JP6970476B1 - Aqueous resin composition, multi-layer film, and method for producing the multi-layer film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous resin composition useful for forming a multi-layer film which is excellent in adhesion between a plurality of coating layers overlapping each other and capable of suppressing swelling between coating layers. SOLUTION: An aqueous resin composition (RY) used for forming a coating layer (Y) overlapping with a coating layer (X) containing a copolymer (PX) is provided. In the above-mentioned copolymer (PX), a carbonyl group-containing polymerizable monomer (AX) and other polymerizable monomers (BX) are simply added to 100 parts by mass of the monomer (BX). The monomer component (MX) contained in a proportion of 0.1 part by mass or more of the weight (AX) is copolymerized. In the above-mentioned aqueous resin composition (RY), a monomer component (MY) containing a carbonyl group-containing polymerizable monomer (AY) and another polymerizable monomer (BY) was copolymerized. It contains a copolymer (PY) and a polyvalent hydrazide compound (Z). The content of the monomer (AY) in the above-mentioned monomer component (MY) is 0.1 part by mass or more with respect to 100 parts by mass of the monomer (BY). The molar ratio of the amount of substance of the polyvalent hydrazide compound (Z) to the amount of substance of the monomer (AY) corresponding to 0.1 part by mass per 100 parts by mass of the monomer (BY) is 1 or more. [Selection diagram] None

Description

The present invention relates to an aqueous resin composition, a multilayer film, and a method for producing a multilayer film.

In recent years, the water-based resin composition has been widely used in film-forming materials such as paints, inks, adhesives, adhesives, and coating agents because of its influence on the global environment and consideration for human health. In the present specification, a layer formed from a resin composition that can be used as the above-mentioned layer-forming material may be referred to as a “coating layer”.

A cross-linking agent may be added to the aqueous resin composition used as the layer forming material in order to enhance the physical properties of the coating layer. Further, for example, in the painting of a building (particularly, the painting of an exterior such as a wall surface of a building), a multi-layer film including a plurality of coating layers is generally provided. In the multi-layer film, for example, an undercoat layer having elasticity that easily adheres to and follows the substrate (base material) is provided, and a topcoat layer having excellent physical properties and aesthetics is often provided on the undercoat layer. ..

For example, Patent Document 1 contains an aqueous dispersion of a carbonyl group-containing copolymer, a polyvalent hydrazide compound, and a pigment, and is used for an elastic base comprising an emulsion coating material having an elongation rate of a formed coating film and a pigment volume concentration within a predetermined range. A painting method using a paint is disclosed. In this coating method, after the above-mentioned elastic base paint is applied, a top coat paint having an elongation rate of the formed coating film within a predetermined range is applied on the coating film of the elastic base paint.

Further, for example, Patent Document 2 contains an emulsion resin having a glass transition temperature in a predetermined range, which is obtained by emulsion polymerization of a monomer mixture containing an acetoacetoxy group-containing unsaturated monomer, and a predetermined amount of an aliphatic dihydrazide compound. Aqueous undercoat material compositions are disclosed.

Japanese Unexamined Patent Publication No. 6-190332 Japanese Unexamined Patent Publication No. 2003-201440

Regarding the multi-layer film including the undercoat layer and the topcoat layer, the present inventors use a resin composition for the undercoat layer so as to easily follow the substrate, and enhance the performance such as stain resistance for the topcoat layer. We investigated the production of an industrially useful multi-layer film by using an easy-to-use resin composition. As a result of the examination, by coating the undercoat layer and the topcoat layer with resins having different properties, the undercoat layer and the topcoat layer have poor interlayer adhesion, and peeling or swelling may occur between the layers. It turned out that there was.

As one means for enhancing the above-mentioned interlayer adhesion, it is conceivable to add an additive to the resin composition. However, in the production of a multi-layer film, when the topcoat layer forming material is applied in a state where the undercoat layer is not sufficiently dried due to a short curing time after application of the undercoat layer forming material, or when the topcoat layer forming material is applied. Shortly after application, it may be affected by water due to rainfall or the like. In these cases, the adhesion between layers is more likely to decrease, so that peeling and swelling between layers are more likely to occur.

Further, as another means for enhancing the above-mentioned interlayer adhesion, it is conceivable to promote the drying and curing of the coating layer. However, in the case of water-based materials, one-component materials, room temperature drying conditions, etc., it is often difficult to accelerate the drying and curing rates.

Therefore, a technique for obtaining a multilayer film having good interlayer adhesion without using the above-mentioned means for adding an additive to the resin composition used for forming the coating layer or the means for accelerating drying and curing. Will be industrially useful.

Therefore, the present invention is intended to provide an aqueous resin composition useful for forming a multi-layer film capable of excellent adhesion between a plurality of coating layers overlapping each other and suppressing swelling between coating layers. Is. Further, the present invention is intended to provide the above-mentioned multilayer film and the method for producing the above-mentioned multilayer film by using the above-mentioned aqueous resin composition.

The present invention provides an aqueous resin composition used for forming the copolymer coating layer containing (P _{X) (X)} and overlap the coating layer (Y),
The copolymer (P _X) represents a carbonyl group-containing polymerizable monomer having at least one selected from the group consisting of aldo group and a keto group and (A _X), wherein the carbonyl group-containing polymerizable monomer (a _X) other than the polymerizable monomer (B _{X) (provided} that optional component hydrophilic group-containing polymerizable monomer (B _X2) than vinyl group-containing polymerizable monomer of the (B _X1) including at least) and the said polymerizable monomer (B _X) the carbonyl group-containing polymerizable monomer with respect to 100 parts by weight (a _X) monomer component containing in a ratio of more than 0.1 part by weight (M _X) is a copolymer obtained by copolymerizing,
The aqueous resin composition is
Carbonyl group-containing polymerizable monomer having at least one selected from the group consisting of aldo group and keto group (A _Y) and a polymerizable monomer other than the carbonyl group-containing polymerizable monomer (A _Y) body (B _Y) monomer containing a _(provided that optional component hydrophilic group-containing polymerizable monomer (B _Y2) a vinyl group-containing polymerizable monomer other than (B _Y1) including at least), the containing body component (M _Y) are copolymerized copolymer (P _Y), and hydrazide groups polyvalent hydrazide compound having at least two (Z),
The content of the monomer component _{(M Y)} the carbonyl group-containing polymerizable monomer in _{(A Y)} is, with respect to the polymerizable monomer _(B Y) 100 parts by weight, 0.1 It ’s more than a department,
The polymerizable monomer to (B _Y) the carbonyl group-containing polymerizable monomer corresponding to 0.1 parts by weight per 100 parts by weight amount of material (A _{Y) (mol),} the polymerizable monomer ( _BY ) Provided is an aqueous resin composition in which the molar ratio of the amount of substance (mol) of the polyvalent hydrazide compound (Z) per 100 parts by mass is 1 or more.

Further, the present invention is a coating layer overlap with each other (X) and the coating layer (Y) a multi-layer film containing the coating layer (X) is the following (1) to the aqueous resin composition shown (R _X) by weight of coating, the coating layer (Y) includes a coating of the following aqueous resin compositions shown in ₍₂₎ (R Y), to provide a multi-layer film.

Furthermore, the present invention provides a method for producing a multi-layer film comprising a coating layer which overlap with each other (X) and the coating layer (Y), by applying the aqueous resin composition shown in the following (1) to (R _X), the aqueous resin composition that forms the coating layer comprising a coating of (R _X) (X); and aqueous resin composition shown in the following (2) by applying a (R _Y), the aqueous resin composition ( forming the coating layer comprising a coating of R _Y) and (Y); to provide a method of manufacturing a multi-layer film containing.

(1); The aqueous resin composition ( _RX ) is
Carbonyl group-containing polymerizable monomer having at least one selected from the group consisting of aldo group and keto group (A _X) and a polymerizable monomer other than the carbonyl group-containing polymerizable monomer (A _X) body (B _X) monomer containing a _(provided that optional component hydrophilic group-containing polymerizable monomer (B _X2) vinyl group-containing polymerizable monomer other than (B _X1) including at least), the containing body component _{(M X)} is copolymerized copolymer _{(P X),}
The content of the monomer component _{(M X)} the carbonyl group-containing polymerizable monomer in _{(A X)} is, with respect to the polymerizable monomer _(B X) 100 parts by weight, 0.1 It is more than a part.

(2); The aqueous resin composition ( _RY ) is
Carbonyl group-containing polymerizable monomer having at least one selected from the group consisting of aldo group and keto group (A _Y) and a polymerizable monomer other than the carbonyl group-containing polymerizable monomer (A _Y) body (B _Y) monomer containing a _(provided that optional component hydrophilic group-containing polymerizable monomer (B _Y2) a vinyl group-containing polymerizable monomer other than (B _Y1) including at least), the containing body component (M _Y) are copolymerized copolymer (P _Y), and hydrazide groups polyvalent hydrazide compound having at least two (Z),
The content of the monomer component _{(M Y)} the carbonyl group-containing polymerizable monomer in _{(A Y)} is, with respect to the polymerizable monomer _(B Y) 100 parts by weight, 0.1 It ’s more than a department,
The polymerizable monomer to (B _Y) the carbonyl group-containing polymerizable monomer corresponding to 0.1 parts by weight per 100 parts by weight amount of material (A _{Y) (mol),} the polymerizable monomer ( _BY ) The molar ratio of the amount of substance (mol) of the polyvalent hydrazide compound (Z) per 100 parts by mass is 1 or more.

According to the present invention, it is possible to provide an aqueous resin composition useful for forming a multilayer film having excellent adhesion between a plurality of coating layers overlapping each other and capable of suppressing swelling between coating layers. can. Further, according to the present invention, the above-mentioned multilayer film and the method for producing the above-mentioned multilayer film can be provided by using the above-mentioned aqueous resin composition.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

The present inventors have investigated a multi-layer film containing at least two coating layers that overlap each other. Specifically, of the two coating layers that overlap each other, a coating layer (undercoat layer) that is applied first and provided as a relatively lower layer, and a coating layer that is applied later and provided as a relatively upper layer. A multi-layer film including a coating layer (top coating layer) was examined. In this study, a resin designed to have a relatively low glass transition temperature (Tg) was used for the undercoat layer so that it could easily follow the substrate (base material), and the topcoat layer had stain resistance and the like. A resin designed to have a relatively high Tg was used so that the performance could be easily improved.

In the examination process, if there is a significant difference in Tg of the resin used for each layer according to the roles of the undercoat layer and the topcoat layer, the adhesion between the undercoat layer and the topcoat layer becomes insufficient. It was found that peeling and swelling may occur between layers.

As one means for enhancing the above-mentioned interlayer adhesion, it is conceivable to add an additive to the resin composition. However, at the actual construction site, the undercoat layer is sufficiently dried due to factors such as the influence of rainfall and the inability to secure a sufficient space between the undercoat and the topcoat due to the need for construction in a limited construction period. The topcoat layer forming material may be applied in the unfinished state. In this case, the interlayer adhesion between the undercoat layer and the topcoat layer may be further lowered, so that peeling or swelling between the layers may be more likely to occur.

Further, as another means for enhancing the above-mentioned interlayer adhesion, it is conceivable to promote the drying and curing of the coating layer. However, in the case of adopting a water-based material, a one-component material, a room temperature drying condition, or the like, it is often difficult to accelerate the drying and curing speed.

Therefore, the present inventors do not rely on the means by adding an additive to the resin composition used for forming the coating layer or the means for accelerating drying or the like, and in the forming material of each layer, the resin constituting the coating layer. By identifying the material, we enthusiastically studied to obtain the desired multi-layer film.

As a result, it was found that it is effective to take the following measures. That is, a cross-linking agent and a cross-linking reaction are carried out as a raw material of the resin (copolymer) in both the resin compositions for the undercoat layer and the top coat layer so that a cross-linking structure is likely to occur between the undercoat layer and the top coat layer. A polymerizable monomer having a functional group that can be generated is used. Further, at least one of the resin composition for the undercoat layer and the resin composition for the topcoat layer contains the above-mentioned cross-linking agent. As the polymerizable monomer having a functional group capable of causing a cross-linking reaction with the cross-linking agent, a carbonyl group-containing polymerizable monomer having at least one selected from the group consisting of an ald group and a keto group is used. .. Further, as the cross-linking agent, a multivalent hydrazide compound having two or more hydrazide groups is used. The present inventors have found that a multi-layer film having excellent adhesion between coating layers and capable of suppressing swelling between coating layers can be obtained by a configuration incorporating the above means, and the present invention has been made. Has been completed.

<Aqueous resin composition ( _RY )>
The aqueous resin composition ( _RY ) of the embodiment of the present invention is mainly a resin composition containing the above-mentioned cross-linking agent (multivalent hydrazide compound) as an essential component. The aqueous resin composition (R _Y) is a copolymer (P _X) coating layer containing a (X) and coating layer (Y) aqueous resin composition used for forming the mutually overlapping (R _Y).

Copolymer (P _X) is at least one carbonyl group-containing polymerizable monomer having a selected from the group consisting of aldo group and a keto group and (A _X), a carbonyl group-containing polymerizable monomer (A _X) other than the polymerizable monomer and (B _X), a copolymer monomer component (M _X) is copolymerized containing. The above polymerizable monomer (B _X) is an optional component hydrophilic group-containing polymerizable monomer (B _X2) than vinyl group-containing polymerizable monomer of the (B _X1) at least comprises, optionally It may contain a hydrophilic group-containing polymerizable monomer ( _BX2 ). The content of the monomer component _{(M X)} carbonyl group-containing polymerizable monomer in _{(A X),} the polymerizable monomer _(B X) with respect to 100 parts by weight, 0.1 parts by weight That is all. The details of the coating layer (X) will be described later.

_{The aqueous resin composition (RY} ) of one embodiment of the present invention _{comprises a carbonyl group-containing polymerizable monomer (A Y} ) having at least one selected from the group consisting of an ald group and a keto group, and a carbonyl group. containing containing polymerizable monomer (a _Y) other than the polymerizable monomer (B _Y) and contains a monomer component (M _Y) are copolymerized copolymer (P _Y). The above polymerizable monomer (B _Y) is an optional component hydrophilic group-containing polymerizable monomer (B _Y2) than vinyl group-containing polymerizable monomer of the (B _Y1) at least comprises, optionally It may contain a hydrophilic group-containing polymerizable monomer ( _BY2 ). The content of the monomer component _{(M Y)} carbonyl group-containing polymerizable monomer in _{(A Y),} the polymerizable monomer _(B Y) with respect to 100 parts by weight, 0.1 parts by weight That is all.

_{Further, the aqueous resin composition (RY} ) according to the embodiment of the present invention further contains a polyvalent hydrazide compound (Z) having two or more hydrazide groups. The content of the polyvalent hydrazide compound (Z), the substance of the polymerizable monomer _(B Y) a carbonyl group-containing polymerizable monomer corresponding to 0.1 parts by weight per 100 parts by weight of _{(A Y)} (mol ), The molar ratio of the amount of substance (mol) of the polyvalent hydrazide compound (Z) per 100 parts by mass of the polymerizable monomer ( _{BY) is 1 or more.}

Coating layer (X) to the copolymerization are contained member (P _X) may have a structural unit derived from a carbonyl group-containing polymerizable monomer _{(A X) (U AX)} . Further, the copolymer (P _X) coating layer containing a (X) and coating layer (Y) aqueous resin composition used for forming the mutually overlapping (R _Y) in the copolymer (P _Y) is also it can have a structural unit derived from a carbonyl group-containing polymerizable monomer _{(a Y) (U AY)} . The aqueous resin composition ( _RY ) contains a specific amount of the multivalent hydrazide compound. Therefore, in the multilayer film containing the coating layer (X) and the coating layer (Y) that overlap each other, the hydrazide group in the polyvalent hydrazide compound in the coating layer (Y) and the hydrazide groups in the coating layers (X) and (Y), respectively. cause of the copolymer _{(P X)} and structural units in _{(P Y) (U AX)} and crosslinked structure by reaction with _{(U AY)} into including the carbonyl group (aldo group and / or keto groups) sell. As a result, the adhesion between the coating layer (X) and the coating layer (Y) is excellent, and swelling between the layers can be suppressed. Further, when the coating layer provided earlier is not sufficiently dried among the coating layer (X) and the coating layer (Y) and the coating layer provided later is laminated, or the curing time after coating is applied. Even when the coating film is short, it is possible to obtain a multi-layer film having excellent adhesion between coating layers and suppressing swelling between coating layers. Therefore, the aqueous resin composition ( _RY ) can contribute to shortening the construction period and thereby reducing the cost.

As described above, in the present specification, the copolymer contained in the coating layer (X) is expressed as "(P _X)", the monomer component forming the copolymer (P _X) (monomer the body mixture) referred to as _{"(M X)".} Similarly, a carbonyl group-containing polymerizable monomers used as the component of the monomer component (M _X) is denoted as "(A _X)", which simply referred to as "monomer (A _X)" Sometimes. Also used as a component of the monomer component (M _X), a carbonyl group-containing polymerizable monomer and (A _X) other than the polymerizable monomer represented by "(B _X)", which simply " it may be referred to as monomer _{(B X)} ". Further, as the polymerizable monomer (B _X), and a hydrophilic group-containing polymerizable monomer optionally used is referred to as "(B _X2)", which simply "monomer (B _X2)" May be described. Further, as the polymerizable monomer (B _X), a vinyl group-containing polymerizable monomer used indispensably indicated by "(B _X1)" is simply described as "monomer (B _X1)" this I have something to do.

Further, as described above, in the present specification, the coating layer (Y) aqueous resin composition for use in the formation of a copolymer (R _Y) contains represented by "(P _Y)", the copolymer the (P _Y) monomer component forming the (monomer mixture) referred to as "(M _Y)". Similarly, a carbonyl group-containing polymerizable monomers used as the component of the monomer component (M _Y) is expressed as "(A _Y)", which simply referred to as "monomer (A _Y)" Sometimes. Also used as a component of the monomer component (M _Y), a carbonyl group-containing polymerizable monomer and (A _Y) other than the polymerizable monomer represented by "(B _Y)", which simply " It may be described as "monomer ( _BY)". Further, the hydrophilic group-containing polymerizable monomer arbitrarily used as the polymerizable monomer ( _{BY ) is described as "(BY2} )", and this is simply referred to as "monomer ( _BY2 )". May be described. Further, the vinyl group-containing polymerizable monomer that is indispensably used as the polymerizable monomer ( _{BY ) is described as "(BY1} )", and this is simply _{described as "monomer (BY1} )". I have something to do.

The aqueous resin composition ( _RY ) is used for forming the coating layer (Y), but may be used for either the topcoat layer or the undercoat layer of the two overlapping coating layers in the multilayer film. good. That is, either the coating layer (X) or the coating layer (Y) may be a relatively topcoat layer or an undercoat layer. In the present specification, it referred to a coating layer formed from an aqueous resin composition (R _Y) as a "coating layer (Y)", overlapping the coating layer (Y) from each other, multilayer film with a coating layer (Y) The coating layer constituting the above is referred to as "coating layer (X)".

As used herein, the term "polymerizable monomer" refers to a radically polymerizable monomer having at least one polymerizable unsaturated bond such as a polymerizable double bond and a polymerizable triple bond in the molecule. means. Examples of the polymerizable unsaturated bond include a vinyl group, an acryloyl group, a methacryloyl group, an allyl group, a 3-butenyl group, an ethynyl group and the like, but the group is limited to those capable of radical polymerization. Not done.

Further, in the present specification, the "structural unit" means a unit of a polymerizable monomer forming a resin (copolymer). The "structural unit derived (from the polymerizable monomer)" is, for example, a single bond (-C-C-) in which the polymerizable double bond (C = C) in the polymerizable monomer is cleaved. Examples include the structural units that have become.

The details of the coating film (X) will be described later. First, the aqueous resin composition ( _RY ) of the embodiment of the present invention used for forming the coating film (Y) has excellent interlayer adhesion and has excellent interlayer adhesion. A preferable configuration will be described from the viewpoint that a multilayer film capable of suppressing swelling between layers can be easily obtained. In the following description of each monomer, unless otherwise specified, any one or more of the monomers in the description can be used. Further, in the present specification, the wording "(meth) acrylic" means that the wording of both "acrylic" and "methacryl" is included. Similarly, the term "(meth) acrylate" means that the term "acrylate" and "methacrylate" are included.

As used herein, "water-based" means "water-soluble" or "water-dispersed". The aqueous resin composition ( _RY ) is a resin composition containing a _{copolymer (PY} ) as a resin capable of exhibiting water-soluble or water-dispersible type. The aqueous resin composition ( _RY ) preferably takes the form of an aqueous dispersion liquid in which the copolymer ( _{PY) is dispersed in an aqueous medium.} In this case, _{a part of the copolymer (PY} ) may take the form of an aqueous solution dissolved in an aqueous medium. The aqueous resin composition (R _Y), it in an aqueous medium as a dispersion medium, a copolymer (P _Y) is the composition of the emulsion type have emulsified and dispersed into particles (droplets) as dispersoid Is more preferable. In this case, the polyvalent hydrazide compound may be dispersed in the aqueous medium or may be dissolved in the aqueous medium and may be present in the _{aqueous resin composition (RY).} The average particle size in this case, the copolymer _{(P Y)} is preferably about 50 to 800 nm. In the present specification, the average particle size is determined by the cumulant method using a particle size distribution measuring device using a dynamic light scattering method (for example, trade name "rich particle size analyzer FPAR-1000", manufactured by Otsuka Electronics Co., Ltd.). It means the average particle size obtained by analysis.

The aqueous resin composition ( _RY ) contains a copolymer ( _PY ). Copolymer (P _Y) is a single containing carbonyl group-containing polymerizable monomer and (A _Y), a carbonyl group-containing polymerizable monomer (A _Y) other than the polymerizable monomer and (B _Y) mer component (M _Y) is a copolymer obtained by copolymerization. Therefore, the copolymer _{(P Y)} is a carbonyl group-containing polymerizable monomer _{(A Y)} and a structural unit derived from _{(U AY),} a structural unit derived from a polymerizable monomer _{(B Y)} (U _BY ) and is included.

The carbonyl group-containing polymerizable monomer ( _AY ) is at least one selected from the group consisting of an ald group and a keto group as a functional group in one molecule (in the present specification, "ald group and / or keto group". It is a polymerizable monomer having (.). Copolymer _{(P Y),} since it contains a monomer _{(A Y)} structural units derived from _{(U AY),} having an aldo group and / or keto groups in the structural unit _{(U AY).} Therefore, it is possible to cause a cross-linking reaction between the aldo group and / or the keto group of the _{copolymer (PY) and the hydrazide group of the polyvalent hydrazide compound.}

The carbonyl group-containing polymerizable monomer ( _AY ) may have at least one of an ald group and a keto group in one molecule. That is, the monomer (A _Y ) may have only one or more ald group among the ald group and the keto group in one molecule, or may have only one or more keto group. , Aldo group and keto group may have one or more of each.

Since the ald group (-RC (= O) -H) and the keto group (-RC (= O) -R') are both functional groups having a carbonyl group, the ald group is used herein. A polymerizable monomer having a group and / or a keto group is referred to as a "carbonyl group-containing polymerizable monomer". However, the ald group and the keto group are the carboxylic acid group (-R-COOH), the ester group (-R-COOR'), and the amide group (-R-CONR'R "), which also have a carbonyl group. Distinguished functional groups.

Examples of the carbonyl group-containing polymerizable monomer ( _AY ) include achlorine, metachlorine, formylstyrene, allyl acetoacetate, diacetone (meth) acrylamide, diacetone (meth) acrylate, acetoacetoxyethyl (meth) acrylate, and the like. Examples thereof include vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketones, vinyl ethyl ketones, vinyl butyl ketones, etc.) and the like. Among these, diacetone (meth) acrylamide and acetoacetoxyethyl (meth) acrylate are preferable. Among them, the monomer ( _AY ) more preferably contains at least one of diacetone acrylamide and acetoacetoxyethyl methacrylate.

In order for the _{coating layer (Y) containing the copolymer (PY} ) to have excellent adhesion to the coating layer (X) and to be a layer in which swelling with the coating layer (X) is suppressed, it is simply necessary. mer component _{(M Y)} carbonyl group-containing polymerizable monomer in the content of _{(a Y)} is the polymerizable monomer _(B Y) 100 parts by weight, is 0.1 part by mass or more Requires. The content of the monomer ( _AY ) is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more. On the other hand, _{the upper limit of the content of the monomer (AY} ) is not particularly limited, and the content can be 0.1 to 900 parts by mass. From the viewpoint of improving the water resistance of the coating layer (Y), the _{content of the monomer (AY} ) is preferably 400 parts by mass or less, more preferably 100 parts by mass or less, and 50. It is more preferably less than or equal to parts by mass. As used herein, the monomer content of the (A _Y), when two or more monomers (A _Y) is used, two or more monomers and the total of (A _Y) It means the content.

The content of the monomer component _{(M Y)} carbonyl group-containing polymerizable monomer in _{(A Y),} based on the total weight of the monomer component _{(M Y),} 0.1 to 90 mass % Is preferable. The content of the monomer ( _AY ) is more preferably 0.2% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. Further, the _{content of the monomer (AY} ) is more preferably 80% by mass or less, further preferably 50% by mass or less, still more preferably 40% by mass or less, 20. It is particularly preferable that it is mass% or less.

The polymerizable monomer ( _BY ) is polymerizable other than the above-mentioned carbonyl group-containing polymerizable monomer (A _Y ) among the monomer components ( _{MY ) forming the copolymer (P Y).} It is a monomer. As the monomer ( _BY ), various types of polymerizable monomers can be used. Therefore, the type of selection and the amount used of the monomer (B _Y), in relation to the combination of a carbonyl group-containing polymerizable monomer as described above (A _Y), various copolymers of (P _Y) It is possible to design. For example, as described below, it is also possible to obtain a copolymer (P _Y) having a desired glass transition temperature (Tg _Y).

Polymerizable monomer (B _Y) includes an optional component hydrophilic group-containing polymerizable monomer (B _Y2) than vinyl group-containing polymerizable monomer of the (B _Y1) at least, containing hydrophilic groups It may contain a polymerizable monomer ( _BY2). As used herein, the "vinyl group-containing polymerizable monomer" is a polymerizable monomer having a vinyl group as a group having a polymerizable unsaturated bond in one molecule, and contains the above-mentioned carbonyl group. It refers to those excluding the polymerizable monomer and the hydrophilic group-containing polymerizable monomer.

Examples of the vinyl group-containing polymerizable monomer ( _BY1 ) include (meth) acrylic acid esters; styrene-based monomers; nitrile group-containing monomers such as acrylonitrile and methacrylonitrile; ethylene, propylene, and butylene. Monoolefin monomers such as; diene monomers such as butadiene and isoprene; carboxylic acid vinyl ester monomers such as vinyl formate, vinyl acetate, and vinyl propionate; vinyl ether monomers such as methyl vinyl ether and ethyl vinyl ether. Saturated alcohol monomers such as vinyl alcohol and allyl alcohol; Vinyl halide monomers such as vinyl chloride and vinyl fluoride; Vinylidene halide monomers such as vinylidene chloride; N-vinylmorpholin, 4-acryloylmorpholin , 4-methacryloylmorpholine, 4-vinylpyridine, and nitrogen atom-containing vinyl monomers such as 1-vinylimidazole; and the like.

Among the specific examples of the vinyl group-containing polymerizable monomer ( _BY1 ) listed above, it is selected from the group consisting of a (meth) acrylic acid ester, a styrene-based monomer, and a nitrile group-containing monomer. At least one is preferable. Among them, at least one selected from the group consisting of (meth) acrylic acid ester, styrene, acrylonitrile, and methacrylonitrile is more preferable.

Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester, (meth) acrylic acid alkoxyalkyl ester, (meth) acrylic acid aralkyl ester, and (meth) acrylic acid aryl ester. .. Of these, (meth) acrylic acid alkyl esters are preferred.

Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl ( Meta) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-undecyl (meth) acrylate, n- Linear or branched chains such as dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate. (Meta) acrylic acid alkyl esters with an alkyl group; as well as cyclohexyl (meth) acrylates, 4-tert-butylcyclohexyl (meth) acrylates, isobornyl (meth) acrylates, dicyclopentanyl (meth) acrylates, and dicyclopentenyls ( Examples thereof include alicyclic (meth) acrylic acid alkyl esters such as meta) acrylates. Among these, a (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 18 (more preferably 1 to 12) carbon atoms is preferable.

Examples of the (meth) acrylic acid alkoxyalkyl ester include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, and 2. -Phenoxyethyl (meth) acrylate and the like can be mentioned.

Examples of the (meth) acrylic acid aralkyl ester include benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, methylbenzyl (meth) acrylate, and naphthylmethyl (meth) acrylate.

Examples of the (meth) acrylic acid aryl ester include phenyl (meth) acrylate, tolyl (meth) acrylate, and naphthyl (meth) acrylate.

Examples of the styrene-based monomer include styrene, α-methylstyrene, o-, m-, p-methylstyrene, o-, m-, p-ethylstyrene, 4-tert-butylstyrene, o-, m. -, P-methoxystyrene, o-, m-, p-ethoxystyrene, o-, m-, p-chlorostyrene, o-, m-, p-bromostyrene, o-, m-, p-fluorostyrene , And o-, m-, p-chloromethylstyrene and the like. Of these, styrene is preferable.

Monomer components for forming the copolymer (P _Y) (M _Y) are contained as the polymerizable monomer (B _Y), an optional component hydrophilic group-containing polymerizable monomer and (B _Y2) You may. As used herein, the term "hydrophilic group-containing polymerizable monomer" refers to a polymerizable monomer having a hydrophilic group, excluding the above-mentioned carbonyl group-containing polymerizable monomer. Further, the "hydrophilic group" refers to a group that exhibits an affinity with water, and includes a group that is ionized in water to become an ion and a group that is hydrated by hydrogen bonds. Examples of the hydrophilic group include an acid group, a hydroxy group, an amide group, a polyoxyethylene group and the like.

Examples of the hydrophilic group-containing polymerizable monomer ( _BY2 ) include an acid group-containing polymerizable monomer, a hydroxy group-containing polymerizable monomer, an amide group-containing polymerizable monomer, and a polyoxyethylene group. Examples thereof include a contained polymerizable monomer.

Examples of the acid group-containing polymerizable monomer include ethylenically unsaturated carboxylic acid monomers such as (meth) acrylic acid, crotonic acid, silicic acid, itaconic acid, maleic acid, fumaric acid, and citraconic acid; Carboxy group-containing monomers such as monoalkyl esters of unsaturated dicarboxylic acids such as monoethyl itaconate, monobutyl fumarate, and monobutyl maleate; sulfonic acid group-containing monomers such as styrene sulfonic acid; and the like can be mentioned. .. Further, the acid group-containing polymerizable monomer may be one that produces a hydrophilic group such as a carboxy group when dissolved in water, and for example, an unsaturated carboxylic acid such as maleic anhydride and itaconic acid anhydride. Anhydrous can also be mentioned.

Examples of the hydroxy group-containing polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate, 3 (Meta) acrylic acid hydroxyalkyl esters such as −hydroxybutyl (meth) acrylates, 4-hydroxybutyl (meth) acrylates, and 6-hydroxyhexyl (meth) acrylates; hydroxy groups such as 4-hydroxyphenyl (meth) acrylates. Have (meth) acrylic acid aryl ester; (meth) acrylic acid alkoxyalkyl ester having a hydroxy group such as 2-hydroxy-3-phenoxypropyl (meth) acrylate; hydroxy group such as o-, m-, p-hydroxystyrene. A styrene-based monomer having the above; and the like can be mentioned.

Examples of the amide group-containing polymerizable monomer include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N, N-diethyl ( Meta) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) acrylamide, N-butoxymethyl (meth) acrylamide, N-vinylacetamide, N-vinyl-N- Examples thereof include methylacetamide and N-vinyl-2-pyrrolidone.

Examples of the polyoxyethylene group-containing polymerizable monomer include methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, and ethoxypolyethylene glycol. (Meta) acrylate and the like can be mentioned.

As the hydrophilic group-containing polymerizable monomer ( _BY2 ), an acid group-containing polymerizable monomer and a hydroxy group-containing polymerizable monomer are preferable, and an ethylenically unsaturated carboxylic acid monomer and (meth) acrylic are used. Acid hydroxyalkyl esters are more preferred, and (meth) acrylic acids are even more preferred.

The content of the monomer component _{(M Y)} in the polymerizable monomer _{(B Y),} based on the total weight of the monomer component _{(M Y),} it is from 10 to 99.9 wt% preferable. The content of the monomer ( _BY ) is more preferably 20% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and 80% by mass. The above is particularly preferable. Further, the _{content of the monomer (BY} ) is more preferably 99.8% by mass or less, further preferably 99.5% by mass or less, and particularly preferably 99% by mass or less. preferable. As used herein, the monomer content of (B _Y), when two or more monomers (B _Y) is used, two or more monomers and the total of (B _Y) It means the content.

The content of the polymerizable monomer (B _Y) optionally hydrophilic group-containing polymerizable monomer may be used (B _Y2), based on the total weight of the polymerizable monomer (B _Y), 0 to It is preferably 50% by mass, more preferably 0 to 30% by mass, and even more preferably 0 to 20% by mass. When using the monomer _{(B Y2)} a monomer component _{(M Y),} the content of the monomer _{(B Y2),} based on the total weight of the polymerizable monomer _{(B Y),} 0 .1% by mass or more is preferable, 0.5% by mass or more is more preferable, and 1% by mass or more is further preferable. As used herein, the monomer content of the (B _Y2), when two or more monomers (B _Y2) is used, two or more monomers and the total of (B _Y2) It means the content.

Depending on the selection and amount of each type of the carbonyl group-containing polymerizable monomer ( _AY ) and the polymerizable monomer _(BY ) contained in the above-mentioned monomer component ( _{MY), the copolymer (Ay)} It is possible to design the glass transition temperature (Tg _Y ) of P _Y ) to be a desired value depending on the use of the multilayer film including the coating layer (Y). The glass transition temperature (Tg _Y ) of the copolymer (P _Y ) is preferably −80 to 80 ° C. The glass transition temperature (Tg _Y ) of the copolymer (P _Y ) is more preferably −70 ° C. or higher, further preferably −60 ° C. or higher, and even more preferably −50 ° C. or higher. .. The glass transition temperature (Tg _Y ) of the copolymer (P _Y ) is more preferably 60 ° C. or lower, further preferably 45 ° C. or lower, and even more preferably 25 ° C. or lower.

In the present disclosure, the glass transition temperature (Tg) of the copolymer takes a value (theoretical value) obtained by the FOX formula. The FOX formula is represented by the following formula (I).
1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ + ... W _n / Tg _n ... (I)
In the above formula (I), Tg represents the glass transition temperature (unit: K) of the copolymer of n kinds of monomer components (monomers 1 to n). W ₁ , W ₂ , ... W _n represent the mass fraction of each monomer (1, 2, ... n) with respect to the total amount of n kinds of monomer components. Tg ₁ , Tg ₂ , ... Tg _n represent the glass transition temperature (unit: K) of the homopolymer of each monomer (1, 2, ... n).

The aqueous resin composition ( _RY ) contains a polyvalent hydrazide compound (Z). The multivalent hydrazide compound (Z) is a compound having two or more hydrazide groups in one molecule. Since the polyvalent hydrazide compound (Z) has two or more hydrazide groups, the polyvalent hydrazide compound (Z) has a carbonyl group (ald group and / or keto group) in each copolymer contained in the coating layer (X) and the coating layer (Y). A cross-linking reaction can occur. Therefore, in the multi-layer film comprising a coating layer (X) and the coating layer (Y), not a polyvalent hydrazide compound was contained in the aqueous resin composition (R _Y) is coat (Y) only, some May be configured to be included in the coating layer (X). Further, the multilayer film may have a homogeneous structure in which the coating layer (X) and the coating layer (Y) cannot be clearly distinguished.

The polyvalent hydrazide compound (Z) preferably contains a dicarboxylic acid dihydrazide from the viewpoint of easy availability. Examples of the dicarboxylic acid dihydrazide include saturated aliphatic dicarboxylic acid dihydrazide having 2 to 18 carbon atoms such as dihydrazide oxalate, dihydrazide malonate, dihydrazide succinate, dihydrazide glutarate, adipic acid dihydrazide, and dihydrazide sebacic acid. Examples include aromatic dicarboxylic acid dihydrazides such as acid dihydrazide, terephthalic acid dihydrazide, and isophthalic acid dihydrazide; and monoolefinic unsaturated dicarboxylic acid dihydrazides such as maleic acid dihydrazide, fumaric acid dihydrazide, and itaconic acid dihydrazide. One of them may be used alone, or two or more thereof may be used in combination. Among them, adipic acid dihydrazide and isophthalic acid dihydrazide are more preferable, and adipic acid dihydrazide is further preferable.

The content of the polyvalent hydrazide compound (Z) in the aqueous resin composition ( _RY ) is 1 in molar ratio with respect to the minimum required amount of the above-mentioned carbonyl group-containing polymerizable monomer (A _Y). It is necessary to be above. As described above, the minimum required amount of the monomer ( _{AY ) is 0.1 part by mass per 100 parts by mass of the polymerizable monomer (BY} ), so that the polyvalent hydrazide compound (Z) is described above. The content is as follows. That is, the polymerizable monomer for _(B Y) a carbonyl group-containing polymerizable monomer corresponding to 0.1 parts by weight per 100 parts by weight amount of material _{(A Y)} (mol), the polymerizable monomer (B _Y ) It is required that the molar ratio of the amount of substance (mol) of the polyvalent hydrazide compound (Z) per 100 parts by mass is 1 or more.

Of the "polymerizable monomer _(B Y) a carbonyl group-containing polymerizable monomer corresponding to 0.1 parts by weight per 100 parts by weight amount of material _{(A Y)} (mol)" is the monomer (A _Y ) represents the minimum required amount of moles. It takes a unique value for the type of the monomer (A _Y), can be calculated based on the molecular weight of the monomer (A _Y). For example, when the monomer (A _Y ) is diacetone acrylamide (DAAM), the molecular weight is 169.2, and the amount of substance of DAAM corresponding to 0.1 g per 100 g _{of the monomer (BY) is 0.} It can be calculated as 1 / 169.2 ≈ 0.59 mmol. Further, for example, when the monomer (A _Y ) is acetoacetoxyethyl methacrylate (AAEM), the molecular weight thereof is 214.2, and the amount of substance of AAEM corresponding to 0.1 g per 100 g _{of the monomer (BY) is} , 0.1 / 214.2 ≈ 0.47 mmol.

On the other hand, the above-mentioned "amount of substance (mol) of the polyvalent hydrazide compound (Z) per 100 parts by mass of the _{polymerizable monomer (BY} )" is the polymerizable monomer in the _{aqueous resin composition (RY).} ( _BY ) It can be calculated based on the content (parts by mass) of the polyvalent hydrazide compound (Z) per 100 parts by mass and the molecular weight of the polyvalent hydrazide compound. For example, aqueous resin composition _{(R Y),} the monomer _(B Y) per 100 g, the amount of substance of ADH when adipic acid dihydrazide (ADH) as a polyvalent hydrazide compound (Z) is used Zg (moles ) Can be calculated by Z / 174.2, where the molecular weight of ADH is 174.2. Further, for example, aqueous resin composition _{(R Y),} the monomer _(B Y) per 100 g, the amount of substance of IDH when polyvalent hydrazide compound (Z) as isophthalic acid dihydrazide (IDH) was used Zg ( The number of moles) can be calculated by Z / 194.2, where the molecular weight of IDH is 194.2.

Therefore, the above molar ratio is [(the _{number of parts by mass of the polyvalent hydrazide compound with respect to 100 parts by mass of the monomer (BY} )) / the molecular weight of the polyvalent hydrazide compound] ÷ [0.1 part by mass / monomer (A). It can be calculated by the molecular weight of _Y)]. When the aqueous resin composition ( _RY ) contains two or more polyvalent hydrazide compounds, the molecule in the fraction of the above formula that can calculate the molar ratio is used as the sum of the values calculated for each polyvalent hydrazide compound. The molar ratio can be calculated. Also, if the aqueous resin composition (R _Y) contains the monomer (A _Y) of two or more, in the denominator in the formula of the fraction capable of calculating the molar ratio of the "monomer of (A _Y) the molecular weight ", as the sum of the monomer value obtained by multiplying the mass fraction of in the monomer (a _Y) on the molecular weight of each monomer used as monomer (a _Y), the molar ratio Can be calculated.

The above molar ratio is preferably 1.5 or more, more preferably 2 or more, and even more preferably 5 or more. The upper limit of the molar ratio is not particularly limited, and can be, for example, 3500 or less, and the molar ratio can be 1 to 3500. The molar ratio is preferably 250 or less, more preferably 100 or less, further preferably 50 or less, and even more preferably 20 or less.

Furthermore, the content of the aqueous resin composition _{(R Y)} polyvalent hydrazide compound in (Z), compared monomer component _(M Y) 100 parts by weight of the above, is 0.05 to 50 parts by weight It is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 10 parts by mass.

As described above, the aqueous resin composition ( _RY ) preferably contains an aqueous medium. The aqueous medium is a liquid medium containing at least water, and only water may be used, or a mixed solvent containing one or more of water and an organic solvent that can be mixed with water is used. May be. It is preferable to use deionized water (ion-exchanged water) as the water. Examples of the organic solvent include, but are not limited to, methanol, ethanol, isopropanol, ethyl carbitol, N-methylpyrrolidone and the like. As the aqueous medium, it is preferable to use water as a main component, and it is more preferable to use 50 to 100% by mass of water based on the total mass of the aqueous medium.

The content of the aqueous medium is not particularly limited. In one aspect of the aqueous resin composition ( _RY ), the content of the aqueous medium is preferably 10 to 90% by mass, preferably 20 to 70% by mass _{, based on the total mass of the aqueous resin composition (RY).} %, More preferably 30 to 60% by mass, even more preferably 35 to 55% by mass.

The aqueous resin composition ( _RY ) may contain various additives, if necessary. Additives include, for example, colorants such as pigments and dyes, metal compounds, solvents, plasticizers, dispersants, surfactants, foaming agents, lubricants, gelling agents, film-forming aids, antifreeze agents, cross-linking agents. , PH adjusters, viscosity regulators, preservatives, fungicides, bactericides, rust inhibitors, flame retardants, wetting agents, antifoaming agents, antioxidants, antiaging agents, UV absorbers, stabilizers, antistatic agents Agents, antiblocking agents and the like can be mentioned.

The method for producing the aqueous resin composition ( _RY ) is not particularly limited. Preferably, the aqueous resin composition (R) is produced by a production method comprising producing a composition containing the above-mentioned copolymer ( _{PY); and adding the above-mentioned multivalent hydrazide compound to the composition. Y} ) can be obtained.

As the composition containing the copolymer ( _PY ), as described above, an _{emulsion in which the copolymer (PY} ) is emulsified and dispersed in an aqueous medium is preferable. The method for producing this emulsion is preferably, but not limited to, copolymerizing the _{above-mentioned monomer component (MY} ) in an aqueous medium such as water usually contained in the emulsion. _{For example, an emulsion can be obtained by post-emulsifying a copolymer (PY} ) produced separately from the aqueous medium by a method such as forced emulsification or self-emulsification. From the viewpoint of productivity in which an emulsion can be easily obtained, it is preferable to copolymerize the _{monomer component (MY) in an aqueous medium in the presence of a surfactant and a polymerization initiator by an emulsion polymerization method.}

Specifically, an aqueous medium, monomer component (M _Y), a polymerization initiator, and method for emulsion polymerization in a batch mixing a surfactant; aqueous medium, monomer component (M _Y), and A method of performing emulsion polymerization using a monomeric emulsion (pre-emulsion) containing a surfactant can be adopted. Among these, the method of performing emulsion polymerization using a preemulsion is preferable. More specifically, the aqueous medium, monomer component (M _Y), and a pre-emulsion prepared surfactant premixed with, respectively and a polymerization initiator was added dropwise to an aqueous medium that has been separately prepared, It is more preferable to emulsify and polymerize the monomer _{component (MY} ) in the aqueous medium. The method of adding (dropping) the preemulsion, the polymerization initiator, etc. is not particularly limited, and for example, a batch addition method, a continuous addition method, a multi-stage addition method, or the like can be adopted, and these addition methods may be appropriately combined. May be good.

The polymerization conditions such as the polymerization temperature and the polymerization time when obtaining the copolymer ( _PY ) can be appropriately determined according to the type of the monomer used, the polymerization initiator and the like, the amount used thereof and the like. .. For example, the polymerization temperature is preferably in the range of about 20 to 100 ° C., more preferably in the range of about 40 to 90 ° C., and the polymerization time is preferably in the range of about 1 to 15 hours.

Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and the like, and one or more of these can be used. As the surfactant, an anionic surfactant and a nonionic surfactant are preferable, and an anionic surfactant is more preferable. That the use amount of the surfactant, based on 100 parts by weight of the monomer component _{(M Y),} preferably from 0.1 to 10 parts by weight and 0.2 to 8 parts by weight Is more preferable.

Examples of the anionic surfactant include fatty acid salts such as sodium stearate; alkyl sulfates such as sodium lauryl sulfate; polyoxyalkylene alkyl ether sulfates such as polyoxyethylene alkyl ether sodium sulfate; and polyoxyethylene poly. Ring phenyl ether sulfate ester salt; alkylbenzene sulfonate such as sodium dodecylbenzene sulfonate; sodium dialkylsulfosuccinate; sodium alkyldiphenyl ether disulfonate; and the like can be mentioned. Further, reactive anionic surfactants such as polyoxyalkylene alkenyl ether ammonium sulfate and polyoxyethylene styrenated propenylphenyl ether ammonium sulfate can also be mentioned. Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyalkylene derivatives such as polyoxyalkylene alkyl ether; and poly. Examples thereof include reactive nonionic surfactants such as oxyalkylene alkenyl ether and polyoxyethylene sterylated propenylphenyl ether.

Examples of the polymerization initiator include peroxides such as persulfates, organic peroxides, and hydrogen peroxides, azo compounds, and the like, and one or more kinds of polymerization initiators may be used. Can be done. The amount of the polymerization initiator used is preferably about 0.1 to 1 part by mass with respect to 100 parts by mass of the total amount of the above-mentioned monomer component ( _MY).

Specific examples of the persulfate include alkali metal persulfates such as potassium persulfate and sodium persulfate, ammonium persulfate and the like. Specific examples of the organic peroxide include diacyl peroxides such as benzoyl peroxide and dilauroyl peroxide, dialkyl peroxides such as t-butylcumyl peroxide and dicumyl peroxide, and t-butylperoxylaurate. And peroxyesters such as t-butylperoxybenzoate, hydroperoxides such as cumenehydroperoxide and t-butylhydroperoxide can be mentioned. Specific examples of the azo compound include 2,2'-azobis (2-amidinopropane) dihydrochloride and 4,4'-azobis (4-cyanopentanoic acid).

When synthesizing a copolymer ( _PY ), a chain transfer agent may be used to adjust the molecular weight of the copolymer. As the chain transfer agent, for example, hexyl mercaptan, lauryl mercaptan, octyl mercaptan, and alkyl mercaptans such as n- or t-dodecyl mercaptan can be used.

In making the emulsion, after obtaining the above monomer component (M _Y) are copolymerized copolymer (P _Y), it is preferable to add a neutralizing agent. Examples of the neutralizing agent include alkali metal compounds such as sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide and calcium carbonate; ammonia; monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and the like. Examples thereof include organic amines such as triethylamine, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, and diethylenetriamine. One kind or two or more kinds of neutralizing agents may be used.

_{A suitable aqueous resin composition (RY} ) is obtained by adding a specific amount of the polyvalent hydrazide compound to the emulsion containing the _{copolymer (PY} ) and the aqueous medium obtained as described above. Can be done.

The pH of the aqueous resin composition ( _RY ) is preferably 6.0 to 10.0, more preferably 6.5 to 9.5, and preferably 7.0 to 9.0. More preferred. The pH of the aqueous resin composition ( _RY ) can be measured in accordance with JIS K6833-1: 2008 and is a value at 25 ° C.

The non-volatile content (solid content) of the aqueous resin composition ( _RY ) is preferably 10 to 90% by mass, more preferably 30 to 80% by mass, and further preferably 40 to 70% by mass. It is preferably 45 to 65% by mass, and even more preferably 45 to 65% by mass. In the present specification, the non-volatile content (solid content) of the aqueous resin composition ( _RY ) can take a value measured in accordance with the provisions of JIS K6833-1: 2008.

The viscosity of the aqueous resin composition ( _RY ) at 25 ° C. can be appropriately adjusted according to the application and environment in which _{the aqueous resin composition (RY) is used.} For example, it is preferable to adjust the viscosity of the aqueous resin composition ( _RY ) in the range of 5 to 50,000 mPa · s under the conditions of 25 ° C. and a rotation speed of 12 rpm. The viscosity of the aqueous resin composition ( _RY ) is in accordance with JIS K6833-1: 2008 and can be measured using a rotational viscometer.

The above-mentioned aqueous resin composition ( _RY ) is used for forming the coating film (Y), and the coating layer (Y) overlaps with the coating layer (X) so that the coating layer (X) is formed. Together with it, it constitutes a multi-layer film. Therefore, the aqueous resin composition ( _RY ) is used for forming a coating layer (Y) in a multilayer film including a coating layer (X) and a coating layer (Y) that overlaps with each other. In that respect, it can be said that the aqueous resin composition ( _RY ) is used for obtaining a multilayer film, and can also be said to be used together with the coating film (X) for that purpose.

Coating layer (X), as described above, a carbonyl group-containing polymerizable monomer _{(A X)} and the polymerizable monomer and _{(B X),} the monomer _(B X) monomer per 100 parts by weight containing body _{(a X)} of the copolymer monomer component containing _{(M X)} is copolymerized at a ratio of more than 0.1 part by weight _{(P X).} Therefore, the copolymer _{(P X)} is the monomer and _{(A X)} from the structural unit _{(U AX),} monomeric structural units _{(U BX)} and the percentage of the derived _{(B X)} Can have at.

Copolymer (P _X) is the raw material of the monomer component (M _X) to a carbonyl group is used containing polymerizable monomer (A _X) is a preferred embodiment, and the monomer component (M _X) It is described in the same manner as _{the above-mentioned carbonyl group-containing polymerizable monomer (AY} ) including the content in the above-mentioned carbonyl group-containing polymerizable monomer (AY). For example, as the monomer _{(A X),} diacetone (meth) acrylamide, and is preferably at least one selected from the group consisting of acetoacetoxyethyl (meth) acrylate, at least one of DAAM and AAEM is more preferable. Further, for example, the content of the monomer component _{(M X)} carbonyl group-containing polymerizable monomer in _{(A X)} is the polymerizable monomer _(B X) 100 parts by weight of 0.1 to 900 it is preferably parts by mass, preferably 0.1 to 90 wt% based on the total weight of the monomer component _{(M X)} as a reference.

The polymerizable monomer used in the monomer component (M _X) (B _X) is a preferred embodiment, and including the content of the monomer in the component (M _X), the aforementioned polymerizable It is explained in the same manner as the monomer ( _BY). For example, the monomer (B _X) is a vinyl group-containing polymerizable monomer (B _X1), selected from (meth) acrylic acid ester, a styrene monomer, and the group consisting of nitrile group-containing monomer It is preferable to contain at least one of these, and may contain a hydrophilic group-containing polymerizable monomer ( _BX2 ). Further, for example, the content of the monomer component _{(M X)} monomer in _{(B X),} based on the total weight of the monomer component _{(M X),} is from 10 to 99.9 wt% Is preferable.

Coating layer (X) is preferably one formed from the copolymer (P _X) aqueous resin composition containing the (R _X). The aqueous resin composition ( _{RX ) is described in the above-mentioned aqueous resin composition (RY} ) with respect to the constitution relating to the aqueous liquid form (aqueous solution, aqueous dispersion, emulsion, average particle size, aqueous medium, etc.). It is preferable that the configuration is the same as described. Further, this aqueous resin composition ( _RX ) may also contain the above-mentioned multivalent hydrazide compound. Further, the aqueous resin composition ( _RX ) may also contain the above-mentioned other components which may be contained in the above-mentioned aqueous resin composition ( _RY).

The method for producing the aqueous resin composition ( _RX ) is not particularly limited. Preferably be obtained by a production method comprising preparing a composition comprising the above copolymer (P _X), the aqueous resin composition (R _X). The aqueous resin composition copolymer in the production method of (R _X) to produce a composition containing (P _X) in the manufacture method of the aqueous resin composition of the aforementioned (R _Y), the copolymer (P It can be carried out by a method as described in the same manner as for producing a composition containing _Y). In the case of producing an aqueous resin composition (R _X) comprising a polyvalent hydrazide compounds, the composition containing the above copolymer (P _X), may be added a polyvalent hydrazide compounds. The aqueous resin composition properties (pH, nonvolatile content, and viscosity, etc.) of (R _X) for also preferably the same as the ranges set forth in the description of the properties of the aqueous resin composition of the aforementioned (R _Y).

As described above, the raw material becomes a monomer component of the copolymer (P _X) contained in the coating layer _(X) (M X), the copolymer contained in the coating layer _(Y) (P Y ) Can be the same as the monomer component ( _MY ) used as the raw material. Therefore, the glass transition temperature of the copolymer _{(P X)} (Tg _X) also, the monomer component _(M X) the type of selection and the amount used of (especially the polymerizable monomer contained therein _(B X)) Therefore, it is possible to design the desired value. For example, the glass transition temperature of the copolymer _{(P X)} (Tg _X) also, similarly to the glass transition temperature (Tg _Y) of the copolymer described above _{(P Y),} it is possible to -80~80 ℃.

With respect to the copolymer _{(P X)} and each of the glass transition temperature of the above-mentioned copolymer _{(P Y)} (Tg), the aqueous resin composition _(R X, R _Y) depending on the application and the environment to be used, It can be decided as appropriate. In one embodiment, of the coating layer (X) and the coating layer (Y), the glass transition temperature of the copolymer contained in the person constituting the relatively undercoat layer (P _X or P _Y) is, relative it is preferably not higher than the glass transition temperature of the copolymer contained in the person constituting the overcoat layer to (P _Y or P _X). As a result, when the base material (base material) is a flexible base material such as a sheet-like or film-like material such as plastic, cloth, and paper, it becomes easy to improve the followability of the undercoat layer to the base material. In addition, it becomes easy to improve the performance such as stain resistance of the topcoat layer.

Further, in one embodiment, of the coating layer (X) and the coating layer (Y), the glass transition temperature of the copolymer contained in the person constituting the relatively undercoat layer (P _X or P _Y) is it is also preferred that the glass transition temperature or higher of the copolymer contained in the person constituting the relatively overcoat layer (P _Y or P _X). This makes it easier to increase the cohesive force of the aqueous resin composition ( _RX or _RY ) that forms the undercoat layer, and the undercoat layer can be used, for example, for DIY, wood, siding boards, concrete surfaces, and the like. It can be more preferably used as a sealer for impregnating a base material. By using the undercoat layer as a sealer, through the sealer to enhance the adhesion between the substrate and the topcoat layer, also suppresses excessive suction of the aqueous resin composition for forming the overcoat layer (R _Y or R _X) It becomes possible.

Co and the viewpoint of the effect according to the above application, the coating layer (X) and the coating layer interlayer adhesion from a more increased in view of (Y), and a glass transition temperature of the copolymer (P _X) (Tg _X) The absolute value (| Tg _{X −} Tg _Y |) of the difference between the polymer (P _Y ) and the glass transition temperature (Tg _Y ) is preferably 0 to 80 ° C, more preferably 0 to 70 ° C. It is preferably 0 to 60 ° C., more preferably 0 to 60 ° C.

As described in detail above, the aqueous resin composition ( _RY ) according to the embodiment of the present invention has excellent adhesion to the coating layer (X) and suppresses swelling with the coating layer (X). It is possible to form a coated layer (Y). Therefore, a water-based resin composition having a small environmental load, which has excellent adhesion between a plurality of coating layers overlapping each other and is useful for forming a multilayer film capable of suppressing swelling between coating layers, is provided. be able to. Therefore, the water-based resin composition ( _RY ) is preferably used as a paint, ink, coating agent, adhesive, pressure-sensitive adhesive, impregnating agent, etc., more preferably used as a paint, and more preferably a building. It is more preferable to use it as an exterior paint. From the above application of the aqueous resin composition ( _RY ), the coating layer includes a coating film with a paint, an ink layer with an ink, a coat layer with a coating agent, an adhesive layer with an adhesive, an adhesive layer with an adhesive, and impregnation. Examples thereof include a base material / impregnating agent integrated layer made of an agent. The multi-layer film is not particularly limited, but suitable examples include a multi-layer coating film, a multi-layer film, and the like, and among them, a multi-layer coating film for the exterior of a building and a siding board for a building material. A more suitable example may be a multi-layer coating film for use.

<Multi-layer film>
As described above, by using the aqueous resin composition ( _RY ), it is possible to provide the multilayer film of one embodiment of the present invention. The multi-layer film includes a coating layer (X) and a coating layer (Y) that overlap each other. Coating layer in the multilayer film (X) comprises a coating of an aqueous resin composition shown below ₍₁₎ (R X). Coating layer in the multilayer film (Y) includes a coating of the following aqueous resin compositions shown in ₍₂₎ (R Y).

(1); the aqueous resin composition (R _X) is a carbonyl group-containing polymerizable monomer having at least one selected from the group consisting of aldo group and a keto group and (A _X), a carbonyl group-containing polymerizable monomer (a _X) other than the polymerizable monomer (B _{X) (provided} that optional component hydrophilic group-containing polymerizable monomer (B _X2) than vinyl group-containing polymerizable monomer (B and including at least) the _X1), containing a monomer component containing a (M _X) is copolymerized copolymer (P _X). The content of the monomer component _{(M X)} carbonyl group-containing polymerizable monomer in _{(A X),} the polymerizable monomer _(B X) with respect to 100 parts by weight, 0.1 part by mass or more Is.

(2); The aqueous resin composition ( _{RY ) has a carbonyl group-containing polymerizable monomer (A Y} ) having at least one selected from the group consisting of an ald group and a keto group, and a carbonyl group-containing polymerizable monomer (A Y). monomer (a _Y) other than the polymerizable monomer (B _{Y) (provided} that optional component hydrophilic group-containing polymerizable monomer (B _Y2) than vinyl group-containing polymerizable monomer (B and including at least) a _Y1), containing a monomer component containing a (M _Y) are copolymerized copolymer (P _Y), and hydrazide groups polyvalent hydrazide compound having two or more (Z). The content of the monomer component _{(M Y)} carbonyl group-containing polymerizable monomer in _{(A Y),} the polymerizable monomer _(B Y) with respect to 100 parts by weight, 0.1 part by mass or more Is. Further, with respect to the polymerizable monomer _(B Y) a carbonyl group-containing polymerizable monomer corresponding to 0.1 parts by weight per 100 parts by weight amount of material _{(A Y)} (mol), the polymerizable monomer (B _Y ) The molar ratio of the amount of substance (mol) of the polyvalent hydrazide compound (Z) per 100 parts by mass is 1 or more.

The multi-layer film may include at least one combination of a coating layer (X) and a coating layer (Y) that overlap each other, and includes a plurality of combinations of the coating layers (X) and the coating layers (Y) that overlap each other. May be good. Further, the multilayer film may include a plurality of coating layers (X) as long as it includes a coating layer (X) and a coating layer (Y) that overlap each other, or may include a plurality of coating layers (Y). May be good. For example, one coating layer (X) may be laminated with another coating layer (X), or one coating layer (Y) may be laminated with another coating layer (Y). May be good.

As described above, in the multi-layer film, a hydrazide group in the polyvalent hydrazide compounds, the copolymer in the copolymer in the coating layer _(X) (P X) and the coating layer _(Y) (P Y) each carbonyl in It is preferably crosslinked with the group. In that case, the multi-layer film, a polyvalent hydrazide compound was contained in the aqueous resin composition (R _Y) is not only the coating layer (Y), configured so that a portion is included in the coating layer (X) The coating layer (X) and the coating layer (Y) may have a homogeneous structure in which they cannot be clearly distinguished. In consideration of these points, the coating layer (X) is mainly said to be film formed from an aqueous resin composition (R _X), coating layer (Y) is primarily aqueous resin composition (R _Y ) Can be said to be a film formed from. Therefore, in this specification, the multi-layer film, coating layer (X) includes a coating of an aqueous resin composition (R _X), coating layer (Y) is a film of the aqueous resin composition (R _Y) It will be included.

<Manufacturing method of multi-layer film>
The multi-layer film can be produced, for example, by the production method of the following embodiment of the present invention. That is, the method of manufacturing a multilayer film of an embodiment of the present invention, by applying the "(1)" aqueous resin composition shown in the (R _X), comprising a coating of an aqueous resin composition (R _X) it formed a coating layer (X); and then applying the "(2)" aqueous resin composition shown in (R _Y), a coating layer comprising a coating of an aqueous resin composition (R _Y) and (Y) To form;

In the multi-layer film, the coating layer (X) and the coating layer (Y) may be relatively the topcoat layer and the undercoat layer. Therefore, the aqueous resin composition ( _RX ) and the aqueous resin composition ( The _{order in which each of RY} ) is applied is not particularly limited. Since it is a method for producing a multilayer film including a coating layer (X) and a coating layer (Y) that overlap each other, it is formed by the previously applied aqueous resin composition ( _RX or _RY ) or the aqueous resin composition. _{The other aqueous resin composition (RY} or _RX ) can be applied onto the coated layer (X or Y).

As the coating method of each aqueous resin composition ( _RX or _RY ), various coating methods, printing methods, coating methods and the like can be adopted depending on the use of the aqueous resin composition. Examples of the coating method include various methods such as roll coating, bar coating, screen coating, die coating, spin coating, knife coating, blade coating, spray coating, dip coating, gravure coating, and brush coating.

After the aqueous resin composition _(R X, R _Y) was applied, by solidifying, it is possible to form an aqueous resin composition _(R X, R _Y) coating layer comprising a film of the (X, Y). As a suitable solidification method, a conventional solidification method such as drying and / or curing reaction can be taken, and since it is an aqueous resin composition, it is preferable to include at least drying. The drying temperature after applying the aqueous resin composition ( _RX , _RY ) is also not particularly limited, and can be appropriately determined depending on the use of the multi-layer film, the thickness of the coating layer, and the like. For example, the drying temperature may be about 50 to 100 ° C., or may be normal temperature (20 ° C. ± 15 ° C.). Further, the thickness of each coating layer (X, Y) is not particularly limited, and can be appropriately determined depending on the use of the multi-layer film and the like. For example, the thickness of each coating layer (X, Y) can be about 1 to 2000 μm.

When the multi-layer film (coating layer (X or Y) constituting the undercoat layer in the multi-layer film) is provided on the base material (base material), the base material is not particularly limited, and for example, various plastic materials, wood, and the like. Examples thereof include glass materials, metal materials, paper materials, concrete materials and the like.

As described in detail above, the present technology can have the following configurations.
[1] An aqueous resin composition used for forming the copolymer coating layer containing (P _{X) (X)} and overlap the coating layer (Y),
The copolymer (P _X) represents a carbonyl group-containing polymerizable monomer having at least one selected from the group consisting of aldo group and a keto group and (A _X), wherein the carbonyl group-containing polymerizable monomer (a _X) other than the polymerizable monomer (B _{X) (provided} that optional component hydrophilic group-containing polymerizable monomer (B _X2) than vinyl group-containing polymerizable monomer of the (B _X1) including at least) and the said polymerizable monomer (B _X) the carbonyl group-containing polymerizable monomer with respect to 100 parts by weight (a _X) monomer component containing in a ratio of more than 0.1 part by weight (M _X) is a copolymer obtained by copolymerizing,
The aqueous resin composition is
Carbonyl group-containing polymerizable monomer having at least one selected from the group consisting of aldo group and keto group (A _Y) and a polymerizable monomer other than the carbonyl group-containing polymerizable monomer (A _Y) body (B _Y) monomer containing a _(provided that optional component hydrophilic group-containing polymerizable monomer (B _Y2) a vinyl group-containing polymerizable monomer other than (B _Y1) including at least), the containing body component (M _Y) are copolymerized copolymer (P _Y), and hydrazide groups polyvalent hydrazide compound having at least two (Z),
The content of the monomer component _{(M Y)} the carbonyl group-containing polymerizable monomer in _{(A Y)} is, with respect to the polymerizable monomer _(B Y) 100 parts by weight, 0.1 It ’s more than a department,
The polymerizable monomer to (B _Y) the carbonyl group-containing polymerizable monomer corresponding to 0.1 parts by weight per 100 parts by weight amount of material (A _{Y) (mol),} the polymerizable monomer ( _BY ) An aqueous resin composition in which the molar ratio of the amount of substance (mol) of the polyvalent hydrazide compound (Z) per 100 parts by mass is 1 or more.
[2] The aqueous resin composition according to the above [1], wherein the molar ratio is 1 to 3,500.
[3] with respect to the content of the monomer component _{(M Y)} the carbonyl group-containing polymerizable monomer in _{(A Y)} is, the polymerizable monomer _(B Y) 100 parts by weight, 0 The aqueous resin composition according to the above [1] or [2], which is 1 to 900 parts by mass.
[4] The aqueous resin composition according to any one of the above [1] to [3], wherein the copolymer (P _Y ) has a glass transition temperature (Tg _{Y) of −80 to 80 ° C.}
[5] relative to the content of the monomer component _{(M X)} the carbonyl group-containing polymerizable monomer in _{(A X)} is, the polymerizable monomer _(B X) 100 parts by weight, 0 The aqueous resin composition according to any one of the above [1] to [4], which is 1 to 900 parts by mass.
[6] of the coating layer (X) and the coating layer (Y), a glass transition temperature of the copolymer contained in the person constituting the relatively undercoat layer (P _X or P _Y) is, the copolymer contained in the person constituting the relatively overcoat layer (P _Y or P _X) aqueous resin composition according to any one of the glass transition temperature of less is the above-mentioned [1] to [5] ..
[7] of the coating layer (X) and the coating layer (Y), a glass transition temperature of the copolymer contained in the person constituting the relatively undercoat layer (P _X or P _Y) is, the copolymer contained in the person constituting the relatively overcoat layer (P _Y or P _X) aqueous resin composition according to any one of the glass transition temperature or higher at which the above-mentioned [1] to [5] ..
[8] the absolute value of the difference between the glass transition temperature (Tg _Y) of the glass transition temperature of the copolymer _{(P X)} (Tg _X) with the copolymer _{(P Y) (| Tg X} -Tg Y |) Is the aqueous resin composition according to any one of the above [1] to [7], which has a temperature of 0 to 80 ° C.
[9] The carbonyl group-containing polymerizable monomer (A _X) and the carbonyl-containing polymerizable monomer (A _Y) are both above containing at least one of diacetone acrylamide and acetoacetoxyethyl methacrylate [ 1] The aqueous resin composition according to any one of [8].
[10] The aqueous resin composition according to any one of the above [1] to [9], wherein the multivalent hydrazide compound contains a dicarboxylic acid dihydrazide.
[11] A multi-layer film including a coating layer (X) and a coating layer (Y) that overlap each other.
The coating layer (X) includes a coating of the aqueous resin composition shown in (1) _{(R X),}
The coating layer (Y) is a multi-layer film containing the film of the _{aqueous resin composition (RY) shown in (2) above.}
[12] A method for producing a multi-layer film including a coating layer (X) and a coating layer (Y) that overlap each other.
Shown and described above (2); by coating the above (1) to the aqueous resin composition showing a (R _X), the aqueous resin composition wherein the coating layer comprising a coating of (R _X) (X) that forms the method for producing a multi-layer film comprising: an aqueous resin composition by coating the (R _Y), wherein forming the coating layer (Y) containing the film of the aqueous resin composition (R _Y).

Hereinafter, further specific examples of the above-mentioned embodiment will be described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following sentences, "parts" or "%" is based on mass ("parts by mass" or "% by mass") unless otherwise specified.

[Examples 1 to 30 and Comparative Examples 1 to 9]
In each example, the first layer aqueous resin composition (R ₁ ) and the second layer aqueous resin composition (R ₂ ) shown in Tables 1 to 5 below were prepared. In each example, in the test described later, the first layer water-based resin composition (R ₁ ) is used as the water-based resin composition for the first undercoat layer, and the second layer water-based resin composition (R ₂ ) is used as the second layer. It was used as an aqueous resin composition for the topcoat layer, and a multi-layer film sample for evaluation described later was produced.

The notation of each monomer in the polymerizable monomer mixture shown in Tables 1 to 5 below is as follows. The Tg in parentheses below represents the glass transition temperature of the homopolymer of the monomer, and those values were used to calculate the Tg by the FOX formula of the synthesized copolymer.
ST: Styrene (Tg: 100 ° C)
2EHA: 2-Ethylhexyl acrylate (Tg: -70 ° C)
MMA: Methyl Methacrylate (Tg: 105 ° C)
AN: Acrylonitrile (Tg: 105 ° C)
AAc: Acrylic acid (Tg: 106 ° C)
MAAc: Methacrylic acid (Tg: 185 ° C)
DAAM: Diacetone Acrylamide (Tg: 77 ° C., molecular weight 169.2)
AAEM: Acetacetoxyethyl methacrylate (Tg: 8 ° C., molecular weight 214.2)

The notation of the polyvalent hydrazide compound shown in Tables 1 to 5 below is as follows, and the amount (part by mass) of the polyvalent hydrazide compound used in the table is the amount used as the compound (active ingredient, solid content). Represents.
ADH: Adipic acid dihydrazide (molecular weight 174.2)
IDH: Isophthalic acid dihydrazide (molecular weight 194.2)

In the columns of the 1st layer aqueous resin composition (R ₁ ) and the 2nd layer aqueous resin composition (R ₂ ) of Tables 1 to 5 below, the copolymers obtained by the preparation of these aqueous resin compositions (respectively). The glass transition temperature (Tg) of the copolymer (P ₁ ) and the copolymer (P ₂ )) according to the FOX formula is shown. Further, in Table 1-5, as denoted with "molar ratio", the aqueous resin composition polyvalent hydrazide compound and monomer (A ₁ or A ₂₎ is blended, the monomer (B _1, B ₂ ) The amount of substance of the polyvalent hydrazide compound per 100 parts _{of the monomer (B 1} , B ₂ ) with respect to the amount of substance of the monomer ( _{A 1} , A ₂ ) corresponding to 0.1 part per 100 parts. The molar ratio is shown.

<Preparation of aqueous resin composition>
(Preparation of First Layer Aqueous Resin Composition (R ₁ ) in Example 1)
In a four-necked separable flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel, 30 parts of deionized water and 0.3 parts of anionic surfactant (trade name "New" manufactured by Nippon Ester Co., Ltd. "Cole 707-SF" (active ingredient = polyoxyethylene polycyclic phenyl ether sulfate ester salt 30%) 1 part) was charged, and the internal temperature was raised to 80 ° C. with stirring.
_{On the other hand, apart from the separable flask, a monomer (B 1} ) component consisting of 60 parts of 2EHA, 38 parts of MMA, and 2 parts of AAc (total amount 100 parts) and a monomer (A ₁ ) component consisting of 2 parts of DAAM Polymerizable monomer mixture (M ₁ ), 1.5 parts of anionic surfactant (trade name "Newcol 707-SF" manufactured by Nippon Emulsifying Co., Ltd. (active ingredient = polyoxyethylene polycyclic phenyl ether sulfate ester salt) 30%) 5 parts) and 50 parts of deionized water were emulsified with a homodisper to prepare a preemulsion.
Next, while maintaining the internal temperature in the separable flask at 80 ° C., the prepared preemulsion was uniformly added dropwise to the deionized water in the separable flask over 3 hours from the dropping funnel, and at the same time. A 5% potassium persulfate (KPS) aqueous solution (0.4 part as KPS) was uniformly added dropwise over 3 hours. After the dropping was completed, the reaction (polymerization) was completed by aging at 80 ° C. for 3 hours. Then, after cooling to room temperature (23 ± 2 ° C.), 5% aqueous ammonia was added for neutralization to adjust the pH to 8.5. _{An acrylic resin emulsion containing the copolymer (P 1} ) polymerized in this manner in the form of particles (droplets) was obtained. This resin emulsion, ADH was added 1 part of a solid content was obtained first layer an aqueous resin composition of 50% _{(R 1).}

(Second layer an aqueous resin composition of Example 1 (Preparation of _{R 2))}
The polymerizable monomer mixture (M ₁ ) used in the preparation of the first layer aqueous resin composition (R ₁ ) in Example 1 was changed to the polymerizable monomer mixture (M _{2) shown in Table 1.} , and except for not using the ADH were carried out in the same manner as process for the preparation of 1-layer aqueous resin composition (R _1). The acrylic resin emulsion containing this manner polymerized copolymer (P ₂₎ to the particle (droplet) form to obtain the second layer an aqueous resin composition (R _2). Further, a film-forming auxiliary (texanol) was added to the second-layer aqueous resin composition (R ₂ ) so that the minimum film-forming temperature was 0 ° C. or lower. The second layer an aqueous resin composition minimum film the temperature is 0 ℃ was added coalescent to be less than the (R _2), the second coating layer by the second layer an aqueous resin composition (R ₂₎ This is to prevent the occurrence of cracks in the above-mentioned, and to more appropriately evaluate the swelling between layers and the adhesion between layers, which will be described later.

(Preparation of aqueous resin composition in other examples and comparative examples)
In Examples 2-30 and Comparative Examples 1-9, the polymerizable monomer mixture in the first layer resin composition _{(R 1) (M 1)} ( monomer _{(B 1)} and the monomer _(A 1) ), Each type of the polymerizable monomer mixture (M ₂ ) (monomer (B ₂ ) and monomer (A ₂ )) in the second layer resin composition (R ₂ ), and the polyvalent hydrazide compound. _{The emulsion-type first-layer resin composition (R 1} ) and the second-layer resin composition (R ₂ ) were used in the same manner as in Example 1 except that the amounts used were as shown in Tables 1 to 5 below. ) Was prepared. _{Further, for the resin compositions (R 1} , R ₂ ) having a minimum film forming temperature of more than 0 ° C. before adding the film forming aid, _{the second layer aqueous resin composition (R 2} ) in the above-mentioned Example 1 is used. Similarly, a film-forming auxiliary (texanol) was added to adjust the minimum film-forming temperature to 0 ° C. or lower.

<Manufacturing of multi-layer film>
Using the first-layer water-based resin composition (R ₁ ) and the second-layer water-based resin composition (R ₂ ) prepared in each example, a base material and a first-layer water-based resin composition provided on the base material ( A multi-layer film sample composed of a _{first coating layer according to R 1} ) and a second coating layer according to the second aqueous resin composition (R _{2) provided on the first coating layer was produced.} For each example, four types of multi-layer films for evaluation under the conditions 1 to 4 shown below were produced. The application of each aqueous resin composition was performed by a brush.

(Condition 1)
In an environment of a temperature of 23 ° C. and a relative humidity of 50%, the first layer water-based resin composition (length 100 mm, width 70 mm, thickness 2 mm) is applied to a methacrylic resin plate (length 100 mm, width 70 mm, thickness 2 mm) specified in JIS K6718: 2015 as a base material. R ₁ ) was applied with a WET film thickness of 150 μm, and after 2 hours, the second layer aqueous resin composition (R ₂ ) was further applied over it with a WET film thickness of 150 μm, cured for 24 hours, and doubled for evaluation. A layered film sample 1 was obtained.

(Condition 2)
Under the same conditions as condition 1, the first layer water-based resin composition (R ₁ ) and the second layer water-based resin composition (R ₂ ) are applied, and the second layer water-based resin composition (R ₂ ) is applied to 3 After curing for a period of time, the obtained multi-layer film sample was immersed in water at 23 ° C. for 24 hours and then pulled up to wipe off the water on the surface to obtain a multi-layer film sample 2 for evaluation.

(Condition 3)
The first layer water-based resin composition (R ₁ ) was applied under the same conditions as condition 1, and after 24 hours, the second layer water-based resin composition (R ₂ ) was further applied on top of it with a WET film thickness of 150 μm. After curing for 24 hours, a multilayer film sample 3 for evaluation was obtained.

(Condition 4)
The first layer water-based resin composition (R ₁ ) was applied under the same conditions as the condition 1, and after 24 hours, the second layer water-based resin composition (R ₂ ) was further applied on top of it with a WET film thickness of 150 μm. After curing for 3 hours, the obtained multi-layer film sample was immersed in water at 23 ° C. for 24 hours and then pulled up to wipe off the water on the surface to obtain a multi-layer film sample 4 for evaluation.

<Evaluation>
(Suppression of swelling between layers)
For each example, the presence or absence of swelling in the coating layer was confirmed by visually observing the appearance of the multi-layer film samples 1 to 4 prepared under the conditions 1 to 4. Then, when the occurrence of swelling is confirmed, the presence or absence of swelling between the first coating layer and the second coating layer (interlayer) is confirmed by cutting the film (coating layer) at the location where the swelling occurs. Then, the effect of suppressing swelling between layers was evaluated according to the following evaluation criteria.
◯: No swelling between layers is confirmed.
X: Swelling between layers is confirmed.

(Interlayer adhesion)
For each example, using the multi-layer film samples 1 to 4 prepared under the conditions 1 to 4, the place where the multi-layer film is in close contact with the substrate was targeted for evaluation, and JIS K5600-5-6: 1999 was applied. The test was performed according to the specified cross-cut method (cut at 2 mm intervals). Then, the interlayer adhesion (adhesion between the first coating layer and the second coating layer) in the multi-layer film sample was evaluated according to the following evaluation criteria. In the following evaluation criteria, A and B were judged to be acceptable, and C was judged to be unacceptable.
A: The cross-cut area is not affected by more than 5%.
B: The cross-cut portion is affected by more than 5% but not more than 15%.
C: More than 15% is affected by the cross-cut part.

The above evaluation results are shown in the lower part of Tables 1-5.

[Example 31]
The first-layer water-based resin composition (R ₁ ) and the second-layer water-based resin composition (R ₂ ) prepared in Example 1 are added to the first and second layers, respectively, and the third layer (water-based resin) is added. The production conditions 1 to 4 of the multi-layer film sample for evaluation, which are also used for the composition (R ₁ )) and the fourth layer (aqueous resin composition (R _{2)), are set to the following conditions 1'to 4', respectively.} changed.

That is, under condition 1', after the second layer water-based resin composition (R ₂ ) is applied and cured under the above condition 1, the water-based resin composition (R ₁ ) is further applied as a third layer on the WET film thickness of 150 μm. Then, the aqueous resin composition (R ₂ ) was applied as a fourth layer and cured for 2 hours with a WET film thickness of 150 μm, and cured for 2 hours to obtain a 4-layer film sample 1 for evaluation.
Under condition 2', after the second layer water-based resin composition (R ₂ ) is applied and cured under the above condition 2, the water-based resin composition (R ₁ ) is further applied as a third layer with a WET thickness of 150 μm. After curing for 2 hours, a water-based resin composition (R ₂ ) was applied as a fourth layer at a WET thickness of 150 μm and cured for 2 hours, and then the obtained 4-layer membrane sample was placed in water at 23 ° C. After soaking for 24 hours, it was pulled up and the water on the surface was wiped off to obtain a 4-layer film sample 2 for evaluation.
Under condition 3', after the second layer water-based resin composition (R ₂ ) is applied and cured under the above condition 3, the water-based resin composition (R ₁ ) is further applied as the third layer with a WET film thickness of 150 μm. After curing for 24 hours, an aqueous resin composition (R ₂ ) was further applied as a fourth layer at a WET film thickness of 150 μm and cured for 24 hours to obtain a 4-layer film sample 3 for evaluation.
Under condition 4', after the second layer water-based resin composition (R ₂ ) is applied and cured under the above condition 4, the water-based resin composition (R ₁ ) is further applied as a third layer with a WET thickness of 150 μm. After curing for 24 hours, a water-based resin composition (R ₂ ) was applied as a fourth layer at a WET thickness of 150 μm and cured for 24 hours, and then the obtained 4-layer membrane sample was placed in water at 23 ° C. After soaking for 24 hours, it was pulled up and the water on the surface was wiped off to obtain a 4-layer film sample 4 for evaluation.

Using the four-layer film samples 1 to 4 for evaluation obtained in Example 31, the above-mentioned "suppression of swelling of the coating layer" and "interlayer adhesion" were evaluated. As a result, in all of the four-layer film samples 1 to 4 for evaluation, the result of suppressing the swelling of the coating layer was ◯, and the interlayer adhesion was A.

[Example 32]
(Manufacturing of pigment paste)
23 parts of ion-exchanged water, pigment dispersant (trade name "SMA-1440H" manufactured by Sartmer Japan Co., Ltd., solid content 35%) 9 parts, defoaming agent (trade name "SN Deformer 373" manufactured by San Nopco Ltd.), After mixing and premixing 0.5 parts of solid content (58%), 0.5 parts of 25% ammonia water, and 67 parts of rutile-type titanium oxide (trade name "CR-50" manufactured by Ishihara Sangyo Co., Ltd.). The mixture was sufficiently mixed with a stirrer (bead mill), and the pigment was dispersed with a tube gauge until the size became 50 μm or less to obtain a pigment paste A.

(Manufacturing of paint composition)
For each of the first layer water-based resin composition (R ₁ ) and the second layer water-based resin composition (R ₂ ) prepared in Example 1, the first layer coating composition and the second layer were as follows. A coating composition was prepared. That is, 57 parts of the aqueous resin composition (R ₁ or R ₂ ), 42 parts of the pigment paste A, 0.5 parts of ethylene glycol, an antifoaming agent (trade name "SN Deformer 373" manufactured by San Nopco Ltd., solid content 58%). 0.2 part and 0.3 part of the thickener (trade name "ADEKA NOL UH-420" manufactured by ADEKA Corporation, solid content 30%) were sequentially added while stirring with a disper to increase the pigment volume concentration (PVC). A 20% by volume coating composition was obtained. PVC was calculated by the following formula.
PVC = pigment volume / (pigment volume + resin volume)

Using the coating compositions of the first layer and the second layer of Example 32, the above-mentioned "suppression of swelling of the coating layer" and "interlayer adhesion" were evaluated. As a result, in all of the multi-layer film samples 1 to 4 for evaluation, the result of suppressing the swelling of the coating layer was ◯, and the interlayer adhesion was A.

[Example 33]
For each of the first layer water-based resin composition (R ₁ ) and the second layer water-based resin composition (R ₂ ) prepared in Example 1, the first layer coating composition and the second layer were as follows. A coating composition was prepared. That is, 15 parts of the aqueous resin composition (R ₁ or R ₂ ), 1 part of the pigment dispersant (trade name "Nopco Santo K" manufactured by San Nopco Ltd., solid content 33%), and an antifoaming agent (product manufactured by San Nopco Ltd.). Name "SN Defoamer 373", solid content 58%) 0.5 parts, 25% ammonia water 0.2 parts, heavy calcium carbonate (trade name "Super S" manufactured by Ishihara Sangyo Co., Ltd.) 80 parts, and thickening. Add 3.5 parts of the agent (trade name "Cerrosize QP-4400H" manufactured by Dow Chemical Japan Co., Ltd., solid content 2%) sequentially with stirring with a dispersion, and paint with a pigment volume concentration (PVC) of 80% by volume. The composition was obtained.

Using the coating compositions of the first layer and the second layer of Example 33, the above-mentioned "suppression of swelling of the coating layer" and "interlayer adhesion" were evaluated. As a result, in all of the multi-layer film samples 1 to 4 for evaluation, the result of suppressing the swelling of the coating layer was ◯, and the interlayer adhesion was A.

From the results of Examples 1 to 33 above, according to the aqueous resin composition of one embodiment of the present invention, it is possible to have excellent adhesion between a plurality of coating layers overlapping each other and to suppress swelling of the coating layer. It was confirmed to be useful for the formation of a possible multilayer film.

Claims (12)

An aqueous resin composition used for forming the copolymer coating layer containing (P _{X) (X)} and overlap the coating layer (Y),
The copolymer (P _X) represents a carbonyl group-containing polymerizable monomer having at least one selected from the group consisting of aldo group and a keto group and (A _X), wherein the carbonyl group-containing polymerizable monomer (a _X) other than the polymerizable monomer (B _{X) (provided} that optional component hydrophilic group-containing polymerizable monomer (B _X2) than vinyl group-containing polymerizable monomer of the (B _X1) including at least) and the polymerizable monomer (B _X) the carbonyl group-containing polymerizable monomer with respect to 100 parts by weight (a _X) capable radical polymerization a proportion of more than 0.1 part by weight monomer component (M _X) is a copolymer obtained by copolymerizing,
The aqueous resin composition is
Carbonyl group-containing polymerizable monomer having at least one selected from the group consisting of aldo group and keto group (A _Y) and a polymerizable monomer other than the carbonyl group-containing polymerizable monomer (A _Y) body (B _Y) a radical polymerization containing as _(provided that optional component hydrophilic group-containing polymerizable monomer (B _Y2) than vinyl group-containing polymerizable monomer (comprising at least the B _Y1)), the possible monomer component (M _Y) are copolymerized copolymer (P _Y), and a hydrazide group containing a polyvalent hydrazide compound having two or more (Z),
The content of the monomer component _{(M Y)} the carbonyl group-containing polymerizable monomer in _{(A Y)} is, with respect to the polymerizable monomer _(B Y) 100 parts by weight, 0.1 It ’s more than a department,
The polymerizable monomer to (B _Y) the carbonyl group-containing polymerizable monomer corresponding to 0.1 parts by weight per 100 parts by weight amount of material (A _{Y) (mol),} the polymerizable monomer ( B _Y) the polyvalent hydrazide compound per 100 parts by weight of the amount of substance of (Z) molar ratio (mol) is state, and are 1 or more,
The polyvalent hydrazide compound (Z), in between the coating layer (X) and the coating layer (Y), and the hydrazide group, the copolymer in the coating layer (X) in (P _X) the carbonyl in the structural unit (U _AX) to including carbonyl group, and the coating layer the copolymer in _(Y) (P Y) derived from the carbonyl group-containing polymerizable monomer (a _X) producing a crosslinked structure by reaction with the carbonyl group contained in the structural unit derived from a group containing polymerizable monomer _{(a Y) (U AY)} , the aqueous resin composition. The aqueous resin composition according to claim 1, wherein the molar ratio is 1 to 3,500. The content of the monomer component _{(M Y)} the carbonyl group-containing polymerizable monomer in _{(A Y)} is, with respect to the polymerizable monomer _(B Y) 100 parts by weight, 0.1 The aqueous resin composition according to claim 1 or 2, which is 900 parts by mass. The aqueous resin composition according to any one of claims 1 to 3, wherein the copolymer (P _Y ) has a glass transition temperature (Tg _{Y) of −80 to 80 ° C.} The content of the monomer component _{(M X)} the carbonyl group-containing polymerizable monomer in _{(A X)} is, with respect to the polymerizable monomer _(B X) 100 parts by weight, 0.1 The aqueous resin composition according to any one of claims 1 to 4, which is 900 parts by mass. The coating layer (X) and the coating layer (Y) of the glass transition temperature of the copolymer contained in the person constituting the relatively undercoat layer (P _X or P _Y) is relatively the copolymer (P _Y or P _X) aqueous resin composition according to any one of claims 1 to 5, a glass transition temperature below that is contained towards constituting the overcoat layer. The coating layer (X) and the coating layer (Y) of the glass transition temperature of the copolymer contained in the person constituting the relatively undercoat layer (P _X or P _Y) is relatively the copolymer (P _Y or P _X) aqueous resin composition according to any one of claims 1 to 5, the glass transition temperature or more contained in the person constituting the overcoat layer. The absolute value of the difference between the glass transition temperature (Tg _Y) of the glass transition temperature of the copolymer _{(P X)} (Tg _X) and the copolymer _{(P Y) (| Tg X} -Tg Y |) is The aqueous resin composition according to any one of claims 1 to 7, wherein the temperature is 0 to 80 ° C. The carbonyl group-containing polymerizable monomer (A _X) and the carbonyl-containing polymerizable monomer (A _Y) are both claim including at least one of diacetone acrylamide and acetoacetoxyethyl methacrylate 1-8 The aqueous resin composition according to any one of the above items. The aqueous resin composition according to any one of claims 1 to 9, wherein the multivalent hydrazide compound contains a dicarboxylic acid dihydrazide. A multi-layer film containing a coating layer (X) and a coating layer (Y) that overlap each other.
The coating layer (X) includes a coating of water-soluble resin composition _{(R X),}
The coating layer (Y) is seen including a coating of water-soluble resin composition _{(R Y),}
Before Symbol aqueous resin composition _{(R X)} is
Carbonyl group-containing polymerizable monomer having at least one selected from the group consisting of aldo group and keto group (A _X) and a polymerizable monomer other than the carbonyl group-containing polymerizable monomer (A _X) body (B _X) a radical polymerization containing as _(provided that optional component hydrophilic group-containing polymerizable monomer (B _X2) than vinyl group-containing polymerizable monomer (comprising at least the B _X1)), the possible monomer component _{(M X)} are contained copolymerized copolymer _{(P X),}
The content of the monomer component _{(M X)} the carbonyl group-containing polymerizable monomer in _{(A X)} is, with respect to the polymerizable monomer _(B X) 100 parts by weight, 0.1 der least part is,
Before Symbol aqueous resin composition _{(R Y)} is
Carbonyl group-containing polymerizable monomer having at least one selected from the group consisting of aldo group and keto group (A _Y) and a polymerizable monomer other than the carbonyl group-containing polymerizable monomer (A _Y) body (B _Y) a radical polymerization containing as _(provided that optional component hydrophilic group-containing polymerizable monomer (B _Y2) than vinyl group-containing polymerizable monomer (comprising at least the B _Y1)), the possible monomer component (M _Y) are copolymerized copolymer (P _Y), and a hydrazide group containing a polyvalent hydrazide compound having two or more (Z),
The content of the monomer component _{(M Y)} the carbonyl group-containing polymerizable monomer in _{(A Y)} is, with respect to the polymerizable monomer _(B Y) 100 parts by weight, 0.1 It ’s more than a department,
The polymerizable monomer to (B _Y) the carbonyl group-containing polymerizable monomer corresponding to 0.1 parts by weight per 100 parts by weight amount of material (A _{Y) (mol),} the polymerizable monomer ( B _Y) the polyvalent hydrazide compound per 100 parts by weight of the amount of substance of (Z) molar ratio (mol) is state, and are 1 or more,
In between the coating layer (X) and the coating layer (Y), the hydrazide group in the polyvalent hydrazide compound (Z) is said in the copolymer in the coating layer (X) (P _X) the carbonyl group in the carbonyl group-containing polymerizable monomer (a _X) carbonyl contained in the structural unit (U _AX) derived based on, and the copolymer of the coating layer _(Y) (P Y) It is crosslinked with a carbonyl group contained in the structural unit derived from a polymerizable monomer containing _{(a Y) (U AY)} , Fukusomaku. A method for producing a multi-layer film including a coating layer (X) and a coating layer (Y) that overlap each other.
Water soluble resin composition was coated (R _X), forms the coating layer (X) containing a coating of the aqueous resin composition (R _X); and
Water resin composition (R _Y) is applied to the forming the coating layer (Y) containing the film of the aqueous resin composition (R _Y); only contains,
Before Symbol aqueous resin composition _{(R X)} is
Carbonyl group-containing polymerizable monomer having at least one selected from the group consisting of aldo group and keto group (A _X) and a polymerizable monomer other than the carbonyl group-containing polymerizable monomer (A _X) body (B _X) a radical polymerization containing as _(provided that optional component hydrophilic group-containing polymerizable monomer (B _X2) than vinyl group-containing polymerizable monomer (comprising at least the B _X1)), the possible monomer component _{(M X)} are contained copolymerized copolymer _{(P X),}
The content of the monomer component _{(M X)} the carbonyl group-containing polymerizable monomer in _{(A X)} is, with respect to the polymerizable monomer _(B X) 100 parts by weight, 0.1 der least part is,
Before Symbol aqueous resin composition _{(R Y)} is
Carbonyl group-containing polymerizable monomer having at least one selected from the group consisting of aldo group and keto group (A _Y) and a polymerizable monomer other than the carbonyl group-containing polymerizable monomer (A _Y) body (B _Y) a radical polymerization containing as _(provided that optional component hydrophilic group-containing polymerizable monomer (B _Y2) than vinyl group-containing polymerizable monomer (comprising at least the B _Y1)), the possible monomer component (M _Y) are copolymerized copolymer (P _Y), and a hydrazide group containing a polyvalent hydrazide compound having two or more (Z),
The content of the monomer component _{(M Y)} the carbonyl group-containing polymerizable monomer in _{(A Y)} is, with respect to the polymerizable monomer _(B Y) 100 parts by weight, 0.1 It ’s more than a department,
The polymerizable monomer to (B _Y) the carbonyl group-containing polymerizable monomer corresponding to 0.1 parts by weight per 100 parts by weight amount of material (A _{Y) (mol),} the polymerizable monomer ( B _Y) the polyvalent hydrazide compound per 100 parts by weight of the amount of substance of (Z) molar ratio (mol) is state, and are 1 or more,
In between the coating layer (X) and the coating layer (Y), and the hydrazide group in the polyvalent hydrazide compound (Z), said in the copolymer in the coating layer (X) (P _X) the carbonyl group in the carbonyl group-containing polymerizable monomer (a _X) carbonyl contained in the structural unit (U _AX) derived based on, and the copolymer of the coating layer _(Y) (P Y) is reacted with a carbonyl group contained in the polymerizable monomer containing (a _Y) derived from the structural unit (U _AY), causes a cross-linked structure, production method of the multi-layer film.