JP2018052057A - Laminate and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which can keep an effect for removing formaldehyde for a long period of time, and to provide a method for producing the same.SOLUTION: A laminate 1 has a medicine-containing layer 12 which contains a microcapsulated formaldehyde reactant and a formaldehyde reactant which is not microcapsulated on at least one surface 11a of a base material 11. A method for producing the laminate 1 includes forming the medicine-containing layer 12 on at least one surface 11a of the base material 11 using a composition for forming the medicine-containing layer obtained by blending the microcapsulated formaldehyde reactant and the formaldehyde reactant which is not microcapsulated.SELECTED DRAWING: Figure 1

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. From such a product, formaldehyde is released, and thus the emitted formaldehyde stays indoors, causing a health hazard to humans and animals. Therefore, development of interior materials such as wallpaper having an effect of removing formaldehyde has been promoted.

  As such an interior material, a formaldehyde scavenger having a function of causing a physical and chemical reaction with formaldehyde to change it into a harmless and odorless state and a wallpaper containing a formaldehyde adsorbent in a resin layer are disclosed. (See Patent Documents 1 and 2).

Japanese Patent Application Laid-Open No. 10-1003004 Japanese Patent Laid-Open No. 2006-113722

The wallpaper disclosed in Patent Documents 1 and 2 is useful as an interior material 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 development of a novel laminate capable of constituting such an interior material is strongly desired.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the laminated body which can maintain the removal effect of formaldehyde for a long term, and its manufacturing method.

  In order to solve the above problems, the present invention comprises a drug-containing layer containing a microencapsulated formaldehyde reagent and a non-microencapsulated formaldehyde reagent on at least one surface of a substrate. Also, a laminate is provided.

In the laminate of the present invention, it is preferable that the formaldehyde reactant in the microcapsule does not have an amino group and a group in which the amino group forms a salt.
In the laminate of the present invention, the formaldehyde reactant that is not microencapsulated preferably has one or both of an amino group and a group in which the amino group forms a salt.
The present invention also provides a method for producing the laminate, comprising: a composition for forming a drug-containing layer comprising a formaldehyde reagent microencapsulated and a formaldehyde reagent not microencapsulated. And a method for producing a laminate, wherein the drug-containing layer is formed on at least one surface of the substrate.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body which can maintain the removal effect of formaldehyde for a long period of time, and its manufacturing method are provided.

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.

<< Laminate >>
The laminate of the present invention is not microencapsulated with a microencapsulated formaldehyde reactant (sometimes referred to herein as “microcapsule agent”) on at least one surface of a substrate. A drug-containing layer containing a formaldehyde reaction agent (sometimes referred to as “non-microcapsule agent” in the present specification) is provided.

  Thus, the laminate of the present invention is provided with the drug-containing layer containing both the microcapsule and the non-microcapsule, so that either one of the microcapsule or the non-microcapsule can be used alone. The formaldehyde removal effect is remarkably superior to the case where the layer is included, and a remarkable synergistic effect is exhibited. More specifically, the laminate of the present invention can maintain the formaldehyde removal effect for a long period of time.

As described later, the drug-containing layer in the laminate of the present invention, which has a remarkably excellent effect of removing formaldehyde, is a drug-containing layer forming composition comprising the microcapsule and the non-microcapsule. Can be formed.
The drug-containing layer in the laminate of the present invention contains both the microcapsule and the non-microcapsule at the beginning of formation.

  The laminate of the present invention may include other layers in addition to the drug-containing layer containing both the microcapsule and the non-microcapsule, and the other layer can be arbitrarily selected according to the purpose. For example, the laminate of the present invention may include a layer containing any one of the microcapsule and the non-microcapsule as the other layer.

The laminated body of the present invention is suitable for providing to an object for removing formaldehyde such as an interior material (for example, wallpaper) and furniture of a building, or a constituent material of these interior material and furniture.
The laminate of the present invention can be provided by a known method such as using an adhesive or using a jig for attachment to the object to be removed of formaldehyde.

The shape of the laminate of the present invention can be arbitrarily selected according to the 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 laminate according to the first embodiment of the present invention. In addition, in order to make the features of the present invention easier to understand, the drawings used in the following description may show the main portions in an enlarged manner for convenience, and the dimensional ratios of the respective components are the same as the actual ones. Not necessarily.
The laminated body 1 shown here includes a drug-containing layer 12 on a base material 11.

[Base material]
It is preferable that the base material 11 is a film form or a sheet form.

Examples of the material of the base material 11 include paper and resin.
Examples of the paper include high-quality paper, art paper, coated paper, cast coated paper, resin coated paper, and synthetic paper.
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, polyethylene naphthalate, Synthetic resins such as 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, butyl rubber, chloroprene rubber, polyisobutylene rubber, ethylene rubber, propylene rubber, silicon rubber, etc. Synthetic rubber, and the like.

Although the base material 11 has shown what is 1 layer here, only 1 layer (single layer) may be sufficient and two or more layers may be sufficient as it. When the substrate 11 has a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of these layers is not particularly limited.
In the present specification, not limited to 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. Means that only some of the layers may be the same ”, and“ a plurality of layers are different from each other ”means“ at least one of the material and thickness of each layer is different from each other ”. means.

Although the thickness of the base material 11 is not specifically limited, It is preferable that it is 40-200 micrometers.
Here, the “thickness of the base material 11” means the thickness of the whole base material 11. For example, the thickness of the base material 11 composed of a plurality of layers is the sum of all the layers constituting the base material 11. Means the thickness.

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} More preferably.

[Drug-containing layer]
The drug-containing layer 12 contains the microcapsule and the non-microcapsule and has a formaldehyde removal activity. That is, the laminated body 1 has the formaldehyde removing ability by including the drug-containing layer 12.

In the laminate 1, the drug-containing layer 12 is provided on one surface (which may be referred to as “first surface” in this specification) 11 a of the base material 11, and the other surface of the base material 11. (The surface opposite to the first surface, which may be referred to as “second surface” in this specification) is not provided on 11b. That is, the laminate 1 includes the drug-containing layer 12 only on the first surface 11 a of both surfaces of the base material 11.
Moreover, the laminated body 1 has both the said microcapsule agent and a non-microcapsule agent in the chemical | medical agent containing layer 12, ie, the same surface of the base material 11. FIG.

The drug-containing layer 12 only needs to contain the microcapsule and non-microcapsule, may contain only the microcapsule and non-microcapsule, or contains other components other than these. You may do it. Here, although the drug-containing layer 12 is shown as a layer having a clear surface, for example, in the case of a drug-containing layer containing only the microcapsule and the non-microcapsule, such a clear It may not have a surface.
The microcapsules and non-microcapsules in the drug-containing layer 12 will be described in detail later.

  As for the said microcapsule agent and non-microcapsule agent in the chemical | medical agent containing layer 12, all may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily. .

The total content of the formaldehyde reactant in the microcapsule and the non-microcapsule (formaldehyde reactant not microencapsulated) in the drug-containing layer 12 is not particularly limited, but is 6% by mass or more. Preferably, it is 8.5% by mass or more, more preferably 11% by mass or more, and particularly preferably 13.5% by mass or more.
The upper limit of the total content of the formaldehyde reactant in the microcapsule and the non-microcapsule of the drug-containing layer 12 is not particularly limited, and is, for example, 24% by mass, 21% by mass, and 18% by mass. Any of these may be sufficient.
The total content of the formaldehyde reactant in the microcapsule and the non-microcapsule in the drug-containing layer 12 is appropriately within a range set by arbitrarily combining the above-described preferable lower limit value and upper limit value. Can be adjusted. For example, a preferable example of the total content includes a range of 6 to 24% by mass.

  In the drug-containing layer 12, the ratio of [content of formaldehyde reactant in microcapsule (part by mass)]: [content of non-microcapsule (formaldehyde reactant not microencapsulated) (part by mass)] (Mass ratio) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, particularly preferably 70:30 to 30:70, for example, 65 : 35-35: 65 and 55: 45-45: 55 may be sufficient. When the ratio in the drug-containing layer 12 is in such a range, the formaldehyde removal ability of the laminate 1 is further improved.

The other components in the drug-containing layer 12 are not particularly limited and can be arbitrarily selected according to the purpose.
The said other component in the chemical | medical agent containing layer 12 may be only 1 type, may be 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.

Preferred examples of the other component include a resin.
As resin in the chemical | medical agent content layer 12, the thing similar to resin in the base material 11 is mentioned, for example.

The total content of the microcapsule and non-microcapsule in the drug-containing layer 12 is not particularly limited, but is preferably 60% by mass or more, more preferably 70% by mass or more, and 80% by mass. It is particularly preferable that the amount be 90% by mass or more, 93% by mass or more, 95% by mass or more, and 97% by mass or more.
The upper limit value of the total content of the microcapsule and the non-microcapsule in the drug-containing layer 12 is not particularly limited, and may be any of 100% by mass, 99% by mass, and 98% by mass, for example. .
The total content of the microcapsule and the non-microcapsule in the drug-containing layer 12 can be appropriately adjusted within a range set by arbitrarily combining the above-described preferable lower limit value and upper limit value. For example, a preferable example of the total content includes a range of 60 to 100% by mass.

  Here, the drug-containing layer 12 is shown as a single layer, but may be a single layer (single layer) or a plurality of layers of two or more layers. When the drug-containing layer 12 is a plurality of layers, these layers may be the same as or different from each other, and the combination of these layers is not particularly limited.

Although the thickness of the chemical | medical agent containing layer 12 is not specifically limited, It is preferable that it is 200-800 micrometers.
Here, the “thickness of the drug-containing layer 12” means the thickness of the entire drug-containing layer 12. For example, the thickness of the drug-containing layer 12 composed of a plurality of layers means all of the drug-containing layer 12. Means the total thickness of the layers.
In addition, when the state of the surface of the drug-containing layer 12 is high, or when the state of the drug-containing layer 12 is not uniform, such as when the drug-containing layer 12 does not have a clear surface as described above, The height of the highest part from the first surface 11 a of the base material 11 of the drug-containing layer 12 may be the thickness of the drug-containing layer 12.

Although the formation amount on the base material 11 of the chemical | medical agent containing layer 12 is not specifically limited, It is preferable that it is 5-60 g / m < ² > * dry.

  The laminated body of the present embodiment is not limited to that shown in FIG. 1, and within the range that does not impair the effects of the present invention, a part of the configuration shown in FIG. 1 is changed, deleted, or added. There may be.

For example, the laminate 1 shown in FIG. 1 includes only the drug-containing layer 12 on the substrate 11, but may include other layers other than the drug-containing layer 12.
The other layers are not particularly limited, and the type and thickness thereof can be arbitrarily selected according to the purpose.
For example, the laminate 1 may include a layer containing any one of the microcapsule and the non-microcapsule as the other layer.

Moreover, the laminated body 1 may be equipped with the other layer on the 2nd surface 11b of the base material 11 separately. Examples of the other layer on the second surface 11b include the same layer as any of the layers on the first surface 11a.
For example, when a drug-containing layer having formaldehyde removal ability is provided on the second surface 11b, the drug-containing layer can have the same form as the drug-containing layer 12 on the first surface 11a. It may be the same as or different from the drug-containing layer 12 on the first surface 11a.

  1 may further include 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. And the said other base material may be laminated | stacked on the base material 11 through the adhesive bond layer.

  Moreover, as for the laminated body 1, the surface of the outermost layer (for example, chemical | medical agent containing layer 12) on the opposite side to the base material 11 side may become uneven | corrugated surfaces, such as an embossed surface. By having such an uneven surface, the design of the laminate 1 is further improved.

Second Embodiment
FIG. 2 is a cross-sectional view schematically showing a laminate according to the second embodiment of the present invention.
2 and the subsequent drawings, the same components as those shown in FIG. 1 are denoted by the same reference numerals as those in FIG. 1, and detailed description thereof is omitted.

  The laminate 2 shown in FIG. 2 includes a resin layer 22 on a base material 21, a print layer 23 on the resin layer 22, and a coating layer 24 on the print layer 23. That is, the laminate 2 is formed by laminating the resin layer 22, the printing layer 23, and the coating layer 24 in this order on the base material 21 in this thickness direction.

Furthermore, in the laminate 2, any one or more of the resin layer 22, the printed layer 23, and the coating layer 24 are layers corresponding to the drug-containing layer 12 in the laminate 1, that is, the microcapsules and the non-microcapsules. It is a layer containing an agent and having a formaldehyde removal activity (drug-containing layer).
The laminated body 2 also has a formaldehyde removing ability by including the drug-containing layer.
In the laminated body 2, it is preferable that either one or both of the resin layer 22 and the coating layer 24 are drug-containing layers.

  Furthermore, in the laminate 2, the base material 21 has a two-layer structure in which a first base material 211 and a second base material 212 are stacked.

  Further, in the laminate 2, an opening is formed on one surface (which may be referred to as “first surface” in this specification) 24 a of the coating layer 24, and the other of the second base material 212 is provided. One or two or more through-holes 20 reaching the surface (sometimes referred to as “second surface” in this specification) 212a are provided.

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

In the laminate 2, the drug-containing layer is formed on one surface of the base material 21 (sometimes referred to as “first surface” in this specification) 21 a, in other words, on one surface of the first base material 211 (the book surface). (It may be referred to as “first surface” in the specification) 211a, and the other surface of the base material 21 (may be referred to as “second surface” in this specification) 21b, Then, it is not provided on one surface (which may be referred to as “second surface” in this specification) 212 b of the second base material 212. That is, the laminate 2 includes a drug-containing layer only on the first surface 21 a of both surfaces of the base material 21.
Moreover, the laminated body 2 has both the said microcapsule agent and a non-microcapsule agent in the chemical | medical agent containing layer, ie, the same surface of the base material 21. FIG.

[Base material]
It is preferable that both the base material 21, ie, the 1st base material 211 and the 2nd base material 212, are a film form or a sheet form.

Both the first base material 211 and the second base material 212 can be the same as the base material 11 in the laminate 1.
The second base 212 may be the same material as the first base 211 or may be a different material.

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

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

The resin in the resin layer 22 is not particularly limited, and preferable examples include the same resins as those in the base material 11 of the laminate 1.
The resin 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 ratio thereof can be arbitrarily selected.

When the resin layer 22 is a drug-containing layer, the microcapsule and non-microcapsule in the resin layer 22 are both the same as the microcapsule and non-microcapsule in the laminate 1.
As for the said microcapsule agent and the non-microcapsule agent in the resin layer 22, all may be only 1 type, 2 types or more, and when they are 2 types or more, those combinations and ratios can be selected arbitrarily.

When the resin layer 22 is a drug-containing layer, the total content of the formaldehyde reactant in the microcapsule and the non-microcapsule (formaldehyde reactant not microencapsulated) of the resin layer 22 is It is preferably 1.5% by mass or more, more preferably 2.5% by mass or more, further preferably 3.5% by mass or more, and particularly preferably 4.5% by mass or more. .
On the other hand, the total content of the formaldehyde reactant in the microcapsule and the non-microcapsule in the resin layer 22 is preferably 16.5% by mass or less, and preferably 15% by mass or less. More preferably, it is 13.5% by mass or less, more preferably 12% by mass or less.
The total content of the formaldehyde reactant in the microcapsule and the non-microcapsule of the resin layer 22 is appropriately adjusted within a range set by arbitrarily combining the above-described preferable lower limit value and upper limit value. it can. For example, a preferable example of the total content includes a range of 1.5 to 16.5% by mass.

  When the resin layer 22 is a drug-containing layer, in the resin layer 22, [content of formaldehyde reagent in microcapsule (part by mass)]: [non-microcapsule (formaldehyde reagent not microencapsulated)] The content (parts by mass)] ratio (mass ratio) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and 70:30 to 30:70. It is particularly preferable that, for example, any of 65:35 to 35:65 and 55:45 to 45:55 may be used. When the ratio in the resin layer 22 is within such a range, the formaldehyde removing ability of the laminate 2 is further improved.

The resin layer 22 may contain other components that do not correspond to any of the resin, microcapsule, and non-microcapsule.
The said other component in the resin layer 22 is not specifically limited, According to the objective, it can select arbitrarily.
The other component in the resin layer 22 may be only one type, or two or more types, and when there are two or more types, the combination and ratio thereof can be arbitrarily selected.

The total content of the resin, microcapsule and non-microcapsule 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 80% by mass. % Is particularly preferable, and for example, it may be 90% by mass or more, 93% by mass or more, 95% by mass or more, and 97% by mass or more.
The upper limit value of the total content of the resin, microcapsule and non-microcapsule in the resin layer 22 is not particularly limited, and may be, for example, any one of 100% by mass, 99% by mass, and 98% by mass. Good.
The total content of the resin, the microcapsule, and the non-microcapsule in the resin layer 22 can be appropriately adjusted within a range set by arbitrarily combining the above-described preferable lower limit value and upper limit value. For example, a preferable example of the total content includes a range of 60 to 100% by mass.

The resin layer 22 may be a foamed resin layer or a non-foamed resin layer, for example.
The laminate 2 in which the resin layer 22 is a foamed resin layer can improve design properties.
Moreover, the laminate 2 in which the resin layer 22 is a foamed resin layer and a drug-containing layer can further improve formaldehyde removal ability.

  In the case where the resin layer 22 is a foamed resin layer and a drug-containing layer, the resin layer 22 may be natural zeolite, acidic clay, diatomaceous earth, synthetic zeolite, artificial zeolite, in addition to the resin, microcapsule and non-microcapsule. One or more inorganic compounds selected from the group consisting of zeolite, activated carbon, titanium oxide and phosphate may be contained. The inorganic compound itself can adsorb formaldehyde, and may further improve the reactivity of the microcapsule and non-microcapsule with formaldehyde. Therefore, the laminate 2 provided with such a resin layer is further improved in formaldehyde removal ability.

  When the resin layer 22 contains the said inorganic compound, content of the said inorganic compound of the resin layer 22 is although it does not specifically limit, It is preferable that it is 0.1-10 mass%.

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

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

Although the thickness of the resin layer 22 is not specifically limited, It is preferable that it is 200-800 micrometers.
Here, the “thickness of the resin layer 22” means the thickness of the entire resin layer 22. For example, the thickness of the resin layer 22 composed of a plurality of layers is the sum of all the layers constituting the resin layer 22. Means the thickness.
The thickness of the resin layer 22 may be specified as in the case of the drug-containing layer 12.

[Print layer]
The printed layer 23 is for imparting information or design properties to the laminate 2.
The print layer 23 may be provided on the entire surface of one surface (which may be referred to as “first surface” in this specification) 22a of the resin layer 22, or may be provided only in a part of the region. If it is provided only in a part of the region, it may be patterned or may not be patterned. When the printing layer 23 is patterned, the pattern is not particularly limited and can be arbitrarily selected according to the purpose.

  When the printed layer 23 is a drug-containing layer, the total content of the formaldehyde reactant in the microcapsule and the non-microcapsule (formaldehyde reactant not microencapsulated) in the printed layer 23, and , [Content of formaldehyde reactant in microcapsule (part by mass)]: [non-microcapsule (formaldehyde reactant not microencapsulated) content (part by mass)] ratio (mass ratio) is These can be the same as in the case of the resin layer 22.

Here, the print layer 23 is a single layer, but it may be a single layer (single layer) or a plurality of layers of two or more layers. When the printing layer 23 is a plurality of layers, these layers may be the same as or different from each other, and the combination of these layers is not particularly limited. Further, the print layer 23 may have regions with different colors in one layer.
When the printing layer 23 is a plurality of layers, only a part of the plurality of layers may be a drug-containing layer, all may be a drug-containing layer, or all may not be a drug-containing layer.

Although the thickness of the printing layer 23 is not specifically limited, It is preferable that it is 1-10 micrometers.
Here, the “thickness of the printing layer 23” means the thickness of the entire printing layer 23. For example, the thickness of the printing layer 23 composed of a plurality of layers is the total of all the layers constituting the printing layer 23. Means the thickness.

[Coating layer]
The covering layer 24 is a layer that covers the outermost layer on the first surface 11 a side of the substrate 11 in the laminate 2. The covering layer 24 protects the entire structure of the stacked body 2 by suppressing physical breakage, chemical alteration, and the like of the stacked body 2.

  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 is referred to as one surface of the print layer 23 (referred to as “first surface” in this specification). Cover the entire surface of 23a. When the printing layer 23 is provided only in a partial region of the first surface 22 a of the resin layer 22, the coating layer 24 includes the entire first surface 23 a of the printing layer 23 and the printing layer 23. The exposed surface of any layer on the substrate 21 that is not provided is covered. 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, and may be transparent, translucent, or opaque. However, when the printing layer 23 is provided, the covering layer 24 is preferably transparent or translucent so that the printing layer 23 can be recognized.

  When the coating layer 24 is a drug-containing layer, the total content of the formaldehyde reactant in the microcapsule and the non-microcapsule (formaldehyde reactant not microencapsulated), and [microcapsule The content (parts by mass) of the formaldehyde reactant in the resin layer is a ratio (mass ratio) of [content (parts by mass) of non-microcapsule (formaldehyde reactant not microencapsulated)]. This can be the same as in the case of 22.

Although the coating layer 24 is shown here as being one layer, it may be a single layer (single layer) or a plurality of layers of two or more layers. When the coating layer 24 is a plurality of layers, these layers may be the same as or different from each other, and the combination of these layers is not particularly limited.
When the coating layer 24 is a plurality of layers, only a part of the plurality of layers may be a drug-containing layer, all may be a drug-containing layer, or all may not be a drug-containing layer.

Although the thickness of the coating layer 24 is not specifically limited, It is preferable that it is 1-50 micrometers.
Here, the “thickness of the coating layer 24” means the thickness of the entire coating layer 24. For example, the thickness of the coating layer 24 composed of a plurality of layers is the sum of all the layers constituting the coating layer 24. Means the thickness.

As described above, in the laminate 2, one or two or more through holes 20 that have openings on the first surface 24 a of the coating layer 24 and reach the second surface 212 a of the second base material 212 are provided. Is provided.
Although the laminated body 2 does not need to be provided with the through-hole 20, the ability to remove formaldehyde is further improved. This is because the formaldehyde to be removed easily reaches the drug-containing layer. In addition, when the second base material 212 has formaldehyde scavenging ability, such as a material made of gypsum, the function of the second base material 212 further increases the formaldehyde removal ability of the laminate 2. improves.

  The end (opening) opposite to the opening of the through hole 20 may end at a portion overlapping the second surface 212a of the second base material 212, or may pass through the second surface 212a. In this case, the second base material 212 may be reached.

Although the hole diameter of the through-hole 20 is not specifically limited, It is preferable that it is 10-1000 micrometers.
In the present specification, “the hole diameter of the through hole” means “the hole diameter of the through hole in a cross section in a direction perpendicular to the longitudinal direction of the through hole”.

The number of the through holes 20 is not particularly limited, it is preferably 500 to 10000 pieces / ^{m 2.}

  In addition, although the example where the through-hole 20 has reached the part which overlaps with the 2nd surface 212a of the 2nd base material 212 is shown here, as long as the through-hole 20 has reached | attained the chemical | medical agent containing layer at least. Good. And the edge part (opening part) on the opposite side to the said opening part of the through-hole 20 may be complete | finished in the site | part which overlaps with the surface far from the base material 21 of a chemical | medical agent containing layer, and passes the said surface. And it may reach even the inside of a medicine content layer.

  Moreover, although the hole diameter of the through hole 20 is shown as the distance from the opening of the through hole 20 toward the opposite end increases, the hole diameter of the through hole 20 is shown here. May increase as the distance increases, may vary irregularly instead of regular as the distance increases, or may be constant regardless of the distance .

  The laminated body of the present embodiment is not limited to that shown in FIG. 2, and within the range that does not impair the effects of the present invention, a part of the configuration shown in FIG. 2 is changed, deleted, or added. There may be.

  For example, in the laminate 2 shown in FIG. 2, any one or two or more of the resin layer 22, the printing layer 23, and the coating layer 24 include any one of the microcapsule agent and the non-microcapsule agent. It may be.

Further, for example, the laminate 2 shown in FIG. 2 has, on the first surface 21 a of the base material 21 (the first surface 211 a of the first base material 211), in addition to the resin layer 22, the print layer 23, and the coating layer 24, Furthermore, another layer may be provided.
The other layers are not particularly limited, and the type and thickness thereof can be arbitrarily selected according to the purpose. For example, the laminate 2 may include a layer containing any one of the microcapsule and the non-microcapsule as the other layer.
When providing the through-hole 20 in the laminated body 2, the through-hole 20 is provided also in said other layer as needed.

Moreover, the laminated body 2 may be equipped with the other layer on the 2nd surface 21b (2nd surface 212b of the 2nd base material 212) of the base material 21 separately. Examples of the other layer on the second surface 21b include the same layer as any one of the layers on the first surface 21a.
For example, when any one or more of a resin layer, a printing layer, and a coating layer are provided on the second surface 21b, these layers are the resin layer 22, the printing layer 23, or the coating on the first surface 21a. The layer 24 may have the same form, and may be the same as or different from the resin layer 22, the printed layer 23, or the coating layer 24. For example, when a drug-containing layer having formaldehyde removal ability is provided on the second surface 21b, the drug-containing layer can have the same form as the drug-containing layer on the first surface 21a. It may be the same as or different from the drug-containing layer on the first surface 11a.

  Moreover, as for the laminated body 2, the surface of the outermost layer (for example, coating layer 24) on the opposite side to the base material 21 side may be uneven | corrugated surfaces, such as an embossed surface. By having such an uneven surface, the design of the laminate 2 is further improved.

<Third Embodiment>
FIG. 3 is a cross-sectional view schematically showing a laminate according to the third embodiment of the present invention.
The laminate 3 shown in FIG. 3 includes a resin layer 22 on a substrate 31, an adhesive layer 25 on the resin layer 22, a printing layer 23 on the adhesion layer 25, and a coating layer 24 on the printing layer 23. It is equipped with. That is, the laminate 3 is formed by laminating the resin layer 22, the adhesion layer 25, the printing layer 23, and the coating layer 24 in this order on the base material 31.
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 thickness direction in this order.

Furthermore, in the laminate 3, any one or more of the resin layer 22, the adhesion layer 25, the printing layer 23, and the coating layer 24 are layers corresponding to the drug-containing layer 12 in the laminate 1, that is, the microcapsule agent. And a layer containing a non-microcapsule and having a formaldehyde removal activity (drug-containing layer).
The laminated body 3 also has a formaldehyde removing ability by including the drug-containing layer.
In the laminated body 3, it is preferable that any one or both of the resin layer 22 and the coating layer 24 are a chemical | medical agent containing layer.

Furthermore, in the laminate 3, one or more through holes 30 that have openings on the first surface 24 a of the covering layer 24 and reach the second surface 212 a of the second base material 212 are provided. Yes.
Although the laminated body 3 does not need to be provided with the through-hole 30, the ability to remove formaldehyde is further improved by providing the laminated body 3 as in the case of the laminated body 2.
In the laminate 3, the through hole 30 is provided in the same manner as the through hole 20 in the laminate 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 or more of the resin layer 22, the adhesion layer 25, the printing layer 23, and the coating layer 24 are layers containing either the microcapsule agent or the non-microcapsule agent alone. May be.

  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 laminate 3, the drug-containing layer is formed on one surface of the substrate 31 (sometimes referred to as “first surface” in this specification) 31 a, in other words, on the first surface 211 a of the first substrate 211. Provided on the second surface 212b of the second base material 212. In other words, it is provided on the second surface 212b of the second base material 212. Absent. That is, the laminate 3 includes a drug-containing layer only on the first surface 31 a of both surfaces of the base material 31.
Moreover, the laminated body 3 has both the said microcapsule agent and a non-microcapsule agent in the chemical | medical agent containing layer, ie, the same surface of the base material 31. FIG.

In the laminate 3, the first base material 211, the second base material 212, the resin layer 22, the print layer 23, and the coating layer 24 are respectively the first base material 211, the second base material 212, and the resin layer 22 in the stack body 2. The printing layer 23 and the coating layer 24 are the same.
The base material 31 is the same as the base material 21 in the laminate 2 except that the adhesive layer 310 is provided.

[Adhesive layer]
The adhesive layer 310 bonds the first base material 211 and the second base material 212 to stabilize the structure of the stacked 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 stabilizes the structure of the stacked body 3 by bringing the resin layer 22 and the printing layer 23 into close contact with each other.
Examples of the adhesion layer 25 include those formed using a known coupling agent or adhesive resin.
The adhesion layer 25 is preferably a film or a sheet.

  Although the thickness of the contact | adherence layer 25 is not specifically limited, It is preferable that it is 1-50 micrometers.

  When the adhesion layer 25 is a drug-containing layer, the total content of the formaldehyde reagent in the microcapsule and the non-microcapsule (formaldehyde reagent not microencapsulated) in the adhesion layer 25, and , [Content of formaldehyde reactant in microcapsule (part by mass)]: [non-microcapsule (formaldehyde reactant not microencapsulated) content (part by mass)] ratio (mass ratio) is These can be the same as in the case of the resin layer 22.

<< Manufacturing Method of Laminate >>
The laminated body of this invention can be manufactured by laminating | stacking the said chemical | medical agent containing layer on the at least one surface of a base material.
As a base material, a commercial item may be used and what was shape | molded by the well-known method according to the material may be used.

  The drug-containing layer can be formed, for example, by applying a composition for forming a drug-containing layer containing a component for forming the drug to the surface on which the drug-containing layer is to be formed and drying the composition. Here, as the “formation target surface of the drug-containing layer”, for example, in the laminate 1 shown in FIG. 1, “the first surface 11 a of the base material 11”, a release treatment surface of a release film to be described later, and the like. It is done.

The composition for forming a drug-containing layer is obtained, for example, by blending the microcapsule, non-microcapsule, and other components other than these as necessary, and further blending a solvent. Is preferred.
In addition, the composition for forming a drug-containing layer is, for example, a non-microcapsule agent and, if necessary, the other components described above are blended into a liquid material (dispersion) obtained by preparing the microcapsule agent. But you can get it.
The drug-containing layer is any one of the above-described resin layer, adhesion layer, printing layer, and coating layer (for example, any of the resin layer 22, adhesion layer 25, printing layer 23, and coating layer 24 in FIG. 2 or 3). In such a case, a composition further containing essential components for constituting these layers may be used as the drug-containing layer forming composition.

The mixing method at the time of preparing the composition for forming a drug-containing layer is not particularly limited, and is a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer, three rolls, a kneader, a bead mill or the like; What is necessary is just to select suitably from well-known methods, such as the method of adding and mixing an ultrasonic wave.
The temperature at the time of preparing the composition for forming a drug-containing layer is not particularly limited as long as each compounding component is not deteriorated.
The time for preparing the composition for forming a drug-containing layer is not particularly limited as long as each compounding component does not deteriorate. For example, it can be 10 minutes to 24 hours, but this is an example.

  The method for applying the composition for forming a drug-containing layer is not particularly limited, and any method may be used as long as it can apply a liquid material. Specific coating methods include, for example, various types of coaters such as air knife coaters, curtain coaters, die coaters, blade coaters, roll coaters, gate roll coaters, bar coaters, rod coaters, gravure coaters, gravure offset coaters; wire bars A known method using an apparatus such as a coater can be used.

  When the laminate of the present invention includes any of a resin layer, an adhesion layer, a printed layer, and a coating layer that are not drug-containing layers, these layers also form these layers in the same manner as the drug-containing layer described above. The composition (resin layer forming composition, adhesion layer forming composition, printing layer forming composition, coating layer forming composition) containing these components is applied to the surface to be formed of each of these layers and dried. Can be formed.

  Each layer other than the base material constituting the laminate of the present invention is laminated by directly forming any of the above-described compositions on any of the adjacent layers in the laminate. Alternatively, the layer formed by applying any of the above-described compositions to the release-treated surface of the release film may be laminated by adhering to any of the formed layers adjacent to the laminate. Good.

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

<Microcapsules>
The microcapsule is a microencapsulated formaldehyde reactant.
The microcapsule contains a polycondensate as a film-forming component and contains a formaldehyde reactant having reactivity with formaldehyde.

[Formaldehyde reagent]
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 includes 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) encapsulated in the microcapsule is an amino group and a group in which the amino group forms a salt (in this specification, abbreviated as “amino group salt-forming group”). Are preferred).
In a microcapsule, a polycondensate is used as a film-forming component, and a microcapsule (microcapsule) containing a formaldehyde reagent is used by using a formaldehyde reagent that does not have an amino group or an amino group salt-forming group. It can be formed stably.

Examples of the amino group salt-forming group include a group in which the amino group is a monovalent cation moiety, and this cation moiety forms a salt with an anion.
Here, examples of the cation moiety include those in which a hydrogen ion (H ⁺ ) is coordinated 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 parts are both 1. In addition, when the anion is n-valent (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 parts is n or less. Is n. In this case, the plurality of the cation moieties may all be the same, all may be different, or only a part may be the same.

  The anion in the amino group salt-forming group is the same as the anion moiety in the group (“—NH—” salt-forming group) described later, wherein the group represented by the formula “—NH—” forms a salt. Things.

The formaldehyde reactant is preferably an organic compound, and as such a formaldehyde reactant, for example, a group represented by the formula “—NH—” (hereinafter abbreviated as ““ —NH— ”group”). And a group represented by the formula “—NH—” is selected from the group consisting of a group forming a salt (hereinafter sometimes abbreviated as ““ —NH— ”salt-forming group”) The compound which has 1 type, or 2 or more types is mentioned. In the formaldehyde reactant, the “—NH—” group indicates reactivity with formaldehyde, and the “—NH—” salt-forming group itself or “—NH—” group becomes this “—NH—” group. The group is presumed to be reactive with formaldehyde.
When the formaldehyde reactant has a “—NH—” group or a “—NH—” salt-forming group, the nitrogen atom in these groups is not only one hydrogen atom already covalently bonded, but also a hydrogen atom. 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 if two or more, these two The above groups may be the same as or different from each other. That is, these two or more groups may all be the same, may all be different, or may be partially the same. Usually, these two or more groups are all identical, i.e., are all "-NH-" groups, or all identical " -NH- "salt-forming groups are preferred.

Examples of the “—NH—” salt-forming group include a group in which the “—NH—” group is a monovalent cation moiety, and this cation moiety forms a salt with an anion.
Here, examples of the cation moiety include those in which a hydrogen ion (H ⁺ ) is coordinate-bonded to the nitrogen atom of the “—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 parts are both 1. When the anion is m-valent (m is an integer of 2 or more), the number of the anions forming the salt is usually 1, the number of the cation parts is m or less, m It is preferable that In this case, the plurality of the cation moieties may all be the same, all may be different, or only a part 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 ions, sulfate ions, hydrogen sulfate ions, carbonate ions, hydrogen carbonate ions, halide ions, and the like, and the halide ions include fluoride ions, chloride ions, bromides. Ions, iodide ions and the like.
Preferable examples of the organic anion include a carboxylic acid anion and a sulfonic acid anion.
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 said anion which a formaldehyde reactant has may be only 1 type, 2 or more types, and when it is 2 or more types, those combinations and ratios can be selected arbitrarily.
That is, when one molecule of formaldehyde reactant has two or more of the anions, these two or more anions may be all the same, all different, or only partly the same. Also good.
However, the formaldehyde reactant is electrically neutral as a whole molecule, that is, the total value of the valence of the cation moiety and the total value of the valence of the anion in one molecule of the formaldehyde reactant are the same. Preferably there is.

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

  The positions of the “—NH—” group and the “—NH—” salt-forming group in the molecule of the formaldehyde reagent are not particularly limited. For example, when the formaldehyde reagent has a chain structure, the terminal of the molecule Any position other than the portion may be used.

  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 monocyclic or polycyclic, may be either an aliphatic ring or an aromatic ring, and the aliphatic ring and aromatic ring are A condensed polycyclic ring may be used.
When the formaldehyde reactant has a cyclic structure, the “—NH—” group and the “—NH—” salt-forming group may form the ring skeleton of the cyclic structure, or without forming the ring skeleton, It may be bonded 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 nitrogen atom or the carbon atom of 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 or two, but one. Is preferred.

That is, as a preferable formaldehyde reactant, for example, a group represented by the formula “—C (═O) —NH—” (an amide bond; hereinafter, abbreviated as ““ —C (═O) —NH— ”group”). And a group represented by the formula “—NH—C (═O) —NH—” (hereinafter, abbreviated as ““ —NH—C (═O) —NH— ”group”). ), A group in which a group represented by the formula “—C (═O) —NH—” forms a salt (hereinafter abbreviated as ““ —C (═O) —NH— ”salt-forming group”). A group represented by the formula “—NH—C (═O) —NH—” forming a salt (hereinafter ““ —NH—C (═O) —NH— ”salt formation) Group ”), a group represented by the formula“ ═N—NH— ”(hereinafter sometimes abbreviated as“ “N—NH—” group ”), a formula“ —HN—N ”. (-)-NH- " Groups (hereinafter sometimes abbreviated as ““ —HN—N (—) — NH— ”group”), groups in which the group represented by the formula “═N—NH—” forms a salt ( Hereinafter, a group represented by “(= N—NH—” salt-forming group ”) and a group represented by the formula“ —HN—N (—) — NH— ”(hereinafter referred to as a salt). And those having one or more selected from the group consisting of “sometimes abbreviated as“ —HN—N (—) — NH— ”salt-forming group” ”. Here, for example, the “—HN—N (—) — NH—” group means one nitrogen atom, two “—NH—” group nitrogen atoms, and another group, Means a single bond.
In the “—NH—C (═O) —NH—” salt forming group and “—HN—N (—) — NH—” salt forming group, the number of “—NH—” salt forming groups may be one. It may be two or more.

  As a preferable formaldehyde reactant having a cyclic structure, for example, one or more selected from the group consisting of “—NH—” group and “—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 Forming group, “—NH—C (═O) —NH—” salt forming group, “═N—NH—” group, “—HN—N (—) — NH—” group, “═N—NH—” A formaldehyde reagent 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 ring skeleton having a cyclic structure is more preferable. .

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

  Particularly preferred formaldehyde reactants include, for example, optionally substituted hydantoin and its salt, optionally substituted 2-imidazolidinone and its salt, and optionally substituted. Preferred 5-pyrazolone and salts thereof, optionally having 3-pyrazolone and salts thereof, optionally having 1,2,4-triazol-3-one and salts and substituents thereof Phthalimide and its salt, optionally substituted glycoluril and its salt, optionally substituted pyrazole and its salt, optionally substituted 1,2,3-triazole and a salt thereof, 1,2,4-triazole optionally having a substituent and a salt thereof, and 1,2,3-benzotriazole optionally having a substituent and The salt etc. It is below.

Hydantoin, 2-imidazolidinone, 5-pyrazolone, 3-pyrazolone, 1,2,4-triazol-3-one, phthalimide, glycoluril, pyrazole, 1,2,3-triazole, 1,2,4-triazole And the structure of 1,2,3-benzotriazole is shown below.
Hydantoin, 2-imidazolidinone, 5-pyrazolone, 3-pyrazolone, 1,2,4-triazol-3-one, pyrazole, 1,2,3-triazole and 1,2,4-triazole are all cyclic It is a compound with 5 members. Both phthalimide and 1,2,3-benzotriazole are compounds having 9 ring members. Glycoluril is a compound having 8 ring members.
The compounds shown here are only examples of formaldehyde reagents.

Here, as a salt of hydantoin, for example, one in which one or both of two “—NH—” groups in hydantoin become “—NH—” salt-forming groups can be mentioned.
As the salt of 2-imidazolidinone, for example, one or both of the two “—NH—” groups in 2-imidazolidinone are “—NH—” salt-forming groups. Is mentioned.
Examples of the salt of 5-pyrazolone include, for example, those in which the “—NH—” group in 5-pyrazolone is converted to a “—NH—” salt-forming group, and the nitrogen atom not bonded to a hydrogen atom is a salt. And those in which the “—NH—” group becomes a “—NH—” salt-forming group and the nitrogen atom that is not bonded to a hydrogen atom forms a salt.
Examples of the salt of 3-pyrazolone include those in which one or both of two “—NH—” groups in 3-pyrazolone are converted to “—NH—” salt-forming groups.
In addition, as a salt of 1,2,4-triazol-3-one, for example, one or both of two “—NH—” groups in 1,2,4-triazol-3-one are What became a "-NH-" salt formation group is mentioned.
Moreover, as a salt of phthalimide, for example, one in which one “—NH—” group in phthalimide becomes a “—NH—” salt-forming group can be mentioned.
Examples of the glycoluril salt include those in which at least one of the four “—NH—” groups in the glycoluril is a “—NH—” salt-forming group.

Examples of the pyrazole salt include those in which the “—NH—” group in the pyrazole becomes a “—NH—” salt-forming group, or the nitrogen atom that is not bonded to a hydrogen atom forms a salt. And a group in which a “—NH—” group becomes a “—NH—” salt-forming group and a nitrogen atom not bonded to a hydrogen atom forms a salt.
Examples of the salt of 1,2,3-triazole include, for example, those in which the “—NH—” group in 1,2,3-triazole is converted to a “—NH—” salt-forming group, and bonded to a hydrogen atom. The one in which one or both of the two non-nitrogen atoms form a salt, and the one in which the “—NH—” group becomes a “—NH—” salt-forming group and is not bonded to a hydrogen atom In which one or both of the two nitrogen atoms form a salt.
Examples of 1,2,4-triazole salts include, for example, those in which the “—NH—” group in 1,2,4-triazole is converted to a “—NH—” salt-forming group, and bonded to a hydrogen atom. The one in which one or both of the two non-nitrogen atoms form a salt, and the one in which the “—NH—” group becomes a “—NH—” salt-forming group and is not bonded to a hydrogen atom In which one or both of the two nitrogen atoms form a salt.
Examples of the salt of 1,2,3-benzotriazole include, for example, those in which the “—NH—” group in 1,2,3-benzotriazole becomes a “—NH—” salt-forming group, Either one or both of the two non-bonded nitrogen atoms form a salt, and the “—NH—” group becomes a “—NH—” salt-forming group and is bonded to a hydrogen atom. One in which either one or both of the two nitrogen atoms which are not present forms a salt.

  In the present specification, “having a substituent” means one or more hydrogen atoms (excluding the hydrogen atom in the “—NH—” group and the “—NH—” salt-forming group) of the original compound. ) Is substituted with a group other than a hydrogen atom (substituent).

In the present specification, hydantoin having a substituent is sometimes referred to as “hydantoin derivative”, and hydantoin and hydantoin derivatives are sometimes collectively referred to as “hydantoin compounds”. And the salt of the hydantoin which has a substituent, ie, the salt of a hydantoin derivative, is what a hydantoin derivative formed a salt like the case of a hydantoin. The term “hydantoin optionally having a substituent and a salt thereof” refers in other words to a hydantoin compound and a salt thereof.
In the present specification, the “derivative” means one in which 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 this specification, 2-imidazolidinone having a substituent is referred to as a “2-imidazolidinone derivative”, and includes both 2-imidazolidinone and 2-imidazolidinone derivatives, and includes “2-imidazolidinone”. It may be referred to as “non-compound”. And, a salt of 2-imidazolidinone having a substituent, that is, a salt of 2-imidazolidinone derivative, formed a salt in the same manner as in the case of 2-imidazolidinone derivative of 2-imidazolidinone. Is. The “2-imidazolidinone optionally having a substituent and a salt thereof” refers in other words to a 2-imidazolidinone 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 derivatives may be collectively referred to as “5-pyrazolone compounds”. And the salt of 5-pyrazolone which has a substituent, ie, the salt of a 5-pyrazolone derivative, is a salt in which a 5-pyrazolone derivative forms a salt as in the case of 5-pyrazolone. The term “5-pyrazolone optionally having a substituent and a salt thereof” refers in other words to a 5-pyrazolone 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 derivatives may be collectively referred to as “3-pyrazolone compounds”. And the salt of 3-pyrazolone having a substituent, that is, the salt of a 3-pyrazolone derivative is a salt of the 3-pyrazolone derivative as in the case of 3-pyrazolone. The “3-pyrazolone optionally having a substituent and a salt thereof” in other words refers to a 3-pyrazolone compound and a salt thereof.

  In the present specification, 1,2,4-triazol-3-one having a substituent is referred to as a “1,2,4-triazol-3-one derivative” and referred to as 1,2,4-triazol-3-one. And 1,2,4-triazol-3-one derivatives may be collectively referred to as “1,2,4-triazol-3-one compounds”. A salt of 1,2,4-triazol-3-one having a substituent, that is, a salt of a 1,2,4-triazol-3-one derivative is 1,2,4-triazol-3-one. The derivative forms a salt as in the case of 1,2,4-triazol-3-one. The phrase “1,2,4-triazol-3-one optionally having a substituent and a salt thereof” means, in other words, a 1,2,4-triazol-3-one compound and a salt thereof. is there.

  In the present specification, a phthalimide having a substituent is referred to as a “phthalimide derivative”, and phthalimide and a phthalimide derivative are sometimes collectively referred to as a “phthalimide compound”. And the salt of the phthalimide which has a substituent, ie, the salt of a phthalimide derivative, forms a salt similarly to the case of a phthalimide derivative. The “phthalimide optionally having a substituent and a salt thereof” refers in other words to a phthalimide compound and a salt thereof.

  In the present specification, glycoluril having a substituent is referred to as “glycoluril derivative”, and glycoluril and glycoluril derivatives are sometimes collectively referred to as “glycoluril-based compounds”. A glycoluril salt having a substituent, that is, a salt of a glycoluril derivative is a salt formed by the glycoluril derivative in the same manner as in the case of glycoluril. The term “glycoluril optionally having a substituent and a salt thereof” refers to a glycoluril-based compound and a salt thereof in other words.

  In the present specification, a pyrazole having a substituent is referred to as a “pyrazole derivative”, and pyrazole and a pyrazole derivative may be collectively referred to as a “pyrazole compound”. And the salt of the pyrazole which has a substituent, ie, the salt of a pyrazole derivative, forms a salt like the case where the pyrazole derivative is pyrazole. The “pyrazole optionally having a substituent and a salt thereof” is, in other words, a pyrazole 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 derivatives. Sometimes referred to as “1,2,3-triazole compounds”. And a salt of 1,2,3-triazole having a substituent, that is, a salt of a 1,2,3-triazole derivative is a case where the 1,2,3-triazole derivative is 1,2,3-triazole. In the same manner as above, a salt is formed. The phrase “1,2,3-triazole optionally having a substituent and a salt thereof” refers to a 1,2,3-triazole compound and a salt thereof in other words.

  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 derivatives. Sometimes referred to as “1,2,4-triazole compounds”. And, a salt of 1,2,4-triazole having a substituent, that is, a salt of a 1,2,4-triazole derivative is a case where the 1,2,4-triazole derivative is 1,2,4-triazole. In the same manner as above, a salt is formed. The phrase “1,2,4-triazole optionally having a substituent and a salt thereof” means, in other words, a 1,2,4-triazole compound and a salt thereof.

  In the present specification, 1,2,3-benzotriazole having a substituent is referred to as a “1,2,3-benzotriazole derivative” and is referred to as 1,2,3-benzotriazole and 1,2,3-benzotriazole. Derivatives are sometimes collectively referred to as “1,2,3-benzotriazole compounds”. A 1,2,3-benzotriazole salt having a substituent, that is, a salt of a 1,2,3-benzotriazole derivative, means that a 1,2,3-benzotriazole derivative is 1,2,3- As in the case of benzotriazole, a salt is formed. The phrase “1,2,3-benzotriazole and a salt thereof optionally having a substituent” refers to a 1,2,3-benzotriazole-based compound and a salt thereof in other words.

  The substituent is not particularly limited, and preferred examples 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 aralkyloxy group, and the like. .

The alkyl group in the substituent may be linear, branched or cyclic, and when it is 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. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. 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 , Isooctyl group, 2-ethylhexyl group, nonyl group, decyl group.

  The cyclic alkyl group preferably has 3 to 10 carbon atoms. 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. , A cyclodecyl group, a norbornyl group, an isobornyl group, a 1-adamantyl group, a 2-adamantyl group, a tricyclodecyl group, and the like. Furthermore, one or more hydrogen atoms of these cyclic alkyl groups are linear, branched Examples thereof include those substituted with a chain or cyclic alkyl group. Here, examples of the linear, branched, and cyclic alkyl groups for substituting a hydrogen atom include the same alkyl groups listed as substituents of the above-mentioned formaldehyde reactant.

  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). Examples include ethenyl group (vinyl group), 2-propenyl group (allyl group), 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 monocyclic or polycyclic, and preferably has 6 to 15 carbon atoms, such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-tolyl group, m-tolyl group, p-tolyl group, xylyl group (dimethylphenyl group), and the like. One or more hydrogen atoms of these aryl groups are further substituted with these aryl groups and the above-mentioned formaldehyde reagents. The thing substituted by the mentioned alkyl group is also mentioned. The aryl group having these substituents preferably has 6 to 15 carbon atoms including the substituents.
The aryl group preferably has 6 to 10 carbon atoms.

Examples of the aralkyl group in the substituent include a monovalent group in which one hydrogen atom of the alkyl group is substituted with the aryl group, such as a benzyl group (phenylmethyl group) and a phenethyl group (phenylethyl group). Is mentioned.
The aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 11 carbon atoms.

Examples of the alkoxy group in the substituent include monovalent groups 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, more preferably 1 to 6, and particularly preferably 1 to 5.

Examples of the alkenyloxy group in the substituent include monovalent groups formed by bonding the alkenyl group to an oxygen atom, such as ethenyloxy group (vinyloxy group), 2-propenyloxy group (allyloxy group), and cyclohexenyloxy group. Is 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 monovalent groups formed by bonding the aryl group 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 monovalent groups in which the aralkyl group is bonded to an oxygen atom, such as a benzyloxy group (phenylmethyloxy group) and a phenethyloxy group (phenylethyloxy group). It is done.
The aralkyloxy group preferably has 7 to 20 carbon atoms, and more preferably 7 to 11 carbon atoms.

Only one substituent may be included in one molecule of formaldehyde reactant, or two or more substituents. When there are two or more substituents, these substituents may be the same as or different from each other. That is, two or more substituents may all be the same, may all be different, or may be the same in only part.
Usually, the number of the substituents contained in one molecule of the formaldehyde reagent is preferably 1 to 4, and more preferably 1 to 3.

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

Among the above-mentioned particularly preferred formaldehyde reagents, those having the above substituents include 5,5-dimethylhydantoin which is a hydantoin derivative; 3-methyl-5-pyrazolone which is a 5-pyrazolone derivative; 3, which is a pyrazole derivative; 5-dimethylpyrazole; 3-n-butyl-1,2,4-triazole, which is 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, which is a 1,2,3-benzotriazole derivative, 5-methyl-1H -A benzotriazole etc. are mentioned.
5,5-dimethylhydantoin, 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 both compounds having 5 ring members. 4-Methyl-1H-benzotriazole and 5-methyl-1H-benzotriazole are both compounds having 9 ring members.
In addition, the compound shown here is only an example of the formaldehyde reagent which has the said substituent.

  The formaldehyde reactant is preferably solid at room temperature. And when using the formaldehyde reagent which is solid at normal temperature, it is preferable to use together the solvent mentioned later. In the present specification, “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and includes a temperature of 15 to 25 ° C., for example.

  Particularly preferred formaldehyde reactants include, for example, hydantoin, 5,5-dimethylhydantoin, 2-imidazolidinone, 5-pyrazolone, 3-methyl-5-pyrazolone, 3-pyrazolone, 3,5-dimethylpyrazole, 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-triazol-3-one, 1,2,3-benzo Examples include triazole, 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole.

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

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

[Film forming component]
The microcapsule uses a polycondensate as a film-forming component. In the present invention, the “film-forming component” is a component that forms an outer shell film that encloses an active formaldehyde reagent.
The polycondensate is an oligomer or polymer and is not particularly limited as long as it is an organic compound having film-forming ability, but an interfacial polycondensate obtained by an interfacial polycondensation method is preferred. By using the interfacial polycondensate, better quality microcapsules can be obtained.

Preferred examples of the polycondensate include polyurea, polyurethane, and polyamide.
Here, “polyurea” means an oligomer or polymer having a bond (urea bond) represented by the formula “—NH—C (═O) —NH—”. It can be obtained by polycondensation reaction of an isocyanate compound having an isocyanate group and an amine compound having two or more amino groups.
“Polyurethane” means an oligomer or polymer having a bond (urethane bond) represented by the formula “—NH—C (═O) —O—”. For example, as a raw material compound, two or more It can be obtained by polycondensation reaction of an isocyanate compound having an isocyanate group and a hydroxy compound having two or more hydroxyl groups (—OH).
In addition, “polyamide” means an oligomer or polymer having a bond (amide bond) represented by the formula “—NH—C (═O) —”. 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 are substituted with a chlorocarbonyl group (—C (═O) —Cl); It can be obtained by polycondensation reaction with an amine compound having two or more amino groups.

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

  The number of isocyanate groups in the 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, The number is more preferably 4, and particularly preferably 2 or 3.

  Examples of the isocyanate compound include tolylene-2,4-diisocyanate, tolylene-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 polyisocyanate compounds (provided that the isocyanate group is not substituted); trimethylol pro of the organic polyisocyanate compounds Emissions adducts; derivative of the organic polyvalent isocyanate compound (provided that the isocyanate groups is not intended to be replaced) include trimethylolpropane adduct of. In the present specification, the trimethylolpropane adduct may be referred to as a trimethylolpropane adduct.

  The said isocyanate compound may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

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

  The number of amino groups in the 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, The number is more preferably 4, and particularly preferably 2 or 3.

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

  The said amine compound may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

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

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

  The said hydroxy compound may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

As said amine compound for manufacturing polyamide, the same thing as the said amine compound for forming the above-mentioned polyurea is mentioned except not having a carboxy group, for example.
Examples of the amine compound for producing polyamide include aliphatic polyvalent amine compounds such as hexamethylenediamine, nonanediamine, methylpentadiamine, and diethylenetriamine.

  The number of amino groups in one molecule of the amine compound for producing the 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 is more preferable, and 2 or 3 is particularly preferable.

  The amine compound for producing the polyamide may be used singly or in combination of two or more, and when two or more are used in combination, their combination and ratio are arbitrarily selected. it can.

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

  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.

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

  The carboxylic acid and the carboxylic acid chloride for producing the polyamide may be used singly or in combination of two or more, when two or more are used in combination, The ratio can be arbitrarily selected.

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

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

  For example, when interfacial polycondensation is performed, microcapsules encapsulating the formaldehyde reactant can be obtained at once by subjecting the raw material compounds to polycondensation in the presence of the encapsulated formaldehyde reactant. Hereinafter, a method for forming the film-forming component and producing the microcapsule by interfacial polycondensation will be described.

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

  For example, when polyurea is obtained by interfacial polycondensation using the isocyanate compound and amine compound, the amount of the isocyanate compound and amine compound used is [number of moles of amino groups in the amine compound]: [in isocyanate compound] The molar ratio of the number of moles of isocyanate groups] 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, a higher quality microcapsule 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 hydroxy compound used is [number of moles of hydroxyl groups in the hydroxy compound]: [in the isocyanate compound The molar ratio of the number of moles of isocyanate groups] 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.

  So far, the polycondensate has been described as one obtained by polycondensation of any of the isocyanate compound, amine compound, hydroxy compound, carboxylic acid and carboxylic acid chloride. It may be obtained by polycondensation of other compounds not corresponding to any of isocyanate compounds, amine compounds, hydroxy compounds, carboxylic acids and carboxylic acid chlorides.

The other compound is not particularly limited as long as it can be polycondensed.
Only one kind of the other compound may be used, or two or more kinds thereof may be used, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily selected.

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

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

  The amount of the formaldehyde reactant used during the 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. Also good.

(solvent)
The microcapsule may contain a solvent in order to dissolve the formaldehyde reactant. In this case, the interfacial polycondensation is preferably performed by emulsifying the reaction solution in a mixed solvent of water and a hydrophobic solvent (plasticizer). In this way, microcapsules that encapsulate the formaldehyde reactant and the hydrophobic solvent can be obtained at once by polycondensation of the raw material compound in the presence of the formaldehyde reactant to be encapsulated and the hydrophobic solvent.
Moreover, when emulsifying a reaction liquid, you may use together the emulsifier mentioned later.

  Examples of the hydrophobic solvent include alcohol, amide, nitrile, ketone, ester, ether, hydrocarbon, halogenated hydrocarbon, phenol (a compound having a phenolic hydroxyl group), carbon sulfide, and carboxylic acid.

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 easily becomes an oil-in-water (O / W type) dispersion in which the oil component is dispersed in water, and the film-forming component And formation of microcapsules becomes easier.
That is, microcapsules enclosing 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:
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 (2-ethylhexyl) sebacate (8.7), n-butyl acetate (8.5), isopropyl acetate (8.4) ), Esters such as isobutyl acetate (8.3) (carboxylic acid esters);
Linear 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);
And carboxylic acids such as acetic acid (10.1). The numerical value in parentheses written in parallel with the solvent name means SP value ((cal / cm ³ ) ^1/2 ).

  The said solvent may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.

  Although the usage-amount of the said solvent is not specifically limited, Usually, it is preferable that it is 200-5000 mass parts with respect to 100 mass parts of usage-amounts of a formaldehyde reagent, and it is more preferable that it is 300-4000 mass parts. 400 to 3000 parts by mass is particularly preferable.

(emulsifier)
The emulsifier may be a known one and is not particularly limited.
Preferred emulsifiers include, for example, polyvinyl alcohol (sometimes abbreviated as “PVA” in the present specification), carboxymethyl cellulose (sometimes abbreviated as “CMC” in the present specification), ethyl cellulose, methyl cellulose, and kaizen. , Gum arabic, gelatin, funnel oil, alkylbenzene sulfonate such as sodium benzenesulfonate, sodium dodecylbenzenesulfonate, polyoxyethylene sulfate, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, Examples include isobutylene-maleic anhydride copolymer and poly (meth) acrylic acid.
In this specification, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”.

The said emulsifier may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be selected arbitrarily.
The usage-amount of the said emulsifier is not specifically limited, What is necessary is just to adjust suitably according to the kind.

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

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

For example, when one or more selected from the group consisting of polyurea, polyurethane, and polyamide is used as a film-forming component, the microcapsule is made of polyurea, polyurethane, and polyamide within a range that does not impair the effects of the present invention. Any one or both of other oligomers and polymers that do not correspond to any of them may be further used as a film-forming component.
As for said other oligomer and polymer, all may be only 1 type, 2 or more types, and when they are 2 or more types, those combinations and ratios can be selected arbitrarily.

In the microcapsule, the ratio of the total content of the other oligomer and polymer to the total content of the film-forming components is preferably 5% by mass or less, more preferably 3% by mass or less. It is particularly preferable that the content is not more than mass%.
That is, in the microcapsule, the ratio of the total content of polyurea, polyurethane and polyamide to the total content of the film-forming components is preferably 95% by mass or more, more preferably 97% by mass or more. It is particularly preferably 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 further preferably 0.5 to 13 μm.
In the present specification, “average particle diameter” means the median value D ₅₀ of the cumulative volume distribution measured by a method using a Coulter counter unless otherwise specified.

  In the microcapsule, the thickness of the outer shell film enclosing the formaldehyde reactant is preferably 30 to 500 nm, and 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.

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

  The microcapsule itself has a sustained release property that gradually releases the encapsulated formaldehyde reaction agent over time. Therefore, the microcapsule can maintain the effect of removing formaldehyde over a long period of time, and is suitable as a component of a remover that removes formaldehyde that tends to stay indoors, for example.

  The microcapsule can be selected from those having a specific range as a constituent material, whereby the strength against water (sometimes referred to as “water resistance” in this specification) can be improved. A microcapsule with high water resistance is advantageous in that the sustained release property of the formaldehyde reagent when coexisting with water can be maintained for a longer period of time. For example, in an aqueous dispersion in which the microcapsule agent is dispersed in water, which corresponds to the composition for forming a drug-containing layer described above, the water resistance of the microcapsule agent is high. The release of formaldehyde reactant into water is more highly suppressed. Therefore, when this aqueous dispersion is used for the intended purpose, the sustained-release property of the formaldehyde reactant can be maintained for a longer period, so that the effect of removing formaldehyde can be continuously obtained for a longer period.

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

In terms of improving the water resistance of the microcapsule, preferable formaldehyde reagents include, for example, the 1,2,3-triazole compound and its salt, the 1,2,4-triazole compound and its salt, And compounds having a triazole skeleton, such as the 1,2,3-benzotriazole compounds and salts thereof.
The 1,2,3-triazole compound is preferably 1,2,3-triazole.
The 1,2,4-triazole compounds include 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 or 3,5-diphenyl-1,2,4-triazole is preferred.
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 microcapsule, the preferred solvent is, 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. And 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 (2-ethylhexyl) sebacate (8.7), n-butyl acetate (8.5), isopropyl acetate (8.4) ), Esters such as isobutyl acetate (8.3) (carboxylic acid esters);
Linear 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);
And carboxylic acids such as acetic acid (10.1).
Among these, as for the said solvent, what has SP value of 6.5-9.5 (cal / cm < ³ >) < ^1/2 > is more preferable.

In terms of improving the water resistance of the microcapsule, a preferable film-forming component is, for example, polyurea.
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 as a raw material compound. What was obtained using the seed | species or 2 or more types is preferable.

  In terms of improving the water resistance of the microcapsule, a preferred example of the emulsifier is carboxymethylcellulose.

<Non-microcapsule>
The non-microcapsule is a formaldehyde reactant that is not microencapsulated, and is contained in the drug-containing layer from the beginning.

Examples of the non-microcapsule (formaldehyde reactant) include those similar to the formaldehyde reactant contained in the microcapsule, such as those having a “—NH—” group or a “—NH—” salt-forming group. .
However, since the non-microcapsule is not encapsulated in a microcapsule, one having an amino group (—NH ₂ ) or an amino group salt-forming group is also preferable. Here, the “amino group salt-forming group” is as described in the microcapsule agent. It is presumed that the amino group salt-forming group itself or an amino group becomes reactive with formaldehyde.

The non-microcapsule having an amino group or an amino group salt-forming group is preferably an organic compound.
The non-microcapsule having an amino group or an amino group salt-forming group may have either or both of a “—NH—” group and a “—NH—” salt-forming group. 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 all be the same, may all be different, or may be partially the same. Usually, since it is easy to prepare the desired non-microcapsule, these two or more groups are all the same, that is, they are all amino groups or all form the same amino group salt. It is preferably a group.
When 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, bonding position, and the like may be the same as in the case of the microcapsule.

  The non-microcapsule is electrically neutral as a whole molecule, that is, the total value of the valence of the cation moiety in one molecule of the non-microcapsule is the same as the total value of the valence of the anion. It 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, and more preferably 1 to 3.

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

  The non-microcapsule 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 monocyclic or polycyclic, may be either an aliphatic ring or an aromatic ring, and may be an aliphatic ring or an aromatic ring. May be a polycyclic condensed ring.

In the non-microcapsule, the nitrogen atom of the amino group and amino group salt-forming group is preferably bonded to the nitrogen atom or the carbon atom of 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 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 preferably one.

Preferred non-microcapsules include, for example, carboxylic acid hydrazides and salts thereof which may have a substituent, and alkylamines and salts thereof which may have a substituent.
More preferable non-microcapsules include, for example, an adipic acid dihydrazide which may have a substituent and a salt thereof, and 1,3-bis (aminomethyl) cyclohexane and a salt thereof which may have a substituent. Etc.

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

  The non-microcapsule preferably has one or both of an amino group and an amino group salt-forming group from the viewpoint of higher reactivity with formaldehyde.

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

[Example 1]
<Manufacture of laminates>
(Manufacture of microcapsules)
Ethyl acetate solution (Mitsui Chemicals Co., Ltd.) of bis (2-ethylhexyl) sebacate (manufactured by Toyokuni Seiyaku Co., Ltd., 20.0 g) and trimethylolpropane adduct (IPDI-TMP adduct) of isophorone diisocyanate having a concentration of 75% by mass. 5-methyl-1H-benzotriazole (manufactured by Wako Pure Chemical Industries, Ltd., 10.0 g) was added to and dissolved in a mixture of “Takenate D-140N” (25.0 g, solid content 18.8 g). . Subsequently, the obtained mixture was added to a carboxymethylcellulose aqueous solution (300 g, solid content 21.0 g) having a concentration of 7% by mass, and using an emulsifier (Primics Co., Ltd.), the rotational speed was 12000 rpm, and the time was 5 minutes. Emulsified under conditions. Interfacial polycondensation was performed by adding 1,3-bis (aminomethyl) cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd., 2.7 g) to the emulsion obtained above and stirring at 80 ° C. for 2 hours. .
As described above, a polycondensate of 1,3-bis (aminomethyl) cyclohexane and an IPDI-TMP adduct is used as a film-forming component, 5-methyl-1H-benzotriazole as a formaldehyde reagent, and sebacic acid as a solvent. Microcapsules each encapsulating bis (2-ethylhexyl) and ethyl acetate were obtained as an aqueous dispersion.

  The microcapsule aqueous dispersion obtained above was coated on fine paper using a bar coater, dried at 105 ° C. for 90 seconds, and then magnified 500 times using an electron microscope (manufactured by JEOL Ltd.). Then, the coating and drying sites were observed to confirm that the desired microcapsules were obtained. When the average particle diameter of the obtained microcapsules was measured using a Coulter counter (manufactured by Beckman Coulter, Inc.), it was 12.0 μm.

(Manufacture of composition for forming drug-containing layer)
The composition for forming a drug-containing layer was obtained by adding adipic acid dihydrazide, which is a formaldehyde reagent, to the microcapsule aqueous dispersion obtained above and stirring at room temperature. In this composition for forming a drug-containing layer, the ratio of the content of 5-methyl-1H-benzotriazole encapsulated in the microcapsule to the total content of components other than the solvent is 5% by mass, and is microencapsulated. The proportion of the content of adipic acid dihydrazide that was not present was 10% by mass.

(Manufacture of laminates)
The drug-containing layer forming composition obtained above is applied to one surface of a high-quality paper having a size of 15 cm × 15 cm and dried to form a drug-containing layer on the high-quality paper. A laminate of the present invention having the same configuration as shown was obtained. The amount of the drug-containing layer formed on the fine paper was 10 g / m ² .

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

Separately, water-based ink (hydric extender / main component acrylic resin, manufactured by Dainippon Seika Co., Ltd.) is coated on the same high-quality paper as that used for the production of the laminate, and dried on the high-quality paper. A printing layer containing no formaldehyde was formed to obtain a standard laminate.
Next, this standard laminate is stored in a desiccator in the same manner as in the case of the laminate, and thereafter, after 1 day, 4 days, 7 days, and 11 days from the start of storage, respectively, in the glass container in the desiccator. A portion of the distilled water contained therein was collected as a standard sample, and the concentration of formaldehyde in the standard sample was measured in accordance with JIS A 6921.

From each measured value obtained above, the formaldehyde removal rate (%) of the laminate was calculated according to the following formula (i).
Then, when the formaldehyde removal rate after 7 days from the start of storage is 10% or more, it is determined that the formaldehyde removal ability of the laminate is acceptable (◯), and the case where it is less than 10% It was determined that the removal ability was rejected (x). The results are shown in Table 1.
1- [formaldehyde concentration of sample] / [concentration of formaldehyde of standard sample] × 100 (i)

<Manufacture and evaluation of laminate>
[Examples 2 to 4, Comparative Example 1]
As shown in Table 1, either or both of the type of formaldehyde reactant and the ratio of the content of formaldehyde reactant to the total content of components other than the solvent in the composition for forming a drug-containing layer The laminated body was manufactured and evaluated by the same method as Example 1 except having performed. The results are shown in Table 1.

[Comparative Example 2]
Adipic acid dihydrazide and 1,3-bis (aminomethyl) cyclohexane, which are formaldehyde reagents, were used in the same water-based ink (hydric extender / main component acrylic resin, manufactured by Dainippon Seika Co., Ltd.) as used in Example 1. Was added at room temperature and stirred to obtain a comparative composition for forming a drug-containing layer. In the composition for forming a drug-containing layer for comparison, the ratio of the contents of adipic acid dihydrazide and 1,3-bis (aminomethyl) cyclohexane with respect to the total content of components other than the solvent is 15% by mass. did.
And it replaced with the composition for chemical | medical agent containing layer formation demonstrated previously, and manufactured and evaluated the laminated body by the same method as Example 1 except the point which used this chemical | medical agent content layer forming composition for comparison. The results are shown in Table 1.

[Comparative Example 3]
To the same water-based ink as used in Example 1 (hydric extender / main component acrylic resin, manufactured by Dainippon Seika Co., Ltd.), formaldehyde reactants 5-methyl-1H-benzotriazole and adipic acid dihydrazide were A composition for forming a drug-containing layer for comparison was obtained by adding and stirring at room temperature. In the composition for forming a drug-containing layer for comparison, the ratio of the contents of 5-methyl-1H-benzotriazole and adipic acid dihydrazide to the total content of components other than the solvent is 7.5% by mass. did.
And it replaced with the composition for chemical | medical agent containing layer formation demonstrated previously, and manufactured and evaluated the laminated body by the same method as Example 1 except the point which used this chemical | medical agent content layer forming composition for comparison. The results are shown in Table 1.

In Table 1, “MCization” means “microencapsulation”. Moreover, each abbreviation of a formaldehyde reagent means the following, respectively.
5-MBTZ: 5-methyl-1H-benzotriazole ADH: adipic acid dihydrazide 1,3-BAC: 1,3-bis (aminomethyl) cyclohexane

In Table 1, “-” in the column of the composition for forming a drug-containing layer means that the component is not blended.
The description of “-” in the evaluation result column means that the item has not been evaluated.

As is clear from the above results, the laminates of Examples 1 to 4 had high formaldehyde removal ability because the drug-containing layer contained both the microcapsule and the non-microcapsule.
On the other hand, the laminates of Comparative Examples 1 to 3 had a low formaldehyde removal ability because the comparative drug-containing layer did not contain either the microcapsule or the non-microcapsule.
When Examples 1-4 and Comparative Examples 1-3 are compared, by using a microcapsule and a non-microcapsule in combination, either one of the microcapsule and the non-microcapsule is used alone. It is clear that it showed an outstanding synergistic effect.

[Example 5]
<Manufacture of laminates>
A laminate of the present invention having the same configuration as that shown in FIG. 2 was produced.
The first base material was obtained by laminating an ethylene vinyl acetate copolymer resin-based foamed resin layer on wallpaper backing paper (“WK665” manufactured by KJ Special Paper Co., Ltd., thickness: 105 μm).
The second base material was a gypsum sheet (thickness 9.5 mm).
The resin layer is an ethylene vinyl acetate copolymer resin-based foamed resin layer (thickness: 220 μm), and the content of 5-methyl-1H-benzotriazole encapsulated in the microcapsule is 1% by mass. The content of non-converted adipic acid dihydrazide was 5% by mass. The thickness of the resin layer forming composition during coating was 250 μm.
The printing layer was a water-based ink layer (thickness 2 μm).
The coating layer was an acrylic resin layer (thickness 50 μm), and the content of adipic acid dihydrazide that was not microencapsulated was 5% by mass. The coating thickness of the composition for forming a coating layer was 50 μm.
The through hole was allowed to reach the second surface of the second base material from the first surface of the coating layer, and the hole diameter was 50 μm.
Table 2 shows the types and contents of formaldehyde reactants contained in the resin layer and the coating layer.

<Evaluation of laminate>
In accordance with JIS A 1905-1, using two small chambers, using MDF material (formaldehyde generation amount 167 mL / min) as a formaldehyde generation source, measuring the formaldehyde concentration in the air for the laminate obtained above Then, the ventilation volume conversion value (m ³ / m ² · h) was calculated. The ventilation volume conversion value is calculated 1 day, 4 days, 7 days, 14 days and 21 days after the start of measurement, and the ventilation volume conversion value after 21 days is 0.5 or more. The removal ability was determined to be acceptable (◯), and the case where the removal capacity was less than 0.5 was determined to be the rejection (x) of the formaldehyde removal ability of the laminate. The results are shown in Table 3.

<Manufacture and evaluation of laminate>
[Example 6, Comparative Example 4]
In either one or both of the resin layer and the coating layer, lamination is performed in the same manner as in Example 5 except that either or both of the type of formaldehyde reactant and the content thereof are as shown in Table 2. The body was manufactured and evaluated. The results are shown in Table 3.

In Table 2, the description of “-” in the column of the resin layer and the coating layer means that the corresponding layer does not contain the component.
In Table 3, "-" in the evaluation result column means that the item has not been evaluated.

  As is clear from the above results, in the laminate of Example 5, the resin layer is a drug-containing layer, and in the laminate of Example 6, the resin layer and the coating layer are drug-containing layers, and these drug-containing layers Contained both the microcapsule and the non-microcapsule, so that the ability to remove formaldehyde was high. The laminate of Example 6 having two drug-containing layers had higher formaldehyde removal ability than the laminate of Example 5 having only one drug-containing layer.

On the other hand, in the laminate of Comparative Example 4, both the resin layer and the coating layer were comparative drug-containing layers, and the formaldehyde removal ability was low because they did not contain the microcapsule.
When Examples 5 to 6 and Comparative Example 4 were compared, the combination of the microcapsule and the non-microcapsule showed a significantly superior synergistic effect compared to the case where the non-microcapsule was used alone. It is clear.

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

  1, 2, 3... Laminated body, 11, 21, 31... Substrate, 21a... First surface of substrate, 21b... Second surface of substrate, 211. Base material, 211a ... first surface of first base material, 212 ... second base material, 212a ... second surface of second base material, 212b ... second surface of second base material , 12 ... Drug-containing layer, 22 ... Resin layer, 22a ... First surface of resin layer, 23 ... Print layer, 23a ... First surface of print layer, 24 ... Coating Layer, 24a ... first surface of coating layer, 25 ... adhesion layer, 310 ... adhesive layer, 20, 30 ... through-hole

Claims (4)

  A laminate comprising a drug-containing layer containing a microencapsulated formaldehyde reagent and a non-microencapsulated formaldehyde reagent on at least one surface of a substrate.   The laminate according to claim 1, wherein the formaldehyde reactant in the microcapsule does not have an amino group and a group in which the amino group forms a salt.   The laminate according to claim 1 or 2, wherein the non-microencapsulated formaldehyde reagent has one or both of an amino group and a group in which the amino group forms a salt. It is a manufacturing method of the layered product according to any one of claims 1 to 3,
The drug-containing layer is formed on at least one surface of the base material by using a composition for forming a drug-containing layer formed by mixing a microencapsulated formaldehyde reagent and a non-microencapsulated formaldehyde reagent. The manufacturing method of the laminated body which forms a layer.

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