WO2019142538A1 - Composition, curable composition, and compound - Google Patents

Abstract

A composition comprising a compound represented by formula (1) and a compound represented by formula (2); a curable composition; and a compound. In formulae (1) and (2), R¹¹, R¹², R²¹, and R²² each independently represent a hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group, or aryloxy group and R¹³, R¹⁴, R²³, and R²⁴ each independently represent a hydrogen atom, aliphatic group, aromatic group, or heterocyclic group. R¹¹ and R¹² may be bonded to each other to form a ring, R¹³ and R¹⁴ may be bonded to each other to form a ring, R²¹ and R²² may be bonded to each other to form a ring, and R²³ and R²⁴ may be bonded to each other to form a ring.

Description

Compositions, curable compositions and compounds

The present invention relates to compositions, curable compositions and compounds. More specifically, the present invention relates to a composition containing a dioxobenzodithiol compound and a dihydroxybenzodithiol compound, a curable composition containing the aforementioned composition, and a dioxobenzodithiol compound.

The dihydroxybenzodithiol compound is excellent in ultraviolet absorptivity and is used as an ultraviolet absorber and the like. For example, Patent Document 1 describes an invention related to a UV absorber containing a specific dihydroxybenzodithiol compound.

On the other hand, Patent Document 2 describes a compound having the following structure.

In addition, Non-Patent Document 1 describes a compound having the following structure.

JP, 2009-263617, A Belgian Patent No. 623104

The dihydroxybenzodithiol compound described in Patent Document 1 is a compound which is excellent in ultraviolet ray absorbability and is useful as an ultraviolet absorber. On the other hand, the ultraviolet light absorbing agent may deteriorate with time due to light irradiation. For this reason, in recent years, further improvement of the light resistance of the ultraviolet absorber is desired.

Patent Document 2 and Non-Patent Document 1 only describe dioxobenzodithiol compounds having a specific structure, and there is no study or description on UV absorbers.

Therefore, an object of the present invention is to provide a composition, a curable composition and a compound which are excellent in light resistance and in which a time-dependent decrease in ultraviolet ray absorbing performance due to light irradiation is suppressed.

According to the study of the present inventor, a composition containing a compound represented by the formula (1) described later and a compound represented by the formula (2) is excellent in light resistance, and has a UV absorbing ability by light irradiation. It has been found that the deterioration over time can be effectively suppressed, and the present invention has been completed. Accordingly, the present invention provides the following.
<1> A composition comprising a compound represented by the formula (1) and a compound represented by the formula (2);

In the above formulas, R ¹¹ and R ¹² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an aliphatic group, R ¹¹ and R ¹² may bond to each other to form a ring, and R ¹³ and R ¹⁴ may bond to each other to form a ring;
R ²¹ and R ²² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and R ²³ and R ²⁴ each independently represent a hydrogen atom, an aliphatic group, an aromatic group or R ²¹ and R ²² may be bonded to each other to form a ring, and R ²³ and R ²⁴ may be bonded to each other to form a ring.
<2> The composition according to <1>, wherein each of R ¹¹ and R ¹² independently represents a hydrogen atom, a halogen atom or an alkyl group.
^{<3> R 13} and ^{R 14} each independently represent a hydrogen atom or an alkyl group, <1> or composition according to <2>.
<4> The composition according to <1>, wherein R ¹¹ and R ¹² each represent a hydrogen atom, and R ¹³ and R ¹⁴ each independently represent an unsubstituted alkyl group.
<5> R ^{13 in} Formula (1) and R ^{23 in} Formula (2) are the same group, and R ¹⁴ in Formula (2) and R ^{24 in} Formula (2) are the same group The composition according to any one of <1> to <4>.
<6> The compound according to any one of <1> to <5>, wherein the ratio of the compound represented by the formula (1) to the compound represented by the formula (2) is 0.0001% by mass or more and 1% by mass or less Composition of
Any one of <1>-<5> whose ratio of the compound represented by Formula (1) with respect to the compound represented by <7> Formula (2) is 0.001 mass% or more and 0.1 mass% or less The composition as described in.
<8> A curable composition comprising the composition according to any one of <1> to <7>, and a curable compound.
The curable composition as described in <8> whose <9> curable compound is a compound which has -O-Si-O- structure.
<10> a compound represented by the formula (1a);

In the formulae, each of R ^11a and R ^12a independently represents a hydrogen atom, a halogen atom or an alkyl group,
R ^13a and R ^14a each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ^13a and R ^14a may combine with each other to form a ring.
<11> The compound according to <10>, wherein each of R ^13a and R ^14a independently represents a hydrogen atom or an alkyl group.
<12> The compound according to <10>, wherein R ^11a and R ^12a each represent a hydrogen atom, and R ^13a and R ^14a each independently represent an unsubstituted alkyl group.

ADVANTAGE OF THE INVENTION According to this invention, the composition, curable composition, and compound which were excellent in light resistance and by which the time-dependent fall of the ultraviolet-ray absorption capability by light irradiation was suppressed can be provided.

Hereinafter, the contents of the present invention will be described in detail.
In the notation of the group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes a group having a substituent together with a group having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, a numerical range represented using “to” means a range including the numerical values described before and after “to” as the lower limit value and the upper limit value.
As used herein, total solids refers to the total amount of all components of the composition excluding the solvent.
In the present specification, “(meth) acrylate” represents both or either of acrylate and methacrylate, “(meth) acryl” represents both or either of acrylic and methacryl, “(meth) acrylate” ) Allyl "represents both or any of allyl and methallyl, and" (meth) acryloyl "represents both or any of acryloyl and methacryloyl.
As used herein, the term "step" does not only mean an independent step, but if the intended function of that step is achieved even if it can not be clearly distinguished from other steps, this term include.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC).

<Composition>
The composition of the present invention comprises a compound represented by Formula (1) and a compound represented by Formula (2). The composition of the present invention is excellent in light resistance, and can suppress the temporal deterioration of the ultraviolet ray absorbing performance due to light irradiation. Although the detailed reason why such an effect is exerted is unknown, the compound represented by the formula (1) interacts with the compound represented by the formula (2) and the compound represented by the formula (2) It is presumed that the degradation and denaturation due to light irradiation can be suppressed, and as a result, excellent light resistance can be obtained.
Among them, better light resistance can be obtained when a compound represented by the formula (1) is a compound in which R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group. In particular, the compound of the formula (1) is particularly excellent when R ¹¹ and R ¹² are hydrogen atoms, and R ¹³ and R ¹⁴ are each independently an unsubstituted alkyl group. Light resistance is obtained. It is presumed that such a compound is more likely to interact with the compound represented by the formula (2).

The composition of the present invention can be preferably used as a UV absorber. In addition, the composition of the present invention can be preferably used for packaging materials, containers, paints, coatings, inks, fibers, building materials, recording media, image display devices, covers for solar cells, glass articles, cosmetic preparations and the like. . The details of these can be referred to the description of Paragraph Nos. 0158 to 0218 of JP 2009-263617 A, the contents of which are incorporated herein.

Hereinafter, the compound represented by Formula (1) and the compound represented by Formula (2) which are used for the composition of this invention are demonstrated.

In the above formulas, R ¹¹ and R ¹² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an aliphatic group, R ¹¹ and R ¹² may bond to each other to form a ring, and R ¹³ and R ¹⁴ may bond to each other to form a ring;
R ²¹ and R ²² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and R ²³ and R ²⁴ each independently represent a hydrogen atom, an aliphatic group, an aromatic group or R ²¹ and R ²² may be bonded to each other to form a ring, and R ²³ and R ²⁴ may be bonded to each other to form a ring.

First, the compound represented by Formula (1) is demonstrated.

In formula (1), R ¹¹ and R ¹² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and preferably a hydrogen atom, a halogen atom or an alkyl group, More preferably, it is a hydrogen atom.

The halogen atom R ¹¹ and R ¹² represents a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The carbon number of the alkyl group and alkoxy group represented by R ¹¹ and R ¹² is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 7 . The alkyl group and the alkoxy group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The cyclic alkyl group and the alkyl group moiety of the cyclic alkoxy group may be a monocyclic cycloalkyl group or a polycyclic alkyl group (bicycloalkyl group, tricycloalkyl group, etc.) . The alkyl group and the alkoxy group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.
The carbon number of the aryl group and aryloxy group represented by R ¹¹ and R ¹² is preferably 6 to 40, more preferably 6 to 30, still more preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 12 . The aryl group and the aryloxy group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.

In formula (1), R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

The carbon number of the aliphatic group represented by R ¹³ and R ¹⁴ is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 7. As a kind of aliphatic group, an alkyl group, an alkenyl group, an alkynyl group and an aralkyl group are mentioned, An alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable. The alkyl group, the alkenyl group, the alkynyl group and the aralkyl group may have a substituent, but is preferably unsubstituted. Examples of the substituent include the groups described for the substituent T described later.
The carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 to 10, and most preferably 1 to 7. The alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
The carbon number of the alkenyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 15, particularly preferably 2 to 10, and most preferably 2 to 7. The alkenyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
The carbon number of the alkynyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 15, particularly preferably 2 to 10, and most preferably 2 to 7. The alkynyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
The number of carbon atoms of the aralkyl group is preferably 7 to 30, more preferably 7 to 20, and still more preferably 7 to 15. The alkyl part of the aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group is the same as the following aryl group.

The aromatic group includes an aryl group. The carbon number of the aromatic group is preferably 6 to 40, more preferably 6 to 30, still more preferably 6 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. As an aryl group, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable. The aryl group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.

The heterocycle in the heterocycle group preferably contains a 5- or 6-membered saturated or unsaturated heterocycle. The heterocyclic ring may be fused with an aliphatic ring, an aromatic ring or another heterocyclic ring. As a hetero atom which comprises the ring of a heterocyclic ring, B, N, O, S, Se and Te are mentioned, N, O and S are preferable. The hetero ring is preferably a carbon atom having a free valence (monovalent) (the hetero ring group is bonded at a carbon atom). The carbon number of the heterocyclic group is preferably 1 to 40, more preferably 1 to 30, and still more preferably 1 to 20. Examples of saturated heterocycles in the heterocycle group include pyrrolidine ring, morpholine ring, 2-bora-1,3-dioxolane ring and 1,3-thiazolidine ring. Examples of the unsaturated heterocyclic ring in the heterocyclic group include an imidazole ring, a thiazole ring, a benzothiazole ring, a benzoxazole ring, a benzotriazole ring, a benzoselenazole ring, a pyridine ring, a pyrimidine ring and a quinoline ring. The heterocyclic group may have a substituent. Examples of the substituent include the groups described for the substituent T described later.

In formula (1), R ¹³ and R ¹⁴ are preferably each independently a hydrogen atom or an aliphatic group, more preferably an aliphatic group, still more preferably an alkyl group, and unsubstituted alkyl Particularly preferred is a group. In addition, R ¹³ and R ¹⁴ are preferably each independently an unsubstituted linear alkyl group having 1 to 20 carbon atoms, and more preferably an unsubstituted linear alkyl group having 1 to 15 carbon atoms It is more preferably a C 1-10 unsubstituted linear alkyl group, and most preferably a C 1-7 unsubstituted linear alkyl group.

In formula (1), R ¹¹ and R ¹² may be bonded to each other to form a ring, and R ¹³ and R ¹⁴ may be bonded to each other to form a ring. These rings are preferably 5- or 6-membered rings. These rings may have a substituent. Examples of the substituent include the groups described for the substituent T described later.

The compound represented by the formula (1) is preferably a compound represented by the formula (1a). The compound represented by the formula (1a) is also a compound of the present invention.

In the formulae, each of R ^11a and R ^12a independently represents a hydrogen atom, a halogen atom or an alkyl group,
R ^13a and R ^14a each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ^13a and R ^14a may combine with each other to form a ring.

The halogen atom and the alkyl group represented by ^{R 11a} and ^{R 12a} of formula (1a), a halogen atom and an alkyl group is described in the section of the ^{R 11} and ^{R 12} of formula (1). It is preferred ^{R 11a} and ^{R 12a} of formula (1a) is a hydrogen atom.

As the aliphatic group, aromatic group and heterocyclic group represented by R ^13a and R ^14a of the formula (1a), the aliphatic group, aromatic group and complex described in the section of R ¹³ and R ¹⁴ of the formula (1) A ring group is mentioned, A preferable range is also the same. R ^13a and R ^{14a in} Formula (1a) are preferably each independently a hydrogen atom or an aliphatic group, more preferably an aliphatic group, still more preferably an alkyl group, and unsubstituted alkyl Particularly preferred is a group. In addition, R ^13a and R ^14a are preferably each independently an unsubstituted linear alkyl group having 1 to 20 carbon atoms, and more preferably an unsubstituted linear alkyl group having 1 to 15 carbon atoms It is more preferably a C 1-10 unsubstituted linear alkyl group, and most preferably a C 1-7 unsubstituted linear alkyl group.

In formula (1a), R ^13a and R ^14a may be bonded to each other to form a ring. The ring formed by combining R ^13a and R ^14a is preferably a 5- or 6-membered ring. The ring formed by combining R ^13a and R ^14a may have a substituent. Examples of the substituent include the groups described for the substituent T described later.

(Substituent T)
As the substituent T,
Halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom);
Alkyl group [linear, branched or cyclic alkyl group. Specifically, a linear or branched alkyl group (preferably a linear or branched alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n -Octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group), cycloalkyl group (preferably, a cycloalkyl group having a carbon number of 3 to 30, for example, cyclohexyl group, cyclopentyl group, 4- 4- n-dodecylcyclohexyl group), a bicycloalkyl group (preferably a bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [2]. 1,2,2] heptan-2-yl group, bicyclo [2,2,2] octan-3-yl group), and more ring structures It is intended to encompass such cycloalkyl structures. The alkyl group (for example, the alkyl group of the alkylthio group) in the substituents described below also represents an alkyl group having such a concept. ];
Alkenyl group [linear, branched or cyclic alkenyl group; Specifically, a linear or branched alkenyl group (preferably a linear or branched alkenyl group having a carbon number of 2 to 30, for example, a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group), a cycloalkenyl group (Preferably, a cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms. For example, 2-cyclopenten-1-yl group, 2 -Cyclohexen-1-yl group), a bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having a carbon number of 5 to 30, ie, a monovalent compound from which one hydrogen atom of a bicycloalkene having one double bond has been removed For example, bicyclo [2,2,1] hept-2-en-1-yl group, bicyclo [2,2,2] oct-2-en-4-i group. Is intended to include a group). ];
An alkynyl group (preferably, a linear or branched alkynyl group having a carbon number of 2 to 30, for example, ethynyl group, propargyl group, trimethylsilylethynyl group);

An aryl group (preferably an aryl group having a carbon number of 6 to 30, for example, a phenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl group, an o-hexadecanoylaminophenyl group);
A heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered aromatic or non-aromatic heterocyclic compound), more preferably a 5- or 6-membered member having 3 to 30 carbon atoms Aromatic heterocyclic group of, for example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group);
Cyano group;
Hydroxyl group;
Nitro group;
Carboxyl group;
An alkoxy group (preferably, a linear or branched alkoxy group having a carbon number of 1 to 30. For example, a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, a 2-methoxyethoxy group);
Aryloxy group (preferably an aryloxy group having a carbon number of 6 to 30. For example, phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group );
A silyloxy group (preferably a silyloxy group having a carbon number of 3 to 20, for example, a trimethylsilyloxy group, a t-butyldimethylsilyloxy group);
A heterocyclic oxy group (preferably, a heterocyclic oxy group having a carbon number of 2 to 30, for example, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group);
Acyloxy group (preferably formyloxy group, alkylcarbonyloxy group having 2 to 30 carbon atoms, arylcarbonyloxy group having 6 to 30 carbon atoms. For example, formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy) A group, p-methoxyphenyl carbonyloxy group);

A carbamoyloxy group (preferably a carbamoyloxy group having a carbon number of 1 to 30. For example, an N, N-dimethylcarbamoyloxy group, an N, N-diethylcarbamoyloxy group, a morpholino carbonyloxy group, an N, N-di-n- group Octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group);
An alkoxycarbonyloxy group (preferably, an alkoxycarbonyloxy group having a carbon number of 2 to 30, for example, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, an n-octylcarbonyloxy group);
An aryloxycarbonyloxy group (preferably, an aryloxycarbonyloxy group having a carbon number of 7 to 30, for example, a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, a pn-hexadecyloxyphenoxycarbonyloxy group);
Amino group (preferably, amino group, alkylamino group having 1 to 30 carbon atoms, anilino group having 6 to 30 carbon atoms. For example, amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group , Diphenylamino group);
Acylamino group (preferably, formylamino group, alkylcarbonylamino group having 1 to 30 carbon atoms, arylcarbonylamino group having 6 to 30 carbon atoms. For example, formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoyl Amino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group);

Aminocarbonylamino group (preferably, an aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholino carbonylamino group);
Alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having a carbon number of 2 to 30. For example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxy Carbonylamino group);
An aryloxycarbonylamino group (preferably, an aryloxycarbonylamino group having a carbon number of 7 to 30, for example, a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, an mn-octyloxyphenoxycarbonylamino group);
A sulfamoylamino group (preferably, a sulfamoylamino group having a carbon number of 0 to 30, for example, a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, an Nn-octylaminosulfonylamino group);
An alkyl or arylsulfonylamino group (preferably an alkylsulfonylamino group having 1 to 30 carbon atoms, an arylsulfonylamino group having 6 to 30 carbon atoms. For example, a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, 2, 3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group);
Mercapto group;
An alkylthio group (preferably, an alkylthio group having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, an n-hexadecylthio group);
An arylthio group (preferably an arylthio group having a carbon number of 6 to 30, for example, a phenylthio group, a p-chlorophenylthio group, an m-methoxyphenylthio group);
A heterocyclic thio group (preferably a heterocyclic thio group having a carbon number of 2 to 30, for example, 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group);

A sulfamoyl group (preferably a sulfamoyl group having a carbon number of 0 to 30. For example, N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfo group Famoyl group, N-benzoylsulfamoyl group, N- (N'-phenylcarbamoyl) sulfamoyl group);
Sulfo group;
An alkyl or arylsulfinyl group (preferably, an alkylsulfinyl group having 1 to 30 carbon atoms, an arylsulfinyl group having 6 to 30 carbon atoms, for example, a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group);
An alkyl or arylsulfonyl group (preferably, an alkylsulfonyl group having 1 to 30 carbon atoms and an arylsulfonyl group having 6 to 30 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, a p-methylphenylsulfonyl group);

An acyl group (preferably a formyl group, an alkylcarbonyl group having 2 to 30 carbon atoms, an arylcarbonyl group having 7 to 30 carbon atoms, a heterocyclic carbonyl group bonded to the carbonyl group at a carbon atom having 4 to 30 carbon atoms. An acetyl group, a pivaloyl group, a 2-chloroacetyl group, a stearoyl group, a benzoyl group, a p-n-octyloxyphenylcarbonyl group, a 2-pyridylcarbonyl group, a 2-furylcarbonyl group);
An aryloxycarbonyl group (preferably, an aryloxycarbonyl group having a carbon number of 7 to 30, for example, a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, a p-t-butylphenoxycarbonyl group);
An alkoxycarbonyl group (preferably, an alkoxycarbonyl group having a carbon number of 2 to 30, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, an n-octadecyloxycarbonyl group);
A carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms. For example, carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methyl) Sulfonyl) carbamoyl group);
An aryl or heterocyclic azo group (preferably an arylazo group having 6 to 30 carbon atoms, a heterocyclic azo group having 3 to 30 carbon atoms, for example, a phenylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4- Thiadiazol-2-ylazo group);
Imide group (preferably, N-succinimide group, N-phthalimide group);
Phosphino group (preferably, phosphino group having 2 to 30 carbon atoms, for example, dimethyl phosphino group, diphenyl phosphino group, methyl phenoxy phosphino group)
A phosphinyl group (preferably a phosphinyl group having a carbon number of 2 to 30, for example, a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group);
A phosphinyl oxy group (preferably, a phosphinyl oxy group having 2 to 30 carbon atoms, for example, a diphenoxy phosphinyl oxy group, a dioctyl oxy phosphinyl oxy group);
A phosphinylamino group (preferably, a phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino group, dimethylaminophosphinylamino group);
A silyl group (preferably, a silyl group having a carbon number of 3 to 30, for example, a trimethylsilyl group, a t-butyldimethylsilyl group, a phenyldimethylsilyl group) can be mentioned.

Among the groups listed above, one or more hydrogen atoms may be substituted with the above-mentioned substituent T for groups having a hydrogen atom. Examples of such functional groups include alkylcarbonylaminosulfonyl group, arylcarbonylaminosulfonyl group, alkylsulfonylaminocarbonyl group and arylsulfonylaminocarbonyl group. Specific examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, a benzoylaminosulfonyl group and the like.

The following compounds may be mentioned as specific examples of the compound represented by the formula (1).

Next, the compound represented by Formula (2) is demonstrated.

In formula (2), R ²¹ and R ²² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group. The halogen atom, the alkyl group, the aryl group, the alkoxy group and the aryloxy group represented by R ²¹ and R ^{22 in} the formula (2) are the halogen atoms described in the section of R ¹¹ and R ^{12 in} the formula (1), an alkyl group, An aryl group, an alkoxy group, and an aryloxy group are mentioned, A preferable range is also the same. R ²¹ and R ^{22 in} Formula (2) are preferably each independently a hydrogen atom, a halogen atom or an alkyl group, and more preferably a hydrogen atom.

In the formula ^{(2), R 23} and ^{R 24} each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The aliphatic group, aromatic group and heterocyclic group represented by R ²³ and R ^{24 in} the formula (2) include the aliphatic group, aromatic group and hetero group described in the section of R ¹³ and R ^{14 in} the formula (1) A ring group is mentioned, A preferable range is also the same. R ²³ and R ^{24 in} Formula (2) are preferably each independently a hydrogen atom or an aliphatic group, more preferably an aliphatic group, still more preferably an alkyl group, and unsubstituted alkyl Particularly preferred is a group. In addition, R ²³ and R ²⁴ are preferably each independently an unsubstituted linear alkyl group having 1 to 20 carbon atoms, and more preferably an unsubstituted linear alkyl group having 1 to 15 carbon atoms It is more preferably a C 1-10 unsubstituted linear alkyl group, and most preferably a C 1-7 unsubstituted linear alkyl group.

In Formula (2), R ²¹ and R ²² may be bonded to each other to form a ring, and R ²³ and R ²⁴ may be bonded to each other to form a ring. These rings are preferably 5- or 6-membered rings. These rings may have a substituent. Examples of the substituent include the groups described above for the substituent T.

The following compounds may be mentioned as specific examples of the compound represented by the formula (2).

In the composition of the present invention, R ¹³ in the formula (1) and R ^{23 in} the formula (2) are the same group (preferably, the same alkyl group, more preferably the same unsubstituted alkyl group) Formula (1) in which R ¹⁴ in Formula (2) and R ²⁴ in Formula (2) are the same group (preferably, the same alkyl group, more preferably the same unsubstituted alkyl group) It is preferable to contain the compound represented by these, and the compound represented by Formula (2). Further, in this embodiment, ^{R 11} and ^{R 12} of formula (1), more preferably ^{R 21} and ^{R 22} of formula (2) are both hydrogen atoms. In the case where the compound of this combination is included, the effects of the present invention tend to be more significantly obtained.

The total content of the compound represented by Formula (1) and the compound represented by Formula (2) in the total solid content of the composition of the present invention is preferably 1% by mass or more, and 50% by mass or more Is more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 99% by mass or more. Moreover, it is particularly preferable that the composition of the present invention is constituted only by the compound represented by the formula (1) and the compound represented by the formula (2). In addition, the composition of the present invention may be dispersed in a medium such as a powder, a solution, or a resin.

In the composition of the present invention, the ratio of the compound represented by the formula (1) to the compound represented by the formula (2) is preferably 0.0001% by mass or more and 1% by mass or less, and 0.001 It is more preferable that the content is not less than mass% and not more than 0.1 mass%. If the ratio of the compound represented by Formula (1) to the compound represented by Formula (2) is in the above range, better light resistance can be obtained. Furthermore, it is easy to obtain excellent transparency and ultraviolet light absorbability.

<Curable composition>
Next, the curable composition of the present invention will be described. The curable composition of the present invention comprises the composition of the present invention described above and a curable compound. Examples of the curable compound include a compound having a group having an ethylenically unsaturated bond, a compound having an epoxy group, a compound having a methylol group, and a compound having a —O—Si—O— structure. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group and a (meth) acryloyl group.

In the present invention, it is preferable to use a compound having an —O—Si—O— structure as the curable compound. According to this aspect, it is possible to manufacture a glass article or the like which is low in coloring and excellent in ultraviolet absorptivity. As a specific example of a glass article, the window glass for motor vehicles, the window glass for construction materials, etc. can be mentioned.

The compound having a -O-Si-O- structure is preferably a hydrolyzable silicon compound, more preferably a hydrolyzable alkoxysilane, and further preferably a trifunctional or tetrafunctional alkoxysilane. preferable. Specific examples of the compound having a -O-Si-O- structure include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane Methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ -Glycidyloxypropyltriethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methac Royloxypropyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, tris- (Trimethoxysilylpropyl) isocyanurate, 4-trimethoxysilylstyrene, 3,3,3-trifluoropropyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n -Propyldimethoxysilane, di-n-propyldiethoxysilane, diphenyldimethoxysilane, divinyldiethoxysilane, bis (triethoxysilylpropyl) tetra Sulfide, 3- (trimethoxysilyl) propyl isocyanate, 3- (triethoxysilyl) propyl isocyanate and the like can be mentioned.

The total content of the compound represented by the formula (1) and the compound represented by the formula (2) in the total solid content of the curable composition of the present invention is 0.01 to 20% by mass Is preferred. In addition, the content of the composition of the present invention described above in the total solid content of the curable composition of the present invention is preferably 0.01 to 20% by mass, and 0.1 to 10% by mass. Is more preferred. The content of the curable compound in the total solid content of the curable composition of the present invention is preferably 0.1 to 99.9% by mass.

The curable composition of the present invention may further contain another ultraviolet absorber other than the compound represented by Formula (1) and the compound represented by Formula (2). As another ultraviolet absorber, the ultraviolet absorber described in Paragraph No. 0065 of international publication WO 2017/122503 can be mentioned, and these can be used.

The curable composition of the present invention can further contain a solvent. The solvent is not particularly limited, and examples thereof include water and alcohol solvents. As alcohol solvents, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 2-ethoxyethanol, 2-butoxy Ethanol, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin and the like can be mentioned. Further, as a solvent, ethylene carbonate, N-methyl pyrrolidone, dioxane, tetrahydrofuran, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, acetonitrile, propionitrile, benzonitrile, carboxylic acid ester, Phosphoric acid esters, phosphonic acid esters, dimethylsulfoxide, sulfolane, dimethylformamide, dimethylacetamide and the like can be used. These may be used alone or in combination of two or more. The content of the solvent is preferably 10 to 90% by mass with respect to the total amount of the curable composition.

The curable composition of the present invention can contain a catalyst. In particular, when a compound having an —O—Si—O— structure is used as the curable compound, it is preferable to contain a catalyst. According to this aspect, the sol-gel reaction is promoted, and a stronger film is easily obtained. Examples of the catalyst include acid catalysts such as hydrochloric acid, sulfuric acid, acetic acid and propionic acid, and base catalysts such as sodium hydroxide, potassium hydroxide and triethylamine. The content of the catalyst is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, still more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the curable compound. . The curable composition of the present invention may contain only one type of catalyst, or may contain two or more types. When two or more catalysts are contained, the total amount thereof is preferably in the above range.

Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In addition, unless there is particular notice, "part" and "%" are mass references. Also, NMR is an abbreviation of nuclear magnetic resonance.

Example 1 Synthesis of Compound (1) -1
Compound (1) -1 was synthesized according to the following scheme. Compound (2) -1 was synthesized based on the synthesis method of synthesis intermediate B described in Synthesis Example 3 of JP-A-2009-263617.

3.94 g (0.010 mol) of the compound (2) -1 and 1.81 g (0.015 mol) of anhydrous magnesium sulfate are mixed, and 25 mL of N, N-dimethylacetamide (DMAc) is added to this mixture. After adding and further adding 4.63 g (0.020 mol) of silver oxide, it stirred at room temperature for 1 hour. Ethyl acetate and dilute hydrochloric acid were added to the resulting reaction solution, and the mixture was partitioned. The organic layer was further washed with dilute aqueous hydrochloric acid and brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent was evaporated under reduced pressure, and the residue was purified by silica gel chromatography using a mixed solvent of hexane and tetrahydrofuran (THF) as an eluent. After concentration, crystallization was performed using a mixed solvent of ethyl acetate and hexane to obtain 1.41 g (yield 35.9%) of a compound (1) -1.
NMR (dimethyl sulfoxide (DMSO)): δ = 7.13 (2 H, brS), 3.62 (4 H, t, J = 7.3 Hz), 1.44 (4 H, tt, J = 7.3, 7 .3 Hz), 1.22 (4 H, tq, J = 7.3, 7.3 Hz), 0.87 (6 H, t, J = 7.3 Hz)

Example 2 Synthesis of Compound (1) -2
Example 6 1.53 g of Compound (1) -2 (yield 42) in the same manner as in Example 1 except that compound (2) -2 was equimolar instead of compound (2) -1. I got 1%).
NMR (DMSO): δ = 7.13 (2H, brS), 3.60 (4H, t, J = 7.3 Hz), 1.40 (4 H, tq, J = 7.3, 7.3 Hz), 0.89 (6 H, t, J = 7.3 Hz)

Example 3 Synthesis of Compound (1) -3
Example 2 2.52 g of Compound (1) -3 (yield: 56) in the same manner as in Example 1 except that compound (2) -3 was used in equimolar amount instead of compound (2) -1. .2%) obtained.
NMR (DMSO): δ = 7.13 (2H, brS), 3.62 (4H, t, J = 7.3 Hz), 1.46 (4 H, tt, J = 7.3, 7.3 Hz), 1.30 to 1.10 (12 H, m), 0.87 (6 H, t, J = 7.3 Hz)

(Example 4) (Production of Composition A-16)
Diethyl malonate 185 mL (1.15 moles) is added to 50.0 g (0.23 moles) of the dihydrochloride of N, N-dibutylhydrazine, and the inside of the reaction system is replaced with nitrogen, and then the ethanol produced in the reaction is distilled off The mixture was stirred at an external temperature of 170 ° C. for 4 hours. The reaction solution was cooled to room temperature, and the pressure was reduced to distill off unreacted diethyl malonate, and then purification on a silica gel column gave synthetic intermediate A in an amount of 43.5 g (yield 88.9%). 19.7 g (0.06 mol) of 1- (4,7-dihydroxybenzo [1,3] dithiole-2-ylidene) piperidinium acetate was added to 14.0 g (0.066 mol) of the synthetic intermediate A obtained. 60 mL of N-methylpyrrolidone was added, and this was stirred at 80 ° C. under air for 1 hour, cooled, added to 600 mL of dilute hydrochloric acid, and the precipitated solid was collected by filtration and dried to obtain a reaction product. The obtained reaction product is a composition in which 0.024% by mass of the compound (1) -1 is mixed with the compound (2) -1 with respect to the compound (2) -1 (composition A-16) Met.

(Example 101)
A composition A-1 was obtained by mixing 0.05 g of the compound (1) -1 synthesized in Example 1 and 100.0 g of the compound (2) -1.
After mixing 1.20 g of the obtained composition A-1, 2.71 g of 3-triethoxysilylpropyl isocyanate, and 20 mL of dry tetrahydrofuran, one drop of di (2-ethylhexanoate) tin is added. The mixture was heated to reflux for 3 hours under a nitrogen atmosphere. Next, 81.0 mg of tetraethoxysilane, 0.602 g of glycidyloxypropyltrimethoxysilane, 1.73 g of ultrapure water, and acetic acid which is an acid catalyst 17.4 of 0.476 g of the mixed solution after heating and refluxing. After 0 mg was added, the mixture was stirred for 30 seconds, then irradiated with ultrasonic waves for 3 minutes, and then stirred in a 50 ° C. water bath for 1 hour to obtain a curable composition. The resulting curable composition was coated on a 0.1 mass% KOH-treated glass substrate using a doctor blade to a thickness of 30 mil (1 mil is 2.54 × 10 ^-5 m). A coated film was formed, and the obtained coated film was left to stand and dried at 80 ° C. for 30 minutes with a blower dryer. Then, it heated at 200 degreeC for 30 minutes, and produced the glass article.

(Examples 102 to 115)
A curable composition was prepared in the same manner as in Example 101, except that compositions A-2 to A-15 described in the following table were used instead of the composition A-1, and A glass article was produced using the curable composition obtained by

(Example 116)
After mixing 1.20 g of the composition A-16 obtained in Example 4, 2.71 g of 3-triethoxysilylpropyl isocyanate, and 20 mL of dry tetrahydrofuran, tin di (2-ethylhexanoate) is obtained. 1 drop was added and heated to reflux for 3 hours under nitrogen atmosphere. Next, 81.0 mg of tetraethoxysilane, 0.602 g of glycidyloxypropyltrimethoxysilane, 1.73 g of ultrapure water, and acetic acid which is an acid catalyst 17.4 of 0.476 g of the mixed solution after heating and refluxing. After 0 mg was added, the mixture was stirred for 30 seconds, then irradiated with ultrasonic waves for 3 minutes, and then stirred in a 50 ° C. water bath for 1 hour to obtain a curable composition. The resulting curable composition was coated on a 0.1 mass% KOH-treated glass substrate using a doctor blade to a thickness of 30 mil (1 mil is 2.54 × 10 ^-5 m). A coated film was formed, and the obtained coated film was left to stand and dried at 80 ° C. for 30 minutes with a blower dryer. Then, it heated at 200 degreeC for 30 minutes, and produced the glass article.

(Example 117)
A curable composition was prepared in the same manner as in Example 101 except that the composition A-17 was used instead of the composition A-1, and a curable composition obtained in the same manner as in Example 101 was obtained. The glass article was produced using.

(Comparative examples 101 and 102)
A curable composition was prepared in the same manner as in Example 101 except that the compositions B-1 and B-2 described in the following table were used instead of the composition A-1, and the same manner as in Example 101 was carried out. A glass article was produced using the curable composition obtained by

(Reference Example 101)
A curable composition was prepared in the same manner as in Example 101 except that the composition C-1 described in the following Table was used instead of the composition A-1, and was obtained in the same manner as in Example 101. The curable composition was used to make a glass article.

 

Compounds H-1 and H-2 in the above table are compounds of the following structures.

The absorption spectra of the glass articles of Examples 101 to 117, Reference Example 101, and Comparative Examples 101 to 102 were measured using a spectrophotometer (UV-3100, manufactured by Shimadzu Corporation), and the absorbance at the maximum absorption wavelength (λmax) A0) was measured. Furthermore, these glass articles are placed in an accelerated weathering tester (Super Xenon Weather Meter SX 75, manufactured by Suga Test Instruments Co., Ltd.), and irradiated with light for 500 hours in an environment of 60 ° C. and 50% relative humidity. The light resistance test was done. In addition, the irradiation light of an accelerated weathering tester has a spectrum close | similar to the sunlight in the outdoors, and the light resistance test which simulated use in the outdoors can be implemented. The absorbance (A1) at the maximum absorption wavelength (λmax) of the glass article after the light resistance test was measured, and the reduction rate of the absorbance of the glass article before and after the light resistance test was determined from the following formula. The smaller this value is, the higher the light resistance is.
Decreasing rate of absorbance (%) = {(A0-A1) / A0} x 100

As shown in the above table, in each of the examples, the light resistance was improved as compared with Reference Example 101, and the examples had excellent light resistance.

Claims (12)

1. A composition comprising a compound represented by the formula (1) and a compound represented by the formula (2);
   

   

   In the above formulas, R ¹¹ and R ¹² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an aliphatic group, R ¹¹ and R ¹² may bond to each other to form a ring, and R ¹³ and R ¹⁴ may bond to each other to form a ring;
   R ²¹ and R ²² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, and R ²³ and R ²⁴ each independently represent a hydrogen atom, an aliphatic group, an aromatic group or R ²¹ and R ²² may be bonded to each other to form a ring, and R ²³ and R ²⁴ may be bonded to each other to form a ring.
2. R ¹¹ and R ¹² each independently represent a hydrogen atom, a halogen atom or an alkyl group, A composition according to claim 1.
3. R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an alkyl group, A composition according to claim 1 or 2.
4. R ¹¹ and ^{R 12} represents a hydrogen ^atom, an unsubstituted alkyl group ^{R 13} and ^{R 14} are each independently composition of claim 1.
5. The claim is that R ^{13 in} Formula (1) and R ²³ in Formula (2) are the same group, and R ¹⁴ in Formula (2) and R ^{24 in} Formula (2) are the same group. The composition according to any one of 1 to 4.
6. The composition according to any one of claims 1 to 5, wherein the ratio of the compound represented by the formula (1) to the compound represented by the formula (2) is 0.0001% by mass or more and 1% by mass or less. .
7. The compound according to any one of claims 1 to 5, wherein the ratio of the compound represented by the formula (1) to the compound represented by the formula (2) is 0.001% by mass to 0.1% by mass. Composition.
8. A curable composition comprising the composition according to any one of claims 1 to 7 and a curable compound.
9. The curable composition according to claim 8, wherein the curable compound is a compound having a -O-Si-O- structure.
10. A compound represented by the formula (1a);
    

    

    In the formulae, each of R ^11a and R ^12a independently represents a hydrogen atom, a halogen atom or an alkyl group,
    R ^13a and R ^14a each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ^13a and R ^14a may combine with each other to form a ring.
11. ^11. The compound according to claim 10, wherein each of R ^13a and R ^14a independently represents a hydrogen atom or an alkyl group.
12. ^11. The compound according to claim 10, wherein R ^11a and R ^12a each represent a hydrogen atom, and R ^13a and R ^14a each independently represent an unsubstituted alkyl group.