JP6979905B2 - Laminated body and its manufacturing method - Google Patents

Description

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

Some building interior materials and furniture are manufactured using formaldehyde-containing adhesives and binders, and some products contain formaldehyde. Since formaldehyde is released from such products, it is a problem that the released formaldehyde stays indoors and causes health hazards to humans and animals. Therefore, the development of interior materials such as wallpaper having the effect of removing formaldehyde is being promoted.

As such an interior material, a wallpaper containing a formaldehyde scavenger having a function of physically and chemically reacting with formaldehyde to change it into a harmless and odorless state and a formaldehyde adsorbent in the resin layer is disclosed. (See Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 10-100334 Japanese Unexamined Patent Publication No. 2016-113722

All of the wallpapers disclosed in Patent Documents 1 and 2 are useful as interior materials having an effect of removing formaldehyde.
However, it is desired that the effect of removing formaldehyde can be maintained for a longer period of time, and the development of a new laminate capable of constructing such an interior material is strongly desired.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a laminate capable of maintaining the effect of removing formaldehyde for a long period of time and a method for producing the same.

In order to solve the above problems, the present invention is a laminate comprising a base material, a second drug-containing layer, a first drug-containing layer, and a coating layer, wherein the second drug-containing layer is a layer. The base material is arranged between the first drug-containing layer, the first drug-containing layer is arranged between the second drug-containing layer and the coating layer, and the coating layer is arranged. The first drug-containing layer, which is the outermost layer of the laminate, contains a microencapsulated formaldehyde reactant and a non-microencapsulated formaldehyde reactant, and is a foamed layer. The second agent-containing layer contains one or both of a microencapsulated formaldehyde reactant and a non-microencapsulated formaldehyde reactant, and the coating layer is a microencapsulated formaldehyde reaction. It is formed by using a composition for forming a coating layer, which comprises a combination of an agent and a formaldehyde reactant which is not microencapsulated, and has a viscosity of 90 mPa · s or more. Provide a laminate.

In the laminate of the present invention, the coating layer is further composed of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, AS resin, ABS resin, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, and the like. Polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyphenylene sulfide, polysulfone, polycarbonate, epoxy resin, melamine resin, phenol resin, urea resin, polyurethane, polyimide, vinyl acetate copolymer resin, polybutadiene rubber, styrene. It is preferable to contain one or more selected from the group consisting of butadiene rubber, acrylonitrile-butadiene rubber, butyl rubber, chloroprene rubber, polyisobutylene rubber, polyethylene rubber, propylene rubber and silicon rubber.

In the laminated body of the present invention, it is preferable that the second drug-containing layer is laminated in direct contact with the base material.
Further, the present invention is a method for producing the laminated body, in which the coating layer is the outermost layer, and the second drug-containing layer is located between the base material and the first drug-containing layer. , These layers are arranged so that the first drug-containing layer is located between the second drug-containing layer and the coating layer, and microencapsulated with the microencapsulated formaldehyde reactant. The first drug-containing layer, which is a foaming layer, is formed by using a composition for forming a first drug-containing layer, which is a mixture of an unmodified formaldehyde reactant and a foaming agent, and microencapsulated formaldehyde. The second drug-containing layer is formed by using a composition for forming a second drug-containing layer, which comprises one or both of a reactant and a formaldehyde reactant that is not microencapsulated. Using a coating layer forming composition in which either one or both of an encapsulated formaldehyde reactant and a non-microencapsulated formaldehyde reactant are blended and the viscosity is 90 mPa · s or more. , Provided is a method for producing a laminated body for forming the coating layer.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a laminate capable of maintaining the effect of removing formaldehyde for a long period of time and a method for producing the same.

It is sectional drawing which shows typically the laminated body of 1st Embodiment of this invention. It is sectional drawing which shows typically the laminated body of 2nd Embodiment of this invention. It is sectional drawing which shows typically the laminated body of 3rd Embodiment of this invention.

<< Laminated body >>
The laminated body of the present invention is a laminated body including a base material, a second drug-containing layer, a first drug-containing layer, and a coating layer, and the second drug-containing layer is the base material. , The first drug-containing layer is arranged between the first drug-containing layer and the second drug-containing layer, and the coating layer is the laminated body. The first drug-containing layer is a microencapsulated formaldehyde reactant (sometimes referred to as "microcapsule" in the present specification) and a non-microencapsulated formaldehyde reactant. (In the present specification, it may be referred to as a "non-microcapsule"), which is a foaming layer, and the second drug-containing layer is a microencapsulated formaldehyde reactant (microcapsule). ) And one or both of a non-microencapsulated formaldehyde reactant (non-microcapsules), and the coating layer is a microencapsulated formaldehyde reactant (microcapsules). Formed using a coating layer forming composition comprising a non-microencapsulated formaldehyde reactant (non-microcapsule) and one or both of them and having a viscosity of 90 mPa · s or higher. It is a thing.

By providing the first drug-containing layer containing both the microcapsules and the non-microcapsules, the laminate of the present invention replaces the first drug-containing layer with the microcapsules. The effect of removing formaldehyde is remarkably superior to that of the case of providing a layer containing either one of the non-microcapsules alone, and the synergistic effect is remarkably excellent. More specifically, the laminate of the present invention can maintain the effect of removing formaldehyde remarkably for a long period of time.
Further, since the first drug-containing layer is a foamed layer, in the laminated body of the present invention, it is possible to impart good designability to the surface of the coating layer.

As will be described later, the first drug-containing layer in the laminate of the present invention can be formed by using the composition for forming the first drug-containing layer, which comprises the microcapsules, the non-microcapsules and the foaming agent.
The first drug-containing layer contains both the microcapsules and the non-microcapsules at the beginning of its formation.

Further, as described above, the laminate of the present invention comprises a second agent-containing layer containing either or both of the microcapsules and the non-microcapsules, whereby such a second agent. The sustainability of the formaldehyde removal effect is higher than that in the case where the content layer is not provided. For example, even if the formaldehyde removing effect of the coating layer described later is lower than the target value, the formaldehyde removing effect of the laminate can be maintained for a long period of time by providing the second agent-containing layer.

As the second drug-containing layer in the laminate of the present invention, as will be described later, a composition for forming a second drug-containing layer in which either one or both of the microcapsules and the non-microcapsules are blended is used. Can be formed.
The second drug-containing layer containing both the microcapsules and the non-microcapsules contains both the microcapsules and the non-microcapsules at the beginning of its formation.

Further, as described above, the laminate of the present invention is formed by using a coating layer forming composition having a viscosity in a specific range, and contains one or both of microcapsules and non-microcapsules. As the outermost layer, the sustainability of the formaldehyde removal effect is higher than that in the case where such an outermost layer is not provided.

The laminate of the present invention may be provided with other layers in addition to the base material, the second drug-containing layer, the first drug-containing layer and the coating layer, and the other layers may be arbitrarily selected depending on the intended purpose. can. For example, the laminate of the present invention includes, as the other layer, a layer containing either one of the microcapsules and the non-microcapsules alone, other than the second drug-containing layer and the coating layer. May be good.

The laminate of the present invention is suitable for being provided on an object for removing formaldehyde, for example, an interior material of a building (for example, wallpaper) or furniture, or a constituent material of the interior material or furniture.
The laminate of the present invention can be provided on a formaldehyde removal target by a known method such as using an adhesive or using a mounting jig.

The shape of the laminated body of the present invention can be arbitrarily selected depending on the intended purpose, and can be, for example, a sheet shape, a plate shape (plate shape), a block shape, or the like.
Hereinafter, the present invention will be described in detail with reference to the drawings.

<First Embodiment>
FIG. 1 is a cross-sectional view schematically showing a laminated body of the first embodiment of the present invention. In addition, in the figure used in the following description, in order to make it easy to understand the features of the present invention, the main part may be enlarged and shown, and the dimensional ratio of each component is the same as the actual one. Is not always the case.

The laminate 1 shown here includes a base material 11, a second drug-containing layer 16, a first drug-containing layer 12, and a coating layer 14.
In the laminated body 1, the second drug-containing layer 16 is arranged between the base material 11 and the first drug-containing layer 12. Further, the first drug-containing layer 12 is arranged between the second drug-containing layer 12 and the coating layer 14. Further, the covering layer 14 is the outermost layer of the laminated body 1. In other words, in the laminated body 1, the base material 11, the second drug-containing layer 16, the first drug-containing layer 12, and the covering layer 14 are laminated in this order in this order, and the covering layer 14 is the laminated body 1. It is the outermost layer.

[Base material]
The base material 11 is preferably in the form of a film or a sheet.

Examples of the material of the base material 11 include paper, resin and the like.
Examples of the paper include high-quality paper, art paper, coated paper, cast-coated paper, resin-coated paper, synthetic paper and the like.
Examples of the resin include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, AS resin, ABS resin, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polyethylene naphthalate. , Polybutylene naphthalate, polyphenylensulfide, polysulfone, polycarbonate, epoxy resin, melamine resin, phenol resin, urea resin, polyurethane, polyimide, ethylene vinyl acetate copolymer resin and other synthetic resins; polybutadiene rubber, styrene / butadiene rubber, acrylonitrile -Examples include synthetic rubbers such as butadiene rubber, butyl rubber, chloroprene rubber, polyisobutylene rubber, ethylene rubber, propylene rubber, and silicon rubber.

The acrylic resin in the base material 11 is a resin having a structural unit derived from (meth) acrylic acid or (meth) acrylic acid ester, and is derived from (meth) acrylic acid or (meth) acrylic acid ester. It may or may not have other structural units other than the structural units.
In addition, in this specification, "(meth) acrylic acid" is a concept including both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth) acrylic acid, for example, "(meth) acryloyl group" is a concept that includes both "acryloyl group" and "methacryloyl group", and "(meth) acrylate". "" Is a concept that includes both "acrylate" and "methacrylate".

Although the base material 11 is shown to be one layer here, it may be only one layer (single layer) or may be a plurality of layers having two or more layers. When the base material 11 has a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.
In the present specification, not only in the case of a base material, "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers are different". It means that only some of the layers may be the same, and "multiple layers are different from each other" means that "at least one of the materials and thicknesses of each layer is different from each other". means.

The thickness of the base material 11 is not particularly limited, but is preferably 40 to 200 μm.
Here, the "thickness of the base material 11" means the thickness of the entire base material 11, for example, the thickness of the base material 11 composed of a plurality of layers is the total of all the layers constituting the base material 11. Means the thickness of.

The basis weight of the base material 11 (mass per surface area 1 m ²⁾ is not particularly limited, is preferably from 20 to 200 g / ^{m 2,} in terms of production cost and mechanical strength, in 70 to 100 / ^{m 2} It is more preferable to have.

[First drug-containing layer]
The first drug-containing layer 12 contains the microcapsules and non-microcapsules and has formaldehyde removing activity. That is, the laminated body 1 has a formaldehyde removing ability because it includes the first drug-containing layer 12.
Further, the first drug-containing layer 12 is a foamed layer and has a large number of fine voids inside thereof. As described above, since the first drug-containing layer 12 is a foamed layer, in the laminated body 1, one surface of the coating layer 14 (sometimes referred to as “first surface” in the present specification) 14a. On the other hand, it is possible to give good design.

In the laminated body 1, the first drug-containing layer 12 is provided on one surface (sometimes referred to as “first surface” in the present specification) 16a of the second drug-containing layer 16.
Further, it can be said that the first drug-containing layer 12 is provided on one surface of the base material 11 (sometimes referred to as the “first surface” in the present specification) 11a, and it can be said that the first drug-containing layer 12 is provided on the base material 11. It is not provided on the other surface (the surface opposite to the first surface, which may be referred to as the "second surface" in the present specification) 11b. That is, the laminated body 1 includes the first drug-containing layer 12 only on the first surface 11a of both surfaces of the base material 11.
Further, the laminated body 1 has both the microcapsules and the non-microcapsules in the first drug-containing layer 12, that is, on the same surface of the base material 11.

From the viewpoint of the components, the first drug-containing layer 12 may contain the microcapsules and the non-microcapsules, and may contain only the microcapsules and the non-microcapsules, or these. It may contain other components other than. Here, the first drug-containing layer 12 is shown as a layer having a clear surface, but for example, in the case of the first drug-containing layer containing only the microcapsules and the non-microcapsules. It may not have such a clear surface.
The microcapsules and non-microcapsules in the first drug-containing layer 12 will be described in detail later.

The microcapsules and non-microcapsules in the first drug-containing layer 12 may be only one type, may be two or more types, and if there are two or more types, the combination and ratio thereof may be arbitrary. You can choose.

The total content of the formaldehyde reactant in the microcapsules and the non-microcapsules (formaldehyde reactants not microencapsulated) in the first drug-containing layer 12 is not particularly limited, but is 1% by mass. The above is preferable, 1.5% by mass or more is more preferable, and 2% by mass or more is particularly preferable.
The upper limit of the total content of the formaldehyde reactant in the microcapsules and the non-microcapsules of the first drug-containing layer 12 is not particularly limited. The total content may be, for example, 24% by mass or less, 21% by mass or less, and 18% by mass or less.
The total content of the formaldehyde reactant and the non-microcapsules in the microcapsules of the first drug-containing layer 12 is within a range set by any combination of the above-mentioned preferable lower limit values and upper limit values. , Can be adjusted as appropriate. For example, a preferable example of the total content is in the range of 1 to 24% by mass.

In the first drug-containing layer 12, [content of formaldehyde reactant in microcapsules (parts by mass)]: [content of non-microcapsules (formula reactant not microencapsulated) (parts by mass)]. The ratio (mass ratio) is preferably 90:10 to 10:90, more preferably 85: 15 to 15:85, and for example, 80:20 to 20:80, 70:30 to 30. : 70, and 60:40 to 40:60 may be used. When the ratio in the first drug-containing layer 12 is in such a range, the formaldehyde removing ability of the laminate 1 is further improved.

The total content of the microcapsules and the non-microcapsules in the first drug-containing layer 12 is not particularly limited, but is preferably 0.5 to 80% by mass, and preferably 1 to 50% by mass. It is more preferably 1 to 30% by mass, and particularly preferably 1 to 30% by mass.

The other components in the first drug-containing layer 12 are not particularly limited and can be arbitrarily selected depending on the intended purpose.
The other components in the first drug-containing layer 12 may be only one kind, two or more kinds, and when two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

Preferred other components include, for example, resins and the like.
Examples of the resin in the first drug-containing layer 12 include the same as the resin in the base material 11.

Examples of the other components include foaming agents and the like. The foaming agent is a component that changes the first agent-containing layer 12 from an unfoamed layer to a foamed layer by its own expansion (foaming). In the present specification, the foaming agent after expansion (foaming) is also referred to as "foaming agent".

The foaming agent may be a known one.
Examples of the foaming agent include chemical foaming agents and microcapsule foaming agents.

Examples of the chemical foaming agent include azodicarbonamide (ADCA), hydrazodicarbonamide (HDCA), p, p'-oxybisbenzenesulponylhydrazide (OBSH), dinitrosopentamethylenetetramine (DPT), and azo. Examples thereof include organic foaming agents such as bisisobutyronitrile (AIBN) and p-toluenesulfonylhydrazide (TSH); and inorganic foaming agents such as sodium hydrogencarbonate.
Moreover, as a chemical foaming agent, a composite foaming agent can also be mentioned. Examples of the composite foaming agent include a mixture of a foaming agent and a component other than the foaming agent (foaming aid, additive, etc.).

The chemical foaming agent in the first agent-containing layer 12 may be only one kind, two or more kinds, and when two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

Examples of the microcapsule foaming agent include a heat-expandable microcapsule foaming agent.
Examples of the heat-expandable microcapsule foaming agent include those in which a shell contains a gas. Examples of such a heat-expandable microcapsule foaming agent include those described in "Patent No. 5092811".

The shell is preferably made of resin (the shell is a polymer shell).
The resin constituting the shell may be either a homopolymer in which one kind of monomer is polymerized or a copolymer in which two or more kinds of monomers are polymerized.
When the resin is a copolymer, the combination and ratio of two or more kinds of monomers constituting the copolymer can be arbitrarily selected.

Examples of the monomer for constituting the resin include nitriles such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, and fumaronitrile; (meth) acrylic acid, itaconic acid, maleic acid, and fumaric acid. Unsaturated carboxylic acids such as citraconic acid; vinylidene chloride; vinyl acetate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid (Meta) acrylic acid esters such as tert-butyl, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, β-carboxyethyl acrylate; styrene, α-methylstyrene, chlorostyrene, etc. Acrylic acid or a derivative thereof; acrylamide such as acrylamide, substituted acrylamide, methacrylicamide, substituted methacrylicamide or a derivative thereof; butadiene and the like.

Examples of the gas contained in the shell include components that are gaseous at a temperature equal to or lower than the softening point of the resin (shell).

Examples of the gas include propane, n-butane, isobutane (2-methylpropane), n-pentane, isopentan (2-methylbutane), neopentane (2,2-dimethylpropane), hexane, heptane, octane, and isooctane (. 2,2,4-trimethylpentane), chain alkanes such as decane; cyclic alkanes such as cyclopentane; petroleum ethers; alkanes such as propene (propylene) and butene; hydrocarbons such as.

The gas contained in one shell may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

The microcapsule foaming agent can be produced by a known method.
For example, the heat-expandable microcapsule foaming agent can be produced by polymerizing the monomer with a polymerization initiator in the coexistence of the gas. The monomer may be polymerized in the coexistence of an arbitrary component such as a cross-linking agent.
As the polymerization initiator and the cross-linking agent, known ones can be used.

The microcapsule foaming agent in the first agent-containing layer 12 may be of only one type, may be of two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When two or more kinds of heat-expandable microcapsule foaming agents are used in the first drug-containing layer 12, for example, as described in "Patent No. 5092811", the heat-expandable microcapsule foaming agent a and the heat expansion It is preferable to use the sex microcapsule foaming agent b.
The heat-expandable microcapsule foaming agent a has an average particle size of 5 to 35 μm, a gas encapsulation rate of 10 to 35%, and a shell film thickness of 0.03 to 0.10 μm at the time of maximum foaming. ..
The heat-expandable microcapsule foaming agent b has an average particle size of 5 to 35 μm, a gas encapsulation rate of 10 to 35%, and a shell film thickness of 0.10 to 0.25 μm at the time of maximum foaming. ..

As used herein, the term "raw grain of a heat-expandable microcapsule foaming agent" means a heat-expandable microcapsule foaming agent before expansion (foaming).
Further, the "gas inclusion ratio (%) of the heat-expandable microcapsule foaming agent" is a volume standard (volume%), and the gas inclusion of the heat-expandable microcapsule foaming agent with respect to the volume of the heat-expandable microcapsule foaming agent. It means the ratio of quantity (volume). The amount of gas contained in the heat-expandable microcapsule foaming agent is, for example, the amount of water is subtracted from the amount of volatile components generated by adding an organic solvent to the heat-expandable microcapsule foaming agent, swelling the shell and destroying it at a high temperature. It is required by that.

In the first drug-containing layer 12, the content ratio (mass ratio) of [content (mass) of heat-expandable microcapsule foaming agent a] / [content (mass) of heat-expandable microcapsule foaming agent b] is Although not particularly limited, for example, it may be preferably 9/1 to 1/9, and may be any of 9 / 1-3 / 7, 9/1 to 5/5, and 9/1 to 7/3. You may.

When the first agent-containing layer 12 contains a foaming agent, it may further contain a filler, an additive, or the like as the other components.

The filler may be either an organic filler or an inorganic filler, but is preferably an inorganic filler.
Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, barium hydroxide, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, ferrous hydroxide, basic zinc carbonate, basic lead carbonate, and silica sand. , Clay, talc, silica, titanium dioxide, magnesium silicate and the like.

Examples of the additive include known additives such as a dispersant, an antifoaming agent, a blocking inhibitor, a wetting agent, a pigment, a thickener, and a surfactant.

The content of the other component in the first drug-containing layer 12 is not particularly limited, and may be appropriately selected depending on the type of the other component.
For example, when the other component is the resin, the content of the resin in the first drug-containing layer 12 is preferably 10 to 80% by mass, more preferably 30 to 70% by mass. It is particularly preferably 40 to 60% by mass. When the content of the resin is at least the lower limit value, the effect of using the resin can be obtained more remarkably. Further, when the content of the resin is not more than the upper limit value, the formaldehyde removing ability of the laminate 1 is further improved.

When the first drug-containing layer 12 contains a chemical foaming agent, the content of the chemical foaming agent in the first drug-containing layer 12 is preferably 1 to 40% by mass, preferably 5 to 15% by mass. More preferred. When the content of the chemical foaming agent is at least the lower limit, the foaming state of the first agent-containing layer 12 becomes better. When the content of the chemical foaming agent is not more than the upper limit, the strength of the first agent-containing layer 12 is further improved.

When the first drug-containing layer 12 contains a microcapsule foaming agent, the content of the microcapsule foaming agent in the first drug-containing layer 12 is preferably 0.1 to 30% by mass, preferably 4 to 15% by mass. Is more preferable. When the content of the microcapsule foaming agent is at least the lower limit value, the foaming state of the first drug-containing layer 12 becomes better. When the content of the microcapsule foaming agent is not more than the upper limit, the strength of the first drug-containing layer 12 is improved.
For example, when the first drug-containing layer 12 contains two or more kinds of microcapsule foaming agents, such as containing a heat-expandable microcapsule foaming agent a and a heat-expandable microcapsule foaming agent b, these two types are contained. The total content of the above microcapsule foaming agents (for example, the total content of the heat-expandable microcapsule foaming agent a and the heat-expandable microcapsule foaming agent b) can be set within the above-mentioned numerical range.

When the first drug-containing layer 12 contains a filler, the content of the filler in the first drug-containing layer 12 is preferably 10 to 60% by mass.
When the first drug-containing layer 12 contains an additive, the content of the additive in the first drug-containing layer 12 is preferably 1 to 10% by mass.

Although the first drug-containing layer 12 is shown here as one layer, it may be only one layer (single layer) or may be a plurality of layers having two or more layers. When the first drug-containing layer 12 is a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

The thickness of the first drug-containing layer 12 is not particularly limited, but is preferably 50 to 800 μm.
Here, the "thickness of the first drug-containing layer 12" means the thickness of the entire first drug-containing layer 12, and for example, the thickness of the first drug-containing layer 12 composed of a plurality of layers is the first. It means the total thickness of all the layers constituting the drug-containing layer 12.
The state of the first drug-containing layer 12 is one, such as when the surface of the first drug-containing layer 12 has a high degree of unevenness or when the first drug-containing layer 12 does not have a clear surface as described above. If this is not the case, the height of the highest portion of the first drug-containing layer 12 from the first surface 16a of the second drug-containing layer 16 may be the thickness of the first drug-containing layer 12.

The amount of the first drug-containing layer 12 formed on the second drug-containing layer 16 is not particularly limited, but is preferably 5 to ^{60 g / m 2 · dry.}

[Coating layer]
The coating layer 14 is provided on one surface (sometimes referred to as “first surface” in the present specification) 12a of the first drug-containing layer 12 in the laminated body 1, and is provided on the first surface of the base material 11. It is the outermost layer on the 1st surface 11a side. The coating layer 14 protects the entire structure of the laminated body 1 by suppressing physical damage, chemical deterioration, and the like of the laminated body 1.

Further, the coating layer 14 was formed by using a coating layer forming composition in which one or both of the microcapsules and the non-microcapsules were blended and the viscosity was 90 mPa · s or more. It is a thing. That is, the coating layer 14 contains either one or both of the microcapsules and non-microcapsules. The coating layer 14 containing both the microcapsules and the non-microcapsules is the same layer as the first drug-containing layer 12.

As described above, the coating layer 14 has a formaldehyde removing activity, and the laminate 1 also has a formaldehyde removing ability even if the covering layer 14 is provided.
When the coating layer 14 contains both the microcapsules and the non-microcapsules, the laminate 1 is placed on the same surface of the base material 11 separately from the microcapsules in the first drug-containing layer 12. You will have both capsules and non-microcapsules.

The microcapsules and non-microcapsules in the coating layer 14 are both similar to the microcapsules and non-microcapsules in the first drug-containing layer 12, and these will be described in detail later.

The microcapsules and non-microcapsules in the coating layer 14 may be of only one type, may be two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The microcapsules and non-microcapsules in the coating layer 14 are of the same type as the microcapsules and non-microcapsules in the first drug-containing layer 12 constituting the same laminate 1 together with the coating layer 14. It may be a different kind.

When the coating layer 14 is a layer similar to the first drug-containing layer, that is, when it contains both the microcapsules and the non-microcapsules, the formaldehyde reactant in the microcapsules and the non-microcapsules. (Unmicroencapsulated formaldehyde reactant) and total content, and [Content of formaldehyde reactant in microcapsules (parts by mass)]: [Non-microcapsules (not microencapsulated) The ratio (mass ratio) of the content (parts by mass) of the formaldehyde reactant) can be the same as in the case of the first drug-containing layer 12.

On the other hand, when the coating layer 14 contains either the microcapsules or the non-microcapsules alone, the formaldehyde reactant in the microcapsules of the coating layer 14 or the non-microcapsules (microencapsulation). The content of the formaldehyde reactant () is not particularly limited, but is preferably 3% by mass or more, more preferably 4% by mass or more, and particularly preferably 5% by mass or more.
The upper limit of the content of the formaldehyde reactant or the non-microcapsule in the microcapsules of the coating layer 14 is not particularly limited. The content may be, for example, 24% by mass or less, 21% by mass or less, and 18% by mass or less.
The content of the formaldehyde reactant or the non-microcapsule in the microcapsules of the coating layer 14 can be appropriately adjusted within a range set by any combination of the above-mentioned preferable lower limit values and upper limit values. For example, a preferable example of the content is in the range of 3 to 24% by mass.

The coating layer 14 may contain either one or both of the microcapsules and the non-microcapsules, but preferably contains other components, and the other components include. It preferably contains a resin.

The components other than the resin in the coating layer 14 are not particularly limited and can be arbitrarily selected depending on the intended purpose.

The other components in the coating layer 14 may be only one kind, two or more kinds, and when two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

Examples of the resin in the coating layer 14 include the same resins as those in the base material 11.

That is, the coating layer 14 is made of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, AS resin, ABS resin, in addition to one or both of the microcapsules and non-microcapsules. , Polyethylene, Polyacetal, Polyethylene terephthalate, Polybutylene terephthalate, Polytrimethylene terephthalate, Polyethylene naphthalate, Polybutylene naphthalate, Polyphenylene sulfide, Polysulfone, Polycarbonate, Epoxy resin, Melamine resin, Phenolic resin, Urea resin, Polyurethane, Polyethylene, One or more selected from the group consisting of ethylene vinyl acetate copolymer resin, polybutadiene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, butyl rubber, chloroprene rubber, polyisobutylene rubber, polyethylene rubber, propylene rubber and silicon rubber. Is preferably contained.

The SP value (dissolution parameter) of the resin in the coating layer 14 ^{is preferably 3 to} 17 (cal / cm 3) ^1/2 , and more preferably 4 to 15 (cal / cm ³ ) ^1/2. , 5 to 13 (cal / cm ³ ) ^1/2 , more preferably 6 to 11 (cal / cm ³ ) ^1/2 . When the SP value of the resin is within such a range, as will be described later, in the coating layer forming composition, the aggregation of the resin is suppressed and the effect of sufficiently dispersing the resin becomes higher.

The total content of the microcapsules and the non-microcapsules in the coating layer 14 is not particularly limited, but is preferably 0.5 to 80% by mass, more preferably 1 to 50% by mass. It is particularly preferably 1 to 30% by mass.

The content of the other component in the coating layer 14 is not particularly limited, and may be appropriately selected depending on the type of the other component.
For example, when the other component is the resin, the content of the resin in the coating layer 14 is preferably 5 to 60% by mass, more preferably 9 to 45% by mass, and 13 to 30%. It is particularly preferable to be% by mass. When the content of the resin is at least the lower limit value, the effect of using the resin can be obtained more remarkably. Further, when the content of the resin is not more than the upper limit value, the formaldehyde removing ability of the laminate 1 is further improved.

The coating layer 14 may be colored or colorless, transparent, translucent or opaque, and can be arbitrarily adjusted according to the intended purpose.

Although the covering layer 14 is shown here as one layer, it may be only one layer (single layer) or may be a plurality of layers having two or more layers. When the covering layer 14 is a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited.
When the coating layer 14 is a plurality of layers, only a part of these plurality of layers may be the first drug-containing layer, all of them may be the first drug-containing layer, and all of them may be the first drug-containing layer. It does not have to be.

The thickness of the coating layer 14 is not particularly limited, but is preferably 1 to 50 μm.
Here, the "thickness of the coating layer 14" means the thickness of the entire coating layer 14, and for example, the thickness of the coating layer 14 composed of a plurality of layers is the total of all the layers constituting the coating layer 14. Means the thickness of.

Since the coating layer 14 is formed by using a coating layer forming composition having a viscosity of 90 mPa · s (90 cps) or more, the laminate 1 can maintain the formaldehyde removing effect for a long period of time. The method for forming the coating layer using the coating layer forming composition will be described in detail later.
As used herein, the term "viscosity" means a measured value measured at 23 ° C. using a B-type viscometer, unless otherwise specified.

In that the above effect becomes more remarkable, the viscosity of the coating layer forming composition is, for example, 400 mPa · s or more, 800 mPa · s or more, 1200 mPa · s or more, 1600 mPa · s or more, 2000 mPa · s or more, and 2400 mPa. -It may be any one of s or more.
Further, in that the above effect becomes more remarkable, the viscosity of the coating layer forming composition is, for example, 28000 mPa · s (28000 cps) or less, 21000 mPa · s or less, 14200 mPa · s or less, 12000 mPa · s or less, 10,000 mPa ·. It may be any one of s or less, 8000 mPa · s or less, 6000 mPa · s or less, and 5000 mPa · s or less.
The viscosity of the coating layer forming composition can be appropriately adjusted within a range set by any combination of the above-mentioned preferable lower limit values and upper limit values.

As will be described later, the more the variation in the thickness of the coating layer 14 is suppressed and the higher the uniformity, the higher the sustainability of the formaldehyde removing effect of the laminate 1 tends to be.
The height of uniformity of the coating layer 14 is, for example, the surface roughness Ra (in the present specification, it may be simply referred to as “Ra”) and the maximum height roughness of the first surface 14a of the coating layer 14. (Rz) (in the present specification, it may be simply referred to as "Rz") can be used as an index for determination.
In addition, in this specification, "surface roughness (Ra)" means the thing measured in accordance with JIS B0601: 2001 (ISO4287: 1997), and "maximum height roughness (Rz)" means. It means the one measured according to JIS B 0601: 1994.

The surface roughness (Ra) of the first surface 14a of the coating layer 14 is, for example, 0 μm or more and less than 25 μm, 0 μm or more and less than 17 μm, 0 μm or more and less than 12 μm, 0 μm or more and less than 7 μm, 0 μm or more and less than 2 μm, and 0 μm or more and less than 1 μm. It may be either. However, these are examples of the surface roughness (Ra) of the first surface 14a of the covering layer 14.

The maximum height roughness (Rz) of the first surface 14a of the coating layer 14 is, for example, 0 μm or more and less than 80 μm, 0 μm or more and less than 60 μm, 0 μm or more and less than 45 μm, 0 μm or more and less than 30 μm, 0 μm or more and less than 18 μm, 0 μm or more and less than 10 μm. , 0 μm or more and less than 5 μm, and 0 μm or more and less than 1 μm.

[Second drug-containing layer]
The second drug-containing layer 16 contains either one or both of the microcapsules and non-microcapsules, and has formaldehyde removing activity. That is, the laminated body 1 also has a formaldehyde removing ability even if it includes the second drug-containing layer 16.
When the second drug-containing layer 16 contains both the microcapsules and the non-microcapsules, the laminate 1 is placed on the same surface of the base material 11 separately from those in the first drug-containing layer 12. , The microcapsules and non-microcapsules are both included.

In the laminated body 1, the second drug-containing layer 16 is provided on one surface of the base material 11 (sometimes referred to as the “first surface” in the present specification) 11a, and the other surface of the base material 11 is provided. Is not provided on the surface (the surface opposite to the first surface, which may be referred to as the "second surface" in the present specification) 11b. That is, the laminated body 1 includes the second drug-containing layer 16 only on the first surface 11a of both surfaces of the base material 11.

Although the second drug-containing layer 16 is shown here as a layer having a clear surface, for example, the second drug containing only one or both of the microcapsules and the non-microcapsules. In the case of the containing layer, it may not have such a clear surface.

The second drug-containing layer 16 may be a foamed layer similar to the first drug-containing layer 12 or a non-foamed layer similar to the covering layer 14, but is preferably a non-foamed layer. .. Since the second agent-containing layer 16 is a non-foaming layer, the sustainability of the formaldehyde removing effect of the laminate 1 becomes higher.

As shown here, the second drug-containing layer 16 is preferably laminated in direct contact with the base material 11. In such a laminated body 1, the sustainability of the formaldehyde removing effect becomes higher.

Although the second drug-containing layer 16 is shown here as one layer, it may be only one layer (single layer) or may be a plurality of layers having two or more layers. When the second agent-containing layer 16 is a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

The thickness of the second drug-containing layer 16 is not particularly limited, but is preferably 0.5 to 10 μm, and more preferably 1 to 3 μm.
Here, the "thickness of the second drug-containing layer 16" means the thickness of the entire second drug-containing layer 16, and for example, the thickness of the second drug-containing layer 16 composed of a plurality of layers is the second. It means the total thickness of all the layers constituting the drug-containing layer 16.
The state of the second drug-containing layer 16 is one, such as when the surface of the second drug-containing layer 16 has a high degree of unevenness or when the second drug-containing layer 16 does not have a clear surface as described above. If this is not the case, the height of the highest portion of the second drug-containing layer 16 from the first surface 11a of the base material 11 may be the thickness of the second drug-containing layer 16.

The surface roughness (Ra) and maximum height roughness (Rz) of the first surface 16a of the second agent-containing layer 16 may be the same as in the case of the first surface 14a of the coating layer 14, and so on. It does not have to be.

The viscosity of the composition for forming the second drug-containing layer used for forming the second drug-containing layer 16 is different from the viscosity of the composition for forming the coating layer described above, and is not particularly limited.

The second agent-containing layer 16 can be the same as the coating layer 14 except for the above points.

As described above, the first drug-containing layer 12 is a foamed layer, and the laminate 1 has a lower sustainability of the formaldehyde removing effect than the case where the first drug-containing layer 12 is a non-foamed layer. There is.
Further, when the variation in the thickness of the coating layer 14 is suppressed and the uniformity is high, the sustainability of the formaldehyde removing effect of the laminate 1 tends to be higher. In other words, if the uniformity of the coating layer 14 is low, the sustainability of the formaldehyde removing effect of the laminate 1 may be low.
As described above, in the laminated body 1, the first drug-containing layer 12 and the coating layer 14 may affect the sustainability of the formaldehyde removal effect, although the degree is low.
However, since the laminate 1 is provided with the second agent-containing layer 16 having a formaldehyde removing ability, the above-mentioned influence is remarkably alleviated, and the sustainability of the formaldehyde removing effect is stable and high. It has become. The effect of such a second drug-containing layer will be described in more detail later.

The laminated body of the present embodiment is not limited to the one shown in FIG. 1, and a part of the structure shown in FIG. 1 is changed, deleted or added within the range not impairing the effect of the present invention. There may be.

For example, the laminate 1 shown in FIG. 1 includes a first drug-containing layer 12 and a coating layer 14 on a base material 11, but the laminate of the present embodiment includes other layers other than these. May be good.
The other layers are not particularly limited, and the type, thickness, and the like can be arbitrarily selected depending on the intended purpose.
For example, the laminate 1 is a first drug-containing layer that is not adjacent to any of the first drug-containing layer 12, the coating layer 14, and the second drug-containing layer 16 as the other layer; the microcapsules and non-microcapsules. A layer containing any one of the agents alone and not adjacent to either the coating layer 14 or the second agent-containing layer 16; a printing layer or the like may be provided as one layer or two or more layers.

Further, the laminated body 1 may separately have another layer on the second surface 11b of the base material 11. Examples of the other layer on the second surface 11b include those similar to any layer on the first surface 11a.
For example, when a layer having a formaldehyde removing ability is provided on the second surface 11b, this layer has the same form as the first drug-containing layer 12 or the second drug-containing layer 16 on the first surface 11a. It may be the same as or different from the first drug-containing layer 12 or the second drug-containing layer 16 on the first surface 11a.

Further, the laminate 1 shown in FIG. 1 may be provided with another base material on the second surface 11b of the base material 11 in addition to the base material 11. The other base material may have the same form as the base material 11, and may be the same as or different from the base material 11. Then, the other base material may be laminated on the base material 11 via an adhesive layer.

Further, the laminate 1 shown in FIG. 1 is provided with a plurality of layers of the base material 11 or on the second surface 11b of the base material 11 with another base material separately from the base material 11. In some cases, a second agent-containing layer may be provided between the plurality of layers of the base materials.

<Second Embodiment>
FIG. 2 is a cross-sectional view schematically showing the laminated body of the second embodiment of the present invention.
In addition, in the drawings after FIG. 2, the same components as those shown in the already explained figures are designated by the same reference numerals as in the case of the already explained figures, and detailed description thereof will be omitted.

The laminate 2 shown in FIG. 2 includes a base material 21, a second drug-containing layer 26, a resin layer 22, a printing layer 23, and a coating layer 24.
In the laminated body 2, the second drug-containing layer 26 is arranged between the base material 21 and the resin layer 22. Further, the resin layer 22 and the printing layer 23 are arranged between the base material 21 and the coating layer 24. The coating layer 24 is the outermost layer of the laminate 2, and the resin layer 22 is arranged closer to the base material 21 than the printing layer 23. In other words, in the laminated body 2, the base material 21, the second drug-containing layer 26, the resin layer 22, the printing layer 23 and the coating layer 24 are laminated in this order in this order, and the coating layer 24 is the laminated body 2. It is the outermost layer of.
The base material 21 has a two-layer structure in which the first base material 211 and the second base material 212 are laminated. The first base material 211 is arranged on the side of the second drug-containing layer 26 with respect to the second base material 212.

Further, in the laminated body 2, one or both of the resin layer 22 and the printed layer 23 contains a layer corresponding to the first drug-containing layer 12 in the laminated body 1, that is, the microcapsules and the non-microcapsules. It is a foaming layer (first drug-containing layer) having an activity of removing formaldehyde.

Further, the coating layer 24 is a layer corresponding to the coating layer 14 in the laminated body 1, and is composed of one or both of the microcapsules and the non-microcapsules, and has a viscosity of 90 mPa · s or more. It is formed by using a certain composition for forming a coating layer. That is, the coating layer 24 contains either one or both of the microcapsules and the non-microcapsules, and has formaldehyde removing activity. The coating layer 24 containing both the microcapsules and the non-microcapsules is the same layer as the first drug-containing layer 12 in the laminate 1.

Further, the second drug-containing layer 26 is a layer corresponding to the second drug-containing layer 16 in the laminated body 1, and contains either one or both of the microcapsules and the non-microcapsules, and has an activity of removing formaldehyde. Has.

As shown here, the second drug-containing layer 26 is directly in contact with and laminated on the base material 21. In such a laminated body 2, the sustainability of the formaldehyde removing effect is higher.

As described above, the laminate 2 is provided with the first drug-containing layer (one or both of the resin layer 22 and the printing layer 23), the second drug-containing layer 26, and the coating layer 24, so that the layered body 2 has a formaldehyde removing ability. Has.

In the laminated body 2, it is preferable that at least the resin layer 22 is the first drug-containing layer.

Further, in the laminated body 2, the one surface of the coating layer 24 (sometimes referred to as the “first surface” in the present specification) 24a has an opening, and the other surface of the second base material 212 has an opening. One or more through holes 20 are provided to reach the surface (sometimes referred to as the "first surface" in the present specification) 212a.

The laminated body 2 corresponds to the laminated body 1 shown in FIG. 1, which is provided with the other layer, further separately provided with another base material on the base material, and further provided with through holes.

In the laminate 2, the second drug-containing layer 26 is one surface of the base material 21 (sometimes referred to as the “first surface” in the present specification) 21a, in other words, one of the first base materials 211. Provided on a surface (sometimes referred to as the "first surface" in the present specification) 211a and the other surface of the substrate 21 (sometimes referred to as the "second surface" in the present specification). 21b, in other words, is not provided on one surface of the second substrate 212 (sometimes referred to herein as the "second surface") 212b. That is, the laminated body 2 includes the second drug-containing layer only on the first surface 21a of both surfaces of the base material 21.

In the laminated body 2, the first drug-containing layer is provided on one surface (sometimes referred to as “first surface” in the present specification) 26a of the second drug-containing layer 26.
Further, it can be said that the first drug-containing layer is provided on the first surface 21a of the base material 21 (first surface 211a of the first base material 211), and the second surface 21b (first surface 21b) of the base material 21 can be said to be provided. 2 Not provided on the second surface 212b) of the base material 212. That is, the laminated body 2 includes the first drug-containing layer only on the first surface 21a of both surfaces of the base material 21.

The laminate 2 has both the microcapsules and the non-microcapsules in the first drug-containing layer (either one or both of the resin layer 22 and the printing layer 23), that is, on the same surface of the base material 21.
When the coating layer 24 contains both the microcapsules and the non-microcapsules, the laminate 2 is placed on the same surface of the base material 21 separately from those in the first drug-containing layer. It will have both the microcapsules and the non-microcapsules.
Further, when the second drug-containing layer 26 contains both the microcapsules and the non-microcapsules, the laminate 2 is on the same surface of the base material 21 as the one in the first drug-containing layer. Separately, it will have both the microcapsules and the non-microcapsules.

[Base material]
The base material 21, that is, the first base material 211 and the second base material 212 are both preferably in the form of a film or a sheet.

Both the first base material 211 and the second base material 212 can be the same as the base material 11 in the laminated body 1.
The second base material 212 may be made of the same material as the first base material 211, or may be made of a different material.

By using a material different from that of the first base material 211 for the second base material 212, the characteristics of the laminated body 2 can be adjusted. For example, by making the second base material 212 have a formaldehyde trapping ability, the formaldehyde removing ability of the laminate 2 can be further improved. Examples of the material having the ability to capture formaldehyde include gypsum and the like. That is, in the present embodiment, as the material of the second base material 212, gypsum and the like can be further mentioned in addition to those mentioned as the material of the base material 11 in the laminated body 1.
When the second base material 212 is made of a material having a formaldehyde trapping ability such as gypsum, the thickness thereof is preferably 40 to 12000 μm, for example.

[Resin layer]
The resin layer 22 may be at least a layer containing a resin, but as described above, it is preferably a first drug-containing layer containing the microcapsules and non-microcapsules and being a foamed layer. ..

The resin in the resin layer 22 is not particularly limited, and preferred ones include, for example, the same as the resin in the base material 11 of the laminate 1 (in other words, the resin in the coating layer 14 of the laminate 1). ..

The resin in the resin layer 22 may be of only one type, may be of two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When the resin layer 22 is not the first drug-containing layer, the content of the resin in the resin layer 22 is preferably 80% by mass or more, more preferably 90% by mass or more, and 97% by mass or more. It is particularly preferable to have. When the content of the resin is at least the lower limit value, the effect of using the resin can be obtained more remarkably.
On the other hand, when the resin layer 22 is not the first drug-containing layer, the content of the resin in the resin layer 22 is 100% by mass or less.

When the resin layer 22 is the first drug-containing layer, the content of the resin in the resin layer 22 can be the same as the content of the resin in the first drug-containing layer 12 in the laminate 1.

When the resin layer 22 is the first drug-containing layer, the microcapsules and the non-microcapsules in the resin layer 22 are all the same as the microcapsules and the non-microcapsules in the laminate 1.
The microcapsules and non-microcapsules in the resin layer 22 may be of only one type, may be of two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

When the resin layer 22 is the first drug-containing layer, the total content of the formaldehyde reactant in the microcapsules and the non-microcapsules (non-microencapsulated formaldehyde reactants) in the resin layer 22. , And [Contents of formaldehyde reactant in microcapsules (parts by mass)]: [Contents of non-microcapsules (formulum reactants not microencapsulated) (parts by mass)] ratio (mass ratio) ) Can be the same as in the case of the first drug-containing layer 12 in the laminated body 1.

The resin layer 22 may contain other components that do not fall under any of the resin, microcapsules and non-microcapsules.
The other components in the resin layer 22 are not particularly limited and can be arbitrarily selected depending on the intended purpose.
The other components in the resin layer 22 may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

The total content of the resin, microcapsules and non-microcapsules in the resin layer 22 is not particularly limited, but is preferably 60% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass. % Or more is particularly preferable, and for example, it may be any one of 90% by mass or more, 93% by mass or more, 95% by mass or more, and 97% by mass or more.
The upper limit of the total content of the resin, microcapsules and non-microcapsules in the resin layer 22 is not particularly limited. The total content may be, for example, 100% by mass or less, 99% by mass or less, and 98% by mass or less.
The total content of the resin, microcapsules and non-microcapsules in the resin layer 22 can be appropriately adjusted within a range set by any combination of the above-mentioned preferable lower limit values and upper limit values. For example, a preferable example of the total content is in the range of 60 to 100% by mass.

The resin layer 22 may be, for example, a foamed resin layer or a non-foamed resin layer.
The laminated body 2 in which the resin layer 22 is a foamed resin layer can improve the design as in the case of the laminated body 1.
Further, the laminate 2 in which the resin layer 22 is a foamed resin layer and is the first drug-containing layer can further improve the formaldehyde removing ability.

When the resin layer 22 is a foamed resin layer and is a first drug-containing layer, the resin layer 22 is further composed of natural zeolite, acidic clay, diatomaceous earth, and synthetic zeolite, in addition to the resin, microcapsules, and non-microcapsules. , Artificial zeolite, activated charcoal, titanium oxide and phosphate may contain one or more inorganic compounds selected from the group. The inorganic compound itself is capable of adsorbing formaldehyde, and may be capable of improving the reactivity of the microcapsules and non-microcapsules with formaldehyde. Therefore, the laminate 2 provided with such a resin layer 22 has a higher formaldehyde removing ability.

When the resin layer 22 contains the inorganic compound, the content of the inorganic compound in the resin layer 22 is not particularly limited, but is preferably 0.1 to 10% by mass.

When the resin layer 22 is a foamed resin layer and is a first drug-containing layer, the resin layer 22 is a laminate 1 as the other component in addition to the resin, the microcapsules and the non-microcapsules. It may contain the same foaming agent as in the case.

When the resin layer 22 is a foamed resin layer and is a first drug-containing layer, the content of the other components in the resin layer 22 is the same as the content of the other components in the first drug-containing layer 12 in the laminate 1. It may be similar.

The resin layer 22 may be provided on the entire surface of the first surface 21a of the base material 21 (first surface 211a of the first base material 211), or may be provided only in a part of the region. It is preferable that it is provided on the entire surface.

Although the resin layer 22 is shown here as one layer, it may be only one layer (single layer) or may be a plurality of layers having two or more layers. When the resin layer 22 is a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.
When the resin layer 22 is a plurality of layers, only a part of these plurality of layers may be the first drug-containing layer, all of them may be the first drug-containing layer, and all of them may be the first drug-containing layer. It does not have to be.

The thickness of the resin layer 22 is not particularly limited, but is preferably 50 to 800 μm.
Here, the "thickness of the resin layer 22" means the thickness of the entire resin layer 22, and for example, the thickness of the resin layer 22 composed of a plurality of layers is the total of all the layers constituting the resin layer 22. Means the thickness of.
The thickness of the resin layer 22 may be specified in the same manner as in the case of the first drug-containing layer 12.

[Print layer]
The print layer 23 is for imparting information, designability, etc. to the laminated body 2.
The print layer 23 may be provided on the entire surface of one surface of the resin layer 22 (sometimes referred to as a “first surface” in the present specification) 22a, or may be provided only in a part of the area. It may be patterned or may not be patterned when it is provided only in a part of the region. When the print layer 23 is patterned, the pattern is not particularly limited and can be arbitrarily selected depending on the intended purpose.

When the printed layer 23 is the first drug-containing layer, the total content of the formaldehyde reactant in the microcapsules and the non-microcapsules (non-microencapsulated formaldehyde reactant) of the printed layer 23. , And [Contents of formaldehyde reactant in microcapsules (parts by mass)]: [Contents of non-microcapsules (formulum reactants not microencapsulated) (parts by mass)] ratio (mass ratio) ) Can be the same as in the case of the first drug-containing layer 12 in the laminated body 1.

Although the print layer 23 is shown here as one layer, it may be only one layer (single layer) or may be a plurality of layers having two or more layers. When the print layer 23 is a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited. Further, the print layer 23 may have regions in which the colors are different from each other in one layer.
When the printing layer 23 is a plurality of layers, only a part of these plurality of layers may be the first drug-containing layer, all of them may be the first drug-containing layer, and all of them may be the first drug-containing layer. It does not have to be.

The thickness of the print layer 23 is not particularly limited, but is preferably 1 to 10 μm.
Here, the "thickness of the print layer 23" means the thickness of the entire print layer 23, and for example, the thickness of the print layer 23 composed of a plurality of layers is the total of all the layers constituting the print layer 23. Means the thickness of.

[Coating layer]
As described above, the covering layer 24 is provided with a through hole 20.

When the print layer 23 is provided on the entire surface of the first surface 22a of the resin layer 22, the coating layer 24 may be referred to as one surface of the print layer 23 (referred to as the "first surface" in the present specification. There is) Cover the entire surface of 23a. When the print layer 23 is provided only in a part of the first surface 22a of the resin layer 22, the coating layer 24 includes the entire surface of the first surface 23a of the print layer 23 and the print layer 23. Covers the exposed surface of any layer on the substrate 21 that is not provided. Here, examples of the exposed surface include the first surface 22a of the resin layer 22 and the like.

The coating layer 24 may be colored or colorless, transparent, translucent or opaque, and can be arbitrarily adjusted according to the intended purpose. However, in order to make the print layer 23 recognizable, the coating layer 24 is preferably transparent or translucent.

The coating layer 24 is the same layer as the coating layer 14 in the laminated body 1 except for the above points. Therefore, further detailed description of the covering layer 24 will be omitted.

As described above, in the laminated body 2, there are one or more through holes 20 having an opening in the first surface 24a of the coating layer 24 and reaching the first surface 212a of the second base material 212. It is provided.
The laminate 2 does not have to have the through hole 20, but if it does, the formaldehyde removing ability is further improved. This is because the formaldehyde to be removed easily reaches the second drug-containing layer. Further, when the second base material 212 has a formaldehyde trapping ability such as one made of gypsum, the action of the second base material 212 further improves the formaldehyde removing ability of the laminate 2. improves.

The end (opening) of the through hole 20 opposite to the opening may end at a portion overlapping the first surface 212a of the second base material 212, or may pass through the first surface 212a. It may reach the inside of the second base material 212.

The hole diameter of the through hole 20 is not particularly limited, but is preferably 10 to 1000 μm.
In addition, in this specification, "the hole diameter of a through hole" means "the hole diameter of a through hole in the cross section in the direction perpendicular to the longitudinal direction of a through hole".

The number of through holes 20 is not particularly limited, but is preferably ^{500 to 100,000 / m 2.}

Here, an example is shown in which the through hole 20 reaches a portion overlapping the first surface 212a of the second base material 212, but the through hole 20 reaches at least the second drug-containing layer. Just do it. The end (opening) of the through hole 20 on the side opposite to the opening may be terminated at a portion overlapping the surface of the second drug-containing layer far from the base material 21, or the surface. It may reach the inside of the second drug-containing layer through the above.

Further, here, an example is shown in which the hole diameter of the through hole 20 becomes smaller as the distance from the opening of the through hole 20 to the opposite end increases, but the hole diameter of the through hole 20 is shown. May increase as the distance increases, may change irregularly rather than regularly as the distance increases, or may be constant regardless of the distance. good.

The laminated body of the present embodiment is not limited to the one shown in FIG. 2, and a part of the structure shown in FIG. 2 is changed, deleted or added within the range not impairing the effect of the present invention. There may be.

For example, in the laminate 2 shown in FIG. 2, either the resin layer 22 or the printing layer 23 may be a layer containing either one of the microcapsules and the non-microcapsules alone.

Further, for example, in the laminate 2 shown in FIG. 2, the second chemical-containing layer 26, the resin layer 22, and the printing layer 23 are placed on the first surface 21a of the base material 21 (the first surface 211a of the first base material 211). And other layers may be provided in addition to the covering layer 24.
The other layers are not particularly limited, and the type, thickness, and the like can be arbitrarily selected depending on the intended purpose.
For example, as the other layer, the laminate 2 is not adjacent to any one of the resin layer 22 and the printing layer 23, which are the first drug-containing layers, the second drug-containing layer 26, and the coating layer 24. 1 drug-containing layer; 1 layer or 2 layers containing either one of the microcapsules and the non-microcapsules alone and not adjacent to either the coating layer 24 or the second drug-containing layer 26. You may have the above.
When the through hole 20 is provided in the laminated body 2, the through hole 20 is also provided in the other layer as needed.

Further, the laminated body 2 may separately have another layer on the second surface 21b of the base material 21 (the second surface 212b of the second base material 212). Examples of the other layer on the second surface 21b include those similar to any layer on the first surface 21a.
For example, when any one or more of the second agent-containing layer, the resin layer, the printing layer and the coating layer is provided on the second surface 21b, these layers are the second agent on the first surface 21a. It can have the same form as the content layer 26, the resin layer 22, the print layer 23 or the coating layer 24, and may be the same as the second agent-containing layer 26, the resin layer 22, the print layer 23 or the coating layer 24. And may be different. For example, when a layer having a formaldehyde removing ability is provided on the second surface 21b, this layer has the same form as the first drug-containing layer or the second drug-containing layer 26 on the first surface 21a. It may be the same as or different from the first drug-containing layer or the second drug-containing layer 26 on the first surface 11a.

<Third Embodiment>
FIG. 3 is a cross-sectional view schematically showing the laminated body of the third embodiment of the present invention.
The laminate 3 shown in FIG. 3 includes a base material 31, a second drug-containing layer 26, a resin layer 22, an adhesion layer 25, a printing layer 23, and a coating layer 24.
In the laminated body 3, the second drug-containing layer 26 is arranged between the base material 31 and the resin layer 22. Further, the resin layer 22, the adhesion layer 25 and the printing layer 23 are arranged between the second agent-containing layer 26 and the coating layer 24. The coating layer 24 is the outermost layer of the laminated body 3, the resin layer 22 is arranged on the base material 31 side of the adhesion layer 25, and the adhesion layer 25 is arranged on the base material 31 side of the printing layer 23. ing. In other words, in the laminated body 3, the base material 31, the second agent-containing layer 26, the resin layer 22, the adhesion layer 25, the printing layer 23 and the coating layer 24 are laminated in this order in this order, and the coating layer 24 is laminated. Is the outermost layer of the laminated body 3.
The base material 31 has a three-layer structure in which the first base material 211, the adhesive layer 310, and the second base material 212 are laminated in this order in the thickness direction thereof. The first base material 211 is arranged on the side of the second drug-containing layer 26 with respect to the second base material 212.

Further, in the laminate 3, any one or more of the resin layer 22, the adhesion layer 25 and the print layer 23 is a layer corresponding to the first drug-containing layer 12 in the laminate 1, that is, the microcapsules and non-microcapsules. It is a foaming layer (first drug-containing layer) containing microcapsules and having an activity of removing formaldehyde.

The laminate 3 also has a first drug-containing layer (one or more of the resin layer 22, the adhesion layer 25, and the printing layer 23), a second drug-containing layer 26, and a coating layer 24 to remove formaldehyde. Has the ability.

In the laminated body 3, it is preferable that at least the resin layer 22 is the first drug-containing layer.

Further, in the laminated body 3, one or more through holes 30 having an opening in the first surface 24a of the coating layer 24 and reaching the first surface 212a of the second base material 212 are provided. There is.
The laminated body 3 does not have to have the through hole 30, but by providing the laminated body 3, the formaldehyde removing ability is further improved as in the case of the laminated body 2.
In the laminated body 3, the through hole 30 is provided in the same manner as the through hole 20 in the laminated body 2, except that the through hole 30 is also formed in the adhesion layer 25 and the adhesive layer 310.

In the laminate 3, any one or two of the resin layer 22, the adhesion layer 25, and the printing layer 23 may be a layer containing either one of the microcapsules and the non-microcapsules alone.

The laminated body 3 is the same as the laminated body 2 shown in FIG. 2, except that the adhesive layer 25 and the adhesive layer 310 are provided, and the through holes 30 are also provided in these layers.

In the laminated body 3, the first drug-containing layer is provided on the first surface 26a of the second drug-containing layer 26.
In the laminate 3, the first drug-containing layer is one surface of the base material 31 (sometimes referred to as the "first surface" in the present specification) 31a, in other words, the first surface of the first base material 211. It can be said that it is provided on 211a, that is, the other surface of the base material 31 (sometimes referred to as “second surface” in the present specification) 31b, in other words, the second surface of the second base material 212. Not provided on 212b. That is, the laminated body 3 includes the drug-containing layer only on the first surface 31a of both surfaces of the base material 31.

The laminate 3 contains the microcapsules and non-microcapsules in the first drug-containing layer (one or more of the resin layer 22, the adhesion layer 25 and the printing layer 23), that is, on the same surface of the base material 31. Have both agents.
When the coating layer 24 contains both the microcapsules and the non-microcapsules, the laminate 3 is placed on the same surface of the base material 31 separately from those in the first drug-containing layer. It will have both the microcapsules and the non-microcapsules.
Further, when the second drug-containing layer 26 contains both the microcapsules and the non-microcapsules, the laminate 3 is on the same surface of the base material 31 as the one in the first drug-containing layer. Separately, it will have both the microcapsules and the non-microcapsules.

As shown here, the second drug-containing layer 26 is directly in contact with and laminated on the base material 31. In such a laminated body 3, the sustainability of the formaldehyde removing effect is higher.

In the laminated body 3, the first base material 211, the second base material 212, the second chemical-containing layer 26, the resin layer 22, the printing layer 23 and the coating layer 24 are the first base material 211 and the second base material 211 in the laminated body 2, respectively. It is the same as the base material 212, the second drug-containing layer 26, the resin layer 22, the printing layer 23, and the coating layer 24.
The base material 31 is the same as the base material 21 in the laminate 2 except that the base material 31 is provided with the adhesive layer 310.

[Adhesive layer]
The adhesive layer 310 adheres the first base material 211 and the second base material 212 to stabilize the structure of the laminated body 3.
The adhesive layer 310 contains a known adhesive resin and is preferably in the form of a film or a sheet.

The thickness of the adhesive layer 310 is not particularly limited, but is preferably 1 to 100 μm.

[Adhesion layer]
The adhesion layer 25 adheres the resin layer 22 and the printing layer 23 to stabilize the structure of the laminated body 3.
Examples of the adhesion layer 25 include those formed by using a known coupling agent, an adhesive resin, or the like.
The adhesion layer 25 is preferably in the form of a film or a sheet.

The thickness of the adhesion layer 25 is not particularly limited, but is preferably 1 to 50 μm.

When the adhesion layer 25 is the first drug-containing layer, the total content of the formaldehyde reactant in the microcapsules and the non-microcapsules (non-microencapsulated formaldehyde reactant) of the adhesion layer 25. , And [Contents of formaldehyde reactant in microcapsules (parts by mass)]: [Contents of non-microcapsules (formulum reactants not microencapsulated) (parts by mass)] ratio (mass ratio) ) Can be the same as in the case of the first drug-containing layer 12 in the laminated body 1.

<< Manufacturing method of laminated body >>
In the laminate of the present invention, the coating layer is the outermost layer, the second drug-containing layer is located between the base material and the first drug-containing layer, and the first drug-containing layer is located between the base material and the first drug-containing layer. These layers are arranged so as to be located between the second agent-containing layer and the coating layer, and microencapsulated formaldehyde reactants, non-microencapsulated formaldehyde reactants, and foaming. The first drug-containing layer, which is a foaming layer, is formed by using the composition for forming the first drug-containing layer, which comprises the agent, and is microencapsulated with the microencapsulated formaldehyde reactant. A formaldehyde reactant in which the second agent-containing layer is formed and microencapsulated by using a composition for forming a second agent-containing layer in which one or both of the formaldehyde reactants are not present is used. By forming the coating layer using a composition for forming a coating layer, which comprises a formaldehyde reactant that is not microencapsulated and one or both of them and has a viscosity of 90 mPa · s or more. Can be manufactured.
As the base material, a commercially available product may be used, or a material obtained by molding by a known method may be used depending on the material.

<Composition for forming a first drug-containing layer>
The composition for forming the first drug-containing layer contains a component for forming the first drug-containing layer.
The first drug-containing layer can be formed, for example, by applying a composition for forming a first drug-containing layer to a surface to be formed of the first drug-containing layer and drying it. Here, as the "plane to be formed of the first drug-containing layer", for example, the "first surface 16a of the second drug-containing layer 16" in the laminate 1 shown in FIG. 1 and the peeling treatment of the release film described later. The surface etc. can be mentioned.

The composition for forming a first drug-containing layer can be obtained, for example, by blending the microcapsules, non-microcapsules, foaming agents, and if necessary, other components, and further blending a solvent. The obtained product is preferable.
Further, the composition for forming the first drug-containing layer is, for example, a liquid substance (dispersion) obtained by preparing the microcapsules, a non-microcapsule, a foaming agent, and, if necessary, the other other. It can also be obtained by blending either one or both of the component and the solvent.
When the first drug-containing layer is any of the above-mentioned resin layer, adhesion layer and printing layer (for example, any of the resin layer 22, the adhesion layer 25 and the printing layer 23 in FIG. 2 or FIG. 3), A composition for forming a first drug-containing layer may be obtained by further blending essential components for forming these layers.

When the first drug-containing layer is a foamed resin layer, a composition for forming a first drug-containing layer in which the resin and the foaming agent are blended as the other components is required. When a foaming agent is blended in the preparation of such a composition for forming a first drug-containing layer, for example, a foamed resin composition in which the resin, the foaming agent, and, if necessary, other components are blended. It may be blended. Further, when preparing such a composition for forming a first drug-containing layer, a resin may be further blended in addition to the resin in the foamed resin composition. The foamed resin composition is preferably obtained by further blending a solvent (dispersion medium) in addition to the above-mentioned components.
The components other than the resin and the foaming agent in the foamed resin composition are not particularly limited and can be arbitrarily selected depending on the intended purpose. Examples of the components other than the resin and the foaming agent include the filler, the additive, and the like, which are the other components in the first drug-containing layer described above.

In the composition for forming the first drug-containing layer, the ratio of the contents of the compounded components that do not vaporize at room temperature is adjusted so as to be the same as the ratio of the contents of each component in the first drug-containing layer. In addition, in this specification, "normal temperature" means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

The mixing method at the time of preparing the composition for forming the first drug-containing layer is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade or the like; mixing using a mixer, three rolls, a kneader, a bead mill or the like. A method of mixing; a method of adding ultrasonic waves and mixing may be appropriately selected from known methods.
The temperature at the time of preparing the composition for forming the first drug-containing layer is not particularly limited as long as each compounding component is not deteriorated, and may be, for example, 5 to 60 ° C., which is an example.
The time at the time of preparing the composition for forming the first drug-containing layer is also not particularly limited as long as each compounding component is not deteriorated, and may be, for example, 10 minutes to 24 hours, which is an example.

The method for applying the composition for forming the first chemical-containing layer is not particularly limited, and any method may be used as long as it can be applied with a liquid substance. Specific coating methods include, for example, various coaters such as air knife coaters, curtain coaters, die coaters, blade coaters, roll coaters, gate roll coaters, bar coaters, rod coaters, gravure coaters, and gravure offset coaters; wire bars. A known method using a device such as a coater can be mentioned.

<Composition for forming a coating layer>
The coating layer forming composition contains a component for forming a coating layer, and its viscosity is 90 mPa · s or more. The coating layer forming composition is usually a dispersion and may be an emulsion.
The coating layer can be formed, for example, by applying a coating layer forming composition to the surface to be formed of the coating layer and drying it. Here, as the "surface to be formed of the coating layer", for example, the "first surface 12a of the first drug-containing layer 12" in the laminate 1 shown in FIG. 1, the peeling-treated surface of the release film described later, and the like are used. Can be mentioned.

The composition for forming a coating layer can be obtained, for example, by blending one or both of the microcapsules and non-microcapsules, and if necessary, other components, and further a solvent (dispersion medium). ) Is blended, and the one obtained is preferable.
When forming a coating layer containing the microcapsules, for example, the liquid material (dispersion) obtained by preparing the microcapsules can be used as it is, or the liquid material can be used as needed. A composition obtained by blending any one or more of a non-microcapsule, the other component and a solvent can be used as a coating layer forming composition.

In the coating layer forming composition, the ratio of the content of the compounding components that do not vaporize at room temperature is adjusted so as to be the same as the ratio of the content of each component in the coating layer.
The mixing method, temperature and time at the time of preparing the coating layer forming composition can be the same as those at the time of preparing the first drug-containing layer forming composition.
The coating method of the coating layer forming composition is the same as the coating method of the first drug-containing layer forming composition.

As described above, the viscosity of the coating layer forming composition is 90 mPa · s or more. The viscosity of the coating layer forming composition can be adjusted, for example, by adjusting the type and amount of the compounding components. In particular, the viscosity of the coating layer forming composition can be more easily adjusted by adjusting the type and amount of the solvent or the compounding component having a large molecular weight as the compounding component. Examples of the compounding component having a large molecular weight include a resin.

The solid content concentration of the coating layer forming composition is preferably 5 to 75% by mass, more preferably 10 to 60% by mass, and particularly preferably 15 to 45% by mass. When the solid content concentration of the coating layer forming composition is within such a range, the coating layer forming composition can be easily applied with high accuracy as described later, and a coating layer having higher uniformity can be obtained. Can be formed.

<Composition for forming a second drug-containing layer>
The composition for forming the second drug-containing layer contains a component for forming the second drug-containing layer.
The second drug-containing layer can be formed, for example, by applying a composition for forming a second drug-containing layer to a surface to be formed of the second drug-containing layer and drying it. Here, as the "surface to be formed of the second drug-containing layer", for example, the "first surface 11a of the base material 11" in the laminate 1 shown in FIG. 1, the peeling-treated surface of the release film described later, and the like are used. Can be mentioned.

The composition for forming a second drug-containing layer can be obtained, for example, by blending one or both of the microcapsules and non-microcapsules, and if necessary, other components, and further a solvent. Those obtained by blending (dispersion medium) are preferable.
Further, when forming a second drug-containing layer containing the microcapsules, for example, the liquid material (dispersion) obtained by preparing the microcapsules is required as it is or as the liquid material. A composition obtained by blending one or more of a non-microcapsule, the other component, and a solvent according to the above can be used as a composition for forming a second drug-containing layer.

In the composition for forming the second drug-containing layer, the ratio of the contents of the compounded components that do not vaporize at room temperature is adjusted so as to be the same as the ratio of the contents of each component in the second drug-containing layer.
The mixing method, temperature, and time at the time of preparing the composition for forming the second drug-containing layer can be the same as those at the time of preparing the composition for forming the first drug-containing layer.
The method for applying the composition for forming the second drug-containing layer is the same as the method for applying the composition for forming the first drug-containing layer.

The reason why the laminate of the present invention is remarkably excellent in the durability of the formaldehyde removing effect is not clear, but it is presumed as follows.
That is, the laminate of the present invention is provided with a first drug-containing layer other than the outermost layer, which has the ability to remove formaldehyde, so that the effect of removing formaldehyde is more durable than that of the conventional laminate. The laminate of the present invention further comprises the above-mentioned specific coating layer having a formaldehyde removing ability as the outermost layer in addition to the first drug-containing layer, whereby the first drug-containing layer is provided. It is more durable in removing formaldehyde than a laminate that is provided and does not have such a coating layer. As described above, since the laminate of the present invention includes both the first drug-containing layer and the coating layer, the formaldehyde removal effect is more durable than the conventional laminate.
Further, when the viscosity of the coating layer forming composition is at least the above lower limit value, repelling on the surface to be coated is suppressed, and the composition can be coated with high accuracy. By being able to apply the coating layer forming composition on the surface to be coated with high accuracy, the coating layer is formed with high uniformity while suppressing variation in thickness. Then, when the coating layer in such a state is dried as it is, the coating layer according to the present invention having similarly high uniformity is formed. In such a highly uniform coating layer, the formaldehyde removing ability of microcapsules and non-microcapsules is maximized.

On the other hand, for example, when the viscosity of the coating layer forming composition is not more than a specific value such as 14200 mPa · s or less as described above, it is formed by using such a coating layer forming composition. The laminate provided with the coating layer is further excellent in the durability of the formaldehyde removing effect. The reason is presumed as follows. That is, in such a coating layer forming composition, the compounding components are sufficiently dispersed during the production thereof, and aggregation is suppressed. Here, the compounding components of the coating layer forming composition are those described above, such as microcapsules, non-microcapsules, and resins. Among these, resin has a particularly high effect of improving dispersion. As described above, the composition for forming a coating layer in which the compounding components are sufficiently dispersed can be easily applied on the surface to be coated, so that the coating layer is formed with high uniformity by suppressing the variation in thickness. Will be done. Then, by drying the coating layer in such a state as it is, a coating layer having high uniformity is formed as well.
As described above, the composition for forming the coating layer can be applied with high accuracy and more easily, so that the variation in the thickness of the coating layer is highly suppressed and the uniformity is remarkably high. A coating layer is formed.
However, if the viscosity of the coating layer forming composition is not less than or equal to a specific value, such an effect may not be obtained. For example, if the compounding component is sufficiently dispersed in the coating layer forming composition and the dispersion conditions are violent, the microcapsule is destroyed when the microcapsule is the compounding component.
Further, as described above, the first drug-containing layer is a foamed layer, and the laminate may have a lower sustainability of the formaldehyde removing effect than in the case of a non-foamed layer.

On the other hand, the laminate of the present invention is provided with a second drug-containing layer having a formaldehyde removing ability in addition to the coating layer and the first drug-containing layer, whereby such a second drug-containing layer is provided. It is superior in the durability of the formaldehyde removal effect to the laminate without the above. More specifically, the second drug-containing layer remarkably alleviates the above-mentioned effects of the coating layer and the first drug-containing layer, and makes the sustainability of the formaldehyde removing effect of the laminate more stable. It has the function of raising and raising.
As described above, it is presumed that the laminate of the present invention is provided with both the first drug-containing layer and the coating layer, and further provided with the second drug-containing layer, so that the sustainability of the formaldehyde removal effect is remarkably excellent. To.

When the laminate of the present invention includes the base material, the first drug-containing layer, the second drug-containing layer, and other layers other than the coating layer (for example, the resin layer, the adhesion layer, the printing layer, etc.), The other layer is also a composition containing a component for forming the other layer (for example, a composition for forming a resin layer) as in the case of the first drug-containing layer, the second drug-containing layer and the coating layer. , A composition for forming an adhesive layer, a composition for forming a printed layer) can be formed by applying the coating to the surface to be formed of the other layers and drying the mixture.

Each layer other than the base material constituting the laminate of the present invention is laminated by directly coating any of the above-mentioned compositions on any of the adjacent formed layers in the laminate. Alternatively, the layer formed by applying any of the above compositions to the peeled surface of the release film is laminated to any of the formed layers adjacent to this layer in the laminated body. You may.

For example, as shown in FIG. 2 or FIG. 3, when a through hole is provided, a needle-shaped member may be inserted into the corresponding portion of the laminated body to form the through hole.
Next, the microcapsules and non-microcapsules contained in the first drug-containing layer will be described in detail.

[Microcapsules]
The microcapsules are microencapsulated formaldehyde reactants.
The microcapsule contains a polycondensate as a film-forming component and contains a formaldehyde reactant having reactivity with formaldehyde.

[Formaldehyde reactant]
The formaldehyde reactant is not particularly limited as long as it has reactivity with formaldehyde. As used herein, "having reactivity with formaldehyde" means having the ability to react with formaldehyde to convert formaldehyde into another compound. That is, the formaldehyde reactant contains a group having reactivity with formaldehyde. Formaldehyde is removed in the form of conversion to another compound by reaction with the formaldehyde reactant.

The formaldehyde reactant (in the microcapsule) contained in the microcapsules is abbreviated as a group in which an amino group and an amino group form a salt (in the present specification, an "amino group salt-forming group"). There is), it is preferable.
By using a polycondensate as a film-forming component and a microcapsule that does not have an amino group and an amino group salt-forming group as a formaldehyde reactant, microcapsules (microcapsules) containing a formaldehyde reactant can be obtained. Can be formed stably.

Examples of the amino group salt-forming group include a group in which an amino group serves as a monovalent cation portion and the cation portion forms a salt together with an anion.
Here, examples of the cation portion include those in which a hydrogen ion (H ⁺ ) is coordinated and bonded to a _{nitrogen atom of an amino group (−NH 2).} In this case, the valence of the anion is not particularly limited, and may be 1 (monovalent) or 2 (divalent) or more. When the anion is monovalent, the number of the anions forming the salt and the number of the cation portions are both 1. When the anion has an n valence (n is an integer of 2 or more), the number of the anions forming the salt is usually 1, and the number of the cation portions is n or less, which is usually the case. Is n. In this case, the plurality of the cation portions may be all the same, all may be different, or only a part thereof may be the same.

The anion in the amino group salt-forming group is the same as the anion portion in the group ("-NH-" salt-forming group) in which the group represented by the formula "-NH-" forms a salt, which will be described later. Things can be mentioned.

The formaldehyde reactant is preferably an organic compound, and such a formaldehyde reactant is, for example, abbreviated as a group represented by the formula "-NH-" (hereinafter, abbreviated as "-NH-" group ". Is) and the group represented by the formula "-NH-" is selected from the group consisting of groups forming a salt (hereinafter, may be abbreviated as "-NH-" salt-forming group). Examples thereof include compounds having one kind or two or more kinds. In formaldehyde reactants, the "-NH-" group exhibits reactivity with formaldehyde, and the "-NH-" salt-forming group itself, or becomes a "-NH-" group, this "-NH-". It is presumed that the group exhibits reactivity with formaldehyde.
When the formaldehyde reactant has a "-NH-" group or a "-NH-" salt-forming group, the nitrogen atom in these groups is further combined with a hydrogen atom in addition to one hydrogen atom already covalently bonded. There is no covalent bond.

The total number of "-NH-" groups and "-NH-" salt-forming groups in one molecule of the formaldehyde reactant may be only one, two or more, and when two or more, these two. The above groups may be the same or different from each other. That is, these two or more groups may be all the same, all may be different, or only a part may be the same. Usually, because of the ease of preparation of the formaldehyde reactant of interest, these two or more groups are all identical, i.e. all "-NH-" groups, or all identical "-NH-" groups. It is preferably a −NH− ”salt-forming group.

Examples of the "-NH-" salt-forming group include a group in which the "-NH-" group serves as a monovalent cation moiety and the cation moiety forms a salt together with an anion.
Here, examples of the cation portion include those in which a hydrogen ion (H ⁺ ) is coordinated and bonded to a nitrogen atom of a “−NH−” group. In this case, the valence of the anion is not particularly limited, and may be 1 (monovalent) or 2 (divalent) or more. When the anion is monovalent, the number of the anions forming the salt and the number of the cation portions are both 1. When the anion has an m valence (m is an integer of 2 or more), the number of the anions forming the salt is usually 1, the number of the cation portions is m or less, and m. Is preferable. In this case, the plurality of the cation portions may be all the same, all may be different, or only a part thereof may be the same.

The anion in the "-NH-" salt-forming group is not particularly limited and may be either an inorganic anion or an organic anion.
Preferred inorganic anions include, for example, nitrate ion, sulfate ion, hydrogen sulfate ion, carbonate ion, hydrogen carbonate ion, halide ion and the like, and examples of the halide ion include fluoride ion, chloride ion and bromide. Ions, iodide ions and the like can be mentioned.
Preferred organic anions include, for example, carboxylic acid anions, sulfonic acid anions and the like.
The anion of the carboxylic acid may be an anion of a monocarboxylic acid (monovalent carboxylic acid) or an anion of a polyvalent carboxylic acid such as a dicarboxylic acid or a tricarboxylic acid.

The anion contained in the formaldehyde reactant may be only one kind, two or more kinds, and when two or more kinds, the combination and the ratio thereof can be arbitrarily selected.
That is, when one molecule of formaldehyde reactant has two or more of the anions, these two or more anions may all be the same, all may be different, or only partly the same. May be good.
However, the formaldehyde reactant is electrically neutral as a whole molecule, that is, the total value of the valence of the cation portion and the total value of the valence of the anion in one molecule of the formaldehyde reactant are the same. It is preferable to have.

The total number of "-NH-" groups and "-NH-" salt-forming groups in one molecule of the formaldehyde reactant is preferably 1 to 4, more preferably 1 to 3.

The positions of the "-NH-" group and the "-NH-" salt-forming group in the molecule of the formaldehyde reactant are not particularly limited, and for example, when the formaldehyde reactant has a chain structure, the end of the molecule Any position may be used as long as it is not a part.

The formaldehyde reactant may be linear, branched or cyclic, and may have both a chain structure and a cyclic structure.

When the formaldehyde reactant has a cyclic structure, the ring may be either monocyclic or polycyclic, and may be either an aliphatic ring or an aromatic ring, and the aliphatic ring and the aromatic ring may be used. It may be a condensed polycyclic ring.
When the formaldehyde reactant has a cyclic structure, the "-NH-" group and the "-NH-" salt-forming group may or may not form a ring skeleton of the cyclic structure, without forming a ring skeleton. It may be attached to a group forming a ring skeleton.

In the formaldehyde reactant, the nitrogen atom of the "-NH-" group and the "-NH-" salt-forming group is preferably bonded to the carbon atom of the nitrogen atom or the carbonyl group.
The total number of "-NH-" groups and "-NH-" salt-forming groups thus bonded to one carbonyl group may be only one or two.
The total number of "-NH-" groups and "-NH-" salt-forming groups thus bonded to one nitrogen atom may be only one, two, or one. Is preferable.

That is, as a preferable formaldehyde reactant, for example, a group represented by the formula "-C (= O) -NH-" (amide bond, hereinafter abbreviated as "-C (= O) -NH-" group ". (May be), a group represented by the formula "-NH-C (= O) -NH-" (hereinafter, may be abbreviated as "-NH-C (= O) -NH-" group ". ), The group represented by the formula "-C (= O) -NH-" is abbreviated as "-C (= O) -NH-" salt-forming group ". There is), a group in which the group represented by the formula "-NH-C (= O) -NH-" forms a salt (hereinafter, "-NH-C (= O) -NH-" salt formation Group may be abbreviated as "group"), group represented by the formula "= N-NH-" (hereinafter, may be abbreviated as "" = N-NH- "group"), formula "-HN-N". A group represented by (-)-NH- "(hereinafter, may be abbreviated as" -HN-N (-)-NH- "group"), represented by the formula "= N-NH-". A group whose group forms a salt (hereinafter, may be abbreviated as "= N-NH-" salt-forming group) and a group represented by the formula "-HN-N (-)-NH-". Has one or more selected from the group consisting of groups forming a salt (hereinafter, may be abbreviated as "-HN-N (-)-NH-" salt-forming group "). Things, etc. Here, for example, the "-HN-N (-)-NH-" group means one nitrogen atom, two "-NH-" groups, and another group. Means a single bond.
In the "-NH-C (= O) -NH-" salt-forming group and the "-HN-N (-)-NH-" salt-forming group, the number of "-NH-" salt-forming groups may be one. It may be two or more.

As a formaldehyde reactant having a cyclic structure, for example, one or more selected from the group consisting of a "-NH-" group and a "-NH-" salt-forming group is a ring skeleton having a cyclic structure. "-C (= O) -NH-" group, "-NH-C (= O) -NH-" group, "-C (= O) -NH-" salt Formaldehyde, "-NH-C (= O) -NH-" salt-forming group, "= N-NH-" group, "-HN-N (-)-NH-" group, "= N-NH-" A formaldehyde reactant in which one or more selected from the group consisting of a salt-forming group and a "-HN-N (-)-NH-" salt-forming group forms a cyclic skeleton is more preferable. ..

When the formaldehyde reactant has a cyclic structure, the number of ring members of the ring skeleton, that is, the number (elements) of the atoms forming the ring skeleton is preferably 5 to 7 when it is monocyclic, more preferably. Is 5 or 6, and when it is polycyclic, it is preferably 8 to 10.

Particularly preferable formaldehyde reactants include, for example, hydantin and a salt thereof which may have a substituent, 2-imidazolidinone which may have a substituent and a salt thereof, and a substituent thereof. Good 5-pyrazolone and its salt, may have a substituent 3-pyrazolone and its salt, may have a substituent 1,2,4-triazole-3-one and its salt, a substituent. It may have a phthalimide and a salt thereof, a glycol uryl and a salt thereof which may have a substituent, a pyrazole and a salt thereof which may have a substituent, and a substituent. 1,2,3-triazole and its salt, may have a substituent 1,2,4-triazole and its salt, and may have a substituent 1,2,3-benzotriazole and The salt and the like can be mentioned.

Hydantin, 2-imidazolidinone, 5-pyrazolone, 3-pyrazolone, 1,2,4-triazole-3-one, phthalimide, glycoluril, pyrazole, 1,2,3-triazole, 1,2,4-triazole And the structure of 1,2,3-benzotriazole is shown below.
Hydantin, 2-imidazolidinone, 5-pyrazolone, 3-pyrazolone, 1,2,4-triazole-3-one, pyrazole, 1,2,3-triazole and 1,2,4-triazole are all rings. It is a compound with 5 members. Both phthalimide and 1,2,3-benzotriazole are compounds having 9 ring members. Glycol uryl is a compound having 8 ring members.
The compound shown here is only one example of a formaldehyde reactant.

Here, examples of the salt of hydantoin include those in which one or both of the two "-NH-" groups in the hydantoin are "-NH-" salt-forming groups.
Further, as the salt of 2-imidazolidinone, for example, one or both of the two "-NH-" groups in 2-imidazolidinone became a "-NH-" salt-forming group. Can be mentioned.
As the salt of 5-pyrazolone, for example, the "-NH-" group in 5-pyrazolone becomes the "-NH-" salt forming group, and the nitrogen atom that is not bonded to the hydrogen atom is the salt. , And those in which the "-NH-" group becomes a "-NH-" salt-forming group and the nitrogen atom which is not bonded to the hydrogen atom forms a salt.
In addition, examples of the salt of 3-pyrazolone include those in which either or both of the two "-NH-" groups in 3-pyrazolone are "-NH-" salt-forming groups.
The salt of 1,2,4-triazole-3-one may be, for example, one or both of the two "-NH-" groups in 1,2,4-triazole-3-one. Examples thereof include those that have become a "-NH-" salt-forming group.
Examples of the phthalimide salt include those in which one "-NH-" group in the phthalimide becomes a "-NH-" salt-forming group.
Examples of the salt of glycoluril include those in which at least one of the four "-NH-" groups in glycoluril is a "-NH-" salt-forming group.

As the salt of pyrazole, for example, the "-NH-" group in pyrazole becomes a "-NH-" salt-forming group, and the nitrogen atom that is not bonded to a hydrogen atom forms a salt. , And the "-NH-" group becomes the "-NH-" salt-forming group, and the nitrogen atom that is not bonded to the hydrogen atom forms the salt.
As the salt of 1,2,3-triazole, for example, the "-NH-" group in 1,2,3-triazole becomes the "-NH-" salt-forming group, which is bonded to a hydrogen atom. One or both of the two nitrogen atoms that do not form a salt, and the "-NH-" group becomes a "-NH-" salt-forming group and is not bonded to a hydrogen atom. Examples thereof include those in which one or both of the two nitrogen atoms of the above form a salt.
As the salt of 1,2,4-triazole, for example, the "-NH-" group in 1,2,4-triazole becomes the "-NH-" salt-forming group, which is bonded to a hydrogen atom. One or both of the two nitrogen atoms that do not form a salt, and the "-NH-" group becomes a "-NH-" salt-forming group and is not bonded to a hydrogen atom. Examples thereof include those in which one or both of the two nitrogen atoms of the above form a salt.
The salt of 1,2,3-benzotriazole includes, for example, a hydrogen atom in which the "-NH-" group in 1,2,3-benzotriazole becomes a "-NH-" salt-forming group. One or both of the two unbonded nitrogen atoms forming a salt, and the "-NH-" group becomes a "-NH-" salt-forming group and are bonded to a hydrogen atom. Examples thereof include one in which one or both of the two non-existent nitrogen atoms form a salt.

In addition, in this specification, "having a substituent" excludes one or more hydrogen atoms of the original compound (however, the hydrogen atom in "-NH-" group and "-NH-" salt forming group is excluded. ) Is substituted with a group (substituent) other than a hydrogen atom.

In the present specification, hydantoin having a substituent may be referred to as "hydantoin derivative", and hydantoin and hydantoin derivative may be collectively referred to as "hydantoin-based compound". The salt of hydantoin having a substituent, that is, the salt of the hydantoin derivative is a salt formed by the hydantoin derivative as in the case of hydantoin. The "hydantoin and its salt which may have a substituent" is, in other words, a hydantoin-based compound and a salt thereof.
As used herein, the term "derivative" means that one or more hydrogen atoms of the original compound are substituted with a group other than a hydrogen atom.

The same applies to compounds other than hydantoin.
That is, in the present specification, 2-imidazolidinone having a substituent is referred to as "2-imidazolidinone derivative", and 2-imidazolidinone and 2-imidazolidinone derivative are collectively referred to as "2-imidazolidinone". It may be referred to as "non-based compound". Then, the salt of 2-imidazolidinone having a substituent, that is, the salt of the 2-imidazolidinone derivative, formed a salt as in the case of the 2-imidazolidinone derivative as in the case of 2-imidazolidinone. It is a thing. The "2-imidazolidinone which may have a substituent and a salt thereof" is, in other words, a 2-imidazolidinone-based compound and a salt thereof.

In the present specification, 5-pyrazolone having a substituent may be referred to as "5-pyrazolone derivative", and 5-pyrazolone and 5-pyrazolone derivative may be collectively referred to as "5-pyrazolone-based compound". The salt of 5-pyrazolone having a substituent, that is, the salt of the 5-pyrazolone derivative is a salt formed by the 5-pyrazolone derivative as in the case of 5-pyrazolone. "5-Pyrazolone and its salt which may have a substituent" is, in other words, a 5-pyrazolone-based compound and a salt thereof.

In the present specification, 3-pyrazolone having a substituent may be referred to as "3-pyrazolone derivative", and 3-pyrazolone and 3-pyrazolone derivative may be collectively referred to as "3-pyrazolone-based compound". The salt of 3-pyrazolone having a substituent, that is, the salt of the 3-pyrazolone derivative is a salt formed by the 3-pyrazolone derivative as in the case of 3-pyrazolone. "3-Pyrazolone and its salt which may have a substituent" is, in other words, a 3-pyrazolone-based compound and a salt thereof.

In the present specification, 1,2,4-triazole-3-one having a substituent is referred to as "1,2,4-triazole-3-one derivative", and 1,2,4-triazole-3-one is referred to as "1,2,4-triazole-3-one". And 1,2,4-triazole-3-one derivatives are collectively referred to as "1,2,4-triazole-3-one-based compounds". The salt of 1,2,4-triazole-3-one having a substituent, that is, the salt of the 1,2,4-triazole-3-one derivative is 1,2,4-triazole-3-one. The derivative is a salt formed as in the case of 1,2,4-triazole-3-one. In other words, "1,2,4-triazole-3-one and its salt which may have a substituent" means a 1,2,4-triazole-3-one compound and a salt thereof. be.

In the present specification, a phthalimide having a substituent may be referred to as a "phthalimide derivative", and the phthalimide and the phthalimide derivative may be collectively referred to as a "phthalimide-based compound". The salt of phthalimide having a substituent, that is, the salt of the phthalimide derivative is a salt formed by the phthalimide derivative as in the case of phthalimide. The "phthalimide which may have a substituent and a salt thereof" is, in other words, a phthalimide compound and a salt thereof.

In the present specification, glycol uryl having a substituent may be referred to as "glycol uryl derivative", and glycol uryl and glycol uryl derivative may be collectively referred to as "glycol uryl-based compound". The salt of glycol uryl having a substituent, that is, the salt of the glycol uryl derivative is a salt formed by the glycol uryl derivative as in the case of glycol uryl. "Glycoluryl and its salt which may have a substituent" is, in other words, a glycoluril-based compound and a salt thereof.

In the present specification, pyrazole having a substituent may be referred to as a "pyrazole derivative", and pyrazole and a pyrazole derivative may be collectively referred to as a "pyrazole-based compound". The salt of pyrazole having a substituent, that is, the salt of the pyrazole derivative is a salt formed by the pyrazole derivative as in the case of pyrazole. "Pyrazole and a salt thereof which may have a substituent" is, in other words, a pyrazole-based compound and a salt thereof.

In the present specification, 1,2,3-triazole having a substituent is referred to as "1,2,3-triazole derivative" and includes 1,2,3-triazole and 1,2,3-triazole derivative. It may be referred to as "1,2,3-triazole-based compound". The salt of 1,2,3-triazole having a substituent, that is, the salt of the 1,2,3-triazole derivative is the case where the 1,2,3-triazole derivative is 1,2,3-triazole. Similarly, it is a salt formed. The "1,2,3-triazole and its salt which may have a substituent" is, in other words, a 1,2,3-triazole-based compound and a salt thereof.

In the present specification, 1,2,4-triazole having a substituent is referred to as "1,2,4-triazole derivative" and includes 1,2,4-triazole and 1,2,4-triazole derivative. It may be referred to as "1,2,4-triazole-based compound". The salt of 1,2,4-triazole having a substituent, that is, the salt of the 1,2,4-triazole derivative is the case where the 1,2,4-triazole derivative is 1,2,4-triazole. Similarly, it is a salt formed. The "1,2,4-triazole and its salt which may have a substituent" is, in other words, a 1,2,4-triazole-based compound and a salt thereof.

In the present specification, 1,2,3-benzotriazole having a substituent is referred to as "1,2,3-benzotriazole derivative", and 1,2,3-benzotriazole and 1,2,3-benzotriazole are referred to as "1,2,3-benzotriazole derivative". Derivatives may be collectively referred to as "1,2,3-benzotriazole-based compounds". The salt of 1,2,3-benzotriazole having a substituent, that is, the salt of the 1,2,3-benzotriazole derivative is the 1,2,3-benzotriazole derivative of 1,2,3-. As in the case of benzotriazole, it is a salt formed. The "1,2,3-benzotriazole and its salt which may have a substituent" is, in other words, a 1,2,3-benzotriazole-based compound and a salt thereof.

The substituent is not particularly limited, but preferred ones include an alkyl group, an alkenyl group, an aryl group, an aralkyl group (arylalkyl group), an alkoxy group, an alkenyloxy group, an aryloxy group, an aryloxy group and the like. ..

The alkyl group in the substituent may be linear, branched or cyclic, and when cyclic, it may be monocyclic or polycyclic.
The alkyl group preferably has 1 to 10 carbon atoms.

The linear or branched alkyl group preferably has 1 to 10 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methyl Pentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl Group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, Examples include a decyl group.

The cyclic alkyl group preferably has 3 to 10 carbon atoms, and examples of the alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group. , Cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclodecyl group and the like, and further, one or more hydrogen atoms of these cyclic alkyl groups are linear and branched. Examples thereof include those substituted with a chain or cyclic alkyl group. Here, examples of the linear, branched, and cyclic alkyl groups that substitute for hydrogen atoms include the same alkyl groups as those mentioned as the substituents of the above-mentioned formaldehyde reactants.

The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 5 carbon atoms.

Examples of the alkenyl group in the substituent include a group in which one single bond (C—C) between carbon atoms of the alkyl group is substituted with a double bond (C = C), and examples thereof include. Examples thereof include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), a cyclohexenyl group and the like.
The alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and particularly preferably 2 to 6 carbon atoms.

The aryl group in the substituent may be either monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, o-. Examples thereof include a trill group, an m-tolyl group, a p-tolyl group, a xylyl group (dimethylphenyl group) and the like, and one or more hydrogen atoms of these aryl groups are further contained by these aryl groups and the above-mentioned formaldehyde reactant. The one substituted with the alkyl group mentioned as a substituent can also be mentioned. The aryl group having these substituents preferably has 6 to 15 carbon atoms including the substituent.
The aryl group preferably has 6 to 10 carbon atoms.

The aralkyl group in the substituent is a monovalent group in which one hydrogen atom of the alkyl group is substituted with the aryl group, for example, a benzyl group (phenylmethyl group), a phenethyl group (phenylethyl group) and the like. Can be mentioned.
The carbon number of the aralkyl group is preferably 7 to 20, more preferably 7 to 11.

Examples of the alkoxy group in the substituent include a monovalent group in which the alkyl group is bonded to an oxygen atom, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group and a cyclopropoxy group.
The alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 6 carbon atoms, and particularly preferably 1 to 5 carbon atoms.

Examples of the alkenyloxy group in the substituent include an ethenyloxy group (vinyloxy group), a 2-propenyloxy group (allyloxy group), a cyclohexenyloxy group and the like, and a monovalent group formed by bonding the alkenyl group to an oxygen atom. Can be mentioned.
The alkenyloxy group preferably has 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and particularly preferably 2 to 6 carbon atoms.

Examples of the aryloxy group in the substituent include a monovalent group in which the aryl group is bonded to an oxygen atom, such as a phenyloxy group and a 1-naphthyloxy group.
The aryloxy group preferably has 6 to 10 carbon atoms.

Examples of the aralkyloxy group in the substituent include a monovalent group in which the aralkyl group is bonded to an oxygen atom, such as a benzyloxy group (phenylmethyloxy group) and a phenylethyloxy group (phenylethyloxy group). Be done.
The aralkyloxy group preferably has 7 to 20 carbon atoms, and more preferably 7 to 11 carbon atoms.

The substituents contained in one molecule of the formaldehyde reactant may be only one, two or more, and when two or more, these substituents may be the same or different from each other. That is, the two or more substituents may be all the same, all may be different, or only a part may be the same.
Usually, the number of the substituents contained in one molecule of the formaldehyde reactant is preferably 1 to 4, and more preferably 1 to 3.

The position of the substituent in the molecule of the formaldehyde reactant is not particularly limited, and for example, when the formaldehyde reactant has a chain structure, it may be the terminal portion of the molecule or other than the terminal portion. It may be a site.
When the formaldehyde reactant has two or more of the above-mentioned substituents, the bonding positions of these substituents may be all the same, all may be different, or only some of them may be the same.

Among the above-mentioned particularly preferable formaldehyde reactants, those having the substituent include 5,5-dimethylhydantoin which is a hydrantin derivative; 3-methyl-5-pyrazolone which is a 5-pyrazolone derivative; and 3, which is a pyrazole derivative. 5-Dimethylpyrazole; 3-n-butyl-1,2,4-triazole, a 1,2,4-triazole derivative, 3,5-dimethyl-1,2,4-triazole, 3,5-di-n -Butyl-1,2,4-triazole, 3,5-diphenyl-1,2,4-triazole; 4-methyl-1H-benzotriazole, 5-methyl-1H, which are derivatives of 1,2,3-benzotriazole. -Benzotriazole and the like can be mentioned.
5,5-dimethylhydantin, 3-methyl-5-pyrazolone, 3,5-dimethylpyrazole, 3-n-butyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 3,5-Di-n-butyl-1,2,4-triazole and 3,5-diphenyl-1,2,4-triazole are all compounds having 5 ring members. Both 4-methyl-1H-benzotriazole and 5-methyl-1H-benzotriazole are compounds having 9 ring members.
The compound shown here is only one example of the formaldehyde reactant having the above-mentioned substituent.

The formaldehyde reactant is preferably a solid at room temperature. When a formaldehyde reactant that is solid at room temperature is used, it is preferable to use a solvent described later in combination.

Particularly preferred formaldehyde reactants include, for example, hydantin, 5,5-dimethylhydantin, 2-imidazolidinone, 5-pyrazolone, 3-methyl-5-pyrazolone, 3-pyrazolone, 3,5-dimethylpyrazole, and the like. Phthalimide, glycoluril, 1,2,3-triazole, 1,2,4-triazole, 3-n-butyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 3 , 5-Di-n-butyl-1,2,4-triazole, 3,5-diphenyl-1,2,4-triazole, 1,2,4-triazole-3-one, 1,2,3-benzo Examples thereof include triazole, 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole and the like.

The formaldehyde reactant contained in the microcapsules may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and the ratio thereof can be arbitrarily selected.

The amount (content) of the formaldehyde reactant contained in the microcapsules is not particularly limited and can be appropriately adjusted according to the purpose.
The amount (content) of the formaldehyde reactant contained in the microcapsules can be adjusted, for example, according to the manufacturing conditions of the microcapsules described later.

[Membrane forming component]
The microcapsules contain a polycondensate as a film-forming component. In the present invention, the "film-forming component" is a component that forms a film of an outer shell that encloses a formaldehyde reactant that is an active ingredient.
The polycondensation product is an oligomer or a polymer, and is not particularly limited as long as it is an organic compound having a film-forming ability, but an interfacial polycondensation product obtained by an interfacial polycondensation method is preferable. By using the interfacial polycondensate, microcapsules of better quality can be obtained.

Preferred polycondensates include, for example, polyurea, polyurethane, polyamide and the like.
Here, "polyurea" means an oligomer or polymer having a bond (urea bond) represented by the formula "-NH-C (= O) -NH-", and for example, two or more as a raw material compound. It is obtained by subjecting an isocyanate compound having an isocyanate group to an amine compound having two or more amino groups to undergo a polycondensation reaction.
Further, "polyurethane" means an oligomer or polymer having a bond (urethane bond) represented by the formula "-NH-C (= O) -O-", and for example, two or more as a raw material compound. It is obtained by subjecting an isocyanate compound having an isocyanate group and a hydroxy compound having two or more hydroxyl groups (-OH) to a polycondensation reaction.
Further, "polyamide" means an oligomer or polymer having a bond (amide bond) represented by the formula "-NH-C (= O)-", and for example, as a raw material compound, two or more carboxy groups. A carboxylic acid having (-C (= O) -OH), or a carboxylic acid chloride in which one or more carboxy groups thereof are substituted with a chlorocarbonyl group (-C (= O) -Cl). It is obtained by subjecting an amine compound having two or more amino groups to a polycondensation reaction.

The isocyanate compound for producing polyurea and polyurethane is preferably one having no amino group or a hydroxyl group, and more preferably one having neither an amino group nor a hydroxyl group.

The number of isocyanate groups contained in one molecule of the isocyanate compound is not particularly limited as long as it is 2 or more, but is preferably 2 to 6, more preferably 2 to 5, and 2 to 5. It is more preferably 4 pieces, and particularly preferably 2 or 3 pieces.

Examples of the isocyanate compound include tolylene-2,4-diisocyanate, tolylen-2,6-diisocyanate, xylylene-1,3-diisocyanate, xylene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, and diphenylmethane. Organic polyvalent isocyanate compounds such as -2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate; Derivatives of the polyvalent isocyanate compound (provided that the isocyanate group is not substituted); Trimethylol propane adduct of the organic polyvalent isocyanate compound; Derivative of the organic polyvalent isocyanate compound (provided that the isocyanate group is not substituted). ) Trimethylol propane adduct and the like. In the present specification, the trimethylolpropane adduct may also be referred to as a trimethylolpropane adduct.

The isocyanate compound may be used alone or in combination of two or more, and when two or more are used in combination, the combination and ratio thereof can be arbitrarily selected.

The amine compound for producing polyurea is preferably one having no isocyanate group or a hydroxyl group, and more preferably one having neither an isocyanate group nor a hydroxyl group.

The number of amino groups contained in one molecule of the amine compound is not particularly limited as long as it is 2 or more, but is preferably 2 to 6, more preferably 2 to 5, and 2 to 5. It is more preferably 4 pieces, and particularly preferably 2 or 3 pieces.

Examples of the amine compound include organic polyvalent amine compounds such as melamine, urea and 1,3-bis (aminomethyl) cyclohexane.

The amine compound may be used alone or in combination of two or more, and when two or more are used in combination, the combination and ratio thereof can be arbitrarily selected.

The hydroxy compound for producing polyurea preferably has no isocyanate group or amino group, and more preferably has neither an isocyanate group nor an amino group.

The number of hydroxyl groups contained in one molecule of the hydroxy compound is not particularly limited as long as it is 2 or more, but is preferably 2 to 6, more preferably 2 to 5, and 2 to 5. It is more preferably 4 pieces, and particularly preferably 2 or 3 pieces.

Examples of the hydroxy compound include organic polyvalent hydroxy compounds, and examples of the organic polyvalent hydroxy compound include alkylene glycols such as ethylene glycol, propylene glycol, and 1,4-butanediol.

The hydroxy compound may be used alone or in combination of two or more, and when two or more are used in combination, the combination and ratio thereof can be arbitrarily selected.

Examples of the amine compound for producing a polyamide include the same amine compounds for forming the above-mentioned polyurea except that they do not have a carboxy group.
In addition, examples of the amine compound for producing a polyamide include aliphatic polyvalent amine compounds such as hexamethylenediamine, nonanediamine, methylpentadiamine, and diethylenetriamine.

The number of amino groups contained in one molecule of the amine compound for producing a polyamide is not particularly limited as long as it is 2 or more, but is preferably 2 to 6, preferably 2 to 5. Is more preferable, 2 to 4 pieces are more preferable, and 2 or 3 pieces are particularly preferable.

As the amine compound for producing a polyamide, one kind may be used alone, two or more kinds may be used in combination, and when two or more kinds are used in combination, the combination and ratio thereof are arbitrarily selected. can.

The carboxylic acid for producing a polyamide does not have an amino group.
The number of carboxy groups contained in one molecule of the carboxylic acid is not particularly limited as long as it is 2 or more, but it is preferably 2 to 6, more preferably 2 to 5, and 2 to 5. It is more preferably 4 pieces, and particularly preferably 2 or 3 pieces.

Examples of the carboxylic acid include adipic acid (hexanedioic acid), sebacic acid (decanedioic acid), terephthalic acid (benzene-1,4-dicarboxylic acid), isophthalic acid (benzene-1,3-dicarboxylic acid) and the like. Organic polyvalent carboxylic acid (aliphatic polyvalent carboxylic acid, aromatic polyvalent carboxylic acid) and the like can be mentioned.

The carboxylic acid chloride for producing polyamide is obtained by substituting one or more carboxy groups of the carboxylic acid with a chlorocarbonyl group, and all the carboxy groups of the carboxylic acid are chlorocarbonyl groups. It may be replaced with.

As the carboxylic acid and the carboxylic acid chloride for producing the polyamide, one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, a combination thereof and a combination thereof and The ratio can be selected arbitrarily.

Among the above, the polycondensate is preferably obtained by using an isocyanate compound, and more preferable ones include polyurea and polyurethane.

The polycondensation may be carried out by a known method, and the conditions may be appropriately selected in consideration of the type of the raw material compound to be used and the like.

For example, in the case of interfacial polycondensation, microcapsules containing a formaldehyde reactant can be obtained at once by polycondensing the raw material compound in the presence of the formaldehyde reactant to be included. Hereinafter, a method for forming a film-forming component and producing the microcapsule by interfacial polycondensation will be described.

The amount of the two essential raw material compounds to be polycondensed may be appropriately adjusted according to the method of polycondensation and the type of the raw material compound. Here, "two essential groups of raw material compounds to be polycondensed" means components essential for constituting the main skeleton of the polycondensate which is a film-forming component, and when the polycondensate is polyurea. Means the isocyanate compound and the amine compound, the isocyanate compound and the hydroxy compound when the polycondensate is polyurethane, and the carboxylic acid or the carboxylic acid chloride and amine when the polycondensate is polyamide. Means a compound.

For example, when polyurea is obtained by interfacial polycondensation using the isocyanate compound and the amine compound, the amount of the isocyanate compound and the amine compound used is [the number of moles of amino groups in the amine compound]: [in the isocyanate compound. The molar ratio of [the number of moles of the isocyanate group] is preferably 10:90 to 60:40, and more preferably 20:80 to 40:60. When the number of moles of amino groups in the amine compound is set to be smaller than the number of moles of isocyanate groups in the isocyanate compound, higher quality microcapsules can be obtained.

For example, when a polyurethane is obtained by interfacial polycondensation using the isocyanate compound and the hydroxy compound, the amount of the isocyanate compound and the hydroxy compound used is [the number of moles of hydroxyl groups in the hydroxy compound]: [in the isocyanate compound. The molar ratio of [the number of moles of the isocyanate group] is preferably 10:90 to 60:40, and more preferably 20:80 to 40:60. When the number of moles of hydroxyl groups in the hydroxy compound is set to be smaller than the number of moles of isocyanate groups in the isocyanate compound, higher quality microcapsules can be obtained.

Up to this point, the polycondensate obtained by polycondensing any of the isocyanate compound, amine compound, hydroxy compound, carboxylic acid and carboxylic acid chloride has been described, but the polycondensate is described above. It may be obtained by polycondensing another compound that does not correspond to any of an isocyanate compound, an amine compound, a hydroxy compound, a carboxylic acid and a carboxylic acid chloride.

The other compounds are not particularly limited as long as they can be polycondensed.
The other compounds may be only one kind, two or more kinds, and when two or more kinds, the combination and ratio thereof can be arbitrarily selected.

For example, when the polyurea is obtained by polycondensing the other compound in addition to the isocyanate compound and the amine compound, the amount of the other compound used is the total amount of the isocyanate compound and the amine compound used. It is preferably 5 mol% or less, more preferably 3 mol% or less, and particularly preferably 1 mol% or less with respect to (number of moles).

Similarly, when the polyurethane is obtained by polycondensing the other compound in addition to the isocyanate compound and the hydroxy compound, the amount of the other compound used is the total use of the isocyanate compound and the hydroxy compound. The amount (number of moles) is preferably 5 mol% or less, more preferably 3 mol% or less, and particularly preferably 1 mol% or less.

Similarly, when the polyamide is obtained by polycondensing the other compound in addition to the carboxylic acid, the carboxylic acid chloride and the amine compound, the amount of the other compound used is the carboxylic acid, the carboxylic acid. The total amount (number of moles) of the acid chloride and the amine compound is preferably 5 mol% or less, more preferably 3 mol% or less, and particularly preferably 1 mol% or less.

The amount of the formaldehyde reactant used during polycondensation is not particularly limited, but is preferably 2 to 65 parts by mass with respect to 100 parts by mass of the total amount of the above-mentioned two essential raw material compounds to be polycondensed. , 2 to 61 parts by mass, more preferably 2 to 57 parts by mass, for example, 2 to 50 parts by mass, 4 to 30 parts by mass, and 6 to 15 parts by mass. May be good.

(solvent)
The microcapsules may contain a solvent in order to dissolve the formaldehyde reactant. In this case, the interfacial polycondensation is preferably carried out by emulsifying the reaction solution in a mixed solvent of water and a hydrophobic solvent (plasticizer). As described above, by polycondensing the raw material compound in the coexistence of the formaldehyde reactant to be encapsulated and the hydrophobic solvent, microcapsules containing the formaldehyde reactant and the hydrophobic solvent can be obtained at once.
When emulsifying the reaction solution, an emulsifier described later may be used in combination.

Examples of the hydrophobic solvent include alcohols, amides, nitriles, ketones, esters, ethers, hydrocarbons, halogenated hydrocarbons, phenols (compounds having a phenolic hydroxyl group), carbon sulfide, carboxylic acids and the like.

The hydrophobic solvent preferably has an SP value (solubility parameter) of 12 (cal / cm ³ ) ^1/2 or less. By using such a solvent, the reaction liquid at the time of interfacial polycondensation tends to be an oil droplet type (O / W type) dispersion liquid in water in a state where oily components are dispersed in water, and a film-forming component. And the formation of microcapsules becomes easier.
That is, the microcapsules containing a solvent having an SP value of 12 (cal / cm ³ ) ^1/2 or less are particularly preferable among the microcapsules in the present invention.

The lower limit of the SP value of the hydrophobic solvent is not particularly limited, but is preferably ^{6.5 (cal / cm 3} ) ^1/2. Such a hydrophobic solvent having an SP value is easily available.

Examples of the solvent having an SP value of 12 (cal / cm ³ ) ^1/2 or less include, for example.
1-propanol (11.9), 2-propanol (11.5), 1-butanol (11.4), cyclohexanol (11.4), 2-methoxyethanol (10.8), 1-hexanol (10) .7), Alcohols such as 2-methyl-2-propanol (10.6), 1-butoxy-2-propanol (10.4), 2-ethylhexanol (9.5);
Amides such as dimethylformamide (12.0);
Nitriles such as acetonitrile (11.8);
Ketones such as acetone (10.0), methyl ethyl ketone (9.3), methyl propyl ketone (8.7), methyl isopropyl ketone (8.5);
Di n-butyl phthalate (9.4), ethyl acetate (9.1), bis sevacinate (2-ethylhexyl) (8.7), n-butyl acetate (8.5), isopropyl acetate (8.4) ), Isobutyl acetate (8.3) and other esters (carboxylic acid esters);
Chained and cyclic ethers such as dioxane (9.9), tetrahydrofuran (9.1), diethyl ether (7.4), isopropyl ether (6.9);
Benzene (9.2), toluene (8.9), xylene (8.8), ethylbenzene (8.8), cyclohexane (8.2), n-octane (7.6), n-hexane (7.). 3), aromatic and aliphatic hydrocarbons such as n-pentane (7.0);
Halogenated hydrocarbons (halogenated aliphatic hydrocarbons) such as methylene chloride (9.7), chloroform (9.3), trichlorethylene (9.2), carbon tetrachloride (8.6);
Carbon sulfide such as carbon disulfide (10.0);
Phenols such as phenol (11.5);
Examples thereof include carboxylic acids such as acetic acid (10.1). The numerical value in parentheses written in parallel with the solvent name means the SP value ((cal / cm ³ ) ^1/2 ).

As the solvent, one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily selected.

The amount of the solvent (water is also treated as a solvent) is not particularly limited, but is usually preferably 200 to 5000 parts by mass and 300 to 4000 parts by mass with respect to 100 parts by mass of the formaldehyde reactant used. It is more preferably parts, and particularly preferably 400 to 3500 parts by mass.

(emulsifier)
The emulsifier may be a known one and is not particularly limited.
Preferred emulsifiers include, for example, alkylbenzene sulfonates such as polyvinyl alcohol, carboxymethyl cellulose, ethyl cellulose, methyl cellulose, Kaizen, gum arabic, gelatin, funnel oil, sodium benzenesulfonate, sodium dodecylbenzenesulfonate, polyoxyethylene sulfate, and the like. Examples thereof include ethylene-maleine anhydride copolymer, styrene-maleine anhydride copolymer, isobutylene-maleine anhydride copolymer, poly (meth) acrylic acid and the like.

The emulsifier may be used alone or in combination of two or more, and when two or more are used in combination, the combination and ratio thereof can be arbitrarily selected.
The amount of the emulsifier used is not particularly limited and may be appropriately adjusted according to the type thereof.

In the present invention, the temperature of the interfacial polycondensation is usually preferably 60 to 110 ° C, more preferably 65 to 100 ° C, and particularly preferably 70 to 90 ° C.
The time of interfacial polycondensation is preferably 0.5 to 5 hours, more preferably 1 to 4 hours, and particularly preferably 1.5 to 3 hours.

After polycondensation, for example, the microcapsules are obtained as an aqueous dispersion.
The obtained microcapsules may be used as they are for the intended purpose, or may be used for the intended purpose after performing known post-treatment, purification, etc. as necessary, and the dispersion medium is removed. After that, it may be used for the intended purpose.

When one or more of the microcapsules selected from the group consisting of polyurea, polyurethane and polyamide are used as film-forming components, the microcapsules are made of polyurea, polyurethane and polyamide within a range that does not impair the effects of the present invention. Either or both of the other oligomers and polymers, which do not fall under any of the above, may be further used as a film-forming component.
The other oligomers and polymers may be of only one kind, may be of two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

In the microcapsules, the ratio of the total content of the other oligomers and polymers to the total content of the film-forming components is preferably 5% by mass or less, more preferably 3% by mass or less, and 1 It is particularly preferable that it is by mass or less.
That is, in the microcapsules, the ratio of the total content of polyurea, polyurethane and polyamide to the total content of the film-forming component is preferably 95% by mass or more, more preferably 97% by mass or more. It is particularly preferable that it is 99% by mass or more.

The average particle size of the microcapsules is not particularly limited, but is preferably 0.5 to 20 μm, more preferably 0.5 to 16 μm, and even more preferably 0.5 to 13 μm.
Incidentally, the "average particle size", as used herein, unless otherwise noted, were measured by a method using a Coulter counter, it means a median D ₅₀ of the cumulative volume distribution.

In the microcapsules, the thickness of the outer shell membrane enclosing the formaldehyde reactant is preferably 30 to 500 nm, more preferably 50 to 300 nm.

The microcapsules (microcapsules) may contain other components in addition to the formaldehyde reactant and the solvent, reflecting the production method thereof.

By selecting a formaldehyde reactant that does not have an amino group and an amino group salt-forming group, the microcapsules (microcapsules) containing the formaldehyde reactant can be obtained even if the film-forming component is a polycondensate. Easy to obtain.
When a formaldehyde reactant having an amino group or an amino group salt-forming group is used, an essential raw material compound to be polycondensed when forming a film-forming component which is a polycondensate during the production of microcapsules (for example). , The isocyanate compound, carboxylic acid, carboxylic acid chloride, etc.) reacts with the formaldehyde reactant having an amino group or an amino group salt forming group, and it is presumed that the formation of microcapsules is inhibited. On the other hand, it is speculated that the inhibition of the formation of such microcapsules may be suppressed by using a formaldehyde reactant having no amino group and an amino group salt forming group.

The microcapsules themselves have a sustained release property that gradually releases the contained formaldehyde reactant to the outside over time. Therefore, the microcapsules can maintain the effect of removing formaldehyde for a long period of time, and are suitable as a component of a removing agent for removing formaldehyde that tends to stay in a room, for example.

The microcapsules can be improved in strength against water (sometimes referred to as "water resistance" in the present specification) by selecting a specific range of the constituent materials of the microcapsules. Microcapsules with high water resistance are advantageous in that they can maintain the sustained release properties of formaldehyde reactants when coexisting with water for a longer period of time. For example, in the aqueous dispersion in which the microcapsules are dispersed in water, which corresponds to the composition for forming the first drug-containing layer described above, the microcapsules have high water resistance, so that the microcapsules are microcapsules. The release of formaldehyde reactants from the inside into the water is more highly suppressed. Therefore, when this aqueous dispersion is used for the purpose, the sustained release property of the formaldehyde reactant can be maintained for a longer period of time, so that the effect of removing formaldehyde can be continuously obtained for a longer period of time.

The water resistance of the microcapsules is determined, for example, by preparing an aqueous dispersion of the microcapsules or a mixture obtained by further adding the aqueous dispersion to water, and after a lapse of a certain period of time, the microcapsules in the aqueous dispersion or the mixture. It can be confirmed by quantifying the amount of formaldehyde reactant released (extracted) from the inside of the capsule and present in water. It can be said that the smaller the amount of formaldehyde reactant in water, the higher the water resistance of the microcapsules.

In terms of improving the water resistance of the microcapsules, preferred formaldehyde reactants include, for example, the 1,2,3-triazole compound and its salt, and the 1,2,4-triazole compound and its salt. Examples thereof include compounds having a triazole skeleton, such as the above 1,2,3-benzotriazole compounds and salts thereof.
The 1,2,3-triazole-based compound is preferably 1,2,3-triazole.
The 1,2,4-triazole compounds are 1,2,4-triazole, 3-n-butyl-1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 3, It is preferably 5-di-n-butyl-1,2,4-triazole or 3,5-diphenyl-1,2,4-triazole.
The 1,2,3-benzotriazole-based compound is preferably 1,2,3-benzotriazole, 4-methyl-1H-benzotriazole, or 5-methyl-1H-benzotriazole.

In terms of improving the water resistance of the microcapsules, the preferable solvent has, for example, an SP value of 6.5 (cal / cm ³ ) ^1/2 or more and less than 10.4 (cal / cm ³ ) ^1/2. More specifically,
Alcohols such as 2-ethylhexanol (9.5);
Ketones such as acetone (10.0), methyl ethyl ketone (9.3), methyl propyl ketone (8.7), methyl isopropyl ketone (8.5);
Di n-butyl phthalate (9.4), ethyl acetate (9.1), bis sevacinate (2-ethylhexyl) (8.7), n-butyl acetate (8.5), isopropyl acetate (8.4) ), Isobutyl acetate (8.3) and other esters (carboxylic acid esters);
Chained and cyclic ethers such as dioxane (9.9), tetrahydrofuran (9.1), diethyl ether (7.4), isopropyl ether (6.9);
Benzene (9.2), toluene (8.9), xylene (8.8), ethylbenzene (8.8), cyclohexane (8.2), n-octane (7.6), n-hexane (7.). 3), aromatic and aliphatic hydrocarbons such as n-pentane (7.0);
Halogenated hydrocarbons (halogenated aliphatic hydrocarbons) such as methylene chloride (9.7), chloroform (9.3), trichlorethylene (9.2), carbon tetrachloride (8.6);
Carbon sulfide such as carbon disulfide (10.0);
Examples thereof include carboxylic acids such as acetic acid (10.1).
Among these, the solvent is more preferably one having an SP value of 6.5 to 9.5 (cal / cm ³ ) ^1/2.

Polyurea is mentioned as a preferable film-forming component in terms of improving the water resistance of the microcapsules.
The polyurea is selected from the group consisting of isophorone diisocyanate, a derivative of isophorone diisocyanate (provided that the isocyanate group is not substituted), and a trimethylolpropane adduct of isophorone diisocyanate as the isocyanate compound which is a raw material compound. Those obtained by using seeds or two or more kinds are preferable.

Preferred examples of the emulsifier in terms of improving the water resistance of the microcapsules include carboxymethyl cellulose.

[Non-microcapsules]
The non-microcapsule is a formaldehyde reactant that is not microencapsulated and is contained in the first drug-containing layer from the beginning of its formation.

Examples of the non-microcapsule (formaldehyde reactant) include those having a "-NH-" group or a "-NH-" salt-forming group, which are similar to those contained in the microcapsules. ..
However, since the non-microcapsules are not encapsulated in microcapsules, those having an amino group (-NH ₂ ) or an amino group salt-forming group are also preferable. Here, the "amino group salt-forming group" is as described in the case of the microcapsules. It is presumed that the amino group salt-forming group itself or becomes an amino group, and this amino group exhibits reactivity with formaldehyde.

The non-microcapsules having an amino group or an amino group salt-forming group are preferably organic compounds.
Further, the non-microcapsule having an amino group or an amino group salt-forming group may have one or both of the "-NH-" group and the "-NH-" salt-forming group, or may be present. You don't have to.

The total number of amino groups and amino group salt-forming groups in one molecule of a non-microcapsule having an amino group or an amino group salt-forming group may be only one, two or more, or two or more. , These two or more groups may be the same or different from each other. That is, these two or more groups may be all the same, all may be different, or only a part may be the same. Usually, because of the ease of preparation of the desired non-microcapsules, these two or more groups are all identical, i.e. all amino groups or all identical amino group salt formations. It is preferably a group.
If the non-microcapsule having an amino group or an amino group salt-forming group has a "-NH-" group or a "-NH-" salt-forming group, the "-NH-" group or the "-NH-" salt-forming group The type, number, binding position, etc. of the microcapsules may be the same as in the case of the microcapsules.

The non-microcapsule is electrically neutral as a whole molecule, that is, the total valence of the cation part and the total valence of the anion in one molecule of the non-microcapsule are the same. Is preferable.

The total number of amino groups or amino group salt-forming groups in one molecule of the non-microcapsule is preferably 1 to 4, more preferably 1 to 3.

The position of the amino group or the amino group salt-forming group in the molecule of the non-microcapsule is not particularly limited, and for example, when the non-microcapsule has a chain structure, it may be the terminal portion of the molecule. It may be other than the terminal part of the molecule.

The non-microcapsules may be linear, branched or cyclic, and may have both a chain structure and a cyclic structure.

When the non-microcapsule has a cyclic structure, the ring may be either monocyclic or polycyclic, and may be either an aliphatic ring or an aromatic ring, and the aliphatic ring and the aromatic ring may be used. May be a condensed polycyclic ring.

In non-microcapsules, the nitrogen atom of the amino group and the amino group salt forming group is preferably bonded to the carbon atom of the nitrogen atom or the hydrocarbon group.
The total number of amino groups and amino group salt-forming groups thus bonded to one carbon atom of the hydrocarbon group may be any of 1 to 3.
The total number of amino groups and amino group salt-forming groups thus bonded to one nitrogen atom may be only one or two, but is preferably one.

Preferred non-microcapsules include, for example, carboxylic acid hydrazide and salts thereof which may have a substituent, alkylamines which may have a substituent and salts thereof and the like.
More preferred non-microcapsules include, for example, adipic acid dihydrazide and its salt which may have a substituent, and 1,3-bis (aminomethyl) cyclohexane and a salt thereof which may have a substituent. And so on.

The structures of adipic acid dihydrazide and 1,3-bis (aminomethyl) cyclohexane are shown below.
The compounds shown here are just one example of non-microcapsules.

The non-microcapsules are preferably those having either or both of an amino group and an amino group salt forming group from the viewpoint of higher reactivity with formaldehyde.

Up to this point, the microcapsules and non-microcapsules contained in the first drug-containing layer have been described, but the same applies to the microcapsules and non-microcapsules contained in the second drug-containing layer and the coating layer. be.
The non-microcapsules contained in the second drug-containing layer and the coating layer are contained therein from the beginning of formation of these (second drug-containing layer, coating layer).

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the examples shown below.

[Example 1]
<Manufacturing of laminated body>
(Manufacturing of microcapsules)
Ethyl acetate solution of bis (2-ethylhexyl) sebacate (20.0 g manufactured by Toyokuni Oil Co., Ltd.) and trimethylolpropane adduct (IPDI-TMP adduct) of isophorone diisocyanate having a concentration of 75% by mass. 5-Methyl-1H-benzotriazole (10.0 g manufactured by Wako Pure Chemical Industries, Ltd.) was added to and dissolved in a mixture of "Takenate D-140N" manufactured by 25.0 g and a solid content of 18.8 g). .. Next, the obtained mixture was added to a carboxymethyl cellulose aqueous solution (300 g, solid content 21.0 g) having a concentration of 7% by mass, and using an emulsifier (manufactured by Primix Corporation), the rotation speed was 12000 rpm and the time was 5 minutes. It was emulsified under the conditions. Interfacial polycondensation was performed by adding 1,3-bis (aminomethyl) cyclohexane (2.7 g manufactured by Tokyo Chemical Industry Co., Ltd.) to the emulsion obtained above and stirring at 80 ° C. for 2 hours. ..
Based on the above, the polycondensate of 1,3-bis (aminomethyl) cyclohexane and the IPDI-TMP adduct is used as a film-forming component, 5-methyl-1H-benzotriazole as a formaldehyde reactant, and sebacic acid as a solvent. Microcapsules (microcapsules) containing bis (2-ethylhexyl) and ethyl acetate, respectively, were obtained as an aqueous dispersion.

The microcapsule aqueous dispersion obtained above is coated on high-quality paper using a bar coater, dried at 105 ° C. for 90 seconds, and then used at an electron microscope (manufactured by JEOL Ltd.) at a magnification of 500 times. The coated and dried parts were observed in the above, and it was confirmed that the desired microcapsules were obtained. The average particle size of the obtained microcapsules was measured using a Coulter counter (manufactured by Beckman Coulter) and found to be 12.0 μm.

(Manufacturing of foamed resin composition)
An aqueous dispersion containing an ethylene-vinyl acetate copolymer resin (EVA) (containing 100 parts by mass of EVA), a heat-expandable microcapsule foaming agent a1 (12 parts by mass), and a heat-expandable microcapsule foaming agent b1 (2 parts by mass). Part), a filler (90 parts by mass), and an additive (10 parts by mass) were blended to obtain a foamed resin composition.
The heat-expandable microcapsule foaming agent a1 has an average particle size of 7 μm, a gas encapsulation rate of 32%, and a shell film thickness of 0.04 μm at the time of maximum foaming.
The heat-expandable microcapsule foaming agent b1 has an average particle size of 31 μm, a gas encapsulation rate of 15%, and a shell film thickness of 0.19 μm at the time of maximum foaming.
The filler is fine-grained heavy calcium carbonate (“MC-100” manufactured by Asahi Mineral Co., Ltd.).
The additive is a special carboxylic acid type polymer surfactant (“P-520” manufactured by Kao Corporation).

(Manufacturing of Composition for Forming First Drug-Containing Layer)
At room temperature, adipic acid dihydrazide (non-microcapsule), which is a formaldehyde reactant, is added to the microcapsule aqueous dispersion obtained above, the foamed resin composition obtained above is added, and the mixture is stirred. As a result, a composition for forming a first drug-containing layer was obtained. In this composition for forming a first drug-containing layer, the ratio of the content of 5-methyl-1H-benzotriazole contained in the microcapsules to the total content of the components other than the solvent is 1% by mass, and microencapsulation is performed. The ratio of the content of the untreated adipate dihydrazide was 2% by mass, the ratio of the content of the ethylene vinyl acetate copolymer resin was 45% by mass, and the ratio of the content of the heat-expandable microcapsule foaming agent a1 was 5. The ratio of the content of the heat-expandable microcapsule foaming agent b1 is 1% by mass, the ratio of the content of the filler is 40% by mass, and the ratio of the content of the additive is 2.2% by mass. %.

(Manufacturing of composition for forming a second drug-containing layer)
Adipic acid dihydrazide (non-microcapsule), which is a formaldehyde reactant, was added to an aqueous dispersion containing an acrylic resin at room temperature, and the mixture was stirred to obtain a composition for forming a second drug-containing layer. .. In this composition for forming a second drug-containing layer, the ratio of the content of adipic acid dihydrazide to the total content of the components other than the solvent was 5% by mass, and the ratio of the content of the acrylic resin was 20% by mass. ..

(Manufacturing of composition for forming a coating layer)
At room temperature, the microcapsule aqueous dispersion obtained above and dihydrazide adipic acid, which is a formaldehyde reactant, are added to the aqueous dispersion containing an acrylic resin (SP value 8 to 9) and stirred. As a result, a composition for forming a coating layer (solid content concentration 40% by mass) was obtained. In this coating layer forming composition, the ratio of the content of 5-methyl-1H-benzotriazole contained in the microcapsules to the total content of the components other than the solvent was 5% by mass, and it was not microencapsulated. The ratio of the content of adipic acid dihydrazide was 4% by mass, and the ratio of the content of the acrylic resin was 20% by mass.

(Manufacturing of laminated body)
Using the composition for forming a first drug-containing layer, the composition for forming a second drug-containing layer, and the composition for forming a coating layer obtained above, the laminate of the present invention has the same configuration as that shown in FIG. Manufactured.
That is, as the base material, a base material having a two-layer structure in which the first base material and the second base material are laminated was used. Here, the first base material is a backing paper for wallpaper (“WK665” manufactured by KJ Special Paper Co., Ltd., thickness 105 μm) on which an ethylene-vinyl acetate copolymer resin-based foamed resin layer is laminated. 2 The base material is a plaster sheet (thickness 9.5 mm).
The composition for forming the second drug-containing layer is applied onto the first base material of the base material to form a coated layer, which is then dried to form a non-foaming resin as the second drug-containing layer. A layer (thickness 1 μm) was formed.
Next, the composition for forming the first drug-containing layer is coated on the second drug-containing layer to form a coated layer having a thickness of 180 μm, which is dried to obtain the first drug-containing layer. Formed.
A water-based ink layer (thickness 2 μm) is formed as a printing layer on the first chemical-containing layer by a printing method using a water-based ink (“Hydric Extender” manufactured by Nippon Fine Chemical Co., Ltd., main component: acrylic resin). did.
The coating layer forming composition is applied onto the printing layer using an applicator to form a coating layer having a thickness of 30 μm, and the coating layer is dried to form a coating layer (thickness 30 μm). Formed.
Next, the obtained laminate was heated in an oven at 170 ° C. for 35 seconds to foam the first drug-containing layer to obtain a foamed resin layer (thickness 600 μm).
Next, by inserting a needle-shaped member from the coating layer side into the laminate provided with the foamed resin layer as the first drug-containing layer, the first surface of the coating layer to the first surface of the second base material are inserted. A through hole (hole diameter 50 μm) was formed. The number of through holes was 62,500 / m ² .
As described above, the second base material, the first base material, the second drug-containing layer, the first drug-containing layer, the printing layer and the coating layer are laminated in this order in this order, and the coating layer becomes the outermost layer. The laminate of the present invention was obtained with through holes reaching from the first surface of the coating layer to the first surface of the second base material.

<Evaluation of composition for forming a coating layer and laminate>
(Viscosity of composition for forming a coating layer)
The viscosity of the coating layer forming composition obtained above was measured at 23 ° C. using a B-type viscometer (“TVB10 type viscometer” manufactured by Toki Sangyo Co., Ltd., rotor: No. 3). The results are shown in Table 1.

(Coatability of coating layer forming composition)
At the time of manufacturing the above-mentioned laminate, the coatability when the coating layer forming composition is applied on the printed layer is described below from the viewpoint of the uniformity of the shape (thickness) of the formed coated layer. It was evaluated according to the evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
A: The uniformity of the coating layer is extremely high.
B: Inferior to A, but the coating layer has uniformity.
Although inferior to C: B, the coating layer has a uniformity that does not cause any problem in practical use.
D: The coating layer clearly has no uniformity.

(Ra and Rz on the surface of the coating layer)
Regarding the surface of the coating layer in the laminate obtained above, the surface roughness (Ra) was measured in accordance with JIS B0601: 2001 (ISO4287: 1997), and the maximum height roughness (Rz) was determined by JIS B. Measured according to 0601: 1994. Then, these measurement results were classified according to the following evaluation criteria. The results are shown in Table 1.
(Ra evaluation criteria)
A: Ra is 0 μm or more and less than 1 μm.
B: Ra is 1 μm or more and less than 2 μm.
C: Ra is 2 μm or more and less than 17 μm.
D: Ra is 17 μm or more.
(Rz evaluation criteria)
A: Rz is 0 μm or more and less than 1 μm.
B: Rz is 1 μm or more and less than 18 μm.
C: Rz is 18 μm or more and less than 60 μm.
D: Rz is 60 μm or more.

(Formaldehyde removing ability of laminated body (1))
In a desiccator having a volume of 1.6 L and an inner diameter of 24 cm, a unglazed plate that partitions the space inside the desiccator was fixed above the bottom surface substantially parallel to the bottom surface.
Next, a glass container containing distilled water (300 mL) was placed on the bottom surface of the desiccator below the unglazed plate.
Next, in the atmosphere, a polyethylene container containing a formaldehyde aqueous solution having a concentration of 5 ppm and the laminate obtained above were placed side by side on the upper surface of the unglazed plate, and the desiccator was immediately sealed. Then, in this state, the laminated body was stored in a desiccator.
After that, 1 day, 4 days, 7 days, and 11 days after the start of storage, a part of the distilled water contained in the glass container in the desiccator was collected as a sample, and the above was made in accordance with JIS A 6921. The concentration of formaldehyde in the sample was measured.

Separately, using the same water-based ink used when manufacturing the laminate, a water-based ink layer (thickness 2 μm) was formed as a printing layer on a substrate having the same two-layer structure by a printing method, and a standard laminate was formed. Got That is, this standard laminate is the same as the laminate obtained above, except that it does not have the second drug-containing layer, the first drug-containing layer, the coating layer, and the through hole.
Next, this standard laminate is stored in a desiccator in the same manner as in the case of the laminate, and thereafter, 1 day, 4 days, 7 days, and 11 days after the start of storage, each of them is placed in a glass container in the desiccator. A part of the contained distilled water was sampled as a standard sample, and the concentration of formaldehyde in the standard sample was measured in accordance with JIS A 6921.

From each of the measured values obtained above, the formaldehyde removal rate (%) of the laminate was calculated according to the following formula (i).
Then, the formaldehyde removing ability (1) of the laminated body was evaluated according to the following evaluation criteria. The results are shown in Table 1.
1- [Concentration of formaldehyde in sample] / [Concentration of formaldehyde in standard sample] x 100 ... (i)
(Evaluation criteria)
A: The formaldehyde removal rate 7 days after the start of storage is 70% or more.
B: The formaldehyde removal rate 7 days after the start of storage is 50% or more and less than 70%.
C: The formaldehyde removal rate 7 days after the start of storage is 30% or more and less than 50%.
D: The formaldehyde removal rate 7 days after the start of storage is less than 30%.

(Formaldehyde removal ability of laminated body (2))
In accordance with JIS A 1905-1, two small chambers are used, an MDF material (formaldehyde generation amount 167 mL / min) is used as a formaldehyde generation source, and the formaldehyde concentration in the air is measured for the laminate obtained above. Then, the ventilation volume conversion value (m ³ / m ² · h) was calculated. Then, the formaldehyde removing ability (2) of the laminated body was evaluated according to the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
A: The ventilation volume conversion value 31 days after the start of measurement is 0.7 or more.
B: The ventilation volume conversion value 31 days after the start of measurement is 0.5 or more and less than 0.7.
C: The ventilation volume conversion value 31 days after the start of measurement is 0.2 or more and less than 0.5.
D: The ventilation volume conversion value 31 days after the start of measurement is less than 0.2.

<Manufacturing of laminated body and evaluation of composition for forming coating layer and laminated body>
[Reference Example 1]
In the case of Example 1, except that an acrylic resin (SP value 7 to 10) different from the above-mentioned acrylic resin (SP value 8 to 9) was used in the production of the coating layer forming composition. A composition for forming a coating layer (solid content concentration 20% by mass) was produced by the same method as above. In this coating layer forming composition, the ratio of the content of 5-methyl-1H-benzotriazole contained in the microcapsules to the total content of the components other than the solvent was 4% by mass, and it was not microencapsulated. The ratio of the content of adipic acid dihydrazide was 4% by mass, and the ratio of the content of the acrylic resin was 8% by mass.
Then, using the obtained composition for forming a coating layer, a laminate was produced by the same method as in Example 1 except that the second drug-containing layer was not formed, and the layer was formed. The composition and laminate were evaluated. That is, in the manufactured laminate, the second base material, the first base material, the first drug-containing layer, the printing layer and the coating layer are laminated in this order in this order, and the coating layer becomes the outermost layer. It is provided with through holes that reach from the first surface of the coating layer to the first surface of the second base material. The results are shown in Table 1.

[Reference Examples 2 to 4]
In the case of Reference Example 1, except that an acrylic resin (SP value 7 to 10) different from the above acrylic resin (SP value 7 to 10) was used in the production of the coating layer forming composition. A composition for forming a coating layer (solid content concentration 20% by mass) was produced by the same method as above. In this coating layer forming composition, 5-methyl-1H-benzotriazole encapsulated in microcapsules, adipic acid dihydrazide not microencapsulated, and an acrylic resin with respect to the total content of components other than the solvent. The ratio of each content is the same as in the case of Reference Example 1. Then, a laminate was produced by the same method as in Reference Example 1 except that the obtained composition for forming a coating layer was used, and the composition for forming a coating layer and the laminate were evaluated. The results are shown in Table 1 or Table 2.

[Reference Examples 5 to 6]
In the case of Reference Example 1, except that an acrylic resin (SP value 8 to 9) different from the above-mentioned acrylic resin (SP value 7 to 10) was used in the production of the coating layer forming composition. A composition for forming a coating layer (solid content concentration: 40% by mass) was produced by the same method as above. In this coating layer forming composition, the ratio of the content of 5-methyl-1H-benzotriazole contained in the microcapsules to the total content of the components other than the solvent was 5% by mass, and it was not microencapsulated. The ratio of the content of adipic acid dihydrazide was 4% by mass, and the ratio of the content of the acrylic resin was 20% by mass.
Then, a laminate was produced by the same method as in Reference Example 1 except that the obtained composition for forming a coating layer was used, and the composition for forming a coating layer and the laminate were evaluated. The results are shown in Table 2.

[Reference Example 7]
In the case of Example 1, except that an acrylic resin (SP value 7 to 10) different from the above-mentioned acrylic resin (SP value 8 to 9) was used in the production of the coating layer forming composition. A composition for forming a coating layer (solid content concentration 20% by mass) was produced by the same method as above. In this coating layer forming composition, the ratio of the content of 5-methyl-1H-benzotriazole contained in the microcapsules to the total content of the components other than the solvent was 4% by mass, and it was not microencapsulated. The ratio of the content of adipic acid dihydrazide was 4% by mass, and the ratio of the content of the acrylic resin was 8% by mass.
Then, a laminate was produced by the same method as in Example 1 except that the obtained composition for forming a coating layer was used, and the composition for forming a coating layer and the laminate were evaluated. The results are shown in Table 1.

[Reference Example 8]
A laminate was produced by the same method as in Example 1 except that the second drug-containing layer was not formed, and the composition for forming the coating layer and the laminate were evaluated. That is, in the manufactured laminate, the second base material, the first base material, the first drug-containing layer, the printing layer and the coating layer are laminated in this order in this order, and the coating layer becomes the outermost layer. It is provided with through holes that reach from the first surface of the coating layer to the first surface of the second base material. The results are shown in Table 2.

[Reference Example 9]
A laminate was produced by the same method as in Reference Example 7 except that the second agent-containing layer was not formed, and the composition for forming the coating layer and the laminate were evaluated. That is, in the manufactured laminate, the second base material, the first base material, the first drug-containing layer, the printing layer and the coating layer are laminated in this order in this order, and the coating layer becomes the outermost layer. It is provided with through holes that reach from the first surface of the coating layer to the first surface of the second base material. The results are shown in Table 2.

[Comparative Example 1]
A first comparative agent containing no 5-methyl-1H-benzotriazole encapsulated in microcapsules in the same manner as in Example 1 except that water was used instead of the microcapsule aqueous dispersion. A composition for forming a containing layer was produced. In this composition for forming a first drug-containing layer for comparison, the ratio of the content of unmicroencapsulated adipic acid dihydrazide to the total content of components other than the solvent was 2% by mass, and ethylene-vinyl acetate was used. The ratio of the content of the polymer resin is 45% by mass.
Moreover, the composition for forming a coating layer was produced by the same method as in the case of Reference Example 1.
Then, instead of the above-mentioned composition for forming the first drug-containing layer, the composition for forming the first drug-containing layer for comparison is used, and instead of the above-mentioned composition for forming the coating layer, the coating produced here is used. A laminate was produced and evaluated by the same method as in Example 1 except that the layer-forming composition was used. The results are shown in Table 1.

[Comparative Example 2]
A first comparative agent containing no 5-methyl-1H-benzotriazole encapsulated in microcapsules in the same manner as in Example 1 except that water was used instead of the microcapsule aqueous dispersion. A composition for forming a containing layer was produced. In this composition for forming a first drug-containing layer for comparison, the ratio of the content of unmicroencapsulated adipic acid dihydrazide to the total content of components other than the solvent was 2% by mass, and ethylene-vinyl acetate was used. The ratio of the content of the polymer resin is 45% by mass.
Moreover, the composition for forming a coating layer was produced by the same method as in the case of Reference Example 6.
Then, instead of the above-mentioned composition for forming the first drug-containing layer, the composition for forming the first drug-containing layer for comparison is used, and instead of the above-mentioned composition for forming the coating layer, the coating produced here is used. A laminate was produced and evaluated by the same method as in Example 1 except that the layer-forming composition was used. The results are shown in Table 1.

[Comparative Example 3]
A laminate was produced by the same method as in Comparative Example 1 except that the second agent-containing layer was not formed, and the composition for forming the coating layer and the laminate were evaluated. That is, in the manufactured laminate, the second base material, the first base material, the first drug-containing layer, the printing layer and the coating layer are laminated in this order in this order, and the coating layer becomes the outermost layer. It is provided with through holes that reach from the first surface of the coating layer to the first surface of the second base material. The results are shown in Table 2.

[Comparative Example 4]
A laminate was produced by the same method as in Comparative Example 2 except that the second agent-containing layer was not formed, and the composition for forming the coating layer and the laminate were evaluated. That is, in the manufactured laminate, the second base material, the first base material, the first drug-containing layer, the printing layer and the coating layer are laminated in this order in this order, and the coating layer becomes the outermost layer. It is provided with through holes that reach from the first surface of the coating layer to the first surface of the second base material. The results are shown in Table 2.

As is clear from the above results, the laminate of Example 1 had good evaluation results of formaldehyde removing ability (1) and (2), and had a high sustaining effect of formaldehyde removing ability.
In Example 1, the viscosity of the coating layer forming composition was 20000 mPa · s (20,000 cps), and although the coatability of this coated layer forming composition was not good, the laminated body was the first drug-containing layer. Since it was provided with a second drug-containing layer, it had a high sustaining effect on formaldehyde removal ability. The coatability of this coating layer forming composition was sufficiently practical.

The evaluation results of the formaldehyde removing ability (1) and (2) of the laminated body of Reference Example 7 were inferior to those of the laminated body of Example 1.
In Reference Example 7, although the laminate includes the first drug-containing layer and the second drug-containing layer, the viscosity of the coating layer forming composition is 80 mPa · s (80 cps), and this coated layer forming composition. The coatability of No. 1 was inferior to that of Example 1.

The evaluation results of the formaldehyde removing ability (1) and (2) of the laminated body of Comparative Examples 1 and 2 were inferior to those of the laminated body of Example 1, and the sustaining effect of the formaldehyde removing ability was inferior.
In Comparative Examples 1 and 2, the laminate includes the second agent-containing layer, and the viscosity of the coating layer forming composition is 100 to 14,000 mPa · s (100 to 14,000 cps). Although the coatability was good, the first drug-containing layer for comparison did not contain the microcapsules.

The laminates of Reference Examples 1 to 6 had good evaluation results of formaldehyde removing ability (1) and (2), and had a high sustaining effect of formaldehyde removing ability. Among them, the laminates of Reference Examples 3 to 6 had a higher sustaining effect of formaldehyde removing ability, and the laminate of Reference Example 3 had a particularly high sustaining effect of formaldehyde removing ability.
In Reference Examples 1 to 6, although the laminate does not have the second drug-containing layer, it does have the first drug-containing layer, and the viscosity of the coating layer forming composition is 100 to 14000 mPa · s (100 to 1 to 1). It was 14000 cps), and the coatability of these coating layer forming compositions was good.

The evaluation results of the formaldehyde removing ability (1) and (2) of the laminated body of Reference Example 8 were inferior to those of the laminated body of Reference Examples 1 to 6.
Similar to the laminates of Reference Examples 1 to 6, the laminate of Reference Example 8 did not have the second agent-containing layer but provided the first agent-containing layer, but the viscosity of the coating layer forming composition was provided. Was 20000 mPa · s (20000 cps), and the coatability of this coating layer forming composition was not good.

The evaluation results of the formaldehyde removing ability (1) and (2) of the laminated body of Reference Example 9 were inferior to those of the laminated body of Reference Examples 1 to 8.
In Reference Example 9, although the laminate has the first drug-containing layer, it does not have the second drug-containing layer, and the viscosity of the coating layer forming composition is 80 mPa · s (80 cps). The coatability of this coating layer forming composition was inferior.

In the laminated bodies of Comparative Examples 3 to 4, the evaluation results of the formaldehyde removing ability (1) and (2) were remarkably inferior, and the sustaining effect of the formaldehyde removing ability was remarkably inferior.
In Comparative Examples 3 to 4, the viscosity of the coating layer forming composition is 100 to 14,000 mPa · s (100 to 14,000 cps), and although the coatability of these coating layer forming compositions is good, the laminated body is the first. The two drug-containing layers were not provided, and the first drug-containing layer for comparison did not contain microcapsules.

From the results of Comparative Examples 1 and 2 and Comparative Examples 3 and 4, it was confirmed that the formaldehyde removing ability of the laminated body was improved by providing the second drug-containing layer.

Then, from the results of Example 1 and Reference Example 8, even if the coating property of the coating layer forming composition is not good, the laminated body includes the second chemical-containing layer to remove formaldehyde from the laminated body. It was confirmed that the sustained effect of Noh was high.

As described above, the sustaining effect of the formaldehyde removing ability of the laminated body was greatly affected by the presence or absence of the second drug-containing layer.

On the other hand, from the results of Reference Examples 1 to 6, even if the laminate does not have the second drug-containing layer, the first drug-containing layer is provided and the viscosity of the coating layer forming composition is within a specific range. It was confirmed that if the coating property of the coating layer forming composition is good, the effect of sustaining the formaldehyde removing ability of the laminate is improved.

The laminates of Comparative Example 3 and Reference Example 1 are the same in that they do not have a second drug-containing layer.
The laminate of Comparative Example 3 has the same coating layer as that of the laminate of Reference Example 1, but the first agent-containing layer for comparison does not contain the microcapsules. Therefore, in the laminated body of Comparative Example 3, the evaluation results of the formaldehyde removing ability (1) and (2) are inferior to those of the laminated bodies of Reference Examples 1 to 6 and Reference Example 8 due to the influence thereof, and formaldehyde removal is performed. The sustained effect of Noh was remarkably low.

The laminates of Comparative Example 4 and Reference Example 6 are the same in that they do not have a second drug-containing layer.
The laminate of Comparative Example 4 has the same coating layer as that of the laminate of Reference Example 6, but the first agent-containing layer for comparison does not contain the microcapsules. Therefore, in the laminated body of Comparative Example 4, the evaluation results of the formaldehyde removing ability (1) and (2) are inferior to those of the laminated bodies of Reference Examples 1 to 6 and Reference Example 8 due to the influence thereof, and formaldehyde removal is performed. The sustained effect of Noh was remarkably low.

In the laminates of Reference Examples 1 to 6 in which the first drug-containing layer contains both microcapsules and non-microcapsules, the first drug-containing layer contains non-microcapsules and contains microcapsules. It was remarkably superior in the sustaining effect of the formaldehyde removing ability to the laminates of Comparative Examples 3 and 4 which had not been used, and showed a synergistic effect by the combined use of microcapsules and non-microcapsules.
In the laminate of Reference Example 9, although the first drug-containing layer contains both microcapsules and non-microcapsules, the coatability of the coating layer forming composition is further higher than that of Reference Example 8. It was inferior, and it was presumed that the formaldehyde removing ability of the coating layer was significantly reduced due to the influence, and the sustaining effect of the formaldehyde removing ability of the laminate was inferior.

The present invention can be used as a formaldehyde removing material such as wallpaper.

1,2,3 ... Laminated body, 11,21,31 ... Base material, 11a, 21a, 31a ... First surface of base material, 11b, 21b, 31b ... Second base material Surfaces, 211 ... 1st base material, 211a ... 1st surface of 1st base material, 212 ... 2nd base material, 212a ... 1st surface of 2nd base material, 212b ... 2nd surface of the 2nd substrate, 12 ... 1st drug-containing layer, 22 ... resin layer, 22a ... 1st surface of the resin layer, 23 ... printing layer, 23a ... printing layer First surface, 14, 24 ... Covering layer, 14a, 24a ... First surface of the coating layer, 16, 26 ... Second drug-containing layer, 16a, 26a ... Second drug-containing layer 1st surface, 25 ... Adhesive layer, 310 ... Adhesive layer, 20, 30 ... Through holes

Claims (4)

A laminate comprising a base material, a second drug-containing layer, a first drug-containing layer, and a coating layer.
The second drug-containing layer is arranged between the base material and the first drug-containing layer.
The first drug-containing layer is arranged between the second drug-containing layer and the coating layer.
The coating layer is the outermost layer of the laminated body, and is
The first drug-containing layer is a foam layer containing a microencapsulated formaldehyde reactant and a non-microencapsulated formaldehyde reactant.
The second agent-containing layer contains one or both of a microencapsulated formaldehyde reactant and a non-microencapsulated formaldehyde reactant.
The coating layer is a coating layer in which one or both of a microencapsulated formaldehyde reactant and a non-microencapsulated formaldehyde reactant are blended and the viscosity is 90 mPa · s or more. A laminated body formed by using a forming composition. The coating layer further comprises polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, AS resin, ABS resin, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polyethylene naphthalate. , Polybutylene naphthalate, polyphenylene sulfide, polysulfone, polycarbonate, epoxy resin, melamine resin, phenol resin, urea resin, polyurethane, polyimide, ethylene vinyl acetate copolymer resin, polybutadiene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, The laminate according to claim 1, which contains one or more selected from the group consisting of butyl rubber, chloropurene rubber, polyisobutylene rubber, polyethylene rubber, propylene rubber and silicon rubber. The laminate according to claim 1 or 2, wherein the second drug-containing layer is laminated in direct contact with the substrate. The method for manufacturing a laminate according to any one of claims 1 to 3.
The coating layer is the outermost layer, the second drug-containing layer is located between the base material and the first drug-containing layer, and the first drug-containing layer is the second drug-containing layer. , These layers are arranged so as to be located between the covering layer and the coating layer.
The first, which is a foaming layer, uses a composition for forming a first drug-containing layer, which comprises a microencapsulated formaldehyde reactant, a non-microencapsulated formaldehyde reactant, and a foaming agent. Form a drug-containing layer,
The second drug-containing layer-forming composition comprising either or both of a microencapsulated formaldehyde reactant and a non-microencapsulated formaldehyde reactant is used to contain the second drug. Form a layer,
A composition for forming a coating layer, which comprises a microencapsulated formaldehyde reactant and a non-microencapsulated formaldehyde reactant, and has a viscosity of 90 mPa · s or more, is used. A method for producing a laminated body, which forms the covering layer.

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