Polymer emulsion, and one-liquid thermosetting resin composition, two-liquid thermosetting resin composition, coating material, resin cured film and coating film using same

Abstract

Provided are: a polymer emulsion having excellent storage stability; a thermosetting resin composition containing the polymer emulsion and having excellent curability at low temperatures; and the like. The present invention includes a polymer emulsion (B) containing a polymer (A) and water, the polymer (A) containing a structural unit (A-1) represented by formula (1). [In formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents a C1-20 2-4-valent aliphatic saturated hydrocarbon group which may have an ether bond and contains a linear or branched chain, or a C6-20 divalent alicyclic hydrocarbon group or aromatic hydrocarbon group which may have a urethane bond, R3 represents a hydrogen atom, a C1-10 alkyl group, or a C6-20 cycloalkyl group or arylalkyl group, and R4 represents a hydrogen atom, a C6-10 alkyl group, or a C6-20 cycloalkyl group or arylalkyl group. R4 represents a hydrogen atom, an alkyl group having 1-10 carbon atoms, or a cycloalkyl group or arylalkyl group having 6-20 carbon atoms, and n represents 1 or 2. ] # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a polymer emulsion, and a one-liquid thermosetting resin composition, a two-liquid thermosetting resin composition, a coating, a resin cured film and a coating film using the polymer emulsion. Background Art

[0002] Blocked isocyanate compounds are compounds obtained by reacting the isocyanate group of a compound having an isocyanate group with a blocking agent to deactivate the reactivity of the isocyanate group (blocking). Since the isocyanate group is blocked, the blocked isocyanate compound and the compound having a functional group such as an active hydrogen group that reacts with the isocyanate group do not necessarily need to be separately modulated and stored, and can also be modulated and stored in advance in the form of a liquid. Therefore, blocked isocyanate compounds have been widely used in adhesives, coating agents, molding materials, resin compositions, etc. In addition, in recent years, due to the improvement of the awareness of global environmental protection, water-based resin compositions have attracted attention.

[0003] For example, Patent Document 1 discloses an active energy ray-curable removable water-dispersible acrylic adhesive composition, which is composed of an acrylic emulsion polymer and a compound having a free radical polymerizable unsaturated bond and a blocked isocyanate group in the molecule, wherein the acrylic emulsion polymer is obtained by emulsion polymerization of a monomer mixture having a (meth)acrylate as a main component and containing a hydroxyl-containing monomer.

[0004] Patent Document 2 discloses a copolymer characterized in that it contains a structural unit (a) having a group represented by a predetermined chemical formula, a structural unit (b) having a hydroxyl group, and a structural unit (c) having an acid group, and has a glass transition temperature of 30° C. or less.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent No. 5132096

[0008] Patent Document 2: International Publication No. 22 / 138159 Summary of the invention

[0009] Problems to be solved by the invention

[0010] In patent document 1, active energy ray-curable re-peeling water-dispersible acrylic adhesive composition is coated on a support such as a base material, and after forming an adhesive composition layer, the adhesive composition layer is heated / dried to form an adhesive layer. By this heating, from a compound having a free radical polymerizable unsaturated bond and a blocked isocyanate group, an isocyanate-blocked body is deblocked to produce an isocyanate group, and the generated isocyanate group reacts with the hydroxyl group in the above-mentioned acrylic emulsion polymer to form an adhesive layer, an acrylic polymer having a free radical polymerizable unsaturated bond as a side chain of a polymer. However, in the adhesive composition before heating, the compound having a free radical polymerizable unsaturated bond and a blocked isocyanate group exists in the form of a monomer, so the blocked isocyanate group is easily unstable with water reaction, and there is room for improvement from the viewpoint of storage stability.

[0011] Patent Document 2 discloses that a solvent having a high effect of suppressing transesterification reaction with hydroxyl groups, such as a primary and / or secondary alcohol solvent and an ether solvent, is suitably used as a solvent for the purpose of providing a resin composition that can obtain a cured product having excellent solvent resistance. However, no research has been conducted on the storage stability of the resin composition when water is used as a solvent. Therefore, in water-based resin compositions, there is room for improvement from the viewpoint of storage stability.

[0012] The present invention is made to solve the above-mentioned problems, and its purpose is to provide a polymer emulsion with excellent storage stability, a thermosetting resin composition containing the polymer emulsion and having excellent curability, a coating containing the thermosetting resin composition, a resin cured film obtained by curing the thermosetting resin composition, and a coating film containing the resin cured film.

[0013] Means for solving problems

[0014] The present invention includes the following aspects [1] to

[14] .

[0015] [1] A polymer emulsion (B) comprising a polymer (A) and water, wherein the polymer (A) comprises a structural unit (A-1) represented by the following formula (1).

[0016]

[0017] [In formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a linear or branched divalent to tetravalent aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond, or a divalent alicyclic hydrocarbon group or aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a urethane bond, R 3represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group or an arylalkyl group having 6 to 20 carbon atoms, and R 4 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group or arylalkyl group having 6 to 20 carbon atoms, and n represents 1 or 2.]

[0018] [2] The polymer emulsion (B) according to [1], wherein the content ratio of the structural unit (A-1) is 0.1 mol% to 40 mol% when the total of all structural units of the polymer (A) is 100 mol%.

[0019] [3] The polymer emulsion (B) according to [1] or [2], wherein the polymer (A) contains a structural unit (A-2) represented by the following formula (2) as a structural unit of the polymer (A).

[0020]

[0021] [In formula (2), R 5 R represents a hydrogen atom or a linear or branched aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms. 6 represents an aliphatic saturated hydrocarbon group having 1 to 18 carbon atoms in which the hydrogen atom may be substituted by a hydroxyl group, an acyl group, an alkoxy group, a carboxyl group, a thiol group, a sulfonyl group, a nitro group, an amino group, a chlorine atom, a fluorine atom, a bromine atom, an iodine atom or an astatine atom, and R 6 Contains no aromatic rings.]

[0022] [4] The polymer emulsion (B) according to any one of [1] to [3], wherein the polymer (A) further comprises a structural unit (A-3) represented by the following formula (3) as a structural unit of the polymer.

[0023]

[0024] [In formula (3), R 7 , R 8 and R 9 Each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 15 carbon atoms, and the hydrocarbon group may contain an ester bond and / or a carboxyl group.]

[0025] [5] The polymer emulsion (B) according to any one of [1] to [4], wherein n of the structural unit (A-1) is 1, R 2 It is a divalent aliphatic saturated hydrocarbon group having 2 to 4 carbon atoms which may have an ether bond.

[0026] [6] A one-liquid thermosetting resin composition (F), comprising the polymer emulsion (B) described in any one of [3] to [5], wherein R of the structural unit (A-2) in the polymer emulsion (B) is6 At least one hydrogen atom is substituted by a hydroxyl group.

[0027] [7] A coating (G) comprising the one-liquid thermosetting resin composition (F) described in [6].

[0028] [8] A cured resin film (H) obtained by curing the one-liquid thermosetting resin composition (F) described in [6].

[0029] [9] A coating film (I) comprising the cured resin film (H) described in [8].

[0030]

[10] A two-liquid thermosetting resin composition (K) comprising the polymer emulsion (B) described in any one of [1] to [5] and an acrylic polyol polymer emulsion (J).

[0031]

[11] The two-liquid thermosetting resin composition (K) according to

[10] , wherein R of the structural unit (A-1) in the polymer emulsion (B) is 3 The ratio of the molar number of hydroxyl groups in the acrylic polyol polymer emulsion (J) is 2:1 to 1:4.

[0032]

[12] A coating (L) comprising the two-liquid thermosetting resin composition (K) according to

[10] or

[11] .

[0033]

[13] A cured resin film (M) obtained by curing the two-liquid thermosetting resin composition (K) according to any one of

[10] or

[11] .

[0034]

[14] A coating film (N) comprising the cured resin film (M) described in

[13] .

[0035] Effects of the Invention

[0036] According to the present invention, a polymer emulsion having excellent storage stability, a thermosetting resin composition containing the polymer emulsion and having excellent curability, a coating containing the thermosetting resin composition, a resin cured film obtained by curing the thermosetting resin composition, and a coating film containing the resin cured film can be provided. DETAILED DESCRIPTION

[0037] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described below.

[0038] In addition, in this specification, when it expresses "(meth)acrylate", it means that it may be either acrylate or methacrylate. In addition, when it expresses "(meth)acrylic acid", it means that it may be either acrylic acid or methacrylic acid.

[0039] <Polymer Emulsion (B)>

[0040] One embodiment of the present invention is a polymer emulsion (B) comprising a polymer (A) and water, wherein the polymer (A) comprises a structural unit (A-1) represented by the following formula (1).

[0041]

[0042] In formula (1), R 1 represents a hydrogen atom or a methyl group. 2 It represents a linear or branched divalent to tetravalent aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond, or a divalent alicyclic hydrocarbon group or aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a urethane bond.

[0043] R 3 It represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group or arylalkyl group having 6 to 20 carbon atoms.

[0044] R 4 It represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group or arylalkyl group having 6 to 20 carbon atoms.

[0045] n represents 1 or 2.

[0046] [Polymer (A)]

[0047] The polymer (A) contains a structural unit (A-1) represented by the formula (1) (hereinafter, also referred to as "structural unit (A-1)"). The polymer (A) preferably further contains a structural unit (A-2) represented by the formula (2) described later (hereinafter, also referred to as "structural unit (A-2)") and / or a structural unit (A-3) represented by the formula (3) described later (hereinafter, also referred to as "structural unit (A-3)").

[0048] [Structural unit (A-1)]

[0049] The structural unit (A-1) is represented by the formula (1).

[0050]

[0051] In formula (1), R 1 represents a hydrogen atom or a methyl group. 2It represents a straight or branched 2- to 4-valent aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond, or a divalent alicyclic hydrocarbon group or aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a carbamate bond, preferably a divalent aliphatic saturated hydrocarbon group having 2 to 4 carbon atoms which may have an ether bond, and more preferably -CH2CH2-.

[0052] R 3 It represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group or arylalkyl group having 6 to 20 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably an ethyl group.

[0053] R 4 It represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group or arylalkyl group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, more preferably a methyl group or an ethyl group, particularly preferably an ethyl group.

[0054] n represents 1 or 2, and is preferably 1.

[0055] In R 3 When the one-component thermosetting resin composition (F) or the two-component thermosetting resin composition (K) containing the polymer (A) is thermally cured, R 3 Ethanol is generated by transesterification with the hydroxyl group of the structural unit (A-2) or the acrylic polyol polymer emulsion (J) described later. Ethanol generated during thermal curing of the resin composition can be easily evaporated and removed by heating for thermal curing the resin composition, and is therefore preferred.

[0056] The structural unit (A-1) is preferably a structural unit derived from a monomer obtained by blocking an isocyanate monomer (a-1-1) with a blocking agent (a-1-2) (hereinafter also referred to as a "blocked isocyanate compound").

[0057] The isocyanate monomer (a-1-1) is preferably represented by the following formula (4).

[0058] (CH2=CR 1 -C(=O)O) n -R 2 -NCO · · · (4)

[0059] In formula (4), R 1 , R 2 and n have the same meanings as the symbols in formula (1).

[0060] Examples of the isocyanate monomer (a-1-1) represented by formula (4) include a (meth)acrylate compound having an isocyanate group and an adduct of a hydroxyl group-containing (meth)acrylate and a diisocyanate compound in a ratio of 1:1 (molar ratio).

[0061] Examples of the (meth)acrylate compound having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate, 3-(meth)acryloyloxy-n-propyl isocyanate, 2-(meth)acryloyloxyisopropyl isocyanate, 4-(meth)acryloyloxy-n-butyl isocyanate, 2-(meth)acryloyloxy-t-butyl isocyanate, 2-(meth)acryloyloxybutyl-4-isocyanate, 2-(meth)acryloyloxybutyl-3-isocyanate, and 2-(meth)acryloyloxybutyl-2-isocyanate. , 2-(meth)acryloyloxybutyl-1-isocyanate, 5-(meth)acryloyloxy-n-pentyl isocyanate, 6-(meth)acryloyloxy-n-hexyl isocyanate, 7-(meth)acryloyloxy-n-heptyl isocyanate, 2-(isocyanatoethyloxy)ethyl (meth)acrylate, 3-(meth)acryloyloxyphenyl isocyanate, 4-(meth)acryloyloxyphenyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)methyl isocyanate, and 1,1-bis(meth)acryloyloxymethyl)ethyl isocyanate.

[0062] Examples of the (meth)acrylate containing a hydroxyl group include 2-hydroxyalkyl (meth)acrylates. The alkyl group of the 2-hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, and more preferably an ethyl group.

[0063] Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4- (or 2,6-) toluene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m- (or p-) xylylene diisocyanate, 1,3- (or 1,4-) bis (isocyanatomethyl) cyclohexane, and lysine diisocyanate.

[0064] Among them, from the perspective of ease of production and / or availability of raw materials, 2-(meth)acryloyloxyethyl isocyanate, 2-(isocyanateethyloxy)ethyl (meth)acrylate, or 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate is preferred, and 2-(meth)acryloyloxyethyl isocyanate is more preferred.

[0065] Examples of the end-capping agent (a-1-2) include methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, pentyl acetoacetate, methyl 3-oxohexanoate, ethyl 3-oxohexanoate, methyl 3-oxopentanoate, and ethyl 3-oxopentanoate, among which methyl acetoacetate and ethyl acetoacetate are preferred.

[0066] The blocked isocyanate compound can be produced by a known method, for example, by reacting an isocyanate monomer (a-1-1) and a blocking agent (a-1-2) in a reaction vessel in the following methods (i) to (iii).

[0067] Method (i), adding the blocking agent (a-1-2) into the reactor, adding the isocyanate monomer (a-1-1) under stirring and reacting

[0068] Method (ii), adding isocyanate monomer (a-1-1) into a reactor, adding blocking agent (a-1-2) under stirring and reacting

[0069] Method (iii) of adding both the blocking agent (a-1-2) and the isocyanate monomer (a-1-1) to a reactor under stirring and reacting them

[0070] The reaction temperature is not particularly limited and can be appropriately set according to the type and amount ratio of the isocyanate monomer (a-1-1) and the blocking agent (a-1-2), for example, preferably -10°C to 90°C, more preferably 5°C to 70°C. In addition, the reaction time is not particularly limited and can be appropriately set, preferably 30 minutes to 168 hours.

[0071] In addition, commercially available blocked isocyanate compounds may be used, such as Calence (registered trademark) MOI-OBE, Calence (registered trademark) AOI-OBE, Calence (registered trademark) MOI-OBM and Calence (registered trademark) AOI-OBM manufactured by Showa Denko K.K.

[0072] The structural unit (A-1) may be used alone or in combination of two or more.

[0073] When the total of the structural units (A-1) to (A-4) (hereinafter referred to as "all structural units") of the polymer (A) is set to 100 mol%, the content of the structural unit (A-1) is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, further preferably 1.0 mol% or more, particularly preferably 2.0 mol% or more, preferably 40.0 mol% or less, more preferably 20.0 mol% or less, further preferably 10.0 mol% or less, and particularly preferably 5.0 mol% or less.

[0074] [Structural unit (A-2)]

[0075] The polymer (A) preferably contains a structural unit (A-2). The structural unit (A-2) is represented by the following formula (2).

[0076]

[0077] In formula (2), R 5 R represents a hydrogen atom or a linear or branched aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms. 6 represents an aliphatic saturated hydrocarbon group having 1 to 18 carbon atoms in which the hydrogen atom may be substituted by a hydroxyl group, an acyl group, an alkoxy group, a carboxyl group, a thiol group, a sulfonyl group, a nitro group, an amino group, a chlorine atom, a fluorine atom, a bromine atom, an iodine atom or an astatine atom, and R 6 Contains no aromatic rings.

[0078] The structural unit (A-2) is not included in the structural unit (A-1).

[0079] The structural unit (A-2) is preferably a structural unit derived from a monomer (a-2). The monomer (a-2) is preferably a structural unit composed of a carboxylic acid compound (a-2-1) and R 6 -OH (a-2-2) to obtain an ester compound.

[0080] As the carboxylic acid compound (a-2-1), (meth)acrylic acid is preferred.

[0081] R 6 In -OH(a-2-2), R 6 The symbols are the same as those in formula (2). 6 Examples thereof include methyl, ethyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-propyl, isopropyl, 2-ethylhexyl and n-dodecyl groups, and methyl, ethyl, butyl, propyl and 2-ethylhexyl groups are preferred.

[0082] Examples of the monomer (a-2) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0083] The structural unit (A-2) may be used alone or in combination of two or more.

[0084] When the total of all structural units of the polymer (A) is set to 100 mol%, the content of the structural unit (A-2) is preferably 0 mol% or more, more preferably 3.0 mol% or more, further preferably 10.0 mol% or more, preferably 99.9 mol% or less, more preferably 95.0 mol% or less, further preferably 70.0 mol% or less.

[0085] [Structural unit (A-3)]

[0086] The polymer (A) preferably contains a structural unit (A-3). The structural unit (A-3) is represented by the following formula (3).

[0087]

[0088] In formula (3), R 7 , R 8 and R 9 Each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 15 carbon atoms, preferably a linear or branched hydrocarbon group having 1 to 6 carbon atoms, and the hydrocarbon group may contain an ester bond and / or a carboxyl group.

[0089] The structural unit (A-3) represented by formula (3) is preferably a structural unit derived from a monomer (a-3). Examples of the monomer (a-3) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, 2-pentenoic acid, and cinnamic acid; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, and itaconic acid; monomethyl fumarate, monoethyl fumarate, mono-n-butyl fumarate, monomethyl maleate, monoethyl maleate, mono-2-ethylhexyl maleate, and mono-n-butyl maleate, butenedioic acid monochain alkyl esters such as monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclopentyl maleate, and monocyclohexyl maleate; itaconic acid monoesters such as monomethyl itaconate, monoethyl itaconate, mono-n-butyl itaconate, and monocyclohexyl itaconate. Among them, unsaturated dicarboxylic acid monoesters such as (meth)acrylic acid, monoethyl fumarate, monopropyl fumarate, monobutyl fumarate, monoethyl itaconate, monopropyl itaconate and monobutyl itaconate are preferred, and (meth)acrylic acid is more preferred.

[0090] The structural unit (A-3) may be used alone or in combination of two or more.

[0091] When the total of all structural units of the polymer (A) is set to 100 mol%, the content of the structural unit (A-3) is preferably 0 mol% or more, more preferably 0.1 mol% or more, further preferably 0.3 mol% or more, preferably 20.0 mol% or less, more preferably 15.0 mol% or less, further preferably 5.0 mol% or less.

[0092] [Other structural units (A-4)]

[0093] The polymer (A) of the present embodiment may contain other structural units (A-4) copolymerizable with the structural units (A-1) to (A-3) as necessary (but excluding structural units belonging to the structural units (A-1) to (A-3)).

[0094] Other structural units (A-4) may be derived from monomers (a-4) that provide other structural units (A-4). Examples of monomers (a-4) include aromatic vinyl compounds such as styrene, α-methylstyrene, and p-methylstyrene, unsaturated sulfonic acids such as p-styrenesulfonic acid and their salts, anhydrides of unsaturated carboxylic acids such as maleic anhydride, and vinyl compounds such as vinyl acetate and vinyl chloride.

[0095] [Method for producing polymer emulsion (B)]

[0096] The polymer emulsion (B) as one embodiment of the present invention can be prepared by, for example, mixing the monomer (a-1) with water, or by adding a surfactant and water after polymerization in an organic solvent and emulsifying, and distilling off the solvent to prepare it, but it is preferably prepared by emulsion polymerization. The preparation of the polymer emulsion (B) using emulsion polymerization can be carried out by a known method. For example, the monomer and water can be pre-emulsified and dispersed preferably with a surfactant to prepare a monomer emulsion, and then, in a container different from the monomer emulsion, water, preferably a mixture of water and a surfactant, is heated, and the previously prepared monomer emulsion is added dropwise thereto, preferably a free radical polymerization initiator is appropriately added, and it is prepared by emulsion polymerization. The reaction temperature and reaction time can be appropriately set according to the type and amount of the monomers used.

[0097] When producing the polymer emulsion (B), the monomer (a-2) and / or the monomer (a-3) may also be used.

[0098] Regarding the blending amounts of the monomer (a-1) used when producing the polymer emulsion (B), the monomer (a-2) and the monomer (a-3) which are suitably used, and the monomer (a-4) which provides the other structural unit (A-4), when these monomers as a whole are taken as 100 mol%, the monomer (a-1) is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, further preferably 1.0 mol% or more, particularly preferably 2.0 mol% or more, preferably 40.0 mol% or less, more preferably 20.0 mol% or less, further preferably 10.0 mol% or less, and particularly preferably 5.0 mol% or less.

[0099] When the total amount of the monomer is set to 100 mol%, the amount of the monomer (a-2) is preferably 0 mol% or more, more preferably 3.0 mol% or more, further preferably 10.0 mol% or more, preferably 99.9 mol% or less, more preferably 95.0 mol% or less, further preferably 70.0 mol% or less.

[0100] When the total amount of the monomer is set to 100 mol%, the amount of the monomer (a-3) is preferably 0 mol% or more, more preferably 0.1 mol% or more, further preferably 0.3 mol% or more, preferably 20.0 mol% or less, more preferably 15.0 mol% or less, further preferably 5.0 mol% or less.

[0101] The amount of each monomer blended is substantially the same as the content of each structural unit when the total of all structural units in the polymer (A) is taken as 100 mol%.

[0102] The value of the functional group equivalent ÷ Mn of the polymer emulsion (B) is preferably 0.001 or more, more preferably 0.01 or more, and further preferably 0.05 or more. If the value of the functional group equivalent ÷ Mn is 0.001 or more, the density of the crosslinking points is relatively large and crosslinking is easy, so it is preferred. The value of the functional group equivalent ÷ Mn of the polymer emulsion (B) is preferably 10 or less, more preferably 5.0 or less, further preferably 3.0 or less, and further particularly preferably 0.8 or less. If the value of the functional group equivalent ÷ Mn is 10 or less, the density of the crosslinking points is relatively large and crosslinking is easy, so it is preferred. Mn represents the number average molecular weight of the polymer (A) in the polymer emulsion (B).

[0103] The functional group equivalent can be calculated from the following formula.

[0104] (Molecular weight of structural unit (A-1))÷(Parts by mass of structural unit (A-1))×100

[0105] When there are two or more structural units (A-1), the value of functional group equivalent / Mn is obtained by calculating the functional group equivalents of the structural units (A-1) using the above formula, summing the calculated sum, and dividing the sum by the number average molecular weight of the polymer (A).

[0106] The solvent of the polymer emulsion (B) is water. The solvent may contain 1% by mass or less of a water-miscible solvent. Examples of water-miscible solvents include alcohols such as methanol, ethanol, and isopropanol; ethers such as ethylene glycol monomethyl ether and propylene glycol monoethyl ether; and ketones such as acetone and methyl ethyl ketone.

[0107] The polymer emulsion (B) is preferably produced in the presence of a surfactant (C), a chain transfer agent (D) and a polymerization initiator (E).

[0108] [Surfactant (C)]

[0109] The production of the polymer emulsion (B) is preferably carried out in the presence of a surfactant (C). The surfactant is not particularly limited, and one or more of the commonly used nonionic emulsifiers, anionic emulsifiers or reactive surfactants can be used. The surfactant (C) is preferably an anionic emulsifier and a reactive surfactant, and is more preferably a reactive surfactant for the purpose of suppressing the exudation of the surfactant to the surface after the polymer emulsion is dried.

[0110] Examples of the nonionic emulsifier include polyoxyethylene alkyl ethers, polyoxyethylene alcohol ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polycyclic phenyl ethers, polyoxyalkylene alkyl ethers, sorbitan fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.

[0111] Examples of the anionic emulsifier include alkylbenzene sulfonates, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, polyoxyalkylene alkyl ether phosphates or salts thereof, polyoxyalkylene alkylphenyl ether phosphates or salts thereof, and fatty acid salts. Examples of the salt include alkali metal salts such as sodium and potassium, and salts such as ammonia and amines.

[0112] Examples of the reactive surfactant include structures represented by formulas (5) to (7).

[0113]

[0114]

[0115] In formulas (5) to (7), R 21 , R 23 , R 24 , R 25 are each independently hydrogen or alkyl, R 22 It is an alkyl group or an alkylphenyl group, A represents an alkylene group such as -CH2-CH2-, M represents an ammonium salt or a metal salt such as potassium or sodium, n represents an integer of 2 to 20, and m represents an integer of 0 to 20.

[0116] Examples of the compound represented by formula (5) include Aqualon (registered trademark) KH-10 and KH-5 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.). Examples of the compound represented by formula (6) include Adekaly Aquasol (registered trademark) SE-10N (manufactured by ADEKA Co., Ltd.). Examples of the compound represented by formula (7) include Aqualon (registered trademark) HS-10 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0117] From the perspective of ensuring particle stability during polymerization and suppressing viscosity increase, the surfactant (C) is preferably contained in an amount of 0.1% by mass to 10.0% by mass, more preferably 0.3% by mass to 7.0% by mass, and even more preferably 0.5% by mass to 5.0% by mass, relative to the solid content of the polymer (A).

[0118] [Chain transfer agent (D)]

[0119] The chain transfer agent (D) can be used as needed to adjust the molecular weight of the polymer (A). The chain transfer agent (D) is not particularly limited, and examples thereof include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, tert-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, and n-octadecyl mercaptan; 2,4-diphenyl-4-methyl-1-pentene, 2,4-diphenyl-4-methyl-2-pentene; xanthogenic acid compounds such as dimethyl xanthogenic ester disulfide and diisopropyl xanthogenic ester disulfide; terpinolene; tetramethylthiuram disulfide, tetraethylthiuram disulfide, and monothiol; Thiuram compounds such as tetramethylthiuram; phenolic compounds such as 2,6-di-tert-butyl-4-methylphenol and styrenated phenol; allyl compounds such as allyl alcohol; halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, and carbon tetrabromide; vinyl ethers such as α-benzyloxystyrene, α-benzyloxyacrylonitrile, and α-benzyloxyacrylamide; triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexyl thioglycolate, etc. One or more of them can be used. The amount of these chain transfer agents used is not particularly limited, and usually, 0 to 5.0% by mass is used relative to the solid content of the polymer (A).

[0120] [Polymerization initiator (E)]

[0121] The production of the polymer emulsion (B) is preferably carried out in the presence of a polymerization initiator (E). Alternatively, a polymerization initiator and a reducing agent may be used together to prepare a redox polymerization initiator. As the reducing agent, potassium bisulfite, sodium bisulfite, potassium sulfite, sodium sulfite, etc. may be used.

[0122] The polymerization initiator (E) is not particularly limited, and examples thereof include inorganic polymerization initiators represented by persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; 2,2-bis(4,4-di(tert-butylperoxy)cyclohexyl)propane, 1-di(tert-hexylperoxy)cyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, 4,4-di(tert-butylperoxy)butyl valerate, 2,2-di(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, di(2-tert-butylperoxy)butane, Isopropyl butyl peroxide, diisopropyl benzene peroxide, diisobutyryl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, disuccinic acid peroxide, dibenzoyl peroxide, di(3-methylbenzoyl) peroxide, benzoyl(3-methylbenzoyl) peroxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, di-sec-butyl peroxydicarbonate, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxypivalate, pivalic acid peroxide Organic peroxides such as tert-butyl ester, 2,5-dimethyl-2,5-di(2-ethylhexanoyl peroxy)hexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-di(benzoyl peroxy)hexane, tert-butyl peroxyacetate, tert-hexyl peroxybenzoate, tert-butyl peroxybenzoate, 2,5-dimethyl-2,5-di(tert-butyl peroxy)hexane Azo initiators such as hydrogen peroxide, azobisisobutyronitrile, 2,2'-azobis(isobutyric acid)dimethyl ester, 4-4'-azobis(4-cyanovaleric acid), 2-2'-azobis[2-(2-imidazolin-2-yl)propane, 2-2'-azobis(propane-2-carboxamidine)2-2'-azobis[N-(2-carboxyethyl)-2-methylpropionamide, 2-2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}, 2-2'-azobis(1-imino-1-pyrrolidinyl-2-methylpropane) and 2-2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}. These polymerization initiators can be used alone or in combination of two or more.The polymerization initiator (E) is preferably potassium persulfate, sodium persulfate, ammonium persulfate, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, hydrogen peroxide, azobisisobutyronitrile, or 2,2'-azobis(isobutyric acid)dimethyl ester, and more preferably potassium persulfate, sodium persulfate, or ammonium persulfate from the viewpoint of good solubility in water.

[0123] The amount of polymerization initiator (E) is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.03% by mass or more and 4% by mass or less, and further preferably 0.05% by mass or more and 3% by mass or less, relative to the solid content of the polymer (A). If the amount of polymerization initiator (E) is within the above range, the amount of residual monomers after the reaction can be reduced, and the influence of the structure of the polymerization initiator on the physical properties can be suppressed, so it is preferred.

[0124] In one embodiment of the present invention, the polymer emulsion (B) may contain a basic salt composed of an acid having a pKa of 2 or higher and an alkali metal.

[0125] Examples of the acid having a pKa of 2 or higher include carbonic acid, acetic acid, nitrous acid, sulfurous acid, phosphoric acid, and boric acid.

[0126] The alkali metal is preferably lithium, sodium, potassium, rubidium, or cesium, and more preferably sodium or potassium.

[0127] Examples of salts containing an acid with a pKa of 2 or more and an alkali metal and being basic include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, cesium hydrogen carbonate, sodium acetate, potassium acetate, sodium nitrite, potassium nitrite, sodium sulfite, potassium sulfite, disodium hydrogen phosphate, trisodium phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, lithium borate, sodium borate, potassium borate, rubidium borate, cesium borate, sodium octaborate, potassium tetraborate, etc. Borates such as lithium borate include polyborates such as lithium polyborate.

[0128] The content of the basic salt containing an acid having pKa=2 or higher and an alkali metal is preferably 0.2 mass % to 7.5 mass %, more preferably 0.3 mass % to 5.0 mass %, and further preferably 0.5 mass % to 3.0 mass %, based on the solid content of the polymer (A).

[0129] The salt containing an acid having pKa=2 or higher and an alkali metal and being basic can also be confirmed by dissolving a cured resin film (H) described later in a solvent and measuring the pH thereof and finding that the salt is basic.

[0130] The polymer emulsion (B) may contain one or more components selected from the group consisting of a defoaming agent, a filler, a leveling agent and a solvent.

[0131] <One-liquid thermosetting resin composition (F)>

[0132] One embodiment of the present invention is a liquid thermosetting resin composition (F), which comprises the above-mentioned polymer emulsion (B), wherein the polymer emulsion (B) comprises a structural unit (A-2), wherein R 6 At least one hydrogen atom of the structural unit (A-2) is substituted by a hydroxyl group. 6 At least one hydrogen atom of the structural unit (A-1) is replaced by a hydroxyl group, thereby being able to 3 The transesterification reaction is carried out and cross-linking is carried out. The one-component thermosetting resin composition (F) may contain a pigment, a dye, an anti-aging agent, a thickener, a filler, etc. as needed. The one-component thermosetting resin composition (F) can be suitably used as a coating material (G).

[0133] <Resin Cured Film (H)>

[0134] One embodiment of the present invention is a resin cured film (H), which is obtained by curing the above-mentioned one-liquid thermosetting resin composition (F). The resin cured film (H) can be obtained by thermally curing the one-liquid thermosetting resin composition (F) using a known method. It is believed that the resin cured film (H) is formed by cross-linking the hydroxyl groups from the structural unit (A-2) within the polymer (A) and between the polymers (A). The temperature during thermal curing is preferably above 60°C, more preferably above 70°C, further preferably above 90°C, preferably below 150°C, and more preferably below 135°C.

[0135] The cured resin film (H) can be suitably used, for example, as a coating film (I), a coating agent, and an adhesive.

[0136] <Two-component thermosetting resin composition (K)>

[0137] One embodiment of the present invention is a two-component thermosetting resin composition (K), which comprises the above-mentioned polymer emulsion (B) and the acrylic polyol polymer emulsion (J) described below. The polymer emulsion (B) and the acrylic polyol polymer emulsion (J) are separately prepared and then mixed for use, or stored in different containers until use. The two-component thermosetting resin composition (K) can be suitably used as a coating (L).

[0138] [Acrylic polyol polymer emulsion (J)]

[0139] As the acrylic polyol polymer emulsion (J), any known emulsion may be used without limitation, but an emulsion containing an acrylic polyol copolymer represented by the following formula (8) is preferred.

[0140]

[0141] In formula (8), R 31 and R 33 Each independently represents a hydrogen atom or a linear or branched aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, preferably an aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms, 32 R represents a divalent aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms which may have an ester bond and / or a carbonyl group, preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. 34 represents a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms. In addition, m represents an integer of 1 or more, and p represents an integer of 0 or 1 or more.

[0142] The acrylic polyol polymer emulsion (J) can be obtained, for example, by copolymerizing a mixture of a hydroxyl-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomers copolymerizable with the hydroxyl-containing polymerizable unsaturated monomer using a known method, such as bulk polymerization, solution polymerization in an organic solvent, emulsion polymerization in water, or the like.

[0143] As the polymerizable unsaturated monomer containing a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxyphenyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, mono-2-((meth)acryloyloxy)ethylsuccinic acid, polyethylene glycol mono(meth)acrylate, a monoesterified product formed by polyols such as polypropylene glycol (meth)acrylate and (meth)acrylic acid, a compound obtained by ring-opening polymerization of the monoesterified product formed by the polyol and (meth)acrylic acid and ε-caprolactone, etc., can be mentioned, and they can be used alone or in combination of two or more. Among them, 2-hydroxyethyl (meth)acrylate can be used appropriately.

[0144] Examples of other copolymerizable polymerizable unsaturated monomers include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, and octadecyl (meth)acrylate; carboxyl group-containing polymerizable unsaturated monomers such as (meth)acrylic acid, maleic acid, and maleic anhydride; aminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and N,N-dimethylaminopropyl (meth)acrylate; and acrylamide, methacrylamide, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylamino (Meth)acrylamide or its derivatives such as ethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N-methylol acrylamide, N-methylol acrylamide methyl ether, N-methylol acrylamide butyl ether; monomers containing quaternary ammonium salt groups such as 2-(methacryloyloxy)ethyltrimethylammonium chloride and 2-(methacryloyloxy)ethyltrimethylammonium bromide; (meth)acrylamide-alkanesulfonic acids such as 2-acrylamide-2-methylpropanesulfonic acid and (meth)acrylic acid sulfoalkyl esters such as 2-sulfoethyl (meth)acrylate; acrylonitrile, methacrylonitrile, vinyl acetate, styrene, vinyltoluene, α-methylstyrene; polyvinyl compounds such as allyl methacrylate; polymerizable unsaturated monomers containing hydrolyzable silyl groups such as γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane and γ-(meth)acryloxypropylmethyldimethoxysilane, etc. They can be used alone or in combination of two or more. Among them, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl acrylate, and cyclohexyl (meth)acrylate can be used appropriately.

[0145] Regarding the mixing ratio of the polymer emulsion (B) and the acrylic polyol polymer emulsion (J), (R of the structural unit (A-1) in the polymer emulsion (B) 3 The ratio of the molar number of hydroxyl groups in the acrylic polyol polymer emulsion (J) to the molar number of hydroxyl groups in the acrylic polyol polymer emulsion (J) is preferably 10:1 to 1:10, more preferably 5:1 to 1:5, further preferably 2:1 to 1:4, particularly preferably 1.25:1 to 1:1.25, and most preferably 1.1:1 to 1:1.1.

[0146] The two-component thermosetting resin composition (K) may contain a pigment, a dye, an anti-aging agent, a thickener, a filler, a film-forming aid, and the like as necessary.

[0147] <Resin Cured Film (M)>

[0148] One embodiment of the present invention is a resin cured film (M), which is obtained by curing the above-mentioned two-liquid thermosetting resin composition (K). The resin cured film (M) can be obtained by mixing the prepared polymer emulsion (B) and the acrylic polyol polymer emulsion (J), and then thermally curing them using a known method. The temperature during thermal curing is preferably above 60°C, more preferably above 70°C, further preferably above 90°C, preferably below 130°C, and more preferably below 125°C. It is believed that the resin cured film (M) is obtained by R in the structural unit (A-1) in the polymer emulsion (B). 3 It is formed by crosslinking with the acrylic polyol polymer in the acrylic polyol polymer emulsion (J).

[0149] The cured resin film (M) of the present embodiment can be suitably used as, for example, a coating film (N), a coating agent, or an adhesive.

[0150] Example

[0151] Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0152] [Evaluation of solid content]

[0153] The polymer emulsion was accurately weighed on an aluminum dish and then heat-treated (141° C. for 30 minutes) to dry it to a solid content. The solid content concentration in the polymer emulsion was calculated from the difference between the mass before drying and the mass after drying.

[0154] 〔Determination of molecular weight〕

[0155] After adding 1.5 mL of tetrahydrofuran to about 0.1 g of the emulsion, the mixture was shaken by hand to dissolve, and measured by GPC (gel permeation chromatography) to calculate the number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer in the polymer emulsion in terms of polystyrene.

[0156] [Evaluation of film tensile strength (Tb), elongation at break (Eb), modulus at 100% elongation (M100), modulus at 300% elongation (M300), and modulus at 500% elongation (M500)]

[0157] After peeling off the resin dried film or the resin cured film obtained in the embodiment or the comparative example from the glass substrate, it was cut into a dumbbell shape of No. 8. Using a tensile compression tester (Autograph AGS-500NX, manufactured by Shimadzu Corporation; tensile speed: 50 mm / min, temperature: 23°C), a tensile test was performed on each of the cut films. The tensile test was performed according to the method of JIS-K7127-1999. Through this test, the modulus at 100% elongation (M100), the modulus at 300% elongation (M300), the modulus at 500% elongation (M500), the tensile strength (Tb) and the elongation at break (Eb) at room temperature were determined.

[0158] 〔Stability test〕

[0159] The terminal group decomposition rate of the polymer emulsion was measured by the following measurement method immediately after preparation, after storage at 25°C for 2 weeks, 1 month, 2 months and 6 months, and after storage at 40°C for 6 weeks.

[0160] In addition, using the above-mentioned measurement method, the tensile strength (Tb), elongation at break (Eb), modulus at 100% elongation (M100), modulus at 300% elongation (M300), and modulus at 500% elongation (M500) of the resin dry film and the resin cured film immediately after modulation and after storage at 40°C for 1 week, 2 weeks, and 4 weeks were measured.

[0161] [Decomposition rate of end-capping group]

[0162] Regarding the decomposition rate of the end-capping group derived from the end-capping agent in the structural unit (A-1), the decomposition rate of the end-capping group derived from the end-capping agent was determined from the amount of alcohol such as ethanol generated by the decomposition of the end-capping group after storage, taking the theoretical value of the amount of alcohol such as ethanol generated when all (A-1) contained in the polymer emulsion is decomposed as a reference (100%). After accurately weighing about 10 g of cyclohexane and about 0.1 g of an internal standard (o-dichlorobenzene) in a glass vial, 1 g of the polymer emulsion was accurately weighed therein, the lid was closed, and the mixture was shaken and mixed for 30 seconds, and then allowed to stand for 5 minutes, and then the supernatant was analyzed by gas chromatography (GC) (the peak of alcohol such as ethanol was detected).

[0163] Analysis conditions: Gas chromatography Agilent 6850 (manufactured by Agilent Co., Ltd.)

[0164] Detector: Flame ionization detector (FID)

[0165] Column: DB-1 (Part No. 123-1033, manufactured by Astron Technology Co., Ltd.

[0166] Inner diameter: 0.32mm, length: 30m, film thickness: 1μm)

[0167] Analysis conditions: Column temperature starts at 70°C, increases at a rate of 20°C / min to 300°C, and then maintains for 3 minutes.

[0168] [Gel fraction]

[0169] After peeling off the resin dry film or resin cured film obtained in the example or comparative example from the glass substrate, cut out about 0.5 g and weigh accurately. Its mass is referred to as the mass before dispersion. Add to 100 ml of acetone and shake overnight to disperse it. After dispersion, filter and dry the filtered solid at 105°C for 30 minutes. This is referred to as the mass after filtration. The gel fraction is determined using the following formula. Gel fraction (mass %) = ((mass before dispersion) - (mass after filtration)) ÷ (mass before dispersion) × 100

[0170] 〔Reagents used〕

[0171] The abbreviations of the compounds used in Examples and Comparative Examples are shown below.

[0172] [Structural unit (A-1)]

[0173] MOI-OBE: Calence (registered trademark) MOI-OBE (reaction product of 2-isocyanatoethyl methacrylate and ethyl acetoacetate, 2-[(1-(ethoxycarbonyl)-2-oxypropyl)carbonylamino]ethyl methacrylate, manufactured by Showa Denko K.K.)

[0174] MOI-OBM: Calence (registered trademark) MOI-OBM (reaction product of 2-isocyanatoethyl methacrylate and methyl acetoacetate, 2-[(1-(methoxycarbonyl)-2-oxypropyl)carbonylamino]ethyl methacrylate, manufactured by Showa Denko K.K.)

[0175] [Structural unit (A-2)]

[0176] BuA: Butyl acrylate (manufactured by Kanto Chemical Co., Ltd.)

[0177] MMA: Methyl methacrylate (manufactured by Kanto Chemical Co., Ltd.)

[0178] HEMA: 2-Hydroxyethyl methacrylate (manufactured by Kanto Chemical Co., Ltd.)

[0179] [Structural unit (A-3)]

[0180] Aa: Acrylic acid (manufactured by Kanto Chemical Co., Ltd.)

[0181] AOI-DEM: Calence (registered trademark) AOI-DEM (reaction product of 2-isocyanatoethyl acrylate and diethyl malonate, 2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl malonate, manufactured by Showa Denko K.K.)

[0182] [Other ingredients]

[0183] NaSS: Sodium styrene sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0184] [Surfactant]

[0185] KH-10: Aqualon (registered trademark) KH-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) [chain transfer agent]

[0186] OTG: 2-ethylhexyl thioglycolate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0187] [Polymerization initiator]

[0188] KPS: Potassium persulfate (manufactured by Kanto Chemical Co., Ltd.)

[0189] [reducing agent]

[0190] SBS: Sodium bisulfite (manufactured by Kanto Chemical Co., Ltd.)

[0191] [Preparation Example 1]

[0192] An acrylic polyol polymer emulsion was prepared as follows.

[0193] 120 g of deionized water was placed in a 1L four-necked flask equipped with a stirrer, a condenser and a thermometer, and the mixture was heated to 80°C in a water bath while the system was purged with nitrogen. 1.0 g of sodium p-styrenesulfonate, 60 g of methyl methacrylate, 90 g of butyl acrylate, 9 g of butyl methacrylate, 20 g of 2-hydroxyethyl methacrylate, 20 g of styrene, 1.6 g of 2-ethylhexyl thioglycolate, 100 g of deionized water, and 3.0 g of Aqualon (registered trademark) KH-10 were placed in another 500 mL glass beaker, and the mixture was stirred vigorously with a stirrer to prepare an emulsion. 30 g of the prepared emulsion was added to a container heated to 80°C, and then a separately prepared catalyst solution A (0.60 g of potassium persulfate, 11.4 g of deionized water) was added at once. 30 minutes after the addition, the remaining emulsion was added over 3 hours, and at the same time, a catalyst solution B (60 mg of potassium persulfate, 1.1 g of deionized water) prepared separately was added over 3 hours. After the addition of the catalyst solution B was completed, aging was further performed for 1.5 hours. After aging was completed, it was cooled to below 30°C and neutralized to a pH of 7.5 or above using ammonia water to obtain the target acrylic polyol polymer emulsion. The solid content concentration was 47.0% by mass.

[0194] [Example 1]

[0195] A two-liquid thermosetting resin composition and a resin cured film were prepared as follows.

[0196] In a 500 mL four-necked flask equipped with a stirrer, a condenser, and a thermometer, 35.5 g of deionized water, 0.05 g of Arcalon (registered trademark) KH-10, and 235 mg of sodium hydrogen sulfite were placed, and the mixture was heated to 50° C. in a water bath while purging the system with nitrogen. In another 300 mL glass beaker, 1.40 g of acrylic acid, 49.0 g of butyl acrylate, 40.1 g of methyl methacrylate, 9.5 g of 2-[(1-(methoxycarbonyl)-2-oxypropyl)carbonylamino]ethyl methacrylate (MOI-OBE), 0.68 g of 2-ethylhexyl thioglycolate, 55.0 g of deionized water, and 5.0 g of Arcalon (registered trademark) KH-10 were placed, and the mixture was vigorously stirred with a stirrer to prepare an emulsion. After adding 16g of the prepared emulsion to a container heated to 50°C, a separately prepared catalyst liquid A (0.13g of potassium persulfate, 2.5g of deionized water) was added at one time. 30 minutes after the addition, the remaining emulsion was added over 4 hours, and at the same time, a separately prepared catalyst liquid B (0.13g of potassium persulfate, 2.5g of deionized water) was added over 4 hours. After the addition of the emulsion and catalyst liquid B was completed, it was further matured for 1.5 hours. After the aging was completed, it was cooled to below 30°C and neutralized to a pH of more than 7.5 with ammonia water to obtain the target polymer emulsion. No residual monomers in the polymer emulsion were detected except 3400ppm of n-butyl acrylate, confirming that the composition of the copolymer put in was substantially the same as the composition of the monomer put in. The solid content concentration was 46.36% by mass.

[0197] The obtained polymer emulsion and the acrylic polyol polymer emulsion obtained in Preparation Example 1 were mixed for 30 minutes at the composition for film production described in Table 1-1 to obtain a two-liquid thermosetting resin composition.

[0198] The obtained two-liquid thermosetting resin composition was applied to a glass substrate coated with a release agent in such a manner that it became 50±20 μm, and dried at 23°C for more than 1 hour to obtain a resin dried film. In addition, the two-liquid thermosetting resin composition was applied to a glass substrate coated with a release agent in such a manner that it became 50±20 μm, and cured at 120°C for 15 minutes to obtain a resin cured film. It should be noted that the storage time recorded is the time when the polymer emulsion was stored at the temperature and time recorded in Table 2-1.

[0199] [Examples 2 to 6, Examples 8 to 9, Comparative Examples 1 to 2]

[0200] The polymer emulsion was prepared in the same manner as in Example 1 except that the composition was set to the composition described in Table 1-1 to Table 1-3, and the polymer emulsion was mixed with the acrylic polyol polymer emulsion obtained in Preparation Example 1 for 30 minutes according to the composition for film production described in Table 1-1 to Table 1-3 to obtain the two-component thermosetting resin compositions of Examples 2 to 6, 8 to 9 and Comparative Examples 1 to 2. Using each of the obtained two-component thermosetting resin compositions, the same operation as in Example 1 was performed to obtain each resin dried film and resin cured film.

[0201] [Example 7]

[0202] According to the composition described in Table 1-2, the copolymer emulsion was prepared in the same manner as in Example 6, and the one-liquid thermosetting resin composition of Example 7 was obtained in the same manner as in Example 6 except that the acrylic polyol polymer emulsion was not used. Using the obtained one-liquid thermosetting resin composition, the same operation as in Example 6 was performed to obtain a resin dried film and a resin cured film.

[0203] The evaluation and measurement results of Examples 1 to 9 and Comparative Examples 1 and 2 are shown in Tables 2-1 to 2-4.

[0204] [Table 1-1]

[0205] (parts by mass)

[0206]

[0207] n / a: Not determined

[0208] N / A: Cannot be determined

[0209] Table 11-2] (parts by mass)

[0210]

[0211] Na not determined

[0212] N / ACannot be determined

[0213] Table 13

[0214] (parts by mass)

[0215]

[0216] n / a: Not determined

[0217] N / A: Unable to determine

[0218] [Table 2-1]

[0219]

[0220] n / a: Not determined

[0221] N / A: Unable to determine

[0222] [Table 2-2]

[0223]

[0224] n / aNot determinedN / A:Cannot be determined

[0225] Table 22--3]

[0226]

[0227] n / a: Not determined

[0228] N / A: Unable to determine

[0229] [Table 2-4]

[0230]

[0231] n / a: Not determined N / A: Cannot be determined

[0232] In the storage stability test of the polymer emulsion of the embodiment at 25°C, the decomposition rate of the end-capping group after 1 month was 5% by mass or less. On the other hand, the decomposition rate of the end-capping group of the polymer emulsions of Comparative Examples 1 and 2 was 10% by mass or more after 14 days, and 20% by mass or more after 2 months. This shows that the storage stability of the polymer emulsion of the embodiment is excellent.

[0233] The polymer emulsion of Comparative Example 2 had a Tb of 9.5 MPa and an Eb of 143% when crosslinked after storage at 25°C for 6 months, while the Tb was 18.8 MPa and the Eb was 113% immediately after synthesis. Although crosslinking itself was carried out, the retention rate of Tb was 50%, and the physical properties of the resin cured film depended on the storage state, and the storage stability was insufficient. It should be noted that, here, the retention rate (%) of Tb (Eb) was calculated by (Tb (Eb) after storage) ÷ (Tb (Eb) immediately after synthesis) × 100. However, in the storage at 40°C for 6 weeks, which is considered to be equivalent to the storage at 25°C for 6 months (accelerated test), the Tb of Example 1 was 14.7 MPa and the Eb was 203%, and crosslinking was able to be carried out. In addition, the retention rate of Tb was 97%, and the physical properties of the resin cured film did not depend on the storage state, and the storage stability was sufficient. It should be noted that, although it depends on other physical properties, in one embodiment, it is preferred that Eb is 50 to 250%, the retention rate of Eb is 50 to 150%, and the retention rate of Tb is 65 to 135%.

Claims

1. A polymer emulsion B comprising a polymer A and water, wherein the polymer A comprises a structural unit A-1 represented by the following formula (1): In formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents a linear or branched divalent to tetravalent aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms which may have an ether bond, or a divalent alicyclic hydrocarbon group or aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a urethane bond, R 3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group or an arylalkyl group having 6 to 20 carbon atoms, and R 4 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl group or arylalkyl group having 6 to 20 carbon atoms, and n represents 1 or 2. 2 . The polymer emulsion B according to claim 1 , wherein the content ratio of the structural unit A-1 is 0.1 mol % or more and 40 mol % or less, when the total of all structural units of the polymer A is 100 mol %.

3. The polymer emulsion B according to claim 1 or 2, wherein the polymer A comprises a structural unit A-2 represented by the following formula (2) as a structural unit of the polymer A, In formula (2), R 5 represents a hydrogen atom or a straight-chain or branched aliphatic saturated hydrocarbon group having 1 to 4 carbon atoms; R 6 represents an aliphatic saturated hydrocarbon group having 1 to 18 carbon atoms in which the hydrogen atom may be substituted by a hydroxyl group, an acyl group, an alkoxy group, a carboxyl group, a thiol group, a sulfonyl group, a nitro group, an amino group, a chlorine atom, a fluorine atom, a bromine atom, an iodine atom or an astatine atom, and R 6 Contains no aromatic rings.

4. The polymer emulsion B according to claim 1 or 2, wherein the polymer A further comprises a structural unit A-3 represented by the following formula (3) as a structural unit of the polymer, In formula (3), R 7 , R 8 and R 9 Each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 15 carbon atoms, and the hydrocarbon group may contain an ester bond and / or a carboxyl group.

5. The polymer emulsion B according to claim 1 or 2, wherein n of the structural unit A-1 is 1, R 2 It is a divalent aliphatic saturated hydrocarbon group having 2 to 4 carbon atoms which may have an ether bond.

6. A one-liquid thermosetting resin composition F, comprising the polymer emulsion B according to claim 3, wherein R 6 At least one hydrogen atom is substituted by a hydroxyl group.

7. A coating G comprising the one-liquid thermosetting resin composition F according to claim 6. 8 . A cured resin film H obtained by curing the one-liquid thermosetting resin composition F according to claim 6 . 9 . A coating film I comprising the cured resin film H according to claim 8 . 10 . A two-liquid thermosetting resin composition K comprising the polymer emulsion B according to claim 1 or 2 and an acrylic polyol polymer emulsion J.

11. The two-liquid thermosetting resin composition K according to claim 10, wherein R of the structural unit A-1 in the polymer emulsion B is 3 The ratio of the mole number of to the mole number of hydroxyl groups in the acrylic polyol polymer emulsion J is 2:1 to 1:

4. 12 . A coating L comprising the two-liquid thermosetting resin composition K according to claim 10 . 13 . A cured resin film M obtained by curing the two-liquid thermosetting resin composition K according to claim 10 . 14 . A coating film N comprising the cured resin film M according to claim 13 .

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