JP2009249605A - Photopolymerizable composition - Google Patents

Abstract

Provided is a photopolymerizable composition that has a low viscosity and is easy to handle, is easy to produce and can be produced at low cost.
The photopolymerizable composition of the first invention is a glycidyl ether having a carbon-carbon double bond capable of polymerizing a terminal hydroxyl group of a hyperbranched polymer in which glycidol is polymerized in a branched manner starting from a hydroxyl group of a core molecule. It contains a polymerizable hyperbranched polymer added to an epoxy group, a polymerizable monomer that can be polymerized, and a photopolymerization initiator. In the photopolymerizable composition of the second invention, the hydroxyl group of the polymerizable hyperbranched polymer in the photopolymerizable composition of the first invention is etherified.
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Description

  The present invention relates to a photopolymerizable composition that is cured by irradiation with energy such as ultraviolet rays, light, or an electron beam.

  Resins that are cured by irradiation with energy such as ultraviolet rays and electron beams are used in various industrial fields. For example, a resin that is cured by light irradiation is used for manufacturing an electronic device as a material for lithography. In recent years, the structure of electronic devices has been further miniaturized, and further improvement in processing accuracy has been demanded in lithography technology using a photocurable resin.

  Conventionally, a photopolymerizable composition used for photolithography starts a photochemical reaction with a polymer resin (prepolymer) that causes a photochemical reaction and a polymerizable low molecule (monomer) as a diluent for the prepolymer. For example (see Patent Documents 1 to 3).

Prepolymers include acrylic acid / 1,6-hexanediol / acrylic acid (formula 1), phthalic anhydride / propylene oxide / acrylic acid (formula 2), trimellitic acid / diethylene glycol / acrylic acid (formula 3 Polyester-based ultraviolet curable resins having a relatively large molecular weight such as

  However, since the prepolymer has a very high viscosity and is difficult to handle such as coating, a polyfunctional monomer copolymerizable with the prepolymer is often added as a diluent. This diluent has a lower molecular weight than the prepolymer, and the viscosity can be lowered by adding it to the prepolymer. Although it is possible to reduce the viscosity by diluting the prepolymer with a solvent, this causes the solvent to volatilize before light irradiation, resulting in irregularities on the surface, which reduces the processing accuracy in photocuring. Problems arise. Further, when the prepolymer is diluted with a solvent, the viscosity changes due to volatilization of the solvent, and handling becomes difficult.

  For this reason, the present inventors have already developed a polymerizable dendritic polymer in which a polymerizable carbon-carbon double bond or an epoxy group is modified at the end of a dendritic polymer having a unique branched structure. (Patent Document 4 and Patent Document 5). These polymerizable dendritic polymers have the property of having a small viscosity for having a large molecular weight. By using this as a prepolymer, a photopolymerizable composition that has a low viscosity and is easy to handle. It becomes.

As a technique related to the present invention, Patent Document 6 describes a method for producing a highly branched polymer in which glycidol is polymerized in a branched form.
JP 2001-270973 A Japanese Patent Laid-Open No. 9-5997 Japanese Patent Laid-Open No. 10-60655 JP 2007-16154 A JP 2007-246483 A Special table 2002-533495 gazette

  However, the polymerizable dendritic polymers described in Patent Documents 4 and 5 are produced by extending the branched structure step by step, so that the number of production steps is large and time-consuming, and the production cost increases. was there. The present invention has been made in view of such conventional circumstances, and solves the problem of providing a photopolymerizable composition that has low viscosity and is easy to handle, easy to manufacture and can be manufactured at low cost. It is an issue that should be done.

  For dendritic polymers with a highly branched structure, a dendrimer formed by the chemical reaction of a monomer with a polyfunctional group step by step and an ABx type monomer are polycondensed to form a branched structure at once. Hyperbranched polymers are known. The polymerizable dendritic polymer described in Patent Documents 4 and 5 is a dendrimer. The inventors have used the above-mentioned conventional problem by using a polymerizable hyperbranched polymer obtained by modifying a polymerizable functional group in a hyperbranched polymer that is easy to produce instead of a dendrimer as a polymerizable component of an optical resin composition. The present invention was completed as a result of diligent research on the idea that the problem could be solved.

  That is, the photopolymerizable composition of the first invention in the present invention is a glycidyl ether having a carbon-carbon double bond capable of polymerizing a terminal hydroxyl group of a highly branched polymer in which glycidol is polymerized in a branched manner starting from the hydroxyl group of the core molecule. It comprises a polymerizable hyperbranched polymer added to the epoxy group, a polymerizable monomer capable of binding to the polymerizable hyperbranched polymer, and a photopolymerization initiator.

  The photopolymerizable composition of the first invention includes a polymerizable hyperbranched polymer modified with a polymerizable carbon-carbon double bond, and a polymerizable monomer capable of binding to the polymerizable hyperbranched polymer. Further, a photopolymerization initiator is included. For this reason, when this photopolymerizable composition is irradiated with energy such as ultraviolet rays, visible rays, and electron beams, a polymerization initiator such as a radical or a cation is generated from the photopolymerization initiator, and a highly branched polymer and a polymerizable monomer are generated. And further, the polymerizable monomers are polymerized and cured. For this reason, it can be used for printing a pattern for forming an integrated circuit.

The polymerizable hyperbranched polymer contained in the photopolymerizable composition of the first invention is a highly branched polymer because the glycidol is polymerized in a branched manner with the hydroxyl group of the core molecule as a base point. Although it has a large molecular weight, it has the property of low viscosity. For this reason, compared with the photopolymerizable composition containing a prepolymer, a viscosity is small and handling is easy, and the precision at the time of printing can also be improved.
In addition, since the polymerizable highly branched polymer can form a branched structure at a stretch by polycondensing monomers, the number of manufacturing steps is small, the synthesis is easy, and the manufacturing cost can be reduced.

  The polymerizable monomer may be any compound that can be bonded to the polymerizable hyperbranched polymer, and includes an oligomer in which several monomers are bonded. As the polymerizable monomer, an acrylic monomer having one or more (meth) acryl groups per molecule can be used. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acryloyl phosphate, tetrahydrofurfryl acrylate, dicyclopentenyloxy acrylate, dicyclopentenyloxyethyl acrylate, 1 , 3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, hydroxypivalate ester neopentyl glycol diacrylate, tripropylene glycol diacrylate Acrylate, 1,3-bis (3′-acryloxyethoxy-2′-hydroxypropyl) -5,5-dimethyl Dantoin, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and the like dipentaerythritol hexaacrylate. The inventors have confirmed that a polymer can be reliably obtained by light irradiation with a photopolymerizable composition using trimethylolpropane triacrylate as an acrylic monomer.

The photopolymerization initiator is preferably a photoradical generator that generates radicals by light irradiation. Examples of photo radical generators include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4- (di-n-butylamino) -4 ′-(diethylamino) stilbene, biacetyl. Acetophenone, benzophenone, benzyl, benzoin, benzoin isobutyl ether, benzyl dimethyl ketal, tetramethyl thiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, and the like. Moreover, it is also preferable to use the photoradical generator of following Chemical formula (4) and Chemical formula (5). Since these photoradical generators generate radicals efficiently even for light with low intensity, a highly sensitive photopolymerizable resin composition can be obtained.

  Moreover, as a polymerizable monomer, the epoxy-type monomer which has one or more epoxy groups in 1 molecule can also be used. Specifically, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 2,2-bis (4-glycidyloxyphenyl) propane, bisphenol A propoxylate diglycidyl ether, bisphenol F diglycidyl ether, glycerol Diglycidyl ether, glycerol propoxylate triglycidyl ether, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyldimethylethoxysilane, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, diglycidyl 1,2-cyclohexanedicarboxy Rate, polyethylene glycol diglycidyl ether, 1,3-butanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexane Methanol diglycidyl ether, N, N-diglycidyl aniline, N, N-diglycidyl-4-glycidyl oxyaniline, neopentyl glycol diglycidyl ether, poly (dimethylsiloxane) diglycidyl ether, poly (propylene glycol) diglycidyl ether, Resorcinol diglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether and the like can be mentioned. In addition, Poly [(phenyl glycidyl ether) -co-formaldehyde] (Poly [(phenyl glycidyl ether) -co-formaldehyde), Poly (bisphenol A-co-epichlorohydrin), glycidyl end-caped (Poly (bisphenol A-co-formaldehyde)) Epichlorohydrin, glycidyl endcapped), etc. Poly [(phenyl glycidyl ether) -co-formaldehyde] (Poly [(phenyl glycidyl ether) -co-formaldehyde) or Poly (bisphenol A-co-) epichlorohydrin), glycidyl end-caped (poly (bisphenol A-co-epichlorohydrin), glycidyl end-capped), etc. The inventors have used 3,4-epoxycyclohexylmethyl 3,4 as epoxy-based monomers. The photopolymerizable composition using 4-epoxycyclohexanecarboxylate and 2,2-bis (4-glycidyloxyphenyl) propane ensures that a cross-linked product is obtained by light irradiation. It is confirmed that

  The photopolymerization initiator is preferably a photoacid generator that generates an acid by light irradiation. Examples of such a photoacid generator include [4-[(2-hydroxytetradecyl) oxy] phenyl] phenyliodonium hexafluoroantimonate, bis (4-tert-butylphenyl) iodonium perfluoro-1-butanesulfonate. Bis (4-tert-butylphenyl) iodonium p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium triflate, diphenyliodonium p-toluenesulfonate, diphenyliodonium triflate, diphenyliodonium-9,10-dimethoxyanthracene -2-sulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate, triphenylsulfonium perfluoro-1-butanesulfonate, tris (4-tert-butylphenyl) sulfonium Fluoro-1-butanesulfonate , Tris (4-tert-butylphenyl) sulfonium triflate, triarylsulfonium hexafluoroantimonate salt, triphenylsulfonium hexafluoroantimonate, triphenylphosphonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio) phenyl Diphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldisulfenyldisulfenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- Diphenyl-sulfonio] phenyl] sulfide-bis-hexafluorophosphate, bi S [4-diphenyl-sulfonio] phenyl] sulfide-bis-hexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe-hexafluorophosphate, etc. Can do. Further, an onium photoacid generator, an ionic photoacid generator of a diphenyliodonium salt of a hydroxy group-containing aromatic sulfonic acid, and a photoacid generator of DNQ (diazonaphthoquinone) described in JP-A-2004-255564 A nonionic photoacid generator of nitrobenzyl sulfonic acids can also be used. Although a small amount of the photoacid generator is catalytically mixed, the specific mixing ratio is preferably 0.5 to 1.0% by weight.

  Furthermore, the photopolymerizable composition of the first invention preferably contains a photosensitizer. If it is like this, a photosensitizer will be excited by light irradiation and a polymerization initiator will generate | occur | produce a cation and a radical by the excited photosensitizer. For this reason, the sensitivity of the polymerizable property to light can be increased. Examples of such a photosensitizer include isopropylthioxanthone.

  As the glycidyl ether having a polymerizable carbon-carbon double bond, any non-target ether having a polymerizable carbon-carbon double bond on the opposite side of the glycidyl group across oxygen can be used. Examples of such glycidyl ether include allyl glycidyl ether and 3,5-bis (3-butenyloxy) benzyl glycidyl ether.

As the core molecule, any molecule having a hydroxyl group capable of reacting with the epoxy group of glycidol can be used. Examples of such core molecules include glycerol, diglycerin, thioglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, meso-erythritol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol. 1,2-propylene glycol, dipropylene glycol, polypropylene glycol, 1,4-butanediol, 1,2,4-butanetriol, hexamethylene glycol, triethanolamine, N, N-bis (2,3-dihydroxy Propyl) benzylamine, N, N-bis (2,3-dihydroxypropyl) octylamine, N, N, N ′, N′-tetrakis (2,3-dihydroxypropyl) ethyl Diamine, N-phenyldiethanolamine, 2-phenyl-1,3-propanediol, 3-methylpentane-1,3,5-triol, 1,2,3-butanetriol, arabitol, ribitol, phloroglucinol, pyrogallol, 1,2,4-trihydroxybenzene, hexahydroxybenzene, leucoquinizarin, quinizarin, anthralphine, chrysazine, bisphenol A, 2,6-dihydroxyanthraquinone, purpurine, alizarin, 1,8,9-trihydroxyanthracene, bis (3 -Hydroxyphenyl) disulfide, 4,4'-dihydroxydiphenyl ether-4,4'-biphenol, 1,3,5-cyclohexanetriol, and threitol.
The inventors have used triethanolamine, N, N-bis (2,3-dihydroxypropyl) benzylamine, N, N-bis (2,3-dihydroxypropyl) octylamine, N, N, N ′ as core molecules. , N′-tetrakis (2,3-dihydroxypropyl) ethylenediamine and N-phenyldiethanolamine, and further a polymerizable monomer and a photopolymerization initiator are mixed to form a photopolymerizable composition. It has been confirmed that it is reliably cured by UV irradiation.

  As described above, in the photopolymerizable composition of the first invention, a glycidyl ether having a carbon-carbon double bond capable of polymerizing a terminal hydroxyl group of a highly branched polymer in which glycidol is polymerized in a branched manner starting from the hydroxyl group of the core molecule. A polymerizable hyperbranched polymer with a structure added to the epoxy group is included, but a polymerizable hyperbranched polymer with a new structure is obtained by etherification of the hydroxyl group generated by ring opening in the addition to the epoxy group. It is good also as a component which comprises a photopolymerizable composition.

  That is, the photopolymerizable composition of the second invention is an epoxy group of a glycidyl ether having a carbon-carbon double bond capable of polymerizing a terminal hydroxyl group of a highly branched polymer in which glycidol is polymerized in a branched manner starting from the hydroxyl group of the core molecule. A polymerizable hyperbranched polymer in which a hydroxyl group generated by ring opening of the epoxy group in the addition is etherified, a polymerizable monomer, and a photopolymerization initiator. It is characterized by that.

  The photopolymerizable composition of the second invention also includes a polymerizable hyperbranched polymer in which a polymerizable carbon-carbon double bond is modified, and a polymerizable monomer capable of binding to the polymerizable hyperbranched polymer. In addition, a photopolymerization initiator is included. For this reason, when this photopolymerizable composition is irradiated with energy such as ultraviolet rays, visible rays, and electron beams, a polymerization initiator such as a radical or a cation is generated from the photopolymerization initiator, and a highly branched polymer and a polymerizable monomer are generated. Are copolymerized and cured. For this reason, it can be used for printing a pattern for forming an integrated circuit.

The polymerizable hyperbranched polymer contained in the photopolymerizable composition of the second invention is a highly branched polymer because glycidol is polymerized in a branched form with the hydroxyl group of the core molecule as a base point. Although it has a large molecular weight, it has the property of low viscosity. For this reason, compared with the photopolymerizable composition containing a prepolymer, a viscosity is small and handling is easy, and the precision at the time of printing can also be improved.
In addition, since the polymerizable highly branched polymer can form a branched structure at a stretch by polycondensing monomers, the number of manufacturing steps is small, the synthesis is easy, and the manufacturing cost can be reduced.

  The polymerizable monomer may be any compound that can be bonded to the polymerizable hyperbranched polymer, and includes an oligomer in which several monomers are bonded. As the polymerizable monomer, an acrylic monomer having one or more (meth) acryl groups per molecule can be used. In this case, the photopolymerization initiator is preferably a photoradical generator that generates radicals by light irradiation. The above-mentioned photo radical generator can be used. The inventors have confirmed that a polymer can be reliably obtained by light irradiation with a photopolymerizable composition using trimethylolpropane triacrylate as an acrylic monomer.

  Moreover, as a polymerizable monomer, the epoxy-type monomer which has one or more epoxy groups in 1 molecule can also be used. In this case, the photopolymerization initiator is preferably a photoacid generator that generates an acid by light irradiation, and the photoacid generator described above can be used. The inventors have used a photopolymerizable composition comprising 2,2-bis (4-glycidyloxyphenyl) propane and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate as an epoxy monomer to provide light irradiation. It has been confirmed that a polymer can be obtained reliably.

  Further, the photopolymerizable composition of the second invention preferably contains a photosensitizer. If it is like this, a photosensitizer will be excited by light irradiation and a polymerization initiator will generate | occur | produce a cation and a radical by the excited photosensitizer. For this reason, the sensitivity of the polymerizable property to light can be increased.

  As the glycidyl ether having a polymerizable carbon-carbon double bond, any non-target ether having a polymerizable carbon-carbon double bond on the opposite side of the glycidyl group across oxygen can be used. Examples of such glycidyl ether include allyl glycidyl ether and 3,5-bis (3-butenyloxy) benzyl glycidyl ether.

  The etherification is preferably one that can be easily modified to a hydroxyl group, and examples thereof include allyl etherification, methyl etherification, and 3,5-bis (butenyloxy) benzyl etherification.

Furthermore, as the core molecule, any molecule having a hydroxyl group capable of reacting with the epoxy group of glycidol can be used. Examples of such core molecules include glycerol, diglycerin, thioglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, meso-erythritol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol. 1,2-propylene glycol, dipropylene glycol, polypropylene glycol, 1,4-butanediol, 1,2,4-butanetriol, hexamethylene glycol, triethanolamine, N, N-bis (2,3-dihydroxy Propyl) benzylamine, N, N-bis (2,3-dihydroxypropyl) octylamine, N, N, N ′, N′-tetrakis (2,3-dihydroxypropyl) ethyl Diamine, N-phenyldiethanolamine, 2-phenyl-1,3-propanediol, 3-methylpentane-1,3,5-triol, 1,2,3-butanetriol, arabitol, ribitol, phloroglucinol, pyrogallol, 1,2,4-trihydroxybenzene, hexahydroxybenzene, leucoquinizarin, quinizarin, anthralphine, chrysazine, bisphenol A, 2,6-dihydroxyanthraquinone, purpurine, alizarin, 1,8,9-trihydroxyanthracene, bis (3 -Hydroxyphenyl) disulfide, 4,4'-dihydroxydiphenyl ether-4,4'-biphenol, 1,3,5-cyclohexanetriol, and threitol.
The inventors have used triethanolamine, N, N-bis (2,3-dihydroxypropyl) benzylamine, N, N-bis (2,3-dihydroxypropyl) octylamine, N, N, N ′ as core molecules. , N′-tetrakis (2,3-dihydroxypropyl) ethylenediamine and N-phenyldiethanolamine, and further a polymerizable monomer and a photopolymerization initiator are mixed to form a photopolymerizable composition. It has been confirmed that it is reliably cured by UV irradiation.

  Hereinafter, embodiments embodying the present invention will be described in detail.

A polymerizable hyperbranched polymer for use in the photopolymerizable composition of the present invention was prepared by the following procedure.
<Preparation of polymerizable hyperbranched polymer>
(Synthesis Example 1)
In Synthesis Example 1, a polymerizable hyperbranched polymer was prepared as follows.
First, triethanolamine was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio (molar ratio) of triethanolamine: glycidol: allyl glycidyl ether was 1: 6: 9. Moreover, diglyme was used as a reaction solvent.

Polymerization step 1.86 g (12.47 mmol) of triethanolamine was heated to 90 ° C under an argon atmosphere, 0.87 g (3.72 mmol) of potassium methoxide (30% methanol solution) was added thereto, and the mixture was stirred for several minutes and then gradually reduced in pressure. The methanol was distilled off. 10 ml of diglyme was added, 5.54 g (74.78 mmol) of glycidol was dissolved in 18 ml of dehydrated THF, and dropwise added over about 5.5 hours while distilling off the THF.

Modification process
After stirring for 30 minutes, 12.82 g (112.32 mmol) of allyl glycidyl ether was dissolved in 35 ml of dehydrated THF and added dropwise over about 11.5 hours while distilling off the THF. The mixture was stirred for about 4 hours at the same temperature, cooled, diluted with 30 ml of methanol, and passed through a 30 ml column of Amberlite IR 120B HAG to neutralize. The column was washed with 30 ml of methanol, and both washing solutions were concentrated under reduced pressure. The residual liquid 15.1 g was purified by silica gel column chromatography (chloroform / methanol = 6/1). The title compound was obtained as a colorless oil (3.13 g). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.82 (6H, m), 3.44-3.67 (72H, br), 3.87 (9H, s), 4.01 and 4.02 (18H, each s), 4.83 ( 9H, s), 5.16 (9H, d, J = 9.9 Hz), 5.30 (9H, d, J = 17.0 Hz), 5.90-5.94 (9H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 54.2, 63.1, 69.2, 69.6, 70.9, 71.1, 71.3, 71.6, 72.0, 72.6, 78.6, 78.9, 80.1, 80.3, 116.0, 134.9

すなわち、上記修飾工程で化合物 3.13 gをトルエン6 mlに溶解しこれに臭化テトラブチルアンモニウム 0.75 g (2.33 mmol) および水5.5 mlに溶解した水酸化ナトリウム4.7 g (117.5 mmol) を加えた。40℃に加温、攪拌下臭化アリル 3.15 g (26.0 mmol)を2 mlのトルエンに溶解して約１時間で滴下した。同温度で18時間攪拌した後水20 ml、トルエン20 mlを加えて抽出、分液した。水層を再度20 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で３回洗浄後無水硫酸ナトリウムで脱水し、濃縮した。微黄色残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝15/1）で精製し、表題化合物を微黄色油状物を2.52 g得た。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 2.79 (6H, s), 3.50-3.71 (81H, br), 3.99 and 4.00 (18H, each s), 4.13 (18H, s), 5.12-5.16 (18H, m), 5.27 (18H, d, J = 17.0 Hz), 5.87-5.95 (18H, m)
¹³C -NMR ((600 MHz, methanol-d₄) δ: 55.6, 71.3, 72.1, 72.6, 73.2, 78.5, 78.8, 79.9, 80.1, 116.9, 117.1, 136.2, 136.6 Etherification Step Further, the hydroxyl group of the compound obtained in the modification step was allyl etherified with allyl bromide to obtain a polymerizable hyperbranched polymer of Synthesis Example 1 (see the following chemical formula).

That is, in the modification step, 3.13 g of the compound was dissolved in 6 ml of toluene, and 0.75 g (2.33 mmol) of tetrabutylammonium bromide and 4.7 g (117.5 mmol) of sodium hydroxide dissolved in 5.5 ml of water were added thereto. The mixture was heated to 40 ° C., and 3.15 g (26.0 mmol) of allyl bromide was dissolved in 2 ml of toluene with stirring and added dropwise in about 1 hour. After stirring at the same temperature for 18 hours, 20 ml of water and 20 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 20 ml of toluene, and the extracts were combined, washed with saturated brine three times, dried over anhydrous sodium sulfate, and concentrated. The slightly yellow residual liquid was purified by silica gel column chromatography (chloroform / methanol = 15/1) to obtain 2.52 g of the title compound as a slightly yellow oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.79 (6H, s), 3.50-3.71 (81H, br), 3.99 and 4.00 (18H, each s), 4.13 (18H, s), 5.12- 5.16 (18H, m), 5.27 (18H, d, J = 17.0 Hz), 5.87-5.95 (18H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 55.6, 71.3, 72.1, 72.6, 73.2, 78.5, 78.8, 79.9, 80.1, 116.9, 117.1, 136.2, 136.6

(Synthesis Example 2)
In Synthesis Example 2, a polymerizable hyperbranched polymer was prepared as follows.
That is, the reaction shown in the following chemical formula was carried out using triethanolamine as the core molecule. The ratio (molar ratio) of triethanolamine: glycidol: allyl glycidyl ether was 1: 9: 12. Moreover, diglyme was used as a reaction solvent.

Polymerization step 1.49 g (0.01 mol) of triethanolamine was heated to 90 ° C under an argon atmosphere, 0.78 ml of potassium methoxide (30% methanol solution) was added thereto, and the mixture was stirred for several minutes. Left. 7.5 ml of diglyme was added, and 6.67 g (0.09 mol) of glycidol was dissolved in 17 ml of dehydrated THF, and dropwise added over about 5.5 hours while distilling off the THF.

Modification Step Then, after stirring for 30 minutes, 13.7 g (0.12 mol) of allyl glycidyl ether was dissolved in 33 ml of dehydrated THF, and dropwise added over about 11.5 hours while distilling off THF. The mixture was stirred at the same temperature for about 5.5 hours, cooled, diluted with 50 ml of methanol, and neutralized by passing through a column of Amberlite IR 120B H AG 30 ml. The column was washed with 40 ml of methanol, and both washing solutions were concentrated under reduced pressure. 14.4 g of the title compound was obtained as a brown oil. NMR of this product was measured, and the following results were obtained. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.83 (6H, b), 3.43-3.67 (99H, m), 3.88 (12H, s), 4.01, 4.02 (each 12H, s), 4.84 ( 12H, s), 5.17 (12H, d, J = 9.9 Hz), 5.29 (12H, d, J = 17.0 Hz), 5.90-5.94 (12H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 54.1, 69.3, 69.7, 70.0, 70.9, 71.2, 71.3, 71.7, 72.0, 72.8, 78.6, 78.8, 80.2, 80.4, 116.0, 134.8, 134.9

Etherification Step Further, the hydroxyl group of the compound obtained in the modification step was allyl etherified with allyl bromide (see the following chemical formula).

That is, 6.5 g of the compound obtained in the above modification step was dissolved in 13 ml of toluene, and 1.55 g (4.8 mmol) of tetrabutylammonium bromide and 9.59 g (239.8 mmol) of sodium hydroxide dissolved in 12 ml of water were added thereto. . With heating and stirring at 40 ° C. under an argon atmosphere, 6.48 g (53.5 mmol) of allyl bromide was dissolved in 4 ml of toluene and added dropwise in about 1 hour. After stirring at the same temperature for 17 hours, 20 ml of water was added to separate the layers. The aqueous layer was extracted with 20 ml of toluene, and the organic layers were combined, washed twice with water, dried over anhydrous sodium sulfate, and concentrated. The slightly yellow residue was purified by silica gel column chromatography (chloroform / methanol = 15/1) to obtain 4.13 g of a slightly yellow oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.79 (6H, bs), 3.51-3.71 (111H, m), 4.00 and 4.01 (24H, each s) 4.15 (24H, s), 5.15 (12H , d, J = 12.1 Hz), 5.17 (12H, d, J = 11.5 Hz), 5.29 (24H, d, J = 17.1 Hz), 5.91-5.96 (24H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 55.6, 71.2, 72.1, 72.5, 73.2, 78.5, 78.8, 79.9, 80.1, 116.9, 117.1, 136.2, 136.6

(Synthesis Example 3)
In Synthesis Example 3, a polymerizable hyperbranched polymer was prepared as follows.
That is, N, N-bis (2,3-dihydroxypropyl) octylamine was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio of N, N-bis (2,3-dihydroxypropyl) octylamine: glycidol: allyl glycidyl ether was 1: 4: 8 (molar ratio).

Polymerization Step N, N-bis (2,3-dihydroxypropyl) octylamine 1.88 g (6.77 mol) in an argon stream was stirred in an oil bath at 80 ° C. and potassium methoxide (30% methanol solution) 0.63 g (2.69 mmol) Was added. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. While adding 5 ml of dehydrated diglyme and heating to 90 ° C., 2.01 g (27.1 mmol) of glycidol was dissolved in 11 ml of dehydrated THF and added dropwise over about 2.5 hours while distilling off THF.

Modification Step Subsequently, 6.19 g (54.2 mmol) of allyl glycidyl ether was dissolved in 22 ml of dehydrated THF, and dropwise added over about 5.5 hours while distilling off the THF. After stirring at the same temperature for 2.5 hours, the mixture was cooled, 30 ml of methanol was added, and neutralized through a column of 25 ml of Amberlite IR 120B H AG. The solvent was distilled off under reduced pressure (80 ° C.), and the residual oil was purified by silica gel column chromatography (chloroform / methanol = 2/1), further treated with activated carbon, and filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 3.57 g of a pale yellow oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 0.91 (3H, bs), 1.32 (10H, bs), 1.49 (2H, bs), 2.59, 3.44-3.77 (58H, m,), 3.88 ( 8H, s), 4.02 (16H, s), 4.85 (8H, s), 5.16 (8H, d, J = 9.3 Hz), 5.28 8H, d, J = 17.6 Hz), 5.88-5.94 (8H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 14.3, 23.7, 28.5, 30.4, 30.6, 33.0, 57.0, 62.8, 64.6, 70.6, 70.9, 71.2, 72.6, 73.0, 73.3, 74.1, 79.8, 80.1, 81.2, 117.3,136.0, 136.1

(Synthesis Example 4)
In Synthesis Example 4, a polymerizable hyperbranched polymer was prepared as follows.
That is, N, N-bis (2,3-dihydroxypropyl) octylamine was used as a core molecule, and a reaction represented by the following chemical formula was performed. N, N-bis (2,3-dihydroxypropyl) octylamine: glycidol: allyl glycidyl ether was in a ratio (molar ratio) of 1:12:16.

Polymerization step While stirring 1.90 g (3.91 mmol) of N, N-bis (2,3-dihydroxypropyl) octylamine in an 80 ° C. oil bath under an argon stream, 0.364 g (1.56 mmol) of potassium methoxide (30% methanol solution) Was added. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. While adding 5 ml of dehydrated diglyme and heating to 90 ° C., 3.47 g (46.9 mmol) of glycidol was dissolved in 11 ml of dehydrated THF and added dropwise over about 3.5 hours while distilling off THF.

Modification Step Subsequently, 7.14 g (62.6 mmol) of allyl glycidyl ether was dissolved in 22 ml of dehydrated THF, and dropwise added over about 7 hours while distilling off the THF. The mixture was stirred at the same temperature for 3 hours, cooled, neutralized through a column of 25 ml of Amberlite IR 120B H AG by adding 30 ml of methanol. The solvent was distilled off under reduced pressure (80 ° C.), and the residual oil was purified by silica gel column chromatography (chloroform / methanol = 3/1), further treated with activated carbon, and filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 3.61 g of a pale yellow oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 0.91 (3H, bs), 1.32 (10H, bs), 1.50 (2H, bs), 2.59 (6H, b), 3.42-3.77 (180H, m ), 3.88 (16H, s), 4.01 (32H, s), 4.84 (16H, s), 5.17 (16H, d, J = 9.3 Hz), 5.30 (16H, d, J = 17.6 Hz), 5.90-5.94 (16H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 14.5, 23.7, 28.5, 30.6, 30.8, 33.0, 57.0, 62.8, 64.3, 70.6, 70.9, 71.2, 72.2, 72.4, 72.6, 73.0, 73.3, 74.1, 79.8, 80.1, 81.4, 136.0, 136.1

すなわち、水3 mlに水酸化ナトリウム2.8 g (70.6 mmol) を溶解し、これに臭化テトラブチルアンモニウム 0.45 g (1.40 mmol) および上記修飾工程で得た化合物1.95 gをトルエン3.5 mlに溶解して加えた。40℃に加温、攪拌下臭化アリル 1.90 g (15.7 mmol)を0.5 mlのトルエンに溶解して滴下した。同温度で21時間攪拌した後水10 ml、トルエン20 mlを加えて抽出、分液した。水層を再度15 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で３回洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/エタノール＝25/1）で精製し、次いでメタノール溶液として0.2μmフィルターで濾過した。減圧下80℃にて溶媒を留去し、無色油状物を1.2 g得た。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 0.91 (3H, bs), 1.32 (10H, bs), 1.46 (2H, bs), 2.51-2.59 (6H, m), 3.49-3.70 (146H, m), 4.01 (32H, s), 4.15 (32H, s), 5.14 (16H, d, J = 11.0 Hz), 5.16 (16H, d, J = 11.5 Hz), 5.29 (32H, d, J = 17.0 Hz,), 5.85-5.91 (32H, m)
¹³C -NMR ((600 MHz, methanol-d₄) δ: 14.6, 23.8, 28.6, 30.6, 33.1, 57.0, 71.3, 72.2, 72.6, 73.3, 78.6, 78.8, 80.0, 80.2, 117.0, 117.2, 136.2, 136.6 (Synthesis Example 5)
In Synthesis Example 5, a polymerizable hyperbranched polymer was prepared by allylating the hydroxyl group of the compound obtained in Synthesis Example 4 with allyl bromide (see the following chemical formula).

That is, 2.8 g (70.6 mmol) of sodium hydroxide was dissolved in 3 ml of water, and 0.45 g (1.40 mmol) of tetrabutylammonium bromide and 1.95 g of the compound obtained in the modification step were dissolved in 3.5 ml of toluene. added. The mixture was heated to 40 ° C., and 1.90 g (15.7 mmol) of allyl bromide was dissolved in 0.5 ml of toluene with stirring. After stirring at the same temperature for 21 hours, 10 ml of water and 20 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 15 ml of toluene, and the extracts were combined and washed three times with saturated brine. The mixture was dehydrated with anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (chloroform / ethanol = 25/1), and then filtered through a 0.2 μm filter as a methanol solution. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 1.2 g of a colorless oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 0.91 (3H, bs), 1.32 (10H, bs), 1.46 (2H, bs), 2.51-2.59 (6H, m), 3.49-3.70 (146H , m), 4.01 (32H, s), 4.15 (32H, s), 5.14 (16H, d, J = 11.0 Hz), 5.16 (16H, d, J = 11.5 Hz), 5.29 (32H, d, J = 17.0 Hz,), 5.85-5.91 (32H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 14.6, 23.8, 28.6, 30.6, 33.1, 57.0, 71.3, 72.2, 72.6, 73.3, 78.6, 78.8, 80.0, 80.2, 117.0, 117.2, 136.2, 136.6

(Synthesis Example 6)
In Synthesis Example 6, a polymerizable hyperbranched polymer was prepared as follows.
That is, N, N-bis (2,3-dihydroxypropyl) octylamine was used as a core molecule, and a reaction represented by the following chemical formula was performed. N, N-bis (2,3-dihydroxypropyl) octylamine: glycidol: allyl glycidyl ether: allyl bromide was in a ratio (molar ratio) of 1: 28: 32: 32.

Polymerization Step N, N-Bis (2,3-dihydroxypropyl) octylamine 0.4 g (1.44 mmol) was stirred in an 80 ° C. oil bath under an argon stream, and potassium methoxide (30% methanol solution) 0.134 g (0.576 mmol) ) Was added. After stirring for several minutes, methanol was distilled off under reduced pressure. While adding 5 ml of dehydrated diglyme and heating to 100 ° C., 2.99 g (40.37 mmol) of glycidol was dissolved in 10 ml of dehydrated THF and added dropwise over about 3 hours while distilling off THF.

Modification Step After stirring for 1 hour, 5.27 g (46.14 mmol) of allyl glycidyl ether was dissolved in 20 ml of dehydrated THF and added dropwise over about 6 hours while distilling off the THF. The mixture was stirred at the same temperature for 3 hours, cooled, added with 25 ml of methanol, and neutralized through a column of 20 ml of Amberlite IR 120B H AG. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 6.53 g of an orange oil.

Etherification step Further, as an etherification step, 3.0 g of the oily substance obtained in the modification step was dissolved in 7 ml of toluene, and 0.69 g (2.14 mmol) of tetrabutylammonium bromide and 4.32 g of sodium hydroxide ( 108.0 mmol) was dissolved in 5 ml of water and added. The mixture was heated to 40 ° C., and 2.90 g (24.0 mmol) of allyl bromide was dissolved in 1 ml of toluene with stirring and added dropwise over 1.5 hours. After stirring at the same temperature for 18 hours, 10 ml each of water and toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 10 ml of toluene, and the organic layers were combined and washed twice with water. After dehydrating with anhydrous sodium sulfate and concentrating, the residual liquid was purified by silica gel column chromatography (chloroform / methanol = 30/1) to obtain 1.4 g of a main fraction. This was purified again by silica gel column chromatography (chloroform / methanol = 20/1), and then filtered through a 0.2 μm filter as a methanol solution. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 0.59 g of a colorless oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 0.91 (3H, bs), 1.32 (10H, bs), 1.46 (2H, bs), 2.52-2.60 (6H, m), 3.33 and 3.52-. 3.66 (306H, m), 4.01 (64H, s), 4.15 (64H, s), 5.14 (32H, d, J = 11.0 Hz), 5.16 (32H, d, J = 11.5 Hz), 5.29 (64H, d , J = 15.9.0 Hz), 5.91-5.92 (64H, m)
¹³ C -NMR ((600 MHz, methanol-d ₄ ) δ: 14.6, 23.8, 28.6, 30.6, 33.1, 57.0, 71.3, 72.2, 72.6, 73.3, 78.6, 78.8, 80.0, 80.2, 117.0, 117.2, 136.2, 136.7

(Synthesis Example 7)
In Synthesis Example 7, a polymerizable hyperbranched polymer was prepared as follows.
Specifically, N, N, N ′, N′-tetrakis (2,3-dihydroxypropyl) ethylenediamine was used as the core molecule, and the reaction represented by the following chemical formula was performed. N, N, N ′, N′-tetrakis (2,3-dihydroxypropyl) ethylenediamine: glycidol: allyl glycidyl ether was in a ratio (molar ratio) of 1: 8: 16.

Polymerization Step N, N, N ′, N′-Tetrakis (2,3-dihydroxypropyl) ethylenediamine 1.67 g (4.7 mmol) in an argon gas stream with stirring in a 90 ° C. oil bath, potassium methoxide (30% methanol solution) 0.88 g (3.76 mmol) was added. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. While adding 10 ml of dehydrated diglyme and 5 ml of DMF and heating to 110 ° C., 2.78 g (37.5 mmol) of glycidol was dissolved in 9 ml of dehydrated THF and added dropwise over about 3 hours while distilling off THF.

Modification Step Subsequently, 8.58 g (75.2 mmol) of allyl glycidyl ether was dissolved in 26 ml of dehydrated THF, and dropwise added over about 6 hours while distilling off the THF. After stirring at the same temperature for 3 hours, the mixture was cooled, 30 ml of methanol was added and neutralized through a column of 30 ml of Amberlite IR 120B H AG. The solvent was distilled off under reduced pressure (80 ° C.), and the residual oil was purified by silica gel column chromatography (chloroform / methanol = 3/1), further treated with activated carbon, and filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 3.67 g of a yellow oil. NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.66 (12H, br), 3.47-3.67 (116H, m), 3.86 (16H, s), 4.01 (32H, s), 4.85 (16H, s ), 5.15-5.17 (16H, m), 5.28 (16H, d, J = 17.6 Hz), 5.88-5.94 (16H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 54.5, 59.3, 70.6, 70.9, 71.2, 72.6, 73.0, 73.3, 74.0, 79.9, 80.2, 117.2, 136.2

すなわち、上記修飾工程で得た化合物4.8 g (1.73 mmol)をトルエン10 mlに溶解し、これに水9 mlに溶解した水酸化ナトリウム7.43 g (185.8 mmol) および臭化テトラブチルアンモニウム 1.2 g (3.72mmol)を加えた。40℃に加温、攪拌下臭化アリル 5.02 g (41.5 mmol)を3 mlのトルエンに溶解して1.5時間で滴下した。同温度で15時間攪拌した後水20 ml、トルエン20 mlを加えて抽出、分液した。水層を再度20 mlのトルエンで抽出し、抽出液を併せて水で洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝15/1）で精製し、次いで0.2μmフィルターで濾過した。減圧下80℃にて溶媒を留去し、黄色油状物を5.19 g得た(収率88.0%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 2.60-2.66 (12H, br), 3.49-3.66 (132H, m), 4.00 (32H, s), 4.14 (32H, s), 5.13 (16H, d, J = 12.1 Hz), 5.15 (16H, d, J = 11.5 Hz), 5.27 (32H, d, J = 17.0 Hz), 5.87-5.92 (32H, m)
¹³C -NMR (600 MHz, methanol-d₄) δ: 54.0, 56.8, 70.1, 70.9, 71.4, 72.0, 77.3, 77.6, 78.7, 79.0, 115.8, 115.9, 135.0, 135.5 (Synthesis Example 8)
In Synthesis Example 8, a hydroxyl group of the compound obtained in Synthesis Example 7 was allyl etherified with allyl bromide to prepare a polymerizable hyperbranched polymer (see the following chemical formula).

That is, 4.8 g (1.73 mmol) of the compound obtained in the above modification step was dissolved in 10 ml of toluene, and 7.43 g (185.8 mmol) of sodium hydroxide and 1.2 g (3.72) of tetrabutylammonium bromide dissolved in 9 ml of water. mmol) was added. While warming to 40 ° C., 5.02 g (41.5 mmol) of allyl bromide was dissolved in 3 ml of toluene with stirring and added dropwise over 1.5 hours. After stirring at the same temperature for 15 hours, 20 ml of water and 20 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 20 ml of toluene, and the extracts were combined and washed with water. The mixture was dehydrated with anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (chloroform / methanol = 15/1), and then filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 5.19 g of a yellow oil (yield: 88.0%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.60-2.66 (12H, br), 3.49-3.66 (132H, m), 4.00 (32H, s), 4.14 (32H, s), 5.13 (16H , d, J = 12.1 Hz), 5.15 (16H, d, J = 11.5 Hz), 5.27 (32H, d, J = 17.0 Hz), 5.87-5.92 (32H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 54.0, 56.8, 70.1, 70.9, 71.4, 72.0, 77.3, 77.6, 78.7, 79.0, 115.8, 115.9, 135.0, 135.5

(Synthesis Example 9)
In Synthesis Example 9, a polymerizable hyperbranched polymer was prepared as follows.
That is, N, N-bis (2,3-dihydroxypropyl) benzylamine was used as a core molecule, and the reaction represented by the following chemical formula was performed. The ratio of N, N-bis (2,3-dihydroxypropyl) benzylamine: glycidol: allyl glycidyl ether was 1:12:16 (molar ratio).

Polymerization process N, N-bis (2,3-dihydroxypropyl) benzylamine (2.05 g, 8.0 mmol) was heated to 100 ° C under argon flow, and potassium methoxide (30% methanol solution) 0.75 g (3.2 mmol) with stirring. Was added. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. 7 ml of dehydrated diglyme and 5 ml of DMF were added, 7.12 g (96.2 mmol) of glycidol was dissolved in 13 ml of dehydrated THF, and the mixture was added dropwise over about 3.6 hours while distilling off THF.

Modification Step Subsequently, 14.6 g (128.2 mmol) of allyl glycidyl ether was dissolved in 26 ml of dehydrated THF, and dropwise added over about 7.4 hours while distilling off THF. The mixture was stirred at the same temperature for 2 hours and then cooled, and 40 ml of methanol was added and neutralized through a column of 30 ml of Amberlite IR 120B H AG. The solvent was distilled off under reduced pressure (80 ° C.), and 10 g of 21.65 g of the residual oil was purified by silica gel column chromatography (chloroform / methanol = 7/3). Filtered. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 7.5 g of a yellow oily substance. (Yield 68.2%) NMR of this product was measured and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.63-2.66 (4H, br), 3.45-3.67 (132H, m), 3.87 (16H, s), 4.01 (32H, s,), 4.77 ( 16H, s), 5.17 (16H, d, J = 9.9 Hz), 5.30 (16H, d, J = 17.0 Hz), 5.90-5.93 (16H, m), 7.25-7.34 (5H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 61.4, 62.8, 64.5, 70.5, 70.9, 71.2, 72.6, 73.0, 73.2, 74.0, 79.8, 80.1, 117.2, 128.1, 129.4, 130.3, 130.4, 136.0 , 136.2,

すなわち、上記修飾工程で得られた化合物4.39 gをトルエン8 mlに溶解し、これに水7.5 mlに溶解した水酸化ナトリウム6.35 g (158.7 mmol) および臭化テトラブチルアンモニウム 1.02 g (3.16mmol)を加えた。アルゴン気流下40℃に加温、攪拌しながら臭化アリル 4.29 g (35.47 mmol)を2 mlのトルエンに溶解して50分で滴下した。同温度で16時間攪拌した後水30 ml、トルエン30 mlを加えて抽出、分液した。水層を再度30 mlのトルエンで抽出し、抽出液を併せて水で洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝25/1）で精製し、次いで0.2μmフィルターで濾過した。減圧下80℃にて溶媒を留去し、表題化合物を微黄色油状物を4.78 g得た(収率89.6%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 2.62 (4H, br), 3.50-3.65 (148H, m), 3.99 (32H, s), 4.13 (32H, s), 5.13 (16H, d, J = 12.1 Hz), 5.15 (16H, d, J = 11.0 Hz), 5.27 (32H, d, J = 17.0 Hz), 5.90-5.91 (32H, m), 7.24-7.33 (5H, m)
¹³C -NMR (600 MHz, methanol-d₄) δ: 57.6, 61.5, 71.2, 72.5, 73.2, 72.1, 78.4, 78.7, 79.9, 80.1, 116.9, 117.1, 136.2, 136.6, 128.0, 129.3, 130.2, 141.0 (Synthesis Example 10)
In Synthesis Example 10, a hydroxyl group of the compound obtained in Synthesis Example 9 was allyl etherified with allyl bromide to prepare a polymerizable hyperbranched polymer (see the following chemical formula).

That is, 4.39 g of the compound obtained in the above modification step was dissolved in 8 ml of toluene, and 6.35 g (158.7 mmol) of sodium hydroxide and 1.02 g (3.16 mmol) of tetrabutylammonium bromide dissolved in 7.5 ml of water were added thereto. added. While being heated to 40 ° C. under an argon stream and stirring, 4.29 g (35.47 mmol) of allyl bromide was dissolved in 2 ml of toluene and added dropwise over 50 minutes. After stirring at the same temperature for 16 hours, 30 ml of water and 30 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 30 ml of toluene, and the extracts were combined and washed with water. The mixture was dehydrated with anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (chloroform / methanol = 25/1), and then filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 4.78 g of the title compound as a pale yellow oil (yield 89.6%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 2.62 (4H, br), 3.50-3.65 (148H, m), 3.99 (32H, s), 4.13 (32H, s), 5.13 (16H, d , J = 12.1 Hz), 5.15 (16H, d, J = 11.0 Hz), 5.27 (32H, d, J = 17.0 Hz), 5.90-5.91 (32H, m), 7.24-7.33 (5H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 57.6, 61.5, 71.2, 72.5, 73.2, 72.1, 78.4, 78.7, 79.9, 80.1, 116.9, 117.1, 136.2, 136.6, 128.0, 129.3, 130.2, 141.0

(Synthesis Example 11)
In Synthesis Example 11, a polymerizable hyperbranched polymer was prepared as follows.
That is, N-phenyldiethanolamine was used as the core molecule, and the reaction represented by the following chemical formula was performed. The ratio (molar ratio) of N-phenyldiethanolamine: glycidol: allyl glycidyl ether was 1: 6: 8.

Polymerization step Under an argon stream, N-phenyldiethanolamine 1.0 g (5.52 mmol) was heated to 90 ° C and melted, and potassium methoxide (30% methanol solution) 0.26 g (1.11 mmol) was added thereto. After stirring for several minutes, the pressure was gradually reduced to distill off methanol, and 5 ml of dehydrated diglyme was added. While being heated to 90 ° C., 2.45 g (33.1 mmol) of glycidol was dissolved in 10 ml of dehydrated THF, and added dropwise over about 3 hours while distilling off THF.

Modification Step Subsequently, 5.04 g (44.2 mmol) of allyl glycidyl ether was dissolved in 20 ml of dehydrated THF, and dropwise added over about 6 hours while distilling off the THF. The mixture was stirred at the same temperature for 5 hours, cooled, added with 25 ml of methanol, and neutralized through a column of 20 ml of Amberlite IR 120B H AG. The solvent was distilled off under reduced pressure (80 ° C.), dissolved in 30 ml of methanol again, treated with activated carbon, and filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 5.06 g of a yellow oil (yield 60.2%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.40-3.66 (68H, m), 3.86 (8H, s), 4.00 (16H, s), 4.75 (8H, s), 5.16 (8H, d , J = 9.4 Hz), 5.28 (8H, d, J = 17.0 Hz), 5.89-5.92 (8H, m), 6.60-6.61 (1H, m), 6.72-6.73 (2H, m), 7.13-7.16 ( 2H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 50.7, 61.5, 63.2, 69.0, 69.3, 69.6, 70.0, 71.2, 71.4, 71.8, 72.0, 72.9, 78.6, 78.8, 80.1, 80.3, 117.2, 113.1 , 117.2, 130.1, 149.1, 135.9, 136.1

(Synthesis Example 12)
In Synthesis Example 12, a polymerizable hyperbranched polymer was prepared by allylating the hydroxyl group of the compound obtained in Synthesis Example 11 with allyl bromide (see the following chemical formula).

That is, 2.0 g of the compound obtained in the modification step was dissolved in 5 ml of toluene, and 0.45 g (1.40 mmol) of tetrabutylammonium bromide and 2.83 g (70.8 mmol) of sodium hydroxide dissolved in 3 ml of water were added thereto. It was. The mixture was heated to 40 ° C., and 1.90 g (15.7 mmol) of allyl bromide was dissolved in 0.5 ml of toluene with stirring and added dropwise over 50 minutes. After stirring at the same temperature for 16.5 hours, 10 ml of water and 15 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 15 ml of toluene, and the extracts were combined and washed with saturated brine. The mixture was dehydrated with anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (chloroform / methanol = 20/1), and then filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 1.48 g of the title compound as a colorless oil. (Yield 61.5%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.50-3.64 (68H, m), 3.99 (16H, s), 4.13 (16H, s), 5.13 (8H, d, J = 11.0 Hz,) , 5.15 (8H, d, J = 11.5 Hz), 5.27 (16H, d, J = 17.1 Hz), 5.89-5.90 (16H, m), 6.58-6.61 (1H, m,), 6.71-6.72 (2H, m,), 7.13-7.15 (2H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 52.0, 70.2, 71.2, 72.1, 72.5, 73.1, 78.4, 78.7, 79.8, 80.1, 116.9, 113.0, 117.1, 130.2, 149.1, 136.2, 136.6

(Synthesis Example 13)
In Synthesis Example 13, a polymerizable hyperbranched polymer was prepared as follows.
That is, the reaction shown in the following chemical formula was carried out using triethanolamine as the core molecule. Triethanolamine: glycidol: 3,5-bis (3-butenyloxy) benzylglycidyl ether was in a ratio (molar ratio) of 1: 9: 12.

Polymerization step Under argon atmosphere, triethanolamine 0.2 g (1.34 mmol) was heated to 90 ° C, potassium methoxide (30% methanol solution) 0.09 g (0.385 mmol) was added thereto, and the mixture was stirred for several minutes and then gradually reduced in pressure. The methanol was distilled off. After 4 ml of diglyme was added and the temperature was raised to 130 ° C., 0.91 g (12.2 mmol) of glycidol was dissolved in 4.5 ml of dehydrated THF, and dropwise added in about 1.5 hours while distilling off THF.

Modification process
After stirring for 30 minutes, 5.0 g (1.4 mmol) of 3,5-bis (3-butenyloxy) benzylglycidyl ether was dissolved in 7 ml of dehydrated THF, and dropwise added over about 3.5 hours while distilling off THF. The mixture was stirred at the same temperature for about 2.5 hours, cooled, diluted with 25 ml of toluene and washed with 20 ml of 0.5% oxalic acid. The mixture was further washed twice with saturated brine and concentrated under reduced pressure. 6.28 g of the residual liquid was purified by silica gel column chromatography (chloroform / methanol = 10/1) to obtain 4.65 g of a yellow oil (yield 77.6%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 2.50 (48H, s), 2.72 (6H, s), 3.30-3.70 (123H, m), 3.95 (48H, s), 4.43 (24H, s), 5.08 (24H, d, J = 8.2 Hz), 5.15 (24H, d, J = 16.5 Hz), 5.86 (24H, bs), 6.36 (12H, s), 6.45 (24H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 33.7, 58.1, 58.2, 67.3, 69.5, 69.8, 70.4, 71.9, 72.2, 72.8, 78.7, 73.4, 100.7, 106.2, 140.7, 160.2, 117.1, 134.6)

すなわち、上記修飾工程で得た化合物0.936 g (0.209 mmol)をトルエン3 mlに溶解し、これに臭化テトラブチルアンモニウム 0.09 g (0.28 mmol) および水3 mlに溶解した水酸化ナトリウム0.6 g (15.0 mmol) およびヨウ化メチル 1.07 g (7.54 mmolを加えた。35-37℃で8時間攪拌した後ヨウ化メチル 0.5 g (3.52 mmol)を追加してさらに16時間攪拌した。水、トルエン各10 mlを加えて抽出、分液し、水層を再度10 mlのトルエンで抽出した。抽出液を併せて水で３回洗浄後無水硫酸ナトリウムで脱水し、濃縮した。残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝20/1）で精製し、次いでクロロホルム溶液として0.2μmフィルターでろ過した。減圧下80℃で濃縮し、表題化合物を淡黄色油状物を0.48 g得た(収率54.7%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, CDCl₃) δ: 2.49 (48H, s), 3.31-3.70 (153H, m), 3.95 (48H, s), 4.43 (24H, s), 5.08 (24H, d, J = 9.4 Hz), 5.14 (24H, d, J = 16.5 Hz), 5.87 (24H, bs), 6.35 (12H, s), 6.46 (24H, s)
¹³C -NMR ((600 MHz, CDCl₃) δ: 33.7, 58.1, 58.2, 67.3, 70.1, 71.6, 78.8, 79.1, 79.5, 79.6, 79.8, 73.4, 100.7, 106.2, 140.8, 160.2, 117.1, 134.5 (Synthesis Example 14)
In Synthesis Example 14, the hydroxyl group of the compound obtained in Synthesis Example 13 was methoxylated with methyl iodide (see the following chemical formula).

That is, 0.936 g (0.209 mmol) of the compound obtained in the above modification step was dissolved in 3 ml of toluene, and 0.6 g (15.0 mg) of sodium hydroxide dissolved in 0.09 g (0.28 mmol) of tetrabutylammonium bromide and 3 ml of water. mmol) and 1.07 g (7.54 mmol) of methyl iodide. After stirring at 35-37 ° C. for 8 hours, 0.5 g (3.52 mmol) of methyl iodide was added and the mixture was further stirred for 16 hours. The aqueous layer was extracted again with 10 ml of toluene, and the combined extracts were washed three times with water, dehydrated with anhydrous sodium sulfate, and concentrated. Chloroform / methanol = 20/1) and then filtered through a 0.2 μm filter as a chloroform solution and concentrated under reduced pressure at 80 ° C. to obtain 0.48 g of the title compound as a pale yellow oil (yield 54.7%). The NMR of this product was measured and the following results were obtained. .
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 2.49 (48H, s), 3.31-3.70 (153H, m), 3.95 (48H, s), 4.43 (24H, s), 5.08 (24H, d, J = 9.4 Hz), 5.14 (24H, d, J = 16.5 Hz), 5.87 (24H, bs), 6.35 (12H, s), 6.46 (24H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 33.7, 58.1, 58.2, 67.3, 70.1, 71.6, 78.8, 79.1, 79.5, 79.6, 79.8, 73.4, 100.7, 106.2, 140.8, 160.2, 117.1, 134.5

すなわち、合成例１３での修飾工程で得た化合物0.84 g (0.188 mmol)をトルエン2 mlに溶解し、これに臭化テトラブチルアンモニウム 0.082 g (0.25 mmol)、3,5-ビス(ブテニルオキシ)ベンジルブロミド 0.88 g (2.83 mmol) および水0.7 mlに溶解した水酸化ナトリウム0.51 g (12.75 mmol) を加えた。40℃に加温して20時間攪拌した後水、トルエン各10 mlを加えて抽出、分液した。水層を再度10 mlのトルエンで抽出し、抽出液を併せて水で３回洗浄後無水硫酸ナトリウムで脱水し、濃縮した。残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/メタノール＝100/0〜20/1）で精製し、次いでクロロホルム溶液として0.2μmフィルターでろ過した。減圧下80℃で濃縮し、黄色油状物を0.7 g得た(収率51.5%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, CDCl₃) δ: 2.45 (96H, s), 2.69 (6H, bs), 3.38-3.70 (101H, m), 3.89 (96H, s), 4.38 and 4.56 (each 24H, s), 5.05 and 5.10 (each 48H, bs), 5.83 (48H, bs), 6.31 (24H, s), 6.43 and 6.46 (48H, each s)
¹³C -NMR ((600 MHz, CDCl₃) δ: 33.7, 67.2, 70.6, 71.0, 72.1, 77.8, 78.7, 79.1, 73.3, 100.6, 106.0, 141.0, 141.4, 160.2, 117.0, 134.6 (Synthesis Example 15)
In Synthesis Example 15, the compound obtained in the modification step of the compound obtained in Synthesis Example 13 was subjected to the reaction represented by the following chemical formula using 3,5-bis (butenyloxy) benzyl bromide as the etherification step.

That is, 0.84 g (0.188 mmol) of the compound obtained in the modification step in Synthesis Example 13 was dissolved in 2 ml of toluene, and 0.082 g (0.25 mmol) of tetrabutylammonium bromide and 3,5-bis (butenyloxy) benzyl were dissolved therein. Sodium bromide 0.51 g (12.75 mmol) dissolved in bromide 0.88 g (2.83 mmol) and water 0.7 ml was added. The mixture was heated to 40 ° C. and stirred for 20 hours, followed by extraction with 10 ml of water and toluene, followed by liquid separation. The aqueous layer was extracted again with 10 ml of toluene, and the extracts were combined, washed three times with water, dried over anhydrous sodium sulfate, and concentrated. The residual liquid was purified by silica gel column chromatography (chloroform / methanol = 100/0 to 20/1), and then filtered through a 0.2 μm filter as a chloroform solution. Concentration under reduced pressure at 80 ° C. gave 0.7 g of a yellow oil (yield 51.5%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 2.45 (96H, s), 2.69 (6H, bs), 3.38-3.70 (101H, m), 3.89 (96H, s), 4.38 and 4.56 (each 24H, s), 5.05 and 5.10 (each 48H, bs), 5.83 (48H, bs), 6.31 (24H, s), 6.43 and 6.46 (48H, each s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 33.7, 67.2, 70.6, 71.0, 72.1, 77.8, 78.7, 79.1, 73.3, 100.6, 106.0, 141.0, 141.4, 160.2, 117.0, 134.6

(Synthesis Example 16)
In Synthesis Example 16, a polymerizable hyperbranched polymer was prepared as follows.
Specifically, N, N-bis (2,3-dihydroxypropyl) octylamine is used as a core molecule, and 3,5-bis (3-butenyloxy) benzylglycidyl ether is used as a glycidyl ether having a polymerizable carbon-carbon double bond. The reaction shown in the chemical formula below was carried out. N, N-bis (2,3-dihydroxypropyl) octylamine: glycidol: 3,5-bis (3-butenyloxy) benzylglycidyl ether was in a ratio (molar ratio) of 1:12:16.

Polymerization process Under argon atmosphere, N, N-bis (2,3-dihydroxypropyl) octylamine 0.29 g (1.04 mmol) was heated to 90 ° C and potassium methoxide (30% methanol solution) 0.096 g (0.41 mmol) was added. And stirred for several minutes. The pressure was gradually reduced, methanol was distilled off, 5 ml of diglyme was added, and the temperature was raised to 140 ° C. 0.91 g (12.3 mmol) of glycidol was dissolved in 5 ml of dehydrated THF and added dropwise over about 2 hours while distilling off the THF.

Modification Step Next, 5.0 g (16.4 mmol) of 3,5-bis (3-butenyloxy) benzylglycidyl ether was dissolved in 15 ml of dehydrated THF, and added dropwise over about 6 hours while distilling off THF. After stirring for 2.5 hours at the same temperature, the reaction solution was diluted with 20 ml of chloroform and washed twice with 20 ml of 0.5% oxalic acid and then with water. The mixture was dehydrated with anhydrous sodium sulfate, concentrated, and purified twice by silica gel column chromatography (chloroform / methanol = 10/1). Furthermore, it filtered with a 0.2 micrometer filter as a chloroform solution, and concentrated under reduced pressure at 80 degreeC. 1.35 g of the title compound was obtained as a light brown oil (yield 21.8%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 0.87 (3H, bs), 1.25 (10H, bs), 1.42 (2H, bs), 2.49 (64H, s), 2.61 (6H, b), 3.45- 3.66 (146H, m), 3.95 (64H, s), 3.98 (16H, s), 4.42 (32H, s), 5.08-5.14 (64H, m), 5.86 (32H, bs), 6.35 (16H, s) , 6.45 (32H, s)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 14.1, 22.8, 27.7, 29.5, 32.0, 33.7, 67.3, 69.5, 71.3, 71.4, 78.8, 73.5, 100.7, 106.2, 140.6, 160.2, 117.1, 134.6

すなわち、上記修飾工程で得た化合物0.85 g (0.14 mmol)をトルエン2.2 mlに溶解し、これに臭化テトラブチルアンモニウム 85 mg (0.26 mmol)、水0.7 mlに溶解した水酸化ナトリウム0.53 g (13.25 mmol)および3,5-ビス(ブテニルオキシ)ベンジルブロミド 0.91 g (2.92 mmol)を加えてアルゴン気流下43-45℃で18時間攪拌した。冷却後水5 ml、トルエン10 mlを加えて抽出、分液した。水層を再度5 mlのトルエンで抽出し、抽出液を併せて水で2回洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（トルエン/エタノール＝100/1〜10/1）で2回精製した。次いでクロロホルム溶液として0.2μmフィルターでろ過した。減圧下80℃で濃縮し、淡褐色油状物を0.35 g得た(25.7%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, CDCl₃) δ: 0.84 (3H, bs), 1.26 (10H, bs), 1.36 (2H, bs), 2.44 (128H, bs), 3.40-3.70 (146H, m), 3.88 (128H, s), 4.38 (32H, s), 4.56 (32H, s), (5.06-5.11 (128H, m), 5.82 (64H, bs), 6.31 (32H, s), 6.42 - 6.45 (64H, m)
¹³C -NMR ((600 MHz, CDCl₃) δ: 33.7 (CH2), 67.2 (OCH2), 70.9, 72.2, 78.8, 73.2, 100.7, 106.0, 140.6, 160.2, 117.0, 134.6 (Synthesis Example 17)
In Synthesis Example 17, the hydroxyl group of the compound obtained in the modification step of the compound obtained in Synthesis Example 16 was etherified with 3,5-bis (butenyloxy) benzyl bromide (see the following chemical formula).

That is, 0.85 g (0.14 mmol) of the compound obtained in the above modification step was dissolved in 2.2 ml of toluene, and 85 mg (0.26 mmol) of tetrabutylammonium bromide and 0.53 g (13.25) of sodium hydroxide dissolved in 0.7 ml of water. mmol) and 3,5-bis (butenyloxy) benzyl bromide (0.91 g, 2.92 mmol) were added, and the mixture was stirred at 43-45 ° C. for 18 hours under an argon stream. After cooling, 5 ml of water and 10 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 5 ml of toluene, and the extracts were combined and washed twice with water. The mixture was dehydrated with anhydrous sodium sulfate and concentrated, and the residue was purified twice by silica gel column chromatography (toluene / ethanol = 100/1 to 10/1). Subsequently, it filtered with the 0.2 micrometer filter as a chloroform solution. Concentration under reduced pressure at 80 ° C. gave 0.35 g of a light brown oil (25.7%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 0.84 (3H, bs), 1.26 (10H, bs), 1.36 (2H, bs), 2.44 (128H, bs), 3.40-3.70 (146H, m), 3.88 (128H, s), 4.38 (32H, s), 4.56 (32H, s), (5.06-5.11 (128H, m), 5.82 (64H, bs), 6.31 (32H, s), 6.42-6.45 (64H , m)
¹³ C -NMR ((600 MHz, CDCl ₃ ) δ: 33.7 (CH2), 67.2 (OCH2), 70.9, 72.2, 78.8, 73.2, 100.7, 106.0, 140.6, 160.2, 117.0, 134.6

(Synthesis Example 18)
In Synthesis Example 18, a polymerizable hyperbranched polymer was prepared as follows.
That is, N, N-bis (2,3-dihydroxypropyl) benzylamine was used as a core molecule, and a reaction represented by the following chemical formula was performed. N, N-bis (2,3-dihydroxypropyl) benzylamine: glycidol: 3,5-bis (3-butenyloxy) benzylglycidyl ether was in a ratio (molar ratio) of 1:12:16.

Polymerization process Under argon atmosphere, N, N-bis (2,3-dihydroxypropyl) benzylamine 0.37 g (1.44 mmol) was heated to 90 ° C., and potassium methoxide (30% methanol solution) 0.13 g (0.56 mmol) And stirred for several minutes. The pressure was gradually reduced, methanol was distilled off, 5 ml of diglyme was added, and the temperature was raised to 130 ° C. 1.28 g (17.3 mmol) of glycidol was dissolved in 5 ml of dehydrated THF and added dropwise over about 2 hours while distilling off the THF.

Modification Step Next, 7.0 g (23.0 mmol) of 3,5-bis (3-butenyloxy) benzylglycidyl ether was dissolved in 15 ml of dehydrated THF, and added dropwise over about 7 hours while distilling off THF. After stirring at the same temperature for 3 hours, the reaction solution was diluted with 50 ml of toluene and washed twice with 30 ml of 0.5% oxalic acid and then with saturated saline. The mixture was dehydrated with anhydrous sodium sulfate, concentrated, and purified twice by silica gel column chromatography (chloroform / methanol = 15/1). Furthermore, it filtered with a 0.2 micrometer filter as a chloroform solution, and concentrated under reduced pressure at 80 degreeC. 4.6 g of the title compound was obtained as a light brown oil (yield 53.5%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 2.49 (64H, s), 2.58 (4H, br), 3.45-3.65 (148H, m), 3.94 (80H, bs), 4.41 (32H, s), 5.07-5.15 (64H, m), 5.85 (32H, bs), 6.35 (16H, s), 6.41 (32H, s), 7.20 (1H, b), 7.26 (4H, br)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 33.7, 67.3, 69.3, 71.3, 78.8, 73.4, 100.7, 106.2, 140.7, 160.2, 117.1, 134.6

すなわち、上記修飾工程で得た化合物2.0 g (0.33 mmol)をトルエン5 mlに溶解し、これに臭化テトラブチルアンモニウム 0.2 g (0.62 mmol)、3,5-ビス(ブテニルオキシ)ベンジルブロミド2.15 g (6.91 mmol) および水1.6 mlに溶解した水酸化ナトリウム1.25 g (31.25 mmol) を加えた。40℃に加温して17時間攪拌した後水10 ml、トルエン20 mlを加えて抽出、分液した。抽出液を飽和食塩水で３回洗浄後無水硫酸ナトリウムで脱水し、濃縮した。残留液をシリカゲルカラムクロマトグラフィー（トルエン/エタノール＝20/1）で精製し、次いでクロロホルム溶液として0.2μmフィルターでろ過した。減圧下80℃で濃縮し、淡褐色油状物を1.6 g得た(収率49.7%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, CDCl₃) δ: 2.41 (132H, s), 3.40-3.67 (148H, m), 3.85 (128H, bs), 4.35 (32H, s), 4.53 (32H, bs), 5.04 (128H, bs), 5.80 (64H, bs), 6.28 (32H, bs), 6.40 (64H, bs), 7.20 (1H, b), 7.26 (4H, br)
¹³C -NMR ((600 MHz, CDCl₃) δ: 33.7, 67.2, 71.0, 72.1, 79.0, 73.2, 100.6, 105.8, 106.0, 141.0, 141.4, 160.1, 117.0, 134.6 (Synthesis Example 19)
In Synthesis Example 19, the hydroxyl group of the compound obtained in the modification step of the compound obtained in Synthesis Example 18 was etherified with 3,5-bis (butenyloxy) benzyl bromide (see the following chemical formula).

That is, 2.0 g (0.33 mmol) of the compound obtained in the above modification step was dissolved in 5 ml of toluene, and 0.2 g (0.62 mmol) of tetrabutylammonium bromide and 2.15 g of 3,5-bis (butenyloxy) benzyl bromide ( 6.91 mmol) and 1.25 g (31.25 mmol) of sodium hydroxide dissolved in 1.6 ml of water were added. After heating to 40 ° C. and stirring for 17 hours, 10 ml of water and 20 ml of toluene were added for extraction and liquid separation. The extract was washed 3 times with saturated brine, dried over anhydrous sodium sulfate, and concentrated. The residual liquid was purified by silica gel column chromatography (toluene / ethanol = 20/1), and then filtered through a 0.2 μm filter as a chloroform solution. Concentration under reduced pressure at 80 ° C. yielded 1.6 g of a light brown oil (yield 49.7%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, CDCl ₃ ) δ: 2.41 (132H, s), 3.40-3.67 (148H, m), 3.85 (128H, bs), 4.35 (32H, s), 4.53 (32H, bs), 5.04 (128H, bs), 5.80 (64H, bs), 6.28 (32H, bs), 6.40 (64H, bs), 7.20 (1H, b), 7.26 (4H, br)
¹³ C-NMR ((600 MHz, CDCl ₃ ) δ: 33.7, 67.2, 71.0, 72.1, 79.0, 73.2, 100.6, 105.8, 106.0, 141.0, 141.4, 160.1, 117.0, 134.6

(Synthesis Example 20)
In Synthesis Example 20, a polymerizable hyperbranched polymer was prepared as follows.
That is, glycerol was used as a core molecule, and a reaction represented by the following chemical formula was performed. The ratio (molar ratio) of glycerol: glycidol: allyl glycidyl ether was 1: 9: 12.

Polymerization step 0.59 g (2.25 mmol) of potassium methoxide (30% methanol solution) was added while stirring 0.69 g (7.5 mmol) of glycerol in a 90 ° C. oil bath under an argon stream. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. While adding 9 ml of dehydrated diglyme and heating to 130 ° C., 5.0 g (67.5 mmol) of glycidol was dissolved in 20 ml of dehydrated THF and added dropwise over about 5.5 hours while distilling off THF.

Following the modification step, 10.3 g (90.0 mmol) of allyl glycidyl ether was dissolved in 30 ml of dehydrated THF and added dropwise over about 10.5 hours while distilling off THF. After stirring at the same temperature for 4 hours, the mixture was cooled, 20 ml of methanol was added and neutralized through a column of 20 ml of Amberlite IR 120B H AG. After activated carbon treatment, the solvent was distilled off under reduced pressure (80 ° C.), and the residual oil was purified by silica gel column chromatography (chloroform / methanol = 5/1) to obtain 10.56 g of a light brown oil (yield 66.2). %). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, Methanol-d ₄ ) δ: 3.44-3.66 (98H, m), 3.86 (12H, s), 4.01 (24H, s), 4.77 (12H, s), 5.16 (12H, d , J = 9.9 Hz), 5.28 (12H, d, J = 17.6 Hz), 5.89-5.93 (12H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 61.5, 69.3, 69.6, 69.7, 70.0, 71.2, 71.4 and 71.8, 72.0, 72.9, 78.6, 78., 116.0, 134.8, 135.0

すなわち、上記修飾工程で得た化合物2.0 gをトルエン6 mlに溶解し、これに水3.5 mlに溶解した水酸化ナトリウム3.4 g (85.0 mmol) および臭化テトラブチルアンモニウム 0.49 g (1.5 mmol)を加えた。40℃に加温、攪拌下臭化アリル 2.05 g (16.9 mmol)を0.5 mlのトルエンに溶解して45分で滴下した。同温度で16時間攪拌した後水10 ml、トルエン15 mlを加えて抽出、分液した。水層を再度15 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/エタノール＝50/1）で精製し、次いで0.2μmフィルターで濾過した。減圧下80℃にて溶媒を留去し、表題化合物を無色油状物を1.98 g得た(収率80.8%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, Methanol-d₄) δ: 3.51-3.71 (110H, m), 4.01 (24H, s), 4.15 (24H, s), 5.15 (12H, d, J = 12.1 Hz), 5.16 (12H, d, J = 11.0 Hz), 5.28 (24H, d, J = 17.0 Hz), 5.91-5.93 (24H, m)
¹³C -NMR (600 MHz, methanol-d₄) δ: 71.2, 72.1, 72.5, 73.2, 78.5, 78.8, 79.9, 80.2, 116.9, 117.1, 136.2, 136.6 Etherification Step Further, the hydroxyl group of the compound obtained in the modification step was allyl etherified with allyl bromide (see the following chemical formula).

That is, 2.0 g of the compound obtained in the above modification step was dissolved in 6 ml of toluene, and 3.4 g (85.0 mmol) of sodium hydroxide and 0.49 g (1.5 mmol) of tetrabutylammonium bromide dissolved in 3.5 ml of water were added thereto. It was. While heating to 40 ° C. and stirring, 2.05 g (16.9 mmol) of allyl bromide was dissolved in 0.5 ml of toluene and added dropwise over 45 minutes. After stirring at the same temperature for 16 hours, 10 ml of water and 15 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 15 ml of toluene, and the extracts were combined and washed with saturated brine. After dehydrating with anhydrous sodium sulfate and concentrating, the residue was purified by silica gel column chromatography (chloroform / ethanol = 50/1) and then filtered through a 0.2 μm filter. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 1.98 g of the title compound as a colorless oil (yield 80.8%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, Methanol-d ₄ ) δ: 3.51-3.71 (110H, m), 4.01 (24H, s), 4.15 (24H, s), 5.15 (12H, d, J = 12.1 Hz), 5.16 (12H, d, J = 11.0 Hz), 5.28 (24H, d, J = 17.0 Hz), 5.91-5.93 (24H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 71.2, 72.1, 72.5, 73.2, 78.5, 78.8, 79.9, 80.2, 116.9, 117.1, 136.2, 136.6

(Synthesis Example 21)
In Synthesis Example 21, a polymerizable hyperbranched polymer was prepared as follows.
That is, the reaction shown in the following chemical formula was carried out using ethylene glycol as the core molecule. The ratio of ethylene glycol: glycidol: allyl glycidyl ether was 1:14:16 (molar ratio).

Polymerization step Under an argon stream, 0.35 g (1.5 mmol) of potassium methoxide (30% methanol solution) was added while stirring and stirring ethylene glycol 0.31 g (5.0 mmol) at 80 ° C. After stirring for several minutes, the pressure was gradually reduced and methanol was distilled off. 5 ml of dehydrated diglyme was added, the temperature was raised to 100 ° C., 5.19 g (70.1 mmol) of glycidol was dissolved in 15 ml of dehydrated THF, and about 5 hours were added dropwise while removing THF.

Modification Step Subsequently, 9.13 g (80.0 mmol) of allyl glycidyl ether was dissolved in 25 ml of dehydrated THF and added dropwise over about 3 hours while distilling off the THF. The mixture was stirred at the same temperature for 3 hours, cooled, added with 25 ml of methanol, and neutralized through a column of 20 ml of Amberlite IR 120B H AG. The solvent was distilled off under reduced pressure, and the residual oil was purified by silica gel column chromatography (chloroform / methanol = 7/1). Filtration through a 0.2 μm filter as a methanol solution and concentration under reduced pressure (80 ° C.) gave 8.84 g of a pale yellow oil (yield 60.4%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.43-3.67 (154H, m), 3.87 (16H, s), 4.01 (16H, s), 4.73 (16H, s), 5.16 (16H, d , J = 8.8 Hz), 5.28 (16H, d, J = 17.0 Hz), 5.88-5.93 (16H, br)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 59.3, 64.5, 70.4, 70.8, 71.1, 72.5, 72.9, 73.2, 74.0, 79.8, 80.0, 117.2, 136.0, 136.1

すなわち、上記修飾工程で得られた化合物3.0 g (1.025 mmol) をトルエン5 mlに溶解し、これに臭化テトラブチルアンモニウム 0.69 g (2.1 mmol)、 次いで水5.5 mlに溶解した水酸化ナトリウム4.47 g (111.8 mmol)を加えた。40℃に加温、攪拌下臭化アリル 2.98 g (24.6 mmol)を2 mlのトルエンに溶解して約１時間で滴下した。同温度で18時間攪拌した後水10 ml、トルエン10 mlを加えて抽出、分液した。水層を再度10 mlのトルエンで抽出し、抽出液を併せて飽和食塩水で洗浄した。無水硫酸ナトリウムで脱水後濃縮し、残留液をシリカゲルカラムクロマトグラフィー（クロロホルム/エタノール＝35/1）で精製し、次いでメタノール溶液として0.2μmフィルターで濾過した。減圧下80℃にて溶媒を留去し、無色油状物を2.59 g得た(収率70.9%)。このもののＮＭＲを測定し、以下の結果を得た。
¹H -NMR (600 MHz, methanol-d₄) δ: 3.50-3.70 (154H, m), 4.00 (32H, s), 4.13 (32H, s), 5.13 (16H, d, J = 12.1 Hz), 5.15 (16H, d, J = 11.0 Hz), 5.27 (32H, d, J = 17.0 Hz), 5.90-5.91 (32H, m)
¹³C -NMR (600 MHz, methanol-d₄) δ: 59.5, 71.2, 71.9, 72.1, 72.5, 73.2, 78.4, 78.7, 79.9, 80.1, 116.9, 117.1, 136.1, 136.6 Etherification Step Further, the hydroxyl group of the compound obtained in the modification step was allyl etherified with allyl bromide (see the following chemical formula).

That is, 3.0 g (1.025 mmol) of the compound obtained in the above modification step was dissolved in 5 ml of toluene, 0.69 g (2.1 mmol) of tetrabutylammonium bromide, and then 4.47 g of sodium hydroxide dissolved in 5.5 ml of water. (111.8 mmol) was added. The mixture was heated to 40 ° C., and 2.98 g (24.6 mmol) of allyl bromide was dissolved in 2 ml of toluene with stirring and added dropwise in about 1 hour. After stirring at the same temperature for 18 hours, 10 ml of water and 10 ml of toluene were added for extraction and liquid separation. The aqueous layer was extracted again with 10 ml of toluene, and the extracts were combined and washed with saturated brine. The mixture was dehydrated with anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography (chloroform / ethanol = 35/1), and then filtered through a 0.2 μm filter as a methanol solution. The solvent was distilled off at 80 ° C. under reduced pressure to obtain 2.59 g of colorless oil (yield 70.9%). NMR of this product was measured, and the following results were obtained.
¹ H -NMR (600 MHz, methanol-d ₄ ) δ: 3.50-3.70 (154H, m), 4.00 (32H, s), 4.13 (32H, s), 5.13 (16H, d, J = 12.1 Hz), 5.15 (16H, d, J = 11.0 Hz), 5.27 (32H, d, J = 17.0 Hz), 5.90-5.91 (32H, m)
¹³ C -NMR (600 MHz, methanol-d ₄ ) δ: 59.5, 71.2, 71.9, 72.1, 72.5, 73.2, 78.4, 78.7, 79.9, 80.1, 116.9, 117.1, 136.1, 136.6

<Viscosity measurement>
The polymerizable hyperbranched polymers of Synthesis Examples 1 to 21 had a lower viscosity than conventional prepolymers and were easy to handle in and out of containers. Further, when stored in a cool and dark place, the polymer was not solidified without adding a polymerization inhibitor and could be stored stably. Viscosity of the polymerizable hyperbranched polymers of Synthesis Examples 1, 2, 8 and 10 was measured using a vibration viscometer. As a result, as shown in Table 1, it was in the range of 170 to 378 mPa · s, and the viscosity was much lower than that of the conventional prepolymer.

<Preparation of polymerizable composition capable of photoradical polymerization>
Using the polymerizable hyperbranched polymers of Synthesis Examples 1 to 19 synthesized as described above, trimethylolpropane triacrylate (hereinafter referred to as “TPA”) as a polymerizable monomer, and photopolymerization initiator as a photopolymerization initiator. (4,4′-bis (diethylamino) benzophenone) (hereinafter referred to as “EMK”) was mixed at a ratio shown in Table 2 to prepare photopolymerizable compositions of Examples 1 to 37 capable of photoradical polymerization. did.

<Curing test by UV irradiation>
The curing test by ultraviolet irradiation of the photopolymerizable compositions of Examples 1 to 37 prepared as described above was performed according to the following procedure. That is, a 7.5 μm polyimide spacer is placed on the slide glass, and the cover glass and the slide glass are fixed with an adhesive while being separated by the thickness of the spacer. In this way, the photopolymerizable composition is soaked through the gap provided between the slide glass and the cover glass, and after irradiating with ultraviolet rays for a predetermined time with a 30 W high-pressure mercury lamp, the cover glass can be peeled off with tweezers. I investigated about it. In the evaluation of curing, the case where the tweezers could not be peeled off was indicated as “◯”, the case where the cover glass could be peeled off but there was considerable resistance, and the case where it was easily peeled off was indicated as “X”.

  As a result, as shown in Table 3, it was found that the photopolymerizable compositions of the examples were cured in a short time by ultraviolet irradiation.

<Preparation of polymerizable composition capable of cationic polymerization>
The polymerizable hyperbranched polymer of Synthesis Example 20 and Synthesis Example 21 was used. As the polymerizable monomer, 2,2-bis (4-glycidyloxyphenyl) propane (hereinafter referred to as “BGP”), A mixture of 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (hereinafter referred to as “EEC”) 1: 1 was mixed as a polymerizable monomer, and a cationic initiator was used as a photoacid generator. A certain [4-[(2-hydroxytetradecyl) oxy] -phenyl] phenyliodonium hexafluoroantimonate was added, and isopropyl-9H-thioxanthen-9-one was further added as a photosensitizer, and Example 38 and The photopolymerizable composition of Example 39 was prepared. Table 4 shows the mixing ratio of each drug.

<Curing test by UV irradiation>
The curing test by ultraviolet irradiation of the photopolymerizable compositions of Example 38 and Example 39 prepared as described above was performed in the same manner as described above. The results are shown in Table 5. As can be seen from this table, Example 38 and Example 39 in which an epoxy monomer was used as the polymerizable monomer and a photoacid generator and a photosensitizer were added could also be easily cured by ultraviolet rays.

  As described above, the photopolymerizable compositions of the examples have a lower viscosity and are easier to handle than general cationic photopolymerizable compositions. In addition, by using a polymerizable hyperbranched polymer as a polymerizable component of the photo resin composition, it is easier to produce and can be produced at a lower cost than a photopolymer composition using a conventional dendrimer.

  The present invention is not limited to the description of the embodiments of the invention. Various modifications may be included in the present invention as long as those skilled in the art can easily conceive without departing from the description of the scope of claims.

  The present invention can be used as a material for photolithography in the production of electronic devices.

Claims (13)

  A polymerizable hyperbranched polymer in which a terminal hydroxyl group of a highly branched polymer in which glycidol is polymerized in a branched manner with the hydroxyl group of the core molecule as a starting point is added to an epoxy group of a glycidyl ether having a polymerizable carbon-carbon double bond, and the polymerizability A photopolymerizable composition comprising a polymerizable monomer capable of binding to a hyperbranched polymer and a photopolymerization initiator.   The polymerizable monomer is an acrylic monomer having one or more (meth) acrylic groups per molecule, and the photopolymerization initiator is a photoradical generator that generates radicals by light irradiation. The photopolymerizable composition according to 1.   The polymerizable monomer is an epoxy monomer having one or more epoxy groups per molecule, and the photopolymerization initiator is a photoacid generator that generates an acid by light irradiation. Photopolymerizable composition.   The photopolymerizable composition according to any one of claims 1 to 3, further comprising a photosensitizer.   The glycidyl ether having a polymerizable carbon-carbon double bond is any of allyl glycidyl ether and 3,5-bis (3-butenyloxy) benzyl glycidyl ether. 2. The photopolymerizable composition according to any one of the above.   The core molecule is glycerol, trimethylolpropane, pentaerythritol, ethylene glycol, polyethylene glycol, 1,4-butanediol, 1,2,4-butanetriol, triethanolamine, N, N-bis (2,3-dihydroxy Propyl) benzylamine, N, N-bis (2,3-dihydroxypropyl) octylamine, N, N, N ′, N′-tetrakis (2,3-dihydroxypropyl) ethylenediamine, N-phenyldiethanolamine and 2-phenyl The photopolymerizable composition according to any one of claims 1 to 5, wherein the photopolymerizable composition is any one of -1,3-propanediol.   The terminal hydroxyl group of the hyperbranched polymer in which the glycidol is polymerized in a branched manner with the hydroxyl group of the core molecule as the starting point has a structure in which it is added to the epoxy group of the glycidyl ether having a polymerizable carbon-carbon double bond. A light comprising a polymerizable hyperbranched polymer in which a hydroxyl group generated by ring-opening of the epoxy group is etherified, a polymerizable monomer capable of binding to the polymerizable hyperbranched polymer, and a photopolymerization initiator. Polymerizable composition.   8. The photopolymerizable composition according to claim 7, wherein the polymerizable monomer is an acrylic monomer having one or more (meth) acrylic groups per molecule, and the photopolymerization initiator is a photoradical generator. object.   The photopolymerizable composition according to claim 7, wherein the polymerizable monomer is an epoxy monomer having one or more epoxy groups per molecule, and the photopolymerization initiator is a photoacid generator.   10. The glycidyl ether having a polymerizable carbon-carbon double bond is allyl glycidyl ether or 3,5-bis (3-butenyloxy) benzyl glycidyl ether. The photopolymerizable composition according to item.   The photopolymerizable composition according to any one of claims 7 to 10, further comprising a photosensitizer.   The core molecule is glycerol, trimethylolpropane, pentaerythritol, ethylene glycol, polyethylene glycol, 1,4-butanediol, 1,2,4-butanetriol, triethanolamine, N, N-bis (2,3-dihydroxy Propyl) benzylamine, N, N-bis (2,3-dihydroxypropyl) octylamine, N, N, N ′, N′-tetrakis (2,3-dihydroxypropyl) ethylenediamine, N-phenyldiethanolamine and 2-phenyl The photopolymerizable composition according to any one of claims 7 to 11, wherein the photopolymerizable composition is any one of -1,3-propanediol.   The etherification of a hydroxyl group generated by ring opening of an epoxy group is allyl etherification, methyl etherification, or 3,5-bis (butenyloxy) benzyl etherification. The photopolymerizable composition according to item.