JP2019116571A - Composition containing microcapsule and laminate - Google Patents

Abstract

To provide a composition containing microcapsule which contains microcapsule and another component suppressing yellowing and can suppress yellowing by the time of a material containing microcapsule provided by using the composition, and the material containing microcapsule.SOLUTION: In a laminate 1 with a backing 11 and a microcapsule containing layer 12 formed on the backing 11, the microcapsule containing layer 12 is formed by using a composition containing microcapsule. The composition containing microcapsule contains microcapsule and antioxidant. A membrane formation component of the microcapsule is polyurea, polyurethane or polyamide. The antioxidant is an organic phosphorus compound.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a microcapsule-containing composition and a laminate.

  Microcapsules containing various active ingredients that exhibit the intended action, including drugs, bactericides, pesticides, perfumes, and other chemical reaction agents, as core substances are effectively effective in the intended environment Since it can release a component or control the sustained release which releases an active ingredient gradually with time, the usage is examined by various fields. Here, the "other chemical reaction agent" is an agent other than a medicine, a bactericide, an agrochemical and a fragrance which inhibits the action of the chemical substance by reacting with a specific chemical substance.

  The microcapsule agent is composed of an outer shell and a core substance enclosed by the outer shell, and the film forming component constituting the outer shell film is usually various resins formed by a polycondensation reaction. is there.

  By the way, with respect to various resins, so-called yellowing, which gradually becomes yellowish with the passage of time during storage, may become a problem. With products using such a resin, the appearance becomes inferior due to yellowing over time. Therefore, various resin products and members capable of suppressing yellowing over time have been studied.

  Such a resinous member is, for example, a film for protecting printed matter, which contains a vinyl chloride resin, a hindered amine having butanetetracarboxylic acid as a light stabilizer, and a benzophenone compound as an ultraviolet light absorber. A substrate is disclosed (see Patent Document 1).

  On the other hand, the microcapsule agent contains a film-forming component composed of a resin. Therefore, even with a microcapsule-containing composition containing a microcapsule and a product or a member containing a microcapsule obtained using this composition, yellowing with time may be a problem. Therefore, microcapsule-containing compositions capable of suppressing yellowing over time have been studied. As microcapsules for achieving such purpose, those having a polyamide formed under specific conditions as a film-forming component are disclosed (see Patent Document 2).

JP, 2016-37542, A Patent No. 2706219 specification

  However, the method of suppressing yellowing using a light stabilizer and a UV absorber disclosed in Patent Document 1 is effective for general resin products and members, but it is in microcapsules. Was not effective.

  In addition, the microcapsules disclosed in Patent Document 2 are obtained by applying specific process conditions at the time of their production, and there is a problem that the production process is complicated. Then, Patent Document 2 does not disclose a method for suppressing yellowing of a microcapsule-containing composition containing the microcapsules by using the microcapsule agent and a component for suppressing yellowing in combination.

  The present invention is a microcapsule-containing composition containing microcapsules and a component that additionally suppresses yellowing, the composition containing microcapsules obtained using this composition being aged It is an object of the present invention to provide a microcapsule-containing composition capable of suppressing yellowing and the above-mentioned microcapsule-containing composition.

  The present invention comprises a microcapsule and an antioxidant, wherein the film-forming component of the microcapsule is polyurea, polyurethane or polyamide, and the antioxidant is an organophosphorus compound. An agent-containing composition is provided.

In the microcapsule-containing composition of the present invention, the organic phosphorus compound is preferably an aliphatic organic phosphorus compound.
Further, the present invention comprises a substrate and a microcapsule-containing layer formed on the substrate, wherein the microcapsule-containing layer is formed using the microcapsule-containing composition. Provide a laminate.

  According to the present invention, there is provided a microcapsule-containing composition comprising the microcapsule and the other component that suppresses yellowing, which is obtained by using this composition. There is provided a microcapsule-containing composition capable of suppressing yellowing over time and the combined microcapsule-containing composition.

It is a sectional view showing typically the layered product concerning one embodiment of the present invention. It is a graph showing transition of (DELTA ⁾ b ^* accompanying aging of the microcapsule-containing layer in Examples 1-4 and Comparative Examples 1-2. 5 is a graph showing the transition of Δb ^* with time of the microcapsule-containing layer in Example 1, Examples 5 to 6 and Comparative Example 1. It is a graph showing transition of (DELTA ⁾ b ^* accompanying aging of the microcapsule agent containing layer in Comparative Examples 1-3.

<< Microcapsule-containing composition >>
A microcapsule-containing composition according to an embodiment of the present invention contains a microcapsule and an antioxidant, and the film forming component of the microcapsule is a polyurea, a polyurethane or a polyamide, and the oxidation is The inhibitor is an organophosphorus compound.

  The microcapsule-containing composition thus contains, as an antioxidant, a compound having a specific range of an organophosphorus compound, thereby suppressing yellowing over time. Then, the microcapsule-containing matter, such as a microcapsule-containing layer described later, which is formed using this composition and contains the microcapsule, is also prevented from yellowing over time.

  In the present specification, the "microcapsule-containing substance" means one obtained using a microcapsule-containing composition and having a different composition or property. As an example of a microcapsule containing material, what dried the microcapsule containing composition was mentioned, However, A microcapsule containing material is not limited to this. The microcapsule-containing layer is formed into a layer using the microcapsule-containing composition among the microcapsule-containing material, and the microcapsule-containing material has another shape other than a layer. May be

The microcapsule-containing composition contains a component for forming the microcapsule-containing substance (for example, a microcapsule-containing layer).
The microcapsule-containing material can be formed, for example, by applying a liquid microcapsule-containing composition to a surface on which the microcapsule-containing material is to be formed and drying it.

<Antioxidant>
The antioxidant is an organophosphorus compound.
In the present specification, the "organophosphorus compound" means an organic compound having a phosphorus atom as a constituent atom.

  Examples of the organic phosphorus compounds include phosphite (phosphorous acid ester) and phosphate (phosphoric acid ester).

Examples of the phosphite include those represented by the following general formula (P1), (P2) or (P3).
Examples of the phosphate include those represented by the following general formula (P4).

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、それぞれ独立にアルキル基、アルケニル基又はアリール基であり；ｎは１、２又は３であり；３個のＲ^１は互いに同一であっても、異なっていてもよく、２個又は３個のＲ^１は、相互に結合して、環を形成していてもよく；２個のＲ^２は互いに同一であっても、異なっていてもよく、２個のＲ^２は、相互に結合して、環を形成していてもよく；２個のＲ^３は互いに同一であっても、異なっていてもよく；ｎが２又は３である場合、ｎ個のＲ^４は互いに同一であっても、異なっていてもよく、ｎが２又は３である場合、２個又は３個のＲ^４は、相互に結合して、環を形成していてもよい。）

(Wherein, R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group, an alkenyl group or an aryl group; n is 1, 2 or 3; three R ^{1 s} are identical to each other) And two or three R ^{1 's} may be bonded to each other to form a ring; and two R ^{2' s} may be the same as or different from each other. And two R ^{2 's} may combine with each other to form a ring; two R ^{3' s} may be the same as or different from each other; n is 2 or 3 And n R ^{4 's} may be the same as or different from each other, and when n is 2 or 3, two or three R ^{4' s} may be bonded to each other to form a ring You may form.)

R ¹ , R ² , R ³ and R ⁴ are each independently an alkyl group, an alkenyl group or an aryl group.
The alkyl group and alkenyl group may be linear, branched or cyclic, and when cyclic, they may be monocyclic or polycyclic.
The aryl group may be monocyclic or polycyclic.

It is preferable that carbon number of the said linear and branched alkyl group is 1-20.
As such a linear or branched alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4 -Methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl Group, 1-ethyl-1-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group , 4-methylhexyl group, 5-methylhexyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethyl group Pentyl group, 4,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 2,2,3-trimethylbutyl group, 1-propylbutyl group , N-octyl group, isooctyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3 -Ethylhexyl group, 4-ethylhexyl group, 5-ethylhexyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, , 3-dimethylhexyl group, 4,4-dimethylhexyl group, 5,5-dimethylhexyl group, 1,2,3-trimethylpentyl group, 1,2,4-trimethylpentyl group, 2,3,4-trimethylpentyl group Pentyl group, 2,4,4-trimethylpentyl group, 1,4,4-trimethylpentyl group, 3,4,4-trimethylpentyl group, 1,1,2-trimethylpentyl group, 1,1,3-trimethyl group Pentyl, 1,1,4-trimethylpentyl, 1,2,2-trimethylpentyl, 2,2,3-trimethylpentyl, 2,2,4-trimethylpentyl, 1,3,3-trimethyl Pentyl, 2,3,3-trimethylpentyl, 3,3,4-trimethylpentyl, 1-propylpentyl, 2-propylpentyl, nonyl, decyl, unde Examples include sil group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.

The carbon number of the cyclic alkyl group is preferably 3 to 20.
As such a cyclic alkyl group, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclodecyl group, etc. are mentioned.
Moreover, as such a cyclic alkyl group, for example, one or more hydrogen atoms of the cyclic alkyl group mentioned above are substituted by a linear, branched or cyclic alkyl group The thing is also mentioned. Here, as the linear, branched or cyclic alkyl group for substituting a hydrogen atom, those exemplified as the alkyl group can be mentioned. It is preferable that carbon number of the cyclic alkyl group which has these substituents is 20 or less including the part of a substituent.

It is preferable that carbon number of the said linear and branched alkenyl group is 2-20.
As such a linear or branched alkenyl group, for example, an ethenyl group (vinyl group), 2-propenyl group (allyl group), octadecenyl group (oleyl group), etc., linear or branched Examples of the alkyl group include groups having a structure in which one single bond (C—C) between carbon atoms is substituted with a double bond (C = C).

The carbon number of the cyclic alkenyl group is preferably 4 to 20.
As such a cyclic alkenyl group, for example, in the cyclic alkyl group such as a cyclohexenyl group, one single bond (C—C) between carbon atoms is substituted with a double bond (C = C) And groups having the following structure.

It is preferable that carbon number of the said aryl group is 6-20.
As such an aryl group, a phenyl group, 1-naphthyl group, 2-naphthyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group (dimethylphenyl group) etc. are mentioned, for example.
In addition, as such an aryl group, for example, those in which one or more hydrogen atoms of the above-mentioned aryl group are substituted with an aryl group or an alkyl group can also be mentioned. Examples of the aryl group substituting a hydrogen atom, include those exemplified above as the alkyl group substituting for a hydrogen atom, include those similar to the alkyl group in R ¹ to R ⁴ above. It is preferable that carbon number of the aryl group which has these substituents is 6-20 including the part of a substituent.

In the general formula (P1), three R ^{1 s} may be the same as or different from each other. That is, all three R ^{1 s} may be the same, all may be different, or only two may be the same.
Two or three R ¹ is bonded to each other, and oxygen atoms to which they R ¹ is attached, together with the phosphorus atom to which they oxygen atoms are attached, they may form a ring. The bonding position of two or three R ^{1 in} this case is not particularly limited, and the ring formed may be either monocyclic or polycyclic.

In the present specification, "a plurality of R ^{1 's} are mutually bonded" means that a plurality of R ¹ form a direct bond between respective carbon atoms constituting R ^1. It means to do. Number of bonds between between the carbon atoms is 1 or more, the number of bonds, the number of R ^1, depending on the type of R ^1, or formed to have ring is either a single cyclic and multi-cyclic It is determined.
These points apply not only to R ¹ but also to R ² and R ⁴ described below.

In the general formula (P2), two R ^{2 s} may be the same as or different from each other.
Two R ² are bonded to each other, and oxygen atoms to which they R ² are attached, together with the phosphorus atom to which they oxygen atoms are attached, may form a ring. The bonding position of the ^two R ^{2 in} this case is not particularly limited, and the ring formed may be either monocyclic or polycyclic.

In the general formula (P3), two R ^{3 s} may be the same as or different from each other.

In the general formula (P4), when n is 1, 2 or 3, and n is 2 or 3, n R ^{4 s} may be the same as or different from each other. For example, when n is 3, all three R ^{4 s} may be the same, all different, or only two.
When n is 2 or 3, two or three R ⁴ may be bonded to each other to form a ring. That is, when n is 2, two R ^4, are bonded to each other, and oxygen atoms to which they R ⁴ are attached, together with the phosphorus atom to which they oxygen atoms are attached, form a ring It may be The bonding position of the two R ^{4 in} this case is not particularly limited, and the ring formed may be either monocyclic or polycyclic. When n is 3, two or three R ^4, they are bonded to each other, and oxygen atoms to which they R ⁴ are attached, together with the phosphorus atom to which they oxygen atoms are attached, form a ring It may be done. The bonding position of two or three R ^{4 in} this case is not particularly limited, and the formed ring may be either monocyclic or polycyclic.

  Examples of the phosphite represented by the above general formula (P1) include trialkyl phosphite, dialkyl monoaryl phosphite, monoalkyl diaryl phosphite, triaryl phosphite, trialkenyl phosphite and the like.

More specifically, examples of the phosphite represented by the general formula (P1) include triethyl phosphite ((C ₂ H ₅ O) ₃ P) and tris (2-ethylhexyl) phosphite ((CH ₃ CH) ₂ CH ₂ CH ₂ CH (CH ₂ CH ₃ ) CH ₂ O) ₃ P), tridecyl phosphite ((C ₁₀ H ₂₁ O) ₃ P), trilauryl phosphite ((C ₁₂ H ₂₅ O) ₃ P ), Tris (tridecyl) phosphite ((C ₁₃ H ₂₇ O) ₃ P), trioleyl phosphite ((C ₁₈ H ₃₅ O) ₃ P), triphenyl phosphite ((C ₆ H ₅ O) ₃ P) ), Trisnonylphenyl phosphite ((C ₉ H ₁₉ C ₆ H ₄ O) ₃ P), tricresyl phosphite ((p-CH ₃ C ₆ H ₄ O) ₃ P), diphenyl Mono (2-ethylhexyl) phosphite ((C ₆ H ₅ O) ₂ POCH ₂ CH (CH ₂ CH ₃ ) CH ₂ CH ₂ CH ₂ CH ₃ ), diphenyl monodecyl phosphite ((C ₆ H ₅ O) ₂ POC ₁₀ H ₂₁ ), diphenyl mono (tridecyl) phosphite ((C ₆ H ₅ O) ₂ POC ₁₃ H ₂₇ ), tris (2,4-di-tert-butylphenyl) phosphite (C ₄₂ H ₆₃ O ₃₎ P) etc.

  As a phosphite represented by said general formula (P2), a dialkyl hydrogen phosphite, a diaryl hydrogen phosphite, a dialkenyl hydrogen phosphite etc. are mentioned, for example.

More specifically, examples of the phosphite represented by the general formula (P2) include diethyl hydrogen phosphite ((C ₂ H ₅ O) ₂ P (= O) -H), bis (2-ethylhexyl) ) Hydrogen phosphite ((CH ₃ CH ₂ CH ₂ CH ₂ CH (CH ₂ CH ₃ ) CH ₂ O) ₂ P (= O) -H), dilauryl hydrogen phosphite ((C ₁₂ H ₂₅ O) ₂ P (= O) -H), dioleyl hydrogen phosphite ((C ₁₈ H ₃₅ O) ₂ P (= O)-H), diphenyl hydrogen phosphite ((C ₆ H ₅ O) ₂ P ( = O) -H) and the like.

  Examples of the phosphite represented by the above general formula (P3) include bis (alkyl) pentaerythritol diphosphite, bis (aryl) pentaerythritol diphosphite, bis (alkenyl) pentaerythritol diphosphite and the like. .

  More specifically, examples of the phosphite represented by the general formula (P3) include those shown below.

  The phosphite is preferably one represented by the general formula (P1) or one represented by the general formula (P3).

  Examples of phosphates represented by the above general formula (P4) include monoalkyl phosphates, dialkyl phosphates, trialkyl phosphates, monoaryl phosphates, diaryl phosphates, triaryl phosphates, monoalkenyl phosphates, dialkenyl phosphates, trialkenyl phosphates, Examples include dialkyl monoaryl phosphate, monoalkyl diaryl phosphate, dialkyl mono alkenyl phosphate, mono alkyl di alkenyl phosphate and the like.

More specifically, as the phosphate represented by the general formula (P4), for example, monoethyl phosphate (C ₂ H ₅ OP (OO) (OH) ₂ ), diethyl phosphate ((C ₂ H ₅ O)) ₂ P (= O) OH), triethyl phosphate ((C ₂ H ₅ O) ₃ P O O), monobutyl phosphate (C ₄ H ₉ OP (O O) (OH) ₂ ), dibutyl phosphate ((C ₄₎ H ₉ O) ₂ P (= O) OH), tributyl phosphate ((C ₄ H ₉ O) ₃ P O O), mono 2-ethylhexyl phosphate (CH ₃ CH ₂ CH ₂ CH ₂ CH (CH ₂ CH ₃ )) _{CH 2 OP (= O) (} OH) 2), di-2-ethylhexyl phosphate _{((CH 3 CH 2 CH 2} CH 2 CH (CH 2 CH 3) CH 2 O) 2 P (= O) OH) Tri-2-ethylhexyl phosphate _{((CH 3 CH 2 CH 2} CH 2 CH (CH 2 CH 3) CH 2 O) 3 P = O), mono-dodecyl phosphate _{(C 10 H 21 OP (=} O) (OH) 2) , Didodecyl phosphate ((C ₁₀ H ₂₁ O) ₂ P (= O) OH), monotridecyl phosphate (C ₁₃ H ₂₇ OP (= O) (OH) ₂ ), ditridecyl phosphate ((C ₁₃ H ₂₇₎ O) ₂ P (= O) OH), monotetradecyl phosphate (C ₁₄ H ₂₉ OP (= O) (OH) ₂ ), ditetradecyl phosphate ((C ₁₄ H ₂₉ O) ₂ P (= O) OH ), mono hexadecyl phosphate _{(C 16 H 33 OP (=} O) (OH) 2), di-hexadecyl phosphate _{((C 16 H 33 O)} 2 P (= O) O ), Mono-octadecyl phosphate _{(C 18 H 37 OP (=} O) (OH) 2), dioctadecyl phosphate _{((C 18 H 37 O)} 2 P (= O) OH), mono-oleyl phosphate (mono octadecenyl _{phosphate) (C 18 H 35 OP (} = O) (OH) 2), or the like dioleyl phosphate (di octadecenyl _{phosphate) ((C 18 H 35 O} ) 2 P (= O) OH) and the like.

  The organophosphorus compound may be, for example, any of an aliphatic organophosphorus compound and an aromatic organophosphorus compound, but is preferably an aliphatic organophosphorus compound. In the present specification, the “aliphatic organophosphorus compound” means an organophosphorus compound having only an aliphatic group and having no aromatic group. And "the aromatic organophosphorus compound" means the organophosphorus compound which has an aromatic group.

Examples of aliphatic organophosphorus compounds include trialkyl phosphites, trialkenyl phosphites, dialkyl hydrogen phosphites, dialkenyl hydrogen phosphites, bis (alkyl) pentaerythritol diphosphites and bis (alkenyl) pentaerythritols. Examples include diphosphites, monoalkyl phosphates, dialkyl phosphates, trialkyl phosphates, monoalkenyl phosphates, dialkenyl phosphates, trialkenyl phosphates, dialkyl monoalkenyl phosphates, monoalkyl dialkenyl phosphates and the like.
Among these, as a preferable aliphatic organophosphorus compound, for example, trialkyl phosphite, bis (alkyl) pentaerythritol diphosphite, monoalkyl phosphate, dialkyl phosphate and the like can be mentioned.

  The phosphate is more preferably one in which n is 1 or 2 among those represented by the above general formula (P4).

The antioxidant contained in the microcapsule-containing composition may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrary. Can be selected.
For example, when the microcapsule-containing composition contains two or more antioxidants, these two or more antioxidants may be only two or more phosphites, or two or more phosphates. It may be only or one or more phosphites and one or more phosphates.

  The content of the antioxidant in the microcapsule-containing composition is not particularly limited, but is preferably 0.3 to 10% by mass, more preferably 0.3 to 8% by mass, and 0.3 It is further more preferable that it is -6 mass%, and it is especially preferable that it is 0.3-4 mass%. When the content of the antioxidant is at least the lower limit value, the effect of suppressing yellowing over time of the microcapsule-containing composition and the microcapsule-containing material formed using the composition becomes higher. When the content of the antioxidant is less than or equal to the above upper limit value, the stability of the microcapsule and the handleability of the microcapsule-containing composition become higher.

<Microcapsule>
The above-mentioned microcapsule agent contains polyurea, polyurethane or polyamide, which is a polycondensate, as a film forming component, and contains a core substance.
In the present specification, those in which the film-forming component is in the form of minute capsules and the core substance is contained therein are referred to as "microcapsule agents". In the present specification, the expression "microcapsule" means microcapsules excluding core material.

[Core substance]
The core substance may be appropriately selected according to the purpose of use of the microcapsule, and is not particularly limited.
As core substances, for example, medicines, germicides, pesticides, perfumes, and other chemical reaction agents (which react with specific chemical substances to inhibit the action of this chemical substance, other than medicines, germicides, pesticides and perfumes Drugs) and the like. Preferable examples of the above-mentioned other chemical reactive agents include formaldehyde reactive agents.

Among the interior materials and furniture of buildings, there are those manufactured using an adhesive and a binder containing formaldehyde, and some products contain formaldehyde. Since formaldehyde is released from such a product, the released formaldehyde stays in the room, causing a problem of causing health damage to humans and animals. The formaldehyde reactive agent solves such problems and has reactivity with formaldehyde. As used herein, "having reactivity with formaldehyde" means having the ability to react with formaldehyde to convert formaldehyde to another compound. That is, the formaldehyde reactive agent contains a group having reactivity with formaldehyde. Formaldehyde is removed in the form of conversion to another compound by reaction with a formaldehyde reactant.
Among the core substances, formaldehyde reactive agents are mentioned as an example of particularly preferable one.

The core substance is preferably one which does not have an amino group and a group in which the amino group forms a salt (which may be abbreviated as "amino group salt forming group" in the present specification).
By using a core substance having no amino group and no amino group salt forming group as the core substance, microcapsules (that is, microcapsules) containing the core substance can be more stably formed.

Examples of the amino group salt forming group include a group in which an amino group is a monovalent cation moiety, and the cation moiety forms a salt with an anion.
Here, as the cationic portion, e.g., a nitrogen atom into hydrogen ions of an amino group (-NH ^₂₎ (H ₊₎ can be cited those coordination bonds. The valence of the anion in this case is not particularly limited, and may be 1 (monovalent) or 2 (divalent) or more. When the anion is monovalent, the number of anions forming the salt and the number of cation parts are both one. When the anion is n-valent (n is an integer of 2 or more), the number of anions forming the salt is usually 1, and the number of cation moieties is n or less Is n. In this case, the plurality of cation moieties may be all the same, all different, or only some of them may be the same.

  The anion in the amino group salt-forming group is the same as the anion moiety in a group ("-NH-" salt-forming group) in which a group represented by the formula "-NH-" described later forms a salt. The thing is mentioned.

The core substance is preferably an organic compound, and such a core substance may be abbreviated as, for example, a group represented by the formula "-NH-" (hereinafter referred to as "" -NH- "group) And a group selected from the group consisting of a group represented by the formula “—NH—” forming a salt (hereinafter sometimes abbreviated as ““ —NH— ”salt forming group”) Or the compound which has 2 or more types is mentioned. In these core materials, the "-NH-" group exhibits reactivity with formaldehyde, and the "-NH-" salt-forming group is itself or "-NH-" as the "-NH-" group. It is assumed that the group is reactive with formaldehyde. Thus, these core materials are suitable as formaldehyde reactants.
When the core substance has an "-NH-" group or a "-NH-" salt forming group, the nitrogen atom in these groups is further covalently bonded to a hydrogen atom in addition to one hydrogen atom which has already been covalently bonded. There is no binding.

  The total number of "-NH-" groups and "-NH-" salt forming groups in one molecule of core substance may be only one, or two or more, or two or more In these cases, these two or more groups may be identical to one another or may be different. That is, these two or more groups may be all the same, all may be different, or only some may be the same. Usually, these two or more groups are all identical, that is, they are all "-NH-" groups or all the same "-," because preparation of the target core material is easy. It is preferred that it is an NH- ′ ′ salt forming group.

As the "-NH-" salt forming group, for example, a group in which the "-NH-" group is a monovalent cation moiety and this cation moiety forms a salt with an anion can be mentioned.
Here, as said cation part, that by which the hydrogen ion (H ^<+> ) coordinate-bonded to the nitrogen atom of "-NH-" group is mentioned, for example. The valence number of the anion in this case is not particularly limited, and may be 1 (monovalent) or 2 (divalent) or more. When the anion is monovalent, the number of anions forming the salt and the number of cation parts are both one. When the anion is m-valent (m is an integer of 2 or more), the number of anions forming the salt is usually 1, and the number of cation parts is m or less, m Is preferred. In this case, the plurality of cation moieties may be all the same, all different, or only some of them may be the same.

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

The anions contained in the core substance may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.
That is, when one molecule of the core substance has two or more of the anions, these two or more anions may be all the same, or all of them may be different, or only part of them may be the same. Good.
However, the core substance is electrically neutral as a whole molecule, that is, the sum of the valences of the cation part in one molecule of the core substance and the sum of the valences of the anion are the same. Is preferred.

  The total number of "-NH-" groups and "-NH-" salt forming groups in one core substance molecule 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 core substance are not particularly limited. For example, when the core substance has a chain structure, Any position may be used.

  The core material may be linear, branched or cyclic, and may have both a chain structure and a cyclic structure.

When the core substance has a cyclic structure, the ring may be either monocyclic or polycyclic, and may be either an aliphatic ring or an aromatic ring, and the aliphatic ring and the aromatic ring may be condensed. It may be a multicyclic ring.
When the core substance has a cyclic structure, the "-NH-" group and the "-NH-" salt forming group may form a ring skeleton of the above-mentioned cyclic structure, or may form a ring without forming a ring skeleton. It may be bonded to a group forming a skeleton.

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

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

  As a preferable core material having a cyclic structure, for example, one or two or more selected from the group consisting of “—NH—” group and “—NH—” salt forming group have a ring skeleton of cyclic structure. And "-C (= O) -NH-" group, "-NH-C (= O) -NH-" group, "-C (= O) -NH-" salt formation. Group, "-NH-C (= O) -NH-" salt forming group, "= N-NH-" group, "-HN-N (-)-NH-" group, "= N-NH-" salt The core material in which one or more selected from the group consisting of the forming group and the “—HN—N (—) — NH—” salt forming group form a ring skeleton of a cyclic structure is more preferable.

  When the core substance has a cyclic structure, the number of ring members of the ring skeleton, that is, the number (number) of atoms forming the ring skeleton is preferably 5 to 7, and more preferably 5 when it is a monocycle. 5 or 6, and in the case of multiple rings, preferably 8 to 10.

  Particularly preferable core substances include, for example, hydantoin which may have a substituent, a salt thereof, 2-imidazolidinone which may have a substituent, and a salt thereof, which may have a substituent 5-pyrazolone and its salt, 3-pyrazolone which may have a substituent, and its salt, 1,2,4-triazol-3-one which may have a substituent and its salt, and a substituent Phthalimide and salts thereof which may have, glycoluril and salts thereof which may have a substituent, pyrazole which may have substituents and salts thereof, and which may have substituents 1 , 2,3-triazole and its salts, optionally substituted 1,2,4-triazole and its salts, and optionally substituted 1,2,3-benzotriazole and its Salt etc. are mentioned.

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 structures of 1,2,3-benzotriazole are 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 rings. It is a compound having 5 members. Phthalimide and 1,2,3-benzotriazole are both compounds having 9 ring members. Glycoluril is a compound having 8 ring members.
In addition, the compound shown here is only one example of the core substance.

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

In addition, as a salt of pyrazole, for example, those in which “—NH—” group in pyrazole becomes “—NH—” salt forming group, and those in which one of nitrogen atoms not bound to hydrogen atom forms a salt And those in which the "-NH-" group is a "-NH-" salt forming group and the nitrogen atom which is not bonded to a hydrogen atom has formed a salt.
In addition, as a salt of 1,2,3-triazole, for example, those in which an “—NH—” group in 1,2,3-triazole becomes an “—NH—” salt forming group, which is bonded to a hydrogen atom In which either or both of the two non-existent nitrogen atoms have formed a salt, and one in which the “—NH—” group is a “—NH—” salt forming group and is not bonded to a hydrogen atom And one in which one or both of the two nitrogen atoms form a salt.
In addition, as a salt of 1,2,4-triazole, for example, those in which an “—NH—” group in 1,2,4-triazole becomes an “—NH—” salt forming group, which is bonded to a hydrogen atom In which either or both of the two non-existent nitrogen atoms have formed a salt, and one in which the “—NH—” group is a “—NH—” salt forming group and is not bonded to a hydrogen atom And one in which one or both of the two nitrogen atoms form a salt.
In addition, as a salt of 1,2,3-benzotriazole, for example, those in which the “—NH—” group in 1,2,3-benzotriazole is a “—NH—” salt forming group, a hydrogen atom and the like 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 Those in which one or both of two non-existent nitrogen atoms have formed a salt can be mentioned.

  In the present specification, "having a substituent" refers to one or more hydrogen atoms of the original compound (with the proviso that hydrogen in "-NH-" group and "-NH-" salt forming group) It means that (excluding the atom) is substituted by a group (substituent) other than a hydrogen atom.

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

The same applies to compounds other than hydantoin.
That is, in the present specification, a 2-imidazolidinone having a substituent is referred to as a "2-imidazolidinone derivative", and includes a 2-imidazolidinone and a 2-imidazolidinone derivative. It may be called "non-compound". And, with the salt of 2-imidazolidinone having a substituent, that is, with the salt of 2-imidazolidinone derivative, the 2-imidazolidinone derivative formed a salt as in the case of 2-imidazolidinone It is a thing. The “optionally substituted 2-imidazolidinone and a salt thereof” mean, in other words, a 2-imidazolidinone compound and a salt thereof.

  In the present specification, 5-pyrazolone having a substituent is sometimes referred to as "5-pyrazolone derivative", and sometimes referred to as "5-pyrazolone compound" including 5-pyrazolone and 5-pyrazolone derivative. And, the salt of 5-pyrazolone having a substituent, that is, the salt of the 5-pyrazolone derivative is a salt in which the 5-pyrazolone derivative forms a salt as in the case of 5-pyrazolone. The "optionally substituted 5-pyrazolone and its salt" mean, in other words, a 5-pyrazolone compound and its salt.

  In the present specification, 3-pyrazolone having a substituent is sometimes referred to as "3-pyrazolone derivative", and sometimes referred to as "3-pyrazolone compound" including 3-pyrazolone and 3-pyrazolone derivative. And, the salt of 3-pyrazolone having a substituent, that is, the salt of 3-pyrazolone derivative is a salt in which the 3-pyrazolone derivative forms a salt as in the case of 3-pyrazolone. The term "optionally substituted 3-pyrazolone and its salt" mean, in other words, 3-pyrazolone compounds and their salts.

  In the present specification, 1,2,4-triazol-3-one having a substituent is referred to as "1,2,4-triazol-3-one derivative", and 1,2,4-triazol-3-one. And the 1,2,4-triazol-3-one derivatives may be collectively referred to as "1,2,4-triazol-3-one compounds". And, 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 "optionally substituted 1,2,4-triazol-3-one 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, phthalimide having a substituent is sometimes referred to as "phthalimide derivative", and includes phthalimide and phthalimide derivatives as "phthalimide compound". The phthalimide salt having a substituent, that is, the salt of the phthalimide derivative is a salt in which the phthalimide derivative forms a salt as in the case of phthalimide. "Phthalimide and its salt which may have a substituent" is, in other words, a phthalimide compound and its salt.

  In the present specification, glycoluril having a substituent is sometimes referred to as "glycoluril derivative", and glycoluril and glycoluril derivatives may be collectively referred to as "glycoluril-based compound". And, the salt of glycoluril having a substituent, that is, the salt of a glycoluril derivative, is a glycoluril derivative in which a salt is formed as in the case of glycoluril. The “glycoluril and its salt which may have a substituent (s)” mean, in other words, a glycoluril compound and its salt.

  In the present specification, a pyrazole having a substituent is sometimes referred to as a "pyrazole derivative", and may be collectively referred to as a "pyrazole compound" including pyrazole and pyrazole derivatives. And, the salt of pyrazole having a substituent, that is, the salt of pyrazole derivative is a salt in which the pyrazole derivative forms a salt as in the case of pyrazole. The phrase "pyrazole which may have a substituent and its salt" mean, in other words, a pyrazole compound and its salt.

  In the present specification, a 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, in the case where the 1,2,3-triazole derivative is 1,2,3-triazole In the same manner as in the above. The “1,2,3-triazole and its salt which may have a substituent” is, in other words, a 1,2,3-triazole compound and its salt.

  In the present specification, a 1,2,4-triazole having a substituent is referred to as “1,2,4-triazole derivative”, and includes 1,2,4-triazole and 1,2,4-triazole derivative. 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 in the above. The term "optionally substituted 1,2,4-triazole and salts thereof" means, in other words, 1,2,4-triazole compounds and salts thereof.

  In the present specification, 1,2,3-benzotriazole having a substituent is referred to as "1,2,3-benzotriazole derivative", and 1,2,3-benzotriazole and 1,2,3-benzotriazole The derivatives may be collectively referred to as "1,2,3-benzotriazole compounds". And, a salt of 1,2,3-benzotriazole having a substituent, that is, a salt of a 1,2,3-benzotriazole derivative is a 1,2,3-benzotriazole derivative which is a 1,2,3-benzotriazole derivative. As in the case of benzotriazole, a salt is formed. The term "optionally substituted 1,2,3-benzotriazole and a salt thereof" means, in other words, a 1,2,3-benzotriazole compound and a salt thereof.

  The substituent is not particularly limited, and preferred examples thereof 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.

It is preferable that carbon number of the said linear or branched alkyl group is 1-10.
As such a linear or branched alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, 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-methylpentyl 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-dimethyl Pentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group Decyl group, and the like.

The carbon number of the cyclic alkyl group is preferably 3 to 10.
As such a cyclic alkyl group, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclodecyl group, etc. are mentioned. Moreover, as such a cyclic alkyl group, for example, one or more hydrogen atoms of the cyclic alkyl group mentioned above are substituted by a linear, branched or cyclic alkyl group The thing is also mentioned. Here, as the linear, branched or cyclic alkyl group for substituting a hydrogen atom, the same ones as the alkyl group mentioned as the substituent of the above-mentioned core substance can be mentioned. It is preferable that carbon number of the cyclic alkyl group which has these substituents is ten or less including the part of a substituent.

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

  The alkenyl group in the substituent may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic.

It is preferable that carbon number of the said linear and branched alkenyl group is 2-10.
As such a linear or branched alkenyl group, for example, a carbon atom in the linear or branched alkyl group such as ethenyl group (vinyl group), 2-propenyl group (allyl group), etc. And a group having a structure in which one single bond (C—C) is substituted with a double bond (C = C).

The carbon number of the cyclic alkenyl group is preferably 4 to 10.
As such a cyclic alkenyl group, for example, in the cyclic alkyl group such as a cyclohexenyl group, one single bond (C—C) between carbon atoms is substituted with a double bond (C = C) And groups having the following structure.

  The aryl group in the substituent may be monocyclic or polycyclic, and when it is cyclic, it may be monocyclic or polycyclic.

It is preferable that carbon number of the said aryl group is 6-15.
As such an aryl group, a phenyl group, 1-naphthyl group, 2-naphthyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group (dimethylphenyl group) etc. are mentioned, for example. In addition, as such an aryl group, for example, those in which one or more hydrogen atoms of the above-mentioned aryl group are substituted with an aryl group or an alkyl group can also be mentioned. Here, as the aryl group and alkyl group which substitute a hydrogen atom, the same thing as the aryl group and alkyl group which were mentioned as a substituent which the above-mentioned core substance has is mentioned. It is preferable that carbon number of the aryl group which has these substituents is 15 or less including the part of a substituent.
The carbon number of the aryl group is more preferably 6 to 10.

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

As an alkoxy group in the said substituent, the monovalent group which has a structure which the said alkyl group couple | bonded with the oxygen atom, such as a methoxy group, an ethoxy group, n-propoxy group, an isopropoxy group, a cyclopropoxy group, is mentioned, for example .
The carbon number of the alkoxy group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 1 to 5.

The alkenyloxy group in the substituent is, for example, a monovalent compound having a structure in which the alkenyl group is bonded to an oxygen atom, such as an ethenyl oxy group (vinyloxy group), a 2-propenyloxy group (allyloxy group), a cyclohexenyloxy group, etc. Groups are mentioned.
The carbon number of the alkenyloxy group is preferably 2 to 10, more preferably 2 to 8, and particularly preferably 2 to 6.

Examples of the aryloxy group in the substituent include a monovalent group having a structure in which the aryl group is bonded to an oxygen atom, such as a phenyloxy group and a 1-naphthyloxy group.
The carbon number of the aryloxy group is preferably 6 to 15, and more preferably 6 to 10.

As the aralkyloxy group in the substituent, for example, a monovalent group having a structure in which the aralkyl group is bonded to an oxygen atom, such as benzyloxy group (phenylmethyloxy group), phenethyloxy group (phenylethyloxy group), etc. It can be mentioned.
The carbon number of the aralkyloxy group is preferably 7 to 20, and more preferably 7 to 11.

The number of substituents contained in the core substance of one molecule may be only one, may be two or more, and in the case of two or more, these substituents may be the same or different from each other . That is, two or more substituents may be all the same, all may be different, or only some of them may be the same.
In general, the number of the substituents contained in the core substance of one molecule is preferably 1 to 4, and more preferably 1 to 3.

The position of the substituent in the molecule of the core substance is not particularly limited. For example, when the core substance has a chain structure, it may be at the end of the molecule or at a site other than the end. It may be.
When the core substance has two or more of the above-mentioned substituents, the bonding positions of these substituents may be all the same, all may be different, or only some of them may be the same.

Among the above-mentioned particularly preferred core substances, those having a substituent are, for example, 5,5-dimethylhydantoin which is a hydantoin derivative; 3-methyl-5-pyrazolone which is a 5-pyrazolone derivative; 3,5 which is a pyrazole derivative -Dimethylpyrazole; a 1,2,4-triazole derivative, 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; 1,2,3-benzotriazole derivative 4-methyl-1H-benzotriazole, 5-methyl-1H- 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, Both 3,5-di-n-butyl-1,2,4-triazole and 3,5-diphenyl-1,2,4-triazole are compounds having 5 ring members. Each of 4-methyl-1H-benzotriazole and 5-methyl-1H-benzotriazole is a compound having 9 ring members.
In addition, the compound shown here is only an example of the core substance which has the said substituent.

  The core substance is preferably solid at normal temperature. And when using the core substance which is solid at normal temperature, it is preferable to use together the solvent mentioned later. In addition, in this specification, "normal temperature" means the temperature which does not cool or heat especially, ie, the normal temperature, for example, the temperature of 15-25 degreeC etc. are mentioned.

  Particularly preferred core materials are, for example, hydantoin, 5,5-dimethylhydantoin, 2-imidazolidinone, 5-pyrazolone, 3-methyl-5-pyrazolone, 3-pyrazolone, 3,5-dimethylpyrazole, phthalimido , Glycoluryl, 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-benzotriazole 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole and the like.

  The core substance encapsulated by the microcapsule may be only one type, or two or more types, and two or more types regardless of the use, and in the case of two or more types, the combination and ratio thereof are optionally It can be selected.

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

[Film-forming component]
The film-forming component is a component that forms an outer shell film that wraps the core substance, and its constituent material is polyurea, polyurethane or polyamide.
These film forming components can be produced, for example, by interfacial polycondensation.

In the present specification, "polyurea" means an oligomer or polymer having a bond (urea bond) represented by the formula "-NH-C (= O) -NH-". Polyurea is obtained, for example, by subjecting an isocyanate compound having two or more isocyanate groups and an amine compound having two or more amino groups as a raw material compound to a polycondensation reaction.
In the present specification, “polyurethane” means an oligomer or polymer having a bond (urethane bond) represented by the formula “—NH—C (OO) —O—”. The polyurethane can be obtained, for example, by a polycondensation reaction of an isocyanate compound having two or more isocyanate groups and a hydroxy compound having two or more hydroxyl groups (-OH) as raw material compounds.
In the present specification, "polyamide" means an oligomer or polymer having a bond (amide bond) represented by the formula "-NH-C (= O)-". In the polyamide, for example, as a raw material compound, a carboxylic acid having two or more carboxy groups (—C (、 O) —OH), or one or two or more carboxy groups thereof is a chlorocarbonyl group (—C (= It is obtained by carrying out the polycondensation reaction of the carboxylic acid chloride which has a structure substituted by O) -Cl), and the amine compound which has two or more amino groups.

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

  The number of isocyanate groups contained in one molecule of the isocyanate compound is not particularly limited as long as it is 2 or more, but is preferably 2 to 6, more preferably 2 to 5, and 2 to 2. 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 polyvalent isocyanate compounds (wherein the isocyanate group is not substituted); trimethylol pro of the organic polyvalent isocyanate 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 is also sometimes referred to as a trimethylolpropane adduct.

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

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

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

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

  The amine compounds may be used alone or in combination of two or more. When two or more are used in combination, the combination and ratio thereof can be optionally selected.

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

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

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

  The hydroxy compounds may be used alone or in combination of two or more. When two or more are used in combination, their combination and ratio can be arbitrarily selected.

As said amine compound for manufacturing a polyamide, the same thing as the said amine compound for forming the above-mentioned polyurea is mentioned, for example except the point which does not have a carboxy group.
Moreover, as said amine compound for manufacturing polyamide, aliphatic polyhydric amine compounds, such as hexamethylene diamine, nonane diamine, methyl penta diamine, diethylene triamine, etc. are mentioned, for example.

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

  The above-mentioned amine compounds for producing polyamide may be used singly or in combination of two or more, and when two or more are used in combination, the combination and ratio thereof are optionally selected it can.

The carboxylic acid for producing the polyamide is one having no amino group.
The number of carboxy groups contained in one molecule of the carboxylic acid is not particularly limited as long as it is 2 or more, but is preferably 2 to 6, more preferably 2 to 5, and 2 to 2. The number is more preferably 4 and particularly preferably 2 or 3.

  Examples of the carboxylic acid include adipic acid (hexanediacid), sebacic acid (decanedioic acid), terephthalic acid (benzene-1,4-dicarboxylic acid), isophthalic acid (benzene-1,3-dicarboxylic acid), etc. Organic polyvalent carboxylic acids (aliphatic polyvalent carboxylic acids, aromatic polyvalent carboxylic acids) and the like.

  The carboxylic acid chloride for producing a polyamide has a structure in which one or more carboxy groups of the carboxylic acid is substituted with a chlorocarbonyl group, and all carboxy groups of the carboxylic acid are chlorocarbonyl groups It may have a structure substituted by

  The carboxylic acids and carboxylic acid chlorides for producing the polyamide may be used alone or in combination of two or more, and in the case of using two or more in combination, a combination thereof and The ratio can be selected arbitrarily.

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

  For example, in the case of interfacial polycondensation, the raw material compound is polycondensed in the coexistence of the core material to be encapsulated, whereby microcapsules (ie, microcapsules) containing the core material can be obtained at once. Hereinafter, the method of producing the above-mentioned microcapsule agent while forming a film-forming component by interfacial polycondensation as described above will be described.

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

  For example, in the case of producing a polyurea by interfacial polycondensation using the isocyanate compound and the amine compound, the amount of the isocyanate compound and the amine compound used is [mole number of amino group in amine compound]: [isocyanate compound It is preferable that it is a quantity which becomes 10:90-60:40, and, as for the molar ratio of the number-of-moles of isocyanate group], it is more preferable that it is a quantity which becomes 20:80-40:60. By setting the number of moles of amino groups in the amine compound to be less than the number of moles of isocyanate groups in the isocyanate compound, higher quality microcapsules can be obtained.

  For example, in the case of obtaining a polyurethane by interfacial polycondensation using the above-mentioned isocyanate compound and hydroxy compound, the amount of the isocyanate compound and hydroxy compound used is [mole number of hydroxyl group in hydroxy compound]: [isocyanate compound] The molar ratio of the number of moles of isocyanate group] is preferably in the range of 10:90 to 60:40, and more preferably in the range of 20:80 to 40:60. By setting the number of moles of hydroxyl groups in the hydroxy compound to be less than the number of moles of isocyanate groups in the isocyanate compound, microcapsules of higher quality can be obtained.

  So far, the thing obtained by polycondensing any of the said isocyanate compound, an amine compound, a hydroxy compound, carboxylic acid, and carboxylic acid chloride as said polycondensate was demonstrated, but the said polycondensate is the said It may be obtained by polycondensation of another compound that does not correspond to any of an isocyanate compound, an amine compound, a hydroxy compound, a carboxylic acid and a carboxylic acid chloride.

The other compounds are not particularly limited as long as they can be polycondensed.
The other compounds may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily selected.

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

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

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

  The amount of core material used during polycondensation is not particularly limited, but is preferably 2 to 65 parts by mass with respect to 100 parts by mass of the total amount of the essential two groups of starting compounds to be polycondensed, The amount is more preferably 2 to 61 parts by mass, and particularly preferably 2 to 57 parts by mass. By setting the amount of core substance used in this range, microcapsules with higher stability can be produced.

In the above-mentioned microcapsules containing polyurea, polyurethane or polyamide as a film forming component, it is preferable that the core substance is azole or a derivative thereof from the viewpoint that the structure of the microcapsules is particularly stable.
As such an azole or a derivative thereof, for example, 1,2,4-triazol-3-one which may have the above-mentioned substituent and a salt thereof, and 1,2 which may have the substituent , 3-Triazole and its salt, optionally substituted 1,2,4-triazole and its salt, and optionally substituted 1,2,3-benzotriazole and its salt, etc. Can be mentioned.

(solvent)
The microcapsules may contain a solvent to dissolve the core substance. In this case, interfacial polycondensation is preferably performed by emulsifying the reaction solution in a mixed solvent of water and a hydrophobic solvent (plasticizer). As described above, by polycondensing the raw material compound in the coexistence of the core substance to be contained and the hydrophobic solvent, the microcapsules containing the core substance and the hydrophobic solvent can be obtained at once.
When the reaction liquid is emulsified, an emulsifying agent described later may be used in combination.

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

The hydrophobic solvent preferably has an SP value (dissolution parameter) of 12 (cal / cm ³ ) ^1/2 or less. By using such a solvent, the reaction liquid during interfacial polycondensation is likely to become an oil-in-water (O / W type) dispersion in a state in which an oil component is dispersed in water, and a film forming component And the formation of microcapsules is easier.
That is, a microcapsule containing a solvent having an SP value of 12 (cal / cm ³ ) ^1/2 or less is particularly preferable among the microcapsules in the present invention.

The lower limit value of the SP value of the hydrophobic solvent is not particularly limited, but is preferably 6.5 (cal / cm ³ ) ^1/2 . Hydrophobic solvents with such SP values are readily available.

As a solvent having an SP value of 12 (cal / cm ³ ) ^1/2 or less, for example,
1-propanol (11.9), 2-propanol (11.5), 1-butanol (11.4), cyclohexanol (11.4), 2-methoxyethanol (10.8), 1-hexanol (10) .7) Alcohols such as 2-methyl-2-propanol (10.6), 1-butoxy-2-propanol (10.4), 2-ethylhexanol (9.5);
Amides such as dimethylformamide (12.0);
Nitriles such as acetonitrile (11.8);
Ketones such as acetone (10.0), methyl ethyl ketone (9.3), methyl propyl ketone (8.7), methyl isopropyl ketone (8.5);
Di n-butyl phthalate (9.4), ethyl acetate (9.1), bis (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 such as methylene chloride (9.7), chloroform (9.3), trichloroethylene (9.2), carbon tetrachloride (8.6) (halogenated aliphatic hydrocarbons);
Sulfurized carbon 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 parenthesis in parallel with the solvent name means the SP value ((cal / cm ³ ) ^1/2 ).

  The solvents may be used alone or in combination of two or more. When two or more are used in combination, their combination and ratio can be arbitrarily selected.

  The use amount of the solvent (water is also handled as a solvent) is not particularly limited, but usually, it is preferably 200 to 5000 parts by mass, 300 to 4000 parts by mass with respect to 100 parts by mass of the core substance used. It is more preferable that it is, and it is especially preferable that it is 400-3500 mass parts.

(emulsifier)
The emulsifier may be a known one and is not particularly limited.
Preferred emulsifiers include, for example, polyvinyl alcohol, carboxymethyl cellulose, ethyl cellulose, methyl cellulose, kaize, gum arabic, gelatin, funnel oil, alkyl benzene sulfonate such as sodium benzene sulfonate, sodium dodecyl benzene sulfonate, polyoxyethylene sulfate, Ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, poly (meth) acrylic acid etc. are mentioned.

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

The reaction temperature during interfacial polycondensation is preferably 60 to 110 ° C., more preferably 65 to 100 ° C., and particularly preferably 70 to 90 ° C.
The time for interfacial polycondensation 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 microcapsule agent is obtained as a water 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. Then, it may be used in the intended application.

In the case where one or more selected from the group consisting of polyurea, polyurethane and polyamide is used as a film-forming component, the microcapsule is, for example, polyurea, polyurethane and polyamide within the range not impairing the effects of the present invention. One or both of other oligomers and polymers which do not correspond to any of the above may further be used as a film forming component.
The other oligomers and polymers may be any one alone or two or more, and in the case of two or more, their combination and ratio can be arbitrarily selected.

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

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

  In the microcapsule, the thickness of the shell film enclosing the core substance is preferably 30 to 500 nm, and more preferably 50 to 300 nm.

  The microcapsules may contain other components in addition to the core substance and the solvent, reflecting the production method.

  When the film-forming component is prepared by the polycondensation method described above, in the microcapsule-containing composition, the ratio of the amount of the antioxidant to the total amount used of the essential raw material compound polycondensed ([oxidation The amount used of the inhibitor (parts by mass) / [the total amount used of the essential raw material compounds polycondensed (parts by mass)] × 100) is preferably 2 to 65% by mass, and 4 to 58% by mass Is more preferable, and 6 to 52% by mass is particularly preferable.

  The microcapsules contained in the microcapsule-containing composition may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are optionally It can be selected.

<Other ingredients>
The microcapsule-containing composition may contain, in addition to the microcapsule and the antioxidant, other components which do not correspond to any of these. For example, when the film-forming component is produced by the above-mentioned polycondensation method, for example, an essential raw material compound which has been left unreacted and which is used for the polycondensation is formed and microcapsules are formed. The remaining core substance, the above-mentioned solvent used at the time of polycondensation, an emulsifier and optional components other than these (solvent, emulsifier), and an unused component at the time of polycondensation, etc. may be mentioned.

Among the above-mentioned other components, examples of the above-mentioned optional components, components not used at the time of polycondensation include salts (preferably inorganic salts).
Moreover, as a component which is not used at the time of polycondensation, resin etc. are mentioned, for example. As said resin, the thing similar to resin in the base material mentioned later is mentioned, for example.

  The other components contained in the microcapsule-containing composition may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof are arbitrary. Can be selected.

  The ratio of the contents of the components which do not vaporize at normal temperature in the microcapsule-containing composition is usually the ratio of the contents of the components in a microcapsule-containing material such as a microcapsule-containing layer described later It will be the same.

  In the microcapsule-containing composition, the ratio of the content of the microcapsule to the total content of the components other than the solvent (the content of the microcapsule of the microcapsule-containing substance such as the microcapsule-containing layer described later) It is preferable that it is 35-70 mass%, and it is more preferable that it is 55-60 mass%. When the ratio is equal to or more than the lower limit value, in the microcapsule-containing composition and the microcapsule-containing composition, the effect of using the microcapsule can be more remarkably obtained. When the ratio is equal to or less than the upper limit value, the microcapsule-containing composition and the microcapsule-containing material can be more easily obtained.

  In the microcapsule-containing composition, the ratio of the content of the antioxidant to the total content of the components other than the solvent (the content of the antioxidant in the microcapsule-containing material such as the microcapsule-containing layer described later) It is preferable that it is 1-35 mass%, It is more preferable that it is 2-20 mass%, It is especially preferable that it is 2.5-15 mass%. When the ratio is equal to or more than the lower limit value, the effect of suppressing yellowing over time of the microcapsule-containing composition and the microcapsule-containing material formed using the composition becomes higher. When the ratio is equal to or less than the upper limit value, the stability of the microcapsule and the handleability of the microcapsule inclusion become higher.

In the microcapsule-containing composition, the ratio of the total content of the microcapsule and the antioxidant to the total content of the components other than the solvent (microcapsule-containing material such as a microcapsule-containing layer described later, etc. The total content of the microcapsule agent and the antioxidant) is, for example, 30 mass% or more, 40 mass% or more, 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more It may be any of the above. By the ratio of the said total content being more than the said lower limit, in the microcapsule-containing composition and the microcapsule-containing material, the effect by using the microcapsule and the antioxidant is more remarkably obtained. . The upper limit value of the ratio of the total content is not particularly limited, and may be 100% by mass.
In other words, in the microcapsule-containing composition, the ratio of the content of the other component to the total content of the components other than the solvent (the microcapsule-containing material such as the microcapsule-containing layer described later) The content of the other components) is, for example, less than 70% by mass, less than 60% by mass, less than 50% by mass, less than 40% by mass, less than 30% by mass, less than 20% by mass and less than 10% by mass May be The lower limit value of the content ratio is not particularly limited, and may be 0% by mass.

  In the microcapsule-containing composition and the microcapsule-containing composition, an antioxidant is present outside the microcapsule, and the microcapsule and the antioxidant are separately present.

Even if the film-forming component is a polycondensate, the microcapsule (microcapsule agent) containing the core substance can be easily selected by selecting the core substance having no amino group and no amino group salt forming group as the core substance. can get.
When a core substance having an amino group or an amino group salt forming group is used, an essential raw material compound to be polycondensed when forming a film forming component which is a polycondensate at the time of production of microcapsules (for example, It is presumed that the above-mentioned isocyanate compound, carboxylic acid, carboxylic acid chloride and the like react with the core substance having an amino group or an amino group salt forming group to inhibit the formation of microcapsules. On the other hand, it is speculated that inhibition of formation of such microcapsules may be suppressed by using a core substance having neither an amino group nor an amino group salt forming group.

  The microcapsules have a sustained release which gradually releases the contained core substance to the outside with time. Thus, for example, when a formaldehyde reactive agent is used as the core substance, the microcapsules can sustain the effect of removing formaldehyde over a long period of time, for example, a removing agent that removes formaldehyde which tends to stay in the room. It is suitable as a component.

The microcapsule-containing composition is obtained, for example, by blending the microcapsule, an antioxidant, and, if necessary, the other components, and is preferably obtained by blending a solvent.
In addition, the microcapsule-containing composition is, for example, a liquid (dispersion) obtained by preparing the microcapsule, an antioxidant, and, if necessary, any one of the other components and a solvent. Or it can be obtained by blending both.

The method of mixing when preparing the microcapsule-containing composition is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; mixing using a mixer, triple roll, kneader, bead mill, etc. Method: A known method such as a method of adding and mixing ultrasonic waves may be appropriately selected.
The temperature when preparing the microcapsule-containing composition is not particularly limited as long as each compounding component is not deteriorated, and may be, for example, 5 to 90 ° C., but this is an example.
The time for preparing the microcapsule-containing composition is also not particularly limited as long as each compounding component is not deteriorated, and may be, for example, 10 minutes to 24 hours, but this is an example.

<< laminate >>
A laminate according to an embodiment of the present invention comprises a substrate, and a microcapsule-containing layer formed on the substrate, wherein the microcapsule-containing layer is the microcapsule-containing composition. It is formed using.

Since the microcapsule-containing layer in the laminate is a microcapsule-containing material formed using the microcapsule-containing composition, yellowing due to aging is suppressed.
The effect can be confirmed by, for example, reducing change in the value of b ^* in the L ^* a ^* b ^* color system of the microcapsule-containing layer before and after aging of the microcapsule-containing layer.

The value of b ^* of the microcapsule-containing layer can be measured, for example, by the following method.
That is, the microcapsule-containing composition is coated on a substrate and dried to form a microcapsule-containing layer. The conditions for forming the microcapsule-containing layer will be described in detail later, but here, for example, the drying temperature can be 100 to 110 ° C., the drying time can be 1 to 3 minutes, and the thickness of the microcapsule-containing layer can be The formation amount of the microcapsule-containing layer can be 15 to 30 μm, and 10 to 25 g / m ² .
The value of b ^* of the formed microcapsule-containing layer can be measured, for example, using a known measuring device such as an integrating sphere spectrophotometer.

The value of b ^* of microcapsules containing layer before aging (immediately after production and in other words) and b ^* _0, and a value of b ^* of microcapsules containing layer b ^* _t when the time in days is t (day) In this case, the fluctuation value Δb ^* _t of the value of b ^* when the number of days elapsed is t (day) can be calculated by the following formula (I). In the laminate according to the present invention, the value of Δb ^* _t is significantly reduced.
(I): Δ b ^* _t = b ^* _t- b ^* ₀ (where, t is the number of days elapsed for the microcapsule-containing layer)

The fluctuation suppressing effect of the value of Δb ^* _t is, for example, by comparing the same as the above except that the microcapsule agent-containing layer does not contain the antioxidant (the organic phosphorus compound). Can be evaluated.
That is, for the microcapsule-containing layer for comparison which does not contain the antioxidant (the organic phosphorus compound), the variation value Δb ^* of the value of b ^* when the number of days elapsed is t (day) by the same method as described above Calculate _tR . Then, the value of the difference Δ (Δb ^* ) _t of these Δb ^* values is calculated by the following formula (II). The larger the value of Δ (Δb ^* ) _t , the higher the fluctuation suppressing effect of the value of Δb ^* _t , that is, the suppressing effect of yellowing of the microcapsule-containing layer with time. This is because, in the case of the microcapsule-containing layer containing the above-mentioned antioxidant (the microcapsule-containing layer in the present invention), Δb ^* _t is small, while the above-mentioned antioxidant is not contained. In the case of the microcapsule-containing layer, Δb ^* _tR is increased.
(II): Δ (Δb ^* ) _t = [Δb ^* _tR ]-[Δb ^* _t ] (wherein t is the number of days elapsed for the microcapsule-containing layer)

In the laminate according to the present invention, Δ (Δb ^* ) _t is significantly large. For example, when the microcapsule-containing layer is aged under the conditions of a temperature of 40 ° C. and a relative humidity of 90%, Δ (Δb ^* ) _t if Δd is 30 days (t = 30 (days)) The corresponding Δ (Δb ^* ) ₃₀ is preferably 0.35 or more, more preferably 0.40 or more, and still more preferably 0.45 or more. In this case, the upper limit value of Δ (Δb ^* ) ₃₀ is not particularly limited. For example, Δ (Δb ^* ) ₃₀ is preferably 1.2 or less in that it is excellent in the actual ease of obtaining the microcapsule-containing layer.

  The above-mentioned aging conditions are more severe than ordinary aging conditions, and yellowing of the microcapsule-containing layer in the laminate according to the present invention is further significantly suppressed if aging is performed under ordinary conditions. . That is, the above-mentioned time-lapse condition is particularly suitable in order to confirm with high reliability the suppression effect of yellowing of the microcapsule-containing layer. However, the aging conditions for confirming the yellowing suppression effect of the microcapsule-containing layer are not limited to the above.

The shape of the laminate may be arbitrarily selected according to the purpose, and may be, for example, a sheet, a plate (plate), or a block.
Hereinafter, the laminate will be described in more detail with reference to the drawings.

  FIG. 1 is a cross-sectional view schematically showing a laminate according to an embodiment of the present invention. Note that the drawings used in the following description may be enlarged for convenience, in order to make the features of the present invention intelligible. Not necessarily.

  The laminate 1 shown here includes a base 11 and a microcapsule-containing layer 12 formed on the base 11. In other words, the laminate 1 is configured by laminating the base 11 and the microcapsule-containing layer 12 in these thickness directions.

  In the laminate 1, the microcapsule-containing layer 12 is provided on one surface (which may be referred to as “first surface” in the present specification) 11 a of the substrate 11, and It is not provided on the other surface (a surface opposite to the first surface, which may be referred to as “second surface” in the present specification) 11 b. That is, the laminate 1 includes the microcapsule-containing layer 12 only on the first surface 11 a of both surfaces of the base material 11. And the 2nd surface 11b of the base material 11 is an exposed surface here.

<Base material>
The substrate 11 is preferably in the form of a film or a sheet.

As a constituent material of the base material 11, paper, resin etc. are mentioned, for example.
Examples of the paper include high quality paper, art paper, coated paper, cast coated paper, resin coated paper, synthetic paper and the like.
Examples of the resin include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, AS resin, ABS resin, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate , Polybutylene naphthalate, polyphenylene sulfide, polysulfone, polycarbonate, epoxy resin, melamine resin, phenol resin, urea resin, polyurethane, polyimide, synthetic resin such as ethylene vinyl acetate copolymer resin; polybutadiene rubber, styrene butadiene rubber, acrylonitrile・ Butadiene rubber, butyl rubber, chloroprene rubber, polyisobutylene rubber, ethylene rubber, propylene rubber, silicone rubber, etc. Synthetic rubber and the like.

The acrylic resin in the substrate 11 is a resin having a structural unit derived from (meth) acrylic acid or (meth) acrylic acid ester, and is derived from (meth) acrylic acid or (meth) acrylic acid ester It may have or may not have other constitutional units other than the constitutional unit.
In the present specification, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”.

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

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

The basis weight (mass per surface area of 1 m ² ) of the substrate 11 is not particularly limited, but is preferably ²⁰ to 200 g / m ² , and in view of manufacturing cost and mechanical strength, 70 to 100 g / m ² It is more preferable that

The substrate 11 can be manufactured by a known method. For example, the base material containing resin can be manufactured by shape | molding the resin composition containing the said resin.
A commercially available product may be used as the substrate 11.

[Microcapsule-containing layer]
The microcapsule-containing layer 12 is formed using the microcapsule-containing composition.
The microcapsule-containing layer 12 contains components derived from the microcapsule-containing composition, such as the microcapsule, the antioxidant, and the other components as necessary, and this microcapsule, in other words, It has an action derived from a core substance in a microcapsule and an action derived from an antioxidant (ie, an antioxidant action). That is, the laminate 1 is provided with the microcapsule-containing layer 12 to exhibit an effect unique to the microcapsule-containing layer 12.

  Here, although the microcapsule-containing layer 12 is shown as a layer having a clear surface, depending on the type of the microcapsule-containing composition, it may not have such a clear surface. .

  Each of the components such as the microcapsule, the antioxidant, and the other components contained in the microcapsule-containing layer 12 may be only one or two or more, respectively. When they are species or more, their combination and ratio can be arbitrarily selected.

  The content of each component of the microcapsule-containing layer 12 such as the microcapsule, the antioxidant, and the other components is the content of each of the components other than the solvent in the microcapsule-containing composition. It becomes the same as the ratio of the content of the component. More specifically, it is as described above.

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

The thickness of the microcapsule-containing layer 12 is not particularly limited, but is preferably 10 to 800 μm.
Here, "the thickness of the microcapsule-containing layer 12" means the entire thickness of the microcapsule-containing layer 12; for example, the thickness of the microcapsule-containing layer 12 composed of a plurality of layers refers to the microcapsule The total thickness of all the layers constituting the agent-containing layer 12 is meant.
The state of the microcapsule-containing layer 12 is one, for example, when the surface of the microcapsule-containing layer 12 has a high degree of unevenness or when the microcapsule-containing layer 12 does not have a clear surface as described above. If this is not the case, the height of the portion that is the highest from the first surface 11 a of the base material 11 of the microcapsule-containing layer 12 may be the thickness of the microcapsule-containing layer 12.

Although the formation amount on the base material 11 of the microcapsule agent containing layer 12 is not specifically limited, It is preferable that it is 10-800 g / m < ² >.

  The laminate of the present embodiment is not limited to the one shown in FIG. 1, but some of the configurations shown in FIG. 1 have been modified, deleted or added within the scope not impairing the effects of the present invention. It may be.

For example, although the layered product 1 shown in FIG. 1 includes the microcapsule-containing layer 12 on the base material 11, the layered product of the present embodiment may include other layers other than this. The other layers are not particularly limited, and the type, thickness, arrangement position and the like can be arbitrarily selected according to the purpose.
For example, the laminate 1 may include the other layer on the opposite side of the microcapsule-containing layer 12 to the base 11 side. Examples of the other layer in this case include an adhesive layer, a printing layer, an adhesive layer, and a microcapsule-containing layer provided separately from the microcapsule-containing layer 12. The separately provided microcapsule-containing layer may have the same form as the microcapsule-containing layer 12 and may be the same as or different from the microcapsule-containing layer 12.

  In the present specification, the “adhesion layer” means a layer for improving the adhesion between two adjacent layers. Also, "adhesive layer" means a layer for bonding two adjacent layers.

  The laminate 1 may include the other layer between the base 11 and the microcapsule-containing layer 12. As said other layer in this case, the same thing as the above-mentioned is mentioned, for example.

The laminate 1 may have any layer on the second surface 11 b of the substrate 11. As the layer on the second surface 11b, the same one as any layer on the first surface 11a can be mentioned.
For example, when the microcapsule-containing layer is provided on the second surface 11b, the microcapsule-containing layer can have the same form as the microcapsule-containing layer 12 on the first surface 11a. , May be the same as or different from the microcapsule-containing layer 12 on the first surface 11a.

  Further, the laminate 1 shown in FIG. 1 may further include another base material separately from the base material 11 on the second surface 11 b of the base material 11. The other base material may be in 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 on the base material 11 via an adhesive bond layer.

  The other layers included in the laminate 1 may be only one layer, or two or more layers, and in the case of two or more layers, the combination and ratio thereof can be arbitrarily selected.

The application of the laminate can be optionally selected according to the purpose (type of core substance in the microcapsule) and is not particularly limited.
For example, the laminate having the function of removing formaldehyde is suitable for providing an object of removal of formaldehyde, such as an interior material of a building (for example, wallpaper, etc.) or furniture, or a component material of the interior material or furniture. is there.
The laminate can be provided to the object to be used by a known method such as using an adhesive or using a jig for attachment.

<< Production method of laminates >>
The laminate can be produced by laminating the microcapsule-containing layer on the substrate.
The microcapsule-containing layer can be formed, for example, by applying the liquid microcapsule-containing composition onto a surface on which the microcapsule-containing layer is to be formed and drying it. Here, for example, the “first surface 11a of the base material 11” in the laminate 1 shown in FIG. It can be mentioned.

  The coating method of the microcapsule-containing composition is not particularly limited, and any method may be used as long as it can coat a liquid material. Specific coating methods include, for example, various coaters such as an air knife coater, curtain coater, die coater, blade coater, blade coater, roll coater, gate roll coater, bar coater, rod coater, gravure coater, gravure offset coater, etc .; There are known methods using an apparatus such as a coater.

  The microcapsule-containing composition may be dried by a known method, for example, under normal pressure, under reduced pressure or under blowing condition, and may be performed under the atmosphere or under an inert gas atmosphere. It is also good. The drying temperature is also not particularly limited, and any of heat drying and normal temperature drying may be used. The drying temperature may be, for example, 15 to 120 ° C. The drying time may be appropriately adjusted depending on the drying temperature, and is not particularly limited. The drying time may be, for example, 1 minute to 24 hours.

The microcapsule-containing layer can be laminated on a substrate, for example, by coating the microcapsule-containing composition on a substrate and drying it.
In addition, the microcapsule-containing composition is applied to the release-treated surface of the release film and dried to form a microcapsule-containing layer on the release film, and the exposed surface of the microcapsule-containing layer (release film The microcapsule-containing layer can also be laminated on the substrate by laminating the surface opposite to the side with the substrate. In this case, the release film may be removed at any time until the use of the laminate.

  The laminate including the other layer can be manufactured by additionally performing the step of laminating the other layer at a suitable position in the above-mentioned manufacturing method.

  Hereinafter, the present invention will be described in more detail by way of specific examples. However, the present invention is not limited at all to the examples shown below.

Example 1
<Production of laminates>
(Manufacturing of microcapsules)
Ethyl acetate solution (Mitsui Chemical Co., Ltd.): bis (2-ethylhexyl) sebacate (55.9 g, manufactured by Toyokuni Oil Co., Ltd.) and trimethylolpropane adduct of isophorone diisocyanate (IPDI-TMP adduct) having a concentration of 75% by mass 5-Methyl-1H-benzotriazole (manufactured by Wako Pure Chemical Industries, Ltd., 27.9 g) is added to and dissolved in a mixture of 69.1 g (solid content: 51.8 g) manufactured by "Takenate D-140N". A solution was obtained. Also, an aqueous solution (838 g) containing carboxymethylcellulose ("Cerogen 7A" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) at a concentration of 7% by mass and potassium sulfate (manufactured by Otsuka Chemical Co.) at a concentration of 7% by mass (ie, The aqueous solution was prepared with 58.7 g of both carboxymethylcellulose and potassium sulfate. And the whole quantity of the solution obtained above was added to this aqueous solution, and it stirred on conditions of rotation speed 1000rpm and time 15 minutes using the stirring wing | blade. Subsequently, the obtained product was emulsified using an emulsifying machine ("Malder" manufactured by Pacific Kiko Co., Ltd.) under the conditions of a rotational speed of 15000 rpm and a generator GMF. Subsequently, 1,3-bis (aminomethyl) cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd., 9.2 g) is added to the emulsion obtained above, and interfacial polycondensation is performed by stirring at 80 ° C. for 2 hours. went.
As described above, polyurea which is 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 core material, and as a solvent Microcapsules each containing bis (2-ethylhexyl) sebacate and ethyl acetate were obtained as a water dispersion.
The amount of 5-methyl-1H-benzotriazole (core substance) used in the polycondensation is the two essential groups of raw material compounds (IPDI-TMP adduct and 1,3-bis (aminomethyl) cyclohexane) to be polycondensed It was 45.7 parts by mass with respect to 100 parts by mass in total.

  The aqueous dispersion of microcapsules obtained above is coated on wood free paper using a bar coater, dried at 105 ° C. for 90 seconds, and then 500 × using an electron microscope (manufactured by Nippon Denshi Co., Ltd.) The coated and dried sites were observed by magnification to confirm that the desired microcapsules were obtained. It was 12.5 micrometers when the average particle diameter of the obtained microcapsule was measured using the Coulter counter (made by Beckman Coulter Inc.).

(Production of Microcapsule-Containing Composition)
To the microcapsule aqueous dispersion (100 g) obtained above at normal temperature, tris (2-ethylhexyl) phosphite ((CH ₃ CH ₂ CH ₂ CH ₂ CH (CH ₂ CH ₃ ) CH) as an antioxidant ₂ O) ₃ P, Johoku Chemical Co., Ltd. “JP-308E”, 1.0 g) is added, and the microcapsule-containing composition is produced by stirring under the conditions of 500 rpm and 10 minutes of time using a stirring blade. I got a thing.
The content of tris (2-ethylhexyl) phosphite in this microcapsule-containing composition was 1.0% by mass.
In this microcapsule-containing composition, the ratio of the amount of tris (2-ethylhexyl) phosphite used to the total amount of 1,3-bis (aminomethyl) cyclohexane and the IPDI-TMP adduct ([tris Use amount of (2-ethylhexyl) phosphite (parts by mass) / {[use amount of 1,3-bis (aminomethyl) cyclohexane (parts by mass)] + use amount of the IPDI-TMP adduct (parts by mass) ] × 100) was 16.4% by mass.

(Production of laminate)
Using a wire bar (No. 30), the microcapsule-containing composition was coated on one side of a paper base (110 kg of "DF color" manufactured by Mitsubishi Paper Mills, about 130 μm thick). A microcapsule-containing layer (thickness 20 μm) was formed by processing and drying at 105 ° C. for 2 minutes. The amount of the microcapsule-containing layer formed on the base was 20.3 g / m ² . The color of the paper base is white.
From the above, a laminate having the same configuration as that shown in FIG. 1 was manufactured.

<Evaluation of laminate (1)>
(Measurement of b ^* of microcapsule-containing layer, calculation of Δb ^* of microcapsule-containing layer after aging)
The microcapsule-containing layer in the laminate immediately after production obtained above was subjected to b ^* (that is, b ^* _0- ) using an integrating sphere type spectrophotometer ("SP60 series" manufactured by X-Rite). ₁ ) was measured.
Then, the laminate was aged by being stored still under conditions of a temperature of 40 ° C. and a relative humidity of 90%. During this time, with respect to the microcapsule-containing layer in the laminate at each stage of time-lapse (after start of standing and storage) day 1, day 4, day 7, day 14, day 21 and day 30. in the ^b _{* 0-1} measured at the same method, each ^{b * _{(i.e., b * 1-1, b * 4-1}} , b * 7-1, b * 14-1, b * 21-1 and b ^* _30-1 ) was measured. Then, according to the following formula (I) -1, Δb ^* at each stage (ie, Δb ^* _1-1 , Δb ^* _4-1 , Δb ^* _7-1 , Δb ^* _14-1 , Δb ^* _21-1 and Δb ^* _30-1 ) was calculated. The results are shown in Table 1. Further, a graph showing the transition of Δb ^* at each stage is shown in FIG. The color of the paper base did not change even as it was white even during the static storage.
(I) -1: Δb ^* _t-1 = b ^* _t-1- b ^* _0-1 (wherein t is the number of days elapsed for the microcapsule-containing layer)

<Production and evaluation of laminate (1)>
Example 2
At the time of preparation of the microcapsule-containing composition, tris (2-ethylhexyl) phosphite (1.0 g) is replaced with tris (tridecyl) phosphite ((C ₁₃ H ₂₇ O) ₃ P, Johoku as an antioxidant. A laminate was manufactured and evaluated in the same manner as in Example 1 except that “JP-333E” manufactured by Kagaku Co., Ltd., 1.0 g) was used.
As b ^* , b ^* _1-2 , b ^* _4-2 , b ^* _7-2 , b ^* _14-2 , b ^* _21-2 and b ^* _30-2 are measured, and the following formula (I)- the 2, as _{^{Δb *, Δb * 1-2, Δb}} * 4-2, Δb * 7-2, Δb * 14-2, were calculated [Delta] b ^* _21-2 and [Delta] b ^* _30-2.
The results are shown in Table 1. Further, a graph showing the transition of Δb ^* at each stage is shown in FIG.
(I) -2: Δb ^* _t-2 = b ^* _t-2- b ^* _0-2 (wherein, t is the number of days elapsed for the microcapsule-containing layer)

[Example 3]
When producing the microcapsule-containing composition, bis (decyl) pentaerythritol diphosphite (manufactured by Johoku Kagaku Co., Ltd. “JPE-10” in place of tris (2-ethylhexyl) phosphite (1.0 g) as an antioxidant The laminate was manufactured and evaluated in the same manner as in Example 1 except that 1.0 g) was used.
As b ^* , b ^* _1-3 , b ^* _4-3 , b ^* _7-3 , b ^* _14-3 , b ^* _21-3 and b ^* _30-3 are measured, and the following formula (I)- by 3, as _{^{Δb *, Δb * 1-3, Δb}} * 4-3, Δb * 7-3, Δb * 14-3, were calculated [Delta] b ^* _21-3 and [Delta] b ^* _30-3.
The results are shown in Table 1. Further, a graph showing the transition of Δb ^* at each stage is shown in FIG.
(I) -3: Δb ^* _t-3 = b ^* _t-3- b ^* _0-3 (wherein, t is the number of days elapsed for the microcapsule-containing layer)

  The structural formula of bis (decyl) pentaerythritol diphosphite is shown below.

Example 4
A mixture of monobutyl phosphate and dibutyl phosphate instead of tris (2-ethylhexyl) phosphite (1.0 g) as an antioxidant during production of the microcapsule-containing composition (JP-504 (Johoku Chemical Co., Ltd.) A laminate was produced and evaluated in the same manner as in Example 1 except that butyl acid phosphate) "and 1.0 g) were used.
As b ^* , b ^* _1-4 , b ^* _4-4 , b ^* _7-4 , b ^* _14-4 , b ^* _21-4 and b ^* _30-4 are measured, and the following formula (I)- by 4, as _{^{Δb *, Δb * 1-4, Δb}} * 4-4, Δb * 7-4, Δb * 14-4, were calculated [Delta] b ^* _21-4 and [Delta] b ^* _30-4.
The results are shown in Table 1. Further, a graph showing the transition of Δb ^* at each stage is shown in FIG.
(I) -4: Δb ^* _t-4 = b ^* _t-4- b ^* _0-4 (wherein t is the number of days elapsed for the microcapsule-containing layer)

  The structural formulas of monobutyl phosphate and dibutyl phosphate are shown below.

[Example 5]
The same as Example 1, except that the blending amount of the antioxidant tris (2-ethylhexyl) phosphite was changed to 1.0 g instead of 1.0 g at the time of production of the microcapsule-containing composition Laminates were manufactured and evaluated in a method.

The content of tris (2-ethylhexyl) phosphite in this microcapsule-containing composition was 0.5% by mass.
In this microcapsule-containing composition, the ratio of the amount of tris (2-ethylhexyl) phosphite used to the total amount of 1,3-bis (aminomethyl) cyclohexane and the IPDI-TMP adduct ([tris Use amount of (2-ethylhexyl) phosphite (parts by mass) / {[use amount of 1,3-bis (aminomethyl) cyclohexane (parts by mass)] + use amount of the IPDI-TMP adduct (parts by mass) ] × 100) was 8.2% by mass.

As b ^* , b ^* _1-5 , b ^* _4-5 , b ^* _7-5 , b ^* _14-5 , b ^* _21-5 and b ^* _30-5 are measured, and the following formula (I)- the 5, as _{^{Δb *, Δb * 1-5, Δb}} * 4-5, Δb * 7-5, Δb * 14-5, were calculated [Delta] b ^* _21-5 and [Delta] b ^* _30-5.
The results are shown in Table 1. Further, a graph showing transition of Δb ^* at each stage is shown in FIG. FIG. 3 also shows the results of Example 1 and Comparative Example 1.
(I) -5: Δb ^* _t-5 = b ^* _t-5- b ^* _0-5 (wherein t is the number of days elapsed for the microcapsule-containing layer)

[Example 6]
The same as Example 1, except that the blending amount of the antioxidant tris (2-ethylhexyl) phosphite was changed to 1.0 g instead of 1.0 g at the time of production of the microcapsule-containing composition Laminates were manufactured and evaluated in a method.

The content of tris (2-ethylhexyl) phosphite in this microcapsule-containing composition was 2.9% by mass.
In this microcapsule-containing composition, the ratio of the amount of tris (2-ethylhexyl) phosphite used to the total amount of 1,3-bis (aminomethyl) cyclohexane and the IPDI-TMP adduct ([tris Use amount of (2-ethylhexyl) phosphite (parts by mass) / {[use amount of 1,3-bis (aminomethyl) cyclohexane (parts by mass)] + use amount of the IPDI-TMP adduct (parts by mass) ] × 100) was 49.2% by mass.

As b ^* , b ^* _1-6 , b ^* _4-6 , b ^* _7-6 , b ^* _14-6 , b ^* _21-6 and b ^* _30-6 are measured, and the following formula (I)- by 6, as _{^{Δb *, Δb * 1-6, Δb}} * 4-6, Δb * 7-6, Δb * 14-6, were calculated [Delta] b ^* _21-6 and [Delta] b ^* _30-6.
The results are shown in Table 1. Further, a graph showing transition of Δb ^* at each stage is shown in FIG.
(I) -6: Δb ^* _t-6 = b ^* _t-6- b ^* _0-6 (wherein t is the number of days elapsed for the microcapsule-containing layer)

Comparative Example 1
In the preparation of the microcapsule-containing composition, tris (2-ethylhexyl) phosphite (1.0 g) was not used. In other words, the microcapsule aqueous dispersion obtained by the same method as in Example 1 was used. A laminate was produced and evaluated in the same manner as in Example 1 except that the composition was used as it was as a microcapsule-containing composition for comparison.
As b ^* , b ^* _1-1R , b ^* _4-1R , b ^* _7-1R , b ^* _14-1R , b ^* _21-1R and b ^* _30-1R are measured, and the following formula (I)- the 1R, as [Delta] b ^*, was calculated _{^{Δb * 1-1R, Δb * 4-1R,}} Δb * 7-1R, Δb * 14-1R, Δb * 21-1R and Δb ^* _30-1R.
The results are shown in Table 1. Further, a graph showing the transition of Δb ^* at each stage is shown in FIG.
(I) -1R: Δb ^* _t-1R = b ^* _t-1R- b ^* _0-1R (wherein t is the number of days _{elapsed for the} microcapsule-containing layer)

Comparative Example 2
At the time of preparation of the microcapsule-containing composition, N, N'-bis {3- (3,5-di-tert-) is used as an antioxidant in place of tris (2-ethylhexyl) phosphite (1.0 g). Manufacture and evaluation of a laminate in the same manner as in Example 1 except that butyl-4-hydroxyphenyl) propionyl} hydrazine (“IRGANOX MD 1024”, 1.0 g, manufactured by Toyotsu Chemiplus Co., Ltd.) was used. did.

The content of N, N'-bis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl} hydrazine in this microcapsule-containing composition was 1.0% by mass .
In this microcapsule-containing composition, N, N'-bis {3- (3,5-di-) relative to the total amount of 1,3-bis (aminomethyl) cyclohexane and IPDI-TMP adduct used. Ratio of the amount used of tert-butyl-4-hydroxyphenyl) propionyl} hydrazine ([, N, N'-bis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl} hydrazine is used Amount (parts by mass) / {[the amount of use of 1,3-bis (aminomethyl) cyclohexane (parts by mass)] + [the amount of the IPDI-TMP adduct used (parts by mass)] × 100) is 16. It was 4% by mass.

As b ^* , b ^* _1-2R , b ^* _4-2R , b ^* _7-2R , b ^* _14-2R , b ^* _21-2R and b ^* _30-2R are measured, and the following formula (I)- the 2R, as [Delta] b ^*, was calculated _{^{Δb * 1-2R, Δb * 4-2R,}} Δb * 7-2R, Δb * 14-2R, Δb * 21-2R and Δb ^* _30-2R.
The results are shown in Table 1. Further, a graph showing the transition of Δb ^* at each stage is shown in FIG.
(I) -2R: Δb ^* _t-2R = b ^* _t-2R- b ^* _0-2R (wherein, t is the number of days _{elapsed for the} microcapsule-containing layer)

  The structural formula of IRGANOX MD 1024 is shown below. IRGANOX MD 1024 is classified into hindered phenolic compounds.

Comparative Example 3
When preparing the microcapsule-containing composition, the compounding amount of the antioxidant N, N'-bis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl} hydrazine is 1. A laminate was manufactured and evaluated in the same manner as in Comparative Example 2 except that 0 g was replaced by 10 g.

The content of N, N'-bis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl} hydrazine in this microcapsule-containing composition was 9.1% by mass .
In this microcapsule-containing composition, N, N'-bis {3- (3,5-di-) relative to the total amount of 1,3-bis (aminomethyl) cyclohexane and IPDI-TMP adduct used. Ratio of the amount used of tert-butyl-4-hydroxyphenyl) propionyl} hydrazine ([, N, N'-bis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl} hydrazine is used Amount (parts by mass) / {[the amount of use of 1,3-bis (aminomethyl) cyclohexane (parts by mass)] + [the amount of the IPDI-TMP adduct used (parts by mass)] x 100) is 164 parts %Met.

As b ^* , b ^* _1-3R , b ^* _4-3R , b ^* _7-3R , b ^* _14-3R , b ^* _21-3R and b ^* _30-3R are measured, and the following formula (I)- the 3R, as [Delta] b ^*, was calculated _{^{Δb * 1-3R, Δb * 4-3R,}} Δb * 7-3R, Δb * 14-3R, Δb * 21-3R and Δb ^* _30-3R.
The results are shown in Table 1. Further, a graph showing the transition of Δb ^* at each stage is shown in FIG. FIG. 4 also shows the results of Comparative Examples 1 and 2.
(I) -3: RΔb ^* _t-3R = b ^* _t-3R- b ^* _0-3R (wherein, t is the number of days _{elapsed for the} microcapsule-containing layer)

<Evaluation of laminate (2)>
(Calculation of Δ (Δb ^* ) value of microcapsule-containing layer after aging)
From the results of Example 1 and Comparative Example 1 above, further, Δ (Δb ^* ) as Δ (Δb ^* ) at the stage of the 30th day (after start of standing and storage) by the following formula (II) -1 ^: _30-1 was calculated. The results are shown in Table 1.
(II) -1: Δ (Δb ^* ) _30-1 = [Δb ^* _30-1R ]-[Δb ^* _30-1 ]

Similarly, from the results of Example 2 and Comparative Example 1 above, Δ (Δb ^* ) at the 30th day of aging (after start of static storage) is further calculated by the following formula (II) -2 The (Δb ^* ) _30-2 was calculated. The results are shown in Table 1.
(II) -2: Δ (Δb ^* ) _30-2 = [Δb ^* _30-1R ]-[Δb ^* _30-2 ]

Similarly, from the results of Example 3 and Comparative Example 1 above, Δ (Δb ^* ) at the 30th day of aging (after start of static storage) is further calculated by the following formula (II) -3. (Δb ^* ) _30-3 was calculated. The results are shown in Table 1.
(II) -3: Δ (Δb ^* ) _30-3 = [Δb ^* _30-1R ]-[Δb ^* _30-3 ]

Similarly, from the results of Example 4 and Comparative Example 1 above, Δ (Δb ^* ) at the 30th day of aging (after start of standing and storage) is further calculated by the following formula (II) -4. (Δb ^* ) _30-4 was calculated. The results are shown in Table 1.
(II) -4: Δ (Δb ^* ) _30-4 = [Δb ^* _30-1R ]-[Δb ^* _30-4 ]

Similarly, from the results of Example 5 and Comparative Example 1 above, Δ (Δb ^* ) at the 30th day of aging (after start of standing and storage) is further determined by the following formula (II) -5: (Δb ^* ) _30-5 was calculated. The results are shown in Table 1.
(II) -5: Δ (Δb ^* ) _30-5 = [Δb ^* _30-1R ]-[Δb ^* _30-5 ]

Similarly, from the results of Example 6 and Comparative Example 1 above, Δ (Δb ^* ) at the 30th day of aging (after start of static storage) is further calculated by The (Δb ^* ) _30-6 was calculated. The results are shown in Table 1.
(II) -6: Δ (Δb ^* ) _30-6 = [Δb ^* _30-1R ]-[Δb ^* _30-6 ]

Similarly, from the results of Comparative Example 2 and Comparative Example 1 above, Δ (Δb ^* ) at the stage of 30th day after the start of standing storage (after start of standing and storage) is further calculated by the following formulas (II) -2R (Δb ^* ) _30-2R was calculated. The results are shown in Table 1.
(II) -2R: .DELTA. ( ^. _DELTA.b ^* ) _30-2R = [ _.DELTA.b ^* _30-1R ]-[ ^. _DELTA.b ^* _30-2R ]

Similarly, from the results of Comparative Example 3 and Comparative Example 1 above, Δ (Δb ^* ) at the stage of the 30th day after the start of standing storage (after start of standing and storage) is further calculated by (Δb ^* ) _30-3R was calculated. The results are shown in Table 1.
(II) -3R: Δ (Δb ^* ) _30-3R = [Δb ^* _30-1R ]-[Δb ^* _30-3R ]

As is clear from Table 1, FIG. 2 and FIG. 3, in Comparative Example 1 in which no antioxidant was used, Δb ^* was significantly increased as the number of days elapsed with time, and the microcapsules in the laminate were The yellowing of the containing layer was not clearly suppressed.

On the other hand, in Examples 1 to 6, a phosphite or phosphate, that is, an organophosphorus compound is used as an antioxidant, and in comparison with Comparative Example 1, Δb ^* is clearly evident at each stage of aging. It was small. In these examples, Δ (Δb ^* ) at the stage of the 30th day was extremely large, 0.50 or more (0.50 to 0.92). Thus, in these examples, yellowing due to aging of the microcapsule-containing layer in the laminate was significantly suppressed.

  When Example 1, 5 and 6 is compared, the suppression effect of yellowing was high in order of Example 6, Example 1, and Example 5. This is the content (% by mass) of the antioxidant in the microcapsule-containing composition or the total amount of the essential starting compound polycondensed for the formation of the film-forming component in the microcapsule-containing composition The higher the ratio of the amount of antioxidant used to the above, the higher the yellowing suppression effect.

On the other hand, as is clear from Table 1, FIG. 2 and FIG. 4, in Comparative Examples 2 to 3, although the antioxidant is used, this antioxidant is a hindered phenol compound, and Comparative Example 1 and By comparison, at each stage of aging, Δb ^* was only slightly smaller. In Comparative Examples 2 to 3, Δ (Δb ^* ) at the 30th day of the passage of time was extremely small at 0.15 or less (0.04 to 0.15). Thus, in Comparative Examples 2 to 3, the effect of suppressing yellowing due to aging of the microcapsule-containing layer in the laminate was low.

  When Comparative Examples 2 and 3 are compared, there is almost no change in the yellowing suppression effect even if the content of the antioxidant is largely increased, and it was within the range of error. This is because the inhibitory effect of yellowing by the hindered phenolic compound is too low.

  The present invention is applicable to all fields using microcapsules, such as a removal material of formaldehyde such as wallpaper.

  DESCRIPTION OF SYMBOLS 1 ... Laminated body, 11 ... Base material, 11a ... 1st surface of a base, 11 ... 2nd surface of a base, 12 ... Microcapsule containing layer

Claims (3)

Contains microcapsules and antioxidants,
The film forming component of the microcapsule agent is polyurea, polyurethane or polyamide,
The microcapsule containing composition whose said antioxidant is an organophosphorus type compound.   The microcapsule-containing composition according to claim 1, wherein the organophosphorus compound is an aliphatic organophosphorus compound. A substrate, and a microcapsule-containing layer formed on the substrate,
A laminate, wherein the microcapsule-containing layer is formed using the microcapsule-containing composition according to claim 1 or 2.

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