trivalent metal atom, m1+m2+m3 is 3, and when M is a tetravalent metal atom, m1+m2+m3 is 4.

In formula (M2),
X ^b4 represents a hydrolyzable silane oligomer residue.
Each of X ^b5 independently represents a hydrolyzable group or an alkyl group having 1 to 4 carbon atoms.

In formula (M1), the metal represented by M also includes semimetals such as Si and Ge. M is preferably a trivalent metal or a tetravalent metal, more preferably Al, Fe, In, Hf, Si, Ti, Sn, and Zr, even more preferably Al, Si, Ti, and Zr, and particularly preferably Si. .

In formula (M1), the hydrolyzable group represented by X ^b1 is the same as the hydrolyzable group represented by L in [-Si(R ¹ ) _n L _3-n ] in the above reactive silyl group. Examples include:
In formula (M1), the total number of hydrolyzable groups represented by X ^b1 is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Further, the number of the hydrolyzable groups is preferably 4 or less.

The siloxane skeleton-containing group represented by X ^b2 has a siloxane unit (-Si-O-) and may be linear or branched. The siloxane unit is preferably a dialkylsilyloxy group, such as a dimethylsilyloxy group or a diethylsilyloxy group. The number of repeating siloxane units in the siloxane skeleton-containing group is 1 or more, preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 to 3.
The siloxane skeleton-containing group may include a divalent hydrocarbon group in a part of the siloxane skeleton. Specifically, some oxygen atoms in the siloxane skeleton may be replaced with divalent hydrocarbon groups. Examples of the divalent hydrocarbon group include alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group.
A hydrolyzable group, a hydrocarbon group (preferably an alkyl group), etc. may be bonded to the terminal silicon atom of the siloxane skeleton-containing group.
The number of elements in the siloxane skeleton-containing group is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less. The number of elements is preferably 10 or more.
The siloxane skeleton-containing group is preferably a group represented by ^* -(O-Si(CH ₃ ) ₂ ) _n CH ₃ , where n is an integer from 1 to 5, and * represents a bond with an adjacent atom. Represents a part.

The hydrocarbon chain-containing group represented by X ^b3 may be a group consisting only of a hydrocarbon chain, or may be a group having an etheric oxygen atom between carbon atoms of the hydrocarbon chain. The hydrocarbon chain may be straight or branched, preferably straight. The hydrocarbon chain may be a saturated hydrocarbon chain or an unsaturated hydrocarbon chain, with a saturated hydrocarbon chain being preferred. The number of carbon atoms in the hydrocarbon chain-containing group is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. The hydrocarbon chain-containing group is preferably an alkyl group, more preferably a methyl group, an ethyl group, or a propyl group.

It is preferable that m1 is 3 or 4.

In formula (M2), the number of silicon atoms contained in the hydrolyzable silane oligomer residue represented by X ^b4 is preferably 3 or more, more preferably 5 or more, and even more preferably 7 or more. The number of silicon atoms is preferably 15 or less, more preferably 13 or less, and even more preferably 10 or less.
The hydrolyzable silane oligomer residue may have an alkoxy group bonded to a silicon atom. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, and methoxy group and ethoxy group are preferred. The hydrolyzable silane oligomer residue may have one or more types of these alkoxy groups, and preferably has one type.
Examples of the hydrolyzable silane oligomer residue include (C ₂ H ₅ O) ₃ Si-(OSi(OC ₂ H ₅ ) ₂ ) ₄ O- ^* and the like. Here, * represents a bonding site with an adjacent atom.

In formula ( ^M2 ), the hydrolyzable group represented by cyano group; allyl group; and isocyanate group, with alkoxy group being preferred, and ethoxy group, methoxy group, and isocyanate group being more preferred.
As X ^b3 , a hydrolyzable group is preferable.

Among the specific metal compounds, when M is Si, compounds represented by the formula (M1) include compounds represented by the following formulas (M1-1) to (M1-5). In the formula, each X ^b1 independently represents a hydrolyzable group. Among these, the compound represented by formula (M1-1) is preferred. As the compound represented by formula (M1-1), tetraethoxysilane, tetramethoxysilane, and triethoxymethylsilane are preferred.
X ^b5 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.

Si(X ^b1 ) ₄ ...(M1-1)
CH ₃ -Si(X ^b1 ) ₃ ...(M1-2)
C ₂ H ₅ -Si(X ^b1 ) ₃ ...(M1-3)
n-C ₃ H ₇ -Si(X ^b1 ) ₃ ...(M1-4)
(CH ₃ ) ₂ CH-Si(X ^b1 ) ₃ ... (M1-5)

Among the specific metal compounds, examples of the compound represented by formula (M2) include (H ₅ C ₂ O) ₃ -Si-(OSi(OC ₂ H ₅ ) ₂ ) ₄ OC ₂ H ₅ and the like.

The content of other components that may be included in the polymerizable composition of the present disclosure is preferably 10% by mass or less, more preferably 1% by mass or less, based on the total amount of the polymerizable composition of the present disclosure.

When the polymerizable composition of the present disclosure contains a specific metal compound, the content of the specific metal compound is preferably 0.001 to 10% by mass, and 0.01 to 5% by mass based on the total amount of the polymerizable composition of the present disclosure. % is more preferable, and 0.03 to 1% by mass is even more preferable.

The solid content concentration of the polymerizable composition of the present disclosure is preferably 0.01 to 60% by mass, more preferably 0.1 to 40% by mass, and 1 to 20% by mass, based on the total amount of the polymerizable composition of the present disclosure. Mass % is more preferred. The solid content concentration of the polymerizable composition of the present disclosure is a value calculated from the mass of the composition before heating and the mass after heating in a convection dryer at 120° C. for 4 hours.

[Polymer]
The polymer of the present disclosure is a polymer obtained by a polymerization reaction of the polymerizable composition of the present disclosure. The polymerization reaction is not particularly limited and can be performed by a known method.

The polymerizable composition of the present disclosure includes a polymerizable compound A and a polymerizable compound B, and contains at least a polymerizable compound having a reactive silyl group. Therefore, the polymer of the present disclosure is derived from the polymerizable compound A. It contains a structural unit and a structural unit derived from the polymerizable compound B, and contains at least a structural unit derived from a polymerizable compound having a reactive silyl group.

In the polymer of the present disclosure, in addition to the structural unit derived from polymerizable compound A and the structural unit derived from polymerizable compound B, a structural unit derived from a polymerizable compound having a reactive silyl group may be included. . Furthermore, in the polymerizable composition of the present disclosure, at least one of the structural unit derived from polymerizable compound A and the structural unit derived from polymerizable compound B is a structural unit derived from a polymerizable compound having a reactive silyl group. There may be. That is, at least one of the structural unit derived from polymerizable compound A and the structural unit derived from polymerizable compound B may have a reactive silyl group.

The polymer of the present disclosure is preferably a polymer obtained by the polymerization reaction of the above embodiments 1 to 7 of the polymer composition of the present disclosure. Among these, the following embodiments of the polymer of the present disclosure are preferable.

- A polymer containing a structural unit derived from a polymerizable compound A having a reactive silyl group and a structural unit originating from a polymerizable compound B not having a reactive silyl group.
- A structural unit derived from polymerizable compound A that does not have a reactive silyl group, a structural unit that originates from polymerizable compound B that does not have a reactive silyl group, and a structural unit that originates from polymerizable compound C that has a reactive silyl group. A polymer containing a structural unit.

[Polymer composition]
The polymer composition of the present disclosure preferably includes the disclosed polymer and a liquid medium. When containing a liquid medium, the polymer composition of the present disclosure only needs to be liquid, and may be a solution or a dispersion.

The content of the polymer of the present disclosure contained in the polymer composition of the present disclosure is preferably 0.01 to 60% by mass, and 0.1 to 40% by mass based on the total amount of the polymer composition of the present disclosure. is more preferable, and even more preferably 1 to 20% by mass.

Preferred embodiments of the liquid medium contained in the polymer composition are the same as those of the liquid medium contained in the polymerizable composition of the present disclosure.

The content of the liquid medium is preferably 40 to 99.99% by mass, more preferably 60 to 99.9% by mass, and even more preferably 80 to 99% by mass, based on the total amount of the polymer composition of the present disclosure.

The polymer composition of the present disclosure may contain other components in addition to the above-mentioned components as long as the effects of the present disclosure are not impaired.
Other components include, for example, an acid catalyst that promotes the hydrolysis and condensation reaction of reactive silyl groups, a basic catalyst, a non-fluorinated polymer, a crosslinking agent, a penetrant, an antifoaming agent, a film-forming agent, and an insect repellent. Examples of additives include known additives such as antifungal agents, antifungal agents, preservatives, flame retardants, antistatic agents, antiwrinkle agents, softeners, and pH adjusters.

Further, preferred embodiments of other components contained in the polymer composition are the same as preferred embodiments of other components contained in the polymerizable composition of the present disclosure.

The content of other components that may be included in the polymer composition of the present disclosure is preferably 10% by mass or less, more preferably 1% by mass or less, based on the total amount of the polymer composition of the present disclosure.

When the polymer composition of the present disclosure contains a specific metal compound, the content of the specific metal compound is preferably 0.001 to 10% by mass, and 0.01 to 5% by mass based on the total amount of the polymer composition of the present disclosure. % is more preferable, and 0.03 to 1% by mass is even more preferable.

The solid content concentration of the polymer composition of the present disclosure is preferably 0.01 to 60% by mass, more preferably 0.1 to 40% by mass, and 1 to 20% by mass, based on the total amount of the polymer composition of the present disclosure. Mass % is more preferred.

Since the polymerizable composition of the present disclosure and the polymer composition of the present disclosure contain a liquid medium, they are useful for coating purposes and can be used as a coating liquid.

[Surface treatment agent]
In one aspect, the surface treatment agent of the present disclosure includes the polymerizable composition of the present disclosure.
In another aspect, the surface treatment agent of the present disclosure includes the polymer of the present disclosure. The surface treatment agent of the present disclosure may include the polymer of the present disclosure and a liquid medium. A preferred embodiment of the liquid medium contained in the surface treatment agent is the same as a preferred embodiment of the liquid medium contained in the polymerizable composition of the present disclosure.

By using the polymer composition of the present disclosure or the surface treatment agent containing the polymer of the present disclosure, a surface treatment layer with excellent slip properties and antifouling properties can be formed.

[Goods]
In one embodiment, the article of the present disclosure includes a base material and a surface treatment layer disposed on the base material and surface treated with the above surface treatment agent.

The surface treatment layer may be formed on a part of the surface of the base material, or may be formed on the entire surface of the base material. The surface treatment layer may be spread over the surface of the base material in the form of a film, or may be scattered in the form of dots.
In the surface treatment layer, the polymer of the present disclosure is contained in a state in which hydrolysis of some or all of the reactive silyl groups has proceeded, and a dehydration condensation reaction of the silanol groups has proceeded.

The thickness of the surface treatment layer is preferably 1 to 100 nm, more preferably 1 to 50 nm. If the thickness of the surface treatment layer is 1 nm or more, the effect of the surface treatment is likely to be sufficiently obtained. If the thickness of the surface treatment layer is 100 nm or less, the utilization efficiency is high. The thickness of the surface treatment layer is determined by using an X-ray diffractometer for thin film analysis (product name "ATX-G", manufactured by RIGAKU) to obtain an interference pattern of reflected X-rays by the X-ray reflectance method. It can be calculated from the vibration period of

The type of base material is not particularly limited, and includes, for example, base materials that are required to have water repellency. As a base material, for example, a base material that may be used in contact with another article (e.g., a stylus) or a person's fingers; a base material that may be held by a person's fingers during operation; , a mounting table).
Examples of the base material include metal, resin, glass, sapphire, ceramic, stone, fiber, nonwoven fabric, paper, wood, natural leather, artificial leather, and composite materials thereof. The glass may be chemically strengthened.

Base materials include building materials, decorative building materials, interior goods, transportation equipment (e.g. automobiles), signboards/bulletin boards, drinking vessels/tableware, aquariums, ornamental equipment (e.g. frames, boxes), laboratory equipment, furniture, textile products. , Packaging containers; Glass or resin used for art, sports, games, etc.; Used for the exterior parts (excluding display parts) of devices such as mobile phones (e.g. smartphones), personal digital assistants, game consoles, remote controls, etc. Examples include glass or resin. The shape of the base material may be plate-like or film-like.

As the base material, a base material for a touch panel, a base material for a display, and an eyeglass lens are suitable, and a base material for a touch panel is particularly suitable. As the material for the touch panel base material, glass or transparent resin is preferable.

The base material may be a base material that has been subjected to surface treatment such as corona discharge treatment, plasma treatment, plasma graft polymerization treatment, etc. on one surface or both surfaces. A surface-treated base material has better adhesion with the surface-treated layer, and the abrasion resistance of the surface-treated layer is further improved. Therefore, it is preferable to perform surface treatment on the surface of the base material that is in contact with the surface treatment layer. Furthermore, when the surface-treated base material is provided with a base layer, which will be described later, the adhesion with the base layer is better, and the wear resistance of the surface-treated layer is further improved. Therefore, when a base layer is provided, it is preferable to perform a surface treatment on the surface of the base material that is in contact with the base layer.

The surface treatment layer may be provided directly on the surface of the base material, or a base layer may be provided between the base material and the surface treatment layer. From the perspective of further improving the water repellency and abrasion resistance of the surface treatment layer, the article of the present disclosure includes a base material, a base layer disposed on the base material, and a surface treatment of the present disclosure disposed on the base layer. It is preferable to include a surface treatment layer whose surface is treated with an agent.

The base layer includes silicon and at least one selected from the group consisting of a group 1 element, a group 2 element, a group 4 element, a group 5 element, a group 13 element, and a group 15 element of the periodic table. A layer containing an oxide containing a specific element is preferable.

Group 1 elements of the periodic table (hereinafter also referred to as "Group 1 elements") mean lithium, sodium, potassium, rubidium, and cesium. As Group 1 elements, lithium, sodium, potassium is preferred, and sodium and potassium are more preferred. The underlayer may contain two or more types of Group 1 elements.

Group 2 elements of the periodic table (hereinafter also referred to as "Group 2 elements") mean beryllium, magnesium, calcium, strontium, and barium. As Group 2 elements, magnesium, calcium, barium, is preferred, and magnesium and calcium are more preferred. The underlayer may contain two or more types of Group 2 elements.

Group 4 elements of the periodic table (hereinafter also referred to as "Group 4 elements") mean titanium, zirconium, and hafnium. As the Group 4 element, titanium and zirconium are preferable from the viewpoint of being able to form a water- and oil-repellent layer more uniformly without defects on the underlayer, or from the viewpoint of suppressing variations in the composition of the underlayer between samples. , titanium is more preferred. The base layer may contain two or more types of Group 4 elements.

Group 5 elements of the periodic table (hereinafter also referred to as "Group 5 elements") mean vanadium, niobium, and tantalum. As the Group 5 element, vanadium is particularly preferred from the viewpoint of providing a water- and oil-repellent layer with better wear resistance. The underlayer may contain two or more types of Group 5 elements.

Group 13 elements of the periodic table (hereinafter also referred to as "Group 13 elements") mean boron, aluminum, gallium, and indium. As Group 13 elements, boron, aluminum, gallium, is preferred, and boron and aluminum are more preferred. The base layer may contain two or more types of Group 13 elements.

Group 15 elements of the periodic table (hereinafter also referred to as "Group 15 elements") mean nitrogen, phosphorus, arsenic, antimony, and bismuth. Group 15 elements include phosphorus, antimony, and bismuth, from the viewpoint of forming a water- and oil-repellent layer on the underlayer more uniformly without defects, or from the viewpoint of suppressing variations in the composition of the underlayer between samples. is preferred, and phosphorus and bismuth are more preferred. The base layer may contain two or more types of Group 15 elements.

As the specific elements contained in the base layer, Group 1 elements, Group 2 elements, and Group 13 elements are preferable because they provide better wear resistance of the water- and oil-repellent layer, and Group 1 elements and Group 2 elements are more preferable. Preferably, Group 1 elements are more preferable.
As the specific element, only one type of element may be included, or two or more types of elements may be included.

The oxide contained in the base layer may be a mixture of oxides of the above elements (silicon and specific elements) alone (for example, a mixture of silicon oxide and an oxide of a specific element), or a mixture of the above elements (silicon and specific elements). It may be a composite oxide containing two or more types, or a mixture of an oxide of the above element alone and a composite oxide.

The ratio of the total molar concentration of the specific element in the underlayer to the molar concentration of silicon in the underlayer (specific element/silicon) is 0.02-2. It is preferably 90, more preferably 0.10 to 2.00, even more preferably 0.20 to 1.80.
The molar concentration (mol %) of each element in the underlayer can be measured, for example, by depth direction analysis using X-ray photoelectron spectroscopy (XPS) using ion sputtering.

The base layer may be a single layer or a multilayer. The base layer may have an uneven surface.
The thickness of the underlayer is preferably 1 to 100 nm, more preferably 1 to 50 nm, and even more preferably 2 to 20 nm. If the thickness of the base layer is equal to or greater than the above lower limit, the adhesion of the surface treatment layer to the base layer will be further improved, and the wear resistance of the surface treatment layer will be more excellent. If the thickness of the base layer is below the above upper limit, the base layer itself will have excellent wear resistance.
The thickness of the base layer is measured by observing a cross section of the base layer using a transmission electron microscope (TEM).

The base layer can be formed, for example, by a vapor deposition method using a vapor deposition material or a wet coating method.

The vapor deposition material used in the vapor deposition method preferably contains an oxide containing silicon and a specific element.
Specific examples of the form of the vapor deposition material include powder, molten body, sintered body, granulated body, and crushed body, and from the viewpoint of ease of handling, molten body, sintered body, and granulated body are preferable.
Here, the melt means a solid obtained by melting the powder of the vapor deposition material at a high temperature and then cooling and solidifying the powder. A sintered body means a solid obtained by firing a powder of a vapor deposition material, and if necessary, a molded body obtained by press-forming the powder may be used instead of a powder of a vapor deposition material. Good too. The granule refers to a solid material obtained by kneading a powder of a vapor deposition material and a liquid medium (for example, water, an organic solvent) to obtain particles, and then drying the particles.

The vapor deposition material can be manufactured, for example, by the following method.
・A method of obtaining a vapor deposition material powder by mixing silicon oxide powder and oxide powder of a specific element.
- A method of kneading the powder of the vapor deposition material and water to obtain particles, and then drying the particles to obtain granules of the vapor deposition material.
・Powders containing silicon (e.g. powder of silicon oxide, silica sand, silica gel) and powders containing specific elements (e.g. powder of oxides of specific elements, carbonates, sulfates, nitrates, oxalic acid) A method of obtaining a sintered body by drying a mixture of salt, hydroxide) and water, and then firing the dried mixture or a press-molded body of the dried mixture.
・Powders containing silicon (e.g. powder of silicon oxide, silica sand, silica gel) and powders containing specific elements (e.g. powder of oxides of specific elements, carbonates, sulfates, nitrates, oxalic acid) (salt, hydroxide) at high temperature, and then cooled and solidified to obtain a molten product.

A specific example of a vapor deposition method using a vapor deposition material includes a vacuum vapor deposition method. The vacuum deposition method is a method in which a deposition material is evaporated in a vacuum chamber and adhered to the surface of a base material.
The temperature during vapor deposition (for example, the temperature of the boat in which the vapor deposition material is placed when using a vacuum vapor deposition apparatus) is preferably 100 to 3,000°C, more preferably 500 to 3,000°C.
The pressure during vapor deposition (for example, when using a vacuum vapor deposition apparatus, the pressure in the tank in which the vapor deposition material is placed) is preferably 1 Pa or less, more preferably 0.1 Pa or less.
When forming the base layer using a vapor deposition material, one vapor deposition material may be used, or two or more vapor deposition materials containing different elements may be used.

Specific examples of evaporation methods include resistance heating, in which the evaporation material is melted and evaporated on a resistance heating boat made of high-melting-point metal, and irradiation of an electron beam onto the evaporation material to directly heat the evaporation material on the surface. An example is the electron gun method, which melts and evaporates. The method of evaporating the deposition material is that it can evaporate high-melting point substances because it can be heated locally, and that there is no risk of reaction with the container or contamination with impurities because the area that is not hit by the electron beam is at a low temperature. Gun law is preferred.
As a method for evaporating the evaporation materials, a plurality of boats may be used, or all the evaporation materials may be placed in a single boat. The vapor deposition method may be codeposition, alternate vapor deposition, or the like. Specifically, examples include mixing silica and a specific element source in the same boat, co-evaporating silica and a specific element source in separate boats, and alternately depositing silica and a specific element source in separate boats. can be mentioned. The conditions, order, etc. of vapor deposition are appropriately selected depending on the structure of the underlying layer.

In the wet coating method, it is preferable to form the base layer on the base material by a wet coating method using a coating liquid containing a compound containing silicon, a compound containing a specific element, and a liquid medium.

Specific examples of silicon compounds include silicon oxide, silicic acid, partial condensates of silicic acid, alkoxysilanes, and partially hydrolyzed condensates of alkoxysilanes.

Specific examples of compounds containing specific elements include oxides of specific elements, alkoxides of specific elements, carbonates of specific elements, sulfates of specific elements, nitrates of specific elements, oxalates of specific elements, and water of specific elements. Examples include oxides.

Examples of the liquid medium include those similar to those contained in the polymerizable composition of the present disclosure.

The content of the liquid medium is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of the coating liquid used for forming the base layer.

Specific examples of wet coating methods for forming the base layer include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet, flow coating, roll coating, Examples include the cast method, Langmuir-Blodgett method, and gravure coating method.

After wet coating the coating liquid, it is preferable to dry the coating film. The drying temperature of the coating film is preferably 20 to 200°C, more preferably 80 to 160°C.

The article of the present disclosure is preferably an optical member. Examples of optical components include medical devices such as car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game devices, eyeglass lenses, camera lenses, lens filters, sunglasses, and gastrocameras. Examples include personal appliances, copying machines, PCs, displays (eg, liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, and antireflection films. In particular, the article is preferably a display or a touch panel.

[Method for manufacturing articles]
A method for producing an article of the present disclosure is, for example, a method of surface-treating a base material using the surface treatment agent of the present disclosure to produce an article in which a surface-treated layer is formed on the base material. . As the surface treatment, a wet coating method can be mentioned. When the molecular weight of the polymer of the present disclosure is low, a dry coating method may also be used.

Examples of the dry coating method include vacuum deposition, CVD, and sputtering. As the dry coating method, a vacuum evaporation method is preferable from the viewpoint of suppressing decomposition of the compound and the simplicity of the apparatus. At the time of vacuum deposition, a pellet-like substance obtained by impregnating a porous metal body such as iron or steel with the compound of the present disclosure may be used. A pellet-like material impregnated with the compound of the present disclosure may be used by impregnating a porous metal body such as iron or steel with a composition containing the compound of the present disclosure and a liquid medium, and drying the liquid medium.

Examples of wet coating methods include spin coating, wipe coating, spray coating, squeegee coating, dip coating, die coating, inkjet coating, flow coating, roll coating, casting, and Langmuir-Blodgett methods. , gravure coating method.

In order to improve the slipperiness and antifouling properties of the surface treatment layer, an operation may be performed to promote the reaction between the polymer of the present disclosure and the base material, if necessary. Such operations include heating, humidification, light irradiation, and the like.
For example, by heating a base material on which a surface treatment layer is formed in a moist atmosphere, a hydrolysis reaction of hydrolyzable groups, a reaction between hydroxyl groups, etc. on the surface of the base material and silanol groups, and a condensation reaction of silanol groups. can promote reactions such as the formation of siloxane bonds.

After the surface treatment, compounds in the surface treatment layer that are not chemically bonded to other compounds or the base material may be removed as necessary. Examples of the removal method include a method of pouring a solvent onto the surface treatment layer, a method of wiping with a cloth impregnated with a solvent, and the like.

Furthermore, when the surface treatment agent of the present disclosure includes the polymerizable composition of the present disclosure, it is preferable to irradiate the surface with active energy rays after surface treatment. Examples of active energy rays include gamma rays, beta rays, electron beams, ultraviolet rays, and visible light. Among these, it is preferable that the active energy rays are ultraviolet rays. The exposure amount of active energy rays is not particularly limited, and is, for example, 10 to 10,000 mJ/cm ² .

The present invention will be explained in more detail below using Examples, but the present invention is not limited to these Examples.

<Raw material of polymerizable compound A>
Raw materials for synthesizing polymerizable compound A are shown below.

-Alkylene oxide adduct of polyhydric alcohol/ethylene oxide adduct of 1,3-propanediol (average number of added moles of EO: 7.5 moles)
・Ethylene oxide adduct of glycerin (average number of added moles of EO: 7.5 moles)
・Propylene oxide adduct of glycerin (average number of added moles of PO: 12 moles)
・Ethylene oxide adduct of erythritol (average number of moles of EO added: 7.5 moles)
・Ethylene oxide adduct of xylitol (average number of added moles of EO: 7.5 moles)
・Ethylene oxide adduct of sorbitol (average number of added moles of EO: 7.5 moles)
EO means ethylene oxide and PO means propylene oxide.
All alkylene oxide adducts of polyhydric alcohols were synthesized by ring-opening polymerization of alkylene oxides to polyhydric alcohols.
The average number of moles of EO added and the average number of moles of PO added above respectively mean the average number of moles of EO or PO added to each hydroxyl group of the polyhydric alcohol.

- Isocyanate with a polymerizable group MOI: 2-isocyanate ethyl methacrylate (product name "Karens MOI", manufactured by Showa Denko)

-Isocyanate with reactive silyl group-
・3-Isocyanatepropyltrimethoxysilane (product code: T2044, manufactured by Tokyo Kasei Co., Ltd.)

<Polymerizable compound B1>
・Polydimethylsiloxane containing a methacryloyl group at one end (product name "X-22-174BX", manufactured by Shin-Etsu Chemical Co., Ltd., number of repeating units: 29.1)

<Polymerizable compound B2>
・StA: Stearyl acrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.)
・BeA: Behenyl acrylate manufactured by Tokyo Kasei Kogyo Co., Ltd.

<Polymerizable compound C>
・3-methacryloxypropyltrimethoxysilane (product name "KBM-503", manufactured by Shin-Etsu Chemical Co., Ltd.)
・Methacrylate C: methacrylate synthesized by the method shown below

<Other polymerizable compounds>
・Octyl acrylate ・PEGMM: Polyethylene glycol monomethacrylate (product name "Blenmar PE-350", manufactured by NOF Corporation, average number of added moles of EO: 8 moles)
・PEGDM: Polyethylene glycol dimethacrylate (product name "Blenmar PDE-450", manufactured by NOF Corporation, average number of added moles of EO: 9 moles)

-Synthesis of methacrylate C-
300 g of methyl isobutyl ketone (MIBK) and 9 g (0.092 mol) of glycerin were added to a 1 L three-necked flask, and the mixture was stirred at 60° C. under a nitrogen atmosphere.
To this, 3-isocyanatepropyltrimethoxysilane was added dropwise over 30 minutes in an amount equivalent to 2/3 molar amount relative to glycerin. Thereafter, the mixture was stirred at 60°C for 3 hours. IR measurement (infrared spectroscopy) of the reaction product was performed, and it was confirmed that no peak derived from isocyanate groups (NCO) was detected.
The reaction product was subjected to flash column chromatography using silica gel (developing solvent: ethyl acetate/hexane). Through purification, a compound obtained by reacting two of the three hydroxyl groups in glycerin with 3-isocyanatepropyltrimethoxysilane was obtained.
MOI was added dropwise to the obtained compound in an amount equivalent to 1/3 molar amount relative to glycerin over 30 minutes. Thereafter, the mixture was stirred at 60°C for 3 hours. IR measurement (infrared spectroscopy) of the reaction product was performed, and it was confirmed that no peak derived from isocyanate groups (NCO) was detected.
MIBK was distilled off under reduced pressure. Methacrylate C having two trimethoxysilyl groups and one methacryloyl group was obtained. Methacrylate C corresponds to polymerizable compound C since it does not have a polyalkylene oxide chain.

[Example 1]
300 g of methyl isobutyl ketone (MIBK) and 100 g (0.092 mol) of an ethylene oxide adduct of glycerin (average number of added moles of EO: 7.5 mol) were added to a 1 L three-necked flask, and the mixture was heated at 60°C under a nitrogen atmosphere. It was stirred with
To this, 3-isocyanatepropyltrimethoxysilane was added dropwise over 30 minutes in an amount equivalent to 2/3 mole relative to the ethylene oxide adduct of glycerin. Thereafter, the mixture was stirred at 60°C for 3 hours. IR measurement (infrared spectroscopy) of the reaction product was performed, and it was confirmed that no peak derived from isocyanate groups (NCO) was detected.
The reaction product was subjected to flash column chromatography using silica gel (developing solvent: ethyl acetate/hexane). Through purification, a compound obtained by reacting two of the three hydroxyl groups in the ethylene oxide adduct of glycerin with 3-isocyanatepropyltrimethoxysilane was obtained.
MOI was added dropwise to the obtained compound over 30 minutes in an amount equivalent to 1/3 molar amount based on the ethylene oxide adduct of glycerin. Thereafter, the mixture was stirred at 60°C for 3 hours. IR measurement (infrared spectroscopy) of the reaction product was performed, and it was confirmed that no peak derived from isocyanate groups (NCO) was detected.
MIBK was distilled off under reduced pressure. A polymerizable compound A was obtained in which the linking group was a glycerin residue, had three polyethylene oxide chains bonded to the linking group, and had two trimethoxysilyl groups and one methacryloyl group.
70 g of the obtained polymerizable compound A was dissolved in 300 g of toluene. Furthermore, 30 g of polydimethylsiloxane containing methacryloyl at one end was added as polymerizable compound B1, and azoisobutyronitrile (AIBN) was added as a polymerization initiator to obtain a polymerizable composition. A polymerization reaction was carried out at 65° C. for 24 hours under a nitrogen atmosphere to obtain a polymer.

In Tables 1 to 3, for polymerizable compound A, the type of linking group, the type of polyalkylene oxide chain, the number of moles of added polyalkylene oxide chain, the number of polymerizable groups, and the number of reactive silyl groups are listed. . Moreover, the contents of polymerizable compound A, polymerizable compound B1, polymerizable compound B2, and polymerizable compound C were described.
In Examples 25 to 27, polymerizable compounds similar to polymerizable compound A were listed in the column of polymerizable compounds.

[Examples 2-10, Examples 21-29]
In Examples 2 to 10 and Examples 21 to 29, the types and contents of polymerizable compound A, polymerizable compound B1, polymerizable compound B2, and polymerizable compound C were changed to those listed in Table 1 or Table 3. A polymerizable composition was obtained in the same manner as in Example 1 except for the following changes. Thereafter, a polymer was obtained in the same manner as in Example 1. In the table, the content of each polymerizable compound represents the proportion to the total amount of the polymerizable composition, and the unit is mass %. In addition, the content of the structural unit derived from each polymeric compound contained in the polymer is the same as the content of each polymerizable compound contained in the polymerizable composition.

[Examples 11 to 15]
In Examples 11 to 15, the types and contents of polymerizable compound A, polymerizable compound B1, and polymerizable compound B2 were changed to those listed in Table 2, and furthermore, polymerizable compound having a reactive silyl group was added. A polymerizable composition was obtained in the same manner as in Example 1 except that Compound C was added.

The polymers obtained in Examples 1 to 10 and Examples 21 to 29 were each diluted with toluene to a concentration of 1% by mass to obtain a surface treatment agent. A glass substrate was surface-treated by a spray coating method using a surface-treating agent to obtain an article having a surface-treated layer on the surface of the glass substrate.

The polymerizable compositions obtained in Examples 11 to 15 were each diluted with toluene to a concentration of 1% by mass to obtain surface treatment agents. After applying a surface treatment agent to a glass substrate using a bar coater, an article having a surface treatment layer on the surface of the glass substrate is produced by irradiating ultraviolet rays of 500 to 2,000 mJ/cm ² using an ultraviolet irradiation device. Obtained.

The obtained article was evaluated for its coefficient of kinetic friction (COF), stain wiping performance, and stain wiping performance after rubbing. The evaluation method is as follows.

<Coefficient of kinetic friction (COF)>
The coefficient of kinetic friction (COF) for medicine packaging paper was measured using a variable load friction and wear test system (product name "HHS2000", manufactured by Shinto Kagakusha Co., Ltd.) under conditions of a contact area of 3 cm x 3 cm and a load of 0.98 N. When the COF is 0.1 or less, slip properties are excellent.

<Easy to wipe off dirt>
1 mL of oleic acid was dropped onto the article and wiped off three times with Kimtowel. After wiping off, the degree of residual oleic acid was visually observed. The stain wiping performance was evaluated based on the degree of residual oleic acid. The evaluation criteria are as follows.
AA: No oleic acid remains.
A: Some oleic acid remains.
B: Although some of the oleic acid has been removed, much of it remains and spreads over the surface of the article.
C: Almost no oleic acid was removed.

<Ease of wiping dirt off after friction>
In accordance with JIS L0849:2013 (ISO 105-X12:2001), steel wool Bonstar (#0000) was tested at a pressure of 98.07 kPa and a speed of 320 cm/min for 2 hours using a reciprocating traverse tester (manufactured by KNT). ,000 round trips.
After performing the friction test, the articles were evaluated in the same way as the stain wiping performance described above. The evaluation criteria are the same as those for the stain wiping property described above.

The evaluation results are shown in Tables 1 to 3.

Examples 1 to 15 are examples, and Examples 21 to 29 are comparative examples.

As shown in Tables 1 and 2, the polymerizable compositions of Examples 1 to 15 contain a polymerizable compound A and a polymerizable compound B, and contain at least a polymerizable compound having a reactive silyl group. It was found that a surface treated layer with excellent slip properties and antifouling properties could be obtained.

On the other hand, as shown in Table 3, the polymerizable compositions of Examples 21 to 27 did not contain polymerizable compound A and were found to be inferior in slipperiness and antifouling properties.
It was found that the polymerizable compositions of Examples 28 and 29 did not contain polymerizable compound B and were inferior in slipperiness and antifouling properties.

The polymerizable compound of the present disclosure is useful as a surface treatment agent. The surface treatment agent can be used, for example, for substrates in display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, and the like. Furthermore, the surface treatment agent can be used for bodies, window glasses (windshields, side glasses, rear glasses), mirrors, bumpers, etc. of transportation equipment such as trains, automobiles, ships, and airplanes. Furthermore, the surface treatment agent can be used for outdoor articles such as building exterior walls, tents, solar power generation modules, sound insulation boards, and concrete; fishing nets, insect nets, and aquariums. Furthermore, the surface treatment agent can be used for various indoor equipment such as kitchens, bathrooms, washstands, mirrors, toilet peripheral parts; ceramics such as chandeliers and tiles; artificial marble, and air conditioners. Furthermore, the surface treatment agent can be used as an antifouling treatment for jigs, inner walls, piping, etc. in a factory. Furthermore, the surface treatment agent can be used for goggles, glasses, helmets, pachinko machines, textiles, umbrellas, play equipment, and soccer balls. Furthermore, the surface treatment agent can also be used as an adhesion prevention agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and the inside of pots. In addition, surface treatment agents are used for medical applications such as car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game equipment, eyeglass lenses, camera lenses, lens filters, sunglasses, and gastrocameras. It can be used for optical members such as appliances, copying machines, PCs, displays (for example, liquid crystal displays, organic EL displays, plasma displays, touch panel displays), touch panels, protective films, and antireflection films.

Claims (18)

A polymerizable compound A having a linking group with a valence of 2 or more, 2 or more polyalkylene oxide chains bonded to the linking group with a valence of 2 or more, and a polymerizable group;
At least one member selected from the group consisting of a polymerizable compound B1 having an organopolysiloxane structure and a polymerizable group, and a polymerizable compound B2 having a linear alkyl group having 12 to 30 carbon atoms and a polymerizable group. A polymerizable compound B,
A polymerizable composition containing at least a polymerizable compound having a reactive silyl group. The polymerizable composition according to claim 1, wherein the polymerizable compound A has the reactive silyl group. The polymerizable composition according to claim 1 or 2, further comprising a polymerizable compound C having the reactive silyl group. The polymerizable composition according to any one of claims 1 to 3, wherein the divalent or higher-valent linking group is a trivalent or higher-valent linking group. The polymerizable composition according to claim 4, wherein the trivalent or higher-valent linking group is a group obtained by removing a hydrogen atom from a hydroxyl group of a sugar alcohol. The polymerizable composition according to any one of claims 1 to 5, wherein the polyalkylene oxide chain is a polyethylene oxide chain. The polymerizable composition according to claim 6, wherein the polyethylene oxide chain has a repeating number of 3 to 15. The polymerizable composition according to any one of claims 1 to 7, wherein a mass ratio of the content of the polymerizable compound A to the content of the polymerizable compound B is 1.5 to 5. The polymerizable composition according to any one of claims 1 to 8, further comprising a liquid medium. A surface treatment agent comprising the polymerizable composition according to any one of claims 1 to 9. A polymer obtained by a polymerization reaction of the polymerizable composition according to any one of claims 1 to 8. A polymer composition comprising the polymer according to claim 11 and a liquid medium. A surface treatment agent comprising the polymer according to claim 11. The surface treatment agent according to claim 13, further comprising a liquid medium. A method for manufacturing an article, comprising performing a surface treatment on a base material using the surface treatment agent according to claim 10, 13, or 14 to manufacture an article having a surface treatment layer formed on the base material. An article comprising a base material and a surface treatment layer disposed on the base material and surface treated with the surface treatment agent according to claim 10, 13 or 14. The article according to claim 16, which is an optical member. 17. The article according to claim 16, which is a display or a touch panel.