WO2015005283A1

WO2015005283A1 - Modified resin and resin composition

Info

Publication number: WO2015005283A1
Application number: PCT/JP2014/068056
Authority: WO
Inventors: 篠畑　雅亮; 裕士小杉; 信寿三宅
Original assignee: 旭化成ケミカルズ株式会社
Priority date: 2013-07-08
Filing date: 2014-07-07
Publication date: 2015-01-15
Also published as: TWI570144B; TW201605915A; TW201605917A; CN113929866B; JPWO2015005283A1; KR101875294B1; TWI565725B; KR20160018726A; CN113929866A; CN105358602B; CN107629183B; TW201605916A; TW201522403A; CN107629183A; TWI564316B; CN105358602A; CN111205424A; TW201605918A; TWI543995B; TWI577705B

Abstract

　The present invention discloses a resin having a nitrogen-carbon-sulfur bond. The nitrogen-carbon-sulfur bond is constituted by a nitrogen atom, a carbon atom, and a sulfur atom, bonding in the stated order, and the bond between the carbon atom and sulfur atom and/or the bond between the carbon atom and nitrogen atom is a single bond. When the number average molecular weight of this resin is defined as Mn and the number of sulfur atoms constituting the nitrogen-carbon-sulfur bonds contained per resin molecule is defined as n¹, Mn is 500 or higher and Mn/n¹ is from 50 to 300 inclusive.

Description

Modified resin and resin composition

The present invention relates to a modified resin and a resin composition.

Isocyanate is known as a raw material for polyurethane and polyurea.

Polyurethane is produced by the reaction of isocyanate groups and hydroxyl groups, has excellent tensile strength, wear resistance, and oil resistance, and is used in paints, adhesives, automobile parts, and the like. For example, Patent Document 1 discloses a two-component polyurethane paint for a packing film.

Polyurea is produced by a reaction between an isocyanate group and an amino group, has excellent heat resistance, mechanical strength, and chemical resistance, and is processed and used for injection molded products, films, fibers, and the like. For example, Patent Document 2 discloses an adhesive using polyurea.

In this way, polyurethane and polyurea based on the reaction of isocyanate groups are applied to the surface of metals, glass and plastics as paints and adhesives, and give functions to the surface. Must be sufficient.

As a method for improving the adhesion, for example, Patent Document 3 discloses a method for controlling the adhesion of urethane by an organic film treatment on the surface of a steel sheet. Moreover, as a method for improving the resin side to be applied, for example, Patent Document 4 discloses a composition containing an acid-modified polyolefin resin dispersion and a polymer containing sulfur element.

The polyisocyanate composition containing a polyfunctional isocyanate compound (polyisocyanate) is used for a wide range of applications such as a coating composition. Such polyisocyanate compositions are listed as, for example, one-pack or two-pack polyurethane coating compositions. Among them, the two-component polyurethane coating composition is capable of forming a dense cross-linked coating film and has a good finished appearance, so that it has a high-quality appearance such as a top coat application for automobiles, information appliances, etc. It is highly evaluated for applications that require excellent weather resistance and durability.

Top coats for automobiles, information appliances, and the like are required to have scratch resistance and higher hardness in addition to high-quality appearance. Moreover, good extensibility is desired for the coating composition for forming the top coat.

Examples of the composition containing polyisocyanate include a polyisocyanate composition containing isocyanurate groups and having a phosphorus concentration of 0.1 to 20 ppm (Patent Document 5), and a coating composition containing polyisocyanates having allophanate groups. (Patent Literature 6, Patent Literature 7), a coating composition (Patent Literature 8) containing a polyisocyanate composition having an allophanate group and a polyol, etc. have been proposed, and its use is being studied together with its production method.

Epoxy resins are used in a wide range of materials such as paints, adhesives, molding materials, composite materials, laminates, and sealing materials because of their excellent balance of heat resistance and chemical resistance.

In recent years, there has been a demand for a resin material with significantly higher performance and higher reliability than conventional resin materials. Conventional modification of resins by various modification methods has been studied. Among them, a modified epoxy resin having a 1-oxa-3-azacycloalkane-2-one structure in which a part of an oxide group is reacted with an isocyanate group is attracting attention as a resin that can achieve both high glass transition temperature and flexibility. Many proposals have been made (see, for example, Patent Document 9, Patent Document 10, and Patent Document 11).

Special Table 2012-1251789 Japanese Translation of PCT Special Publication 2010-507689 JP 2001-219498 A JP 2010-163579 A Japanese Patent No. 4201582 Japanese Patent Laid-Open No. 8-188856 JP-A-7-304724 International Publication No. 2002/32979 JP 59-135265 A Japanese Patent Laid-Open No. 61-181820 JP-A-5-222160

Polyurethanes and polyureas based on the reaction of isocyanate groups are applied as paints or adhesives to the surfaces of metals, glass, and plastics, and give functions to the surfaces, but further improvements in heat resistance are required.

Therefore, in one aspect, an object of the present invention is to provide a modified resin composition having high heat resistance.

On the other hand, the method of performing surface treatment as in Patent Document 3 is often difficult to apply depending on the surface shape and surface material. Moreover, in the resin mixture like patent document 4, adhesiveness falls on the contrary by phase separation of resin, and the function of the coating film itself may be impaired.

Therefore, in another aspect, an object of the present invention is to provide a modified resin composition having high adhesion.

In addition, as a result of studies by the present inventors, the polyisocyanate compositions as described in Patent Documents 5 to 8 have room for improvement in terms of adhesion to adherends, particularly in terms of adhesion to metals. It turned out to be.

In still another aspect, an object of the present invention is to provide a polyisothiocyanate having good adhesion to an adherend and a method for producing the same.

Furthermore, as a result of studies by the present inventors, a modified epoxy resin having a 1-oxa-3-azacycloalkane-2-one structure as described in Patent Documents 9 to 11 depends on the application. It has been found that there is room for improvement in terms of adhesion to metal, particularly to metal.

In yet another aspect, the present invention provides a modified epoxy resin having good adhesion to an adherend while maintaining the properties of a compound such as an epoxy resin and an episulfide resin, and a modification having good adhesion to an adherend. It is an object of the present invention to provide compounds such as episulfide resins and methods for producing these compounds.

As a result of intensive studies to solve the above problems, the present inventors solved the above problems with a resin containing a compound having a specific structure in the molecule and a compound obtained by reacting a compound having a specific functional group. The present inventors have found that the present invention can be accomplished and have completed the present invention.

That is, the present invention relates to the following.
[1]
It is composed of a nitrogen atom, a carbon atom and a sulfur atom, which are bonded in this order, and at least one of the bond between the carbon atom and the sulfur atom and the bond between the carbon atom and the nitrogen atom is a single bond A resin having a nitrogen-carbon-sulfur bond, wherein the number average molecular weight of the resin is Mn, and the number of sulfur atoms constituting the nitrogen-carbon-sulfur bond contained per molecule of the resin is n. ₁ , Mn is 500 or more, Mn / n ₁ is 50 or more and 300 or less, and n ₁ is a formula: n ₁ = X ¹ · Mn (X ¹ is the nitrogen-containing amount per 1 g of the resin) (Representing the number of sulfur atoms constituting the carbon-sulfur bond).

[2]
The resin according to [1], wherein the resin has a 5% thermal weight loss temperature of 300 ° C or higher.

[3]
A compound having at least one functional group selected from the group consisting of monovalent groups represented by the following formula (1), (2), (3), (4) or (5);
At least one compound selected from the group consisting of monoisocyanate, polyisocyanate, monoisothiocyanate and polyisothiocyanate;
Resin obtained by the reaction of

[4]
The compound having at least one functional group selected from the group consisting of monovalent groups represented by formulas (1) to (5), and at least one compound selected from monoisothiocyanate and polyisothiocyanate, Alternatively, the resin according to [3], which is a resin obtained by a reaction with monoisothiocyanate or polyisothiocyanate.

[5]
The resin according to [3] or [4], wherein the monoisothiocyanate includes or is a compound represented by the following formula (30).

(Where
R ⁵ represents an organic group. R ⁵ may be an aliphatic group having 1 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic compound, or an aromatic group having 6 to 25 carbon atoms.

[6]
Any one of [3] to [5], wherein the resin has a cyclic structure derived from a reaction between the functional group represented by the formulas (3) to (5) and an isocyanate group or an isothiocyanate group. Resin.

[7]
The group containing the cyclic structure has two or more structural units (groups) selected from the group consisting of divalent groups represented by the following formula (6), (7) or (8). The resin according to [6].

(Where
Y ¹ represents an organic group, and a plurality of Y ¹ in the same molecule may be the same or different. Y ¹ may be a —NH— group. )

[8]
Resin which has 2 or more of at least 1 type of structural unit (group) chosen from the group which consists of a bivalent group represented by following formula (6), (7) or (8).

(Where
Y ¹ represents an organic group, a plurality of Y ¹ in the same molecule may be the same or different. Y ¹ may be a —NH— group. )

[9]
The number average molecular weight of the resin is Mn, type contained per the resin molecule (6), when (7) or the sum of the number of the structural unit represented by (8) is n _2, Mn Is 500 or more, Mn / n ₂ is 50 or more and 300 or less, and n ₂ is a formula: n ₂ = X ² · Mn (X ² is a formula (6), (7) or ( The resin according to [7] or [8], which is calculated according to 8).

[10]
A resin obtained by reacting a compound having a nitrogen-carbon-sulfur bond, which is composed of a nitrogen atom, a carbon atom and a sulfur atom, and these are bonded in this order, with a polyisothiocyanate.

[11]
The resin according to any one of [3] to [7] and [10], wherein the polyisothiocyanate includes or is a compound represented by the following formula (32).

(Where
R ⁶ represents an organic group,
a represents an integer of 2 to 1000. )

[12]
The polyisothiocyanate includes a polymer having two or more repeating units represented by the following formula (33), or is the polymer, according to any one of [3] to [7] and [10] resin.

(Where
R ⁷ represents an organic group,
R ⁸ represents an organic group or a single bond,
b represents an integer of 1 or more,
g represents 1 or 2,
A plurality of R ⁷ , R ⁸ , b and g in the same molecule may be the same or different. )

[13]
The polyisothiocyanate has two or more structural units represented by the following formula (40) and the following formulas (41), (42), (43), (44), (45), (46) or (47). And at least one structural unit selected from the group consisting of monovalent, divalent or trivalent groups (units) represented by the formula: wherein the nitrogen atom in the compound is a carbon atom; The resin according to any one of [3] to [7] and [10], which is bound, contains a compound, or is the compound.

(Where
R ³ represents an organic group, R ⁴ represents an aliphatic group or an aromatic group, or an aliphatic hydrocarbon group or an aromatic hydrocarbon group, X ³ represents an oxygen atom or a sulfur atom, and a plurality of them in the same molecule R ³ , R ⁴ and X ³ may be the same or different. )

[14]
The resin according to any one of [3] to [7] and [10], wherein the polyisothiocyanate includes or is a compound represented by the following formula (33).

(Where
R ³ represents an organic group. )

[15]
Resin obtained by the method including superposing | polymerizing the compound represented by following formula (33).

(Where
R ³ represents an organic group. )

[16]
The method for producing a resin according to [15], comprising polymerizing the compound represented by the formula (33) in the presence of a catalyst.

[17]
Two or more structural units represented by the following formula (40),
A group consisting of a monovalent, divalent or trivalent group (structural unit) represented by the following formula (41), (42), (43), (44), (45), (46) or (47) And at least one structural unit selected from
A nitrogen atom (N) in one of the structural units represented by formulas (41) to (47) is a nitrogen atom (N) in the other structural unit represented by formulas (41) to (47); Resin that is not directly bonded. R ³ in the structural units represented by formulas (41) to (47) may be directly bonded to an isothiocyanate group to form the structural unit of formula (40).

(Where
R ³ represents an organic group, R ⁴ represents an aliphatic group or an aromatic group,
X ³ represents an oxygen atom or a sulfur atom,
A plurality of R ³ , R ⁴ and X ³ in the same molecule may be the same or different. )

[18]
The resin according to [13], [14], [15] or [17], wherein R ³ is an aliphatic group or an aromatic group.

[19]
The resin according to [18], wherein R ³ is a hydrocarbon group represented by the following formula (301), (302), (303), (304), (305) or (306).

(Where
i represents an integer of 1 to 12, and may be 1 to 10. )

[20]
A resin composition comprising the resin according to any one of [1] to [15] and [17] to [19].

[21]
[20] A coating material formed from the resin composition according to [20] or formed using the resin composition.

[22]
A water-based paint containing the resin composition according to [20].

[23]
Resin containing the molecular chain represented by following formula (10).

(Where
P ¹ represents an aliphatic group and / or an aromatic group, and Q ¹ is selected from the group consisting of divalent groups represented by the following formula (11), (12), (13) or (14). It represents one or more structural units (groups), and a plurality of P ¹ and Q ¹ may be the same or different, and n represents an integer of 2 or more. )

(Where
R ¹ represents an aliphatic group or an aromatic group,
X ² and Y ² each independently represent an oxygen atom or a sulfur atom, and a plurality of R ¹ , X ² and Y ² in the same molecule may be the same or different. One or more of X ² and Y ^{2 in} one Q ¹ is a sulfur atom. )

[24]
R ¹ is a residue obtained by removing two isocyanate groups (—NCO) constituting the polyisocyanate from polyisocyanate, or two isothiocyanate groups (—NCS) constituting the polyisothiocyanate from polyisothiocyanate. The resin according to [23], which is a removed residue.

[25]
At least one compound selected from polyisocyanates and polyisothiocyanates;
Resin as described in [23] or [24] obtained by reaction with the compound represented by following formula (20).

(Where
R ² represents an aliphatic group or an aromatic group,
Y ² represents an oxygen atom or a sulfur atom. Plural Y ² in one unit may be the same or different. )

[26]
The resin according to [25], wherein the at least one compound selected from polyisocyanate and polyisothiocyanate includes a compound represented by the following formula (31).

(Where
R ¹ represents an aliphatic group or an aromatic group,
X represents an oxygen atom or a sulfur atom. At least one of X and Y ² in one unit may be a sulfur atom. )

[27]
The resin according to [25] or [26], wherein R ² is a monovalent group represented by the following formula (201), (202), (203) or (204).

[28]
R ¹ is an aliphatic group having 1 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic group (aromatic compound), or an aromatic group having 6 to 25 carbon atoms [23 ] The resin according to any one of [27] to [27].

[29]
R ¹ is a hydrocarbon group selected from the group consisting of hydrocarbon groups represented by the following formula (301), (302), (303), (304), (305) or (306), [23] The resin according to any one of [27].

(Where
i represents an integer of 1 to 12, and may be 1 to 10. )

[30]
The resin according to any one of [23] to [28], wherein R ¹ does not contain a spiro atom.

[31]
[23] A curable composition comprising the resin according to any one of [30] and a curing agent.

[32]
The method according to [25] or [26], comprising reacting at least one compound selected from polyisocyanate and polyisothiocyanate with the compound represented by formula (20) in the presence of a catalyst. Resin production method.

According to the present invention, a modified resin composition having high heat resistance can be provided.
According to the present invention, it is possible to provide a modified resin composition having high adhesion.
ADVANTAGE OF THE INVENTION According to this invention, the polyisothiocyanate with favorable adhesiveness to a to-be-adhered body and its manufacturing method can be provided.
According to the present invention, a modified epoxy resin having good adhesion to an adherend, a modified episulfide resin having good adhesion to an adherend and the like while retaining the properties of a compound such as an epoxy resin and an episulfide resin. Compounds and methods for producing these compounds can be provided.

3 is a ¹ H-NMR spectrum of the solid obtained in Example 17. FIG. 3 is a diagram showing a ¹ H-NMR chart of polyisothiocyanate. FIG. 3 is a diagram showing a ¹ H-NMR chart of a compound containing an oxazolidine-2-thione ring.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof.

In this specification, compound names are often based on the description of Nomenclature (IUPAC Nomenclature of Organic Chemistry) defined by IUPAC (The International Union of Pure and Applied Chemistry). “Organic” refers to a general group of compounds that are subject to the nomenclature disclosed in the rules. The subject may be a subject described in a recommendation issued in 1993. However, the “organic” compounds targeted by the above-mentioned Nomenclature include organometallic compounds and metal complexes. In this embodiment, the term “organic” and / or “organic group” and / or “substituent” will be used to describe the compounds used in this embodiment below. They are composed of atoms that do not contain metal atoms and / or metalloids. Selected from H (hydrogen atom), C (carbon atom), N (nitrogen atom), O (oxygen atom), S (sulfur atom), Cl (chlorine atom), Br (bromine atom), I (iodine atom) As the structure composed of atoms, “organic compound”, “organic group”, and “substituent” are used in this embodiment.

In the following explanation, the terms “aliphatic” and “aromatic” are frequently used. According to the above IUPAC rules, it is described that organic compounds are classified into aliphatic compounds and aromatic compounds. An aliphatic compound is a definition of a group in line with an aliphatic compound based on the 1995 IUPAC recommendation. The recommendation defines an aliphatic compound as “Acyclic or cyclic, saturated or unsaturated carbon compounds, and excluded aromatic compounds”. In addition, the aliphatic compound and the aliphatic group used in the description of this embodiment include both saturated and unsaturated, chain and cyclic, and the above-described H (hydrogen atom); C (carbon atom); N (nitrogen) Atoms); O (oxygen atoms); S (sulfur atoms); Si (silicon atoms); halogen atoms selected from Cl (chlorine atoms), Br (bromine atoms) and I (iodine atoms); Can be done.

A group having an aromatic group bonded to an aliphatic group, such as an “aralkyl group”, is an “aliphatic group substituted with an aromatic group”, “aromatic aliphatic group” or “an aliphatic group bonded to an aromatic group”. Often referred to as a “group consisting of a group”. This is based on the reactivity in the present embodiment, and the property related to the reaction of a group such as an aralkyl group is very similar to the reactivity of aliphatic rather than aromatic. In addition, non-aromatic reactive groups including aralkyl groups, alkyl groups, etc. are often referred to as “aliphatic groups optionally substituted with aromatics”, “aliphatic groups substituted with aromatics”, “aromatic groups May be included in the “aliphatic group”.

In describing the general formula of the compound used in the present specification, the definition in accordance with the above-mentioned Nomenclature rule defined by IUPAC is used, but the name of a specific group, the exemplified compound name is often a common name. Is used. In this specification, the number of atoms, the number of substituents, and the number are often described, and they all represent integers.

When the substituents and compounds exemplified in the present specification have structural isomers, these structural isomers are included unless otherwise specified.

<Resin composition>
The resin composition according to some embodiments contains a resin having a nitrogen-carbon-sulfur bond and / or a nitrogen-carbon-oxygen bond. Here, the nitrogen-carbon-sulfur bond refers to a structure in which a nitrogen atom, a carbon atom, and a sulfur atom are bonded in this order. The nitrogen-carbon bond and the carbon-sulfur bond in the bond are a single bond. Or an unsaturated bond. However, at least one of the nitrogen-carbon bond and the carbon-sulfur bond may be a single bond. The nitrogen atom and sulfur atom that form the bond may be bonded to other atoms such as a carbon atom, a nitrogen atom, an oxygen atom, or a silicon atom. Nitrogen-carbon-oxygen bonds are defined similarly.

Preferred examples of the group containing a nitrogen-carbon-sulfur bond and / or nitrogen-carbon-oxygen bond include structural units represented by the following formulae.

(Where
R ¹ is a residue obtained by removing two isocyanate groups (—NCO) constituting the polyisocyanate from polyisocyanate, or two isothiocyanate groups (—NCS) constituting the polyisothiocyanate from polyisothiocyanate. Represents the residue removed,
X ² and Y ² each independently represent an oxygen atom or a sulfur atom,
One or more of X ² and Y ^{2 in} one structural unit is a sulfur atom. )

(Where
R ³ and R ⁴ each independently represent an aliphatic group or an aromatic group, and a plurality of R ³ and R ⁴ may be the same or different,
X ³ represents an oxygen atom or a sulfur atom. )

A resin composition containing a resin having such a structural unit in the molecule has an effect of greatly improving the adhesion with a metal. In addition, since the refractive index is high, it is effective for improving the physical properties of paint such as gloss.

As a characteristic when a coating film is formed, heat resistance is one of the important characteristics. Specifically, it may be a resin composition containing a resin having a 5% thermal weight loss temperature of 250 ° C. or higher or 300 ° C. or higher. As used herein, the 5% thermogravimetric decrease temperature refers to room temperature (20 ° C. to 20 ° C.) when the resin is heated in a furnace whose temperature rises at 10 ° C./min in an inert gas atmosphere such as nitrogen, helium or argon. This is the temperature of the furnace when a 5% weight loss is observed with respect to the resin weight at 30 ° C., and is generally measured using a device commercially available as a thermogravimetric analyzer. Can do.

The resin composition exhibiting the heat resistance effect varies depending on the main chain skeleton, the bonding mode, the molecular weight, the content of bonds contributing to the expression of heat resistance, and the like. From the viewpoint of the binding mode, among the above, it is represented by the above formulas (6) to (8), (11) to (14), (41), (42), (45), (46) or (47). A resin composition containing a resin having a structural unit is preferred.

The number average molecular weight of the resin is preferably 500 or more, more preferably 1000 or more, and still more preferably 5000 or more. In general, the higher the molecular weight, the better the heat resistance. On the other hand, if the molecular weight is too high, the handling property when forming a coating film (miscibility with other components) The number average molecular weight is preferably 1 million or less, more preferably 500,000 or less, and still more preferably 200,000 or less. The number average molecular weight here is measured using gel permeation chromatography having at least one column with an exclusion limit molecular weight of 10 million or more, and the retention time is converted into molecular weight using a standard substance such as polystyrene. It is the value calculated by. A person skilled in the art can easily determine the number average molecular weight. Calculations are made excluding peaks originating from the solvent.

The content of bonds that contribute to the development of heat resistance also correlates with the number average molecular weight Mn described above. Nitrogen contained per one molecule - carbon - number of sulfur atoms and nitrogen constituting the sulfur bonds - carbon - the value obtained by dividing the number average molecular weight of the resin by the number n ¹ of oxygen atoms constituting the oxygen binding (Mn / n ¹ ) Is preferably 300 or less, more preferably 200 or less, still more preferably 150 or less. The resin composition of the present embodiment has an effect in terms of adhesion to a metal as described above. From the viewpoint of exhibiting such an effect, the resin has many bonds per molecule. It is preferable to have. On the other hand, when the resin has too many of the above bonds, in particular, the resin has the above formulas (6) to (8), (11) to (14), (41), (42), (45) , (46) or (47), the flexibility, which is one of the coating film performances, may be impaired. From such a viewpoint, Mn / n ¹ is preferably 50 or more, more preferably 70 or more. n ¹ is, for example, the number X ¹ (unit mol / g) of the bonds per resin unit weight (1 g) determined by, for example, an infrared absorption spectrum, ¹ H-NMR, etc., and calculated from the above-mentioned number average molecular weight (Mn). , N ¹ = Mn · X ¹ . When the resin contains both nitrogen-carbon-sulfur bonds and nitrogen-carbon-oxygen bonds, n ¹ is the total number of sulfur atoms and oxygen atoms constituting each bond.

The resin contained in the resin composition of the present embodiment is characterized by the bonds (structural units) constituting the molecular chain as described above, and the skeleton structure between the bonds is not particularly limited. Specifically, a skeleton structure derived from a raw material compound used in the method for producing a resin composition of the present embodiment exemplified below is preferably used.

Among such resins, structural units represented by the above formulas (6) to (8), (11) to (14), (41), (42), (45), (46) or (47) The resin containing is good in properties and can be preferably used. Hereinafter, these resins will be described.

≪Resin having a heterocyclic ring≫
<Preferred structure>
A preferred first resin in the present embodiment is a resin having two or more structural units selected from the group consisting of monovalent groups represented by the above formulas (6) to (8). The resin having the structural units represented by the above formulas (6) to (8) is surprisingly high in heat resistance and excellent in adhesion, particularly adhesion to the metal surface. Although the mechanism that exerts such an effect is not clear, the present inventors have found that a ring structure having a conjugated system contributes to heat resistance, and sulfur atoms contained in the structural unit, particularly the above formula (6). It is speculated that the thiol group (—SH group) possessed by the structural unit may have the effect of improving the adhesion. From such a viewpoint, a resin containing the structural unit represented by the above formula (6) and / or the structural unit represented by the above formula (7) is preferable.

As described above, the resin of the present embodiment is characterized by the bonding mode contained in the molecule, and the skeletal structure other than the bonding is not particularly limited, but more preferable forms are as follows.

The content of bonds that contribute to the development of heat resistance also correlates with the number average molecular weight Mn described above. Nitrogen contained per one molecule - carbon - number of sulfur atoms and nitrogen constituting the sulfur bonds - carbon - the value obtained by dividing the number average molecular weight of the resin by the number n ¹ of oxygen atoms constituting the oxygen binding (Mn / n ¹ ) Is preferably 300 or less, more preferably 200 or less, still more preferably 150 or less. The resin composition of the present embodiment has an effect in terms of adhesion to a metal as described above. From the viewpoint of exhibiting such an effect, the resin has many bonds per molecule. It is preferable to have. On the other hand, when the resin has too many of the above bonds, in particular, the resin has the above formulas (6) to (8), (11) to (14), (41), (42), (45) , (46) or (47), the flexibility, which is one of the coating film performances, may be impaired. From such a viewpoint, (Mn / n ¹ is preferably 50 or more, more preferably 70 or more. For example, n ¹ is the number of bonds per unit weight (1 g) of the resin X ¹ (unit mol / g). ) Can be calculated by, for example, infrared absorption spectrum, ¹ H-NMR, etc., and calculated from the above-mentioned number average molecular weight (Mn) by the formula: n ¹ = Mn · X ^{1. The} resin is a nitrogen-carbon-sulfur bond. N ¹ is the total number of sulfur atoms and oxygen atoms constituting each bond, and when the resin has structural units of formulas (6) to (8), when the number sum of the structural units of the formula contained per the resin molecule (6) to (8) is _{^{n 2,}} Mn / _{n 2} is 50 to 300 .n ² formula It is calculated by ⁿ 2 ^{= X} 2 · Mn: .X ² is the sum of the number of structural units represented by the formula contained per the resin 1g (6) ~ (8) , can be obtained in the same manner as X ^1.

The structure provided between the structural units is not particularly limited, but is preferably an aliphatic group having 1 to 25 carbon atoms and an aromatic group having 6 to 25 carbon atoms. Specifically, methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane , Benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane, and the like are residues obtained by removing two hydrogen atoms. In addition, when an isomer exists, this isomer is also included.

Among these, resins having a structure represented by the following formulas (301) to (306) are preferable.

(In the formula, i represents an integer of 1 to 12, and may be 1 to 10.)

<Preferred production method>
The preferred first resin of the present embodiment is preferably a compound having at least one functional group selected from the group consisting of monovalent groups represented by the following formulas (1) to (5):
At least one compound selected from monoisocyanate, polyisocyanate, monoisothiocyanate and polyisothiocyanate;
It is resin obtained by the method including making this react.

In this specification, the group represented by the above formula (1) is a hydroxyl group, the group represented by the above formula (2) is an amino group, the group represented by the above formula (3) is a hydrazide group, and the above formula (4) ) May be referred to as a semicarbazide group, and the group represented by the above formula (5) may be referred to as a thiosemicarbazide group. The group of formula (2) is defined as a group different from the groups of formulas (3) to (5).

Hereinafter, an example of a preferable first resin production method of the present embodiment will be described.

[Preferably used compounds]
The compound having at least two groups selected from the group consisting of a hydroxyl group, an amino group, a hydrazide group, a semicarbazide group, and a thiosemicarbazide group is not particularly limited, and a hydroxyl group (—OH), amino group (—NH ₂ ) , Hydrazide group (—C (═O) —NH—NH ₂ ), semicarbazide group (—NH—C (═O) —NH—NH ₂ ), thiosemicarbazide group (—NH—C (═S) —NH— It suffices if it contains at least one group selected from the group consisting of NH ₂ ). For example, a compound represented by the following formula (70) or formula (71) may be used.

(Where
R ¹² , R ¹³ and R ¹⁴ each independently represents an organic group, R ¹⁵ represents an organic group or a single bond, and A ¹ and E ¹ each independently represent a hydroxyl group, amino group, hydrazide group, semicarbazide group, thiol Represents a group selected from the group consisting of a semicarbazide group, and B ¹ and D ¹ are each independently a group selected from the group consisting of a hydroxyl group, an amino group, a hydrazide group, a semicarbazide group, and a thiosemicarbazide group, an organic group, or a hydrogen atom F ¹ represents a hydrogen atom or an organic group, d represents an integer of 2 to 1000, e represents an integer of 1 to 3, x represents an integer of 1 or more, and y represents 0 or 1 or more of Represents an integer. A plurality of R ¹² , R ¹³ , R ¹⁴ , A ¹ , E ¹ , B ¹ , D ¹ , F ¹ , and e in the same molecule may be the same or different.

In the above formula, R ¹² is preferably an aliphatic group having 1 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic group (aromatic compound), or a group having 6 to 25 carbon atoms. It is an aromatic group. Specific examples of R ¹² are methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyl. It is a residue obtained by removing one hydrogen atom from dicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane and the like. In the present specification, the “C7-25 aliphatic group substituted with an aromatic group” is a group composed of a combination of an aromatic group and an aliphatic group, and the aromatic group and the aliphatic group are oxygen This means a group that may contain heteroatoms such as atoms, nitrogen atoms, sulfur atoms, etc., and the total number of carbon atoms contained in the group is 7 to 25. Other similar terms are defined similarly.

In the above formula, R ¹³ and R ¹⁴ are preferably an aliphatic group having 2 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic group, or an aromatic group having 8 to 25 carbon atoms. It is. Specific examples of R ¹³ and R ¹⁴ are ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylethane, ethylbenzene. , A residue obtained by removing three hydrogen atoms from diethylbenzene, diphenylethane, tetramethyldiphenylethane and the like.

In the above formula, R ¹⁵ represents an organic group or a single bond. When it is an organic group, R ¹⁵ is an alkylene group having 1 to 25 carbon atoms, an aromatic hydrocarbon group having 6 to 25 carbon atoms, or the following formula (72) Or it is group represented by Formula (73).

(Where
R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represents an alkylene group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a single bond, and z represents an integer of 1 to 10. )

When R ¹⁵ is an alkylene group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 25 carbon atoms, specifically, R ¹⁵ is methane, ethane, propane, butane, propane, hexane, octane, 2 from decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane, etc. A residue obtained by removing one hydrogen atom.

The term “R ¹⁵ is a single bond” means that R ¹⁵ is not present as a group and E ¹ is bonded to R ¹³ . Hereinafter, “single bond” in this specification is defined and used in the same manner.

In the above formula (72) and formula (73), R ¹⁶ , R ¹⁷ and R ¹⁸ are preferably methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, A residue obtained by removing two hydrogen atoms from dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane, etc. . When an isomer exists, the isomer is also included.

In the above formula (71), when B ¹ , D ¹ and F ¹ are organic groups, the organic group is preferably an alkyl group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 25 carbon atoms. Or a group represented by the following formulas (74) to (76).

(Where
R ¹⁹ , R ²⁰ and R ²¹ each independently represents an alkylene group having 1 to 10 carbon atoms or an aromatic group having 6 to 10 carbon atoms, and z represents an integer of 1 to 10. )

In the above formulas (74) to (76), R ¹⁹ , R ²⁰ and R ²¹ are preferably an alkylene group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 25 carbon atoms. R ¹⁹ , R ²⁰ and R ²¹ are specifically methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethyl A residue obtained by removing two hydrogen atoms from ethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane, and the like. When an isomer exists, the isomer is also included.

Specific examples of the compound containing at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a hydrazide group, a semicarbazide group and a thiosemicarbazide group are shown below.

(A) Examples of the compound having a hydroxyl group include polyhydric alcohols such as ethylene glycol, propylene glycol and openaerythritol, and polyols having repeating units.

Examples of the polyol include acrylic polyol, polyolefin polyol, polyvinyl alcohol and the like. Acrylic polyol is obtained by copolymerizing an ethylenically unsaturated bond-containing monomer having a hydroxyl group alone or a mixture thereof with another ethylenically unsaturated bond-containing monomer copolymerizable therewith. Is obtained.

Examples of the ethylenically unsaturated bond-containing monomer having a hydroxyl group include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate. It is done. Preferred are hydroxyethyl acrylate and hydroxyethyl methacrylate.

Other ethylenically unsaturated bond-containing monomers copolymerizable with the above monomers include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, acrylate-n-butyl, isobutyl acrylate, Acrylic acid esters such as acrylic acid-n-hexyl, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, benzyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate Methacrylic acid-n-butyl, isobutyl methacrylate, methacrylic acid-n-hexyl, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, benzyl methacrylate, phenyl methacrylate, etc. Unsaturated carboxylic acids such as acid esters, acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylamide, methacrylamide, N, N-methylenebisacrylamide, diacetone acrylamide, diacetone methacrylamide, maleic amide, maleimide, etc. Unsaturated amides, vinyl monomers such as glycidyl methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, dibutyl fumarate, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ- (meth) acryloxypropyltrimethoxy Examples thereof include vinyl monomers having hydrolyzable silyl groups such as silane.

Examples of the polyolefin polyol include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene. The number of hydroxyl groups (hereinafter, the average number of hydroxyl groups) possessed by one statistical molecule of polyol is preferably 2 or more. When the average number of hydroxyl groups of the polyol is 2 or more, a decrease in the crosslinking density of the obtained coating film can be suppressed.

As polyvinyl alcohol, polyvinyl alcohol obtained by saponifying polyvinyl ester obtained by polymerizing vinyl ester; modified polyvinyl alcohol obtained by graft copolymerization of a comonomer on the main chain of polyvinyl alcohol; copolymerizing vinyl ester and comonomer Modified polyvinyl alcohol produced by saponification of the modified polyvinyl ester; so-called polyvinyl acetal resin obtained by crosslinking a part of hydroxyl groups of unmodified polyvinyl alcohol or modified polyvinyl alcohol with aldehydes such as formalin, butyraldehyde, benzaldehyde, etc. Is mentioned.

Examples of the vinyl ester used in the production of polyvinyl alcohol include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate, and vinyl benzoate. Is mentioned. Among these, vinyl acetate is preferable from the viewpoint of ease of production, availability, and cost of polyvinyl alcohol. The above-mentioned comonomer used for the production of the modified polyvinyl alcohol is copolymerized mainly for the purpose of modifying the polyvinyl alcohol, and is used within a range not impairing the gist of the present invention. Examples of such comonomer include olefins such as ethylene, propylene, 1-butene, and isobutene; acrylic acid or a salt thereof; methyl acrylate, ethyl acrylate, propyl acrylate (including isomers), butyl acrylate ( Acrylic esters such as isomers), octyl acrylate (including isomers), dodecyl acrylate (including isomers); methacrylic acid or salts thereof; methyl methacrylate, ethyl methacrylate, propyl methacrylate (including isomers) ), Butyl methacrylate (including isomers), octyl methacrylate (including isomers), dodecyl methacrylate (including isomers), octadecyl methacrylate (including isomers) and the like; acrylamide, N-methylacrylamide N-ethylacrylamide, N, N-di Acrylamide derivatives such as til acrylamide, diacetone acrylamide, acrylamide propane sulfonic acid or salts thereof, acrylamide propyldimethylamine or salts thereof, N-methylol acrylamide or derivatives thereof; methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, Methacrylamide derivatives such as methacrylamide propanesulfonic acid or salts thereof, methacrylamide propyldimethylamine or salts thereof, N-methylol methacrylamide or derivatives thereof; N- such as N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, etc. Vinyl amides; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether vinyl ethers such as i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether and stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride; Examples include allyl compounds such as allyl acetate and allyl chloride; maleic acid or salts or esters thereof; itaconic acid or salts or esters thereof; vinylsilyl compounds such as vinyltrimethoxysilane; isopropenyl acetate and the like. Among these, α-olefins (for example, α-olefins having 2 to 30 carbon atoms), unsaturated carboxylic acids or derivatives thereof, unsaturated sulfonic acids or derivatives thereof are preferable, α-olefins are more preferable, and ethylene is particularly preferable. . In the modified polyvinyl alcohol, the amount of modification by the comonomer is preferably 15 mol% or less, more preferably 5 mol% or less, based on the number of moles of all structural units constituting the modified polyvinyl alcohol.

Among the polyols listed above, acrylic polyols and polyester polyols are preferred.

(B) Specific examples of the compound having an amino group include ethylenediamine, propylenediamine, butylenediamine, triethylenediamine, hexamethylenediamine, 4,4′-diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, norbornanediamine. Diamines such as phenylenediamine, 4,4′-diaminodiphenyl, 1,3-bis (3-aminophenoxy) benzene, 3,3′-diaminodiphenylsulfone, diethyltoluenediamine, bisaniline, bishexamethylenetriamine, diethylenetriamine Chain polyamines having three or more amino groups, such as triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, tetrapropylenepentamine, , 10,13,16-hexaazacyclooctadecane, 1,4,7,10-tetraazacyclodecane, 1,4,8,12-tetraazacyclopentadecane, 1,4,8,11-tetraazacyclotetradecane And cyclic polyamines such as polyallylamine, polyvinylamine, and polymeric polyamines such as polyamines represented by the following formulas (77) to (80). Among these, polyallylamine and polyvinylamine are preferable. As polyallylamine and polyvinylamine, any of those conventionally produced by known methods can be used, and the degree of polymerization is not particularly limited. Moreover, the copolymer with another monomer may be sufficient.

(Where
g ′ represents an integer of 2 to 70. )

(Where
h ′ represents an integer of 2 to 40,
i ′ and j ′ each represent an integer of 1 to 6, and the sum of i ′ and j ′ is an integer of 2 to 7. )

(Where
R ³⁵ represents a group selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group,
s represents an integer of 0 or 1,
r, t and u each represents 0 or an integer of 1 or more;
The sum of r, t and u is 5 to 90. )

(C) Examples of the compound having a hydrazide group include saturated dicarboxylic acids having 2 to 18 carbon atoms such as oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, and sebacic acid dihydrazide. Dihydrazide; monoolefinic unsaturated dicarboxylic acid dihydrazide such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; poly obtained by reacting a low polymer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate And hydrazide. Polymerization of ethylenically unsaturated bond-containing monomers having a hydroxyl group, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, etc. It may be a polymer obtained by reacting a product (which may be a copolymer) with hydrazine, or a vinyl ester (for example, vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, It may be a polymer obtained by reacting hydrazine with a polymer (which may be a copolymer) of vinyl tickate, vinyl laurate, vinyl stearate, vinyl benzoate and the like.

(D) Examples of the compound having a semicarbazide group include bissemicarbazide; diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate or polyisocyanate compounds derived therefrom, N, N-substituted hydrazines such as N, N-dimethylhydrazine, and the above. Examples thereof include polyfunctional semicarbazide obtained by reacting the exemplified hydrazine.

(E) Examples of the compound having a thiosemicarbazide group include bisthiosemicarbazide; diisothiocyanates such as hexamethylene diisothiocyanate and isophorone diisothiocyanate, or polyisothiocyanate compounds derived therefrom, N, N-dimethylhydrazine, etc. N, N-substituted hydrazine and polyfunctional thiosemicarbazide obtained by reacting the above-exemplified hydrazine.

The polyol mentioned as an example of the compound having a hydroxyl group may be a polyester polyol, a polyether polyol, a fluorine polyol, a polycarbonate polyol, or a polyurethane polyol.

As the polyester polyol, for example, a dibasic acid selected from the group of carboxylic acids such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, or a mixture thereof Polyester polyol obtained by a condensation reaction with a single or mixture of polyhydric alcohols selected from the group of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, glycerin, and the like, and for example, polyhydric alcohol And polycaprolactones obtained by ring-opening polymerization of ε-caprolactone.

As the polyether polyol, a polybasic hydroxy compound alone or in a mixture, for example, a hydroxide such as lithium, sodium or potassium, a strongly basic catalyst such as alcoholate or alkylamine, ethylene oxide, propylene oxide, Polyether polyols obtained by adding a single or mixture of alkylene oxides such as butylene oxide, cyclohexene oxide and styrene oxide, polyether polyols obtained by reacting alkylene oxide with a polyfunctional compound such as ethylenediamine, and So-called polymer polyols obtained by polymerizing acrylamide or the like using these polyethers as a medium are included.

As a polyvalent hydroxy compound,
(1) Diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc.
(2) sugar alcohol compounds such as erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, rhamnitol,
(3) monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, ribodesose,
(4) disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose,
(5) Trisaccharides such as rafitose, gentianose, and meletitose,
(6) tetrasaccharides such as stachyose,
Etc.

The fluorine polyol is a polyol containing fluorine in the molecule. For example, fluoroolefin, cyclovinyl ether, hydroxyalkyl vinyl ether, monocarboxylic acid disclosed in JP-A-57-34107 and JP-A-61-275311 There are copolymers such as vinyl esters.

Polycarbonate polyols are polycondensation of low-molecular carbonate compounds such as dialkyl carbonates such as dimethyl carbonate, alkylene carbonates such as ethylene carbonate, diaryl carbonates such as diphenyl carbonate, and low-molecular polyols used in the aforementioned polyester polyols. Can be obtained.

Polyurethane polyol can be obtained by a conventional method, for example, by reacting polyol and polyisocyanate. Examples of the polyol having no carboxyl group include ethylene glycol and propylene glycol as low molecular weights, and examples of the high molecular weight include acrylic polyol, polyester polyol, and polyether polyol.

The compound having one repeating unit containing one group selected from the group consisting of a hydroxyl group, an amino group, a hydrazide group, a semicarbazide group and a thiosemicarbazide group is a compound represented by the following formula (81). is there.

(Where
R ²² represents an organic group,
A ¹ represents a group defined by the above formula (70). )

In the above formula, R ²² is preferably an aliphatic group having 1 to 25 carbon atoms, an aliphatic group substituted with an aromatic group having 7 to 25 carbon atoms, or an aromatic group having 6 to 25 carbon atoms. R ²² is specifically methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetra A residue obtained by removing one hydrogen atom from methyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane and the like. When an isomer exists, the isomer is also included.

Specific examples of the compound represented by the above formula (81) include methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octadecanol, cyclohexanol, cyclooctanol, and dimethylcyclohexanol. , Diethylcyclohexanol, trimethylcyclohexanol, trimethylethylcyclohexanol, dicyclohexylmethanol, tetramethyldicyclohexylmethanol, hydroxy compounds such as phenol, methylphenol, xylenol, ethylphenol, diethylphenol, ethylamine, propylamine, butylamine, pentylamine, hexyl Amine, octylamine, decylamine, dodecylamine, cyclohexylamine, Chrooctylamine, dimethylcyclohexylamine, phenylamine, methylphenylamine, dimethylphenylamine, ethylphenylamine, diethylphenylamine and other amines, ethyl hydrazide, propyl hydrazide, butyl hydrazide, pentyl hydrazide, hexyl hydrazide, octyl hydrazide, decyl hydrazide Hydrazide such as dodecyl hydrazide, cyclohexyl hydrazide, cyclooctyl hydrazide, dimethylcyclohexyl hydrazide, phenyl hydrazide, methylphenyl hydrazide, dimethylphenyl hydrazide, ethylphenyl hydrazide, diethylphenyl hydrazide, butyl semicarbazide, butyl semicarbazide, pentyl semicarbazide, Semicarbazide Octyl semicarbazide, decyl semicarbazide, dodecyl semicarbazide, cyclohexyl semicarbazide, cyclooctyl semicarbazide, dimethylcyclohexyl semicarbazide, phenyl semicarbazide, methylphenyl semicarbazide, dimethylphenyl semicarbazide, ethylphenyl semicarbazide, diethylphenyl semicarbazide, ethylthiosemicarbazide, ethylthiosemicarbazide, Butylthiosemicarbazide, pentylthiosemicarbazide, hexylthiosemicarbazide, octylthiosemicarbazide, decylthiosemicarbazide, dodecylthiosemicarbazide, cyclohexylthiosemicarbazide, cyclooctylthiosemicarbazide, dimethylcyclohexylthiosemicarbazide, fe Examples thereof include thiosemicarbazides such as nilthiosemicarbazide, methylphenylthiosemicarbazide, dimethylphenylthiosemicarbazide, ethylphenylthiosemicarbazide, and diethylphenylthiosemicarbazide.

The compound represented by the above formula (81) may be a compound represented by the following formula (82).

(Where
R ²³ represents an unsaturated aliphatic hydrocarbon group having 1 to 25 carbon atoms,
R ¹⁵ and E ¹ represent a group defined by the above formula (71). )

The compound represented by the above formula (82) is more preferably a compound represented by the following formulas (83) to (85).

(Where
R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms,
R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms,
R ³¹ represents a saturated hydrocarbon group having 1 to 6 carbon atoms or a single bond, E ¹ represents a group defined by the above formula (71),
w represents an integer of 1 to 3. )

<Isothiocyanate compound>
An isothiocyanate compound is a compound having one or more isothiocyanate groups in one molecule, and is classified into a monoisothiocyanate and a polyisothiocyanate.

In the resin composition of the present embodiment, monoisothiocyanate is a compound having one isothiocyanate group in one molecule, and preferably a compound represented by the following formula (30).

(Where
R ⁵ represents an organic group. )

In the above formula (30), R ⁵ is preferably an aliphatic group having 1 to 25 carbon atoms or an aromatic group having 6 to 25 carbon atoms. R ⁵ may be an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic group. R ⁵ is specifically methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, It is a residue obtained by removing one hydrogen atom from tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane and the like. When an isomer exists, the isomer is also included.

Specific examples of the compound represented by the above formula (1) include methane isothiocyanate, ethane isothiocyanate, propane isothiocyanate, butane isothiocyanate, pentane isothiocyanate, hexane isothiocyanate, octane isothiocyanate, decane isothiocyanate, dodecane isothiocyanate. Thiocyanate, octadecane isothiocyanate, cyclohexane isothiocyanate, cyclooctane isothiocyanate, dimethyl cyclohexane isothiocyanate, diethyl cyclohexane isothiocyanate, trimethyl cyclohexane isothiocyanate, trimethyl ethyl cyclohexane isothiocyanate, dicyclohexyl methane isothiocyanate, tetramethyl dicyclohexyl methane isothiocyanate, phen Isothiocyanate, toluene isothiocyanate, xylene isothiocyanate, ethyl benzene isothiocyanate, diethylbenzene isothiocyanate, diphenylmethane isothiocyanate, tetramethyl diphenyl methane isothiocyanate, and the like.

The compound represented by the above formula (30) may be a compound represented by the following formula (86).

(Where
R ¹⁵ and R ²³ represent a group defined by the above formula (82). )

The compound represented by the above formula (30) is more preferably a compound represented by the following formulas (87) to (89).

(Where
R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms;
R ²⁷ , R ²⁸ , R ²⁹ and R ³⁰ each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms,
R ³¹ represents a saturated hydrocarbon group having 1 to 6 carbon atoms or a single bond,
w represents an integer of 1 to 3. )

Specific examples of the compounds represented by formulas (87) to (89) include isothiocyanatomethyl acrylate, isothiocyanatomethyl methacrylate, acrylic acid (2-isothiocyanatoethyl), methacrylic acid (2-isothiocyana Toethyl), acrylic acid (3-isothiocyanatopropyl), methacrylic acid (3-isothiocyanatopropyl), 2-isothiocyanatoethyl vinyl ether, 4-isothiocyanatobutyl vinyl ether, p- (isocyanatomethyl) styrene , P- (isocyanatoethylstyrene) and the like.

In the resin composition of the present embodiment, polyisothiocyanate is a compound having two or more isothiocyanate groups in one molecule, for example, a compound represented by the following formula (32).

A preferred first embodiment of such a polyisothiocyanate is a polymer containing at least two repeating units represented by the following formula (33).

(Where
R ⁷ represents an organic group,
R ⁷ represents an organic group or a single bond,
b represents an integer of 1 or more,
g represents 1 or 2; A plurality of R ⁷ , R ⁸ , b and g in the same molecule may be the same or different. )

The polymer as a preferable first aspect of the polyisothiocyanate described herein may have one or more kinds of repeating units other than the repeating unit represented by the above formula (33). The terminal of the polymer is a group derived from a polymerization initiator, a polymerization terminator, and a terminal modifier, and varies depending on the production method, but is not particularly limited as long as it does not contradict the gist of the present embodiment. That is, the preferable first aspect of the polyisothiocyanate is more preferably a compound represented by the following formula (90).

(Where
R ³² represents an organic group,
R ³³ represents an organic group or a single bond,
B ² and D ² each independently represent at least one group selected from the group consisting of an isothiocyanate group, an organic group other than an isothiocyanate group, and a hydrogen atom;
G 1 ^~ G ^x represents an organic group or may not include isothiocyanate group, x is an integer of 1 or more, n _x represents an integer of 1 or more,
g represents 1 or 2,
f represents an integer of 1 or more,
m represents an integer of 2 or more. A plurality of R ³² , R ³³ , f and g in the same molecule may be the same or different. )

In the above formula (90), G ¹ to G ^x represent a repeating unit other than the repeating unit represented by the above formula (33). Further, _{n x} represents the number of repeating units of ^{G x.} For example, in addition to the repeating unit represented by the above formula (43), when there are n ₁ , n ₂ , and n _{3 of} G ¹ , G ² , and G ³ , respectively, G ¹ n ₁ G ² n ₂ G ³ n ₃ .

In the above formula (90), R ³² is preferably an aliphatic group having 2 to 25 carbon atoms, an aliphatic group substituted with an aromatic compound having 7 to 25 carbon atoms, or an aromatic group having 8 to 25 carbon atoms. is there. Specific examples of R ³² include ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylethane, ethylbenzene, diethylbenzene, Diphenylethane, tetramethyldiphenylethane, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octadecanol, cyclohexanol, cyclooctanol, dimethylcyclohexanol, diethylcyclohexanol, trimethylcyclohexanol, trimethylethylcyclo Hexanol, dicyclohexyl ethanol, etc. These residues are obtained by removing three hydrogen atoms.

In the above formula (90), R ³³ represents an organic group or a single bond. When it is an organic group, R ³³ represents an alkylene group having 1 to 25 carbon atoms, an aromatic hydrocarbon group having 6 to 25 carbon atoms, or It is group represented by Formula (91) or Formula (92).

(Where
R ³⁴ , R ³⁶ and R ³⁷ each independently represents an alkylene group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a single bond,
l represents an integer of 1 to 10. )

When R ³⁴ is an alkylene group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 25 carbon atoms, specifically, methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, 2 hydrogen atoms from octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane, etc. It is a residue excluding.

In the above formulas (91) and (92), R ³⁴ , R ³⁶ and R ³⁷ are preferably methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane. , Diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane and the like are residues obtained by removing two hydrogen atoms. In addition, when an isomer exists, this isomer is also included.

In the above formula (90), when B ² and D ² are organic groups, the organic group is preferably an alkyl group having 1 to 25 carbon atoms, an aromatic hydrocarbon group having 6 to 25 carbon atoms, or And groups represented by formulas (93) to (95).

(Where
R ³⁸ , R ³⁹ and R ⁴⁰ each independently represents an alkylene group having 1 to 25 carbon atoms or an aromatic group having 6 to 25 carbon atoms,
p represents an integer of 1 to 10. )

In the above formulas (93) to (95), R ³⁸ , R ³⁹ and R ⁴⁰ are preferably an alkylene group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 25 carbon atoms. , Methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene , Xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane and the like are residues obtained by removing two hydrogen atoms. In addition, when an isomer exists, this isomer is also included.

The first aspect of the polyisothiocyanate shown above may be, for example, a polymer of monoisothiocyanate represented by the above formula (41), and the polymer is a copolymer with other monomers. May be. Specifically, isothiocyanatomethyl acrylate is a copolymer of methyl acrylate, a copolymer of isothiocyanatomethyl methacrylate and methyl methacrylate, acrylic acid (2-isothiocyanatoethyl) and methyl acrylate. Copolymer, copolymer of methacrylic acid (2-isothiocyanatoethyl) and methyl methacrylate, copolymer of acrylic acid (3-isothiocyanatopropyl) and methyl acrylate, methacrylic acid (3-isothiocyanato Propyl) and methyl methacrylate copolymer. These compounds can be produced by known methods.

In the resin composition of the present embodiment, the second aspect of the polyisothiocyanate is a group consisting of a structural unit represented by the following formula (40) and units represented by the following formulas (41) to (47). And a polyisothiocyanate in which a nitrogen atom constituting the polyisothiocyanate is bonded to a carbon atom.

(Where
Each R ³ independently represents an organic group;
R ⁴ represents an aliphatic group or an aromatic group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group,
A plurality of R ³ and R ⁴ may be the same or different,
X ³ represents an oxygen atom or a sulfur atom. )

In the above formulas (40) and (41) to (47), R ³ is preferably an aliphatic group having 1 to 25 carbon atoms or an aromatic group having 6 to 25 carbon atoms. R ³ is specifically methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, It is a residue obtained by removing two hydrogen atoms from tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane and the like. When an isomer exists, the isomer is also included.

The group —X ³ —R ⁴ contained in the above formulas (43) and (45) will be described.

As will be described later, in the production of the polyisothiocyanate of the present invention, an N, N′-disubstituted dithioalophanoic acid bond represented by the above formula (43) or an N-substitution represented by the above formula (45) is used. When an —O-substituted thiocarbamate group (when X ³ is an oxygen atom) or an N-substituted —S-substituted dithiocarbamate group (when X ³ is a sulfur atom) is formed, a hydroxy compound or thiol Use a kind. The group —X ³ —R ⁴ is a group derived from this hydroxy compound or thiols. When a hydroxy compound is used, X ³ is an oxygen atom, and when using a thiol, X ³ is a sulfur atom.

R ⁴ may be a hydrocarbon group. The hydrocarbon group has at least one of an aliphatic group and an aromatic group, and may contain an oxygen atom, a nitrogen atom, or the like in addition to a carbon atom. R ⁴ is an aliphatic group or an aromatic group, preferably an aliphatic group or an aromatic group having 6 to 22 carbon atoms having 1 to 22 carbon atoms, more preferably, fats having 1 to 22 carbon atoms And a group having 7 to 22 carbon atoms in which an aliphatic group having 1 to 22 carbon atoms and an aromatic group having 6 to 22 carbon atoms are bonded. Specific examples of R ⁴ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, cyclohexane Heptyl group, cyclooctyl group, methylcyclopentyl group, ethylcyclopentyl group, methylcyclohexyl group, ethylcyclohexyl group, propylcyclohexyl group, butylcyclohexyl group, pentylcyclohexyl group, hexylcyclohexyl group, dimethylcyclohexyl group, diethylcyclohexyl group, dibutylcyclohexyl group , Phenyl group, methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, octylphenyl group, nonylphenyl Group, cumylphenyl group, dimethylphenyl group and the like.

The polyisothiocyanate in the present embodiment may be a polyisothiocyanate obtained by further polymerizing a compound represented by the following formula (33), which is one type of the polyisothiocyanate of the present embodiment.

(Where
R ³ represents an organic group. )

R ³ in the above formula (33) is preferably an aliphatic group having 1 to 25 carbon atoms or an aromatic group having 6 to 25 carbon atoms. Specific examples of R ³ are methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyl. A residue obtained by removing two hydrogen atoms from dicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane and the like. When an isomer exists, the isomer is also included. R ³ is more preferably a group represented by the following formulas (300) to (306).

(In the formula, i represents an integer of 1 to 12, and may be 1 to 10.)

More preferably, the compound represented by the above formula (33) is hexamethylene diisothiocyanate, isophorone diisothiocyanate, 4,4′-dicyclohexylmethane diisothiocyanate, 4,4′-diphenylmethane diisothiocyanate, toluene diene. Examples include isothiocyanate (each isomer) and naphthalene dithiocyanate (each isomer).

Examples of the compound represented by the above formula (33) include phenylene diisothiocyanate, 4,4′-diisothiocyanatodiphenyl ether, 1,3-bis (3-isothiocyanatophenoxy) benzene, 3,3′-diisothione. There can also be mentioned, for example, oocyanatodiphenylsulfone, diethyltoluene diisothiocyanate.

Hereinafter, the resin (polyisothiocyanate) obtained by polymerizing the compound represented by the above formula (33) will be described. In the following description, the compound represented by the formula (33) may be described as a “monomer” in the sense of a compound before polymerization.

The polyisothiocyanate produced by the polymerization of the “monomer” represented by the above formula (33) can use a hydroxy compound and / or a thiol as an auxiliary material in the production.

Hydroxy compounds include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, dodecanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, methylcyclopentanol, ethylcyclopentanol, Methylcyclohexanol, ethylcyclohexanol, propylcyclohexanol, butylcyclohexanol, pentylcyclohexanol, hexylcyclohexanol, dimethylcyclohexanol, diethylcyclohexanol, dibutylcyclohexanol, phenol, methylphenol, ethylphenol, propylphenol, butylphenol, pentyl Phenol, hexylphenol, o Tylphenol, nonylphenol, cumylphenol, dimethylphenol, methylethylphenol, methylpropylphenol, methylbutylphenol, methylpentylphenol, diethylphenol, ethylpropylphenol, ethylbutylphenol, dipropylphenol, dicumylphenol, trimethylphenol, triethylphenol And naphthol.

Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, 1,6-hexanediol, neopentyl glycol, neo Low molecular weight compounds such as pentyl glycol hydroxypivalate, 2-ethyl-1,3-hexanediol, trimethylolpropane, glycerin, 1,2,6-hexanetriol, and polyester polyols having a molecular weight of about 200 to 10,000, poly Ether polyols can also be used.

Thiols include methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, decanethiol, dodecanethiol, cyclopentanethiol, cyclohexanethiol, cycloheptanethiol, cyclooctanethiol, Methylcyclopentanethiol, ethylcyclopentanethiol, methylcyclohexanethiol, ethylcyclohexanethiol, propylcyclohexanethiol, butylcyclohexanethiol, pentylcyclohexanethiol, hexylcyclohexanethiol, dimethylcyclohexanethiol, diethylcyclohexanethiol, dibutylcyclohexanethiol, thiophenol, methylthio Fenault , Ethylthiophenol, propylthiophenol, butylthiophenol, pentylthiophenol, hexylthiophenol, octylthiophenol, nonylthiophenol, cumylthiophenol, dimethylthiophenol, methylethylthiophenol, methylpropylthiophenol, methylbutylthio Examples include phenol, methylpentylthiophenol, diethylthiophenol, ethylpropylthiophenol, ethylbutylthiophenol, dipropylthiophenol, dicumylthiophenol, trimethylthiophenol, triethylthiophenol, thionaphthol, and the like.

When a hydroxy compound is used, the isothiocyanate group / hydroxyl group equivalent ratio of the above-mentioned hydroxy compound and the “monomer” represented by the above formula (33) is selected from a value of about 10 to 100 according to the purpose. Similarly, when thiols are used, the isothiocyanate group / thiol group equivalent ratio is selected from a value of about 10 to 100 according to the purpose.

An isothiocyanurate group represented by the formula (41) can be formed by the polymerization reaction of the monomer of the formula (33). The isothiocyanurate-forming catalyst for forming the isothiocyanurate group represented by the formula (41) is preferably a quaternary ammonium salt, more preferably a quaternary ammonium hydroxide, a quaternary ammonium carboxylic acid, More preferred is quaternary ammonium carboxylic acid. Specific examples include tetraalkylammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; weak organic acids such as tetramethylammonium acetate, tetraethylammonium acetate, and tetrabutylammonium acetate. Examples include salt. Although metal salts of alkyl carboxylic acids such as acetic acid, valeric acid, isovaleric acid, caproic acid, octylic acid, and myristic acid can be used, organic weak acid salts and the like are preferable from the viewpoint of reducing the amount used.

Examples of the hydroxy compound for diluting the isothiocyanurate-forming catalyst include methanol, ethanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1,2-propylene glycol, 1,3-propylene glycol, Examples thereof include alcoholic hydroxy compounds such as 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, glycerin and cyclohexanol, and phenolic hydroxy compounds such as phenol, cresol, xylenol and trimethylphenol. From the viewpoint of crystallinity of the polyisocyanate obtained from these, alcohols having side chains such as 2-butanol, 2-methyl-1-propanol, 1,3-butanediol, and 2,3-butanediol are preferred. Two or more types may be mixed. Thiols may be used in place of the hydroxy compound.

When the monomer represented by the above formula (33) or the monomer obtained by urethanizing the isothiocyanate group with a hydroxy compound in the presence of the above-mentioned isothiocyanuration catalyst, The concentration of the diluted isothiocyanurate catalyst is 1 to 20% by mass. The concentration is preferably 1 to 10% by mass. If the concentration is 1% by mass or more, the amount of the hydroxy compound accompanying the isothiocyanurate-forming catalyst does not increase excessively, and the physical properties of the resulting polyisothiocyanate and the coating film formed thereby are unlikely to deteriorate. If the concentration is 20% by mass or less, the cocatalyst effect of the accompanying hydroxy compound does not decrease, and as a result, the amount of the isothiocyanurate-forming catalyst used is increased and the polyisothiocyanate is not easily colored.

Except for the case where the isothiocyanuration catalyst is deactivated by an acidic component contained in a trace amount in the raw material such as the monomer represented by the formula (33), the amount of the isothiocyanuration catalyst used is the monomer It is 1 ppm to 10%, preferably 10 ppm to 5%, based on the weight of diisothiocyanate. If this amount is 1 ppm or more, the function as an isothiocyanurate-forming catalyst can be sufficiently exhibited. If this amount is 3% or less, the amount of acidic phosphoric acid compound and acidic phosphoric acid ester compound (described later) added to deactivate the isothiocyanurate-forming catalyst is reduced.

During the reaction, a solvent may or may not be used, but the use of a solvent having no reaction activity with the isothiocyanate group makes it easier to control the reaction.

Examples of solvents include esters or ethers such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, mesitylene, etc. Is possible. Of course, a mixture of two or more solvents can be used.

The isothiocyanuration reaction is performed at 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C. The progress of the reaction can be confirmed by ¹ H-NMR analysis of the reaction solution.

When the reaction reaches the desired conversion rate, the reaction is stopped by deactivating the catalyst by adding a reaction terminator. The conversion rate is suitably selected in the range of 10 to 60%, preferably 10 to 30%. With a low conversion rate, it is possible to obtain a polyisothiocyanate having a lower viscosity, but a conversion rate of 10% or more is preferable from the viewpoint of productivity. On the other hand, if the conversion is 60% or less, the viscosity of the polyisothiocyanate does not become too high, which is preferable.

The conversion rate can be obtained by the following formula.
^{In the 1} H-NMR chart, the methyl group peak of tetramethylsilane is set to 0 ppm, and the conversion rate is calculated from the integral value (A) of the 3.5 ppm peak and the integral value (B) of the 4.8 ppm peak according to the following formula. calculate.
Conversion rate (%) = B / (A + B) × 100

As the terminator for the isothiocyanuration reaction, one or more compounds of an acidic phosphate compound and an acidic phosphate compound are used.

The acidic phosphoric acid compound is an inorganic acid, and examples thereof include phosphoric acid, phosphorous acid, hypophosphorous acid, diphosphorous acid, hypophosphoric acid, pyrophosphoric acid, and peroxophosphoric acid. The acidic phosphoric acid compound is preferably phosphoric acid.

The acidic phosphate ester compound is a compound having an acidic group and an ester group. For example, the monoalkyl phosphate having 2 to 8 carbon atoms, the monoalkyl phosphite, or the dialkyl phosphate having 4 to 16 carbon atoms, dialkyl phosphite, Alternatively, dilauryl phosphate, diphenyl phosphate, monolauryl phosphate, monophenyl phosphate, dilauryl phosphite, diphenyl phosphite, monolauryl phosphite, monophenyl phosphite and the like can be mentioned. The acidic phosphate ester compound is preferably a monoalkyl phosphate having 3 to 8 carbon atoms, or a dialkyl phosphate having 6 to 16 carbon atoms, more preferably dioctyl phosphate or monooctyl phosphate. Among these, it is preferable to use an acidic phosphoric acid compound. The addition amount of the acidic phosphoric acid compound is preferably 1 to 10 equivalents, more preferably 1 to 6 equivalents, relative to the stoichiometric amount of the isothiocyanuration catalyst. If the addition amount is 1 equivalent or more, the isothiocyanuration catalyst can be sufficiently deactivated. If the addition amount is 10 equivalents or less, it is preferable without filtering the insoluble matter generated.

The polyisothiocyanate of this embodiment may be a compound represented by the following formulas (96) to (99).

(Where
k represents an integer of 1 to 4. )

(Where
R ³⁵ represents a group selected from the group consisting of a hydrogen atom, a methyl group, and an ethyl group,
s represents an integer of 0 or 1,
r, t and u each represents 0 or an integer of 1 or more, and the sum of r, t and u is 5 to 90. )

(Where
v represents an integer of 2 to 70. )

[Reaction method]
A compound having at least one group selected from the group consisting of a hydroxyl group, an amino group, a hydrazide group, a semicarbazide group and a thiosemicarbazide group, and an isothiocyanate (monoisothiocyanate or polyisothiocyanate may be used). The method of reacting with the above may be described.

The resin composition of the present embodiment is
1. A resin obtained by reacting a compound having at least one group selected from the group consisting of a hydroxyl group, an amino group, a hydrazide group, a semicarbazide group and a thiosemicarbazide group with a monoisothiocyanate,
2. A resin obtained by reacting a compound having one group selected from the group consisting of a hydroxyl group, an amino group, a hydrazide group, a semicarbazide group and a thiosemicarbazide group with a polyisothiocyanate;
3. A resin obtained by reacting a compound having at least one group selected from the group consisting of a hydroxyl group, an amino group, a hydrazide group, a semicarbazide group and a thiosemicarbazide group with a polyisothiocyanate,
Any of these can be contained. In any case, the combination of the functional groups to be reacted is the same and can be performed in accordance with the method described herein.

In the following explanation, a reaction formula is shown for easy understanding of the reaction, and the reaction formula describes a monofunctional compound as an example, but it goes without saying that the same reaction proceeds even in a polyfunctional compound.

[Reaction with a compound having a hydroxyl group]
The reaction between the compound having a hydroxyl group and isothiocyanate is represented by the following formula (100).

(In the formula, R ⁴¹ and R ⁴² each independently represents an organic group.)

The reaction can be carried out in the presence or absence of a solvent. The solvent used in the presence of a solvent is preferably a solvent inert to the hydroxyl group and the isothiocyanate group, or a solvent that reacts with the isothiocyanate group but has a very slow rate for the intended reaction. Preferred solvents include hydrocarbon compounds such as pentane, hexane, heptane, octane, nonane, decane, dodecane, tetradecane, pentadecane, hexadecane, octadecane, nonadecane; ethyl ether, tetrahydrofuran, octyl ether, nonyl ether, decyl ether, dodecyl ether, Ethers in which hydrocarbon compounds such as tetradecyl ether, pentadecyl ether, hexadecyl ether, octadecyl ether and tetraethylene glycol dimethyl ether are bonded via an ether bond; dimethyl sulfide, diethyl sulfide, dibutyl sulfide, dihexyl sulfide, octyl sulfide, Nonyl sulfide, decyl sulfide, dodecyl sulfide, tetradecyl sulfide, pentadecyl sulfi Thioethers in which hydrocarbon compounds such as hexadecyl sulfide, octadecyl sulfide, and nonadecyl sulfide are bonded via a thioether bond; benzene, toluene, ethylbenzene, butylbenzene, pentylbenzene, hexylbenzene, octylbenzene, biphenyl, terphenyl, Aromatic hydrocarbon compounds such as diphenylethane, (methylphenyl) phenylethane, dimethylbiphenyl, benzyltoluene; diphenyl ether, di (methylbenzyl) ether, di (ethylbenzyl) ether, di (butylbenzyl) ether, di (pentylbenzyl) ) Aromatic hydrocarbon compounds such as ether, di (hexylbenzyl) ether, di (octylbenzyl) ether, diphenylether, dibenzylether Diphenyl sulfide, di (methylbenzyl) sulfide, di (ethylbenzyl) sulfide, di (butylbenzyl) sulfide, di (pentylbenzyl) sulfide, di (hexylbenzyl) sulfide, di ( Aromatic thioethers in which aromatic hydrocarbon compounds such as octylbenzyl) sulfide, di (methylphenyl) sulfide, dibenzylsulfide and the like are bonded via a thioether bond; methoxybenzene, ethoxybenzene, butoxybenzene, dimethoxybenzene, diethoxybenzene , A compound in which a hydrocarbon compound such as dibutoxybenzene and an aromatic hydrocarbon compound are bonded via an ether bond; chloromethane, chloroethane, chloropentane, chlorooctane, bromomethane, bromoethane, Halogenated compounds such as bromopentane, bromooctane, dichloroethane, dichloropentane, dichlorooctane, dibromoethane, dibromopentane, dibromooctane, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone And the like; ketones such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, amides such as N, N-dimethylformamide; sulfoxides such as dimethyl sulfoxide; water.

The reaction temperature is not particularly limited, but it can be carried out in the range of 0 ° C to 300 ° C. Any reaction time can be set as the reaction time. For example, the remaining amount of the isothiocyanate group may be traced with an infrared spectrometer, and the reaction may be stopped when the desired remaining amount is reached.

In general, since the reaction between the hydroxyl group and the isothiocyanate group is slow, a catalyst may be used. Examples of the catalyst include Lewis acids and transition metal compounds that generate Lewis acids, organotin compounds, copper group metals, zinc, and iron group metal compounds. Table Specific examples of the _catalyst, in _{_{_{_{AlX 3, TiX 3, TiX 4}}}} , VOX 3, VX 5, ZnX 2, FeX 3, SnX 4 (X in this case, a halogen, an acetoxy group, an alkoxy group, an aryloxy group) Lewis acid and transition metal compound that generates Lewis acid; (CH ₃ ) ₃ SnOCOCH ₃ , (C ₂ H ₅ ) SnOCOC ₆ H ₅ , Bu ₃ SnOCOCH ₃ , Ph ₃ SnOCOCH ₃ , Bu ₂ Sn (OCOCH ₃ ) ₂ , Bu ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , Ph ₃ SnOCH ₃ , (C ₂ H ₅ ) ₃ SnOPh, Bu ₂ Sn (OCH ₃ ) ₂ , Bu ₂ Sn (OC ₂ H ₅ ) ₂ , Bu ₂ Sn _{_{_{_{(OPh) 2, Ph 2 Sn}}}} (CH 3) 2, (C 2 H 5) 3 SnOH, PhSnOH, Bu 2 SnO, ( Organotin compounds represented by C ₈ H ₁₇ ) ₂ SnO, Bu ₂ SnCl ₂ , BuSnO (OH), etc .; CuCl, CuCl ₂ , CuBr, CuBr ₂ , CuI, CuI ₂ , Cu (OAc) ₂ , Cu (acac ) ₂ , copper olefinate, Bu ₂ Cu, (CH ₃ O) ₂ Cu, AgNO ₃ , AgBr, silver picrate, AgC ₆ H ₆ ClO _{4 and} other compounds of copper group metals; zinc such as Zn (acac) ₂ A compound of Fe (C ₁₀ H ₈ ) (CO) ₅ , Fe (CO) ₅ , Fe (C ₄ H ₆ ) (CO) ₃ , Co (mesitylene) ₂ (PEt ₂ Ph ₂ ), CoC ₅ F ₅ ( CO) ₇ and iron group metal compounds such as ferrocene (Bu represents a butyl group, Ph represents a phenyl group, and acac represents an acetylacetone chelate ligand).

[Reaction with a compound having an amino group]
The reaction between the compound having an amino group and isothiocyanate is represented by the following formula (101).

^{^(Wherein, R} ^41, R ⁴² is a group as defined by formula (100).)

The reaction can be carried out in the presence or absence of a solvent. The solvent used in the presence of a solvent is preferably a solvent inert to the amino group and the isothiocyanate group, or a solvent that reacts with the isothiocyanate group but has a very slow rate for the intended reaction. Preferred solvents include hydrocarbon compounds such as pentane, hexane, heptane, octane, nonane, decane, dodecane, tetradecane, pentadecane, hexadecane, octadecane, nonadecane; ethyl ether, tetrahydrofuran, octyl ether, nonyl ether, decyl ether, dodecyl ether, Ethers in which hydrocarbon compounds such as tetradecyl ether, pentadecyl ether, hexadecyl ether, octadecyl ether and tetraethylene glycol dimethyl ether are bonded via an ether bond; dimethyl sulfide, diethyl sulfide, dibutyl sulfide, dihexyl sulfide, octyl sulfide, Nonyl sulfide, decyl sulfide, dodecyl sulfide, tetradecyl sulfide, pentadecyl sulfi Thioethers in which hydrocarbon compounds such as hexadecyl sulfide, octadecyl sulfide, and nonadecyl sulfide are bonded via a thioether bond; benzene, toluene, ethylbenzene, butylbenzene, pentylbenzene, hexylbenzene, octylbenzene, biphenyl, terphenyl, Aromatic hydrocarbon compounds such as diphenylethane, (methylphenyl) phenylethane, dimethylbiphenyl, benzyltoluene; diphenyl ether, di (methylbenzyl) ether, di (ethylbenzyl) ether, di (butylbenzyl) ether, di (pentylbenzyl) ) Aromatic hydrocarbon compounds such as ether, di (hexylbenzyl) ether, di (octylbenzyl) ether, diphenylether, dibenzylether Diphenyl sulfide, di (methylbenzyl) sulfide, di (ethylbenzyl) sulfide, di (butylbenzyl) sulfide, di (pentylbenzyl) sulfide, di (hexylbenzyl) sulfide, di ( Aromatic thioethers in which aromatic hydrocarbon compounds such as octylbenzyl) sulfide, di (methylphenyl) sulfide, dibenzylsulfide and the like are bonded via a thioether bond; methoxybenzene, ethoxybenzene, butoxybenzene, dimethoxybenzene, diethoxybenzene , A compound in which a hydrocarbon compound such as dibutoxybenzene and an aromatic hydrocarbon compound are bonded via an ether bond; chloromethane, chloroethane, chloropentane, chlorooctane, bromomethane, bromoethane, Listed are halides such as bromopentane, bromooctane, dichloroethane, dichloropentane, dichlorooctane, dibromoethane, dibromopentane, dibromooctane, chlorobenzene, bromobenzene, dichlorobenzene, and dibromobenzene; water.

The reaction temperature is not particularly limited, but it can be carried out in the range of −50 ° C. to 250 ° C. Any reaction time can be set as the reaction time. For example, the remaining amount of the isothiocyanate group may be traced with an infrared spectrometer, and the reaction may be stopped when the desired remaining amount is reached.

Generally, since the reaction between an amino group and an isothiocyanate group is fast, it is not necessary to use a catalyst, but the use itself is not denied. As the catalyst, the catalysts mentioned in the above [Reaction with a compound having a hydroxyl group] can be used.

[Reaction with a compound having a hydrazide group, a semicarbazide group or a thiosemicarbazide group]
Various reactions may occur in the reaction of a compound having a hydrazide group, a semicarbazide group or a thiosemicarbazide group with an isothiocyanate, depending on the compound used, for example, a reaction represented by the following formula (102).

(Where
R ⁴¹ and R ⁴² are groups defined by the above formula (100),
Y represents an —NH— group or a CH ₂ — group,
Z represents an oxygen atom or a sulfur atom. )

The reaction between a compound having a hydrazide group, a semicarbazide group or a thiosemicarbazide group and an isothiocyanate can be carried out in the presence or absence of a solvent. Solvents used in the presence of a solvent include, in addition to the solvents mentioned in [Reaction with a compound having a hydroxyl group], alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol; methyl acetate, ethyl acetate, Esters such as propyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, methyl lactate, ethyl lactate, and butyl lactate can also be used.

The reaction may be performed in the presence or absence of a catalyst. When a catalyst is used, the catalyst mentioned in the above [Reaction with a compound having a hydroxyl group] can be used.

In the case of a reaction between a compound having a hydrazide group or a semicarbazide group and isothiocyanate, it is also preferable to perform a heat treatment. The heat treatment may have an effect of improving mechanical properties such as rigidity, hardness, workability, impact resistance, and bending fatigue resistance of the resin composition. Although the mechanism that exerts such an effect is not clear, the present inventors have performed heat treatment, for example, by a reaction in which the bond on the right side of the formula (102) is represented by the following formula (103) or formula (104). It is speculated that this may be due to the formation of a ring structure in the molecular chain.

(Where
R ⁴¹ , R ⁴² , Y, and Z are groups defined by the above formula (102). )

One preferred aspect of the resin of the present embodiment is a resin having two or more structural units selected from the group consisting of divalent groups represented by the following formulas (6) to (8).

(Where
Y ¹ represents an organic group and may be an —NH— group. )

Y ¹ is preferably an aliphatic group having 1 to 12 carbon atoms or an aromatic group having 6 to 12 carbon atoms. Examples of the aliphatic group having 1 to 12 carbon atoms include divalent groups derived from hydrocarbon compounds such as methane, ethane, propane, butane, pentane, hexane, octane, decane, cyclohexane, cyclooctane, cyclodecane, and methylcyclohexane. Derived from a compound having a cyclic hydrocarbon group such as ethylcyclohexane, butylcyclohexane and dimethylcyclohexane, and an aromatic hydrocarbon compound such as benzene, methylbenzene, ethylbenzene, butylbenzene and hexylbenzene And a divalent group.

The resin according to some embodiments has at least one group selected from the group consisting of groups represented by the above formulas (6) to (8) in the main chain skeleton. For example, the resin has structural units represented by the following formulas (105) to (108).

(Where
R ⁴³ represents an organic group,
A plurality of R ⁴³ may be the same or different,
J represents a divalent group represented by the above formula (6), (7) or (8), and a plurality of R ⁴³ and J in the same molecule may be the same or different. )

R ⁴³ is preferably an aliphatic group having 2 to 25 carbon atoms, an aliphatic group substituted with an aromatic compound having 7 to 25 carbon atoms, or an aromatic group having 8 to 25 carbon atoms. Specific examples of R ⁴³ include ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylethane, ethylbenzene, diethylbenzene. , Diphenylethane, tetramethyldiphenylethane, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octadecanol, cyclohexanol, cyclooctanol, dimethylcyclohexanol, diethylcyclohexanol, trimethylcyclohexanol, trimethylethyl Cyclohexanol, dicyclohexyl ethanol And a residue obtained by removing three hydrogen atoms from ru and the like.

More preferably, the resin composition of the present embodiment contains a resin represented by the following formula (109).

(Where
K ¹ to K ^c are each independently
Represents at least one group selected from the group consisting of the above formulas (6) to (8);
L ¹ to L ^c each independently represents an organic group that may or may not contain a group selected from the group consisting of formulas (6) to (8), c represents an integer of 1 or more,
M ¹ and M ² each independently represents an organic group that may or may not contain an isothiocyanate group;
w _c represents an integer of 1 or more. )

In the above formula (109), w _c represents the number of repeating units of K ^c -L ^c . For example, in the case of a resin composed of two kinds of repeating units of K ¹ -L ¹ and K ² -L ² , the above formula (109) is represented by the following formula (110).

A method for producing a resin composition containing a resin having at least one structural unit selected from the group consisting of the groups represented by the above formulas (6) to (8) is not particularly limited. For example, a hydrazide group And a compound having a semicarbazide group or thiosemicarbazide group and an isothiocyanate can be produced.

The reaction apparatus used for carrying out the reaction is not particularly limited, and a known reactor can be used. As the reaction apparatus, for example, conventionally known reactors such as a stirring tank, a pressurized stirring tank, a reduced pressure stirring tank, a tower reactor, a distillation tower, a packed tower, and a thin film distillation apparatus can be used in appropriate combination. The material of the reactor is not particularly limited, and a known material can be used. As the material of the reactor, for example, glass, stainless steel, carbon steel, Hastelloy, glass lining of the base material, or Teflon (registered trademark) coating can be used. SUS304, SUS316, SUS316L, etc. are inexpensive and can be preferably used. If necessary, a known process device such as an instrument such as a flow meter or a thermometer, a reboiler, a pump, or a condenser may be added, and heating may be performed by a known method such as steam or a heater, and cooling may also be performed. Known methods such as natural cooling, cooling water, and brine can be used. A process can also be added as needed.

By such a method, a modified resin composition containing a resin containing at least one structural unit selected from the group consisting of the groups represented by the above formulas (6) to (8) can also be produced. However, depending on the reaction conditions, the target resin may not be obtained. In such a case, the target resin can be produced by further performing the following heat treatment.

The heat treatment is preferably performed in the range of 100 ° C. to 300 ° C., more preferably in the range of 150 ° C. to 250 ° C. The heat treatment can be performed in the air or in an inert gas atmosphere, but is preferably performed in an inert gas atmosphere. The inert gas here refers to a gas such as nitrogen, helium, argon, or neon. The pressure may be increased, reduced, or atmospheric. The time for performing the heat treatment is not particularly limited and can be in the range of 1 minute to 500 hours. For example, the generation of the groups represented by the above formulas (6) to (8) using an infrared spectrometer The amount may be tracked and heating may be stopped when the desired amount is reached.

In the production method described above, it is considered that the groups represented by the above formulas (6) to (8) are generated by various reaction routes. For example, the reaction represented by the following formula (111), followed by the following formula ( It is estimated that the reaction on the right side compound in (111) forms a ring structure by the following formula (112) or formula (113).

(Where
R ⁴¹ and R ⁴² are groups defined by the above formula (100),
Y represents an —NH— group or an organic group,
Z represents an oxygen atom or a sulfur atom. )

The modified resin composition of the present embodiment may be used alone or mixed with other resins. The other resin to be mixed may be any resin, and various known resins can be used.

The modified resin composition of the present embodiment can be used for various known applications, among which a coating material is formed on the surface of at least one material selected from the group consisting of metal, glass and plastic. The use as is suitable. Moreover, since the resin composition of this Embodiment is formed by reaction of a functional group stable with respect to water, the use to a water-system coating material is also preferable.

The modified resin composition of the present embodiment has a large effect of improving the adhesion to the metal surface by containing sulfur atoms in the molecular chain. Therefore, the resin composition can be suitably used for imparting cosmetic properties, weather resistance, acid resistance, rust resistance, chipping resistance, adhesion, and the like to pre-coated metal including an anti-rust steel plate, automobile coating, and the like. .

≪Oxazolidinethione≫
<Preferred structure>
A preferred second resin in the present embodiment is a resin containing a molecular chain represented by the following formula (10).

(Where
P ¹ represents an aliphatic group and / or an aromatic group, and Q ¹ is selected from the group consisting of divalent groups represented by the following formula (11), (12), (13) or (14). 1 or more types of structural units are represented, Plural P ¹ and Q ¹ may be the same or different, and n represents an integer of 2 or more. )

In the formula, R ¹ represents an aliphatic group or an aromatic group, X ² and Y ² each independently represent an oxygen atom or a sulfur atom, and a plurality of R ¹ , X ² and Y ² in the same molecule are each It may be the same or different. One or more of X ² and Y ^{2 in} one Q ¹ is a sulfur atom. In other words, one Q1 contains one or more sulfur atoms.

The structure represented by the above formulas (11) to (14) constituting the resin is surprisingly excellent in adhesion, particularly adhesion to a metal surface. Although it is not clear about the mechanism that exerts such an effect, the present inventors presume that the sulfur atom or oxygen atom contained in the bond may have an effect of improving adhesion.

The content of bonds that contribute to the development of heat resistance also correlates with the number average molecular weight Mn described above. The value (Mn / n ¹ ) obtained by dividing the number average molecular weight of the resin by the number n ¹ of sulfur atoms constituting the nitrogen-carbon-sulfur bond and oxygen atoms constituting the nitrogen-carbon-oxygen bond contained per molecule is , Preferably 300 or less, more preferably 200 or less, still more preferably 150 or less. The resin composition of the present embodiment has an effect in terms of adhesion to a metal as described above. From the viewpoint of exhibiting such an effect, the resin has many bonds per molecule. It is preferable to have. On the other hand, when the resin has too many of the above bonds, in particular, the resin has the above formulas (6) to (8), (11) to (14), (41), (42), (45) , (46) or (47), the flexibility, which is one of the coating film performances, may be impaired. From such a viewpoint, (Mn / n ¹ is preferably 50 or more, more preferably 70 or more. For example, n ¹ is the number of bonds per unit weight (1 g) of the resin X ¹ (unit mol / g). ) Can be calculated by, for example, infrared absorption spectrum, ¹ H-NMR, etc., and can be calculated from the number average molecular weight (Mn) by the formula: n ¹ = Mn · X ^{1. The} resin is a nitrogen-carbon-sulfur bond. And n ¹ is the total number of sulfur atoms and oxygen atoms constituting each bond.

R ¹ in the above formulas (11) to (14) is an aliphatic group or an aromatic group. The hydrocarbon group has at least one of an aliphatic group and an aromatic group, and may contain an oxygen atom, a nitrogen atom or the like in addition to the carbon atom. The aliphatic group is preferably an aliphatic group having 1 to 22 carbon atoms, and more preferably an aliphatic group having 1 to 18 carbon atoms. The aromatic group is preferably an aromatic group having 6 to 22 carbon atoms, more preferably an aromatic group having 6 to 15 carbon atoms. A group having 7 to 20 carbon atoms in which an aliphatic group having 1 to 5 carbon atoms and an aromatic group having 6 to 15 carbon atoms are bonded is also preferable.

Specific examples of R ¹ are linear hydrocarbon groups such as methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene; cyclopentane, cyclohexane, cycloheptane, cyclooctane, bis (cyclohexyl) alkane, etc. Groups derived from unsubstituted alicyclic hydrocarbons; methylcyclopentane, ethylcyclopentane, methylcyclohexane (each isomer), ethylcyclohexane (each isomer), propylcyclohexane (each isomer), butylcyclohexane (each isomer) ), Groups derived from alkyl-substituted cyclohexane such as pentylcyclohexane (each isomer), hexylcyclohexane (each isomer); dimethylcyclohexane (each isomer), diethylcyclohexane (each isomer), dibutylcyclohexane (each isomer), etc. of Groups derived from dialkyl-substituted cyclohexane; 1,5,5-trimethylcyclohexane, 1,5,5-triethylcyclohexane, 1,5,5-tripropylcyclohexane (each isomer), 1,5,5-tributylcyclohexane (each Isomers) derived from trialkyl-substituted cyclohexanes; monoalkyl-substituted benzenes such as toluene, ethylbenzene, and propylbenzene; dialkyl-substituted benzenes such as xylene, diethylbenzene, and dipropylbenzene; derived from aromatic hydrocarbons such as diphenylalkane and benzene And the like.

Among these, groups derived from hexane, benzene, diphenylmethane, toluene, cyclohexane, xylene, methylcyclohexane, isophorone or dicyclohexylmethane are preferable. The “derived group” refers to a group having a structure in which two hydrogen atoms are removed from the compound.

Alternatively, R ¹ is preferably an aliphatic group having 1 to 25 carbon atoms or an aromatic group having 6 to 25 carbon atoms. R ¹ is preferably a group not containing a spiro atom. Specific examples of R ¹ are methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyl. A residue obtained by removing two hydrogen atoms from dicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane and the like. When an isomer exists, the isomer is also included.

Among these, R ¹ is preferably a divalent group represented by the following formulas (301) to (306).

(Where
i represents an integer of 1 to 12, and may be 1 to 10. )

In the above formula (10), P ¹ is an aliphatic group and / or an aromatic group. P ¹ may have an oxygen atom, a nitrogen atom or the like in addition to the carbon atom.

P ¹ in the above formula (10) more preferably includes an ether bond or an ester bond, and more preferably a group represented by the following formula (114).

(Where
R ⁴³ represents an aliphatic group or an aromatic group,
b ² represents an integer of 1 to 3. A plurality of R ⁴³ and b ² in the same molecule may be the same or different. )

In the above formula (114), R ⁴³ represents an aliphatic group or an aromatic group. R ⁴³ may have an oxygen atom, a nitrogen atom or the like in addition to the carbon atom. The aliphatic group may be cyclic or acyclic. The aliphatic group is preferably an aliphatic group having 1 to 22 carbon atoms, and more preferably an aliphatic group having 1 to 18 carbon atoms. The aromatic group is preferably an aromatic group having 6 to 22 carbon atoms, more preferably an aromatic group having 6 to 15 carbon atoms. A group having 7 to 20 carbon atoms having an aliphatic group having 1 to 5 carbon atoms and an aromatic group having 6 to 15 carbon atoms bonded thereto is also preferable.

A preferred specific structure of R ⁴³ in the above formula (114) includes a group represented by the following formula (115).

(Where
R ⁴⁴ represents one or more groups selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom and a methyl group,
R ⁴⁵ represents a group selected from the group consisting of groups represented by the following formula (116), (117), (118) or (119),
A plurality of R ⁴⁴ may be the same or different. )

More specifically, P ¹ in the above formula (10) is preferably a group represented by the following formulas (201) to (204).

In the above formulas (11) to (14), X ² and Y ² each independently represent an oxygen atom or a sulfur atom, and X ² and Y ^{2 in} one unit are not oxygen atoms at the same time. That is, at least one of X ² and Y ² in one unit is a sulfur atom. By containing a sulfur atom, the adhesion to the adherend, particularly the adhesion to the metal surface is improved.

Although the structure represented by the above formula (10) does not represent a terminal structure, the gist of the present invention is, in one aspect, an improvement in adhesion in an epoxy resin and a modified epoxy resin, as described above. It is important that the compound of the present invention contains a sulfur atom and / or an oxygen atom (as an atom constituting the compound of the present invention), and the influence due to the difference in terminal structure is not necessarily large. As described later, the compound represented by the formula (10) includes a compound having a terminal epoxy group, a compound having a terminal isothiocyanate group (—NCS), a compound having a terminal episulfide group, and a terminal isocyanate group (— NCO), or a combination of a compound having a terminal episulfide group and a compound having a terminal isothiocyanate group. Depending on the compound used to obtain the compound of formula (10), the terminal structure can be an epoxy group, episulfide group, isocyanate group, or isothiocyanate group. In addition, as described in <Production Method>, an isocyanurate group in which an isocyanate group is trimerized (or an isothiocyanurate group in the case of an isothiocyanurate group) may be included in the compound according to this embodiment. N-substituted-O-substituted thiocarbamate group derived from reaction of alcoholic hydroxyl group and isothiocyanate group in epoxy resin (described later), derived from reaction of thiol group and isocyanate group in episulfide resin (described later) N-substituted-S-substituted thiocarbamate groups, and dithiocarbamate groups derived from the reaction of thiol groups and isothiocyanate groups in episulfide resins may be included.

<Manufacturing method>
The compound (resin) according to this embodiment includes, for example, a compound having a terminal epoxy group and a compound having a terminal isothiocyanate group (—NCS), a compound having a terminal episulfide group, and a compound having a terminal isocyanate group (—NCO), Alternatively, it can be produced by a combination of a compound having a terminal episulfide group and a compound having a terminal isothiocyanate group.

The compound (resin) according to this embodiment includes a compound represented by the following formula (31) (a compound having a terminal isocyanate group, a compound having a terminal isothiocyanate group) and a compound represented by the following formula (20) ( A compound having a terminal epoxy group or a compound having a terminal episulfide group) is preferably used.

(Where
R ² represents an aliphatic group or an aromatic group,
R ¹ represents an aliphatic group or an aromatic group, and X and Y ² each independently represent an oxygen atom or a sulfur atom. )
The combination of the compound represented by Formula (31) and the compound represented by Formula (20) is a compound of Formula (31) in which X is a sulfur atom and / or Formula (20) in which Y ² is a sulfur atom. ) Is selected so as to include one or more compounds.

When the compound represented by the formula (31) and the compound represented by the formula (20) are used in combination to carry out the reaction, a plurality of R ¹ and R ² may be the same or different.

Among the compounds represented by the above formula (20), the compound having a terminal epoxy group (also referred to as an epoxy resin) is preferably a compound represented by the following formula (120).

(Where
R ² represents an aliphatic group or an aromatic group. )

Specific examples of the compound represented by the formula (120) include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A. Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as tetrachlorobisphenol A and tetrafluorobisphenol A, and other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene Epoxy resin, 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) ) Epoxy resin obtained by glycidylation of trisphenols such as phenyl) ethylidene) bisphenol, epoxy resin obtained by glycidylation of tetrakisphenols such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane, phenol novolac, Glycidyl ethers such as novolak-type epoxy resins obtained by glycidylation of novolaks such as cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, glycidyl esters such as diglycidyl esters of hexahydrophthalic acid and dimer acid And the like. These compounds having a terminal epoxy group may be used alone or in combination.

Among the compounds represented by the above formula (20), the compound having a terminal episulfide group (also referred to as episulfide resin) is preferably a compound represented by the following formula (121).

(Where
R ² represents an aliphatic group or an aromatic group. )

Specific examples of the compound represented by the formula (121) include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A. Bisphenol type episulfide resin obtained by thioglycidylation of bisphenols such as tetrachlorobisphenol A and tetrafluorobisphenol A, and other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene Thioglycidylated episulfide resin, 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) ) -1-Methylethyl) phenyl) ethylidene) episulfide resins obtained by thioglycidylation of trisphenols such as bisphenol, tetrakisphenols such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane and thioglycidyl Thioglycidyl ethers such as novolak-type episulfide resins obtained by thioglycidylation of novolaks such as modified episulfide resins, phenol novolaks, cresol novolaks, bisphenol A novolaks, brominated phenol novolaks, brominated bisphenol A novolaks, And thioglycidyl esters such as dithioglycidyl ester of dimer acid. These compounds having a terminal episulfide group may be used alone or in combination of two or more.

R ¹ in the formula (31) is preferably a hydrocarbon group selected from the group consisting of hydrocarbon groups represented by the following formulas (301) to (306).

(Where
i represents an integer of 1 to 12, and may be 1 to 10. )

Among the compounds represented by the above formula (31), the compound having a terminal isocyanate group (isocyanate compound) is preferably a compound represented by the following formula (122).

(Where
R ¹ represents an aliphatic group or an aromatic group. )

Specific examples of the compound represented by the formula (122) include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, lysine diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) -cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, toluene diisocyanate (each isomer), naphthalene diisocyanate (each isomer), etc. it can. More preferably, the compound represented by the formula (122) is an aliphatic diisocyanate having 4 to 20 carbon atoms or an alicyclic diisocyanate having 8 to 20 carbon atoms. Among these, hexamethylene diisocyanate and isophorone diisocyanate are preferable in terms of weather resistance, heat-resistant yellowing, and industrial availability. These isocyanate compounds may be used alone or in combination of two or more.

Among the compounds represented by the above formula (31), the compound having a terminal isothiocyanate group (isothiocyanate compound) is preferably a compound represented by the following formula (123).

(Where
R ¹ represents an aliphatic group or an aromatic group. )

Specific examples of the compound represented by the formula (123) include tetramethylene diisothiocyanate, pentamethylene diisothiocyanate, hexamethylene diisothiocyanate, 2,2,4-trimethyl-1,6-diisothiocyanatohexane. Lysine diisothiocyanate, isophorone diisothiocyanate, 1,3-bis (isothiocyanatomethyl) -cyclohexane, 4,4'-dicyclohexylmethane diisothiocyanate, 4,4'-diphenylmethane diisothiocyanate, toluene diisothiocyanate (Each isomer), naphthalene diisothiocyanate (each isomer) and the like. More preferably, the compound represented by the formula (123) is an aliphatic diisocyanate having 4 to 20 carbon atoms or an alicyclic diisothiocyanate having 8 to 20 carbon atoms. These compounds having a terminal isothiocyanate group may be used alone or in combination.

Hereinafter, the method for producing a compound according to this embodiment will be described by taking the reaction between an epoxy resin and an isothiocyanate compound as an example. The same method is used when an episulfide resin is used instead of an epoxy resin. In the following description, an epoxy resin can be read as an episulfide resin, and an epoxy group can be read as an episulfide group. The same applies to the case where an isocyanate compound is used instead of the isothiocyanate compound, and the isothiocyanate group can be read as an isocyanate group in the isothiocyanate compound and isocyanate compound in the following description.

The isothiocyanate compound is preferably used in such an amount that the isothiocyanate group is 20 to 60 equivalent% with respect to the epoxy group. The amount of the isothiocyanate compound used is more preferably 25 to 50 equivalent%, still more preferably 30 to 47 equivalent%, and still more preferably 30 to 45 equivalent%. The isocyanate group in the isocyanate compound reacts with an epoxy group to form a ring structure. In addition, an isothiocyanurate ring is formed by forming a thiourethane bond with an alcoholic hydroxyl group in an epoxy resin or by cyclization trimerization of an isothiocyanate group. Used to form.

The reaction is usually performed in the presence of a catalyst. Examples of the catalyst include metal alcoholates such as butoxylithium and methoxysodium, Lewis acids such as lithium chloride and aluminum chloride, and mixtures of Lewis acids and Lewis bases such as triphenylphosphine oxide, tetramethylammonium, tetraethylammonium, and tetrabutyl. Chlorides such as ammonium and benzyltributylammonium, quaternary ammonium salts such as bromide, iodide and acetate, triethylamine, N, N-dimethylbenzylamine, 1,8-diazabicyclo [5.4.0] undecene-7, 1,4 -Tertiary amines such as diazabicyclo [2.2.2] octane, and imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole. These catalysts may be used alone or in combination of two or more. As the catalyst, quaternary ammonium salts and tertiary amines are particularly preferable.

The amount of catalyst used is usually in the range of 5 ppm to 2 wt% with respect to the total weight of the epoxy resin. The amount of catalyst used is preferably 20 ppm to 0.5 wt%. The catalyst can also be used after diluting in a suitable solvent.

The production method according to this embodiment can be carried out without a solvent or in the presence of a suitable solvent.

When using a solvent, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, xylene, toluene, methyl cellosolve acetate, tetrahydrofuran It is preferable to use a solvent which does not contain active hydrogen such as.

The reaction temperature is usually from 80 ° C to 300 ° C. The temperature is preferably 100 ° C to 260 ° C, more preferably 120 ° C to 220 ° C. If the reaction temperature is too low, the activity of the catalyst is low, and side reactions such as formation of isocyanurate rings occur. Moreover, even if the reaction temperature is too high, the activity of the catalyst is lowered and the side reaction proceeds.

In the production of the compound according to the present embodiment, it is preferable that the epoxy resin is heated to a predetermined temperature, and moisture in the resin is removed as much as possible by blowing dry air, nitrogen, etc., and then the isothiocyanate compound and the catalyst are added. . The charging method of the isothiocyanate compound and the catalyst can be selected as appropriate, and may be charged all at once, may be charged in several times, or the isothiocyanate compound is charged continuously. May be. At this time, the isothiocyanate and the catalyst may be charged simultaneously or separately. In the case of continuous charging, the charging time is preferably 1 to 10 hours, more preferably 2 to 5 hours. When the charging time is short, the amount of isothiocyanurate ring produced may increase.

In the compound according to this embodiment, preferably, 20 to 45 equivalent% (preferably 22 to 42 equivalent%, more preferably 25 to 40 equivalent%) of the epoxy group in the epoxy resin is the isothiocyanate group in the isothiocyanate compound. To form an oxazolidin-2-thione ring (thiazoline-2-one ring in the reaction of episulfide resin and isocyanate compound, and thiazoline thione ring in the reaction of episulfide resin and isothiocyanate compound).

The proportion of epoxy groups in the epoxy resin that are involved in the oxazolidine-2-thione ring is, for example, an instrument such as a method for measuring the Oxdation rate by a chemical method, infrared spectroscopy, or nuclear magnetic resonance spectroscopy. It can be determined by a quantitative method using an analytical technique.

The Oxdation rate is, for example, an equivalent percentage of the epoxy group forming the oxazolidine-2-thione ring to the original epoxy group. When the epoxy group is not substantially consumed except for the reaction that forms an oxazolidine-2-thione ring, the epoxy equivalent (referred to as Ep1) and weight (referred to as Wt1) of the used epoxy resin, and the obtained oxazolidine-2 -Using the epoxy equivalent (referred to as Ep2) and weight (referred to as Wt2) of the thione ring-containing epoxy resin, the Oxd conversion rate is obtained by the following formula.
Oxd conversion rate = 100− (Wt2 ÷ Ep2) ÷ (Wt1 ÷ Ep1) × 100

The compound (resin) according to this embodiment may contain a thiourethane bond obtained by a reaction between a part or all of the alcoholic hydroxyl groups in the epoxy resin and the isothiocyanate group in the isothiocyanate compound. The amount of thiourethane bonds is preferably 0.9 equivalent / kg or less, more preferably 0.01 to 0.7 equivalent / kg, still more preferably 0.05 to 0.6 equivalent / kg, and still more preferably 0.1 ~ 0.5 equivalent / kg.

The compound (resin) according to this embodiment can contain an isothiocyanurate ring in which the isothiocyanate group in the isothiocyanate compound is cyclized and trimerized. The content of the isothiocyanurate ring is preferably 40 equivalent% or less of the content of the oxazolidine-2-thione ring, more preferably 30 equivalent% or less, still more preferably 20 equivalent% or less, and even more preferably 10 equivalent% or less. is there. If there are too many isothiocyanurate rings, the polymerization stability may be reduced during production.

It is preferable that the compound (resin) according to this embodiment does not substantially contain an isocyanate group.

The melt viscosity of the compound (resin) according to this embodiment is preferably low in order to improve the flowability. Specifically, the melt viscosity at 125 ° C. is preferably 8000 mPa · s or less. More preferably, it is 6000 mPa * s or less, More preferably, it is 4000 mPa * s or less, More preferably, it is 3000 mPa * s or less.

The amount of hydrolyzable chlorine in the compound (resin) according to the present embodiment is not particularly limited, but is preferably 500 ppm or less when used in, for example, electric / electronic applications. More preferably, it is 100 ppm or less.

When the compound (resin) of the present invention has an epoxy group, part or all of the epoxy group can be modified with a modifier.

The modifier is not particularly limited as long as it has a functional group that reacts with an epoxy group. For example, phenols such as xylenol, t-butylphenol, nonylphenol, bisphenol A, hydroquinone, n-butanol, butyl cellosolve, polyethylene Alcohols such as glycol monoethyl ether, ethylene glycol, polypropylene glycol, butylamine, octylamine, diethylamine, methylbutylamine, monoethanolamine, diethanolamine, N-methylethanolamine, triethylamine hydrochloride, N, N-dimethylethanolamine acetate , Amines such as aminoethylethanolamine dimethyl ketimine, acetic acid, lactic acid, 2-ethylhexanoic acid, lauric acid, 12-hydroxystear Phosphate, benzoic acid, carboxylic acids such as dimethanol propionic acid, sulfides such as diethyl disulfide acetate mixture, .gamma.-mercaptopropyl dimethoxymethyl silane, such as mercaptans such as .gamma.-mercaptopropyl trimethoxysilane.

Further, for example, after modification with amines, conversion to an ionic group such as conversion of an amino group into an ammonium salt using acetic acid or the like can also be performed.

[Curable composition]
The compound (resin) according to the present embodiment can be mixed with a curing agent and used to prepare a curable composition.

When the curing form is curing using an epoxy group, examples of the curing agent include ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, aliphatic amines such as N-ethylaminopiperazine, and metaphenylenediamine. , Aromatic amines such as paraphenylenediamine, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenolsulfone, 4,4′-diaminodiphenolmethane, 4,4′-diaminodiphenol ether , Mercaptans such as mercaptopropionic acid esters, terminal mercapto compounds of epoxy resins, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, biphenol, dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1 -(4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) phenol resins such as bisphenol, phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak Acid anhydrides such as polyazeline acid anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride Imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, hydrazines such as adipic acid dihydrazide, dimethylbenzylamine, 1,8-diazabicyclo [5.4.0] undecene-7 And tertiary amines such as dicyandiamide and the like. Moreover, these hardening | curing agents may be used individually or may use multiple types together.

In the case of curing using a crosslinkable group incorporated by modification of an epoxy group or a secondary hydroxyl group generated by modification, examples of the curing agent include a melamine resin, a polyisocyanate compound, and a blocked isocyanate compound. Used. Moreover, these hardening | curing agents may be used individually or may use multiple types together.

Examples of the melamine resin include hexamethoxymethylol melamine, methyl butylated melamine, butylated melamine and the like. These melamine resins may be used alone or in combination of two or more.

Polyisocyanate compounds include tetramethylene diisocyanate, pentamethylene diisocyanate, HDI, 2,2,4 (or 2,4,4) -trimethyl-1,6-diisocyanatohexane, lysine diisocyanate, isophorone diisocyanate, 1,3 -Bis (isocyanatomethyl) -cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, Examples include diisocyanates such as norbornane diisocyanate and polyisocyanates derived from these diisocyanates. These polyisocyanates may be used alone or in combination of two or more.

Examples of the polyisocyanate derived from diisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, and allophanate type polyisocyanate. These polyisocyanate compounds may be used alone or in combination.

As the blocked isocyanate compound, a compound obtained by blocking the diisocyanate and / or polyisocyanate compound with a blocking agent is used.

Examples of the blocking agent include alcohols, phenols, oximes, lactams, active methylenes and the like. These blocking agents may be used alone or in combination of two or more.

The amount of the curing agent used can be arbitrarily selected with respect to the total amount including the compound according to the present embodiment, but is usually 0.1 to 90% by weight. The amount of the curing agent used is preferably 0.1 to 50% by weight.

The curable composition can contain a solvent, if necessary. Examples of the solvent include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, naphtha, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ether acetate. Can be appropriately selected from the group of esters such as methanol, isopropanol, n-butanol, alcohols such as butyl cellosolve and butyl carbitol, and water according to the purpose and application. These solvents may be used alone or in combination of two or more.

The curable composition can contain a curing accelerator as necessary. Examples of the curing accelerator include imidazoles, tertiary amines, phosphines, aminotriazoles, tin-based and zinc-based metal catalysts. These curing accelerators may be used alone or in combination of two or more.

In the curable composition, pigments, fillers, additives and the like commonly used in the technical field as shown below can be used. For example, organic pigments such as quinacridone, azo, and phthalocyanine, inorganic pigments such as titanium oxide, metal foil pigments, rust preventive pigments, fillers such as barium sulfate, calcium carbonate, silica, carbon black, talc, clay, UV absorbers such as hindered amines, benzotriazoles, and benzophenones, hindered phenols, phosphorus, sulfur and hydrazide antioxidants, silane and titanium coupling agents, leveling agents, rheology control Additives, pigment dispersants, anti-repellent agents, antifoaming agents and the like. Moreover, reinforcing materials, such as glass fiber, glass cloth, and carbon fiber, can be contained as needed.

The curable composition according to this embodiment has both excellent adhesion and good flowability, and paints such as powder paints, electrodeposition paints and PCM paints, adhesives, sealing materials, molding materials, composite materials, and laminates. It is suitably used as a material such as a plate or a sealing material.

≪Resin having an isothiocyanurate structure≫
<Preferred structure>
A preferred third resin in the present embodiment has two or more structural units represented by the following formula (40). The resin further has one or more structural units selected from the group consisting of monovalent, divalent or trivalent groups represented by the following formulas (41) to (47). R ³ in the structural units represented by formulas (41) to (47) may be directly bonded to the isothiocyanate group to form the structural unit of formula (40). N in one structural unit represented by formulas (41) to (47) is not directly bonded to N in the other structural units represented by formulas (41) to (47).

(Where
R ³ represents an organic group, R ⁴ represents an aliphatic group or an aromatic group, X ³ represents an oxygen atom or a sulfur atom. A plurality of R ³ , R ⁴ and X ³ in the same molecule may be the same or different. R ³ may be an aliphatic group or an aromatic group. )

Usually, substantially all of the nitrogen atoms that make up the polyisothiocyanate are bonded to at least one carbon atom. That is, the respective structural units are not directly bonded with each other. In addition, R ³ in each structural unit may be directly bonded to an isothiocyanate group to form a structural unit represented by the formula (40). For example, a monofunctional repeating unit represented by the formula (46) or a bifunctional repeating unit represented by the formula (47) is obtained by bonding the structural unit represented by the formula (41) and the isothiocyanate group. Units may be formed. The polyisothiocyanate may have an isothiocyanate group that is not bound to R ³ .

The functional group represented by —X ³ —R ⁴ contained in the formulas (43) and (45) will be described.

In a method for producing a polyisothiocyanate described later, an N, N′-disubstituted dithioalophanoic acid bond represented by formula (43) or an N-substituted-O-substituted thiocarbamic acid represented by formula (45) When producing a polyisothiocyanate having an ester group or an N-substituted-S-substituted dithiocarbamate group, a hydroxy compound or a thiol is used. The functional group represented by —X ³ —R ⁴ is a group derived from this hydroxy compound or thiols. When a hydroxy compound is used, X ³ is an oxygen atom, and when thiols are used, X ³ is a sulfur atom. It is.

R ³ in the formulas (40) to (47) is preferably an aliphatic group having 1 to 22 carbon atoms, more preferably an aliphatic group having 1 to 18 carbon atoms, as the aliphatic group. As the aromatic group, an aromatic group having 6 to 22 carbon atoms is preferable, and an aromatic group having 6 to 15 carbon atoms is more preferable. A group having 7 to 20 carbon atoms having an aliphatic group having 1 to 5 carbon atoms and an aromatic group having 6 to 15 carbon atoms bonded to the aliphatic group is also preferable.

Among these, R ³ is preferably a divalent group represented by the following formulas (301) to (306).

(Where
i represents an integer of 1 to 12, and may be 1 to 10. )

Specific examples of R ^4, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, a cyclopentyl group, a cyclohexyl group, Cycloheptyl group, cyclooctyl group, methylcyclopentyl group, ethylcyclopentyl group, methylcyclohexyl group, ethylcyclohexyl group, propylcyclohexyl group, butylcyclohexyl group, pentylcyclohexyl group, hexylcyclohexyl group, dimethylcyclohexyl group, diethylcyclohexyl group, dibutylcyclohexyl Group, phenyl group, methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, octylphenyl group, nonylphenyl Group, cumylphenyl group, dimethylphenyl group and the like.

The structural units represented by the above formulas (41) to (47) constituting the resin are surprisingly high in heat resistance and excellent in adhesion, particularly adhesion to a metal surface. Although it is not clear about the mechanism that exerts such an effect, the present inventors have improved the heat resistance by having a stable six-membered ring structure, and the sulfur atom contained in the bond increases the adhesion. I guess it will be effective.

The content of bonds that contribute to the development of heat resistance also correlates with the number average molecular weight Mn described above. The value (Mn / n ¹ ) obtained by dividing the number average molecular weight of the resin by the number n ¹ of sulfur atoms constituting the nitrogen-carbon-sulfur bond and oxygen atoms constituting the nitrogen-carbon-oxygen bond contained per molecule is , Preferably 300 or less, more preferably 200 or less, still more preferably 150 or less. The resin composition of the present embodiment has an effect in terms of adhesion to a metal as described above. From the viewpoint of exhibiting such an effect, the resin has many bonds per molecule. It is preferable to have. On the other hand, when the resin has too many of the above bonds, in particular, the resin has the above formulas (6) to (8), (11) to (14), (41), (42), (45) , (46) or (47), the flexibility, which is one of the coating film performances, may be impaired. From such a viewpoint, (Mn / n ¹ is preferably 50 or more, more preferably 70 or more. For example, n ¹ is the number of bonds per unit weight (1 g) of the resin X ¹ (unit mol / g). ), for example determined by the infrared absorption spectrum and ¹ H-NMR or the like, the number average molecular weight above from (Mn), ^formula. can be calculated by n ¹ = Mn · ^X 1 resin nitrogen - carbon - sulfur bonds And n ¹ is the total number of sulfur atoms and oxygen atoms constituting each bond.

<Preferred production method>
The resin according to the present embodiment is preferably a resin obtained by reacting a compound having a nitrogen-carbon-sulfur bond with polyisoisothiocyanate. The nitrogen-carbon-sulfur bond is composed of a nitrogen atom, a carbon atom, and a sulfur atom, which are bonded in this order.

In addition, the resin according to this embodiment is preferably a resin obtained by a method including polymerizing a compound represented by the following formula (33).

(Where
R ³ represents an organic group and may be an aliphatic group or an aromatic group. )

In the above formula (30), R ³ represents an aliphatic group, an aromatic group or a group composed of a combination thereof (aliphatic group substituted with an aromatic group). The compound of the formula (30) used as a monomer for polymerization may be a combination of two or more compounds having different R ³ . The aliphatic group and aromatic group as R ³ may have an oxygen atom, a nitrogen atom or the like in addition to the carbon atom. As the aliphatic group, an aliphatic group having 1 to 22 carbon atoms is preferable, and an aliphatic group having 1 to 18 carbon atoms is more preferable. The aromatic group is preferably an aromatic group having 6 to 22 carbon atoms, more preferably an aromatic group having 6 to 15 carbon atoms. A group having 7 to 20 carbon atoms having an aliphatic group having 1 to 5 carbon atoms and an aromatic group having 6 to 15 carbon atoms bonded to the aliphatic group is also preferable.

Specific examples of R ³ include linear hydrocarbon groups such as methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene; cyclopentane, cyclohexane, cycloheptane, cyclooctane, bis (cyclohexyl) methane, etc. A group derived from an unsubstituted alicyclic hydrocarbon; methylcyclopentane, ethylcyclopentane, methylcyclohexane (each isomer), ethylcyclohexane (each isomer), propylcyclohexane (each isomer), butylcyclohexane (each isomer) ), Pentylcyclohexane (each isomer), hexylcyclohexane (each isomer) and other alkyl-substituted cyclohexane-derived groups; dimethylcyclohexane (each isomer), diethylcyclohexane (each isomer), dibutylcyclohexane (each isomer) Groups derived from dialkyl-substituted cyclohexane such as 1,5,5-trimethylcyclohexane, 1,5,5-triethylcyclohexane, 1,5,5-tripropylcyclohexane (each isomer), 1,5,5-tributylcyclohexane Groups derived from trialkyl-substituted cyclohexane such as (each isomer); monoalkyl-substituted benzenes such as toluene, ethylbenzene, and propylbenzene; dialkyl-substituted benzenes such as xylene, diethylbenzene, and dipropylbenzene; derived from aromatic hydrocarbons such as benzene Group and the like.

Among these, one or more groups selected from the group consisting of groups derived from hexane, benzene, diphenylmethane, toluene, cyclohexane, xylenyl, methylcyclohexane, isophorone, or dicyclohexylmethane are preferable. The “derived group” refers to a group having a structure in which two hydrogen atoms are removed from the compound.

R ³ in the above formula (30) is more preferably a group represented by the following formulas (301) to (306).

(Where
i represents an integer of 1 to 12, and may be 1 to 10. )

More preferably, the isothiocyanate represented by the formula (30) is hexamethylene diisothiocyanate, isophorone diisothiocyanate, 4,4′-dicyclohexylmethane diisothiocyanate, 4,4′-diphenylmethane diisothiocyanate, toluene. Examples include diisothiocyanate (each isomer) and naphthalene dithiocyanate (each isomer).

Next, a method for producing a resin (polyisothiocyanate) according to this embodiment will be described.

The polyisothiocyanate according to this embodiment can be obtained, for example, by polymerizing monomer diisothiocyanate alone. The polymerization of the monomer diisothiocyanate is preferably performed in the presence of a catalyst such as an isothiocyanurate-forming catalyst described later. In addition, when polymerizing the monomer diisothiocyanate, using a hydroxy compound or thiols as an auxiliary material, a part of the isothiocyanate group is urethanated by the reaction between the diisothiocyanate and the hydroxy compound or thiols, Polyisothiocyanate can also be obtained by allophanatization.

Monomer diisothiocyanate refers to a compound represented by the above formula (33).

Hydroxy compounds include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, dodecanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, methylcyclopentanol, ethylcyclopentanol, Methylcyclohexanol, ethylcyclohexanol, propylcyclohexanol, butylcyclohexanol, pentylcyclohexanol, hexylcyclohexanol, dimethylcyclohexanol, diethylcyclohexanol, dibutylcyclohexanol, phenol, methylphenol, ethylphenol, propylphenol, butylphenol, pentyl Phenol, hexylphenol, o Tylphenol, nonylphenol, cumylphenol, dimethylphenol, methylethylphenol, methylpropylphenol, methylbutylphenol, methylpentylphenol, diethylphenol, ethylpropylphenol, ethylbutylphenol, dipropylphenol, dicumylphenol, trimethylphenol, triethylphenol And naphthol. Further, ethylene glycol, 1,2- or 1,3-propylene glycol, 1,3-, 1,4- or 2,3-butylene glycol, 1,6-hexanediol, neopentyl glycol, neopentyl glycol hydroxypivalin Low molecular weight compounds such as acid esters, 2-ethyl-1,3-hexanediol, trimethylolpropane, glycerin, 1,2,6-hexanetriol, and polyester polyols and polyether polyols having a number average molecular weight of about 200 to 10,000 Etc. can also be used.

When a hydroxy compound is used, the isothiocyanate group / hydroxyl group equivalent ratio of the hydroxy compound and the monomer diisothiocyanate can be selected from a value of about 10 to 100 according to the purpose. Similarly, when using thiols, the isothiocyanate group / thiol group equivalent ratio can be selected from a value of about 10 to 100 according to the purpose.

The isothiocyanurate-forming catalyst for forming the isothiocyanurate group represented by the above formula (41), (46) or (47) is preferably a quaternary ammonium salt, more preferably a quaternary ammonium hydroxy. And quaternary ammonium carboxylic acid, more preferably quaternary ammonium carboxylic acid.

Specific examples of the isothiocyanuration catalyst include tetraalkylammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium acetate, tetraethylammonium acetate, tetrabutyl acetate. Examples include organic weak acid salts such as ammonium salts. Metal salts of alkyl carboxylic acids such as acetic acid, valeric acid, isovaleric acid, caproic acid, octylic acid and myristic acid can also be used, but organic weak acid salts and the like are preferred from the viewpoint of reducing the amount used.

The above isothiocyanuration catalyst may be diluted. A hydroxy compound can be used as a diluent. Examples of the hydroxy compound include methanol, ethanol, 1- or 2-butanol, 2-methyl-1-propanol, 1,2- or 1,3-propylene glycol, 1,3-, 1,4- or 2, Examples thereof include alcoholic hydroxy compounds such as 3-butylene glycol, glycerin and cyclohexanol, and phenolic hydroxy compounds such as phenol, cresol, xylenol and trimethylphenol. From the viewpoint of the crystallinity of the polyisocyanates obtained from these, alcohols having side chains such as 2-butanol, 2-methyl-1-propanol, 1,3- or 2,3-butanediol are preferred. Two or more types may be mixed. Thiols may be used in place of the hydroxy compound.

When the above-mentioned monomer diisothiocyanate alone or the isothiocyanate compound obtained by urethanizing the monomer diisothiocyanate with a hydroxy compound was reacted in the presence of the above-mentioned isothiocyanuration catalyst, it was diluted with the hydroxy compound. The concentration of the isothiocyanuration catalyst can be 1 to 20% by mass. The concentration is preferably 1 to 10% by mass. If it is 1 mass% or more, the amount of the hydroxy compound entrained in the isothiocyanurate-forming catalyst does not increase too much, and the resulting polyisothiocyanate and the physical properties of the coating film formed thereby are unlikely to deteriorate. When the concentration is 20% by mass or less, the cocatalyst effect of the accompanying hydroxy compound is not lowered, and as a result, the amount of the isothiocyanurate-forming catalyst used is increased and the polyisothiocyanate is hardly colored.

Unless the isothiocyanurate catalyst is deactivated by an acidic component contained in a trace amount in a raw material such as monomeric diisothiocyanate, the amount of the isothiocyanurate catalyst used is based on the weight of the monomeric diisothiocyanate. The content is 1 ppm to 10%, preferably 10 ppm to 5%. If the amount of the catalyst is 1 ppm or more, the function as an isothiocyanurate-forming catalyst can be sufficiently exerted. If the amount of the catalyst is 3% or less, the isothiocyanurate-forming catalyst is deactivated, so that the amount of addition of a reaction terminator (described later) such as an acidic phosphoric acid compound or acidic phosphoric acid ester compound can be reduced.

The isothiocyanuration reaction is performed at 30 ° C to 120 ° C, preferably 50 ° C to 100 ° C. The progress of the reaction can be confirmed by ¹ H-NMR analysis of the reaction solution. When the reaction reaches a desired conversion rate, the reaction is stopped by deactivating the catalyst by adding a reaction terminator. The conversion rate is suitably selected in the range of 10 to 60%, preferably 10 to 30%. With a low conversion rate, it is possible to obtain a polyisothiocyanate having a lower viscosity, but a conversion rate of 10% or more is preferable from the viewpoint of productivity. On the other hand, if the conversion is 60% or less, the viscosity of the polyisothiocyanate does not become too high, which is preferable.

The conversion rate can be obtained by the following formula. In the ¹ H-NMR chart, the conversion rate is calculated from the peak of the methyl group of tetramethylsilane at 0 ppm and the integrated value (A) of the peak of 3.5 ppm and the integrated value (B) of the peak of 4.8 ppm. Calculated by the formula.
Conversion rate (%) = B / (A + B) × 100

As the reaction terminator for the isothiocyanuration reaction, one or more compounds selected from the group consisting of acidic phosphate compounds and acidic phosphate ester compounds are used.

The acidic phosphoric acid compound is an inorganic acid, and examples thereof include phosphoric acid, phosphorous acid, hypophosphorous acid, diphosphorous acid, hypophosphoric acid, pyrophosphoric acid, and peroxophosphoric acid. Preferably, it is phosphoric acid.

The acidic phosphate ester compound is a compound having an acidic group and an ester group, for example, a monoalkyl phosphate having 2 to 8 carbon atoms, a monoalkyl phosphite, a dialkyl phosphate having 4 to 16 carbon atoms, a dialkyl phosphite, and dilauryl. Examples include phosphate, diphenyl phosphate, monolauryl phosphate, monophenyl phosphate, dilauryl phosphite, diphenyl phosphite, monolauryl phosphite, and monophenyl phosphite. Preferably, it is a monoalkyl phosphate having 3 to 8 carbon atoms, or a dialkyl phosphate having 6 to 16 carbon atoms, more preferably dioctyl phosphate or monooctyl phosphate.

Of these, it is preferable to use an acidic phosphate compound. The addition amount of the acidic phosphoric acid compound is preferably 1 to 10 equivalents, more preferably 1 to 6 equivalents, relative to the stoichiometric amount of the isothiocyanuration catalyst. If the addition amount is 1 equivalent or more, the isothiocyanuration catalyst can be sufficiently deactivated. If the addition amount is 10 equivalents or less, it is preferable without filtering the insoluble matter generated.

When an acidic phosphoric acid compound is used, the deactivated isothiocyanurate-forming catalyst often becomes an insoluble matter and can be removed by filtration. By removing by filtration, the phosphorus derived from the acidic phosphoric acid compound in the polyisothiocyanate can be reduced to the extent that it is detected in a very small amount.

When an acidic phosphoric acid ester compound is used, the salt with the acidic phosphoric acid ester and the isothiocyanuration catalyst is dissolved in the polyisothiocyanate, so that it is mixed into the modified polyisocyanate after the monomeric diisothiocyanate is removed. There is a case.

From the viewpoint of phosphorus concentration in polyisothiocyanate, it is preferable to use an acidic phosphoric acid compound. When an acidic phosphoric acid compound is used, the acidic phosphoric acid compound is added and then maintained at 90 to 150 ° C., preferably 100 to 120 ° C. for 30 to 120 minutes. Improves.

After obtaining the polyisothiocyanate, an acidic phosphoric acid compound and an acidic phosphoric acid ester compound may be added, and particularly an acidic phosphoric acid compound may be added.

As described above, after the isothiocyanuration reaction is stopped, the unreacted monomeric diisothiocyanate and the solvent are removed from the reaction solution for purification. Examples of the purification method include vacuum distillation, solvent extraction and the like, and generally a thin film distiller can be used.

The content of monomeric diisothiocyanate in the purified polyisothiocyanate is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less. The recovered unreacted monomeric diisothiocyanate can be used again.

Polyisothiocyanate can be used by mixing with an organic solvent. In this case, the organic solvent preferably does not have a functional group that reacts with a hydroxyl group and an isocyanate group. As such an organic solvent, an ester compound, a ketone compound, an aromatic compound, or the like can be used.

Polyisothiocyanate has various additives such as curing accelerators, pigments, leveling materials, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, surfactants, etc., depending on the purpose. Can also be used in combination.

Polypolyisothiocyanate can be used in a wide range of fields, including two-component polyurethane paints, sealants, adhesives, inks, coating agents, casting materials, elastomers, foams, plastic raw materials, fiber treatment agents, and one-component curable polyisothiocyanates. .

Hereinafter, the present invention will be specifically described based on examples, but the scope of the present invention is not limited to these examples. “Parts” or “%” in the examples and comparative examples are based on weight unless otherwise specified.

[Analysis method]
(1) ¹ H-NMR analysis About 0.3 g of a sample was weighed, about 0.7 g of deuterated chloroform (Aldrich, USA, 99.8%) and tetramethylsilane (Japan, Jun Wako) as an internal standard substance. A solution in which 0.05 g of Yakuhin Kogyo Co., Ltd., Wako Grade 1) was added and mixed uniformly was used as an NMR analysis sample. The sample was analyzed with a JNM-A400FT-NMR system manufactured by JEOL Ltd.
In addition, the conversion rate of the isocyanate group at the time of polyisocyanate manufacture was computed with the following method.
^{In the 1} H-NMR chart, the methyl group signal of tetramethylsilane was set to 0 ppm, the integrated value (A) of the 3.3 ppm signal derived from the monomeric diisocyanate and the 3.8 ppm signal derived from the isocyanurate structure. The conversion rate was calculated from the integral value (B) according to the following equation.
Conversion rate (%) = B / (A + B) × 100
Moreover, the conversion rate of the isothiocyanate group at the time of polyisothiocyanate manufacture was computed with the following method.
^{In the 1} H-NMR chart, the methyl group signal of tetramethylsilane was set to 0 ppm, the integrated value (A) of the 3.5 ppm signal derived from the monomer diisothiocyanate and the 4.8 ppm derived from the isothiocyanurate structure. The conversion was calculated from the integral value (B) of the signal of
Conversion rate (%) = B / (A + B) × 100

(2) Number average molecular weight Gel permeation chromatography analysis using GPC-8020 manufactured by Tosoh Corporation as a measuring device, tetrahydrofuran as a developing solvent, and TSKgel SuperH3000, SuperH2000 and SuperH1000 manufactured by Tosoh Corporation as columns. Analysis was carried out. About 10 mg of the sample was dissolved in 10 mL of tetrahydrofuran to prepare a measurement sample, and the injection volume was 10 μL. The number average molecular weight was determined by comparison with the elution time of polystyrene having a known molecular weight observed with a differential refractive index detector.

(3) Heat resistance evaluation method TG-8120 (manufactured by RIGAKU) was used to measure thermogravimetric loss under a nitrogen atmosphere under the conditions of 10 mg sample and a heating rate of 10 ° C / min. A was not observed, and B was 5% weight loss within 300 ° C.

(4) Coating Film Evaluation Method The coating film adhesion evaluation was performed as follows. A 1 mm square cut was made in a coating film formed on an aluminum plate (length 10 cm, width 10 cm, thickness 5 mm) and immersed in acetone together with the aluminum plate, and it was examined whether the coating film remained after 24 hours. The same test was conducted 10 times per sample, and A was given when 8 or more films remained, and B was given otherwise.

(5) Copper peel strength Copper peel strength was measured in accordance with JIS C 6481. The copper peel strength is indicated by A, and the bad copper peel strength is indicated by B.

[Example 1]
Adipic acid dihydrazide and polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Corporation) were charged so that the equivalent ratio of isocyanate group to hydrazide group was 1.0, and butyl acetate was mixed to disperse the solid content to 10%. A liquid was prepared. This dispersion was stirred at 120 ° C. for 12 hours. When a part of the reaction solution was collected and analyzed by ¹ H-NMR, a peak around 3.3 ppm derived from isocyanate disappeared. After removing butyl acetate with a rotary evaporator, the heat resistance was evaluated. The evaluation results are shown in Table 1.

[Example 2]
36 g of hydrazine monohydrate was dissolved in 1 L of isopropanol, cooled to 0 ° C., and 50 g of hexamethylene diisothiocyanate was added with stirring. The produced solid was recovered by filtration and analyzed by ¹ H-NMR, whereby it was 4,4′-hexamethylenebisthiosemicarbazide.
The 4,4′-hexamethylene bisthiosemicarbazide and polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Corporation) were evaluated in the same manner as in Example 1 to evaluate heat resistance. The evaluation results are shown in Table 1.

[Example 3]
36 g of hydrazine monohydrate was dissolved in 1 L of isopropanol, cooled to 0 ° C., and 50 g of hexamethylene diisocyanate was added with stirring. The produced solid was recovered by filtration and analyzed by ¹ H-NMR, whereby it was 4,4′-hexamethylene bissemicarbazide.
The 4,4′-hexamethylene bissemicarbazide and polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Corporation) were evaluated in the same manner as in Example 1 to evaluate heat resistance. The evaluation results are shown in Table 1.

[Example 4]
36 g of hydrazine monohydrate was dissolved in 1 L of isopropanol, cooled to 0 ° C., and 280 g of 2-isocyanatoethyl methacrylate was added with stirring. The produced solid was recovered by filtration and analyzed by ¹ H-NMR to find methacrylic acid (2- (hydrazinecarboamido) ethyl).
Next, 100 g of the methacrylic acid (2- (hydrazinecarboamido) ethyl) was dissolved in 1 L of toluene, and 80 g of methyl methacrylate and 0.5 g of azobisisobutyronitrile were added and heated to 80 ° C. After 3 hours, the reaction solution was collected and analyzed by ¹ H-NMR. As a result, the double bond constituting methyl methacrylate disappeared. Toluene was distilled off with a rotary evaporator to obtain a polymer having a semicarbazide group.
The polymer and polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Corporation) were evaluated in the same manner as in Example 1 to evaluate heat resistance. The evaluation results are shown in Table 1.

[Examples 5 to 8]
Except that hexamethylene diisocyanate was used instead of polyisocyanate, the same method as in Example 1 was performed to evaluate heat resistance. The evaluation results are shown in Table 1.

[Example 9]
In the same manner as in Example 4, methacrylic acid (2- (hydrazinecarboamido) ethyl) was produced. The methacrylic acid (2- (hydrazinecarboamido) ethyl) and polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Corporation) were evaluated in the same manner as in Example 1 to evaluate the heat resistance. The evaluation results are shown in Table 1.

[Reference Example 1]
The heat resistance was evaluated in the same manner as in Example 1 except that hexamethylenediol was used instead of adipic acid dihydrazide in Example 1. The evaluation results are shown in Table 1.

[Reference Example 2]
The heat resistance was evaluated in the same manner as in Example 1 except that hexamethylenediamine was used instead of adipic acid dihydrazide in Example 1. The evaluation results are shown in Table 1.

[Reference Example 3]
100 g of methacrylic acid (2-hydroxyethyl) was dissolved in 1 L of toluene, 80 g of methyl methacrylate and 0.5 g of azobisisobutyronitrile were added and heated to 80 ° C. After 3 hours, the reaction solution was collected and analyzed by ¹ H-NMR. As a result, the double bond constituting methyl methacrylate disappeared. Toluene was distilled off with a rotary evaporator to obtain a polymer having a hydroxy group. The polymer and polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Corporation) were evaluated in the same manner as in Example 1 to evaluate heat resistance. The evaluation results are shown in Table 1.

[Reference Examples 4 to 6]
Except that hexamethylene diisocyanate was used in place of the polyisocyanate of Comparative Example 1, the same method as in Example 1 was performed to evaluate the heat resistance. The evaluation results are shown in Table 1.

[Reference Example 7]
The heat resistance was evaluated in the same manner as in Example 1 except that methacrylic acid (2-hydroxyethyl) was used instead of adipic acid dihydrazide in Example 1. The evaluation results are shown in Table 1.

[Production Example 1] Production of polyisothiocyanate A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube was placed in a nitrogen atmosphere, and 600 g of hexamethylene diisothiocyanate was charged. Was maintained at 130 ° C., and 1.0 g of the cyclic trimerization catalyst tetramethylammonium capryate was added. When the conversion of the isothiocyanate group reached 30%, phosphoric acid was added to stop the reaction. After the reaction solution was filtered, unreacted hexamethylene isothiocyanate was removed with a thin-film distiller. The number average molecular weight of the obtained polyisothiocyanate was 620, and the average number of isothiocyanate groups was 3.2.

[Example 10]
Acrylic polyol (Setalux 1903; manufactured by NUPLEX, trade name; hydroxyl group concentration 4.5% (resin basis), resin solid content 75%) and the polyisothiocyanate obtained in Production Example 1 have an equivalent ratio of isothiocyanate groups to hydroxyl groups. Then, 0.5 mass% of dibutyltin dilaurate was added to the resin, and butyl acetate was mixed to prepare a resin composition having a solid content of 50%. This resin composition was applied to an aluminum plate with an applicator so that the resin film thickness was 40 μm. After setting for 10 minutes at room temperature, it was kept in an oven at 150 ° C. for 10 hours to obtain a cured coating film. The adhesion of the obtained cured coating film was evaluated. The evaluation results are shown in Table 2.

[Example 11]
4,4′-dicyclohexylmethanediamine and the polyisothiocyanate obtained in Production Example 1 were charged so that the equivalent ratio of isothiocyanate groups to amino groups was 1.0, and butyl acetate was mixed to obtain a solid content of 50 % The same method as in Example 1 was performed except that a resin composition was prepared. Table 2 shows the evaluation results of the cured coating film.

[Example 12]
Adipic acid dihydrazide and the polyisothiocyanate obtained in Production Example 1 were charged so that the equivalent ratio of the isothiocyanate group and hydrazide group was 1.0, and ethanol was mixed to prepare a resin composition having a solid content of 10%. Except that, the same method as in Example 10 was performed. Table 2 shows the evaluation results of the cured coating film.

[Example 13]
36 g of hydrazine monohydrate was dissolved in 1 L of isopropanol, cooled to 0 ° C., and 280 g of 2-isocyanatoethyl methacrylate was added with stirring. The produced solid was recovered by filtration and analyzed by ¹ H-NMR to find methacrylic acid (2- (hydrazinecarboamido) ethyl).
Next, 100 g of the methacrylic acid (2- (hydrazinecarboamido) ethyl) was dissolved in 1 L of toluene, and 80 g of methyl methacrylate and 0.5 g of azobisisobutyronitrile were added and heated to 80 ° C. After 3 hours, the reaction solution was collected and analyzed by ¹ H-NMR. As a result, the double bond constituting methyl methacrylate disappeared. Toluene was distilled off with a rotary evaporator to obtain a polymer having a semicarbazide group.
The polymer and the polyisothiocyanate obtained in Production Example 1 were charged so that the equivalent ratio of the isothiocyanate group and the semicarbazide group was 1.0, and butyl acetate was mixed to prepare a resin composition having a solid content of 25%. did. Table 2 shows the results obtained by conducting the same method as in Example 10 using the resin composition and evaluating the cured coating film.

[Example 14]
36 g of hydrazine monohydrate was dissolved in 1 L of isopropanol, cooled to 0 ° C., and 50 g of hexamethylene diisothiocyanate was added with stirring. The produced solid was recovered by filtration and analyzed by ¹ H-NMR, whereby it was 4,4′-hexamethylenebisthiosemicarbazide.
The 4,4′-hexamethylene bisthiosemicarbazide and the polyisothiocyanate obtained in Production Example 1 were charged so that the equivalent ratio of the isothiocyanate group to the thiosemicarbazide group was 1.0, and butyl acetate was mixed. A resin composition having a solid content of 25% was prepared. Table 2 shows the results obtained by conducting the same method as in Example 10 using the resin composition and evaluating the cured coating film.

[Reference Examples 8 to 12]
Evaluation of cured coating film was carried out in the same manner as in Examples 10 to 14 except that isocyanurate type polyisocyanate (Duranate TPA-100; trade name, manufactured by Asahi Kasei Chemicals Corporation) was used instead of polyisothiocyanate. Went. The results are shown in Table 2.

[Example 15]
2-hydroxyethyl methacrylate and the polyisothiocyanate obtained in Production Example 1 were charged so that the equivalent ratio of isothiocyanate groups and hydroxyl groups was hydroxyl group / isothiocyanate group = 1.3, and butyl acetate was added to obtain a solid content of 50 % Resin composition. The resin composition was heated at 130 ° C., isothiocyanate groups heating was continued until the disappearance in ^{1 H-NMR.} Next, this resin composition was applied to an aluminum plate with an applicator so that the resin film thickness was 40 μm. After setting for 10 minutes at room temperature, it was kept in an oven at 150 ° C. for 10 hours to obtain a cured coating film. The adhesion of the obtained cured coating film was evaluated. The evaluation results are shown in Table 2.

[Reference Example 13]
The same method as in Example 15 was carried out except that isocyanurate type polyisocyanate (Duranate TPA-100; trade name, manufactured by Asahi Kasei Chemicals Corporation) was used instead of the polyisothiocyanate obtained in Production Example 1. The cured coating film evaluation results are shown in Table 2.

[Example 16]
In the same manner as in Example 13, methacrylic acid (2- (hydrazinecarboamido) ethyl) was produced, and then a polymer of methacrylic acid (2- (hydrazinecarboamido) ethyl) was obtained.
The polymer and allyl isothiocyanate were charged so that the equivalent ratio of the isothiocyanate group and the semicarbazide group was 1.0, and butyl acetate was mixed to prepare a resin composition having a solid content of 25%. The resin composition was applied to an aluminum plate with an applicator so that the resin film thickness was 40 μm. After setting for 10 minutes at room temperature, it was kept in an oven at 150 ° C. for 10 hours to obtain a cured coating film. The adhesion of the obtained cured coating film was evaluated. The evaluation results are shown in Table 2.

[Reference Example 14]
The same procedure as in Example 16 was performed, except that 2-isocyanatoethyl methacrylate was used instead of allyl isothiocyanate. Table 2 shows the evaluation results of the cured coating film.

[Example 17]
After adding 345 g of tetramethylene diisothiocyanate and 384 g of adipic acid dihydrazide to a 2 L eggplant-shaped flask containing 200 g of water and 800 g of tetrahydrofuran and stirring at 60 ° C. for 12 hours, 7 g of ethyl isothiocyanate was further added and precipitated. The solid was filtered and collected. Next, the above-mentioned solid was added to a 2 L eggplant-shaped flask containing 1000 g of a 2% by weight aqueous sodium hydroxide solution, stirred at 100 ° C. for 8 hours, and the precipitated solid was collected with filter paper. ¹ H-NMR of the collected solid was measured to identify the structure. FIG. 1 shows the ¹ H-NMR spectrum of the solid obtained in Example 17. It is presumed that a resin represented by the following formula (124) was obtained. The number average molecular weight was 5900, and Mn / n ^{1 as} defined above was 150. X ¹ is the integral of the charged concentration of the ¹ H-NMR measurement sample, the peak of the chloroform (7.26 ppm), and the peak of the methylene chain directly bonded to the nitrogen atom forming the ring (2.6 ppm). Obtained from the ratio of values.

[Example 18]
A four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube was placed in a nitrogen atmosphere, 100 g of hexamethylene diisothiocyanate was charged, and the temperature in the reactor was kept at 100 ° C. with stirring. Thereafter, 2 g of tetramethylammonium acetate (2-butanol 5.0 mass% solution) was added as a catalyst and stirred. The reaction solution was appropriately sampled, and when the conversion of the isothiocyanate group reached 21% by ¹ H-NMR analysis, 0.28 g of phosphoric acid (85 mass% aqueous solution) was added to stop the reaction. Thereafter, the mixture was further heated at 100 ° C. for 1 hour, cooled to room temperature, the reaction solution was filtered to remove insoluble matters, and then the monomer diisothiocyanate was removed with a thin-film distiller. The monomer diisothiocyanate concentration was 0.4 mass%, and the number average molecular weight was 860.
A ¹ H-NMR chart of the obtained polyisothiocyanate is shown in FIG. From the NMR chart, it was confirmed that the polyisothiocyanate contains at least a structural unit represented by the formula (28). The number average molecular weight was 1200, and Mn / n ¹ according to the above definition was 100. X ¹ represents the preparation concentration of the ¹ H-NMR measurement sample, the peak of the methylene chain (3.8 ppm) directly bonded to the chloroform peak (7.26 ppm) and the nitrogen atom forming the isothiocyanurate ring. ).
The obtained polyisothiocyanate and acrylic polyol (manufactured by DIC Corporation, trade name: ACRYDIC A-801) were blended so that the isothiocyanate group / hydroxyl group ratio (equivalent) was 1.0, and dibutyltin dilaurate was respectively added. 0.5% based on the solid content of the paint, and a mixture of ethyl acetate / toluene / butyl acetate / xylene / propylene glycol monomethyl ether acetate (weight ratio = 30/30/20/15/5) as a thinner added. The obtained coating solution is adjusted with an air spray gun so as to have a dry film thickness of 50 μm, coated on a copper foil having a thickness of 35 μm, and the copper foil having a thickness of 35 μm is stacked thereon, and an oven maintained at 120 ° C. After baking for 30 minutes, the copper peel strength was evaluated. The results are shown in Table 3.

[Examples 19 to 23]
A polyisothiocyanate was produced in the same manner as in Example 18 with the formulation and conditions shown in Table 3. A coating solution was prepared in the same manner as in Example 18 except that the obtained polyisothiocyanate was used, and the copper peel strength was evaluated. The results are shown in Table 3.

[Comparative Example 15]
Hexamethylene diisocyanate is used instead of hexamethylene diisothiocyanate, 0.1 g of tetramethylammonium acetate (2-butanol 5.0 mass% solution) is used as a catalyst, and phosphoric acid (85 mass% aqueous solution) 12 mg is used. A polyisocyanate was produced in the same manner as in Example 18 except that. The number average molecular weight was 1100. A coating solution was prepared in the same manner as in Example 18 except that the obtained polyisocyanate was used, and the copper peel strength was evaluated. The results are shown in Table 4.

[Comparative Examples 16 to 20]
Polyisocyanate was produced in the same manner as in Example 18 with the formulation and conditions shown in Table 4, and the copper peel strength was evaluated. The results are shown in Table 4.

[Example 24]
A separable flask containing 100 parts of a bisphenol A type epoxy resin (epoxy equivalent 189) was equipped with a stirrer, thermometer, reflux condenser, and nitrogen blowing tube, and the temperature was raised to 150 ° C. with stirring while blowing nitrogen into the flask. The mixture was warmed and stirring was continued for 30 minutes after reaching 150 ° C. While maintaining the reaction temperature at 150 ° C., a mixture of 18.5 parts of hexamethylene diisothiocyanate and 0.05 part of tetrabutylammonium chloride (Wako Pure Chemical) was added dropwise over 2 hours. After completion of dropping, the reaction was carried out while maintaining the temperature at 150 ° C. As a result of ¹ H-NMR analysis (FIG. 3), it was found that a compound containing an oxazolidine-2-thione ring represented by the following formula (125) or (126) was obtained. The number average molecular weight of the obtained compound was 2,000, and no number average molecular weight was 20,000 or more. The number average molecular weight was analyzed by gel permeation chromatography using shodex A-804, A-803, A-802, and A802 manufactured by Showa Denko KK as columns. About 10 mg of the sample was dissolved in 10 mL of tetrahydrofuran to prepare a measurement sample, and the injection volume was 10 μL. The number average molecular weight was determined by comparison with the elution time of polystyrene having a known molecular weight group observed with a differential refractive index detector. Mn / n ¹ according to the above definition was 220. X ¹ is the ratio of the integrated concentration of the charged concentration of the ¹ H-NMR measurement sample and the peak of toluene added as an internal standard (2.3 ppm) and the peak of methine forming a ring structure (4.8 ppm). I asked for it.

The obtained compound, a curing agent (dicyandiamide) and a curing catalyst (2-methylimidazole) are added, and the resulting resin composition is impregnated into a glass cloth and dried to obtain a prepreg having a resin content of 50% by mass. It was. A laminate was produced by stacking four prepregs, and superposing copper foils having a thickness of 35 μm on the top and bottom of the prepregs for 60 minutes under conditions of a temperature of 190 ° C. and a pressure of 20 kg / cm ² . The copper peel strength of the laminate was evaluated. The results are shown in Table 5.

[Examples 25 to 29]
The compounds shown in Table 5 were reacted in the same manner as in Example 24 and subjected to ¹ H-NMR analysis. As a result, an oxazolidine-2-thione ring represented by the above formula (125) or (126) was contained. A compound was obtained. Using the obtained compound, the copper peel strength was evaluated in the same manner as in Example 24. The results are shown in Table 5.

[Examples 30 to 35]
When the compound shown in Table 6 was reacted in the same manner as in Example 24 and subjected to ¹ H-NMR analysis, a compound containing a thiazoline thione ring represented by the following formula (127) or (128) was obtained. It was. Using the obtained compound, the copper peel strength was evaluated in the same manner as in Example 24. The results are shown in Table 6.

[Examples 36 to 41]
The compounds shown in Table 7 were reacted in the same manner as in Example 24 and subjected to ¹ H-NMR analysis. As a result, a thiazolin-2-one ring represented by the following formula (129) or (130) was contained. A compound was obtained. Using the obtained compound, the copper peel strength was evaluated in the same manner as in Example 24. The results are shown in Table 7.

[Examples 42 to 59]
The compounds shown in Tables 8 to 10 were reacted in the same manner as in Example 24 and subjected to ¹ H-NMR analysis. As a result, the oxazolidine-2-thione ring represented by the above formula (125) or (126) was obtained. A compound containing was obtained. Using the obtained compound, the copper peel strength was evaluated in the same manner as in Example 24. The results are shown in Tables 8-10.

[Examples 60 to 62]
Using the compounds shown in Table 11, it was reacted in the same manner as in Example ^24, was subjected to 1 H-NMR analysis, including thiazoline-2-one ring represented by the formula (129) or (130) A compound was obtained. Using the obtained compound, the copper peel strength was evaluated in the same manner as in Example 24. The results are shown in Table 11.

[Comparative Examples 21 to 26]
The compounds shown in Table 12 were reacted in the same manner as in Example 24 and subjected to ¹ H-NMR analysis. As a result, a compound containing an oxazolidone ring represented by the following formula (131) or (132) was obtained. . Using the obtained compound, the copper peel strength was evaluated in the same manner as in Example 24. The results are shown in Table 12.

Claims

It is composed of a nitrogen atom, a carbon atom and a sulfur atom, which are bonded in this order, and at least one of the bond between the carbon atom and the sulfur atom and the bond between the carbon atom and the nitrogen atom is a single bond A resin having a nitrogen-carbon-sulfur bond,
When the number average molecular weight of the resin is Mn and the number of sulfur atoms constituting the nitrogen-carbon-sulfur bond contained per molecule of the resin is n 1 , Mn is 500 or more, Mn / n 1 Is from 50 to 300, and n 1 is represented by the formula: n 1 = X 1 · Mn (X 1 represents the number of sulfur atoms constituting the nitrogen-carbon-sulfur bond contained per 1 g of the resin). Calculated resin.
The resin according to claim 1, wherein the resin has a 5% thermal weight loss temperature of 300 ° C or higher.
A compound having at least one functional group selected from the group consisting of monovalent groups represented by the following formula (1), (2), (3), (4) or (5);
At least one compound selected from the group consisting of monoisocyanate, polyisocyanate, monoisothiocyanate and polyisothiocyanate;
Resin obtained by the reaction of
The compound having at least one functional group selected from the group consisting of monovalent groups represented by formula (1), (2), (3), (4) or (5);
At least one compound selected from monoisothiocyanate and polyisothiocyanate;
The resin of Claim 3 which is resin obtained by reaction of these.
The resin according to claim 3 or 4, wherein the monoisothiocyanate includes a compound represented by the following formula (30).

(In the formula, R 5 represents an aliphatic group having 1 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic group, or an aromatic group having 6 to 25 carbon atoms.)
The cyclic structure derived from a reaction between the functional group represented by the formula (3), (4) or (5) and an isocyanate group or an isothiocyanate group is described in any one of claims 3 to 5. Resin.
The group containing the cyclic structure has two or more structural units selected from the group consisting of divalent groups represented by the following formula (6), (7) or (8). Resin.

(Where
Y 1 represents an organic group, a plurality of Y 1 in the same molecule may be the same or different. )
Resin which has 2 or more of at least 1 type of structural unit chosen from the group which consists of a bivalent group represented by following formula (6), (7) or (8).

(Where
Y 1 represents an organic group, a plurality of Y 1 in the same molecule may be the same or different. )
The number average molecular weight of the resin is Mn, type contained per the resin molecule (6), when (7) or the sum of the number of the structural unit represented by (8) is n 2, Mn Is 500 or more, Mn / n 2 is 50 or more and 300 or less, and n 2 is a formula: n 2 = X 2 · Mn (X 2 is a formula (6), (7) or ( The resin according to claim 7 or 8, which is calculated by the following formula: 8) representing the sum of the number of the structural units represented by 8).
A resin obtained by reacting a compound having a nitrogen-carbon-sulfur bond, which is composed of a nitrogen atom, a carbon atom and a sulfur atom and bonded in this order, with a polyisothiocyanate.
The resin according to any one of claims 3 to 7 and 10, wherein the polyisothiocyanate contains a compound represented by the following formula (32).

(Where
R 6 represents an organic group,
a represents an integer of 2 to 1000. )
The resin according to any one of claims 3 to 7 and 10, wherein the polyisothiocyanate includes a polymer having two or more repeating units represented by the following formula (33).

(Where
R 7 represents an organic group,
R 8 represents an organic group or a single bond,
b represents an integer of 1 or more,
g represents 1 or 2,
A plurality of R 7 , R 8 , b and g in the same molecule may be the same or different. )
The polyisothiocyanate is
Two or more structural units represented by the following formula (40),
At least selected from the group consisting of monovalent, divalent or trivalent groups represented by the following formula (41), (42), (43), (44), (45), (46) or (47) The resin according to any one of claims 3 to 7 and 10, which comprises a compound having one structural unit, wherein a nitrogen atom in the compound is bonded to a carbon atom.

(Where
R 3 represents an organic group, R 4 represents an aliphatic group or an aromatic group, X 3 represents an oxygen atom or a sulfur atom, and a plurality of R 3 , R 4 and X 3 in the same molecule may be the same May be different. )
The resin according to any one of claims 3 to 7 and 10, wherein the polyisothiocyanate contains a compound represented by the following formula (33).

(Where
R 3 represents an organic group. )
Resin obtained by the method including superposing | polymerizing the compound represented by following formula (33).

(Where
R 3 represents an organic group. )
The method for producing a resin according to claim 15, comprising polymerizing the compound represented by the formula (33) in the presence of a catalyst.
Two or more structural units represented by the following formula (40),
At least selected from the group consisting of monovalent, divalent or trivalent groups represented by the following formula (41), (42), (43), (44), (45), (46) or (47) One structural unit, and
The nitrogen atom in one said structural unit represented by Formula (41), (42), (43), (44), (45), (46) or (47) is represented by Formula (41), (42 ), (43), (44), (45), (46) or a resin not directly bonded to a nitrogen atom in the other structural unit represented by (47).

(Where
R 3 represents an organic group, R 4 represents an aliphatic group or an aromatic group,
X 3 represents an oxygen atom or a sulfur atom,
A plurality of R 3 , R 4 and X 3 in the same molecule may be the same or different. )
The resin according to claim 13, 14, 15 or 17, wherein R 3 is an aliphatic group or an aromatic group.
The resin according to claim 18, wherein R 3 is a group represented by the following formula (301), (302), (303), (304), (305) or (306).

(Where
i represents an integer of 1 to 12. )
A resin composition comprising the resin according to any one of claims 1 to 15 and 17 to 19.
A coating material formed from the resin composition according to claim 20.
A water-based paint containing the resin composition according to claim 20.
A resin having a molecular chain represented by the following formula (10).

(Where
P 1 represents an aliphatic group and / or an aromatic group, and Q 1 is selected from the group consisting of divalent groups represented by the following formula (11), (12), (13) or (14). 1 or more types of structural units are represented, Plural P 1 and Q 1 may be the same or different and n represents an integer of 2 or more. )

(Where
R 1 represents an aliphatic group or an aromatic group,
X 2 and Y 2 each independently represent an oxygen atom or a sulfur atom,
A plurality of R 1 , X 2 and Y 2 in the same molecule may be the same or different,
One or more of X 2 and Y 2 in one Q 1 is a sulfur atom. )
R 1 is a residue obtained by removing two isocyanate groups constituting the polyisocyanate from polyisocyanate or a residue obtained by removing two isothiocyanate groups constituting the polyisothiocyanate from polyisothiocyanate. Item 24. The resin according to item 23.
At least one compound selected from polyisocyanates and polyisothiocyanates;
The resin according to claim 23 or 24, which is obtained by a reaction with a compound represented by the following formula (20).

(Where
R 2 represents an aliphatic group or an aromatic group,
Y 2 represents an oxygen atom or a sulfur atom. )
The resin according to claim 25, wherein the at least one compound selected from polyisocyanate and polyisothiocyanate includes a compound represented by the following formula (31).

(Where
R 1 represents an aliphatic group or an aromatic group,
X represents an oxygen atom or a sulfur atom. )
The resin according to claim 25 or 26, wherein R 2 is a monovalent group represented by the following formula (201), (202), (203) or (204).
R 1 is an aliphatic group having 1 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic group, or an aromatic group having 6 to 25 carbon atoms. The resin according to claim 1.
R 1 is a hydrocarbon group selected from the group consisting of hydrocarbon groups represented by the following formula (301), (302), (303), (304), (305) or (306). Item 28. The resin according to any one of Items 23 to 27.

(Where
i represents an integer of 1 to 12. )
The resin according to any one of claims 23 to 28, wherein R 1 does not contain a spiro atom.
A curable composition comprising the resin according to any one of claims 23 to 30 and a curing agent.
27. The resin according to claim 25, comprising reacting at least one compound selected from polyisocyanate and polyisothiocyanate with the compound represented by formula (20) in the presence of a catalyst. Production method.