WO2015163321A1 - Polymère séquencé - Google Patents

Polymère séquencé Download PDF

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WO2015163321A1
WO2015163321A1 PCT/JP2015/062112 JP2015062112W WO2015163321A1 WO 2015163321 A1 WO2015163321 A1 WO 2015163321A1 JP 2015062112 W JP2015062112 W JP 2015062112W WO 2015163321 A1 WO2015163321 A1 WO 2015163321A1
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polymer
polymerizable monomer
meth
molecular weight
polymerization
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PCT/JP2015/062112
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Japanese (ja)
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竹内　一雅
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日立化成株式会社
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Priority to JP2016514947A priority Critical patent/JPWO2015163321A1/ja
Priority to CN201580020336.7A priority patent/CN106232652A/zh
Priority to KR1020167026306A priority patent/KR20160147722A/ko
Publication of WO2015163321A1 publication Critical patent/WO2015163321A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof

Definitions

  • the present invention relates to a (meth) acrylic block polymer obtained by polymerizing a monomer having three or more components.
  • (Meth) acrylic polymers can be easily produced by radical polymerization of (meth) acrylic monomers, and resin properties can be improved by copolymerizing several (meth) acrylic monomers depending on the purpose. Since it can be widely changed, it is widely manufactured industrially. In addition, bulk polymerization, solution polymerization, suspension polymerization, and the like are widespread as methods for producing (meth) acrylic polymers, and are selected in view of the molecular weight or cost of the (meth) acrylic polymer to be produced. Conventionally, since (meth) acrylic polymers are generally produced by free radical polymerization, (meth) acrylic polymers obtained from multi-component monomers are random copolymers and have a wide molecular weight distribution.
  • (Meth) acrylic polymers can exhibit characteristics such as transparency, adhesiveness, low elasticity, and high hardness by selecting monomer types, and are being developed in the fields of optics, electronic materials, and structural materials. Further, acrylic acid or methacrylic acid is copolymerized as a component of (meth) acrylic polymer to impart alkali aqueous solubility, and is used as a photosensitive resist material. Further, it is possible to incorporate curing reactivity by copolymerizing glycidyl methacrylate, and it is possible to incorporate photoreactivity by introducing a photoreactive group. Thereby, for example, it is possible to increase the heat resistance of the adhesive or to impart photosensitivity.
  • RAFT reversible addition-fragmentation chain transfer
  • RAFT polymerization can polymerize acrylic acid or methacrylic acid without a protective group, and enables copolymerization with various acrylic esters, methacrylic esters, styrene, and the like (see Patent Documents 1 and 2 below). reference).
  • the present invention provides a block polymer in which the block properties of other monomers are improved so that the physical properties of the polymer resulting from a specific polymerizable monomer in a multi-component copolymer polymer of three or more components are not changed by the sequence of the polymer. Is an issue.
  • the present invention is a (meth) acrylic polymer obtained by polymerizing a polymerizable monomer having three or more components, and includes a structural unit derived from a first polymerizable monomer and a structural unit derived from a second polymerizable monomer.
  • the present invention also relates to the block polymer in which the second polymer unit is bonded to one end or both ends of the first polymer unit.
  • the present invention also relates to the block polymer, wherein the first polymerizable monomer is (meth) acrylic acid (acrylic acid or methacrylic acid).
  • the present invention also relates to the block polymer, wherein the second polymerizable monomer is styrene.
  • the present invention also relates to the block polymer, wherein the third polymerizable monomer is a (meth) acrylic acid ester (acrylic acid ester or methacrylic acid ester).
  • the present invention also relates to the above block polymer having a weight average molecular weight of 10,000 to 200,000. Furthermore, the present invention relates to the block polymer having a molecular weight dispersity of 1.2 to 4.0.
  • the block polymer of the present invention is a multi-component copolymer polymer having three or more components, in which the block properties of other monomers are enhanced so that the physical properties of the polymer resulting from a specific polymerizable monomer do not change due to the sequence of the polymer. .
  • the obtained (meth) acrylic block polymer is applicable as a photosensitive resist, an adhesive, a photo-curing resin and the like exhibiting good characteristics.
  • FIG. 1 shows a gel permeation chromatogram during synthesis of the first polymer unit of Example 1 and after elongation of the second polymer unit chain.
  • FIG. 2 shows the 1 H-NMR spectrum obtained when the first polymer unit of Example 1 was synthesized.
  • FIG. 3 shows the 1 H-NMR spectrum after extension of the second polymer unit chain of Example 1.
  • (meth) acrylic acid means acrylic acid or methacrylic acid corresponding thereto.
  • (meth) acrylic acid ester means acrylic acid or methacrylic acid corresponding thereto.
  • a or B only needs to include either A or B, and may include both.
  • the materials exemplified below may be used singly or in combination of two or more unless otherwise specified.
  • the block polymer of this embodiment is a (meth) acrylic polymer obtained by polymerizing a polymerizable monomer having three or more components, and a structural unit derived from the first polymerizable monomer and a structural unit derived from the second polymerizable monomer.
  • a second polymer unit comprising: a first polymer unit comprising: a structural unit derived from the first polymerizable monomer; and a structural unit derived from a third polymerizable monomer different from the second polymerizable monomer. It has a polymer unit.
  • the third polymerizable monomer is different from the first polymerizable monomer.
  • the three or more polymerizable monomers contain at least (meth) acrylic acid.
  • the block polymer of this embodiment is a multi-component copolymer polymer having three or more components, in which the block properties of other monomers are enhanced so that the physical properties of the polymer due to a specific polymerizable monomer do not change due to the sequence of the polymer. is there.
  • the block polymer of the present embodiment is a (meth) acrylic block polymer obtained by polymerizing a polymerizable monomer containing at least three components including (meth) acrylic acid, and other than (meth) acrylic acid. It is a block polymer that can block a structural unit derived from a polymerizable monomer and is excellent in solubility in a solvent and an aqueous alkali solution.
  • the block polymer of the present embodiment has a first polymer unit as a block, and a second polymer unit is bonded as a block to one end (one end) or both ends of the first polymer unit (first block). It is preferable to have a second polymer unit at one or both ends of one polymer unit).
  • the first polymerizable monomer is a block polymer that is (meth) acrylic acid (acrylic acid or methacrylic acid).
  • the second polymerizable monomer is styrene.
  • the third polymerizable monomer is a (meth) acrylic acid ester (acrylic acid ester or methacrylic acid ester).
  • the molecular weight of the block polymer of this embodiment is not particularly limited, but the weight average molecular weight of the block polymer of this embodiment is preferably 10,000 to 200,000.
  • the molecular weight dispersity of the block polymer of this embodiment is preferably 1.2 to 4.0.
  • the ratio of each monomer and the ratio of each polymer unit are not particularly limited, and various types can be mentioned.
  • the ratio of the first polymerizable monomer and the second polymerizable monomer in the block polymer of the present embodiment is the former (first polymerizable monomer) / the latter from the viewpoint of solubility in a solvent, compatibility control, and the like.
  • the molar ratio of (second polymerizable monomer) may be 1/99 to 80/20, 3/97 to 70/30, or 5/95 to 60/40. Good.
  • the ratio of the first polymerizable monomer to the third polymerizable monomer is determined by the former (first polymerizable monomer) / the latter (third polymerizable monomer) from the viewpoints of solubility in a solvent and compatibility control.
  • the ratio of the first polymer unit and the second polymer unit is the molar ratio of the former (first polymer unit) / the latter (second polymer unit) from the viewpoints of high elongation, high strength, high adhesion, etc. It may be 10/90 to 90/10, 20/80 to 80/20, or 30/70 to 70/30.
  • the amount of each polymerizable monomer in the above ratio is the total amount in the entire block polymer.
  • the ratio of the first polymerizable monomer and the second polymerizable monomer in the block polymer of this embodiment is 1 / (molar ratio of the former (first polymerizable monomer) / the latter (second polymerizable monomer)). 99 to 80/20, and the ratio of the first polymerizable monomer to the third polymerizable monomer is 1 in terms of a molar ratio of the former (first polymerizable monomer) / the latter (third polymerizable monomer). / 99 to 80/20, and the ratio of the first polymer unit to the second polymer unit is 10/90 to the molar ratio of the former (first polymer unit) / the latter (second polymer unit). The aspect which is 90/10 is mentioned.
  • the manufacturing method of the block polymer of this embodiment is not particularly limited.
  • the block polymer of this embodiment is obtained by polymerizing the first polymerizable monomer and the second polymerizable monomer by living polymerization to obtain the first polymer unit, and then the first polymerizable monomer and the third polymerizable monomer. It can be obtained by adding a polymerizable monomer and chain extending the second polymer unit.
  • Living polymerization includes anion polymerization, atom transfer radical polymerization (ATRP), nitroxide living radical polymerization (NMP), reversible addition-fragmentation chain transfer (RAFT) polymerization, organic tellurium mediated living radical polymerization (TERP), reversible chain transfer catalytic polymerization. (RTCP) or the like can be used.
  • ATRP atom transfer radical polymerization
  • NMP nitroxide living radical polymerization
  • RAFT reversible addition-fragmentation chain transfer
  • TERP organic tellurium mediated living radical polymerization
  • RTCP reversible chain transfer catalytic polymerization.
  • RAFT reversible addition-fragmentation chain transfer polymerization
  • a thioester as a protecting group which is a chain transfer agent
  • it has many polymerizable monomer species and can directly copolymerize acrylic acid or methacrylic acid.
  • a thiocarbonate compound having a structure represented by the following general formula (1) can be used as a chain transfer agent.
  • R cumyl group, cyanopropyl group, phenylpropyl group, cyanophenylmethyl group, ethylcarboxypropyl group, 2,4,4-trimethylpentan-2-yl group, 1-cyanoethyl group, 1-phenyl Preferred examples include an ethyl group, a tert-butyl group, a cyanomethyl group, and a benzyl group.
  • Z is preferably a phenyl group, methylthioyl group, pyrrole group, methyl group, phenoxy group, ethoxy group, dimethylamino group or the like.
  • chain transfer agents include cumyl dithiobenzoate, 2-cyano-2-propylbenzothioate, 4-cyano-4 [(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid, cyanomethylmethyl (phenyl) Carbamodithioate, 4-cyano-4- (phenylcarbonothioylthio) pentanoic acid, 2-cyano-2-propyldodecyltrithiocarbonate, 2- (dodecylthiocarbonothioylthio) -2-methylpropionic acid, And cyanomethyldodecyl trithiocarbonate. Although these are marketed, a chain transfer agent is not limited to these.
  • (meth) acrylic monomer refers to a monomer having an acryloyl group (CH ⁇ CH—CO—) or a methacryloyl group (CH ⁇ C (CH 3 ) —CO—)
  • (meth) “Acrylic polymer” refers to a polymer obtained by polymerization using at least a part of monomers having these groups.
  • a (meth) acrylic polymer using a (meth) acrylic monomer and a styrene monomer as a polymerizable monomer is preferable.
  • a 1st polymerizable monomer For example, a carboxyl group containing monomer is mentioned, Especially, (meth) acrylic acid (acrylic acid or methacrylic acid) etc. are mentioned as a preferable thing. .
  • the second polymerizable monomer and the third polymerizable monomer (meth) acrylic monomer, styrene monomer, (meth) acrylic acid ester, acrylonitrile, etc. other than the first polymerizable monomer are preferable.
  • styrene is preferable as the second polymerizable monomer.
  • the third polymerizable monomer (meth) acrylic acid ester (acrylic acid ester or methacrylic acid ester) is preferable.
  • the styrene monomer include styrene and ⁇ -methylstyrene.
  • (Meth) acrylates include benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and lauryl (meth) acrylate Etc.
  • the first polymerizable monomer is (meth) acrylic acid
  • the second and third polymerizable monomers are styrene, (meth ) Benzyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, and the like.
  • the block polymer of this embodiment may further include a third polymer unit different from the first polymer unit and the second polymer unit.
  • the third polymer unit has, for example, a structural unit derived from the first polymerizable monomer similar to the first polymer unit and the second polymer unit.
  • the polymerizable monomer giving the third polymer unit the above polymerizable monomer used for obtaining the first polymer unit and the second polymer unit can be used.
  • the thiocarbonate compound having the structure represented by the general formula (1) is used as a chain transfer agent, and the first polymerizable monomer (for example, acrylic acid or methacrylic acid) and the second polymerizable monomer are living.
  • the first polymer unit is synthesized by polymerization, the polymer that becomes the first polymer unit is recovered by reprecipitation or distillation under reduced pressure after the polymerization has progressed to some extent, and then the first polymerizable monomer and By adding with the third polymerizable monomer, the second polymer unit can be chain extended. In this case, a small amount of radical initiator may be added.
  • the first polymer unit is synthesized by polymerizing the first polymerizable monomer and the second polymerizable monomer by living polymerization using the thiocarbonate compound having the structure represented by the general formula (1) as a chain transfer agent.
  • the first polymer monomer and the third polymer monomer are added to the same reactor to extend the second polymer unit, thereby causing the block polymer of the present embodiment. Can be obtained.
  • Molar amounts of the first polymerizable monomer used first, the second polymerizable monomer polymerizable with the first polymerizable monomer, the first polymerizable monomer charged later, and the third polymerizable monomer polymerizable with the first polymerizable monomer By controlling the molar ratio of the thiocarbonate compound represented by the general formula (1), the molecular weight of the obtained block polymer, the molecular weight (chain length) of the first polymer unit, and the second polymer unit It is possible to adjust the molecular weight (chain length).
  • the molar ratio of the chain transfer agent (specifically, for example, the compound represented by the general formula (1)) to the radical initiator (chain transfer agent / radical initiator) is 20/1 to 1/5. 10/1 to 1/4 is more preferable. Since the ratio of the chain transfer agent (the compound represented by the general formula (1)) and the radical initiator is 20/1 or less, the polymerization reaction rate can be increased while maintaining monodispersity. Industrially preferable. On the other hand, by setting the ratio to 1/5 or more, chain transfer from the radical initiator directly to the monomer can be avoided, and various polymers (random polymer, first polymer different from the block polymer of this embodiment) can be avoided. It is possible to suppress a by-product of a polymer unit alone, a second polymer unit alone, or the like, and obtain a good block polymer.
  • the temperature of the polymerization reaction varies depending on the decomposition temperature of the radical initiator to be used, and is not particularly limited.
  • the half-life decomposition temperature is minus 2 ° C. to plus 20 ° C. (half-life decomposition temperature ⁇ 2 ° C. to half) It is preferable to carry out at the periodical decomposition temperature + 20 ° C.).
  • radical initiators for synthesizing the block polymer of this embodiment include benzoyl peroxide, acetyl peroxide, lauroyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, and the like.
  • peroxide initiators such as AIBN (2,2′-azobisisobutyronitrile), V-65 (azobisdimethylvaleronitrile) and the like. Of these, AIBN (2,2'-azobisisobutyronitrile) is preferable.
  • the block polymer of this embodiment can be synthesized by solution polymerization, suspension polymerization, emulsion polymerization, solid phase polymerization, etc., but solution polymerization is preferable to obtain a resin having a weight average molecular weight of 2000 to 300,000. Suspension polymerization is preferred to obtain a resin having a weight average molecular weight of 300,000 to 1,000,000.
  • the polymerization method is appropriately selected depending on the polarity or reactivity of the monomer to be used, but when acrylic acid or methacrylic acid is used, in order to synthesize a (meth) acrylic polymer soluble in a solvent, a solution is used. It is preferable to carry out by polymerization.
  • the weight average molecular weight of the block polymer of this embodiment is not particularly limited, but is preferably 10,000 or more, more preferably 12,000 or more, and further preferably 15,000 or more from the viewpoint of strength, elongation, adhesiveness, and the like.
  • the weight average molecular weight of the block polymer is preferably 200000 or less, more preferably 180000 or less, and further preferably 150,000 or less from the viewpoint of solubility and the like. From these viewpoints, the molecular weight of the block polymer is preferably 10,000 to 200,000, more preferably 12,000 to 180000, and further preferably 15,000 to 150,000.
  • the molecular weight dispersity (weight average molecular weight Mw / number average molecular weight Mn) of the block polymer of this embodiment is preferably 1.1 or more, and more preferably 1.2 or more, from the viewpoint of high elongation, high strength, high adhesion, and the like. .
  • the molecular weight dispersity of the block polymer is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.0 or less, from the viewpoints of dispersibility, compatibility and the like. From these viewpoints, the molecular weight dispersity of the block polymer is preferably 1.1 to 4.0, more preferably 1.2 to 3.0, and still more preferably 1.2 to 2.0.
  • molecular weight (weight average molecular weight Mw and number average molecular weight Mn) can be calculated
  • Solution polymerization is performed by dissolving a polymerizable monomer, a chain transfer agent, and a radical initiator in a solvent capable of dissolving the produced resin and heating to a temperature determined by the radical initiator. At this time, the polymerization can be carried out even under air, but it is preferably carried out under nitrogen.
  • the solvent used in the solution polymerization is not particularly limited as long as it can dissolve a polymerizable monomer, a chain transfer agent, a radical initiator, and a resin to be formed, but preferably has a boiling point equal to or higher than the temperature at which the polymerization is performed.
  • the temperature at which the polymerization is carried out is higher than the boiling point of the solvent used, the polymerization can be carried out by a reaction under pressure.
  • Solvents used include methoxyethanol, ethoxyethanol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanol, cyclohexanone, butyl acetate, chlorobenzene, dioxane, propylene glycol monomethyl ether, etc. Not. These can be used alone or in appropriate mixture.
  • RAFT polymerization in general, chain transfer from the acrylic growth terminal to the methacrylate monomer does not occur. Therefore, the monomer blending procedure or combination when copolymerizing a plurality of monomers is important. Therefore, when simultaneously charging a plurality of monomers, it is preferable to carry out a combination of only monomers having an acryloyl group or only a monomer having a methacryloyl group.
  • polymerization is performed with a combination of only monomers having an acryloyl group, or a monomer having a methacryloyl group is polymerized only with a combination of monomers having a methacryloyl group. Thereafter, it is preferable to polymerize a monomer having an acryloyl group.
  • the block polymer of this embodiment is expected to exhibit various characteristics in applications such as photosensitive materials, adhesives, adhesives, coating materials, and dispersants.
  • Example 1 In a 500 mL (milliliter) separable flask equipped with a reflux condenser, thermometer, stirrer, and nitrogen inlet tube, 25.0 g (290 mmol) of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), styrene (Wako Pure Chemical Industries, Ltd.) 67.5 g (648 mmol), cumyldithiobenzoate 1.46 g (5.36 mmol), and azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd., purity 98%) 0.45 g (2.73 mmol) was bubbled with nitrogen at room temperature and stirred for 30 minutes. The temperature was raised to 65 ° C.
  • Example 2 In a 500 mL separable flask equipped with a reflux condenser, thermometer, stirrer, and nitrogen inlet tube, 25.0 g (290 mmol) of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), styrene (manufactured by Wako Pure Chemical Industries, Ltd.) 67 0.5 g (648 mmol), cumyl dithiobenzoate 0.68 g (2.5 mmol), and azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd., purity 98%) 0.21 g (1.28 mmol) were charged, Nitrogen was bubbled at room temperature and stirred for 30 minutes.
  • the temperature was raised to 65 ° C. and stirred for 30 minutes, after which the temperature was raised to 70 ° C.
  • 46 g of a toluene / propylene glycol monomethyl ether (2/3 mass ratio) mixed solution separately bubbled with nitrogen for 30 minutes was added and further stirred.
  • the mixture was stirred at 80 ° C. for 2 hours, and the solid content and molecular weight were measured.
  • the polymerization rate calculated from the solid content was 92%, the weight average molecular weight (Mw) of the styrene / methacrylic acid unit was 21,400, and the number average molecular weight (Mn) was 16,900.
  • Example 3 In a 500 mL separable flask equipped with a reflux condenser, thermometer, stirrer, and nitrogen inlet tube, 25.0 g (290 mmol) of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), styrene (manufactured by Wako Pure Chemical Industries, Ltd.) 67 0.5 g (648 mmol), cumyl dithiobenzoate 1.12 g (4.11 mmol), and azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd., purity 98%) 0.17 g (1.01 mmol) were charged, Nitrogen was bubbled at room temperature and stirred for 30 minutes.
  • methacrylic acid manufactured by Wako Pure Chemical Industries, Ltd.
  • styrene manufactured by Wako Pure Chemical Industries, Ltd.
  • cumyl dithiobenzoate 1.12 g (4.11 mmol
  • the temperature was raised to 65 ° C. and stirred for 30 minutes, after which the temperature was raised to 70 ° C.
  • 46 g of a toluene / propylene glycol monomethyl ether (2/3 mass ratio) mixed solution separately bubbled with nitrogen for 30 minutes was added and further stirred.
  • the mixture was stirred at 80 ° C. for 2 hours, and the solid content and molecular weight were measured.
  • the polymerization rate calculated from the solid content was 92%, the weight average molecular weight (Mw) of the styrene / methacrylic acid unit was 11300, and the number average molecular weight (Mn) was 9000.
  • reaction solution was reprecipitated with hexane and vacuum dried at 40 ° C. 50.0 g of the obtained solid, 46 g of a toluene / propylene glycol monomethyl ether (2/3 mass ratio) mixed solution, 15.5 g (181 mmol) of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), and benzyl methacrylate (Hitachi) 42.0 g (238 mmol) of a product made by Kasei Co., Ltd. (Fancryl FA-BZM) was added and stirred. After the solid matter was dissolved, the temperature was raised to 70 ° C. and stirred.
  • the final (meth) acrylic polymer including the methacrylic acid / benzyl methacrylate unit had a weight average molecular weight (Mw) of 30,500, a number average molecular weight (Mn) of 23800, and a varnish solid content of 34% by mass.
  • Example 6 A (meth) acrylic polymer was obtained according to Example 1 except that the combinations of monomers and RAFT agents shown in Table 2 and Table 3 below were used.
  • Example 7 In a 500 mL separable flask equipped with a reflux condenser, thermometer, stirrer, and nitrogen inlet tube, 25.0 g (290 mmol) of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), styrene (manufactured by Wako Pure Chemical Industries, Ltd.) 67 0.5 g (648 mmol), cumyl dithiobenzoate 1.46 g (5.36 mmol), and azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd., purity 98%) 0.45 g (2.73 mmol) were charged, Nitrogen was bubbled at room temperature and stirred for 30 minutes.
  • the temperature was raised to 65 ° C. and stirred for 30 minutes, after which the temperature was raised to 70 ° C.
  • 46 g of a toluene / propylene glycol monomethyl ether (2/3 mass ratio) mixed solution separately bubbled with nitrogen for 30 minutes was added and further stirred.
  • the mixture was stirred at 80 ° C. for 4 hours, and the solid content and molecular weight were measured.
  • the polymerization rate calculated from the solid content was 93%, the weight average molecular weight (Mw) of the styrene / methacrylic acid unit was 12900, and the number average molecular weight (Mn) was 10400.
  • the weight average molecular weight of the obtained polymer was 34600, the number average molecular weight was 26400, and the total polymerization rate was 94%.
  • the reaction solution was cooled to room temperature to obtain a toluene / propylene glycol monomethyl ether (2/3 mass ratio) mixed solution of (meth) acrylic polymer having three polymer units.
  • Example 8 A toluene / propylene glycol monomethyl ether of a (meth) acrylic polymer having three types of polymer units according to Example 7 except that the monomer added for the third time was lauryl methacrylate / methacrylic acid in the amount shown in Table 4. A 2/3 mass ratio) mixed solution was obtained.
  • the temperature was raised to 65 ° C. and stirred for 30 minutes, then the temperature was raised to 70 ° C. and stirred for 2 hours, and further stirred at 80 ° C. for 2 hours, and the solid content and molecular weight were measured.
  • the polymerization rate calculated from the solid content was 96%, the weight average molecular weight (Mw) of the styrene / benzyl methacrylate unit was 14100, and the number average molecular weight (Mn) was 11300.
  • Comparative Example 2 A (meth) acrylic polymer having benzyl methacrylate and styrene as block units was obtained in accordance with Comparative Example 1 except that the monomers shown in Table 5 were used.
  • the temperature was raised to 65 ° C. and stirred for 30 minutes, and then the temperature was raised to 70 ° C. and stirred for 2 hours.
  • the viscosity of the reaction solution increased, 46 g of propylene glycol monomethyl ether that had been separately bubbled with nitrogen for 30 minutes was added. Stir further. Furthermore, it stirred at 80 degreeC for 4 hours and measured solid content and molecular weight. The polymerization rate calculated from the solid content was 96%.
  • a toluene / propylene glycol monomethyl ether (2/3 mass ratio) mixed solution of (meth) acrylic polymer was obtained.
  • the weight average molecular weight (Mw) of the obtained polymer was 31,000, the number average molecular weight (Mn) was 25400, and the solid content of the varnish was 34% by mass.
  • the number average molecular weight (Mn), weight average molecular weight (Mw), and Mw / Mn of the (meth) acrylic polymer of Examples and Comparative Examples are the chromatograms of the molecular weight distribution of the (meth) acrylic polymer by GPC (gel permeation chromatography). ) And calculated from the elution time of standard polystyrene at 25 ° C.
  • the measuring device is EcoSEC, HLC-8320GPC manufactured by Tosoh Corporation, and tetrahydrofuran is used as the eluent of the gel.
  • the columns are Gelpack GL-A-150 and Gelpack GL-A-10 (Hitachi High-Technologies Corporation). (Product name, product name) directly connected. In addition, it measured similarly about the molecular weight of the polymer in a reaction liquid.
  • FIG. 1 shows a gel permeation chromatogram at the time of synthesizing the first polymer unit of Example 1 and after the second polymer unit chain extension.
  • Reference numeral 1 denotes a gel permeation at the time of synthesizing the first polymer unit.
  • a chromatogram is shown
  • reference numeral 2 denotes a gel permeation chromatogram after the second polymer unit chain extension.
  • FIG. 2 shows a 1 H-NMR spectrum during the synthesis of the first polymer unit of Example 1.
  • Reference numeral 3 indicates an OH signal of methacrylic acid
  • reference numeral 4 indicates a signal of an aromatic ring of styrene.
  • reference numeral 5 indicates the OH signal of methacrylic acid
  • reference numeral 6 indicates the aromatic ring of styrene and benzyl methacrylate
  • symbol 7 shows the signal of the methylene of benzyl methacrylate.
  • x 10 ⁇ Vf ⁇ 56.1 / (Wp ⁇ I) ( ⁇ )
  • x represents an acid value (mgKOH / g)
  • Vf represents a titration amount (mL) of a 0.1N KOH aqueous solution
  • Wp represents the mass (g) of the measured resin solution
  • I Indicates the ratio (mass%) of the non-volatile content in the measured resin solution.
  • Elongation at break (%) [(Distance between chucks when fractured ⁇ First distance between chucks (60 mm)) / First distance between chucks (60 mm)] ⁇ 100

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Abstract

La présente invention concerne un polymère séquencé qui est un polymère (méth)acrylique formée par polymérisation d'au moins trois constituants monomères polymérisables, ledit polymère séquencé ayant : une première unité polymère qui comprend une unité structurale dérivée d'un premier monomère polymérisable et une unité structurale dérivée d'un deuxième monomère polymérisable ; et une seconde unité polymère qui comprend une unité structurale dérivée du premier monomère polymérisable et une unité structurale dérivée d'un troisième monomère polymérisable qui est différent du deuxième monomère polymérisable.
PCT/JP2015/062112 2014-04-21 2015-04-21 Polymère séquencé WO2015163321A1 (fr)

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WO2020149386A1 (fr) * 2019-01-16 2020-07-23 積水フーラー株式会社 Copolymere sequence reticulable, son procede de fabrication ainsi qu'adhesif thermofusible
WO2022044825A1 (fr) * 2020-08-25 2022-03-03 大日精化工業株式会社 Copolymère à blocs a-b, émulsion de polymère et encre pour jet d'encre à base d'eau
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WO2020149386A1 (fr) * 2019-01-16 2020-07-23 積水フーラー株式会社 Copolymere sequence reticulable, son procede de fabrication ainsi qu'adhesif thermofusible
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