JP2019206613A - Block polymer - Google Patents

Abstract

To provide a novel block polymer obtained by combining a (meth) acrylic resin and a polyamide unit.SOLUTION: The problem is solved by a block polymer having a (meth) acrylic resin unit (A) and a polyamide unit (B) coupled to each other, the (meth) acrylic resin unit (A) having a molecular weight dispersion of 1.25 or more, where the coupling site of the block polymer may be an amide bond and/or imide bond.SELECTED DRAWING: None

Description

The present invention relates to a block polymer formed by combining a (meth) acrylic resin unit and a polyamide unit.

  A block polymer is a structure in which a plurality of polymer units with different properties are linked for a specific physical property such as solubility, and uses characteristics such as micelle formation in solution and phase separation structure formation in bulk. Thus, it has been widely studied in fields such as adhesives, elastomers, functional pigment dispersants, compatibilizers, and drug delivery systems.

  As such a polymer unit, an acrylic material is preferably used because the degree of freedom of monomer selection is large 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 obtained by connecting three different types of acrylic units are used.

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

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

  The acrylic polymer obtained by the living polymerization method is characterized by a narrow molecular weight dispersity of 1.0 to 1.2 as compared with ordinary free radical polymerization. For pressure-sensitive adhesive applications that require dispersion of certain fillers and high adhesiveness, the uniformity of the polymer structure that is often derived from the molecular weight dispersity being too narrow and the high microphase separation ability resulting from it are It may cause defects and adhesive strength, and the properties of block polymers having a high molecular weight dispersion were expected.

JP 2009-215472 A

An object of the present invention is to provide a novel block polymer obtained by combining a (meth) acrylic resin and a polyamide unit.

  The present invention is a block polymer in which a (meth) acrylic resin unit (A) and a polyamide unit (B) are connected, and the molecular weight dispersity of the (meth) acrylic resin unit (A) is 1.25 or more. It relates to a featured block polymer.

  The present invention also relates to the block polymer, wherein the (meth) acrylic resin unit (A) and the polyamide unit (B) are connected by an amide bond and / or an imide bond.

  In the present invention, 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 with the polyamide unit (B). It is related with the said block polymer characterized.

  The present invention also relates to the 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.

  Moreover, this invention relates to the laminated body which consists of the said block polymer and a base material.

  According to the present invention, (meth) acrylic resin and polyamide can be expected to be used for dispersants, compatibilizers, bonding agents, porous materials, support materials, separation membranes, optical materials, electronic materials, medical materials, carbon materials, and the like. It was possible to provide a novel block polymer composed of

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 an embodiment of the present invention, and the present invention does not exceed the gist thereof. Not specific to the content.

The block polymer formed by combining the (meth) acrylic resin unit (A) and the polyamide unit (B) of the present invention is a block polymer in which the (meth) acrylic resin unit (A) and the polyamide unit (B) are connected. As long as the molecular weight dispersity of the (meth) acrylic resin unit (A) is 1.25 or more, each unit can use two or more types without any limitation.

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

As the component of each unit constituting the block polymer, for example, (meth) acrylic monomers used for known (meth) acrylic polymerization, diamines, dicarboxylic acids, cyclic lactones, etc. used for known polyamide synthesis can be used. .

  Although there is no restriction | limiting in particular as a connection method of a (meth) acrylic resin unit (A) and a polyamide unit (B), Preferably it is the connection by an amide bond and / or an imide bond. More preferably, an amide bond and / or an imide bond is formed with the polyamide unit (B) by the chain transfer agent residue introduced at the end of the (meth) acrylic resin unit (A). is there. As the chain transfer agent, a compound having two carboxyl groups and one or more thiol groups in the molecule is preferable.

  The compound having two carboxyl groups and one or more thiol groups in the molecule is not limited to the following examples. Specifically, 2-mercaptosuccinic acid, 2-mercaptoglutaric acid, 2,2-methylenebis (Thioglycolic acid), 2,3-dimercaptosuccinic acid, 4,5-dimercaptophthalic acid and the like can be mentioned, among which 2-mercaptosuccinic acid is particularly preferable.

As a linking method using a residue of a chain transfer agent, for example, after polymerization of a (meth) acrylic monomer by a known chain transfer polymerization reaction using 2-mercaptosuccinic acid, two 2-mercaptosuccinic acid residues are used. The carboxyl group is converted to an acid anhydride by a known acid anhydride reaction to obtain a (meth) acrylic polymer having an acid anhydride group at one end, and the resulting (meth) acrylic polymer having an acid anhydride group at one end is obtained. Polycondensation of the compound with diamine and dicarboxylic acid, self-condensation of ω-amino-ω ′ carboxylic acid, polycondensation of ω-amino-ω ′ carboxylic acid with diamine and / or dicarboxylic acid, or ring opening of cyclic lactam A (meth) acrylic resin unit (A) and a polyamide unit (B) are obtained by condensing a polyamide having an amino group at the terminal obtained from a condensation reaction such as polymerization. It can be obtained of the block polymer. The condensation reaction for forming the polyamide may be performed in the presence of a (meth) acrylic polymer having an acid anhydride group at one end.

  When an acid anhydride group is used as the linking site, the linkage between the (meth) acrylic resin unit (A) and the polyamide unit (B) becomes an amide bond or imide bond, which is chemically stable compared to an ester bond. This is preferable.

As an 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) acryl monomer and a chain transfer agent, a radical polymerization initiator is added, By performing the radical polymerization reaction at a reaction temperature of about 60 to 150 ° C., an acrylic polymer having a chain transfer agent residue at the terminal can be obtained. The reaction may be performed in the absence of a solvent, but it is preferable to use a solvent because the viscosity can be easily controlled.

As an 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) acryl monomer and a chain transfer agent, a radical polymerization initiator is added, By performing the radical polymerization reaction at a reaction temperature of about 60 to 150 ° C., an acrylic polymer having a chain transfer agent residue at the terminal can be obtained. The reaction may be performed in the absence of a solvent, but it is preferable to use a solvent because the viscosity can be easily controlled.

The (meth) acrylic monomer is not limited to the following examples. For example, 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) Alkyl (meth) acrylates such as acrylate;
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) acrylate;
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;
By product name, polydimethylsiloxane (meth) acrylates such as Silaplane FM-0711 and Silaplane FM-0721 (above, manufactured by Chisso Corporation);
By product name, Cheminox FAAC-4, Cheminox FAAC-6, Cheminox FAMAC-4, Cheminox FAMAC-6 (above, 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 ( Fluorine-containing (meth) acrylates such as Biscoat-3F, Biscoat-3FM, Biscoat-4F, Biscoat-8F, Biscoat-8FM (above, Osaka Organic Chemical Industry Co., Ltd.);
In the product name, macromonomer AA-6 (methyl methacrylate macromonomer), macromonomer AB-6 (butyl (meth) acrylate macromonomer), macromonomer AW-6S (isobutyl (meth) acrylate macromonomer),
Vinyl monomers such as macromonomer AS-6 (styrene macromonomer), macromonomer AN-6S (styrene / acrylonitrile macromonomer), macromonomer AK-5 (dimethylsiloxane macromonomer) (manufactured by Toagosei Co., Ltd.) Polymerized macromonomers;
(Meth) acrylic acid multimeric (meth) acrylates such as biscoat # 150D (tetrahydrofurfuryl alcohol oligoacrylate) and biscoat # 190D (ethoxydiethylene glycol oligoacrylate) (above, 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) Examples include various (meth) acrylates such as acrylate, ethyl carbitol (meth) acrylate, butoxyethyl (meth) acrylate, and cyanoethyl (meth) acrylate. In addition to these, radically polymerizable styrene and vinyl acetate are also used. be able to.
These (meth) acrylic monomers can be appropriately selected according to the purpose of use, and one kind may be used alone, or two or more kinds may be used in combination.

Examples of the polymerization initiator include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and di (2-ethoxyethyl) peroxydicarbonate. Tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-butylperoxybivalate, (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 ( Azo compounds such as 4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] Can be mentioned. These polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solvent 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 can be mentioned. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

The method for converting the two carboxyl groups, which are the chain transfer agent residues at the end of the obtained (meth) acrylic polymer, to acid anhydrides is not limited to the following examples. For example, acetic anhydride or 2,6- It can be obtained by intramolecular dehydration condensation using an intramolecular condensation catalyst such as bis [(2,2,6,6-tetramethyl-1-piperidinyl) methyl] phenylboronic acid. Alternatively, a method of performing 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) is preferably 1,500 to 100,000 from the viewpoint of control of solubility and viscosity. The (meth) acrylic resin unit (A) includes a residue of an introduced chain transfer agent.

  The molecular weight dispersity (Mw / Mn) of the (meth) acrylic resin unit (A) is 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.

Examples of the polyamide resin having the polyamide unit (B) include polycondensation of diamine and dicarboxylic acid, self-condensation of ω-amino-ω ′ carboxylic acid, ω-amino-ω ′ carboxylic acid and diamine and / or dicarboxylic acid. Examples thereof include polyamide resins produced by a method such as polycondensation with an acid or ring-opening polymerization of a cyclic lactam. Here, monoamine or monocarboxylic acid can be used as a polymerization regulator in the polycondensation, self-condensation, and ring-opening polymerization.

The diamine is not limited to the following examples. For example, p-phenylenediamine, m-phenylenediamine, 4,4-methylene-bis (2,6-ethylaniline), 4,4′-methylene-bis ( 2-isopropyl-6-methylaniline), 4,4′-methylene-bis (2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6- Tetramethyl-1,4-phenylenediamine, o-tolidine, m-tolidine, 3,3 ′, 5,5′-tetramethylbenzidine, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2- Bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4′-diamino- , 3′-dimethyldicyclohexylmethane, 4,4′-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 2,2-bis (4-anilino) hexafluoropropane, 2,2-bis (3-anilino) hexafluoropropane, 2,2-bis (3-amino-4-toluyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) ) Benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane and the like. In addition, dimeramine amines such as “PRIAMINE 1071”, “PRIAMINE 1073”, “PRIAMINE 1074”, “PRIAMINE 1075” (manufactured by CRODA JAPAN), “VERSAMIN 551” (manufactured by BASF) are used as product names. May be.
These diamines may be used alone or in combination of two or more.

Examples of the dicarboxylic acid include, but are not limited to, for example, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, tetradecanedicarboxylic acid, octadecanedicarboxylic acid, Examples thereof include fumaric acid, phthalic acid, xylylene dicarboxylic acid and the like. In addition, the product names “Pripole 1004”, “Pripole 1006”, “Pripole 1009”, “Pripole 1013”, “Puripole 1015”, “Puripole 1017”, “Puripole 1022”, “Puripole 1025”, “Puripole 1040” (Established by Croda Japan), “Empole 1008”, “Empole 1012”, “Empole 1016”, “Empole 1026”, “Empole 1028”, “Empole 1043”, “Empole 1061”, “Empole 1062” Dimer carboxylic acid such as BASF) may be used.
These dicarboxylic acids may be used individually by 1 type, and may be used in combination of 2 or more type.

The ω-amino-ω ′ carboxylic acid is not limited to the following examples, but examples thereof include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid. Is mentioned.

The cyclic lactam is not limited to the following examples, and examples thereof include ε-caprolactam, ω-enantolactam, and ω-lauryl lactam.

The condensation method of the polyamide unit is not particularly limited and can be appropriately selected from conventionally known methods. As an example of the polycondensation method, for example, a heat polymerization method in which diamine and dicarboxylic acid are subjected to dehydration condensation under high temperature and high pressure;
A method of increasing the molecular weight of a low-order condensate (oligomer) obtained by polycondensation of diamine and dicarboxylic acid under pressure and heating;
Examples thereof include an interfacial polymerization method in which an aqueous solution in which a diamine is dissolved and a solution in which a dicarboxylate is dissolved in an aqueous solvent or an organic solvent are brought into contact with each other and polycondensed at these interfaces.

In the formation of the polyamide, the ratio of the number of moles of amino groups in the diamine to the number of moles of carboxyl groups in the dicarboxylic acid is not particularly limited and can be appropriately selected according to the purpose of use. If the number of moles of the group / the number of moles of the carboxyl group in the dicarboxylic acid is in the range of 1.0 to 2.0, the terminal functional group of the polyamide becomes an amino group and has an acid anhydride group at one end (meth) Since connection with an acrylic polymer becomes easy, it is preferable.

By modifying at least part of the terminal amino group in the polyamide with an acid anhydride group in the (meth) acrylic polymer having an acid anhydride group at one end, the (meth) acrylic resin unit (A) and A block polymer of the polyamide unit (B) can be obtained.

  The reaction between the acid anhydride group in the (meth) acrylic polymer having an acid anhydride group at one end and the amino group in the polyamide may be carried out by selecting the form of bonding according to the purpose. An amide bond is formed and linked by reacting at a temperature of 110 ° C. to 110 ° C., and an imide bond is formed and linked by further reacting at a high temperature of 120 ° C. to 200 ° C. The reaction may be performed in the absence of a solvent, but it is preferable to use a solvent because the viscosity can be easily controlled.

When connecting a (meth) acrylic polymer having an acid anhydride group at one end and a polyamide, the number of moles of acid anhydride groups in the (meth) acrylic polymer having an acid anhydride group at one end and in the polyamide The ratio of the amino group to the number of moles of the amino group can be appropriately selected according to the purpose of use, but preferably the mole of the acid anhydride group in the (meth) acrylic polymer having an acid anhydride group at one end. The number / number of moles of amino groups in the polyamide is 0.3 to 1.0, and the reaction is easily controlled within this range.

The solvent for forming the block polymer is not limited to the following examples. For example, methanol, ethanol, propanol, diacetone alcohol, 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- Examples include cresol, γ-butyrolactone, γ-valerolactone, and the like. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The proportion of the (meth) acrylic resin unit (A) in the block polymer may be appropriately adjusted in accordance with the purpose of use, but preferably the (meth) acrylic resin unit (A) is 10 in 100% by weight of the block polymer. ~ 80% by weight. Within this range, various effects can be expected from the block polymerization.

Although it does not restrict | limit especially as an application method to a base material, For example, bar coating, blade coating, spin coating, reverse coating, diting, spray coating, roll coating, gravure coating, micro gravure coating, lip coating, air knife coating Dipping or the like can be used.

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

The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight” and “%” represents “% by weight”. In addition, the measurement method of the resin solid content concentration, number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight dispersity (PDI), and acid anhydride value in the examples is as follows.

<Resin solid content concentration>
Based on JISK5601-1-2, the heating residue when measured at a heating temperature of 150 ° C. and a heating time of 20 minutes was defined as a resin solid content concentration (%).
<Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight dispersity distribution (PDI)>
Using GPC equipped with an RI detector (manufactured by Shodex, GPC-104), using the molecular weight in terms of polystyrene when using Shodex GPCLF-604 (manufactured by Shodex) as a column and THF as a developing solvent, the number average molecular weight ( Mn) and a weight average molecular weight (Mw) were measured, and a molecular weight dispersity (PDI = Mw / Mn) was calculated.
<Acid anhydride value measurement>
The acid anhydride value is determined as follows. Specifically, a (g) a (meth) acrylic polymer having an acid anhydride group at one end is weighed and then dissolved in xylene, and b (mmol) of octylamine equal to or more than the acid anhydride group is added. Thus, the acid anhydride group and the primary amino group were reacted. Thereafter, the mixture was cooled to room temperature, and the amount of remaining octylamine was quantified by titrating with 0.1 M ethanolic perchloric acid. When the titration amount is c (ml), the acid anhydride value X of the (meth) acrylic polymer having an acid anhydride group at one end is obtained from the following formula.
X = (b−0.1 × c) / a

Abbreviations of compounds used in the examples are as follows.
PGMEA: Propylene glycol monomethyl ether acetate AIBN: 2,2-azobisisobutyronitrile PME-200: Product name “Blenmer PME-200” (methoxy polyethylene glycol monomethacrylate, manufactured by NOF Corporation, molecular weight 276)
Dimer acid: Product name “Pripol 1009” (manufactured by Croda Japan)
Dimer Amine: Product name “Puriamine 1075” (Claude Japan)
IPA: isopropyl alcohol DBA: N, N-dimethylbenzylamine

(Synthesis Example 1) <Synthesis of (meth) acrylic resin unit (A-1)>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 832 parts of PGMEA and PME-200 and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and 24.0 parts of 2-mercaptosuccinic acid and 8.0 parts of AIBN were added and reacted for 12 hours. It was confirmed that 95% had reacted by solid content measurement.
After the obtained solution was cooled to 50 ° C., 16.3 parts of acetic anhydride was charged into the reaction vessel and reacted at 100 ° C. for 9 hours. It was made to react until the terminal dicarboxylic acid of 95% or more of the chain transfer agent converted into an acid anhydride in the measurement of the acid anhydride value. The solution of the obtained (meth) acrylic resin unit (A-1) has a resin solid content 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. It 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 blending amounts of 2-mercaptosuccinic acid and acetic anhydride were changed to 40 parts and 27.2 parts, respectively. The solution of the obtained (meth) acrylic resin unit (A-2) has an acid anhydride group at one end, the resin solid content concentration is 50%, the number average molecular weight is 3,000, and the weight average molecular weight. Was 4,500 and the molecular weight dispersity was 1.5.

(Synthesis Example 3) <Synthesis of Polyamide Unit (B-1)>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer is charged with 45.6 parts of Pripol 1009 as dimer acid, 54.4 parts of Priamine 1075 as dimer amine, and 3.0 parts of toluene, and the exothermic temperature is constant. Stir until. After the temperature was stabilized, the temperature was raised to 110 ° C., and then the dehydration reaction was continued while raising the temperature by 10 ° C. every 30 minutes. When the temperature reached 230 ° C., the reaction was continued for 3 hours at the same temperature, and kept for 1 hour under a vacuum of about 2 kPa. After the temperature was lowered, a toluene / IPA mixed solvent (mixing ratio 60:40) was added. After 400 parts were charged and stirred for a while to completely dissolve, the reaction was completed. The design molecular weight of the polyamide unit (B-1) was 5,000, and the resin solid content concentration of the obtained polyamide unit (B-1) solution was 20%.

(Synthesis Example 4) <Synthesis of polyamide unit (B-2)>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer is charged with 48.3 parts of Pripol 1009 as dimer acid, 51.7 parts of Priamine 1075 as dimer amine, and 3.0 parts of toluene, and the exothermic temperature is constant. Stir until. After the temperature was stabilized, the temperature was raised to 110 ° C., and then the dehydration reaction was continued while raising the temperature by 10 ° C. every 30 minutes. When the temperature reached 230 ° C., the reaction was continued for 3 hours at the same temperature, and kept for 1 hour under a vacuum of about 2 kPa. After the temperature was lowered, a toluene / IPA mixed solvent (mixing ratio 60:40) was added. After 400 parts were charged and stirred for a while to completely dissolve, the reaction was completed. The design molecular weight of the polyamide unit (B-2) was 10,000, and the resin solid content concentration of the obtained polyamide unit (B-2) solution was 20%.

(Example 1) <Block polymer (AB-1)>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 250 parts of the polyamide unit (B-1) solution and 330 parts of IPA were charged and replaced with nitrogen gas. While slowly stirring at room temperature, 220 parts of the (meth) acrylic resin unit (A-1) solution was slowly added, the reaction vessel was heated to 70 ° C., and 1850 cm ⁻ derived from the acid anhydride group by infrared absorption spectrum measurement. ^After confirming the disappearance of absorption of ¹ , the reaction was terminated. The resin solid content concentration of the obtained block polymer (AB-1) solution was 20%.

(Examples 2 to 4) <Block polymers (AB-2) to (AB-4)>
The same operations as in Example 1 were carried out except that the types and amounts of the (meth) acrylic resin unit solution, polyamide unit, and solvent were changed as shown in Table 1, and block polymers (AB-2) to (AB-4) ) Table 1 shows the design molecular weight of the polyamide unit in the block polymer and the resin solid concentration of the obtained block polymer (AB-2) to (AB-4) solution.

<Evaluation of block polymer>
In order to confirm the formation of the block polymer, the solution of the block polymer obtained in Examples 1 to 4 and the resin solution of the (meth) acrylic resin unit and the polyamide unit obtained in Synthesis Examples 1 to 4 were as follows. Solubility tests were performed. Table 2 shows the determination results.
(Solubility)
The obtained resin solution was diluted with methanol so that the solid content concentration of the resin would be 1%, and the solubility in methanol was determined according to the following evaluation criteria.
○: Completely dissolved.
Δ: Precipitates and aggregates are slightly generated.
X: Insoluble.

The triblock polymers obtained in Examples 1 to 4 and the (meth) acrylic resin units obtained in Synthesis Examples 1 and 2 are both soluble in methanol, whereas in contrast to those obtained in Synthesis Examples 3 to 4. Since the polyamide unit was insoluble in methanol, it was confirmed that the polyamide unit was solubilized in methanol due to the effect of coupling with the (meth) acrylic resin unit.

Claims (6)

  A block polymer in which a (meth) acrylic resin unit (A) and a polyamide unit (B) are linked, and the molecular weight dispersion of the (meth) acrylic resin unit (A) is 1.25 or more. polymer.   The block polymer according to claim 1, wherein the (meth) acrylic resin unit (A) and the polyamide unit (B) are linked by an amide bond and / or an imide bond.   The amide bond and / or the imide bond with the polyamide unit (B) are formed by the chain transfer agent residue introduced into the terminal portion of the (meth) acrylic resin unit (A). The block polymer described.   4. The block polymer according to claim 3, wherein the chain transfer agent is 2-mercaptosuccinic acid.   The block polymer according to claim 1, which is a triblock polymer. A laminate comprising the block polymer according to claim 1 and a substrate.