Modified polyisocyanates, coatings and coated metal materials

Abstract

The problem addressed by the present invention is to provide a modified polyisocyanate which has high adhesion even to non-ferrous metals and is applicable even to single-coat paints. The invention provides a modified polyisocyanate, a method for preparing the modified polyisocyanate, and a coating comprising the modified polyisocyanate. The modified polyisocyanate is a reaction product formed from components comprising, as starting materials, a primary amino group-containing alkoxysilane (a1), an unsaturated carboxylic acid alkyl ester (a2) or a saturated carboxylic acid alkyl ester (a3), and a polyisocyanate (a4), in which the unsaturated carboxylic acid alkyl ester (a2) is a branched alkyl ester (a2-1) selected from the group consisting of unsaturated dicarboxylic acids, and at least one of the group consisting of a branched alkyl ester of the unsaturated monocarboxylic acid, which may contain a heteroatom, or an alkyl ester having a cyclic structure (a2-2).

Description

Technical Field

[0001] The present invention relates to modified polyisocyanates, coatings and coated metal materials. Background Art

[0002] Polyisocyanate compounds are highly reactive and are widely used as starting materials for chemical products such as polyurethane foams, sealing materials, adhesives, and paints. In recent years, modified polyisocyanates obtained by various modifications have been developed according to the functions required for such chemical products.

[0003] As an example of modified polyisocyanate, PTL 1 discloses silyl-isocyanate obtained by reacting polyisocyanate with a silane starting material, and discloses that the silyl-isocyanate has excellent adhesion to glass and can be used as a fixing agent used in combination with a polyurethane resin.

[0004] PTL 2 discloses a reaction product of an amino-alkylalkoxysilane with a maleate or a fumarate, and discloses that the reaction product can be used as a modifier for polyisocyanates.

[0005] PTL 3 discloses a crosslinkable silyl group-containing polyurethane resin mixture obtained by reacting a compound containing one or more active hydrogens and one or more crosslinkable silyl groups per molecule with an isocyanate group-containing urethane prepolymer.

[0006] The compound containing one or more active hydrogen groups and one or more cross-linkable silyl groups per molecule is obtained by reacting a compound containing two or more active hydrogen groups and one or more cross-linkable silyl groups per molecule with an acrylic acid compound and / or a methacrylic acid compound,

[0007] The isocyanate group-containing urethane prepolymer is obtained by reacting an organic polyisocyanate with a polymer polyol under the condition that the isocyanate group is excessive relative to the active hydrogen.

[0008] Citation List

[0009] Patent Literature

[0010] PTL 1: JPH06-212141A

[0011] PTL 2: JPH06-211879A

[0012] PTL 3: JP2001-323040A Summary of the invention

[0013] In recent years, high hopes have been placed on the development of direct metal coatings. Direct metal coatings refer to coatings that form a protective coating film having both corrosion resistance and weather resistance by simply applying one type of paint directly to the metal surface. Painting the metal is usually carried out by multi-layer coating, first applying a primer to inhibit rust, and then applying a topcoat to achieve excellent weather resistance and appearance. In contrast, direct metal coatings achieve the desired performance with a single-layer coating, and are therefore advantageous in reducing the number of processing times and shortening production time. However, in general, the corrosion resistance and weather resistance of the coating film are in a contradictory relationship, and it is difficult to achieve both at the same time. In addition, compared to iron, the coating film is less likely to adhere to non-ferrous metals, and the coating film on the non-ferrous metal is easy to peel off. Therefore, it is extremely difficult to develop a paint that not only has corrosion resistance and weather resistance but also has excellent adhesion to non-ferrous metals.

[0014] Although various modified polyisocyanates are disclosed in the above-mentioned PTL 1 to PTL 3, there is no disclosure of a modified polyisocyanate which has excellent adhesion even to non-ferrous metals and is suitable even for a single-coat paint.

[0015] The inventors of the present application have conducted extensive research on the above problems and proposed the use of polyisocyanates modified by alkoxysilanes having primary amino groups and specific unsaturated carboxylic acid alkyl esters or saturated carboxylic acid alkyl esters. Then, the inventors of the present application found that such modified polyisocyanates are excellent as materials that adhere to metals, and that coatings containing such modified polyisocyanates have excellent adhesion not only to iron but also to non-ferrous metals.

[0016] Specifically, the present invention relates to the following contents.

[0017] Project 1.

[0018] A modified polyisocyanate used together with an active hydrogen-containing compound as a curing agent for coatings,

[0019] The modified polyisocyanate is a reaction product formed from components including a primary amino group-containing alkoxysilane (a1), an unsaturated carboxylic acid alkyl ester (a2) or a saturated carboxylic acid alkyl ester (a3) ​​and a polyisocyanate (a4) as starting materials,

[0020] The unsaturated carboxylic acid alkyl ester (a2) is at least one selected from the group consisting of:

[0021] Branched alkyl esters of unsaturated dicarboxylic acids (a2-1), and

[0022] Branched alkyl esters of unsaturated monocarboxylic acids each optionally containing a heteroatom or an alkyl ester having a cyclic structure (a2-2).

[0023] Project 2.

[0024] The modified polyisocyanate according to item 1, wherein the primary amino group-containing alkoxysilane (a1) is a compound represented by the following formula (1):

[0025]

[0026] In formula (1),

[0027] R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, R 3 is a C1-C8 straight chain or branched chain alkylene group, preferably a C1-C5 straight chain or branched chain alkylene group, and n is an integer of 0 to 2.

[0028] Project 3.

[0029] The modified polyisocyanate according to item 1 or 2, wherein the branched alkyl ester of unsaturated dicarboxylic acid (a2-1) is a compound represented by the following formula (2).

[0030] R 4 OC(=O)-HC=CH-C(=O)-OR 5 (2)

[0031] In formula (2), R 4 and R 5 are the same or different, and each represents a C1-C8 branched alkyl group.

[0032] Project 4.

[0033] The modified polyisocyanate according to item 1 or 2, wherein the branched alkyl ester or the alkyl ester having a cyclic structure (a2-2) of the unsaturated monocarboxylic acid each optionally containing a hetero atom is a compound represented by the following formula (3).

[0034] H2C=CH-C(=O)-OR 6 (3)

[0035] In formula (3), R 6 It is C3-C 18 A branched alkyl group or an alkyl group having a cyclic structure, or a C1-C1 alkyl group obtained by introducing a heteroatom (e.g., an oxygen atom, a nitrogen atom, or a sulfur atom) into a molecule of an alkyl group having a branched or cyclic structure or an arylalkyl group. 18 Group.

[0036] Item 5.

[0037] The modified polyisocyanate according to item 1 or 2, wherein the saturated carboxylic acid alkyl ester (a3) ​​is a compound represented by the following formula (4).

[0038] R 7 -C(=O)-OR 8 (4)

[0039] In formula (4), R 7 and R 8 are the same or different and each represents a C1-C 18 An alkyl group or a C1-C12 group obtained by introducing a heteroatom (such as an oxygen atom, a nitrogen atom or a sulfur atom) into a molecule of an alkyl group or an arylalkyl group and having no unsaturated group. 18 Group.

[0040] Item 6.

[0041] The modified polyisocyanate according to any one of items 1 to 4 has a structure in which a secondary amino group of an N-modified alkoxysilane obtained by adding a primary amino group of the alkoxysilane (a1) to an unsaturated carbon-carbon bond of the unsaturated carboxylic acid alkyl ester (a2) is added to at least one isocyanate group of the polyisocyanate (a4).

[0042] Item 7.

[0043] The modified polyisocyanate according to any one of items 1, 2 and 5 has a structure in which a secondary amide group of an N-modified alkoxysilane obtained by reacting a primary amino group of the alkoxysilane (a1) with an ester group of the saturated carboxylic acid alkyl ester (a3) ​​is added to at least one isocyanate group of the polyisocyanate (a4).

[0044] Item 8.

[0045] The modified polyisocyanate according to item 6, wherein the unsaturated carboxylic acid alkyl ester (a2) is a branched alkyl ester (a2-1) of an unsaturated dicarboxylic acid, and the N-modified alkoxysilane is a compound represented by the following formula (5).

[0046]

[0047] In formula (5), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, R 3 is a C1-C8 straight or branched chain alkylene group, preferably a C1-C5 straight or branched chain alkylene group, R 4 and R 5are the same or different and each represents a C1-C8 branched alkyl group, and n is an integer from 0 to 2.

[0048] Item 9.

[0049] The modified polyisocyanate according to any one of items 6 to 8, wherein the reaction ratio of the N-modified alkoxysilane having a secondary amino group and the polyisocyanate (a4) is such that the amount of the secondary amino group is 40 mol or less relative to 100 mol of the isocyanate group.

[0050] Item 10.

[0051] The modified polyisocyanate according to item 6, wherein the unsaturated carboxylic acid alkyl ester (a2) is a branched alkyl ester of an unsaturated monocarboxylic acid each optionally containing a heteroatom or an alkyl ester having a cyclic structure (a2-2), and the N-modified alkoxysilane is a compound represented by the following formula (6).

[0052]

[0053] In formula (6), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, R 3 is a C1-C8 straight or branched chain alkylene group, preferably a C1-C5 straight or branched chain alkylene group, R 6 It is a C3-C4-C5- 18 or a C1-C1 alkyl group obtained by introducing a heteroatom (such as an oxygen atom, a nitrogen atom or a sulfur atom) into the molecule of an alkyl group or an arylalkyl group having a branched or cyclic structure. 18 group, and n is an integer from 0 to 2.

[0054] Item 11.

[0055] The modified polyisocyanate according to any one of items 6 to 10, wherein the reaction ratio of the mixture containing the N-modified alkoxysilane having a secondary amino group and the polyisocyanate (a4) is such that the total molar number of the primary amino group and the secondary amino group is 40 mol or less relative to 100 mol of the isocyanate group.

[0056] Item 12.

[0057] The modified polyisocyanate according to item 7, wherein the N-modified alkoxysilane obtained by reacting the alkoxysilane (a1) with the saturated carboxylic acid alkyl ester (a3) ​​is an N-acylated product having a secondary amide group represented by the following formula (7).

[0058]

[0059] In formula (7), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, n is an integer from 0 to 2, R 3 is a C1-C8 straight or branched chain alkylene group, preferably a C1-C5 straight or branched chain alkylene group, and R 7 It is a C1-C 18 An alkyl group or a C1-C12 group having no unsaturated group obtained by introducing a heteroatom (such as an oxygen atom, a nitrogen atom or a sulfur atom) into the molecule of the alkyl group. 18 Group.

[0060] Item 13.

[0061] The modified polyisocyanate according to item 1 or 12 is prepared by the following steps:

[0062] Step (1), reacting the primary amino group-containing alkoxysilane (a1) with the saturated carboxylic acid alkyl ester (a3) ​​in the presence of a basic catalyst;

[0063] Step (2), adding an acidic compound;

[0064] Step (3), removing part or all of the alcohol formed as a by-product to prepare an intermediate containing the N-acylated product represented by the following formula (7); and

[0065] Step (4), reacting the intermediate with the polyisocyanate (a4).

[0066]

[0067] In formula (7), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, R 3 is a C1-C8 straight chain or branched chain alkylene group, preferably a C1-C5 straight chain or branched chain alkylene group, n is an integer from 0 to 2, and R 7It is a C1-C 18 An alkyl group or a C1-C12 group having no unsaturated group obtained by introducing a heteroatom (such as an oxygen atom, a nitrogen atom or a sulfur atom) into the molecule of the alkyl group. 18 Group.

[0068] Item 14.

[0069] The modified polyisocyanate according to item 12 or 13, wherein the reaction ratio of the N-acylated product to the polyisocyanate (a4) is such that the total molar number of the secondary amide group and the primary amino group is 40 mol or less relative to 100 mol of the isocyanate group.

[0070] Item 15.

[0071] The method for preparing the modified polyisocyanate described in item 1 comprises:

[0072] Step (1), reacting a primary amino group-containing alkoxysilane (a1) with a saturated carboxylic acid alkyl ester (a3) ​​in the presence of a basic catalyst;

[0073] Step (2), adding an acidic compound;

[0074] Step (3), removing part or all of the alcohol formed as a by-product to prepare an intermediate containing an N-acylated product represented by the following formula (7); and

[0075] Step (4), reacting the intermediate with polyisocyanate (a4).

[0076]

[0077] In formula (7), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, R 3 is a C1-C8 straight chain or branched chain alkylene group, preferably a C1-C5 straight chain or branched chain alkylene group, n is an integer from 0 to 2, and R 7 It is a C1-C 18 An alkyl group or a C1-C12 group having no unsaturated group obtained by introducing a heteroatom (such as an oxygen atom, a nitrogen atom or a sulfur atom) into the molecule of the alkyl group. 18 Group.

[0078] Item 16.

[0079] The modified polyisocyanate according to item 6, wherein the unsaturated carboxylic acid alkyl ester (a2) is a branched alkyl ester of an unsaturated monocarboxylic acid, each of which optionally contains a heteroatom, or an alkyl ester having a cyclic structure (a2-2), and the reaction of the N-modified alkoxysilane having a secondary amino group with the polyisocyanate (a4) is carried out in the presence of the primary amino group-containing alkoxysilane (a1) and a tertiary amino group-containing compound represented by the following formula (8) as a by-product.

[0080]

[0081] In formula (8), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, R 3 is a C1-C8 straight or branched chain alkylene group, preferably a C1-C5 straight or branched chain alkylene group, R 6 It is a C3-C4-C5- 18 or a C1-C1 alkyl group obtained by introducing a heteroatom (such as an oxygen atom, a nitrogen atom or a sulfur atom) into the molecule of an alkyl group or an arylalkyl group having a branched or cyclic structure. 18 group, and n is an integer from 0 to 2.

[0082] Item 17.

[0083] The modified polyisocyanate according to any one of items 1, 2, 5, 7, 12, 13 and 14, wherein the saturated carboxylic acid alkyl ester (a3) ​​is an alkyl ester of a linear carboxylic acid having a structure in which two or more hydrogen atoms are present at the α position or an alkyl ester of a branched carboxylic acid having a structure in which two hydrogen atoms are present at the α position.

[0084] Item 18.

[0085] The method for preparing the modified polyisocyanate according to item 15, wherein the saturated carboxylic acid alkyl ester (a3) ​​is an alkyl ester of a linear carboxylic acid having two or more hydrogen atoms at the α position.

[0086] Item 19.

[0087] A coating comprising an active hydrogen-containing compound and the modified polyisocyanate described in any one of items 1 to 14 and 16 to 17.

[0088] Item 20.

[0089] The coating according to item 19, wherein the active hydrogen-containing compound comprises acrylic polyol and / or a bisaspartic acid ester derivative.

[0090] Item 21.

[0091] The coating material according to item 19 or 20 further comprises at least one selected from the group consisting of a rust inhibitor, a catalyst, a coloring pigment and an extender pigment.

[0092] Item 22.

[0093] A coating according to any one of items 19 to 21 which is a single-coat paint.

[0094] Item 23.

[0095] A protective coating film obtained by curing the coating material described in any one of items 19 to 22.

[0096] Item 24.

[0097] A coated metal material comprising the protective coating film according to item 23 on a metal substrate.

[0098] Beneficial effects of the present invention

[0099] In this specification, singular forms (e.g., a, an, and the) shall include both singular and plural forms, unless otherwise specified herein or clearly contradictory to the context. The modified polyisocyanate of the present invention has excellent storage stability and can be used in coatings as a metal adhesion improver. By using the modified polyisocyanate, a coating forming a protective coating film having excellent adhesion not only to iron but also to non-ferrous metals is obtained. DETAILED DESCRIPTION

[0100] The modified polyisocyanate of the present invention is a reaction product formed from components including a primary amino group-containing alkoxysilane (a1), an unsaturated carboxylic acid alkyl ester (a2) or a saturated carboxylic acid alkyl ester (a3), and a polyisocyanate (a4) as starting materials.

[0101] The starting material of the modified polyisocyanate of the present invention comprises an unsaturated carboxylic acid alkyl ester (a2) or a saturated carboxylic acid alkyl ester (a3) ​​as a carboxylic acid alkyl ester. In a first embodiment, the present invention provides a modified polyisocyanate (referred to as "modified polyisocyanate (X)") formed from an unsaturated carboxylic acid alkyl ester (a2) as a starting material. In a second embodiment, the present invention provides a modified polyisocyanate (referred to as "modified polyisocyanate (Y)") formed from a saturated carboxylic acid alkyl ester (a3) ​​as a starting material.

[0102] When an unsaturated carboxylic acid alkyl ester (a2) is used as the carboxylic acid alkyl ester, the unsaturated carboxylic acid alkyl ester (a2) is at least one selected from the group consisting of:

[0103] Branched alkyl esters of unsaturated dicarboxylic acids (a2-1) and

[0104] Branched alkyl esters of unsaturated monocarboxylic acids each optionally containing a heteroatom or an alkyl ester having a cyclic structure (a2-2).

[0105] In the present invention, unsaturated carboxylic acid alkyl ester (a2) or saturated carboxylic acid alkyl ester (a3) ​​is used as a modifier, thereby obtaining a modified polyisocyanate that can be stably diluted with an organic solvent and has excellent storage stability, and is used in combination with the active hydrogen group-containing compound described below to form a protective coating film having excellent adhesion to various metal substrates.

[0106] In the present invention, when a group in a general formula (such as formula (1) and formula (5)) is substituted, the substituent may be, for example, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an amino group, a monoalkylamino group, a dialkylamino group, a carboxyl group, a hydroxyl group, a hydroxyalkyl group, a hydroxyalkoxy group, an aryl group, an aryloxy group and a heteroaryl group, unless otherwise specified.

[0107] In the present invention, each substituent may be as follows unless otherwise specified.

[0108] Alkyl refers to a straight chain, branched or cyclic saturated hydrocarbon group, unless otherwise specified. The number of carbon atoms in the alkyl group is not particularly limited, and can be, for example, 1 to 18, 1 to 10, 1 to 8, 1 to 6, 1 to 4 and 1 to 3. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-stearyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

[0109] The cycloalkyl group may refer to a cyclic hydrocarbon group in which all carbon-carbon bonds are single bonds. The number of carbon atoms is, for example, 3 to 8. More specific examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

[0110] The hydroxyalkyl group may be, for example, a group in which the above-mentioned alkyl group is substituted with one or more (for example, one to three, one to two, or one) hydroxyl groups.

[0111] The alkoxy group may be, for example, an alkoxy group whose alkyl portion is the above-mentioned alkyl group.

[0112] The hydroxyalkoxy group may be, for example, a group in which the above-mentioned alkoxy group is substituted with one or more (for example, one to three, one to two, or one) hydroxyl groups.

[0113] Alkenyl refers to a straight or branched hydrocarbon group with a carbon-carbon double bond. The number of carbon atoms in the alkenyl is not particularly limited, and for example, can be 2 to 18, 2 to 10, 2 to 8, 2 to 6, 2 to 4 and 2 to 3. The number of carbon-carbon double bonds in the alkenyl is not limited, and for example, can be 1 to 2, and preferably 1. Examples of such alkenyls include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 1-pentenyl, 1,4-pentadienyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl, 1-decenyl, 2-undecenyl, 3-dodecenyl, 1-tridecenyl, 2-tetradecenyl, 3-pentadecenyl, 1-hexadecenyl, 2-heptenyl and 3-octadecenyl.

[0114] Alkynyl refers to a straight or branched hydrocarbon group with a carbon-carbon triple bond. The number of carbon atoms in the alkynyl is not particularly limited, and for example, can be 2 to 18, 2 to 10, 2 to 8, 2 to 6, 2 to 4 and 2 to 3. The number of carbon-carbon triple bonds in the alkynyl is not limited, and for example, can be 1 or 2, and preferably 1. Examples of such alkynyls include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 1-pentynyl, 1,4-pentadiynyl, 1-hexynyl, 1-heptynyl, 1-octynyl, 1-nonynyl, 1-decynyl, 2-undecynyl, 3-dodecynyl, 1-tridecynyl, 2-tetradecynyl, 3-pentadecenyl, 1-hexadecynyl, 2-heptadecynyl and 3-octadecynyl.

[0115] The cycloalkenyl group may be a cyclic hydrocarbon group having a carbon-carbon double bond and all other carbon-carbon bonds being single bonds. The number of carbon atoms is, for example, 3 to 8. The number of carbon-carbon double bonds in the cycloalkenyl group is not limited, and may be, for example, 1 to 2, and preferably 1. More specific examples of such cycloalkyl groups include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cycloheptenyl and cyclooctenyl.

[0116] Aryl refers to a monovalent group formed by removing a hydrogen atom from a monocyclic or polycyclic aromatic hydrocarbon compound, and can be, for example, a group having 6 to 18 carbon atoms. In the present invention, the monocyclic or polycyclic aromatic hydrocarbon compound can be any hydrocarbon containing an aromatic ring, and can be a group having a cyclic structure substituted by one or more (e.g., one to three, one to two or one) acyclic hydrocarbons (e.g., straight or branched alkyl, alkenyl and alkynyl (preferably straight or branched alkyl, etc.)). Similarly, in the present invention, aryl includes not only a group having a cyclic structure, but also a group having a cyclic structure substituted by one or more acyclic hydrocarbons. Examples of aryl include phenyl, naphthyl, anthracenyl, biphenyl, methylphenyl, dimethylphenyl and dodecylphenyl.

[0117] The arylalkyl group refers to, for example, the above-mentioned alkyl group having one or more (usually one) aryl groups.

[0118] Heteroaryl refers to, for example, a 5- to 14-membered saturated or unsaturated group having a cyclic structure having at least one (e.g., one to three, one to two, or one) selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. Examples include tetrahydrofuranyl, dihydrobenzofuranyl, pyridyl, pyrimidyl, thienyl, oxathiolanyl, quinolyl, and benzoquinolyl. Heteroaryl can be a monocyclic or bicyclic group.

[0119] The alkyl group with cyclic structure refers to the hydrocarbon group with cyclic structure in at least a part of its structure. It is preferred that the group does not have a carbon-carbon double bond. The alkyl group with cyclic structure can be a group formed by a hydrocarbon with a cyclic structure (e.g., a cycloalkyl group or a bicycloalkyl group), or can be a group in which the group formed by the hydrocarbon with a cyclic structure is replaced by (e.g., one to five, preferably one to four) hydrocarbon groups (e.g., an alkyl group (preferably a C1-C3 alkyl group)). The number of carbon atoms in the alkyl group with cyclic structure is not limited, and for example can be 6 to 23, and preferably 6 to 11.

[0120] The bicycloalkyl group may refer to a monovalent group obtained by removing one hydrogen atom from a C5-C8 condensed ring. Examples include bicyclo[1.1.1]pentyl, bicyclo[2.1.1]hexyl, bicyclo[2.2.1]heptyl, and bicyclo[2.2.2]octyl.

[0121] Primary amino group-containing alkoxysilane (a1)

[0122] In the present invention, the primary amino group-containing alkoxysilane (a1) is a compound represented by the following formula (1).

[0123]

[0124] In formula (1), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group; R 3 is a C1-C8, preferably a C1-C5 straight chain or branched chain alkylene group, and n is an integer of 0 to 2.

[0125] Specific examples of compound (a1) include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl-methyldiethoxysilane, 3-aminopropyl-methyldimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltriethoxysilane, and combinations thereof. Particularly preferred are 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

[0126] Unsaturated carboxylic acid alkyl ester (a2)

[0127] In the present invention, the unsaturated carboxylic acid alkyl ester (a2) is at least one selected from the group consisting of:

[0128] Branched alkyl esters of unsaturated dicarboxylic acids (a2-1) and

[0129] Branched alkyl esters of unsaturated monocarboxylic acids each optionally containing a heteroatom or an alkyl ester having a cyclic structure (a2-2).

[0130] Branched chain alkyl ester of unsaturated dicarboxylic acid (a2-1)

[0131] The branched alkyl ester of unsaturated dicarboxylic acid (a2-1) is a branched alkyl esterification product of fumaric acid or maleic acid, and may be, for example, a compound represented by the following formula (2).

[0132] R 4 OC(=O)-HC=CH-C(=O)-OR 5 (2)

[0133] In formula (2), R 4 and R 5 are the same or different, and each represents a C1-C8 branched alkyl group.

[0134] In the present specification, the term "branched alkyl" refers to an alkyl group whose carbon skeleton constituting the alkyl group is branched. Examples of the branched alkyl group may include isopropyl, 1-methylpropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl and 2-ethylhexyl.

[0135] Branched alkyl esters of unsaturated monocarboxylic acids each optionally containing a heteroatom or having a cyclic structure (a2-2)

[0136] In the present invention, the branched alkyl ester of an unsaturated monocarboxylic acid each optionally containing a hetero atom or the alkyl ester having a cyclic structure (a2-2) is specifically a compound represented by the following formula (3).

[0137] H2C=CH-C(=O)-OR 6 (3)

[0138] In formula (3), R 6 It is C3-C 18 A branched alkyl group or an alkyl group having a cyclic structure, or a C1-C1 alkyl group obtained by introducing a heteroatom (such as an oxygen atom, a nitrogen atom, or a sulfur atom) into the molecule of an alkyl group having a branched or cyclic structure. 18 Group.

[0139] Examples of branched alkyl groups include isopropyl, 1-methylpropyl, isobutyl, tert-butyl, isopentyl, tert-pentyl, 2-ethylhexyl, isononyl, isodecyl, isotridecyl, and isostearyl. Examples of alkyl groups having a cyclic structure include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, benzyl, trimethylcyclohexyl, isobornyl, dicyclopentyl, and adamantyl.

[0140] The group obtained by introducing a heteroatom (such as an oxygen atom, a nitrogen atom or a sulfur atom) into the molecule of an alkyl or arylalkyl group refers to a group equivalent to the following group: a group in which carbon atoms (usually carbon atoms other than terminal carbon atoms) in an alkyl or arylalkyl group (for an arylalkyl group, usually carbon atoms in the alkyl part) are partially substituted by heteroatoms or by groups consisting of heteroatoms and hydrogen (e.g., -O-, -N=, -NH- or -S-). For example, a dimethylaminoethyl group is equivalent to a group in which the carbon atom at the 3-position of an isopentyl group is substituted by -N=. The carbon atom may be substituted by a heteroatom (e.g., an oxygen atom, a nitrogen atom or a sulfur atom) or by a group consisting of heteroatoms and hydrogen at one or more positions (e.g., one to three positions, one to two positions or one position). The number of carbon atoms in the "group obtained by introducing a heteroatom into the molecule of an alkyl or arylalkyl group" refers to the number of carbon atoms in a structure in which some carbon atoms in an alkyl or arylalkyl group are substituted by heteroatoms or by groups consisting of heteroatoms and hydrogen (e.g., the number of carbon atoms in a dimethylaminoethyl group is four). Examples of the group obtained by introducing a heteroatom into the molecule of the alkyl group include a tetrahydrofurfuryl group, a phenoxyethyl group, and a dimethylaminoethyl group.

[0141] Saturated carboxylic acid alkyl ester (a3)

[0142] In the present invention, the saturated carboxylic acid alkyl ester (a3) ​​may be, for example, a compound represented by the following formula (4).

[0143] R 7 -C(=O)-OR 8 (4)

[0144] In formula (4), R 7 and R 8 The same or different, and each represents C1-C 18 An alkyl group or a C1-C1-C1-alkyl group obtained by introducing a heteroatom (such as an oxygen atom, a nitrogen atom or a sulfur atom) into the molecule of the alkyl group.18 or by introducing a heteroatom (such as an oxygen atom, a nitrogen atom or a sulfur atom) into the 7 or R 8 The group obtained by the alkyl group represented by the alkyl group has no unsaturated group in the molecule.

[0145] Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, 1-methylpropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, n-dodecyl, isotridecyl, isostearyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, trimethylcyclohexyl, isobornyl, adamantyl, and 2,2,4-trimethylpentyl. Examples of the group obtained by introducing a heteroatom into the molecule of the alkyl or arylalkyl group include tetrahydrofurfuryl, phenoxyethyl, and dimethylaminoethyl.

[0146] Specific examples of the saturated carboxylic acid alkyl ester (a3) ​​include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, cyclohexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, 1-methylpentyl acetate (alternative name: sec-hexyl acetate), 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, 3-ethoxybutyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, n-pentyl propionate, isopentyl propionate, Methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate, tert-butyl butyrate, methyl valerate, ethyl valerate, methyl octanoate, methyl laurate, methoxypropyl acetate, ethyl 3-ethoxypropionate, butyl glycol acetate, butyl diglycol acetate, methyl isovalerate, ethyl isovalerate, methyl 3,3,5-trimethylhexanoate, methyl isobutyrate, ethyl isobutyrate, isobutyl isobutyrate, n-butyl isobutyrate, tert-butyl isobutyrate, methyl 2-ethylhexanoate, methyl pivalate, ethyl 2-hydroxy-2-methylpropionate, methyl neodecanoate, and combinations thereof.

[0147] The saturated carboxylic acid alkyl ester (a3) ​​is preferably an alkyl ester of a linear carboxylic acid having a structure in which two or more hydrogen atoms are present at the α-position or an alkyl ester of a branched carboxylic acid having a structure in which two hydrogen atoms are present at the α-position. Compared with an alkyl ester having a branched structure in which only one hydrogen atom is present at the α-position, an alkyl carboxylate having such a structure is less affected by steric hindrance at the α-position and is therefore preferred because the reaction with the alkoxysilane (a1) can proceed at an appropriate rate.

[0148] Specific examples of the alkyl ester of a linear carboxylic acid having a structure in which two or more hydrogen atoms are present at the α-position include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, cyclohexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, 1-methylpentyl acetate (alternative name: sec-hexyl acetate), 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate , 3-ethoxybutyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, n-pentyl propionate, isopentyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate, tert-butyl butyrate, methyl valerate, ethyl valerate, methyl octanoate, methyl laurate, methoxypropyl acetate, ethyl 3-ethoxypropionate acetate, butyl glycol acetate, butylene glycol acetate, and combinations thereof.

[0149] Specific examples of the alkyl ester of the branched carboxylic acid having a structure in which two hydrogen atoms are present at the α-position include methyl isovalerate, ethyl isovalerate, methyl 3,3,5-trimethylhexanoate, and a combination thereof.

[0150] Polyisocyanate (a4)

[0151] In the present invention, polyisocyanate (a4) is a compound having at least two isocyanate groups per molecule. Examples of polyisocyanate (a4) include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates and derivatives thereof, and combinations thereof.

[0152] Examples of aliphatic polyisocyanates include aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and 2,6-isocyanatohexanoic acid methyl ester ( Common name: lysine diisocyanate); and aliphatic triisocyanates such as 2-isocyanatoethyl 2,6-diisocyanatohexanoate, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane.

[0153] Examples of alicyclic polyisocyanates include alicyclic diisocyanates such as 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate), 4-methyl-1,3-cyclohexylene diisocyanate (common name: hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, isocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, and methylenebis(4,1-cyclohexanediyl)diisocyanate (common name: hydrogenated MDI) and norbornane diisocyanate; and alicyclic triisocyanates such as 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2-(3-isocyanatopropyl)isocyanate, 2-(3-isocyanatopropyl)-2,6-bis(isocyanatomethyl)-bicyclo(2.2.1)heptane, 3-(3-isocyanatopropyl)-2,5-bis(isocyanatomethyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2.2 .1)) heptane, 6-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane and 6-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane.

[0154] Examples of the aromatic-aliphatic polyisocyanate include aromatic-aliphatic diisocyanates such as methylenebis(4,1-phenylene) diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω,ω'-diisocyanato-1,4-diethylbenzene and 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof; and aromatic-aliphatic triisocyanates such as 1,3,5-triisocyanatomethylbenzene.

[0155] Examples of the aromatic polyisocyanate include aromatic diisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-biphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4-toluene diisocyanate (common name: 2,4-TDI) or 2,6-toluene diisocyanate (common name: 2,6-TDI) or a mixture thereof, 4,4′-toluidine diisocyanate and 4,4′-diphenyl ether diisocyanate; aromatic triisocyanates such as triphenylmethane-4,4′,4″-triisocyanate, 1,3,5-triisocyanatobenzene and 2,4,6-triisocyanatotoluene; and aromatic tetraisocyanates such as 4,4′-biphenylmethane-2,2′,5,5′-tetraisocyanate.

[0156] Examples of derivatives of polyisocyanates include dimers, trimers, biuret, allophanate, urethodiones, ureaimines, isocyanurates, oxadiazinetriones, polymethylene polyphenyl polyisocyanates (crude MDI, polymeric MDI) or crude TDI of the above-mentioned polyisocyanates. In addition, the polyisocyanate derivatives can be modified with known polyol compounds (including diols or triols, and / or known monool compounds) to adjust the number of functional groups of the isocyanate group or to adjust the compatibility or physical properties.

[0157] The polyisocyanate (a4) is preferably a polyisocyanate derivative having an isocyanate group content of 10% by mass or more, or 12% by mass or more, and 30% by mass or less, or 25% by mass or less.

[0158] Here, the isocyanate group content of the polyisocyanate (a4) is the amount of isocyanate groups in the polyisocyanate (a4) expressed as a mass fraction. The isocyanate group content can be measured according to the catalog value or in accordance with the isocyanate content determination method specified in JIS K1603-1.

[0159] Modified polyisocyanate and preparation method thereof

[0160] In the present invention, the modified polyisocyanate according to the first embodiment is a reaction product (referred to as "modified polyisocyanate (X)") formed from components including a primary amino group-containing alkoxysilane (a1), an unsaturated carboxylic acid alkyl ester (a2), and a polyisocyanate (a4) as starting materials, and is preferably a modified polyisocyanate in which a secondary amino group of an N-modified alkoxysilane represented by formula (5) or formula (6) obtained by adding a primary amino group of the alkoxysilane (a1) to an unsaturated carbon-carbon bond of the unsaturated carboxylic acid alkyl ester (a2) is added to at least one isocyanate group of the polyisocyanate (a4):

[0161]

[0162] In formula (5), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group; R 3 is a C1-C8 straight chain or branched chain alkylene group, preferably a C1-C5 straight chain or branched chain alkylene group; R 4 and R 5 are the same or different and each represents a C1-C8 branched alkyl group, and n is an integer from 0 to 2.

[0163]

[0164] In formula (6), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group; R 3 is a C1-C8 straight or branched chain alkylene group, preferably a C1-C5 straight or branched chain alkylene group; R 6 It is a C1-C with a branched or cyclic structure. 18 An alkyl group, or a C1-C1 alkyl group obtained by introducing a heteroatom into an alkyl group or an arylalkyl group having a branched or cyclic structure. 18 group; and n is an integer from 0 to 2.

[0165] Alternatively, in a second embodiment, the modified polyisocyanate is a reaction product (referred to as "modified polyisocyanate (Y)") formed from components comprising a primary amino group-containing alkoxysilane (a1), a saturated carboxylic acid alkyl ester (a3), and a polyisocyanate (a4) as starting materials. Preferably, the modified polyisocyanate is obtained by adding a secondary amide group of an N-modified alkoxysilane to at least one isocyanate group of the polyisocyanate (a4), wherein the N-modified alkoxysilane is obtained by reacting the alkoxysilane (a1) with the saturated carboxylic acid alkyl ester (a3), and wherein the N-modified alkoxysilane is a secondary amide group-containing N-acylated product represented by the following formula (7).

[0166]

[0167] In formula (7), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group; n is an integer from 0 to 2; R 3is a C1-C8 straight chain or branched chain alkylene, preferably a C1-C5 straight chain or branched chain alkylene; and R 7 It is a C1-C 18 An alkyl group or a C1-C ... 18 Group.

[0168] The method for producing the modified polyisocyanate (X) or (Y) may be a method comprising reacting a primary amino group-containing alkoxysilane (a1), an unsaturated carboxylic acid alkyl ester (a2) or a saturated carboxylic acid alkyl ester (a3) ​​with a polyisocyanate (a4) at the same time. The method is preferably a method comprising reacting an alkoxysilane (a1) with an unsaturated carboxylic acid alkyl ester (a2) or a saturated carboxylic acid alkyl ester (a3) ​​in advance to obtain an N-modified alkoxysilane having a secondary amino group or a secondary amide group, and further reacting the N-modified alkoxysilane with the polyisocyanate (a4).

[0169] Method for producing modified polyisocyanate (X)

[0170] For the modified polyisocyanate (X), the blending ratio of the primary amino group-containing alkoxysilane (a1) and the unsaturated carboxylic acid alkyl ester (a2) is preferably, for example, 0.7 mol% or more, or 0.85 mol% or more, and 1.5 mol% or less, or 1.25 mol% or less, per mole of the primary amino group-containing alkoxysilane (a1), the unsaturated carboxylic acid alkyl ester (a2).

[0171] For the modified polyisocyanate (X), when the unsaturated carboxylic acid alkyl ester (a2) is a branched alkyl ester of an unsaturated dicarboxylic acid (a2-1), in terms of the adhesion and curing properties of the coating to iron and non-ferrous metals and the storage stability of the modified polyisocyanate, it is preferred to adjust the reaction ratio of the N-modified alkoxysilane having a secondary amino group to the polyisocyanate (a4) so ​​that the amount of the secondary amino group is 40 mol% or less, preferably 3 mol% or more and 35 mol% or less per 100 mol of isocyanate groups.

[0172] For the modified polyisocyanate (X), when the unsaturated carboxylic acid alkyl ester (a2) is a branched alkyl ester of an unsaturated monocarboxylic acid, each of which optionally contains a heteroatom, or an alkyl ester having a cyclic structure (a2-2), the reaction between the primary amino group-containing alkoxysilane (a1) and the unsaturated carboxylic acid alkyl ester (a2) can produce a compound represented by the following formula (8) as a by-product in addition to the N-modified alkoxysilane represented by the formula (6), and thus a mixture containing the N-modified alkoxysilane mixed with the unreacted primary amino group-containing alkoxysilane (a1) can be obtained.

[0173]

[0174] In formula (8), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group; R 3 is a C1-C8 straight or branched chain alkylene group, preferably a C1-C5 straight or branched chain alkylene group; R 6 It is a C1-C with a branched or cyclic structure. 18 An alkyl group or a C1-C1 alkyl group obtained by introducing a heteroatom into an alkyl group or an arylalkyl group having a branched or cyclic structure. 18 group; and n is an integer from 0 to 2.

[0175] Therefore, in this case, the reaction of the N-modified alkoxysilane having a secondary amino group with the polyisocyanate (a4) is carried out in the presence of unreacted primary amino group-containing alkoxysilane (a1) and the tertiary amino group-containing compound represented by formula (8) produced as a by-product.

[0176] For the modified polyisocyanate (X), when the unsaturated carboxylic acid alkyl ester (a2) is a branched alkyl ester of an unsaturated monocarboxylic acid, each of which optionally contains a heteroatom, or an alkyl ester having a cyclic structure (a2-2), in terms of the adhesion and curing properties of the coating to iron and non-ferrous metals and the storage stability of the modified polyisocyanate (X), it is preferred to adjust the reaction ratio of the mixture containing N-modified alkoxysilane and the polyisocyanate (a4) so ​​that the total molar number of primary and secondary amino groups relative to 100 mol of isocyanate groups is 40 mol% or less, and preferably 3 mol% or more and 35 mol% or less.

[0177] The reaction of the alkoxysilane (a1) containing primary amino groups with the unsaturated carboxylic acid alkyl ester (a2) to obtain the N-modified alkoxysilane can be carried out at 0 to 110 ° C, while blowing air as needed. The reaction time is 1 hour to 2 weeks, and the specific time varies according to the temperature. For the reaction, the unsaturated carboxylic acid alkyl ester (a2) can be added to the alkoxysilane (a1) containing primary amino groups, or mixed by adding the alkoxysilane (a1) containing primary amino groups to the unsaturated carboxylic acid alkyl ester (a2). In order to avoid the polymerization of the unsaturated carboxylic acid alkyl ester (a2), if necessary, a small amount of known aromatic polymerization inhibitors, such as methoxyhydroquinone, or nitroso compounds, such as N-oxyl radicals, can be used together.

[0178] The reaction of N-modified alkoxysilane and polyisocyanate (a4) obtained by alkoxysilane (a1) containing primary amino group and unsaturated carboxylic acid alkyl ester (a2) is not particularly limited, and can be carried out under known and conventional reaction conditions. Specifically, the reaction can be carried out, for example, by stirring 0.1 to 5 hours while mixing N-modified alkyl alkoxysilane and polyisocyanate (a4) all at once or dropping at 0 to 80 ° C. In this case, according to the desired performance, N-modified alkoxysilane can be added to polyisocyanate (a4), or by adding polyisocyanate (a4) to N-modified alkoxysilane for mixing. In this reaction, if necessary, Lewis acid catalysts, alkaline catalysts and organic solvents can also be used. If necessary, the mixture containing the obtained reaction product can be aged for one day to one month at 0 to 80 ° C.

[0179] Production method of modified polyisocyanate (Y)

[0180] In the reaction of obtaining N-modified alkoxysilane from the primary amino group-containing alkoxysilane (a1) and the saturated carboxylic acid alkyl ester (a3), the blending ratio of the primary amino group-containing alkoxysilane (a1) and the saturated carboxylic acid alkyl ester (a3) ​​is preferably, for example, 0.7 mol or more, or 0.85 mol or more, and 1.5 mol or less, or 1.25 mol or less, per mole of the primary amino group-containing alkoxysilane (a1), the saturated carboxylic acid alkyl ester (a3).

[0181] The reaction of the primary amino group-containing alkoxysilane (a1) and the saturated carboxylic acid alkyl ester (a3) ​​can be carried out by heating to 100 to 250° C., or can be carried out at 0 to 160° C. by adding a basic catalyst or a Lewis acid catalyst. When adding a catalyst, it is preferred to use a basic catalyst that can produce an effect in a small amount. In any case, if necessary, the reaction can be carried out under pressure. In order to suppress coloration, etc., the reaction can also be carried out in the presence of a known antioxidant such as methoxyhydroquinone. The reaction time is generally about 1 hour to 3 days, and the specific time varies according to temperature, etc. It is preferred that the components are mixed all at once or mixed by dropwise addition, and further combined and aged as needed.

[0182] When the alkaline catalyst or the Lewis acid catalyst is added, it may be added after the primary amino group-containing alkoxysilane (a1) and the saturated carboxylic acid alkyl ester (a3) ​​are mixed, it may be added to the primary amino group-containing alkoxysilane (a1) in advance and then mixed with the saturated carboxylic acid alkyl ester (a3), or it may be added to the saturated carboxylic acid alkyl ester (a3) ​​in advance and then mixed with the primary amino group-containing alkoxysilane (a1).

[0183] In the present invention, the modified polyisocyanate (Y) is preferably prepared by the following steps:

[0184] Step (1), reacting the primary amino group-containing alkoxysilane (a1) with the saturated carboxylic acid alkyl ester (a3) ​​in the presence of a basic catalyst;

[0185] Step (2), adding an acidic compound to the mixture containing the reaction product obtained in step (1) as needed;

[0186] Step (3), removing part or all of the alcohol produced as a by-product to prepare an intermediate containing an N-acylated product represented by the following formula (7); and

[0187] Step (4), reacting the intermediate with the polyisocyanate (a4).

[0188]

[0189] In formula (7), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group; R 3 is a C1-C8 straight or branched chain alkylene group, preferably a C1-C5 straight or branched chain alkylene group; n is an integer from 0 to 2; and R 7 It is a C1-C 18 An alkyl group or a C1-C12 group having no unsaturated group obtained by introducing a heteroatom (such as an oxygen atom, a nitrogen atom or a sulfur atom) into the molecule of the alkyl group. 18 Group.

[0190] These production methods make it possible to easily obtain modified polyisocyanates having excellent adhesion to non-ferrous metals.

[0191] Examples of the alkaline catalyst added in step (1) include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; carbonates such as sodium carbonate and potassium carbonate; bicarbonates such as sodium bicarbonate and potassium bicarbonate; metal alkoxides such as sodium methoxide and potassium tert-butoxide; organic metals such as butyl lithium; potassium silicon alkoxide; and nitrogen compounds such as ammonia gas, aqueous ammonia, methylamine, trimethylamine, triethylamine, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and 1,5-diazabicyclo[4.3.0]-5-nonene (DBN). These alkaline catalysts may be used without being dissolved in an organic solvent, or may be added after being dissolved in a solvent (e.g., water; alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; and ethers such as tetrahydrofuran, cyclopentyl methyl ether, and trimethyl orthoacetate) in advance.

[0192] Examples of the acidic compound added in step (2) include inorganic Bronsted acids such as hydrogen chloride, hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; organic Bronsted acids such as carboxylic acids, alkylsulfonic acids, arylsulfonic acids, monoalkylphosphoric acids, dialkylphosphoric acids and arylphosphonic acids; and acyl chlorides such as acetyl chloride and benzoyl chloride. These acidic catalysts may be used without being dissolved in an organic solvent, or may be added after being dissolved in a solvent (e.g., water; alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; and ethers such as tetrahydrofuran, cyclopentyl methyl ether and trimethyl orthoacetate) in advance. The addition of the acidic compound is preferably performed before step (3). However, the addition may also be performed during step (3).

[0193] In step (3), part or all of the alcohol formed as a by-product in step (1), and optionally the primary amino group-containing alkoxysilane (a1) and / or saturated carboxylic acid alkyl ester (a3) ​​remaining as unreacted starting materials are removed by heating and optionally by decompression. In the present invention, removal can be performed by either of two methods, i.e., concentration or distillation. Concentration is a method of removing the desired compound from the system and leaving the desired compound in the system, while distillation is a method of collecting the desired compound outside the system. The N-acylated product obtained by distillation is a purified N-acylated product with high purity; however, the process and equipment required for distillation are complex, and distillation requires a large amount of energy, thereby placing a heavy burden on the environment. On the other hand, the N-acylated product obtained by concentration is a crude N-acylated product with low purity, which not only contains impurities such as catalyst residues, but also, in some cases, contains still unreacted primary amino group-containing alkoxysilane (a1) and / or saturated carboxylic acid alkyl ester (a3). However, the process and equipment required for concentration are simple, and in addition, concentration requires a small amount of energy, thereby placing a small burden on the environment. From the viewpoint of ease of production, removal by concentration is more advantageous.

[0194] In the present invention, even when step (3) is performed by concentration rather than distillation, a modified polyisocyanate as a paint curing agent having sufficient performance can be provided by reaction with polyisocyanate (a4). However, in order to further improve the corrosion resistance of the coating film, a saturated carboxylic acid alkyl ester having a branched structure and two hydrogen atoms at the α position is used as the saturated carboxylic acid alkyl ester (a3), and the obtained crude N-acylated product can be purified by distillation as needed before use. On the other hand, the crude N-acylated product obtained by using a carboxylic acid ester having a straight-chain structure and two or more hydrogen atoms at the α position as the saturated carboxylic acid alkyl ester (a3) ​​can obtain a coating film having extremely high corrosion resistance and weather resistance even when used without purification by distillation, and is therefore more preferred from the viewpoint of ease of production.

[0195] Step (4) can be carried out at 40 to 200° C. without adding a catalyst, or can be carried out at 20 to 140° C. with the addition of a basic catalyst or a Lewis acid catalyst. When a catalyst is added in step (4), it is preferred to use a Lewis acid catalyst that produces an effective effect in a small amount. The Lewis acid catalyst used may be a known catalyst. Examples include tin compounds such as dialkyltin dicarboxylates, monoalkyltin tricarboxylates, dialkyltin oxides, and tin dicarboxylates; zinc compounds such as zinc dicarboxylates and zinc di(acetylacetonate); zirconium compounds such as tetraalkoxy zirconium, di(acetylacetonate)dialkoxy zirconium, and tetra(acetylacetonate) zirconium; titanium compounds such as tetraalkoxytitanium, di(acetylacetonate)dialkoxytitanium, and tetra(acetylacetonate)titanium; aluminum compounds such as tri(acetylacetonate)aluminum; and bismuth compounds such as bismuth tricarboxylates.

[0196] In each of steps (1), (2), (3) and (4), a filtering operation may be performed using a known filtering material as required.

[0197] In the production of the modified polyisocyanate (Y), it is preferred to adjust the reaction ratio of the purified N-modified alkoxysilane or crude N-modified alkoxysilane obtained from the primary amino group-containing alkoxysilane (a1) and the saturated carboxylic acid alkyl ester (a3) ​​and the polyisocyanate (a4) so ​​that the total molar number of the secondary amide group and the primary amino group is 40 mol% or less, preferably 3 mol% or more and 35 mol% or less, relative to 100 mol of the isocyanate group.

[0198] As described above, the modified polyisocyanate of the present invention is preferably prepared by using an N-modified alkoxysilane having a secondary amino group or a secondary amide group, such as the modified polyisocyanate (X) or the modified polyisocyanate (Y), to produce an effect of improving compatibility with the active hydrogen group-containing compound described below and an organic solvent.

[0199] For the purpose of improving stability and the like, the modified polyisocyanate of the present invention can also be prepared by reacting an N-modified alkoxysilane having a secondary amino group or a secondary amide group with polyisocyanate and then adding the above-mentioned acidic compound as required.

[0200] For obtaining N-modified alkoxysilanes in order to adjust the properties of a coating film obtained by using a modified polyisocyanate as a curing agent, a primary amino group-containing alkoxysilane (a1) can be reacted with an unsaturated carboxylic acid alkyl ester (a2) or a saturated carboxylic acid alkyl ester (a3), while an alkoxysilane having both a primary amino group and a secondary amino group, such as 3-(2-aminoethylamino)propyltrialkoxysilane, is used in combination.

[0201] In view of the curability of the coating film, the adhesion to nonferrous metals, weather resistance and corrosion resistance, the amount of isocyanate groups in the modified polyisocyanate of the present invention is preferably, for example, 1.0 mmol or more, or 2.0 mmol or more in the non-volatile components per gram of the modified polyisocyanate. The upper limit of the amount of isocyanate groups in the modified polyisocyanate is not limited, and can be designed to be, for example, 5.5 mmol or less, or 5.0 mmol or less in the non-volatile components per gram of the modified polyisocyanate.

[0202] The amount of isocyanate groups in the modified polyisocyanate can be determined, for example, by adding 10 ml of a 0.1 mol / L dibutylamine solution to 0.1 g of a sample to react the NCO groups and then titrating the remaining dibutylamine with aqueous hydrochloric acid using bromophenol blue as a titration indicator.

[0203] In the present specification, the nonvolatile content refers to a residue after removing a volatile component such as an organic solvent, and can be measured according to the standard of JIS K5601 1-2 (heating temperature: 125° C., heating time: 60 minutes).

[0204] In the present invention, the organic solvent can be used as a reaction solvent for producing modified polyisocyanate or as a diluting solvent for diluting the modified polyisocyanate to a viscosity suitable for use as a paint curing agent. The organic solvent used can be a solvent commonly used in the paint field. Specific examples include aliphatic solvents such as n-butane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane and cyclobutane; aromatic solvents such as toluene and xylene; ketone solvents such as methyl tert-butyl ketone; ether solvents such as n-butyl ether, dioxane and cyclopentyl methyl ether; ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate and butyl carbitol acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone; and combinations thereof. In addition, organic solvents with weak dissolving power, which are generally referred to as weak solvents in the paint field, such as gasoline, kerosene, coal tar naphtha (including solvent naphtha), petroleum ether, petroleum naphtha, light petroleum, turpentine and mineral spirits (including mineral thinner, petroleum spirits, white spirits and mineral turpentine) can also be fully used.

[0205] In the present invention, the organic solvent may be included in any main agent and curing agent. The amount of the organic solvent included in the curing agent is preferably 200 parts by mass or less in the non-volatile components in 100 parts by mass of the modified polyisocyanate, and more preferably 10 parts by mass or more to 100 parts by mass or less. In a typical embodiment, the modified polyisocyanate of the present invention is used as a curing agent for coating. Therefore, in one embodiment, the present invention provides a curing agent containing modified polyisocyanate. In this embodiment, the curing agent of the present invention is preferably used in combination with a compound containing active hydrogen. In addition, in the present invention, the modified polyisocyanate can be used alone as a curing agent. Alternatively, the modified polyisocyanate can be used as a curing agent composition, which also includes the above-mentioned solvent, catalyst, ultraviolet absorber, light stabilizer, rheology control agent, surface conditioner, dehydrating agent, etc. in addition to the modified polyisocyanate. These components except the modified polyisocyanate can be used alone or in combination of two or more. In an embodiment of the curing agent composition, the content of the modified polyisocyanate in the composition is not limited, and can be set to, for example, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more.

[0206] Active hydrogen group containing compounds

[0207] In the present invention, the compound containing active hydrogen groups is a compound used as an adhesive component together with the modified polyisocyanate. The compound containing active hydrogen groups is not particularly limited as long as it has an active hydrogen group, and can be any compound known and commonly used in the field of paint. The active hydrogen group used herein refers to a group that can react with the isocyanate group of the modified polyisocyanate, and can be, for example, a hydroxyl, a primary amino group or a secondary amino group or a thiol group. Specific examples of compounds containing active hydrogen groups include polyol compounds, such as acrylic polyols, polyester polyols, polyether polyols, polycarbonate polyols, epoxy polyols, dihydroxy alkanes, trihydroxy alkanes and dihydroxy cycloalkanes; and polyamino compounds, such as acrylic resins with pendant amino groups, polyallylamines, polyether polyamines, polylysine and polyethyleneamine, polymers with multiple secondary amino groups and aspartic acid ester structures, diaminoalkanes, diaminocycloalkanes, dialkylene triamines, trialkylene tetramines and bis-aspartic acid ester derivatives. These compounds can be used alone or in combination.

[0208] Among them, the active hydrogen group-containing compound preferably comprises an acrylic polyol and / or a bisaspartic acid ester derivative from the viewpoints of, for example, improving the weather resistance of the coating film to be formed, improving the compatibility of the paint, increasing the non-volatile concentration of the paint, and controlling the reaction rate with the isocyanate group. In order to adjust the flexibility of the coating film, etc., a polyester polyol and a polyether polyol may also be used in combination if necessary.

[0209] The acrylic polyol used may be one prepared by copolymerizing, for example, a hydroxyl group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer (a polymerizable unsaturated monomer other than the hydroxyl group-containing polymerizable unsaturated monomer), or may be a commercially available product or the like.

[0210] A hydroxyl-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl groups and one or more polymerizable unsaturated groups per molecule. Examples of hydroxyl-containing polymerizable unsaturated monomers include monoesterification products of (meth)acrylic acid with a diol having 2 to 8 carbon atoms (e.g., 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate); ε-caprolactone-modified products of such monoesterification products of (meth)acrylic acid with a diol having 2 to 8 carbon atoms; adducts of (meth)acrylic acid with epoxy-containing compounds (e.g., Cardura E10P, trade name, produced by Hexion, neodecanoic acid glycidyl ester); N-hydroxymethyl (meth)acrylamide; allyl alcohol; and (meth)acrylates containing hydroxyl-terminated polyoxyethylene chains.

[0211] As another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer, for example, monomers listed in (1) to (7) below can be used. These polymerizable unsaturated monomers may be used alone or in combination of two or more.

[0212] (1) Acid group-containing polymerizable unsaturated monomer

[0213] Acid group-containing polymerizable unsaturated monomers are compounds having one or more acid groups and one or more polymerizable unsaturated groups per molecule. Examples of monomers include carboxyl-containing monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and maleic anhydride; sulfonic acid-containing monomers such as vinyl sulfonic acid and (meth) 2-sulfoethyl acrylate; acidic phosphate monomers such as 2-(meth) acryloyloxyethyl phosphate, 2-(meth) acryloyloxypropyl phosphate, 2-(meth) acryloyloxy-3-chloropropyl phosphate and 2-methacryloyloxyethyl phenyl phosphate. These monomers can be used alone or in combination of two or more.

[0214] (2) Esterification products of acrylic acid or methacrylic acid and monohydric alcohols having 1 to 20 carbon atoms

[0215] Specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, isostearyl acrylate (trade name, produced by Osaka Organic Chemical Industry, Ltd.), lauryl (meth)acrylate, tridecyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, cyclohexyl (meth)acrylate and isobornyl (meth)acrylate.

[0216] (3) Alkoxysilyl-containing polymerizable unsaturated monomer

[0217] The polymerizable unsaturated monomer containing alkoxysilyl group is a compound having one or more alkoxysilyl groups and one or more polymerizable unsaturated groups per molecule. Examples of polymerizable unsaturated monomer containing alkoxysilyl group include vinyl trimethoxysilane, vinyl triethoxysilane, acryloxyethyl trimethoxysilane, methacryloxyethyl trimethoxysilane, acryloxypropyl trimethoxysilane, methacryloxypropyl trimethoxysilane, acryloxypropyl triethoxysilane, methacryloxypropyl triethoxysilane and vinyl tris (β-methoxyethoxy) silane.

[0218] (4) Aromatic vinyl monomers

[0219] Specific examples include styrene, α-methylstyrene, and vinyltoluene.

[0220] When an aromatic-based vinyl monomer is used as a constituent component, the proportion thereof is preferably 3% by mass or more, or 5% by mass or more, and 50% by mass or less, or 40% by mass or less, based on the total amount of the monomer components.

[0221] (5) Glycidyl-containing polymerizable unsaturated monomers

[0222] The glycidyl group-containing polymerizable unsaturated monomer is a compound having one or more glycidyl groups and one or more polymerizable unsaturated groups per molecule. Specific examples include glycidyl acrylate and glycidyl methacrylate.

[0223] (6) Compounds containing nitrogen and polymerizable unsaturated groups

[0224] Examples include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-[3-(dimethylamino)propyl](meth)acrylamide, N-butoxymethyl(meth)acrylamide, diacetone(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylate, vinylpyridine, vinylimidazole, acrylonitrile, and methacrylonitrile.

[0225] (7) Other vinyl compounds

[0226] Examples include vinyl acetate, vinyl propionate, vinyl chloride, and vinyl versatate.

[0227] The term "polymerizable unsaturated monomer" as used herein refers to a monomer having one or more (e.g., one to four) polymerizable unsaturated groups. A polymerizable unsaturated group refers to an unsaturated group that can undergo free radical polymerization. Examples of polymerizable unsaturated groups include vinyl, (meth)acryloyl, (meth)acrylamide, vinyl ether, allyl, propenyl, isopropenyl, and maleimide.

[0228] As used herein, the term "(meth)acrylate" means acrylate or methacrylate. The term "(meth)acrylic acid" means acrylic acid or methacrylic acid. The term "(meth)acryloyl" means acryloyl or methacryloyl. The term "(meth)acrylamide" means acrylamide or methacrylamide.

[0229] In terms of weather resistance and corrosion resistance of the coating film to be formed, the acrylic polyol preferably has a hydroxyl value of 5 mg KOH / g or more, or 10 mg KOH / g or more, and 160 mg KOH / g or less, or 100 mg KOH / g or less, and a weight average molecular weight of 3,000 or more, or 10,000 or more, and 100,000 or less, or 50,000 or less.

[0230] In this specification, the weight average molecular weight refers to a value calculated from a chromatogram measured by gel permeation chromatography based on the weight average molecular weight of standard polystyrene. For gel permeation chromatography, HLC is used. 81 20GPC (produced by Tosoh Corporation). The measurement was performed using four columns TSKgel G-4000HXL, TSKgel G-3000HXL, TSKgel G-2500HXL and TSKgel G-2000HXL (trade names, all produced by Tosoh Corporation) under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40°C, flow rate: 1 mL / min, and detector: RI.

[0231] The bis-aspartic acid ester derivative is not limited as long as it is a maleic acid diester or a fumaric acid diester added to an aspartic acid compound having two amino groups. Examples include N,N'-(methylenebis-4,1-cyclohexanediyl)-bis-aspartic acid tetraethyl ester, N,N'-(methylenebis(2-methyl-di-4,1-cyclohexanediyl))-bis-aspartic acid tetraethyl ester, and N,N'-(2-methyl-1,5-pentanediyl)-bis-aspartic acid tetraethyl ester. More specific examples include Desmophen NH 1420, Desmophen NH 1520, Desmophen NH 1220, Desmophen NH 1422, Desmophen NH 1423LF, Desmophen NH 1720, Desmophen NH 1723LF, Desmophen NH 1523LF and Desmophen NH 1521 manufactured by Covestro; and Amicure IC-133, Amicure IC-166 and Amicure IC-186 manufactured by Evonik (all are trade names).

[0232] coating

[0233] The present invention provides a coating comprising a compound containing active hydrogen and a modified polyisocyanate. The coating of the present invention also includes a two-component composition, which comprises a separately stored curing agent containing a modified polyisocyanate and a main agent containing a compound containing an active hydrogen group. In a typical embodiment, the coating of the present invention is obtained by mixing the separately stored curing agent containing a modified polyisocyanate with the main agent containing a compound containing an active hydrogen group before applying the coating. The coating of the present invention can also be called a paint composition.

[0234] As for the ratio used, the equivalent ratio of the modified polyisocyanate relative to 1 equivalent of the active hydrogen group contained in the active hydrogen group-containing compound is preferably 0.5 or more, or 0.7 or more. The equivalent ratio of the modified polyisocyanate is not limited, and can be designed to be, for example, 2.5 or less, or 1.5 or less relative to 1 equivalent of the active hydrogen group contained in the active hydrogen group-containing compound.

[0235] If necessary, the coating of the present invention may also appropriately contain rust inhibitors, catalysts, coloring pigments, extender pigments, effect pigments, dispersants, ultraviolet absorbers, light stabilizers, defoamers, rheology control agents, surface conditioners, dehydrating agents, organic solvents, crosslinking agents, binder components other than active hydrogen group-containing compounds, and the like.

[0236] Among them, the rust inhibitor may be a rust inhibitor known in the paint field and commercially available. The rust inhibitor may be an inorganic compound or an organic compound, and may be in any form, such as a single compound, a composite compound, a composition obtained by combining these compounds, and a composition obtained by baking these compounds. Specific examples include:

[0237] Metal compounds based on phosphoric acid, such as zinc phosphate, magnesium phosphate, magnesium-ammonium phosphate eutectic mixture, magnesium monohydrogen phosphate, magnesium dihydrogen phosphate, magnesium-calcium phosphate eutectic mixture, magnesium phosphate-cobalt eutectic mixture, magnesium phosphate-nickel eutectic mixture, calcium phosphate, calcium ammonium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium chlorofluorophosphate, aluminum phosphate, and aluminum hydrogen phosphate;

[0238] Metal compounds based on phosphorous acid, such as magnesium phosphite, calcium phosphite, magnesium-calcium phosphite eutectic mixture, basic zinc phosphite, barium phosphite, manganese phosphite and calcium hypophosphite;

[0239] Silicate metal salts such as calcium silicate, zinc silicate, aluminum silicate, aluminum orthosilicate, hydrated aluminum silicate, aluminosilicates, borosilicates, beryllium silicate, calcium aluminum silicate, sodium aluminum silicate, beryllium aluminum silicate, sodium silicate, calcium orthosilicate, calcium metasilicate, sodium calcium silicate, zirconium silicate, magnesium orthosilicate, magnesium metasilicate, manganese silicate, and barium silicate;

[0240] Metal ion-exchanged silica based compounds, such as magnesium ion-exchanged silica and calcium ion-exchanged silica;

[0241] Condensed phosphoric acid-based metal compounds such as aluminum tripolyphosphate, aluminum tripolyphosphate-magnesium oxide complex, aluminum tripolyphosphate, and aluminum tripolyphosphate-zinc oxide complex;

[0242] Vanadium-based metal compounds, such as vanadium pentoxide, calcium vanadate, magnesium vanadate, and ammonium metavanadate, as well as roasting products of manganese oxide and vanadium oxide, and roasting products of calcium phosphate and vanadium oxide;

[0243] Metal compounds based on molybdic acid, such as aluminum molybdate, calcium molybdate, and aluminum molybdate phosphate;

[0244] Zinc-based compounds, such as zinc and zinc oxide;

[0245] Silica-based compounds, such as silicon dioxide and colloidal silicon dioxide;

[0246] Composite metal iron oxides, such as composite iron oxides of iron oxide and magnesium oxide, composite iron oxides of iron oxide and calcium oxide, and composite iron oxides of iron oxide and zinc oxide; and

[0247] Sulfur-containing organic compounds such as triazole compounds, thiol compounds, thiadiazole compounds and thiazole compounds.

[0248] When the coating of the present invention contains a rust inhibitor, the amount of the rust inhibitor is preferably 1 part by mass or more, or 3 parts by mass or more, and 70 parts by mass or less, or 60 parts by mass or less relative to 100 parts by mass of nonvolatile components in the active hydrogen-containing compound.

[0249] The catalyst may be a conventional compound known to be used for coatings. Specific examples include organic metal compounds and amine compounds.

[0250] Examples of the organometallic compound include diacetyltin diacetate, diacetyltin dioctanoate, dioctyltin diacetate, dioctyltin di(2-ethylhexanoate), dioctyltin dilaurate, dioctyltin dineodecanoate, dioctyltin oxide, dibutyltin diacetate, dibutyltin di(2-ethylhexanoate), dibutyltin dioctanoate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin sulfide, fatty acid dibutyltin salts, tin octanoate, zinc octanoate, zinc naphthenate, fatty acid zinc, bismuth octanoate, bismuth 2-ethylhexanoate, bismuth oleate, bismuth neodecanoate, bismuth versatate, bismuth naphthenate, cobalt naphthenate, calcium octanoate, copper naphthenate, and tetra(2-ethylhexyl) titanate.

[0251] Examples of the amine compound include aliphatic amines such as trimethylamine, triethylamine, 2-(dimethylamino)ethyl methacrylate, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, 1-methylpiperidine and 1-methylpyrrolidine; and pyridine, 4-dimethylaminopyridine, 4-(1-piperidinyl)pyridine, N-methylimidazole and N,N-dimethylaniline.

[0252] When the coating material of the present invention contains a catalyst, the content of the catalyst is preferably 0.005 mass % or more, or 0.01 mass % or more, and 2 mass % or less, or 1 mass % or less based on the mass of the nonvolatile components in the active hydrogen group-containing compound.

[0253] Examples of the coloring pigment include titanium oxide, zinc oxide, carbon black, red iron oxide, cadmium red, molybdenum red, chrome yellow, chromium oxide, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, threnepigments, and perylene pigments.

[0254] Examples of extender pigments include talc, clay, kaolin, barite, barium sulfate, barium carbonate, calcium carbonate, and alumina white.

[0255] Examples of effect pigments include aluminum pigments, mica pigments, mica pigments coated with titanium oxide, and aluminum oxide pigments coated with titanium oxide.

[0256] Dehydrating agents include compounds that consume water by chemical reaction with water, or compounds that physically absorb water. Examples of the former include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, toluenesulfonyl isocyanate, vinyl trimethoxysilane, and vinyl triethoxysilane. Examples of the latter include zeolites and molecular sieves.

[0257] application

[0258] Since the modified polyisocyanate of the present invention has excellent adhesion to metal substrates, the coating comprising the modified polyisocyanate of the present invention is applied to the metal substrate. The metal substrate includes both ferrous substrates and nonferrous metals. Specific examples include steel, galvanized steel, stainless steel, magnesium alloys, aluminum and aluminum alloys. These can be surface treated with phosphates, chromates, etc. The metal substrate also includes metal components that constitute existing structures and retain old coating films or rust on its surface, etc.

[0259] The coating of the present invention can be diluted to a viscosity suitable for application with an organic solvent, etc. as required, and can be applied by air spraying, airless spraying, electrostatic coating, brushing, roller coating, building spray gun, multi-purpose gun, etc. Drying can be carried out at normal temperature. It is also possible to dry by heating. Normal temperature varies according to the atmospheric temperature of the environment in which the application is carried out, and refers to a temperature without temperature control (such as forced heating or cooling), while drying by heating refers to a temperature at which a device (such as a drying oven) is used for forced heating operation.

[0260] Since the coating of the present invention has excellent adhesion, it is possible to omit the application of primer before applying the coating. In addition, since the coating of the present invention also has excellent weather resistance, it is also possible to omit the application of topcoat coating on the coating of the present invention. The coating of the present invention itself can form a protective coating film with excellent corrosion resistance and weather resistance on a metal substrate, so that it can achieve a single-layer coating and also allows it to be applied as a single-coat paint. Therefore, the present invention provides a cured product of the above-mentioned coating. The cured product can be used as a protective coating film. The present invention also provides a coated product, wherein the cured product of the coating is formed on a substrate (coated product, including a cured product of the coating on a substrate and a substrate). The coated product is preferably, for example, a coated metal material, wherein the cured product of the coating is formed on a metal substrate.

[0261] Example

[0262] The following examples are used to illustrate the present invention in more detail. However, the present invention is not limited to these examples. Here, "parts" and "%" refer to "parts by mass" and "% by mass" respectively.

[0263] Preparation of modified polyisocyanate curing agent solution using alkyl esters of unsaturated dicarboxylic acids

[0264] Example 1

[0265] 179 parts of 3-aminopropyltrimethoxysilane and 0.07 parts of methoxyhydroquinone were placed in a flask and heated to 80°C. Air was passed into the liquid and bubbled to stir the mixture. After 220 parts of diisopropyl fumarate were added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 80°C for 1 hour and further aged at 50°C for 1 week to obtain 399 parts of 3-(N-(1,2-bis(isopropoxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane compound represented by formula (5), wherein R 2 is methyl, R 3 is propylene, R 4 and R 5 All are isopropyl groups, and n is 0). 400 parts of mineral spirits, 320 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 550 parts of "Duranate TSA-100" (product name, produced by Asahi Kasei Corporation, a modified isocyanurate-type polyisocyanate based on hexamethylene diisocyanate, isocyanate group content: 20.6 wt%) were placed in another flask and stirred at room temperature. 359 parts of a mixture containing 95% of 3-(N-(1,2-bis(isopropoxycarbonyl)ethyl)amino)propyltrimethoxysilane was added dropwise thereto over a period of 2 hours, and the resulting mixture was maintained at 60° C. for 1 hour and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-1) having a non-volatile concentration of 55%. The concentration of the isocyanate group contained in 1 g of the curing agent solution (HE-1) was 1.10 mmol / g (2.02 mmol / g component in terms of non-volatile content).

[0266] Example 2

[0267] 179 parts of 3-aminopropyltrimethoxysilane and 0.07 parts of methoxyhydroquinone were placed in a flask and heated to 80°C. Air was introduced into the liquid and bubbled to stir the mixture. After 251 parts of di(methylpropyl)fumarate were added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 80°C for 1 hour and further aged at 50°C for 1 week to obtain 430 parts of 3-(N-(1,2-bis(1-methylpropoxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane represented by formula (5), wherein R 2 is methyl, R 3 is propylene, R 4 and R 5400 parts of mineral spirits, 320 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 550 parts of "Duranate TSA-100" (product name, produced by Asahi Kasei Corporation, a modified isocyanurate-type polyisocyanate based on hexamethylene diisocyanate, isocyanate group content: 20.6 wt%) were placed in another flask and stirred at room temperature. 387 parts of a mixture containing 95% of 3-(N-(1,2-bis(1-methylpropoxycarbonyl)ethyl)amino)propyltrimethoxysilane was added dropwise thereto over a period of 2 hours, and the resulting mixture was kept at 60° C. for 1 hour and then cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-2) having a non-volatile concentration of 55%. The concentration of the isocyanate group in 1 g of the curing solution (HE-2) was 1.08 mmol / g (1.96 mmol / g component in terms of non-volatile content).

[0268] Example 3

[0269] 89.5 parts of 3-aminopropyltrimethoxysilane and 0.04 parts of methoxyhydroquinone were placed in a flask and heated to 80°C. Air was passed into the liquid and bubbled to stir the mixture. After 110 parts of diisopropyl fumarate were added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 80°C for 1 hour and further aged at 50°C for 1 week to obtain 199 parts of 3-(N-(1,2-bis(isopropoxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane compound represented by formula (5), wherein R 2 is methyl, R 3 is propylene, R 4 and R 5320 parts of mineral spirits, 256 parts of "Swasol 1000" (naphtha-based solvent, product name, produced by Maruzen Petrochemical Co., Ltd.) and 550 parts of "Duranate TSA-100" (modified isocyanurate type polyisocyanate based on hexamethylene diisocyanate, product name, produced by Asahi Kasei Corporation, isocyanate group content: 20.6 wt.%) were placed in another flask and stirred at room temperature. 162 parts of a mixture containing 95% of 3-(N-(1,2-bis(isopropoxycarbonyl)ethyl)amino)propyltrimethoxysilane was added dropwise thereto over a period of 2 hours, and the resulting mixture was kept at 60° C. for 1 hour and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-3) having a non-volatile concentration of 55%. The concentration of the isocyanate group in 1 g of the curing agent solution (HE-3) was 1.78 mmol / g (3.26 mmol / g component in terms of non-volatile content).

[0270] Example 4

[0271] 89.5 parts of 3-aminopropyltrimethoxysilane and 0.04 parts of methoxyhydroquinone were placed in a flask and heated to 80°C. Air was introduced into the liquid and bubbled to stir the mixture. After 110 parts of diisopropyl fumarate were added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 80°C for 1 hour and further aged at 50°C for 1 week to obtain 199 parts of 3-(N-(1,2-bis(isopropoxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane compound represented by formula (5), wherein R 2 is methyl, R 3 is propylene, R 4 and R 5All are isopropyl groups, and n is 0). 280 parts of mineral spirits, 224 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 550 parts of "Duranate TSA-100" (product name, produced by Asahi Kasei Corporation, a modified isocyanurate-type polyisocyanate based on hexamethylene diisocyanate, isocyanate group content: 20.6 wt%) were placed in another flask and stirred at room temperature. 108 parts of a mixture containing 95% of 3-(N-(1,2-bis(isopropoxycarbonyl)ethyl)amino)propyltrimethoxysilane was added dropwise thereto over a period of 2 hours, and the resulting mixture was maintained at 60° C. for 1 hour and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-4) having a non-volatile concentration of 56%. The concentration of the isocyanate group in 1 g of the curing agent solution (HE-4) was 2.09 mmol / g (3.72 mmol / g component in terms of non-volatile content).

[0272] Example 5

[0273] 221 parts of 3-aminopropyltriethoxysilane and 0.07 parts of methoxyhydroquinone were placed in a flask and heated to 80°C. Air was introduced into the liquid and bubbled to stir the mixture. After 220 parts of diisopropyl fumarate were added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 80°C for 1 hour and further aged at 50°C for 1 week to obtain 441 parts of 3-(N-(1,2-bis(isopropoxycarbonyl)ethyl)amino)propyltriethoxysilane (N-modified alkoxysilane compound represented by formula (5), wherein R 2 is ethyl, R 3 is propylene, R 4 and R 5400 parts of mineral spirits, 320 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 550 parts of "Duranate TSA-100" (modified isocyanurate-type polyisocyanate based on hexamethylene diisocyanate, product name, produced by Asahi Kasei Corporation, isocyanate group content: 20.6 wt.%) were placed in another flask and stirred at room temperature. 397 parts of a mixture containing 95% of 3-(N-(1,2-bis(isopropoxycarbonyl)ethyl)amino)propyltriethoxysilane was added dropwise thereto over a period of 2 hours, and the resulting mixture was kept at 60° C. for 1 hour and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-5) having a non-volatile concentration of 56%. The concentration of the isocyanate group in 1 g of the curing agent solution (HE-5) was 1.08 mmol / g (1.94 mmol / g component in terms of non-volatile content).

[0274] Example 6

[0275] 179 parts of 3-aminopropyltrimethoxysilane and 0.07 parts of methoxyhydroquinone were placed in a flask and heated to 80°C. Air was passed into the liquid and bubbled to stir the mixture. After 260 parts of diisopropyl fumarate were added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 80°C for 1 hour and further aged at 50°C for 1 week to obtain 439 parts of 3-(N-(1,2-bis(isopropoxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane compound represented by formula (5), wherein R 2 is methyl, R 3 is propylene, R 4 and R 5 are all isopropyl, and a mixture wherein n is 0).

[0276] 400 parts of mineral spirits, 280 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 550 parts of "Duranate TSA-100" (product name, produced by Asahi Kasei Corporation, a modified isocyanurate-type polyisocyanate based on hexamethylene diisocyanate, isocyanate group content: 20.6 wt%) were placed in another flask and the resulting mixture was stirred at room temperature. 394 parts of a mixture containing 86% of 3-(N-(1,2-bis(isopropoxycarbonyl)ethyl)amino)propyltrimethoxysilane was added dropwise thereto over a period of 2 hours, and the resulting mixture was maintained at 60° C. for 1 hour and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-6) having a non-volatile concentration of 55%. The concentration of the isocyanate group in 1 g of the curing agent solution (HE-6) was 1.11 mmol / g (2.03 mmol / g component in terms of non-volatile content).

[0277] Example 7

[0278] 179 parts of 3-aminopropyltrimethoxysilane and 0.07 parts of methoxyhydroquinone were placed in a flask and heated to 80° C., and air was passed into the liquid and bubbled to stir the mixture. After 180 parts of diisopropyl fumarate was added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 80° C. for 1 hour and further aged at 50° C. for 1 week to obtain 359 parts of 3-(N-(1,2-bis(isopropoxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane represented by formula (5), wherein R 2 is methyl, R 3 is propylene, R 4 and R 5 are all isopropyl, and a mixture wherein n is 0).

[0279] 400 parts of mineral spirits, 320 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 550 parts of "Duranate TSA-100" (product name, produced by Asahi Kasei Corporation, a modified isocyanurate-type polyisocyanate based on hexamethylene diisocyanate, isocyanate group content: 20.6 wt%) were placed in another flask and stirred at room temperature. 323 parts of a mixture containing 99% of 3-(N-(1,2-bis(isopropoxycarbonyl)ethyl)amino)propyltrimethoxysilane was added dropwise thereto over a period of 2 hours, and the resulting mixture was maintained at 60° C. for 1 hour and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-7) having a non-volatile concentration of 55%. The concentration of the isocyanate group in 1 g of the curing solution (HE-7) was 1.13 mmol / g (2.06 mmol / g component in terms of non-volatile content).

[0280] Comparative Example 1

[0281] 179 parts of 3-aminopropyltrimethoxysilane and 0.07 parts of methoxyhydroquinone were placed in a flask and heated to 80°C. Air was passed into the liquid and bubbled to stir the mixture. After 189 parts of diethyl fumarate were added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 80°C for 1 hour and further aged at 50°C for 1 week to obtain 368 parts of 3-(N-(1,2-bis(ethoxycarbonyl)ethyl)amino)propyltrimethoxysilane (in the case of N-modified alkoxysilane represented by formula (5), R 2 Corresponding to methyl, R 3 Corresponding to propylene, R 4 and R 5 All correspond to ethyl, and a mixture where n is 0).

[0282] 400 parts of mineral spirits, 320 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 550 parts of "Duranate TSA-100" (product name, produced by Asahi Kasei Corporation, a modified isocyanurate-type polyisocyanate based on hexamethylene diisocyanate, isocyanate group content: 20.6 wt%) were placed in another flask and stirred at room temperature. 331 parts of a mixture containing 95% of 3-(N-(1,2-bis(ethoxycarbonyl)ethyl)amino)propyltrimethoxysilane was added dropwise thereto over a period of 2 hours, and the resulting mixture was maintained at 60° C. for 1 hour and cooled to room temperature to obtain a polyisocyanate curing agent solution (HR-1) modified with a linear alkyl ester of an unsaturated dicarboxylic acid (non-volatile concentration: 54%). The concentration of the isocyanate group in 1 g of the curing agent solution (HR-1) was 1.12 mmol / g (2.08 mmol / g component in terms of non-volatile content).

[0283] Comparative Example 2

[0284] 179 parts of 3-aminopropyltrimethoxysilane and 0.07 parts of methoxyhydroquinone were placed in a flask and heated to 80°C, and air was passed into the liquid and bubbled to stir the mixture. After 251 parts of dibutyl maleate were added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 80°C for 1 hour and further aged at 50°C for 1 week to obtain 430 parts of 3-(N-(1,2-bis(butoxycarbonyl)ethyl)amino)propyltrimethoxysilane (in the case of the N-modified alkoxysilane represented by formula (5), R 2 is methyl, R 3 is propylene, R 4 and R 5 are all n-butyl, and a mixture in which n is 0).

[0285] 400 parts of mineral spirits, 320 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 550 parts of "Duranate TSA-100" (product name, produced by Asahi Kasei Corporation, a modified isocyanurate-type polyisocyanate based on hexamethylene diisocyanate, isocyanate group content: 20.6 wt.%) were placed in another flask and stirred at room temperature. 387 parts of a mixture containing 95% of 3-(N-(1,2-bis(butoxycarbonyl)ethyl)amino)propyltrimethoxysilane was added dropwise thereto over a period of 2 hours, and the resulting mixture was maintained at 60° C. for 2 hours and then cooled to room temperature to obtain a polyisocyanate curing agent solution (HR-2) modified with a linear alkyl ester of an unsaturated dicarboxylic acid (non-volatile concentration: 55%). The concentration of the isocyanate group in 1 g of the curing agent solution (HR-2) was 1.08 mmol / g (1.96 mmol / g component in terms of non-volatile content).

[0286] Comparative Example 3

[0287] 400 parts of mineral spirits, 320 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 880 parts of "Duranate TSA-100" (product name, produced by Asahi Kasei Corporation, a modified isocyanurate type polyisocyanate based on hexamethylene diisocyanate, isocyanate group content: 20.6 wt%) were placed in a container and stirred at room temperature to obtain a polyisocyanate curing agent solution (HR-3) not modified with aminoalkoxysilane or unsaturated carboxylic acid dialkyl ester (non-volatile concentration: 55%). The concentration of the isocyanate group in 1 g of the curing agent solution (HR-3) was 2.70 mmol / g (4.90 mmol / g component in terms of non-volatile content).

[0288] Comparative Example 4

[0289] 179 parts of 3-aminopropyltrimethoxysilane and 0.07 parts of methoxyhydroquinone were placed in a flask and heated to 80° C. Air was passed into the liquid and bubbled to stir the mixture, thereby obtaining 179 parts of a mixture.

[0290] 400 parts of mineral spirits, 180 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 550 parts of "Duranate TSA-100" (product name, produced by Asahi Kasei Corporation, a modified isocyanurate-type polyisocyanate based on hexamethylene diisocyanate, isocyanate group content: 20.6 wt%) were placed in another flask and the resulting mixture was stirred at room temperature. After 161 parts of a mixture containing 3-(N-(1,2-bis(1-methylpropoxycarbonyl)ethyl)amino)propyltrimethoxysilane was added dropwise thereto over a period of 2 hours, the resulting mixture was maintained at 60° C. for 1 hour and then cooled to room temperature in an attempt to obtain a polyisocyanate curing agent solution (HR-4) (non-volatile concentration: 54%) modified with aminoalkoxysilane but not modified with unsaturated carboxylic acid dialkyl ester. However, the curing agent precipitated and the obtained liquid entered a non-uniform state. Since it was found that the obtained liquid could not be used as a curing agent solution, the subsequent evaluation was stopped. The concentration of isocyanate groups in 1 g of the curing agent solution (HR-4) was 1.39 mmol / g (2.56 mmol / g component in terms of non-volatile content).

[0291] Table 1 below shows the composition, blending molar ratio or reaction molar ratio, state, and residual NCO (%) in each curing agent solution obtained in Examples and Comparative Examples.

[0292] Table 1

[0293]

[0294] Note 1: Actual reaction molar ratio of primary amino group to unsaturated carbon-carbon bond: The actual reaction molar ratio refers to the molar ratio of aminoalkoxysilane added to unsaturated carboxylic acid dialkyl ester. When an excess of unsaturated carboxylic acid dialkyl ester is mixed, the excess unsaturated carboxylic acid dialkyl ester does not undergo addition reaction and remains unreacted. Therefore, the numerical value of the reaction ratio is different from the numerical value of the blending ratio.

[0295] Note 2: Reaction molar ratio of amino group to isocyanate group: The amino group in the reaction molar ratio refers to the total amount of amino groups, that is, the total amount of primary amino groups and 1,2-bis(alkoxycarbonyl)ethylamino groups derived from alkoxysilanes having unreacted amino groups.

[0296] Evaluation Project

[0297] (*) State of curing agent solution

[0298] Each curing solution was sealed in a 250 ml glass bottle and evaluated according to the following criteria: In the table, Grade A was judged as "acceptable", and Grades B and C were judged as "failed".

[0299] The initial state (just after production) and the state after storage for 1 year were visually observed in an atmosphere of 25° C. and 60% humidity in a sealed constant temperature chamber.

[0300] A: No abnormality; no two-phase separation, turbidity, and precipitation were observed in the curing agent solution.

[0301] B: Two-phase separation or turbidity was observed in the curing agent solution.

[0302] C: The curing agent precipitates out from the curing agent solution.

[0303] (*) Residual NCO in curing agent solution (%)

[0304] The polyisocyanate curing agent solutions obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were calculated according to the following formula. The higher the value, the better.

[0305] [(Total number of moles of NCO groups contained in the curing agent solution 12 months after the preparation of the curing agent solution) / (Total number of moles of NCO groups contained in the curing agent solution immediately after the preparation of the curing agent solution)]×100(%)

[0306] The storage conditions were a temperature of 25° C. and a humidity of 60%. The total mole number of NCO groups was calculated by adding 10 ml of a 0.1 mol / L dibutylamine solution to 0.1 g of a sample to react the NCO groups, and then titrating the remaining dibutylamine with an aqueous hydrochloric acid solution by using bromophenol blue as a titration indicator.

[0307] Preparation of modified polyisocyanate curing agent solution using alkyl esters of unsaturated monocarboxylic acids

[0308] Example 8

[0309] 179 parts of 3-aminopropyltrimethoxysilane, 0.07 parts of methoxyhydroquinone and 60 parts of "Swasol1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) were placed in a flask. Air was passed into the liquid and bubbled to stir the mixture. After 128 parts of isobutyl acrylate was added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 50° C. for 1 hour and further aged at 50° C. for 1 week to obtain 313 parts of 3-(N-(2-(isobutoxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane represented by formula (6) in a molar ratio of 74 / 13 / 13, wherein R 2is methyl, R 3 is propylene, R 6 isobutyl, and n is 0), 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(isobutyloxycarbonyl))amino)propyltrimethoxysilane (compounds represented by formula (8) wherein R 2 is methyl, R 3 is propylene, R 6 is an isobutyl group, and n is a mixture of 0. The total amount of primary and secondary amino groups in 1 g of the mixture was 2.78 mmol.

[0310] 282 parts of mineral spirits, 231 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" (product name, produced by Asahi Kasei Corporation, a modified isocyanurate type polyisocyanate based on hexamethylene diisocyanate, isocyanate group content: 20.6 wt %) were placed in another flask and the resulting mixture was stirred at room temperature. After adding 132 parts of a mixture containing 3-(N-(2-(isobutoxycarbonyl)ethyl)amino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(isobutoxycarbonyl)ethyl)amino)propyltrimethoxysilane in a molar ratio of 74 / 13 / 13 over a period of 2 hours, the resulting mixture was kept at 60° C. for 2 hours and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-8) having a non-volatile concentration of 55%. The concentration of the isocyanate group in the curing agent solution (HE-8) was 1.82 mmol / g (3.31 mmol / g component in terms of non-volatile content).

[0311] Example 9

[0312] 179 parts of 3-aminopropyltrimethoxysilane, 0.07 parts of methoxyhydroquinone and 6 parts of "Swasol1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) were placed in a flask. Air was introduced into the liquid and bubbled to stir the mixture. After 128 parts of tert-butyl acrylate was added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 50° C. for 1 hour and further aged at 50° C. for 1 week to obtain 313 parts of 3-(N-(2-(tert-butoxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane represented by formula (6) in a molar ratio of 78 / 11 / 11, wherein R 2 is methyl, R 3 is propylene, R 6is tert-butyl, and n is 0), 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(tert-butyloxycarbonyl))amino)propyltrimethoxysilane (compounds represented by formula (8) wherein R 2 is methyl, R 3 is propylene, R 6 is a tert-butyl group, and n is a mixture of 0. The total amount of primary and secondary amino groups in 1 g of the mixture was 2.84 mmol.

[0313] 281 parts of mineral spirits, 230 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. After 130 parts of a mixture containing 3-(N-(2-(tert-butoxycarbonyl)ethyl)amino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(tert-butoxycarbonyl)ethyl)amino)propyltrimethoxysilane in a molar ratio of 78 / 11 / 11 was added dropwise thereto over a period of 2 hours, the resulting mixture was maintained at 60° C. for 2 hours and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-9) having a non-volatile concentration of 55%. The concentration of the isocyanate group in the curing agent solution (HE-9) was 1.83 mmol / g (3.32 mmol / g component in terms of non-volatile content).

[0314] Example 10

[0315] 89.5 parts of 3-aminopropyltrimethoxysilane, 0.04 parts of methoxyhydroquinone and 4 parts of "Swasol1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) were placed in a flask. Air was passed into the liquid and bubbled to stir the mixture. After 92 parts of 2-ethylhexyl acrylate were added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 50° C. for 1 hour and further aged at 50° C. for 1 week to obtain 186 parts of 3-(N-(2-(2-ethylhexyloxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane represented by formula (6) in a molar ratio of 66 / 17 / 17, wherein R 2 is methyl, R 3 is propylene, R 6 is 2-ethylhexyl, and n is 0), 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(2-ethylhexyloxycarbonyl))amino)propyltrimethoxysilane (a compound represented by formula (8) wherein R 2 is methyl, R3 is propylene, R 6 is 2-ethylhexyl, and n is a mixture of 0. The total amount of primary and secondary amino groups in 1 g of the mixture was 2.24 mmol.

[0316] 296 parts of mineral spirits, 242 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. 164 parts of a mixture containing 3-(N-(2-(2-ethylhexyloxycarbonyl)ethyl)amino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(2-ethylhexyloxycarbonyl)ethyl)amino)propyltrimethoxysilane in a molar ratio of 66 / 17 / 17 was added dropwise thereto over a period of 2 hours, and the resulting mixture was maintained at 60° C. for 2 hours and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-10) having a non-volatile concentration of 55%. The concentration of the isocyanate group in the curing agent solution (HE-10) was 1.73 mmol / g (3.15 mmol / g component in terms of non-volatile content).

[0317] Embodiment 11

[0318] 89.5 parts of 3-aminopropyltrimethoxysilane, 0.04 parts of methoxyhydroquinone and 4 parts of "Swasol1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) were placed in a flask. Air was introduced into the liquid and bubbled to stir the mixture. After 104 parts of isobornyl acrylate were added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 50° C. for 1 hour and further aged at 50° C. for 1 week to obtain 198 parts of 3-(N-(2-(isobornyloxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane represented by formula (6) in a molar ratio of 74 / 13 / 13, wherein R 2 is methyl, R 3 is propylene, R 6 isobornyl, and n is 0), 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(isobornyloxycarbonyl))amino)propyltrimethoxysilane (compounds represented by formula (8) wherein R 2 is methyl, R 3 is propylene, R 6 isobornyl, and n is 0). The total amount of primary and secondary amino groups in 1 g of the mixture was 2.20 mmol.

[0319] 297 parts of mineral spirits, 243 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. After 167 parts of a mixture containing 3-(N-(2-(isobornyloxycarbonyl)ethyl)amino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(isobornyloxycarbonyl)ethyl)amino)propyltrimethoxysilane in a molar ratio of 74 / 13 / 13 was added dropwise thereto over a period of 2 hours, the resulting mixture was maintained at 60° C. for 2 hours and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-11) having a non-volatile concentration of 55%. The concentration of the isocyanate group in the curing agent solution (HE-11) was 1.73 mmol / g (3.14 mmol / g component in terms of non-volatile content).

[0320] Example 12

[0321] 221 parts of 3-aminopropyltriethoxysilane, 0.07 parts of methoxyhydroquinone and 7 parts of "Swasol1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) were placed in a flask. Air was introduced into the liquid and bubbled to stir the mixture. After 128 parts of isobutyl acrylate was added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 50° C. for 1 hour and further aged at 50° C. for 1 week to obtain 356 parts of 3-(N-(2-(isobutoxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane represented by formula (6) in a molar ratio of 80 / 10 / 10, wherein R 2 is methyl, R 3 is propylene, R 6 isobutyl, and n is 0), 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(isobutyloxycarbonyl))amino)propyltrimethoxysilane (compounds represented by formula (8) wherein R 2 is methyl, R 3 is propylene, R 6is an isobutyl group, and n is 0). The total amount of primary and secondary amino groups in 1 g of the mixture was 2.53 mmol. 298 parts of mineral spirits, 235 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. After 145 parts of a mixture containing 3-(N-(2-(isobutoxycarbonyl)ethyl)amino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(isobutoxycarbonyl)ethyl)amino)propyltrimethoxysilane in a molar ratio of 80 / 10 / 10 was added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 60° C. for 2 hours and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-12) having a non-volatile concentration of 55%. The concentration of the isocyanate group in the curing agent solution (HE-12) was 1.78 mmol / g (3.24 mmol / g component in terms of non-volatile content).

[0322] Example 13

[0323] 179 parts of 3-aminopropyltrimethoxysilane, 0.07 parts of methoxyhydroquinone and 60 parts of "Swasol1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) were placed in a flask. Air was introduced into the liquid and bubbled to stir the mixture. After 128 parts of tert-butyl acrylate was added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 50° C. for 1 hour and further aged at 50° C. for 1 week to obtain 313 parts of 3-(N-(2-(tert-butoxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane represented by formula (6) in a molar ratio of 78 / 11 / 11, wherein R 2 is methyl, R 3 is propylene, R 6 is tert-butyl, and n is 0), 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(tert-butyloxycarbonyl))amino)propyltrimethoxysilane (compounds represented by formula (8) wherein R 2 is methyl, R 3 is propylene, R 6 is a tert-butyl group, and n is a mixture of 0. The total amount of primary and secondary amino groups in 1 g of the mixture was 2.84 mmol.

[0324] 348 parts of mineral spirits, 284 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. After 285 parts of a mixture containing 3-(N-(2-(tert-butoxycarbonyl)ethyl)amino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(tert-butoxycarbonyl)ethyl)amino)propyltrimethoxysilane in a molar ratio of 78 / 11 / 11 was added dropwise thereto over a period of 2 hours, the resulting mixture was maintained at 60° C. for 2 hours and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-13) having a non-volatile concentration of 55%. The concentration of the isocyanate group in the curing agent solution (HE-13) was 1.16 mmol / g (2.11 mmol / g component in terms of non-volatile content).

[0325] Embodiment 14

[0326] 89.5 parts of 3-aminopropyltrimethoxysilane, 0.04 parts of methoxyhydroquinone and 4 parts of "Swasol1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) were placed in a flask. Air was introduced into the liquid and bubbled to stir the mixture. After 104 parts of isobornyl acrylate were added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 50° C. for 1 hour and further aged at 50° C. for 1 week to obtain 198 parts of 3-(N-(2-(isobornyloxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane represented by formula (6) in a molar ratio of 74 / 13 / 13, wherein R 2 is methyl, R 3 is propylene, R 6 isobornyl, and n is 0), 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(isobornyloxycarbonyl))amino)propyltrimethoxysilane (compounds represented by formula (8) wherein R 2 is methyl, R 3 is propylene, R 6 isobornyl, and n is 0). The total amount of primary and secondary amino groups in 1 g of the mixture was 2.20 mmol.

[0327] 273 parts of mineral spirits, 223 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. After 111 parts of a mixture containing 3-(N-(2-(isobornyloxycarbonyl)ethyl)amino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(isobornyloxycarbonyl)ethyl)amino)propyltrimethoxysilane in a molar ratio of 74 / 13 / 13 was added dropwise over a period of 2 hours, the resulting mixture was maintained at 60° C. for 2 hours and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-14) having a non-volatile concentration of 55%. The concentration of the isocyanate group in the curing agent solution (HE14) was 1.99 mmol / g (3.62 mmol / g component in terms of non-volatile content).

[0328] Embodiment 15

[0329] 179 parts of 3-aminopropyltrimethoxysilane, 0.07 parts of methoxyhydroquinone and 6 parts of "Swasol1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) were placed in a flask. Air was passed into the liquid and bubbled to stir the mixture. After 141 parts of isobutyl acrylate was added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 50° C. for 1 hour and further aged at 50° C. for 1 week to obtain 326 parts of 3-(N-(2-(isobutoxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane represented by formula (6) in a molar ratio of 77 / 6 / 17, wherein R 2 is methyl, R 3 is propylene, R 6 isobutyl, and n is 0), 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(isobutyloxycarbonyl))amino)propyltrimethoxysilane (compounds represented by formula (8) wherein R 2 is methyl, R 3 is propylene, R 6 is an isobutyl group, and n is a mixture of 0. The total amount of primary and secondary amino groups in 1 g of the mixture was 2.55 mmol.

[0330] 308 parts of mineral spirits, 252 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. After 192 parts of a mixture containing 3-(N-(2-(isobutoxycarbonyl)ethyl)amino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(isobutoxycarbonyl)ethyl)amino)propyltrimethoxysilane in a molar ratio of 77 / 6 / 17 was dropped thereinto over a period of 2 hours, the resulting mixture was maintained at 60° C. for 2 hours and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-15) having a non-volatile concentration of 55%. The concentration of the isocyanate group in the curing agent solution (HE-15) was 1.57 mmol / g (2.85 mmol / g component in terms of non-volatile content).

[0331] Example 16

[0332] 110.5 parts of 3-aminopropyltriethoxysilane, 0.04 parts of methoxyhydroquinone and 4 parts of "Swasol1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) were placed in a flask. Air was introduced into the liquid and bubbled to stir the mixture. After 93.6 parts of isobornyl acrylate were added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 50° C. for 1 hour and further aged at 50° C. for 1 week to obtain 208 parts of 3-(N-(2-(isobornyloxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane represented by formula (6) in a molar ratio of 80 / 15 / 5, wherein R 2 is methyl, R 3 is propylene, R 6 isobornyl, and n is 0), 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(isobornyloxycarbonyl))amino)propyltrimethoxysilane (N-modified alkoxysilane compounds represented by formula (8) wherein R 2 is methyl, R 3 is propylene, R 6 isobornyl, and n is 0). The total amount of primary and secondary amino groups in 1 g of the mixture was 2.28 mmol.

[0333] 271 parts of mineral spirits, 222 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. After 108 parts of a mixture containing 3-(N-(2-(isobornyloxycarbonyl)ethyl)amino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(isobornyloxycarbonyl)ethyl)amino)propyltrimethoxysilane in a molar ratio of 80 / 15 / 15 was added dropwise thereto over a period of 2 hours, the resulting mixture was maintained at 60° C. for 2 hours and cooled to room temperature to obtain a polyisocyanate curing agent solution (HE-16) having a non-volatile concentration of 55%. The concentration of the isocyanate group in the curing agent solution (HE-16) was 2.01 mmol / g (3.65 mmol / g component in terms of non-volatile content).

[0334] Comparative Example 5

[0335] 179 parts of 3-aminopropyltrimethoxysilane, 0.07 parts of methoxyhydroquinone and 80 parts of "Swasol1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) were placed in a flask. Air was introduced into the liquid and bubbled to stir the mixture. After 128 parts of n-butyl acrylate was added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 50° C. for 1 hour and further aged at 50° C. for 1 week to obtain 313 parts of 3-(N-(2-(n-butoxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane compound represented by formula (6) containing 66 / 17 / 17 molar ratios, wherein R 2 is methyl, R 3 is propylene, R 6 is n-butyl, and n is 0), 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(n-butyloxycarbonyl))amino)propyltrimethoxysilane (compounds represented by formula (8) wherein R 2 is methyl, R 3 is propylene, R 6 is a mixture of n and n is 0. The total amount of primary and secondary amino groups in 1 g of the mixture was 2.65 mmol.

[0336] 285 parts of mineral spirits, 233 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. After 139 parts of a mixture containing 3-(N-(2-(n-butoxycarbonyl)ethyl)amino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(n-butoxycarbonyl)ethyl)amino)propyltrimethoxysilane in a molar ratio of 66 / 17 / 17 was added thereto over a period of 2 hours, the resulting mixture was maintained at 60° C. for 2 hours and cooled to room temperature to obtain a polyisocyanate curing agent solution (HR-5) having a non-volatile concentration of 55%. The concentration of the isocyanate group in the curing agent solution (HR-5) was 1.80 mmol / g (3.28 mmol / g component in terms of non-volatile content).

[0337] Comparative Example 6

[0338] 179 parts of 3-aminopropyltrimethoxysilane, 0.07 parts of methoxyhydroquinone and 6 parts of "Swasol1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) were placed in a flask. Air was passed into the liquid and bubbled to stir the mixture. After 100 parts of ethyl acrylate was added dropwise thereto over a period of 2 hours, the resulting mixture was kept at 50° C. for 1 hour and further aged at 50° C. for 1 week to obtain 285 parts of 3-(N-(2-(ethoxycarbonyl)ethyl)amino)propyltrimethoxysilane (N-modified alkoxysilane represented by formula (6) in a molar ratio of 66 / 17 / 17, wherein R 2 is methyl, R 3 is propylene, R 6 is ethyl, and n is 0), 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(ethoxycarbonyl))amino)propyltrimethoxysilane (a compound represented by formula (8) in which R 2 is methyl, R 3 is propylene, R 6 is ethyl, and n is 0). The total amount of primary and secondary amino groups in 1 g of the mixture was 2.91 mmol.

[0339] 297 parts of mineral spirits, 243 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. After 169 parts of a mixture containing 3-(N-(2-(ethoxycarbonyl)ethyl)amino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane and 3-(N,N-bis(2-(ethoxycarbonyl)ethyl)amino)propyltrimethoxysilane in a molar ratio of 66 / 17 / 17 was dropped over a period of 2 hours, the resulting mixture was maintained at 60° C. for 2 hours and cooled to room temperature to obtain a polyisocyanate curing agent solution (HR-6) having a non-volatile concentration of 55%. The concentration of the isocyanate group contained in the curing agent solution (HR-6) was 1.62 mmol / g (2.95 mmol / g component in terms of non-volatile content).

[0340] Comparative Example 7

[0341] 225 parts of mineral spirits, 184 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" were placed in a container, and the resulting mixture was stirred at room temperature to obtain a polyisocyanate curing agent solution (HR-7) not modified with aminoalkoxysilane or unsaturated carboxylic acid dialkyl ester (non-volatile concentration: 55%). The concentration of the isocyanate group in 1 g of the curing agent solution (HR-7) was 2.70 mmol / g (4.91 mmol / g component in terms of non-volatile content).

[0342] Comparative Example 8

[0343] 179 parts of 3-aminopropyltrimethoxysilane, 0.07 parts of methoxyhydroquinone and 4 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., naphtha-based solvent) were placed in a flask and heated to 80° C. Air was passed into the liquid and bubbled to stir the mixture, thereby obtaining 183 parts of a mixture.

[0344] 254 parts of mineral spirits, 208 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. After 67 parts of a mixture containing 3-aminopropyltrimethoxysilane were added dropwise over a period of 2 hours, the resulting mixture was kept at 60°C for 1 hour and cooled to room temperature in an attempt to obtain a polyisocyanate curing agent solution (HR-8) modified with aminoalkoxysilane but not modified with unsaturated carboxylic acid dialkyl ester (non-volatile concentration: 54%). However, the curing agent precipitated and the liquid entered a non-uniform state and could not be used as a curing agent solution. Therefore, further evaluation was stopped.

[0345] Table 2

[0346]

[0347] Note 3: The molar ratio of 3-(N-(2-(alkoxycarbonyl)ethyl)amino)propyltrialkoxysilane, 3-aminopropyltrialkoxysilane and 3-(N,N-di(2-(alkoxycarbonyl)ethyl)amino)propyltrialkoxysilane in the mixture is calculated by converting the proton integral value obtained by H-NMR (proton nuclear magnetic resonance analysis).

[0348] Evaluation Project

[0349] (*) State of curing agent solution

[0350] After production, each curing agent solution was sealed in a 250 ml glass bottle, and its state was visually observed after storage in a sealed state in a thermostatic chamber at 20° C. and 60% humidity for 3 months, and its state was visually observed after storage in a sealed state in a thermostatic chamber at 5° C. and 60% humidity for 2 weeks. In Table 2, Grade A was judged as pass, and Grade B and Grade C were judged as fail.

[0351] A: Two-phase separation, turbidity and precipitation of the curing agent solution were not observed in the curing agent solution.

[0352] B: Two-phase separation or turbidity of the curing agent solution was observed.

[0353] C: Starch slurry polymer precipitates from the curing agent solution.

[0354] Production of modified polyisocyanates using saturated carboxylic acid alkyl esters

[0355] Embodiment 17

[0356] 89 parts of methyl acetate (which is a linear saturated ester) and 179 parts of 3-aminopropyltrimethoxysilane are placed in a flask under a nitrogen atmosphere and stirred at room temperature. 0.58 parts of a 28% methanol solution of sodium methoxide are added as a catalyst, stirred, heated to 70°C, and aged for 1 day. The conversion rate of 3-aminopropyltrimethoxysilane is 97%, and methanol is produced as a by-product in an approximately equimolar amount to the reacted 3-aminopropyltrimethoxysilane. Then, after adding 1.1 parts of bis(2-ethylhexyl)phosphoric acid as an acidic compound, the resulting mixture is concentrated by removing methanol and remaining methyl acetate at 50°C to 70°C under reduced pressure. Finally, 222 parts of crude 3-acetamidopropyltrimethoxysilane containing catalyst-derived residues (a compound represented by formula (7), wherein R 2 is methyl, R 3 is propylene, R 7 is methyl, and n is 0) as an N-acylated intermediate. Under a nitrogen atmosphere, 250 parts of mineral spirits, 204 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. 55 parts of crude 3-acetamidopropyltrimethoxysilane were added thereto, and the resulting mixture was heated at 110° C. for 10 hours to add the secondary amide group to the isocyanate group, thereby obtaining a polyisocyanate curing agent solution (HE-17) having a non-volatile concentration of 55%. The concentration of the isocyanate group in the curing agent solution (HE-17) was 2.14 mmol / g (3.89 mmol / g component in terms of non-volatile content).

[0357] Embodiment 18

[0358] 89 parts of methyl acetate (which is a linear saturated ester) and 179 parts of 3-aminopropyltrimethoxysilane are placed in a flask under a nitrogen atmosphere and stirred at room temperature. 0.58 parts of a 28% methanol solution of sodium methoxide are added as a catalyst, stirred, heated to 70°C, and aged for 1 day. The conversion rate of 3-aminopropyltrimethoxysilane is 97%, and methanol is produced as a by-product in an approximately equimolar amount to the reacted 3-aminopropyltrimethoxysilane. Then, after adding 0.58 parts of p-toluenesulfonic acid as an acidic compound, the resulting mixture is concentrated by removing methanol and remaining methyl acetate at 50°C to 70°C under reduced pressure. Finally, 222 parts of crude 3-acetamidopropyltrimethoxysilane containing catalyst-derived residues (a compound represented by formula (7), wherein R 2 is methyl, R 3 is propylene, R 7is methyl, and n is 0) as an N-acylated intermediate. Under a nitrogen atmosphere, 62 parts of butyl acetate and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. 55 parts of crude 3-acetamidopropyltrimethoxysilane were added thereto, and the mixture was heated at 110° C. for 7 hours to add the secondary amide group to the isocyanate group, thereby obtaining a polyisocyanate curing agent solution (HE-18) having a non-volatile concentration of 90%. The concentration of the isocyanate group in the curing agent solution (HE-18) was 3.49 mmol / g (3.88 mmol / g component in terms of non-volatile content).

[0359] Embodiment 19

[0360] 89 parts of methyl acetate (which is a linear saturated ester) and 179 parts of 3-aminopropyltrimethoxysilane are placed in a flask under a nitrogen atmosphere and stirred at room temperature. 0.58 parts of a 28% methanol solution of sodium methoxide is added thereto as a catalyst, and the resulting mixture is stirred, heated to 70°C, and aged for 1 day. The conversion rate of 3-aminopropyltrimethoxysilane is 97%, and methanol is produced as a by-product in an approximately equimolar amount to the reacted 3-aminopropyltrimethoxysilane. Then, after adding 1.1 parts of bis(2-ethylhexyl)phosphoric acid as an acidic compound, the resulting mixture is concentrated by removing methanol and remaining methyl acetate at 50°C to 70°C under reduced pressure. Finally, 222 parts of crude 3-acetamidopropyltrimethoxysilane containing a catalyst-derived residue (a compound represented by formula (7), wherein R 2 is methyl, R 3 is propylene, R 7 is methyl, and n is 0) as an N-acylated intermediate. Under a nitrogen atmosphere, 62 parts of butyl acetate and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. 55 parts of crude 3-acetamidopropyltrimethoxysilane were added thereto, and the resulting mixture was heated at 110° C. for 7 hours to add the secondary amide group to the isocyanate group, thereby obtaining a polyisocyanate curing agent solution (HE-19) having a non-volatile concentration of 90%. The concentration of the isocyanate group in the curing agent solution (HE-19) was 3.49 mmol / g (3.88 mmol / g component in terms of non-volatile content).

[0361] Embodiment 20

[0362] 89 parts of methyl acetate (which is a linear saturated ester) and 179 parts of 3-aminopropyltrimethoxysilane are placed in a flask under a nitrogen atmosphere and stirred at room temperature. 0.58 parts of a 28% methanol solution of sodium methoxide are added as a catalyst, stirred, heated to 70°C, and aged for 1 day. The conversion rate of 3-aminopropyltrimethoxysilane is 97%, and methanol is produced as a by-product in an approximately equimolar amount to the reacted 3-aminopropyltrimethoxysilane. Then, after adding 1.03 parts of dodecylbenzenesulfonic acid as an acidic compound, the resulting mixture is concentrated by removing methanol and remaining methyl acetate at 50°C to 70°C under reduced pressure. Finally, 222 parts of crude 3-acetamidopropyltrimethoxysilane containing catalyst-derived residues (a compound represented by formula (7), wherein R 2 is methyl, R 3 is propylene, R 7 is methyl, and n is 0) as an N-acylated intermediate. Under a nitrogen atmosphere, 62 parts of butyl acetate and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. 55 parts of crude 3-acetamidopropyltrimethoxysilane were added thereto, and the mixture was heated at 110° C. for 7 hours to add the secondary amide group to the isocyanate group, thereby obtaining a polyisocyanate curing agent solution (HE-20) having a non-volatile concentration of 90%. The concentration of the isocyanate group in the curing agent solution (HE-20) was 3.49 mmol / g (3.88 mmol / g component in terms of non-volatile content).

[0363] Embodiment 21

[0364] 190 parts of methyl octanoate (which is a linear saturated ester) and 179 parts of 3-aminopropyltrimethoxysilane are placed in a flask under a nitrogen atmosphere and stirred at room temperature. 1.16 parts of a 28% methanol solution of sodium methoxide are added thereto as a catalyst, and the resulting mixture is stirred, heated to 70°C, and aged for 2 days. The conversion rate of 3-aminopropyltrimethoxysilane is 94%, and methanol is produced as a by-product in an approximately equimolar amount to the reacted 3-aminopropyltrimethoxysilane. Then, after adding 2.2 parts of bis(2-ethylhexyl)phosphoric acid as an acidic compound, the resulting mixture is concentrated by removing methanol at 50°C to 70°C under reduced pressure to obtain 331 parts of crude 3-octanamidopropyltrimethoxysilane containing a catalyst-derived residue (a compound represented by formula (7), wherein R 2 is methyl, R 3 is propylene, R 7Is heptyl, and n is 0) as an N-acylated intermediate. Under a nitrogen atmosphere, 65 parts of butyl acetate and 500 parts of "Duranate TSA-100" are placed in another flask, and the resulting mixture is stirred at room temperature. 82 parts of crude 3-octanamidopropyltrimethoxysilane are added thereto, and the resulting mixture is heated at 110°C for 12 hours to add the secondary amide group to the isocyanate group. After cooling, the resulting mixture is filtered through filter paper to obtain a polyisocyanate curing agent solution (HE-21) with a non-volatile concentration of 90%. The concentration of the isocyanate group in the curing agent solution (HE-21) is 3.18mmol / g (3.53mmol / g component in terms of non-volatile content).

[0365] Embodiment 22

[0366] 106 parts of methyl propionate (which is a linear saturated ester) and 179 parts of 3-aminopropyltrimethoxysilane are placed in a flask under a nitrogen atmosphere and stirred at room temperature. 0.58 parts of a 28% methanol solution of sodium methoxide is added thereto as a catalyst, and the resulting mixture is stirred, heated to 70°C, and aged for 2 days. The conversion rate of 3-aminopropyltrimethoxysilane is 97%, and methanol is produced as a by-product in an approximately equimolar amount with the reacted 3-aminopropyltrimethoxysilane. Then, after adding 1.1 parts of bis(2-ethylhexyl)phosphoric acid as an acidic compound, the resulting mixture is concentrated by removing methanol and the remaining methyl propionate at 50°C to 80°C under reduced pressure, thereby obtaining 236 parts of crude 3-propionamidopropyltrimethoxysilane containing catalyst-derived residues (a compound represented by formula (7), wherein R 2 is methyl, R 3 is propylene, R 7 is ethyl, and n is 0) as an N-acylated intermediate. Under a nitrogen atmosphere, 60 parts of butyl acetate and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. 41 parts of crude 3-propionamidopropyltrimethoxysilane were added thereto, and the resulting mixture was heated at 110° C. for 9 hours to add the secondary amide group to the isocyanate group, thereby obtaining a polyisocyanate curing agent solution (HE-22) having a non-volatile concentration of 90%. The concentration of the isocyanate group in the curing agent solution (HE-22) was 3.67 mmol / g (4.08 mmol / g component in terms of non-volatile content).

[0367] Embodiment 23

[0368] 96 parts of methyl acetate (which is a linear saturated ester) and 179 parts of 3-aminopropyltrimethoxysilane are placed in a flask under a nitrogen atmosphere and stirred at room temperature. 0.58 parts of a 28% methanol solution of sodium methoxide is added thereto as a catalyst, and the resulting mixture is stirred, heated to 70°C, and aged for 1 day. The conversion rate of 3-aminopropyltrimethoxysilane is 98%, and methanol is produced as a by-product in an approximately equimolar amount to the reacted 3-aminopropyltrimethoxysilane. After then adding 1.1 parts of bis(2-ethylhexyl)phosphoric acid as an acidic compound, the resulting mixture is concentrated by removing methanol and the remaining methyl acetate at 50°C to 70°C under reduced pressure, and further distilled under reduced pressure at a vacuum degree of 4 mmHg to obtain 200 parts of purified 3-acetamidopropyltrimethoxysilane (a compound represented by formula (7), wherein R 2 is methyl, R 3 is propylene, R 7 Is methyl, and n is 0) as an N-acylated intermediate. Under a nitrogen atmosphere, 114 parts of propylene glycol monomethyl ether acetate and 500 parts of "Sumidur N-3300" (product name, produced by Sumitomo Covestro Urethane Co., Ltd., isocyanurate polyisocyanate based on hexamethylene diisocyanate, isocyanate group content: 21.8wt%) are placed in another flask and stirred at room temperature. 144 parts of purified 3-acetamidopropyltrimethoxysilane are added thereto, and the resulting mixture is heated at 110°C for 9 hours to add the secondary amide group to the isocyanate group, thereby obtaining a polyisocyanate curing agent solution (HE-23) having a non-volatile concentration of 85%. The concentration of the isocyanate group in the curing agent solution (HE-23) is 2.50mmol / g (2.94mmol / g component in terms of non-volatile content).

[0369] Embodiment 24

[0370] Under a nitrogen atmosphere, 206 parts of 3,3,5-trimethylhexanoic acid methyl ester (which is a branched saturated ester) having two hydrogen atoms at the α-position and 179 parts of 3-aminopropyltrimethoxysilane were placed in a flask and stirred at room temperature. 1.16 parts of a 28% methanol solution of sodium methoxide were added as a catalyst, stirred, heated to 70°C, and aged for 2 days. The conversion rate of 3-aminopropyltrimethoxysilane was 71%, and methanol was produced as a by-product in an approximately equimolar amount with the reacted 3-aminopropyltrimethoxysilane. After then adding 2.2 parts of bis(2-ethylhexyl)phosphoric acid as an acidic compound, the resulting mixture was concentrated by removing methanol and remaining methyl acetate at 50°C to 70°C under reduced pressure, and further distilled under reduced pressure at a vacuum degree of 4 mmHg to obtain 170 parts of purified 3-(3,3,5-trimethylhexanamide)propyltrimethoxysilane (a compound represented by formula (7), wherein R 2 is methyl, R 3 is propylene, R 7 is 2,2,4-trimethylpentyl, and n is 0) as an N-acylated intermediate. Under a nitrogen atmosphere, 64 parts of butyl acetate and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. 79 parts of purified 3-(3,3,5-trimethylhexanamide)propyltrimethoxysilane were added thereto, and the resulting mixture was heated at 110° C. for 9 hours to add the secondary amide group to the isocyanate group, thereby obtaining a polyisocyanate curing agent solution (HE-24) having a non-volatile concentration of 90%. The concentration of the isocyanate group in the curing agent solution (HE-24) was 3.39 mmol / g (3.77 mmol / g component in terms of non-volatile content).

[0371] Embodiment 25

[0372] The same process as in Example 17 was repeated except that bis(2-ethylhexyl)phosphoric acid was not added to obtain 222 parts of crude 3-acetamidopropyltrimethoxysilane (a compound represented by the formula (7) wherein R 2 is methyl, R 3 is propylene, R 7is methyl, and n is 0) as an N-acylated intermediate. Under a nitrogen atmosphere, 62 parts of propylene glycol monomethyl ether acetate and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. 55 parts of crude 3-acetamidopropyltrimethoxysilane were added thereto, and the mixture was heated at 110° C. for 7 hours to add the secondary amide group to the isocyanate group, thereby obtaining a polyisocyanate curing agent solution (HE-25) having a non-volatile concentration of 90%. The concentration of the isocyanate group in the curing agent solution (HE-25) was 3.13 mmol / g (3.48 mmol / g component in terms of non-volatile content).

[0373] Embodiment 26

[0374] Under a nitrogen atmosphere, 206 parts of 3,3,5-trimethylhexanoic acid methyl ester (which is a branched saturated ester) having two hydrogen atoms at the α-position and 179 parts of 3-aminopropyltrimethoxysilane are placed in a flask and stirred at room temperature. 1.16 parts of a 28% methanol solution of sodium methoxide are added as a catalyst, and the resulting mixture is stirred, heated to 70°C, and aged for 2 days. The conversion rate of 3-aminopropyltrimethoxysilane is 71%, and methanol is produced as a by-product in an approximately equimolar amount to the reacted 3-aminopropyltrimethoxysilane. Then, after adding 2.2 parts of bis(2-ethylhexyl)phosphoric acid as an acidic compound, the resulting mixture is concentrated by removing methanol and remaining methyl acetate at 50°C to 70°C under reduced pressure to obtain 365 parts of crude 3-(3,3,5-trimethylhexanamide)propyltrimethoxysilane containing catalyst-derived residues (a compound represented by formula (7), wherein R 2 is methyl, R 3 is propylene, R 7is 2,2,4-trimethylpentyl, and n is 0) as an N-acylated intermediate. Because the product is not purified by distillation, a large amount of 3-aminopropyltrimethoxysilane derived from the raw material remains, and the product is a mixture of 71mol% of 3-(3,3,5-trimethylhexanamide)propyltrimethoxysilane and 29mol% of 3-aminopropyltrimethoxysilane. Under a nitrogen atmosphere, 65 parts of propylene glycol monomethyl ether acetate and 500 parts of "Duranate TSA-100" are placed in another flask and stirred at room temperature. 90 parts of crude 3-(3,3,5-trimethylhexanamide)propyltrimethoxysilane are added thereto, and the mixture is heated at 110°C for 7 hours to add the secondary amide group to the isocyanate group, thereby obtaining a polyisocyanate curing agent solution (HE-26) with a non-volatile concentration of 90%. The concentration of the isocyanate group in the curing agent solution (HE-26) was 3.25 mmol / g (3.61 mmol / g component in terms of non-volatile content).

[0375] Comparative Example 9

[0376] Under a nitrogen atmosphere, 56 parts of butyl acetate and 500 parts of "Duranate TSA-100" were placed in another flask to obtain a polyisocyanate curing agent solution (HR-9) having a non-volatile concentration of 90%. The concentration of the isocyanate group in the curing agent solution (HR-9) was 4.46 mmol / g (4.96 mmol / g component in terms of non-volatile content).

[0377] Comparative Example 10

[0378] Under a nitrogen atmosphere, 248 parts of mineral spirits, 198 parts of "Swasol 1000" (product name, produced by Maruzen Petrochemical Co., Ltd., a naphtha-based solvent) and 500 parts of "Duranate TSA-100" were placed in another flask, and the resulting mixture was stirred at room temperature. When 44.3 parts of 3-aminopropyltrimethoxysilane was added dropwise thereto, a curing agent solution (HR-10) was obtained; however, since a starch slurry-like substance began to precipitate, the evaluation was stopped.

[0379] Table 3

[0380]

[0381] Evaluation Project

[0382] (*) Formation of N-acylated products

[0383] The yields (%) of the N-acylated products in Examples 17 to 26 were calculated and evaluated according to the following criteria. In the table, good, fair and poor have the following meanings. The higher the yield (%), the better.

[0384] Good: The yield is 80% or more.

[0385] Normal: The yield is 30% or more and less than 80%.

[0386] Poor: Yield less than 30%.

[0387] (*) Ease of preparation of intermediates containing N-acylated products

[0388] The preparation ease of the polyisocyanate curing agent solutions obtained in Examples 17 to 26 was evaluated according to the following criteria. AA and A were judged to be acceptable. In the column "Application of a distillation apparatus", "yes" means that a distillation apparatus was used, and "no" means that a distillation apparatus was not used.

[0389] AA: Intermediates can be produced without the use of a distillation unit.

[0390] A: Intermediates can be produced by using a distillation apparatus.

[0391] B: Since the yield of the N-acylated product is low, it is difficult to produce the intermediate even using a distillation apparatus.

[0392] (*) Isocyanate stability at 20°C

[0393] The residual NCO (%) of the polyisocyanate curing agent solutions obtained in Examples 17 to 26 and Comparative Example 9 after storage at 20° C. for 3 months was measured in the same manner as in Example 1 and evaluated according to the following criteria. The higher the residual NCO (%), the better.

[0394] Good: 95% or more.

[0395] Normal: 90% or more and less than 95%.

[0396] Poor: less than 90%.

[0397] Production of clear coatings

[0398] Examples 27 to 57 and Comparative Examples 11 to 18

[0399] The main agent was prepared according to the formulation shown in Table 4, Table 5 and Table 6 below, and mixed with polyisocyanate curing agent solutions (HE-1) to (HE-26), (HR-1) to (HR-3), (HR-5) to (HR-7) and (HR-9), which were left to stand for 3 days after production to obtain clear coatings (U-1) to (U-41).

[0400] Similarly, old polyisocyanate curing agent solutions (HE-1) to (HE-7) and (HR-3) left standing for 12 months after production were mixed with the main agent shown in Table 4 to produce clear coatings (U′-1) to (U′-9) and (U′-12).

[0401] In addition, old polyisocyanate curing agent solutions (HE-8) to (HE-16) and (HR-5) to (HR-7) left standing for 3 months after production were mixed with the main agent shown in Table 5 to produce clear coatings (U′-13) to (U′-26).

[0402] Similarly, polyisocyanate curing agent solutions (HE-8) to (HE-16) and (HR-7) stored in a sealed state at 5°C under low temperature conditions for 2 weeks after production were mixed with the main agent shown in Table 5 to produce clear coatings (U"-13) to (U"-23) and (U"-26).

[0403] Similarly, old polyisocyanate curing agent solutions (HE-17) to (HE-26) and (HR-9) left standing for 3 months after production were mixed with the main agent shown in Table 6 to produce clear coatings (U'-27) to (U'-41).

[0404] Each numerical value shown in Table 4, Table 5, and Table 6 does not represent the mass of non-volatile components but represents the total mass including volatile components.

[0405] Table 4. Each numerical value shown in the table represents the mass including volatile components.

[0406]

[0407] Table 5. Each numerical value shown in the table represents the mass including volatile components.

[0408]

[0409] Table 6. Each numerical value shown in the table represents the mass including volatile components.

[0410]

[0411] Note 4: Polyol solution 1: A copolymer solution containing styrene, isobutyl methacrylate, 2-ethylhexyl acrylate and hydroxyethyl methacrylate in a ratio of 30 / 30 / 30 / 10, weight average molecular weight: 20,000, hydroxyl value of each non-volatile component: 43 mgKOH / g, non-volatile concentration: 50%, solvent: a mixture of mineral spirits and "Swasol 1000" in a mass ratio of 1 / 1

[0412] Note 5: Polyol solution 2: A copolymer solution containing styrene, isobutyl methacrylate, 2-ethylhexyl acrylate, hydroxyethyl methacrylate and acrylic acid in a ratio of 30 / 35 / 29 / 5 / 1, weight average molecular weight: 20,000, hydroxyl value of each non-volatile component: 22 mgKOH / g, non-volatile concentration: 50%, solvent: a mixture of mineral spirits and "Swasol 1000" in a mass ratio of 1 / 1

[0413] Note 6: Aspartic acid ester 1: Desmophen NH 1523LF (tetraethyl N,N'-(methylenebis(2-methyl-di-4,1-cyclohexanediyl))-bis-aspartic acid, content: >99%, amine value: 200 mgKOH / g) produced by Covestro

[0414] Note 7: NEOSTANN U-830: Trade name, manufactured by Nitto Kasei Co., Ltd., dioctyltin compound

[0415] Note 8: Aspartic acid ester 2: Desmophen NH 1423LF (tetraethyl N,N'-(methylenebis(di-4,1-cyclohexanediyl))-bis-aspartic acid, content: >99%, amine value: 205 mgKOH / g) produced by Covestro

[0416] Performance Evaluation

[0417] The following performance evaluation tests were performed on the clear coatings obtained in the above Examples and Comparative Examples. In these tests, each coating was applied immediately after mixing the main agent and the curing agent.

[0418] (*) Curing

[0419] Each clear coating is applied to a glass plate by coating with a 200 μm applicator, and dried in a room at 23°C and 50% humidity for 7 days. The coating film obtained is peeled off from the glass plate, wrapped on a 200 mesh stainless steel wire mesh, and immersed in a mixed solution of acetone / methanol (mass ratio=1 / 1) for 24 hours. The wire mesh wrapped with the coating film is then taken out, and dried at 100°C for 1 hour. The insoluble content (%) is measured by the mass of the coating film remaining on the wire mesh. Grade A and Grade B are determined to be qualified, and Grade C and Grade D are determined to fail.

[0420] A: The insoluble matter content is 85% or more.

[0421] B: The insoluble matter content is 70% or more and less than 85%.

[0422] C: The insoluble matter content is 55% or more and less than 70%.

[0423] D: The insoluble matter content is less than 55%.

[0424] (*) Adhesion

[0425] As substrates, two types of metal plates (ferrous metal: degreased SPCC-SD (cold rolled steel plate with matte surface) metal plate, and nonferrous metal: metal plate made by sanding a 5052P aluminum plate with 240 grit sandpaper) (3.2 mm × 70 mm × 150 mm) were prepared. Each clear coating was applied to the metal plate by coating with a 200 μm coater, and then dried in a room at room temperature of 23° C. and 50% humidity for 7 days to obtain a separate test coated plate.

[0426] A grid of 10 squares x 10 squares, a total of 100 squares, with a width of 2 mm, was cut from the coating film using a cutter, and a peeling test was performed 3 times. Specifically, in the peeling test, the tape was adhered to the squares, then peeled off, and the number of squares that were not peeled off was counted. Grades A and B were determined to be acceptable, and Grades B and C were determined to be unsuccessful.

[0427] A: There are 100 squares left.

[0428] B: 75 squares or more and 99 squares or less.

[0429] C: 51 squares or more and 74 squares or less.

[0430] D: 50 squares or less.

[0431] (*) Waterproof adhesion

[0432] Two types of metal plates, iron and aluminum, were prepared in the same manner as the metal plates used in the above adhesion test. Each clear coating was applied to the two types of metal plates by coating with a 200 μm applicator and then dried in a room at a room temperature of 23° C. and a humidity of 50% for 7 days to obtain a separate test coated plate.

[0433] Each test coated plate was immersed in 40°C warm water for 3 days, immersed in 20°C water for 1 hour, and then taken out. The water on the coated surface of the test plate was wiped off, and the coated film was immediately cut into a grid of 10×10 squares using a cutter, a total of 100 squares, and a width of 2mm. Then 3 peeling tests were performed. Specifically, in the peeling test, the tape was adhered to the squares, then peeled off, and the number of unpeeled squares was counted. Grades A and B were determined to be qualified, and Grades B and C were determined to be failed.

[0434] A: There are 100 squares left.

[0435] B: 75 squares or more and 99 squares or less.

[0436] C: 51 squares or more and 74 squares or less.

[0437] D: 50 squares or less.

[0438] Production of single-layer coatings

[0439] Example 60 to Example 92 and Comparative Examples 19 to Comparative Examples 26

[0440] The main agent was prepared according to the formulations shown in Tables 7, 8 and 9 below, and mixed with polyisocyanate curing agent solutions (HE-1) to (HE-26), (HR-1) to (HR-3), (HR-5) to (HR-7) and (HR-9), respectively, which were left to stand for 3 days after production to obtain single-layer coatings (U-42) to (U-82).

[0441] Similarly, old polyisocyanate curing agent solutions (HE-1) to (HE-7) and (HR-3) left standing for 12 months after production were mixed with the main agent shown in Table 7 to produce single-layer coatings (U′-42) to (U′-50) and (U′-53).

[0442] In addition, old polyisocyanate curing agent solutions (HE-8) to (HE-16) and (HR-5) to (HR-7) left standing for 3 months after production were mixed with the main agent shown in Table 8 to produce single-layer coatings (U′-54) to (U′-67).

[0443] Similarly, polyisocyanate curing agent solutions (HE-8) to (HE-16) and (HR-7) stored in a sealed state at 5°C under low temperature conditions for 2 weeks after preparation were mixed with the main agent shown in Table 8 to produce single-layer coatings (U"-54) to (U"-64) and (U"-67).

[0444] Similarly, old polyisocyanate curing agent solutions (HE-17) to (HE-26) and (HR-9) left standing for 3 months after production were mixed with the main agent shown in Table 9 to produce single-layer coatings (U'-68) to (U'-82).

[0445] Each numerical value in Table 7, Table 8 and Table 9 does not represent the mass of non-volatile components but represents the total mass including volatile components.

[0446] Each numerical value shown in Table 7 represents the mass including volatile components.

[0447]

[0448] Each numerical value shown in Table 8 represents the mass including volatile components.

[0449]

[0450] Each numerical value shown in Table 9 represents the mass including volatile components.

[0451]

[0452] Note 9: Antirust pigment composition: a product of magnesium phosphate / "Silysia 710" (trade name, produced by Fuji Silysia Chemical Co., Ltd., silicon dioxide) / calcium silicate=50 / 30 / 20 mixed and modified.

[0453] Performance Evaluation

[0454] (*) Curing property:

[0455] The curability was tested in the same manner as the curing test using the clear coating layer, and evaluated according to the following criteria.

[0456] (*)Corrosion resistance:

[0457] A single layer of coating was prepared by mixing the base and curing agent. Within 30 minutes after preparation, each single layer of coating was applied by brushing at 100 g / m 2 The coating amount of 2000 g / cm2 was applied to a SPCC steel plate (size 3.2 mm x 70 mm x 150 mm) treated with zinc phosphate. After the coated plate was aged for 7 days at 20° C., a 8 cm long cut was cut out on the substrate material with a cutter to prepare a test coated plate. Each test coated plate thus obtained was tested at a temperature of 35° C. in a 5% salt spray tester for 240 hours, and the appearance of the test plate was then observed and evaluated on a four-point scale.

[0458] A: The maximum width of rust extending from the cut portion (on one side) is less than 15 mm; there is no abnormality in the general portion.

[0459] B: The maximum width of rust extending from the cut portion (on one side) is 15 mm or more and less than 20 mm; there is no abnormality in the general portion.

[0460] C: The maximum width of rust extending from the cut portion (on one side) was less than 20 mm; however, blistering and rusting occurred in the general portion.

[0461] D: The maximum width of rust extending from the cut portion (on one side) exceeded 20 mm, and blistering and rusting occurred in the general portion.

[0462] (*) Weather resistance

[0463] A single layer of coating was prepared by mixing the base and curing agent. Within 30 minutes after preparation, each single layer of coating was applied by brushing at 100 g / m 2 A coating amount of 1000 g was applied to a zinc phosphate treated SPCC steel plate. The coated plate was aged at 20° C. for 7 days to obtain a test coated plate.

[0464] After each of the test coated plates thus obtained was exposed to light for 300 hours in an accelerated weather resistance test according to JIS K 5600-7-7 (xenon lamp method), the test coated plates were evaluated according to the following criteria.

[0465] A: No change in gloss was observed compared to the initial gloss.

[0466] B: A change in gloss was observed, but only to a moderate level.

[0467] C: A clear change in gloss was observed compared to the initial gloss.

[0468] D: A significant change in gloss was observed compared to the initial gloss.

Claims

1. A modified polyisocyanate used together with a compound containing active hydrogen as a curing agent for coatings, The modified polyisocyanate is a reaction product formed from components including a primary amino group-containing alkoxysilane (a1), an unsaturated carboxylic acid alkyl ester (a2) or a saturated carboxylic acid alkyl ester (a3) ​​and a polyisocyanate (a4) as starting materials, The unsaturated carboxylic acid alkyl ester (a2) is at least one selected from the group consisting of: Branched alkyl esters of unsaturated dicarboxylic acids (a2-1), and Branched alkyl esters of unsaturated monocarboxylic acids each optionally containing a heteroatom or an alkyl ester having a cyclic structure (a2-2).

2. The modified polyisocyanate according to claim 1, wherein the primary amino group-containing alkoxysilane (a1) is a compound represented by the following formula (1): In formula (1), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, R 3 is a C1-C8 straight or branched chain alkylene group, and n is an integer of 0 to 2.

3. The modified polyisocyanate according to claim 1, wherein the branched alkyl ester of unsaturated dicarboxylic acid (a2-1) is a compound represented by the following formula (2): R 4 O-C(=O)-HC=CH-C(=O)-OR 5 (2) In formula (2), R 4 and R 5 are the same or different, and each represents a C1-C8 branched alkyl group.

4. The modified polyisocyanate according to claim 1, wherein the branched alkyl ester of the unsaturated monocarboxylic acid each optionally containing a heteroatom or the alkyl ester having a cyclic structure (a2-2) is a compound represented by the following formula (3): H2C=CH-C(=O)-OR 6 (3) In formula (3), R 6 It is C3-C 18 A branched alkyl group or an alkyl group having a cyclic structure, or a C1-C ... 18 Group.

5. The modified polyisocyanate according to claim 1, wherein the saturated carboxylic acid alkyl ester (a3) ​​is a compound represented by the following formula (4): R 7 -C(=O)-OR 8 (4) In formula (4), R 7 and R 8 are the same or different and each represents a C1-C 18 An alkyl group or a C1-C ... 18 Group.

6. The modified polyisocyanate according to claim 1, having a structure in which a secondary amino group of an N-modified alkoxysilane obtained by adding a primary amino group of the alkoxysilane (a1) to an unsaturated carbon-carbon bond of the unsaturated carboxylic acid alkyl ester (a2) is added to at least one isocyanate group of the polyisocyanate (a4).

7. The modified polyisocyanate according to claim 1, having a structure in which a secondary amide group of an N-modified alkoxysilane obtained by reacting a primary amino group of the alkoxysilane (a1) with an ester group of the saturated carboxylic acid alkyl ester (a3) ​​is added to at least one isocyanate group of the polyisocyanate (a4).

8. The modified polyisocyanate according to claim 6, wherein the unsaturated carboxylic acid alkyl ester (a2) is a branched alkyl ester (a2-1) of an unsaturated dicarboxylic acid, and the N-modified alkoxysilane is a compound represented by the following formula (5): In formula (5), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, R 3 is a C1-C8 straight or branched chain alkylene group, R 4 and R 5 are the same or different and each represents a C1-C8 branched alkyl group, and n is an integer from 0 to 2.

9. The modified polyisocyanate according to claim 7, wherein the reaction ratio of the N-modified alkoxysilane having a secondary amino group to the polyisocyanate (a4) is such that the amount of the secondary amino group is 40 mol or less relative to 100 mol of the isocyanate group.

10. The modified polyisocyanate according to claim 6, wherein the unsaturated carboxylic acid alkyl ester (a2) is a branched alkyl ester of an unsaturated monocarboxylic acid each optionally containing a heteroatom or an alkyl ester having a cyclic structure (a2-2), and the N-modified alkoxysilane is a compound represented by the following formula (6): In formula (6), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, R 3 is a C1-C8 straight or branched chain alkylene group, R 6 It is a C1-C with a branched or cyclic structure. 18 An alkyl group or a C1-C1 alkyl group obtained by introducing a heteroatom into an alkyl group or an arylalkyl group having a branched or cyclic structure. 18 group, and n is an integer from 0 to 2.

11. The modified polyisocyanate according to claim 8, wherein the reaction ratio of the mixture containing the N-modified alkoxysilane having a secondary amino group and the polyisocyanate (a4) is such that the total molar number of the primary amino group and the secondary amino group is 40 mol or less relative to 100 mol of the isocyanate group.

12. The modified polyisocyanate according to claim 7, wherein the N-modified alkoxysilane obtained by reacting the alkoxysilane (a1) with the saturated carboxylic acid alkyl ester (a3) ​​is an N-acylated product having a secondary amide group represented by the following formula (7): In formula (7), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, R 3 is a C1-C8 straight or branched chain alkylene group, n is an integer from 0 to 2, and R 7 It is a C1-C 18 An alkyl group or a C1-C12 group having no unsaturated group obtained by introducing a heteroatom into the molecule of an alkyl group or an arylalkyl group 18 Group.

13. The modified polyisocyanate according to claim 1, prepared by the following steps: Step (1), reacting the primary amino group-containing alkoxysilane (a1) with the saturated carboxylic acid alkyl ester (a3) ​​in the presence of a basic catalyst; Step (2), adding an acidic compound; Step (3), removing part or all of the alcohol formed as a by-product to prepare an intermediate containing an N-acylated product represented by the following formula (7); and Step (4), reacting the intermediate with the polyisocyanate (a4); In formula (7), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, R 3 is a C1-C8 straight or branched chain alkylene group, n is an integer from 0 to 2, and R 7 It is a C1-C 18 An alkyl group or a C1-C ... 18 Group.

14. The modified polyisocyanate according to claim 12, wherein the reaction ratio of the N-acylated product to the polyisocyanate (a4) is such that the total number of moles of the secondary amide group and the primary amino group is 40 mol or less relative to 100 mol of the isocyanate group.

15. A method for preparing the modified polyisocyanate according to claim 1, comprising: Step (1), reacting a primary amino group-containing alkoxysilane (a1) with a saturated carboxylic acid alkyl ester (a3) ​​in the presence of a basic catalyst; Step (2), adding an acidic compound; Step (3), removing part or all of the alcohol formed as a by-product to prepare an intermediate containing an N-acylated product represented by the following formula (7); as well as Step (4), reacting the intermediate with polyisocyanate (a4); In formula (7), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, R 3 is a C1-C8 straight or branched chain alkylene group, n is an integer from 0 to 2, and R 7 It is a C1-C 18 An alkyl group or a C1-C ... 18 Group.

16. The modified polyisocyanate according to claim 6, wherein the unsaturated carboxylic acid alkyl ester (a2) is a branched alkyl ester of an unsaturated monocarboxylic acid each optionally containing a heteroatom or an alkyl ester having a cyclic structure (a2-2), and the reaction of the N-modified alkoxysilane having a secondary amino group with the polyisocyanate (a4) is carried out in the presence of the primary amino group-containing alkoxysilane (a1) and a tertiary amino group-containing compound represented by the following formula (8) as a by-product: In formula (8), R 1 and R 2 The same or different, and each represents C1-C 18 An optionally substituted straight or branched chain alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, R 3 is a C1-C8 straight or branched chain alkylene group, R 6 It is a C1-C with a branched or cyclic structure. 18 An alkyl group or a C1-C1 alkyl group obtained by introducing a heteroatom into an alkyl group or an arylalkyl group having a branched or cyclic structure. 18 group, and n is an integer from 0 to 2.

17. The modified polyisocyanate according to claim 1, wherein the saturated carboxylic acid alkyl ester (a3) ​​is an alkyl ester of a linear carboxylic acid having a structure in which two or more hydrogen atoms are present at the α position or an alkyl ester of a branched carboxylic acid having a structure in which two hydrogen atoms are present at the α position.

18. The method for preparing the modified polyisocyanate according to claim 15, wherein the saturated carboxylic acid alkyl ester (a3) ​​is an alkyl ester of a linear carboxylic acid having two or more hydrogen atoms at the α position.

19. A coating comprising an active hydrogen-containing compound and the modified polyisocyanate according to any one of claims 1 to 17.

20. The coating according to claim 19, wherein the active hydrogen-containing compound comprises an acrylic polyol and / or a bisaspartic acid ester derivative.

21. The coating according to claim 19, further comprising at least one selected from the group consisting of a rust inhibitor, a catalyst, a coloring pigment, and an extender pigment.

22. The coating of claim 19 which is a one-coat paint.

23. A protective coating film obtained by curing the coating material according to claim 19.

24. A coated metallic material comprising the protective coating film of claim 23 on a metallic substrate.

Images