JP2021161231A - Curable resin composition - Google Patents

Abstract

To provide a curable resin composition that can form a cured film having water resistance while having a low water contact angle, and a cured film obtained by curing the same.SOLUTION: A curable resin composition has a crosslinker (A) having two or more functional groups, and a polysiloxane resin (B) having, as constitutional units, (a) a functional group reactable with the crosslinker (A), (b) a repeating structure derived from a monomer having a radical polymerizable group, and (c) a salt structure composed of an acid and a base.SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition and a cured film.

In general, it is known that when the water contact angle of a coating film is lowered, low pollution property can be expected and anti-fog property is excellent. Therefore, a material capable of forming such a hydrophilic coating film (hereinafter, may be referred to as a "cured film") is extremely useful as a coating agent or the like, and therefore development is underway.

As a material capable of forming a hydrophilic coating film, for example, Patent Document 1 comprises a solution I containing an alkoxysilyl group-containing compound having a thiol group and a solution II containing a (meth) acrylic compound. Two-component surface modifiers and the like are described.

Further, Patent Document 2 describes a surfactant silane coupling agent which is a reaction product of a specific surfactant and a silane coupling agent having a functional group capable of reacting with active hydrogen in the surfactant. An antifogging coating composition containing a hydrolyzate and the like are described.

Japanese Unexamined Patent Publication No. 2011-219613 JP-A-2017-71724

However, in the technique of Patent Document 1, since the substrate adhesion is derived from a specific monomer, there is a concern that the application is limited to a specific substrate. Further, in the technique of Patent Document 2, since the surfactant may be dissolved in water and separated from the surface of the base material, there is a concern about maintaining the durability, water resistance and low contact angle of the coating film. rice field. That is, there was room for improvement in the material capable of forming the hydrophilic coating film.

Therefore, an object of the present invention is to provide a curable resin composition capable of forming a cured film having a low water contact angle and having water resistance, and a cured film obtained by curing the cured resin composition.

As a result of diligent studies to solve the above problems, the present inventors have made a resin composition containing a specific cross-linking agent and a specific polysiloxane-based resin, so that when a cured film is formed, low water contact is achieved. For the first time, it was discovered that a cured film having horns and water resistance could be obtained, and the present invention was completed.

Therefore, one aspect of the present invention includes the following configurations.
<1> A cross-linking agent (A) having two or more functional groups and
As a constituent unit
(A) A functional group that reacts with the cross-linking agent (A),
(B) A polysiloxane-based resin (B) having a repeating structure derived from a monomer having a radically polymerizable group, and (c) a salt structure composed of an acid and a base.
Curable resin composition containing.
<2> The polysiloxane-based resin (B) is
A silane compound (I-1) having the above (a) and a hydrolyzable silyl group and / or a single amount having the above (a) and a radically polymerizable group and having no hydrolyzable silyl group. The structural unit (i) derived from the body (I-2) and
A structural unit (ii) derived from a silane compound (II) having a radically polymerizable group and a hydrolyzable silyl group, and
A structural unit (iii) derived from the monomer (III) having the above (c) and a radically polymerizable group and not having a hydrolyzable silyl group, and
A structural unit (iv) derived from a monomer (IV) having a radically polymerizable group and not having a hydrolyzable silyl group other than the above (I-2) and (III),
The curable resin composition according to <1>.
<3> The polysiloxane-based resin (B) is
Further, other than the above (I-1) and (II), the following general formula (1):
R ¹ _n −Si− (OR ² ) _4-n ... (1)
(In the formula, R ¹ is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and R ² is independently a hydrogen atom or 1 to 10 carbon atoms, respectively. The curability according to <1> or <2>, which is an alkyl group of 10 and has a structural unit (v) derived from the silane compound (V) represented by (n) an integer of 0 to 3. Resin composition.
<4> The curable resin composition according to any one of <1> to <3>, wherein the cross-linking agent (A) and the polysiloxane-based resin (B) are soluble in water.
<5> The curable resin composition according to any one of <1> to <4>, wherein the cross-linking agent (A) is an epoxy compound and the (a) is an amino group.
<6>, the resin composition (β) containing the polysiloxane-based resin (B) is contained as the first liquid, and the composition (α) containing the cross-linking agent (A) is contained as the second liquid, <1>. The curable resin composition according to any one of ~ <5>.
<7> The curable resin according to any one of <1> to <6>, wherein the resin composition (β) contains water in an amount of 30% by weight or more and a non-aqueous solvent in an amount of 10% by weight or less. Composition.
<8> The ratio of the functional group of the cross-linking agent (A) to (a) in the polysiloxane-based resin (B) is 0.6: 1 to 1.8: 1 in terms of molar ratio. The curable resin composition according to any one of 1> to <7>.
<9> An aqueous solution containing the curable resin composition according to any one of <1> to <8>.
A cured film formed by applying the aqueous solution according to <10> and <9>.
<11> A cured film <12> obtained by curing the curable resin composition according to any one of <1> to <8>, the contact angle of water is 30 degrees or less, <10> or <11>. The cured film according to.

According to one aspect of the present invention, it is possible to provide a curable resin composition capable of forming a cured film having a low water contact angle and having water resistance, and a cured film obtained by curing the cured resin composition.

An embodiment of the present invention will be described in detail below. Unless otherwise specified in the present specification, "A to B" representing a numerical range means "A or more and B or less". In addition, all of the documents described herein are incorporated herein by reference.

[1. Outline of the present invention]
The curable resin composition (hereinafter, referred to as "the present curable resin composition") according to one embodiment of the present invention is used.
A cross-linking agent (A) having two or more functional groups and
As a constituent unit
(A) A functional group that reacts with the cross-linking agent (A),
(B) A polysiloxane-based resin (B) having a repeating structure derived from a monomer having a radically polymerizable group, and (c) a salt structure composed of an acid and a base.
Contains.

As described above, in the coating film, if the water contact angle is lowered, there are advantages that low pollution property can be expected and anti-fog property is excellent. On the other hand, as the water contact angle decreases, the affinity with water increases, so that there is a problem that the water resistance decreases. When the water resistance is lowered, it is a problem that the low contact angle property disappears after immersion in water even when the coating film dissolves in water or does not dissolve in water. These are due to the fact that the hydrophilic component in the coating film dissolves in water.

Here, a water-soluble resin is known as a material for forming a coating film. Since the water-soluble resin has a high affinity with water, the contact angle tends to be low when it is formed into a coating film. However, on the other hand, the water-soluble resin has extremely poor water resistance, and there is a problem that the coating film dissolves (elutes) when immersed in water.

Therefore, the present inventor will provide a new hydrophilic coating film if the water resistance can be improved (preventing re-dissolution in water) while maintaining the hydrophilicity (low contact angle) of the coating film. Was possible and considered to have industrial advantages. Then, as a result of diligent studies on means capable of solving the above problems, the present inventor has found that a coating film having good hydrophilicity and good water resistance can be obtained by devising the following points.
(1) The toughness of the resin itself is ensured by using polysiloxane as a base.
(2) By introducing a salt structure into the polysiloxane-based resin, the hydrophilicity of the polysiloxane-based resin and the cured film obtained by curing the polysiloxane-based resin is ensured. Further, by making the cross-linking agent water-soluble, the hydrophilicity of the cured film is ensured.
(3) A coating film is formed by forming a system in which a crosslink occurs between a functional group (for example, an epoxy group) in a cross-linking agent and a functional group (for example, an amine group) in a polysiloxane-based resin at the time of curing. Ensure a dramatic increase in molecular weight over time.

It is surprising, for the first time, to report a curable resin composition capable of forming a cured film having seemingly contradictory properties of low water contact angle and water resistance.

Therefore, the present curable resin composition is extremely useful as a coating agent, particularly as a material for forming a hydrophilic coating film.

In the following, the "crosslinking agent (A) having two or more functional groups" is simply referred to as "crosslinking agent (A)", and "as a constituent unit, (a) a functional that reacts with the crosslinking agent (A)". The "polysiloxane-based resin (B) having a group, (b) a repeating structure derived from a monomer having a radically polymerizable group, and (c) a salt structure composed of an acid and a base" is simply referred to as "polysiloxane-based resin (B). The "(a) functional group that reacts with the cross-linking agent (A)" is simply referred to as "(a)", and the "(c) salt structure composed of an acid and a base" is simply referred to as "(()". c) ”may be referred to.

Further, in the following, the "silane compound (I-1) having the above (a) and a hydrolyzable silyl group" is simply referred to as "silane compound (I-1)", and "radical polymerization with the above (a)". A "monomer (I-2)" having a sex group and no hydrolyzable silyl group is simply referred to as "monomer (I-2)", and "radical polymerizable group and water are added". The "silane compound (II) having a degradable silyl group" is simply referred to as "silane compound (II)", and "having the above (c) and a radically polymerizable group and having a hydrolyzable silyl group". "No monomer (III)" is simply referred to as "monomer (III)", and has a radically polymerizable group other than the above (I-2) and (III) and is hydrolyzable. The "monomer (IV) having no silyl group" is simply referred to as "monomer (IV)", and the following general formula (1): R ^{1 other than "the above (I-1) and (II)" is used.} _{The "silane compound (V) represented by n-} Si- (OR ² ) _4-n ... (1)" may be simply referred to as "silane compound (V)".

Further, in the following, "a silane compound (I-1) having the above (a) and a hydrolyzable silyl group and / or a radically polymerizable group having the above (a) and a hydrolyzable silyl group. The "constituent unit (i)" derived from the monomer (I-2) without The "constituent unit (ii) derived from (II)" is simply referred to as "constituent unit (ii)" and has "the above (c) and a radically polymerizable group and has a hydrolyzable silyl group". A "constituent unit (iii) derived from a non-monomeric (III)" is simply referred to as a "constituent unit (iii)" and has a radically polymerizable group other than "the above (I-2) and (III)". The "constituent unit (iv) derived from the monomer (IV) having no hydrolyzable silyl group" is simply referred to as "constituent unit (iv)", and "(I-1) and (II) above. ), The following general formula (1): R ¹ _n- Si- (OR ² ) _4-n ... A structural unit (v) derived from the silane compound (V) represented by (1) "is simply expressed. It may be referred to as a "constituent unit (v)".

In addition, "the silane compound (I-1) having the said (a) and a hydrolyzable silyl group and / or having the said (a) and a radically polymerizable group, and having a hydrolyzable silyl group. "No monomer (I-2)" may be collectively referred to as "reactive compound (I)".

Further, in the present specification, "silane compound (I-1)", "monomer (I-2)", "silane compound (II)", "monomer (III)", "monomer (monomer) "IV)" and "silane compound (V)" shall not overlap each other as substances. In other words, "silane compound (I-1)" does not contain "silane compound (II)", and "silane compound (II)" does not contain "silane compound (I-1)" and "silane". "Compound (V)" does not contain "silane compound (I-1)" and "silane compound (II)", and "monomer (I-2)" contains "monomer (III)". However, "monomer (III)" does not contain "monomer (I-2)", and "monomer (IV)" is "monomer (I-2)" and "single amount". Does not include "body (III)".

[2. Curable resin composition]
The curable resin composition is repeatedly derived from a cross-linking agent (A), (a) a functional group that reacts with the cross-linking agent (A), and (b) a monomer having a radically polymerizable group as a constituent unit. It is a resin composition containing a structure and (c) a polysiloxane-based resin (B) having a salt structure composed of an acid and a base. Further, the present curable resin composition contains a single amount of the cross-linking agent (A), the structural unit (i) derived from the reactive compound (I), and the structural unit (ii) derived from the silane compound (II). In other words, it is a resin composition containing a polysiloxane-based resin (B) having a structural unit (iii) derived from the body (III) and a structural unit (iv) derived from the monomer (IV). You can also do it. Further, in one embodiment of the present invention, the polysiloxane-based resin (B) contained in the present curable resin composition is converted into a structural unit (i) and a silane compound (II) derived from the reactive compound (I). In addition to the structural unit (ii) from which it is derived, the structural unit (iii) from which the monomer (III) is derived, and the structural unit (iv) which is derived from the monomer (IV), it is further derived from the silane compound (V). It has a structural unit (v) to be formed.

The polysiloxane-based resin (B) having the structural units (i) to (iv) (or the structural units (i) to (v)) includes the reactive compound (I), the silane compound (II), and the like. Monomer (III) and monomer (IV), or the above-mentioned reactive compound (I), silane compound (II), monomer (III), monomer (IV) and silane compound (V). It is obtained by dehydration condensation polymerization and radical polymerization.

Hereinafter, each composition of the present curable resin composition will be described in detail.

[2-1. Crosslinking agent (A)]
The cross-linking agent (A) in the present curable resin composition has two or more functional groups. When the cross-linking agent (A) has two or more functional groups, appropriate cross-linking can be performed with the polysiloxane-based resin (B), and a cured film exhibiting the effects of the present invention can be obtained.

The functional group of the cross-linking agent (A) is not particularly limited as long as it can react with (a) in the polysiloxane-based resin (B) and form a cross-linked structure with the polysiloxane-based resin (B). .. Examples of the functional group of the cross-linking agent (A) include a carbonyl group, an isocyanate group, an epoxy group, an amino group and the like.

In one embodiment of the present invention, the two or more functional groups contained in the cross-linking agent (A) may all be the same functional group or may be different functional groups.

The number of functional groups in the cross-linking agent (A) is not particularly limited as long as it is two or more, but is, for example, two, three, or four. Further, the number of functional groups in the cross-linking agent (A) may be polyfunctional.

In one embodiment of the present invention, examples of the cross-linking agent (A) include epoxy compounds (eg, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, pentaerythritol polyglycidyl ether, etc.) and dicarbonyl. Examples include compounds. Preferably, it is an epoxy compound from the viewpoint of availability and stability.

In one embodiment of the present invention, the cross-linking agent (A) is preferably soluble in water. Since the cross-linking agent (A) is soluble in water, it can be used as a material for forming a hydrophilic cured film.

[2-2. Polysiloxane resin (B)]
In the present specification, the "polysiloxane-based resin" means a resin containing a main chain containing a polysiloxane structure and a side chain (graft chain) bonded to the main chain by polymerization. The polysiloxane-based resin is not particularly limited as long as it satisfies the above definition, but is, for example, by dehydration condensation of a silane compound (I-1), a silane compound (II), and / or a silane compound (V) described later. Examples of the obtained polysiloxane main chain include a polysiloxane-based resin obtained by polymerizing a monomer (I-2), a monomer (III), and / or a monomer (IV).

As described above, the polysiloxane-based resin (B) has, as a constituent unit, (a) a functional group that reacts with the cross-linking agent (A), and (b) a repeating structure derived from a monomer having a radically polymerizable group. And (c) it has a salt structure consisting of an acid and a base. Further, the above (a) to (c) are derived from the reactive compound (I), the silane compound (II) and the monomer (III), respectively. Hereinafter, each configuration will be described in detail.

(Silane compound (I-1), monomer (I-2))
The reactive compound (I) has a silane compound (I-1) having (a) and a hydrolyzable silyl group and / or (a) and a radically polymerizable group, and has a hydrolyzable silyl group. It is a monomer (I-2) that does not have. That is, the reactive compound (I) is a silane compound (I-1) having a functional group that reacts with the cross-linking agent (A) and a hydrolyzable silyl group, and / or a functional that reacts with the cross-linking agent (A). It is a monomer (I-2) having a group and a radically polymerizable group and not having a hydrolyzable silyl group. The silane compound (I-1) is a silane compound (I-1) and / or a silane compound (II), or a silane compound (I-1), a silane compound (II) and / or a silane compound (V) described later. To form a polysiloxane, which is the main chain. Further, the radically polymerizable group in the monomer (I-2) is derived from the monomer (I-2) by performing radical polymerization with the radically polymerizable group in the silane compound (II). Form a graft chain. A certain amount of (a) derived from the silane compound (I-1) and / or the monomer (I-2) is contained in the polysiloxane-based resin (B), so that the cross-linking agent (A) and the cross-linking agent (A) are contained. Appropriate cross-linking can be performed. The silane compound (I-1) does not have a radically polymerizable group.

The functional group contained in the silane compound (I-1) and the monomer (I-2) that reacts with the cross-linking agent (A) reacts with the cross-linking agent (A) and has a cross-linked structure with the cross-linking agent (A). Is not particularly limited as long as it can form. Examples of the functional group that reacts with the cross-linking agent (A) include an epoxy group, a hydroxyl group, an amino group and the like. The functional group that reacts with the cross-linking agent (A) can be appropriately selected depending on the type of the functional group contained in the cross-linking agent (A). For example, when the functional group of the cross-linking agent (A) is an epoxy group, the functional group that reacts with the cross-linking agent (A) is preferably an amino group, a hydroxyl group or the like, and the functional group of the cross-linking agent (A) is carboxyl. In the case of a group, the functional group that reacts with the cross-linking agent (A) is preferably a carbodiimide group, an oxazoline group or the like. The preferred combination of the functional group of the cross-linking agent (A) and the functional group that reacts with the cross-linking agent (A) is an epoxy group and an amino group. These combinations may be reversed. For example, an embodiment in which the functional group of the cross-linking agent (A) is an amino group and the functional group that reacts with the cross-linking agent (A) is an epoxy group is also included in the scope of the present invention.

The silane compound (I-1) is not particularly limited, but for example, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl). Examples thereof include -3-aminopropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanuppropyltriethoxysilane.

The monomer (I-2) has a radically polymerizable group together with (a). The radically polymerizable group in that case is not particularly limited, and examples thereof include a (meth) acryloyl group, a (meth) acrylamide group, and a vinyl group. A (meth) acryloyl group is preferred from the standpoint of high reactivity and versatility.

The monomer (I-2) is not particularly limited, and examples thereof include dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, and glycidyl methacrylate.

In one embodiment of the present invention, the ratio of the functional group of the cross-linking agent (A) to (a) in the polysiloxane-based resin (B) is, for example, 0.6: 1 to 1.8 in terms of molar ratio. It is 1, preferably 0.65: 1 to 1.6: 1, and more preferably 0.7: 1 to 1.4: 1. When the ratio of the functional group of the cross-linking agent (A) to the (a) in the polysiloxane-based resin (B) is within the above range, the tack property and the water resistance are excellent.

In one embodiment of the present invention, the content of the silane compound (I-1) and / or the monomer (I-2) from which (a) is derived is not particularly limited, but the reaction with the cross-linking agent (A). In order to ensure water resistance, for example, it is 1% by weight or more, preferably 1.5% by weight or more, more preferably 1.5% by weight or more, based on 100% by weight of the total amount of the polysiloxane-based resin (B). 2% by weight or more. The upper limit of the content of the silane compound (I-1) and / or the monomer (I-2) from which (a) is derived is not particularly limited, but from the viewpoints of storage stability, production stability, cost and the like. Therefore, it is preferably 10.0% by weight or less, more preferably 5.0% by weight or less, and further preferably 4.5% by weight or less.

(Silane compound (II))
The silane compound (II) is a silane compound having a radically polymerizable group and a hydrolyzable silyl group. The silane compound (II) is dehydrated with the silane compound (I-1) and / or the silane compound (II), or with the silane compound (I-1), the silane compound (II) and / or the silane compound (V) described later. Condenses to form polysiloxane. Further, the radically polymerizable group in the silane compound (II) is a radical between the radically polymerizable group in the monomer (I-2), the monomer (III) and / or the monomer (IV). Polymerization is carried out to form a graft chain derived from the monomer (I-2), the monomer (III) and / or the monomer (IV). When the silane compound (II) is contained in the polysiloxane in a certain amount, the polymerization reaction proceeds smoothly, and there is an advantage that a polysiloxane having a graft chain can be obtained.

In one embodiment of the present invention, the silane compound (II) is represented by the following general formula (2):
R ³ _a R ⁴ _b- Si- (OR ⁵ ) _4-ab ... (1)
(In the formula, R ³ may have a substituted alkyl group having 1 to 10 carbon atoms having a polymerizable unsaturated group, an alkenyl group, or a polymerizable unsaturated group and optionally other substituents. It is an aryl group, R ⁴ is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and R ⁵ is independently a hydrogen atom or 1 to 10 carbon atoms, respectively. A is a compound having a hydrolyzable silyl group represented by (a is an integer of 1 to 3, b is an integer of 0 to 2, and a + b is an integer of 1 to 3). be.

^{R 3} of the general formula (2) is a substituted alkyl group having 1 to 10 carbon atoms having a radical polymerizable group, an alkenyl group, and an unsubstituted or substituted aryl group having a radical polymerizable group. The radically polymerizable group is not particularly limited, and examples thereof include a (meth) acryloyl group and a (meth) acrylamide group.

Examples of the silane compound in which R ³ is an alkyl group having a radically polymerizable group include (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethylmethyldimethoxysilane, and (meth) acryloximethyldimethylmethoxysilane. (Meta) Acryloxymethyltriethoxysilane, (Meta) Acryloxymethylmethyldiethoxysilane, (Meta) Acryloxymethyldimethylethoxysilane, 2- (Meta) Acryloxyethyltrimethoxysilane, 2- (Meta) Acryloxy Ethylmethyldimethoxysilane, 2- (meth) acryloxyethyldimethylmethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 2- (meth) acryloxyethylmethyldiethoxysilane, 2- (meth) acryloxiethyl Dimethylethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxipropyldimethylmethoxysilane, γ- (meth) acryloxipropyltriethoxy Silane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, 4- (meth) acryloxybutyltrimethoxysilane, 4- (meth) acryloxibutylmethyldimethoxysilane , 4- (meth) acryloxybutyldimethylmethoxysilane, 4- (meth) acryloxybutyltriethoxysilane, 4- (meth) acryloxybutylmethyldiethoxysilane, 4- (meth) acryloxybutyldimethylethoxysilane, 5- (Meta) acryloxipentylmethyldimethoxysilane, 5- (meth) acryloxipentylmethyldimethoxysilane, 5- (meth) acryloxipentyldimethylmethoxysilane, 5- (meth) acryloxipentyl triethoxysilane, 5- (Meta) Acryloxypentylmethyldiethoxysilane, 5- (Meta) Acryloxipentyldimethylethoxysilane, 6- (Meta) Acryloxyhexyltrimethoxysilane, 6- (Meta) Acryloxyhexylmethyldimethoxysilane, 6-( Examples thereof include (meth) acryloxyhexyldimethylmethoxysilane, 6- (meth) acryloxyhexyltriethoxysilane, 6- (meth) acryloxyhexylmethyldiethoxysilane, and 6- (meth) acryloxihexyldimethylethoxysilane.

Examples of the silane compound in which R ³ is an alkenyl group include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, and vinyldimethylethoxysilane.

Examples of the silane compound in which R ³ is an aryl group having a polymerizable unsaturated group and optionally having other substituents include p-styryltrimethoxysilane, p-styrylmethyldimethoxysilane, and the like. Examples thereof include p-styryldimethylmethoxysilane, p-styryltriethoxysilane, p-styrylmethyldiethoxysilane, and p-styryldimethylethoxysilane.

Among these, from the viewpoint of high and versatility of reactivity, the R ^3, preferably (meth) acryloyl group-substituted alkyl group.

^{R 4} of the general formula (2) is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, respectively.

Specific examples of the alkyl group for R ⁴ in the general formula (2), for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, amyl group, isoamyl group, a hexyl group, a cyclohexyl group, cyclohexyl Examples thereof include a methyl group, a cyclohexylethyl group, a heptyl group, an isoheptyl group, an n-octyl group, an isooctyl group and a 2-ethylhexyl group.

Specific examples of the aryl group for R ⁴ in the general formula (2), for example, a phenyl group, a naphthyl group, a benzyl group.

^{R 5} of the general formula (2) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group or a decyl group. Group etc. can be mentioned.

The silane compound (II) is condensed with the silane compound (I-1) and / or the silane compound (II), or the silane compound (I-1), the silane compound (II) and / or the silane compound (V) described later. from the viewpoint of easy to carbon atoms in the alkyl group R ⁵ in the general formula (2) 1 to 3 are preferred, most preferably 1.

In one embodiment of the present invention, the content of the silane compound (II) from which (b) is derived is, for example, 2 to 14% by weight, preferably 2 to 14% by weight, based on 100% by weight of the total amount of the polysiloxane-based resin (B). Is 3 to 12% by weight, more preferably 4 to 10% by weight. When the content of the silane compound (II) from which (b) is derived is within the above range, a target product having good dispersibility or solubility in water can be obtained.

(Monomer (III))
The monomer (III) is a monomer having (c) and a radically polymerizable group and having no hydrolyzable silyl group. That is, the monomer (III) is a monomer having a salt structure composed of an acid and a base, a radically polymerizable group, and not having a hydrolyzable silyl group. The radically polymerizable group in the monomer (III) is between the silane compound (II) and / or the monomer (I-2) and / or the radically polymerizable group in the monomer (IV) described later. Radical polymerization is carried out in (III) to form a graft chain derived from the monomer (III). Since the monomer (III) has a salt structure composed of an acid and a base, the polysiloxane-based resin (B) becomes soluble in water. The monomer (III) excludes those containing (a).

As used herein, the term "salt structure" means the structure of a neutral salt obtained by neutralizing an acid and a base. Here, the acid used for neutralization may be a strong acid or a weak acid. Further, the base to be neutralized may be a strong base or a weak base.

In one embodiment of the present invention, the salt structure is, for example, a neutral salt structure of a strong acid and a strong base, a neutral salt structure of a strong acid and a weak base, and a neutral salt structure of a weak acid and a strong base. Or it is the structure of a neutral salt of a weak acid and a weak base. More specific salt structures include, for example, sodium sulfonate, potassium sulfonate, calcium sulfonate, sodium nitrate, potassium nitrate, calcium nitrate (structure of neutral salt of strong acid and strong base), ammonium sulfonate, ammonium nitrate. Etc. (Structure of neutral salt of strong acid and weak base), Sodium acetate, Potassium acetate, Calcium acetate, Sodium phosphate, Potassium phosphate, Calcium phosphate, etc. (Structure of neutral salt of weak acid and strong base), Ammonium acetate , Ammonium phosphate and the like (structure of neutral salt of weak acid and weak base) and the like. In one embodiment of the invention, the salt structure is preferably sodium sulfonate.

In the present specification, "soluble in water" means that the haze value at 1 atm and 25 ° C. when the resin is dissolved or dispersed in water so as to have a solid content concentration of 20% is 20.0. It means that it is as follows. The haze value is measured by the method described in Examples described later.

The radically polymerizable group in the monomer (III) can contribute to radical polymerization with the silane compound (II) and / or the monomer (I-2) and / or the monomer (IV) described later. If so, it is not particularly limited. Examples of the radically polymerizable group in the monomer (III) include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group and the like. A (meth) acryloyl group is preferred from the standpoint of reactivity and versatility.

The monomer (III) is not particularly limited as long as it has a salt structure composed of an acid and a base and has a radically polymerizable group, and is not particularly limited. For example, sodium sulfoethyl methacrylate and acrylamide-t. Sodium butyl sulfonate, sodium 2- (methacryloyloxy) ethanesulfonate, sodium 2- (methacryloyloxy) polyalkylene oxide sulfonate, sodium acrylamide-t butyl sulfonate, potassium 2- (methacryloyloxy) ethanesulfonate, 2- Potassium (methacryloyloxy) polyalkylene oxide sulfonate, potassium acrylamide-t butyl sulfonate, calcium 2- (methacryloyloxy) ethanesulfonate, calcium 2- (methacryloyloxy) polyalkylene oxide sulfonate, calcium acrylamide-t butyl sulfonate , Ammonium sulfoethyl methacrylate, ammonium acrylamide-t butyl sulfonate, ammonium 2- (methacryloyloxy) ethanesulfonate, ammonium 2- (methacryloyloxy) polyalkylene oxide sulfonate, ammonium acrylamide-t butyl sulfonate, sodium acrylate , Potassium acrylate, calcium acrylate, ammonium acrylate, sodium methacrylate, potassium methacrylate, calcium methacrylate, ammonium methacrylate and the like.

In addition, the monomer (III) can be obtained as a commercially available product. Examples of such commercially available products include "Antox MS-2N-D" manufactured by Nippon Emulsion Co., Ltd., "ATBS-Na" manufactured by Toagosei Co., Ltd., and "Ereminol RS-3000" manufactured by Sanyo Chemical Industries, Ltd. , "Sodium acrylate" manufactured by Asada Chemical Industries, Ltd., "Potassium acrylate" and the like.

In one embodiment of the present invention, the content of the monomer (III) from which (c) is derived is, for example, 4% by weight or more, preferably 4% by weight or more, based on 100% by weight of the total amount of the polysiloxane-based resin (B). Is 4.5% by weight or more, more preferably 5% by weight or more, and particularly preferably 5.5% by weight or more. When the content of the monomer (III) from which (c) is derived is 4% by weight or more, the hydrophilicity (water solubility) of the cured film using the polysiloxane-based resin (B) can be ensured. The upper limit of the content of the monomer (III) from which (c) is derived is, for example, 14% by weight or less, preferably 13.5% by weight or less, and more preferably 13% by weight or less. Is. When the content of the monomer (III) from which (c) is derived is 14% by weight or less, the water resistance of the cured film using the polysiloxane-based resin (B) can be ensured.

(Monomer (IV))
The monomer (IV) is a monomer having a radically polymerizable group and not having a hydrolyzable silyl group other than the above (I-2) and (III). The radically polymerizable group in the monomer (IV) is a radical between the silane compound (II) and / or the radically polymerizable group in the monomer (I-2) and / or the monomer (III). Polymerization is carried out to form a graft chain derived from the monomer (IV). In addition, the monomer (IV) can form a structural unit (iv) in the polysiloxane-based resin (B).

The monomer (IV) is not particularly limited as long as it is a monomer having a radically polymerizable group other than the monomer (I-2) and the monomer (III), but as shown below, for example. Examples thereof include monomers other than the (meth) acrylic acid alkyl ester and the (meth) acrylic acid alkyl ester.

<(Meta) acrylic acid alkyl ester>
In one embodiment of the present invention, the (meth) acrylic acid alkyl ester is a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms and does not contain a functional group such as a hydroxyl group or an epoxy group (meth). ) Alkyl monomer. In one embodiment of the present invention, the alkyl group in the (meth) acrylic acid alkyl ester may be linear or branched, or may be a cyclic cycloalkyl group. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, and benzyl (meth) acrylate. Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) methacrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, isobonyl (meth) acrylate and the like can be mentioned.

<Monomers other than (meth) acrylic acid alkyl esters>
Examples of the monomer other than the (meth) acrylic acid alkyl ester include a nitrile group-containing radically polymerizable monomer such as (meth) acrylonitrile; 2-sulfoethyl methacrylate sodium, 2-sulfoethyl methacrylate ammonium, and polyoxyalkylene. Hydrophilic monomer having hydrophilicity such as radically polymerizable monomer having a chain; polymerizable unsaturated such as polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, allyl (meth) acrylate Monomer having two or more bonds; trifluoro (meth) acrylate, pentafluoro (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, β- (perfluoro) Fluorohydrate-containing radically polymerizable monomers such as octyl) ethyl (meth) acrylate; and the like.

The radically polymerizable monomer having a polyoxyalkylene chain is not particularly limited, but an acrylic acid ester or a methacrylic acid ester having a polyoxyalkylene chain is preferable. Specific examples thereof include, for example, Blemmer AE-90, AE-200, AE-350, PP-500, PP-800, PP-1000, AP-400, AP-550, AP-800 manufactured by NOF CORPORATION. , 700PEP-350B, 10PEP-550B, 55PET-400, 30PET-800, 55PET-800, 30PPT-800, 50PPT-800, 70PPT-800, PME-100, PME-200, PME-400, PME-1000, PME -4000, AME-400, 50POEP-800B, 50AOEP-800B, AEP, AET, APT, PLE, ALE, PSE, ASE, PKE, AKE, PNE, ANE, PNP, ANP, PNEP-600, Kyoeisha Chemical Co., Ltd. Light Ester 130MA, 041MA, MTG, Light Acrylate EC-A, MTG-A, 130A, DPM-A, P-200A, NP-4EA, NP-8EA, EHDG-A, MA-30 manufactured by NOF CORPORATION , MA-50, MA-100, MA-150, RMA-1120, RMA-564, RMA-568, RMA-506, MPG130-MA, Antox MS-60, MPG-130MA, RMA-150M, RMA-300M, RMA-450M, RA-1020, RA-1120, RA-1820, NK-ESTER M-20G, M-40G, M-90G, M-230G, AMP-10G, AMP-20G manufactured by Shin-Nakamura Chemical Industry Co., Ltd. , AMP-60G, AM-90G, LA and the like.

In one embodiment of the present invention, the content of the monomer (IV) from which the structural unit (iv) is derived is, for example, 10% by weight or more based on 100% by weight of the total amount of the polysiloxane-based resin (B). It is preferably 15% by weight or more, and more preferably 20% by weight or more. When the content of the monomer (IV) from which the structural unit (iv) is derived is 10% by weight or more with respect to 100% by weight of the total amount of the polysiloxane-based resin (B), the polysiloxane is stabilized and easily. You can get the target product. The upper limit of the content of the monomer (IV) from which the structural unit (iv) is derived is not particularly limited as long as the effect of the present invention is obtained, but is, for example, 80% by weight or less, preferably 60% by weight. It is less than, more preferably 50% by weight or less.

(Silane compound (V))
In one embodiment of the present invention, the polysiloxane-based resin (B) further has a structural unit (v) derived from the silane compound (V) other than the above (I-1) and (II). That is, in one embodiment of the present invention, the silane compound (V) can form a structural unit (v) in the polysiloxane-based resin (B).

The silane compound (V) is a silane compound represented by the general formula (1) R ¹ _n- Si- (OR ² ) _4-n ) ... (1) other than the above (I-1) and (II). Is. The silane compound (V) dehydrates and condenses with the silane compound (I-1), the silane compound (II) and / or the silane compound (V) to form a polysiloxane.

In one embodiment of the present invention, the silane compound (V) is a general formula (1):
R ¹ _n −Si− (OR ² ) _4-n ... (1)
(In the formula, R ¹ is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and R ² is independently a hydrogen atom or 1 to 10 carbon atoms, respectively. It is an alkyl group of 10 and n is an integer of 0 to 3), which is a compound having a hydrolyzable silyl group.

^{Specific examples of the alkyl group in R 1} of the general formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an amyl group, an isoamyl group, a hexyl group, a cyclohexyl group and a cyclohexyl. Examples thereof include a methyl group, a cyclohexylethyl group, a heptyl group, an isoheptyl group, an n-octyl group, an isooctyl group and a 2-ethylhexyl group.

^{Specific examples of the aryl group in R 1} of the general formula (1) include a phenyl group, a naphthyl group, a benzyl group and the like.

^{R 2} of the general formula (1) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group and a decyl group. Group etc. can be mentioned.

Specific compounds represented by the general formula (1) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, and ethyl. Triethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltriisopropoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane Silane, hexyltriisopropoxysilane, octyltrimethoxysilane, octylriethoxysilane, octyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, trimethylmono Examples thereof include methoxysilane and triphenylmonomethoxysilane.

Although n in the general formula (1) may be an integer of 0 to 3, a trialkoxysilane compound in which n is 1 or a dialkoxysilane compound in which n is 2 is particularly preferable. When n is 1, the number of crosslinkable hydrolyzable silyl groups becomes three, and a polymer having a tough network structure can be formed. Specific examples of the compound having n of 1 include methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane and the like as suitable compounds from the viewpoint of availability. Further, when n is 2, the number of crosslinkable hydrolyzable silyl groups becomes two, and toughness and storage stability can be expected. Specific examples of the compound having n of 2 include dimethyldimethoxysilane, diphenyldimethoxysilane, and the like as suitable compounds from the viewpoint of availability.

Silane compound (V), silane compound (I-1), silane compound (II) and / or silane compounds and (V) from the viewpoint of easy condensation, formula in (1) an alkyl group R ² carbons The number is preferably 1 to 3, most preferably 1.

In one embodiment of the present invention, the content of the silane compound (V) from which the structural unit (v) is derived is, for example, 10 to 80% by weight based on 100% by weight of the total amount of the polysiloxane-based resin (B). , It is preferably 30 to 65% by weight, and more preferably 20 to 50% by weight. If the content of the silane compound (V) from which the structural unit (v) is derived is 10% by weight or more with respect to 100% by weight of the total amount of the polysiloxane-based resin (B), the toughness of the coating film cannot be ensured. , It is possible to avoid a situation in which dissolution (elution) occurs in water after film formation. Further, when the content of the silane compound (V) from which the structural unit (v) is derived is 80% by weight or less with respect to 100% by weight of the total amount of the polysiloxane-based resin (B), the toughness is lowered, and as a result, the toughness is lowered. , It is possible to avoid the situation where cracks occur during film formation.

(Manufacturing method of polysiloxane resin (B))
In one embodiment of the present invention, the polysiloxane-based resin (B) includes a silane compound (I-1), a monomer (I-2), a silane compound (II), and a monomer (III). , The monomer (IV) is produced by a method including a step of dehydration condensation and radical polymerization. In the production method, the dehydration condensation and radical polymerization are carried out at the same time. Further, in one embodiment of the present invention, the production method further comprises reacting the silane compound (V) at the same time.

In the method for producing the polysiloxane-based resin (B), examples of the method for simultaneously performing dehydration condensation and radical polymerization of each compound and monomer include methods including (step 1) and (step 2) shown below. Be done.

(Step 1)
In step 1, in the reaction vessel, silane compounds (I-1) and (II) as needed, or silane compounds (I-1), (II) and (V) as needed (hereinafter, these are added. A mixture containing "silane compound for dehydration condensation"), water, and a dehydration condensation catalyst is subjected to dehydration condensation.

(Step 2)
In step 2, after the weight average molecular weight of the entire mixture reaches a specific range in step 1, the reaction vessel is filled with the silane compound (II) and, if necessary, the monomer (I-2). , Monomer (III), Monomer (IV), and Radical Polymerization Initiator are continuously added to carry out at least radical polymerization. Further, in step 2, at the same time as the radical polymerization, dehydration condensation may occur between the alkoxysilyl groups derived from the dehydration condensation silane compound.

For the silane compound (I-1) and the monomer (I-2), at least the silane compound (I-1) is used in step 1 or the monomer (I-2) is used in step 2. good. The embodiment may be in which the silane compound (I-1) is used in step 1 and the monomer (I-2) is used in step 2.

In one embodiment of the present invention, the number of moles of water added in step 1 is, for example, 0.25 times or more, preferably 0.5, with respect to the total number of moles of the dehydration condensation silane compound. More than double. When the number of moles of water is 0.25 times or more the total number of moles of the silane compound for dehydration condensation, condensation can be appropriately performed, and sufficient water resistance, weather resistance, and low tack resistance can be obtained. You can expect it. The number of moles of water is not particularly limited as long as it is large, but from the viewpoint of production cost, it is preferable to keep the number of moles of water 4.0 times or less with respect to the total number of moles of the silane compound for dehydration condensation. Based on these viewpoints, the number of moles of water is preferably 0.25 to 4.0 times, more preferably 0.5 to 3.0 times, 1) the total number of moles of the silane compound for dehydration condensation. .0 to 2.5 times is particularly preferable.

The dehydration condensation catalyst in step 1 is not particularly limited as long as it is a substance capable of accelerating the dehydration condensation reaction of a mixture containing the dehydration condensation silane compound, water, and the dehydration condensation catalyst.

In one embodiment of the present invention, examples of the dehydration condensation catalyst include an acidic catalyst, a basic catalyst, a neutral salt catalyst and the like.

As the acidic catalyst, an organic acid catalyst is preferable because of compatibility with the dehydration condensation silane compound and a diluting solvent, and a phosphoric acid ester or a carboxylic acid can be preferably used. Specific examples of the organic acid include ethyl acid phosphate, butyl acid phosphate, dibutyl pyrophosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, isotridecyl acid phosphate, dibutyl phosphate, bis (2-ethylhexyl) phosphate, and the like. Examples thereof include formic acid, acetic acid, butyric acid and isobutyric acid.

As the basic catalyst, an organic base catalyst is preferable and an amine compound can be preferably used because of the compatibility with the dehydration condensation silane compound and the diluting solvent. Specific examples of the organic base include, for example, triethylamine, diazabicycloundecene, 1,4-diazabicyclo [2.2.2] octane and the like.

Neutral salts used as neutral salt catalysts include, for example, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, franchium chloride, berylium chloride, magnesium chloride, calcium chloride, strontium chloride, barium chloride, chloride. Radium, Tetramethylammonium Chloride, Tetraethylammonium Chloride, Tetrapropylammonium Chloride, Tetrabutylammonium Chloride, Tetrapentylammonium Chloride, Tetrahexyl Ammonium Chloride, Ganidium Chloride; Lithium Bromide, Sodium Bromide, Potassium Bromide, Rubidium Bromide, Cesium bromide, Francium bromide, berylium bromide, magnesium bromide, calcium bromide, strontium bromide, barium bromide, radium bromide, tetramethylammonium bromium, tetraethylammonium bromide, tetrapropylammonium bromide, odor Tetrabutylammonium bromide, tetrapentylammonium bromide, tetrahexylammonium bromide, guanidium bromide; lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, franchium iodide, berylium iodide, iodide Magnesium iodide, calcium iodide, strontium iodide, barium iodide, radium iodide, tetramethylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, tetrapentylammonium iodide, tetrapentylammonium iodide Tetrahexylammonium, guanidium iodide; lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, cesium sulfate, franchium sulfate, beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, radium sulfate, tetramethylammonium sulfate, sulfate Tetraethylammonium, tetrapropylammonium sulfate, tetrabutylammonium sulfate, tetrapentylammonium sulfate, tetrahexylammonium sulfate, guanidium sulfate; lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, franchium nitrate, beryllium nitrate, magnesium nitrate, nitrate Calcium, strontium nitrate, barium nitrate, radium nitrate, tetramethylammonium nitrate, tetraethylammonium nitrate, tetrapropylammonium nitrate, tetrabutylammonium nitrate, tetrapentylammo nitrate Nium, tetrahexyl ammonium nitrate, guanidium nitrate; lithium perchlorate, sodium perchlorate, potassium perchlorate, rubidium perchlorate, cesium perchlorate, francium perchlorate, berylium perchlorate, magnesium perchlorate, Calcium perchlorate, strontium perchlorate, barium perchlorate, radium perchlorate, tetramethylammonium perchlorate, tetraethylammonium perchlorate, tetrapropylammonium perchlorate, tetrabutylammonium perchlorate, perchloric acid Examples thereof include tetrapentyl ammonium, tetrahexyl ammonium perchlorate, and guanidium perchlorate.

The above-mentioned basic catalyst and neutral salt catalyst can be used alone or in combination of two or more.

The mixture of step 1 may contain a diluting solvent in addition to the silane compound for dehydration condensation, water and a dehydration condensation catalyst. Since the silane compound for dehydration condensation is hydrophobic and water is used during the reaction, the diluting solvent is preferably water-soluble. The amount of the diluting solvent is not limited, but it is not preferable from the viewpoint of production cost because the concentration of the obtained polysiloxane decreases as the amount increases. Examples of the diluting solvent include ether esters such as cellosolve cate; ketones such as methyl ethyl ketone, ethyl acetoacetate, acetylacetone, methyl isobutyl ketone and acetone; methanol, 2-propanol, n-butanol, isobutanol, hexanol, octanol and the like. Examples include alcohols. In one embodiment of the invention, the diluting solvent is preferably alcohols, more preferably 2-propanol.

The radical polymerization initiator in step 2 may be a substance capable of initiating a radical polymerization reaction between the substance having a radical polymerization group used in step 1 and the substance having a radical polymerization group in step 2. For example, there is no particular limitation.

In one embodiment of the present invention, the radical polymerization initiator includes, for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'. -Azobis (2-methylbutyronitrile), tert-butylperoxypivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide, cumenehydroper Examples thereof include oxide and diisopropylperoxycarbonate.

In one embodiment of the present invention, the amount of the radical polymerization initiator is, for example, 0.01 to 10% by weight, preferably 0.05 to 7% by weight, based on 100% by weight of the total amount of the polysiloxane-based resin. %, More preferably 0.1 to 5% by weight. When the amount of the radical polymerization initiator is 0.01% by weight or more, the polymerization proceeds appropriately. Further, when the amount of the radical polymerization initiator is 10% by weight or less, a polymer having an appropriate molecular weight can be obtained.

In step 2, in addition to the silane compound (II), optionally monomer (I-2), monomer (III), monomer (IV) and radical polymerization initiator, the present invention. Any additive may be added as long as the effect is achieved. Such additives may be appropriately selected by those skilled in the art.

In one embodiment of the present invention, the dehydration condensation and radical polymerization in the production method can be carried out in a non-aqueous solvent. As the non-aqueous solvent, for example, the non-aqueous solvent described below (others) can be used.

In one embodiment of the present invention, the production method preferably includes a step of substituting the non-aqueous solvent with an aqueous solvent after the dehydration condensation and radical polymerization steps. By including this step, a polysiloxane-based resin that can be used as a water-based paint and is uniformly dispersed or soluble in water can be obtained.

In one embodiment of the present invention, the step of substituting the non-aqueous solvent with the aqueous solvent can be performed, for example, by the step described in Examples described later.

In one embodiment of the present invention, the manufacturing method is the method described in the examples.

(others)
In one embodiment of the present invention, the ratio of the polysiloxane in the polysiloxane resin (B) to the graft chain is, for example, 30:70 to 80:20, preferably 35:65 to 75:25. It is more preferably 38:62 to 70:30. The upper limit of the ratio is preferably 80:20 or less from the viewpoint of storage stability. Further, the lower limit of the above ratio is preferably 30:70 or more from the viewpoint of water resistance, weather resistance, low tack resistance and the like.

In one embodiment of the present invention, the weight average molecular weight of the polysiloxane-based resin (B) is not particularly limited, but is, for example, 5000 to 500000, preferably 8000 to 10000, and more preferably 1000 to 80000. be. The weight average molecular weight of the polysiloxane-based resin (B) is measured by using a high-speed gel permeation chromatography (GPC) apparatus HLC-8320GPC manufactured by Tosoh Corporation.

In one embodiment of the present invention, the polysiloxane-based resin (B) is preferably soluble in water. Since the polysiloxane resin (B) is soluble in water, it can be used as a material for forming a hydrophilic cured film.

In one embodiment of the present invention, the curable resin composition contains the resin composition (β) containing the polysiloxane-based resin (B) as the first liquid, and contains the cross-linking agent (A) ( This is a two-component resin composition containing α) as the second solution.

In the present specification, the "two-component type" means a mode in which both components are separately separated so as not to be mixed before use, and both are mixed and reacted at the time of use.

In one embodiment of the present invention, in the present curable resin composition, the resin composition (β) contains, for example, 30% by weight or more of water and a non-aqueous solvent with respect to the polysiloxane-based resin (B). 10% by weight or less, preferably 35% by weight or more of water and 5% by weight or less of a non-aqueous solvent, more preferably 37% by weight or more of water and a non-aqueous solvent. It can be contained in a proportion of 3% by weight or less.

As used herein, the term "non-aqueous solvent" means all solvents other than water. The "non-aqueous solvent" in the present specification may be a mixed solvent containing water, and includes a solvent containing water in an amount of less than 50% by weight. The non-aqueous solvent is not particularly limited as long as it satisfies the above definition, but for example, hydrocarbons such as toluene, xylene, n-hexane and cyclohexane; acetate esters such as ethyl acetate and butyl acetate; ethyl cellosolve, Cellosolves such as butyl cellosorb; ether esters such as cellosolve acetate; ketones such as methyl ethyl ketone, ethyl acetate, acetyl acetone, methyl isobutyl ketone and acetone; alcohols such as methanol, isopropyl alcohol, n-butanol, isobutanol, hexanol and octanol. Kind and the like. In one embodiment of the invention, the non-aqueous solvent is preferably alcohols, more preferably isopropyl alcohol.

Further, the present curable resin composition may contain a curing catalyst in addition to the cross-linking agent (A) and the polysiloxane-based resin (B). When coating this resin composition, a curing catalyst that promotes a possible cross-linking reaction between the cross-linking agent (A) and the polysiloxane-based resin (B) and a hydrolysis / condensation reaction of an alkoxysilyl group is added. Therefore, the cross-linking reaction is promoted.

The curing catalyst that promotes the hydrolysis condensation reaction of the alkoxysilyl group is not particularly limited, and examples thereof include an organic metal compound, an acidic catalyst, and a basic catalyst. Among them, examples of the organic tin compound in which an organic tin compound, an acidic phosphoric acid ester, and a reaction product of the acidic phosphoric acid ester and an amine compound are preferable from the viewpoint of activity include dibutyltin dilaurate, dibutyltin zimarate, and dibutyltin dioleyl. Malate, dioctyl tin dilaurate, dibutyl tin diacetate, dibutyl tin dimethoxide, dibutyl tin thioglycolate, dibutyl tin bisisononyl 3-mercaptopropionate, dibutyl tin bisisooctyl thioglycolate, dibutyl tin bis 2-ethylhexyl thioglycolate , Dimethyltin bisdodecyl mercaptide, dimethyltin bis (octylthioglucolate) salt, tin octylate and the like.

Among them, from the viewpoint of stability in water, dibutyl tin thioglycolate, dibutyl tin bisisononyl 3-mercaptopropionate, dibutyl tin bisisooctyl thioglycolate, dibutyl tin bis 2-ethylhexyl thioglycolate, dimethyl tin bis Dodecyl mercaptide, dibutyl tin bisdodecyl mercaptide, dimethyl tin bis (octylthioglucolate) salt and other mercaptides are preferred.

Examples of the acidic phosphoric acid ester compound include propyl acid phosphate, dibutyl phosphate, 2-ethylhexyl acid phosphate, di-2-ethylhexyl phosphate, monoisodecyl acid phosphate, diisodecyl phosphate, lauryl acid phosphate, stearyl acid phosphate and the like. ..

Examples of the amine compound that can react with the above-mentioned acidic phosphate ester compound include triethylamine, n-butylamine, hexylamine, triethanolamine, diazabicycloundecene, and ammonia.

In one embodiment of the present invention, the amount of the curing catalyst added is preferably 0.1 to 10 parts by weight, preferably 0.5 to 5.0 parts by weight, based on 100 parts by weight of the solid content of the resin composition. More preferably, 1.0 to 3.0 parts by weight is particularly preferable. When the amount of the curing catalyst added is 0.1 part by weight or more with respect to 100 parts by weight of the solid content of the resin composition, appropriate curing activity can be obtained. Further, when the amount of the curing catalyst added is 10 parts by weight or less with respect to 100 parts by weight of the solid content of the resin composition, the pot life of the paint is shortened, and as a result, cracks due to curing shrinkage and embrittlement of the cured product are made. Can be avoided.

The present curable resin composition may contain additives usually used in the technical field (particularly, the field of paint) as long as the effects of the present invention are exhibited. Such additives include, for example, agents, fillers, plasticizers, film forming aids, wetting / dispersing agents, thickeners, antifoaming agents, preservatives, antioxidants, antioxidants, leveling agents, etc. Examples thereof include ultraviolet absorbers, antistatic agents, antifreeze agents, antibacterial agents, antifungal agents, tackifiers, rust preventives and the like. As the additive, only one kind may be contained, or two or more kinds may be contained. The amount of these additives can be appropriately set by those skilled in the art according to the purpose of use.

The various components that can be contained in the present curable resin composition may be contained in either the first liquid or the second liquid. In addition, the various components that can be contained in the present curable resin composition may be contained in both the first liquid and the second liquid.

The present curable resin composition can be suitably used in various coating agent fields, for example, as an anti-fog coating agent, a self-cleaning coating agent, and the like. This curable resin composition can be used, for example, for interior and exterior of buildings, for automobiles such as metallic bases or clears on metallic bases, for direct coating of metals such as aluminum, stainless steel, and silver, slate, concrete, roof tiles, mortar, gypsum board, etc. Suitable as a paint or top treatment agent for ceramic direct coating such as asbestos slate, asbestos board, precast concrete, lightweight aerated concrete, calcium silicate board, tile, brick, etc., for glass, mirror, natural marble, stone material such as Mikage stone, etc. Used for.

Further, in one embodiment of the present invention, an aqueous solution containing the present curable resin composition (hereinafter, referred to as "the present aqueous solution") can be provided. Since this aqueous solution contains the above-mentioned curable resin composition, it is useful as a material for a cured film having a low water contact angle and water resistance.

As used herein, the term "aqueous solution" means that the haze value at 1 atm and 25 ° C. when the resin is dissolved or dispersed in water so as to have a solid content concentration of 20% is 20.0 or less. .. The haze value is measured using a spectrocolorimeter (for example, COH400 manufactured by Nippon Denshoku Kogyo Co., Ltd.) using pure water as a standard solution.

In one embodiment of the present invention, the aqueous solution is, for example, a solution containing 90% by weight or more of water in all the media, and contains a medium other than water (for example, an organic solvent) in an amount of less than 10%. You may be.

[3. Hardened film]
In one embodiment of the present invention, there is provided a cured film obtained by curing the present curable resin composition. Further, in one embodiment of the present invention, there is provided a cured film coated with the present aqueous solution. Together, these cured films will be referred to as the "main cured film". Since the present curable resin composition is used as a material, the present cured film can have a low water contact angle and can have water resistance.

In one embodiment of the present invention, the contact angle of water in the cured film is, for example, 30 degrees or less, preferably 28 degrees or less, and more preferably 25 degrees or less. When the contact angle of water in the cured film is 30 degrees or less, high affinity for water can be obtained. Further, the lower limit of the contact angle of water in the cured film is not particularly limited, and the lower the lower limit, the better. The contact angle of water in the cured film is measured by the method described in Examples. The water resistance of the cured film is also measured by the method described in Examples.

[4. Production method〕
In one embodiment of the present invention, a method for producing the present curable resin composition (hereinafter, referred to as “the present production method”) is provided.

The present production method includes a step of mixing the cross-linking agent (A) and the polysiloxane-based resin (B). That is, the present production method only needs to include a step of mixing the cross-linking agent (A) and the polysiloxane-based resin (B), and the resin composition (β) containing the polysiloxane-based resin (B) can be obtained. A method including a step of mixing the 1st liquid containing the liquid and the 2nd liquid containing the composition (α) containing the cross-linking agent (A) is also included in the scope of the present production method.

In this production method, the cross-linking agent (A) and the polysiloxane-based resin (B) are used in the above [2-1. Crosslinker (A)] and [2-2. Polysiloxane-based resin (B)] is used.

The method for mixing the cross-linking agent (A) and the polysiloxane-based resin (B) is not particularly limited, and a method known in the art can be appropriately used.

In one embodiment of the present invention, the compounding ratio of the cross-linking agent (A) and the polysiloxane-based resin (B) is the functional group of the cross-linking agent (A) and the (B) in the polysiloxane-based resin (B). The molar ratio to a) is, for example, 0.6: 1 to 1.8: 1, preferably 0.65: 1 to 1.6: 1, and more preferably 0.7: 1. ~ 1.4: 1. When the compounding ratio of the bridging agent (A) and the polysiloxane resin (B) is within the above range, the tack property and water resistance are excellent. The ratio of the functional group of the cross-linking agent (A) to the (a) in the polysiloxane-based resin (B) can be adjusted by adjusting the equivalent value of each functional group. For example, the ratio of the functional group of the cross-linking agent (A) to the (a) in the polysiloxane-based resin (B) can be adjusted according to the equivalent amount described in the examples.

The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and the embodiments obtained by appropriately combining the technical means disclosed in the different embodiments. Is also included in the technical scope of the present invention.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

〔material〕
The following materials were used in Examples and Comparative Examples.

(Reactive compound (I))
3-Aminopropyltrimethoxysilane: "KBM-903" manufactured by Shin-Etsu Chemical Co., Ltd.
N-2- (aminoethyl) -3-aminopropyltrimethoxysilane: "KBM-603" manufactured by Shin-Etsu Chemical Co., Ltd.
(Silane compound (II))
γ-Methoxyloxypropyltrimethoxysilane (3- (trimethoxysilyl) propylmethacrylate, abbreviated as “TSMA”): “A-174” manufactured by Momentive Performance Materials Japan LLC
(Monomer (III))
Sodium acrylamide-t butyl sulfonate (abbreviation "ATBS-Na"): "ATBS-Na" manufactured by Toagosei Co., Ltd.
(Monomer (IV))
Methyl methacrylate (abbreviation "MMA"): Mitsubishi Gas Chemical Company, Ltd. Butyl acrylate (abbreviation "BA"): Nippon Catalyst Co., Ltd. (silane compound (V))
Methyltrimethoxysilane (abbreviation "MTMS"): "Z-6033" manufactured by Dow Toray Co., Ltd.
Dimethyldimethoxysilane (abbreviation "DMDMS"): "Z-6329" manufactured by Dow Toray Co., Ltd.
(Crosslinking agent (A))
3-Glysidyloxypropyltrimethoxysilane: "A-187" manufactured by Momentive Performance Materials Co., Ltd.
Diglycerol polyglycidyl ether: "EX-411" manufactured by Nagase ChemteX Corporation
Polyethylene glycol diglycidyl ether: "EX-861" manufactured by Nagase ChemteX Corporation
Lauryl alcohol glycidyl ether: "EX-171" manufactured by Nagase ChemteX Corporation
(others)
Pure water dehydration condensation catalyst: Dibutyl phthalate: "DBP" manufactured by Johoku Chemical Industry Co., Ltd.
Radical polymerization initiator: 2,2'-azobis (2,4-dimethylvaleronitrile) (abbreviation "V-65"): manufactured by Tokyo Chemical Industry Co., Ltd. [Measurement and evaluation method]
Measurements and evaluations in Examples and Comparative Examples were performed by the following methods.

(Water solubility evaluation)
The water solubility of the polysiloxane-based resin was evaluated with reference to Japanese Patent No. 52527558. Briefly, the polysiloxane-based resin obtained in the synthetic example was diluted with pure water to bring the resin solid content concentration to 20%. The haze value of the polysiloxane resin was measured using pure water as a standard solution using COH400 manufactured by Nippon Denshoku Kogyo Co., Ltd. at 1 atm and 25 ° C. When the haze value was 20.0 or less, it was designated as “◯”, and when it exceeded 20.0, it was designated as “x”. That is, "○" means "soluble in water".

(transparency)
The aqueous solution of the curable resin composition obtained in each example was applied to a glass plate using a 6 mil applicator and cured at 23 ° C. and 50% RH for 1 week. Then, the haze value of the obtained coating film was measured using COH400 manufactured by Nippon Denshoku Kogyo Co., Ltd., using an uncoated glass plate as a standard plate. The case where the haze value was 20.0 or less was regarded as “◯”.

(Tackiness)
The aqueous solution of the curable resin composition obtained in each example was applied to a glass plate using a 6 mil applicator and cured at 23 ° C. and 50% RH for 24 hours. Then, the tackiness was evaluated by touching the obtained coating film with a finger. The case where no tackiness was felt was A, the case where the glass plate was slightly tacky but not lifted was B, and the case where the tackiness was felt and the coated plate was lifted for a moment was C.

(water resistant)
The aqueous solution of the curable resin composition obtained in each example was applied to a glass plate using a 6 mil applicator, and cured at 23 ° C. and 50% RH for 1 week. Next, the coated glass plate was immersed in water at 50 ° C. and 23 ° C. for 1 week, and then the water resistance of the coating film was evaluated from the appearance when taken out.
A: There is no change in the appearance of the coating film even if it is immersed in hot water at 50 ° C for 1 week. Even if it does, the appearance of the coating film does not change. C: Whitening is seen when immersed in water at 23 ° C for 1 week, but it returns to the original appearance when taken out of water. Elutes to).

(Contact angle)
The aqueous solution of the curable resin composition obtained in each example was applied to a glass plate using a 6 mil applicator, cured at 23 ° C. and 50% RH for 1 week, and then the static contact angle of water was adjusted. It was measured with a contact angle measuring device (manufactured by Kyowa Interface Science: S-150).

[Synthesis Example 1]
(Step 1)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux cooler, a nitrogen gas introduction tube and a dropping funnel, the types and amounts of the reactive compounds (I), silane compounds (II-1) and silane compounds shown in Table 1 ( V), pure water, and 0.02 g of dibutyl phosphate were charged and reacted at a reaction vessel temperature of 70 ° C. for 1 hour with stirring to obtain a mixture.

(Step 2)
With respect to the mixture of (step 1), the silane compound (II-2), the monomer (III) and the monomer (IV) of the types and amounts shown in Table 1 are maintained while maintaining the temperature inside the reaction vessel at 70 ° C. , And 1.5 g of a mixed solution of V-65 was added dropwise from the dropping funnel at a constant velocity over 2 hours, followed by stirring at 70 ° C. for 1 hour. Then, the obtained mixed solution was degassed by a rotary evaporator until the non-volatile component became 90% or more, and then diluted with water so that the non-volatile component became 40%. The mixture was cooled to room temperature to obtain a polysiloxane resin.

The silane compound (II) may be described separately as "silane compound (II-1)" and "silane compound (II-2)" depending on the difference in the charging time.

[Synthesis Example 2]
A polysiloxane-based resin was obtained in the same manner as in Synthesis Example 1 except that the amounts of the monomer (III) and the monomer (IV) were changed as shown in Table 1.

[Synthesis Example 3]
The same method as in Synthesis Example 1 except that the amounts of the reactive compound (I), the silane compound (II-1), the silane compound (II-2) and the silane compound (V) were changed as shown in Table 1. Then, a polysiloxane-based resin was obtained.

[Synthesis Example 4]
Except that the amounts of the reactive compound (I), the silane compound (II-1), the silane compound (II-2), the monomer (IV) and the silane compound (V) were changed as shown in Table 1. A polysiloxane-based resin was obtained in the same manner as in Synthesis Example 1.

[Synthesis Example 5]
A polysiloxane-based resin was obtained in the same manner as in Synthesis Example 1 except that the type of the reactive compound (I) was changed as shown in Table 1.

[Synthesis Example 6]
A polysiloxane-based resin was obtained in the same manner as in Synthesis Example 1 except that the amount of the silane compound (V) was changed as shown in Table 1 and the reactive compound (I) was not used.

[Synthesis Example 7]
A polysiloxane-based resin was obtained in the same manner as in Synthesis Example 1 except that the amount of the monomer (IV) was changed as shown in Table 1 and the monomer (III) was not used.

[Synthesis Example 8]
Synthesis Example 1 except that the amount of the monomer (IV) was changed as shown in Table 1 and the reactive compound (I), the silane compound (II-1) and the silane compound (V) were not used. A polysiloxane-based resin was obtained in the same manner as in the above.

[Synthesis Example 9]
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas introduction tube and dropping funnel, the types and amounts of silane compound (V), crosslinkable silane compound, pure water, and dibutyl phosphate 0 shown in Table 1 .02 g was charged and reacted at a reaction vessel temperature of 70 ° C. for 4 hours with stirring to obtain a mixture. Then, the obtained mixed solution was degassed by a rotary evaporator until the non-volatile component became 90% or more, and then diluted with water so that the non-volatile component became 40%. The mixture was cooled to room temperature to obtain a polysiloxane resin as a cross-linking agent (A).

[Example 1]
After weighing the polysiloxane resin (B) in a container, the cross-linking agent (A) was added and stirred for 1 minute to obtain a curable resin composition. Further, a cured film was obtained according to the coating film evaluation method described above.

[Example 2]
A curable resin composition was obtained in the same manner as in Example 1 except that the type and amount of the cross-linking agent were changed as shown in Table 2. Further, a cured film was obtained according to the coating film evaluation method described above.

[Example 3]
A curable resin composition was obtained in the same manner as in Example 1 except that the type and amount of the cross-linking agent were changed as shown in Table 2. Further, a cured film was obtained according to the coating film evaluation method described above.

[Example 4]
A curable resin composition was obtained in the same manner as in Example 1 except that the amount of the cross-linking agent was changed as shown in Table 2. Further, a cured film was obtained according to the coating film evaluation method described above.

[Example 5]
A curable resin composition was obtained in the same manner as in Example 1 except that the amount of the cross-linking agent was changed as shown in Table 2. Further, a cured film was obtained according to the coating film evaluation method described above.

[Example 6]
A curable resin composition was obtained in the same manner as in Example 1 except that the type of the polysiloxane resin and the amount of the cross-linking agent were changed as shown in Table 2. Further, a cured film was obtained according to the coating film evaluation method described above.

[Example 7]
A curable resin composition was obtained in the same manner as in Example 1 except that the type of the polysiloxane resin and the amount of the cross-linking agent were changed as shown in Table 2. Further, a cured film was obtained according to the coating film evaluation method described above.

[Example 8]
A curable resin composition was obtained in the same manner as in Example 1 except that the type of the polysiloxane resin and the amount of the cross-linking agent were changed as shown in Table 2. Further, a cured film was obtained according to the coating film evaluation method described above.

[Example 9]
A curable resin composition was obtained in the same manner as in Example 1 except that the type of the polysiloxane resin and the amount of the cross-linking agent were changed as shown in Table 2. Further, a cured film was obtained according to the coating film evaluation method described above.

[Comparative Example 1]
A curable resin composition was obtained in the same manner as in Example 1 except that the type and amount of the cross-linking agent were changed as shown in Table 3. Further, a cured film was obtained according to the coating film evaluation method described above.

[Comparative Example 2]
A curable resin composition was obtained in the same manner as in Example 1 except that no cross-linking agent was used. Further, a cured film was obtained according to the coating film evaluation method described above.

[Comparative Example 3]
A curable resin composition was obtained in the same manner as in Example 1 except that the type of the polysiloxane resin was changed as shown in Table 3. Further, a cured film was obtained according to the coating film evaluation method described above.

[Comparative Example 4]
A curable resin composition was obtained in the same manner as in Example 1 except that the type of the polysiloxane resin and the amount of the cross-linking agent were changed as shown in Table 3. Further, a cured film was obtained according to the coating film evaluation method described above.

[Comparative Example 5]
A curable resin composition was obtained in the same manner as in Example 1 except that the type of the polysiloxane resin was changed as shown in Table 3. Further, a cured film was obtained according to the coating film evaluation method described above.

The results of Examples 1 to 9 and Comparative Examples 1 to 5 are shown in Tables 2 and 3.

〔result〕
From Tables 2 and 3, it was found that in the examples, a cured film having a low water contact angle and water resistance could be obtained. It was also found that the cured film was also excellent in tackiness. From the above, it was shown that the present curable resin composition can be used as a material for a cured film having a low water contact angle and water resistance.

This curable resin composition forms a cured film having a low water contact angle and having water resistance by coating and curing at room temperature without requiring pretreatment on the coating substrate. be able to. Therefore, the present invention can be suitably used in various coating agent fields.

Claims (12)

A cross-linking agent (A) having two or more functional groups and
As a constituent unit
(A) A functional group that reacts with the cross-linking agent (A),
(B) A polysiloxane-based resin (B) having a repeating structure derived from a monomer having a radically polymerizable group, and (c) a salt structure composed of an acid and a base.
Curable resin composition containing. The polysiloxane resin (B) is
A silane compound (I-1) having the above (a) and a hydrolyzable silyl group and / or a single amount having the above (a) and a radically polymerizable group and having no hydrolyzable silyl group. The structural unit (i) derived from the body (I-2) and
A structural unit (ii) derived from a silane compound (II) having a radically polymerizable group and a hydrolyzable silyl group, and
A structural unit (iii) derived from the monomer (III) having the above (c) and a radically polymerizable group and not having a hydrolyzable silyl group, and
A structural unit (iv) derived from a monomer (IV) having a radically polymerizable group and not having a hydrolyzable silyl group other than the above (I-2) and (III),
The curable resin composition according to claim 1. The polysiloxane resin (B) is
Further, other than the above (I-1) and (II), the following general formula (1):
R ¹ _n −Si− (OR ² ) _4-n ... (1)
(In the formula, R ¹ is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and R ² is independently a hydrogen atom or 1 to 10 carbon atoms, respectively. The curable resin composition according to claim 1 or 2, wherein the alkyl group is 10 and n has a structural unit (v) derived from the silane compound (V) represented by (0 to 3). thing. The curable resin composition according to any one of claims 1 to 3, wherein the cross-linking agent (A) and the polysiloxane-based resin (B) are soluble in water. The curable resin composition according to any one of claims 1 to 4, wherein the cross-linking agent (A) is an epoxy compound and the (a) is an amino group. Any of claims 1 to 5, wherein the resin composition (β) containing the polysiloxane-based resin (B) is contained as the first liquid, and the composition (α) containing the cross-linking agent (A) is contained as the second liquid. The curable resin composition according to item 1. The curable resin composition according to any one of claims 1 to 6, wherein the resin composition (β) contains 30% by weight or more of water and 10% by weight or less of a non-aqueous solvent. Claims 1 to 1, wherein the ratio of the functional group of the cross-linking agent (A) to (a) in the polysiloxane-based resin (B) is 0.6: 1 to 1.8: 1 in terms of molar ratio. 7. The curable resin composition according to any one of 7. An aqueous solution containing the curable resin composition according to any one of claims 1 to 8. A cured film obtained by applying the aqueous solution according to claim 9. A cured film obtained by curing the curable resin composition according to any one of claims 1 to 8. The cured film according to claim 10 or 11, wherein the contact angle of water is 30 degrees or less.