JP7151172B2 - block polymer - Google Patents

Description

The present invention relates to a block polymer comprising a (meth)acrylic resin unit and a resin unit having a urethane bond and/or a urea bond.

A block polymer is generally a structure in which multiple polymer units with different physical properties such as solubility are connected, and properties such as micelle formation in solution and phase separation structure formation in bulk are used. As such, it is widely studied in the fields of adhesives, elastomers, functional pigment dispersants, compatibilizers, drug delivery systems, and the like.

As such a polymer unit, an acrylic material is preferably used because it has a large degree of freedom in monomer selection and a block polymer structure can be obtained relatively easily by using a living polymerization method. Acrylic block polymers such as diblock polymers and triblock polymers in which three different types of acrylic units are linked together are used.

However, the acrylic block polymer obtained by the living polymerization method is generally limited to a block structure between acrylic units due to the characteristics of the manufacturing method, and it is difficult to combine with polymer units other than acrylic.

On the other hand, for example, Patent Document 1 discloses a method of introducing a functional group to the end of an acrylic unit for the purpose of adding new value to an acrylic polymer obtained by a living polymerization method. By using such a method, although there is a possibility that the functional group introduced at the end of the acrylic unit can be used as a starting point to link with a polymer unit other than acrylic, most of the living polymerization methods have a complicated production process, In addition, since it is difficult to effectively remove heavy metals and halogen compounds that are catalysts, the applications that can be used have been limited.

In addition, the acrylic polymer obtained by the living polymerization method is characterized by a narrow molecular weight dispersity of 1.0 to 1.2 compared to the normal free radical polymerization method, but for example, the particle size distribution is not uniform like that of pigments. Dispersion of certain fillers and pressure sensitive adhesive applications that require high adhesiveness often result in homogeneity of the polymer structure resulting from too narrow a molecular weight dispersity and high microphase separation resulting from this. It may cause defects and poor adhesive strength, and the properties of block polymers with high molecular weight dispersity have been expected.

JP 2009-215472

An object of the present invention is to provide a novel block polymer obtained by combining a (meth)acrylic resin unit and a resin unit having a urethane bond and/or a urea bond.

The present invention is a block polymer in which a (meth)acrylic resin unit (A) and a resin unit (B) having a urethane bond and/or a urea bond are linked, and the molecular weight dispersity of the (meth)acrylic resin unit (A) is is 1.25 or more.

Further, the present invention is characterized in that the (meth)acrylic resin unit (A) and the resin unit (B) having a urethane bond and/or a urea bond are linked by an amide bond and/or an imide bond. Regarding block polymers.

In addition, the present invention provides an amide bond and/or It relates to the above-mentioned block polymer characterized by forming an imide bond.

The present invention also relates to the above block polymer, wherein the chain transfer agent is 2-mercaptosuccinic acid.

The present invention also relates to the block polymer, which is a triblock polymer.

The present invention also relates to a laminate comprising the block polymer and a substrate.

According to the present invention, a (meth)acrylic resin unit and a resin unit having a urethane bond and/or a urea bond, which can be expected to be used for dispersants, compatibilizers, bonding agents, optical materials, electronic materials, medical materials, etc. It was possible to provide a novel block polymer formed by combining

Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of embodiments of the present invention, and the present invention does not exceed the gist thereof. Not specified in content.

The block polymer obtained by combining the (meth)acrylic resin unit (A) of the present invention with the resin unit (B) having a urethane bond and/or a urea bond is composed of the (meth)acrylic resin unit (A) and the urethane bond. and / or a block polymer linked with a resin unit (B) having a urea bond, and the (meth)acrylic resin unit (A) is not particularly limited as long as the molecular weight dispersity of the (A) is 1.25 or more. Two or more of each can be used. The resin unit (B) having a urethane bond and/or a urea bond may be a polymer having a urethane bond and/or a urea bond in the molecule and a terminal hydroxyl group, amino group or isocyanato group. There are no particular restrictions.

The mode of the block polymer may be a diblock polymer, a triblock polymer, or a multiblock polymer, but a diblock polymer or a triblock polymer is preferable because the reaction can be easily controlled.

Components of each unit constituting the block polymer include, for example, known (meth)acrylic monomers used for (meth)acrylic polymerization, known polyurethanes and polyurethaneureas, and polyols and polyamines used for polyurea synthesis, and polyisocyanates. etc. can be used.

The method of connecting the (meth)acrylic resin unit (A) and the resin unit (B) having a urethane bond and/or a urea bond is not particularly limited, but is preferably via an amide bond and/or an imide bond. More preferably, the chain transfer agent residue introduced at the end of the (meth)acrylic resin unit (A) forms an amide bond and/or An imide bond is formed. A compound having two carboxyl groups and one or more thiol groups in the molecule is preferable as the chain transfer agent.

Compounds having two carboxyl groups and one or more thiol groups in the molecule are not limited to the following examples, but specific examples include 2-mercaptosuccinic acid, 2-mercaptoglutaric acid, 2,2-methylenebis (thioglycolic acid), 2,3-dimercaptosuccinic acid, 4,5-dimercaptophthalic acid, and the like, among which 2-mercaptosuccinic acid is particularly preferred.

As a linking method using a chain transfer agent residue, for example, after polymerizing a (meth)acrylic monomer by a known chain transfer polymerization reaction using 2-mercaptosuccinic acid, two 2-mercaptosuccinic acid residues A (meth)acrylic polymer having an acid anhydride group at one end is obtained by converting a carboxyl group into an acid anhydride by a known acid anhydride conversion reaction, and the obtained (meth)acrylic polymer having an acid anhydride group at one end. (Meth)acrylic resin unit (A) by reacting the acid anhydride group in the coalescence with any of the hydroxyl group, amino group and isocyanato group in the resin unit (B) having a urethane bond and/or a urea bond. and a block polymer of the resin unit (B) having a urethane bond and/or a urea bond.

When an acid anhydride group is used as a linking site, the (meth)acrylic resin unit (A) and the resin unit (B) having a urethane bond and/or a urea bond are linked in the form of an amide bond or an imide bond, resulting in an ester bond. It is preferable because it is chemically stable as compared with the like.

As the acrylic polymerization reaction using a chain transfer agent, a chain transfer reaction using a known thiol compound can be used. For example, in the presence of a (meth)acrylic monomer and a chain transfer agent, a radical polymerization initiator is added, By conducting a radical polymerization reaction at a reaction temperature of about 60 to 150° C., an acrylic polymer having a chain transfer agent residue at its terminal can be obtained. Although the reaction may be carried out in the absence of a solvent, it is preferable to use a solvent because the viscosity can be easily controlled.

Examples of (meth)acrylic monomers include, but are not limited to, the following examples, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl ( meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate Alkyl (meth)acrylates such as acrylates;
Dimethylaminoethyl (meth)acrylate, Dimethylaminopropyl (meth)acrylate, Dimethylaminobutyl (meth)acrylate, Diethylaminoethyl (meth)acrylate, Diethylaminopropyl (meth)acrylate, Dipropylaminoethyl (meth)acrylate, Dibutylaminoethyl Aminoalkyl (meth)acrylates such as (meth)acrylates;
Dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, dimethylaminobutyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide, dipropylaminoethyl (meth)acrylamide, dibutylaminoethyl Aminoalkyl (meth)acrylamides such as (meth)acrylamide;
(meth)acrylates having an alkylene oxide chain such as polyalkylene glycol mono(meth)acrylate monoalkyl ether;
Polydimethylsiloxane (meth)acrylates such as Silaplane FM-0711 and Silaplane FM-0721 (manufactured by Chisso Corporation) under product names;
Product names: Cheminox FAAC-4, Cheminox FAAC-6, Cheminox FAMAC-4, Cheminox FAMAC-6 (manufactured by Unimatec), R-1110, R-1210, R-1420, R-1620, R-5210 , R-5410, R-5610, M-1110, M-1210, M-1420, M-1620, M-5210, M-5410, M-5610 (manufactured by Daikin), light acrylate FA-108 ( Kyoeisha Chemical Co., Ltd.), Viscoat-3F, Viscoat-3FM, Viscoat-4F, Viscoat-8F, Viscoat-8FM (manufactured by Osaka Organic Chemical Industry Co., Ltd.) fluorine-containing (meth) acrylates;
The product names are macromonomer AA-6 (methyl methacrylate macromonomer), macromonomer AB-6 (butyl (meth)acrylate macromonomer), macromonomer AW-6S (isobutyl (meth)acrylate macromonomer), macromonomer Vinyl copolymerization of monomer AS-6 (styrene-based macromonomer), macromonomer AN-6S (styrene/acrylonitrile-based macromonomer), macromonomer AK-5 (dimethylsiloxane-based macromonomer) (manufactured by Toagosei Co., Ltd.), etc. system macromonomers;
Product names include (meth)acrylic acid polymer type (meth)acrylates such as Viscoat #150D (tetrahydrofurfuryl alcohol oligoacrylate) and Viscoat #190D (ethoxydiethylene glycol oligoacrylate) (manufactured by Osaka Organic Chemical Industry Co., Ltd.);
Benzyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate Examples include various (meth)acrylates such as acrylate, ethyl carbitol (meth)acrylate, butoxyethyl (meth)acrylate, and cyanoethyl (meth)acrylate, and in addition to these, radically polymerizable styrene, vinyl acetate, and the like are also used. be able to.
These (meth)acrylic monomers can be appropriately selected according to the purpose of use, and one type may be used alone, or two or more types may be used in combination.

Examples of polymerization initiators include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di(2-ethoxyethyl) peroxydicarbonate. , tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, organic peroxides such as diacetyl peroxide;
2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane 1-carbonitrile), 2,2′-azobis(2, 4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis ( 4-cyanovaleric acid), 2,2′-azobis(2-hydroxymethylpropionitrile), 2,2′-azobis[2-(2-imidazolin-2-yl)propane] and other azo compounds is mentioned. One of these polymerization initiators may be used alone, or two or more thereof may be used in combination.

Examples of solvents include, but are not limited to, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, toluene, xylene, anisole, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, m-cresol, γ-butyrolactone, γ-valerolactone and the like. These solvents may be used singly or in combination of two or more.

The method for converting the two carboxyl groups, which are chain transfer agent residues at the ends of the obtained acrylic polymer, into an acid anhydride is not limited to the following examples, but for example, acetic anhydride or 2,6-bis[( It can be obtained by intramolecular dehydration condensation using an intramolecular condensation catalyst such as 2,2,6,6-tetramethyl-1-piperidinyl)methyl]phenylboronic acid. Alternatively, a method of intramolecular dehydration condensation under high-temperature heating conditions without using a catalyst may be used.

The number average molecular weight (Mn) of the (meth)acrylic resin unit (A) may be appropriately adjusted according to the purpose of use, but from the viewpoint of controlling solubility and viscosity, it is preferably 1,500 to 100,000. is. The (meth)acrylic resin unit (A) includes the residue of the introduced chain transfer agent.

The (meth)acrylic resin unit (A) has a molecular weight dispersity (Mw/Mn) of 1.25 or more, preferably in the range of 1.25 to 5.0. Within this range, the solubility and viscosity can be easily controlled.

The resin unit (B) having a urethane bond and/or a urea bond may be a polymer having a urethane bond and/or a urea bond in the molecule and a terminal hydroxyl group, amino group or isocyanato group. There is no particular limitation, and specific examples include polyurethane, polyurethane urea, polyurea, and the like.

The polyurethane is, for example, a polyurethane having terminal hydroxyl groups or isocyanato groups obtained by reacting polyol and polyisocyanate in such a range that the molar ratio of hydroxyl groups to isocyanato groups (NCO/OH) is 0.5 to 2. As the polyurethane urea unit, for example, the above-described isocyanato group-terminated polyurethane and polyamine are reacted in a range where the molar ratio (NCO/NH) of the amino group to the isocyanate group is 0.5 to 2. Examples of polyureas include polyurethane ureas having amino groups or isocyanato groups at their ends, which are obtained from the above. Examples include polyurea having an amino group or an isocyanato group at the terminal, which is obtained by reacting within the range of .

The method for producing the resin unit (B) having a urethane bond and/or a urea bond is not particularly limited, and known urethanization or ureaization reactions can be used. The reaction may be carried out in the presence of a solvent or in the absence of a solvent. Tertiary amines such as triethylamine may also be used in combination as a catalyst for accelerating the reaction.

As a method for connecting the resin unit (B) having a urethane bond and/or a urea bond having a hydroxyl group at the end and the (meth)acrylic resin unit (A) having an acid anhydride group at one end, for example, in the presence of a solvent and heating at an arbitrary temperature of 50°C to 150°C.

As a method for linking the resin unit (B) having a urethane bond and/or a urea bond having an amino group at one end and the (meth)acrylic resin unit (A) having an acid anhydride group at one end, for example, A method of heating at an arbitrary temperature of 15° C. to 100° C. is mentioned below. Further, as a method for dehydrating and imidizing the bond, a known thermal imidization method or chemical imidization method can be used. After applying and removing the solvent to obtain a dry coating film, imidization can be easily carried out by heating at a high temperature of 150 to 250°C. In the chemical imidization method, for example, a base such as pyridine or triethylamine and acetic anhydride are added to a block polymer solution containing a solvent in an amount of 2 molar equivalents or more and less than 10 equivalents with respect to the starting material diamine, and the reaction is carried out at 0 to 50°C. It can be imidized by performing a conversion reaction.

As a method for connecting the resin unit (B) having a urethane bond and/or a urea bond having an isocyanato group at the end and the (meth)acrylic resin unit (A) having an acid anhydride group at one end, for example, and heating at any temperature of 50 to 250°C, preferably 100 to 200°C. A tertiary amine may be used in combination as a catalyst for promoting imidization.

The number average molecular weight (Mn) of the resin unit (B) having a urethane bond and/or urea bond may be appropriately adjusted according to the purpose of use, but the number average molecular weight (Mn) is preferably 1,000 to 500. ,000, more preferably in the range of 2,000 to 100,000. Within this range, the solubility and viscosity can be easily controlled.

Typical polyols include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, and the like. These polyols may be used singly or in combination of two or more.

Examples of polyether polyols include polymers or copolymers such as methylene oxide, ethylene oxide, propylene oxide, and tetrahydrofuran, specifically polyethylene glycol, polypropylene glycol, poly(ethylene/propylene) glycol, and polytetramethylene glycol. etc. In addition, polyether polyols obtained by condensation of hexanediol, methylhexanediol, heptanediol, octanediol, or mixtures of these may also be used.

Examples of polyester polyols include, but are not limited to, adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, pimelic acid, azelaic acid, and sebacine. acid, suberic acid, glutaric acid, 1,4-cyclohexyldicarboxylic acid, dimer acid, dibasic acid such as hydrogenated dimer acid,
Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9 -nonanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 3,3,5-trimethylpentanediol, 2,4-diethyl-1,5- Pentanediol, 1,12-octadecanediol, 1,2-alkanediol, 1,3-alkanediol, 1-monoglyceride, 2-monoglyceride, 1-monoglycerol ether, 2-monoglycerol ether, dimer diol, hydrogenated dimer a condensate obtained by an esterification reaction with a diol such as a diol;
Polyester diols such as caprolactone polymer, valerolactone polymer, methylvalerolactone polymer, lactic acid polymer, and castor oil fatty acid polymer obtained using the above diol as an initiator may be mentioned.
For the purpose of imparting a branched structure, a compound having three or more hydroxyl groups in the molecule, such as glycerin, trimethylolpropane, and pentaerythritol, may be used in combination.

Polycarbonate polyols are not limited to the following examples, but are obtained by the carbonic acid esterification reaction of dialkyl carbonates, alkylene carbonates, diaryl carbonates such as dimethyl carbonate, diethyl carbonate, ethylene carbonate and diaryl carbonate, diaryl carbonates, and the above diols. Examples include polycarbonate diols.

Examples of polyolefin-based polyols include, but are not limited to, the following examples, including hydroxyl-containing polybutadiene, hydrogenated hydroxyl-containing polybutadiene, hydroxyl-containing polyisoprene, hydrogenated hydroxyl-containing polyisoprene, hydroxyl-containing chlorinated polypropylene, and hydroxyl-containing chlorinated polyethylene. etc.

As the polyisocyanate, known aromatic, aliphatic and alicyclic isocyanates used in conventional urethanization reactions can be used, and are not limited to the following examples. isocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, lysine diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, Aromatic diisocyanates such as 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, and 1,5-tetrahydronaphthalene diisocyanate ;
Aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate;
alicyclic diisocyanates such as isophorone diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and the like; These may be used individually by 1 type, and may be used in combination of 2 or more type.

As the polyamine, any polyamine having at least two primary and/or secondary amino groups can be used, which is conventionally used as a chain extender in the synthesis of polyurea and the like. Examples include, but are not limited to, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 2-methyl-1,3-propanediamine, pentamethylenediamine, hexamethylenediamine, 2,2-dimethyl-1,3 -propanediamine, 2,2,4-trimethylhexamethylenediamine, tolylenediamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, phenylenediamine, xylylenediamine, N,N-dimethylethylenediamine, N,N- Diethylethylenediamine, N,N'-di-tert-butylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, N-methyl-1,3-propanediamine, N,2-methyl-1,3-propanediamine, N -isopropylethylenediamine, N-isopropyl-1,3-diaminopropane, N-lauryl-1,3-propanediamine and other diamines.
For the purpose of imparting a branched structure, methanetriamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, butane-1,1,4,4,-tetraamine, etc. may be used in combination. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of solvents include, but are not limited to, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, cyclohexanone, xylene, anisole, N, N - dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, m-cresol, diglyme, triglyme, Tetraglyme, γ-butyrolactone, γ-valerolactone and the like. Moreover, in the reaction for forming a urea bond, an alcoholic solvent such as methanol, ethanol, or isopropyl alcohol can also be used. These solvents may be used singly or in combination of two or more.

Tertiary amines and the like can be used as the catalyst, and specific examples include trimethylamine, triethylamine, tripropylamine, tributylamine, triethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, Triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline, isoquinoline and the like.

The ratio of the (meth)acrylic resin unit (A) in the block polymer may be appropriately adjusted according to the purpose of use. ~80% by weight. Within this range, various effects can be expected by block polymerization.

The coating method to the substrate is not particularly limited, and examples include bar coating, blade coating, spin coating, reverse coating, dyeing, spray coating, roll coating, gravure coating, microgravure coating, lip coating, and air knife coating. , dipping, etc. can be used.

Silicon wafers, metals, metal oxides, ceramics, resin films and the like can be used as the substrate.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the examples below do not limit the scope of the present invention. In the examples, "part" means "part by weight" and "%" means "% by weight".
The methods for measuring the resin solid content concentration, number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight dispersity (PDI), acid anhydride value, and amine value in the examples are as follows.

<Resin solid content concentration>
Based on JISK5601-1-2, the heating residue measured at a heating temperature of 150° C. for a heating time of 20 minutes was defined as the resin solid content concentration (%).
<Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight dispersity (PDI)>
GPC (manufactured by Shodex, GPC-104) equipped with an RI detector, Shodex GPCLF-604 (manufactured by Shodex) as a column, using the polystyrene equivalent molecular weight when using THF as a developing solvent, the number average molecular weight ( Mn) and weight average molecular weight (Mw) were measured to calculate the molecular weight dispersity (PDI=Mw/Mn). In addition, when the resin had amino groups at its terminals, all amino groups at both terminals were reacted with α,α-dimethyl-3-isopropenylbenzyl isocyanate as a pretreatment, and then the same measurement was performed.
<Acid anhydride value measurement>
The acid anhydride value is obtained as follows. Specifically, after weighing a (g) of a (meth)acrylic polymer having an acid anhydride group at one end, it is dissolved in xylene, and b (mmol) of octylamine equivalent to or more than the acid anhydride group is added. By doing so, the acid anhydride group and the primary amino group were reacted. It was then cooled to room temperature and the amount of remaining octylamine was quantified by titration with 0.1 M ethanolic perchloric acid. Assuming that the titer is c (ml), the acid anhydride value X of the (meth)acrylic polymer having an acid anhydride group at one end can be obtained from the following formula.
X=(b−0.1×c)/a
<Amine value measurement>
An amine value is calculated|required as follows. Specifically, about 3 g of a solution of a resin unit having a urethane bond and/or a urea bond was weighed into a flask, dissolved in 50 ml of methanol, and titrated by potentiometric titration using a 0.1 mol/l hydrochloric acid standard solution. , was calculated by the following formula from the obtained neutralization point.
Amine value = a x f x 5.61/(s x w)
a: Amount of 0.1 mol/l hydrochloric acid solution used (ml)
f: titer of 0.1 mol/l hydrochloric acid solution s: polyurethane urea resin solution (g)
w: Resin solid content concentration (%)

The abbreviations of the compounds used in the examples are as follows.
PGMEA: propylene glycol monomethyl ether acetate BA: normal butyl acrylate MMA: methyl methacrylate AIBN: 2,2-azobisisobutyronitrile IPA: isopropyl alcohol THF: tetrahydrofuran

(Synthesis Example 1) <Synthesis of (meth)acrylic resin unit (A-1)>
832 parts of PGMEA and 800 parts of MMA were charged into a reaction vessel equipped with a gas inlet pipe, a thermometer, a condenser and a stirrer, and the contents were purged with nitrogen gas. The reaction vessel was heated to 80° C., 24.0 parts of 2-mercaptosuccinic acid and 8.0 parts of AIBN were added and reacted for 12 hours. Solid content measurement confirmed that 95% had reacted.
After cooling the obtained solution to 50° C., 16.3 parts of acetic anhydride was charged into the reaction vessel and reacted at 100° C. for 9 hours. The reaction was carried out until 95% or more of the terminal dicarboxylic acid of the chain transfer agent was converted into an acid anhydride by measuring the acid anhydride value. The obtained solution of the (meth)acrylic resin unit (A-1) had a resin solid concentration of 50%, a number average molecular weight of 5,000, a weight average molecular weight of 9,000, and a molecular weight dispersity of 1.0. was 8.

(Synthesis Example 2) <Synthesis of (meth)acrylic resin unit (A-2)>
The same operation as in Synthesis Example 1 was performed except that the amounts of 2-mercaptosuccinic acid and acetic anhydride were changed to 40.0 parts and 27.2 parts, respectively. The obtained solution of the (meth)acrylic resin unit (A-2) had a resin solid concentration of 50%, a number average molecular weight of 3,000, a weight average molecular weight of 4,500, and a molecular weight dispersity of 1.0. was 5.

(Synthesis Example 3) <Synthesis of (meth)acrylic resin unit (A-3)>
The same operation as in Synthesis Example 1 was performed except that the (meth)acrylic monomer was changed from MMA to BA. The obtained solution of the (meth)acrylic resin unit (A-3) had a resin solid concentration of 50%, a number average molecular weight of 5,000, a weight average molecular weight of 9,500, and a molecular weight dispersity of 1.0. was 9.

(Synthesis Example 4) <Synthesis of (meth)acrylic resin unit (A-4)>
The same operation as in Synthesis Example 2 was performed except that the (meth)acrylic monomer was changed from MMA to BA. The obtained solution of the (meth)acrylic resin unit (A-4) had a resin solid concentration of 50%, a number average molecular weight of 3,000, a weight average molecular weight of 4,500, and a molecular weight dispersity of 1.0. was 5.

(Synthesis Example 5) <Synthesis of resin unit (B-1) having urethane bond and/or urea bond>
A flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube was charged with 366.7 parts of a polycondensate of adipic acid and 1,2-propanediol (number average molecular weight: 2000) as a polyester diol, and 96 parts of isophorone diisocyanate. 6 parts were charged and reacted at 90° C. for 6 hours under a nitrogen stream to obtain a polyurethane having an isocyanato group. Next, 198.6 parts of ethyl acetate was added to the obtained polyurethane having isocyanato groups to obtain a uniform solution of polyurethane having isocyanato groups. Next, to a mixture of 46.7 parts of isophoronediamine, 515.0 parts of ethyl acetate, and 476.4 parts of IPA, the solution of the polyurethane having an isocyanato group was added dropwise over 1 hour, followed by reaction for 1 hour to form urethane bonds and / Or a solution of the resin unit (B-1) having a urea bond was obtained. The obtained solution of the resin unit (B-1) having a urethane bond and/or a urea bond had a resin solid content concentration of 30% by weight, an amine value of the resin solid content of 5.6 mg KOH/1 g of resin, a number average molecular weight of 16, was 200.

(Synthesis Example 6) <Synthesis of resin unit (B-2) having urethane bond and/or urea bond>
A flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube was charged with 456.1 parts of a polyol (product name: "Kuraray Polyol P-2010", number average molecular weight: 2000, manufactured by Kuraray Co., Ltd.) and 100 parts of isophorone diisocyanate. 1 part was charged and reacted at 90° C. for 6 hours under a nitrogen stream to obtain a polyurethane having an isocyanato group. Next, 238.4 parts of ethyl acetate was added to the obtained polyurethane having isocyanato groups to obtain a uniform solution of polyurethane having isocyanato groups. Next, to a mixture of 43.8 parts of isophoronediamine, 513.0 parts of ethyl acetate, and 648.6 parts of IPA, the solution of the polyurethane having an isocyanato group was added dropwise over 1 hour, followed by reaction for 1 hour to form urethane bonds and / Or a solution of a resin unit (B-2) having a urea bond was obtained. The obtained solution of the resin unit (B-2) having a urethane bond and/or a urea bond has a resin solid content concentration of 30% by weight, an amine value of the resin solid content of 5.3 mg KOH/1 g of resin, a number average molecular weight of 17, 000.

(Example 1) <Block polymer (AB-1)>
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer was charged with 100.0 parts of a solution of the (meth)acrylic resin unit (A-1) and a resin unit (B-1) having a urethane bond and/or a urea bond. ) and 66.7 parts of THF were charged and purged with nitrogen gas. The reaction vessel was heated to 70° C., and the disappearance of the absorption at 1850 cm ⁻¹ derived from the acid anhydride group was confirmed by infrared absorption spectroscopy to complete the reaction. The resulting block polymer (AB-1) had a number average molecular weight of 27,600 and a resin solid content concentration of the solution of 30%.

(Examples 2 to 4) <Block Polymers (AB-2) to (AB-4)>
The same operation as in Example 1 was performed except that the blending amounts of the solution of the (meth)acrylic resin unit (A) and the solution of the resin unit (B) having a urethane bond and/or a urea bond were changed as shown in Table 1, Block polymers (AB-2) to (AB-4) were obtained. Table 1 shows the number average molecular weights of the obtained block polymers (AB-2) to (AB-4) and the resin solid content concentrations of the obtained block polymers (AB-2) to (AB-4) solutions.

<Evaluation of block polymer>
In order to confirm the formation of block polymers, solutions of the block polymers obtained in Examples 1 to 4, and (meth)acrylic resin units obtained in Synthesis Examples 1 to 6, having urethane bonds and/or urea bonds The following solubility test was performed on the resin solution of the resin unit. Table 2 shows the determination results.
(solubility)
The obtained resin solution was diluted with acetonitrile or toluene so that the solid content concentration of the resin was 1%, and the solubility in acetonitrile or toluene was determined according to the following evaluation criteria.
○: Completely dissolved.
Δ: Precipitation and aggregates are slightly generated.
x: Insoluble.

Both the triblock polymers obtained in Examples 1 and 2 and the (meth)acrylic resin units obtained in Synthesis Examples 1 and 2 are soluble in acetonitrile. Since the resin unit (B-1) having a bond and/or a urea bond is insoluble in acetonitrile, the resin unit (B-1) having a urethane bond and/or a urea bond is linked to the (meth)acrylic resin unit. It was confirmed that it was solubilized in acetonitrile by the effect of Similarly, the triblock polymers obtained in Examples 3 and 4 and the (meth)acrylic resin units obtained in Synthesis Examples 3 and 4 are both soluble in toluene. Since the resin unit (B-2) having a urethane bond and/or a urea bond is insoluble in toluene, the resin unit (B-2) having a urethane bond and/or a urea bond is a (meth)acrylic resin. It was confirmed that it was solubilized in toluene due to the effect of connecting with the unit.

Claims (2)

A block polymer represented by the following general formula (1), (2) or (3) in which a (meth)acrylic resin unit (A) and a resin unit (B) having a urethane bond and/or a urea bond are linked and the (meth)acrylic resin unit (A) has a molecular weight dispersity of 1.25 or more.
General formula (1)

general formula (2)

General formula (3)

general formula (4)

general formula (5)

general formula (6)

[In general formulas (1) to (6),
(A) is a (meth) acrylic resin unit,
(B) is a resin unit having a urethane bond and/or a urea bond;
Y ¹ is a hydrogen atom,
one of Y ² and Y ³ is a substituent represented by the general formula (4) or (5), and the other is a carboxyl group;
M ¹ is -NH- or -O-,
X is the point of attachment to Y ⁴ or Y ⁵ ,
One of Y ⁴ and Y ⁵ is a bonding site with X, and the other is a carboxyl group. ] A method for producing a block polymer in which a (meth)acrylic resin unit (A) and a resin unit (B) having a urethane bond and/or a urea bond are linked,
A step of polymerizing a (meth)acrylic monomer by a chain transfer polymerization reaction using 2-mercaptosuccinic acid to synthesize a (meth)acrylic polymer;
A step of converting the two carboxyl groups of the 2-mercaptosuccinic acid residue in the (meth)acrylic polymer into an acid anhydride by an acid anhydride conversion reaction to synthesize a (meth)acrylic polymer having an acid anhydride group at one end. When,
The acid anhydride group in the (meth)acrylic polymer having an acid anhydride group at one end and the hydroxyl group, amino group, or isocyanato group in the resin unit (B) having a urethane bond and/or a urea bond and reacting,
A method for producing a block polymer, wherein the (meth)acrylic resin unit (A) has a molecular weight dispersity of 1.25 or more.