Laminate and method for manufacturing the same

Abstract

To provide a laminate that ensures superior bonding between adjacent layers.SOLUTION: A laminate includes a substrate, a primer layer, and a sealing layer in the stated order, where the primer layer is a layer composed of a composition (I) including a polysiloxane resin and water, where the polysiloxane resin includes a constitutional unit derived from a specific monomer with a radical-polymerizable group, and where the sealing layer is a layer composed of a composition (II) including a specific resin (Y).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a laminate and a method for producing the same.

Background Art

[0002] Conventionally, a sealing material has been used between members or joints of structures such as buildings, civil engineering works, and vehicles for the purpose of improving waterproofing and sealing properties. A technique of performing a primer treatment on the surface of a base material is known for the purpose of improving the adhesiveness between the base material constituting the structure and the sealing material (for example, Patent Document 1).

[0003] Here, since the primer composition used when forming the primer layer on the surface of the base material generally contains an organic solvent, there have been problems such as the generation of odors during construction. Therefore, from the viewpoint of environmental compatibility, a primer composition (aqueous primer composition) using water as a medium that can be stably dispersed or dissolved (aqueous) in an aqueous medium has been demanded.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, there has been room for improvement in terms of the adhesiveness of the primer layer containing the aqueous primer composition to the base material and the sealing material. <X

[0006] Therefore, an object of the present invention is to provide a laminate including a base material, an aqueous primer layer , and a sealing layer, and having excellent adhesiveness between adjacent layers.

Means for Solving the Problems

[0007] As a result of diligent research to solve the aforementioned problems, the inventors have discovered for the first time that, in a laminate comprising a substrate, a primer layer, and a sealing layer in that order, a laminate with excellent adhesion between adjacent layers can be obtained by composing the primer layer and the sealing layer with specific components, thereby completing the present invention.

[0008] Accordingly, one aspect of the present invention is a laminate comprising a substrate, a primer layer, and a sealing layer in this order, wherein the primer layer is a layer formed from composition (I) containing a polysiloxane resin and water, the polysiloxane resin has a polymer as a constituent unit which includes constituent units derived from monomers having radical polymerizable groups, the monomers include (i) monomers having a salt structure consisting of an acid and a base, being soluble in water and not forming micelles in water, and (ii) monomers capable of forming micelles in water, the sealing layer is a layer formed from composition (II) containing resin (Y), the resin (Y) has silicon groups having hydroxyl groups or hydrolyzable groups which can be crosslinked by siloxane bonds, and the main chain skeleton of resin (Y) is one or more resins selected from the group consisting of polyethers, polyacrylates, and polyisobutylene, wherein the laminate (hereinafter referred to as "this laminate") is a laminate.

[0009] Furthermore, one aspect of the present invention is a method for producing a laminate comprising a substrate, a primer layer, and a sealing layer in that order, comprising the steps of: applying composition (I) onto the substrate to form the primer layer; and applying composition (II) on the primer layer to form the sealing layer, wherein composition (I) is a composition containing a polysiloxane resin and water, the polysiloxane resin has a polymer containing constituent units derived from monomers having radical polymerizable groups, and the monomers are (i) from acids and bases A method for producing a laminate (hereinafter referred to as "this production method") comprises (ii) a monomer having a salt structure, being soluble in water and not forming micelles in water, and (ii) a monomer capable of forming micelles in water, wherein composition (II) is a curable composition containing resin (Y), and resin (Y) has silicon groups having hydroxyl groups or hydrolyzable groups that can be crosslinked by siloxane bonds, and the main chain skeleton of resin (Y) is one or more resins selected from the group consisting of polyether, polyacrylate and polyisobutylene. [Effects of the Invention]

[0010] According to one aspect of the present invention, a laminate comprising a substrate, a water-based primer layer, and a sealing layer can be provided, wherein adjacent layers exhibit excellent adhesion to each other. [Modes for carrying out the invention]

[0011] One embodiment of the present invention will be described in detail below. Unless otherwise specified in this specification, "A to B" representing a numerical range means "greater than or equal to A and less than or equal to B". Furthermore, all references cited in this specification are incorporated herein by reference.

[0012] [1. Outline of the present invention] As mentioned above, conventional sealing materials generally contain organic solvents, which has led to problems such as odor generation during application. For example, in the invention described in Patent Document 1, the primer layer is formed from a composition containing (A) a crosslinkable silicon group-containing acrylic polymer, (B) a silane compound having an amino group and / or its reaction product, and (C) an organotin curing catalyst that does not contain sulfur. In other words, the composition forming the primer layer in Patent Document 1 contains an organic solvent and a curing catalyst.

[0013] In contrast, water-based primer compositions that do not use organic solvents, etc., have low odor generation and excellent environmental compatibility, and are therefore in high demand in the market. The inventors of this invention investigated the formation of a primer layer using a water-based primer composition and found that when using a water-based primer composition, the adhesion to the substrate and sealant is insufficient, indicating room for improvement.

[0014] Therefore, the inventors conducted diligent research to solve the above problems and, as a result, discovered for the first time that in a laminate containing a substrate, a primer layer, and a sealing layer in that order, a laminate with excellent adhesion between adjacent layers can be obtained by composing the primer layer and the sealing layer with specific components. Specifically, the inventors succeeded in obtaining the following findings: In a laminate comprising a substrate, a primer layer, and a sealing layer in this order, the primer layer is formed from a composition (I) containing a polysiloxane resin and water that satisfies the following (a): (a) A polymer comprising a constituent unit derived from a monomer having a radical polymerizable group, wherein the monomer includes (i) a monomer having a salt structure consisting of an acid and a base, being soluble in water and not forming micelles in water, and (ii) a monomer capable of forming micelles in water. The sealing layer is formed from a composition (II) containing a resin (Y) that satisfies the following (b) to (c): (b) Having a silicon group having a hydroxyl group or a hydrolyzable group that can be crosslinked by a siloxane bond. (c) The main chain skeleton is one or more resins selected from the group consisting of polyethers, polyacrylates, and polyisobutylenes. This results in a laminate with excellent adhesion between adjacent layers.

[0015] Thus, by using a primer layer and a sealing layer (especially the primer layer) with a specific configuration, the adhesion between adjacent layers of the laminate can be improved, which is something that could not have been conceived from conventional knowledge, and therefore the present invention is extremely superior.

[0016] Furthermore, the above configuration reduces water and soil pollution compared to conventional technologies by having a low or no organic solvent content. Therefore, it can contribute to achieving goals such as Goal 15 of the United Nations' Sustainable Development Goals (SDGs), "Protect and restore life on land."

[0017] [2. Laminate] The laminate comprises a substrate, a primer layer, and a sealing layer in that order, wherein the primer layer is formed from a composition (I) containing a polysiloxane resin and water, the polysiloxane resin has a polymer containing constituent units derived from monomers having radical polymerizable groups, the monomers include (i) monomers having a salt structure consisting of an acid and a base, being soluble in water and not forming micelles in water, and (ii) monomers capable of forming micelles in water, the sealing layer is formed from a composition (II) containing a resin (Y), the resin (Y) having silicon groups having hydroxyl groups or hydrolyzable groups that can be crosslinked by siloxane bonds, and the main chain skeleton of the resin (Y) is one or more resins selected from the group consisting of polyethers, polyacrylates, and polyisobutylene. The laminate has the advantage that, having the above configuration, adjacent layers among the layers constituting the laminate have excellent adhesion to each other. Furthermore, since the primer layer contained in this laminate contains water-soluble components, this laminate also has the advantage of having high film-forming and impregnation properties.

[0018] In one embodiment of the present invention, it is preferable that the primer layer and the sealing layer are directly bonded together. This configuration has the advantage that the adhesion between adjacent layers among the layers constituting the laminate is improved.

[0019] (2-1. Primer layer) In one embodiment of the present invention, the primer layer is a layer formed from composition (I) containing a polysiloxane resin and water. In this specification, the "primer layer according to one embodiment of the present invention" may be referred to as the "primer layer."

[0020] (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 "this composition (I)".

[0021] <Polysiloxane-based resin> In one embodiment of the present invention, the polysiloxane resin has a polymer as a constituent unit that includes a constituent unit derived from a monomer having a radical polymerizable group, wherein the monomer includes (i) a monomer having a salt structure consisting of an acid and a base, being soluble in water and not forming micelles in water, and (ii) a monomer capable of forming micelles in water. In this specification, "the polysiloxane resin according to one embodiment of the present invention" may be referred to as "this polysiloxane resin".

[0022] This polysiloxane-based resin, having the above-described structure, can be stably dispersed or dissolved (water-based) in an aqueous medium, and provides a polysiloxane-based resin that has an appropriate viscosity when water-based.

[0023] As used herein, the "polysiloxane resin" means a resin containing a polysiloxane structure as a main component. The polysiloxane resin is not particularly limited as long as it satisfies the above definition. For example, resins having a polysiloxane structure as a main component obtained by dehydration condensation of a single compound represented by the following general formula (IV) or co-condensation of a plurality of compounds represented by the following general formula (IV) can be mentioned: R 5 , 4 , 5 , 4 , , , , 4 , 4-n ,

[0024] , n , , 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, an alkenyl group, or an aryl group having a polymerizable unsaturated group and optionally having other substituents, R 2 are each independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, R 3 are each 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 addition, in one embodiment of the present invention, the polysiloxane resin can be a resin having a polysiloxane structure as a main component obtained by co-condensing a single compound represented by the above general formula (IV), or a plurality of compounds, with a single compound represented by the following general formula (III), or a plurality of compounds: R 4 n -Si-(OR 5 ) 4-n ···(III) (In the formula, R 4 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 they may be the same or different, R 5 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.).

[0024] In this specification, the polysiloxane structure, which is the main component of a polysiloxane resin, that is, the structural unit formed by condensing monomers having hydrolyzable silyl groups, may be referred to as the "main chain," and the structural unit consisting of monomers having radically polymerizable groups that are bonded to the main chain by radical polymerization may be referred to as the "side chain."

[0025] The side chains of this polysiloxane resin consist of a polymer containing constituent units derived from monomers having radical polymerizable groups. The monomers constituting the side chains of this polysiloxane resin are not particularly limited as long as they include (i) monomers having a salt structure consisting of an acid and a base, being soluble in water and not forming micelles in water, and (ii) monomers capable of forming micelles in water. The side chains of this polysiloxane resin may consist only of the monomers described in (i) and (ii), or may contain other monomers. In the monomers constituting the side chains of one embodiment of the present invention, monomers other than those described in (i) and (ii) are preferably monomers that do not have hydrolyzable silyl groups, and optionally may include monomers that have hydrolyzable silyl groups. Therefore, the polysiloxane resin can also be expressed as a preferred example as follows: a polysiloxane resin having a side chain made of a polymer containing a constituent unit derived from a monomer having a radical polymerizable group, wherein the constituent units of the side chain include a constituent unit (b) derived from a monomer (B) that (does not have a polyoxyalkylene structure) has a salt structure consisting of an acid and a base and a radical polymerizable group, and does not have a hydrolyzable silyl group, is soluble in water, and does not form micelles in water, and a constituent unit (c) derived from a monomer (C) that (has a polyoxyalkylene structure) has a structure that can form micelles in water and a radical polymerizable group, and does not have a hydrolyzable silyl group.

[0026] In one embodiment of the present invention, the polysiloxane resin preferably comprises: 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, but lacking 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, lacking a hydrolyzable silyl group, and capable of forming micelles in water. In one embodiment of the present invention, it is preferable that the polysiloxane resin has structural unit (a) forming the main chain and structural units (b) and (c) forming the side chains.

[0027] Furthermore, in one embodiment of the present invention, the polysiloxane resin, in addition to (A) to (C) above, optionally includes the following general formula (III) as a main chain constituent unit: R 4 n -Si-(OR 5 ) 4-n ...(III) (In the formula, R 4 Each of these is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and R 4 If there are multiple, they may be the same or different, R 5 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer from 0 to 3. It is more preferable to further include a constituent unit (d) derived from the silane compound (D) shown in the diagram.

[0028] In the following, "constituent unit (a) derived from a silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group" will be simply referred to as "constituent unit (a)," and "constituent unit (b) derived from a monomer (B) having a salt structure consisting of an acid and a base and a radically polymerizable group, but lacking a hydrolyzable silyl group, being soluble in water, and not forming micelles in water" will be simply referred to as "constituent unit (b)," and "polyoxyalkylene structure and radical heavy A constituent unit (c) derived from a monomer (C) having a polymeric group and lacking a hydrolyzable silyl group, and capable of forming micelles in water, is simply referred to as "constituent unit (c)," a constituent unit (d) derived from a silane compound (D) represented by general formula (III) is simply referred to as "constituent unit (d)," and a constituent unit (e) derived from a monomer (E) having a radical polymerizable group other than (A), (B), and (C) is simply referred to as "constituent unit (e)." Furthermore, in the following, "silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group" will be simply referred to as "silane compound (A)" or "monomer (A)", "monomer (B) having a salt structure consisting of an acid and a base and a radically polymerizable group, but lacking a hydrolyzable silyl group, being soluble in water, and not forming micelles in water" will be simply referred to as "monomer (B)", "monomer (C) having a polyoxyalkylene structure and a radically polymerizable group, but lacking a hydrolyzable silyl group, and capable of forming micelles in water" will be simply referred to as "monomer (C)", "silane compound (D) represented by general formula (III)" will be simply referred to as "silane compound (D)" or "monomer (D)", and "monomer (E) having a radically polymerizable group other than (A), (B), and (C)" will be simply referred to as "monomer (E)".

[0029] (Constituent unit (a)) The constituent unit (a) is derived from a silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group.

[0030] Silane compound (A) having a radically polymerizable unsaturated group and a hydrolyzable silyl group is given by the following general formula (IV): R 1 a R2 b -Si-(OR 3 ) 4-a-b ...(IV) (In the formula, R 1 R is a substituted alkyl group having 1 to 10 carbon atoms having a polymerizable unsaturated group, an alkenyl group, or an aryl group having a polymerizable unsaturated group and optionally having other substituents. 2 Each of these is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and R 3 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, where a is an integer from 1 to 3, b is an integer from 0 to 2, and a+b is an integer from 1 to 3. It is a silane compound having a hydrolyzable silyl group, represented by [formula].

[0031] R in general formula (IV) 1 These are substituted alkyl groups, alkenyl groups, or unsubstituted or substituted aryl groups having radically polymerizable unsaturated groups, all having 1 to 10 carbon atoms. Examples of radically polymerizable unsaturated groups include (meth)acryloyl groups.

[0032] R 1Examples of silane compounds (A) in which is an alkyl group having a radically polymerizable unsaturated group include (meth)acryloxymethyltrimethoxysilane, (meth)acryloxymethylmethyldimethoxysilane, (meth)acryloxymethyldimethylmethoxysilane, (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)acryloxybutylmethyldimethoxysilane, 4-(meth)acryloxybutyldimethylmethoxysilane, 4-(meth)acryloxybutyltriethoxysilane, 4-(meth)acryloxybutylmethyldiethoxysilane, 4-(meth)acryloxybutyldimethylethoxysilane, 5-(meth)acryloxypentyltrimethoxysilane, 5-(meth)acryloxypentylmethyldimethoxysilane, 5-(meth) (T) Acryloxypentyl dimethyl methoxysilane, 5-(meth)acryloxypentyl triethoxysilane, 5-(meth)acryloxypentyl methyl diethoxysilane, 5-(meth)acryloxypentyl dimethyl ethoxysilane, 6-(meth)acryloxyhexyl trimethoxysilane, 6-(meth)acryloxyhexyl methyl dimethoxysilane, 6-(meth)acryloxyhexyl dimethyl methoxysilane, 6-(meth)acryloxyhexyl triethoxysilane, 6-(meth)acryloxyhexyl methyl diethoxysilane,Examples include 6-(meth)acryloxyhexyldimethylethoxysilane.

[0033] R 1 Examples of silane compounds (A) in which the group is an alkenyl group include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, and vinyldimethylethoxysilane.

[0034] R 1 Examples of silane compounds (A) in which the aryl group has a polymerizable unsaturated group and may optionally have other substituents include p-styryltrimethoxysilane, p-styrylmethyldimethoxysilane, p-styryldimethylmethoxysilane, p-styryltriethoxysilane, p-styrylmethyldiethoxysilane, and p-styryldimethylethoxysilane.

[0035] Among these, R 1 (Meth)acryloyl group-substituted alkyl groups are preferred.

[0036] R in general formula (IV) 2 Each of these is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group.

[0037] R in general formula (IV) 2 Specific examples of alkyl groups in this context include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, heptyl group, isoheptyl group, n-octyl group, isooctyl group, and 2-ethylhexyl group.

[0038] R in general formula (IV) 2 Specific examples of aryl groups in this context include, for example, phenyl, naphthyl, and benzyl groups.

[0039] R in general formula (IV) 2 When a is 1 and b is 1, it is preferable that it is a methyl group.

[0040] R in general formula (IV) 3 The group is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, amyl 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.

[0041] From the viewpoint of easily condensing silane compound (A) with other silane compounds that do not have radical polymerizable unsaturated groups (silane compound (D)), the R in general formula (IV) 2 and R 3 The alkyl group preferably has 1 to 3 carbon atoms, and most preferably 1 carbon atom.

[0042] In one embodiment of the present invention, the content of constituent 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. When the content of constituent unit (a) is within the above range, graft polymerization can be sufficiently performed directly or indirectly with constituent unit (b) and / or constituent unit (c), and as a result, a polysiloxane resin that can be stably dispersed or dissolved (water-based) in an aqueous medium can be obtained. Furthermore, the upper limit of the content of constituent unit (a) is not particularly limited as long as the effects of the present invention are achieved, but for example, it is 10% by weight or less, preferably 8% by weight or less, and more preferably 5% by weight or less.

[0043] (Constituent unit (b)) The constituent unit (b) is derived from monomer (B), which has a salt structure consisting of an acid and a base, a radical polymerizable group, does not have a hydrolyzable silyl group, is soluble in water, and does not form micelles in water.

[0044] In this specification, "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. Similarly, the base used for neutralization may be a strong base or a weak base.

[0045] In one embodiment of the present invention, the salt structure may be, for example, the structure of a neutral salt of a strong acid and a strong base, the structure of a neutral salt of a strong acid and a weak base, the structure of a neutral salt of a weak acid and a strong base, or 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, etc. (structure of a neutral salt of a strong acid and a strong base), ammonium sulfonate, 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, etc. (structure of a neutral salt of a weak acid and a weak base), etc. In one embodiment of the present invention, the salt structure is preferably sodium sulfonate.

[0046] In this specification, "water soluble" means that when an aqueous solution is prepared by adding 1 g of the monomer to 10 g of water at 25°C, stirring it thoroughly, letting it stand for one week under conditions of 25°C, and observing its appearance visually, no precipitate, dispersion, or separation of layers is observed in the aqueous solution, and it is transparent.

[0047] In one embodiment of the present invention, the content of constituent 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 constituent unit (b) is within the above range, it has the effect of being uniformly dispersed or soluble in water. Furthermore, the upper limit of the content of constituent unit (b) is not particularly limited as long as the effects of the present invention are achieved, but for example, it is 20% by weight or less, preferably 15% by weight or less, and more preferably 10% by weight or less.

[0048] In this specification, "stable dispersion or dissolution in an aqueous medium" means that no "precipitate" is formed when a solution containing polysiloxane resin is evaluated by the following method: An aqueous solution of polysiloxane resin prepared by the method described in the examples is left to stand for one week at 25°C, and its appearance is evaluated by visual observation.

[0049] In other words, "stable dispersion or dissolution in an aqueous medium" means that when a solution containing polysiloxane resin is evaluated using the method described above, the solution containing polysiloxane resin is evaluated as uniformly "colorless and transparent," "bluish-white and transparent," or "white dispersion." If "precipitates" are observed, it does not qualify as "stable dispersion or dissolution in an aqueous medium."

[0050] Monomer (B) is a monomer that has a salt structure composed of an acid and a base and radical polymerizable groups, does not have hydrolyzable silyl groups, is soluble in water, and does not form micelles in water. The radical polymerizable groups in monomer (B) undergo radical polymerization with the radical polymerizable groups in monomer (A), forming graft chains derived from monomer (B) on the polysiloxane main chain. Because monomer (B) has a salt structure composed of an acid and a base and is soluble in water, this polysiloxane-based resin can be stably dispersed or dissolved in an aqueous medium.

[0051] The radical polymerizable unsaturated group in monomer (B) is not particularly limited as long as it can contribute to radical polymerization with monomer (A). Examples of radical polymerizable unsaturated groups in monomer (B) include (meth)acryloyl groups, (meth)acrylamide groups, and vinyl groups. From the viewpoint of high reactivity and versatility, (meth)acryloyl groups or (meth)acrylamide groups are preferred.

[0052] The monomer (B) is not particularly limited as long as it has a salt structure consisting of an acid and a base and a radical polymerizable group, but examples include sodium sulfoethyl methacrylate, sodium acrylamide-t butylsulfonate, sodium 2-(methacryloyloxy)ethanesulfonate, sodium acrylamide-t butylsulfonate, potassium 2-(methacryloyloxy)ethanesulfonate, potassium acrylamide-t butylsulfonate, calcium 2-(methacryloyloxy)ethanesulfonate, calcium acrylamide-t butylsulfonate, ammonium sulfoethyl methacrylate, ammonium acrylamide-t butylsulfonate, ammonium 2-(methacryloyloxy)ethanesulfonate, ammonium acrylamide-t butylsulfonate, sodium acrylate, potassium acrylate, calcium acrylate, ammonium acrylate, sodium methacrylate, potassium methacrylate, calcium methacrylate, and ammonium methacrylate.

[0053] Furthermore, monomer (B) can be obtained as a commercial product. Examples of such commercial products include "Antox MS-2N-D" manufactured by Nippon Emulsifier Co., Ltd., "ATBS-Na" manufactured by Toagosei Co., Ltd., and "Sodium Acrylate" and "Potassium Acrylate" manufactured by Asada Chemical Industries, Ltd.

[0054] Furthermore, whether or not a monomer is "capable of forming micelles in water" is measured by the method described in the section on (constituent unit (c)).

[0055] (Constituent unit (c)) The constituent unit (c) is derived from monomer (C), which has radical polymerizable groups but lacks hydrolyzable silyl groups and is capable of forming micelles in water. The radical polymerizable groups in monomer (C) undergo radical polymerization directly or indirectly with the radical polymerizable groups in monomer (A), forming graft chains derived from monomer (C) on the polysiloxane main chain. Because this polysiloxane resin has constituent unit (c), viscosity adjustment is easily made when the polysiloxane resin is converted to a water-based system by forming micelles, making it suitable for use as a water-based paint.

[0056] In this specification, "micelle" refers to an aggregate formed by the association of amphiphilic molecules through hydrophobic interactions. Here, an amphiphilic molecule is defined as a molecule having both a hydrophobic group and a hydrophilic group within it. Therefore, a "structure capable of forming micelles in water" refers to a structure having both a hydrophobic group and a hydrophilic group within it.

[0057] In one embodiment of the present invention, monomer (C) may be an amphiphilic molecule that does not have a hydrolyzable silyl group.

[0058] The determination of whether or not "micelle formation is possible in water" is made by the following method: Add 1 g of the monomer in question to a two-layer solution containing 10 g of water and 2 g of butyl acetate, stir thoroughly, and after standing for 12 hours, if a uniform turbidity is observed, the monomer in question is judged to be capable of forming micelles in water. If, after standing for 12 hours, a clear layer of water and butyl acetate separates, the monomer in question is judged not to form micelles in water (micelle formation is impossible).

[0059] The monomer (C) is not particularly limited as long as it has radical polymerizable groups, a structure that forms micelles in water (i.e., a structure having both hydrophobic and hydrophilic groups within the molecule), and does not have hydrolyzable silyl groups.

[0060] The hydrophobic group within the monomer (C) is not particularly limited, but examples include alkyl groups having 3 or more carbon atoms and having radical polymerizable groups, aryl groups, etc.

[0061] The hydrophilic groups within the monomer (C) are not particularly limited, but examples include anionic hydrophilic groups such as sulfonates, carboxylates, and sulfate esters; cationic hydrophilic groups such as amine salts and quaternary ammonium salts; amphoteric hydrophilic groups such as betaine; and nonionic hydrophilic groups such as polyoxyalkylenes.

[0062] In one embodiment of the present invention, monomer (C) preferably has a polyoxyalkylene structure from the viewpoint of versatility. Examples of such monomers include polyoxyethylene and polyoxypropylene. Monomer (C) preferably has a polyoxyalkylene structure having 1 to 100 repeating oxyalkylene units, more preferably has a polyoxyalkylene structure having 2 to 50 units, and even more preferably has a polyoxyalkylene structure having 5 to 20 units.

[0063] The monomer (C) is not particularly limited as long as it is included in the above definition, but for example, Adekaria Soap 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, ER-40 manufactured by ADEKA Corporation, and Antox-MS-60, RMA-1120, RMA-564, RMA-568, RMA-506, MA-30, 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.), Eleminor JS-2, JS-20, RS-30 (manufactured by Sanyo Chemical Industries, Ltd.), Latemul (manufactured by Kao Corporation) S-180, S-180A, PD-104, PD-420, PD-430, Blenmar PE-90, PE-200, PE-350, AE-90, AE-200, AE-350, PP-500, PP-800, PP-1000, AP-40 manufactured by NOF Corporation 0, AP-550, AP-800, 700PEP-350B, 10PEP-550B, 55PET-400, 30PET-800, 55PET-800, 30PPT-800, 50PPT-800, 70PPT-800, PME-100, PME-200, Examples include 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 from Kyoeisha Chemical Co., Ltd., and NK-ESTER M-20G, M-40G, M-90G, M-230G, AMP-10G, AMP-20G, AMP-60G, AM-90G, and LA from Shin Nakamura Chemical Industry Co., Ltd.From the viewpoint of versatility and micelle stability, Adekarya Soap SR-10 is preferred.

[0064] In one embodiment of the present invention, 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.

[0065] In one embodiment of the present invention, the content of constituent unit (c) is, for example, 0.5% by weight or more, preferably 1% by weight or more, and more preferably 2% by weight or more, based on 100% by weight of the total amount of the polysiloxane resin. When the content of constituent unit (c) is within the above range, viscosity adjustment becomes easier when the polysiloxane resin is dissolved in an aqueous medium, and it can be suitably used as an aqueous paint. Furthermore, the upper limit of the content of constituent 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 constituent unit (c) is within the above range, the water resistance of the resulting primer layer is good.

[0066] (Constituent unit (d)) The constituent unit (d) is given by the following general formula (III): R 4 n -Si-(OR 5 ) 4-n ...(III) It is a constituent unit derived from the silane compound (D) shown below. The silane compound (D) is represented by the following general formula (III): R 4 n -Si-(OR 5 ) 4-n ...(III) (In the formula, R 4 Each of these is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and R 4 If there are multiple, they may be the same or different, R 5 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer from 0 to 3. This is a silane compound having a hydrolyzable silyl group represented by . Silane compound (D) undergoes dehydration condensation with silane compound (A) and / or (D) to form a polysiloxane. Silane compound (D) can also be described as a silane compound that does not have a radically polymerizable unsaturated group and has a hydrolyzable silyl group. In this specification, silane compound (D) may be referred to as monomer (D). The constituent unit (d) may consist of only one type of silane compound (D) represented by general formula (III), or it may consist of a combination of two or more types of silane compounds (D).

[0067] R in general formula (III) 4 Specific examples of alkyl groups in this context include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, heptyl group, isoheptyl group, n-octyl group, isooctyl group, and 2-ethylhexyl group.

[0068] R in general formula (III) 4 Specific examples of aryl groups in this context include, for example, phenyl, naphthyl, and benzyl groups.

[0069] R in general formula (III) 5The group is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, etc.

[0070] Specific compounds represented by general formula (III) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltriisopropoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltriisopropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltriisopropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, trimethylmonomethoxysilane, triphenylmonomethoxysilane, and the like.

[0071] (Constituent unit (e)) The constituent unit (e) is derived from monomer (E) having a radically polymerizable unsaturated group, other than (A), (B), and (C) above. Monomer (E) from which constituent unit (e) is derived is directly or indirectly bonded to monomer (A) and / or (B) and / or (C) by radical polymerization, and is bonded to constituent units (a) and / or (b) and / or (c).

[0072] The monomer (E) from which the constituent unit (e) is derived is not particularly limited as long as it is a monomer having a radically polymerizable unsaturated group other than (A), (B), and (C) above, but examples include alkyl (meth)acrylates and monomers other than alkyl (meth)acrylates as shown below.

[0073] ≪(meth)acrylate alkyl ester≫ In one embodiment of the present invention, the alkyl (meth)acrylate is a (meth)acrylate ester having an alkyl group having 1 to 18 carbon atoms, and may be a (meth)alkyl monomer that does not contain functional groups such as hydroxyl groups or epoxy groups. In one embodiment of the present invention, the alkyl group in the alkyl (meth)acrylate may be linear or branched, or it may be a cyclic cycloalkyl group. Specific examples 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, isobonyl (meth)acrylate, and the like.

[0074] <<Monomers other than alkyl methacrylates>> Examples of monomers other than alkyl (meth)acrylates include nitrile group-containing radical polymerizable monomers such as (meth)acrylonitrile; hydroxyl group-containing radical polymerizable monomers such as glycidyl (meth)acrylate; 2-hydroxypropyl (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 radical 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.

[0075] 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 instrument HLC-8320GPC manufactured by Tosoh Corporation.

[0076] <Water> Composition (I) contains water. The water content in Composition (I) is not particularly limited, but may be, for example, 30% to 90% by weight, preferably 35% to 80% by weight, and more preferably 40% to 70% by weight, relative to the polysiloxane resin. This configuration has the advantage that the resulting composition is easily usable as an aqueous paint.

[0077] <Other ingredients> Composition (I) may contain a non-aqueous solvent, to the extent that it provides the effects of the present invention. In this specification, "non-aqueous solvent" means all solvents other than water. In this specification, "non-aqueous solvent" may be a mixed solvent containing water, and includes solvents containing water in an amount of less than 50% by weight. Non-aqueous solvents are not particularly limited as long as they satisfy the above definition, but examples include hydrocarbons such as toluene, xylene, n-hexane, and cyclohexane; acetic acid esters such as ethyl acetate and butyl acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; ether esters such as cellosolve acetate; ketones such as methyl ethyl ketone, acetate acetate, acetylacetone, methyl isobutyl ketone, and acetone; alcohols such as methanol, 2-propanol, n-butanol, isobutanol, hexanol, and octanol; and film-forming aids for aqueous coatings such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, dipropylene glycol-n-butyl ether, and dipropylene glycol dimethyl ether.

[0078] Composition (I) may contain additives commonly used in the art (particularly in the field of coatings) to the extent that it achieves the effects of the present invention. Examples of such additives include pigments, fillers, plasticizers, film-forming aids, wetting agents, dispersants, thickeners, defoamers, preservatives, antioxidants, anti-settling agents, leveling agents, UV absorbers, antistatic agents, antifreeze agents, antibacterial agents, antifungal and anti-algal agents, tackifiers, rust inhibitors, hydrophilic agents, and the like. The composition may contain only one type of additive, or two or more types. The amounts of these additives can be appropriately determined by those skilled in the art depending on their intended use.

[0079] In one embodiment of the present invention, the method for producing the polysiloxane resin may be the method described in the examples.

[0080] (2-2. Sealing layer) A sealing layer according to one embodiment of the present invention (hereinafter referred to as "the sealing layer") is a layer formed from a composition (II) containing a resin (Y). The resin (Y) has silicon groups having hydroxyl groups or hydrolyzable groups that can be crosslinked by siloxane bonds, and the main chain skeleton of the resin (Y) is one or more resins selected from the group consisting of polyethers, polyacrylates, and polyisobutylenes.

[0081] Having the above-described structure, this sealing layer can be used as an elastic waterproof layer.

[0082] (Resin (Y)) In one embodiment of the present invention, the resin (Y) has silicon groups having hydroxyl groups or hydrolyzable groups that can be crosslinked by siloxane bonds (hereinafter sometimes referred to as "crosslinkable silicon groups"), and the main chain skeleton of the resin (Y) is one or more resins selected from the group consisting of polyethers, polyacrylates, and polyisobutylenes.

[0083] The main chain skeleton of resin (Y) is one or more selected from the group consisting of polyether, polyacrylate, and polyisobutylene.

[0084] Resin (Y) may be used alone or in combination of two or more types.

[0085] Typical examples of silicon groups having hydroxyl groups or hydrolyzable groups that can be crosslinked by siloxane bonds in resin (Y) include:

[0086] [ka]

[0087] (In the formula, R 6 and R 7 Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an α-haloalkyl group having 1 to 10 carbon atoms, or a triorganosiloxy group represented by R'3SiO- (where R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's may be the same or different), and R 6 or R 7 When there are two or more of these, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when there are two or more X's, they may be the same or different. b represents 0, 1, or 2. c represents 0, 1, 2, or 3. Also, m of

[0088] [ka]

[0089] The values ​​of b in the base represented by do not need to be the same. m represents an integer from 0 to 19, where (sum of b) + c ≥ 1. A base represented by ) is also an example.

[0090] The hydrolyzable group represented by X above is not particularly limited and may be any conventionally known hydrolyzable group. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, acyloxy groups, amino groups, amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. Among these, alkoxy groups, acyloxy groups, amino groups, amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups are preferred, with alkoxy groups being particularly preferred from the viewpoint of mild hydrolysis and ease of handling.

[0091] The hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in a range of 1 to 3, and (sum of b) + c is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to a silicon atom, they may be the same or different.

[0092] The silicon atoms forming the aforementioned crosslinkable silicon group may be one or two or more, but in the case of silicon atoms linked by siloxane bonds, etc., there may be about 20 of them.

[0093] [ka]

[0094] (In the formula, R 1 This represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an α-haloalkyl group having 1 to 10 carbon atoms, or a triorganosiloxy group represented by R'3SiO- (where R' is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R's may be the same or different), and R 1 When there are two or more of these, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when there are two or more of X, they may be the same or different. a represents 1, 2, or 3. A crosslinkable silicon group represented by ) is preferred because it is readily available.

[0095] R in the above chemical formula1 Examples of such groups include alkyl groups such as methyl and ethyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, α-chloroalkyl groups such as α-chloromethyl groups, and triorganosiloxy groups represented by R'3SiO- where R' is a methyl or phenyl group. Among these, methyl groups are preferred due to a good balance between the curability and stability of the polymer, and α-chloromethyl groups are preferred because of their particularly fast curing rate for the sealing layer. Of these, methyl groups are particularly preferred due to their availability.

[0096] For information regarding the types and average number of crosslinkable silicon groups, as well as the method for introducing crosslinkable silicon groups, refer to the International Publication No. 2016 / 024584.

[0097] The main chain skeleton of a polyether may consist of only one type of repeating unit, or it may contain other repeating units. Examples of repeating units include those resulting from ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, etc. Polymers mainly composed of polypropylene oxide containing 80% or more, preferably 90% or more, of propylene oxide units are preferred due to their amorphous nature and relatively low viscosity.

[0098] The main chain skeleton of a polyacrylate may consist of only one type of repeating unit, or it may contain other types of repeating units. The repeating units include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, isopropoxyethyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,22-Trifluoroethyl, Glycidyl (meth)acrylate, 1-Ethylcyclopentyl ether (meth)acrylate, Dimethylaminoethyl (meth)acrylate, Nonyl (meth)acrylate, Decyl (meth)acrylate, Undecyl (meth)acrylate, Dodecyl (meth)acrylate, Tridecyl (meth)acrylate, Tetradecyl (meth)acrylate, Pentadecyl (meth)acrylate, Hexadecyl (meth)acrylate, Heptadecyl (meth)acrylate, Octadecyl (meth)acrylate, Eicosyl (meth)acrylate, Docosyl (meth)acrylate, Oleyl (meth)acrylate, Linoleyl (meth)acrylate, Isobornyl (meth)acrylate, 2-Aminoethyl (meth)acrylate, γ-(methacryloyloxypropyl) Repeating units derived from trimethoxysilane, ethylene oxide adducts of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, etc. are examples. It is particularly preferable to have one or more repeating units selected from those derived from ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate. The main chain structure composed of these repeating units easily adjusts the glass transition temperature to 0°C or below.

[0099] The number-average molecular weight and molecular weight distribution (Mw / Mn) of resin (Y) are as described in International Publication No. 2016 / 024584.

[0100] The amount of resin (Y) used is preferably 10 to 90% by weight, more preferably 20 to 50% by weight, of the solid content of composition (II).

[0101] Furthermore, the glass transition temperature (Tg) of the resin forming the main chain skeleton of resin (Y) is preferably 0°C or lower, and more preferably -10°C or lower. With this configuration, the resulting laminate can be suitably used as an elastic waterproof coating film.

[0102] Furthermore, as the composition (II) containing resin (Y), Sunrise MSI's "SR Seal S70" or the like can be used.

[0103] (2-3. Base material) This laminate includes a substrate. In one embodiment of the present invention, the substrate is not particularly limited and may be either an organic substrate or an inorganic substrate. Specifically, the substrate can be metal (e.g., aluminum, stainless steel), glass, porcelain, stone, wood, resin molded product, mortar, slate, etc.

[0104] [3. Method for manufacturing laminates] The present manufacturing method is a method for manufacturing a laminate comprising a substrate, a primer layer and a sealing layer in that order, comprising the steps of: applying composition (I) onto the substrate to form the primer layer; and applying composition (II) on the primer layer to form the sealing layer, wherein composition (I) is a composition containing a polysiloxane resin and water, the polysiloxane resin has a polymer containing constituent units derived from monomers having radical polymerizable groups, the monomers include (i) monomers having a salt structure consisting of an acid and a base, being soluble in water and not forming micelles in water, and (ii) monomers capable of forming micelles in water, the composition (II) is a curable composition containing resin (Y), the resin (Y) has silicon groups having hydroxyl groups or hydrolyzable groups that can be crosslinked by siloxane bonds, and the main chain skeleton of resin (Y) is one or more resins selected from the group consisting of polyethers, polyacrylates and polyisobutylene, and is a method for manufacturing a laminate.

[0105] This manufacturing method, having the above configuration, results in a laminate in which adjacent layers exhibit excellent adhesion to each other.

[0106] Furthermore, this manufacturing method includes construction methods and sealing methods using this laminate.

[0107] In this manufacturing method, from the viewpoint of versatility, (ii) the monomer capable of forming micelles in water is preferably a monomer having a polyoxyalkylene structure.

[0108] In this manufacturing method, it is preferable that the primer layer and the sealing layer are directly bonded. This configuration has the advantage of providing good adhesion between the primer layer and the sealing layer.

[0109] In this manufacturing method, the polysiloxane resin contained in composition (I) comprises: 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, but lacking a hydrolyzable silyl group, being soluble in water, and not forming micelles in water; a structural unit (c) derived from a monomer (C) having a polyoxyalkylene structure and a radically polymerizable group, lacking a hydrolyzable silyl group, and capable of forming micelles in water; and optionally, a monomer other than (A), (B), and (C) of the following general formula (III): R 4 n -Si-(OR 5 ) 4-n ...(III) (In the formula, R 4 Each of these is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and R 4 If there are multiple, they may be the same or different, R 5 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer from 0 to 3. It is preferable to include a constituent unit (d) derived from a silane compound (D) represented by . This configuration has the advantage of good adhesion between the primer layer and the layer in contact with it.

[0110] Furthermore, in this manufacturing method, it is preferable that the polysiloxane resin contained in composition (I) further contains constituent units (e) derived from monomers (E) having radical polymerizable groups, other than (A), (B), and (C). With this configuration, the polysiloxane resin can be stably dispersed or dissolved in an aqueous medium and can have an appropriate viscosity.

[0111] In this manufacturing method, the polysiloxane resin contained in composition (I) preferably contains 1 to 20% by weight of the constituent unit (b) and 1 to 10% by weight of the constituent unit (c) based on 100% by weight of the total amount of the polysiloxane resin. This configuration has the advantage of easily achieving both the compatibility of the polysiloxane resin with water and the water resistance of the primer layer.

[0112] In this manufacturing method, the polysiloxane resin contained in composition (I) preferably contains at least 10% by weight of the constituent units (a) and (d) in total, based on 100% by weight of the total amount of the polysiloxane resin. This configuration has the advantage of easily achieving both the viscosity of the polysiloxane resin and the water resistance of the primer layer.

[0113] In this manufacturing method, a narrow molecular weight distribution (Mw / Mn) of the resin (Y) contained in composition (II) is preferable from the viewpoint of reducing the viscosity of composition (II). The molecular weight distribution (Mw / Mn) is more preferably 1.6 or less, even more preferably 1.5 or less, and particularly preferably 1.2 or less. This configuration has the advantage of improving physical properties such as elongation when a sealing layer is formed. The molecular weight distribution (Mw / Mn) is measured using GPC (polystyrene equivalent).

[0114] (3-1. Process of forming the primer layer) This manufacturing method includes a step of forming a primer layer by applying the composition (I) described in section (2-1-1. Composition (I)) onto the substrate described in section (2-3. Substrate).

[0115] In one embodiment of the present invention, the method for forming the primer layer is not particularly limited, but examples include applying and curing a water-based solution, dispersion, or aqueous paint containing the composition (I). The method will be described in detail below.

[0116] In this specification, a solution or dispersion containing Composition (I) in a water medium is also referred to as "the solution or dispersion." In this specification, "solution in a water medium" means 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 whose haze value at 1 atmosphere and 25°C is 20.0 or less. In this specification, "dispersion in a water medium" means 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 whose haze value at 1 atmosphere and 25°C is higher than 20.0. The haze value is measured using a COH400 manufactured by Nippon Denshoku Industries Ltd., with pure water as the standard solution.

[0117] Since this solution or dispersion contains the composition (I) described above, it can be stably dispersed or dissolved in a water-based solution, and when used as a water-based paint, it is useful because it yields a paint with appropriate viscosity.

[0118] Furthermore, in this specification, an aqueous coating containing the resin composition, the solution, or the dispersion is also referred to as the "aqueous coating." Because the aqueous coating contains the aqueous solution or dispersion described above, it can be stably dispersed or dissolved in a water-based solution and has a suitable viscosity, making it useful.

[0119] In addition to the aqueous solution or dispersion described above, this water-based paint may also contain additives commonly used in the relevant art (particularly in the field of paints). The additives that this water-based paint may contain should be appropriately referenced from the description in the section on "Other Components" above.

[0120] The method of applying this solution, dispersion, or water-based paint is not particularly limited. For example, it may be applied using brushes, rollers, air sprays, airless sprays, etc., commonly used in general painting. It may also be applied using methods such as reverse coating, gravure coating, bar coating, die coating, spray coating, kiss coating, wire bar coating, or curtain coating.

[0121] As described above, this primer layer can also be described as a primer layer obtained by curing composition (I), or by applying and curing this solution, dispersion, or aqueous paint.

[0122] (3-2. Process of forming the sealing layer) The process for forming the sealing layer is not particularly limited, and for example, the method described in International Publication No. 2016 / 024584 can be cited.

[0123] The present invention is not limited to the embodiments described above, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0124] In other words, one aspect of the present invention includes the following: [1] A laminate comprising a substrate, a primer layer, and a sealing layer in this order, The primer layer is A layer formed from composition (I) containing a polysiloxane resin and water, The aforementioned polysiloxane-based resin is The polymer has constituent units that include constituent units derived from monomers having radical polymerizable groups. The monomer is (i) A monomer having a salt structure consisting of an acid and a base, soluble in water, and not forming micelles in water, (ii) comprising monomers capable of forming micelles in water, The sealing layer is a layer formed from a composition (II) containing resin (Y), The aforementioned resin (Y) is It has a silicon group having a hydroxyl group or a hydrolyzable group that can be crosslinked by a siloxane bond, The laminate is wherein the main chain skeleton of the resin (Y) is one or more resins selected from the group consisting of polyethers, polyacrylates, and polyisobutylenes. [2] The laminate according to [1], wherein the monomer capable of forming micelles in water is a monomer having a polyoxyalkylene structure. [3] The laminate according to [1] or [2], wherein the primer layer and the sealing layer are directly bonded to each other. [4] The polysiloxane resin 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 monomer (B) having a salt structure consisting of an acid and a base and a radical polymerizable group, but lacking a hydrolyzable silyl group, being soluble in water, and not forming micelles in water, A constituent unit (c) derived from a monomer (C) having a polyoxyalkylene structure and radical polymerizable groups, but lacking hydrolyzable silyl groups, and capable of forming micelles in water, Optionally, the following general formula (III), other than (A), (B), and (C): R 4 n -Si-(OR 5 ) 4-n ...(III) (In the formula, R 4 Each of these is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and R 4 If there are multiple, they may be the same or different, R 5 Each of these is independently either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer from 0 to 3. A constituent unit (d) derived from the silane compound (D) shown, A laminate containing any one of [1] to [3]. [5] The laminate according to [4], further comprising a constituent unit (e) derived from a monomer (E) having a radical polymerizable group, other than (A), (B), and (C). [6] The laminate according to [4] or [5], comprising 1 to 20% by weight of the constituent unit (b) and 1 to 10% by weight of the constituent unit (c) based on 100% by weight of the total amount of the polysiloxane resin. [7] A laminate according to any one of [4] to [6], comprising 10% by weight or more of the constituent units (a) and (d) in total, based on 100% by weight of the total amount of the polysiloxane resin. [8] A method for manufacturing a laminate comprising a substrate, a primer layer, and a sealing layer in this order, A step of applying composition (I) onto the substrate to form the primer layer, The process includes the step of applying composition (II) onto the primer layer to form the sealing layer, The aforementioned composition (I) is This composition contains a polysiloxane resin and water. The polysiloxane-based resin has a polymer containing constituent units derived from monomers having radical polymerizable groups, The monomer is (i) A monomer having a salt structure consisting of an acid and a base, soluble in water, and not forming micelles in water, (ii) comprising monomers capable of forming micelles in water, The composition (II) is a curable composition containing resin (Y), The aforementioned resin (Y) is It has a silicon group having a hydroxyl group or a hydrolyzable group that can be crosslinked by a siloxane bond, A method for producing a laminate, wherein the main chain skeleton of the resin (Y) is one or more resins selected from the group consisting of polyethers, polyacrylates, and polyisobutylenes. [Examples]

[0125] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0126] 〔material〕 The following materials were used in the examples and comparative examples.

[0127] <Base material> Mortar manufactured by TP Giken Co., Ltd. (ISO standard) Aluminum (A5052P) manufactured by ETS Corporation <Primer layer> (Monomer (A)) γ-(meth)acryloxypropyltrimethoxysilane (abbreviated as "TSMA"): "A-174" manufactured by Momentive Performance Materials Japan LLC. (Monomer (B)) Acrylamide-t-butylsulfonate sodium (abbreviated as "ATBS-Na"): "ATBS-Na" manufactured by Toagosei Co., Ltd. (Monomer (C)) Ether sulfate type ammonium salt (abbreviated as "SR-10"): "Adekaria Soap SR-10" manufactured by ADEKA Corporation, commercially classified as "reactive anionic emulsifier", a compound represented by the following formula (A):

[0128] [ka]

[0129] (Monomer (D)) Methyltrimethoxysilane (abbreviated as "M-TMS"): "Z-6033" manufactured by Dow Toray Industries, Inc. Phenyltrimethoxysilane (abbreviated as "Ph-TMS"): "Z-6124" manufactured by Dow Toray Industries, Inc. (Monomer (E)) Methyl methacrylate (abbreviated as "MMA"): Manufactured by Mitsubishi Gas Chemical Company, Inc. Butyl acrylate (abbreviated as "BA"): Manufactured by Nippon Shokubai Co., Ltd. (others) pure water Lithium chloride: "LiCl" manufactured by Tokyo Chemical Industry Co., Ltd. 2-Propanol: Manufactured by Nacalai Tesque Co., Ltd. Radical polymerization initiator: 2,2'-Azobis(2,4-dimethylvaleronitrile): Manufactured by Tokyo Chemical Industry Co., Ltd. (Antifoaming agent) Acrylic defoaming agent: "Agitan295" manufactured by MUNZING CHEMIE. (Film-forming aid) 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate: "CS-12" manufactured by JNC Corporation (Thickening agent) Sunopco's "SN Thickener 612NC" <Sealing layer> "SR Seal S70" manufactured by Sunrise MSI (main component is an oligomer with a main chain of polyoxypropylene with a molecular weight of 1000 to 10000 and an alkoxysilyl group at the end, with a glass transition temperature of 0°C or less) [Measurement and evaluation methods] Measurements and evaluations in the examples and comparative examples were performed using the following methods.

[0130] (Adhesion test) Formulas 1-4 were applied twice as primer layers to the substrate, left for 30 minutes to 1 hour, and then SR Seal S70 was filled as a sealing layer into the H-shaped substrate assembled according to the method for preparing tensile adhesion test specimens specified in JIS A 1439. This was cured at 23°C and 50% relative humidity for 3 days, and then at 50°C for 4 days to prepare H-shaped samples. Using these H-shaped samples, tensile tests (tensile speed 50 mm / min) were performed in a constant temperature room at 23°C and 50% relative humidity using a Shimadzu Autograph (AGS-J) according to the tensile adhesion test method of JIS A 1439, and the fracture status of the test specimens was evaluated. The fracture status was defined as follows: cohesive failure of the sealing layer was "CF", interfacial delamination between the sealing layer and the primer layer was "AF", and interfacial delamination between the primer layer and the substrate was "TF", and the percentage of each fracture status at the time of fracture was evaluated.

[0131] In this embodiment, if the result of the adhesion test of the laminate performed by the method described above is CF > AF, it is determined that "adjacent layers of the laminate have excellent adhesion to each other." In this embodiment, it is preferable that the result of the adhesion test of the laminate is CF > AF, and it is more preferable that CF > AF and CF is 90% or more.

[0132] (Weather resistance (gloss retention rate)) Weather resistance was evaluated by referring to International Publication No. 2016 / 052636 and Japanese Patent No. 5555449.

[0133] In short, accelerated weathering tests were conducted on primer layers on test specimens prepared using the method described later, employing a metal halide lamp type testing machine (manufactured by Daipla Wintes Co., Ltd., model KU-R5CI-A). The 60° gloss value of the primer layer was measured around 400 hours into the accelerated weathering test, and the gloss retention rate was calculated. A higher gloss retention rate indicates better weather resistance.

[0134] The test conditions for the accelerated weathering test are as follows: Illuminance: 85mW / cm 2 Irradiation: 63℃ 50% 6 hours Condensation: 30℃ 98% 2 hours Shower: 30 seconds before and after condensation.

[0135] [Synthesis Example 1] (Preparation of the co-condensate (main chain, silane monomer)) In a reactor equipped with a stirrer, thermometer, and reflux condenser, 3.7 parts by weight of TSMA, 58.0 parts by weight of M-TMS, 20.3 parts by weight of Ph-TMS, 20.6 parts by weight of pure water, and 0.023 parts by weight of LiCl were charged and reacted at a reaction temperature of 105°C for 3 hours with stirring to obtain a cocondensate.

[0136] (Preparation of graft cocondensates (polymerization of side chains (graft monomers))) In a reactor equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube, and dropping funnel, 10 parts by weight of pure water and 15 parts by weight of 2-propanol were charged. After raising the temperature to 75°C while introducing nitrogen gas, a mixed solution of the aforementioned cocondensate, 3.0 parts by weight of ATBS-Na, 5 parts by weight of SR-10, 21.00 parts by weight of MMA, 21.00 parts by weight of BA, 1.2 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile), 10 parts by weight of pure water, and 10 parts by weight of 2-propanol was added dropwise from the dropping funnel at a constant rate over 5 hours. Next, a mixed solution of 0.12 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) and 5 parts by weight of 2-propanol was added dropwise at a constant rate over 1 hour. Subsequently, the mixture was stirred at 75°C for 2 hours, and then degassed using a rotary evaporator until the non-volatile components amounted to 90% or more. Next, the mixture was diluted with water until the non-volatile components amounted to 50%. After cooling to room temperature, composition (I) containing polysiloxane resin and water was obtained. Table 1 shows the amount of each monomer used in the obtained composition (I). In Table 1, the unit for each component amount is "parts by weight". Table 2 shows the content of each constituent unit in the polysiloxane resin (the amount used shown in Table 1 minus the weight of the generated volatile components). In Table 2, the unit for each component amount is also "parts by weight".

[0137] [Synthesis Example 2] Composition (I) was obtained by the same method as in Synthesis Example 1, except that the amount of each monomer used was changed to the amount shown in Table 1, and the amount of pure water used in (preparation of co-condensate (main chain, silane monomer)) was 15.6 parts by weight and LiCl was 0.018 parts by weight.

[0138] [Synthesis Example 3] Composition (I) was obtained by the same method as in Synthesis Example 1, except that the amount of each monomer used was changed to the amount shown in Table 1, and the amount of pure water used in (preparation of the co-condensate (main chain, silane monomer)) was changed to 12.5 parts by weight and LiCl to 0.014 parts by weight.

[0139] [Table 1]

[0140] [Table 2]

[0141] [Synthesis Example 4] In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen gas inlet tube, and dropping funnel, 160 parts by weight of deionized water, 1.4 parts by weight of Newcol-707SF (manufactured by Nippon Emulsifier Co., Ltd.), and 1.0 part by weight of 5% sodium bicarbonate aqueous solution were charged, and the mixture was heated to 50°C while introducing nitrogen gas. After heating, 2.0 parts by weight of 7% t-butyl hydroperoxide aqueous solution, 1.1 parts by weight of 20% Bruggolite FF-6 aqueous solution, and 1.4 parts of a mixed aqueous solution of ferrous sulfate heptahydrate (0.10%) / ethylenediaminetetraacetate disodium (0.40%) were added. Next, 200 parts by weight of a monomer mixture containing 54.2 parts by weight of 2-ethylhexyl acrylate, 142.0 parts by weight of isobutyl methacrylate, and 3.8 parts by weight of γ-methacryloxypropyl methyldimethoxysilane were added to 200 parts by weight of Adekarya soap SR-1025 (manufactured by ADEKA Corporation: 25% active ingredient), 1.9 parts by weight of Adekarya soap ER-20 (manufactured by ADEKA Corporation: 75% active ingredient), and 71 parts by weight of deionized water. This monomer emulsion was then added at a constant rate over 200 minutes. During this time, 2.2 parts by weight of a 7% t-butyl hydroperoxide aqueous solution and 1.8 parts by weight of a 2.5% Bruggolite FF- aqueous solution were added in three separate additions. Polymerization was carried out 1 hour after the completion of the addition of the monomer emulsion. Furthermore, 0.6 parts by weight of a 7% t-butyl hydroperoxide aqueous solution, 2.2 parts by weight of a 2.5% Bruggolite FF- aqueous solution, and 1.4 parts of a mixed aqueous solution of ferrous sulfate heptahydrate (0.10%) / ethylenediaminetetraacetate disodium (0.40%) were added. Subsequently, 200 parts by weight of a monomer mixture containing 20.0 parts by weight of methyl methacrylate, 165.0 parts by weight of butyl methacrylate, 2.0 parts by weight of γ-methacryloxypropyltriethoxysilane, 12.0 parts by weight of methacrylate 100 (a hydrophilic vinyl monomer containing a polyoxyethylene chain with 10 repeating units (manufactured by Nippon Emulsifier Co., Ltd.)), and 1.0 part by weight of n-dodecyl mercaptan were added to 200 parts by weight, to which 12 parts by weight of Adekarya soap SR-1025, 1.9 parts by weight of Adekarya soap ER-20, and 71 parts by weight of deionized water were added at a constant rate over 200 minutes. During this time, 2.4 parts by weight of a 7% t-butyl hydroperoxide aqueous solution and 3.4 parts by weight of a 2.5% Bruggolite FF-6 aqueous solution were added in four separate additions.Polymerization was carried out 1.5 hours after the addition of the monomer emulsion was completed. 22 parts of a 5% sodium bicarbonate aqueous solution were added to the resulting synthetic resin emulsion, and then the solid content was adjusted to 50% with deionized water.

[0142] [Formulation examples 1 to 4] (Preparation of water-based paint) Water-based paints were prepared by blending the components of compositions (I) from Synthesis Examples 1-4 according to the formulations shown in Table 3. In Table 3, the unit for the amount of each component is "parts by weight".

[0143] [Table 3]

[0144] [Examples 1-6, Comparative Examples 1-2] (Fabrication of laminates) A laminate was obtained according to the specimen preparation method described in the (Adhesion Test) section above. The results of the adhesion test on the obtained laminate are shown in Table 4.

[0145] [Comparative Examples 3-4] Laminates were obtained using the same method as described in Examples 1-6 and Comparative Examples 1-2 above, except that a primer layer was not applied to the substrate. The results of the adhesion test of the obtained laminates are shown in Table 4.

[0146] [Table 4]

[0147] [Examples 7-9, Comparative Example 5] (Preparation of weather resistance (gloss retention rate) test specimens) Referring to International Publication No. 2016 / 052636, the weather resistance of the water-based paints of formulations 1 to 4 was measured. Briefly, the water-based paints of formulations 1 to 4 were applied to an aluminum plate (50 mm x 150 mm) using an air spray so that the dry film thickness (film thickness of the cured film after drying) was approximately 40 μm, and then dried at 23°C and 50% RH for 4 hours (first application). Furthermore, the water-based paints of formulations 1 to 4 were applied again using an air spray on the dried film obtained from the first application so that the dry film thickness was approximately 40 μm (i.e., a total of approximately 80 μm), and then dried at 23°C and 50% RH for 1 week (second application). The resulting laminate was used as a test specimen to measure the weather resistance of the water-based paints of formulations 1 to 4. The results are shown in Table 5.

[0148] [Table 5] [Industrial applicability]

[0149] This laminate is suitably used, for example, as a laminate for building interiors and exteriors, for automotive applications such as metallic bases or clear coatings on metallic bases, for direct coating of metals such as aluminum, stainless steel, and silver, for direct coating of ceramic materials such as slate, concrete, tiles, mortar, gypsum board, asbestos slate, asbestos board, precast concrete, lightweight aerated concrete, calcium silicate board, tiles, and bricks, for glass, and for stone materials such as natural marble and granite.

Claims

1. A laminate comprising a substrate, a primer layer, and a sealing layer in this order, The primer layer is A layer formed from composition (I) containing a polysiloxane resin and water, The aforementioned polysiloxane-based resin is The following general formula (IV): R 1 a R 2 b -Si-(OR 3 ) 4-ab...(IV) A constituent unit (a) derived from a silane compound (A) having a radical polymerizable unsaturated group and a hydrolyzable silyl group, represented by the formula (wherein R1 is a substituted alkyl group having 1 to 10 carbon atoms having a polymerizable unsaturated group, an alkenyl group, or an aryl group having a polymerizable unsaturated group and optionally having other substituents; R2 is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group; R3 is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a is an integer from 1 to 3; b is an integer from 0 to 2; and a+b is an integer from 1 to 3.) A constituent unit (b) derived from monomer (B) having a salt structure consisting of an acid and a base and a radical polymerizable group, but lacking a hydrolyzable silyl group, being soluble in water, and not forming micelles in water, A constituent unit (c) derived from a monomer (C) having a polyoxyalkylene structure and radical polymerizable groups, but lacking hydrolyzable silyl groups, and capable of forming micelles in water, Other than (A), (B), and (C) above, the following general formula (III): R 4 n -Si- (OR 5 ) 4-n...(III) (In the formula, each R4 is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and if there are multiple R4s, they may be the same or different; each R5 is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and n is an integer from 0 to 3.) A constituent unit (d) derived from the silane compound (D) shown, Includes, In the polysiloxane resin, the silane compound (A) and the silane compound (D) co-condense to form the main chain of constituent units (a) and (d), and the monomers (B) and (C) bond to the main chain by radical polymerization to form the side chains of constituent units (b) and (c). The sealing layer is a layer formed from a composition (II) containing resin (Y), The aforementioned resin (Y) is It has a silicon group having a hydroxyl group or a hydrolyzable group that can be crosslinked by a siloxane bond, A laminate in which the main chain skeleton of the resin (Y) is one or more resins selected from the group consisting of polyethers, polyacrylates, and polyisobutylenes.

2. The laminate according to claim 1, wherein the primer layer and the sealing layer are directly bonded together.

3. The polysiloxane resin further comprises a constituent unit (e) derived from a monomer (E) having a radical polymerizable group, other than (A), (B), and (C), The laminate according to claim 1, wherein the constituent unit (e) is formed by the monomer (E) being bonded to the constituent units (a) and / or (b) and / or (c) by radical polymerization with (A) and / or (B) and / or (C).

4. The laminate according to claim 1, comprising 1 to 20% by weight of the constituent unit (b) and 1 to 10% by weight of the constituent unit (c) based on 100% by weight of the total amount of the polysiloxane resin.

5. The laminate according to claim 1, wherein the constituent units (a) and (d) together amount to 10% by weight or more of the total amount of the polysiloxane resin.

6. A method for manufacturing a laminate comprising a substrate, a primer layer, and a sealing layer in this order, A step of applying composition (I) onto the substrate to form the primer layer, The process includes the step of applying composition (II) onto the primer layer to form the sealing layer, The aforementioned composition (I) is This composition contains a polysiloxane resin and water. The aforementioned polysiloxane-based resin is The following general formula (IV): R 1 a R 2 b -Si-(OR 3 ) 4-ab...(IV) A constituent unit (a) derived from a silane compound (A) having a radical polymerizable unsaturated group and a hydrolyzable silyl group, represented by the formula (wherein R1 is a substituted alkyl group having 1 to 10 carbon atoms having a polymerizable unsaturated group, an alkenyl group, or an aryl group having a polymerizable unsaturated group and optionally having other substituents; R2 is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group; R3 is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a is an integer from 1 to 3; b is an integer from 0 to 2; and a+b is an integer from 1 to 3.) A constituent unit (b) derived from monomer (B) having a salt structure consisting of an acid and a base and a radical polymerizable group, but lacking a hydrolyzable silyl group, being soluble in water, and not forming micelles in water, A constituent unit (c) derived from a monomer (C) having a polyoxyalkylene structure and radical polymerizable groups, but lacking hydrolyzable silyl groups, and capable of forming micelles in water, Other than (A), (B), and (C) above, the following general formula (III): R 4 n -Si- (OR 5 ) 4-n...(III) (In the formula, each R4 is independently an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, or an unsubstituted or substituted aryl group, and if there are multiple R4s, they may be the same or different; each R5 is independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and n is an integer from 0 to 3.) A constituent unit (d) derived from the silane compound (D) shown, Includes, In the polysiloxane resin, the silane compound (A) and the silane compound (D) co-condense to form the main chain of constituent units (a) and (d), and the monomers (B) and (C) bond to the main chain by radical polymerization to form the side chains of constituent units (b) and (c). The composition (II) is a curable composition containing resin (Y), The aforementioned resin (Y) is It has a silicon group having a hydroxyl group or a hydrolyzable group that can be crosslinked by a siloxane bond, A method for producing a laminate, wherein the main chain skeleton of the resin (Y) is one or more resins selected from the group consisting of polyethers, polyacrylates, and polyisobutylenes.

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