JP2024044177A - Laminate and manufacturing method thereof - Google Patents

Abstract

[Problem] To provide a laminate that is excellent in reducing water permeability to a base layer including a base material for civil engineering and building materials. [Solution] A laminate having a base layer including a base material for civil engineering and building materials and a coating layer, the coating layer being a layer formed from a composition (I) containing a polysiloxane resin composed of specific components and water. [Selected Figure] None

Description

The present invention relates to a laminate and a method for manufacturing the same.

When water adheres to a base material for civil engineering and construction materials such as concrete due to rain, etc., the water gets inside the base material for civil engineering and construction materials, causing calcium hydroxide, etc. in the base material for civil engineering and construction materials. dissolve. The dissolved calcium hydroxide precipitates on the surface layer of the base material for civil engineering and construction materials, dries, and becomes insoluble calcium carbonate by reacting with carbon dioxide in the air. The calcium carbonate causes efflorescence, which impairs the aesthetic appearance of the base material for civil engineering and construction materials.

Therefore, it is known to use a silane-based impregnating agent as a protective agent for base materials for civil engineering and construction materials such as concrete (for example, Patent Document 1).

Japanese Patent Application Publication No. 9-278562

However, the above-mentioned conventional techniques have room for improvement from the viewpoint of reducing water permeability to base materials for civil engineering and construction materials.

The present invention aims to provide a laminate having a base layer including a base material for civil engineering and building materials and a coating layer, and having excellent water permeability reduction to the base layer including the base material for civil engineering and building materials.

As a result of intensive research to solve the above problems, the inventors discovered for the first time that in a laminate having a base layer including a base material for civil engineering and building materials and a coating layer, by forming the coating layer from a specific component, it is possible to obtain a laminate that is excellent in reducing water permeability to the base layer including the base material for civil engineering and building materials, and thus completed the present invention.

Therefore, one aspect of the present invention is a laminate having a base layer including a base material for civil engineering and construction materials, and a coating layer, the coating layer being a layer formed from a composition (I) containing a polysiloxane-based resin and water, the polysiloxane-based resin having a polymer including a constituent unit derived from a monomer having a radically polymerizable group as a constituent unit, the monomer including (i) a monomer having a salt structure consisting of an acid and a base, soluble in water, and not forming micelles in water, and (ii) a monomer capable of forming micelles in water (hereinafter referred to as "the laminate").

Further, one aspect of the present invention is a method for producing a laminate having a base material layer including a base material for civil engineering and construction materials, and a coating layer, the composition (I) being coated on the base material layer. The composition (I) is a composition containing a polysiloxane resin and water, and the polysiloxane resin has a radically polymerizable component as a constituent unit. The monomer (i) has a salt structure consisting of an acid and a base, is soluble in water, and forms micelles in water. This is a method for producing a laminate (hereinafter referred to as "this production method"), which includes a monomer that does not form micelles, and (ii) a monomer that can form micelles in water.

According to one aspect of the present invention, the material has a base material layer including a base material for civil engineering and building materials, and a coating layer, and is excellent in reducing water permeability to the base material layer including the base material for civil engineering and building materials. A laminate can be provided.

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

1. Overview of the Invention
As described above, conventionally, there has been a problem of efflorescence (whitening phenomenon) that is caused by water penetration into the interior of base materials for civil engineering and building materials, such as concrete, which impairs the aesthetic appearance of the base materials for civil engineering and building materials.

It is known to use silane-based impregnating materials as protective agents for civil engineering and building material substrates. For example, the invention described in Patent Document 1 discloses a surface finishing material for concrete that is characterized by being composed of an aqueous emulsion of an acrylic copolymer having an alkoxysilyl group and a silane compound having a hydrolyzable functional group.

However, the above-mentioned conventional techniques leave room for improvement in terms of reducing the water permeability of civil engineering and construction material substrates.

Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventor has developed a laminate having a base material layer containing a base material for civil engineering and construction materials, and a coating layer, in which the coating layer is made of a specific component. It was discovered for the first time that by configuring the present invention, it is possible to obtain a laminate that is excellent in reducing water permeability to a base material layer including a base material for civil engineering and construction materials. Specifically, we succeeded in obtaining the following knowledge:
- In a laminate having a base material layer containing a base material for civil engineering and construction materials and a coating layer, the coating layer is made of a composition (I) containing a polysiloxane resin that satisfies the following (a) and water. ):
(a) It has a polymer containing, as a structural unit, a structural unit derived from a monomer having a radically polymerizable group, and the monomer (i) has a salt structure consisting of an acid and a base, and (ii) a monomer that is soluble in water and does not form micelles in water; and (ii) a monomer that can form micelles in water. It is possible to obtain a laminate that is excellent in reducing water permeability.

In this way, by forming a coating layer having a specific configuration, it is possible to obtain a laminate that is excellent in reducing water permeability to a base layer, including a base material for civil engineering and construction materials. This is something that could not have been imagined based on conventional knowledge, and the present invention is extremely superior.

In addition, according to the above configuration, the resulting laminate contains little or no organic solvent, which reduces contamination of water and soil compared to conventional techniques. Therefore, it can contribute to achieving, for example, Goal 15 of the Sustainable Development Goals (SDGs) advocated by the United Nations, "Protect and sustain the life of land."

[2. Laminate]
The present laminate is a laminate having a base material layer containing a base material for civil engineering and construction materials, and a coating layer, the coating layer comprising a composition (I) containing a polysiloxane resin and water. The polysiloxane resin has a polymer containing, as a structural unit, a structural unit derived from a monomer having a radically polymerizable group, and the monomer is (i) It includes a monomer that has a salt structure consisting of an acid and a base, is soluble in water, and does not form micelles in water, and (ii) a monomer that can form micelles in water.

This laminate has the advantage that by having the above-mentioned structure, a laminate can be obtained that is excellent in reducing water permeability to the base material layer containing the base material for civil engineering and construction materials.

In one embodiment of the present invention, the base layer and the coating layer are preferably directly bonded to each other. This configuration has the advantage of reducing the number of steps by eliminating the step of applying a primer.

(2-1. Coating layer)
In one embodiment of the present invention, the coating layer is a layer formed from a composition (I) containing a polysiloxane resin and water. In this specification, the "coating layer according to one embodiment of the present invention" may be referred to as the "coating layer of the present invention."

(2-1-1. Composition (I))
In one embodiment of the present invention, composition (I) contains a polysiloxane resin and water. In this specification, "composition (I) according to one embodiment of the present invention" may be referred to as "composition (I)".

<Polysiloxane Resin>
In one embodiment of the present invention, the polysiloxane-based resin has a polymer containing, as a constituent unit, a constituent unit derived from a monomer having a radical polymerizable group, and the monomer includes (i) a monomer having a salt structure consisting of an acid and a base, which is soluble in water and does not form micelles in water, and (ii) a monomer capable of forming micelles in water. In this specification, the "polysiloxane-based resin according to one embodiment of the present invention" may be referred to as the "present polysiloxane-based resin".

By having the above-mentioned configuration, the present polysiloxane-based resin can be stably dispersed or dissolved in an aqueous medium (made aqueous), and when made aqueous, it is possible to provide a polysiloxane-based resin that has an appropriate viscosity.

In this specification, the term "polysiloxane-based resin" refers to a resin containing a polysiloxane structure as a main component. The polysiloxane-based resin is not particularly limited as long as it satisfies the above definition, but examples thereof include resins containing a polysiloxane structure as a main component, which are obtained by dehydration condensation of a single compound represented by the following general formula (IV) or by co-condensation of multiple compounds represented by the following general formula (IV):
R ¹ _a R ² _b —Si—(OR ³ ) _4-a-b ... (IV)
(In the formula, R ¹ is a substituted alkyl group having 1 to 10 carbon atoms and having a polymerizable unsaturated group, an alkenyl group, or an aryl group having a polymerizable unsaturated group and optionally having other substituents; each R ² is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group; each R ³ is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; 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.)
In one embodiment of the present invention, the polysiloxane-based resin may be a resin having a polysiloxane structure as a main component, obtained by co-condensation of a single compound or multiple compounds represented by the above general formula (IV) and a single compound or multiple compounds represented by the following general formula (III):
R ⁴ _n —Si—(OR ⁵ ) _4-n (III)
(In the formula, R ⁴ 's are each independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and when there are a plurality of R ⁴ 's, they may be the same or different, R ⁵ 's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 3.)

In this specification, the polysiloxane structure that is the main component of the polysiloxane resin, that is, the structural unit formed by condensing monomers having a hydrolyzable silyl group, may be referred to as the "main chain", and the above-mentioned A structural unit made of a monomer having a radically polymerizable group that is bonded to the main chain by radical polymerization is sometimes referred to as a "side chain."

The side chain of the present polysiloxane resin is made of a polymer containing a structural unit derived from a monomer having a radically polymerizable group. The monomers constituting the side chains of the present polysiloxane resin are (i) monomers that have a salt structure consisting of an acid and a base, are soluble in water, and do not form micelles in water; (ii) There is no particular limitation as long as it includes a monomer capable of forming micelles in water. The side chain of the present polysiloxane resin may be composed only of the monomers (i) and (ii) above, or may contain other monomers. Among the monomers constituting the side chain of one embodiment of the present invention, monomers other than the above (i) and (ii) are preferably monomers that do not have a hydrolyzable silyl group, and optionally , may also contain a monomer having a hydrolyzable silyl group. Therefore, as a preferable example, the present polysiloxane resin can also be expressed as follows: As a constitutional unit, the side chain is composed of a polymer containing a constitutional unit derived from a monomer having a radically polymerizable group. has a salt structure consisting of an acid and a base and a radical polymerizable group (without having a polyoxyalkylene structure) as a constitutional unit of the side chain, and does not have a hydrolyzable silyl group, A structural unit (b) derived from a monomer (B) that is soluble in water and does not form micelles in water, a structure (having a polyoxyalkylene structure) capable of forming micelles in water, and A polysiloxane resin containing a structural unit (c) derived from a monomer (C) having a radically polymerizable group and not having a hydrolyzable silyl group.

In one embodiment of the present invention, the polysiloxane resin preferably includes a structural unit (a) derived from a silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group, a structural unit (b) derived from a monomer (B) having a salt structure consisting of an acid and a base and a radically polymerizable group, not having a hydrolyzable silyl group, being soluble in water, and not forming micelles in water, and a structural unit (c) derived from a monomer (C) having a polyoxyalkylene structure and a radically polymerizable group, not having a hydrolyzable silyl group, and capable of forming micelles in water. In one embodiment of the present invention, the polysiloxane resin preferably includes a structural unit (a) forming a main chain, and structural units (b) and (c) forming side chains.

In one embodiment of the present invention, the polysiloxane resin may further include, in addition to the above-mentioned (A) to (C), a main chain structural unit represented by the following general formula (III):
R ⁴ _n —Si—(OR ⁵ ) _4-n (III)
(In the formula, R ⁴ 's are each independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and when there are a plurality of R ⁴ 's, they may be the same or different, R ⁵ 's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 3.)
It is more preferable that the compound further contains a structural unit (d) derived from a silane compound (D) represented by the following formula:

In addition, hereinafter, "the structural unit (a) derived from the silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group" will be simply referred to as "the structural unit (a)", and will be referred to as "the structural unit (a)" A structure derived from a monomer (B) that has a salt structure consisting of a base and a radically polymerizable group, does not have a hydrolyzable silyl group, is soluble in water, and does not form micelles in water. "Unit (b)" is simply referred to as "constituent unit (b)," and "unit (b) has a polyoxyalkylene structure and a radically polymerizable group, does not have a hydrolyzable silyl group, and forms micelles in water. The structural unit (c) derived from the monomer (C) capable of "Unit (d)" is simply referred to as "Structural unit (d)" and "A structure derived from a monomer (E) having a radically polymerizable group other than the above (A), (B) and (C)" unit (e)" is simply referred to as "constituent unit (e)." In addition, hereinafter, "the silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group" is simply referred to as "silane compound (A)" or "monomer (A)", and "acid A monomer (B) that has a salt structure consisting of a base and a radically polymerizable group, does not have a hydrolyzable silyl group, is soluble in water, and does not form micelles in water, Simply referred to as "monomer (B)," it is a monomer that has a polyoxyalkylene structure and a radically polymerizable group, does not have a hydrolyzable silyl group, and is capable of forming micelles in water. ``silane compound (D)'' is simply referred to as ``monomer (C)'', and ``silane compound (D) represented by general formula (III)'' is simply referred to as ``silane compound (D)'' or ``monomer (C)''. D)", and "monomer (E) having a radically polymerizable group other than the above (A), (B) and (C)" is simply referred to as "monomer (E)".

(Structural Unit (a))
The structural unit (a) is derived from a silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group.

The silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group has the following general formula (IV):
R ¹ _a R ² _b -Si-(OR ³ ) _4-ab ...(IV)
(In the formula, R ¹ has a substituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, or a polymerizable unsaturated group having a polymerizable unsaturated group, and may optionally have other substituents. is an aryl group, R ² is each independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and R ³ is each independently a hydrogen atom or a C 1 to 10 (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.)
It is a silane compound having a hydrolyzable silyl group represented by:

R ¹ in general formula (IV) is a substituted alkyl group having 1 to 10 carbon atoms and having a radically polymerizable unsaturated group, an alkenyl group, or an unsubstituted or substituted aryl group having a radically polymerizable unsaturated group. Examples of the radically polymerizable unsaturated group include a (meth)acryloyl group.

Examples of the silane compound (A) in which R ¹ is an alkyl group having a radically polymerizable unsaturated group include (meth)acryloxymethyltrimethoxysilane, (meth)acryloxymethylmethyldimethoxysilane, (meth)acryloxy Methyldimethylmethoxysilane, (meth)acryloxymethyltriethoxysilane, (meth)acryloxymethylmethyldiethoxysilane, (meth)acryloxymethyldimethylethoxysilane, 2-(meth)acryloxyethyltrimethoxysilane, 2- (meth)acryloxyethylmethyldimethoxysilane, 2-(meth)acryloxyethyldimethylmethoxysilane, 2-(meth)acryloxyethyltriethoxysilane, 2-(meth)acryloxyethylmethyldiethoxysilane, 2-( meth)acryloxyethyldimethylethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropyldimethylmethoxysilane, γ-(meth) Acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldiethoxysilane, γ-(meth)acryloxypropyldimethylethoxysilane, 4-(meth)acryloxybutyltrimethoxysilane, 4-(meth)acrylic Roxybutylmethyldimethoxysilane, 4-(meth)acryloxybutyldimethylmethoxysilane, 4-(meth)acryloxybutyltriethoxysilane, 4-(meth)acryloxybutylmethyldiethoxysilane, 4-(meth)acryloxy Butyldimethylethoxysilane, 5-(meth)acryloxypentyltrimethoxysilane, 5-(meth)acryloxypentylmethyldimethoxysilane, 5-(meth)acryloxypentyldimethylmethoxysilane, 5-(meth)acryloxypentyltrimethoxysilane Ethoxysilane, 5-(meth)acryloxypentylmethyldiethoxysilane, 5-(meth)acryloxypentyldimethylethoxysilane, 6-(meth)acryloxyhexyltrimethoxysilane, 6-(meth)acryloxyhexylmethyldimethoxy Silane, 6-(meth)acryloxyhexyldimethylmethoxysilane, 6-(meth)acryloxyhexyltriethoxysilane, 6-(meth)acryloxyhexylmethyldiethoxysilane, 6-(meth)acryloxyhexyldimethylethoxysilane etc.

Examples of the silane compound (A) in which R ¹ is an alkenyl group include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, and vinyldimethylethoxysilane.

Examples of the silane compound (A) in which R ¹ is an aryl group having a polymerizable unsaturated group and optionally having other substituents include p-styryltrimethoxysilane, p-styrylmethyldimethoxysilane, p-styryldimethylmethoxysilane, p-styryltriethoxysilane, p-styrylmethyldiethoxysilane, and p-styryldimethylethoxysilane.

Among these, from the viewpoint of thermal radical polymerization reactivity, R ¹ is preferably an alkyl group substituted with a (meth)acryloyl group.

In general formula (IV), R ² 's each independently represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group.

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

Specific examples of the aryl group for R ² in general formula (IV) include phenyl group, naphthyl group, benzyl group, and the like.

When a is 1 and b is 1, R ² in the general formula (IV) is preferably a methyl group.

R ³ in general formula (IV) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, amyl group, etc. group, isoamyl group, hexyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, heptyl group, isoheptyl group, octyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, etc. .

From the viewpoint of facilitating condensation of the silane compound (A) with another silane compound not having a radically polymerizable unsaturated group (silane compound (D)), the number of carbon atoms in the alkyl groups of R ² and R ³ in general formula (IV) is preferably 1 to 3, and most preferably 1.

In one embodiment of the present invention, the content of the structural unit (a) is, for example, 1% by weight or more, preferably 2% by weight or more, based on 100% by weight of the total amount of the polysiloxane resin. It is. When the content of the structural unit (a) is within the above range, sufficient graft polymerization can be carried out directly or indirectly with the structural unit (b) and/or the structural unit (c), and as a result, it is stable in an aqueous medium. It is possible to obtain a polysiloxane resin that can be dispersed or dissolved (made into an aqueous system). Further, the upper limit of the content of the structural unit (a) is not particularly limited as long as the effects of the present invention are achieved, but is, for example, 10% by weight or less, preferably 8% by weight or less, and more preferably 5% by weight or less. % by weight or less.

(Structural Unit (b))
The structural unit (b) is derived from a monomer (B) which has a salt structure consisting of an acid and a base and a radically polymerizable group, does not have a hydrolyzable silyl group, is soluble in water, and does not form micelles in water.

In this specification, the term "salt structure" refers to 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. The base used for neutralization may be a strong base or a weak base.

In one embodiment of the present invention, the salt structure is, for example, a structure of a neutral salt of a strong acid and a strong base, a structure of a neutral salt of a strong acid and a weak base, a structure of a neutral salt of a weak acid and a strong base, Alternatively, it may have 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 a neutral salt of a strong acid and a strong base), ammonium sulfonate, and ammonium nitrate. etc. (Structure of a neutral salt of a strong acid and a weak base), Sodium acetate, Potassium acetate, Calcium acetate, Sodium phosphate, Potassium phosphate, Calcium phosphate, etc. (Structure of a neutral salt of a weak acid and a strong base), Ammonium acetate , ammonium phosphate (a structure of a neutral salt of a weak acid and a weak base), and the like. In one embodiment of the invention, the salt structure is preferably sodium sulfonate.

In this specification, "soluble in water" means that an aqueous solution of 1 g of the monomer of interest in 10 g of water at 25°C is thoroughly stirred, left to stand for one week at 25°C, and visually observed. This means that when the appearance is observed in the aqueous solution, no precipitate, dispersion, layer separation, etc. are observed in the aqueous solution, and the solution is transparent.

In one embodiment of the present invention, the content of the structural unit (b) is, for example, 1% by weight or more, preferably 2% by weight or more, and more preferably 4% by weight or more, based on 100% by weight of the total amount of the polysiloxane resin. When the content of the structural unit (b) is within the above range, the structural unit (b) is uniformly dispersed or soluble in water. The upper limit of the content of the structural unit (b) is not particularly limited as long as the effects of the present invention are achieved, but is, for example, 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less.

In this specification, "stably dispersed or dissolved in an aqueous medium" means that no "precipitate" is produced when a solution containing a polysiloxane-based resin is evaluated using the following method: An aqueous solution of a polysiloxane-based resin produced using the method described in the Examples is left to stand at 25°C for one week, and the appearance of the aqueous solution is evaluated by visual observation.

In other words, "stably dispersed or dissolved in an aqueous medium" means that when a solution containing a polysiloxane-based resin is evaluated using the above method, the solution containing the polysiloxane-based resin is uniformly evaluated as "colorless and transparent," "blue-white transparent," or "white dispersion." If "precipitates" are observed, the solution does not meet the criteria of "stably dispersed or dissolved in an aqueous medium."

Monomer (B) is a monomer that has a salt structure consisting of an acid and a base and a radically polymerizable group, does not have a hydrolyzable silyl group, is soluble in water, and does not form micelles in water. The radically polymerizable group in monomer (B) undergoes radical polymerization with the radically polymerizable group in monomer (A) to form a graft chain derived from monomer (B) to the polysiloxane main chain. Since monomer (B) has a salt structure consisting of an acid and a base and is soluble in water, this polysiloxane resin can be stably dispersed or dissolved in an aqueous medium.

The radically polymerizable unsaturated group in the monomer (B) is not particularly limited as long as it can contribute to radical polymerization with the monomer (A). Examples of the radically polymerizable unsaturated group in the monomer (B) include a (meth)acryloyl group, a (meth)acrylamide group, and a vinyl group. From the viewpoint of high reactivity and versatility, a (meth)acryloyl group or a (meth)acrylamide group is preferred.

The monomer (B) is not particularly limited as long as it has a salt structure consisting of an acid and a base and has a radical polymerizable group, but examples thereof include sodium sulfoethyl methacrylate, sodium acrylamide-t-butyl sulfonate, sodium 2-(methacryloyloxy)ethanesulfonate, sodium acrylamide-t-butyl sulfonate, potassium 2-(methacryloyloxy)ethanesulfonate, potassium acrylamide-t-butyl sulfonate, calcium 2-(methacryloyloxy)ethanesulfonate, calcium acrylamide-t-butyl sulfonate, ammonium sulfoethyl methacrylate, ammonium acrylamide-t-butyl sulfonate, ammonium 2-(methacryloyloxy)ethanesulfonate, ammonium acrylamide-t-butyl sulfonate, sodium acrylate, potassium acrylate, calcium acrylate, ammonium acrylate, sodium methacrylate, potassium methacrylate, calcium methacrylate, and ammonium methacrylate.

Moreover, monomer (B) can be obtained as a commercial item. Examples of such commercial products include "Antox MS-2N-D" manufactured by Nippon Nyukazai Co., Ltd., "ATBS-Na" manufactured by Toagosei Co., Ltd., and "Acrylic" manufactured by Asada Chemical Industry Co., Ltd. Examples include "sodium acrylate" and "potassium acrylate".

Note that whether or not a monomer is "capable of forming micelles in water" is determined by the method described in the section (Structural unit (c)).

(Structural Unit (c))
The structural unit (c) is derived from a monomer (C) that has a radical polymerizable group, does not have a hydrolyzable silyl group, and can form micelles in water. The radical polymerizable group in the monomer (C) undergoes direct or indirect radical polymerization with the radical polymerizable group in the monomer (A) to form a graft chain derived from the monomer (C) to the polysiloxane main chain. By having the structural unit (c), the polysiloxane resin forms micelles when made into a water-based composition, making it easy to adjust the viscosity, and the polysiloxane resin can be suitably used as a water-based paint.

In this specification, "micelle" refers to an aggregate formed by amphipathic molecules associating with each other through hydrophobic interactions. Here, an amphipathic molecule refers to a molecule having both a hydrophobic group and a hydrophilic group within the molecule. Therefore, a "structure capable of forming a micelle in water" refers to a structure having both a hydrophobic group and a hydrophilic group within the molecule.

In one embodiment of the invention, monomer (C) may be an amphiphilic molecule without a hydrolyzable silyl group.

Whether or not "micelles can be formed in water" is judged as follows: 1 g of the target monomer is added to a two-layer liquid containing 10 g of water and 2 g of butyl acetate, thoroughly stirred, and then left to stand for 12 hours. If uniform white turbidity is observed, it is judged that the target monomer is capable of forming micelles in water. If separate, transparent layers of water and butyl acetate are observed after leaving to stand for 12 hours, it is judged that the target monomer does not form micelles in water (is unable to form micelles).

Monomer (C) has a radically polymerizable group, has a structure that forms micelles in water (i.e., a structure that has a hydrophobic group and a hydrophilic group in the molecule), and has a structure that forms micelles in water, and There are no particular limitations as long as the monomer does not have a decomposable silyl group.

The hydrophobic group in the monomer (C) is not particularly limited, but includes, for example, an alkyl group having 3 or more carbon atoms and an aryl group having a radically polymerizable group.

The hydrophilic group in the monomer (C) is not particularly limited, but includes, for example, anionic hydrophilic groups such as sulfonate, carboxylate, sulfuric ester salt, amine salt, quaternary ammonium salt, etc. Examples include cationic hydrophilic groups such as , amphoteric hydrophilic groups such as betaine, and nonionic hydrophilic groups such as polyoxyalkylene.

In one embodiment of the present invention, from the viewpoint of versatility, it is preferable that the monomer (C) has a polyoxyalkylene structure. Examples of such monomers include polyoxyethylene and polyoxypropylene. It is preferable that the monomer (C) has a polyoxyalkylene structure having 1 to 100 oxyalkylene repeating units, more preferably a polyoxyalkylene structure having 2 to 50 oxyalkylene repeating units, and even more preferably a polyoxyalkylene structure having 5 to 20 oxyalkylene repeating units.

The monomer (C) is not particularly limited as long as it falls within the above definition, but examples thereof include ADEKA REASOAP SR-05, SR-10, SR-20, SR-1025, SR-2025, SR-3025, SR-10S, NE-10, NE-20, NE-30, NE-40, SE-10, SE-20, ER-10, ER-20, ER-30, and ER-40 manufactured by ADEKA CORPORATION, and Antox-MS-60, RMA-1120, RMA-564, RMA-568, RMA-506, MA-30, and MA- 50, MA-100, MA-150, RMA-1120, MPG130-MA, MPG-130MA, RMA-150M, RMA-300M, RMA-450M, RA-1020, RA-1820, Aqualon KH-05, KH-10, RN-20, RN-30, RN-50, RN-2025, HS-10, HS-20, HS-1025, BC05, BC10, BC0515, BC1025 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Eleminol JS-2, JS-20, RS-30 manufactured by Sanyo Chemical Industries, Ltd., and Latemul manufactured by Kao Corporation S-180, S-180A, PD-104, PD-420, PD-430, Nippon Oil & Fats Co., Ltd.'s Blenmar PE-90, PE-200, PE-350, AE-90, AE-200, AE-350, PP-500, PP-800, PP-1000, AP-400, AP-550, AP-800, 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, Light Ester 130MA, 041MA, MTG, Light Acrylate EC-A, MTG-A, 130A, DPM-A, P-200A, NP-4EA, NP-8EA, EHDG-A, and NK-ESTER manufactured by Shin-Nakamura Chemical Co., Ltd. Examples include M-20G, M-40G, M-90G, M-230G, AMP-10G, AMP-20G, AMP-60G, AM-90G, and LA. From the viewpoint of versatility and micelle stability, Adeka Reasoap SR-10 is preferred.

In one embodiment of the present invention, the monomer (C) may have a salt structure consisting of an acid and a base. The salt structure may be, 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, a neutral salt structure of a weak acid and a strong base, or a neutral salt structure 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, etc. (neutral salt structure of a strong acid and a strong base), ammonium sulfonate, ammonium nitrate, etc. (neutral salt structure of a strong acid and a weak base), sodium acetate, potassium acetate, calcium acetate, sodium phosphate, potassium phosphate, calcium phosphate, etc. (neutral salt structure of a weak acid and a strong base), ammonium acetate, ammonium phosphate, etc. (neutral salt structure of a weak acid and a weak base), etc. In one embodiment of the present invention, the salt structure is preferably sodium sulfonate or ammonium sulfonate.

In one embodiment of the present invention, the content of the structural unit (c) is, for example, 0.5% by weight or more, preferably 1% by weight, based on 100% by weight of the total amount of the polysiloxane resin. % or more, more preferably 2% by weight or more. When the content of the structural unit (c) is within the above range, the viscosity can be easily adjusted when the polysiloxane resin is made into a solution in an aqueous medium, and it can be suitably used as a water-based paint. Further, the upper limit of the content of the structural unit (c) is, for example, 15% by weight or less, preferably 10% by weight or less, and more preferably 8% by weight or less. When the content of the structural unit (c) is within the above range, the resulting coating layer will have good water resistance.

(Structural Unit (d))
The structural unit (d) is represented by the following general formula (III):
R ⁴ _n —Si—(OR ⁵ ) _4-n (III)
The silane compound (D) is a structural unit derived from a silane compound represented by the following general formula (III):
R ⁴ _n —Si—(OR ⁵ ) _4-n (III)
(In the formula, R ⁴ 's are each independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and when there are a plurality of R ⁴ 's, they may be the same or different, R ⁵ 's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 3.)
The silane compound (D) is a silane compound having a hydrolyzable silyl group represented by the formula (III). The silane compound (D) undergoes dehydration condensation with the silane compound (A) and/or (D) to form a polysiloxane. It can also be said that the silane compound (D) is a silane compound having no radical polymerizable unsaturated group and having a hydrolyzable silyl group. In this specification, the silane compound (D) may be referred to as a monomer (D). The structural unit (d) may be composed of only one type of silane compound (D) represented by the formula (III), or may be composed of a combination of two or more types of silane compounds (D).

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

Specific examples of the aryl group in ^R4 of the general formula (III) include a phenyl group, a naphthyl group, and a benzyl group.

R ⁵ in the general formula (III) is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group. Examples include groups.

Specific compounds represented by general formula (III) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Triethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltriisopropoxysilane, hexyltrimethoxysilane, hexyltriethoxy Silane, hexyltriisopropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyl Examples include dimethoxysilane, trimethylmonomethoxysilane, triphenylmonomethoxysilane, and the like.

(Constituent unit (e))
The structural unit (e) is derived from a monomer (E) having a radically polymerizable unsaturated group other than the above (A), (B) and (C). The monomer (E) from which the structural unit (e) is derived is directly or indirectly bonded to the monomer (A) and/or (B) and/or (C) by radical polymerization, and the structural unit (e) is derived from the monomer (E). a) and/or (b) and/or (c).

The monomer (E) from which the structural unit (e) is derived is not particularly limited as long as it is a monomer having a radically polymerizable unsaturated group other than the above (A), (B) and (C). Examples include (meth)acrylic acid alkyl esters and monomers other than (meth)acrylic acid alkyl esters as shown below.

<(Meth)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 may be a (meth)alkyl monomer that does not contain a functional group such as a hydroxyl group or an epoxy group. 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, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)methacrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, and the like.

<Monomers other than (meth)acrylic acid alkyl esters>
Examples of monomers other than (meth)acrylic acid alkyl esters include nitrile group-containing radically polymerizable monomers such as (meth)acrylonitrile; hydroxyl group-containing radically polymerizable monomers such as glycidyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate; monomers having two or more polymerizable unsaturated bonds such as ethylene glycol di(meth)acrylate and allyl (meth)acrylate; fluorine-containing radically polymerizable monomers such as trifluoro(meth)acrylate, pentafluoro(meth)acrylate, perfluorocyclohexyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl methacrylate and β-(perfluorooctyl)ethyl (meth)acrylate; and the like.

In one embodiment of the present invention, the weight average molecular weight of the polysiloxane resin is not particularly limited, but is, for example, 5,000 to 500,000, preferably 8,000 to 100,000, and more preferably 10,000 to 80,000. The weight average molecular weight of the polysiloxane resin is measured using a high-speed GPC device HLC-8320GPC manufactured by Tosoh Corporation.

<Water>
The composition (I) contains water. The content of water in the composition (I) is not particularly limited, but may be, for example, 30% by weight or more and 90% by weight or less, preferably 35% by weight or more and 80% by weight or less, more preferably 40% by weight or more and 70% by weight or less, based on the polysiloxane resin. This configuration has the advantage that the obtained composition can be easily used as a water-based paint.

<Other ingredients>
The present composition (I) may contain a non-aqueous solvent within the range that achieves the effects of the present invention. As used herein, "non-aqueous solvent" means all solvents other than water. The "non-aqueous solvent" herein 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 includes, 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 cellosolub; Ether esters such as cellosolve acetate; Ketones such as methyl ethyl ketone, ethyl acetoacetate, acetylacetone, methyl isobutyl ketone, acetone; methanol, 2-propanol, n-butanol, isobutanol, hexanol, octanol, etc. Alcohols; 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, dipropylene glycol-n-butyl ether, dipropylene Examples include film-forming aids for water-based paints such as glycol dimethyl ether.

The composition (I) may contain additives that are commonly used in the technical field (particularly in the field of paints) within the scope of the effects of the present invention. Examples of such additives include pigments, fillers, plasticizers, film-forming aids, wetting agents, dispersants, thickeners, defoamers, preservatives, antioxidants, antisettling agents, leveling agents, UV absorbers, antistatic agents, antifreeze agents, antibacterial agents, antifungal and antialgae agents, tackifiers, rust inhibitors, and hydrophilizing agents. Only one type of additive may be contained, or two or more types may be contained. The amount of these additives can be appropriately determined by a person skilled in the art depending on the purpose of use.

In one embodiment of the present invention, the method for producing the polysiloxane resin may be the method described in the Examples.

(2-2. Base Material Layer)
The laminate has a substrate layer including a substrate for civil engineering and construction materials.

In this specification, the term "substrate for civil engineering and building materials" refers to a substrate used in buildings and civil engineering structures. Examples of substrate for civil engineering and building materials include organic substrates (including wood) and inorganic substrates. In one embodiment of the present invention, the substrate for civil engineering and building materials preferably does not contain metal.

In one embodiment of the invention, the substrate for civil engineering and construction materials is preferably a porous organic and/or inorganic substrate.

The porous organic base material is not particularly limited, but for example, wood, plywood, particle board, laminated wood, MDF (medium density fiberboard), etc. are preferable.

The porous inorganic base material is not particularly limited, but for example, in addition to a base material obtained by curing a cement-containing composition, stone, ceramic tile, gypsum board, and calcium silicate board are preferable.

Base materials obtained by curing cement-containing compositions include extruded cement boards, lightweight cellular concrete, precast concrete, siding boards, wood cement boards, pulp cement boards, slate boards, fiber-reinforced cement boards, and concrete blocks. , inorganic substrates including prestressed concrete.

Examples of cement-containing compositions include concrete, mortar, cement milk, etc.

As used herein, concrete refers to a material containing cement, sand, water and gravel. In the present specification, concrete may contain chemical admixtures such as AE agents and water reducing agents as other components, and may further include ethylene vinyl acetate resin, acrylic ester resin, styrene butadiene rubber, etc. A miscible polymer may also be included.

In this specification, mortar refers to a mixture of cement and fine aggregate (sand) mixed with water. In this specification, mortar may contain other components such as chemical admixtures, such as air entraining agents and water reducers, and may further contain admixture polymers, such as ethylene vinyl acetate resins, acrylic ester resins, and styrene butadiene rubbers.

In this specification, cement milk is intended to be obtained by kneading cement with only water.

In this specification, the term "cement" refers to a powder whose main raw materials are limestone, clay, silica, iron oxide, etc., and which hardens through a chemical reaction with water.

More specifically, examples of porous inorganic substrates include exposed concrete, lightweight concrete, precast concrete, lightweight foamed concrete (ALC), mortar, joint mortar, asbestos cement board, pulp cement board, wood wool cement board, cement-based extrusion molding board, glass fiber cement board (GRC), carbon fiber cement board, calcium silicate board, gypsum board, hardboard, plaster, gypsum plaster, dolomite plaster, blocks, bricks, tiles, roof tiles, natural stone, artificial stone, glass wool, rock wool, ceramic fiber, etc.

In addition, when the substrate layer is composed of two or more types of substrates including a substrate for civil engineering and building materials, each substrate may be configured in a layered form. In one embodiment of the present invention, the substrate for civil engineering and building materials is preferably disposed lower in the substrate layer, and more preferably disposed at the bottom of the substrate layer. This configuration has the advantage of being even more effective in reducing water permeability to the substrate layer including the substrate for civil engineering and building materials.

[3. Method for manufacturing laminate]
This manufacturing method is a method for manufacturing a laminate having a base material layer containing a base material for civil engineering and construction materials, and a coating layer, the composition (I) being applied onto the base material layer to coat the laminate. The composition (I) is a composition containing a polysiloxane resin and water, and the polysiloxane resin has a monomer having a radically polymerizable group as a constituent unit. (i) the monomer has a salt structure consisting of an acid and a base, is soluble in water, and does not form micelles in water; (ii) a monomer capable of forming micelles in water.

By having the above-mentioned configuration, this manufacturing method has the advantage of being excellent at reducing water permeability to base material layers, including base materials for civil engineering and construction materials.

This manufacturing method also includes a construction method and a sealing method using this laminate.

In this production method, from the viewpoint of versatility, (ii) the monomer capable of forming micelles in water is preferably a monomer having a polyoxyalkylene structure.

In this production method, the polysiloxane-based resin contained in the composition (I) comprises a constituent unit (a) derived from a silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group, a constituent unit (b) derived from a monomer (B) which has a salt structure consisting of an acid and a base and a radically polymerizable group, does not have a hydrolyzable silyl group, is soluble in water, and does not form micelles in water, a constituent unit (c) derived from a monomer (C) which has a polyoxyalkylene structure and a radically polymerizable group, does not have a hydrolyzable silyl group, and is capable of forming micelles in water, and optionally a constituent unit represented by the following general formula (III) other than the above (A), (B), and (C):
R ⁴ _n —Si—(OR ⁵ ) _4-n (III)
(In the formula, R ⁴ 's are each independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and when there are a plurality of R ⁴ 's, they may be the same or different, R ⁵ 's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 3.)
and a structural unit (d) derived from a silane compound (D) represented by the following formula:

In this manufacturing method, it is preferable that the polysiloxane resin contained in the composition (I) further contains a structural unit (e) derived from a monomer (E) having a radical polymerizable group other than the above-mentioned (A), (B), and (C).

In this production method, the polysiloxane resin contained in the composition (I) contains 1 to 20% by weight of the structural unit (b) based on 100% by weight of the total amount of the polysiloxane resin, and , preferably contains 1 to 10% by weight of the structural unit (c).

In this manufacturing method, the polysiloxane resin contained in composition (I) preferably contains the structural units (a) and (d) in a total amount of 10% by weight or more relative to the total amount of the polysiloxane resin (100% by weight).

(3-1. Step of forming a coating layer)
This manufacturing method includes applying the composition (I) described in the above (2-1-1. Composition (I)) onto the base material described in the above (2-2. Base material layer). The method includes a step of forming a coating layer by coating.

In one embodiment of the present invention, the method for forming the coating layer is not particularly limited, but includes, for example, applying a water-based solution, dispersion, or water-based paint containing the present composition (I), Examples include a method of curing. The method will be described in detail below.

In this specification, a solution or dispersion containing the present composition (I) in water is also referred to as the present solution or dispersion. In this specification, a "solution in water" refers to a liquid that is transparent in appearance when the resin solids concentration is 20% and the proportion of water in the total medium is 90% by weight or more, more specifically, a liquid with a haze value of 20.0 or less at 1 atmosphere and 25°C. In addition, in this specification, a "dispersion in water" refers to a liquid that is cloudy in appearance when the resin solids concentration is 20% and the proportion of water in the total medium is 90% by weight or more, more specifically, a liquid with a haze value of more than 20.0 at 1 atmosphere and 25°C. The haze value is measured using COH400 manufactured by Nippon Denshoku Kogyo Co., Ltd. and pure water as a standard liquid.

Since this solution or this dispersion contains the above-mentioned composition (I), it can be stably dispersed or dissolved in a solution using water as a medium, and has an appropriate viscosity when used as a water-based paint. It is useful because it yields paint.

In addition, in this specification, the water-based paint containing the resin composition, the solution, or the dispersion is also referred to as the "water-based paint." The water-based paint contains the above-mentioned aqueous solution or dispersion, and is therefore useful because it can be stably dispersed or dissolved in a solution in which water is the medium and has a suitable viscosity.

In addition to the aqueous solution or dispersion described above, the aqueous paint may contain additives that are commonly used in the relevant technical field (particularly in the field of paints). For additives that may be contained in the aqueous paint, the description in the <Other Components> section above is incorporated as appropriate.

The method for applying this solution, this dispersion, or this water-based paint is not particularly limited, and may be, for example, a brush, roller, air spray, airless spray, or the like used in general painting, or it may be applied by a reverse coating method, gravure coating method, bar coating method, die coating method, spray coating method, kiss coating method, wire bar coating method, curtain coating method, or the like.

As mentioned above, the present coating layer can be said to be a coating layer formed by curing the present composition (I), or by applying and curing the present solution, the present dispersion, or the present aqueous paint.

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

That is, one aspect of the present invention includes the following.

[1] A laminate having a base layer including a base material for civil engineering and building materials and a coating layer,
The coating layer is
A layer formed from a composition (I) containing a polysiloxane-based resin and water,
The polysiloxane resin is
The polymer has, as a structural unit, a structural unit derived from a monomer having a radical polymerizable group,
The monomer is
A laminate comprising: (i) a monomer having a salt structure consisting of an acid and a base, which is soluble in water and does not form micelles in water; and (ii) a monomer capable of forming micelles in water.

[2] The laminate according to [1], wherein the base material for civil engineering and construction materials is a porous organic and/or inorganic base material.

[3] The laminate according to [1] or [2], wherein the monomer (ii) capable of forming micelles in water is a monomer having a polyoxyalkylene structure.

[4] The polysiloxane resin comprises a structural unit (a) derived from a silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group;
Derived from a monomer (B) that has a salt structure consisting of an acid and a base and a radically polymerizable group, does not have a hydrolyzable silyl group, is soluble in water, and does not form micelles in water. a structural unit (b) that
A structural unit (c) derived from a monomer (C) that has a polyoxyalkylene structure and a radically polymerizable group, does not have a hydrolyzable silyl group, and is capable of forming micelles in water. ,
Optionally, the following general formula (III) other than the above (A), (B) and (C):
R ⁴ _n -Si-(OR ⁵ ) _4-n ...(III)
(In the formula, R ⁴ is each independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and when there is a plurality of R ⁴ s, they may be the same or different, R ⁵ is each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 3.)
A structural unit (d) derived from the silane compound (D) represented by
The laminate according to any one of [1] to [3], comprising:

[5] The laminate according to [4], further comprising a structural unit (e) derived from a monomer (E) having a radical polymerizable group other than the above (A), (B), and (C).

[6] Contains 1 to 20% by weight of the structural unit (b) and 1 to 10% by weight of the structural unit (c) based on 100% by weight of the total amount of the polysiloxane resin [4] Or the laminate according to [5].

[7] The laminate according to any one of [4] to [6], which contains a total of 10% by weight or more of the structural units (a) and (d) relative to 100% by weight of the total amount of the polysiloxane resin.

[8] A method for producing a laminate comprising a base material layer containing a base material for civil engineering and construction materials, and a coating layer, comprising:
a step of applying composition (I) on the base layer to form the coating layer,
The composition (I) is
A composition containing a polysiloxane resin and water,
The polysiloxane resin has a polymer containing a structural unit derived from a monomer having a radically polymerizable group as a structural unit,
The monomer is
(i) A monomer that has a salt structure consisting of an acid and a base, is soluble in water, and does not form micelles in water, and (ii) A monomer that can form micelles in water. A method for manufacturing a laminate, including:

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

〔material〕
The following materials were used in the examples and comparative examples.

<Base material>
Mortar test specimen manufactured by Engineering Test Service Co., Ltd. <Coating layer>
(Monomer (A))
γ-(meth)acryloxypropyltrimethoxysilane (abbreviated as “TSMA”): “A-174” manufactured by Momentive Performance Materials Japan LLC
(Monomer (B))
Sodium acrylamide-t-butylsulfonate (abbreviation “ATBS-Na”): “ATBS-Na” manufactured by Toagosei Co., Ltd.
(Monomer (C))
Ether sulfate type ammonium salt (abbreviated as "SR-10"): "Adekariasoap SR-10" manufactured by ADEKA Co., Ltd., commercially available classification "reactive anion emulsifier", compound represented by the following formula (A):

(Monomer (D))
Methyltrimethoxysilane (abbreviated as “M-TMS”): “Z-6033” manufactured by Dow Toray Industries, Inc.
Phenyltrimethoxysilane (abbreviation “Ph-TMS”): “Z-6124” manufactured by Dow Toray Industries, Inc.
(Monomer (E))
Methyl methacrylate (abbreviation “MMA”): Manufactured by Mitsubishi Gas Chemical Co., Ltd. Butyl acrylate (abbreviation “BA”): Manufactured by Nippon Shokubai Co., Ltd. (Others)
Pure water dibutyl phosphate: “DBP” manufactured by Johoku Chemical Industry Co., Ltd.
2-propanol: Nacalai Tesque Co., Ltd. Radical polymerization initiator: 2,2'-azobis(2,4-dimethylvaleronitrile): Tokyo Chemical Industry Co., Ltd. (Composition constituting the coating layer used in the comparative example) thing)
Aqua Seal 50E manufactured by Daido Paint Co., Ltd.
In addition, Aqua Seal 50E does not satisfy the constitution of the composition constituting the coating layer in the present invention.

Synthesis Example 1
(Preparation of co-condensation product (main chain))
A reactor equipped with a stirrer, a thermometer, and a reflux condenser was charged with 2.4 parts by weight of TSMA, 25.7 parts by weight of M-TMS, 21.8 parts by weight of Ph-TMS, 14.6 parts by weight of pure water, and 0.015 parts by weight of DBP, and the mixture was reacted at a reaction temperature of 105° C. for 3 hours with stirring to obtain a co-condensation product.

(Preparation of graft cocondensate (side chain polymerization))
10.8 parts by weight of 2-propanol was charged into a reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction pipe, and a dropping funnel, and the temperature was raised to 75°C while introducing nitrogen gas. Condensate, 2.2 parts by weight of ATBS-Na, 6.0 parts by weight of SR-10, 29.3 parts by weight of MMA, 32.5 parts by weight of BA, and 2,2-azobis(2,4- A mixed solution of 1.4 parts by weight of dimethylvaleronitrile) was added dropwise from the dropping funnel at a constant rate over 3 hours. Next, a mixed solution of 0.14 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) and 4 parts by weight of 2-propanol was added dropwise at a uniform rate over 1 hour. Thereafter, the mixture was continuously stirred at 75° C. for 2 hours, and then degassed using a rotary evaporator until the nonvolatile components became 90% or more. Subsequently, it was diluted with water so that the nonvolatile components were 50%. It was cooled to room temperature to obtain a graft cocondensate (P-1).

Synthesis Example 2
(Preparation of co-condensation product (main chain))
A reactor equipped with a stirrer, a thermometer, and a reflux condenser was charged with 2.4 parts by weight of TSMA, 25.7 parts by weight of M-TMS, 21.8 parts by weight of Ph-TMS, 14.6 parts by weight of pure water, and 0.015 parts by weight of DBP, and the mixture was reacted at a reaction temperature of 105° C. for 3 hours with stirring to obtain a co-condensation product.

(Preparation of graft cocondensate (side chain polymerization))
10.8 parts by weight of 2-propanol was charged into a reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction pipe, and a dropping funnel, and the temperature was raised to 75°C while introducing nitrogen gas. Condensate, 2.5 parts by weight of ATBS-Na, 6.0 parts by weight of SR-10, 29.3 parts by weight of MMA, 32.5 parts by weight of BA, and 2,2-azobis(2,4- A mixed solution of 1.4 parts by weight of dimethylvaleronitrile) was added dropwise from the dropping funnel at a constant rate over 3 hours. Next, a mixed solution of 0.14 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) and 4 parts by weight of 2-propanol was added dropwise at a uniform rate over 1 hour. Thereafter, the mixture was continuously stirred at 75° C. for 2 hours, and then degassed using a rotary evaporator until the nonvolatile components became 90% or more. Subsequently, it was diluted with water so that the nonvolatile components were 50%. It was cooled to room temperature to obtain a graft cocondensate (P-2).

[Examples 1 and 2 and Comparative Example 1]
(Creation of coating layer)
The graft co-condensation product obtained in the above examples or Aquaseal 50E (manufactured by Daido Paint Co., Ltd.), which is a silicone-based penetrating water absorption inhibitor (water-based type), was evenly painted with a brush onto one surface of the mortar test specimen, which was the substrate, at 0.2 kg/ ^m2 . Thereafter, the specimen was cured for one week at a temperature of 23°C and a humidity of 50%, to prepare a coating layer (cured product).

[Measurement and evaluation methods]
Measurements and evaluations in the examples and comparative examples were carried out by the following methods.

(Water permeability test)
In accordance with JIS A 6909 (Water permeability test method B), a Cemedine POS seal was attached to the Osmo on-site water permeability tester (for horizontal sections) manufactured by Linac Yachiyo Co., Ltd. on the test surface of the prepared coating layer (cured product) and the original specimen. It was fixed with (modified silicone sealant). After the sealant had sufficiently hardened, water was added from the top of the test device to fill it, paraffin was added to prevent the test water from evaporating, the lid was closed, and the test was started. The height of the water head was read 7 days after the start of the test, and the water permeability was calculated from the difference from the height at the start of the test. Further, the water permeability ratio in the test using the original test specimen was set as 100, and the water permeability ratio was calculated from the water permeation amount of the test specimen.

Examples 1 and 2 have lower water permeability and water permeability ratio than the comparative example, and have a high effect of suppressing efflorescence. Therefore, it was shown that by forming the coating layer with a composition containing water and a polysiloxane resin composed of the specific components of the present invention, the water permeability to the substrate is reduced.

The present invention is suitably used as a laminate having a base material layer containing a base material for civil engineering and construction materials.

Claims (8)

A laminate having a base layer including a civil engineering and building material base material and a coating layer,
The coating layer is
A layer formed from a composition (I) containing a polysiloxane-based resin and water,
The polysiloxane resin is
The polymer has, as a structural unit, a structural unit derived from a monomer having a radical polymerizable group,
The monomer is
A laminate comprising: (i) a monomer having a salt structure consisting of an acid and a base, which is soluble in water and does not form micelles in water; and (ii) a monomer capable of forming micelles in water. The laminate according to claim 1, wherein the civil engineering and building material substrate is a porous organic and/or inorganic substrate. The laminate according to claim 1, wherein the monomer (ii) capable of forming micelles in water is a monomer having a polyoxyalkylene structure. The polysiloxane resin includes a structural unit (a) derived from a silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group;
Derived from a monomer (B) that has a salt structure consisting of an acid and a base and a radically polymerizable group, does not have a hydrolyzable silyl group, is soluble in water, and does not form micelles in water. a structural unit (b) that
A structural unit (c) derived from a monomer (C) that has a polyoxyalkylene structure and a radically polymerizable group, does not have a hydrolyzable silyl group, and is capable of forming micelles in water. ,
Optionally, the following general formula (III) other than the above (A), (B) and (C):
R ⁴ _n -Si-(OR ⁵ ) _4-n ...(III)
(In the formula, R ⁴ is each independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and when there is a plurality of R ⁴ s, they may be the same or different, R ⁵ is each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 0 to 3.)
A structural unit (d) derived from the silane compound (D) represented by
The laminate according to any one of claims 1 to 3, comprising: The laminate according to claim 4, further comprising a structural unit (e) derived from a monomer (E) having a radical polymerizable group other than the (A), (B), and (C). 5. The composition according to claim 4, wherein the structural unit (b) is contained in an amount of 1 to 20% by weight and the structural unit (c) is contained in an amount of 1 to 10% by weight based on the total amount of the polysiloxane resin (100% by weight). laminate. The laminate according to claim 4, which contains the structural units (a) and (d) in a total amount of 10% by weight or more based on 100% by weight of the total amount of the polysiloxane resin. A method for producing a laminate comprising a base material layer containing a base material for civil engineering and construction materials, and a coating layer, the method comprising:
a step of applying composition (I) on the base layer to form the coating layer,
The composition (I) is
A composition containing a polysiloxane resin and water,
The polysiloxane resin has a polymer containing a structural unit derived from a monomer having a radically polymerizable group as a structural unit,
The monomer is
(i) A monomer that has a salt structure consisting of an acid and a base, is soluble in water, and does not form micelles in water, and (ii) A monomer that can form micelles in water. A method for manufacturing a laminate, including: