TWI564316B - Modified resin and resin composition - Google Patents

Description

Modified resin and resin composition

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

Isocyanates are known as raw materials for polyurethanes and polyureas.

Polyurethane can be produced by the reaction of an isocyanate group and a hydroxyl group, and is excellent in tensile strength, abrasion resistance, and oil resistance, and can be used for paints, adhesives, automobile parts, and the like. For example, in Patent Document 1, a two-component polyurethane coating for a packaging film is disclosed.

Polyurea can be produced by the reaction of an isocyanate group and an amine group, and is excellent in heat resistance, mechanical strength, and chemical resistance, and can be processed and used for injection molding, film, fiber, and the like. For example, in Patent Document 2, an adhesive using polyurea is disclosed.

Therefore, the polyurethane and polyurea which are reacted based on the isocyanate group can be applied to the surface of metal, glass or plastic as a coating or an adhesive, and the function is imparted on the surface thereof, so that it is necessary to have sufficient adhesion to the surface.

A method of improving the adhesion, for example, in Patent Document 3, A method of controlling the adhesion of an amine ester by an organic film treatment on the surface of a steel sheet is disclosed. Meanwhile, in the method of improving the resin side to be applied, for example, Patent Document 4 discloses a composition containing a polymer of an acid-modified polyolefin resin dispersion and a sulfur-containing element.

The polyisocyanate composition containing a polyfunctional isocyanate compound (polyisocyanate) can be used for a wide range of applications such as coating compositions. Such a polyisocyanate composition is, for example, a one-liquid or two-liquid polyurethane coating composition which has been marketed. Among them, the two-component polyurethane coating composition requires a high-quality appearance and excellent weather resistance and durability because it is possible to form a dense cross-linked coating film and to make the appearance of the finished product good, such as a top coat such as an automobile or an information appliance. The use of sex has been highly evaluated.

In addition to high-quality appearance, topcoats for automotive applications and information appliance applications are also required to have abrasion resistance and higher hardness. At the same time, it is desirable to have good stretchability in the coating composition used to form the topcoat.

A composition containing a polyisocyanate, a polyisocyanate composition having a trimeric isocyanate group, a phosphorus concentration of 0.1 to 20 ppm (Patent Document 5), and a coating composition containing a polyisocyanate having a urea group (Patent) have been proposed. Document 6, Patent Document 7), a coating composition containing a polyisocyanate composition having a urea carboxylate group and a polyol (Patent Document 8), etc., and a production method and utilization thereof have been studied.

The epoxy resin is excellent in balance between heat resistance and chemical resistance, and can be used in a wide range of fields as a material such as a paint, an adhesive, a molding material, a composite material, a laminate, or a sealing material.

In recent years, after comparing with the conventional resin materials, it is apparent that a resin material having high performance and high reliability is desired. The modification of the conventional resin has been explored by various modification methods. Among them, a modified epoxy resin having a 1-oxa-3-azinolan-2-one structure which reacts a part of an oxide group with an isocyanate group can have both high glass transition temperature and flexibility. The resin has been attracting attention, and a number of proposals have been made (for example, refer to Patent Document 9, Patent Document 10, and Patent Document 11).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2012-517489

[Patent Document 2] Japanese Patent Publication No. 2010-507689

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-219498

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-163579

[Patent Document 5] Japanese Patent No. 4201582

[Patent Document 6] Japanese Patent Laid-Open No. Hei 8-188566

[Patent Document 7] Japanese Patent Laid-Open No. Hei 7-304724

[Patent Document 8] International Publication No. 2002/32979

[Patent Document 9] Japanese Laid-Open Patent Publication No. 59-135265

[Patent Document 10] Japanese Laid-Open Patent Publication No. 61-181820

[Patent Document 11] Japanese Patent Laid-Open No. Hei 5-222160

Polyurethane or polyurea based on the reaction of isocyanate groups It can be applied to the surface of metal, glass or plastic as a coating or an adhesive. Although it can impart functions on its surface, it seeks to improve the heat resistance.

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 surface treatment performed in the patent document 3 is often difficult to apply depending on the surface shape and the surface material. Meanwhile, in the resin mixture of Patent Document 4, the adhesion may be lowered due to phase separation between the resins, or 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.

Meanwhile, according to the findings of the present inventors, the polycyanate composition as described in Patent Documents 5 to 8 is in terms of the adhesion of the adherend, particularly to the adhesion of the metal. There is still room for improvement.

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

Further, it has been found by the present inventors that a modified epoxy resin having a 1-oxa-3-azinolan-2-one structure as described in Patent Documents 9 to 11 is used depending on the use thereof. The adhesion of the adherend, especially for the adhesion of the metal, still has room for improvement.

In another aspect, the subject of the present invention is to provide a modified epoxy resin which is excellent in adhesion to an adherend while maintaining the properties of a compound such as an epoxy resin or an episulfide resin. Compounds such as modified cyclic sulfur resins having good adhesion to the body, and manufacturers of such compounds law.

As a result of intensive investigations to solve the above problems, the present inventors have found that the above problems can be solved by a resin having a specific structure in a molecule and a compound having a specific functional group, thereby completing the present invention. .

That is, the present invention relates to the following.

[1] A resin having a nitrogen-carbon-sulfur bond-bonded resin, the nitrogen-carbon-sulfur bond being composed of a nitrogen atom, a carbon atom, and a sulfur atom, such that the atoms are bonded in this order, and At least one of a bond between the carbon atom and the sulfur atom and a bond between the carbon atom and the nitrogen atom is a single bond, and the number average molecular weight of the resin is Mn, and the resin is contained in one molecule. nitrogen - carbon - sulfur bonds of the number of sulfur atoms when n ¹ is, Mn is 500 or more and Mn / n ¹ is 50 or more 300 or less, n ¹ to follow the ^{formula: n 1 = X 1 ‧Mn (} X 1 represents the system The number of sulfur atoms constituting the nitrogen-carbon-sulfur bond contained in 1 g of the resin is calculated.

[2] The resin according to [1], wherein the temperature at which the resin is reduced by 5% by weight is 300 ° C or higher.

[3] A resin which can be at least 1 in a group consisting of a monovalent group selected from the group consisting of the following formula (1), (2), (3), (4) or (5); The functional group compound is obtained by reacting at least one compound selected from the group consisting of monoisocyanate, polyisocyanate, monoisothiocyanate, and polyisothiocyanate.

-OH (1) -NH ₂ (2)

[4] The resin according to [3], wherein the aforementioned compound having at least one functional group selected from the group consisting of the monovalent groups represented by the formulae (1) to (5), A resin obtained by reacting at least one compound selected from the group consisting of a monoisothiocyanate and a polyisothiocyanate, or a monoisothiocyanate or a polyisothiocyanate.

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

R ⁵ -NCS (30) (wherein R ⁵ represents an organic group. R ⁵ may also be an aliphatic group having 1 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted by an aromatic group or carbon A number of 6 to 25 aromatic groups).

[6] The resin according to any one of [3] to [5] wherein the aforementioned resin has the aforementioned functional group represented by the formula (3), the formula (4) or (5), and an isocyanate group or A cyclic structure derived from the reaction of an isothiocyanate group.

[7] The resin according to [6], wherein the group containing the cyclic structure has two or more divalent groups selected from the group consisting of the following formula (6), (7) or (8); At least one of the constituent groups (bases).

(Wherein, Y ¹ represents an organic group based, in the same molecule a plurality of Y ¹ may be the same or different .Y ¹ may also be a -NH- group.)

[8] A resin having at least one structural unit (group) selected from the group consisting of two or more divalent groups represented by the following formula (6), (7) or (8).

(Wherein, Y ¹ represents an organic group based, in the same molecule a plurality of Y ¹ may be the same or different .Y ¹ may also be a -NH- group.)

[9] The resin according to [7] or [8] wherein the number average molecular weight of the resin is Mn, and the resin represented by the above formula (6), (7) or (8) per molecule When the sum of the number of constituent units is n ₂ , Mn is 500 or more, and Mn/n ₂ is 50 or more and 300 or less, and n ₂ can be represented by the formula: n ₂ = X ² ‧ Mn (X ² represents the resin per 1 g The sum of the number of the above-mentioned constituent units represented by the formula (6), (7) or (8) contained therein is calculated.

[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 in which the atoms are bonded in this order, and a polyisothiocyanate. By.

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

(wherein R ⁶ represents an organic group, and a represents an integer of 2 to 1,000.)

[12] The resin according to any one of [3], wherein the polyisothiocyanate contains two or more of the following formula (33-1). The polymer of the repeating unit, or the polymer.

(wherein 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, and plural R ⁷ , R ⁸ , b in the same molecule and g, can be the same or different.)

[13] as described in any of [3] to [7] and [10] In the resin, the polyisothiocyanate includes the following compound having two or more constituent units: two or more constituent units represented by the following formula (40), and one selected from the following formulas (41) and (42); a compound of at least one of the group consisting of a monovalent, divalent or trivalent group (unit) represented by (43), (44), (45), (46) or (47), wherein The nitrogen atom in the compound is bonded to a carbon atom.

SCN-R ³ - (40)

(wherein 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, and X ³ represents an oxygen atom or a sulfur atom, and a plurality of R ³ in the same molecule , R ⁴ and X ³ , can be the same or different.)

[14] The resin according to any one of [3], wherein the polyisothiocyanate contains a compound represented by the following formula (33).

SCN-R ³ -NCS (33) (wherein R ³ represents an organic group.)

[15] A resin obtained by a method comprising the step of polymerizing a compound represented by the following formula (33).

SCN-R ³ -NCS (33) (wherein R ³ represents an organic group.)

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

[17] A resin comprising two or more constituent units represented by the following formula (40) and selected from the following formulas (41), (42), (43), (44), (45), ( 46) or at least one constituent unit of the group consisting of a monovalent, divalent or trivalent group (constituting unit) represented by (47), and one of the aforementioned constituent units represented by the formulas (41) to (47) The nitrogen atom (N) is not directly bonded to the nitrogen atom (N) in the other structural units represented by the formulae (41) to (47). R ³ in the above structural unit represented by the formulae (41) to (47) may be directly bonded to an isothiocyanate group to form the above-mentioned constituent unit of the formula (40).

SCN-R ³ - (40)

(wherein R ³ represents an organic group, R ⁴ represents an aliphatic group or an aromatic group, and 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 respectively the same , can also be 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).

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

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

[21] A coating film which can be formed from the resin composition described in [20] or formed using the resin composition.

[22] An aqueous coating comprising the resin composition described in [20].

[23] A resin comprising a molecular chain represented by the following formula (10).

(In the formula, P ¹ represents an aliphatic group and/or an aromatic group, and Q ¹ represents a group formed by a divalent group represented by the following formula (11), (12), (13) or (14); In the group of one or more constituent units (base), plural P ¹ and Q ¹ may be the same or different, and n is an integer of 2 or more.)

(wherein R ¹ represents an aliphatic group or an aromatic group, and 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, respectively It may be different. Among X ² and Y ² in one Q ¹ , one or more are sulfur atoms.)

[24] The resin according to [23], wherein R ¹ is a residue obtained by removing two isocyanate groups (-NCO) constituting the polyisocyanate from the polyisocyanate, or is removed from the polyisothiocyanate 2 The residues which constitute the isothiocyanate group (-NCS) of the polyisothiocyanate.

[25] The resin according to [23] or [24] which is a compound represented by the following formula (20) by at least one compound selected from the group consisting of polyisocyanates and polyisothiocyanates The reaction comes.

(In the formula, R ² represents an aliphatic group or an aromatic group, and Y ² represents an oxygen atom or a sulfur atom. The plural Y ² groups in one unit may be the same or different.)

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

XCN-R ¹ -NCX (31) (wherein R ¹ represents an aliphatic group or an aromatic group, and X represents an oxygen atom or a sulfur atom. At least one of X and Y ² in one unit may also be sulfur. atom.)

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

[28] The resin according to any one of [23] to [27] wherein R ¹ is an aliphatic group having 1 to 25 carbon atoms, and a carbon number substituted by an aromatic group (aromatic compound) An aliphatic group of 25 or an aromatic group having 6 to 25 carbon atoms.

[29] [23] according to [27] in terms of the resin, in which R ¹ is selected from the following formulas (301), (302), (303), (304), (305) Or a hydrocarbon group in the group formed by the hydrocarbon group represented by (306).

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

[30] [23] according to [28] in terms of the resin, in which R ¹ does not contain a spiro atom.

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

[32] The method for producing a resin according to [25] or [26], which comprises at least one of the foregoing compounds selected from the group consisting of polyisocyanates and polyisothiocyanates, and the aforementioned compound represented by formula (20) React in the presence of a catalyst.

According to the present invention, a modified resin composition having high heat resistance can be provided.

According to the present invention, a highly dense modified resin composition can be provided.

According to the present invention, it is possible to provide a polyisothiocyanate having good adhesion to an adherend and a method for producing the same.

According to the present invention, it is possible to provide a modified epoxy resin having good adhesion to a adherend while maintaining the properties of a compound such as an epoxy resin or an episulfide resin, and a good adhesion to the adherend. A compound such as a cyclic sulfonate or a method of producing such a compound.

Fig. ^{1 is a 1} H-NMR spectrum of the solid obtained in Example 17.

Fig. 2 shows a ¹ H-NMR chart of polyisothiocyanate.

Fig. 3 shows a ¹ H-NMR chart of a compound containing an oxazolidine-2-thione ring.

Hereinafter, the mode for carrying out the invention (hereinafter referred to as "this embodiment") will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit and scope of the invention.

In the present specification, the names of the compounds are mostly the names of the rules described in the Nomenclature (IUPAC Nomenclature of Organic Chemistry) defined by IUPAC (The International Union of Pure and Applied Chemistry). "Organic" means a group of general compounds that can be the subject of nomenclature as disclosed in the rules. This object can also be the object described in the recommendations listed in 1993. However, the "organic" compound of the above-mentioned Nomenclature also contains an organometallic compound and a metal complex. In the present embodiment, the terms "organic" and/or "organic group" and/or "substituent" are used, and the compounds used in the present embodiment will be described below. Unless otherwise stated, these compounds are not It consists of atoms containing metal atoms and/or semimetals. From the group consisting of H (hydrogen atom), C (carbon atom), N (nitrogen atom), O (oxygen atom), S (sulfur atom), Cl (chlorine atom), Br (bromine atom), I (iodine atom) In the present embodiment, the "organic compound", the "organic group", and the "substituent group" are used.

In the following descriptions, the words "aliphatic" and "aromatic" are often used. According to the above IUPAC rules, organic compounds are classified into aliphatic compounds and aromatic compounds. Aliphatic compound refers to the definition of an aliphatic compound that is used in accordance with the recommendations of the IUPAC 1995. In this proposal, an aliphatic compound is defined as "no ring or ring" "Acyclic or cyclic, unsaturated or unsaturated carbon compounds, "excluding aromatic compounds". At the same time, the aliphatic compounds and aliphatic groups used in the description of the present embodiment Any one of saturated and unsaturated, chain-like and cyclic, which may be selected from the above-mentioned H (hydrogen atom); C (carbon atom); N (nitrogen atom); O (oxygen atom); S (sulfur atom) Si (deuterium atom); a halogen atom selected from the group consisting of Cl (chlorine atom), Br (bromine atom), and I (iodine atom).

Like "aralkyl", a group having an aromatic group bonded to an aliphatic group, sometimes often labeled as "aromatic group substituted by an aromatic group", "aromatic aliphatic group" or "aromatic group" The base of the bonded aliphatic group." This is based on the reactivity in the present embodiment, and the nature of the reaction of a group such as an aralkyl group is not aromatic and is very similar to aliphatic reactivity. Meanwhile, a non-aromatic reactive group containing an aralkyl group, an alkyl group or the like is often labeled as "an aliphatic group which may also be substituted by an aromatic group", "an aromatic group substituted with an aromatic group" "aromatic bond" The aliphatic group" is sometimes included in the "aliphatic group".

In the description of the general formula of the compound used in the present specification, the definition along the above-mentioned Nomenclature rule by UPAC is used, but the specific base name and the exemplified compound name are often used. Meanwhile, in the present specification, although the number of atoms, the number of substituents, and the number are often described, those represent all integers.

When a substituent or a compound exemplified in the present specification has a structural isomer, these structural isomers are included unless otherwise specified.

<Resin composition>

The resin composition of some embodiments is a resin containing 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, and a nitrogen-carbon bond or a carbon-sulfur bond in the bond may be a single bond. Can be unsaturated. However, at least one of the nitrogen-carbon bond and the carbon-sulfur bond may be a single bond. The nitrogen atom and the sulfur atom forming the bond may be bonded to other atoms such as a carbon atom, a nitrogen atom, an oxygen atom, a helium atom or the like. Nitrogen-carbon-oxygen bonds can also be defined similarly.

The group containing a nitrogen-carbon-sulfur bond and/or a nitrogen-carbon-oxygen bond is preferably a structural unit represented by the following formula.

(wherein R ¹ represents a residue obtained by removing two isocyanate groups (-NCO) constituting the polyisocyanate from the polyisocyanate, or two of the polyisothiocyanates are removed to form the polyisothiocyanate. The residue after the ester isothiocyanate group (-NCS), X ² and Y ² each independently represent an oxygen atom or a sulfur atom, and one or more of X ² and Y ² in one constituent unit is a sulfur atom. )

(In the formula, 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, and X ³ represents an oxygen atom or a sulfur atom. )

The resin composition containing a resin having such a constituent unit in the molecule exhibits an effect of greatly improving the adhesion to metal. At the same time, since the refractive index is high, the improvement of the physical properties of the coating such as gloss can also be effective.

The heat resistance is one of the important characteristics when forming a coating film. Specifically, it may be a resin composition containing a resin having a temperature of 5% by weight or less and a temperature of 250 ° C or more or 300 ° C or more. Here, the temperature at which the heat weight is reduced by 5% means that when the resin is heated in a furnace at a temperature of 10 ° C per minute under an atmosphere of an inert gas such as nitrogen, helium or argon, it is confirmed that it is relatively temperature-dependent ( The furnace temperature at which the weight of the resin is reduced by 5% by weight from 20 ° C to 30 ° C can be generally measured using a commercially available apparatus as a thermogravimetric analyzer.

The resin composition exhibiting the heat resistance effect has various forms depending on the main chain skeleton, the bonding pattern, the molecular weight, and the content of the bond which exhibits heat resistance. In terms of the bonding pattern, among the above, it is preferred to have the above formula (6) to (8), (11) to (14), (43), (44), (45), (46) or ( 47) A resin composition of a resin constituting the unit.

The number average molecular weight of the resin is preferably 500 or more, more preferably 1,000 or more, and still more preferably 5,000 or more. In general, a high molecular weight tends to have good heat resistance, but on the other hand, when it is too high molecular weight, handling property at the time of forming a coating film (mixability with other components, fluidity, expandability, etc.) There are unfavorable conditions, so The average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less. The number average molecular weight herein is measured by using a gel permeation chromatograph having at least one column having a molecular weight exclusion of 10 million or more, and is calculated by converting a residence time into a molecular weight using a standard substance such as polystyrene. The value. If it is a manufacturer in the field, the number average molecular weight can be easily obtained. The calculation is performed after the peaks from the solvent are excluded.

The content of the bond which contributes to the development of heat resistance is also related to the above-described number average molecular weight Mn. The number average molecular weight of the resin is divided by the number of sulfur atoms constituting the nitrogen-carbon-sulfur bond contained in one molecule and the number n ¹ of oxygen atoms constituting the nitrogen-carbon-oxygen bond (Mn/n ¹ ), preferably 300 or less, and preferably 200 or less, and 150 or less. As described above, the resin composition of the present embodiment has an effect on the adhesion to the metal. However, it is preferable that the resin has a large amount of the above-mentioned bond per molecule. On the other hand, when the resin has too many such bonding, the resin has the above formulas (6) to (8), (11) to (14), (43), (44), (45), (46). When the constituent unit represented by (47) is used, the flexibility of one of the coating properties may be impaired. From this point of view, Mn/n ¹ is preferably 50, and more preferably 70 or more. n ^{1 ,} for example, by infrared absorption spectrum or ¹ H-NMR or the like, for example, the number of the bonds per unit weight (1 g) of the resin X ¹ (unit: m/g) can be obtained from the above number average molecular weight (Mn). Formula: n ¹ = Mn‧X ^{1 is} calculated. When the resin contains both a nitrogen-carbon-sulfur bond and a nitrogen-carbon-oxygen bond, n ¹ constitutes the total number of sulfur atoms and oxygen atoms respectively bonded.

The resin contained in the resin composition of the present embodiment, As described above, the bonds (constituting units) constituting the molecular chain are characterized, and the skeleton structure between the respective bonds is not particularly limited. Specifically, it is preferable to use a skeleton structure of a raw material compound used in the method for producing a resin composition of the present embodiment exemplified below.

Among such resins, the constituent units represented by the above formulas (6) to (8), (11) to (14), (43), (44), (45), (46) or (47) are contained. The resin has good properties and can be preferably used. The resins relating to these are described below.

≫Hole resin with heterocyclic ring

<better structure>

The first resin which is preferable in the present embodiment is a resin having at least one constituent unit selected from the group consisting of monovalent groups represented by the above formulas (6) to (8). The resin having the constituent units represented by the above formulas (6) to (8) is surprisingly high in heat resistance and adhesion, and is particularly excellent in adhesion to a metal surface. The mechanism for exerting such an effect is not clear, but the inventors have speculated that a ring structure having a conjugation may contribute to heat resistance, and the sulfur atom contained in the constituent unit particularly has the above formula (6). The thiol group (-SH group) of the constituent unit exhibits an effect of improving the adhesion. In this regard, a resin containing the constituent unit represented by the above formula (6) and/or the constituent unit represented by the above formula (6) is preferred.

Therefore, the resin of the present embodiment is characterized by a bonding pattern contained in the molecule, and the skeleton structure other than the bonding is not particularly limited, but a more preferable embodiment is as follows.

The number average molecular weight of the resin is preferably 500 or more, more preferably 1,000 or more, and still more preferably 5,000 or more. Usually high scores In the case of a small amount, heat resistance tends to be good, but on the other hand, when the molecular weight is too high, the handleability (mixing property with other components, fluidity, stretchability, etc.) may be disadvantageous in forming a coating film. Therefore, the number average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less. Here, the number average molecular weight is measured by using a gel permeation chromatograph having at least one column having a molecular weight limit of 10 million or more, and the retention time is converted into a molecular weight by using a standard substance such as polystyrene. The value. The number average molecular weight can be easily determined as long as it is in the art. The calculation is performed after the peaks from the solvent are excluded.

The content of the bond which contributes to the development of heat resistance is also related to the above-described number average molecular weight Mn. The number average molecular weight of the resin is divided by the number of sulfur atoms constituting the nitrogen-carbon-sulfur bond per molecule and the number of oxygen atoms n ¹ constituting the nitrogen-carbon-oxygen bond (Mn/n ¹ ), preferably 300 or less, and preferably 200 or less, and 150 or better. The resin composition of the present embodiment is effective in adhesion to metal as described above, but it is preferable that the resin has a large amount of the above-mentioned bond per molecule. On the other hand, when the resin has too many such bonding, the resin has the above formulas (6) to (8), (11) to (14), (43), (44), (45), (46). In the case of the constituent unit represented by (47), the flexibility of one of the coating film properties may be impaired. In this connection, Mn/n ¹ is preferably 50, and more preferably 70 or more. n ^{1 is obtained by,} for example, infrared absorption spectrum or ¹ H-NMR or the like, for example, the number of bonds of the equivalent resin per unit weight (1 g) of X ¹ (unit: m/g), from the above number average molecular weight (Mn) Formula: n ¹ = Mn‧X ^{1 is} calculated. When the resin contains both a nitrogen-carbon-sulfur bond and a nitrogen-carbon-oxygen bond, n ¹ constitutes the total number of sulfur atoms and oxygen atoms bonded to each other. When the resin has the constituent units of the formulae (6) to (8), when the sum of the number of the constituent units represented by the formulae (6) to (8) contained in one molecule is n ² , Mn/n ² is 50 or more and 300 or less. n ² can be calculated by the formula: n ² = X ² ‧ Mn. The sum of the number of the constituent units represented by the formulae (6) to (8) contained in 1 g of the resin of X ² can be determined by the same method as X ¹ .

The structure provided between the above constituent units is not particularly limited, but an aliphatic group having 1 to 25 carbon atoms and an aromatic group having 6 to 25 carbon atoms are preferred. Specifically, it is derived from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, Diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethyl A residue obtained by removing two hydrogen atoms, such as benzene, diphenylmethane or tetramethyldiphenylmethane. Further, if an isomer is present, the isomer is also included.

Among these resins, a resin having a structure represented by the following formulas (301) to (306) is preferred.

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

<Preferred manufacturing method>

The preferred first resin of the present embodiment is preferably a compound containing at least one functional group selected from the group consisting of monovalent groups represented by the following formulas (1) to (5). A resin obtained by a method of reacting with at least one compound selected from the group consisting of monoisocyanates, polyisocyanates, monoisothiocyanates, and polyisothiocyanates.

-OH (1) -NH ₂ (2)

In the present specification, the group represented by the above formula (1) may be referred to as a hydroxyl group, and the group represented by the above formula (2) may be referred to as an amine group, and the group represented by the above formula (3) may also be referred to as a group. The group represented by the above formula (4) is sometimes referred to as an aminoureido group, and the group represented by the above formula (5) is sometimes referred to as a thioaminoureido group. The group of the formula (2) is defined as a group different from the formulae (3) to (5).

An example of a method for producing the first resin which is preferable in the present embodiment will be described below.

[Preferred compound]

The compound having at least one group selected from the group consisting of a hydroxyl group, an amine group, a thiol group, an aminoureido group, and a thioaminoureido group is not particularly limited as long as it contains two The above is selected from the group consisting of hydroxyl (-OH), amine (-NH ₂ ), mercapto (-C(=O)-NH-NH ₂ ), and aminoureido (-NH-C(=O)-NH- At least one of the group of NH ₂ ) and thioaminoureido (-NH-C(=S)-NH-NH ₂ ) may be used. For example, a compound represented by the following formula (70) or formula (71) can be used.

(wherein R ¹² , R ¹³ and R ¹⁴ each independently represent 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, an amine group, a decyl group, an amine group. The groups in the group formed by the ureido group and the thioaminoureido group, and the B ¹ and D ¹ groups respectively represent independently selected from the group consisting of a hydroxyl group, an amine group, a thiol group, an aminoureido group, and a thioaminoureido group. The group, the organic group or the hydrogen atom in the group formed, F ¹ represents a hydrogen atom or an organic group, d represents an integer of 2 to 1,000, e represents an integer of 1 to 3, and x represents an integer of 1 or more. y is an integer of 0 or 1. The plural 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 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. good. Specific examples of R ¹² are from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethyl ring Hexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, A residue obtained by removing one hydrogen atom such as diethylbenzene, diphenylmethane or tetramethyldiphenylmethane. In the present specification, the "aliphatic group having 7 to 25 carbon atoms substituted by an aromatic group" means a group composed of a combination of an aromatic group and an aliphatic group, and the aromatic group and the aliphatic group contain an oxygen atom. A hetero atom such as a nitrogen atom or a sulfur atom, and the total number of carbon atoms contained in the group is 7 to 25. Other identical terms can be defined as well.

In the above formula, preferred R ¹³ and R ^{14 are} an aliphatic group having 2 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted by an aromatic group, or an aromatic group having 8 to 25 carbon atoms. . Specific examples of R ¹³ and R ¹⁴ are from ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethyl Cyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylethane, ethylbenzene, diethylbenzene, diphenylethane, tetramethyl A residue obtained by removing three hydrogen atoms, such as diphenylethane.

In the above formula, R ¹⁵ represents an organic group or a single bond, and when it is an organic group, it 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 formula ( 73) The base of the representation.

(wherein R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent 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 is 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} derived from methane, ethane, propane, butane, and propylene (which should be pentane). Hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethyl b 2 cyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane, etc. The residue after the hydrogen atom.

R ¹⁵ is a single bond, which means that R ¹⁵ is absent from the group, and E ^{1 is} bonded to R ¹³ . Hereinafter, the "single bond" referred to in the present specification is used in the same manner.

In the above formula (72) and formula (73), preferred R ¹⁶ , R ¹⁷ and R ¹⁸ are from methane, ethane, propane, butane, pentane, hexane, octane, decane, and twelve. Alkane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, four A residue obtained by removing two hydrogen atoms, such as methyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane or tetramethyldiphenylmethane. Further, when an isomer is present, the isomer is also included.

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

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

In the above formulas (74) (76), preferred R ^19, R ²⁰ and R ^21, lines 1 to 25 carbon atoms, alkylene group, or an aromatic hydrocarbon group having a carbon number of 6 to 25. Specifically, R ¹⁹ , R ²⁰ and R ^{21 are} derived from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane. , dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene A residue obtained by removing two hydrogen atoms, such as ethylbenzene, diethylbenzene, diphenylmethane or tetramethyldiphenylmethane. When an isomer is present, 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 amine group, a thiol group, an aminoureido group, and a thioaminoureido group are as follows.

(a) a compound having a hydroxyl group, which may be a polyol such as ethylene glycol, propylene glycol or neopentyl alcohol, and a polyol having a repeating unit

Examples of the polyhydric alcohol include, for example, acrylic polyols, poly Olefin polyol, polyvinyl alcohol, and the like. The acrylic polyol can be obtained by copolymerizing a monomer having an ethylenically unsaturated bond having a hydroxyl group, alone or in a mixture, with a monomer or other monomer containing an ethylenically unsaturated bond copolymerizable therewith.

The monomer having an ethylenically unsaturated bond having a hydroxyl group may, for example, be hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate or hydroxybutyl methacrylate. Ester and the like. It is preferably hydroxyethyl acrylate or hydroxyethyl methacrylate.

Other monomers containing an ethylenically unsaturated bond copolymerizable with the above monomers may, for example, be methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate or isobutyl acrylate. Acrylates such as n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, benzyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, methyl Propyl acrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, A A methacrylate such as lauryl acrylate, benzyl methacrylate or phenyl methacrylate; an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid or itaconic acid, or acrylamide; Methyl acrylamide, N,N-methylenebisacrylamide, diacetone acrylamide, diacetone methacrylamide, maleic acid decylamine, maleimide, etc. Indoleamine, and glyceryl methacrylate, benzene a vinyl monomer such as ethylene, vinyl toluene, vinyl acetate, acrylonitrile or dibutyl fumarate, A vinyl-based monomer having a hydrolyzable alkylene group such as vinyltrimethoxydecane, vinylmethyldimethoxydecane or γ-(meth)acryloxypropyltrimethoxydecane.

The polyolefin polyol may, for example, be a polybutadiene having two or more hydroxyl groups, a hydrogenated polybutadiene, a polyisoprene or a hydrogenated polyisoprene. The number of hydroxyl groups held by one molecule of the polyol (hereinafter, the "average number of hydroxyl groups") is preferably 2 or more. Since the average number of hydroxyl groups of the polyol is 2 or more, it is possible to suppress a decrease in the crosslinking density of the obtained coating film.

The polyvinyl alcohol may, for example, be a polyvinyl alcohol obtained by saponifying a polyvinyl ester obtained by polymerizing a vinyl ester; a modified polyvinyl alcohol obtained by graft-copolymerizing a comonomer on a main chain of a polyvinyl alcohol; and a vinyl ester a modified polyvinyl alcohol obtained by saponification of a modified polyvinyl ester copolymerized with a comonomer; a part of a hydroxyl group of an unmodified polyvinyl alcohol or a modified polyvinyl alcohol, such as formaldehyde, butyraldehyde, or benzene A so-called polyacetal resin or the like in which an aldehyde such as formaldehyde is crosslinked.

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, vinyl benzoate and the like. Among these vinyl esters, vinyl acetate is preferred in terms of easiness in production of polyvinyl alcohol, ease of availability, cost, and the like. Meanwhile, the comonomer used in the production of the modified polyvinyl alcohol is mainly used for copolymerization of the polyvinyl alcohol for the purpose of copolymerization, and can be used without departing from the gist of the present invention. Such a comonomer may, for example, be an olefin such as ethylene, propylene, 1-butene or isobutylene; acrylic acid or a salt thereof; methyl acrylate, ethyl acrylate or propyl acrylate (including isomerism) Acrylates, butyl acrylate (including isomers), octyl acrylate (including isomers), decyl acrylate (including isomers) and the like; methacrylic acid or its salt; methacrylic acid Ester, ethyl methacrylate, propyl methacrylate (including isomers), butyl methacrylate (including isomers), octyl methacrylate (including isomers), dodecane methacrylate Methacrylates such as esters (including isomers) and octadecyl methacrylate (including isomers); acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N, N-dimethyl methacrylate, diacetone acrylamide, acrylamidamine sulfonic acid or a salt thereof, acrylamidopropyl dimethylamine or a salt thereof, N-methylol acrylamide or a derivative thereof Ethylene decylamine derivative; methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamide sulfonic acid or its salt, methacrylamide a methacrylamide derivative such as propyldimethylamine or a salt thereof, N-methylolmethacrylamide or a derivative thereof; N-vinylformamide, N-vinylacetamide, N -vinylpyrrolidone N-vinyl decylamine; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, iso-propyl vinyl ether, n-butyl vinyl ether, isobutyl butyl Vinyl ethers such as ether, tert-butyl vinyl ether, dodecyl vinyl ether, and octadecyl vinyl ether; nitriles such as acryl, methacrylonitrile; vinyl chloride, vinylidene chloride, Halogenated ethylene such as fluorinated ethylene or fluorinated vinylidene chloride; allyl compound such as allyl acetate or chloropropene; maleic acid or its salt or ester; itaconic acid or its salt or ester; A vinyl fluorenyl compound such as trimethoxy decane; isopropenyl acetate or the like. Among these comonomers, an α-olefin (for example, an α-olefin having 2 to 30 carbon atoms), an unsaturated carboxylic acid or a derivative thereof, an unsaturated sulfonic acid or a derivative thereof is preferred, and α is used. - The olefin is better, and the ethylene is particularly preferred. Modification The quality of the comonomer in the polyvinyl alcohol is preferably 15 mol% or less based on the number of moles of the entire structural unit constituting the modified polyvinyl alcohol, and more preferably 5 mol% or less.

Among the above-exemplified polyols, acrylic polyols and polyester polyols are preferred.

Specific examples of the (b) compound having an amine group include, for example, ethylenediamine, propylenediamine, butanediamine, triethylenediamine, hexamethylenediamine, and 4,4'-diaminobicyclic ring. Hexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, norbornanediamine, phenylenediamine, 4,4'-diaminodiphenyl, 1,3-bis(3- Amines such as aminophenoxy)benzene, 3,3'-diaminodiphenylphosphonium, diethyltoluenediamine, diphenylamine, dihexamethylenetriamine, diethylenetriamine, triethylamine Chain polyamines having three or more amine groups such as tetraamine, tetraethylenepentamine, pentamethylamine, tetrapropylpentamine, etc., 1,4,7,10,13,16-hexazacyclotetradecene Alkane, 1,4,7,10-tetraazacyclononane, 1,4,8,12-tetraazacyclopentadecane, 1,4,8,11-tetraazacyclotetradecane, etc. A polyamine such as polyamine, polyallylamine, polyvinylamine, or a polyamine represented by the following formulas (77) to (80). Among these, polyallylamine and polyvinylamine are preferred. Further, the polyallylamine or the polyvinylamine can be any one produced by a conventionally known method, and the degree of polymerization and the like are not particularly limited. At the same time, it can also be a copolymer with other monomers.

(wherein g' represents an integer from 2 to 70.)

(wherein h' represents an integer from 2 to 40, i', j' each represents an integer from 1 to 16, and the sum of i' and j' is an integer from 2 to 7.)

(wherein 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, and r, t, and u each represent 0 or 1 or more. The integer, r and the sum of t and u are 5 to 90.)

(c) a compound having a mercapto group, for example, diterpene oxalate, diammonium malonate, diterpene glutarate, diterpene succinate, diammonium adipate, sebacic acid a saturated dicarboxylic acid dioxane having 2 to 18 carbon atoms; a monoolefin unsaturated group such as diammonium maleate, diammonium fumarate or diterpene itaconate Dicarboxylic acid ruthenium; polyfluorene obtained by reacting a low polymer having a lower alkyl carboxylate group with hydrazine or hydrazine hydrate. At the same time, it may be a monomer having a hydroxyl group and having an ethylenically unsaturated bond, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl A polymer obtained by reacting hydrazine in a polymer such as hydroxybutyl acrylate (which may also be a copolymer) may also be used in a vinyl ester (for example, vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate). A polymer obtained by reacting hydrazine in a polymer of vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate or the like.

(d) a compound having an aminoureido group, for example, a diamine urea; an N,N-substituted anthracene such as N,N-dimethylhydrazine or the above-exemplified anthracene, in hexamethylene diisocyanate or different A polyfunctional amine urea or the like obtained by reacting a diisocyanate such as ketone diisocyanate or a polyisocyanate compound derived therefrom.

(e) a compound having a thioaminoureido group, for example, a dithioamino urea; an N,N-substituted anthracene such as N,N-dimethylhydrazine or the above-exemplified anthracene in hexamethylene A polyfunctional thioaminourea obtained by reacting a diisothiocyanate such as isothiocyanate or isophorone diisothiocyanate or a polyisothiocyanate compound derived therefrom.

The polyol exemplified as the compound having a hydroxyl group may also be a polyester polyol, a polyether polyol, a fluorine polyol, a polycarbonate polyol, or a polyurethane polyol.

The polyester polyol may, for example, be selected from the group consisting of succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, phthalic acid and the like. a single or a mixture of dibasic acids, alone or in combination with a polyol selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, glycerol, etc. The obtained polyester polyol and, for example, polycaprolactones obtained by ring-opening polymerization of ε-caprolactone of a polyhydric alcohol.

The polyether polyols include: addition of an ethylene oxide to a single or a mixture of polyvalent hydroxy compounds using a strong basic catalyst such as a hydroxide, an alcoholate or an alkylamine such as lithium, sodium, potassium or the like. a polyether polyol obtained by separately or in combination of an alkylene oxide such as propylene oxide, butylene oxide, cyclohexene oxide or styrene oxide, or a polyfunctional compound such as an alkylene oxide. The obtained polyether polyol and the so-called polymer polyol obtained by polymerizing such a polyether as a medium, such as acrylamide.

Examples of the polyvalent hydroxy compound include (1) diglycerin, ditrimethylolpropane, neopentyl alcohol, and dipentaerythritol, and (2) butanol, D-threitol, and L-arabinose. Alcohol, ribitol, xylitol, sorbitol, mannitol, galactitol, rhamnitol and other sugar alcohol compounds, (3) arabinose, ribose, xylose, glucose, mannose, Half milk Monosaccharides such as sugar, fructose, sorbose, rhamnose, fucose, deoxyribose, and (4) disaccharides such as trehalose, sucrose, maltose, cellobiose, gentisan, lactose, and melibiose, (5) ) Trisaccharides such as raffinose, gentianose, and pine triose, and (6) tetrasaccharides such as stachyose.

The fluoropolyol is a fluoroalkene, a cyclovinyl ether or a hydroxyalkane disclosed in JP-A-57-34107 A copolymer of a vinyl ether, a monocarboxylic acid ester or the like.

Examples of the polycarbonate polyols include, for example, a low molecular carbonate compound such as a dialkyl carbonate such as dimethyl carbonate or a alkylene carbonate such as ethylene carbonate or a diaryl carbonate such as diphenyl carbonate. The low molecular polyol used in the polyester polyol is obtained by condensation polymerization.

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

A compound having a repeating unit containing one group selected from the group consisting of a hydroxyl group, an amine group, a thiol group, an aminoureido group, and a thioaminoureido group, which is represented by the following formula (81) compound of.

R ²² -A ¹ (81) (wherein R ²² represents an organic group, and A ¹ represents a group defined in the above formula (70).)

In the above formula, preferred R ²² is an aliphatic group having 1 to 25 carbon atoms, an aliphatic group substituted with an aromatic group having 7 to 25 carbon atoms, and an aromatic group having 6 to 25 carbon atoms. Specifically, R ^{22 is} derived from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane. Alkane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, two A residue obtained by removing one hydrogen atom such as ethylbenzene, diphenylmethane or tetramethyldiphenylmethane. Further, when an isomer is present, the isomer is also included.

Specific examples of the compound represented by the above formula (81) include methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, nonanol, dodecanol, stearyl alcohol, and cyclohexane. Alcohol, cyclooctanol, dimethylcyclohexanol, diethylcyclohexanol, trimethylcyclohexanol, trimethylethylcyclohexanol, dicyclohexylmethanol, tetramethyldicyclohexylmethanol, phenol , hydroxyphenols such as methyl phenol, xylenol, ethyl phenol, diethyl phenol, ethylamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, decylamine, dodecylamine, cyclohexylamine, ring Amine, dimethylcyclohexylamine, aniline, methylaniline, dimethylaniline, ethylaniline, diethylaniline, etc., ethyl hydrazine, propyl hydrazine, butyl hydrazine, pentyl hydrazine肼, hexyl hydrazine, octyl hydrazine, hydrazinyl, dodecyl fluorene, cyclohexyl hydrazine, cyclooctyl hydrazine, dimethylcyclohexyl fluorene, phenyl hydrazine, methyl phenyl Anthraquinone, dimethylphenylhydrazine, ethylphenylhydrazine, diethylphenylhydrazine, etc., ethylamino urea, propylamino urea, butylamino urea, Amylamino urea, hexylamino urea, octylamino urea, decylamino urea, dodecylamino urea, cyclohexylamino urea, cyclooctylamino urea, dimethylcyclohexylamino Urea, phenylamino urea, methylphenylamino urea, dimethylphenylamino urea, ethylphenylamino urea, diethylphenylamino urea and other amine urea, ethyl thio Amino urea, propyl thioamino urea, butyl thioamino urea, pentyl thioamino urea, hexyl thioamino urea, octyl thioamino urea, thiol thioguanyl urea , dodecylthioamino urea, cyclohexylthioamino urea, cyclooctylthioamino urea, dimethylcyclohexylthioamino urea, phenylthioamino urea, methylphenyl A thioaminourea such as thioaminourea, dimethylphenylthioamino urea, ethylphenylthioamino urea, diethylphenylthioamino urea.

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

R ²³ -R ¹⁵ -E ¹ (82) (wherein R ²³ represents an unsaturated aliphatic hydrocarbon group having 1 to 25 carbon atoms, and 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).

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

<isothiocyanate compound>

The isothiocyanate compound is a compound having one or more isothiocyanate groups in one molecule, and can be classified into a monoisothiocyanate and a polyisothiocyanate.

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

R ⁵ -NCS (30) (wherein R ⁵ represents an organic group.)

In the above formula (30), preferred R ⁵ is an aliphatic group having 1 to 25 carbon atoms or an aromatic group having 6 to 25 carbon atoms. R ⁵ may also be an aliphatic group substituted with an aromatic group having 7 to 25 carbon atoms. Specifically, R ^{5 is} derived from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane. Alkane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, two A residue obtained by removing one hydrogen atom such as ethylbenzene, diphenylmethane or tetramethyldiphenylmethane. Further, when an isomer is present, the isomer is also included.

Specifically, examples of the compound represented by the above formula (1) include methane isothiocyanate, ethane isothiocyanate, propane isothiocyanate, butane isothiocyanate, and pentane isosulfide. Cyanate ester, hexane isothiocyanate, octane isothiocyanate, decane isothiocyanate, dodecane isothiocyanate, octadecane isothiocyanate, cyclohexane Thiocyanate, cyclooctane isothiocyanate, dimethylcyclohexane isothiocyanate, diethylcyclohexane isothiocyanate, trimethylcyclohexane isothiocyanate, Trimethylethylcyclohexane isothiocyanate, dicyclohexylmethane isothiocyanate, tetramethyldicyclohexylmethane isothiocyanate, phenyl isothiocyanate, toluene isothiocyanate Ester, xylene isothiocyanate, ethyl phenyl isothiocyanate, diethyl phenyl isothiocyanate, diphenylmethane isothiocyanate, tetramethyldiphenylmethane isothiocyanate Ester and the like.

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

^{R 23 -R 15 -NCS (86)} ( wherein, R ^15, R ²³ lines in the above formula represents a group (82) defined.)

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

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

Specific examples of the compounds represented by the formulae (87) to (89) may be Listed: for example, methyl isothiocyanate, methyl isothiocyanate, ethyl acrylate (2-isothiocyanate), methacrylic acid (2-isothiocyanate), acrylic acid (3) -propyl isothiocyanate), methacrylic acid (3-isothiocyanate), 2-isothiocyanate ethyl ether, 4-isothiocyanate vinyl ether, p-(isocyanide) Methyl ester) styrene, p-(ethyl isocyanate styrene), and the like.

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

(wherein R ⁶ represents an organic group, and a represents an integer of 2 to 1,000.)

A preferred first aspect of the polyisothiocyanate is a polymer containing at least two repeating units represented by the following formula (33-1).

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

The polymer of the first aspect of the polyisothiocyanate described herein may have one or several repeating units in addition to the repeating unit represented by the above formula (33-1). The term of the polymer is different depending on the method of producing the polymerization initiator, the polymerization stopper, and the terminal modifier. However, it is not particularly limited as long as it does not contradict the gist of the embodiment. In other words, the preferred first embodiment of the polyisothiocyanate is more preferably a compound represented by the following formula (90).

(wherein R ³² represents an organic group, R ³³ represents an organic group or a single bond, and B ² and D ² each independently represent an organic group other than an isothiocyanate group or an isothiocyanate group; At least one group in the group of hydrogen atoms, G ¹ to G ^x means an organic group having or not containing an isothiocyanate group, x is an integer of 1 or more, and n _x is an integer of 1 or more. g is 1 or 2, f is an integer of 1 or more, and m is 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 (33-1). Meanwhile, n _x represents the number of repeating units of G ^x . For example, in the case of the repeating unit represented by the above formula (43), when three kinds of repeating units of G ¹ , G ² , and G ³ respectively have n ₁ , n ₂ , and n ₃ , the system is G ¹ n ₁ G ² n ₂ G ^{3 .} n ₃ .

In the above formula (90), preferred R ³² is 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 ³² are from ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane. , diethyl cyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylethane, ethylbenzene, diethylbenzene, diphenylethane, tetramethyldiphenyl Ethylethane, ethanol, propanol, butanol, pentanol, hexanol, octanol, decyl alcohol, dodecanol, stearyl alcohol, cyclohexanol, cyclooctanol, dimethylcyclohexanol, two A residue obtained by removing three hydrogen atoms, such as ethylcyclohexanol, trimethylcyclohexanol, trimethylethylcyclohexanol or dicyclohexylethanol.

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

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

When R ³⁴ is an alkylene group having 1 to 25 carbon atoms and an aromatic hydrocarbon group having 6 to 25 carbon atoms, specifically, it is derived from methane, ethane, propane, butane, pentane, hexane, octane, and anthracene. Alkane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, bicyclo A residue from which two hydrogen atoms are removed, such as hexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane or tetramethyldiphenylmethane.

In the above formulae (91) and (92), preferred R ³⁴ , R ³⁶ and R ^{37 are} derived from methane, ethane, propane, butane, pentane, hexane, octane, decane or dodecane. , octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyl A residue from which two hydrogen atoms are removed, such as dicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane or the like. Further, when an isomer is present, the isomer is also included.

In the above formula (90), when B ² and D ² are an organic group, the organic group is an alkyl group having 1 to 25 carbon atoms, an aromatic hydrocarbon group having 6 to 25 carbon atoms, or the following formula (93) to ( 95) The base indicated is better.

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

In the above formulae (93) to (95), R ³⁸ , R ³⁹ and R ⁴⁰ are preferably an alkylene group having 1 to 25 carbon atoms and an aromatic hydrocarbon 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, A residue of two hydrogen atoms removed by tetramethyldiphenylmethane or the like. Further, when an isomer is present, the isomer is also included.

The first aspect of the polyisothiocyanate shown above may be, for example, a polymer of a monoisothiocyanate represented by the above formula (41), and the polymer may be a copolymer with another monomer. Specifically, for example, a copolymer of methyl thiocyanate and methyl acrylate, methyl group Copolymer of methyl isothiocyanate and methyl methacrylate, copolymer of acrylic acid (ethyl 2-isothiocyanate) and methyl acrylate, methacrylic acid (ethyl 2-isothiocyanate) a copolymer with methyl methacrylate, a copolymer of acrylic acid (propyl isothiocyanate) and methyl acrylate, methacrylic acid (3-isothiocyanate) and methacrylic acid a copolymer of an ester or the like. These compounds can be produced using known methods.

In the resin composition of the present embodiment, the second aspect of the polyisothiocyanate has a constituent unit selected from the following formula (40) and a unit represented by the following formulas (41) to (47). At least one constituent unit in the group is a polyisothiocyanate constituting a nitrogen atom of a polyisothiocyanate bonded to a carbon atom.

SCN-R ³ - (40)

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

In the above formula (40) and formulas (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. Specifically, R ^{3 is} derived from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane. Alkane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, two A residue from which two hydrogen atoms are removed, such as ethylbenzene, diphenylmethane or tetramethyldiphenylmethane. When an isomer is present, the isomer is also included.

The base -X ³ -R ⁴ contained in the above formula (43) and formula (45) will be described.

As described later, in the production of the polyisothiocyanate of the present invention, the N,N'-disubstituted dithiourea bond represented by the above formula (43) or the N-substitution represented by the above formula (45) is produced. When a -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), a hydroxy compound is used. Or thiols. The group -X ³ -R ⁴ is a group derived from the hydroxy compound or a thiol group. When a hydroxy compound is used, when X ^{3 is} an oxygen atom or a thiol, X ³ is a sulfur atom.

R ⁴ is obtained as a hydrocarbon group. The hydrocarbon group may have 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, and preferably an aliphatic group having 1 to 22 carbon atoms or an aromatic group having 6 to 22 carbon atoms, and an aliphatic group having 1 to 22 carbon atoms and a carbon number of 1 to The aromatic group of 22, or the aliphatic group having 1 to 22 carbon atoms and the aromatic group having 6 to 22 carbon atoms are bonded to the group having 7 to 22 carbon atoms. Specific examples of R ⁴ include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, dodecyl, octadecyl, cyclopentyl. , cyclohexyl, cycloheptyl, cyclooctyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, pentylcyclohexyl, hexyl Cyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, dibutylcyclohexyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexyl Phenyl, octylphenyl, nonylphenyl, cumylphenyl, dimethylphenyl, and the like.

The polyisothiocyanate of the present embodiment may be a polyisothiocyanate obtained by repolymerizing a compound represented by the following formula (33) of one type of polyisothiocyanate of the present embodiment. .

SCN-R ³ -NCS (33) (wherein 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 from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethyl ring Hexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, A residue from which two hydrogen atoms are removed, such as diethylbenzene, diphenylmethane or tetramethyldiphenylmethane. When an isomer is present, 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 from 1 to 12, and may also be from 1 to 10.)

The compound represented by the above formula (33) is more preferably hexamethylene diisothiocyanate, isophorone diisothiocyanate, 4,4'-dicyclohexylmethane diisothiocyanate, 4, 4'-diphenylmethane diisothiocyanate, toluene diisothiocyanate (each isomer), naphthalene diisothiocyanate (each isomer), and the like.

The compound represented by the above formula (33) may, for example, be benzoyl isothiocyanate, 4,4'-diisothiocyanate diphenyl ether or 1,3-bis(3-isothiocyanate benzene). Oxylate) benzene, 3,3'-diisothiocyanate diphenyl hydrazine, diethyltoluene diisothiocyanate, and the like.

Hereinafter, a resin (polyisothiocyanate) which can be obtained by polymerizing the compound represented by the above formula (33) will be described. Further, in the following description, the compound represented by the above formula (33) may be referred to as a "monomer" of the compound before polymerization.

The polyisothiocyanate which can be produced by the polymerization of the "monomer" represented by the above formula (33) can be used in the production of a hydroxy compound and / or mercaptans as an auxiliary material.

The hydroxy compound may, for example, be exemplified by methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decyl alcohol, dodecanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctane. Alcohol, methylcyclopentanol, ethylcyclopentanol, methylcyclohexanol, ethylcyclohexanol, propylcyclohexanol, butylcyclohexanol, pentylcyclohexanol, hexylcyclohexanol, two Methylcyclohexanol, diethylcyclohexanol, dibutylcyclohexanol, phenol, methylphenol, ethylphenol, propyl phenol, butyl phenol, amyl phenol, hexyl phenol, octyl phenol, hydrazine Phenol, cumene phenol, dimethyl phenol, methyl ethyl phenol, methyl propyl phenol, methyl butyl phenol, methyl amyl phenol, diethyl phenol, ethyl propyl phenol, Butyl phenol, dipropyl phenol, diisopropyl phenol, trimethyl phenol, triethyl phenol, naphthol and the like.

Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol can also be used. , low molecular weight compounds such as neopentyl glycol, neopentyl glycol hydroxypivalate, 2-ethyl-1,3-hexanediol, trimethylolpropane, glycerin, 1,2,6-hexanetriol And a polyester polyol, a polyether polyol, or the like having a molecular weight of about 200 to 10,000.

Examples of the mercaptan include methanethiol, ethanethiol, propane thiol, butane thiol, pentane thiol, hexane thiol, heptane thiol, octane thiol, decane thiol, Dodecanethiol, cyclopentanethiol, cyclohexanethiol, cycloheptanethiol, cyclooctanethiol, methylcyclopentanethiol, ethylcyclopentanethiol, methylcyclohexane Alkyl mercaptan, ethyl cyclohexane mercaptan, propyl cyclohexane mercaptan, butyl cyclohexane mercaptan, pentyl cyclohexane mercaptan, hexyl cyclohexane mercaptan, dimethyl cyclohexane sulfur Alcohol, diethylcyclohexanethiol, dibutylcyclohexanethiol, thiophenol, methyl thiophenol, ethyl thiophenol, propyl benzene Thiol, butyl thiophenol, pentyl thiophenol, hexyl thiophenol, octyl thiophenol, mercapto thiophenol, cumylthiophenol, dimethyl thiophenol, Methyl ethyl thiophenol, methyl propyl thiophenol, methyl butyl thiophenol, methyl amyl thiophenol, diethyl thiophenol, ethyl propyl thiophenol, ethyl butyl Alkylthiophenol, dipropylthiophenol, dicumylthiophenol, trimethylthiophenol, triethylthiophenol, naphtholthiol, and the like.

When a hydroxy compound is used, the ratio of the hydroxy compound to the isomeric thiocyanate group/hydroxy group equivalent of the "monomer" represented by the above formula (33) is about 10 to 100 depending on the purpose. Similarly, when a thiol is used, the isothiocyanate group/thiol group equivalent ratio is selected to have a value of about 10 to 100 depending on the purpose.

The trimeric isothiocyanate group represented by the formula (41) can be formed by polymerization of a monomer of the formula (33). The formation of a trimeric isothiocyanate-based trimeric isothiocyanurate catalyst represented by the formula (41) is preferably a quaternary amine salt, and is a tetra-ammonium hydroxide or a quaternary ammonium carboxylic acid. More preferably, the quaternary ammonium carboxylic acid is more preferred. Specific examples thereof include tetraalkylammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; tetramethylammonium acetate; tetraethylammonium acetate; An organic weak acid salt such as tetrabutylammonium acetate or the like. A metal salt such as an alkyl carboxylic acid such as acetic acid, n-valeric acid, isovaleric acid, caproic acid, caprylic acid or myristic acid may be used. However, it is preferable to use an organic weak acid salt or the like in order to reduce the amount of use. .

The hydroxy compound which dilutes the above-mentioned trimeric isothiocyanate catalyst may, for example, be methanol, ethanol, 1-butanol, 2-butanol, 2-methyl-1-propanol or 1,2-propanediol. 1,3-propanediol, 1,3-butanediol, 1,4-butane An alcoholic hydroxy compound such as an alcohol, 2,3-butanediol, glycerin or cyclohexanol, or a phenolic hydroxy compound such as phenol, cresol, xylenol or trimethylphenol. In terms of the crystallinity of the polyisocyanate obtainable by such a compound, 2-butanol, 2-methyl-1-propanol, 1,3-butanediol, 2,3-butanediol, etc. have a side The alcohol of the chain is preferred. At the same time, two or more kinds may be mixed. Further, the hydroxy compound may be substituted with a thiol.

When the monomer represented by the above formula (33) or the monomer in which the isothiocyanate group is esterified with the hydroxy compound is reacted in the presence of the above-mentioned trimeric isothiocyanate catalyst, the above hydroxyl group is reacted. The concentration of the compound-diluted trimeric isothiocyanate catalyst is carried out at 1 to 20% by mass. The concentration is preferably from 1 to 10% by mass. When the concentration is 1% by mass or more, the amount of the hydroxy compound accompanying the trimeric isothiocyanate catalyst becomes too large, and the physical properties of the obtained polyisothiocyanate and the coating film formed thereby are not easily lowered. . When the concentration is 20% by mass or less, the catalytic effect of the hydroxy compound is not lowered, and as a result, the use amount of the trimeric isothiocyanate catalyst or the coloring of the polyisothiocyanate is less likely to occur. Wait.

When the acidic component contained in a small amount of a raw material such as the monomer represented by the above formula (33) is removed, the trimeric isothiocyanate catalyst is deactivated, and the weight of the monomeric diisothiocyanate is three. The polyisothiocyanate catalyst is used in an amount of from 1 ppm to 10%, preferably from 10 ppm to 5%. When the amount is 1 ppm or more, the function as a trimeric isothiocyanate catalyst can be sufficiently exhibited. When the amount is 3 ppm or less, the amount of addition of the acidic phosphoric acid compound and the acidic phosphate compound (described later) for deactivating the trimeric isothiocyanate catalyst is small.

The solvent may or may not be used in the reaction, but it is easier to control the reaction by using a solvent which is not reactive with the isothiocyanate group.

For the solvent, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or other esters or ethers, benzene, toluene, xylene, ethylbenzene, etc. can be used. An aromatic hydrocarbon such as trimethylbenzene. Of course, two or more solvents may be used in combination.

The trimeric isothiocyanate reaction is carried out at 30 ° C to 120 ° C, preferably at 50 ° C to 100 ° C. The progress of the reaction was confirmed by ¹ H-NMR analysis of the reaction mixture.

When the reaction reaches the desired conversion rate, the reaction can be stopped by injecting the reaction stopper to deactivate the catalyst. The conversion ratio is suitably selected in the range of 10 to 60%, and preferably 10 to 30%. Among the low conversion ratios, it is possible to obtain a polyisocyanate having a lower viscosity, but in terms of productivity, a conversion ratio of 10% or more is preferred. On the other hand, if the conversion ratio is 60% or less, the viscosity of the polyisothiocyanate becomes too high.

The conversion rate can be obtained by the following formula.

In the ¹ H-NMR chart, the peak of the methyl group of tetramethylnonane was set to 0 ppm, and the conversion ratio was calculated from the integral value (A) of the peak of 3.5 ppm and the integrated value (B) of the peak of 4.8 ppm.

Conversion rate (%) = B / (A + B) × 100

The stopper for the trimeric isothiocyanation reaction is one or more compounds using an acidic phosphoric acid compound and an acidic phosphate compound.

Examples of the acidic phosphoric acid-based inorganic acid include phosphoric acid, phosphorous acid, hypophosphorous acid, diphosphoric acid, hypophosphorous acid, pyrophosphoric acid, and peroxyphosphoric acid. The acidic phosphoric acid compound is preferably phosphoric acid.

The acidic phosphate compound is a compound having an acidic group and an ester group, and examples thereof include a monoalkyl phosphate of 2 to 8 carbon atoms, a monoalkyl phosphite, or a dialkyl phosphate having a carbon number of 4 to 16, and a phosphorous acid. An alkyl ester, or dilauryl phosphate, diphenyl phosphate, monolauryl phosphate, monophenyl phosphate, dilauryl phosphite, diphenyl phosphite, monolauryl phosphite, monophenyl phosphite, and the like. The acid phosphate compound is preferably a monoalkyl phosphate having 3 to 8 carbon atoms or a dialkyl phosphate having 6 to 16 carbon atoms, and more preferably dioctyl phosphate or monooctyl phosphate. Among these compounds, an acidic phosphoric acid compound is preferably used. The acid phosphate compound is preferably added in an amount of from 1 to 10 equivalents to 1 to 6 equivalents, based on the stoichiometric amount of the trimeric isothiocyanate catalyst. When the amount added is 1 equivalent or more, the trimeric isothiocyanate catalyst can be sufficiently deactivated. When the amount of addition is 10 equivalents or less, filtration of the insoluble matter generated can be performed without difficulty.

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

(wherein h' represents an integer from 2 to 40, i', j' are integers from 1 to 6, respectively, and the sum of i' and j' is an integer from 2 to 7.)

(wherein k is an integer of 1 to 4.)

(wherein 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, and r, t and u each represent an integer of 0 or more; , the sum of r, t and u is 5 to 90.)

(wherein v is 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 amine group, a thiol group, an aminoureido group, and a thioaminoureido group, and an isothiocyanate (the isothiocyanate) of the present embodiment will be described. It can be a reaction of a monoisothiocyanate or a polyisothiocyanate.

The resin composition of the present embodiment may contain any one of the following resins:

1. A compound having at least one group selected from the group consisting of a hydroxyl group, an amine group, a thiol group, an aminoureido group, and a thioaminoureido group, and a monoisothiocyanate Reactive resin,

2. reacting a compound having one group selected from the group consisting of a hydroxyl group, an amine group, a thiol group, an aminoureido group, and a thioaminoureido group with a polyisothiocyanate The resulting resin.

3. A compound having at least one group selected from the group consisting of a hydroxyl group, an amine group, a thiol group, an aminoureido group, and a thioaminoureido group, and a polyisothiocyanate Reactive resin.

The combinations of functional groups of the reaction are all the same and can be carried out according to the methods described herein.

In the following description, the reaction formula is shown for easy understanding of the reaction. Although the reaction formula is described by taking a monofunctional compound as an example, it is of course possible to carry out the same reaction in a polyfunctional compound.

[Reaction with a compound having a hydroxyl group]

The reaction of the compound having a hydroxyl group with an isothiocyanate can be represented by the following formula (100).

(wherein R ⁴¹ and R ⁴² each independently represent an organic group.)

The reaction system can be carried out in the presence of a solvent or in the absence of a solvent. The solvent used in the presence of a solvent is preferably a solvent which is inactive with respect to a hydroxyl group and an isothiocyanate group, or a solvent which reacts with an isothiocyanate group but has a very slow rate of reaction for the purpose. good. Preferred solvents include, for example, pentane, hexane, heptane, octane, decane, decane, dodecane, tetradecane, pentadecane, hexadecane, octadecane, nonadecane, and the like. Hydrocarbon compound; hydrocarbon such as diethyl ether, tetrahydrofuran, octyl ether, decyl ether, decyl ether, dodecyl ether, tetradecyl ether, pentadecyl ether, cetyl ether, stearyl ether, tetraethylene glycol dimethyl ether An ether in which a compound is bonded via an ether bond; dimethyl sulfide, diethyl sulfide, dibutyl sulfide, dihexyl sulfide, octyl sulfide, mercapto sulfide, mercapto sulfide, Hydrocarbon compounds such as dodecyl sulfide, tetradecyl sulfide, pentadecyl sulfide, hexadecyl sulfide, octadecyl sulfide, and decyl sulfide are separated by a thioether bond. Bonded thioethers; benzene, toluene, ethylbenzene, butylbenzene, pentylbenzene, hexylbenzene, octylbenzene, biphenyl, terphenyl, diphenylethane, (methylphenyl)phenyl An aromatic hydrocarbon compound such as ethane, dimethylbiphenyl or benzyltoluene; diphenyl ether, bis(methylbenzyl)ether, di(ethylbenzyl)ether, di(butylbenzyl) Ether, bis(pentylbenzyl)ether, di(hexylbenzene) ) Ether, bis (octylphenyl) ether, diphenyl ether, anisole and other aromatic Aromatic hydrocarbons bonded by an aromatic hydrocarbon compound via an ether bond; diphenyl sulfide, bis(methylbenzyl) sulfide, di(ethylbenzyl) sulfide, di(butylbenzyl) Thioether, bis(pentylbenzyl) sulfide, bis(hexylbenzyl) sulfide, bis(octylbenzyl) sulfide, bis(methylphenyl) sulfide, diphenyl An aromatic thioether bonded to an aromatic hydrocarbon compound such as thioether via a thioether bond; methoxybenzene, ethoxybenzene, butoxybenzene, dimethoxybenzene, diethoxybenzene, and a compound in which a hydrocarbon compound such as butoxybenzene is bonded to an aromatic hydrocarbon compound via an ether bond; methyl chloride, ethyl chloride, chloropentane, chlorooctane, methyl bromide, ethyl bromide, bromopentane, bromooctane , dichloroethane, dichloropentane, dichlorooctane, dibromoethane, dibromopentane, dibromooctane, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, etc.; acetone; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone; N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethyl Indoleamines such as carbamide and hydrazines such as dimethyl hydrazine; water.

The reaction temperature is not particularly limited, but can be carried out in the range of 0 ° C to 300 ° C. The reaction time can be set to any reaction time. For example, the residual amount of the isothiocyanate group can also be traced by an infrared spectrometer, and the reaction is stopped when the desired residual amount is reached.

Generally, a catalyst can also be used because the reaction of a hydroxyl group with an isothiocyanate group is slow. The catalyst is a Lewis acid and a transition metal compound capable of forming a Lewis acid, an organotin compound, a copper group metal, a zinc, and an iron group metal compound. Specific examples of the catalyst include: e.g. _{AlX 3, TiX 3, TiX 4} , VOX 3, VX 5, ZnX 2, FeX 3, SnX 4 ( In this case, X-based halogen, acetyl, alkoxy, Lewis acid represented by aryloxy) and transition metal compound capable of forming 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, (C ₈ H ₁₇ ) ₂ SnO, Bu ₂ SnCl ₂ , BuSnO (OH An organotin compound such as 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 , a compound of a copper group metal such as AgNO ₃ , AgBr, silver picrate, AgC ₆ H ₆ OClO ₄ ; a compound of zinc such as Zn(acac) ₂ ; 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 , a compound of an iron group metal such as ferrocene, etc. Ding , Ph represents a phenyl-based, acac represents Acetylacetonates chelate ligand based seat.).

[Reaction with a compound having an amine group]

The reaction of the compound having an amine group with an isothiocyanate is represented by the following formula (101).

(wherein R ⁴¹ and R ⁴² are groups defined in the above formula (100).)

The reaction can be carried out in the presence of a solvent or in the absence of a solvent. The solvent used in the presence of a solvent is preferably a solvent which is inactive with respect to the amine group and the isothiocyanate group, or a solvent which reacts with the isothiocyanate group but has a very slow rate of reaction for the purpose. Preferred solvents include pentane, hexane, heptane, octane, decane, decane, dodecane, tetradecane, pentadecane, hexadecane, octadecane, nonadecane, and the like. Hydrocarbon compound Hydrocarbon compounds such as diethyl ether, tetrahydrofuran, octyl ether, decyl ether, decyl ether, dodecyl ether, tetradecyl ether, pentadecyl ether, cetyl ether, stearyl ether, tetraethylene glycol dimethyl ether Ether-bonded ethers; dimethyl sulfide, diethyl sulfide, dibutyl sulfide, dihexyl sulfide, octyl sulfide, mercapto sulfide, mercapto sulfide, dodecane Hydrocarbon compounds such as thioether, tetradecyl sulfide, pentadecyl sulfide, hexadecyl sulfide, octadecyl sulfide, and hexadecyl sulfide are bonded via a thioether bond. Thioethers; benzene, toluene, ethylbenzene, butylbenzene, pentylbenzene, hexylbenzene, octylbenzene, biphenyl, terphenyl, diphenylethane, (methylphenyl)phenylethane, An aromatic hydrocarbon compound such as dimethylbiphenyl or benzyltoluene; diphenyl ether, bis(methylbenzyl)ether, di(ethylbenzyl)ether, di(butylbenzyl)ether, An aromatic hydrocarbon compound such as bis(pentylbenzyl)ether, di(hexylbenzyl)ether, di(octylbenzyl)ether, diphenyl ether or diphenyl ether is bonded via an ether bond Aromatic ethers; diphenyl sulfide, bis(methylbenzyl) sulfide, two ( Benzomethyl) sulfide, bis(butylbenzyl) sulfide, bis(pentylbenzyl) sulfide, bis(hexylbenzyl) sulfide, bis(octylbenzyl) sulfide An aromatic hydrocarbon compound in which an aromatic hydrocarbon compound such as di(methylphenyl) sulfide or diphenyl sulfide is bonded via a thioether bond; methoxybenzene, ethoxybenzene, butoxybenzene a compound in which a hydrocarbon compound such as dimethoxybenzene, diethoxybenzene or dibutoxybenzene is bonded to an aromatic hydrocarbon compound via an ether bond; methyl chloride, ethyl chloride, chloropentane, chlorooctane , methyl bromide, ethyl bromide, bromopentane, bromooctane, dichloroethane, dichloropentane, dichlorooctane, dibromoethane, dibromopentane, dibromooctane, chlorobenzene, bromobenzene , dichlorobenzene, dibromobenzene and other halides; water.

The reaction temperature is not particularly limited, but may be -50 ° C to It is carried out in the range of 250 °C. The reaction time can be set to any reaction time. For example, an infrared spectrometer can also be used to trace the residual amount of the isothiocyanate group, and the reaction is stopped when the desired residual amount is reached.

Usually, the reaction between the amine group and the isothiocyanate group is rapid, and although it is not necessary to use a catalyst, it cannot be denied by its use. As the catalyst, the catalysts listed in the above [Reaction with a compound having a hydroxyl group] can be used.

[Reaction with a compound having a mercapto group, an aminoureido group or a thioaminoureido group]

The reaction of a compound having a mercapto group, an aminoureido group or a thioaminoureido group with an isothiocyanate may also be subjected to various reactions depending on the compound to be used, but for example, the following formula (102) The reaction indicated.

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

The reaction of a compound having a mercapto group, an aminoureido group or a thioaminoureido group with an isothiocyanate can be carried out in the presence of a solvent or in the absence of a solvent. The solvent used in the presence of a solvent may be an alcohol such as methanol, ethanol, propanol or butanol in addition to the solvent listed in the above [Reaction with a compound having a hydroxyl group]; methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methoxybutyl acetate, ceramide acetate, acetic acid pentane Esters such as esters, methyl lactate, ethyl lactate, and butyl lactate.

The reaction temperature is not particularly limited, but can be carried out in the range of 0 ° C to 300 ° C. The reaction time can be set to any reaction time. For example, an infrared spectrometer can also be used to trace the residual amount of the isothiocyanate group, and the reaction is stopped when the desired residual amount is reached.

The reaction can be carried out in the presence of a catalyst, in the absence of any conditions. When a catalyst is used, the catalysts listed in the above [Reaction with a compound having a hydroxyl group] can be used.

When the compound having a mercapto group or an aminoureido group is reacted with an isothiocyanate, it is preferably subjected to heat treatment. By this heat treatment, the effects of mechanical properties such as rigidity, hardness, workability, impact resistance, and bending fatigue of the resin composition can be improved. Although the mechanism for exerting such an effect is not clear, the inventors of the present invention presumed that, for example, the right side bond of the above formula (102) may be reacted by the following formula (103) or formula (104) by heat treatment. It is caused by the formation of a ring structure in the molecular chain.

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

One of the preferred patterns of the resin of the present embodiment, the tie There are two or more resins selected from the group consisting of the divalent groups represented by the following formulas (6) to (8).

(In the formula, Y ¹ represents an organic group or a -NH- group.)

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

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

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

The above 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 are from ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane. , diethyl cyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylethane, ethylbenzene, diethylbenzene, diphenylethane, tetramethyldiphenyl Ethylethane, ethanol, propanol, butanol, pentanol, hexanol, octanol, decyl alcohol, dodecanol, stearyl alcohol, cyclohexanol, cyclooctanol, dimethylcyclohexanol, two A residue in which three hydrogen atoms are removed, such as ethylcyclohexanol, trimethylcyclohexanol, trimethylethylcyclohexanol, or dicyclohexylethanol.

The resin composition of the present embodiment is more preferably a resin represented by the following formula (109).

(wherein, K ¹ to K ^c each independently represent at least one group selected from the group consisting of the above formulas (6) to (8), and L ¹ to L ^c each independently represent that it may or may not contain An organic group selected from the group consisting of the formulae (6) to (8), wherein c represents an integer of 1 or more, and M ¹ and M ² each independently represent an isothiocyanate. The organic 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) represents the following formula (110).

Resin composition of a resin containing at least one constituent unit having two or more groups selected from the group represented by the above formulas (6) to (8) The method for producing the substance is not particularly limited, and for example, it can be produced by a reaction of a compound having a mercapto group, an aminoureido group or a thioaminoureido group with an isothiocyanate.

The reaction of a compound having a mercapto group, an aminoureido group or a thioaminoureido group with an isothiocyanate can be carried out in the presence of a solvent or in the absence of a solvent. The solvent used in the presence of a solvent may be an alcohol such as methanol, ethanol, propanol or butanol in addition to the solvent listed in the above [Reaction with a compound having a hydroxyl group]; methyl acetate, ethyl acetate, Ethyl acetate, butyl acetate, methoxybutyl acetate, ceramide acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate and the like.

The reaction temperature is not particularly limited, but can be carried out in the range of 0 ° C to 300 ° C. The reaction time can be set to any reaction time. For example, an infrared spectrometer can also be used to trace the residual amount of isothiocyanate, and the reaction is stopped when the desired residual amount is reached.

The reaction can be carried out in the presence of a catalyst, in the absence of any conditions. When a catalyst is used, the catalysts listed in the above [Reaction with a compound having a hydroxyl group] can be used.

The reaction apparatus used in carrying out the reaction is not particularly limited, and a known reactor can be used. For the reaction apparatus, for example, a conventionally known reactor such as a stirring tank, a pressurized agitation tank, a reduced pressure stirring tank, a column reactor, a distillation column, a packed column, and a thin film distiller can be suitably used in combination. The material of the reactor is also not particularly limited, and a known material can be used. For the material of the reactor, for example, glass, stainless steel, carbon steel, Hastelloy, or glass lining on a substrate, or Teflon can be used. Registered trademark) coated person. SUS304, SUS316, SUS316L, etc. are cheap and should be used. It is also possible to add a known flow-through device such as a flow meter, a thermometer, or the like to a meter machine, a reboiler, a pump, a condenser, etc., and heat it, as long as it is carried out by a known method such as steam or a heater, and can be used for cooling. Known methods of natural cooling, cooling water, brine, and the like. Additional steps can be added as needed.

In this way, a modified resin composition containing a resin containing at least one constituent unit selected from the group consisting of the groups represented by the above formulas (6) to (8) may be produced, but there are also The target resin could not be obtained depending on the reaction conditions. In this case, the intended resin can be obtained by further performing heat treatment as described below.

The heat treatment is preferably carried out in the range of 100 ° C to 300 ° C, and more preferably in the range of 150 ° C to 250 ° C. The heat treatment can be carried out under the atmosphere or under the atmosphere of an inert gas, and is preferably carried out under the atmosphere of an inert gas. The term "inert gas" as used herein refers to a gas such as nitrogen, helium, argon or helium. At the same time, the pressure can be pressurized, decompressed, or atmospheric. The time for performing the heat treatment is not particularly limited and may be carried out in the range of 1 minute to 500 hours. For example, an infrared spectrometer may be used to trace the amount of formation of the base represented by the above formulas (6) to (8). Heating is stopped when the desired amount is reached.

In the above-described production method, it is considered that the groups represented by the above formulas (6) to (8) are produced by various reaction routes, but it is presumed that the reaction of the following formula (111) is followed by the following formula. The compound on the right side of (111) produces a reaction in which a ring structure is formed by the following formula (112) or formula (113).

(wherein R ⁴¹ and R ⁴² represent a group defined by the above formula (100), Y represents an -NH- group or an organic group, and Z represents an oxygen atom or a sulfur atom.)

The modified resin composition of the present embodiment may be used singly or in combination with other resins. Other resins which can be mixed may be any resin, and various known resins can be used.

The modified resin composition of the present embodiment can be used in various known applications, and is suitable for use as a coating film on a surface of at least one material selected from the group consisting of metal, glass, and plastic. The use of materials. At the same time, the composition of the present embodiment is also applicable to aqueous coatings because it can be formed by a reaction with a water-stable functional group.

Since the modified resin composition of the present embodiment contains a sulfur atom in the molecular chain, the effect of improving the adhesion to the metal surface is large. Therefore, since the resin composition is in the precoated gold containing the rustproof steel sheet It can be applied to a genus, a car, or the like to impart beauty, weather resistance, acid resistance, rust resistance, cutting resistance, adhesion, and the like.

Oxazolidinethion≫

<better structure>

The second resin which is preferable in the present embodiment is a resin containing a molecular chain represented by the following formula (10).

(wherein P ¹ represents an aliphatic group and/or an aromatic group, and Q ¹ represents a divalent group selected from the group consisting of the following formula (11), (12), (13) or (14); In the group of one or more constituent units, plural P ¹ and Q ¹ may be the same or different, and n is an integer of 2 or more.)

In the formula, R ¹ represents an aliphatic group or an aromatic group, and 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 the same or different. Among X ² and Y ² in one Q ¹ , one or more are sulfur atoms. In other words, one Q ¹ system contains one or more sulfur atoms.

The structure represented by the above formulas (11) to (14) constituting the resin is surprisingly excellent in adhesion, and particularly excellent in adhesion to a metal surface. Although the mechanism for exerting such an effect is not clear, the inventors of the present invention presumed that the sulfur atom or the oxygen atom contained in the bond may improve the adhesion.

Therefore, the resin of the present embodiment has a characteristic in the bonding state contained in the molecule, and the skeleton structure other than the bond is not particularly limited, but a more preferable form is as follows.

The number average molecular weight of the resin is preferably 500 or more, more preferably 1,000 or more, and still more preferably 5,000 or more. In general, in the case of a high molecular weight, the heat resistance tends to be good. On the other hand, when the molecular weight is too high, handling properties at the time of forming a coating film (mixing property with other components, fluidity, expandability, etc.) may be disadvantageous. Therefore, the number average molecular weight is preferably 1,000,000 or less, and more preferably 500,000 or less, and more preferably 200,000 or less. In this case, the number average component is measured by a gel permeation chromatograph having at least one column having a molecular weight of 10 million or more, and the retention time is converted into a molecular weight calculated value using a standard substance such as polystyrene. . The number average molecular weight can be easily determined by those skilled in the art. Calculated by excluding the peaks from the solvent.

The content of the bond which contributes to the heat resistance is also related to the above-described number average molecular weight Mn. The number average molecular weight of the resin is divided by the value of the number of n ¹ (Mn/n ¹ ) of the sulfur atom constituting the nitrogen-carbon-sulfur bond and the number of oxygen atoms constituting the nitrogen-carbon-oxygen bond per molecule. 300 or less is preferable, and it is preferably 200 or less, and more preferably 150 or less. The resin composition of the present embodiment may exhibit an effect on adhesion to metal as described above, and in order to exhibit such an effect, it is preferred that the resin has too many such bonds per molecule. On the other hand, when the resin has too much of the above bonding, in particular, the resin has the above formulas (6) to (8), (11) to (14), (43), (44), (45), (46). In the case of the constituent unit represented by (47), the flexibility of one of the coating properties may be impaired. In this connection, Mn/n ^{1 is} preferably 50 or more, and more preferably 70 or more. In the n ¹ system, for example, the number of the bonds per unit weight (1 g) of the resin X ¹ (unit mol/g) can be determined by an infrared absorption spectrum or ¹ H-NMR or the like, and the above-mentioned number average molecular weight (Mn), Calculated by the formula: n ¹ = Mn‧X ¹ . When the resin contains both a nitrogen-carbon-sulfur bond and a nitrogen-carbon-oxygen bond, n ¹ constitutes the total number of sulfur atoms and oxygen atoms bonded to each other.

R ¹ in the above formulae (11) to (14) is an aliphatic group or an aromatic group. The hydroxyl group has at least one of an aliphatic group and an aromatic group, and may have an oxygen atom or a nitrogen atom in addition to a 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, and more preferably an aromatic group having 6 to 15 carbon atoms. The aliphatic group having 1 to 5 carbon atoms is preferably bonded to the aromatic group having 6 to 15 carbon atoms, and the carbon number of 7 to 20 is preferably 7 to 20 carbon atoms.

Specific examples of R ¹ include, for example, a straight-chain hydroxyl group such as a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group or an octamethylene group; a group of unsubstituted alicyclic hydrocarbons such as alkane, cyclohexane, cycloheptane, cyclooctane, bis(cyclohexyl)alkane; from methylcyclopentane, ethylcyclopentane, methylcyclohexane ( Each isomer), ethylcyclohexane (each isomer), propylcyclohexane (each isomer), butylcyclohexane (each isomer), pentylcyclohexane (different a structure, an alkyl-substituted cyclooctane group such as hexylcyclohexane (each isomer); from dimethylcyclohexane (each isomer), diethylcyclohexane (each isomer) a dialkyl-substituted cyclooctane group such as dibutylcyclohexane (each isomer); from 1,5,5-trimethylcyclohexane, 1,5,5-triethylcyclohexane , 1,5,5-tripropylcyclohexane (each isomer), 1,5,5-tributylcyclohexane (each isomer) and the like, a trialkyl-substituted cyclooctane group; toluene a monoalkyl-substituted benzene such as ethylbenzene or propylbenzene; a dialkyl-substituted benzene such as xylene, diethylbenzene or dipropylbenzene; and an aromatic hydrocarbon derived from diphenylalkane or benzene Group.

Among these, a group derived from hexane, benzene, diphenylmethane, toluene, cyclohexane, xylene, methylcyclohexane, isophorone or dicyclohexylmethane is preferred. The "base from" is a group representing a structure in which two hydrogen atoms are removed from the compound.

Or, preferably, R ¹ is an aliphatic group having 1 to 25 carbon atoms and an aromatic group having 6 to 25 carbon atoms. R ¹ is preferably a group which does not contain a spiro atom. Specific examples of R ¹ are from methane, ethane, propane, butane, pentane, hexane, octane, decane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, Ethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene Residues of two hydrogen atoms, such as diphenylmethane or tetramethyldiphenylmethane. When an isomer is present, the isomer is also included.

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

(In the formula, 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. In addition to a carbon atom, P ¹ may have an oxygen atom, a nitrogen atom or the like.

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

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

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

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

(wherein 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, and R ⁴⁵ represents a formula selected from the following formula (116); The basis of the group formed by (117), (118) or (119), the plurality of R ⁴⁴ may be the same or different.

P ¹ in the above formula (10) is more preferably a system represented by the following formulas (201) to (204).

In the above formulae (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 simultaneously an oxygen atom. That is, at least one of X ² and Y ² in one unit is a sulfur atom. Since it contains a sulfur atom, the adhesion to the adherend can be improved, and in particular, the adhesion to the metal surface can be improved.

Although the structure represented by the above formula (10) does not show the structure of the terminal, the object of the present invention is to improve the adhesion of the epoxy resin and the modified epoxy resin in one aspect, as described above. Among the compounds of the invention (the atoms constituting the compound of the present invention), the sulfur atom and/or the acid atomic system are mainly contained, and it is considered that the structure of the terminal does not necessarily have much influence. Meanwhile, as described later, the compound represented by the above formula (10) may be a compound having an epoxy group at the terminal and a compound having an isothiocyanate group (-NCS) at the terminal, a compound having a terminal thio group at the terminal, and an isocyanate group at the terminal. A compound of (-NCO) or a compound having a terminal thio group at the terminal is produced in combination with a compound having an isothiocyanate group at the terminal. According to the compound used to obtain the compound of the above formula (10), the terminal structure may be an epoxide group or a cyclosulfide group. Isocyanate group or isothiocyanate group. Meanwhile, as described in <Production Method>, a trimeric isocyanate group which is an isocyanate group trimer (a trimeric isothiocyanate group in the case of a trimeric isothiocyanate group) is also included in The compound of this embodiment. The N-substituted-O-substituted thiourethane group derived from the reaction of an alcoholic hydroxyl group and an isothiocyanate group in an epoxy resin (described later) may be contained in an episulfide resin (described later). An N-substituted-S-substituted thiocarbamate group in which a thiol group reacts with an isocyanate group, a dithiocarboyl group derived from a reaction of a thiol group and an isothiocyanate group in an episulfide resin Acid ester group.

<Manufacturing method>

The compound (resin) of the present embodiment may have, for example, a compound having an epoxy group at the terminal and a compound having an isothiocyanate group (-NCS) at the terminal, a compound having a terminal thio group at the terminal, and an isocyanate group at the terminal (- A compound of NCO), or a compound having a terminal thio group at the terminal, and a compound having an isothiocyanate group at the terminal are produced.

The compound (resin) of the present embodiment is a compound represented by the following formula (31) (a compound having an isocyanate group at the terminal end and a compound having an isothiocyanate group at the terminal), and is represented by the following formula (20). It is preferred to obtain a reaction of a compound (a compound having an epoxy group at the terminal and a compound having a terminal thio group at the terminal).

XCN-R ¹ -NCX (31)

(In the formula, 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 the formula (31) and the compound represented by the formula (20) may be selected as the formula (20) containing one or more compounds of the formula (31) wherein X is a sulfur atom and/or Y ² is a sulfur atom. Compound.

When a plurality of compounds represented by the formula (31) and a compound represented by the formula (20) are combined and reacted, a plurality of kinds of R ¹ and R ² may be the same or different.

Among the compounds represented by the above formula (20), a compound having an epoxy group at the terminal (which may also be represented by an epoxy resin) is preferably a compound represented by the following formula (120).

(wherein 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, tetramethyl bisphenol A, tetramethyl bisphenol F, and tetramethyl bisphenol. Bisphenol type epoxy resin, bisphenol, dihydroxynaphthalene, bisphenols such as AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, and tetrafluorobisphenol A Other divalent phenols such as 9,9-bis(4-hydroxyphenyl)fluorene, glycidylated epoxy resin, 1,1,1-paraxyl (4-hydroxyphenyl)methane, 4,4- (1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)benzene Glycolylation of anthraquinones such as 1,2,2,2-anthracene (4-hydroxyphenyl)ethane with glycidylated epoxy resins Epoxy resin, phenolic phenolic aldehyde, cresol novolac, bisphenol A phenolic, brominated phenolic phenolic, brominated bisphenol A phenolic phenolic phenolic glycidyl phenolic epoxy resin glycidyl ether, six A glycidyl ester such as hydrogen phthalic acid or a dimerized acid diglycidyl ester. These compounds having an epoxy group at the terminal may be used singly or in combination of plural kinds.

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

(wherein 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, tetramethyl bisphenol A, tetramethyl bisphenol F, and tetramethyl bisphenol. Bisphenol type epoxidized bisphenol type epoxy resin, bisphenol, dihydroxynaphthalene, such as AD, tetramethyl bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, etc. , 9,9-bis(4-hydroxyphenyl)phosphonium and other divalent phenols, thioglycidated episulfide resin, 1,1,1-parade (4-hydroxyphenyl)methane, 4 , 4-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene) bisphenol phenolic thioglycidated episulfide resin And thiol such as 1,1,2,2-anthracene (4-hydroxyphenyl)ethane Glycidated episulfide resin, phenolic phenolic phenol, cresol novolac, bisphenol A phenolic, brominated phenolic phenolic, brominated bisphenol A phenolic phenolic phenolic thiol glycosylated phenolic cyclic sulfur resin A thioglycidyl ester such as a glycidyl ether, a hexahydrophthalic acid or a dithioglycidyl dimer acid. These compounds having an episulfide group at the terminal may be used singly or in combination of several kinds.

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).

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

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

O=C=NR ¹ -N=C=O (122) (wherein R ¹ represents an aliphatic group or an aromatic group.)

Specific examples of the compound represented by the formula (122) include, For example, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanate hexane, diazonic acid diisocyanate, isophorone Diisocyanate, 1,3-bis(isocyanatemethyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, toluene diisocyanate (isomers) ), naphthalene diisocyanate (each isomer), and the like. 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 compounds, hexamethylene diisocyanate and isophorone diisocyanate are preferred in terms of weather resistance, heat yellowing resistance, and industrial availability. These isocyanate compounds may be used singly or in combination of several kinds.

Among the compounds represented by the above formula (31), the terminal has a different The cyanate group-containing compound (isocyanate compound) is preferably a compound represented by the following formula (123).

S=C=NR ¹ -N=C=S (123) (wherein R ¹ represents an aliphatic group or an aromatic group.)

Specific examples of the compound represented by the formula (123) include, for example, tetramethylene diisothiocyanate, penta methylene diisothiocyanate, hexamethylene diisothiocyanate, and 2,2,4. - Trimethyl-1,6-diisothiocyanate hexane, isobutyl thiocyanate, isophorone diisothiocyanate, 1,3-bis(isothiocyanate) Base)-cyclohexane, 4,4'-dicyclohexylmethane diisothiocyanate, 4,4'-diphenylmethane diisothiocyanate, toluene diisothiocyanate (isomeric , naphthalene diisothiocyanate (each isomer), and the like. More preferably, the formula (123) The compound is an aliphatic diisocyanate having 4 to 20 carbon atoms and an alicyclic diisocyanate having 8 to 20 carbon atoms. These compounds having an isothiocyanate group at the terminal may be used singly or in combination of several kinds.

Hereinafter, a method for producing the compound of the present embodiment will be described by taking the reaction of an epoxy resin and an isothiocyanate compound as an example. When an epoxy resin is used instead of the epoxy resin, the same method is also employed. In the following description, when the epoxy resin is replaced with an epoxy resin, the epoxy group may be replaced with an epoxy group. Meanwhile, when an isocyanate compound is used in place of the isothiocyanate compound, the same method can be employed. In the isothiocyanate compound and the isocyanate compound described below, the isothiocyanate group can be replaced with an isocyanate group.

The amount of the isothiocyanate compound to be used is preferably from 20 to 60 equivalent % based on the epoxy group. The isothiocyanate compound is used in an amount of preferably 25 to 50 equivalent %, more preferably 30 to 47 equivalent %, and most preferably 30 to 45 equivalent %. The isocyanate group in the isocyanate compound may be formed by a reaction with an epoxy group to form a ring structure, or a thioamine ester bond of an alcoholic hydroxyl group in an epoxy resin or a cyclization of an isothiocyanate group. Formation of a trimeric isothiocyanate ring by trimerization.

The reaction is usually carried out in the presence of a catalyst. Examples of the catalyst include a metal alkoxide such as lithium butoxide or sodium methoxide, a Lewis acid such as lithium chloride or aluminum chloride, a mixture of a Lewis acid such as a Lewis acid and a Lewis base such as triphenylphosphine oxide, and tetramethylammonium. Tetra-ammonium salts such as tetraethylammonium, tetrabutylammonium, benzyltributylammonium chloride, bromide, iodide, acetate, etc., triethylamine, N,N-dimethyl Benzylamine, 1,8-diazaheterocycle [5.4.0] eleven A tertiary amine such as alkene-7 or 1,4-diazacyclo[2.2.2]octane, 2-ethyl-4-methylimidazole or 2-phenylimidazole. These catalysts may be used singly or in combination of two or more. The catalyst is preferably a quaternary ammonium salt and a tertiary amine.

The amount of the catalyst used is usually in the range of 5 ppm to 2% by weight based on the total weight of the epoxy resin. The amount of the catalyst used is preferably from 20 ppm to 0.5% by weight. The catalyst can also be used after dilution in a suitable solvent.

The production method of the present embodiment can be carried out in a solvent-free manner or in a suitable solvent.

When a solvent is used, N,N-dimethylformamide, N,N-diethylformamide, N-methyl-2-pyrrolidone, dimethyl hydrazine, dimethyl acetamide are used. Preferably, a solvent containing no active hydrogen such as methyl ethyl ketone, methyl isobutyl ketone, xylene, toluene, methyl cyproterone acetate or tetrahydrofuran is preferred.

The reaction temperature is usually from 80 ° C to 300 ° C. It is preferably 100 ° C to 260 ° C, and more preferably 120 ° C to 220 ° C. When the reaction temperature is too low, the catalytic activity is lowered, and side reactions such as formation of a trimeric isocyanate ring are generated. Further, even if the reaction temperature is too high, the catalytic activity is lowered, and a side reaction is performed.

In the method for producing the compound of the present embodiment, the epoxy resin is heated to a predetermined temperature, and the water in the resin is removed by blowing air such as dry air or nitrogen, and then the isothiocyanate compound and the catalyst are introduced. good. The method of introducing the isothiocyanate compound and the catalyst can be appropriately selected, and it can be added all at once, or can be divided into several injections, or the isothiocyanate compound can be continuously supplied. At this time, isothiocyanate compounds and catalysts The inputs can be made simultaneously or separately. When continuously input, the investment time is preferably from 1 to 10 hours, and more preferably from 2 to 5 hours. When the input time is short, the amount of formation of the trimeric isothiocyanate ring may increase.

The compound of the present embodiment is preferably 20 to 45 equivalent % (preferably 22 to 42 equivalent %, more preferably 25 to 40 equivalents) of the epoxy group in the epoxy resin, and the isothiocyanate compound. The isothiocyanate group reacts to form an oxazolidine-2-thione ring (in the reaction of an episulfide resin with an isocyanate compound, a thiazolin-2-one ring, in an episulfide resin and an isothiocyanate compound) In the reaction, it is a thiazolinthione ring).

Among the epoxy groups in the epoxy resin, the ratio associated with the oxazolidine-2-thione ring can be analyzed, for example, by a method of chemically measuring the Oxdization rate, an infrared spectroscopy method, and a nuclear magnetic resonance spectroscopy method. The method of quantitative method is obtained.

The Oxdization ratio is, for example, an equivalent weight of an epoxy group in which an oxazolidine-2-thione ring has been formed with respect to the original epoxy group. When the epoxy group is formed into a oxazolidine-2-thione ring, the epoxy equivalent (referred to as Ep1) and the weight (referred to as Wt1) of the epoxy resin used can be used without substantially being consumed. The epoxy equivalent (referred to as Ep2) and the weight (referred to as Wt2) of the epoxy resin containing the oxazolidine-2-thione ring were determined by the following formula.

Oxd rate = 100 - (Wt2 ÷ Ep2) ÷ (Wt1 ÷ Ep1) × 100

The compound (resin) of the present embodiment may contain a thioamine ester bond obtained by reacting a part or all of an alcoholic hydroxyl group in an epoxy resin with an isothiocyanate group in an isothiocyanate compound. Knot. The amount of the thioaminate bond is preferably 0.9 equivalent/kg or less, and is 0.01 to 0.7 equivalent/ More preferably, kg is more preferably 0.05 to 0.6 equivalent/kg, and most preferably 0.1 to 0.5 equivalent/kg.

The compound (resin) of the present embodiment may contain a trithioisothiocyanate ring in which the isothiocyanate group in the isothiocyanate compound is a cyclized trimer. The content of the trimeric isothiocyanate ring is preferably such that the content of the oxazolidine-2-thione ring is 40 equivalent% or less, more preferably 30 equivalent% or less, and even 20 equivalent% or less. More preferably, it is preferably 10 equivalent% or less. If the trimeric isothiocyanate ring is too much, the polymerization stability may be lowered during production.

The compound (resin) of the present embodiment is preferably substantially free of isocyanate groups.

The melt viscosity of the compound (resin) of the present embodiment is preferably lower in order to improve fluidity. Specifically, the melt viscosity at 125 ° C is preferably 8,000 mPa ‧ or less. More preferably, it is 6,000 mPa ‧ or less, and more preferably 4,000 mPa ‧ s or less, and the best is 3,000 mPa ‧ or less

The amount of the hydrolyzable chlorine of the compound (resin) of the present embodiment is not particularly limited. For example, when it is used for electrical or electronic use, it is preferably 500 ppm or less. It is preferably 100 ppm or less.

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

The modifier is not particularly limited as long as it has a functional group reactive with an epoxy group, and examples thereof include xylenol, tert-butylphenol, nonylphenol, bisphenol A, and hydroquinone. Alcohols such as phenols, n-butanol, butyl quercetin, polyethylene glycol monoethyl ether, ethylene glycol, polypropylene glycol, Butylamine, octylamine, diethylamine, methylbutylamine, monoethanolamine, diethanolamine, N-methylethanolamine, triethylamine chlorate, N,N-dimethylethanolamine acetate, Amines such as trimethyl ketone imine of aminoethylethanolamine, carboxylic acids such as acetic acid, lactic acid, 2-ethylhexanoic acid, lauric acid, 12-hydroxystearic acid, benzoic acid, dimethanol propionic acid, and the like Sulfides such as sulfonate and acetic acid mixtures, thiols such as γ-thiol propyl dimethoxymethyl decane and γ-thiol propyl trimethoxy decane.

Meanwhile, for example, after upgrading with an amine, the amine group may be converted into an ammonium salt or the like by using acetic acid or the like to be converted into an ionic group.

[Sclerosing composition]

The compound (resin) of the present embodiment can be used in combination with a curing agent to prepare a curable composition.

When the hardening form is hardening using an epoxy group, examples of the curing agent include aliphatic groups such as ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, and N-ethylaminopiperazine. Amines, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylphosphonium, 4,4'-diaminodiphenol methane , such as aromatic amines such as 4,4'-diaminodiphenol ether, thiol propionates, thiols such as terminal thiol compounds of epoxy resins, bisphenol A, bisphenol F, and bisphenol AD , bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A , bisphenol, dihydroxynaphthalene, 1,1,1-gin (4-hydroxyphenyl)methane, 4,4-(1-(4-(1-(4-hydroxyphenyl)-1-methyl) Phenyl)ethylidene)bisphenol, phenolic phenolic aldehyde, cresol novolac, bisphenol A phenolic, brominated phenolic phenolic, brominated bisphenol A phenolic phenolic resin, polysebacic anhydride, methyltetrahydroortho Phthalic anhydride, Anhydride such as methylhexahydrophthalic anhydride, methyl HIMIC anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, 2-methylimidazole, 2-ethyl-4-methylimidazole, a third-grade amine such as an imidazole such as 2-phenylimidazole or an anthracene such as diammonium adipate, dimethylbenzylamine or 1,8-diazabicyclo[5.4.0]undecene-7 , dicyandiamide and the like. Further, these hardeners may be used singly or in combination of several kinds.

The hardening form is a hardening agent which can be used by using a crosslinkable group which is incorporated by modification of an epoxy group or a secondary hydroxyl group which is formed by modification, for example, a melamine resin, a polyisocyanate compound, and a block. Isocyanate compounds and the like. At the same time, these hardeners may be used singly or in combination of several.

The melamine resin may, for example, be hexamethoxymethylol melamine, methyl/butylated melamine or butylated melamine. Meanwhile, these melamine resins may be used singly or in combination of several kinds.

The polyisocyanate compound can be exemplified by, for example, tetramethylene diisocyanate, pentamethylene diisocyanate, HDI, 2,2,4 (or 2,4,4)-trimethyl-1,6-diisocyanate hexane, and Amino acid diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, tetramethylene xylene diisocyanate, toluene a diisocyanate such as diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, xylene diisocyanate or norbornane diisocyanate, and may be derived from such a diisocyanate Polyisocyanate. These polyisocyanates may be used singly or in combination of several use.

The polyisocyanate derived from the diisocyanate may be a polyisocyanate type polyisocyanate, a biuret type polyisocyanate, an amine ester type polyisocyanate, an allophanate type polyisocyanate or the like. These polyisocyanate compounds may be used singly or in combination of plural kinds.

As the blocked isocyanate compound, a compound in which the above-mentioned diisocyanate compound and/or polyisocyanate compound is blocked with a blocking agent can be used.

Examples of the terminal blocking agent include alcohols, phenols, anthraquinones, indoleamines, and active methylene groups. These blocking agents may be used singly or in combination of several kinds.

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

The curable composition may contain a solvent as needed. The solvent may be selected according to the purpose and use, and is preferably selected from hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral oil, and naphtha, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like. Esters such as ketones, ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, alcohols such as methanol, isopropanol, n-butanol, methyl cyproterone, butyl carbitol, water, etc. In the group. These solvents may be used singly or in combination of two or more.

The curable composition may contain a hardening accelerator as needed. As the hardening accelerator, for example, metal catalysts such as imidazoles, tertiary amines, phosphines, aminotriazoles, tin-based or zinc-based ones can be used. These hardening accelerators, They may be used singly or in combination of two or more.

In the curable composition, pigments, fillers, additives and the like which are 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 pigment, and rust preventive pigment, barium sulfate, calcium carbonate, cerium oxide, carbon black, talc, and clay. Other additives such as a filler such as a filler, a hindered amine system, a benzotriazole-based or a benzophenone-based ultraviolet absorber, a hindered phenol-based, a phosphorus-based, an iodine-based or a lanthanide-based antioxidant, a decane-based or a titanium-based coupling agent, Additives such as leveling agents, rheology control agents, pigment dispersants, anti-ballistic agents, antifoaming agents, etc. At the same time, it can contain reinforcing materials such as glass fiber, glass cloth and carbon fiber as needed.

The curable composition of the present embodiment has excellent adhesion and good fluidity, and can be suitably used as a coating material for a powder coating, an electrodeposition coating, a PCM coating, an adhesive, a sealing material, a molding material, and a composite. Materials such as materials, laminates, and sealing materials.

≫Resin with trimeric isothiocyanate structure≫

<better structure>

The third resin which is preferable in the present embodiment has two or more constituent units represented by the following formula (40). The resin further has one or more constituent units selected from the group consisting of monovalent, divalent or trivalent groups represented by the following formulas (41) to (47). R ³ of the constituent unit represented by the formulae (41) to (47) may be directly bonded to the isothiocyanate group to form a constituent unit of the formula (40). N of one of the constituent units represented by the formulae (41) to (47) is not directly bonded to N in the other constituent units represented by the formulae (41) to (47).

SCN-R ³ - (40)

(wherein R ³ represents an organic group, R ⁴ represents an aliphatic group or an aromatic group, and 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. It may also be different. R ³ may also be an aliphatic group or an aromatic group.)

Usually, substantially all of the nitrogen atoms constituting the polyisothiocyanate are bonded to at least one carbon atom. That is, the constituent elements are not directly bonded to each other by N. Meanwhile, R ³ in each constituent unit may be directly bonded to an isothiocyanate group to form a constituent unit represented by the formula (40). For example, a constituent unit represented by the formula (41) may be bonded to an isothiocyanate group to form a monofunctional repeating unit represented by the formula (46) or a difunctional repeating unit represented by the formula (47). The polyisothiocyanate may also have an isothiocyanate group that is not bonded to R ³ .

The functional groups represented by -X ³ -R ⁴ contained in the formulae (43) and (45) are illustrated.

In the method for producing a polyisothiocyanate to be described later, an N,N'-disubstituted dithiourea bond represented by the formula (43) or an N-substituted-O- group represented by the formula (45) is produced. When a thiourethane group or an N-substituted-O-substituted dithiocarbamate-based polyisothiocyanate is used, a hydroxy compound or a thiol is used. The functional group represented by -X ³ -R ⁴ is a group derived from the hydroxy compound or a thiol group. When a hydroxy compound is used, X ³ is an oxygen atom, and when a thiol is used, X ³ is a sulfur atom.

R ³ in the formulae (40) to (47), 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, and more preferably an aromatic group having 6 to 15 carbon atoms. The aliphatic group having 1 to 5 carbon atoms and the carbon group having 6 to 15 carbon atoms bonded to the aliphatic group on the aliphatic group are also preferably a group having 7 to 20 carbon atoms.

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

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

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

The constituent units represented by the above formulas (41) to (47) constituting the resin are surprisingly high in heat resistance, excellent in adhesion, and particularly in adhesion to a metal surface. Although the mechanism for exhibiting such effects is not clear, the inventors of the present invention presumed that the heat resistance may be improved by the stable six-membered ring structure, and the effect of improving the adhesion of the sulfur atom contained in the bond may be obtained.

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

The number average molecular weight of the resin is preferably 500 or more, more preferably 1,000 or more, and still more preferably 5,000 or more. In general, when the molecular weight is too high, the heat resistance tends to be good. On the other hand, when the molecular weight is too high, the handleability at the time of forming a coating film (mixing property with other components, fluidity, ductility, etc.) is disadvantageous. In the case of the case, the number average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less. The term "number average molecular weight" as used herein refers to a gel permeation chromatography apparatus having at least one column having an exclusion limit molecular weight of 10 million or more. The value calculated by converting the residence time into a molecular weight using a standard substance such as polystyrene was measured. As long as the manufacturer can easily determine the number average molecular weight. The calculation is performed by excluding the peaks from the solvent.

The content of the bond which contributes to the development of heat resistance is also related to the above-described number average molecular weight Mn. The value (Mn/n ¹ ) of the number n ¹ of the number of oxygen atoms constituting the sulfur atom containing a nitrogen-carbon-sulfur bond per molecule and the oxygen atom constituting the nitrogen-carbon-oxygen bond is defined by the number average molecular weight of the resin. 300 or less is preferable, and it is preferably 200 or less, and more preferably 150 or less. The resin composition of the present embodiment exhibits an effect on the adhesion to the metal as described above. However, in order to exhibit such an effect, it is preferable that the resin has a large amount of the above-mentioned bond per molecule. On the other hand, when the resin has too many such bonds per molecule, in particular, the resin has the above formulas (6) to (8), (11) to (14), (43), (44), (45). In the case of the constituent unit represented by (46) or (47), the flexibility of one of the coating properties may be impaired. In this regard, (Mn/n ¹ is preferably 50 or more, and more preferably 70 or more. n ¹ can be obtained by, for example, infrared absorption spectrum or ¹ H-NMR, etc., per unit weight (1 g) of the resin. The number X ¹ (unit: m/g) can be calculated from the above number average molecular weight (Mn) by the formula: n ¹ = Mn‧X ^{1. The} resin contains two nitrogen-carbon-sulfur bonds and nitrogen-carbon-oxygen bonds. In the case of n ¹ , the total number of sulfur atoms and oxygen atoms constituting each bond is determined.

<Preferred manufacturing method>

The resin of the present embodiment is preferably a resin obtained by reacting a compound having a nitrogen-carbon-sulfur bond with a polyisothiocyanate. The nitrogen-carbon-sulfur bond is composed of a nitrogen atom, a carbon atom and a sulfur atom, and these atoms are bonded in this order.

At the same time, the resin of the present embodiment is included The resin obtained by the method of polymerizing the compound represented by the formula (30) is preferred.

SCN-R ³ -NCS (33) (wherein R ³ represents an organic group, and may be an aliphatic group or an aromatic group.)

In the above formula (33), R ³ represents an aliphatic group, an aromatic group or a group formed by a combination of such groups (an aliphatic group substituted with an aromatic group). A compound of the formula (33) which is a monomer to be polymerized may be used, or a combination of two or more compounds in which R ³ is used may be used. The aliphatic group and the aromatic group of R ³ may have an oxygen atom, a nitrogen atom or the like in addition to a 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, and more preferably an aromatic group having 6 to 15 carbon atoms. The aliphatic group having 1 to 5 carbon atoms and the carbon group having 6 to 15 carbon atoms bonded to the aliphatic group are also preferably a carbon number of 7 to 20.

Specific examples of R ³ include, for example, a straight-chain hydrocarbon group such as a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group or an octamethylene group; a group of unsubstituted alicyclic hydrocarbons such as alkane, cyclohexane, cycloheptane, cyclooctane, bis(cyclohexyl)methane; from methylcyclopentane, ethylcyclopentane, methylcyclohexane ( Each isomer), ethylcyclohexane (each isomer), propylcyclohexane (each isomer), butylcyclohexane (each isomer), pentylcyclohexane (different a structure, an alkyl-substituted cyclohexane group such as hexylcyclohexane (each isomer); from dimethylcyclohexane (each isomer), diethylcyclohexane (each isomer) a dialkyl-substituted cyclohexane group such as dibutylcyclohexane (each isomer); from 1,5,5-trimethylcyclohexane, 1,5,5-triethylcyclohexane , 1,5,5-tripropylcyclohexane (each isomer), 1,5,5-tributylcyclohexane (each isomer) and other trialkyl-substituted cyclohexane groups; toluene a monoalkyl-substituted benzene such as ethylbenzene or propylbenzene; a dialkyl-substituted benzene such as xylene, diethylbenzene or dipropylbenzene; a group derived from an aromatic hydrocarbon such as benzene.

Among these groups, and selected from the group consisting of hexane, benzene, diphenylmethane, toluene, cyclohexane, xylyl, methylcyclohexane, isophorone or dicyclohexylmethane More than one group in the group is preferred. The "base from" is a group indicating a structure in which two hydrogen atoms are removed from a compound.

R ³ in the above formula (33) is more preferably a group represented by the following formulas (301) to (306).

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

The isothiocyanate represented by the above formula (33) is more preferably, for example, hexamethylene diisothiocyanate, isophorone diisothiocyanate or 4,4'-dicyclohexylmethane. Diisothiocyanate, 4,4'-diphenylmethane diisothiocyanate, toluene diisothiocyanate (each isomer), naphthalene diisothiocyanate (each isomer) and the like.

Next, a method for producing the resin (polyisothiocyanate) of the present embodiment will be described.

The polyisothiocyanate of the present embodiment can be obtained, for example, by polymerizing a monomeric diisothiocyanate alone. The polymerization of the monomeric diisothiocyanate is preferably carried out in the presence of a catalyst such as a trimeric isothiocyanate catalyst described later. Meanwhile, in the polymerization of the monomeric diisothiocyanate, a hydroxy compound or a thiol can also be used as an auxiliary raw material, and the isothiocyanate is reacted with a hydroxy compound or a thiol to make isothiocyanate. A part of the ester group is esterified with an amine, urea esterified with a formic acid or the like to obtain a polyisothiocyanate.

The monomeric diisothiocyanate means a compound represented by the above formula (33).

Examples of the hydroxy compound include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decyl alcohol, dodecanol, cyclopentanol, cyclohexanol, cycloheptanol, and a ring. Octanol, methylcyclopentanol, ethylcyclopentanol, methylcyclohexanol, ethylcyclohexanol, propylcyclohexanol, butylcyclohexanol, pentylcyclohexanol, hexylcyclohexanol, Dimethylcyclohexanol, diethylcyclohexanol, dibutylcyclohexanol, phenol, methylphenol, ethylphenol, propylphenol, butylphenol, amylphenol, hexylphenol, octylphenol, Nonylphenol, cumene phenol, dimethyl phenol, methyl ethyl phenol, methyl propyl phenol, methyl butyl phenol, methyl amyl phenol, diethyl phenol, ethyl propyl phenol, Ethyl butyl phenol, dipropyl phenol, dicumyl phenol, trimethyl phenol, triethyl phenol, naphthol, and the like. At the same time, ethylene glycol, 1,2- or 1,3-propanediol, 1,3-, 1,4- or 2,3-butanediol, 1,6-hexanediol, neopentyl glycol can also be used. , neopentyl glycol hydroxypivalate, 2- Low molecular weight compounds such as 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 Wait.

Examples of the mercaptan include methanethiol, ethanethiol, propane thiol, butane thiol, pentane thiol, hexane thiol, heptane thiol, octane thiol, decane thiol, Dodecanethiol, cyclopentanethiol, cyclohexanethiol, cycloheptanethiol, cyclooctanethiol, methylcyclopentanethiol, ethylcyclopentanethiol, methylcyclohexane Alkyl mercaptan, ethyl cyclohexane mercaptan, propyl cyclohexane mercaptan, butyl cyclohexane mercaptan, pentyl cyclohexane mercaptan, hexyl cyclohexane mercaptan, dimethyl cyclohexane sulfur Alcohol, diethylcyclohexanethiol, dibutylcyclohexanethiol, thiophenol, methyl thiophenol, ethyl thiophenol, propyl thiophenol, butyl thiophenol, pentyl Thiophenol, hexyl thiophenol, octyl thiophenol, mercapto thiophenol, cumene thiophenol, dimethyl thiophenol, methyl ethyl thiophenol, methyl propyl benzene sulphur Phenol, methyl butyl thiophenol, methyl amyl thiophenol, diethyl thiophenol, ethyl propyl thiophenol, ethyl butyl thiophenol, dipropyl thiophenol, diiso Propyl phenyl thiophenol, trimethyl thiophenol, triethyl thiophenol, naphthol thiophenol, and the like.

When a hydroxy compound is used, the isothiocyanate group/hydroxyl equivalent ratio of the above hydroxy compound to the monomeric diisothiocyanate can be selected from a value of from about 10 to 100 depending on the purpose. Similarly, when a thiol is used, the isothiocyanate group/thiol group equivalent ratio can be selected from a value of about 10 to 100 depending on the purpose.

The trimeric isothiocyanate catalyst for forming the trimeric isothiocyanate represented by the above formula (41), (46) or (47) is a quaternary ammonium salt. Preferably, it is more preferably a quaternary ammonium hydroxide or a quaternary ammonium carboxylic acid, and a quaternary ammonium carboxylic acid is more preferred.

Specific examples of the trimeric isothiocyanate catalyst include, for example, tetraalkylammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrabutylammonium hydroxide, and tetramethyl acetate. An organic weak acid salt such as an ammonium salt, a tetraethylammonium acetate or a tetrabutylammonium acetate. Although a metal salt of an alkyl carboxylic acid such as acetic acid, valeric acid, isovaleric acid, caproic acid, caprylic acid or myristic acid may be used, it is preferable to use an organic weak acid salt or the like in order to reduce the amount of use.

The above trimeric isothiocyanate catalyst can also be used after dilution. A hydroxy compound can be used as the diluent. The hydroxy compound may, for example, be methanol, ethanol, 1- or 2-butanol, 2-methyl-1-propanol, 1,2- or 1,3-propanediol, 1,3, 1,4- or 2, An alcoholic hydroxy compound such as 3-butanediol, glycerin or cyclohexanol, or a phenolic hydroxy compound such as phenol, cresol, xylenol or trimethylphenol. In terms of the crystallinity of the polyisocyanate obtainable by such a compound, an alcohol having a side chain such as 2-butanol, 2-methyl-1-propanol, 1,3 or 2,3-butanediol is used. good. At the same time, two or more kinds may be mixed. Mercaptans can also be used in place of the hydroxy compound.

An isothiocyanate compound which esterifies the above-mentioned monomeric diisothiocyanate alone or monomeric diisothiocyanate with a hydroxy compound amine in the presence of the above-mentioned trimeric isothiocyanate catalyst In the reaction, the concentration of the trimeric isothiocyanate catalyst diluted with the above hydroxy compound may be from 1 to 20% by mass. The above concentration is preferably from 1 to 10% by mass. When the amount of the hydroxy compound of the trimeric isothiocyanate catalyst is too large as long as it is 1% by mass or more, the physical properties of the obtained polyisothiocyanate and the coating film formed using the same are not Easy to reduce. When the concentration is 20% by mass or less, the effect of the assisting catalyst of the hydroxy compound is not lowered, and as a result, the amount of the trimeric isothiocyanate catalyst is increased, and the polyisothiocyanate is less likely to be caused. Coloring, etc.

In addition to the inactivation of the trimeric isothiocyanate catalyst due to the acidic component contained in a small amount of a raw material such as a monomeric diisothiocyanate, the amount of the trimeric isothiocyanate catalyst used is It is preferably from 1 ppm to 10%, and preferably from 10 ppm to 5%, based on the weight of the monomeric diisothiocyanate. As long as the amount of the catalyst is 1 ppm or more, the function of the trimeric isothiocyanate catalyst can be fully exerted. When the amount of the catalyst is 3% or less, in order to deactivate the isothiocyanurate catalyst, the amount of the reaction stop agent (described later) such as an acidic phosphoric acid compound or an acidic phosphate compound can be deleted.

The solvent may or may not be used in the reaction, but it is easier to control the reaction by using a solvent which is not reactive with the isothiocyanate group.

For the solvent, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or other esters or ethers, benzene, toluene, xylene, ethylbenzene, etc. can be used. An aromatic hydrocarbon such as trimethylbenzene. Of course, two or more types may be used in combination.

The trimeric isothiocyanate reaction can be carried out at 30 ° C to 120 ° C, preferably at 50 ° C to 100 ° C. The progress of the reaction was confirmed by ¹ H-NMR analysis of the reaction mixture. When the reaction solution reaches a desired conversion rate, the reaction can be stopped by injecting a reaction stopper to deactivate the catalyst. The conversion ratio is suitably selected in the range of 10 to 60%, and preferably 10 to 30%. Among the low conversion ratios, although a lower viscosity polyisothiocyanate may be obtained, in terms of productivity, a conversion ratio of 10% or more is preferred. On the other hand, as long as the conversion ratio is 60% or less, the viscosity of the polyisothiocyanate does not become too high.

The conversion rate can be obtained by the following formula. In the ¹ H-NMR chart, the above conversion ratio is a peak of a methyl group of tetramethylnonane of 0 ppm, an integral value (A) of a peak of 3.5 ppm and a peak of a peak of 4.8 ppm (B), and the following formula Calculate.

Conversion rate (%) = B / (A + B) × 100

The reaction stopper for the trimeric isothiocyanation reaction is one or more compounds selected from the group consisting of an acidic phosphoric acid compound and an acidic phosphate compound.

Examples of the acidic phosphoric acid-based inorganic acid include phosphoric acid, phosphorous acid, hypophosphorous acid, diphosphoric acid, hypophosphorous acid, pyrophosphoric acid, and peroxyphosphoric acid. And it should be phosphoric acid.

The acidic phosphate compound is a compound having an acidic group and an ester group, and examples thereof include a monoalkyl phosphate having 2 to 8 carbon atoms, a monoalkyl phosphite, a dialkyl phosphate having 4 to 16 carbon atoms, and a phosphorous acid di An alkyl ester, dilauryl phosphate, diphenyl phosphate, monolauryl phosphate, monophenyl phosphate, dilauryl phosphite, diphenyl phosphite, monolauryl phosphite, monophenyl phosphite, and the like. It is preferably a monoalkyl phosphate having a carbon number of 3 to 8 or a dialkyl phosphate having a carbon number of 6 to 16, and more preferably dioctyl phosphate or monooctyl phosphate.

Among these acidic phosphates, an acidic phosphoric acid compound is preferably used. The amount of the acidic phosphoric acid compound added is preferably from 1 to 10 equivalents, and is 1 relative to the stoichiometric amount of the trimeric isothiocyanate catalyst. More preferably up to 6 equivalents. When the amount added is 1 equivalent or more, the trimeric isothiocyanate catalyst can be sufficiently deactivated. As long as the amount of addition is 10 equivalents or less, the insoluble matter generated can be preferably filtered without difficulty.

When an acidic phosphoric acid compound is used, the inactive trimeric isothiocyanurate catalyst system often becomes insoluble in many cases and can be removed by filtration. Since it can be removed by filtration, the phosphorus derived from the acidic phosphoric acid compound in the polyisothiocyanate can be reduced to a level that is extremely small.

When an acidic phosphoric acid compound is used, the acid phosphate and the salt of the trimeric isothiocyanate catalyst are dissolved in the polyisothiocyanate, so that it may be mixed after the removal of the monomeric diisothiocyanate. Polyisocyanate.

In terms of the phosphorus concentration in the polyisothiocyanate, it is preferred to use an acidic phosphoric acid compound. When the acidic phosphoric acid compound is used, after the acidic phosphoric acid compound is added, it is maintained at 90 to 150 ° C, and preferably at 100 to 120 ° C for 30 to 120 minutes, so that the filtration property for shortening the filtration time can be improved in the filtration step.

After obtaining the polyisothiocyanate, an acidic phosphoric acid compound or an acidic phosphate compound may be added, and in particular, an acidic phosphoric acid compound may be added.

After the trimeric isothiocyanate reaction is stopped as described above, the unreacted monomeric diisothiocyanate and the solvent are removed from the reaction liquid and purified. Examples of the purification method include vacuum distillation, solvent extraction, and the like, and a thin film distiller can be usually used.

Monomeric diisothiocyanate in refined polyisothiocyanate The content of the acid ester is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less. The recovered unreacted monomeric diisothiocyanate can be reused.

The polyisothiocyanate can also be used by mixing with an organic solvent. In this case, the organic solvent is preferably a functional group which does not have a reaction 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.

In the polyisothiocyanate, for example, a curing accelerator, a pigment, a leveling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, and a surfactant which can promote an amine esterification reaction or the like can be mixed according to the purpose. Used in various additives.

Polyisothiocyanate can be widely used in two-component polyurethane coatings, sealing materials, adhesives, inks, coating agents, castables, elastomers, foams, plastic materials, fiber treatment agents, one-liquid hardening polyiso In the field of thiocyanates and the like.

[Examples]

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

[Analytical method]

(1) ¹ H-NMR analysis

Approximately 0.3 g of the sample was weighed, and about 0.7 g of heavy chloroform (manufactured by Aldrich Co., Ltd., 99.8%) and tetramethyl decane (manufactured by Nippon Pure Chemical Co., Ltd., and Koichi) were added as an internal standard substance. Evenly mixed The solution was analyzed as a sample by NMR. The sample was analyzed by a JNM-A400 FT-NMR system manufactured by JEOL Ltd.

Further, the conversion ratio of the isocyanate group at the time of production of the polyisocyanate was calculated by the following method.

^{In the 1} H-NMR chart, the signal of the methyl group of tetramethylnonane was taken as 0 ppm, and the integral value (A) of the signal from the 3.3 ppm signal of the monomeric diisocyanate and the signal of 3.8 ppm from the structure of the isocyanurate was integrated. The value (B), the conversion rate is calculated by the following formula.

Conversion rate (%) = B / (A + B) × 100

Meanwhile, the conversion ratio of the isothiocyanate group at the time of production of the polyisothiocyanate was calculated by the following formula.

^{In the 1} H-NMR chart, the signal of the methyl group of tetramethylnonane was taken as 0 ppm, and the integrated value (A) from the 3.5 ppm signal from the monomeric diisothiocyanate and 4.8 ppm from the structure of the isocyanurate. The integral value (B) of the signal, and the conversion rate is calculated by the following formula.

Conversion rate (%) = B / (A + B) × 100

(2) number average molecular weight

GPC-8020 manufactured by Tosoh Corporation was used as a measuring device, and tetrahydrofuran was used as a developing solvent, and TSKgel SuperH3000, SuperH2000, and SuperH1000 manufactured by Tosoh Corporation were used as a column to perform gel permeation chromatography analysis (GPC analysis). About 10 mg of the sample was dissolved in 10 mL of tetrahydrofuran as a measurement sample, and the injection amount was 10 μL. The number average molecular weight was determined by comparing the observed molecular weight with the known dissolution time of polystyrene using a differential refractive index detector.

(3) Heat resistance evaluation method

Using TG-8120 (manufactured by RIGAKU Co., Ltd.), the measurement of the thermal weight reduction was carried out under the conditions of a sample of 10 mg and a temperature increase rate of 10 ° C/min under a nitrogen atmosphere, and it was confirmed that the reduction of 5% by weight was not possible within 300 ° C. A, when it is confirmed that the reduction of 5% by weight is within 300 ° C, it is set to B.

(4) Coating film evaluation method

The adhesion evaluation of the coating film was carried out as follows. The coating film formed on an aluminum plate (緃10 cm, width 10 cm, thickness: 5 mm) was patterned with a 1 mm square indentation, and the entire aluminum plate was immersed in acetone. After 24 hours, it was investigated whether or not the coating film remained. Each sample was subjected to the same test 10 times, and when the coating film remained 8 or more, it was set to A, and the rest was set to B.

(5) Copper peel strength

The copper peel strength was measured in accordance with JIS C 6481. A indicates that the copper peel strength is good, and B indicates a bad one.

[Example 1]

Dioxane adipate and polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd., trade name) were charged so that the equivalent ratio of isocyanate group to sulfhydryl group was 1.0, and butyl acetate was mixed to prepare solid content 10 % dispersion. The dispersion was stirred at 120 ° C for 12 hours. A part of the reaction liquid was collected and analyzed by ¹ H-NMR, and a peak from the vicinity of 3.3 ppm of the isocyanate disappeared. After the butyl acetate was distilled off by a rotary evaporator, heat resistance was evaluated. The evaluation results are shown in Table 1.

[Embodiment 2]

36 g of 肼‧1 hydrate was dissolved in 1 L of isopropyl alcohol, cooled to 0 ° C, and 50 g of hexamethylene diisothiocyanate was added while stirring. The resulting solid was recovered by filtration and analyzed by ¹ H-NMR, which was 4, 4'-hexamethylenedithiocarbazone.

The 4,4'-hexamethylenebisthiocarbazone was treated in the same manner as in Example 1 in the same manner as in Example 1 using a polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd.) to evaluate heat resistance. The evaluation results are shown in Table 1.

[Example 3]

36 g of 肼‧1 hydrate was dissolved in 1 L of isopropyl alcohol, cooled to 0 ° C, and 50 g of hexamethylene diisocyanate was added while stirring. The resulting solid was recovered by filtration and analyzed by ¹ H-NMR, which was 4,4'-hexamethylenediamine urea.

The 4,4'-hexamethylenediamine urea was treated with the polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd., trade name) in the same manner as in Example 1 to evaluate the heat resistance. The evaluation results are shown in Table 1.

[Example 4]

36 g of 肼‧1 hydrate was dissolved in 1 L of isopropyl alcohol, cooled to 0 ° C, and 280 g of 2-isocyanatoethyl methacrylate was added while stirring. The resulting solid was recovered by filtration and analyzed by ¹ H-NMR, which was (2-(decalin)ethyl) methacrylate.

Next, 100 g of this 2-(indolylamine)ethyl methacrylate 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. The double bond constituting methyl methacrylate disappeared. After the toluene was distilled off by a rotary evaporator, a polymer having an amine urea group was obtained.

The polymer and polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd., trade name) were subjected to the same method as in Example 1 to evaluate the heat resistance. The evaluation results are shown in Table 1.

[Examples 5 to 8]

The heat resistance was evaluated in the same manner as in Example 1 except that hexamethylene diisocyanate was used instead of the polyisocyanate. The evaluation results are shown in Table 1.

[Embodiment 9]

The same procedure as in Example 4 was carried out to produce (2-(indolyl)ethyl) methacrylate. The methacrylic acid (2-(decalin)ethyl) ester and polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd., trade name) were subjected to the same method as in Example 1 to evaluate 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 hexanediol was used instead of the dioxane adipate of 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 diammonium adipate. The evaluation results are shown in Table 1.

[Reference Example 3]

100 g of (2-hydroxyethyl) methacrylate 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, and the double bond constituting methyl methacrylate disappeared. After toluene was distilled off by a rotary evaporator, a polymer having a hydroxyl group was obtained. The polymer and polyisocyanate (Duranate TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd., trade name) were subjected to the same method as in Example 1 to evaluate the heat resistance. The evaluation results are shown in Table 1.

[Reference Examples 4 to 6]

The heat resistance was evaluated in the same manner as in Example 1 except that hexamethylene diisocyanate was used instead of the polyisocyanate of Comparative Example 1. The evaluation results are shown in Table 1.

[Reference Example 7]

The evaluation of the heat resistance was carried out in the same manner as in Example 1 except that 2-(hydroxyethyl) methacrylate was used instead of the diammonium adipate of Example 1. The evaluation results are shown in Table 1. .

[Manufacturing Example 1] Production of Polyisothiocyanate

A nitrogen gas atmosphere was formed in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas injection tube, and 600 g of hexamethylene diisothiocyanate was charged, and the temperature in the reactor was maintained at 300 ° C under stirring. 1.0 g of a cyclic trimer catalyst tetramethylammonium phthalate was added. When the conversion ratio of the isothiocyanate became 30%, phosphoric acid was added to stop the reaction. After filtering the reaction liquid, unreacted hexamethylene diisothiocyanate was removed using 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.

[Embodiment 10]

An acrylic polyol (Setalux 1903; manufactured by NUPLEX Co., Ltd., trade name; hydroxyl group concentration: 4.5% (resin basis), resin solid content: 75%) and the polyisothiocyanate obtained in Production Example 1 were charged to make isothiocyanate. The equivalent ratio of the acid ester group to the hydroxyl group was 1.0, and 0.5% by 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 coated on an aluminum plate by a coating machine to have a resin film thickness of 40 μm. After standing at room temperature for 10 minutes, it was kept in an oven at 150 ° C for 10 hours to obtain a hardened coating film. The adhesion of the obtained hardened coating film was evaluated. The evaluation results are shown in Table 2.

[Example 11]

In addition to the 4,4'-dicyclohexylmethanediamine and the polyisothiocyanate obtained in Production Example 1, the equivalent ratio of the isothiocyanate group to the hydroxyl group was 1.0, and butyl acetate was mixed to prepare The same method as in Example 1 was carried out, except that the resin composition was 50% of the solid content. The evaluation results of the hardened coating film are shown in Table 2.

[Embodiment 12]

The polyisothiocyanate obtained in Production Example 1 was charged in the same manner as in the above, so that the equivalent ratio of the isothiocyanate group to the fluorenyl group was 1.0, and ethanol was mixed to prepare a solid content of 10%. The same method as in Example 10 was carried out except for the resin composition. The evaluation results of the hardened coating film are shown in Table 2.

[Example 13]

36 g of 肼‧1 hydrate was dissolved in 1 L of isopropyl alcohol, cooled to 0 ° C, and 280 g of 2-isocyanatoethyl methacrylate was added while stirring. The resulting solid was recovered by filtration and analyzed by ¹ H-NMR to be (2-(decalin)ethyl) methacrylate.

Next, 100 g of this 2-(indolylamine)ethyl methacrylate 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, and the double bond constituting methyl methacrylate disappeared. The toluene was distilled off by a rotary evaporator to obtain a polymer having an amine urea group.

The polymer and the polyisothiocyanate obtained in Production Example 1 were charged so that the equivalent ratio of the isothiocyanate group to the aminoureido group became 1.0, and butyl acetate was mixed to prepare a solid content of 25%. Resin composition. The same results as in Example 10 were carried out using this resin composition, and the results of evaluation of the cured coating film are shown in Table 2.

[Embodiment 14]

36 g of 肼‧1 hydrate was dissolved in 1 L of isopropyl alcohol, cooled to 0 ° C, and 50 g of hexamethylene diisothiocyanate was added while stirring. The resulting solid was recovered by filtration and analyzed by ¹ H-NMR to be 4,4'-hexamethylenedithiocarbazone.

The 4,4'-hexamethylenedithiocarbazone was charged with the polyisothiocyanate obtained in Production Example 1 to obtain an equivalent ratio of the isothiocyanate group to the thioaminoureido group. The composition was 1.0, and butyl acetate was mixed to prepare a resin composition having a solid content of 25%. The same results as in Example 10 were carried out using this resin composition, and the results of evaluation of the cured coating film are shown in Table 2.

[Reference Examples 8 to 12]

In addition to the use of trimeric isocyanate type polyisocyanate (Duranate) TPA-100, manufactured by Asahi Kasei Chemicals Co., Ltd., trade name) was subjected to the same method as in Examples 10 to 14 except for the polyisothiocyanate, and the evaluation of the cured coating film was carried out. The results are shown in Table 2.

[Example 15]

2-hydroxyethyl methacrylate was added to the polyisothiocyanate obtained in Production Example 1 so that the equivalent ratio of the isothiocyanate group to the hydroxyl group became a hydroxyl group/isothiocyanate group = 1.3. A butyl acetate was added to obtain a resin composition having a solid content of 50%. The resin composition was heated at 130 ° C and heated until the disappearance of the isothiocyanate group by ¹ H-NMR. Next, this resin composition was applied on an aluminum plate by a coating machine until a resin film thickness of 40 μm was formed. After standing at room temperature for 10 minutes, it was kept in an oven at 150 ° C for 10 hours to obtain a hardened coating film. The adhesion of the obtained hardened 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 the polyisocyanate type polyisocyanate (Duranate TPA-100, trade name, manufactured by Asahi Kasei Chemicals Co., Ltd.) was used instead of the polyisothiocyanate obtained in Production Example 1. The evaluation results of the hardened coating film are shown in Table 2.

[Example 16]

In the same manner as in Example 13, a (2-(decalin)ethyl) methacrylate was produced, followed by obtaining a polymer of (2-(decalin)ethyl) methacrylate.

The polymer and the allyl isothiocyanate are charged so that the equivalent ratio of the isothiocyanate group to the aminoureido group becomes 1.0, and butyl acetate is mixed to prepare a solid form. 25% of the resin composition. The resin composition was applied on an aluminum plate by a coater to form a resin film having a thickness of 40 μm. After standing at room temperature for 10 minutes, it was kept in an oven at 150 ° C for 10 hours to obtain a hardened coating film. The adhesion of the obtained hardened coating film was evaluated. The evaluation results are shown in Table 2.

[Reference Example 14]

The same procedure as in Example 16 was carried out except that 2-isocyanatoethyl methacrylate was used instead of allyl isothiocyanate. The evaluation results of the hardened coating film are shown in Table 2.

[Example 17]

In a 2L eggplant type flask filled with 200 g of water and 800 g of tetrahydrofuran, 345 g of tetramethylene diisothiocyanate and 384 g of diammonium adipate were added, and the mixture was stirred at 60 ° C for 12 hours, and then 7 g of ethyl isothiocyanate was added, and the precipitated solid was collected by filtration. Next, the solid was added to a 2 L eggplant type flask to which 1,000 g of a 2% by weight aqueous sodium hydroxide solution had been added, and the mixture was stirred at 100 ° C for 8 hours, and the precipitated solid was collected as a filter paper. The ¹ H-NMR of the recovered solid was measured to identify the structure. Fig. 1 shows the ¹ H-NMR spectrum of the solid obtained in Example 17. It is inferred that a resin represented by the following formula (124) can be obtained. The number average molecular weight is 5,900, and the Mn/n ¹ system defined above is 150. Further, X ¹ is an integral value of 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) from the ¹ H-NMR measurement sample. More than seeking.

[Embodiment 18]

A nitrogen atmosphere was formed in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen sparge tube, and 100 g of hexamethylene diisothiocyanate was charged, and the temperature in the reactor was maintained at 100 ° C under stirring. . Then, 2 g of tetramethylammonium acetate (2-butanol 5.0% by mass solution) was added as a catalyst and stirred. A suitable reaction liquid was sampled, and when the conversion ratio of the isothiocyanate became 21%, ¹ H-NMR analysis was carried out, and 0.28 g of phosphoric acid (85 mass% aqueous solution) was added to stop the reaction. Then, the mixture was further heated at 100 ° C for 1 hour, cooled to room temperature, and the reaction liquid was filtered to remove insoluble matter, and then the monomeric diisothiocyanate was removed by a thin film distillation apparatus. The concentration of the monomeric diisothiocyanate was 0.4% by mass, and the number average molecular weight was 860.

The ¹ H-NMR chart of the obtained polyisothiocyanate is shown in Fig. 2 . It was confirmed from the NMR chart that the polyisothiocyanate contained at least the constituent unit represented by the formula (28). The number average molecular weight is 1,200, and the Mn/n ² system 100 defined above. Further, X ¹ is a peak of a sample prepared from ¹ H-NMR and a peak of chloroform (7.26 ppm) and a peak of a methylene chain directly bonded to a nitrogen atom forming a trimeric isothiocyanate ring. The ratio of the integral values of (3.8 ppm) was obtained.

The obtained polyisothiocyanate and acrylic polyol (manufactured by DIC Corporation, trade name: Acrydic A-801) were prepared so that the isosulfate group/hydroxyl ratio (equivalent) became 1.0, and the solid content of each coating was added. 0.5% dibutyltin dilaurate, to which is a mixture of ethyl acetate/toluene/butyl acetate/xylene/propylene glycol monomethyl ether acetate (weight ratio=30/30/20/15/5) As a diluent. The obtained coating solution was coated on a copper foil having a thickness of 35 μm, and the obtained coating solution was adjusted to a dry film thickness of 50 μm by an air blasting gun, and a copper foil of 35 μm was superposed thereon, and baked in an oven maintained at 120 ° C. After 30 minutes, the evaluation of the copper peel strength was performed. The results are shown in Table 3.

[Examples 19 to 23]

Polyisocyanate was produced in the same manner as in Example 18 under 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]

In addition to using hexamethylene diisocyanate instead of hexamethylene diisothiocyanate, 0.1 g of tetramethylammonium acetate (2-butanol 5.0% by mass solution) was used as a catalyst, and 12 mg of phosphoric acid (85) was used. Polyisocyanate was produced in the same manner as in Example 18 except for the mass % aqueous solution. The number average molecular weight is 1,100. 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]

Using the formulation and conditions shown in Table 4, a polyisocyanate was produced in the same manner as in Example 18, and the copper peel strength was evaluated. The results are shown in Table 4.

[Example 24]

In a separate flask in which 100 parts of a bisphenol A type epoxy resin (epoxy equivalent 189) was placed, a stirrer, a thermometer, a reflux condenser, and a nitrogen gas injection tube were attached, and nitrogen gas was sprayed into the flask. The temperature was raised to 150 ° C with stirring, and after stirring to 150 ° C, stirring was continued for 30 minutes. The reaction temperature was maintained at 150 ° C, and a mixture of 18.5 parts of hexamethylene diisothiocyanate and 0.05 parts of tetrabutylammonium chloride (and pure ruthenium; practical grade) was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was carried out while maintaining the temperature at 150 °C. From the 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 the number average molecular weight was not found to be 20,000 or more. In addition, 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 Corporation as a column. About 10 mg of the sample was dissolved in 10 mL of tetrahydrofuran as a measurement sample, and the amount of injection was 10 μL. The number average molecular weight was determined by comparing the molecular weight group observed by the differential refractive index detector with the known dissolution time of polystyrene. The Mn/n ¹ system 220 as defined above. Further, X ¹ was determined from the ^ratio of the loading concentration of the sample measured by ¹ H-NMR to the integrated value of the peak of toluene (2.3 ppm) added as an internal standard and the peak of methine forming a ring structure (4.8 ppm). .

The obtained compound, a hardener (dicyanoimide) and a hardening catalyst (2-methylimidazole) were added, and the obtained resin composition was impregnated in a glass cloth, and dried to obtain a prepreg having a resin content of 50% by mass. body. Four sheets of the prepreg were stacked, and a copper foil having a thickness of 35 μm was attached to the upper and lower sides thereof, and heated and pressed for 60 minutes under the conditions of a temperature of 190 ° C and a pressure of 20 kg/cm ² to prepare a laminate. The copper peel strength of the laminate was evaluated. The results are shown in Table 5.

[Examples 25 to 29]

Using the compound shown in Table 5, the reaction was carried out in the same manner as in Example 24, and subjected to ¹ H-NMR analysis to obtain the oxazolidine-2-thione ring represented by the above formula (125) or (126). Compound. The copper peel strength was evaluated in the same manner as in Example 24 using the obtained compound. The results are shown in Table 5.

[Examples 30 to 35]

Using the compound shown in Table 6, the reaction was carried out in the same manner as in Example 24, and ¹ H-NMR analysis was carried out to obtain a compound containing a thiazolinthione ring represented by the following formula (127) or (128). The copper peel strength was evaluated in the same manner as in Example 24 using the obtained compound. The results are shown in Table 6.

[Examples 36 to 41]

Using the compound shown in Table 7, the reaction was carried out in the same manner as in Example 24, and subjected to ¹ H-NMR analysis to obtain a compound containing a thiazolin-2-one ring represented by the following formula (129) or (130). . The copper peel strength was evaluated in the same manner as in Example 24 using the obtained compound. The results are shown in Table 7.

[Examples 42 to 59]

Using the compounds shown in Tables 8 to 10, the reaction was carried out in the same manner as in Example 24, and subjected to ¹ H-NMR analysis to obtain the oxazolidine-2-thione represented by the above formula (125) or (126). a compound of the ring. The copper peel strength was evaluated in the same manner as in Example 24 using the obtained compound. The results are shown in Tables 8 to 10.

[Examples 60 to 62]

Using the compound shown in Table 11, the reaction was carried out in the same manner as in Example 24, and ¹ H-NMR analysis was carried out to obtain a compound containing the thiazolin-2-one ring represented by the above formula (129) or (130). The copper peel strength was evaluated in the same manner as in Example 24 using the obtained compound. The results are shown in Table 11.

[Comparative Examples 21 to 26]

Using the compound shown in Table 12, the reaction was carried out in the same manner as in Example 24, and ¹ H-NMR analysis was carried out to obtain a compound containing an oxazolidinone ring represented by the following formula (131) or (132). The copper peel strength was evaluated in the same manner as in Example 24 using the obtained compound. The results are shown in Table 12.

Claims (16)

A resin which is a compound selected from the group consisting of at least one functional group selected from the group consisting of a monovalent group represented by the following formula (2), (4) or (5), and a compound selected from the group consisting of monoisosulfur a reaction of at least one compound selected from the group consisting of cyanate esters and polyisothiocyanates, or a group consisting of a monovalent group selected from the group consisting of the following formula (4) or (5) Reaction of at least one compound of at least one functional group with at least one compound selected from the group consisting of monoisocyanate, polyisocyanate, monoisothiocyanate, and polyisothiocyanate, and obtains -NH ₂ (2) The resin according to claim 1, wherein the monoisothiocyanate contains a compound represented by the following formula (30), and in the formula R ⁵ -NCS (30), R ⁵ represents a carbon number of 1 to An aliphatic group of 25, an aliphatic group substituted with an aromatic group and having 7 to 25 carbon atoms or an aromatic group having 6 to 25 carbon atoms. The resin according to claim 1 or 2, wherein A cyclic structure obtained by reacting the aforementioned functional group represented by the formula (4) or (5) with an isocyanate group or an isothiocyanate group. The resin according to claim 3, wherein the group containing the cyclic structure has two or more groups selected from the group consisting of divalent groups represented by the following formula (7) or (8). At least one constituent unit, In the formula, Y ¹ represents an organic group, and several Y ¹ systems in the same molecule may be the same or different. The resin according to claim 4, wherein the number average molecular weight of the resin is Mn, and the sum of the number of the constituent units represented by the formula (7) or (8) contained in the molecule per molecule When n ² is ² , Mn is 500 or more, Mn/n ² is 50 or more and 300 or less, and n ^{2 is} represented by the formula: n ² = X ² ‧ Mn (X ² represents the formula (7) contained per 1 g of the resin Or (8) the sum of the number of the above-mentioned constituent units) is calculated. The resin according to claim 1 or 2, wherein the polyisothiocyanate contains a compound represented by the following formula (32). In the formula, R ⁶ represents an organic group, and a represents an integer of 2 to 1,000. The resin according to claim 1 or 2, wherein the polyisothiocyanate contains a polymer having two or more repeating units represented by the following formula (33-1). In the formula, 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, and plural R ⁷ , R ⁸ , b and g in the same molecule. They can be the same or different. The resin according to claim 1 or 2, wherein the polyisothiocyanate comprises a compound having the following structural unit: two or more constituent units represented by the following formula (40), and selected from the group consisting of At least 1 of the group consisting of monovalent, divalent or trivalent groups represented by the following formula (41), (42), (43), (44), (45), (46) or (47) a constituent unit in which a nitrogen atom in the compound is bonded to a carbon atom, SCN-R ³ - (40) In the formula, R ³ represents an organic group, R ⁴ represents an aliphatic group or an aromatic group, and 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. It can also be different. The resin according to claim 1 or 2, wherein the polyisothiocyanate contains a compound represented by the following formula (33), and in the formula SCN-R ³ -NCS (33), R ³ represents Organic base. The resin of claim 8, wherein R ³ is an aliphatic group or an aromatic group. The resin of claim 9, wherein R ³ is an aliphatic group or an aromatic group. The resin according to claim 10, wherein R ³ is a group represented by the following formula (301), (302), (303), (304), (305) or (306), In the formula, i represents an integer of 1 to 12. The resin according to claim 11, wherein R ³ is a group represented by the following formula (301), (302), (303), (304), (305) or (306), In the formula, i represents an integer of 1 to 12. A resin composition containing the resin according to any one of claims 1 to 13. A coating film formed by the resin composition described in claim 14 of the patent application. A water-based paint comprising the resin composition described in claim 14 of the patent application.