WO2017110083A1 - Procédé de production de polymère réticulé soluble - Google Patents

Procédé de production de polymère réticulé soluble Download PDF

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Publication number
WO2017110083A1
WO2017110083A1 PCT/JP2016/005184 JP2016005184W WO2017110083A1 WO 2017110083 A1 WO2017110083 A1 WO 2017110083A1 JP 2016005184 W JP2016005184 W JP 2016005184W WO 2017110083 A1 WO2017110083 A1 WO 2017110083A1
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Prior art keywords
meth
acrylate
monomer
polymerization initiator
producing
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PCT/JP2016/005184
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English (en)
Japanese (ja)
Inventor
顕夫 田村
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富士フイルム株式会社
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Priority to JP2017557707A priority Critical patent/JPWO2017110083A1/ja
Publication of WO2017110083A1 publication Critical patent/WO2017110083A1/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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • 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
    • C08F4/00—Polymerisation catalysts

Definitions

  • the present invention relates to a method for producing a soluble cross-linked polymer.
  • a hard coat film having a hard coat layer is provided on a support in order to prevent damage to the display surface.
  • Many of such films are produced by laminating coating films.
  • a leveling agent such as a fluorine-containing polymer is usually added to the hard coat layer composition in order to enhance the homogeneity of the coating film of the hard coat layer itself.
  • the surface of the hard coat layer is hydrophobized by the hydrophobicity of the leveling agent, and the recoatability (lamination property) is lowered. Therefore, a specific fluorosurfactant or a fluorine-containing polymer is added for the purpose of improving the uniform coatability on the substrate during coating and improving the recoatability after coating.
  • even a coating composition containing them does not have sufficient uniformity and recoatability of the coating film itself.
  • dendritic polymers such as hyperbranched polymers and dendrimers
  • Such highly branched polymers have properties different from ordinary linear polymers, such as low melt viscosity, low melt viscosity, and high solubility, and are expected to be applied as surfactants and surface modifiers.
  • the properties of the polymer itself and the properties of the coating film surface formed by adding the polymer and the interface of the laminated film when the coating film is laminated are also important.
  • a method for producing a hyperbranched polymer there is a method of radical polymerization of a system containing a vinyl monomer, but it is difficult to control the molecular weight, and an insoluble and infusible polymer may be produced. Therefore, an initiator-incorporated radical polymerization in which a monomer is polymerized in the presence of a high concentration radical polymerization initiator has been proposed.
  • Patent Document 1 discloses that a monomer A having two or more radically polymerizable double bonds in the molecule is a polymerization initiator in an amount of 5 mol% to 200 mol% with respect to 1 mol of the monomer A in an organic solvent.
  • a method of polymerizing under reflux at a temperature 20 ° C. or more higher than the 10-hour half-life temperature of the polymerization initiator B in the presence of B is disclosed. It is described that according to this production method, the molecular weight can be controlled by a simple method, and the weight average molecular weight can be controlled within a range that can be dissolved in a solvent.
  • Patent Document 2 discloses a monomer (A) having one radical polymerizable unsaturated double bond and a monomer (B) having two or more radical polymerizable unsaturated double bonds (A ) And (B), a method of polymerizing in the presence of 15 to 170 mol% of a polymerization initiator (C) is disclosed. According to this production method, it is described that a three-dimensional polymer having a volume average particle diameter of 1 nm to 300 nm can be easily obtained.
  • the present inventors have used a surface modifier as a coating composition for producing a hard coat layer using a hyperbranched polymer obtained by the method described in the above-mentioned patent document for an image display device such as a liquid crystal display device.
  • a surface modifier for producing a hard coat layer using a hyperbranched polymer obtained by the method described in the above-mentioned patent document for an image display device such as a liquid crystal display device.
  • spot-like defects were generated on the surface of the cured film. This is caused by insoluble components in the matrix of various resins constituting the film.
  • a highly branched polymer is added to the coating composition as a surface modifier or the like, it is required to suppress the generation of impurities at a higher level (mainly below the detection limit).
  • the present invention has been made in view of the above circumstances, and when the highly branched polymer is used as an additive of the coating composition, the compatibility with the matrix is good, and the composition is used as a coating film. It is an object of the present invention to provide a method for producing a soluble cross-linked polymer in which uneven defects are satisfactorily reduced.
  • the monomer A having two or more radical polymerizable double bonds in the molecule is added in the presence of 210 mol% or more of the polymerization initiator B with respect to 1 mol of the monomer A. It is what is polymerized.
  • the polymerization initiator B is preferably 260 mol% or more with respect to 1 mol of the monomer.
  • Monomer A is preferably polymerized in an organic solvent at a temperature 20 ° C. or more higher than the 10-hour half-life temperature of polymerization initiator B.
  • the method for producing a soluble cross-linked polymer according to the present invention includes an organic solvent in which a solution containing the monomer A, the polymerization initiator B, and the organic solvent is maintained at a temperature 20 ° C. or more higher than the 10-hour half-life temperature of the polymerization initiator B.
  • the monomer A may be polymerized by dropping it into the inside.
  • the monomer A and the monomer C may be polymerized by adding the monomer C having one radical polymerizable double bond in the molecule.
  • Monomer C is preferably a radically polymerizable compound having a fluorine atom.
  • the weight average molecular weight of the soluble cross-linked polymer is preferably 1,000 to 300,000 in terms of polystyrene by gel permeation chromatography.
  • the weight average molecular weight of the soluble cross-linked polymer is more preferably 1,000 to 50,000 in terms of polystyrene by gel permeation chromatography.
  • the monomer A having two or more radical polymerizable double bonds in the molecule is added in the presence of 210 mol% or more of the polymerization initiator B with respect to 1 mol of the monomer A. It is what is polymerized. According to this method, the molecular weight of the polymer can be controlled well. For this reason, when the obtained polymer is used as an additive in the coating composition, the compatibility with the matrix is good, so that a film having well-formed defects can be obtained.
  • a method for producing the soluble cross-linked polymer of the present invention will be described. The following description may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • Method for producing soluble cross-linked polymer In the production method of the soluble cross-linked polymer of the present invention, the monomer A having two or more radical polymerizable double bonds in the molecule is added in the presence of 210 mol% or more of the polymerization initiator B with respect to 1 mol of the monomer A. It is what is polymerized. First, the material used for the manufacturing method of a soluble bridge
  • Monomer A is a polyfunctional monomer having two or more radically polymerizable double bonds in the molecule.
  • Examples of the polyfunctional monomer used for the monomer A include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, and ethylene glycol di (meth) acrylate.
  • Monomer A may be a polyfunctional acrylate compound having three or more (meth) acryloyl groups in the molecule.
  • Specific examples include KAYARAD DPHA, DPHA-2C, PET-30, TMPTA, TPA-320, TPA-330, RP-1040, T-1420, and D from Nippon Kayaku Co., Ltd. -310, DPCA-20, DPCA-30, DPCA-60, GPO-303, Osaka Organic Chemical Industry Co., Ltd. V # 400, V # 36095D, etc. Can be mentioned.
  • UV-1400B Purple light UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7630B, UV-7640B UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310EA, UV-3310B, UV-3500BA UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2250EA (manufactured by Nippon Synthetic Chemical Co., Ltd.), UL-503LN (manufactured by Kyoeisha Chemical Co., Ltd.), Unidic 17-80 17-813, V-4030, V-4000BA (Dainippon Ink Chemical Co., Ltd.), EB-1290K, EB-220, EB-5129,
  • the polymerization initiator B is present in an amount of 210 mol% or more with respect to 1 mol of the monomer A, and the monomer A is polymerized.
  • the molecular weight can be controlled favorably, and when used as an additive of a coating composition, so-called bumpy defects can be reduced well.
  • content of the polymerization initiator B 260 mol% or more is more preferable with respect to 1 mol of monomers A.
  • polymerization initiator B examples include an azo polymerization initiator, a peroxide polymerization initiator, a redox polymerization initiator using a peroxide polymerization initiator and a reducing agent in combination, and a mixture of two or more of the above.
  • an oil-soluble azo polymerization initiator is preferable.
  • 2,2′-azobisisobutyronitrile and dimethyl 2,2′-azobisisobutyrate are particularly preferable.
  • the following oil-soluble peroxide polymerization initiators are preferably used.
  • ketone peroxide methyl ethyl peroxide, methyl isobutyl peroxide, acetylacetone peroxide, cyclohexanone peroxide, etc.
  • Hydroperoxide (1,1,3,3-tetramethylbutyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, etc.
  • Diacyl peroxide isobutyryl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, etc.
  • Dialkyl peroxide dicumyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, t-butyl
  • ketone peroxide preferred are (1) ketone peroxide, (2) hydroperoxide, (4) dialkyl peroxide and (6) alkyl perester, and particularly preferred are methyl ethyl ketone peroxide and cumene hydroperoxide. Oxides, di-t-butyl peroxide and t-butyl peroxybenzoate.
  • An oil-soluble redox polymerization initiator is used as the redox polymerization initiator.
  • the peroxide polymerization initiator include oils such as hydroperoxide (t-butylhydroxyperoxide, cumene hydroperoxide, etc.), dialkyl peroxide (lauroyl peroxide, etc.) and diacyl peroxide (benzoyl peroxide, etc.). Examples thereof include soluble peroxides.
  • Reducing agents include oil-soluble reducing agents such as tertiary amines (triethylamine, tributylamine, etc.), naphthenates, mercaptans (mercaptoethanol, lauryl mercaptan, etc.), organometallic compounds (triethylaluminum, triethylboron, diethylzinc, etc.) Etc.
  • oil-soluble reducing agents such as tertiary amines (triethylamine, tributylamine, etc.), naphthenates, mercaptans (mercaptoethanol, lauryl mercaptan, etc.), organometallic compounds (triethylaluminum, triethylboron, diethylzinc, etc.) Etc.
  • examples of preferable specific combinations of the peroxide polymerization initiator and the reducing agent include cumene hydroperoxide-triethylaluminum, benzoyl peroxide-
  • monomer A and monomer C may be copolymerized.
  • Monomer C is a monofunctional monomer having one radical polymerizable double bond in the molecule. By copolymerizing the monofunctional monomer, the molecular weight can be further reduced and the molecular weight distribution of the polymer can be stabilized.
  • preferred specific examples of the monomer C will be described.
  • the monomer C include, for example, styrene compounds such as styrene and ⁇ -methylstyrene; acrylonitrile compounds such as acrylonitrile and methacrylonitrile; N-vinyl compounds such as N-vinylformamide; (meth) acrylamide, N -Methylol (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, (meth) acryloylmorpholine, (meth) (Meth) acrylamide compounds such as acrylamide; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,
  • the monomer C may have a fluorine atom.
  • Monomer C having a fluorine atom is particularly useful as a surfactant and a surface modifier.
  • the monomer C having a fluorine atom one in which a part of the substituents of the monomer C is substituted with fluorine can be used. Specific examples are shown below.
  • the monomer A is preferably polymerized in an organic solvent at a temperature 20 ° C. or more higher than the 10-hour half-life temperature of the polymerization initiator B.
  • organic solvents include the following organic solvents.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, cyclohexane; methyl chloride, bromide Halogen solvents such as methyl, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, orthodichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol Ester or ester ether solvents such as monomethyl ether acetate; diethyl ether, tetrahydrofuran, 1,4-dioxane, ethyl cell
  • an organic solvent having a boiling point of 90 ° C. to 200 ° C. under atmospheric pressure for example, toluene, xylene, orthodichlorobenzene, butyl acetate, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide.
  • organic solvents for example, toluene, xylene, orthodichlorobenzene, butyl acetate, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide.
  • Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, n-propanol and the like are particularly preferable organic solvents.
  • the content of the organic solvent is preferably 0.3 to 100 parts by weight, more preferably 0.5 to 50 parts by weight with respect to 1 part by weight of the monomer A. .
  • polymerization method In the method for producing a soluble crosslinked polymer of the present invention, monomer A is polymerized in the presence of polymerization initiator B.
  • the polymerization method include known methods, solution polymerization, dispersion polymerization, precipitation polymerization, and bulk polymerization. Of these, solution polymerization in an organic solvent is preferred.
  • the polymerization reaction is carried out under normal pressure, under pressure and under pressure, or under reduced pressure, and is preferably carried out under normal pressure in view of simplicity of apparatus and operation. Further, preferably carried out in an atmosphere of inert gas such as N 2.
  • the solution containing the monomer A, the polymerization initiator B, and the organic solvent was maintained at a temperature higher by 20 ° C. than the 10-hour half-life temperature of the polymerization initiator B. You may superpose
  • the organic solvent of the solution containing the monomer A and the polymerization initiator B can use the said organic solvent similarly. Further, it is more preferable to carry out the polymerization reaction at the reflux temperature under the reaction pressure of the organic solvent. By setting the reflux temperature, the polymerization temperature can be made constant and the molecular weight can be easily controlled. Furthermore, the polymer can be produced safely even on an industrial scale.
  • the dropping method by setting the organic solvent to a temperature that is 20 ° C. or more higher than the 10-hour half-life temperature of the polymerization initiator B, the decomposition of the polymerization initiator proceeds rapidly, and the initiator fragment radicals and the growth terminal of the polymer are grown. It is possible to control the molecular weight so that the termination reaction with the radical proceeds without stagnation and is soluble in the matrix.
  • the weight average molecular weight Mw of the soluble crosslinked polymer obtained by the production method of the present invention is 1,000 to 300,000 in terms of polystyrene by gel permeation chromatography. From the viewpoint of compatibility with the matrix, 1,000 to 50,000 are preferable, and 2,000 to 4,000 are more preferable.
  • the weight average molecular weight Mw and the number average molecular weight Mn can be measured by the methods described in Examples described later. Further, Mw / Mn as an index of molecular weight distribution is preferably 1.30 to 10.00, and more preferably 1.50 to 6.00. Due to such molecular weight distribution, the compatibility with the matrix is good, and when used as an additive, coating film failures such as spot-like defects can be satisfactorily prevented.
  • the polymers (1) and (2) having a fluorine atom are useful as additives such as surface modifiers.
  • Table 1 lists materials used in the synthesis examples and comparative synthesis examples, their blend ratios, and molecular weights.
  • the polymer had a weight average molecular weight (Mw) of 4,800 and a molecular weight distribution Mw / Mn of 2.20.
  • the weight average molecular weight Mw and the number average molecular weight Mn were calculated in terms of polystyrene by gel permeation chromatography (GPC).
  • the column used was TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (manufactured by Tosoh Corporation), and tetrahydrofuran was used as the carrier.
  • T is the temperature of the organic solvent on the side to be dropped, that represents the polymerization temperature
  • T 10 represents a 10-hour half-life temperature of the polymerization initiator.
  • TT 10 indicates these differences.
  • DA-314 Glycerin polyglycidyl ether (acrylic acid modified product)
  • DVB divinylbenzene
  • EGDMA ethylene glycol dimethacrylate
  • TAIC triallyl isocyanurate
  • DCP tricyclodecane dimethanol dimethacrylate
  • AH-600 phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer
  • C6FA 2- (perfluorohexyl) ethyl acrylate MMA: Methyl methacrylate
  • DPE Diphenylethylene AIBN: Azobisisobutyronitrile
  • the compounds 102 to 109 and the compounds H101 to 104 are described below.
  • the molecular weight of the polymer is determined by setting the amount of the polymerization initiator within the range of the present invention. It was found that it can be reduced and the variation in molecular weight can be reduced. From this, it is presumed that the present invention can prevent the generation of impurities at a high level.
  • a hard coat layer was produced using the polymers obtained in the above synthesis examples and comparative synthesis examples.
  • preparation of a coating solution for the hard coat layer A-1 of Example 1 will be described.
  • ⁇ Preparation of coating solution for hard coat layer A-1> Each component was mixed so as to have the following composition to prepare a coating solution for hard coat layer A-1 having a solid content concentration of about 55% by mass.
  • Compound 1 was synthesized by the method described in Example 1 of Japanese Patent No. 4841935. The structural formula of Compound 1 is shown below.
  • Coating for hard coat layer A-2 to A-15 was carried out in the same manner as the preparation of the coating liquid for hard coat layer A-1, except that compound 101 of the present invention was replaced with compounds 102 to 111 and H101 to H104. A liquid was prepared.
  • TJ25 triacetyl cellulose film
  • each coating solution was applied onto a support at a conveyance speed of 30 m / min by a die coating method using a slot die described in Example 1 of JP-A-2006-122889 at 60 ° C.
  • the produced hard coat film was evaluated by the following evaluation method.
  • the film thickness of the hard coat layer was calculated by measuring the film thickness of a hard coat film produced using a contact-type film thickness meter, and subtracting the thickness of the support measured in the same manner. In all the hard coat films, the film thickness of the hard coat layer was 6.0 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Le problème décrit par la présente invention est de produire un procédé de production d'un polymère réticulé soluble qui est hautement compatible avec des matrices, et qui réduit de façon satisfaisante les défauts de type cloque sur un film de revêtement lorsqu'il est utilisé comme additif. La solution selon l'invention porte sur un procédé de production d'un polymère réticulé soluble par polymérisation d'un monomère A, qui présente au moins deux doubles liaisons polymérisables par voie radicalaire par molécule, en présence d'un initiateur de polymérisation B en une quantité d'au moins 210 % molaire par mole du monomère A1.
PCT/JP2016/005184 2015-12-24 2016-12-20 Procédé de production de polymère réticulé soluble WO2017110083A1 (fr)

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JP2017557707A JPWO2017110083A1 (ja) 2015-12-24 2016-12-20 可溶性架橋型ポリマーの製造方法

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JP2015-251365 2015-12-24

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63249112A (ja) * 1987-04-03 1988-10-17 Mitsubishi Rayon Co Ltd 光フアイバ
JPH0543604A (ja) * 1991-08-13 1993-02-23 Ricoh Co Ltd 重合体粒子の製造方法
JP2002302583A (ja) * 2001-04-06 2002-10-18 Sekisui Chem Co Ltd 粘弾性組成物及び制振材
JP2003015293A (ja) * 2001-07-03 2003-01-15 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いたパターン製造法及び電子部品
JP2004300173A (ja) * 2003-03-28 2004-10-28 Taiyo Ink Mfg Ltd 光硬化性・熱硬化性樹脂組成物及びそれを用いたプリント配線板
JP2009155619A (ja) * 2007-12-28 2009-07-16 Lion Corp ハイパーブランチポリマーの合成方法およびレジスト組成物
JP2016113580A (ja) * 2014-12-17 2016-06-23 新日鉄住金化学株式会社 発泡用スチレン系樹脂組成物、スチレン系樹脂発泡シート、その製造方法及び食品包装容器

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63249112A (ja) * 1987-04-03 1988-10-17 Mitsubishi Rayon Co Ltd 光フアイバ
JPH0543604A (ja) * 1991-08-13 1993-02-23 Ricoh Co Ltd 重合体粒子の製造方法
JP2002302583A (ja) * 2001-04-06 2002-10-18 Sekisui Chem Co Ltd 粘弾性組成物及び制振材
JP2003015293A (ja) * 2001-07-03 2003-01-15 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いたパターン製造法及び電子部品
JP2004300173A (ja) * 2003-03-28 2004-10-28 Taiyo Ink Mfg Ltd 光硬化性・熱硬化性樹脂組成物及びそれを用いたプリント配線板
JP2009155619A (ja) * 2007-12-28 2009-07-16 Lion Corp ハイパーブランチポリマーの合成方法およびレジスト組成物
JP2016113580A (ja) * 2014-12-17 2016-06-23 新日鉄住金化学株式会社 発泡用スチレン系樹脂組成物、スチレン系樹脂発泡シート、その製造方法及び食品包装容器

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