WO2015162666A1 - Procédé de production d'un polymère séquencé - Google Patents

Procédé de production d'un polymère séquencé Download PDF

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WO2015162666A1
WO2015162666A1 PCT/JP2014/061171 JP2014061171W WO2015162666A1 WO 2015162666 A1 WO2015162666 A1 WO 2015162666A1 JP 2014061171 W JP2014061171 W JP 2014061171W WO 2015162666 A1 WO2015162666 A1 WO 2015162666A1
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polymerizable monomer
polymer
polymerization
monomer
molecular weight
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PCT/JP2014/061171
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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 JP2016514562A priority patent/JP6372565B2/ja
Publication of WO2015162666A1 publication Critical patent/WO2015162666A1/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

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  • the present invention relates to a method for producing a block polymer in which a monomer having three or more components is polymerized.
  • Acrylic polymers can be easily produced by radical polymerization of acrylic monomers, and the properties of the resin can be widely changed by copolymerizing several types of acrylic monomers depending on the purpose. Widely manufactured industrially. Further, bulk polymerization, solution polymerization, suspension polymerization and the like are widely used as the production method, and are selected in view of the molecular weight and cost of the acrylic polymer to be produced. Conventional acrylic polymers are generally produced by free radical polymerization, so acrylic polymers obtained from multi-component monomers are random copolymers and have a broad molecular weight distribution.
  • Acrylic polymers can develop 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.
  • acrylic acid or methacrylic acid as a component thereof, it is provided with a photosensitive resist material by imparting alkali aqueous solubility.
  • copolymerizing glycidyl methacrylate it is possible to incorporate a thermosetting reaction or introduce a photoreactive group to incorporate photoreactivity, for example, to increase the heat resistance of the adhesive, It is possible to impart sex.
  • RAFT Reversible addition-fragmentation chain transfer
  • RAFT polymerization takes the behavior of living polymerization by using a chain transfer agent having a thiocarbonate structure to cause reversible addition cleavage at the polymer growth terminal and causing chain transfer to a monomer.
  • RAFT polymerization can polymerize acrylic acid and methacrylic acid without protecting groups, and enables copolymerization with various acrylic esters, methacrylic esters, styrene, etc. (see Patent Documents 1 and 2). ).
  • the present invention can improve the block property of other monomers so that the physical properties of the polymer due to the specific polymerizable monomer do not change due to the sequence of the polymer. It is an object to obtain a possible block polymer.
  • the purpose is to produce such a block polymer as an acrylic polymer, and among them, in a multicomponent copolymer of three or more components including acrylic acid or methacrylic acid, structural units other than those derived from acrylic acid or methacrylic acid are used.
  • An object of the present invention is to obtain an acrylic polymer that can be blocked and has properties that do not reduce solvent solubility or solubility in an aqueous alkali solution.
  • the present invention is a block polymer production method for polymerizing a polymerizable monomer having three or more components, and a step of polymerizing a first polymerizable monomer and a second polymerizable monomer by living polymerization to obtain a first polymer unit.
  • a block polymer having a first polymerizable monomer, and then a step B for adding a third polymerizable monomer different from the second polymerizable monomer to chain extend the second polymer unit. It relates to a manufacturing method.
  • a first polymerizable monomer and a fourth polymerizable monomer different from the third polymerizable monomer are added to chain the third polymer unit.
  • the present invention relates to a method for producing the block polymer having the step C of stretching.
  • the step of chain-extending the n + 1th polymerizable monomer different from the first polymerizable monomer and the immediately preceding nth polymerizable monomer is further repeated one or more steps.
  • the present invention relates to a method for producing a block polymer.
  • the present invention also relates to a method for producing each block polymer, wherein the first polymerizable monomer is a carboxyl group-containing polymerizable monomer. Furthermore, the present invention relates to a method for producing each of the block polymers, wherein the second and subsequent polymerizable monomers are acrylic monomers, styrenic monomers or acrylonitrile.
  • the block property of another monomer is controlled so that the physical properties of the polymer due to the specific polymerizable monomer are not changed by the sequence of the polymer. Can be increased. Further, according to the production method of the present invention, it is possible to easily produce a block polymer having acrylic acid or methacrylic acid which is excellent in solubility in a solvent or an alkaline aqueous solution, and the resulting acrylic polymer is a photosensitive resist. It can be suitably applied as an adhesive and a photo-curing resin.
  • the production method of the present invention is a production method of a block polymer obtained by polymerizing a polymerizable monomer having three or more components, wherein the first polymerizable monomer and the second polymerizable monomer are polymerized by living polymerization.
  • Step A to obtain a polymer unit of the following, followed by Step B of chain-extending the second polymer unit by adding a first polymerizable monomer and a third polymerizable monomer different from the second polymerizable monomer Have
  • step A and the step B a first polymerizable monomer and a fourth polymerizable monomer different from the third polymerizable monomer are added, and the third polymerizable monomer is added. It is possible to have step C of chain extending the polymer unit. Furthermore, in the production method of the present invention, after the step C, the step of chain-extending the first polymerizable monomer and the (n + 1) th polymerizable monomer different from the immediately preceding nth polymerizable monomer further includes one step. It is possible to repeat the above.
  • Living polymerization in the present invention includes anionic 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.
  • Living radical polymerization reversibly protects the growing radical in radical polymerization, and the molecular chain is gradually changed by repeating deprotection (activation), addition of monomer (growth), and protection (inactivation) of the protecting group, The polymer grows almost uniformly and a polymer with a narrow molecular weight distribution is obtained.
  • RAFT reversible addition-fragmentation chain transfer polymerization
  • a thiocarbonate compound having a structure represented by the 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 tertiary butyl group, a cyanomethyl group, and a benzyl group.
  • Z is preferably a phenyl group, a methylthioyl group, a pyrrole group, a methyl group, a phenoxy group, an ethoxy group, a 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, Although cyanomethyl dodecyl trithio carbonate etc. are mentioned and these are marketed, it is not limited to these.
  • the polymerizable monomer includes a monomer having a polymerizable carbon-carbon unsaturated double bond, and specifically includes an acrylic monomer, a styrene monomer, acrylonitrile and the like.
  • the acrylic monomer refers to a monomer having an acryloyl group (CH ⁇ CH—CO—) or a methacryloyl group (CH ⁇ C (CH 3 ) —CO—).
  • the production method of the present invention is preferably applied to the production of a block polymer of an acrylic polymer (referred to a polymer using the acrylic monomer as a polymerization component) using an acrylic monomer or a styrene monomer as a polymerizable monomer.
  • the first polymerizable monomer is not particularly limited, and examples thereof include a carboxyl group-containing monomer, among which acrylic acid, methacrylic acid and the like are preferable.
  • the second polymerizable monomer, the third polymerizable monomer, the fourth, fifth, sixth,... Polymerizable monomer (that is, the (n + 1) th polymerizable monomer different from the nth polymerizable monomer. ) May be preferably acrylic monomers, styrene monomers, acrylonitrile, etc. other than the first polymerizable monomer.
  • the first polymerizable monomer (meth) acrylic acid, the second and subsequent monomers; styrene, (meth) acrylic acid benzyl, (meth) Examples thereof include methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, and the like.
  • ((Meth) acrylic acid OO means acrylic acid XX or methacrylic acid XX.)
  • the first polymerizable monomer for example, acrylic acid or methacrylic acid
  • the second polymerizable monomer are living polymerized using the thiocarbonate compound having the structure represented by the general formula (1) as a chain transfer agent.
  • the first polymer unit is synthesized by polymerization, and when the polymerization proceeds to some extent, the polymer that becomes the first polymer unit is recovered by reprecipitation or reduced pressure distillation, and then the first polymerizable monomer and the first polymer unit are collected.
  • the second polymer unit can be chain extended. In this case, a small amount of radical initiator may be added.
  • a thiocarbonate compound having a structure represented by the general formula (1) is used as a chain transfer agent, and a first polymer unit and a second polymerizable monomer are polymerized by living polymerization to synthesize a first polymer unit.
  • the first polymer monomer and the third polymer monomer are added to the same reactor, and the second polymer unit is chain-extended to obtain the block polymer of the present invention. be able to.
  • the first polymerizable monomer used first, the second monomer polymerizable with this, the first polymerizable monomer charged later, the third monomer polymerizable with this, and the molar amount and the general formula By controlling the molar ratio of the thiocarbonate compound represented by 1), the molecular weight of the resulting block polymer, the molecular weight of the first polymer unit (chain length), and the molecular weight of the second polymer unit (chain length) It is possible to adjust.
  • the molar ratio of the serial transfer agent, specifically the compound represented by the general formula (1) and the radical initiator is preferably 20/1 to 1/5, more preferably 10/1 to 1/4.
  • the ratio of the compound represented by the general formula (1) to the radical initiator is 20/1 or less, which is industrially preferable because the polymerization reaction rate can be increased while maintaining monodispersity.
  • the temperature of the polymerization reaction varies depending on the decomposition temperature of the radical initiator to be used, and is not particularly limited, but it is generally preferable to carry out at a half-life decomposition temperature of minus 2 ° C. to plus 20 ° C. By controlling the temperature within this range with respect to the half-life decomposition temperature, it is possible to reduce the molecular weight distribution, and it is possible to suppress a decrease in blocking due to a by-product of a polymer not having the structure of the general formula (1).
  • radical initiators for synthesizing the block polymers of the present invention include peroxides such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, and dicumyl peroxide.
  • peroxides such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, and dicumyl peroxide.
  • oxide initiators such as AIBN (2,2′-azobisisobutyronitrile), V-65 (azobisdimethylvaleronitrile), and the like. Of these, AIBN (2,2'-azobisisobutyronitrile) is preferred.
  • the block polymer of the present invention can be synthesized by solution polymerization, suspension polymerization, emulsion polymerization, solid phase polymerization, etc., but solution polymerization is required to obtain a resin having a weight average molecular weight of 2,000 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 and reactivity of the monomer used, but when acrylic acid or methacrylic acid is used, solution polymerization may be performed to synthesize an acrylic polymer that is soluble in a solvent from the viewpoint of its solubility. preferable.
  • the molecular weight of the block polymer produced according to the present invention is not particularly limited, but in general, the weight average molecular weight is preferably 10,000 to 200,000. In general, the molecular dispersity is preferably 1.2 to 4.0. In addition, molecular weight can be calculated
  • Solution polymerization is performed by dissolving a polymerizable monomer, a chain transfer agent, a radical initiator, and a resin to be produced in a solvent that can be dissolved, and then heating to a temperature determined by the radical initiator. At this time, it is possible to carry out the polymerization under air, but it is preferred to carry 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. When 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.
  • organic solvent to be used methoxyethanol, ethoxyethanol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanol, cyclohexanone, butyl acetate, chlorobenzene, dioxane, propylene glycol monomethyl ether and the like are used, and are not particularly limited. These can be used alone or in combination.
  • RAFT polymerization chain transfer from the acrylic growth end to the methacrylate monomer generally does not occur. Therefore, the monomer blending procedure and combination when copolymerizing a plurality of monomers are 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 in order to grow a polymer stepwise by block polymerization, polymerization is performed with a combination of monomers having an acryloyl group, or after polymerization of a monomer having a methacryloyl group with a combination of monomers having a methacryloyl group only. It is preferable to polymerize a monomer having an acryloyl group.
  • the block polymer obtained by the present invention is expected to exhibit excellent properties in applications such as photosensitive materials, adhesives, adhesives, coating materials, and dispersants.
  • Example 1 In a 500 ml separable flask equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen introduction tube, 25.0 g (290 mmol) of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), styrene monomer (manufactured by Wako Pure Chemical Industries, Ltd.) 67.5 g (648 mmol), cumyl dithiobenzoate 1.46 g (5.36 mmol), azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd., purity 98%) 0.45 g (2.73 mmol) were charged at room temperature.
  • methacrylic acid manufactured by Wako Pure Chemical Industries, Ltd.
  • styrene monomer manufactured by Wako Pure Chemical Industries, Ltd.
  • cumyl dithiobenzoate 1.46 g (5.36 mmol)
  • azobisisobutyronitrile (Wako Pure Chemical Industries,
  • Nitrogen was bubbled 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 weight 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 94%
  • the weight average molecular weight (Mw) of the styrene / methacrylic acid unit was 12,900
  • the number average molecular weight (Mn) was 9,200.
  • Example 2 In a 500 ml separable flask equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen introduction tube, 25.0 g (290 mmol) of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), styrene monomer (manufactured by Wako Pure Chemical Industries, Ltd.) 67.5 g (648 mmol), cumyl dithiobenzoate 0.68 g (2.5 mmol), azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd., purity 98%) 0.21 g (1.28 mmol) were charged at room temperature. Nitrogen was bubbled and stirred for 30 minutes.
  • methacrylic acid manufactured by Wako Pure Chemical Industries, Ltd.
  • styrene monomer manufactured by Wako Pure Chemical Industries, Ltd.
  • cumyl dithiobenzoate 0.68 g (2.5 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 weight ratio) mixed solution in which nitrogen was bubbled 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, a thermometer, a stirrer, and a nitrogen introduction tube, 25.0 g (290 mmol) of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), styrene monomer (manufactured by Wako Pure Chemical Industries, Ltd.) 67.5 g (648 mmol), cumyl dithiobenzoate 1.12 g (4.1 mmol), azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd., purity 98%) 0.17 g (1.01 mmol) were charged at room temperature. Nitrogen was bubbled and stirred for 30 minutes.
  • methacrylic acid manufactured by Wako Pure Chemical Industries, Ltd.
  • styrene monomer manufactured by Wako Pure Chemical Industries, Ltd.
  • cumyl dithiobenzoate 1.12 g (4.1 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 weight ratio) mixed solution in which nitrogen was bubbled 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 11,300, and the number average molecular weight (Mn) was 9,000.
  • reaction solution was reprecipitated with hexane and vacuum dried at 40 ° C. 50.0 g of the obtained solid, 46 g of toluene / propylene glycol monomethyl ether (2/3 weight ratio) mixed solution, 8.4 g (97.6 mmol) of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), benzyl methacrylate (Hitachi Chemical) 22.7 g (128.8 mmol) of FANCLIL FA-BZM (manufactured by Co., Ltd.) was added and stirred. After the solid matter dissolved, the temperature was raised to 70 ° C. and stirred.
  • Example 4 According to Example 1, an acrylic polymer was obtained with a combination of a monomer and a RAFT agent shown in the following table.
  • Example 7 In a 500 ml separable flask equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen introduction tube, 16.0 g (186 mmol) of methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), styrene monomer (manufactured by Wako Pure Chemical Industries, Ltd.) 40.0 g (384 mmol), cumyl dithiobenzoate 0.63 g (2.33 mmol), azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd., purity 98%) 0.20 g (1.16 mmol) were charged at room temperature. Was bubbled with nitrogen and stirred for 30 minutes.
  • methacrylic acid manufactured by Wako Pure Chemical Industries, Ltd.
  • styrene monomer manufactured by Wako Pure Chemical Industries, Ltd.
  • cumyl dithiobenzoate 0.63 g (2.33 mmol
  • the temperature was raised to 65 ° C. and stirred for 30 minutes, after which the temperature was raised to 70 ° C.
  • 56 g of a toluene / propylene glycol monomethyl ether (2/3 weight ratio) mixed solution in which nitrogen was bubbled 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 12,900, and the number average molecular weight (Mn) was 10,400. Met.
  • the weight average molecular weight of the obtained polymer was 34,600, the number average molecular weight was 26,400, 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 weight ratio) mixed solution of acrylic polymer having three polymer units.
  • Example 8 According to Example 7, except that the monomer added in the third time was methacrylic acid and styrene in the first time, a mixed solution of toluene / propylene glycol monomethyl ether (2/3 weight ratio) of acrylic polymer having three polymer units was prepared. 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 14,100, and the number average molecular weight (Mn) was 11,300.
  • Comparative Example 2 According to Comparative Example 1, an acrylic polymer having benzyl methacrylate and styrene as block units was obtained.
  • 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 bubbled with nitrogen for 30 minutes was further added. Stir. 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 mixed solution of acrylic polymer in toluene / propylene glycol monomethyl ether (2/3 weight ratio) was obtained.
  • the weight average molecular weight (Mw) of the obtained polymer was 24,500, the number average molecular weight (Mn) was 25,400, 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 acrylic polymers of Examples and Comparative Examples were measured by GPC (gel permeation chromatography) by measuring the chromatogram of the molecular weight distribution of the acrylic polymer. It calculated
  • 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) was directly connected.

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Abstract

La présente invention concerne un procédé permettant de produire un polymère séquencé formé en polymérisant au moins trois composants monomères polymérisables, ledit procédé comportant une étape (A) consistant à obtenir une première unité polymère en polymérisant un premier monomère polymérisable et un deuxième monomère polymérisable par polymérisation vivante, et une étape (B) consistant à ajouter, après l'étape (A), un troisième monomère polymérisable différent du premier monomère polymérisable et du deuxième monomère polymérisable et à soumettre une seconde unité polymère à une extension de chaîne.
PCT/JP2014/061171 2014-04-21 2014-04-21 Procédé de production d'un polymère séquencé WO2015162666A1 (fr)

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JP2016514562A JP6372565B2 (ja) 2014-04-21 2014-04-21 ブロックポリマの製造方法

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JP2006124588A (ja) * 2004-10-29 2006-05-18 Kaneka Corp 熱可塑性エラストマー組成物および成形品
JP2007506810A (ja) * 2003-06-30 2007-03-22 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン ゼロ価金属で開始された気相蒸着重合（ｇｄｐ）
JP2007532711A (ja) * 2004-04-09 2007-11-15 アルケマ フランス 配列されたコポリマー
JP2009504830A (ja) * 2005-08-09 2009-02-05 アルケマ フランス 制御されたフリーラジカル重合によって製造されるマルチブロックコポリマーを含むポリマー材料の製造方法
JP2011527372A (ja) * 2008-07-07 2011-10-27 アーケマ・インコーポレイテッド 両親媒性ブロックコポリマー配合物
WO2012123192A1 (fr) * 2011-03-14 2012-09-20 Evonik Rohmax Additives Gmbh Copolymères comprenant des groupes esters et utilisation desdits copolymères dans des lubrifiants
JP2013216714A (ja) * 2012-04-04 2013-10-24 Sanyo Shikiso Kk カラーフィルター用共重合体、顔料分散体及びレジスト組成物

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003501517A (ja) * 1999-06-03 2003-01-14 ピーピージー インダストリーズ オハイオ， インコーポレイテッド 制御されたラジカル重合によって調製されるブロックコポリマーおよび流動改変剤としてのその使用
JP2003527458A (ja) * 1999-09-01 2003-09-16 ロディア・シミ 少なくとも１つの水溶性ブロックと少なくとも１つの疎水性ブロックとを含有するブロックコポリマーを含むゲル化水性組成物
JP2007506810A (ja) * 2003-06-30 2007-03-22 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン ゼロ価金属で開始された気相蒸着重合（ｇｄｐ）
JP2007532711A (ja) * 2004-04-09 2007-11-15 アルケマ フランス 配列されたコポリマー
JP2006124588A (ja) * 2004-10-29 2006-05-18 Kaneka Corp 熱可塑性エラストマー組成物および成形品
JP2009504830A (ja) * 2005-08-09 2009-02-05 アルケマ フランス 制御されたフリーラジカル重合によって製造されるマルチブロックコポリマーを含むポリマー材料の製造方法
JP2011527372A (ja) * 2008-07-07 2011-10-27 アーケマ・インコーポレイテッド 両親媒性ブロックコポリマー配合物
WO2012123192A1 (fr) * 2011-03-14 2012-09-20 Evonik Rohmax Additives Gmbh Copolymères comprenant des groupes esters et utilisation desdits copolymères dans des lubrifiants
JP2013216714A (ja) * 2012-04-04 2013-10-24 Sanyo Shikiso Kk カラーフィルター用共重合体、顔料分散体及びレジスト組成物

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