CN113929866B - Modified resin and resin composition - Google Patents

Abstract

The invention provides modified resins and resin compositions. A resin having a molecular chain represented by the following formula (10), wherein P is represented by the formula (10) ¹ Represents an aliphatic and/or aromatic group, Q ¹ Represents 1 or more structural units selected from the group consisting of 2-valent groups represented by the following formulas (11), (12), (13) and (14), and 2 or more P ¹ And Q ¹ Identical or different, n represents an integer of 2 or more; in the formulae (11), (12), (13) and (14), R ¹ Represents an aliphatic or aromatic group, X ² And Y ² Each independently represents an oxygen atom or a sulfur atom, and 2 or more R's in the same molecule ¹ 、X ² And Y ² Respectively identical or different, a Q ¹ X in (2) ² And Y ² More than 1 of them are sulfur atoms.

Description

Modified resin and resin composition

The present application is a divisional application of divisional application, the international application number of which is PCT/JP2014/068056, the international application date is 7 months 7 days in 2014, the national application number in china is 201480038533.7, and the date of entry into china is 2016, 1 month 5 days, and the invention is named "modified resin and resin composition". The filing date of the divisional application corresponding to the present application is 202010115257.7 and the filing date is 25/2/2020, and the name of the modified resin and resin composition is.

Technical Field

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

Background

Isocyanates are known as starting materials for polyurethanes and polyureas.

Polyurethanes are produced by reacting isocyanate groups with hydroxyl groups, and are excellent in tensile strength, abrasion resistance and oil resistance, and are used in paints, adhesives, automobile parts, and the like. For example, patent document 1 discloses a two-component polyurethane coating for packaging films.

Polyureas are produced by reacting isocyanate groups with amino groups, and are excellent in heat resistance, mechanical strength, and chemical resistance, and are used in injection molded articles, films, fibers, and the like. For example, patent document 2 discloses a cement using polyurea.

In this way, polyurethane and polyurea based on the reaction of isocyanate groups are applied as a coating or adhesive to the surfaces of metals, glass, and plastics to impart a function to the surfaces, but for this purpose, the adhesion to the surfaces must be sufficient.

As a method for improving adhesion, for example, patent document 3 discloses a method for controlling adhesion of urethane by an organic coating treatment of a steel sheet surface. As a method for improving the coated resin side, for example, patent document 4 discloses a composition containing a polymer containing an acid-modified polyolefin resin dispersion and a sulfur element.

Polyisocyanate compositions containing polyfunctional isocyanate compounds (polyisocyanates) are used in a wide variety of applications such as coating compositions. Such polyisocyanate compositions are sold, for example, as one-part or two-part polyurethane coating compositions. Among them, the two-component polyurethane coating composition can form a dense crosslinked coating film and has a good appearance as a finished product, and thus has been highly evaluated in applications requiring a high quality appearance and excellent weather resistance and durability, such as automotive and information home appliance top coating applications.

In addition to high-quality appearance, the top coat for automobile applications, information home appliances, and the like is required to have scratch resistance and high hardness. In addition, good extensibility is desirable for the coating composition used to form the top coat.

As the composition containing the polyisocyanate, for example, there are proposed: a polyisocyanate composition containing isocyanurate groups and having a phosphorus concentration of 0.1 to 20ppm (patent document 5); coating compositions containing a polyisocyanate having an allophanate group (patent documents 6 and 7); a coating composition containing a polyol and a polyisocyanate composition having an allophanate group (patent document 8) and the like, and a method for producing the composition and use thereof have been studied.

Epoxy resins are excellent in balance between heat resistance, chemical resistance, and the like, and are used in a wide range of fields as materials such as paints, adhesives, molding materials, composite materials, laminated boards, and sealing materials.

In recent years, a resin material having significantly higher performance and higher reliability than conventional resin materials has been demanded. Various modification methods have been studied to modify the existing resins. Among them, a modified epoxy resin having a 1-oxa-3-azacyclo-alkane-2-one structure obtained by reacting a part of an oxide group with an isocyanate group has been attracting attention as a resin capable of achieving both a high glass transition temperature and flexibility, and many proposals have been made (for example, refer to patent document 9, patent document 10, and patent document 11).

Prior art literature

Patent literature

Patent document 1: japanese patent application laid-open No. 2012-517489

Patent document 2: japanese patent application laid-open No. 2010-507689

Patent document 3: japanese patent laid-open No. 2001-219498

Patent document 4: japanese patent application laid-open No. 2010-163579

Patent document 5: japanese patent No. 4201582

Patent document 6: japanese patent laid-open No. 8-188566

Patent document 7: japanese patent laid-open No. 7-304724

Patent document 8: international publication No. 2002/32979

Patent document 9: japanese patent laid-open No. 59-135265

Patent document 10: japanese patent laid-open No. 61-181820

Patent document 11: japanese patent laid-open No. 5-222160

Disclosure of Invention

Problems to be solved by the invention

Polyurethane and polyurea based on the reaction of isocyanate groups are applied as a coating or adhesive to the surface of metal, glass, plastic to impart a function to the surface thereof, but further improvement in heat resistance is demanded.

Accordingly, in one aspect, the present invention provides a modified resin composition having high heat resistance.

On the other hand, the method of performing the surface treatment as in patent document 3 is difficult to apply in many cases due to the surface shape and the surface material. In the case of the resin mixture described in patent document 4, adhesion may be adversely reduced due to phase separation between resins, or the function of the coating film itself may be impaired.

Accordingly, in another aspect, the present invention provides a modified resin composition having high adhesion.

Further, as a result of studies by the present inventors, it has been found that the polyisocyanate compositions described in patent documents 5 to 8 have room for improvement in terms of adhesion to an adherend, in particular, adhesion to a metal.

In another aspect, the present invention provides a polyisothiocyanate having good adhesion to an adherend, and a method for producing the polyisoisothiocyanate.

Further, as is clear from the studies of the present inventors, the modified epoxy resins having a 1-oxa-3-azacyclo-alkane-2-one structure described in patent documents 9 to 11 have room for improvement in terms of adhesion to an adherend, particularly adhesion to a metal, depending on the application thereof.

Still further, another object of the present invention is to provide a modified epoxy resin having excellent adhesion to an adherend while maintaining the properties of a compound such as an epoxy resin or an episulfide resin; a modified episulfide resin or other compound having excellent adhesion to an adherend; and a process for producing these compounds.

Means for solving the problems

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

Namely, the present invention relates to the following means.

[1]

A resin having a nitrogen-carbon-sulfur bond composed of a nitrogen atom, a carbon atom and a sulfur atom, wherein the atoms are bonded in this order, at least one of the bonding of the carbon atom to the sulfur atom and the bonding of the carbon atom to the nitrogen atom is a single bond, and when the number average molecular weight of the resin is Mn, the number of sulfur atoms constituting the nitrogen-carbon-sulfur bond contained in each 1 molecule of the resin is n ₁ When Mn is 500 or more, mn/n ₁ 50 to 300, n ₁ The formula is as follows: n is n ₁ ＝X ¹ ·Mn(X ¹ The number of sulfur atoms constituting the above nitrogen-carbon-sulfur bonds per 1g of the resin).

[2]

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

[3]

A resin obtained by reacting a compound having at least 1 functional group selected from the group consisting of 1 valent groups represented by the following formulas (1), (2), (3), (4) or (5) with at least 1 compound selected from the group consisting of monoisocyanate, polyisocyanate, monoisothiocyanate and polyisothiocyanate.

[4]

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

[5]

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

R ⁵ -NCS (30)

(wherein R is ⁵ Represents an organic group. R is R ⁵ The aromatic compound may be an aliphatic group having 1 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic compound, or an aromatic group having 6 to 25 carbon atoms. )

[6]

The resin according to any one of [3] to [5], wherein the resin has a cyclic structure derived from a reaction of the functional group represented by the formulae (3) to (5) with an isocyanate group or an isothiocyanate group.

[7]

The resin according to [6], wherein the resin has 2 or more structural units (groups) selected from at least 1 of the group consisting of 2-valent groups represented by the following formulas (6), (7) and (8) as the group containing the above-mentioned cyclic structure.

(wherein Y is ¹ Represents an organic group, more than 2Y's in the same molecule ¹ May be the same or different. Y is Y ¹ Can be-NH-group. )

[8]

A resin having at least 1 structural unit (group) selected from the group consisting of 2-valent groups represented by the following formulas (6), (7) or (8) 2 or more.

(wherein Y is ¹ Represents an organic group, more than 2Y's in the same molecule ¹ May be the same or different. Y is Y ¹ Can be-NH-group. )

[9]

Such as [7]]Or [8 ]]The resin, wherein when the number average molecular weight of the resin is Mn, the sum of the numbers of the above structural units represented by the formula (6), (7) or (8) contained in each 1 molecule of the resin is n ₂ When Mn is 500 or more, mn/n ₂ 50 to 300, n ₂ The formula is as follows: n is n ₂ ＝X ² ·Mn(X ² The sum of the numbers of the structural units represented by the formulae (6), (7) or (8) contained in 1g of the resin.

[10]

A resin obtained by reacting a compound having a nitrogen-carbon-sulfur bond constituted of a nitrogen atom, a carbon atom and a sulfur atom, which are bonded in this order, with a polyisothiocyanate.

[11]

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

(wherein R is ⁶ Represents an organic group, and a represents an integer of 2 to 1000. )

[12]

The resin according to any one of [3] to [7] and [10], wherein the polyisothiocyanate comprises or is a polymer having 2 or more repeating units represented by the following formula (33).

(wherein R is ⁷ Represents an organic group of which the organic group is,

R ⁸ Represents an organic group or a single bond,

b represents an integer of 1 or more,

g represents a group consisting of 1 and 2,

more than 2R in the same molecule ⁷ 、R ⁸ Each of b and g may be the same or different. )

[13]

The resin according to any one of [3] to [7] and [10], wherein the polyisothiocyanate comprises or is a compound having: 2 or more structural units represented by the following formula (40); and at least 1 structural unit selected from the group consisting of a 1-valent, 2-valent, or 3-valent group (unit) represented by the following formulas (41), (42), (43), (44), (45), (46), or (47), in which a nitrogen atom is bonded to a carbon atom.

SCN-R ³ - (40)

(wherein R is ³ Represents an organic group, R ⁴ Represents an aliphatic group or an aromatic group, or an aliphatic hydrocarbon group or an aromatic hydrocarbon group, X ³ Represents an oxygen atom or a sulfur atom, and more than 2R's in the same molecule ³ 、R ⁴ And X ³ The two may be the same or different. )

[14]

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

SCN-R ³ -NCS (33)

(wherein R is 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 is ³ Represents an organic group. )

[16]

[15] The method for manufacturing the resin comprises the following steps: polymerizing the above compound represented by formula (33) in the presence of a catalyst.

[17]

A resin, having:

2 or more structural units represented by the following formula (40); and

at least 1 structural unit selected from the group consisting of 1-valent, 2-valent, and 3-valent groups (structural units) represented by the following formulas (41), (42), (43), (44), (45), (46), and (47),

the nitrogen atom (N) in 1 of the structural units represented by the formulas (41) to (47) is not directly bonded to the nitrogen atom (N) in the other structural units represented by the formulas (41) to (47).

R in the above structural units represented by the formulas (41) to (47) ³ The structural unit of formula (40) may be formed by direct bonding to an isothiocyanate group.

(wherein R is ³ Represents an organic group, R ⁴ Represents an aliphatic group or an aromatic group,

X ³ represents an oxygen atom or a sulfur atom,

more than 2R in the same molecule ³ 、R ⁴ And X ³ The two may be the same or different. )

[18]

Such as [13 ]]、[14]、[15]Or [17 ]]The resin, wherein R ³ Is an aliphatic group or an aromatic group.

[19]

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

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

[20]

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

[21]

A coating material formed from the resin composition of [20], or formed using the resin composition.

[22]

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

[23]

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

(wherein P ¹ Represents an aliphatic and/or aromatic group, Q ¹ Represents 1 or more structural units (groups) selected from the group consisting of 2-valent groups represented by the following formulas (11), (12), (13) or (14), and 2 or more P ¹ And Q ¹ And n represents an integer of 2 or more. )

(wherein R is ¹ Represents an aliphatic group or an aromatic group,

X ² and Y ² Each independently represents an oxygen atom or a sulfur atom, and 2 or more R's in the same molecule ¹ 、X ² And Y ² The two may be the same or different. Q (Q) ¹ X in (2) ² And Y ² More than 1 of them are sulfur atoms. )

[24]

Such as [23 ]]The resin, wherein R ¹ The residue after removing 2 isocyanate groups (-NCO) constituting the polyisocyanate or the residue after removing 2 isothiocyanate groups (-NCS) constituting the polyisothiocyanate.

[25]

The resin according to [23] or [24], which is obtained by reacting at least 1 compound selected from the group consisting of a polyisocyanate and a polyisothiocyanate with a compound represented by the following formula (20).

(wherein R is ² Represents an aliphatic group or an aromatic group,

Y ² represents an oxygen atom or a sulfur atom. More than 2Y in one unit ² May be the same or different. )

[26]

The resin according to [25], wherein at least 1 of the above-mentioned compounds selected from the group consisting of polyisocyanates and polyisothiocyanates contains a compound represented by the following formula (31).

XCN-R ¹ -NCX (31)

(wherein R is ¹ Represents an aliphatic group or an aromatic group,

x represents an oxygen atom orA sulfur atom. X and Y in one unit ² At least one of which may be a sulfur atom. )

[27]

Such as [25]]Or [26 ]]The resin, wherein R ² Is a 1-valent group represented by the following formula (201), (202), (203) or (204).

[28]

Such as [23]]～[27]The resin of any one of claims, wherein R ¹ Is an aliphatic group having 1 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic group (aromatic compound), or an aromatic group having 6 to 25 carbon atoms.

[29]

Such as [23]]～[27]The resin of any one of claims, wherein R ¹ Is a hydrocarbon group selected from the group consisting of hydrocarbon groups represented by the following formulas (301), (302), (303), (304), (305) or (306).

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

[30]

Such as [23]]～[28]The resin of any one of claims, wherein R ¹ Does not contain a spiro atom.

[31]

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

[32]

[25] The method of producing a resin according to [26], comprising the steps of: reacting at least 1 of the above-mentioned compounds selected from the group consisting of polyisocyanate and polyisothiocyanate with the above-mentioned compound represented by formula (20) in the presence of a catalyst.

ADVANTAGEOUS EFFECTS OF INVENTION

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

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

According to the present invention, a polyisothiocyanate having good adhesion to an adherend and a method for producing the polyisoisothiocyanate can be provided.

According to the present invention, a modified epoxy resin having excellent adhesion to an adherend while maintaining the characteristics of a compound such as an epoxy resin or an episulfide resin can be provided; a modified episulfide resin or other compound having excellent adhesion to an adherend; and a process for producing these compounds.

Drawings

FIG. 1 is a solid obtained in example 17 ¹ H-NMR spectrum.

FIG. 2 is a schematic illustration of a polyisothiocyanate ¹ And (3) a graph of an H-NMR spectrum.

FIG. 3 is a schematic diagram showing a compound containing an oxazolidine-2-thione ring ¹ And (3) a graph of an H-NMR spectrum.

Detailed Description

Next, this embodiment (hereinafter referred to as "this embodiment") will be described in detail. The present invention is not limited to the following embodiments, and can be implemented by various modifications within the scope of the gist thereof.

In the present specification, the compound name is used in many cases by a name based on a rule described in a nomenclature (IUPAC organic chemistry nomenclature) specified by IUPAC (international union of pure and applied chemistry). "organic" refers to a generic group of compounds that are the subject of the nomenclature disclosed in this rule. The object may be an object described in the suggestion made in 1993. Among these, "organic" compounds, which are the subject of the above nomenclature, also include organometallic compounds and metal complexes. In this embodiment, terms such as "organic" and/or "organic group" and/or "substituent" are used, and the compounds used in this embodiment are described below, and unless otherwise specified, they are composed of atoms that do not include a metal atom and/or a semimetal. In this embodiment, as a structure composed of atoms selected from H (hydrogen atom), C (carbon atom), N (nitrogen atom), O (oxygen atom), S (sulfur atom), cl (chlorine atom), br (bromine atom), and I (iodine atom), an "organic compound", "organic group", and a "substituent" are used.

In the following description, terms such as "aliphatic" and "aromatic" are often used. According to the IUPAC rules described above, it is described that organic compounds are classified into aliphatic compounds and aromatic compounds. Aliphatic refers to the definition of the groups of aliphatic compounds according to IUPAC recommendations based on 1995. The aliphatic compounds are defined in this proposal as "Acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds (acyclic or cyclic, saturated or unsaturated carbon compounds, except aromatic compounds)". The aliphatic compound and the aliphatic group used in the description of the present embodiment may contain any one of saturated and unsaturated, chain-like and cyclic, and may be selected from the group consisting of H (hydrogen atom); c (carbon atom); n (nitrogen atom); o (oxygen atom); s (sulfur atom); si (silicon atom); a halogen atom selected from Cl (chlorine atom), br (bromine atom) and I (iodine atom); is composed of atoms in (a).

A group having an aromatic group bonded to an aliphatic group such as "aralkyl" is sometimes referred to as a "group having an aliphatic group substituted with an aromatic group", "an aromatic aliphatic group", or "a group constituted of an aliphatic group to which an aromatic group is bonded". This is based on the reactivity in this embodiment, since the properties related to the reaction of such groups as aralkyl are very similar to aliphatic reactivity, not aromatic. The non-aromatic reactive group including an aralkyl group, an alkyl group, and the like may be referred to as an "aliphatic group which may be substituted with an aromatic group", "aliphatic group to which an aromatic group is bonded", or the like, and may be included in the "aliphatic group".

In describing the general formula of the compounds used in the present specification, definitions according to the nomenclature rules defined in IUPAC are used, but specific names of groups and exemplified compound names may be used by conventional names. In the present specification, the number of atoms, the number of substituents, and the number of substituents may be expressed as integers.

In the case where the substituents and compounds exemplified in the present specification have structural isomers, the structural isomers thereof are included unless otherwise specified.

< resin composition >

The resin composition according to several embodiments contains a resin having a nitrogen-carbon-sulfur bond and/or a nitrogen-carbon-oxygen bond. The nitrogen-carbon-sulfur bond as used herein refers to a structure in which nitrogen atoms, carbon atoms, and sulfur atoms are bonded in this order, and the nitrogen-carbon bond and carbon-sulfur bond in the bond may be a single bond or an unsaturated bond. Wherein 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 bond other atoms, for example, a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, or the like. Nitrogen-carbon-oxygen bonds are also defined.

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

(wherein R is ¹ Is a residue after removing 2 isocyanate groups (-NCO) constituting the polyisocyanate from the polyisocyanate or a residue after removing 2 isothiocyanate groups (-NCS) constituting the polyisothiocyanate from the polyisothiocyanate,

X ² and Y ² Each independently represents an oxygen atom or a sulfur atom,

x in one structural unit ² And Y ² More than 1 of them are sulfur atoms. )

/>

(wherein R is ³ And R is ⁴ Each of which is a single pieceIndependently represent an aliphatic group or an aromatic group, and 2 or more R' s ³ And R is ⁴ May be the same or different from each other,

X ³ represents an oxygen atom or a sulfur atom. )

The resin composition containing the resin having such a structural unit in the molecule can have an effect of greatly improving adhesion to a metal. Further, the refractive index is high, and thus the coating composition is effective in improving the physical properties such as gloss.

As characteristics at the time of forming a coating film, heat resistance is one of important characteristics. Specifically, the resin composition may be a resin composition containing 5% of a resin having a thermal weight loss temperature of 250 ℃ or more or 300 ℃ or more. The 5% weight loss temperature referred to herein means the following temperature: when the resin is heated in a furnace in which the temperature is raised by 10 ℃ per minute under an inert gas atmosphere such as nitrogen, helium or argon, the temperature of the furnace at the time when a weight reduction of 5% is confirmed with respect to the weight of the resin at room temperature (20 to 30 ℃) can be measured usually by using a commercially available device as a thermogravimetric analyzer.

The resin composition having an effect of heat resistance is various depending on the main chain skeleton, bonding system, molecular weight, the content of bonds contributing to the heat resistance, and the like. From the aspect of the bonding method, among the above, a resin composition containing a resin having the structural unit represented by the above formulae (6) to (8), (11) to (14), (41), (42), (45), (46) or (47) is preferable.

The number average molecular weight of the resin is preferably 500 or more, more preferably 1000 or more, and still more preferably 5000 or more. Generally, the higher the molecular weight, the better the heat resistance tends to be; on the other hand, when the molecular weight is too high, the number average molecular weight is preferably 100 ten thousand or less, more preferably 50 ten thousand or less, and even more preferably 20 ten thousand or less, because the handling property (mixing property with other components, fluidity, ductility, etc.) at the time of forming a coating film is sometimes disadvantageous. The number average molecular weight referred to herein is a value calculated as follows: the retention time is calculated by measuring the gel permeation chromatography using a column having at least 1 column having a exclusion limit molecular weight of 1000 ten thousand or more and converting the retention time into a molecular weight using a standard substance such as polystyrene. The number average molecular weight can be readily determined by those skilled in the art. Calculation was performed after excluding the peak from the solvent.

The content of bonds contributing to the heat resistance performance is also related to the above-mentioned number average molecular weight Mn. Dividing the number average molecular weight of the resin by the number n of sulfur atoms constituting nitrogen-carbon-sulfur bonds and the number n of oxygen atoms constituting nitrogen-carbon-oxygen bonds contained in each 1 molecule ¹ The value (Mn/n) ¹ ) Preferably 300 or less, more preferably 200 or less, and still more preferably 150 or less. As described above, the resin composition of the present embodiment can exert an effect in terms of adhesion to a metal, and it is preferable to have a large number of the above bonds per 1 molecule of resin from the viewpoint of exhibiting such an effect. On the other hand, when the resin has too many of the above-mentioned bonds, in particular, when the resin has structural units represented by the above-mentioned formulae (6) to (8), (11) to (14), (41), (42), (45), (46) or (47), flexibility as one of coating properties may be impaired. In this respect Mn/n ¹ Preferably 50 or more, more preferably 70 or more. n is n ¹ For example, it can be calculated as follows: for example by infrared absorption spectroscopy or ¹ The number X of the bonds per unit weight (1 g) of the resin was obtained by H-NMR or the like ¹ (in mol/g), according to the formula: n is n ¹ ＝Mn·X ¹ Calculated from the number average molecular weight (Mn) described above. In the case where the resin contains both nitrogen-carbon-sulfur bonds and nitrogen-carbon-oxygen bonds, n ¹ Is the total number of sulfur atoms and oxygen atoms constituting each bond.

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

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

Resins with heterocyclic rings

< Structure preferable >

In the present embodiment, the 1 st resin is preferably a resin having 2 or more structural units selected from at least one of the group consisting of 1-valent groups represented by the above formulas (6) to (8). Surprisingly, the resins having the structural units represented by the above formulas (6) to (8) have high heat resistance and excellent adhesion, particularly adhesion to metal surfaces. The principle by which such an effect can be achieved is not clear, but the present inventors speculate that the ring structure having the conjugated system contributes to heat resistance, and that the sulfur atom contained in the structural unit, particularly the thiol group (-SH group) contained in the structural unit of the above formula (6), can exert an effect of improving adhesion. From this viewpoint, a resin containing the structural unit represented by the above formula (6) and/or the structural unit represented by the above formula (7) is preferable.

As described above, the resin according to the present embodiment is characterized by the bonding system contained in the molecule, and the skeleton structure other than the bonding is not particularly limited, and more preferable modes are as follows.

The number average molecular weight of the resin is preferably 500 or more, more preferably 1000 or more, and still more preferably 5000 or more. Generally, the higher the molecular weight, the better the heat resistance tends to be; on the other hand, when the molecular weight is too high, the number average molecular weight is preferably 100 ten thousand or less, more preferably 50 ten thousand or less, and even more preferably 20 ten thousand or less, because the handling property (mixing property with other components, fluidity, ductility, etc.) at the time of forming a coating film is sometimes disadvantageous. The number average molecular weight referred to herein is a value calculated as follows: the retention time is calculated by measuring the gel permeation chromatography using a column having at least 1 column having a exclusion limit molecular weight of 1000 ten thousand or more and converting the retention time into a molecular weight using a standard substance such as polystyrene. The number average molecular weight can be readily determined by those skilled in the art. Calculation was performed after excluding the peak from the solvent.

The content of bonds contributing to the heat resistance performance is also related to the above-mentioned number average molecular weight Mn. Dividing the number average molecular weight of the resin by 1 minute The number of sulfur atoms constituting the nitrogen-carbon-sulfur bond and the number of oxygen atoms n constituting the nitrogen-carbon-oxygen bond contained in the child ¹ The value (Mn/n) ¹ ) Preferably 300 or less, more preferably 200 or less, and still more preferably 150 or less. As described above, the resin composition of the present embodiment can exert an effect in terms of adhesion to a metal, and it is preferable to have a large number of the above bonds per 1 molecule of resin from the viewpoint of exhibiting such an effect. On the other hand, when the resin has too many of the above-mentioned bonds, in particular, when the resin has structural units represented by the above-mentioned formulae (6) to (8), (11) to (14), (41), (42), (45), (46) or (47), flexibility as one of coating properties may be impaired. In this respect Mn/n ¹ Preferably 50 or more, more preferably 70 or more. n is n ¹ For example, it can be calculated as follows: for example by infrared absorption spectroscopy or ¹ The number X of the bonds per unit weight (1 g) of the resin was obtained by H-NMR or the like ¹ (in mol/g), according to the formula: n is n ¹ ＝Mn·X ¹ Calculated from the number average molecular weight (Mn) described above. In the case where the resin contains both nitrogen-carbon-sulfur bonds and nitrogen-carbon-oxygen bonds, n ¹ Is the total number of sulfur atoms and oxygen atoms constituting each bond. In the case where the resin has structural units represented by the formulae (6) to (8), the sum of the numbers of the structural units represented by the formulae (6) to (8) contained in each 1 molecule of the resin is n ₂ Mn/n when ² 50 to 300. n is n ² By the formula: n is n ² ＝X ² Mn calculation. X is X ² Is the sum of the amounts of the structural units represented by the formulae (6) to (8) contained in each 1g of the resin, and X ¹ The same procedure was used to obtain the samples.

The structure provided between the structural units is not particularly limited, but an aliphatic group having 1 to 25 carbon atoms or an aromatic group having 6 to 25 carbon atoms is preferable. Specifically, the residue is obtained by removing 2 hydrogen atoms from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane, and the like. In the case where an isomer exists, the isomer is also included.

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

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

< preferred production method >

The preferred 1 st resin of the present embodiment is preferably a resin obtained by a method comprising the steps of: reacting a compound having at least one functional group selected from the group consisting of 1-valent groups represented by the following formulas (1) to (5) with at least one compound selected from the group consisting of monoisocyanate, polyisocyanate, monoisothiocyanate and polyisothiocyanate.

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

Next, an example of a preferred method for producing the 1 st resin according to the present embodiment will be described.

[ Compounds to be preferably used ]

The compound having 2 or more groups selected from at least one of the group consisting of hydroxyl group, amino group, hydrazide group, semicarbazide group and thiocarbazide group is not particularly limited as long as it contains 2 or more groups selected from the group consisting of hydroxyl group (-OH), amino group (-NH) ₂ ) Acyl groupHydrazino (-C (=O) -NH) ₂ ) Semicarbazide (-NH-C (=o) -NH ₂ ) Thiosemicarbazide (-NH-C (=s) -NH ₂ ) At least one group selected from the group consisting of. For example, a compound represented by the following formula (70) or formula (71) can be used.

(wherein R is ¹² 、R ¹³ And R is ¹⁴ Each independently represents an organic group, R ¹⁵ Represents an organic group or a single bond, A ¹ And E is ¹ Each independently represents a group selected from the group consisting of hydroxyl, amino, hydrazide, semicarbazide, thiocarbazide, B ¹ And D ¹ Each independently represents a group selected from the group consisting of hydroxyl, amino, hydrazide, semicarbazide, thiocarbazide, organic group, or hydrogen atom, F ¹ Represents a hydrogen atom or an organic group, d represents an integer of 2 to 1000, e represents an integer of 1 to 3, x represents an integer of 1 or more, and y represents an integer of 0 or 1 or more. More than 2R in the same molecule ¹² 、R ¹³ 、R ¹⁴ 、A ¹ 、E ¹ 、B ¹ 、D ¹ 、F ¹ And e may be the same or different, respectively.

In the above formula, R ¹² Preferably an aliphatic group having 1 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic group (aromatic compound), or an aromatic group having 6 to 25 carbon atoms. R is R ¹² Specific examples of (C) are residues obtained by removing 1 hydrogen atom from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane and the like. In the present specification, "aliphatic having 7 to 25 carbon atoms substituted with aromatic group The aliphatic group "is a group including a combination of an aromatic group and an aliphatic group, and the aromatic group and the aliphatic group may contain hetero atoms such as an oxygen atom, a nitrogen atom, and a sulfur atom, and the total number of carbon atoms contained in the group is 7 to 25. Other like terms are similarly defined.

In the above formula, R ¹³ And R is ¹⁴ Preferably an aliphatic group having 2 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic group, or an aromatic group having 8 to 25 carbon atoms. R is R ¹³ And R is ¹⁴ Specific examples of (a) are residues obtained by removing 3 hydrogen atoms from ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylethane, ethylbenzene, diethylbenzene, diphenylethane, tetramethyldiphenylethane and the like.

In the above formula, R ¹⁵ The organic group is an alkylene group having 1 to 25 carbon atoms, an aromatic hydrocarbon group having 6 to 25 carbon atoms, or a group represented by the following formula (72) or (73).

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

R ¹⁵ R is an alkylene group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 25 carbon atoms ¹⁵ Specifically, the catalyst is selected from methane, ethane, propane, butane, propane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, and diphenylResidues after removal of 2 hydrogen atoms from methyl hydride, tetramethyl diphenyl methane, and the like.

R ¹⁵ Is represented by a single bond, R ¹⁵ Not as a group, but R ¹³ And E is connected with ¹ Bonding occurs. Hereinafter, the term "single bond" as used in the present specification is defined and used in the same manner.

In the above formula (72) and formula (73), R ¹⁶ 、R ¹⁷ And R is ¹⁸ Preferred are residues obtained by removing 2 hydrogen atoms from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane and the like. Where an isomer is present, that isomer is also included.

In the above formula (71), B ¹ 、D ¹ And F ¹ In the case of an organic group, the organic group is preferably an alkyl group having 1 to 25 carbon atoms, an aromatic hydrocarbon group having 6 to 25 carbon atoms, or a group represented by the following formulas (74) to (76).

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

In the above formulae (74) to (76), R ¹⁹ 、R ²⁰ And R is ²¹ An alkylene group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 25 carbon atoms is preferable. R is R ¹⁹ 、R ²⁰ And R is ²¹ In particular from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, bicycloResidues after 2 hydrogen atoms are removed from hexyl methane, tetramethyl dicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethyl benzene, diphenyl methane, tetramethyl diphenyl methane, and the like. Where an isomer is present, that isomer is also included.

Specific examples of the compound containing at least 1 functional group selected from the group consisting of a hydroxyl group, an amino group, a hydrazide group, a semicarbazide group, and a thiosemicarbazide group are shown below.

Examples of the compound (a) having a hydroxyl group include polyols such as ethylene glycol, propylene glycol, pentaerythritol, and polyols having a repeating unit.

Examples of the polyol include acrylic polyol, polyolefin polyol, and polyvinyl alcohol. The acrylic polyol can be obtained by copolymerizing a single substance or a mixture of monomers having an ethylenically unsaturated bond with hydroxyl groups and a single substance or a mixture of other ethylenically unsaturated bond-containing monomers capable of copolymerizing therewith.

Examples of the ethylenically unsaturated bond-containing monomer having a hydroxyl group include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate. Preferably hydroxyethyl acrylate or hydroxyethyl methacrylate.

Examples of the other ethylenically unsaturated bond-containing monomer copolymerizable with the above-mentioned monomer include acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, benzyl acrylate, and phenyl acrylate; methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, benzyl methacrylate, and phenyl methacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, and the like; unsaturated amides such as acrylamide, methacrylamide, N-methylenebisacrylamide, acetylacetone acrylamide, acetylacetone methacrylamide, maleic amide, and maleimide; vinyl monomers such as glycidyl methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, and dibutyl fumarate; vinyl monomers having a hydrolyzable silyl group such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and γ - (meth) acryloxypropyltrimethoxysilane.

Examples of the polyolefin polyol include polybutadiene having 2 or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and the like. The polyol preferably has a hydroxyl number (hereinafter, average number of hydroxyl groups) of 2 or more in a molecule of 1 in statistics. By setting the average number of hydroxyl groups of the polyol to 2 or more, a decrease in the crosslinking density of the resulting coating film can be suppressed.

The polyvinyl alcohol may be: polyvinyl alcohol obtained by saponifying a polyvinyl ester obtained by polymerizing a vinyl ester; a modified polyvinyl alcohol obtained by grafting a comonomer to a main chain of a polyvinyl alcohol; a modified polyvinyl alcohol produced by saponifying a modified polyvinyl ester obtained by copolymerizing a vinyl ester and a comonomer; and so-called polyvinyl acetal resins obtained by crosslinking a part of hydroxyl groups of unmodified polyvinyl alcohol or modified polyvinyl alcohol with aldehydes such as formaldehyde, butyraldehyde, benzaldehyde, etc.

Examples of the vinyl ester used in the production of polyvinyl alcohol include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate, and vinyl benzoate. Among them, vinyl acetate is preferable in terms of ease of production, ease of obtaining, cost and the like of polyvinyl alcohol. The above-mentioned comonomer used in the production of the modified polyvinyl alcohol is mainly copolymerized for the purpose of modifying the polyvinyl alcohol, and is used in a range not to impair the gist of the present invention. Examples of such a comonomer include olefins such as ethylene, propylene, 1-butene, and isobutylene; acrylic acid or a salt thereof; acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate (including isomers), butyl acrylate (including isomers), octyl acrylate (including isomers), and dodecyl acrylate (including isomers); methacrylic acid or a salt thereof; methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate (including isomers), butyl methacrylate (including isomers), octyl methacrylate (including isomers), dodecyl methacrylate (including isomers), and octadecyl methacrylate (including isomers); acrylamide derivatives such as acrylamide, N-methacrylamide, N-ethylacrylamide, N-dimethylacrylamide, diacetone acrylamide, acrylamide propane sulfonic acid or a salt thereof, acrylamide propyl dimethylamine or a salt thereof, and N-methylolacrylamide or a derivative thereof; methacrylamide derivatives such as methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamide propane sulfonic acid or salt thereof, methacrylamide propyl dimethylamine or salt thereof, N-hydroxymethyl methacrylamide or derivative thereof; n-vinyl amides such as N-vinyl formamide, N-vinyl acetamide and N-vinyl pyrrolidone; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether and stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; maleic acid or a salt or ester thereof; itaconic acid or a salt or ester thereof; vinyl silyl compounds such as vinyl trimethoxy silane; isopropenyl acetate, and the like. Among them, preferred are α -olefins (for example, α -olefins having 2 to 30 carbon atoms, etc.), unsaturated carboxylic acids or derivatives thereof, and unsaturated sulfonic acids or derivatives thereof, more preferred are α -olefins, and particularly preferred is ethylene. The amount of modification based on the comonomer in the modified polyvinyl alcohol is preferably 15 mol% or less, more preferably 5 mol% or less, based on the number of moles of all the structural units constituting the modified polyvinyl alcohol.

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

Specific examples of the compound having an amino group include cyclic polyamines having 3 or more amino groups such as ethylenediamine, propylenediamine, butylenediamine, triethylenediamine, 1, 6-hexamethylenediamine, 4' -diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, norbornanediamine, phenylenediamine, 4' -diaminobiphenyl, 1, 3-bis (3-aminophenoxy) benzene, 3' -diaminodiphenylsulfone, diethylethylenediamine, diamines such as diphenylamine, bishexamethylenetriamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, tetrapropylenepentamine, and the like, and polyamines represented by the following formulae (77) such as 1,4,7,10,13, 16-hexaazaoctadecane, 1,4,7, 10-tetraazadecane, 1,4,8, 12-tetraazapentadecane, 1,4,8, 11-tetraazatetradecane, polyallylamine, and the like. Among them, polyallylamine and polyvinylamine are preferable. The polyallylamine and the polyvinylamine may be any one produced by a conventionally known method, and the polymerization degree and the like are not particularly limited. In addition, copolymers with other monomers may be used.

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

(wherein h' represents an integer of 2 to 40,

i 'and j' each represent an integer of 1 to 6, and the sum of i 'and j' is an integer of 2 to 7. )

(wherein R is ³⁵ Represents a group selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group,

s represents an integer of 0 or 1,

r, t, u each represent an integer of 0 or 1 or more,

the sum of r, t and u is 5-90. )

Examples of the compound (c) having a hydrazide group include saturated dicarboxylic acid dihydrazide having 2 to 18 carbon atoms such as oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide; monoethylenically unsaturated dicarboxylic dihydrazide such as maleic dihydrazide, fumaric dihydrazide, itaconic dihydrazide and the like; and polyhydrazides obtained by reacting an oligomer having a carboxylic acid lower alkyl ester group with hydrazine or hydrazine hydrate. The polymer may be a polymer obtained by reacting a polymer (may be a copolymer) of a monomer having an ethylenically unsaturated bond and having a hydroxyl group, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, or the like, with hydrazine, or a polymer (may be a copolymer) of a vinyl ester (for example, vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, or the like) with hydrazine.

Examples of the compound (d) having a semicarbazide group include a bis-semicarbazide; and polyfunctional semicarbazide obtained by reacting a diisocyanate such as hexamethylene diisocyanate or isophorone diisocyanate or a polyisocyanate compound derived therefrom with an N, N-substituted hydrazine such as N, N-dimethylhydrazine or the hydrazine exemplified above.

Examples of the compound (e) having a thiosemicarbazide group include a dithiosemicarbazide; and polyfunctional thiocarbamides obtained by reacting diisoisothiocyanate such as hexamethylene diisoisothiocyanate or isophorone diisoisothiocyanate or a polyisothiocyanate compound derived therefrom with N, N-substituted hydrazine such as N, N-dimethylhydrazine or the hydrazine exemplified above.

Examples of the compound having a hydroxyl group include polyester polyol, polyether polyol, fluorine polyol, polycarbonate polyol, and polyurethane polyol.

Examples of the polyester polyol include: polyester polyol obtained by condensation reaction of a single substance or a mixture of dibasic acids selected from the group consisting of carboxylic acids such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and the like with a single substance or a mixture of polyhydric alcohols selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, glycerin, and the like; and polycaprolactone obtained by ring-opening polymerization of epsilon-caprolactone using a polyol, for example.

As polyether polyols, there are: polyether polyols obtained by adding a single substance or a mixture of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, cyclohexane oxide, styrene oxide to a single substance or a mixture of polyhydric hydroxyl compounds using a strong basic catalyst such as hydroxides, alcoholates, alkylamines of lithium, sodium, potassium, etc.; polyether polyols obtained by reacting an alkylene oxide with a polyfunctional compound such as ethylenediamine; so-called polymer polyols obtained by polymerizing acrylamide or the like with these polyethers as a medium; etc.

Examples of the polyhydric hydroxyl compound include

(1) Diglycerol, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like,

(2) Sugar alcohol compounds such as erythritol, D-threitol, L-arabitol, ribitol, xylitol, sorbitol, mannitol, galactitol, and mouse Li Tangchun,

(3) Monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose and deoxyribose,

(4) Disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, melibiose, etc,

(5) Trisaccharides such as raffinose, gentian trisaccharide, melezitose and the like,

(6) Tetrasaccharides such as stachyose, and the like.

The fluorine-containing polyol is a polyol containing fluorine in the molecule, and includes, for example, copolymers of fluoroolefins, cyclic vinyl ethers, hydroxyalkyl vinyl ethers, vinyl monocarboxylic acid esters and the like disclosed in Japanese unexamined patent publication Nos. 57-34107 and 61-275311.

Examples of the polycarbonate polyol include a product obtained by polycondensing a low-molecular carbonate compound such as dialkyl carbonate such as dimethyl carbonate, alkylene carbonate such as ethylene carbonate, diaryl carbonate such as diphenyl carbonate, and a low-molecular polyol used in the above polyester polyol.

The polyurethane polyols may be obtained by conventional methods, such as reacting polyols with polyisocyanates. Examples of the polyhydric alcohol having no carboxyl group include ethylene glycol and propylene glycol, and examples of the low molecular weight substance include an acrylic polyol, a polyester polyol and a polyether polyol.

The compound which may have a repeating unit containing one 1 group selected from the group consisting of a hydroxyl group, an amino group, a hydrazide group, a semicarbazide group and a thiosemicarbazide group is a compound represented by the following formula (81).

R ²² -A ¹ (81)

(wherein R is ²² Represents an organic group of which the organic group is,

A ¹ represents a group defined by the above formula (70). )

In the above formula, R ²² Preferably an aliphatic group having 1 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic group, or an aromatic group having 6 to 25 carbon atoms. Specifically, R ²² Is selected from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylMethane, tetramethyl dicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyl diphenylmethane, etc., after 1 hydrogen atom has been removed. Where an isomer is present, that isomer is also included.

Specific examples of the compound represented by the formula (81) include hydroxyl compounds such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octadecanol, cyclohexanol, cyclooctanol, dimethylcyclohexanol, diethylcyclohexanol, trimethylcyclohexanol, trimethylethylcyclohexanol, dicyclohexylmethanol, tetramethyldicyclohexylmethanol, phenol, methylphenol, xylenol, ethylphenol, diethylphenol, and the like; amines such as ethylamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, decylamine, dodecylamine, cyclohexylamine, cyclooctylamine, dimethylcyclohexylamine, phenylamine, methylphenylamine, dimethylphenylamine, ethylphenylamine, diethylphenylamine and the like; hydrazides such as ethyl hydrazide, propyl hydrazide, butyl hydrazide, amyl hydrazide, hexyl hydrazide, octyl hydrazide, decyl hydrazide, dodecyl hydrazide, cyclohexyl hydrazide, cyclooctyl hydrazide, dimethylcyclohexyl hydrazide, phenyl hydrazide, methylphenyl hydrazide, dimethylphenyl hydrazide, ethylphenyl hydrazide, diethylphenyl hydrazide; ethyl semicarbazide, propyl semicarbazide, butyl semicarbazide, amyl semicarbazide, hexyl semicarbazide, octyl semicarbazide, decyl semicarbazide, dodecyl semicarbazide, cyclohexyl semicarbazide, cyclooctyl semicarbazide, dimethyl cyclohexyl semicarbazide, phenyl semicarbazide, methylphenyl semicarbazide, dimethylphenyl semicarbazide, ethylphenyl semicarbazide, diethylphenyl semicarbazide and the like; thiosemicarbazides such as ethylthio semicarbazides, propylthio semicarbazides, butylthio semicarbazides, pentylthiosemicarbazides, hexylthio semicarbazides, octylthio semicarbazides, decylthiosemicarbazides, dodecylthio semicarbazides, cyclohexylthio semicarbazides, cyclooctylthio semicarbazides, dimethylcyclohexylthio semicarbazides, phenylthio semicarbazides, methylphenylthiosemicarbazides, dimethylphenylthiosemicarbazides, ethylphenylthio semicarbazides, diethylphenylthio semicarbazides and the like.

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)

(in the formula (I),

R ²³ represents an unsaturated aliphatic hydrocarbon group having 1 to 25 carbon atoms,

R ¹⁵ 、E ¹ represents 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).

(in the formula (I),

R ²⁴ 、R ²⁵ and R is ²⁶ Each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms,

R ²⁷ 、R ²⁸ 、R ²⁹ and R is ³⁰ Each independently represents a saturated hydrocarbon group having 1 to 6 carbon atoms,

R ³¹ represents a saturated hydrocarbon group having 1 to 6 carbon atoms or a single bond, E ¹ Represents a group defined by the above formula (71), and w represents an integer of 1 to 3. )

< isothiocyanate Compound >

Isothiocyanate compounds are compounds having 1 or more isothiocyanate groups in 1 molecule, and are classified into monoisothiocyanates and polyisoisothiocyanates.

In the resin composition of the present embodiment, the monoisothiocyanate is a compound having 1 isothiocyanate group in 1 molecule, and is preferably a compound represented by the following formula (30).

R ⁵ -NCS (30)

(wherein R is ⁵ Represents an organic group. )

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

Specifically, the compound represented by the above formula (30) may be exemplified by methane isothiocyanate, ethane isothiocyanate, propane isothiocyanate, butane isothiocyanate, pentane isothiocyanate, hexane isothiocyanate, octane isothiocyanate, decane isothiocyanate, dodecane isothiocyanate, octadecane isothiocyanate, cyclohexane isothiocyanate, cyclooctane isothiocyanate, dimethylcyclohexane isothiocyanate, diethylcyclohexane isothiocyanate, trimethylcyclohexane isothiocyanate, trimethylethylcyclohexane isothiocyanate, dicyclohexylmethane isothiocyanate, tetramethyldicyclohexylmethane isothiocyanate, phenyl isothiocyanate, toluene isothiocyanate, xylene isothiocyanate, ethylbenzene isothiocyanate, diethylbenzene isothiocyanate, diphenylmethane isothiocyanate, tetramethyldiphenylmethane isothiocyanate, and the like.

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

R ²³ -R ¹⁵ -NCS (86)

(wherein R is ¹⁵ 、R ²³ Represents a group defined by the above formula (82). )

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

(in the formula (I),

R ²⁴ 、R ²⁵ and R is ²⁶ Each independently represents a saturated hydrocarbon group having 1 to 6 carbon atoms,

R ²⁷ 、R ²⁸ 、R ²⁹ and R is ³⁰ Each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms,

R ³¹ represents a saturated hydrocarbon group having 1 to 6 carbon atoms or a single bond,

w represents an integer of 1 to 3. )

Specific examples of the compounds represented by the formulas (87) to (89) include methyl acrylate, methyl methacrylate, 2-ethyl isothiocyanate acrylate, 2-ethyl methacrylate, 3-propyl acrylate, 3-propyl methacrylate, 2-ethyl isothiocyanate, 4-butyl isothiocyanate, p- (isocyanatomethyl) styrene, p- (isocyanatoethyl) styrene, and the like.

In the resin composition of the present embodiment, the polyisothiocyanate is a compound having 2 or more isothiocyanate groups in 1 molecule, and is represented by the following formula (32), for example.

(wherein R is ⁶ Represents an organic group of which the organic group is,

a represents an integer of 2 to 1000. )

A preferred mode 1 of such a polyisothiocyanate is a polymer comprising at least 2 repeating units represented by the following formula (33).

(wherein R is ⁷ Represents an organic group of which the organic group is,

R ⁸ represents an organic group or a single bond,

b represents an integer of 1 or more,

g represents 1 or 2. More than 2R in the same molecule ⁷ 、R ⁸ Each of b and g may be the same or different. )

The polymer of embodiment 1, which is a preferred polyisothiocyanate, may have 1 or 2 or more kinds of repeating units other than the repeating unit represented by the above formula (33). The terminal of the polymer is a group derived from a polymerization initiator, a polymerization terminator and a terminal modifier, and is not particularly limited as long as it does not violate the gist of the present embodiment, as the production method varies. That is, the preferred mode 1 of the polyisothiocyanate is more preferably a compound represented by the following formula (90).

(wherein R is ³² Represents an organic group of which the organic group is,

R ³³ represents an organic group or a single bond,

B ² and D ² Each independently represents at least 1 group selected from the group consisting of an isothiocyanate group, an organic group other than an isothiocyanate group, and a hydrogen atom,

G ¹ ～G ^x Represents an organic group which may or may not contain an isothiocyanate group, x is an integer of 1 or more, and n _x Represents an integer of 1 or more,

g represents a group consisting of 1 and 2,

f represents an integer of 1 or more,

m represents an integer of 2 or more. More than 2R in the same molecule ³² 、R ³³ The f and g may be the same or different. )

In the above formula (90), G ¹ ～G ^x Represents a repeating unit other than the repeating unit represented by the above formula (33). In addition, n _x Represents G ^x Is a number of repeating units of (a). For example, in addition to the repeating unit represented by the above formula (43), G ¹ 、G ² 、G ³ The 3 repeating units are each n ₁ 、n ₂ 、n ₃ In the case of G ¹ n ₁ G ² n ₂ G ³ n ₃ 。

In the above formula (90), R ³² Preferably an aliphatic group having 2 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic compound, or an aromatic group having 8 to 25 carbon atoms. R is R ³² Specific examples of (a) are residues obtained by removing 3 hydrogen atoms from ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylethane, ethylbenzene, diethylbenzene, diphenylethane, tetramethyldiphenylethane, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octadecanol, cyclohexanol, cyclooctanol, dimethylcyclohexanol, diethylcyclohexanol, trimethylcyclohexanol, trimethylethylcyclohexanol, dicyclohexylethanol and the like.

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

(wherein R is ³⁴ 、R ³⁶ And R is ³⁷ Each independently represents an alkylene group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a single bond,

l represents an integer of 1 to 10. )

R ³⁴ In the case of an alkylene group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 25 carbon atoms, the aromatic hydrocarbon group is specifically selected from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane and trimethylcyclohexaneResidues after 2 hydrogen atoms are removed from hexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane, and the like.

In the formulas (91) and (92), R ³⁴ 、R ³⁶ And R is ³⁷ Preferred are residues obtained by removing 2 hydrogen atoms from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane and the like. In the case where an isomer is present, the isomer is also included.

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

(wherein R is ³⁸ 、R ³⁹ And R is ⁴⁰ Each independently represents an alkylene group having 1 to 25 carbon atoms or an aromatic group having 6 to 25 carbon atoms,

p represents an integer of 1 to 10. )

In the formulae (93) to (95), R ³⁸ 、R ³⁹ And R is ⁴⁰ Preferred is an alkylene group having 1 to 25 carbon atoms or an aromatic hydrocarbon group having 6 to 25 carbon atoms, specifically selected from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethylResidues after removal of 2 hydrogen atoms from alkanes, tetramethyldiphenylmethane, and the like. When an isomer is present, the isomer is also included.

The 1 st mode of the polyisothiocyanate shown above may be, for example, a polymer of the monoisothiocyanate represented by the above formula (41), and the polymer may be a copolymer with other monomers. Specifically, there may be mentioned: copolymers of methyl acrylate and methyl acrylate, copolymers of methyl methacrylate and methyl methacrylate, copolymers of (2-ethyl isothiocyanate) acrylate and methyl acrylate, copolymers of (2-ethyl isothiocyanate) methacrylate, copolymers of (3-propyl isothiocyanate) acrylate and methyl acrylate, copolymers of (3-propyl isothiocyanate) methacrylate and methyl methacrylate, and the like. These compounds can be produced by a known method.

In the resin composition of the present embodiment, the 2 nd aspect of the polyisothiocyanate is a polyisoisothiocyanate having a structural unit represented by the following formula (40) and at least one structural unit selected from the group consisting of units represented by the following formulas (41) to (47), and a nitrogen atom constituting the polyisoisothiocyanate is bonded to a carbon atom.

(wherein R is 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,

more than 2R ³ And R is ⁴ May be the same or different from each other,

X ³ represents an oxygen atom or a sulfur atom. )

In the above formulas (40) and (41) to (47), R ³ Aliphatic groups having 1 to 25 carbon atoms and aromatic groups having 6 to 25 carbon atoms are preferable. Specifically, R ³ Is prepared from methane, ethane, propane and butane2 hydrogen atoms of the residue are removed from alkane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane, and the like. Where an isomer is present, that isomer is also included.

For the group-X contained in the above formula (43) and formula (45) ³ -R ⁴ An explanation is given.

As will be described later, in the production of the polyisothiocyanate of the present invention, an N, N' -disubstituted dithiocarbamic acid bond represented by the above formula (43) or an N-substituted-O-substituted thiocarbamate group represented by the above formula (45) is produced (X ³ In the case of an oxygen atom) or an N-substituted-S-substituted dithiocarbamate group (X) ³ In the case of a sulfur atom), a hydroxyl compound or a thiol is used. radical-X ³ -R ⁴ Is a group derived from the hydroxyl compound or a thiol, X in the case of using a hydroxyl compound ³ In the case of using thiols, X is an oxygen atom ³ Is a sulfur atom.

R ⁴ May be a hydrocarbon group. The hydrocarbon group has at least one of an aliphatic group and an aromatic group, and may contain an oxygen atom, a nitrogen atom, and the like in addition to a carbon atom. R is R ⁴ The aliphatic group or the aromatic group is preferably an aliphatic group having 1 to 22 carbon atoms or an aromatic group having 6 to 22 carbon atoms, more preferably an aliphatic group having 1 to 22 carbon atoms, an aromatic group having 1 to 22 carbon atoms, or a group having 7 to 22 carbon atoms in which an aliphatic group having 1 to 22 carbon atoms and an aromatic group having 6 to 22 carbon atoms are bonded. As R ⁴ Specific examples of (C) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexylAmyl cyclohexyl, hexyl cyclohexyl, dimethyl cyclohexyl, diethyl cyclohexyl, dibutyl cyclohexyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, octylphenyl, nonylphenyl, cumylphenyl, dimethylphenyl, and the like.

The polyisothiocyanate in the present embodiment may be a polyisothiocyanate obtained by further polymerizing a compound represented by the following formula (33), which is 1 kinds of the polyisoisothiocyanates in the present embodiment.

SCN-R ³ -NCS (33)

(wherein R is ³ Represents an organic group. )

R in the above formula (33) ³ Aliphatic groups having 1 to 25 carbon atoms and aromatic groups having 6 to 25 carbon atoms are preferable. R is R ³ Specific examples of (a) are residues obtained by removing 2 hydrogen atoms from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane and the like. Where an isomer is present, that isomer is also included. R is R ³ More preferably, the groups represented by the following formulas (300) to (306).

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

Further preferable examples of the compound represented by the above formula (33) include hexamethylene diisoisothiocyanate, isophorone diisoisothiocyanate, 4 '-dicyclohexylmethane diisoisothiocyanate, 4' -diphenylmethane diisoisothiocyanate, toluene diisoisothiocyanate (each isomer), naphthalene diisoisothiocyanate (each isomer), and the like.

Examples of the compound represented by the above formula (33) include phenylene diisoisothiocyanate, 4 '-diisocyanato diphenyl ether, 1, 3-bis (3-isothiocyanato-phenoxy) benzene, 3' -diisocyanato-diphenyl sulfone, diethyltoluenediisoisothiocyanate and the like.

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

In the polyisothiocyanate produced by polymerization of the "monomer" represented by the above formula (33), a hydroxyl compound and/or a thiol compound is used as a secondary raw material in the production thereof.

Examples of the hydroxyl compound include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, dodecanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, methylcyclopentanol, ethylcyclopentanol, methylcyclohexanol, ethylcyclohexanol, propylcyclohexanol, butylcyclohexanol, pentylcyclohexanol, hexylcyclohexanol, dimethylcyclohexanol, diethylcyclohexanol, dibutylcyclohexanol, phenol, methylphenol, ethylphenol, propylphenol, butylphenol, pentylphenol, hexylphenol, octylphenol, nonylphenol, cumylphenol, dimethylphenol, methylethylphenol, methylpropylphenol, methylbutylphenol, methylpentylphenol, diethylphenol, ethylpropylphenol, ethylbutylphenol, diethylphenol, dicumylphenol, trimethylphenol, triethylphenol, naphthol, and the like.

It is also possible to use ethylene glycol, 1, 2-propylene glycol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 1, 6-hexanediol, neopentyl glycol hydroxypivalate, 2-ethyl-1, 3-hexanediol, trimethylolpropane, glycerol, 1,2, 6-hexanetriol and other low molecular weight compounds and polyester polyols, polyether polyols and the like having a molecular weight of about 200 to 10,000.

Examples of the thiol include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, decyl mercaptan, dodecyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, cycloheptyl mercaptan, cycloocta mercaptan, methylcyclopentyl mercaptan, ethylcyclohexyl mercaptan, propylcyclohexyl mercaptan, butylcyclohexyl mercaptan, pentylcyclohexyl mercaptan, hexylcyclohexyl mercaptan, dimethylcyclohexyl mercaptan, diethylcyclohexyl mercaptan, dibutylcyclohexyl mercaptan, thiophenol, methylphenol, ethylphenylthiophenol, propylthiophenol, butylthiophenol, pentylphenol, hexylthiophenol, octylthiophenol, nonylphenol, cumylphenol, dimethylphenol, methylethylthiophenol, methylpropylthiophenol, methylbutylthiophenol, methylpentylthiophenol, diethylthiophenol, ethylpropylthiophenol, diethylthiophenol, dicumylphenol, trimethylthiophenol, triethylthiophenol, and naphthol.

When a hydroxyl compound is used, the equivalent ratio of the isothiocyanate group/hydroxyl group of the hydroxyl compound to the "monomer" represented by the formula (33) may be selected from values of about 10 to 100 according to the purpose. Similarly, when thiols are used, the equivalent ratio of isothiocyanate groups to thiol groups can be selected from values of about 10 to 100, depending on the purpose.

The isocyanuric acid group represented by formula (41) can be formed by polymerization of the monomer of formula (33). The isocyanurating catalyst for forming the isocyanurating group represented by the formula (41) is preferably a quaternary ammonium salt, more preferably a quaternary ammonium hydroxide or a quaternary ammonium carboxylic acid, and still more preferably a quaternary ammonium carboxylic acid. Specific examples thereof include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; organic weak acid salts such as tetramethylammonium acetate, tetraethylammonium acetate, tetrabutylammonium acetate, and the like. Metal salts of alkyl carboxylic acids such as acetic acid, valeric acid, isovaleric acid, caproic acid, caprylic acid, and tetradecanoic acid may be used, and organic weak acid salts are preferable from the viewpoint of reducing the amount.

Examples of the hydroxyl compound used to dilute the above-mentioned isocyanuric acid catalyst include alcoholic hydroxyl compounds such as methanol, ethanol, 1-butanol, 2-methyl-1-propanol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, glycerol, cyclohexanol, and phenolic hydroxyl compounds such as phenol, cresol, xylenol, and trimethylphenol. From the viewpoint of crystallinity of the polyisocyanate thus obtained, alcohols having side chains such as 2-butanol, 2-methyl-1-propanol, 1, 3-butanediol, 2, 3-butanediol and the like are preferable. In addition, two or more kinds may be mixed. In addition, thiols may be used instead of the hydroxyl compound.

When the monomer represented by the above formula (33) or the monomer in which an isothiocyanate group has been urethanized with a hydroxyl compound is reacted in the presence of the above isothiocyanation catalyst, the reaction is carried out under conditions such that the concentration of the isothiocyanation catalyst after dilution with the above hydroxyl compound is 1 to 20% by mass. The concentration is preferably 1 to 10 mass%. When the concentration is 1 mass% or more, the amount of the hydroxyl compound accompanying the isocyanuration catalyst does not become excessive, and physical properties of the obtained polyisothiocyanate and a coating film formed therefrom are hardly degraded. When the concentration is 20 mass% or less, the co-catalytic effect of the hydroxy compound is not reduced, and as a result, it is difficult to cause an increase in the amount of the isothiocyanation catalyst, coloring of the polyisothiocyanate, and the like.

The amount of the isothiocyanation catalyst used is 1ppm to 10%, preferably 10ppm to 5% based on the weight of the monomer diisocyanato, except that the isothiocyanation catalyst is deactivated by an acidic component contained in a small amount in the raw material such as the monomer represented by the above formula (33). When the amount is 1ppm or more, the catalyst can sufficiently function as an isocyanuric acid catalyst. If the amount is 3% or less, the amount of the acid phosphate compound and the acid phosphate compound (described later) to be added for inactivating the isocyanuric acid esterification catalyst is reduced.

The reaction may be carried out with or without using a solvent, but by using a solvent which is not reactive with an isothiocyanate group, the reaction can be controlled more easily.

Examples of the solvent include esters and ethers such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene. Of course, two or more solvents may be used in combination.

The isothiocyanation reaction is carried out at 30 to 120℃and preferably at 50 to 100 ℃. The reaction may be carried out by the reaction liquid ¹ H-NMR analysis confirmed.

At the point when the reaction reaches the desired conversion, the reaction is stopped by inactivating the catalyst by adding a reaction terminator. The conversion is suitably selected in the range of 10 to 60%, preferably 10 to 30%. When the conversion is low, a polyisothiocyanate having a lower viscosity can be obtained, but from the viewpoint of productivity, the conversion is preferably 10% or more. On the other hand, if the conversion is 60% or less, the viscosity of the polyisothiocyanate will not become too high, which is preferred.

The conversion can be determined by the following formula.

At the position of ¹ In the H-NMR spectrum, the peak of methyl group of tetramethylsilane was set to 0ppm, and the conversion was calculated from the integrated value (A) of the peak at 3.5ppm and the integrated value (B) of the peak at 4.8ppm according to the following formula.

Conversion (%) =b/(a+b) ×100

As the terminator for the isocyanuric acid reaction, at least 1 kind of acid phosphate compound and acid phosphate ester compound is used.

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

The acidic phosphate compound is a compound having an acidic group and an ester group, and examples thereof include monoalkyl phosphate having 2 to 8 carbon atoms, monoalkyl phosphite, dialkyl phosphate having 4 to 16 carbon atoms, dialkyl phosphite, dilauryl phosphate, diphenyl phosphate, monolauryl phosphate, monophenyl phosphate, dilauryl phosphite, diphenyl phosphite, monolauryl phosphite, monophenyl phosphite, and monophenyl phosphite. The acidic 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, an acid phosphate compound is preferably used. The amount of the acidic phosphoric acid compound to be added is preferably 1 to 10 equivalents, more preferably 1 to 6 equivalents, to the stoichiometric amount of the isocyanuric acid catalyst. When the amount is 1 equivalent or more, the isocyanuric acid catalyst can be sufficiently deactivated. When the amount of the additive is 10 equivalents or less, filtration of the insoluble matter produced does not become difficult, and is preferable.

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

(wherein h' represents an integer of 2 to 40,

i 'and j' each represent an integer of 1 to 6, and the sum of i 'and j' is an integer of 2 to 7. )

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

(wherein R is ³⁵ Represents a group selected from the group consisting of a hydrogen atom, a methyl group, and an ethyl group,

s represents an integer of 0 or 1,

r, t and u each represent an integer of 0 or 1 or more, and the sum of r, t and u is 5 to 90. )

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

[ reaction method ]

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

The resin composition of the present embodiment may contain all of the following resins.

1. A resin obtained by reacting a compound having 2 or more groups selected from at least 1 of a group consisting of a hydroxyl group, an amino group, a hydrazide group, a semicarbazide group, and a thiosemicarbazide group with a monoisothiocyanate;

2. a resin obtained by reacting a compound having 1 group selected from the group consisting of a hydroxyl group, an amino group, a hydrazide group, a semicarbazide group, and a thiosemicarbazide group with a polyisothiocyanate;

3. A resin obtained by reacting a compound having 2 or more groups selected from at least 1 of a group consisting of a hydroxyl group, an amino group, a hydrazide group, a semicarbazide group and a thiosemicarbazide group with a polyisothiocyanate.

In all cases, the combination of the functional groups to be reacted is the same and can be carried out according to the methods described herein.

In the following description, a reaction formula is shown for easy understanding of the reaction, and the reaction formula is described by taking a monofunctional compound as an example, but the same reaction is certainly performed in the case of a polyfunctional compound.

[ reaction with Compound having hydroxyl group ]

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

(wherein R is ⁴¹ 、R ⁴² Each independently represents an organic group. )

The reaction may be carried out in the presence of a solvent or may be carried out in the absence of a solvent. Regarding the solvent used when it is carried out in the presence of a solvent, a solvent inert to hydroxyl groups and isothiocyanate groups is preferable; or a solvent which, although reacting with the isothiocyanate group, is extremely slow with respect to the target reaction. Preferable examples of the solvent include hydrocarbon compounds such as pentane, hexane, heptane, octane, nonane, decane, dodecane, tetradecane, pentadecane, hexadecane, octadecane, and nonadecane; ethers in which hydrocarbon compounds such as diethyl ether, tetrahydrofuran, octyl ether, nonyl ether, decyl ether, dodecyl ether, tetradecyl ether, pentadecyl ether, hexadecyl ether, octadecyl ether, and tetraethyleneglycol dimethyl ether are bonded by an ether bond; sulfide obtained by bonding hydrocarbon compounds such as dimethyl sulfide, diethyl sulfide, dibutyl sulfide, dihexyl sulfide, octyl sulfide, nonyl sulfide, decyl sulfide, dodecyl sulfide, tetradecyl sulfide, pentadecyl sulfide, hexadecyl sulfide, octadecyl sulfide, and nonadecyl sulfide with sulfide bonds; aromatic hydrocarbon compounds such as benzene, toluene, ethylbenzene, butylbenzene, pentylbenzene, hexylbenzene, octylbenzene, biphenyl, terphenyl, diphenylethane, (methylphenyl) phenylethane, dimethylbiphenyl, and benzyltoluene; aromatic ethers obtained by bonding aromatic hydrocarbon compounds such as diphenyl ether, di (methylbenzyl) ether, di (ethylbenzyl) ether, di (butylbenzyl) ether, di (pentylbenzyl) ether, di (hexylbenzyl) ether, di (octylbenzyl) ether, diphenyl ether, and dibenzyl ether with an ether bond; aromatic thioethers obtained by bonding aromatic hydrocarbon compounds such as diphenyl sulfide, di (methylbenzyl) sulfide, di (ethylbenzyl) sulfide, di (butylbenzyl) sulfide, di (pentylbenzyl) sulfide, di (hexylbenzyl) sulfide, di (octylbenzyl) sulfide, di (methylphenyl) sulfide, and dibenzyl sulfide by sulfide bonds; a compound in which a hydrocarbon compound such as methoxybenzene, ethoxybenzene, butoxybenzene, dimethoxybenzene, diethoxybenzene, or dibutoxybenzene and an aromatic hydrocarbon compound are bonded via an ether bond; halides such as methyl chloride, ethyl chloride, chloropentane, chlorooctane, methyl bromide, ethyl bromide, bromopentane, bromooctane, dichloroethane, dichloropentane, dichlorooctane, dibromoethane, dibromopentane, dibromooctane, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, and the like; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone; amides such as N-methyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide; sulfoxides such as dimethyl sulfoxide; and (3) water.

The reaction temperature is not particularly limited, and may be in the range of 0℃to 300 ℃. The reaction time may be set to any desired one, and for example, the reaction may be stopped after the residual amount of the isothiocyanate group is tracked by an infrared spectrometer and the desired residual amount is reached.

In general, the reaction of hydroxyl groups with isothiocyanate groups is slow, and thus catalysts may be used. The catalyst is Lewis acid and transition metal compound generating Lewis acid, organic tin compound, copper group metal, zinc and iron group metal compound. Specific examples of the catalyst include AlX ₃ 、TiX ₃ 、TiX ₄ 、VOX ₃ 、VX ₅ 、ZnX ₂ 、FeX ₃ 、SnX ₄ (herein, X is a Lewis acid represented by halogen, acetoxy, alkoxy, aryloxy) and a Lewis acid-generating transition metal compound; (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 Organotin compounds represented by BuSnO (OH) and the like; cuCl, cuCl ₂ 、CuBr、CuBr ₂ 、CuI、CuI ₂ 、Cu(OAc) ₂ 、Cu(acac) ₂ Copper olefine acid, bu ₂ Cu、(CH ₃ O) ₂ Cu、AgNO ₃ AgBr, silver picrate, agC ₆ H ₆ ClO ₄ Compounds of copper group metals; zn (acac) ₂ An isozinc compound; fe (C) ₁₀ H ₈ )(CO) ₅ 、Fe(CO) ₅ 、Fe(C ₄ H ₆ )(CO) ₃ Co (trimethylbenzene) ₂ (PEt ₂ Ph ₂ )、CoC ₅ F ₅ (CO) ₇ Iron group metal compounds such as ferrocene (Bu represents butyl, ph represents phenyl, acac represents an acetylacetonate chelate ligand).

[ reaction with Compound having amino group ]

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

(wherein R is ⁴¹ 、R ⁴² A group defined by the above formula (100). )

The reaction may be carried out in the presence of a solvent or may be carried out in the absence of a solvent. Regarding the solvent used when it is carried out in the presence of a solvent, a solvent inert to amino groups and isothiocyanate groups is preferable; or a solvent that is extremely slow relative to the target reaction, although it reacts with the isothiocyanate group. Preferable examples of the solvent include hydrocarbon compounds such as pentane, hexane, heptane, octane, nonane, decane, dodecane, tetradecane, pentadecane, hexadecane, octadecane, and nonadecane; ethers in which hydrocarbon compounds such as diethyl ether, tetrahydrofuran, octyl ether, nonyl ether, decyl ether, dodecyl ether, tetradecyl ether, pentadecyl ether, hexadecyl ether, octadecyl ether, and tetraethyleneglycol dimethyl ether are bonded by an ether bond; sulfide obtained by bonding hydrocarbon compounds such as dimethyl sulfide, diethyl sulfide, dibutyl sulfide, dihexyl sulfide, octyl sulfide, nonyl sulfide, decyl sulfide, dodecyl sulfide, tetradecyl sulfide, pentadecyl sulfide, hexadecyl sulfide, octadecyl sulfide, and nonadecyl sulfide with sulfide bonds; aromatic hydrocarbon compounds such as benzene, toluene, ethylbenzene, butylbenzene, pentylbenzene, hexylbenzene, octylbenzene, biphenyl, terphenyl, diphenylethane, (methylphenyl) phenylethane, dimethylbiphenyl, and benzyltoluene; aromatic ethers obtained by bonding aromatic hydrocarbon compounds such as diphenyl ether, di (methylbenzyl) ether, di (ethylbenzyl) ether, di (butylbenzyl) ether, di (pentylbenzyl) ether, di (hexylbenzyl) ether, di (octylbenzyl) ether, diphenyl ether, and dibenzyl ether with an ether bond; aromatic thioethers obtained by bonding aromatic hydrocarbon compounds such as diphenyl sulfide, di (methylbenzyl) sulfide, di (ethylbenzyl) sulfide, di (butylbenzyl) sulfide, di (pentylbenzyl) sulfide, di (hexylbenzyl) sulfide, di (octylbenzyl) sulfide, di (methylphenyl) sulfide, and dibenzyl sulfide by sulfide bonds; a compound in which a hydrocarbon compound such as methoxybenzene, ethoxybenzene, butoxybenzene, dimethoxybenzene, diethoxybenzene, or dibutoxybenzene and an aromatic hydrocarbon compound are bonded via an ether bond; halides such as methyl chloride, ethyl chloride, chloropentane, chlorooctane, methyl bromide, ethyl bromide, bromopentane, bromooctane, dichloroethane, dichloropentane, dichlorooctane, dibromoethane, dibromopentane, dibromooctane, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, and the like; and (3) water.

The reaction temperature is not particularly limited, and may be in the range of-50℃to 250 ℃. The reaction time may be set to any desired one, and for example, the reaction may be stopped after the residual amount of the isothiocyanate group is tracked by an infrared spectrometer and the desired residual amount is reached.

Generally, the amino group reacts rapidly with the isothiocyanate group, and thus no catalyst is required, nor is the use itself negated. 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 hydrazide group, a semicarbazide group or a thiosemicarbazide group ]

The reaction between a compound having a hydrazide group, a semicarbazide group or a thiosemicarbazide group and an isothiocyanate may take place in various ways depending on the compound used, and examples thereof include a reaction represented by the following formula (102).

(wherein R is ⁴¹ 、R ⁴² For the groups defined by the above formula (100),

y represents-NH-or CH ₂ -a base group comprising a base group,

z represents an oxygen atom or a sulfur atom. )

The reaction of the compound having a hydrazide group, a semicarbazide group, or a thiosemicarbazide group with the isothiocyanate may be carried out in the presence of a solvent or may be carried out in the absence of a solvent. As the solvent used when it is carried out in the presence of a solvent, alcohols such as methanol, ethanol, propanol, butanol and the like can be used in addition to the solvents listed in the above [ reaction with a compound having a hydroxyl group ]; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, methyl lactate, ethyl lactate, and butyl lactate.

The reaction temperature is not particularly limited, and may be in the range of 0℃to 300 ℃. The reaction time may be set to any desired one, and for example, the reaction may be stopped after the residual amount of the isothiocyanate group is tracked by an infrared spectrometer and the desired residual amount is reached.

The reaction may be carried out in the presence or absence of a catalyst. In the case of using a catalyst, the catalysts listed in the above [ reaction with a compound having a hydroxyl group ] can be used.

In the case where a compound having a hydrazide group or a semicarbazide group is reacted with an isothiocyanate, further heat treatment is preferably performed. This heat treatment may have an effect of improving mechanical properties such as rigidity, hardness, processability, impact resistance, and bending fatigue of the resin composition. The principle of this effect is not clear, and the inventors speculate that it may be due to: by the heat treatment, the bonding on the right side of the above formula (102) forms a ring structure in the molecular chain according to the reaction represented by the following formula (103) or formula (104).

(wherein R is ⁴¹ 、R ⁴² Y, Z are groups defined by the above formula (102). )

One of the preferred modes of the resin of the present embodiment is a resin having at least 1 structural unit selected from the group consisting of 2 or more groups represented by the following formulas (6) to (8).

(wherein Y is ¹ Represents an organic group, and may be an-NH-group. )

Y ¹ Preferably an aliphatic group having 1 to 12 carbon atoms or an aromatic group having 6 to 12 carbon atoms. Examples of the aliphatic group having 1 to 12 carbon atoms include a 2-valent group derived from a hydrocarbon compound such as methane, ethane, propane, butane, pentane, hexane, octane, decane, etc.; a 2-valent group derived from a compound having a cyclic hydrocarbon group such as cyclohexane, cyclooctane, cyclodecane, methylcyclohexane, ethylcyclohexane, butylcyclohexane, dimethylcyclohexane, or the like; and a 2-valent group derived from an aromatic hydrocarbon compound such as benzene, toluene, ethylbenzene, butylbenzene, hexylbenzene, etc.

The resins of several modes have at least 1 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 structural units represented by the following formulas (105) to (108).

(wherein R is ⁴³ Represents an organic group of which the organic group is,

more than 2R ⁴³ May be the same or different from each other,

j represents a 2-valent group represented by the above formula (6), (7) or (8), and 2 or more R's in the same molecule ⁴³ And J may be the same or different. )

R is as described above ⁴³ Preferably an aliphatic group having 2 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic compound, or an aromatic group having 8 to 25 carbon atoms. As R ⁴³ Specific examples of (a) include residues obtained by removing 3 hydrogen atoms from ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylethane, ethylbenzene, diethylbenzene, diphenylethane, tetramethyldiphenylethane, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octadecanol, cyclohexanol, cyclooctanol, dimethylcyclohexanol, diethylcyclohexanol, trimethylcyclohexanol, dicyclohexylethanol, and the like.

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

(wherein, K ¹ ～K ^c Each independently represents at least 1 group selected from the group consisting of the above formulas (6) to (8),

L ¹ ～L ^c each independently represents an organic group which may or may not contain a group selected from the group consisting of formulae (6) to (8), c represents an integer of 1 or more,

M ¹ and M ² Each independently represents an organic group which may or may not contain an isothiocyanate group,

w _c and represents an integer of 1 or more. )

In the above formula (109), w _c Represent K ^c -L ^c Is a number of repeating units of (a). For example, in the process of K ¹ -L ¹ And K ² -L ² In the case of a resin comprising 2 repeating units, the above formula (109) is represented by the following formula (110)And (3) representing.

The method for producing the resin composition containing the resin having at least one structural unit selected from the group consisting of 2 or more groups represented by the above formulas (6) to (8) is not particularly limited, and the resin composition can be produced, for example, by a reaction of a compound having a hydrazide group, a semicarbazide group or a thiosemicarbazide group with an isothiocyanate.

The reaction of the compound having a hydrazide group, a semicarbazide group, or a thiosemicarbazide group with the isothiocyanate may be carried out in the presence of a solvent or may be carried out in the absence of a solvent. As the solvent used when it is carried out in the presence of a solvent, alcohols such as methanol, ethanol, propanol, butanol and the like can be used in addition to the solvents listed in the above [ reaction with a compound having a hydroxyl group ]; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, cellosolve acetate, amyl acetate, methyl lactate, ethyl lactate, and butyl lactate.

The reaction temperature is not particularly limited, and may be in the range of 0℃to 300 ℃. The reaction time may be set to any desired one, and for example, the reaction may be stopped after the residual amount of the isothiocyanate group is tracked by an infrared spectrometer and the desired residual amount is reached.

The reaction may be carried out in the presence or absence of a catalyst. In the case of using a catalyst, 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 may be used. The reaction apparatus may be, for example, a stirred tank, a pressurized stirred tank, a depressurized stirred tank, a column reactor, a distillation column, a packed column, a thin film distiller, or any other conventionally known reactor. The material of the reactor is not particularly limited, and known materials can be used. As a material of the reactor, for example, a material of glass, stainless steel, carbon steel, hastelloy, a material of glass lining a substrate, or a material of teflon (registered trademark) coating can be used. SUS304, SUS316L, etc. are low in cost, and can be preferably used. If necessary, a known process device such as a flowmeter, a thermometer, a reboiler, a pump, a condenser, or the like may be added, heating may be performed by a known method such as steam or a heater, or cooling may be performed by a known method such as natural cooling, cooling water, or a coolant. Additional steps may be added as needed.

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

The heat treatment is preferably performed at a temperature in the range of 100 to 300 ℃, more preferably 150 to 250 ℃. The heat treatment may be performed under an atmosphere or an inert gas atmosphere, and is preferably performed under an inert gas atmosphere. The inert gas as used herein refers to nitrogen, helium, argon, neon, and the like. In addition, the pressure may be increased, decreased, or atmospheric pressure. The time for the heat treatment is not particularly limited, and may be in the range of 1 minute to 500 hours, and for example, the amount of the group represented by the above formulas (6) to (8) may be tracked by an infrared spectrometer, and the heating may be stopped after the desired amount is reached.

In the above production method, it is considered that the groups represented by the above formulas (6) to (8) are produced by various reaction pathways, and for example, it is presumed that a reaction based on the following formula (111) is produced, and then a reaction in which the right compound in the following formula (111) forms a ring structure by the following formula (112) or formula (113) is produced.

(in the formula (I),R ⁴¹ and R is ⁴² For the groups defined by the above formula (100),

y represents an-NH-group or an organic group,

z represents an oxygen atom or a sulfur atom. )

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

The modified resin composition of the present embodiment can be used in various known applications, and among them, the application as a coating material formed on the surface of at least one material selected from the group consisting of metal, glass and plastic is suitable. The resin composition of the present embodiment is preferably used for a water-based paint because it is formed by a reaction of functional groups stable to water.

The modified resin composition of the present embodiment contains sulfur atoms in the molecular chain, and thus the effect of improving adhesion to the metal surface is increased. Therefore, the resin composition can be suitably used for imparting aesthetic properties, weather resistance, acid resistance, rust resistance, chipping resistance, adhesion, and the like to precoated metals including rust-resistant steel sheets, automobile coatings, and the like.

Oxazolidinethiones

< Structure preferable >

In the present embodiment, the 2 nd resin is preferably a resin containing a molecular chain represented by the following formula (10).

(wherein P ¹ Represents an aliphatic and/or aromatic group, Q ¹ Represents 1 or more structural units selected from the group consisting of 2-valent groups represented by the following formulas (11), (12), (13) and (14), and 2 or more P ¹ And Q ¹ And n represents an integer of 2 or more. )

Wherein R is ¹ Represents an aliphatic or aromatic group, X ² And Y ² Each independently represents an oxygen atom or a sulfur atom, and 2 or more R's in the same molecule ¹ 、X ² And Y ² The two may be the same or different. Q (Q) ¹ X in (2) ² And Y ² More than 1 of them are sulfur atoms. In other words, one Q1 contains 1 or more sulfur atoms.

Surprisingly, the structures represented by the above formulas (11) to (14) constituting the resin are excellent in adhesion, particularly adhesion to a metal surface. The principle of such an effect is not clear, but the present inventors speculate that the sulfur atom or oxygen atom contained in the bond plays an effect of improving adhesion.

As described above, the resin according to the present embodiment is characterized by the bonding system contained in the molecule, and the skeleton structure other than the bonding is not particularly limited, and more preferable modes are as follows.

The number average molecular weight of the resin is preferably 500 or more, more preferably 1000 or more, and still more preferably 5000 or more. Generally, the higher the molecular weight, the better the heat resistance tends to be; on the other hand, when the molecular weight is too high, the number average molecular weight is preferably 100 ten thousand or less, more preferably 50 ten thousand or less, and even more preferably 20 ten thousand or less, because the handling property (mixing property with other components, fluidity, ductility, etc.) at the time of forming a coating film is sometimes disadvantageous. The number average molecular weight referred to herein is a value calculated as follows: the retention time is calculated by measuring the gel permeation chromatography using a column having at least 1 column having a exclusion limit molecular weight of 1000 ten thousand or more and converting the retention time into a molecular weight using a standard substance such as polystyrene. The number average molecular weight can be readily determined by those skilled in the art. Calculation was performed after excluding the peak from the solvent.

The content of bonds contributing to the heat resistance performance is also related to the above-mentioned number average molecular weight Mn. Dividing the number average molecular weight of the resin by the number average molecular weight of the resin contained in each 1 moleculeNumber n of sulfur atoms constituting nitrogen-carbon-sulfur bonds and oxygen atoms constituting nitrogen-carbon-oxygen bonds ¹ The value (Mn/n) ¹ ) Preferably 300 or less, more preferably 200 or less, and still more preferably 150 or less. As described above, the resin composition of the present embodiment can exert an effect in terms of adhesion to a metal, and it is preferable to have a large number of the above bonds per 1 molecule of resin from the viewpoint of exhibiting such an effect. On the other hand, when the resin has too many of the above-mentioned bonds, in particular, when the resin has structural units represented by the above-mentioned formulae (6) to (8), (11) to (14), (41), (42), (45), (46) or (47), flexibility as one of coating properties may be impaired. In this respect Mn/n ¹ Preferably 50 or more, more preferably 70 or more. n is n ¹ For example, it can be calculated as follows: for example by infrared absorption spectroscopy or ¹ The number X of the bonds per unit weight (1 g) of the resin was obtained by H-NMR or the like ¹ (in mol/g), according to the formula: n is n ¹ ＝Mn·X ¹ Calculated from the number average molecular weight (Mn) described above. In the case where the resin contains both nitrogen-carbon-sulfur bonds and nitrogen-carbon-oxygen bonds, n ¹ Is the total number of sulfur atoms and oxygen atoms constituting each bond.

R in the above formulae (11) to (14) ¹ Is an aliphatic group or an aromatic group. The hydrocarbon group has at least 1 or more of an aliphatic group and an aromatic group, and 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, 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. It is also preferable that the aliphatic group having 1 to 5 carbon atoms is bonded to an aromatic group having 6 to 15 carbon atoms, and the group has 7 to 20 carbon atoms.

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

Of these, groups derived from hexane, benzene, diphenylmethane, toluene, cyclohexane, xylene, methylcyclohexane, isophorone or dicyclohexylmethane are preferred. "Source group" means a group of structure after 2 hydrogen atoms have been removed from the compound.

Alternatively, R ¹ Aliphatic groups having 1 to 25 carbon atoms and aromatic groups having 6 to 25 carbon atoms are preferable. R is R ¹ Preferred are groups which do not contain spiro atoms. R is R ¹ Specific examples of (C) are residues obtained by removing 2 hydrogen atoms from methane, ethane, propane, butane, pentane, hexane, octane, decane, dodecane, octadecane, cyclohexane, cyclooctane, dimethylcyclohexane, diethylcyclohexane, trimethylcyclohexane, trimethylethylcyclohexane, dicyclohexylmethane, tetramethyldicyclohexylmethane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, diphenylmethane, tetramethyldiphenylmethane and the like. Where an isomer is present, that isomer is also included.

Among these, R ¹ The 2-valent groups represented by the following formulas (301) to (306) are preferable.

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

In the above formula (10), P ¹ Is an aliphatic group and/or an aromatic group. P (P) ¹ In addition to having a carbon atom, an oxygen atom, a nitrogen atom, and the like may be also be present.

P in the above formula (10) ¹ More preferably, the compound contains an ether bond or an ester bond, and still more preferably, the compound represented by the following formula (114).

(wherein R is ⁴³ Represents an aliphatic group or an aromatic group,

b ² an integer of 1 to 3. More than 2R in the same molecule ⁴³ And b ² The two may be the same or different. )

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

R in the above formula (114) ⁴³ The preferable specific structure of (a) may be a group represented by the following formula (115).

(wherein R is ⁴⁴ Represents 1 or more selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom and a methyl group,

R ⁴⁵ Is represented by the following formula(116) A group selected from the group consisting of the groups represented by (117), (118) and (119),

more than 2R ⁴⁴ May be the same or different. )

More specifically, P in the above formula (10) ¹ The groups represented by the following formulas (201) to (204) are preferable.

In the above formulas (11) to (14), X ² And Y ² Each independently represents an oxygen atom or a sulfur atom, X in one unit ² And Y ² Not both oxygen atoms. I.e. X in one unit ² And Y ² At least one of them is a sulfur atom. By containing sulfur atoms, adhesion to an adherend, particularly adhesion to a metal surface, is improved.

The structure represented by the above formula (10) does not show the terminal structure, but the gist of the present invention is to improve the adhesion between an epoxy resin and a modified epoxy resin or the like, and as described above, it is important that the compound of the present invention (an atom constituting the compound of the present invention) contains a sulfur atom and/or an oxygen atom, and it is considered that the difference in terminal structure does not have to exert a large influence. As will be described later, the compound represented by the formula (10) can be produced by combining a compound having a terminal epoxy group with a compound having a terminal isothiocyanate group (-NCS), a compound having a terminal thio group with a compound having a terminal isocyanate group (-NCO), or a compound having a terminal thio group and a compound having a terminal isothiocyanate group. Depending on the compound used to obtain the compound of formula (10), the terminal structure may be an epoxy group, a alkylthio group, an isocyanate group, or an isothiocyanate group. As described in < method of production >, an isocyanurate group (in the case of an isocyanuric acid ester group, an isocyanuric acid ester group) obtained by trimerizing an isocyanate group may be included in the compound of the present embodiment. N-substituted-O-substituted thiocarbamate groups derived from the reaction of alcoholic hydroxyl groups and isothiocyanate groups in an epoxy resin (described below), N-substituted-S-substituted thiocarbamate groups derived from the reaction of thiol groups and isocyanate groups in an episulfide resin (described below), and dithio-carbamate groups derived from the reaction of thiol groups and isothiocyanate groups in an episulfide resin are also sometimes included.

< manufacturing method >

The compound (resin) of the present embodiment can be produced, for example, by a combination of a compound having a terminal epoxy group and a compound having a terminal isothiocyanate group (-NCS), a compound having a terminal alkylthio group and a compound having a terminal isocyanate group (-NCO), or a compound having a terminal thio group and a compound having a terminal isothiocyanate group.

The compound (resin) of the present embodiment is preferably obtained by reacting a compound represented by the following formula (31) (a compound having a terminal isocyanate group, a compound having a terminal isothiocyanate group), and a compound represented by the following formula (20) (a compound having a terminal epoxy group, a compound having a terminal sulfur group).

(wherein R is ² Represents an aliphatic group or an aromatic group,

R ¹ represents an aliphatic or aromatic group, X and Y ² Each independently represents 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) is a compound represented by the formula (31) wherein X is a sulfur atom and/or Y ² The compound of formula (20) which is a sulfur atom is selected in such a manner that it contains 1 or more.

2 or more kinds of compounds represented by the formula (31), In the reaction of the combination of compounds represented by the formula (20), at least 2R ¹ And R is ² May be the same or different.

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

(wherein R is ² Represents an aliphatic group or an aromatic group. )

Specific examples of the compound represented by the formula (120) include: bisphenol epoxy resins obtained by glycidylating bisphenols such as bisphenol a, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol a, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol a, tetrachlorobisphenol a, tetrafluorobisphenol a, and the like; epoxy resins obtained by glycidylating other dihydric phenols such as biphenol, dihydroxynaphthalene, and 9, 9-bis (4-hydroxyphenyl) fluorene; epoxy resins obtained by glycidylating triphenols such as 1, 1-tris (4-hydroxyphenyl) methane and 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylene) bisphenol; an epoxy resin obtained by glycidylating tetraphenols such as 1,2, -tetrakis (4-hydroxyphenyl) ethane; glycidyl ethers such as novolak type epoxy resins obtained by glycidylating novolak type compounds such as novolak, cresol novolak, bisphenol a novolak, brominated novolak and brominated bisphenol a novolak; glycidyl esters such as diglycidyl esters of hexahydrophthalic acid or dimer acid. These compounds having a terminal epoxy group may be used alone or in combination of two or more.

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

(wherein R is ² Represents an aliphatic group or an aromatic group. )

Specific examples of the compound represented by the formula (121) include bisphenol-type episulfide resins obtained by sulfoglycidylating bisphenols such as bisphenol a, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol a, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol a, tetrachlorobisphenol a, tetrafluorobisphenol a, and the like; an episulfide resin obtained by performing thioglycidylation of other dihydric phenols such as biphenol, dihydroxynaphthalene, 9-bis (4-hydroxyphenyl) fluorene and the like; an episulfide resin obtained by the thioglycidylation of triphenols such as 1, 1-tris (4-hydroxyphenyl) methane, 4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylene) bisphenol and the like; an episulfide resin obtained by sulfoglycidylating tetraphenols such as 1,2, -tetrakis (4-hydroxyphenyl) ethane; thioglycidyl ethers such as a novolak type episulfide resin obtained by thioglycidylating a novolak type such as novolak, cresol novolak, bisphenol A novolak, brominated novolak and brominated bisphenol A novolak; thioglycidyl esters such as dithioglycidyl esters of hexahydrophthalic acid or dimer acid. These compounds having terminal thio groups may be used alone or in combination of two or more.

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

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

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

O＝C＝N-R ¹ -N＝C＝O (122)

(wherein R is ¹ Representing fatA group or an aromatic group. )

Specific examples of the compound represented by the formula (122) include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2, 4-trimethyl-1, 6-diisocyanatohexane, lysine diisocyanate, isophorone diisocyanate, 1, 3-bis (isocyanatomethyl) -cyclohexane, 4 '-dicyclohexylmethane diisocyanate, 4' -diphenylmethane diisocyanate, toluene diisocyanate (each isomer), 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 a cycloaliphatic diisocyanate having 8 to 20 carbon atoms. Among these, hexamethylene diisocyanate and isophorone diisocyanate are preferable from the viewpoints of weather resistance, heat resistance Huang Gaixing, and ease of industrial availability. These isocyanate compounds may be used alone or in combination of two or more.

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

S＝C＝N-R ¹ -N＝C＝S (123)

(wherein R is ¹ Represents an aliphatic group or an aromatic group. )

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

The method for producing the compound according to the present embodiment will be described below by taking a reaction of an epoxy resin and an isothiocyanate compound as an example. The same applies to the case where an episulfide resin is used instead of an epoxy resin, and the epoxy resin in the following description may be replaced with an episulfide resin and the epoxy group may be replaced with an episulfide group. In addition, in the case of using an isocyanate compound instead of an isothiocyanate compound, the isothiocyanate compound in the following description may be replaced with an isocyanate compound, and the isothiocyanate group may be replaced with an isocyanate group.

Regarding the amount of the isothiocyanate compound to be used, it is preferable that the isothiocyanate group is used in an amount of up to 20 to 60 equivalent% with respect to the epoxy group. The amount of the isothiocyanate compound used is more preferably 25 to 50 equivalent%, still more preferably 30 to 47 equivalent%, still more preferably 30 to 45 equivalent%. The isocyanate groups in the isocyanate compound are used to form a thiocarbamate bond with alcoholic hydroxyl groups in the epoxy resin or to form an isothiocyanuric acid ester ring by cyclization 3 polymerization based on an isothiocyanate group, in addition to the ring structure by reaction with the epoxy groups.

The reaction is generally carried out in the presence of a catalyst. Examples of the catalyst include metal alkoxides such as lithium butoxide and sodium methoxide, lewis acids such as lithium chloride and aluminum chloride, mixtures of Lewis acids with Lewis bases such as triphenylphosphine oxide, chlorides such as tetramethylammonium, tetraethylammonium, tetrabutylammonium and benzyltributylammonium, quaternary ammonium salts such as bromide, iodide and acetate, triethylamine, N-dimethylbenzylamine, tertiary amines such as 1, 8-diazabicyclo [5.4.0] undec-7-ene and 1, 4-diazabicyclo [2.2.2] octane, imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole, and the like. These catalysts may be used alone or in combination of 2 or more. As the catalyst, quaternary ammonium salts and tertiary amines are particularly preferable.

The catalyst is generally used in an amount ranging from 5ppm to 2wt% relative to the total weight of the epoxy resin. The catalyst is preferably used in an amount of 20ppm to 0.5 wt.%. The catalyst may also be diluted in a suitable solvent for use.

The production method of the present embodiment may be performed under a solvent-free condition or in the presence of an appropriate solvent.

When a solvent is used, a solvent containing no active hydrogen such as N, N-dimethylformamide, N-diethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, xylene, toluene, methyl cellosolve acetate, tetrahydrofuran, or the like is preferably used.

The reaction temperature is generally from 80℃to 300 ℃. Preferably 100℃to 260℃and more preferably 120℃to 220 ℃. If the reaction temperature is too low, the activity of the catalyst is low, and side reactions such as formation of isocyanurate rings may occur. In addition, when the reaction temperature is too high, the activity of the catalyst is lowered, and the side reaction still proceeds.

In the production of the compound of the present embodiment, it is preferable that the epoxy resin is heated to a specific temperature, and then the moisture in the resin is removed as much as possible by blowing dry air, nitrogen, or the like, and then the isothiocyanate compound and the catalyst are added. The method of adding the isothiocyanate compound and the catalyst may be appropriately selected, may be added at one time, may be added in multiple times, and may be added continuously. In this case, the isothiocyanate and the catalyst may be added simultaneously or separately. In the case of continuous feeding, the feeding time is preferably 1 to 10 hours, more preferably 2 to 5 hours. When the time for the addition is short, the amount of the isocyanuric acid ring may increase.

The compound of the present embodiment preferably has 20 to 45% by weight (preferably 22 to 42% by weight, more preferably 25 to 40% by weight) of the epoxy group in the epoxy resin and the isothiocyanate group in the isothiocyanate compound react to form an oxazolidine-2-thione ring (thiazolin-2-one ring in the reaction of the episulfide resin and the isocyanate compound and thiazolin-thione ring in the reaction of the episulfide resin and the isothiocyanate compound).

The ratio of epoxy groups related to the oxazolidine-2-thione ring in the epoxy resin can be determined, for example, by the following method: a method for measuring Oxd conversion by chemical means; a method for quantification by a method of machine analysis such as infrared spectroscopy and nuclear magnetic resonance spectroscopy.

Oxd the conversion is equivalent% of the epoxy groups forming, for example, an oxazolidine-2-thione ring relative to the original epoxy groups. When the epoxy group is not substantially consumed except for the reaction for forming the oxazolidine-2-thione ring, the Oxd conversion can be obtained by using the epoxy equivalent (referred to as Ep 1) and weight (referred to as Wt 1) of the epoxy resin to be used, and the epoxy equivalent (referred to as Ep 2) and weight (referred to as Wt 2) of the epoxy resin containing the oxazolidine-2-thione ring to be obtained.

Oxd conversion=100- (Wt 2/Ep 2)/(Wt 1/Ep 1) ×100

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

The compound (resin) of the present embodiment may contain an isothiocyanuric acid ester ring obtained by cyclizing 3-polymerizing an isothiocyanate group in an isothiocyanate compound. The content of the isothiocyanamide ring is preferably 40 equivalent% or less, more preferably 30 equivalent% or less, further preferably 20 equivalent% or less, further preferably 10 equivalent% or less of the content of the oxazolidine-2-thione ring. If the number of the isocyanurates is too large, the polymerization stability may be lowered during production.

The compound (resin) of the present embodiment preferably contains substantially no isocyanate group.

In order to improve fluidity, the melt viscosity of the compound (resin) of the present embodiment is preferably low. Specifically, the melt viscosity at 125℃is preferably 8000 mPas or less. More preferably 6000 mPas or less, still more preferably 4000 mPas or less, and still more preferably 3000 mPas or less.

The amount of hydrolyzable chlorine in the compound (resin) of the present embodiment is not particularly limited, and is preferably 500ppm or less when used for electric and electronic applications, for example. More preferably 100ppm 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 is a compound having a functional group reactive with an epoxy group, and examples thereof include phenols such as xylenol, t-butylphenol, nonylphenol, bisphenol a, and hydroquinone; alcohols such as n-butanol, butyl cellosolve, polyethylene glycol monoethyl ether, ethylene glycol, and polypropylene glycol; amines such as butylamine, octylamine, diethylamine, methylbutylamine, monoethanolamine, diethanolamine, N-methylethanolamine, triethylamine hydrochloride, N-dimethylethanolamine acetate, and dimethylketimine of aminoethylethanolamine; carboxylic acids such as acetic acid, lactic acid, 2-ethylhexanoic acid, lauric acid, 12-hydroxystearic acid, benzoic acid, and dimethanol propionic acid; sulfides such as diethyl disulfide and acetic acid mixture, thiols such as gamma-mercaptopropyl dimethoxy methyl silane and gamma-mercaptopropyl trimethoxy silane, and the like.

For example, the conversion to an ionic group may be performed by further converting an amino group into an ammonium salt using acetic acid or the like after the modification with an amine.

[ curable composition ]

The compound (resin) of the present embodiment may be mixed with a curing agent to prepare a curable composition.

In the case of curing using an epoxy group, examples of the curing agent include aliphatic amines such as ethylenediamine, triethylenediamine, 1, 6-hexamethylenediamine, dimer acid-modified ethylenediamine, and N-ethylaminopiperazine; aromatic amines such as m-phenylenediamine, p-phenylenediamine, 3' -diaminodiphenyl sulfone, 4' -diaminodiphenyl methane, and 4,4' -diaminodiphenyl ether; thiols such as mercaptopropionate and terminal mercapto compounds of epoxy resins; phenolic resins such as bisphenol a, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol a, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol a, tetrachlorobisphenol a, tetrafluorobisphenol a, biphenol, dihydroxynaphthalene, 1-tris (4-hydroxyphenyl) methane, 4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylene) bisphenol, novolak, cresol novolak, bisphenol a novolak, brominated novolak, and brominated bisphenol a novolak; anhydrides such as polyazelaic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, phthalic anhydride, trimellitic anhydride, and pyromellitic dianhydride; imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole; hydrazines such as adipic acid dihydrazide; tertiary amines such as dimethylbenzylamine and 1, 8-diazabicyclo [5.4.0] undec-7-ene; dicyandiamide, and the like. These curing agents may be used alone or in combination of two or more.

In the case of curing using a crosslinkable group introduced by modification of an epoxy group or a secondary hydroxyl group generated by modification, a melamine resin, a polyisocyanate compound, a blocked isocyanate compound, or the like is used as a curing agent. These curing agents may be used alone or in combination of two or more.

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

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

As the polyisocyanate derived from the diisocyanate, isocyanurate type polyisocyanates, biuret type polyisocyanates, urethane type polyisocyanates, allophanate type polyisocyanates and the like are included. These polyisocyanate compounds may be used alone or in combination of two or more.

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

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

The amount of the curing agent to be used is arbitrarily selected with respect to the total amount of the compounds of the present embodiment, and is usually 0.1 to 90% by weight. The curing agent is preferably used in an amount of 0.1 to 50% by weight.

The curable composition may contain a solvent as required. As the solvent, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral essential oil, naphtha, and the like can be used depending on the purpose and use; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, and the like; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol, and the like; water and the like are suitably selected for use. These solvents may be used alone or in combination of two or more.

The curable composition may contain a curing accelerator as needed. As the curing accelerator, for example, metal catalysts such as imidazoles, tertiary amines, phosphines, aminotriazoles, tin-based, zinc-based, and the like are used. These curing accelerators may be used alone or in combination of two or more.

Pigments, fillers, additives, and the like commonly used in the art as shown below can be used in the curable composition. Examples thereof include organic pigments such as quinacridone type, azo type and phthalocyanine type, inorganic pigments such as titanium dioxide, metallic foil type pigments and rust preventive pigments, fillers such as barium sulfate, calcium carbonate, silica, carbon black, talc and clay, ultraviolet absorbers such as hindered amine type, benzotriazole type and benzophenone type, antioxidants such as hindered phenol type, phosphorus type, sulfur type and hydrazide type, coupling agents such as silane type and titanium type, leveling agents, rheology control agents, pigment dispersants, anti-cratering agents, and additives such as antifoaming agents. Further, a reinforcing material such as glass fiber, glass cloth, or carbon fiber may be contained as necessary.

The curable composition of the present embodiment has both excellent adhesion and good fluidity, and is suitable for use as a material such as a powder coating, an electrodeposition coating, a PCM coating, a coating material, a bonding agent, a sealing material, a molding material, a composite material, a laminate, and a potting material.

Resin having an Isothiocyanurate Structure

< Structure preferable >

In the present embodiment, the 3 rd resin preferably has 2 or more structural units represented by the following formula (40). The resin further has 1 or more structural units selected from the group consisting of 1-valent, 2-valent, and 3-valent groups represented by the following formulas (41) to (47). R in the structural units represented by the formulae (41) to (47) ³ Can be directly bonded to an isothiocyanate group to form a structural unit of formula (40). N in 1 structural unit represented by the formulas (41) to (47) is not directly bonded to N in the other structural units represented by the formulas (41) to (47).

(wherein R is ³ Represents an organic group, R ⁴ Represents an aliphatic or aromatic group, X ³ Represents an oxygen atom or a sulfur atom. More than 2R in the same molecule ³ 、R ⁴ And X ³ May be the same or different. R is R ³ May be aliphatic or aromatic. )

Typically, substantially all of the nitrogen atoms comprising the polyisothiocyanate are bound to at least 1 carbon atom. That is, the structural units are not directly bonded to each other through N. In addition, R in each structural unit ³ Can be directly bonded to an isothiocyanate group to form a structural unit represented by the formula (40). For example, the structural unit represented by the formula (41) is bonded to an isothiocyanate group, whereby a monofunctional repeating unit represented by the formula (46) or a difunctional repeating unit represented by the formula (47) can be formed. Polyisothiocyanates may have a structure other than R ³ A bonded isothiocyanate group.

for-X contained in formulas (43) and (45) ³ -R ⁴ The functional groups represented are illustrated.

In the method for producing a polyisothiocyanate described below, a hydroxyl compound or a thiol is used when producing a polyisoisothiocyanate having an N, N' -disubstituted dithiocarbamic acid bond represented by formula (43) or an N-substituted-O-substituted thiocarbamate group or an N-substituted-S-substituted dithiocarbamic acid group represented by formula (45). -X ³ -R ⁴ The functional group represented is a group derived from the hydroxyl compound or thiol, and in the case of using a hydroxyl compound, X ³ In the case of using thiols, X is an oxygen atom ³ Is a sulfur atom.

R in the formulae (40) to (47) ³ 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. It is also preferable that the aliphatic group having 1 to 5 carbon atoms and the aromatic group having 6 to 15 carbon atoms bonded to the aliphatic group have 7 to 20 carbon atoms.

Among these, R ³ The 2-valent groups represented by the following formulas (301) to (306) are preferable.

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

As R ⁴ Specific examples of (a) may beExamples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, cyclopentyl, 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.

Surprisingly, the structural units represented by the above formulas (41) to (47) constituting the resin have high heat resistance and excellent adhesion, particularly adhesion to a metal surface. The principle by which such an effect can be achieved is not clear, and the present inventors have speculated that the heat resistance can be improved when the stable 6-membered ring structure is provided, and that the sulfur atom contained in the bond can have an effect of improving the adhesion.

As described above, the resin according to the present embodiment is characterized by the bonding system contained in the molecule, and the skeleton structure other than the bonding is not particularly limited, and more preferable modes are as follows.

The number average molecular weight of the resin is preferably 500 or more, more preferably 1000 or more, and still more preferably 5000 or more. Generally, the higher the molecular weight, the better the heat resistance tends to be; on the other hand, when the molecular weight is too high, the number average molecular weight is preferably 100 ten thousand or less, more preferably 50 ten thousand or less, and even more preferably 20 ten thousand or less, because the handling property (mixing property with other components, fluidity, ductility, etc.) at the time of forming a coating film is sometimes disadvantageous. The number average molecular weight referred to herein is a value calculated as follows: the retention time is calculated by measuring the gel permeation chromatography using a column having at least 1 column having a exclusion limit molecular weight of 1000 ten thousand or more and converting the retention time into a molecular weight using a standard substance such as polystyrene. The number average molecular weight can be readily determined by those skilled in the art. Calculation was performed after excluding the peak from the solvent.

Bond contributing to heat resistance performanceThe content is also related to the number average molecular weight Mn described above. Dividing the number average molecular weight of the resin by the number n of sulfur atoms constituting nitrogen-carbon-sulfur bonds and oxygen atoms constituting nitrogen-carbon-oxygen bonds contained in each 1 molecule ¹ The value (Mn/n) ¹ ) Preferably 300 or less, more preferably 200 or less, and still more preferably 150 or less. As described above, the resin composition of the present embodiment can exert an effect in terms of adhesion to a metal, and it is preferable to have a large number of the above bonds per 1 molecule of resin from the viewpoint of exhibiting such an effect. On the other hand, when the resin has too many of the above-mentioned bonds, in particular, when the resin has structural units represented by the above-mentioned formulae (6) to (8), (11) to (14), (41), (42), (45), (46) or (47), flexibility as one of coating properties may be impaired. In this respect Mn/n ¹ Preferably 50 or more, more preferably 70 or more. n is n ¹ For example, it can be calculated as follows: for example by infrared absorption spectroscopy or ¹ The number X of the bonds per unit weight (1 g) of the resin was obtained by H-NMR or the like ¹ (in mol/g), according to the formula: n is n ¹ ＝Mn·X ¹ Calculated from the number average molecular weight (Mn) described above. In the case where the resin contains both nitrogen-carbon-sulfur bonds and nitrogen-carbon-oxygen bonds, n ¹ Is the total number of sulfur atoms and oxygen atoms constituting each bond.

< preferred production 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, which are bonded in turn.

The resin according to the present embodiment is preferably a resin obtained by a method including a step of polymerizing a compound represented by the following formula (33).

SCN-R ³ -NCS (30)

(wherein R is ³ Represents an organic group, which may be an aliphatic group or an aromatic group. )

In the above formula (30), R ³ Represents an aliphatic group, an aromatic group, or a group formed by a combination thereof (an aliphatic group substituted with an aromatic group). As a means ofThe compound of formula (30) used in the polymerized monomer may be R ³ Combinations of 2 or more different compounds. As R, in addition to carbon atoms ³ The aliphatic group and the aromatic group of (a) may have an oxygen atom, a nitrogen atom, or the like. 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. It is also preferable that the aliphatic group having 1 to 5 carbon atoms and the aromatic group having 6 to 15 carbon atoms bonded to the aliphatic group have 7 to 20 carbon atoms.

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

Of these, 1 or more selected from the group consisting of hexane, benzene, diphenylmethane, toluene, cyclohexane, xylene, methylcyclohexane, isophorone and dicyclohexylmethane-derived groups are preferable. "Source group" means a group of structure after 2 hydrogen atoms have been removed from the compound.

Above-mentionedR in formula (30) ³ More preferably, the groups represented by the following formulas (301) to (306).

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

Further preferable examples of the isothiocyanate represented by the above formula (30) include hexamethylene diisoisothiocyanate, isophorone diisoisothiocyanate, 4 '-dicyclohexylmethane diisoisothiocyanate, 4' -diphenylmethane diisoisothiocyanate, toluene diisoisothiocyanate (each isomer), naphthalene diisoisothiocyanate (each isomer) and the like.

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

The polyisothiocyanate of the present embodiment can be obtained, for example, by homopolymerizing a monomeric diisoisothiocyanate. The polymerization of the monomer diisoisothiocyanate is preferably carried out in the presence of a catalyst such as an isocyanuric acid catalyst described later. In addition, when a monomer diisoisothiocyanate is polymerized, a hydroxyl compound or a thiol may be used as a side material, and a part of the isothiocyanate group may be urethanized, allophanated, or the like by a reaction of the diisoisothiocyanate with the hydroxyl compound or the thiol, thereby obtaining a polyisoisothiocyanate.

The monomer diisoisothiocyanate is a compound represented by the above formula (33).

Examples of the hydroxyl compound include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, dodecanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, methylcyclopentanol, ethylcyclopentanol, methylcyclohexanol, ethylcyclohexanol, propylcyclohexanol, butylcyclohexanol, pentylcyclohexanol, hexylcyclohexanol, dimethylcyclohexanol, diethylcyclohexanol, dibutylcyclohexanol, phenol, methylphenol, ethylphenol, propylphenol, butylphenol, pentylphenol, hexylphenol, octylphenol, nonylphenol, cumylphenol, dimethylphenol, methylethylphenol, methylpropylphenol, methylbutylphenol, methylpentylphenol, diethylphenol, ethylpropylphenol, ethylbutylphenol, diethylphenol, dicumylphenol, trimethylphenol, triethylphenol, naphthol, and the like. Further, a polyester polyol, polyether polyol or the like having a number average molecular weight of about 200 to 10,000, which is a low molecular weight compound such as ethylene glycol, 1, 2-propylene glycol or 1, 3-propylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol or 2, 3-butylene glycol, 1, 6-hexylene glycol, neopentyl glycol hydroxypivalate, 2-ethyl-1, 3-hexylene glycol, trimethylolpropane, glycerin, 1,2, 6-hexanetriol, or the like, may be used.

Examples of the thiol include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, pentyl mercaptan, hexyl mercaptan, heptyl mercaptan, octyl mercaptan, decyl mercaptan, dodecyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, cycloheptyl mercaptan, cycloocta mercaptan, methylcyclopentyl mercaptan, ethylcyclohexyl mercaptan, propylcyclohexyl mercaptan, butylcyclohexyl mercaptan, pentylcyclohexyl mercaptan, hexylcyclohexyl mercaptan, dimethylcyclohexyl mercaptan, diethylcyclohexyl mercaptan, dibutylcyclohexyl mercaptan, thiophenol, methylphenol, ethylphenylthiophenol, propylthiophenol, butylthiophenol, pentylphenol, hexylthiophenol, octylthiophenol, nonylphenol, cumylphenol, dimethylphenol, methylethylthiophenol, methylpropylthiophenol, methylbutylthiophenol, methylpentylthiophenol, diethylthiophenol, ethylpropylthiophenol, diethylthiophenol, dicumylphenol, trimethylthiophenol, triethylthiophenol, and naphthol.

When a hydroxyl compound is used, the isothiocyanate group/hydroxyl equivalent ratio of the hydroxyl compound to the monomer diisoisothiocyanate may be selected from values of about 10 to 100 depending on the purpose. Similarly, when thiols are used, the equivalent ratio of isothiocyanate groups to thiol groups can be selected from values of about 10 to 100, depending on the purpose.

The isocyanurating catalyst for forming the isocyanurated group represented by the above formula (41), (46) or (47) is preferably a quaternary ammonium salt, more preferably a quaternary ammonium hydroxide or a quaternary ammonium carboxylic acid, and even more preferably a quaternary ammonium carboxylic acid.

Specific examples of the isocyanuric acid catalyst include tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; organic weak acid salts such as tetramethylammonium acetate, tetraethylammonium acetate, tetrabutylammonium acetate, and the like. Metal salts of alkyl carboxylic acids such as acetic acid, valeric acid, isovaleric acid, caproic acid, caprylic acid, and tetradecanoic acid may be used, and organic weak acid salts are preferable from the viewpoint of reducing the amount.

The above-mentioned isocyanuric acid esterification catalyst may be used after dilution. As the diluent, a hydroxyl compound may be used. Examples of the hydroxyl compound include alcoholic hydroxyl compounds such as methanol, ethanol, 1-butanol or 2-butanol, 2-methyl-1-propanol, 1, 2-propanediol or 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol or 2, 3-butanediol, glycerol, and cyclohexanol, and phenolic hydroxyl compounds such as phenol, cresol, xylenol, and trimethylphenol. From the viewpoint of crystallinity of the polyisocyanate thus obtained, alcohols having a side chain such as 2-butanol, 2-methyl-1-propanol, 1, 3-butanediol, and 2, 3-butanediol are preferable. In addition, two or more kinds may be mixed. Instead of the hydroxyl compound, thiols may be used.

When the monomer diisoisothiocyanate is reacted alone or in the presence of the isothiocyanation catalyst, the isothiocyanate compound obtained by urethanizing the monomer diisoisothiocyanate with a hydroxyl compound is reacted under the condition that the concentration of the isothiocyanation catalyst after dilution with the hydroxyl compound is 1 to 20 mass%. The concentration is preferably 1 to 10 mass%. When the concentration is 1 mass% or more, the amount of the hydroxyl compound accompanying the isocyanuration catalyst does not become excessive, and physical properties of the obtained polyisothiocyanate and a coating film formed therefrom are hardly degraded. When the concentration is 20 mass% or less, the co-catalytic effect of the hydroxy compound is not reduced, and as a result, it is difficult to cause an increase in the amount of the isothiocyanation catalyst, coloring of the polyisothiocyanate, and the like.

The amount of the isothiocyanation catalyst to be used is 1ppm to 10%, preferably 10ppm to 5% based on the weight of the monomer diisocyanato, except that the isothiocyanation catalyst is deactivated by an acidic component contained in a small amount in the raw material such as the monomer diisocyanato. When the amount of the catalyst is 1ppm or more, the catalyst can sufficiently function as an isocyanuric acid catalyst. If the amount of the catalyst is 3% or less, the amount of a reaction terminator (described later) such as an acid phosphate compound or an acid phosphate compound for inactivating the isocyanurating catalyst can be reduced.

The reaction may be carried out with or without using a solvent, but by using a solvent which is not reactive with an isothiocyanate group, the reaction can be controlled more easily.

Examples of the solvent include esters and ethers such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene. Of course, two or more solvents may be used in combination.

The isothiocyanation reaction is carried out at 30 to 120℃and preferably at 50 to 100 ℃. The reaction may be carried out by the reaction liquid ¹ H-NMR analysis confirmed. At the point when the reaction reaches the desired conversion, the reaction is stopped by inactivating the catalyst by adding a reaction terminator. The conversion is suitably selected in the range of 10 to 60%, preferably 10 to 30%. When the conversion is low, a polyisothiocyanate having a lower viscosity can be obtained, but from the viewpoint of productivity, the conversion is preferably 10% or more. On the other hand, if the conversion is 60% or less, the viscosity of the polyisothiocyanate will not become too high, which is preferred.

The conversion can be determined by the following formula. Regarding the above conversion, in ¹ In the H-NMR spectrum, the peak of methyl group of tetramethylsilane was set to 0ppm, and the conversion was calculated from the integrated value (A) of the peak at 3.5ppm and the integrated value (B) of the peak at 4.8ppm according to the following formula.

Conversion (%) =b/(a+b) ×100

As a reaction terminator for the isocyanuric acid esterification reaction, 1 or more compounds selected from the group consisting of acid phosphoric acid compounds and acid phosphate ester compounds are used.

The acidic phosphoric acid compound is an inorganic acid, and examples thereof include phosphoric acid, phosphorous acid, hypophosphorous acid, diphosphorous acid, hypophosphorous acid, pyrophosphoric acid, and peroxyphosphoric acid. Phosphoric acid is preferred.

The acidic phosphate compound is a compound having an acidic group and an ester group, and examples thereof include monoalkyl phosphates having 2 to 8 carbon atoms, monoalkyl phosphites, dialkyl phosphates having 4 to 16 carbon atoms, dialkyl phosphites, dilauryl phosphate, diphenyl phosphate, monolauryl phosphate, monophenyl phosphate, dilauryl phosphite, diphenyl phosphite, monolauryl phosphite, monophenyl phosphite, and the like. The monoalkyl phosphate having 3 to 8 carbon atoms or the dialkyl phosphate having 6 to 16 carbon atoms is preferable, and dioctyl phosphate or monooctyl phosphate is more preferable.

Among these, an acid phosphate compound is preferably used. The amount of the acidic phosphoric acid compound to be added is preferably 1 to 10 equivalents, more preferably 1 to 6 equivalents, to the stoichiometric amount of the isocyanuric acid catalyst. When the amount is 1 equivalent or more, the isocyanuric acid catalyst can be sufficiently deactivated. When the amount of the additive is 10 equivalents or less, filtration of the insoluble matter produced does not become difficult, and is preferable.

In the case of acid phosphate compounds, the deactivated isocyanuric acid catalyst may in many cases form insoluble materials which can be removed by filtration. By removing the phosphorus from the acid phosphate compound in the polyisothiocyanate by filtration, the phosphorus can be reduced to such an extent that only a very small amount is detected.

In the case of using an acid phosphate compound, the acid phosphate and a salt with an isothiocyanation catalyst are dissolved in the polyisothiocyanate, and thus may be mixed in the modified polyisocyanate after the removal of the monomeric diisoisothiocyanate.

From the viewpoint of the concentration of phosphorus in the polyisothiocyanate, an acid phosphate compound is preferably used. In the case of using an acid phosphate compound, the filtration time is shortened in the filtration step and the filterability is improved by maintaining the temperature at 90 to 150 ℃, preferably 100 to 120 ℃ for 30 to 120 minutes after adding the acid phosphate compound.

After the polyisothiocyanate is obtained, an acid phosphate compound, in particular an acid phosphate compound, may be added.

As described above, after the completion of the isocyanuric acid esterification reaction, unreacted monomer diisothiocyanate and solvent are removed from the reaction solution, and purification is performed. The purification method includes reduced pressure distillation, solvent extraction, and the like, and a thin film distiller is generally used.

The content of the monomeric diisoisothiocyanate in the polyisothiocyanate after purification may be preferably 1.0 mass% or less, more preferably 0.5 mass% or less. The recovered unreacted monomeric diisothiocyanate may be reused.

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

Depending on the purpose, various additives such as a curing accelerator for accelerating the urethanization reaction, a pigment, a leveling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, and a surfactant may be mixed with the polyisothiocyanate.

The polyisothiocyanate can be effectively used in a wide range of fields such as two-part polyurethane coating materials, sealing materials, adhesives, inks, coating agents, casting materials, elastomers, foams, plastic materials, fiber treating agents, one-part curable polyisothiocyanates, and the like.

Examples

The present invention will be specifically described with reference to examples, but the scope of the present invention is not limited to these examples. Unless otherwise specified, "parts" or "%" in examples and comparative examples are weight basis.

[ analytical methods ]

(1) ¹ H-NMR analysis

About 0.3g of a sample was weighed, about 0.7g of deuterated chloroform (manufactured by Aldrich, 99.8%) and 0.05g of tetramethylsilane (manufactured by Wako pure chemical industries, ltd., and light first order) as an internal standard substance were added and uniformly mixed, and the resulting solution was used as an NMR analysis sample. Using this sample, analysis was performed by JNM-A400FT-NMR system manufactured by Japan electronic Co., ltd.

The conversion of the isocyanate groups in the production of the polyisocyanate was calculated by the following method.

At the position of ¹ In the H-NMR spectrum, the signal of methyl group of tetramethylsilane was set to 0ppm, and the conversion was calculated from the integral value (A) of the signal of 3.3ppm from the monomeric diisocyanate and the integral value (B) of the signal of 3.8ppm from the isocyanurate structure, according to the following formula.

Conversion (%) =b/(a+b) ×100

The conversion of the isothiocyanate group in the production of polyisothiocyanate was calculated by the following method.

At the position of ¹ In the H-NMR spectrum, the signal of methyl group of tetramethylsilane was set to 0ppm, and the conversion was calculated from the integral value (A) of the signal of 3.5ppm from the monomer diisothiocyanate and the integral value (B) of the signal of 4.8ppm from the isocyanurate structure.

Conversion (%) =b/(a+b) ×100

(2) Number average molecular weight

Gel permeation chromatography (GPC analysis) was performed using GPC-8020 manufactured by eastern Cao She as a measurement device, tetrahydrofuran as a developing solvent, and TSKgel SuperH3000, superH2000, and SuperH1000 manufactured by eastern Cao She as columns. About 10mg of the sample was dissolved in 10mL of tetrahydrofuran as a measurement sample, and the injection amount was 10. Mu.L. The number average molecular weight was determined by comparing the elution time with that of polystyrene of known molecular weight observed by a differential refractive index detector.

(3) Heat resistance evaluation method

The thermal weight loss was measured under a nitrogen atmosphere at a temperature of 10mg and a heating rate of 10 ℃/min by TG-8120 (manufactured by RIGAKU Co., ltd.), and the case where no 5% weight loss was observed at 300℃was designated as A and the case where 5% weight loss was observed at 300℃was designated as B.

(4) Coating film evaluation method

The adhesion of the coating film was evaluated as follows. A1 mm square incision was made in a coating film formed on an aluminum plate (length: 10cm, width: 10cm, thickness: 5 mm), and the coating film was immersed in acetone together with the aluminum plate, and after 24 hours, whether or not the coating film remained was examined. The same test was performed 10 times for each 1 sample, and the case where 8 or more coating films remained was designated as a, and the other cases were designated as B.

(5) Copper peel strength

Copper peel strength was measured according to JIS C6481. The case where the copper peel strength was good was denoted as a, and the case where the copper peel strength was poor was denoted as B.

Example 1

Adipic acid dihydrazide and polyisocyanate (DURANATE TPA-100, manufactured by Asahi Kasei chemical Co., ltd.) were charged so that the equivalent ratio of isocyanate groups to hydrazide groups was 1.0, and butyl acetate was mixed to prepare a dispersion having a solid content of 10%. The dispersion was stirred at 120℃for 12 hours. Collecting a part of the reaction solution, using ¹ H-NMR analysis showed that the peak around 3.3ppm from isocyanate disappeared. After butyl acetate was distilled off by a rotary evaporator, heat resistance was evaluated. The evaluation results are shown in Table 1.

Example 2

36g of hydrazine monohydrate was dissolved in 1L of isopropyl alcohol, and 50g of hexamethylene diisothiocyanate was added while stirring, after cooling to 0 ℃. Recovery of the solids produced by filtration, utilization ¹ H-NMR analysis gave 4,4' -hexamethylenedithiosemicarbazide.

The heat resistance of the 4,4' -hexamethylenedithiosemicarbazide and polyisocyanate (DURANATE TPA-100, manufactured by Asahi chemical Co., ltd.) was evaluated in the same manner as in example 1. The evaluation results are shown in Table 1.

Example 3

36g of hydrazine monohydrate was dissolved in 1L of isopropyl alcohol, and 50g of hexamethylene diisocyanate was added thereto while cooling to 0 ℃. Recovery of the solids produced by filtration, utilization ¹ H-NMR analysis gave 4,4' -hexamethylenebis-semicarbazide.

The heat resistance of the 4,4' -hexamethylenebis-semicarbazide and polyisocyanate (DURANATE TPA-100, manufactured by Asahi chemical Co., ltd.) was evaluated in the same manner as in example 1. The evaluation results are shown in Table 1.

Example 4

36g of hydrazine monohydrate was dissolved in 1L of isopropyl alcohol, and 280g of 2-isocyanatoethyl methacrylate was added thereto while cooling to 0 ℃. Recovery of the solids produced by filtration, utilization ¹ H-NMR analysis gave (2- (hydrazinecarboxamide) ethyl methacrylate).

Next, 100g of this methacrylic acid (2- (hydrazinecarboxamide) ethyl ester was dissolved in 1L of toluene, 80g of methyl methacrylate and 0.5g of azobisisobutyronitrile were added thereto, and the mixture was heated to 80 ℃. Collecting reaction solution after 3 hours, utilizing ¹ As a result of the analysis by H-NMR, the double bond constituting methyl methacrylate was eliminated. Toluene was distilled off using a rotary evaporator to obtain a polymer having semicarbazide groups.

The heat resistance of the polymer and polyisocyanate (DURANATE TPA-100, manufactured by Asahi chemical Co., ltd.) was evaluated in the same manner as in example 1. The evaluation results are shown in Table 1.

Examples 5 to 8

The same procedure as in example 1 was repeated except that hexamethylene diisocyanate was used instead of polyisocyanate, and heat resistance was evaluated. The evaluation results are shown in Table 1.

Example 9

The same procedure as in example 4 was conducted to produce 2- (hydrazinecarboxamide) ethyl methacrylate. The heat resistance of the methacrylic acid (2- (hydrazinecarboxamide) ethyl ester) and the polyisocyanate (DURANATE TPA-100, manufactured by Asahi chemical Co., ltd.) was evaluated in the same manner as in example 1. 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 hexamethylene glycol was used instead of adipic dihydrazide in example 1. The evaluation results are shown in Table 1.

Reference example 2

The heat resistance was evaluated in the same manner as in example 1 except that 1, 6-hexamethylenediamine was used instead of adipic dihydrazide in example 1. The evaluation results are shown in Table 1.

Reference example 3

100g of methacrylic acid (2-hydroxyethyl) was dissolved in 1L of toluene, 80g of methyl methacrylate and 0.5g of azobisisobutyronitrile were added thereto, and the mixture was heated to 80 ℃. Collecting reaction solution after 3 hours, utilizing ¹ As a result of H-NMR analysis, the double bond constituting methyl methacrylate was eliminated. Toluene was distilled off by a rotary evaporator to obtain a polymer having hydroxyl groups. The heat resistance of the polymer and polyisocyanate (DURANATE TPA-100, manufactured by Asahi chemical Co., ltd.) was evaluated in the same manner as in example 1. 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 heat resistance was evaluated in the same manner as in example 1 except that (2-hydroxyethyl) methacrylate was used instead of adipic dihydrazide of example 1. The evaluation results are shown in Table 1.

TABLE 1

PREPARATION EXAMPLE 1 preparation of Polyisothiocyanate

600g of hexamethylene diisothiocyanate was charged into a 4-neck flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen blowing tube under a nitrogen atmosphere, the temperature in the reactor was kept at 130℃under stirring, and 1.0g of tetramethylammonium octoate as a cyclic trimerization catalyst was added. At the time when the conversion of the isothiocyanate group reached 30%, phosphoric acid was added to stop the reaction. After the reaction solution was filtered, unreacted hexamethylene diisothiocyanate was removed by a thin film distiller. The number average molecular weight of the obtained polyisothiocyanate was 620 and the average number of isothiocyanate groups was 3.2.

Example 10

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 so that the equivalent ratio of isothiocyanate group to hydroxyl group was 1.0, and dibutyltin dilaurate was added in an amount of 0.5% by mass relative to the resin, and butyl acetate was mixed to prepare a resin composition having a solid content of 50%. The resin composition was applied to an aluminum plate by an applicator so that the resin film thickness was 40. Mu.m. After being left at room temperature for 10 minutes, the cured coating film was obtained by holding in an oven at 150℃for 10 hours. The adhesion of the obtained cured coating film was evaluated. The evaluation results are shown in Table 2.

Example 11

The same procedure as in example 1 was repeated except that 4,4' -dicyclohexylmethane diamine and the polyisothiocyanate obtained in production example 1 were charged so that the equivalent ratio of isothiocyanate group to amino group was 1.0, and butyl acetate was mixed to prepare a resin composition having a solid content of 50%. The evaluation results of the cured coating film are shown in Table 2.

Example 12

The same procedure as in example 10 was repeated except that adipic acid dihydrazide and the polyisothiocyanate obtained in production example 1 were charged so that the equivalent ratio of the isothiocyanate group to the hydrazide group was 1.0, and ethanol was mixed to prepare a resin composition having a solid content of 10%. The evaluation results of the cured coating film are shown in Table 2.

Example 13

36g of hydrazine monohydrate was dissolved in 1L of isopropyl alcohol, and 280g of 2-isocyanatoethyl methacrylate was added thereto while cooling to 0 ℃. Recovery of the solids produced by filtration, utilization ¹ H-NMR analysis gave (2- (hydrazinecarboxamide) ethyl methacrylate).

Next, 100g of this methacrylic acid (2- (hydrazinecarboxamide) ethyl ester was dissolved in 1L of toluene, 80g of methyl methacrylate and 0.5g of azobisisobutyronitrile were added thereto, and the mixture was heated to 80 ℃. Collecting reaction solution after 3 hours, utilizing ¹ As a result of H-NMR analysis, the double bond constituting methyl methacrylate was eliminated. Toluene was distilled off using a rotary evaporator to obtain a polymer having semicarbazide groups.

The polymer and the polyisothiocyanate obtained in production example 1 were charged so that the equivalent ratio of isothiocyanate groups to semicarbazide groups was 1.0, and butyl acetate was mixed to prepare a resin composition having a solid content of 25%. The cured coating film was evaluated in the same manner as in example 10 using the resin composition, and the results are shown in table 2.

Example 14

36g of hydrazine monohydrate was dissolved in 1L of isopropyl alcohol, and 50g of hexamethylene diisothiocyanate was added while stirring, after cooling to 0 ℃. Recovery of the solids produced by filtration, utilization ¹ H-NMR analysis gave 4,4' -hexamethylenedithiosemicarbazide.

The 4,4' -hexamethylenedithiosemicarbazide and the polyisothiocyanate obtained in production example 1 were charged so that the equivalent ratio of the isothiocyanate group to the thiocarbamate group was 1.0, and butyl acetate was mixed to prepare a resin composition having a solid content of 25%. The cured coating film was evaluated in the same manner as in example 10 using the resin composition, and the results are shown in Table 2.

Reference examples 8 to 12

The cured coatings were evaluated in the same manner as in examples 10 to 14, except that isocyanurate type polyisocyanate (DURANATE TPA-100; manufactured by Asahi chemical Co., ltd., trade name) was used instead of polyisothiocyanate. The results are shown in Table 2.

Example 15

2-hydroxyethyl methacrylate and the polyisothiocyanate obtained in production example 1 were charged so that the equivalent ratio of isothiocyanate group to hydroxyl group was hydroxyl group/isothiocyanate group=1.3, and butyl acetate was added to prepare a resin composition having a solid content of 50%. Heating the resin composition at 130deg.C, and continuing to heat ¹ The isothiocyanate group is disappeared in H-NMR. Next, the resin composition was applied to an aluminum plate by an applicator so that the resin film thickness became 40 μm. After being left at room temperature for 10 minutes, the cured coating film was obtained by holding in an oven at 150℃for 10 hours. The adhesion of the obtained cured coating film was evaluated. The evaluation results are shown in Table 2.

Reference example 13

The same procedure as in example 15 was conducted except that isocyanurate type polyisocyanate (DURANATE TPA-100; manufactured by Asahi chemical Co., ltd., trade name) was used instead of the polyisothiocyanate type polyisocyanate obtained in production example 1. The evaluation results of the cured coating film are shown in Table 2.

Example 16

The same procedure as in example 13 was followed to produce 2- (hydrazinecarboxamide) ethyl methacrylate, and then a polymer of 2- (hydrazinecarboxamide) ethyl methacrylate was obtained.

The polymer and allyl isothiocyanate were charged so that the equivalent ratio of isothiocyanate groups to semicarbazide groups was 1.0, and butyl acetate was mixed to prepare a resin composition having a solid content of 25%. The resin composition was applied to an aluminum plate by an applicator so that the resin film thickness was 40. Mu.m. After being left at room temperature for 10 minutes, the cured coating film was obtained by holding in an oven at 150℃for 10 hours. The adhesion of the obtained cured coating film was evaluated. The evaluation results are shown in Table 2.

Reference example 14

The same procedure as in example 16 was conducted except that 2-isocyanatoethyl methacrylate was used instead of allyl isothiocyanate. The evaluation results of the cured coating film are shown in Table 2.

TABLE 2

	Adhesion of		Adhesion of
				Example 10	A	Reference example 8	B
Example 11	A	Reference example 9	B
				Example 12	A	Reference example 10	B
Example 13	A	Reference example 11	B
				Example 14	A	Reference example 12	B
Example 15	A	Reference example 13	B
				Example 16	A	Reference example 14	B

Example 17

To a 2L eggplant-shaped flask containing 200g of water and 800g of tetrahydrofuran were added 345g of tetramethylene diisothiocyanate and 384g of adipic dihydrazide, and after stirring at 60℃for 12 hours, 7g of ethyl isothiocyanate was further added, and the precipitated solid was recovered by filtration. Next, the above solid was put into a 2L eggplant-shaped flask containing 1000g of a 2 wt% sodium hydroxide aqueous solution, stirred at 100℃for 8 hours, and the precipitated solid was recovered by a filter paper. Determination of recovered solids ¹ H-NMR, structure was identified. The solids obtained in example 17 are shown in FIG. 1 ¹ H-NMR spectrum. The resin represented by the following formula (124) is presumed to be obtained. A number average molecular weight of 5900 based on Mn/n as defined above ¹ 150. X is as follows ¹ From the following components ¹ The ratio of the concentration of the sample charged and the integral value of the peak of chloroform (7.26 ppm) to the peak of methylene chain directly bonded to the ring-forming nitrogen atom (2.6 ppm) was determined by H-NMR measurement.

Example 18

The 4-neck flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen blowing tube was filled with nitrogen gas100g of hexamethylene diisothiocyanate was charged in the atmosphere, and the temperature in the reactor was kept at 100℃with stirring. Thereafter, 2g of tetramethyl ammonium acetate (2-butanol 5.0 mass% solution) as a catalyst was added thereto and stirred. Sampling the reaction solution appropriately in ¹ When the conversion of the isothiocyanate group reached 21% in the H-NMR analysis, 0.28g of phosphoric acid (85% by mass aqueous solution) was added thereto to stop the reaction. Thereafter, the reaction mixture was further heated at 100℃for 1 hour, cooled to room temperature, and the insoluble matter was removed by filtration, and then the monomer diisothiocyanate was removed by a thin film distiller. The concentration of the monomer diisoisothiocyanate was 0.4 mass% and the number average molecular weight was 860.

The obtained polyisothiocyanate ¹ The H-NMR spectrum is shown in FIG. 2. From the NMR spectrum, it was confirmed that the polyisothiocyanate contains at least the structural unit represented by formula (28). A number average molecular weight of 1200, mn/n based on the above definition ¹ 100. X is as follows ¹ From the following components ¹ The ratio of the concentration of the sample charged and the integral value of the peak of chloroform (7.26 ppm) to the peak of methylene chain directly bonded to the nitrogen atom forming the isocyanuric acid ring (3.8 ppm) was determined by H-NMR measurement.

The obtained polyisothiocyanate and acrylic polyol (trade name: acryca-801 manufactured by DIC corporation) were mixed so that the isothiocyanate group/hydroxyl group ratio (equivalent weight) was 1.0, and dibutyltin dilaurate was added in an amount of 0.5% relative to the solid content of the paint, respectively, to which a mixed solution of ethyl acetate/toluene/butyl acetate/xylene/propylene glycol monomethyl ether acetate (weight ratio= 30/30/20/15/5) was added as a diluent. The resulting coating solution was applied to a copper foil having a thickness of 35 μm by an air spray gun, the film was adjusted to have a dry film thickness of 50 μm, a copper foil having a thickness of 35 μm was stacked on top, and the copper foil was sintered in an oven maintained at 120℃for 30 minutes, and then the copper peel strength was evaluated. The results are shown in Table 3.

Examples 19 to 23

Polyisothiocyanate was prepared in the same manner as in example 18 with the formulation and conditions shown in Table 3. A coating solution was prepared in the same manner as in example 18 except that the obtained polyisothiocyanate was used, and the copper peel strength was evaluated. The results are shown in Table 3.

TABLE 3

Comparative example 15

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

Comparative examples 16 to 20

Polyisocyanates were produced in the same manner as in example 18 under the formulation and conditions shown in table 4, and the copper peel strength was evaluated. The results are shown in Table 4.

TABLE 4

Example 24

A detachable flask containing 100 parts of bisphenol A epoxy resin (epoxy equivalent 189) was equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen blowing tube, and nitrogen was blown into the flask while heating to 150℃with stirring, and stirring was continued for 30 minutes after reaching 150 ℃. The reaction temperature was maintained at 150℃and a mixture of 18.5 parts of hexamethylene diisoisothiocyanate and 0.05 part of tetrabutylammonium chloride (Wako pure chemical industries, ltd.) was added dropwise thereto over 2 hours. After the completion of the dropwise addition, the temperature was kept at 150℃to effect a reaction. From the following components ¹ As a result of H-NMR analysis (FIG. 3), it was found that a compound containing an oxazolidine-2-thione ring represented by the following formula (125) or (126) was obtained. The number average molecular weight of the obtained compound was 2,000, and no number average molecular weight was foundIs more than 2 ten thousand substances. The number average molecular weight was analyzed by gel permeation chromatography using Shodex A-804, A-803, A-802, and A802 manufactured by Showa electric company as columns. About 10mg of the sample was dissolved in 10mL of tetrahydrofuran as a measurement sample, and the injection amount was 10. Mu.L. The number average molecular weight was determined by comparing the elution time with that of polystyrene of known molecular weight observed by a differential refractive index detector. Mn/n based on the above definition ¹ 220. X is as follows ¹ From the following components ¹ The H-NMR measurement of the sample concentration and the ratio of the integral value of the peak (2.3 ppm) of toluene added as an internal standard to the peak (4.8 ppm) of methine group having a ring structure were obtained.

The obtained compound, a curing agent (dicyandiamide) and a curing catalyst (2-methylimidazole) were added, and the obtained resin composition was infiltrated into a glass cloth and dried, whereby a prepreg having a resin content of 50 mass% was obtained. 4 pieces of the prepreg were stacked, and copper foil having a thickness of 35 μm was stacked on top of each other, and the prepreg was heated at 190℃under a pressure of 20kg/cm ² Is heated and pressurized for 60 minutes under the condition of (2) to thereby produce a laminate. The laminate was evaluated for copper peel strength. The results are shown in Table 5.

Examples 25 to 29

Using the compounds shown in Table 5, they were reacted by the same manner as in example 24, and conducted ¹ As a result of H-NMR analysis, a compound containing an oxazolidine-2-thione ring represented by the above formula (125) or (126) was obtained. Using the obtained compound, copper peel strength was evaluated in the same manner as in example 24. The results are shown in Table 5.

TABLE 5

Examples 30 to 35

Using the compounds shown in Table 6, they were reacted by the same manner as in example 24, and ¹ as a result of H-NMR analysis, a compound containing a thiazolinethione ring represented by the following formula (127) or (128) was obtained. Using the obtained compound, copper peel strength was evaluated in the same manner as in example 24. The results are shown in Table 6.

TABLE 6

Examples 36 to 41

Using the compounds shown in Table 7, they were reacted by the same manner as in example 24, and ¹ as a result of H-NMR analysis, a compound containing a thiazolin-2-one ring represented by the following formula (129) or (130) was obtained. Using the obtained compound, copper peel strength was evaluated in the same manner as in example 24. The results are shown in Table 7.

TABLE 7

Examples 42 to 59

Using the compounds shown in tables 8 to 10, they were reacted in the same manner as in example 24, and the reaction was performed ¹ As a result of H-NMR analysis, a compound containing an oxazolidine-2-thione ring represented by the above formula (125) or (126) was obtained. Using the obtained compound, copper peel strength was evaluated in the same manner as in example 24. ResultsAre listed in tables 8-10.

TABLE 8

TABLE 9

TABLE 10

Examples 60 to 62

Using the compounds shown in Table 11, they were reacted by the same manner as in example 24, and conducted ¹ As a result of H-NMR analysis, a compound containing a thiazolin-2-one ring represented by the above formula (129) or (130) was obtained. Using the obtained compound, copper peel strength was evaluated in the same manner as in example 24. The results are shown in Table 11.

TABLE 11

Comparative examples 21 to 26

Using the compounds shown in Table 12, they were reacted by the same manner as in example 24, and conducted ¹ As a result of H-NMR analysis, a compound containing an oxazolidone ring represented by the following formula (131) or (132) was obtained. Using the obtained compound, copper peel strength was evaluated in the same manner as in example 24. The results are shown in Table 12.

TABLE 12

/>

Claims (10)

1. A resin having a molecular chain represented by the following formula (10),

wherein P is ¹ Represents an aliphatic and/or aromatic group, Q ¹ Represents 1 or more structural units selected from the group consisting of 2-valent groups represented by the following formulas (11), (12), (13) and (14), and 2 or more P ¹ And Q ¹ Identical or different, n represents an integer of 2 or more,

wherein R is ¹ Represents an aliphatic group or an aromatic group,

X ² and Y ² Each independently represents an oxygen atom or a sulfur atom,

more than 2R in the same molecule ¹ 、X ² And Y ² Respectively, are the same or different from each other,

q (Q) ¹ X in (2) ² And Y ² More than 1 of them are sulfur atoms.

2. The resin of claim 1 wherein R ¹ The residue after removing 2 isocyanate groups constituting the polyisocyanate or the residue after removing 2 isothiocyanate groups constituting the polyisothiocyanate from the polyisothiocyanate.

3. The resin according to claim 1 or 2, which is obtained by reacting at least 1 compound selected from the group consisting of polyisocyanates and polyisothiocyanates with a compound represented by the following formula (20),

wherein R is ² Represents an aliphatic group or an aromatic group,

Y ² represents an oxygen atom or a sulfur atom.

4. The resin according to claim 3, wherein at least 1 of the compounds selected from the group consisting of polyisocyanates and polyisothiocyanates comprises a compound represented by the following formula (31),

XCN-R ¹ -NCX (31)

wherein R is ¹ Represents an aliphatic group or an aromatic group,

x represents an oxygen atom or a sulfur atom.

5. A resin according to claim 3 wherein R ² A 1-valent group represented by the following formula (201), (202), (203) or (204),

6. the resin of claim 1 or 2, wherein R ¹ Is an aliphatic group having 1 to 25 carbon atoms, an aliphatic group having 7 to 25 carbon atoms substituted with an aromatic group, or an aromatic group having 6 to 25 carbon atoms.

7. The resin of claim 1 or 2, wherein R ¹ Is a hydrocarbon group selected from the group consisting of hydrocarbon groups represented by the following formulas (301), (302), (303), (304), (305) or (306),

wherein i represents an integer of 1 to 12.

8. The resin of claim 1 or 2, wherein R ¹ Does not contain a spiro atom.

9. A curable composition comprising the resin according to any one of claims 1 to 8 and a curing agent.

10. The method for producing a resin according to claim 3 or 4, comprising the steps of: reacting at least 1 of the compounds selected from the group consisting of polyisocyanates and polyisothiocyanates with the compound represented by formula (20) in the presence of a catalyst.

Images