KR102479607B1 - Antifouling composition solution and manufacturing method thereof - Google Patents

Abstract

A metal catalyst (D) and water (E) are added to a hydrolyzate of a tetrafunctional silane-based compound [component (A)] having a specific structure and a hydrolyzate of a trifunctional silane-based compound [component (B)] having a specific structure. It relates to a solution of an antifouling composition formed by blending.

Description

Antifouling composition solution and manufacturing method thereof

The present invention relates to a solution of an antifouling composition and a method for producing the same.

In general, architectural glass windows, automobile glass windows, windshields of vehicles, aircrafts, ships, etc., water tanks, dock windows, films for preventing adhesion of aquatic organisms to the bottom of ships, road panels such as sound barriers, mirrors installed in bathrooms, glass containers, and glass It is preferable that objects obstructing vision, such as water droplets, scratches, and stains, do not adhere to the surface of molded articles such as ornaments.

It is practiced to impart antifouling properties such as water repellency to the surface of such a molded product by coating it with a film made of an antifouling substance or by attaching an antifouling sheet thereon.

For example, in Patent Document 1, a base material such as glass is covered by a laminate having an underlayer formed of an inorganic compound and a water-repellent film formed of a fluorine-containing compound covering the surface of the underlayer. A water-repellent film-coated article is disclosed.

Japanese Unexamined Patent Publication No. 2010-285574

However, since the water-repellent coated article described in Patent Document 1 has a water-repellent film formed from a fluorine-containing compound, it is not preferable from the viewpoint of environmental protection.

Therefore, antifouling materials with less load on the environment are required.

An object of the present invention is to provide an antifouling composition solution having a long usable time (pot life) and a method for producing the same.

The inventors of the present invention found that a solution of an antifouling composition obtained by blending a hydrolyzate of a tetrafunctional silane-based compound having a specific structure and a hydrolyzate of a trifunctional silane-based compound having a specific structure, with a metal catalyst and water can solve the above problems. found out and completed the present invention.

That is, the present invention provides the following [1] to [15].

[1] A solution of an antifouling composition obtained by blending a metal catalyst (D) and water (E) with a hydrolyzate of the following component (A) and a hydrolyzate of the following component (B).

Component (A): A tetrafunctional silane-based compound represented by the following general formula (a)

Si(OR ¹ ) _p (X ¹ ) _4-p (a)

[In general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When there are a plurality of R ¹ and X ¹ , the plurality of R ¹ and X ¹ may be the same as or different from each other. p represents an integer from 0 to 4.]

Component (B): Trifunctional silane-based compound represented by the following general formula (b)

R ² Si(OR ³ ) _q (X ² ) _3-q (b)

[In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ represents an alkyl group of 1 to 6 carbon atoms, and X ² represents a halogen atom. When a plurality of R ³ and X ² are present, the plurality of R ³ and X ² may be the same as or different from each other. q represents an integer from 0 to 3.]

[2] The antifouling composition solution according to [1] above, wherein the component (B) contains at least one of the following components (B-1).

Component (B-1): Trifunctional silane-based compound represented by the following general formula (b-1)

R ⁴ Si(OR ⁵ ) _r (X ³ ) _3-r (b-1)

[In general formula (b-1), R ⁴ represents an alkyl group having 6 to 24 carbon atoms, and the alkyl group may have a substituent. R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and X ³ represents a halogen atom. When a plurality of R ⁵ and X ³ are present, the plurality of R ⁵ and X ³ may be the same as or different from each other. r represents an integer from 0 to 3.]

[3] The antifouling composition solution according to [1] or [2] above, wherein the component (B) contains at least one of the following components (B-2).

Component (B-2): Trifunctional silane-based compound represented by the following general formula (b-2)

R ⁶ Si(OR ⁷ ) _s (X ⁴ ) _3-s (b-2)

[In general formula (b-2), R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent. R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and X ⁴ represents a halogen atom. When there are a plurality of R ⁷ and X ⁴ , the plurality of R ⁷ and X ⁴ may be the same as or different from each other. s represents an integer from 0 to 3.]

[4] The antifouling composition solution according to [3] above, which further satisfies the following condition (II).

Condition (II): Ratio of the compounding amount of component (B-1) to the total compounding amount of component (B-1) and component (B-2) [(B-1)/{(B-1) + (B-1) 2)}] (molar ratio) A, 0.020 or more

[5] The antifouling composition solution according to any one of [1] to [4] above, which further satisfies the following condition (I).

Condition (I): The ratio of the compounding amount of component (A) to the compounding amount of component (B) [(A)/(B)] (molar ratio) is 0.01 or more and 50.00 or less

[6] The above [1] to [, in which the metal catalyst (D) is at least one selected from the group consisting of titanium catalysts, zirconium catalysts, palladium catalysts, tin catalysts, aluminum catalysts, and zinc catalysts. The antifouling composition solution according to any one of [5].

[7] Any one of [1] to [6] above, wherein the compounding amount of the metal catalyst (D) is 0.01 mol% or more and 50.00 mol% or less with respect to 100 mol% of the total compounding amount of component (A) and component (B). The antifouling composition solution described in .

[8] In any one of the above [1] to [7], wherein the blending amount of water (E) is 0.01 mol% or more and 100,000 mol% or less with respect to 100 mol% of the total blending amount of component (A) and component (B) A solution of the antifouling composition described.

[9] A method for producing an antifouling composition solution comprising the following steps (1) and the following steps (2) in this order.

Step (1): Step of hydrolyzing the following component (A) and the following component (B)

Component (A): A tetrafunctional silane-based compound represented by the following general formula (a)

Si(OR ¹ ) _p (X ¹ ) _4-p (a)

[In general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When there are a plurality of R ¹ and X ¹ , the plurality of R ¹ and X ¹ may be the same as or different from each other. p represents an integer from 0 to 4.]

Component (B): Trifunctional silane-based compound represented by the following general formula (b)

R ² Si(OR ³ ) _q (X ² ) _3-q (b)

[In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ represents an alkyl group of 1 to 6 carbon atoms, and X ² represents a halogen atom. When a plurality of R ³ and X ² are present, the plurality of R ³ and X ² may be the same as or different from each other. q represents an integer from 0 to 3.]

Step (2): Step of mixing a metal catalyst (D) and water (E) with the hydrolyzate of component (A) and the hydrolyzate of component (B) obtained in step (1)

[10] Step (2) is a step of mixing water (E) after mixing the metal catalyst (D), or a step of simultaneously mixing the metal catalyst (D) and water (E) [9] The method for preparing the antifouling composition solution described in .

[11] The method for producing the antifouling composition solution according to [9] or [10] above, in step (1), using an acid catalyst (C).

[12] The acid catalyst (C) is at least one member selected from the group consisting of hydrochloric acid, phosphoric acid, acetic acid, formic acid, sulfuric acid, methanesulfonic acid, hydrobromic acid, p-toluenesulfonic acid, and trifluoroacetic acid according to the above [11] The method for preparing the antifouling composition solution described in .

[13] The antifouling property described in [11] or [12] above, wherein the compounding amount of the acid catalyst (C) is 0.010 mol% or more and 1.000 mol% or less with respect to 100 mol% of the total compounding amount of component (A) and component (B). A method for preparing a composition solution.

[14] An antifouling composition solution obtained by the production method according to any one of [9] to [13] above.

[15] A solution formed by blending water (E) with a hydrolyzate of the following component (A) and a hydrolyzate of the following component (B).

Component (A): A tetrafunctional silane-based compound represented by the following general formula (a)

Si(OR ¹ ) _p (X ¹ ) _4-p (a)

[In general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When there are a plurality of R ¹ and X ¹ , the plurality of R ¹ and X ¹ may be the same as or different from each other. p represents an integer from 0 to 4.]

Component (B): Trifunctional silane-based compound represented by the following general formula (b)

R ² Si(OR ³ ) _q (X ² ) _3-q (b)

[In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ represents an alkyl group of 1 to 6 carbon atoms, and X ² represents a halogen atom. When a plurality of R ³ and X ² are present, the plurality of R ³ and X ² may be the same as or different from each other. q represents an integer from 0 to 3.]

ADVANTAGE OF THE INVENTION According to this invention, the antifouling composition solution with a long usable time (pot life) and its manufacturing method can be provided.

1 is a cross-sectional view of an antifouling sheet having a substrate, which is an example of an antifouling sheet obtained by using an antifouling composition solution of the present invention.
Fig. 2 is a cross-sectional view of an antifouling sheet having no substrate, which is an example of an antifouling sheet obtained by using the antifouling composition solution of the present invention.

[Antifouling composition solution]

The antifouling composition solution of the present invention is a hydrolyzate of a tetrafunctional silane-based compound [component (A)] represented by the general formula (a) and a hydrolyzate of a trifunctional silane-based compound [component (B)] represented by the general formula (b) It is a solution of an antifouling composition formed by blending a decomposition product with a metal catalyst (D) and water (E).

Further, the antifouling composition solution of the present invention may contain, in addition to these components, an acid catalyst (C) described later, and may contain other additives other than these components, within a range not impairing the effects of the present invention. .

When the antifouling layer is formed, first, the alkoxy groups (OR ¹ in general formula (a) and OR ³ in general formula (b)) in component (A) and component (B) in the antifouling composition are hydrolyzed, resulting in uncondensation. A hydrolyzate of component (A) and a hydrolyzate of component (B) having a sum of silanol groups are produced.

Next, when the silanol groups in these hydrolyzates undergo a condensation reaction to form a polymer, the coating film formed from the antifouling composition is cured to form an antifouling layer.

Here, in order to accelerate the hydrolysis reaction of components (A) and (B) in the previous stage, it is preferable to use an acid catalyst (C) described later.

And in order to accelerate the condensation reaction of a later stage, it becomes possible to fully improve the hardenability of the antifouling composition solution by using a metal catalyst (D).

Thus, in the antifouling composition solution, excellent curability can be realized in a short time by using the metal catalyst (D).

On the other hand, when the antifouling composition solution is prepared and then stored for a long time and then cured, the curability decreases, and sufficient curability may not be obtained.

Therefore, from the viewpoint of obtaining an antifouling composition solution having a long usable time (also referred to as "pot life"), there is room for further examination of the antifouling composition solution.

It is estimated that such a fall of hardenability arises by the following reason.

As described above, the curing reaction of the antifouling composition proceeds in two steps: a hydrolysis reaction in the previous stage and a condensation reaction in the subsequent stage. When the antifouling composition solution is stored for a long time without accelerating curing by heating or the like after preparation, the subsequent condensation reaction already proceeds, and it is considered that a large amount of polymers or oligomers are mainly produced. Therefore, when it is attempted to obtain a three-dimensional cross-linked structure by subsequent heat treatment, it is estimated that sufficient silanol groups required for the cross-linking reaction are not present and good curability is not obtained.

On the other hand, it is presumed that similarly sufficient curability is not obtained even when the hydrolysis reaction in the previous stage is not sufficiently advanced.

Therefore, in order to control the curability of the antifouling composition solution, the inventors of the present invention, after sufficiently advancing the hydrolysis reaction of components (A) and (B), until the final curing reaction, component (A) ) and the suppression of the condensation reaction between the silanol groups of the hydrolyzate of component (B).

And the present inventors guess that the condensation reaction of silanol groups can be effectively suppressed by further adding water (E) with respect to the hydrolyzate of component (A) and the hydrolyzate of component (B), A review was conducted.

As a result, it was found that an antifouling composition solution having a longer usable time was obtained, and the present invention was completed.

In addition, as described later, in this specification, "water (E)" refers to water to be blended later with respect to the system in which the hydrolyzate of component (A) and the hydrolyzate of component (B) exist.

Here, even if the amount of water previously mixed for hydrolyzing components (A) and (B) or water used to dilute the acid catalyst (C) is increased, for example, as shown in comparative examples described later, Likewise, the effect of the present application is not well obtained.

In addition, even when the metal catalyst (D) is blended with the hydrolyzate of component (A) and the hydrolyzate of component (B) and water (E) is not blended, the hydrolyzate of component (A) and the component ( The condensation reaction between the silanol groups in the hydrolyzate of B) is promoted, and the usable time of the antifouling composition solution is shortened.

Therefore, the excellent effect of this invention is acquired by further mixing the said water (E) with respect to the hydrolyzate of component (A) and the hydrolyzate of component (B). The reason for this is not certain, but it is speculated as follows.

The condensation reaction between the silanol groups of the hydrolyzate of component (A) and the hydrolyzate of component (B) is an equilibrium reaction, and water is produced by the condensation reaction. That is, the condensation reaction is dehydration condensation. Therefore, with respect to the hydrolyzate of component (A) and the hydrolyzate of component (B), it is presumed that the progress of the above-mentioned condensation reaction (dehydration condensation), which is an equilibrium reaction, is suppressed by the presence of water (E) blended later. do.

Hereinafter, each component contained in the antifouling composition solution of the present invention will be described.

<Hydrolyzate of component (A)>

The antifouling composition solution of the present invention contains a hydrolyzate of component (A) described later. The hydrolyzate of component (A) is obtained by hydrolyzing the alkoxy group in component (A), and has a silanol group in its molecular structure.

(Component (A): tetrafunctional silane-based compound represented by general formula (a))

The component (A) is a tetrafunctional silane-based compound represented by the following general formula (a).

Si(OR ¹ ) _p (X ¹ ) _4-p (a)

In general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When there are a plurality of R ¹ and X ¹ , the plurality of R ¹ and X ¹ may be the same as or different from each other. p represents an integer of 0 to 4;

The number of carbon atoms in the alkyl group that can be selected as R ¹ is preferably 4 or less, more preferably 3 or less, still more preferably 2 or less.

Examples of the alkyl group that can be selected as R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, and n-pentyl group. , n-hexyl group, neopentyl group, methylpentyl group, etc. are mentioned. Among these, from the viewpoint of obtaining better curability, a methyl group, an ethyl group, or an n-propyl group is preferable, and a methyl group or an ethyl group is more preferable.

The alkyl group that can be selected as R ¹ may be either straight chain or branched chain, but is preferably straight chain.

As a halogen atom that can be selected as X ¹ , a chlorine atom, a bromine atom, or an iodine atom is preferable, and a chlorine atom is more preferable.

In addition, you may use the silane-type compound represented by the said general formula (a) individually or in combination of 2 or more types.

Moreover, as a component (A), it is preferable that p in the said general formula (a) contains the silane type compound which is 4.

<Hydrolyzate of component (B)>

The antifouling composition solution of the present invention contains a hydrolyzate of component (B) together with the hydrolyzate of component (A). The hydrolyzate of component (B) is obtained by hydrolyzing the alkoxy group in component (B), and has a silanol group in its molecular structure.

(Component (B): trifunctional silane-based compound represented by general formula (b))

Component (B) is a trifunctional silane-based compound represented by the following general formula (b).

R ² Si(OR ³ ) _q (X ² ) _3-q (b)

In the general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ represents an alkyl group of 1 to 6 carbon atoms, and X ² represents a halogen atom. When a plurality of R ³ and X ² are present, the plurality of R ³ and X ² may be the same as or different from each other. q represents an integer of 0 to 3;

The number of carbon atoms of the alkyl group which can be selected as R ² is 1-24.

When the number of carbon atoms in the alkyl group exceeds 24, the curability of the antifouling composition solution is inferior. In addition, as the number of carbon atoms in the alkyl group increases, the antifouling composition solution tends to gel, and the surface state of the antifouling layer formed from the antifouling composition solution tends to deteriorate. From such a viewpoint, the number of carbon atoms in the alkyl group is preferably 22 or less, more preferably 20 or less, still more preferably 18 or less.

In addition, carbon number of the arbitrary substituent which the said alkyl group may have is not included in carbon number of the alkyl group which can be selected as ^R2 .

Examples of the alkyl group that can be selected as R ² include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n- Octadecyl group, n-nonadecyl group, n-icosyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, methylpentyl group, isohexyl group, pentylhexyl group, butylpentyl group, and 2-ethylhexyl group; and the like.

The alkyl group that can be selected as R ² may be a straight chain or a branched chain, but from the viewpoint of improving the curability of the antifouling composition solution and the planar state of the antifouling layer formed from the antifouling composition solution, a straight chain is preferred. desirable.

The alkyl group that can be selected as R ² may have a substituent.

As such a substituent, For example, Halogen atoms, such as a chlorine atom, a bromine atom, and an iodine atom; hydroxyl group; nitro group; amino group; cyano group; mercapto group; Epoxy group; glycidoxy group; acryloyloxy group; methacryloyloxy group; a cycloalkyl group having 3 to 12 ring carbon atoms (preferably 6 to 10 ring carbon atoms); an aryl group having 6 to 12 ring carbon atoms; a heteroaryl group having 6 to 12 ring atoms and containing a hetero atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom; an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 3 carbon atoms); aryloxy groups having 6 to 12 ring carbon atoms; and the like, and these substituents may be further substituted.

However, it is preferable that it is an alkyl group which does not have a substituent as an alkyl group which can be selected as ^R2 .

Examples of the alkyl group selectable as R ³ and the halogen atom selectable as X ² include the same ones as the alkyl group selectable as R ¹ and the halogen atom selectable as X ¹ in the general formula (a) described above.

In addition, you may use the trifunctional silane type compound represented by the said general formula (b) individually or in combination of 2 or more types.

Moreover, as a component (B), it is preferable to contain the trifunctional silane type compound whose q in the said general formula (b) is 3.

(About condition (I))

Regarding the relationship between component (A) and component (B), a solution of the antifouling composition that satisfies the following condition (I) is preferred.

Condition (I): The ratio of the compounding amount (molar amount) of component (A) to the compounding amount (molar amount) of component (B) [(A)/(B)] (molar ratio) is 0.01 or more and 50.00 or less

When the [(A)/(B)] (molar ratio) is 0.01 or more, the curability of the antifouling composition solution becomes good. From such a viewpoint, the [(A)/(B)] (molar ratio) is more preferably 0.10 or more, still more preferably 0.50 or more, even more preferably 0.80 or more, still more preferably 1.00 or more. .

Further, the [(A)/(B)] (molar ratio) is preferably 50.00 or less. When the [(A)/(B)] (molar ratio) is 50.00 or less, the antifouling layer formed from the antifouling composition solution has better water repellency due to the presence of the alkyl group represented by R ² in component (B). From such a viewpoint, the [(A)/(B)] (molar ratio) is more preferably 30.00 or less, still more preferably 25.00 or less, still more preferably 20.00 or less, still more preferably 10.00 or less. .

In addition, the compounding amount (molar amount) of component (A) is the amount of component (A) and component (B) from the viewpoint of improving the curability of the antifouling composition solution and obtaining a good surface state of the antifouling layer formed from the antifouling composition solution. The compounding amount (molar amount) is preferably 0.50 mol% or more, more preferably 10.00 mol% or more, even more preferably 30.00 mol% or more, even more preferably 45.00 mol% or more, still more preferably, with respect to 100 mol% in total of the compounding amount (molar amount). It is 50.00 mol% or more. The blending amount (molar amount) is preferably 98.00 mol% or less, more preferably 96.00 mol% or less, still more preferably 94.00 mol% or less, still more preferably 90.00 mol% or less.

In addition, the "content (mol) of the hydrolyzate of component (A)" in the antifouling composition solution of the present invention can be regarded as substantially the same as the "compounding amount (mol) of component (A)" before hydrolysis.

This is the same also about component (B), component (B-1), and component (B-2).

[Component (B-1): Trifunctional silane-based compound represented by general formula (b-1)]

It is preferable that component (B) contains at least 1 sort(s) of component (B-1) which is a trifunctional silane type compound represented by the following general formula (b-1).

R ⁴ Si(OR ⁵ ) _r (X ³ ) _3-r (b-1)

In general formula (b-1), R ⁴ represents an alkyl group having 6 to 24 carbon atoms, and the alkyl group may have a substituent. R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and X ³ represents a halogen atom. When a plurality of R ⁵ and X ³ are present, the plurality of R ⁵ and X ³ may be the same as or different from each other. r represents an integer of 0 to 3;

The number of carbon atoms of the alkyl group which can be selected as R ⁴ is 6-24.

When the number of carbon atoms of the alkyl group represented by R ⁴ is 6 or more, an antifouling layer having good water repellency is obtained, which is preferable. From such a viewpoint, as said R< ⁴ >, Preferably it is 8 or more. The preferable upper limit of the number of carbon atoms in the alkyl group represented by R ⁴ is the same as the preferable upper limit of R ² described above, and is preferably 22 or less, more preferably 20 or less, still more preferably 18 or less. The reason for setting each preferable upper limit value is also as described above for R ² .

In addition, carbon number of the arbitrary substituent which the said alkyl group may have is not included in carbon number of the alkyl group which can be selected as said R< ⁴ >.

Examples of the alkyl group that can be selected as R ⁴ include n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n -tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, n-henico Sil group, n-docosyl group, n-tricosyl group, n-tetracosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, methyl A pentyl group, an isohexyl group, a pentylhexyl group, a butylpentyl group, and a 2-ethylhexyl group, etc. are mentioned.

The alkyl group that can be selected as R ⁴ may be a straight chain or a branched chain, but from the viewpoint of improving the curability of the antifouling composition solution and the planar state of the antifouling layer formed from the antifouling composition solution, a straight chain is preferred. desirable. As the alkyl group that can be selected as R ⁴ , an n-nonyl group, an n-decyl group, or an n-dodecyl group is preferable from the same viewpoint.

The alkyl group that can be selected as R ⁴ may have a substituent. In addition, the substituent which the alkyl group which can be selected as R ⁴ has is the same as the substituent which the alkyl group which can be selected as R ² has is mentioned above.

However, it is preferable that it is an alkyl group which does not have a substituent also as an alkyl group which can be selected as R< ⁴ >.

Examples of the alkyl group selectable as R ⁵ and the halogen atom selectable as X ³ include the same ones as the alkyl group selectable as R ¹ in the above general formula (a) and the halogen atom selectable as X ¹ .

In addition, you may use the trifunctional silane type compound represented by general formula (b-1) individually or in combination of 2 or more types.

Moreover, as a component (B-1), it is preferable that r in general formula (b-1) contains the trifunctional silane type compound which is 3.

[Component (B-2): Trifunctional silane-based compound represented by general formula (b-2)]

It is preferable that component (B) contains at least 1 sort(s) of component (B-2) which is a trifunctional silane type compound represented by the following general formula (b-2).

R ⁶ Si(OR ⁷ ) _s (X ⁴ ) _3-s (b-2)

In general formula (b-2), R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent. R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and X ⁴ represents a halogen atom. When there are a plurality of R ⁷ and X ⁴ , the plurality of R ⁷ and X ⁴ may be the same as or different from each other. s represents the integer of 0-3.

The number of carbon atoms of the alkyl group which can be selected as R ⁶ is 1-3.

When the number of carbon atoms in the alkyl group is within this range, the antifouling composition solution has excellent curability. In addition, carbon number of the arbitrary substituent which the said alkyl group may have is not included in carbon number of the alkyl group which can be selected as R< ⁶ >.

Examples of the alkyl group that can be selected as R ⁶ include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, and from the viewpoint of obtaining curability, a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

The alkyl group that can be selected as R ⁶ may have a substituent. Substituents of the alkyl group that can be selected as R ⁶ include the same substituents as those described above for the substituents of the alkyl group that can be selected as R ² .

However, it is preferable that it is an alkyl group which does not have a substituent as an alkyl group which can be selected as R< ⁶ >.

Examples of the alkyl group selectable as R ⁷ and the halogen atom selectable as X ⁴ include the same ones as the alkyl group selectable as R ¹ and the halogen atom selectable as X ¹ in the general formula (a) described above.

In addition, you may use the trifunctional silane type compound represented by general formula (b-2) individually or in combination of 2 or more types.

Moreover, as a component (B-2), it is preferable to include the trifunctional silane type compound whose s in General formula (b-2) is 3.

The antifouling composition solution used in the present invention more preferably contains both component (B-1) and component (B-2) as component (B), which is a raw material of the hydrolyzate of component (B). As the component (B), by using the component (B-1) and the component (B-2) in combination, the surface of the antifouling layer formed from the curable antifouling composition solution and the antifouling composition solution, compared to the case of using either one alone. condition can be improved.

(About condition (II))

As component (B), when component (B-1) and component (B-2) are used together, the following condition (II) is satisfied in the relationship between component (B-1) and component (B-2) it is desirable

Condition (II): Ratio of the compounding amount (molar amount) of component (B-1) to the total compounding amount (molar amount) of component (B-1) and component (B-2) [(B-1)/{(B- 1) + (B-2)}] (molar ratio) A, 0.020 or more

When the [(B-1)/{(B-1) + (B-2)}] (molar ratio) is 0.020 or more, the static friction coefficient and the dynamic friction coefficient of the antifouling layer formed from the antifouling composition solution are low, Excellent friction properties. In addition, the presence of the alkyl group represented by R ⁴ in component (B-1) makes the antifouling layer formed from the antifouling composition solution have better water repellency. From such a viewpoint, the [(B-1)/{(B-1) + (B-2)}] (molar ratio) is more preferably 0.035 or more, still more preferably 0.045 or more, still more preferably is 0.050 or more, still more preferably 0.100 or more, still more preferably 0.150 or more, still more preferably 0.250 or more, still more preferably 0.500 or more.

The upper limit of [(B-1)/{(B-1) + (B-2)}] (molar ratio) is preferably 0.995 or less, more preferably 0.990 or less, still more preferably 0.980 or less. , more preferably 0.950 or less, still more preferably 0.850 or less.

In addition, the antifouling composition solution of the present invention contains component (B-1) and component (B-2) as trifunctional silane-based compounds so as to satisfy the above conditions (I) and (II), It is preferable because it is possible to achieve both high surface hardness and low friction coefficient of the antifouling layer to be formed. In addition, by including the component (B-2), the weather resistance of the antifouling layer formed from the antifouling composition solution can be expected to be improved.

As the component (B), when component (B-1) and component (B-2) are used together, the compounding amount (molar amount) of the component (B-1) is the curable property of the antifouling composition solution and the antifouling agent formed from the antifouling composition solution. From the viewpoint of improving the surface condition of the five layers, the blending amount (molar amount) of component (A), component (B-1) and component (B-2) is preferably 0.30 mol% or more, more preferably 0.30 mol% or more, relative to 100 mol% in total. It is preferably 0.50 mol% or more, more preferably 1.00 mol% or more, and even more preferably 5.00 mol% or more. The blending amount (molar amount) is preferably 45.00 mol% or less, more preferably 40.00 mol% or less, still more preferably 38.00 mol% or less.

In addition, when component (B-1) and component (B-2) are used together as component (B), the compounding amount (molar amount) of component (B-2) is formed from the curable and antifouling composition solution of the antifouling composition solution. From the viewpoint of improving the surface condition of the antifouling layer to be formed, the blending amount (molar amount) of component (A), component (B-1) and component (B-2) is preferably 0.50 mol% or more, relative to 100 mol% in total; More preferably, it is 0.80 mol% or more, still more preferably 1.00 mol% or more, and still more preferably 1.30 mol% or more. The blending amount (molar amount) is preferably 40.00 mol% or less, more preferably 38.00 mol% or less, even more preferably 25.00 mol% or less, still more preferably 18.00 mol% or less.

In addition, as component (B), when component (B-1) and component (B-2) are used together, in the relationship between component (A) and component (B-1), the compounding amount of component (B-1) The ratio [(A)/(B-1)] (molar ratio) of the compounding amount (molar amount) of component (A) to (molar amount) is preferably 0.5 or more, from the viewpoint of improving the curability of the antifouling composition solution. It is preferably 0.8 or more, more preferably 1.0 or more, and still more preferably 1.2 or more.

And it is preferable that [(A)/(B-1)] (molar ratio) is 300.0 or less. When the [(A)/(B-1)] (molar ratio) is 300.0 or less, the antifouling layer formed from the antifouling composition has better water repellency due to the presence of the alkyl group represented by R ⁴ in component (B-1). have From such a viewpoint, the [(A)/(B-1)] (molar ratio) is more preferably 200.0 or less, still more preferably 150.0 or less, even more preferably 100.0 or less, still more preferably 90.0 or less, more preferably 50.0 or less, still more preferably 10.0 or less.

Further, as the component (B), when the component (B-1) and the component (B-2) are used together, the compounding amount of the component (B-2) in the relationship between the component (A) and the component (B-2) The ratio [(A)/(B-2)] (molar ratio) of the compounding amount (molar amount) of component (A) to (molar amount) is not particularly limited, and is preferably 1.0 or more. Further, the [(A)/(B-2)] (molar ratio) is preferably 70.0 or less, more preferably 50.0 or less, still more preferably 20.0 or less.

In the case of using the component (B-1) and the component (B-2) together as the component (B), in the relationship between the component (A), the component (B-1) and the component (B-2), the component Ratio of the compounding amount (molar amount) of component (A) to the total compounding amount (molar amount) of (B-1) and component (B-2) [(A)/{(B-1) + (B-2)}] (Molar ratio) is preferably 0.01 or more, more preferably 0.10 or more, still more preferably 0.50 or more, still more preferably 0.80 or more, still more preferably 1.00 or more. The [(A)/{(B-1) + (B-2)}] (molar ratio) is preferably 50.00 or less, more preferably 25.00 or less, even more preferably 20.00 or less, still more preferably It is less than 10.00.

In addition, when component (B-1) and component (B-2) are used together as component (B), the total compounding amount of component (B-1) and component (B-2) in component (B) is With respect to 100 mass% of the total amount of the component (B) blended, it is preferably 50 mass% or more, more preferably 65 mass% or more, still more preferably 80 mass% or more, still more preferably 90 mass% or more, It is still more preferably 95% by mass or more, still more preferably 99% by mass or more, and preferably 100% by mass or less. Moreover, the said content is more preferably 100 mass %.

(Acid catalyst (C))

The hydrolyzate of component (A) and the hydrolyzate of component (B) used in the antifouling composition solution of the present invention are hydrolyzed hydrolyzed using an acid catalyst (C) from the viewpoint of further improving the curability of the antifouling composition solution. It is preferable that it is a decomposition product.

The acid catalyst (C) is not particularly limited as long as it is a component having an action of accelerating the hydrolysis of the reactive functional groups of components (A) and (B). For example, from the viewpoint of further improving the curability of the antifouling composition solution, one selected from the group consisting of hydrochloric acid, phosphoric acid, acetic acid, formic acid, sulfuric acid, methanesulfonic acid, hydrobromic acid, p-toluenesulfonic acid, and trifluoroacetic acid It is preferable to include the above, and it is more preferable to include hydrochloric acid.

Moreover, as said acid catalyst (C), you may use individually or in combination of 2 or more types.

<Metal Catalyst (D)>

The antifouling composition solution of the present invention further contains a metal catalyst (D) together with the hydrolyzate of component (A) and the hydrolyzate of component (B). When the metal catalyst (D) is not included, the condensation reaction of the hydrolyzate of component (A) and the hydrolyzate of component (B) cannot be effectively promoted, and the curability of the antifouling composition solution cannot be sufficiently improved.

Further, in the case of the antifouling composition solution containing no metal catalyst (D), the curing reaction cannot sufficiently proceed at a relatively low temperature (130°C or lower). Therefore, for example, when it is intended to form an antifouling layer formed from the solution of the antifouling composition on a substrate having low heat resistance, such as a vinyl chloride resin, the antifouling layer is maintained at a low temperature sufficient to suppress thermal shrinkage of the substrate. If it is intended to form, there is a possibility that the antifouling layer composition solution may be insufficiently cured. Conversely, when curing is attempted at a relatively high temperature (exceeding 130° C.) in order to sufficiently advance the curing reaction, there is a risk that the base material may cause thermal contraction.

As a metal catalyst (D), it is preferable that it is a metal catalyst which does not require light irradiation for the expression of a catalytic action.

In addition, in this specification, the "metal catalyst which does not require light irradiation for the expression of a catalytic action" expresses a catalytic action for the condensation reaction of the hydrolyzate of component (A) and the hydrolyzate of component (B) It refers to a metal catalyst that does not require light irradiation to do so. For example, titanium oxide (TiO ₂ ), zinc oxide (ZnO), etc., which generate electrons and holes by light irradiation to cause oxidation and reduction reactions. Light irradiation is required for the expression of a catalytic action. , which are commonly called photocatalysts are excluded.

Further, when the antifouling composition solution contains the above "metal catalyst that does not require light irradiation for the expression of a catalytic action", problems that may occur when a photocatalyst is used can be avoided. Problems that may occur in the case of using the photocatalyst include, for example, a decrease in water repellency due to an increase in surface roughness of the antifouling layer obtained due to the fact that the photocatalyst itself is a solid substance, and a hydrophilic effect of the photocatalyst. problems such as deterioration of water repellency due to

The metal catalyst (D) is preferably at least one selected from the group consisting of titanium-based catalysts, zirconium-based catalysts, palladium-based catalysts, tin-based catalysts, aluminum-based catalysts, and zinc-based catalysts.

The titanium-based catalyst is preferably a compound other than a photocatalyst containing a titanium atom, and examples thereof include titanium alkoxide, titanium chelate, and titanium acylate. Hydroxides, acetates, and carbonates of titanium , sulfate, nitrate, or chloride may be used.

Examples of the titanium alkoxide include titanium tetraisopropoxide, titanium tetranormal butoxide, titanium butoxide dimer, and titanium tetra-2-ethylhexoxide.

Examples of the titanium chelate include titanium acetylacetonates such as titanium diisopropoxybis(acetylacetonate) and titanium tetraacetylacetonate; Titanium ethyl acetoacetate, such as titanium diisopropoxybis (ethyl acetoacetate); titanium triethanol laminates such as titanium diisopropoxybis (triethanol laminate); titanium octylene glycolates such as titanium tetraoctylene glycolate, titanium dioctyloxybis (octylene glycolate), and titanium di-2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide); Titanium lactate, titanium lactate ammonium salt, etc. are mentioned.

As a titanium acylate, polyhydroxy titanium stearate etc. are mentioned, for example.

The zirconium-based catalyst is preferably a compound other than a photocatalyst containing a zirconium atom, and examples thereof include zirconium alkoxide, zirconium chelate, and zirconium acylate. Hydroxides, acetates, and carbonates of zirconium , sulfate, nitrate, or chloride may be used.

As zirconium alkoxide, zirconium tetra normal propoxide, zirconium tetra normal butoxide, etc. are mentioned, for example.

Examples of the zirconium chelate include zirconium acetylacetonates such as zirconium tributoxymonoacetylacetonate and zirconium tetraacetylacetonate; zirconium ethyl acetoacetates such as zirconium dibutoxybis(ethyl acetoacetate); A zirconyl chloride compound, zirconium lactate ammonium salt, etc. are mentioned.

As zirconium acylate, an octylic acid zirconium compound, stearic acid zirconium, etc. are mentioned, for example.

The palladium-based catalyst is preferably a compound other than a photocatalyst containing a palladium atom, and examples thereof include palladium, palladium chloride, palladium hydroxide, and a palladium carbon catalyst (Pd/C).

The tin-based catalyst is preferably a compound other than a photocatalyst containing a tin atom, and examples thereof include stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, and dibutyltin mercaptide. , organic tin compounds such as dibutyltin dithiocarboxylate, dibutyltin dimaleate, dioctyltin mercaptide, and dioctyltinthiocarboxylate, or inorganic tin compounds.

The aluminum-based catalyst is preferably a compound other than a photocatalyst containing an aluminum atom, and examples thereof include an acetoacetate complex of aluminum and an acetylacetonate complex of aluminum.

Examples of the acetoacetate complex of aluminum include diisopropoxy aluminum monooleyl acetoacetate, monoisopropoxy aluminum bisoleyl acetoacetate, monoisopropoxy aluminum monooleate monoethyl acetoacetate, diisopro Poxy aluminum monolauryl acetoacetate, diisopropoxy aluminum monostearylacetoacetate, diisopropoxy aluminum monoisostearyl acetoacetate, monoisopropoxy aluminum mono-N-lauroyl-β-alanate mono Uryl acetoacetate, aluminum trisacetylacetonate, etc. are mentioned.

As the acetylacetonate complex of aluminum, for example, monoacetylacetonate aluminum bis (isobutylacetoacetate) chelate, monoacetylacetonate aluminum bis (2-ethylhexylacetoacetate) chelate, monoacetylacetonate aluminum bis ( dodecyl acetoacetate) chelate, monoacetylacetonate aluminum bis(oleyl acetoacetate) chelate, and the like.

The zinc-based catalyst is preferably a compound other than a photocatalyst containing a zinc atom, and examples thereof include zinc-chromium oxide, zinc-aluminum oxide, zinc-aluminum-chromium oxide, zinc-chromium-manganese oxide, Zinc-iron oxide, zinc-iron-aluminum oxide, etc. are mentioned.

In addition, as a metal catalyst (D), you may use individually or in combination of 2 or more types.

In addition, from the viewpoint of effectively promoting the condensation reaction between silane-based compounds to improve the curability of the antifouling composition solution, and from the viewpoint of obtaining an antifouling composition solution capable of advancing the curing reaction even at a relatively low temperature (130 ° C. or less), It is preferable to contain at least the said titanium catalyst.

As the titanium-based catalyst, titanium chelate is preferable, titanium ethylacetoacetate, titanium acetylacetonate or titanium octylene glycolate is more preferable, titanium ethylacetoacetate is still more preferable, and titanium diisopropoxybis(ethyl acetoacetate) is even more preferred.

The compounding amount (molar amount) of the metal catalyst (D) in the antifouling composition solution is from the viewpoint of improving the curability of the antifouling composition solution and from the viewpoint of making the antifouling composition solution capable of advancing a curing reaction even at a relatively low temperature (130°C or less) , the total compounding amount (molar amount) of component (A) and component (B) relative to 100 mol% is preferably 0.010 mol% or more, more preferably 0.100 mol% or more, still more preferably 0.150 mol% or more, and more More preferably, it is 0.300 mol% or more, still more preferably 0.500 mol% or more, and still more preferably 1.000 mol% or more.

The blending amount (molar amount) is preferably 50.000 mol% or less, more preferably 30.000 mol% or less, even more preferably 20.000 mol% or less, still more preferably 10.000 mol% or less, still more preferably 6.000 mol% or less, more preferably 3.000 mol% or less.

In addition, the content of the metal catalyst (D) in the antifouling composition solution is from the viewpoint of improving the curability of the antifouling composition solution and from the viewpoint of making the antifouling composition solution capable of advancing a curing reaction even at a relatively low temperature (130°C or less). , Preferably it is 0.01 mass % or more, More preferably, it is 0.05 mass % or more, More preferably, it is 0.1 mass % or more. The content is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less.

In addition, the said content can also be computed from the compounding quantity at the time of mix|blending each component.

＜Water (E)＞

As the water (E) used in the present invention, it is preferable to use pure or ultrapure water such as distilled water, deionized water, purified water, RO (Reverse Osmosis) water, or the like.

As described above, in this specification, "water (E)" refers to water to be blended later with respect to the system in which the hydrolyzate of component (A) and the hydrolyzate of component (B) exist. Therefore, for example, water mixed in advance to hydrolyze the aforementioned components (A) and (B) and water used to dilute the acid catalyst (C) are excluded.

From the viewpoint of improving the curability of the antifouling composition solution, the blending amount (molar amount) of water (E) in the antifouling composition solution is preferably based on 100 mol% of the total blending amount (molar amount) of component (A) and component (B). 0.01 mol% or more, more preferably 0.10 mol% or more, still more preferably 0.50 mol% or more, still more preferably 1.00 mol% or more, still more preferably 10.0 mol% or more, still more preferably 100 mol% more than 1% The blending amount (molar amount) is preferably 100,000 mol% or less, more preferably 50,000 mol% or less, even more preferably 10,000 mol% or less, still more preferably 5,000 mol% or less, still more preferably 2,000 mol% or less, more preferably 1,000 mol% or less, still more preferably 500 mol% or less.

In addition, the total content of water including water (E) in the antifouling composition solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably from the viewpoint of improving the curability of the antifouling composition solution. is 1.00% by mass or more, more preferably 2.50% by mass or more, still more preferably 5.00% by mass or more. The content is preferably 99.00% by mass or less, more preferably 95.00% by mass or less, even more preferably 90.00% by mass or less, still more preferably 70.00% by mass or less, still more preferably 50.00% by mass. or less, more preferably 25.00% by mass or less.

In addition, the total content of the water is in the antifouling composition solution, which includes, in addition to water (E), water used to dilute the acid catalyst (C) described above and water contained in other components, for example. It refers to the amount of water contained in

The content can also be calculated from, for example, the amount of water (E) and the amount of water in the acid catalyst (C), and the amount of water produced by dehydration condensation of components (A) and (B). For example, the water content can also be measured by adding magnesium sulfate to the antifouling composition solution to adsorb water and measuring the water content by the Karl Fischer method.

<Other additives>

The antifouling composition solution may contain other additives in addition to the components described above, within a range not impairing the effect of the present invention.

Examples of other additives include resin components, curing agents, anti-aging agents, light stabilizers, flame retardants, conductive agents, antistatic agents, and plasticizers.

The content of these additives is each independently preferably 0 to 20% by mass, more preferably 0 to 10% by mass, still more preferably 0 to 5% by mass, and even more preferably 0 to 5% by mass, relative to the total amount of the antifouling composition solution. Preferably it is 0-2 mass %.

In addition, the said content can also be computed from the compounding quantity at the time of mix|blending each component.

In addition, the total compounding amount of component (A), component (B), and metal catalyst (D) in the antifouling composition solution is preferably 50 mass% or more, more than 100 mass% of all active ingredients in the antifouling composition solution. preferably 65% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, even more preferably 99% by mass or more, and, Preferably it is 100 mass % or less. Moreover, the said compounding quantity is more preferably 100 mass %.

In the present invention, the active ingredient in the antifouling composition solution is a liquid component excluding solvents (water or organic solvent) not directly involved in the reaction, and a solid component at room temperature, among components contained in the antifouling composition solution. point

<Characteristics of antifouling composition solution>

The antifouling composition solution of the present invention has a long usable time, and even when used after a certain period of time has elapsed after preparation, it is possible to maintain good curability.

The usable time is, for example, preferably 24 hours or more, more preferably 168 hours or more, still more preferably 336 hours or more, and preferably 4,500 hours or less.

Thus, unlike conventional antifouling composition solutions, the antifouling composition solution of the present invention can exhibit good curability even after a long period of time has elapsed since preparation.

The antifouling composition solution of the present invention includes the antifouling composition solution after 24 hours have elapsed after preparing the antifouling composition solution.

[Method for Producing Antifouling Composition Solution]

The manufacturing method of the antifouling composition solution of this invention has the following process (1) and process (2) in this order.

Step (1): Step of hydrolyzing the following component (A) and the following component (B)

Component (A): A tetrafunctional silane-based compound represented by the following general formula (a)

Si(OR ¹ ) _p (X ¹ ) _4-p (a)

[In general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When there are a plurality of R ¹ and X ¹ , the plurality of R ¹ and X ¹ may be the same as or different from each other. p represents an integer from 0 to 4.]

Component (B): Trifunctional silane-based compound represented by the following general formula (b)

R ² Si(OR ³ ) _q (X ² ) _3-q (b)

[In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ represents an alkyl group of 1 to 6 carbon atoms, and X ² represents a halogen atom. When a plurality of R ³ and X ² are present, the plurality of R ³ and X ² may be the same as or different from each other. q represents an integer from 0 to 3.]

Step (2): Step of mixing a metal catalyst (D) and water (E) with the hydrolyzate of component (A) and the hydrolyzate of component (B) obtained in step (1)

<Process (1)>

Step (1) is a step of hydrolyzing component (A) and component (B).

The said component (A) and component (B) are the same as the above-mentioned component (A) and component (B), respectively, and the preferable aspect is also the same. In addition, the compounding quantity of component (A) and component (B) is also the same as the compounding quantity of the above-mentioned component (A) and component (B), and the preferable range is also the same.

The method for hydrolyzing components (A) and (B) is not particularly limited, but it is preferable to hydrolyze using an acid catalyst (C).

As an acid catalyst (C), it is the same as that of the acid catalyst (C) mentioned above, and the preferable aspect is also the same.

The blending amount (molar amount) of the acid catalyst (C) is preferably 0.010 mol with respect to 100 mol% of the total blending amount (molar amount) of components (A) and (B) from the viewpoint of further improving the curability of the antifouling composition solution. % or more, more preferably 0.030 mol% or more, even more preferably 0.050 mol% or more, still more preferably 0.060 mol% or more. The blending amount (molar amount) is preferably 1.000 mol% or less, more preferably 0.500 mol% or less, still more preferably 0.100 mol% or less, still more preferably 0.075 mol% or less.

When hydrolysis of component (A) and component (B) is carried out using acid catalyst (C), the temperature at the time of carrying out step (1) is There is no particular restriction as long as the temperature allows hydrolysis, but it is preferably 5°C or higher, more preferably 10°C or higher, still more preferably 15°C or higher, from the viewpoint of suppressing the progress of unintended condensation reaction due to heating. . The temperature is preferably 100°C or lower, more preferably 75°C or lower, even more preferably 50°C or lower, and still more preferably 40°C or lower.

In the case of hydrolysis of component (A) and component (B) using an acid catalyst (C), the reaction time when performing the hydrolysis reaction in step (1) is ) is not particularly limited as long as the time can sufficiently promote hydrolysis of the reactive functional group, and can be appropriately adjusted depending on the amount of the components (A) and (B), the amount of the acid catalyst (C), the reaction temperature, etc. .

Therefore, the reaction time can be appropriately adjusted depending on the above conditions, but is, for example, preferably 0.10 hour or more, more preferably 0.15 hour or more, even more preferably 0.20 hour or more, and still more preferably It is more than 0.25 hours. The reaction time is preferably 24.00 hours or less, more preferably 12.00 hours or less, even more preferably 3.00 hours or less, and still more preferably 1.00 hours or less.

In step (1), the components (A) and (B) may be dissolved in an organic solvent to form a silane-based compound solution, followed by hydrolysis.

Examples of the organic solvent include methanol, ethanol, propanol, butanol, isopropyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, and mineral spirits. .

The total concentration of component (A) and component (B) in the silane-based compound solution obtained in step (1) is not particularly limited as long as the concentration allows hydrolysis of the reactive functional groups of component (A) and component (B), but is preferred. It is preferably 0.50 mol/L or more, more preferably 0.80 mol/L or more, and still more preferably 1.00 mol/L or more. The concentration is preferably 3.00 mol/L or less, more preferably 2.00 mol/L or less, and still more preferably 1.60 mol/L or less.

In step (1), the hydrolysis of component (A) and the hydrolysis of component (B) may be carried out independently, and preferably after mixing components (A) and (B), components (A) and Component (B) is hydrolyzed.

＜Process (2)＞

Step (2) is a step of mixing a metal catalyst (D) and water (E) with the hydrolyzate of component (A) and the hydrolyzate of component (B) obtained in step (1).

The metal catalyst (D) and the water (E) are the same as the metal catalyst (D) and water (E) described above, respectively, and their preferred embodiments are also the same. The blending amount of the metal catalyst (D) and water (E) is also the same as the blending amount of the metal catalyst (D) and water (E) described above, and the preferable range thereof is also the same.

The order of mixing the metal catalyst (D) and water (E) with the hydrolyzate of component (A) and the hydrolyzate of component (B) obtained in step (1) is not particularly limited, but the metal catalyst (D) is mixed It is preferable to mix the water (E) after doing it, or to mix the metal catalyst (D) and the water (E) simultaneously.

In step (2), by mixing water (E), an antifouling composition solution having a long usable time can be obtained.

In addition, in step (2), in the case of mixing water (E) after mixing the metal catalyst (D), before mixing the water (E), an organic solvent is further mixed, and component (A) You may adjust the density|concentration of the solution containing the hydrolyzate of , the hydrolyzate of component (B), and a metal catalyst (D) suitably.

As the said organic solvent, the various organic solvents mentioned above are mentioned, for example.

In this case, the total concentration of the hydrolyzate of component (A), the hydrolyzate of component (B), and the metal catalyst (D) in the solution is preferably 0.20 mol/L or more, more preferably 0.40 mol/L. L or more, more preferably 0.50 mol/L or more. The concentration is preferably 3.00 mol/L or less, more preferably 2.00 mol/L or less, and still more preferably 1.00 mol/L or less.

In addition, in the case where the hydrolyzate of component (A) and the hydrolyzate of component (B) were obtained independently in step (1), after mixing the metal catalyst (D) and water (E) with respect to each hydrolyzate, those may be mixed with each other, or the metal catalyst (D) and water (E) may be mixed after mixing the hydrolyzate of component (A) and the hydrolyzate of component (B).

In step (2), it is preferable to mix the metal catalyst (D) and water (E) with the mixture of the hydrolyzate of component (A) and the hydrolyzate of component (B). Further, after obtaining a mixture of component (A) and component (B) in step (1), hydrolysis is performed, and in step (2), to a mixture of a hydrolyzate of component (A) and a hydrolyzate of component (B) It is more preferable to mix the metal catalyst (D) and water (E).

In addition, you may further mix|blend the other additives mentioned above with the antifouling composition solution obtained through process (1) and process (2).

Examples of the other additives include the same as those described above, and the preferred blending amount of these additives is the same as the above-mentioned content.

[Solution used for antifouling composition solution]

For the solution of the antifouling composition of the present invention, a solution formed by blending water (E) with a hydrolyzate of the following component (A) and a hydrolyzate of the following component (B) can be used.

Component (A): A tetrafunctional silane-based compound represented by the following general formula (a)

Si(OR ¹ ) _p (X ¹ ) _4-p (a)

[In general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When there are a plurality of R ¹ and X ¹ , the plurality of R ¹ and X ¹ may be the same as or different from each other. p represents an integer from 0 to 4.]

Component (B): Trifunctional silane-based compound represented by the following general formula (b)

R ² Si(OR ³ ) _q (X ² ) _3-q (b)

[In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ represents an alkyl group of 1 to 6 carbon atoms, and X ² represents a halogen atom. When a plurality of R ³ and X ² are present, the plurality of R ³ and X ² may be the same as or different from each other. q represents an integer from 0 to 3.]

The hydrolyzate of component (A), the hydrolyzate of component (B), and water (E) are the same as the above-mentioned hydrolyzate of component (A), hydrolyzate of component (B), and water (E), respectively. And the preferable aspect is also the same.

In addition, the method for producing the solution is produced using the same method as the method for producing the antifouling composition solution described above, except that the metal catalyst (D) is not used in step (2) of the method for producing the antifouling composition solution described above. can do.

In addition, the said solution may contain the organic solvent used when dissolving the hydrolyzate of component (A) and the hydrolyzate of component (B).

As the said organic solvent, the various organic solvents mentioned above are mentioned, for example.

The antifouling composition solution can be obtained by mixing the metal catalyst (D) with the solution. The metal catalyst (D) is the same as the above-mentioned metal catalyst (D), and its preferable aspect is also the same.

Preferably, when forming the antifouling layer, the antifouling composition solution can be prepared and used by mixing the metal catalyst (D) with the solution.

The blending amount of component (A), the blending amount of component (B), the blending amount of water (E), and the total water content in the solution, when the metal catalyst (D) is blended with respect to the solution, are respectively the aforementioned antifouling composition. It is preferable that it is an amount equal to the preferable blending amount and content of each component in the solution.

In addition, you may further mix the other additives mentioned above with the antifouling composition solution obtained through process (1) and process (2).

Examples of other additives include the same as those described above, and the preferred content of these additives is also the same.

<Substrate to be coated with antifouling composition>

The object to which the antifouling composition of the present invention is applied is not particularly limited as long as antifouling properties are required, but it can be preferably used for glass, metal, alloy, semiconductor, rubber, cloth, plastic, ceramics, wood, paper, fiber, etc. , can be used more preferably for glass and metal. In addition, it can be suitably used also for a metal oxide film or a resin-coated surface.

When applying the antifouling composition to a body to be coated, it is preferable to dissolve it in an organic solvent, form a solution, and apply it by a known coating method.

As the said organic solvent, the various organic solvents mentioned above are mentioned, for example.

As a method of applying the antifouling composition solution to the object to be coated, for example, spin coating method, spray coating method, bar coating method, knife coating method, roll knife coating method, roll coating method, blade coating method, dip coating method A coat method, a curtain coat method, a die coat method, a gravure coat method, etc. are mentioned.

[Antifouling sheet]

The antifouling composition solution can be suitably used for an antifouling sheet. The antifouling sheet is not particularly limited as long as it has an antifouling layer formed from the above-described solution of the antifouling composition of the present invention.

<Configuration of antifouling sheet>

1 is a cross-sectional view of an antifouling sheet having a substrate, which is an example of an antifouling sheet obtained by using the above antifouling composition solution.

As an antifouling sheet with a substrate, for example, an antifouling sheet 1a having an antifouling layer 11 on a substrate 12 as shown in FIG. 1(a) is exemplified.

In addition, as shown in FIG. 1(b) , an antifouling property in which an adhesive layer 13 and a release material 14 are further formed on the surface opposite to the surface of the substrate 12 having the antifouling layer 11 It is good also as a sheet|seat 1b.

Further, a release material may be further provided on the antifouling layer 11 of the antifouling sheet 1a, 1b to protect the antifouling layer during storage.

Fig. 2 is a cross-sectional view of an antifouling sheet having no substrate, which is an example of an antifouling sheet obtained by using the above antifouling composition solution.

As an antifouling sheet having no substrate, for example, an antifouling sheet 2a having a configuration in which the antifouling layer 11 is sandwiched by two release materials 14 and 14' as shown in FIG. 2(a) can be heard

Further, in the structure shown in FIG. 2(a) as shown in FIG. 2(b), an antifouling sheet in which an adhesive layer 13 is further provided between the antifouling layer 11 and the release material 14' (2b) may be used.

The antifouling layer of the antifouling sheet can be formed from the solution of the antifouling composition of the present invention described above.

The thickness of the antifouling layer is preferably 0.001 μm or more, more preferably 0.005 μm or more, still more preferably 0.01 μm or more, still more preferably 0.05 μm or more, and still more preferably 0.10 μm or more. In addition, the thickness is preferably 40 μm or less, more preferably 25 μm or less, still more preferably 15 μm or less, even more preferably 5.0 μm or less, even more preferably 1.0 μm or less, still more preferably It is preferably 0.80 μm or less.

Examples of substrates usable for the antifouling sheet include paper substrates, resin films, resin sheets, substrates obtained by laminating paper substrates with resin, porous substrates such as fiber sheets, glass sheets, metal foils, and metal sheets. There is, and it can select suitably according to the use of an antifouling sheet.

Examples of the paper constituting the paper substrate include thin paper, medium quality paper, high quality paper, impregnated paper, coated paper, art paper, sulfated paper, and glassine paper.

Examples of the resin constituting the resin film or resin sheet include polyolefin-based resins such as polyethylene and polypropylene; vinyl resins of ethylene-methacrylic acid copolymers such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymers, and ethylene-vinyl alcohol copolymers; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polystyrene; Acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; and urethane-based resins such as polyurethane and acrylic-modified polyurethane.

Examples of the substrate obtained by laminating a paper substrate with a resin include laminated paper obtained by laminating the above paper substrate with a thermoplastic resin such as polyethylene.

Examples of the fibrous sheet include various fibrous sheets such as woven fabric, nonwoven fabric, and knit. The fiber sheet is preferably a fiber sheet containing at least one selected from the group consisting of organic fibers and inorganic fibers, more preferably at least one selected from the group consisting of cellulose nanofibers, synthetic fibers and glass fibers. a fiber sheet containing species, more preferably a glass fiber sheet containing at least glass fibers.

Examples of the organic fibers include polyolefin-based resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polylactic acid; aliphatic polyamides such as nylon 6 and nylon 66; wholly aromatic polyamides such as para- or meta-aramid; polyvinyl alcohol (PVA); The synthetic fiber spun from the above-mentioned resin, and various natural pulps such as NBKP, LBKP, and abaca pulp, and cellulose nanofibers derived from the natural pulp are exemplified.

Examples of the inorganic fiber include glass fiber; ceramic fibers composed of ceramic raw materials such as alumina, alumina-silica, and zirconia; and metal fibers made of iron, copper, brass, titanium, aluminum, stainless steel and the like.

Further, when the glass fiber sheet contains synthetic fibers together with glass fibers, it is preferable that the synthetic fibers are PVA fibers.

Although it does not specifically limit as a metal foil or metal sheet, For example, metal foil or metal sheet which consists of various metals, such as aluminum, nickel, stainless steel, copper, brass, titanium, or tungsten, is mentioned.

Further, as the base material used for the antifouling sheet, a primer layer-coated base material in which a primer layer is formed on the surface of the above-mentioned base material may be used from the viewpoint of improving adhesion to the antifouling layer or the weathering layer described later.

Examples of the component constituting the primer layer include polyester-based resins, urethane-based resins, polyesterurethane-based resins, acrylic resins, and the like, and these resins may be used alone or in combination of two or more. .

In addition, as a substrate used for the antifouling sheet, a weather resistant layer formed by further forming a weather resistant layer made of a polymer ultraviolet absorber on the surface of the substrate or the surface of the substrate on which the primer layer is formed (the weather resistant layer and the substrate) may have a primer layer in between) may be used. The polymeric ultraviolet absorber has a structure in which the ultraviolet absorbing skeleton is covalently bonded within the polymer structure, and the weight average molecular weight is preferably 5,000 or more, more preferably 10,000 or more.

In addition, when the base material used for the antifouling sheet is a resin film or resin sheet, from the viewpoint of improving adhesion to the antifouling layer, the surface of the resin film or resin sheet is subjected to an oxidation method or a roughening method, etc., as necessary. processing may be performed.

The oxidation method is not particularly limited, and examples thereof include corona discharge treatment, plasma treatment, chromic acid oxidation (wet), flame treatment, hot air treatment, ozone/ultraviolet irradiation treatment, and the like.

In addition, it does not specifically limit as a roughening method, For example, a sandblasting method, a solvent treatment method, etc. are mentioned.

These surface treatments are appropriately selected depending on the type of substrate, but corona discharge treatment is preferred from the viewpoints of improved adhesion to the antifouling layer and operability.

In addition, you may use a metal-deposited film or metal-deposited sheet in which metal was deposited on the surface of the various base materials mentioned above. The metal is not particularly limited, and examples thereof include various metals such as aluminum, nickel, iron, copper, gold, silver, and chromium, and carbides, oxides, and nitrides thereof.

The thickness of the substrate is appropriately set depending on the use of the antifouling sheet, but is preferably 10 to 250 μm, more preferably 15 to 200 μm, still more preferably 20 to 150 μm, from the viewpoints of handleability and economy.

In addition, the base material may further contain ultraviolet absorbers other than the polymeric ultraviolet absorbers described above, light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, colorants, and the like.

Examples of the release material that can be used for the antifouling sheet include a release sheet subjected to a double-sided release treatment, a release sheet subjected to a single-side release treatment, and the like, in which a release agent is applied on a base material for the release material.

Examples of the substrate for the release material include a paper substrate, a resin film, a resin sheet, and a substrate obtained by laminating a paper substrate with a resin, which can be used as a substrate of one embodiment of the antifouling sheet of the present invention.

Examples of the release agent include rubber-based elastomers such as silicone-based resins, olefin-based resins, isoprene-based resins, and butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.

The thickness of the release material is not particularly limited, and is preferably 10 to 200 μm, more preferably 25 to 150 μm.

In the case where the antifouling layer has a structure sandwiched by two release materials, the two release materials may be the same as or different from each other.

When the antifouling sheet has a pressure-sensitive adhesive layer, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer can be appropriately selected according to the use of the antifouling sheet.

Examples of the pressure-sensitive adhesive include acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, and curable pressure-sensitive adhesives that are cured by energy rays such as ultraviolet rays.

You may use these adhesives individually or in combination of 2 or more types.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, and is preferably 1 to 100 μm, more preferably 5 to 80 μm.

The antifouling sheet obtained by using the antifouling layer composition solution of the present invention is, for example, a film for preventing adhesion of aquatic organisms to architectural glass windows, automobile glass windows, windshields of vehicles, aircrafts, ships, etc., water tanks, dock windows, and ship bottoms; It is suitable as an antifouling sheet for preventing the adhesion of water droplets, scratches, stains, and the like, to the surface of molded products such as road panels such as soundproof walls, mirrors installed in bathrooms, etc., glass containers, and glass ornaments.

Example

[Preparation of antifouling composition solution]

Examples 1 and 2, Comparative Examples 1 and 2

(Process 1)

Component (A), component (B-1), and component (B-2) were blended according to the types and blending ratios (active ingredient ratio, mol%) shown in Table 1, and diluted with ethanol as a solvent to obtain an active ingredient concentration of 1.30. A solution of M was obtained.

To this solution, hydrochloric acid (excluding dilution water) as the acid catalyst (C) was further blended at 0.067 mol% with respect to 100 mol% of the total of components (A) and (B), and stirred for 15 minutes. After stirring, the solution was allowed to stand for 15 minutes.

(Process 2)

Subsequently, titanium diisopropoxybis(ethylacetoacetate) as the metal catalyst (D) was blended in the compounding ratio (active ingredient ratio, mol%) shown in Table 1, and then diluted by adding ethanol as a solvent to dilute the active ingredient. A solution with a concentration of 0.65 M was obtained.

Purified water as water (E) was blended with the solution at the compounding ratio (mol%) shown in Table 1 to prepare an antifouling composition solution.

Comparative Example 3

With respect to the 0.01 M hydrochloric acid used in step 1, purified water was previously blended so as to have the blend shown in Table 1, using as the acid catalyst (C), and in step 2, except that water (E) was not blended, In the same manner as in Example 1, an antifouling composition solution was prepared.

Details of each component listed in Table 1 used in preparing the antifouling composition solutions in Examples and Comparative Examples are as follows.

<Component (A): Tetrafunctional silane-based compound represented by general formula (a)>

"TEOS": Tetraethoxysilane, a tetrafunctional silane-based compound in which p = 4 and R ¹ = ethyl group (carbon number: 2) in the general formula (a) above.

<Component (B-1): Trifunctional silane-based compound represented by general formula (b-1)>

・ “Decyltrimethoxysilane”: A trifunctional silane-based compound in which r = 3, R ⁴ = n-decyl group (carbon number: 10), R ⁵ = methyl group (carbon number: 1) in the above general formula (b-1) .

<Component (B-2): Trifunctional silane-based compound represented by general formula (b-2)>

- "Methyltrimethoxysilane": A trifunctional silane-based compound in which s = 3, R ⁶ = methyl group (carbon number: 1), and R ⁷ = methyl group (carbon number: 1) in the general formula (b-2) above.

<Acid Catalyst (C)>

· 「Hydrochloric acid」: 0.01 M hydrochloric acid.

<Metal Catalyst (D)>

- "Titanium-based catalyst": titanium diisopropoxybis(ethylacetoacetate) [manufactured by Matsumoto Fine Chemical Co., Ltd., product name "Orgatics TC-750"].

＜Water (E)＞

· Purified water.

The properties of the antifouling composition solutions shown in Table 1 prepared in each Example and each Comparative Example were evaluated based on the following methods. The results are shown in Table 2.

<Production of antifouling sheet for evaluation>

For evaluation of the antifouling composition solution, an antifouling sheet was prepared using the method shown below.

As a substrate, slide glass was used.

The antifouling composition solution prepared in each Example and each Comparative Example was left still for 24 hours after preparation, and was used as a coating solution, and dip-coated on the base material to form a coating film. Next, the coating film was dried at 80°C for 2 minutes to prepare an antifouling sheet for evaluation.

<Curability of Antifouling Composition Solution>

The surface of the antifouling layer of each antifouling sheet for evaluation prepared using the antifouling composition solution prepared in each Example and each Comparative Example was rubbed with a finger 20 times, and then the antifouling layer was visually observed, and the antifouling layer was determined according to the following criteria. The curability of was evaluated.

· A: Compared with before rubbing with a finger, no change was observed.

B: Although slightly discolored, it is tolerable.

· C: Discolored to white.

D: The coating film made of the antifouling composition was not cured, and an antifouling layer could not be formed.

<State of antifouling layer>

The surface of the antifouling layer of each antifouling sheet for evaluation prepared using the antifouling composition solution prepared in each Example and each Comparative Example was visually observed, and the surface state of the antifouling layer was evaluated according to the following criteria.

A: It was transparent.

B: A little haze was confirmed.

C: Haze occurred and uniform application was not possible.

<Water contact angle of antifouling layer>

The water contact angle of the antifouling layer was evaluated using a fully automatic contact angle measuring device (product name "DM-701") manufactured by Kyowa Interface Science Co., Ltd. using the antifouling composition solution prepared in each Example and each Comparative Example. It was measured as a contact angle with respect to 2 µl of water with respect to the surface of the antifouling layer of the antifouling sheet.

From Tables 1 and 2, the antifouling composition solution of Example 1 or 2 has good curability even when used after preparing the antifouling composition solution and storing it for 24 hours, and the antifouling layer prepared from the antifouling composition solution, The surface condition and water repellency were good.

On the other hand, from Tables 1 and 2, the antifouling composition solutions of Comparative Examples 1 to 3 were inferior in curability when the antifouling composition solutions were prepared and stored for 24 hours.

The antifouling composition solution of the present invention has good curability even after long-term storage, and the surface state and water repellency of the antifouling layer formed from the antifouling composition are also good.

Therefore, the antifouling composition solution of the present invention has a long usable time and can be preferably used even when it takes time from preparation of the antifouling composition solution to formation of the antifouling layer. Further, the antifouling composition solution can also be suitably used when storage or transportation is required after preparation.

1a, 1b, 2a, 2b antifouling sheet
11 antifouling layer
12 registration
13 adhesive layer
14, 14' release material

Claims (15)

To a hydrolyzate of the following component (A) and a hydrolyzate of the component (B) containing at least one of the following components (B-1) and at least one of the following components (B-2), a metal catalyst (D) and An antifouling composition solution obtained by blending water (E), which further satisfies the following condition (II).
Component (A): A tetrafunctional silane-based compound represented by the following general formula (a)
Si(OR ¹ ) _p (X ¹ ) _4-p (a)
[In general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When there are a plurality of R ¹ and X ¹ , the plurality of R ¹ and X ¹ may be the same as or different from each other. p represents an integer from 0 to 4.]
Component (B): Trifunctional silane-based compound represented by the following general formula (b)
R ² Si(OR ³ ) _q (X ² ) _3-q (b)
[In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ represents an alkyl group of 1 to 6 carbon atoms, and X ² represents a halogen atom. When a plurality of R ³ and X ² are present, the plurality of R ³ and X ² may be the same as or different from each other. q represents an integer from 0 to 3.]
Component (B-1): Trifunctional silane-based compound represented by the following general formula (b-1)
R ⁴ Si(OR ⁵ ) _r (X ³ ) _3-r (b-1)
[In general formula (b-1), R ⁴ represents an alkyl group having 6 to 24 carbon atoms, and the alkyl group may have a substituent. R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and X ³ represents a halogen atom. When a plurality of R ⁵ and X ³ are present, the plurality of R ⁵ and X ³ may be the same as or different from each other. r represents an integer from 0 to 3.]
Component (B-2): Trifunctional silane-based compound represented by the following general formula (b-2)
R ⁶ Si(OR ⁷ ) _s (X ⁴ ) _3-s (b-2)
[In general formula (b-2), R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent. R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and X ⁴ represents a halogen atom. When there are a plurality of R ⁷ and X ⁴ , the plurality of R ⁷ and X ⁴ may be the same as or different from each other. s represents an integer from 0 to 3.]
Condition (II): Ratio of the compounding amount of component (B-1) to the total compounding amount of component (B-1) and component (B-2) [(B-1)/{(B-1) + (B-1) 2)}] (molar ratio) A, 0.020 or more and 0.995 or less
However, the substituents that R ² in the general formula (b), R ⁴ in the general formula (b-1), and R ⁶ in the general formula (b-2) may have are each independently a nitrogen atom, an oxygen atom, and A heteroaryl group having 6 to 12 ring atoms including a hetero atom selected from a sulfur atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, a cyano group, a mercapto group, an acryloyloxy group, methacryloyloxy It is at least one selected from the group consisting of a group, a cycloalkyl group of 3 to 12 ring carbon atoms, an aryl group of 6 to 12 ring carbon atoms, an alkoxy group of 1 to 6 carbon atoms, and an aryloxy group of 6 to 12 ring carbon atoms. . According to claim 1,
Further, a solution of an antifouling composition that satisfies the following condition (I).
Condition (I): The ratio of the compounding amount of component (A) to the compounding amount of component (B) [(A)/(B)] (molar ratio) is 0.01 or more and 50.00 or less According to claim 1 or 2,
The antifouling composition solution, wherein the metal catalyst (D) is at least one selected from the group consisting of titanium catalysts, zirconium catalysts, palladium catalysts, tin catalysts, aluminum catalysts, and zinc catalysts. According to claim 1 or 2,
The antifouling composition solution in which the compounding amount of the metal catalyst (D) is 0.01 mol% or more and 50.00 mol% or less with respect to 100 mol% of the total compounding amount of component (A) and component (B). According to claim 1 or 2,
The antifouling composition solution in which the compounding amount of water (E) is 0.01 mol% or more and 100,000 mol% or less with respect to 100 mol% of the total compounding amount of component (A) and component (B). A method for producing a solution of an antifouling composition having the following step (1) and the following step (2) in this order, and further satisfying the following condition (II).
Step (1): a step of hydrolyzing a component (B) containing at least one of the following components (A) and the following component (B-1) and at least one of the following components (B-2)
Component (A): A tetrafunctional silane-based compound represented by the following general formula (a)
Si(OR ¹ ) _p (X ¹ ) _4-p (a)
[In general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When there are a plurality of R ¹ and X ¹ , the plurality of R ¹ and X ¹ may be the same as or different from each other. p represents an integer from 0 to 4.]
Component (B): Trifunctional silane-based compound represented by the following general formula (b)
R ² Si(OR ³ ) _q (X ² ) _3-q (b)
[In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ represents an alkyl group of 1 to 6 carbon atoms, and X ² represents a halogen atom. When a plurality of R ³ and X ² are present, the plurality of R ³ and X ² may be the same as or different from each other. q represents an integer from 0 to 3.]
Component (B-1): Trifunctional silane-based compound represented by the following general formula (b-1)
R ⁴ Si(OR ⁵ ) _r (X ³ ) _3-r (b-1)
[In general formula (b-1), R ⁴ represents an alkyl group having 6 to 24 carbon atoms, and the alkyl group may have a substituent. R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and X ³ represents a halogen atom. When a plurality of R ⁵ and X ³ are present, the plurality of R ⁵ and X ³ may be the same as or different from each other. r represents an integer from 0 to 3.]
Component (B-2): Trifunctional silane-based compound represented by the following general formula (b-2)
R ⁶ Si(OR ⁷ ) _s (X ⁴ ) _3-s (b-2)
[In general formula (b-2), R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent. R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and X ⁴ represents a halogen atom. When there are a plurality of R ⁷ and X ⁴ , the plurality of R ⁷ and X ⁴ may be the same as or different from each other. s represents an integer from 0 to 3.]
However, the substituents that R ² in the general formula (b), R ⁴ in the general formula (b-1), and R ⁶ in the general formula (b-2) may have are each independently a nitrogen atom, an oxygen atom, and A heteroaryl group having 6 to 12 ring atoms including a hetero atom selected from a sulfur atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, a cyano group, a mercapto group, an acryloyloxy group, methacryloyloxy It is at least one selected from the group consisting of a group, a cycloalkyl group of 3 to 12 ring carbon atoms, an aryl group of 6 to 12 ring carbon atoms, an alkoxy group of 1 to 6 carbon atoms, and an aryloxy group of 6 to 12 ring carbon atoms. .
Step (2): Step of mixing a metal catalyst (D) and water (E) with the hydrolyzate of component (A) and the hydrolyzate of component (B) obtained in step (1)
Condition (II): Ratio of the compounding amount of component (B-1) to the total compounding amount of component (B-1) and component (B-2) [(B-1)/{(B-1) + (B-1) 2)}] (molar ratio) A, 0.020 or more and 0.995 or less According to claim 6,
Step (2) is a step of mixing water (E) after mixing the metal catalyst (D), or a step of mixing the metal catalyst (D) and water (E) simultaneously. According to claim 6,
Method for producing an antifouling composition solution using an acid catalyst (C) in step (1). According to claim 8,
The acid catalyst (C) is at least one selected from the group consisting of hydrochloric acid, phosphoric acid, acetic acid, formic acid, sulfuric acid, methanesulfonic acid, hydrobromic acid, p-toluenesulfonic acid, and trifluoroacetic acid A method for producing a solution of an antifouling composition. According to claim 8,
A method for producing an antifouling composition solution, wherein the blending amount of the acid catalyst (C) is 0.010 mol% or more and 1.000 mol% or less with respect to 100 mol% of the total blending amount of the component (A) and the component (B). An antifouling composition solution obtained by the production method according to any one of claims 6 to 10. Water (E) is blended with a hydrolyzate of the following component (A) and a hydrolyzate of the component (B) containing at least one of the following components (B-1) and at least one of the following components (B-2) and further satisfies the following condition (II).
Component (A): A tetrafunctional silane-based compound represented by the following general formula (a)
Si(OR ¹ ) _p (X ¹ ) _4-p (a)
[In general formula (a), R ¹ represents an alkyl group having 1 to 6 carbon atoms, and X ¹ represents a halogen atom. When there are a plurality of R ¹ and X ¹ , the plurality of R ¹ and X ¹ may be the same as or different from each other. p represents an integer from 0 to 4.]
Component (B): Trifunctional silane-based compound represented by the following general formula (b)
R ² Si(OR ³ ) _q (X ² ) _3-q (b)
[In general formula (b), R ² represents an alkyl group having 1 to 24 carbon atoms, and the alkyl group may have a substituent. R ³ represents an alkyl group of 1 to 6 carbon atoms, and X ² represents a halogen atom. When a plurality of R ³ and X ² are present, the plurality of R ³ and X ² may be the same as or different from each other. q represents an integer from 0 to 3.]
Component (B-1): Trifunctional silane-based compound represented by the following general formula (b-1)
R ⁴ Si(OR ⁵ ) _r (X ³ ) _3-r (b-1)
[In general formula (b-1), R ⁴ represents an alkyl group having 6 to 24 carbon atoms, and the alkyl group may have a substituent. R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and X ³ represents a halogen atom. When a plurality of R ⁵ and X ³ are present, the plurality of R ⁵ and X ³ may be the same as or different from each other. r represents an integer from 0 to 3.]
Component (B-2): Trifunctional silane-based compound represented by the following general formula (b-2)
R ⁶ Si(OR ⁷ ) _s (X ⁴ ) _3-s (b-2)
[In general formula (b-2), R ⁶ represents an alkyl group having 1 to 3 carbon atoms, and the alkyl group may have a substituent. R ⁷ represents an alkyl group having 1 to 6 carbon atoms, and X ⁴ represents a halogen atom. When there are a plurality of R ⁷ and X ⁴ , the plurality of R ⁷ and X ⁴ may be the same as or different from each other. s represents an integer from 0 to 3.]
Condition (II): Ratio of the compounding amount of component (B-1) to the total compounding amount of component (B-1) and component (B-2) [(B-1)/{(B-1) + (B-1) 2)}] (molar ratio) A, 0.020 or more and 0.995 or less
However, the substituents that R ² in the general formula (b), R ⁴ in the general formula (b-1), and R ⁶ in the general formula (b-2) may have are each independently a nitrogen atom, an oxygen atom, and A heteroaryl group having 6 to 12 ring atoms including a hetero atom selected from a sulfur atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, a cyano group, a mercapto group, an acryloyloxy group, methacryloyloxy It is at least one selected from the group consisting of a group, a cycloalkyl group of 3 to 12 ring carbon atoms, an aryl group of 6 to 12 ring carbon atoms, an alkoxy group of 1 to 6 carbon atoms, and an aryloxy group of 6 to 12 ring carbon atoms. . delete delete delete

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