JP2021091878A - Block copolymer and method for producing the same - Google Patents

Abstract

To provide a block copolymer which has high compatibility with a resin, facilitates reaction control, and is excellent in storage stability, and a method for producing the same.SOLUTION: A block copolymer is obtained by bonding a polyorganosiloxane block [A] and a polyether block [B] through a connection segment [Z], has an acid dissociation constant pKa obtained by measuring 0.5 g/dL of a solution using tetrahydrofuran as a solvent at 25°C of larger than 7.0 and 9.0 or smaller, and contains 0.3 or more and 3.0 mmol/g or less of a carboxyl group.SELECTED DRAWING: None

Description

The present invention relates to block copolymers and methods for producing them.

Since block copolymers exhibit excellent properties such as weather resistance, durability and toughness, practical development has progressed and they are used in a wide range of fields such as cosmetics, adhesives, paints and electronic materials.

Among them, it is widely known that a block copolymer in which a silicone component is introduced into a skeleton is useful as a material capable of modifying the mechanical properties and fluidity of a resin.

However, such a block copolymer has a problem that it has poor solubility in a resin and is inferior in handleability. Further, in order to solve this problem, it is often used as a masterbatch in which a block copolymer is concentrated in a resin in advance, but it causes thickening during storage and deteriorates the mechanical properties of the obtained molded product. There was also a problem.

In recent years, it has been considered important and effective to control the reaction of block copolymers in response to such problems, and the development of structural design for block copolymers is progressing. For example, a method of master-batching a block copolymer composed of a vinyl-terminal siloxane component and a polypropylene component by melt-kneading is disclosed (Patent Document 1). Further, a polyoxyalkylene copolymer having one end modified with a carboxyl group is disclosed (Patent Document 2). Further, a block copolymer having a highly reactive functional group in the side chain by reacting a polysiloxane having a polar group with a polyalkylene glycol is disclosed (Patent Document 3).

Special Table 2017-507233 Gazette Japanese Unexamined Patent Publication No. 2001-24674 International Publication No. 2018/221373

However, in Patent Document 1, the affinity with the resin is low, and it is necessary to knead using an extruder when making a masterbatch, and there is a problem that a complicated manufacturing process is required. Further, there is a problem that thickening of the resin composition is caused by subjecting the resin composition containing the block copolymer to a certain degree of shearing.

In Patent Document 2, it is difficult to control the reaction when the resin and the block copolymer are compatible with each other, and there is a problem that the block copolymer aggregates in the resin composition, thickening of the resin composition, and the like. There was a problem.

Patent Document 3 has excellent affinity with the resin and good mechanical properties, but does not mention at all the control of the reaction when the block copolymer is blended with the resin and the storage stability.

The present invention provides a block copolymer having a high affinity for a resin, easy reaction control, and excellent storage stability, and a method for producing the same.

As a result of diligent studies by the present inventors in order to solve the above problems, the following inventions have been reached. The present invention
"<1> Block [A] and block [B] are block copolymers bonded via a connecting segment [Z], and block [A] has a structural unit represented by the general formula (1). And

(R ₁ represents hydrogen, an alkyl group or an aryl group having 1 to 10 carbon atoms, which may be the same or different. N represents a repeating unit of 5 to 70.)
The block [B] has a structural unit represented by the general formula (2) and has a structural unit.

(R ₂ represents an alkylene group or an arylene group having 1 to 10 carbon atoms, which may be the same or different. M represents a repeating unit of 3 to 100.)
In addition, for a 0.5 g / dL solution using tetrahydrofuran as a solvent, the acid dissociation constant pKa measured at 25 ° C. is in the range of 9.0 or less, which is larger than 7.0, and the carboxyl group is 0.3 or more and 3. A block copolymer characterized by containing a carboxyl group of 0 mmol / g or less.

<2> A compound [A'] having a structural unit represented by the general formula (1) and having any functional group selected from a hydroxyl group, a thiol group, and an amino group at the end, and the general formula. A link having a compound [B'] having a structural unit represented by (2) and having any functional group selected from a hydroxyl group, a thiol group, and an amino group at the end and a cyclic acid anhydride at the end. A method for producing a block copolymer, which is obtained by reacting an agent [Z']. ".

According to the present invention, it is possible to provide a block copolymer having a high affinity with a resin, easy reaction control, and excellent storage stability, and a method for producing the same.

The block copolymer in the present invention has a structure in which a block [A] and a block [B] are bonded via a connecting segment [Z].

Here, the block [A] of the present invention has a structural unit represented by the general formula (1). Since such a structural unit has a siloxane skeleton, it has excellent viscosity of a resin composition containing a block copolymer. Further, the molded product obtained from such a resin composition has improved mechanical properties such as durability, toughness and elastic modulus.

_{In addition, R 1} of the general formula (1) represents hydrogen, an alkyl group or an aryl group having 1 to 10 carbon atoms, and may be the same or different from each other. R ₁ is preferably any of a methyl group, an ethyl group and a propyl group, and more preferably a methyl group.

n represents the number of repeating units of 5 to 70. As the lower limit of the repeating unit n, 7 or more is preferable, 10 or more is more preferable, and 12 or more is particularly preferable. The upper limit of the repeating unit n is preferably 60 or less, more preferably 55 or less, and particularly preferably 50 or less.

The block [B] in the present invention has a structural unit represented by the general formula (2). Such a structural unit has a high affinity with a resin and has good dispersibility in a resin composition, so that mechanical properties such as toughness of a molded product are improved.

R ₂ represents an alkylene group or an arylene group having 1 to 10 carbon atoms, and may be the same or different from each other. The preferred carbon number of R _{2 is 3 or 4.}

m represents the number of repeating units from 3 to 100. As the lower limit of the repeating unit m, 5 or more is preferable, 7 or more is more preferable, and 10 or more is particularly preferable. The upper limit of the repeating unit n is preferably 90 or less, more preferably 80 or less, and particularly preferably 70 or less.

The connecting segment [Z] in the present invention means a connecting portion connecting the block [A] and the block [B]. Such a linking segment [Z] is indispensable for enhancing the affinity between the block [A] and the block [B] and promoting the reaction in the process of producing the block copolymer. In addition, it plays an important role because the acid dissociation constant pKa (hereinafter, may be referred to as pKa) of the block copolymer of the present invention can be controlled.

The connecting segment [Z] of the present invention preferably has a functional group exhibiting reactivity. As such a functional group, a carboxyl group is preferable. Such a carboxyl group is preferably substituted with a cyclic skeleton from the viewpoint that pKa can be controlled within the range of the present invention. Specifically, the connected segment [Z] of the present invention preferably has at least one structure selected from the general formulas (3) to (7).

(X of [Chemical formula 3] to [Chemical formula 7] is a carboxyl group.)

Further, the connecting segment [Z] preferably has a polar group in the structure in order to enhance the affinity with the resin. Specifically, it is preferable to have at least one selected from an ester group, a thioester group, and an amide group. The connecting segment [Z] preferably contains an ester group and an amide group, and more preferably contains an ester group.

The block copolymer in the present invention has an acid dissociation constant pKa measured at 25 ° C. in a range of 9.0 or less, which is larger than 7.0 for a 0.5 g / dL solution using tetrahydrofuran as a solvent.

The inventors have found that by setting the pKa of the block copolymer in the above range, it has a high affinity with the resin, the reaction control with the resin is easy, and the storage stability is excellent. Specifically, when the block copolymer is dissolved in a resin to form a masterbatch, it has a high affinity with the resin, so that the heat history that has been conventionally required can be reduced. As a result, it becomes possible to suppress the thickening of the master batch. Further, even in the form of a masterbatch, the reaction does not proceed at room temperature, so that the storage stability is excellent. On the other hand, as the temperature is increased, the reaction starts in a specific temperature range and proceeds efficiently.

When the pKa is 7.0 or less, the reactivity of the block copolymer becomes high, the reaction proceeds even at room temperature, and the storage stability is inferior. The lower limit of pKa is preferably 7.2 or more, and more preferably 7.5 or more. On the other hand, when pKa is larger than 9.0, the reactivity does not proceed at room temperature and the storage stability is excellent, but the reaction does not proceed easily even when heated, so that the affinity with the resin deteriorates. The upper limit of pKa is preferably 8.8 or less, more preferably 8.5 or less.

The pKa of the block copolymer of the present invention is obtained by preparing a 0.5 g / dL solution using tetrahydrofuran as a solvent and titrating with a methanol solution of potassium methoxyd using an automatic potential difference titrator. It can be calculated from the first equivalence point.

The content of the carboxyl group of the block copolymer in the present invention needs to be in the range of 0.3 or more and 3.0 mmol / g or less from the viewpoint of improving the affinity with the resin. When the carboxyl group is less than 0.3 mmol / g, the number of reaction points with the resin is reduced, the affinity with the resin is lowered, and the adhesiveness at the interface of the obtained molded product is lowered. The lower limit of the carboxyl group is more preferably 0.4 mmol / g or more, and particularly preferably 0.5 mmol / g or more. When the carboxyl group exceeds 3.0 mmol / g, self-assembly of the block copolymer occurs, aggregates are formed, and the handleability deteriorates. Further, when such a block copolymer is blended with a resin, the reaction proceeds excessively due to the large number of reaction points, and the fluidity of the resin composition decreases. The upper limit of the carboxyl group is more preferably 2.5 mmol / g or less, further preferably 2.0 mmol / g or less, particularly preferably 1.5 mmol / g or less, and most preferably 1.2 mmol / g or less.

The content of the carboxyl group of the block copolymer is calculated by dissolving the block copolymer in tetrahydrofuran and titrating it with 0.1 mol / L alcoholic potassium hydroxide using phenolphthalein as an indicator according to JISK0070. ..

The block copolymer of the present invention preferably contains 0.015 mmol / g or less of the compound containing an acid anhydride group. Due to the high reactivity of the acid anhydride group, when blended with the resin, the reaction may proceed and the resin composition may thicken. The upper limit of the compound containing an acid anhydride group is more preferably 0.0125 mmol / g or less, further preferably 0.010 mmol / g or less, and particularly preferably 0.008 mmol / g or less. The smaller the amount of the compound containing an acid anhydride group, the better the viscosity, which is preferable, and the lower limit is 0 mmol / g.

_{The weight average molecular weight (M w} ) of the block copolymer of the present invention is preferably in the range of 5,000 or more and 50,000 or less. When the weight average molecular weight is less than 5,000, the toughness of the block copolymer is lowered, so that the toughness of the molded product may also be lowered. The lower limit of the weight average molecular weight is preferably 5,000 or more, more preferably 7,000 or more, more preferably 10,000 or more, still more preferably 12,000 or more, and particularly preferably 12,000 or more. It is over 15,000. When the weight average molecular weight is larger than 50,000, the viscosity of the block copolymer tends to increase and the fluidity tends to deteriorate. Further, when a molded product in which a block copolymer is blended with a resin is obtained, it cannot penetrate into the details of the mold at the time of molding, which causes molding defects, which is not preferable. The upper limit of the weight average molecular weight is preferably 50,000 or less, more preferably 45,000 or less, more preferably 40,000 or less, still more preferably 35,000 or less, and most preferably 30. It is less than 000.

The weight average molecular weight of the block copolymer referred to here refers to the weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent and converted into polymethylmethacrylate.

_{The molecular weight distribution (M w} / M _n ) of the block copolymer of the present invention is preferably 5 or less, more preferably 3 or less, still more preferably 2 or less. The lower limit is 1. The molecular weight distribution (M _w / M _n ) is calculated from the weight average molecular weight (M _w ) and the number average molecular weight (M _n ) measured as described above using gel permeation chromatography.

The block copolymer in the present invention has a structural unit represented by the general formula (1) and has a functional group selected from a hydroxyl group, a thiol group, and an amino group at the end of the compound [A'. ], And a compound [B'] having a structural unit represented by the general formula (2) and having any functional group selected from a hydroxyl group, a thiol group, and an amino group at the end, and a cyclic compound at the end. It can be produced by reacting a linking agent [Z'] having an acid anhydride.

Such compound [A'] has a structural unit represented by the general formula (1) and has any functional group selected from a hydroxyl group, a thiol group, and an amino group at the terminal. The functional group may be present at both ends or only at one end. As the functional group of the compound [A'], a hydroxyl group and an amino group are preferable from the viewpoint of suppressing a side reaction between the bond formed by the reaction with the linking agent [Z'] and the reactive group of the other polymer component, and the hydroxyl group is used. Is more preferable.

The weight average molecular weight of the compound [A'] having any functional group selected from such a hydroxyl group, a thiol group, and an amino group at the terminal is not particularly limited, but the lower limit thereof is preferably 500 or more. It is more preferably 800 or more, still more preferably 1,000 or more. The upper limit of the weight average molecular weight is preferably 8,000 or less, more preferably 5,000 or less, still more preferably 4,000 or less, and most preferably 3,000 or less. When the weight average molecular weight of the compound [A'] having any functional group selected from a hydroxyl group, a thiol group, and an amino group at the terminal is small, the characteristics derived from the siloxane skeleton are not exhibited, and the obtained block copolymer is obtained. Is not preferable because the performance as a resin modifier when the siloxane is added to the epoxy resin may be lowered. When the weight average molecular weight of compound [A'] is large, compound [A'] and compound [B'] are phase-separated, polymerization does not proceed in a uniform state, and a homogeneous block copolymer is obtained. It may not be possible. The weight average molecular weight of the compound [A'] having any functional group selected from a hydroxyl group, a thiol group, and an amino group at the end was measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. , Refers to the weight average molecular weight converted to polymethyl methacrylate.

Examples of such compound [A'] include KF-6000, KF-6001, KF-6002, KF-6003, X-22-160AS, X-22-1821, and X-, which are commercially available from Shin-Etsu Chemical Industry Co., Ltd. 22-167B, X-22-167C, PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, X-22- Examples thereof include 9409, X-22-170BX, X-22-170DX, BY16-201, SF8427Fluid, BY16-853U, BY16-871, which are commercially available from Toray Dow Corning Co., Ltd.

Such compound [B'] has a structural unit represented by the general formula (2) and has any functional group selected from a hydroxyl group, a thiol group, and an amino group at the terminal. The functional group may be present at both ends or only at one end. From the viewpoint of suppressing side reactions, hydroxyl groups and amino groups are preferable, and hydroxyl groups are more preferable. The weight average molecular weight of compound [B'] is not particularly limited, but its lower limit is preferably 500 or more, more preferably 800 or more, and further preferably 1,000 or more. The upper limit of the weight average molecular weight is preferably 8,000 or less, more preferably 5,000 or less, still more preferably 4,000 or less, and most preferably 3,000 or less. When the weight average molecular weight of the compound [B'] is small, the performance as a resin modifier when the obtained block copolymer is added to the epoxy resin may be lowered, which is not preferable. Further, when the weight average molecular weight of the compound [B'] is large, the compound [B'] and the compound [A'] are phase-separated and the polymerization does not proceed in a uniform state, so that a homogeneous block copolymer is obtained. It is not preferable because it cannot be used. The weight average molecular weight of the compound [B'] having any functional group selected from a hydroxyl group, a thiol group, and an amino group at the end was measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. , Refers to the weight average molecular weight converted to polymethyl methacrylate.

Compound [B'] has a structural unit represented by the general formula (2). Specifically, polyneopentyl glycol which is a penten group in which _{R 2 is branched, polytetramethylene glycol in which R 2} is a linear butylene group, polypropylene glycol which is a propylene group in which _{R 2 is branched, and R 2} is an ethylene group. Polyethylene glycol, and copolymers thereof and the like. In particular, polyneopentyl glycol, polytetramethylene glycol, polypropylene glycol, and polypropylene glycol / polyethylene glycol copolymers are preferable because they have excellent affinity with the compound [A'] and a homogeneous block copolymer can be obtained. Polytetramethylene glycol, polypropylene glycol, polypropylene glycol / polyethylene glycol copolymers are more preferable because of their excellent affinity with other polymer components, and polypropylene glycol / polyethylene is particularly excellent in reactivity with compound [Z']. Glycol copolymers are particularly preferred.

The linking agent [Z'] is preferably an acid anhydride having a cyclic acid anhydride at the terminal and the adjacent group thereof being an alicyclic hydrocarbon. Specifically, 1,2,3,4-butanetetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1, 2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexanetetracarboxylic dianhydride, 1 , 2,4,5-Cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, meso-butane-1, 2,3,4-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 4- (2,5- Dioxotetrakidian-3-yl) -1,2,3,4-tetraline-1,2-dicarboxylic acid anhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic Examples thereof include acid dianhydride and dicyclohexyl-3,4,3', 4'-tetracarboxylic dianhydride. In particular, since it has excellent solubility in compound [A'] and compound [B'] and excellent reactivity, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4- Cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, mesobutane-1,2,3,4-tetracarboxylic acid dianhydride, 5- (2,5) −Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 4- (2,5-dioxotetrahydrofuryl) -1,2,3,4-tetraline- At least one selected from 1,2-dicarboxylic acid anhydride and dicyclohexyl-3,4,3', 4'-tetracarboxylic acid dianhydride is preferable.

The block copolymer of the present invention has a structural unit represented by the general formula (1) and has a functional group selected from a hydroxyl group, a thiol group, and an amino group at the end of the compound [A'. ], And a compound [B'] having a structural unit represented by the general formula (2) and having any functional group selected from a hydroxyl group, a thiol group, and an amino group at the end, and a cyclic compound at the end. It can be obtained by reacting a linking agent [Z'] having an acid anhydride. Examples of the method include a method in which compound [A'], compound [B'] and a linking agent [Z'] are mixed and reacted by heating. If necessary, the method is carried out in an organic solvent. You may. If necessary, the reaction may be carried out in a nitrogen atmosphere.

The temperature at which the compound [A'], the compound [B'] and the linking agent [Z'] are reacted is preferably 220 ° C. or lower, more preferably 200 ° C., in order to suppress side reactions and decomposition of the polymer. Below, it is more preferably 180 ° C. or lower, and particularly preferably 160 ° C. or lower. The lower limit of the reaction temperature is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 100 ° C. or higher.

The reaction time depends on the combination of functional groups possessed by each, but is preferably 20 hours or less, more preferably 15 hours or less, and further preferably 10 hours or less from the viewpoint of productivity.

When an organic solvent is used in the reaction, the organic solvent is preferably a good solvent of the compound [A'], the compound [B'] and the linking agent [Z']. For example, hydrocarbon solvents such as toluene, xylene, benzene, 2-methylnaphthalene; ester solvents such as ethyl acetate, methyl acetate, butyl acetate, butyl propionate, butyl butyrate, ethyl acetoacetate; chloroform, bromoform, methylene chloride. , 1,2-Dichloroethane, 1,1,1-trichloroethane, chlorobenzene, 2,6-dichlorotoluene, 1,1,1,3,3,3-hexafluoroisopropanol and other halogenated hydrocarbons Solvents: Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl butyl ketone; alcohol solvents such as methanol, ethanol, 1-propanol and 2-propanol; N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide ( Aprotonic polar solvents such as DMSO), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), propylene carbonate, trimethylphosphate, 1,3-dimethyl-2-imidazolidinone, sulfolane, etc. Carous acid solvents such as formic acid, acetic acid, propionic acid, butyric acid and lactic acid; ether solvents such as anisole, diethyl ether, tetrahydrofuran, diisopropyl ether, dioxane, diglime and dimethoxyethane; 1-butyl-3-methylimidazolium acetate, Ionic liquids such as 1-butyl-3-methylimidazolium hydrogen sulfate, 1-ethyl-3-imidazolium acetate, 1-ethyl-3-methylimidazolium thiocyanate; or mixtures thereof. Of these, toluene, xylene or ethyl acetate is preferable from the viewpoint of the balance between the reaction rate and the removal of the solvent after the reaction. Further, these organic solvents may be used alone or in combination of two or more.

When the reaction is carried out in an organic solvent, the organic solvent can be removed and purified by a method such as heating, reduced pressure, or reprecipitation. A plurality of steps may be combined to remove the organic solvent.

However, when an organic solvent is not used, a purification step for removing the organic solvent is not required, the production process is simple, and the reaction temperature can be raised, so that the metal of the reaction accelerator can be used. Even in a system that does not use a catalyst, the reaction rate can be increased, which is preferable because the productivity is improved.

Further, although a reaction accelerator or the like may be added at the time of the reaction, it is preferable to carry out the reaction without using a reaction accelerator because there is a possibility of accelerating the side reaction between the block copolymer and other polymer components. It is possible to easily obtain the desired block copolymer without adding a reaction accelerator.

As a method for producing a block copolymer of the present invention, the ratio of the number of moles of the linking agent [Z'] to the total molar number of the compound [A'] and the compound [B'] may be 0.5 to 0.8. preferable. When the ratio is lower than 0.5, the acid anhydride group of the linking agent [Z'] is insufficient with respect to the functional groups of the compound [A'] and the compound [B'], and the compound [A'] And the compound [B'] remain, which is not preferable. When the ratio of the number of moles of the linking agent [Z'] to the total molar sum of the compound [A'] and the compound [B'] exceeds 0.8, the compound containing the acid anhydride group of the obtained block copolymer is high. As a result, reaction controllability and storage stability may decrease. The lower limit of the ratio of the number of moles is preferably 0.52, more preferably 0.54, and even more preferably 0.55. The upper limit of the molar ratio is preferably 0.78, more preferably 0.76, and even more preferably 0.75.

When adjusting the ratio of the number of moles of the linking agent [Z'] to the total number of moles of the compound [A'] and the compound [B'], the number of moles of the compound [A'] and the compound [B'] is the functional group equivalent. Can be calculated as the molecular weight by doubling the number. When the compound [A'] and / or [B'] has a functional group at one end, the equivalent amount of the functional group can be calculated as the molecular weight. The functional group equivalent can be measured according to JIS K0070.

Next, the present invention will be described in more detail based on Examples. The present invention is not limited to these examples. The measurement methods used in the examples are as follows.

(1) Measurement of acid dissociation constant pKa 0.5 g of block copolymer was dissolved in 100 mL of tetrahydrofuran, and 0.1 mol / L potassium methoxyde was used using an automatic potential difference titrator (AT-610 manufactured by Kyoto Denshi Kogyo Co., Ltd.). Titration was performed with a benzene-methanol solution, and pKa was calculated from the first equivalence point of the obtained titration curve.

(2) Quantification of carboxyl groups Calculated according to JISK0070. Specifically, 0.5 g of the block copolymer was dissolved in 10 g of tetrahydrofuran and titrated with 0.1 mol / L alcoholic potassium hydroxide using phenolphthalein as an indicator to quantify the carboxyl group.

(3) Quantification of compound containing acid anhydride group 7 g of block copolymer is dissolved in 20 g of 2-propanol, 20 mg of aniline is added, and the mixture is stirred for 1 hour, and then 0.1 mol / L 2 using methyl orange as an indicator. -The compound was titrated with propanol hydrochloric acid, and the compound containing an acid anhydride group was quantified from the residual amount of aniline.

(4) Measurement of Weight Average Molecular Weight The weight average molecular weight of the block copolymer and the compound [A'] having a functional group at the end and the compound [B'] having a functional group at the end are determined by gel calibration chromatography. Then, the measurement was carried out under the following conditions, and the molecular weight was calculated using a calibration curve with polymethyl methacrylate.
Equipment: Shimadzu Corporation LC-20AD Series Column: Showa Denko Corporation KF-806L x 2
Flow velocity: 1.0 mL / min
Mobile phase: Tetrahydrofuran Detection: Differential refractometer Column temperature: 40 ° C

(5) Measurement of heat generation start temperature of the composition of block copolymer and epoxy resin 3.0 g of block copolymer and bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., "jER" (registered trademark) 828) 6. The composition obtained by stirring and mixing 0 g at room temperature was weighed in a 5 mg aluminum pan, and measured with DSC (Q20 manufactured by TA Instruments) under the following conditions to determine the heat generation start temperature.
Measurement temperature: 20 ° C to 250 ° C
Temperature rise rate: 10 ° C / min Atmosphere: Nitrogen flow rate: 50 mL / min

(6) Viscosity measurement of block copolymer and epoxy resin composition 1.5 g of block copolymer and 8.5 g of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., "jER" (registered trademark) 828) are added at room temperature. The viscosity of the mixture obtained by stirring and mixing with the above was measured using a leometer (MCR501 manufactured by Antonio Par) under the following conditions to determine the viscosity, and the viscosity after 1 minute of measurement time was compared with the viscosity after 3 hours of measurement time. Was calculated and used as the magnification of viscosity.
Jig: φ25mm Parallel plate Frequency: 5Hz
Strain: 100%
Gap: 1 mm
Measurement temperature: 120 ° C
Measurement time: 3 hours Atmosphere: Nitrogen

[Manufacturing Example 1]
Both-terminal amino group-modified silicone oil (manufactured by Shinetsu Chemical Industry Co., Ltd., KF-8010, functional group equivalent 430 g / mol, molecular weight 860 g / mol, weight average molecular weight 1400 g / mol) as compound [A'] in a 100 mL two-necked flask. Mol) was 8.0 g (9.3 mmol), and as compound [B'], polypropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "polypropylene glycol, diol type, 1000", molecular weight 1000, weight average molecular weight 1200) was added 12. 0 g (12.0 mmol) and 4.4 g (19.6 mmol) of cyclohexanetetracarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 224 g / mol) were added as a linking agent [Z'], and nitrogen substitution was performed. .. Then, it heated to 100 degreeC and reacted for 6 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Manufacturing Example 2]
Both-terminal hydroxyl-modified silicone oil (manufactured by Shinetsu Chemical Industry Co., Ltd., KF-6001, hydroxyl value 62 mgKOH / g, functional group equivalent 900 g / mol, molecular weight 1800 g / mol, as compound [A'] in a 100 mL two-necked flask, Weight average molecular weight 3000 g / mol) 12.0 g (6.6 mmol), polytetramethylene glycol as compound [B'] (manufactured by Wako Pure Chemical Industries, Ltd., "polytetramethylene oxide 2000", molecular weight 2000 g / mol, weight 8.0 g (4.0 mmol) with an average molecular weight of 7300 g / mol), and 1.6 g (7.1 mmol) of cyclohexanetetracarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 224 g / mol) as a linking agent [Z']. ) Was added, and nitrogen substitution was performed. Then, it heated to 180 degreeC and reacted for 8 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Manufacturing Example 3]
Both-terminal mercapto group-modified silicone oil (manufactured by Shinetsu Chemical Industry Co., Ltd., X-22-167B, functional group equivalent 1700 g / mol, molecular weight 3400 g / mol, weight average molecular weight) as compound [A'] in a 100 mL two-necked flask. 6.0 g (2.1 mmol) of 6400 g / mol), polypropylene glycol as compound [B'] (manufactured by Wako Pure Chemical Industries, Ltd., "polypropylene glycol, diol type, 2000", molecular weight 2000 g / mol, weight average molecular weight 3400 g) 13.0 g (6.5 mmol) of / mol) and 1.0 g (4.5 mmol) of cyclohexanetetracarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 224 g / mol) as a linking agent [Z'] were added. , Nitrogen substitution was performed. Then, it heated to 160 degreeC and reacted for 8 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Manufacturing Example 4]
Both-terminal amino group-modified silicone oil (manufactured by Shinetsu Chemical Industry Co., Ltd., X-22-161A, functional group equivalent 800 g / mol, molecular weight 1600 g / mol, weight average molecular weight) as compound [A'] in a 100 mL two-necked flask. 2800 g / mol) as 10.0 g (6.3 mmol), compound [B'] with both-terminal amino-modified polypropylene glycol (manufactured by Huntsman, "Jeffamine" (registered trademark) D-2000, molecular weight 2000 g / mol, weight average. 10.0 g (5.0 mmol) with a molecular weight of 4000 g / mol) and 1.6 g (7.6 mmol) of cyclopentanetetracarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 210 g / mol) as a linking agent [Z']. ) Was added, and nitrogen substitution was performed. Then, it heated to 100 degreeC and reacted for 6 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Manufacturing Example 5]
Hydroxyl-terminated silicone oil at both ends (manufactured by Shinetsu Chemical Industry Co., Ltd., KF-6000, hydroxyl value 120 mgKOH / g, functional group equivalent 500 g / mol, molecular weight 1000 g / mol, as compound [A'] in a 100 mL two-necked flask, Weight average molecular weight 1700 g / mol) is 12.0 g (12.0 mmol), as compound [B'], polypropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "polypropylene glycol, diol type, 400", molecular weight 400 g / mol, weight) 8.0 g (20.0 mmol) with an average molecular weight of 500 g / mol), and 6.2 g (31.6 mmol) of cyclobutanetetracarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 196 g / mol) as a linking agent [Z']. ) Was added, and nitrogen substitution was performed. Then, it heated to 160 degreeC and reacted for 8 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Manufacturing Example 6]
Hydroxyl-terminated silicone oil with both ends as compound [A'] in a 100 mL two-necked flask (KF-6001, hydroxyl value 62 mgKOH / g, functional group equivalent 900 g / mol, molecular weight 1800 g / mol, Weight average molecular weight 3000 g / mol) 10.0 g (5.5 mmol), polytetramethylene glycol as compound [B'] (manufactured by Wako Pure Chemical Industries, Ltd., "polytetramethylene glycol, diol type, 2000", molecular weight 2000 g 10.0 g (5.0 mmol) with a weight average molecular weight of 7300 g / mol, and 1.4 g of butanetetracarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight of 198 g / mol) as a linking agent [Z']. (7.1 mmol) was added and nitrogen substitution was performed. Then, it heated to 180 degreeC and reacted for 10 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Manufacturing Example 7]
Both-terminal hydroxyl-modified silicone oil (manufactured by Shinetsu Chemical Industry Co., Ltd., KF-6000, hydroxyl value 120 mgKOH / g, functional group equivalent 500 g / mol, molecular weight 900 g / mol, as compound [A'] in a 100 mL two-necked flask, Weight average molecular weight 1700 g / mol) is 8.0 g (8.6 mmol), and as compound [B'], polypropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polypropylene glycol, diol type, 1000", molecular weight 1000 g / mol, weight) 12.0 g (12.0 mmol) with an average molecular weight of 1200 g / mol), and dicyclohexyl-3,4,3', 4'-tetracarboxylic acid dianhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a linking agent [Z']. 4.4 g (14.4 mmol) having a molecular weight of 306 g / mol was added, and nitrogen substitution was carried out. Then, it heated to 160 degreeC and reacted for 8 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Manufacturing Example 8]
Both-terminal hydroxyl-modified silicone oil (manufactured by Shinetsu Chemical Industry Co., Ltd., KF-6001, hydroxyl value 62 mgKOH / g, functional group equivalent 900 g / mol, molecular weight 1800 g / mol, as compound [A'] in a 100 mL two-necked flask, Weight average molecular weight 3000 g / mol) 14.0 g (7.8 mmol), polypropylene glycol as compound [B'] (manufactured by Wako Pure Chemical Industries, Ltd., "polypropylene glycol, diol type, 2000", molecular weight 2000 g / mol, weight 6.0 g (3.0 mmol) with an average molecular weight of 3400 g / mol) and 4- (2,5-dioxo tetrahydrofuran-3-yl) -tetraline-1,2-dicarboxylic acid anhydride as the linking agent [Z']. (Made by Tokyo Kasei Kogyo Co., Ltd., molecular weight 300 g / mol) 1.9 g (6.3 mmol) was added, and nitrogen substitution was performed. Then, it heated to 160 degreeC and reacted for 8 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Manufacturing Example 9]
Both-terminal hydroxyl-modified silicone oil (manufactured by Shinetsu Chemical Industry Co., Ltd., KF-6001, hydroxyl value 62 mgKOH / g, functional group equivalent 900 g / mol, molecular weight 1800 g / mol, as compound [A'] in a 100 mL two-necked flask, Weight average molecular weight 3000 g / mol) 8.0 g (4.4 mmol), polypropylene glycol as compound [B'] (manufactured by Wako Pure Chemical Industries, Ltd., "polypropylene glycol, diol type, 2000", molecular weight 2000 g / mol, weight 12.0 g (6.0 mmol) with an average molecular weight of 3400 g / mol), and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic as the linking agent [Z']. 1.6 g (6.1 mmol) of an acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 264 g / mol) was added, and nitrogen substitution was carried out. Then, it heated to 160 degreeC and reacted for 8 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Manufacturing Example 10]
Both-terminal hydroxyl-modified silicone oil (manufactured by Shinetsu Chemical Industry Co., Ltd., KF-6002, hydroxyl value 35 mgKOH / g, functional group equivalent 1600 g / mol, molecular weight 3200 g / mol, as compound [A'] in a 100 mL two-necked flask, Weight average molecular weight 6200 g / mol) 14.0 g (4.4 mmol), polytetramethylene glycol as compound [B'] (manufactured by Wako Pure Chemical Industries, Ltd., "tetramethylene oxide 2000", molecular weight 2000 g / mol, weight average 6.0 g (3.0 mmol) with a molecular weight of 7300 g / mol) and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid as a linking agent [Z']. 1.4 g (5.3 mmol) of an anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 264 g / mol) was added, and nitrogen substitution was performed. Then, it heated to 160 degreeC and reacted for 8 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Manufacturing Example 11]
Both-terminal hydroxyl-modified silicone oil (manufactured by Shinetsu Chemical Industry Co., Ltd., KF-6001, hydroxyl value 62 mgKOH / g, functional group equivalent 900 g / mol, molecular weight 1800 g / mol, as compound [A'] in a 100 mL two-necked flask, Weight average molecular weight 3000 g / mol) is 14 g (7.8 mmol), and as compound [B'], "New Pole" (registered trademark) PE-61 (manufactured by Sanyo Kasei Kogyo Co., Ltd., polypropylene glycol / polyethylene glycol copolymer, molecular weight) 2000 g / mol, weight average molecular weight 2800 g / mol) 6 g (3.0 mmol), and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, as the linking agent [Z'], 2.0 g (7.6 mmol) of 2-dicarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd., average molecular weight 264 g / mol) was added, and nitrogen substitution was performed. Then, it heated to 160 degreeC and reacted for 8 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Manufacturing Example 12]
Both-terminal hydroxyl-modified silicone oil (manufactured by Shinetsu Chemical Industry Co., Ltd., KF-6002, hydroxyl value 35 mgKOH / g, functional group equivalent 1600 g / mol, molecular weight 3200 g / mol, as compound [A'] in a 100 mL two-necked flask, Weight average molecular weight 6200 g / mol) is 11.2 g (3.5 mmol), as compound [B'], polypropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "Polypropylene glycol, diol type, 2000", molecular weight 2000 g / mol, weight. 8.8 g (4.4 mmol) with an average molecular weight of 3400 g / mol), and dicyclohexyl-3,4,3', 4'-tetracarboxylic acid dianhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a linking agent [Z']. 1.3 g (4.1 mmol) having a molecular weight of 306 g / mol was added, and nitrogen substitution was carried out. Then, it heated to 160 degreeC and reacted for 8 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Manufacturing Example 13]
Both-terminal hydroxyl-modified silicone oil (manufactured by Shinetsu Chemical Industry Co., Ltd., KF-6001, hydroxyl value 62 mgKOH / g, functional group equivalent 900 g / mol, molecular weight 1800 g / mol, as compound [A'] in a 100 mL two-necked flask, Weight average molecular weight 3000 g / mol) is 11.0 g (6.1 mmol), polypropylene glycol as compound [B'] (manufactured by Wako Pure Chemical Industries, Ltd., "polypropylene glycol, diol type, 2000", molecular weight 2000 g / mol, weight. 4.6 g (2.3 mmol) of 4.6 g (2.3 mmol) with an average molecular weight of 3400 g / mol) and 6 of polypropylene glycol monobutyl ether (manufactured by Wako Pure Chemical Industries, Ltd., "antifoaming agent PE-L", molecular weight of 1170 g / mol, weight average molecular weight of 2100) .7 g (5.7 mmol) and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride as binder [Z'] (Tokyo Kasei Kogyo Co., Ltd.) 2.6 g (10.0 mmol) manufactured by the company and having an average molecular weight of 264 g / mol was added, and nitrogen substitution was carried out. Then, it heated to 160 degreeC and reacted for 8 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Reference example 1]
Hydroxyl-terminated silicone oil at both ends (manufactured by Shinetsu Chemical Industry Co., Ltd., KF-6001, hydroxyl value 62 mgKOH / g, functional group equivalent 900 g / mol, molecular weight 1800 g / mol, weight average molecular weight 3000 g / mol) in a 100 mL two-necked flask ) Is 7.5 g (4.2 mmol), polypropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "polypropylene glycol, diol type, 2000", molecular weight 2000 g / mol, weight average molecular weight 3400 g / mol) is 6.0 g (3). (0.0 mmol) and 1.5 g (6.9 mmol) of pyromellitic dianhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 218 g / mol) were added to carry out nitrogen substitution. Then, it heated to 160 degreeC and reacted for 8 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Reference example 2]
Hydroxyl-terminated silicone oil at both ends (manufactured by Shinetsu Chemical Industry Co., Ltd., KF-6000, hydroxyl value 120 mgKOH / g, functional group equivalent 500 g / mol, molecular weight 1000 g / mol, weight average molecular weight 1700 g / mol) in a 100 mL two-necked flask ) Is 10.0 g (10.7 mmol), polypropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "polypropylene glycol, diol type, 1000", molecular weight 1000 g / mol, weight average molecular weight 1200 g / mol) is 10.0 g (10). 0.0 mmol) and 3.0 g (13.8 mmol) of pyromellitic dianhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 218 g / mol) were added, and nitrogen substitution was performed. Then, it heated to 160 degreeC and reacted for 8 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Reference example 3]
4. Hydroxyl-terminated silicone oil at both ends (KF-6000, hydroxyl value 120 mgKOH / g, functional group equivalent 500, molecular weight 1000, weight average molecular weight 1700 g / mol) in a 100 mL two-necked flask. 10.0 g (40.0 mmol) of 0 g (4.0 mmol), polypropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., "polypropylene glycol, diol type, 400", molecular weight 400 g / mol, weight average molecular weight 500 g / mol), And 9.9 g (44.0 mmol) of cyclohexanetetracarboxylic acid anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 224 g / mol) was added, and nitrogen substitution was carried out. Then, it heated to 160 degreeC and reacted for 8 hours to obtain a block copolymer. The results are shown in Tables 1 and 2.

[Example 1]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Production Example 1 was 125 ° C., and the viscosity ratio was 3.3 times. The results are shown in Table 2.

[Example 2]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Production Example 2 was 147 ° C., and the viscosity ratio was 2.6 times. The results are shown in Table 2.

[Example 3]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Production Example 3 was 143 ° C., and the viscosity ratio was 2.1 times. The results are shown in Table 2.

[Example 4]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Production Example 4 was 152 ° C., and the viscosity ratio was 1.7 times. The results are shown in Table 2.

[Example 5]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Production Example 5 was 121 ° C., and the viscosity ratio was 3.8 times. The results are shown in Table 2.

[Example 6]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Production Example 6 was 140 ° C., and the viscosity ratio was 2.4 times. The results are shown in Table 2.

[Example 7]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Production Example 7 was 181 ° C., and the viscosity ratio was 1.2 times. The results are shown in Table 2.

[Example 8]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Production Example 8 was 167 ° C., and the viscosity ratio was 1.1 times. The results are shown in Table 2.

[Example 9]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Production Example 9 was 175 ° C., and the viscosity ratio was 1.1 times. The results are shown in Table 2.

[Example 10]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Production Example 10 was 184 ° C., and the viscosity ratio was 1.2 times. The results are shown in Table 2.

[Example 11]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Production Example 11 was 177 ° C., and the viscosity ratio was 1.1 times. The results are shown in Table 2.

[Example 12]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Production Example 12 was 185 ° C., and the viscosity ratio was 1.1 times. The results are shown in Table 2.

[Example 13]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Production Example 13 was 182 ° C., and the viscosity ratio was 1.2 times. The results are shown in Table 2. [Comparative Example 1]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Reference Example 1 was 96 ° C., and the viscosity ratio was 4.4 times. The results are shown in Table 2.

[Comparative Example 2]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Reference Example 2 was 103 ° C., and the viscosity ratio was 4.1 times. The results are shown in Table 2.

[Comparative Example 3]
The heat generation start temperature of the composition of the block copolymer and the bisphenol A type epoxy resin obtained in Reference Example 3 was 115 ° C., and the viscosity ratio was 4.1 times. The results are shown in Table 2.

The block copolymer of the present invention is useful as various additives such as surfactants and resin modifiers, and its application to cosmetics, adhesives, paints, electronic material applications and the like is described.

Claims (7)

A block copolymer in which a block [A] and a block [B] are bonded via a connecting segment [Z], and the block [A] has a structural unit represented by the general formula (1).

(R ₁ represents hydrogen, an alkyl group or an aryl group having 1 to 10 carbon atoms, which may be the same or different. N represents a repeating unit of 5 to 70.)
The block [B] has a structural unit represented by the general formula (2) and has a structural unit.

(R ₂ represents an alkylene group or an arylene group having 1 to 10 carbon atoms, which may be the same or different. M represents a repeating unit of 3 to 100.)
The connecting segment [Z] has a carboxyl group and has a carboxyl group.
Moreover, for a 0.5 g / dL solution using tetrahydrofuran as a solvent, the acid dissociation constant pKa measured at 25 ° C. is in the range of 9.0 or less, which is larger than 7.0, and is 0.3 or more and 3.0 mmol / g. A block copolymer characterized by containing the following carboxyl groups. The block copolymer according to claim 1, wherein the connecting segment [Z] contains at least one structure selected from the general formulas (3) to (7).

(X represents a carboxyl group.) The block copolymer according to claim 1 or 2, which contains 0.015 mmol / g or less of a compound containing an acid anhydride group. The block copolymer according to any one of claims 1 to 3, wherein the block copolymer has a weight average molecular weight of 5,000 to 50,000. The block copolymer according to any one of claims 1 to 4, wherein the linking segment [Z] contains an ester group. A compound [A'] having a structural unit represented by the general formula (1) and having any functional group selected from a hydroxyl group, a thiol group, and an amino group at the end, and the general formula (2). A compound [B'] having a structural unit represented by, and having any functional group selected from a hydroxyl group, a thiol group, and an amino group at the end, and a linking agent [Z] having a cyclic acid anhydride at the end. A method for producing a block copolymer, wherein the block copolymer according to any one of claims 1 to 5 is obtained by reacting']. The method for producing a block copolymer according to claim 6, wherein the ratio of the number of moles of the linking agent [Z'] to the total molar number of the compound [A'] and the compound [B'] is 0.5 to 0.8. ..