WO2014065327A1 - Acrylic or methacrylic compound having hydroxyl group, and method for producing same - Google Patents

Acrylic or methacrylic compound having hydroxyl group, and method for producing same Download PDF

Info

Publication number
WO2014065327A1
WO2014065327A1 PCT/JP2013/078711 JP2013078711W WO2014065327A1 WO 2014065327 A1 WO2014065327 A1 WO 2014065327A1 JP 2013078711 W JP2013078711 W JP 2013078711W WO 2014065327 A1 WO2014065327 A1 WO 2014065327A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
hydrogen atom
hydroxyl group
compound
Prior art date
Application number
PCT/JP2013/078711
Other languages
French (fr)
Japanese (ja)
Inventor
佳和 原田
近藤　光正
耕平 後藤
Original Assignee
日産化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to KR1020157012763A priority Critical patent/KR20150074059A/en
Priority to JP2014543325A priority patent/JPWO2014065327A1/en
Priority to CN201380051748.8A priority patent/CN104718184A/en
Publication of WO2014065327A1 publication Critical patent/WO2014065327A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C07C275/10—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton being further substituted by singly-bound oxygen atoms

Definitions

  • the present invention relates to provision of an acrylic or methacrylic compound having a hydroxyl group, which is expected to be used as an additive for imparting a function to a resin composition, and a method for producing these.
  • the photoreactive group has an acrylic group or a methacryl group, and has a plurality of hydroxy groups that are crosslinkable groups. Certain compounds are also known (Patent Document 2).
  • a technique for enhancing the function by forming a strong network by introducing a crosslinking agent and a low-molecular compound that reacts with the crosslinking agent into the resin composition is often used.
  • satisfactory characteristics cannot be obtained after the light irradiation step, and there are problems that peeling due to the film strength is observed and the deterioration rate is high.
  • a compound having an aromatic ring generally has an ability to absorb ultraviolet light, it absorbs light energy, impairs photopatterning, and transparency may be impaired by coloring by an oxidation reaction, which is not preferable.
  • the present inventors have produced a compound having an acrylic group or a methacrylic group that is a photoreactive group and a plurality of hydroxy groups that are crosslinkable groups. A method was found and the present invention was completed. That is, the present invention 1.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a hydroxyl alkyl group having 1 to 20 carbon atoms
  • R 4 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms.
  • R 1 is a hydrogen atom or a methyl group
  • glycidyl acrylate or glycidyl methacrylate represented by the following formula (B)
  • R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a hydroxyl alkyl group having 1 to 20 carbon atoms, and R 4 is a hydroxyl group or having 1 to 20 carbon atoms.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a hydroxyl alkyl group having 1 to 20 carbon atoms
  • R 4 is a hydroxyl group or a hydroxyl alkyl group having 1 to 20 carbon atoms.
  • R 2 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 3 and R 4 are both hydroxymethyl groups. 7).
  • R 5 is a hydrogen atom or a methyl group
  • R 6 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms
  • R 7 and R 8 are a hydroxylalkyl group having 1 to 20 carbon atoms
  • L is alkylene having 2 to 20 carbon atoms).
  • R 6 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms
  • R 7 and R 8 are hydroxylalkyl groups having 1 to 20 carbon atoms.
  • R 5 is a hydrogen atom or a methyl group
  • R 6 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms
  • R 7 and R 8 are a hydroxylalkyl group having 1 to 20 carbon atoms
  • L is alkylene having 2 to 20 carbon atoms.
  • the function of the resin composition can be improved by the crosslinking effect, and further improvement of the function can be expected by the crosslinking effect after the light irradiation step. Moreover, since it is a compound which does not contain an aromatic ring, there is no fear of coloring, it is excellent in transparency, and the resin composition excellent in durability, such as heat resistance and water resistance, can be obtained.
  • a method for producing an acrylic or methacrylic compound having a hydroxyl group represented by the above formula [1] (hereinafter abbreviated as compound 1) is represented by the following reaction scheme. That is, the target compound 1 is produced by reacting glycidyl acrylate (GA) or glycidyl methacrylate (GMA) represented by the following formula (A) with a carboxylic acid compound represented by the following formula (B).
  • G glycidyl acrylate
  • GMA glycidyl methacrylate
  • B carboxylic acid compound represented by the following formula (B).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a hydroxylalkyl group having 1 to 20 carbon atoms
  • 4 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms may be linear or branched. Specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl- n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n- Butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, Examples include
  • the hydroxyalkyl group having 1 to 20 carbon atoms is preferably a hydroxy group substituted at the terminal of the alkyl group, such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6 -Hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 11-hydroxyundecyl, 12-hydroxydodecyl, 13-hydroxytridecyl, 14-hydroxytetradecyl, 15-hydroxy Examples include pentadecyl, 16-hydroxyhexadecyl, 17-hydroxyheptadecyl, 18-hydroxyoctadecyl, 19-hydroxynonadecyl and 20-hydroxyeicosyl.
  • the amount of the carboxylic acid compound used with respect to GA or GMA is not particularly limited, but a method of removing excess carboxylic acid compound by washing with water after GA or GMA is eliminated is efficient. That is, the amount of the carboxylic acid compound is preferably 1.0 to 3.0 equivalents relative to GA or GMA. More preferably, it is 1.0 equivalent to 1.2 equivalent.
  • the reaction solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogens such as carbon tetrachloride, chloroform and 1,2-dichloroethane Hydrocarbons; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; ethyl acetate and ethyl propionate N-containing aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone; Dimethyl sul
  • Sulfur aprotic polar solvent pyridine, pyridines picoline and the like. These solvents may be used alone, or two or more of these may be mixed and used. Preferred are DMF, ethyl acetate, acetonitrile, and 1,4-dioxane, and more preferred are DMF and ethyl acetate.
  • the amount of the solvent used is not particularly limited, but the reaction may be carried out without using a solvent.
  • the solvent is 0.1 to 100 times the mass of GA or GMA. May be used.
  • the amount is preferably 1 to 10 times by mass, more preferably 2 to 5 times by mass.
  • the reaction temperature is not particularly limited, but is, for example, ⁇ 90 to 200 ° C., preferably 0 to 150 ° C., and more preferably 50 ° C. to 120 ° C.
  • the reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.
  • a polymerization inhibitor may be added.
  • BHT 2,6-di-tert-butyl-para-cresol
  • hydroquinone para-methoxyphenol, etc.
  • para-methoxyphenol para-methoxyphenol
  • the addition amount in the case of adding a polymerization inhibitor is not particularly limited, but is preferably 0.00001 mol to 0.1 mol with respect to the number of moles of the acrylic ester compound (GA) or methacrylic ester compound (GMA). Is 0.001 to 0.01 mol.
  • Catalysts may be added to shorten the reaction time, examples of which include benzyltrimethylammonium chloride (BTMAC), benzyltriethylammonium chloride (BTEAC), benzyltrimethylammonium bromide (BTMAB), benzyltriethylammonium bromide (BTEAB). ), Quaternary ammonium salts such as tetrabutylammonium chloride (TBAC) and tetrabutylammonium bromide (TBAB), and quaternary phosphonium salts such as tetraphenylphosphonium bromide (TPPB).
  • BTMAC benzyltrimethylammonium chloride
  • BTEAC benzyltriethylammonium chloride
  • BTMAB benzyltrimethylammonium bromide
  • BTEAB benzyltriethylammonium bromide
  • Quaternary ammonium salts such as
  • a base catalyst may be added, and examples thereof include triethylamine, trimethylamine, tripropylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, N, N-dimethylamino-4-pyridine, 1,8-diazabicyclo Organic bases such as [5.4.0] undecene-7 (DBU), 1,5-diaza-bicyclo [4.3.0] nonene-5 (DBN), alkali metal hydroxides such as sodium hydroxide Alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkaline earth metal carbonates such as barium carbonate and calcium carbonate Alkali metal bicarbonates such as sodium bicarbonate, bicarbonate Alkali metal salts of inorganic acids such as potassium, for example inorganic bases such as 2- or 3-sodium phosphate, 2- or 3-potassium phosphate.
  • DBU undecene
  • the amount added may be 0.003 to 1 mol, preferably 0.03 to 0.5 mol, more preferably 0.05 to 0.00 mol per mol of GA or GMA. 2 moles.
  • the amount of the catalyst is large, a large amount of water is required for removing the catalyst, and it is not economically preferable.
  • the amount of the catalyst is small, the reaction is delayed, and it takes a long time to complete the reaction.
  • This reaction can be carried out at normal pressure or under pressure, and may be batch or continuous.
  • the amount of water used for washing may be any amount that can remove the catalyst used in the reaction, but if the amount of water is large, the target product moves to the aqueous layer and the recovery rate decreases. Therefore, the ratio of water to the washing solvent is preferably 5: 1 to 1: 100, more preferably 2: 1 to 1:20.
  • a method for producing an acrylic or methacrylic compound having a hydroxyl group represented by the above formula [3] is represented by the following reaction scheme. That is, by reacting an isocyanatoalkyl acrylate (IAA) or isocyanatoalkyl methacrylate (IAM) represented by the following formula (C) with an amine compound represented by the following formula (D), the desired compound 3 Is manufactured.
  • R 5 is a hydrogen atom or a methyl group
  • R 6 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms
  • R 7 and R 8 are a hydroxylalkyl group having 1 to 20 carbon atoms
  • L is alkylene having 2 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms may be linear or branched. Specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl- n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n- Butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, Examples include
  • the hydroxyalkyl group having 1 to 20 carbon atoms is preferably a hydroxy group substituted at the terminal of the alkyl group, such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6 -Hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 11-hydroxyundecyl, 12-hydroxydodecyl, 13-hydroxytridecyl, 14-hydroxytetradecyl, 15-hydroxy Examples include pentadecyl, 16-hydroxyhexadecyl, 17-hydroxyheptadecyl, 18-hydroxyoctadecyl, 19-hydroxynonadecyl and 20-hydroxyeicosyl.
  • alkylene having 2 to 20 carbon atoms examples include divalent groups in which one hydrogen atom is further removed from the above alkyl group having 1 to 20 carbon atoms having 2 or more carbon atoms.
  • the amount of IAA or IAM used with respect to the amine compound is not particularly limited, but is preferably 0.9 equivalent to 3.0 equivalent with respect to the amine compound. More preferably, it is 1.0 equivalent to 1.2 equivalent.
  • the reaction solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogens such as carbon tetrachloride, chloroform and 1,2-dichloroethane Hydrocarbons; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; ethyl acetate and ethyl propionate N-containing aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone; Dimethyl sul
  • Sulfur aprotic polar solvent pyridine, pyridines picoline and the like. These solvents may be used alone, or two or more of these may be mixed and used. Among them, a solvent that dissolves IAA and IMA but hardly dissolves compound 3 is preferable in that compound 3 obtained can be easily isolated by filtration.
  • solvents are preferably tetrahydrofuran, ethyl acetate, Toluene and acetonitrile are preferable, and tetrahydrofuran is more preferable.
  • the amount of the solvent used is not particularly limited, but the reaction may be carried out without using a solvent, and when a solvent is used, the solvent is 0.1 to 100 times by mass with respect to IAA or IAM. May be used.
  • the amount is preferably 1 to 10 times by mass, more preferably 2 to 5 times by mass.
  • the reaction temperature is not particularly limited, but is, for example, ⁇ 90 to 200 ° C., preferably ⁇ 50 to 150 ° C., and more preferably ⁇ 20 ° C. to 120 ° C.
  • the reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.
  • a polymerization inhibitor may be added.
  • BHT 2,6-di-tert-butyl-para-cresol
  • hydroquinone para-methoxyphenol, etc.
  • para-methoxyphenol para-methoxyphenol
  • the addition amount in the case of adding a polymerization inhibitor is not particularly limited, but is preferably 0.00001 mol to 0.1 mol with respect to the number of moles of the acrylic ester compound (IAA) or the methacrylic ester compound (IAM). Is 0.001 to 0.01 mol.
  • Catalysts may be added to shorten the reaction time, examples of which include benzyltrimethylammonium chloride (BTMAC), benzyltriethylammonium chloride (BTEAC), benzyltrimethylammonium bromide (BTMAB), benzyltriethylammonium bromide (BTEAB). ), Quaternary ammonium salts such as tetrabutylammonium chloride (TBAC) and tetrabutylammonium bromide (TBAB), and quaternary phosphonium salts such as tetraphenylphosphonium bromide (TPPB).
  • BTMAC benzyltrimethylammonium chloride
  • BTEAC benzyltriethylammonium chloride
  • BTMAB benzyltrimethylammonium bromide
  • BTEAB benzyltriethylammonium bromide
  • Quaternary ammonium salts such as
  • a base catalyst may be added, and examples thereof include triethylamine, trimethylamine, tripropylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, N, N-dimethylamino-4-pyridine, 1,8-diazabicyclo Organic bases such as [5.4.0] undecene-7 (DBU), 1,5-diaza-bicyclo [4.3.0] nonene-5 (DBN), alkali metal hydroxides such as sodium hydroxide Alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkaline earth metal carbonates such as barium carbonate and calcium carbonate Alkali metal bicarbonates such as sodium bicarbonate, bicarbonate Alkali metal salts of inorganic acids such as potassium, for example inorganic bases such as 2- or 3-sodium phosphate, 2- or 3-potassium phosphate.
  • DBU undecene
  • the amount added may be 0.001 to 1 mol, preferably 0.005 to 0.5 mol, more preferably 0.01 to 0.00 mol per mol of IAA or IAM. 2 moles.
  • This reaction can be carried out at normal pressure or under pressure, and may be batch or continuous.
  • the precipitated compound 3 crystals are collected by filtration and washed with a solvent such as tetrahydrofuran or ethyl acetate to obtain the target compound.
  • a solvent such as tetrahydrofuran or ethyl acetate.
  • GMA glycidyl methacrylate 2HM-PA: 2,2-bis (hydroxymethyl) propionic acid
  • BHT 2,6-di-tert-butyl-p-cresol
  • BTMAC benzyltriethylammonium chloride
  • BTEAC benzyltriethylammonium chloride
  • TPPB tetraphenyl Phosphonium bromide
  • DMF dimethylformamide
  • Example 2 The same operation as Example 1 was implemented until the water washing operation, and the following operation was performed after water washing. 803.0 g of PGME and 262.2 g of magnesium sulfate were added to the organic layer after washing twice, and after stirring for 1 hour, the magnesium sulfate was filtered. The filtrate was distilled off at 45 ° C. with an evaporator at 100 Torr. Concentrate until no more to give 1102.2 g of solution. This solution was confirmed to be a 52.9 wt% solution of GMA-2HM-PAE from the results of quantitative analysis by high performance liquid chromatography.
  • Example 3 Under a nitrogen stream, DMF 1350.0 g, GMA 458.2 g (3.22 mol) and 2HM-PA 528.8 g (3.94 mol), BHT 4.6 g (20.87 mmol), BTMAC 13.5 g (72. 70 mmol) was charged at room temperature, heated to 80 ° C. with magnetic stirring, and stirred for 24 hours. After confirming that GMA was less than 0.5 area%, DMF was concentrated. To the DMF concentrate, 4101.0 g of ethyl acetate was added, followed by 4059.0 g of pure water, washed with water in a separatory funnel, and the aqueous layer was discarded.
  • Example 4 A series of operations were carried out in the same manner as in Example 1. Only the catalyst was changed to BTMAC, and the mixture was heated and stirred for 21 hours. As a result of analyzing the reaction solution by high performance liquid chromatography, it was confirmed that GMA was 0.5 area% or less.
  • Example 5 A series of operations were carried out in the same manner as in Example 1. The catalyst was changed to TPPB, and the mixture was heated and stirred for 21 hours. As a result of analyzing the reaction solution by high performance liquid chromatography, it was confirmed that GMA was 0.5 area% or less.
  • Example 6 A series of operations were carried out in the same manner as in Example 1, except that only the catalyst was changed to BTMAC, and the amount of catalyst was 0.025 mol relative to the number of moles of GMA. As a result of analyzing the reaction solution by high performance liquid chromatography after 21 hours, it was confirmed that 17.5 area% GMA remained and GMA was 0.5 area% or less after 44 hours. It was.
  • Example 7 Each cured film forming composition of Example 7 and Comparative Example 1 was prepared with the composition shown in Table 2. Next, a cured film was formed using each cured film forming composition, and adhesion, orientation sensitivity, pattern formability, and transmittance were evaluated for each of the obtained cured films.
  • a film having a thickness of 1.0 ⁇ m was formed. This film was exposed at 1000 mJ / cm 2 to polymerize the polymerizable liquid crystal to produce a retardation material. A crosscut (1 mm ⁇ 1 mm ⁇ 100 squares) was put into the retardation material on the obtained substrate using a cutter knife, and then a cellophane tape was attached. Next, when the cellophane tape was peeled off, the number of squares remaining in the retardation material on the substrate where the polymerized polymerizable liquid crystal film was not peeled off on the lower cured film was counted. The evaluation results are “initial” and are shown in Table 2 in the form of (number of cells remaining without peeling off the film) / 100. Adhesiveness was judged to be good when 90 or more squares remained without peeling off the film, that is, 90/100 to 100/100.
  • Each of the cured film forming compositions of Examples and Comparative Examples was spin-coated on an alkali glass at 2000 rpm for 30 seconds using a spin coater, and then heated and dried in a thermal circulation oven at a temperature of 110 ° C. for 120 seconds to obtain a cured film. Formed. Each cured film was vertically irradiated with 313 nm linearly polarized light to form an alignment material. On the alignment material on the substrate, a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, and then pre-baked on a hot plate at 60 ° C. for 60 seconds to obtain a film thickness.
  • a 1.0 ⁇ m coating film was formed.
  • the coating film on this substrate was exposed at 1000 mJ / cm 2 to produce a retardation material.
  • the retardation material on the prepared substrate is sandwiched between a pair of polarizing plates, the state of retardation property development in the retardation material is observed, and the exposure amount of polarized UV necessary for the alignment material to exhibit liquid crystal alignment is determined. It was.
  • the evaluation results are summarized in Table 2 later.
  • the alignment materials formed using each of the cured film forming compositions of Examples 1 to 3 and Comparative Example each have an exposure amount of polarized UV necessary to exhibit liquid crystal alignment of 20 mJ / cm 2 to 40 mJ. The value was as low as / cm 2 , indicating good alignment sensitivity.
  • a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, and then pre-baked on a hot plate at 60 ° C. for 60 seconds to form a film.
  • a coating film having a thickness of 1.0 ⁇ m was formed.
  • the coating film on this substrate was exposed at 1000 mJ / cm 2 to prepare a patterned retardation material in which two types of regions having different retardation characteristics were regularly arranged.
  • the patterned phase difference material on the produced substrate was observed using a polarizing microscope, and evaluation was made with ⁇ indicating that the phase difference pattern was formed without alignment defects, and ⁇ indicating that the alignment defects were observed. The evaluation results are shown later in Table 3.
  • the cured film obtained using the cured film forming composition of Example 7 maintained high adhesion even after high temperature and high humidity treatment, and exhibited excellent adhesion durability.
  • the cured film obtained using the cured film-forming composition of Comparative Example 1 was difficult to maintain the initial adhesion after the high temperature and high humidity treatment.
  • the alignment material obtained using the cured film-forming composition of Example 7 was polarized UV necessary for exhibiting liquid crystal alignment properties, similar to the alignment material obtained using the cured film-forming composition of Comparative Example.
  • the amount of exposure are both a low and 20mJ / cm 2 ⁇ 40mJ / cm 2, it showed a good alignment sensitivity.
  • the alignment material obtained using the cured film-forming composition of Example 7 showed good pattern-forming properties, similar to the alignment material obtained using the cured film-forming composition of the comparative example.
  • the cured film obtained using the cured film-forming composition of Example 7 was 100% of light having a wavelength of 400 nm, similarly to the cured film obtained using the cured film-forming composition of the comparative example.
  • the transmittance was shown and good light transmission characteristics were exhibited.
  • the compound of the present invention has the effect of improving the adhesion durability of the cured film-forming composition, and also affects the properties such as light transmittance and pattern formability. It was confirmed not to give.
  • Example 8 Synthesis of 2- (3- (1,3-dihydroxy-2- (hydroxymethyl) propan-2-yl) ureido) ethyl methacrylate Under a nitrogen stream, THF (tetrahydrofuran) 100 ml, THAM (trishydroxymethylaminomethane) 2.42 g (20.0 mmol) and BHT (2,6-di-tert-butyl-p-cresol) 33.0 mg (0. 150 mmol) was charged at 25 ° C., and 3.26 g (21.0 mmol) of 2-IEM (2-isocyanatoethyl methacrylate) was added with stirring with a magnetic stirrer.
  • THF tetrahydrofuran
  • THAM trishydroxymethylaminomethane
  • BHT 2,6-di-tert-butyl-p-cresol
  • the compound of the present invention improves the performance of a cured film obtained by adding it to a resin composition used in the field of displays such as a television using a liquid crystal panel and in the semiconductor field, and has characteristics such as transparency. Is useful as an additive or the like that does not affect.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

[Problem] To provide an acrylic or methacrylic compound having a hydroxyl group, and a method for producing the same. [Solution] An acrylic or methacrylic compound having a hydroxyl group represented by formula (1). (In the formula, R1 represents a hydrogen atom or a methyl group, R2 and R3 each independently represent a hydrogen atom, a C1-20 alkyl group or a C1-20 hydroxy-alkyl group, and R4 represents a hydroxyl group or a C1-20 hydroxy-alkyl group.)

Description

ヒドロキシル基を有するアクリルまたはメタクリル化合物及びその製造方法Acrylic or methacrylic compound having hydroxyl group and method for producing the same
　本発明は、樹脂組成物に機能を付与するための添加剤としての利用が期待されるヒドロキシル基を有するアクリルまたはメタクリル化合物の提供、並びに、これらの製造方法に関する。 The present invention relates to provision of an acrylic or methacrylic compound having a hydroxyl group, which is expected to be used as an additive for imparting a function to a resin composition, and a method for producing these.
　近年、液晶パネルを用いたテレビ等のディスプレイの分野や、半導体分野においては、ある種の樹脂組成物を基板に塗布した後、光を照射することでパターニングを行う場面が増加している。また、高性能化に向けた取り組みとして、そのような樹脂組成物に低分子化合物を添加し、紫外線に対する感度を増加させたり、膜の硬度を増加させる等のことが行われている。 In recent years, in the fields of displays such as televisions using liquid crystal panels and semiconductors, there is an increasing number of cases where patterning is performed by irradiating light after applying a certain resin composition to a substrate. Moreover, as an effort toward high performance, a low molecular compound is added to such a resin composition to increase the sensitivity to ultraviolet rays, increase the hardness of the film, and the like.
　ここで、同一分子内に、光反応性基であるアクリル基またはメタクリル基を有し、なおかつ、架橋性の基であるヒドロキシ基を複数有する化合物であれば、そのような樹脂組成物の高性能化に寄与することが大いに期待される。エポキシ基とアクリレート基を有する化合物と、ヒドロキシル基を含んだカルボン酸ポリマーとを反応させることはすでに知られている（例えば、特許文献１）。また、エポキシ基とアクリレート基を有する化合物とサリチル酸との反応例によるモノマーの合成例も知られている（例えば、非特許文献１）。
　また、イソシアネート基とアミノ基とを反応させることにより得られる、同一分子内に、光反応性基であるアクリル基またはメタクリル基を有し、なおかつ、架橋性の基であるヒドロキシ基を複数有する、ある種の化合物も知られている（特許文献２）。 Here, if it is a compound having an acrylic group or a methacryl group which is a photoreactive group in the same molecule and a plurality of hydroxy groups which are crosslinkable groups, the high performance of such a resin composition It is highly expected to contribute to the transformation. It is already known to react a compound having an epoxy group and an acrylate group with a carboxylic acid polymer containing a hydroxyl group (for example, Patent Document 1). In addition, a monomer synthesis example based on a reaction example between a compound having an epoxy group and an acrylate group and salicylic acid is also known (for example, Non-Patent Document 1).
Moreover, in the same molecule obtained by reacting an isocyanate group and an amino group, the photoreactive group has an acrylic group or a methacryl group, and has a plurality of hydroxy groups that are crosslinkable groups. Certain compounds are also known (Patent Document 2).
特開２００６－３９１０３号公報JP 2006-39103 A 特開２００１－１２５２５７号公報JP 2001-125257 A
　基板に樹脂組成物を塗布する場合において、樹脂組成物中に架橋剤と、架橋剤と反応する低分子化合物の導入により強固なネットワークを形成させて機能を高める手法はよく用いられるが、光反応性基を有していない場合、光照射工程後に満足な特性が得られず、膜強度に起因する剥離が見られたり、劣化速度が速いという課題があった。
　さらに、一般的に芳香環を有する化合物は紫外線吸収能を持つため光エネルギーを吸収し、光パターニングを阻害したり、酸化反応による着色によって透明性が損なわれることもあり、好ましくない。 In the case of applying a resin composition to a substrate, a technique for enhancing the function by forming a strong network by introducing a crosslinking agent and a low-molecular compound that reacts with the crosslinking agent into the resin composition is often used. In the case of not having a functional group, satisfactory characteristics cannot be obtained after the light irradiation step, and there are problems that peeling due to the film strength is observed and the deterioration rate is high.
Furthermore, since a compound having an aromatic ring generally has an ability to absorb ultraviolet light, it absorbs light energy, impairs photopatterning, and transparency may be impaired by coloring by an oxidation reaction, which is not preferable.
　本発明者らは、上記の課題を解決するために鋭意努力した結果、光反応性基であるアクリル基またはメタクリル基を有し、なおかつ、架橋性の基であるヒドロキシ基を複数有する化合物の製造方法を見出し、本発明を完成させた。すなわち、本発明は、
１．下記式［１］で表されるヒドロキシル基を有するアクリルまたはメタクリル化合物。 As a result of diligent efforts to solve the above-mentioned problems, the present inventors have produced a compound having an acrylic group or a methacrylic group that is a photoreactive group and a plurality of hydroxy groups that are crosslinkable groups. A method was found and the present invention was completed. That is, the present invention
1. An acrylic or methacrylic compound having a hydroxyl group represented by the following formula [1].
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
（式中、Ｒ1は水素原子またはメチル基であり、Ｒ2及びＲ3は、互いに独立して水素原子、炭素数１から２０のアルキル基または炭素数１から２０のヒドロキシルアルキル基であり、Ｒ4は、ヒドロキシル基または炭素数１から２０のヒドロキシルアルキル基である。）、
２．Ｒ2及びＲ3の少なくとも１つが炭素数１から２０のヒドロキシルアルキル基である上記１に記載のヒドロキシル基を有するアクリルまたはメタクリル化合物、
３．下記式［２］で表されるヒドロキシル基を有するアクリルまたはメタクリル化合物、 (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a hydroxyl alkyl group having 1 to 20 carbon atoms, R 4 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms).
2. An acrylic or methacrylic compound having a hydroxyl group as described in 1 above, wherein at least one of R 2 and R 3 is a hydroxylalkyl group having 1 to 20 carbon atoms;
3. An acrylic or methacrylic compound having a hydroxyl group represented by the following formula [2],
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
（式中、Ｒ1は水素原子またはメチル基であり、Ｒ2は、水素原子または炭素数１から２０のアルキル基である。）、
４．下記式（A） (Wherein R 1 is a hydrogen atom or a methyl group, and R 2 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms),
4). Following formula (A)
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
（式中、Ｒ1は水素原子またはメチル基である。）で表されるグリシジルアクリレートあるいはグリシジルメタクリレートと下記式（B） (Wherein R 1 is a hydrogen atom or a methyl group) and glycidyl acrylate or glycidyl methacrylate represented by the following formula (B)
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
（式中、Ｒ2及びＲ3は、互いに独立して水素原子、炭素数１から２０のアルキル基または炭素数１から２０のヒドロキシルアルキル基であり、Ｒ4は、ヒドロキシル基または炭素数１から２０のヒドロキシルアルキル基である。）で表されるヒドロキシル基を有するカルボン酸化合物とを反応させることを特徴とする下記式［１］ (In the formula, R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a hydroxyl alkyl group having 1 to 20 carbon atoms, and R 4 is a hydroxyl group or having 1 to 20 carbon atoms. And a carboxylic acid compound having a hydroxyl group represented by the following formula [1]:
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
（式中、Ｒ1は水素原子またはメチル基であり、Ｒ2及びＲ3は、互いに独立して水素原子、炭素数１から２０のアルキル基または炭素数１から２０のヒドロキシルアルキル基であり、Ｒ4は、ヒドロキシル基または炭素数１から２０のヒドロキシルアルキル基である。）で表されるヒドロキシル基を有するアクリルまたはメタクリル化合物の製造方法、
５．Ｒ2及びＲ3の少なくとも１つが炭素数１から２０のヒドロキシルアルキル基である上記４に記載の製造方法、
６．Ｒ2が水素原子または炭素数１から２０のアルキル基であり、Ｒ3とＲ4がともにヒドロキシメチル基である上記４に記載の製造方法、
７．反応させる際に重合禁止剤の存在下反応させることを特徴とする上記４～６のいずれかに記載の製造方法、
８．反応させる際に触媒の存在下反応させることを特徴とする上記４～７のいずれかに記載の製造方法、
９．下記式［３］で表されるヒドロキシル基を有するアクリルまたはメタクリル化合物。 (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a hydroxyl alkyl group having 1 to 20 carbon atoms, R 4 is a hydroxyl group or a hydroxyl alkyl group having 1 to 20 carbon atoms.) A method for producing an acrylic or methacrylic compound having a hydroxyl group represented by:
5). 5. The production method according to 4 above, wherein at least one of R 2 and R 3 is a hydroxylalkyl group having 1 to 20 carbon atoms,
6). 5. The production method according to 4 above, wherein R 2 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 3 and R 4 are both hydroxymethyl groups.
7). The production method according to any one of the above 4 to 6, wherein the reaction is carried out in the presence of a polymerization inhibitor when the reaction is carried out,
8). The production method according to any one of the above 4 to 7, wherein the reaction is carried out in the presence of a catalyst when the reaction is carried out,
9. An acrylic or methacrylic compound having a hydroxyl group represented by the following formula [3].
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
（式中、Ｒ5は水素原子またはメチル基であり、Ｒ6は、ヒドロキシル基または炭素数１から２０のヒドロキシルアルキル基であり、Ｒ7及びＲ8は、炭素数１から２０のヒドロキシルアルキル基であり、Lは炭素数２から２０のアルキレンである。）、
１０．下記式（C） Wherein R 5 is a hydrogen atom or a methyl group, R 6 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms, and R 7 and R 8 are a hydroxylalkyl group having 1 to 20 carbon atoms. And L is alkylene having 2 to 20 carbon atoms).
10. Following formula (C)
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
（式中、Ｒ5は水素原子またはメチル基であり、Lは炭素数２から２０のアルキレンである。）で表されるイソシアネート化合物と下記式（D） (Wherein R 5 is a hydrogen atom or a methyl group, L is an alkylene having 2 to 20 carbon atoms) and the following formula (D)
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
（式中、Ｒ6は、ヒドロキシル基または炭素数１から２０のヒドロキシルアルキル基であり、Ｒ7及びＲ8は、炭素数１から２０のヒドロキシルアルキル基である。）で表されるヒドロキシル基を有するアミン化合物とを反応させることを特徴とする下記式［３］ (Wherein R 6 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms, and R 7 and R 8 are hydroxylalkyl groups having 1 to 20 carbon atoms). The following formula [3], wherein the amine compound is reacted with
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
（式中、Ｒ5は水素原子またはメチル基であり、Ｒ6は、ヒドロキシル基または炭素数１から２０のヒドロキシルアルキル基であり、Ｒ7及びＲ8は、炭素数１から２０のヒドロキシルアルキル基であり、Lは炭素数２から２０のアルキレンである。）で表されるヒドロキシル基を有するアクリルまたはメタクリル化合物の製造方法、
１１．反応させる際に重合禁止剤の存在下反応させることを特徴とする上記１０記載の製造方法、
１２．反応させる際に触媒の存在下反応させることを特徴とする上記１０又は１１記載の製造方法、
である。 Wherein R 5 is a hydrogen atom or a methyl group, R 6 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms, and R 7 and R 8 are a hydroxylalkyl group having 1 to 20 carbon atoms. And L is alkylene having 2 to 20 carbon atoms.) A method for producing an acrylic or methacrylic compound having a hydroxyl group represented by:
11. The production method according to 10 above, wherein the reaction is carried out in the presence of a polymerization inhibitor when the reaction is carried out,
12 The production method according to 10 or 11 above, wherein the reaction is carried out in the presence of a catalyst when the reaction is carried out,
It is.
　本発明の化合物によれば、架橋効果により樹脂組成物の機能を向上させることができ、なおかつ、光照射工程後の架橋効果によりさらなる機能の向上が期待できる。また芳香環を含まない化合物であることから着色のおそれがなく透明性に優れ、耐熱性、耐水性などの耐久性に優れる樹脂組成物を得ることができる。 According to the compound of the present invention, the function of the resin composition can be improved by the crosslinking effect, and further improvement of the function can be expected by the crosslinking effect after the light irradiation step. Moreover, since it is a compound which does not contain an aromatic ring, there is no fear of coloring, it is excellent in transparency, and the resin composition excellent in durability, such as heat resistance and water resistance, can be obtained.
　以下、本発明についてさらに詳しく説明する。
　上記式［１］で表されるヒドロキシル基を有するアクリルまたはメタクリル化合物（以下、化合物１略記する）の製造法は、下記の反応スキームで表される。すなわち、下記式（A）で表されるグリシジルアクリレート（ＧＡ）またはグリシジルメタクリレート（ＧＭＡ）と、下記式（B）で表されるカルボン酸化合物とを反応させることにより、目的の化合物１が製造される。 Hereinafter, the present invention will be described in more detail.
A method for producing an acrylic or methacrylic compound having a hydroxyl group represented by the above formula [1] (hereinafter abbreviated as compound 1) is represented by the following reaction scheme. That is, the target compound 1 is produced by reacting glycidyl acrylate (GA) or glycidyl methacrylate (GMA) represented by the following formula (A) with a carboxylic acid compound represented by the following formula (B). The
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　式中、Ｒ1は水素原子またはメチル基であり、Ｒ2及びＲ3は、互いに独立して水素原子、炭素数１から２０のアルキル基または炭素数１から２０のヒドロキシルアルキル基であり、Ｒ4は、ヒドロキシル基または炭素数１から２０のヒドロキシルアルキル基である。 In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a hydroxylalkyl group having 1 to 20 carbon atoms, 4 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms.
　炭素数１から２０のアルキル基としては、直鎖及び分岐のいずれでもよい。
　その具体例としては、メチル、エチル、ｎ－プロピル、ｉ－プロピル、ｎ－ブチル、ｉ－ブチル、ｓ－ブチル、ｔ－ブチル、ｎ－ペンチル、１－メチル－ｎ－ブチル、２－メチル－ｎ－ブチル、３－メチル－ｎ－ブチル、１，１－ジメチル－ｎ－プロピル、ｎ－ヘキシル、１－メチル－ｎ－ペンチル、２－メチル－ｎ－ペンチル、１，１－ジメチル－ｎ－ブチル、１－エチル－ｎ－ブチル、１，１，２－トリメチル－ｎ－プロピル、ｎ－ヘプチル、ｎ－オクチル、ｎ－ノニル、ｎ－デシル、ｎ－ウンデシル、ｎ－ドデシル、ｎ－トリデシル、ｎ－テトラデシル、ｎ－ペンタデシル、ｎ－ヘキサデシル、ｎ－ヘプタデシル、ｎ－オクタデシル、ｎ－ノナデシル及びｎ－エイコシル基等が一例として挙げられる。
なお、ｎはノルマルを、ｉはイソを、ｓはセカンダリーを、ｔはターシャリーを、それぞれ表す。 The alkyl group having 1 to 20 carbon atoms may be linear or branched.
Specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl- n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n- Butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, Examples include n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicosyl groups.
Note that n represents normal, i represents iso, s represents secondary, and t represents tertiary.
　炭素数１から２０のヒドロキシアルキル基としては、ヒドロキシ基がアルキル基の末端に置換したものが好ましく、ヒドロキシメチル、２－ヒドロキシエチル、３－ヒドロキシプロピル、４－ヒドロキシブチル、５－ヒドロキシペンチル、６－ヒドロキシヘキシル、７－ヒドロキシヘプチル、８－ヒドロキシオクチル、９－ヒドロキシノニル、１０－ヒドロキシデシル、１１－ヒドロキシウンデシル、１２－ヒドロキシドデシル、１３－ヒドロキシトリデシル、１４－ヒドロキシテトラデシル、１５－ヒドロキシペンタデシル、１６－ヒドロキシヘキサデシル、１７－ヒドロキシヘプタデシル、１８－ヒドロキシオクタデシル、１９－ヒドロキシノナデシル及び２０－ヒドロキシエイコシル等が一例として挙げられる。 The hydroxyalkyl group having 1 to 20 carbon atoms is preferably a hydroxy group substituted at the terminal of the alkyl group, such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6 -Hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 11-hydroxyundecyl, 12-hydroxydodecyl, 13-hydroxytridecyl, 14-hydroxytetradecyl, 15-hydroxy Examples include pentadecyl, 16-hydroxyhexadecyl, 17-hydroxyheptadecyl, 18-hydroxyoctadecyl, 19-hydroxynonadecyl and 20-hydroxyeicosyl.
　ＧＡまたはＧＭＡに対するカルボン酸化合物の使用量は特に限定されないが、ＧＡまたはＧＭＡを消失させた上で、過剰のカルボン酸化合物を水洗により除去する方法が効率的である。すなわちカルボン酸化合物の量はＧＡまたはＧＭＡに対し１．０当量～３．０当量が好ましい。さらに好ましくは１．０当量～１．２当量である。 The amount of the carboxylic acid compound used with respect to GA or GMA is not particularly limited, but a method of removing excess carboxylic acid compound by washing with water after GA or GMA is eliminated is efficient. That is, the amount of the carboxylic acid compound is preferably 1.0 to 3.0 equivalents relative to GA or GMA. More preferably, it is 1.0 equivalent to 1.2 equivalent.
　反応溶媒としては、反応に不活性なものであれば特に限定はないが、例えば、ヘキサン、シクロヘキサン、ベンゼン、トルエン等の炭化水素類；四塩化炭素、クロロホルム、１，２－ジクロロエタン等のハロゲン系炭化水素類；ジエチルエーテル、ジイソプロピルエーテル、１，４－ジオキサン、テトラヒドロフラン等のエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類；アセトニトリル、プロピオニトリル等のニトリル類；酢酸エチル、プロピオン酸エチル等のカルボン酸エステル類；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、１，３－ジメチル－２－イミダゾリジノン等の含窒素非プロトン性極性溶媒；ジメチルスルホキシド、スルホラン等の含硫黄非プロトン性極性溶媒；ピリジン、ピコリン等のピリジン類等が挙げられる。これらの溶媒は単独で用いても、これらのうちの２種類以上を混合して用いても良い。好ましくはＤＭＦ、酢酸エチル、アセトニトリル、１，４－ジオキサン、であり、さらに好ましくはＤＭＦ、酢酸エチルである。 The reaction solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogens such as carbon tetrachloride, chloroform and 1,2-dichloroethane Hydrocarbons; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; ethyl acetate and ethyl propionate N-containing aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone; Dimethyl sulfoxide, sulfolane, etc. Sulfur aprotic polar solvent; pyridine, pyridines picoline and the like. These solvents may be used alone, or two or more of these may be mixed and used. Preferred are DMF, ethyl acetate, acetonitrile, and 1,4-dioxane, and more preferred are DMF and ethyl acetate.
　溶媒の使用量（反応濃度）は特に限定されないが、溶媒を用いずに反応を実施しても良く、また溶媒を使用する場合にはＧＡまたはＧＭＡに対し、０．１～１００質量倍の溶媒を用いてもよい。好ましくは１～１０質量倍であり、さらに好ましくは２～５質量倍である。 The amount of the solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent. When a solvent is used, the solvent is 0.1 to 100 times the mass of GA or GMA. May be used. The amount is preferably 1 to 10 times by mass, more preferably 2 to 5 times by mass.
　反応温度は特に限定されないが、例えば－９０～２００℃、好ましくは０～１５０℃で、さらに好ましくは５０℃から１２０℃である。 The reaction temperature is not particularly limited, but is, for example, −90 to 200 ° C., preferably 0 to 150 ° C., and more preferably 50 ° C. to 120 ° C.
　反応時間は、通常、０．０５ないし２００時間、好ましくは０．５ないし１００時間である。 The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.
　反応させる際に、重合禁止剤を添加してもよい。そのような重合禁止剤としてはＢＨＴ（２，６－ジ－ターシャリーブチル－パラ－クレゾール）やハイドロキノン、パラ－メトキシフェノールなどを用いることができ、アクリル基、メタクリル基の重合を阻害するものであれば特に限定はされない。 In the reaction, a polymerization inhibitor may be added. As such a polymerization inhibitor, BHT (2,6-di-tert-butyl-para-cresol), hydroquinone, para-methoxyphenol, etc. can be used, which inhibits polymerization of acrylic groups and methacrylic groups. If there is no particular limitation.
　重合禁止剤を添加する場合の添加量は特に限定されないが、アクリル酸エステル化合物（ＧＡ）またはメタクリル酸エステル化合物（ＧMＡ）のモル数に対し、０．００００１モル～０．１モルであり、好ましくは０．００１～０．０１モルである。 The addition amount in the case of adding a polymerization inhibitor is not particularly limited, but is preferably 0.00001 mol to 0.1 mol with respect to the number of moles of the acrylic ester compound (GA) or methacrylic ester compound (GMA). Is 0.001 to 0.01 mol.
　反応時間を短縮させるために触媒を添加してもよく、その例としては、ベンジルトリメチルアンモニウムクロリド（ＢＴＭＡＣ）、ベンジルトリエチルアンモニウムクロリド(ＢＴＥＡＣ)、ベンジルトリメチルアンモニウムブロミド（ＢＴＭＡＢ）、ベンジルトリエチルアンモニウムブロミド(ＢＴＥＡＢ)、テトラブチルアンモニウムクロリド（ＴＢＡＣ）、テトラブチルアンモニウムブロミド（ＴＢＡＢ）などの第４級アンモニウム塩や、テトラフェニルホスホニウムブロミド（ＴＰＰＢ）などの第４級ホスホニウム塩などを挙げることができる。 Catalysts may be added to shorten the reaction time, examples of which include benzyltrimethylammonium chloride (BTMAC), benzyltriethylammonium chloride (BTEAC), benzyltrimethylammonium bromide (BTMAB), benzyltriethylammonium bromide (BTEAB). ), Quaternary ammonium salts such as tetrabutylammonium chloride (TBAC) and tetrabutylammonium bromide (TBAB), and quaternary phosphonium salts such as tetraphenylphosphonium bromide (TPPB).
　触媒としては、塩基触媒を加えてもよく、その例としてはトリエチルアミン、トリメチルアミン、トリプロピルアミン、トリブチルアミン、ジイソプロピルエチルアミン、ピリジン、イミダゾール、Ｎ，Ｎ－ジメチルアミノ－４－ピリジン、１，８－ジアザビシクロ[５．４．０]ウンデセン－７（ＤＢＵ）、１，５－ジアザ－ビシクロ[４．３．０]ノネン－５（ＤＢＮ）などの有機塩基や、アルカリ金属水酸化物、例えば水酸化ナトリウム、水酸化カリウムなど、アルカリ土類金属水酸化物、例えば水酸化カルシウム、水酸化バリウムなど、アルカリ金属炭酸塩、例えば炭酸ナトリウム、炭酸カリウムなど、アルカリ土類金属炭酸塩、例えば炭酸バリウム、炭酸カルシウムなど、アルカリ金属重炭酸塩、例えば炭酸水素ナトリウム、炭酸水素カリウムなど、無機酸のアルカリ金属塩、例えばリン酸２－または３－ナトリウム、リン酸２－または３－カリウムなどの無機塩基が挙げられる。 As the catalyst, a base catalyst may be added, and examples thereof include triethylamine, trimethylamine, tripropylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, N, N-dimethylamino-4-pyridine, 1,8-diazabicyclo Organic bases such as [5.4.0] undecene-7 (DBU), 1,5-diaza-bicyclo [4.3.0] nonene-5 (DBN), alkali metal hydroxides such as sodium hydroxide Alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkaline earth metal carbonates such as barium carbonate and calcium carbonate Alkali metal bicarbonates such as sodium bicarbonate, bicarbonate Alkali metal salts of inorganic acids such as potassium, for example inorganic bases such as 2- or 3-sodium phosphate, 2- or 3-potassium phosphate.
　触媒を添加する場合の添加量は、ＧＡまたはＧＭAの１モルに対し０．００３～１モル使用してもよく、好ましくは０．０３～０．５モル、さらに好ましくは０．０５～０．２モルである。触媒量が多い場合には触媒除去のために多量の水が必要となり、また、経済的にも好ましくない。一方触媒量が少ない場合には反応が遅延し、反応完結までに多大な時間を要するため好ましくない。 When the catalyst is added, the amount added may be 0.003 to 1 mol, preferably 0.03 to 0.5 mol, more preferably 0.05 to 0.00 mol per mol of GA or GMA. 2 moles. When the amount of the catalyst is large, a large amount of water is required for removing the catalyst, and it is not economically preferable. On the other hand, when the amount of the catalyst is small, the reaction is delayed, and it takes a long time to complete the reaction.
　本反応は、常圧または加圧下で行うことができ、また回分式でも連続式でもよい。 This reaction can be carried out at normal pressure or under pressure, and may be batch or continuous.
　反応後は、有機溶媒と水を加えて分液操作を行い、有機相を濃縮してから減圧乾燥すると目的化合物が得られる。 After the reaction, an organic solvent and water are added to carry out a liquid separation operation, and the organic phase is concentrated and then dried under reduced pressure to obtain the target compound.
　水洗に使用する水の量は反応に使用した触媒を除去できる量であればよいが、水の量が多い場合には目的物が水層へ移行してしまい回収率が低下する。そのため、水と水洗溶媒の比率は５対１～１対１００が好ましく、より好ましくは２対１～１対２０である。 The amount of water used for washing may be any amount that can remove the catalyst used in the reaction, but if the amount of water is large, the target product moves to the aqueous layer and the recovery rate decreases. Therefore, the ratio of water to the washing solvent is preferably 5: 1 to 1: 100, more preferably 2: 1 to 1:20.
　上記式［３］で表されるヒドロキシル基を有するアクリルまたはメタクリル化合物（以下、化合物３と略記する）の製造法は、下記の反応スキームで表される。すなわち、下記式（C）で表されるイソシアナトアルキルアクリレート（ＩＡＡ）またはイソシアナトアルキルメタクリレート（ＩＡＭ）と、下記式（Ｄ）で表されるアミン化合物とを反応させることにより、目的の化合物３が製造される。 A method for producing an acrylic or methacrylic compound having a hydroxyl group represented by the above formula [3] (hereinafter abbreviated as compound 3) is represented by the following reaction scheme. That is, by reacting an isocyanatoalkyl acrylate (IAA) or isocyanatoalkyl methacrylate (IAM) represented by the following formula (C) with an amine compound represented by the following formula (D), the desired compound 3 Is manufactured.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　式中、Ｒ5は水素原子またはメチル基であり、Ｒ6は、ヒドロキシル基または炭素数１から２０のヒドロキシルアルキル基であり、Ｒ7及びＲ8は、炭素数１から２０のヒドロキシルアルキル基であり、Lは炭素原子数２乃至２０のアルキレンである。 In the formula, R 5 is a hydrogen atom or a methyl group, R 6 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms, and R 7 and R 8 are a hydroxylalkyl group having 1 to 20 carbon atoms. And L is alkylene having 2 to 20 carbon atoms.
　炭素数１から２０のアルキル基としては、直鎖及び分岐のいずれでもよい。
　その具体例としては、メチル、エチル、ｎ－プロピル、ｉ－プロピル、ｎ－ブチル、ｉ－ブチル、ｓ－ブチル、ｔ－ブチル、ｎ－ペンチル、１－メチル－ｎ－ブチル、２－メチル－ｎ－ブチル、３－メチル－ｎ－ブチル、１，１－ジメチル－ｎ－プロピル、ｎ－ヘキシル、１－メチル－ｎ－ペンチル、２－メチル－ｎ－ペンチル、１，１－ジメチル－ｎ－ブチル、１－エチル－ｎ－ブチル、１，１，２－トリメチル－ｎ－プロピル、ｎ－ヘプチル、ｎ－オクチル、ｎ－ノニル、ｎ－デシル、ｎ－ウンデシル、ｎ－ドデシル、ｎ－トリデシル、ｎ－テトラデシル、ｎ－ペンタデシル、ｎ－ヘキサデシル、ｎ－ヘプタデシル、ｎ－オクタデシル、ｎ－ノナデシル及びｎ－エイコシル基等が一例として挙げられる。
なお、ｎはノルマルを、ｉはイソを、ｓはセカンダリーを、ｔはターシャリーを、それぞれ表す。 The alkyl group having 1 to 20 carbon atoms may be linear or branched.
Specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl- n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n- Butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, Examples include n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicosyl groups.
Note that n represents normal, i represents iso, s represents secondary, and t represents tertiary.
　炭素数１から２０のヒドロキシアルキル基としては、ヒドロキシ基がアルキル基の末端に置換したものが好ましく、ヒドロキシメチル、２－ヒドロキシエチル、３－ヒドロキシプロピル、４－ヒドロキシブチル、５－ヒドロキシペンチル、６－ヒドロキシヘキシル、７－ヒドロキシヘプチル、８－ヒドロキシオクチル、９－ヒドロキシノニル、１０－ヒドロキシデシル、１１－ヒドロキシウンデシル、１２－ヒドロキシドデシル、１３－ヒドロキシトリデシル、１４－ヒドロキシテトラデシル、１５－ヒドロキシペンタデシル、１６－ヒドロキシヘキサデシル、１７－ヒドロキシヘプタデシル、１８－ヒドロキシオクタデシル、１９－ヒドロキシノナデシル及び２０－ヒドロキシエイコシル等が一例として挙げられる。 The hydroxyalkyl group having 1 to 20 carbon atoms is preferably a hydroxy group substituted at the terminal of the alkyl group, such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6 -Hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 11-hydroxyundecyl, 12-hydroxydodecyl, 13-hydroxytridecyl, 14-hydroxytetradecyl, 15-hydroxy Examples include pentadecyl, 16-hydroxyhexadecyl, 17-hydroxyheptadecyl, 18-hydroxyoctadecyl, 19-hydroxynonadecyl and 20-hydroxyeicosyl.
　炭素数２から２０のアルキレンとしては、上記炭素数１～２０のアルキル基のうち、炭素原子数２以上のものから水素原子をさらに１つ取り去った２価の基が挙げられる。 Examples of the alkylene having 2 to 20 carbon atoms include divalent groups in which one hydrogen atom is further removed from the above alkyl group having 1 to 20 carbon atoms having 2 or more carbon atoms.
　アミン化合物に対するＩＡＡまたはＩＡＭの使用量は特に限定されないが、アミン化合物に対し、０．９当量～３．０当量が好ましい。さらに好ましくは１．０当量～１．２当量である。 The amount of IAA or IAM used with respect to the amine compound is not particularly limited, but is preferably 0.9 equivalent to 3.0 equivalent with respect to the amine compound. More preferably, it is 1.0 equivalent to 1.2 equivalent.
　反応溶媒としては、反応に不活性なものであれば特に限定はないが、例えば、ヘキサン、シクロヘキサン、ベンゼン、トルエン等の炭化水素類；四塩化炭素、クロロホルム、１，２－ジクロロエタン等のハロゲン系炭化水素類；ジエチルエーテル、ジイソプロピルエーテル、１，４－ジオキサン、テトラヒドロフラン等のエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類；アセトニトリル、プロピオニトリル等のニトリル類；酢酸エチル、プロピオン酸エチル等のカルボン酸エステル類；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、１，３－ジメチル－２－イミダゾリジノン等の含窒素非プロトン性極性溶媒；ジメチルスルホキシド、スルホラン等の含硫黄非プロトン性極性溶媒；ピリジン、ピコリン等のピリジン類等が挙げられる。これらの溶媒は単独で用いても、これらのうちの２種類以上を混合して用いても良い。中でも、得られる化合物３をろ過で簡便に単離することができるという点で、ＩＡＡやＩＭＡは溶解するが化合物３を溶解しにくい溶媒が好ましく、そのような溶媒として好ましくはテトラヒドロフラン、酢酸エチル、トルエン、アセトニトリルであり、さらに好ましくはテトラヒドロフランである。 The reaction solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene; halogens such as carbon tetrachloride, chloroform and 1,2-dichloroethane Hydrocarbons; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitriles such as acetonitrile and propionitrile; ethyl acetate and ethyl propionate N-containing aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone; Dimethyl sulfoxide, sulfolane, etc. Sulfur aprotic polar solvent; pyridine, pyridines picoline and the like. These solvents may be used alone, or two or more of these may be mixed and used. Among them, a solvent that dissolves IAA and IMA but hardly dissolves compound 3 is preferable in that compound 3 obtained can be easily isolated by filtration. Such solvents are preferably tetrahydrofuran, ethyl acetate, Toluene and acetonitrile are preferable, and tetrahydrofuran is more preferable.
　溶媒の使用量（反応濃度）は特に限定されないが、溶媒を用いずに反応を実施しても良く、また溶媒を使用する場合にはＩＡＡまたはＩＡＭに対し、０．１～１００質量倍の溶媒を用いてもよい。好ましくは１～１０質量倍であり、さらに好ましくは２～５質量倍である。 The amount of the solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent, and when a solvent is used, the solvent is 0.1 to 100 times by mass with respect to IAA or IAM. May be used. The amount is preferably 1 to 10 times by mass, more preferably 2 to 5 times by mass.
　反応温度は特に限定されないが、例えば－９０～２００℃、好ましくは－５０～１５０℃で、さらに好ましくは－２０℃から１２０℃である。 The reaction temperature is not particularly limited, but is, for example, −90 to 200 ° C., preferably −50 to 150 ° C., and more preferably −20 ° C. to 120 ° C.
　反応時間は、通常、０．０５ないし２００時間、好ましくは０．５ないし１００時間である。 The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.
　反応させる際に、重合禁止剤を添加してもよい。そのような重合禁止剤としてはＢＨＴ（２，６－ジ－ターシャリーブチル－パラ－クレゾール）やハイドロキノン、パラ－メトキシフェノールなどを用いることができ、アクリル基、メタクリル基の重合を阻害するものであれば特に限定はされない。 In the reaction, a polymerization inhibitor may be added. As such a polymerization inhibitor, BHT (2,6-di-tert-butyl-para-cresol), hydroquinone, para-methoxyphenol, etc. can be used, which inhibits polymerization of acrylic groups and methacrylic groups. If there is no particular limitation.
　重合禁止剤を添加する場合の添加量は特に限定されないが、アクリル酸エステル化合物（ＩＡＡ）またはメタクリル酸エステル化合物（ＩＡＭ）のモル数に対し、０．００００１モル～０．１モルであり、好ましくは０．００１～０．０１モルである。 The addition amount in the case of adding a polymerization inhibitor is not particularly limited, but is preferably 0.00001 mol to 0.1 mol with respect to the number of moles of the acrylic ester compound (IAA) or the methacrylic ester compound (IAM). Is 0.001 to 0.01 mol.
　反応時間を短縮させるために触媒を添加してもよく、その例としては、ベンジルトリメチルアンモニウムクロリド（ＢＴＭＡＣ）、ベンジルトリエチルアンモニウムクロリド(ＢＴＥＡＣ)、ベンジルトリメチルアンモニウムブロミド（ＢＴＭＡＢ）、ベンジルトリエチルアンモニウムブロミド(ＢＴＥＡＢ)、テトラブチルアンモニウムクロリド（ＴＢＡＣ）、テトラブチルアンモニウムブロミド（ＴＢＡＢ）などの第４級アンモニウム塩や、テトラフェニルホスホニウムブロミド（ＴＰＰＢ）などの第４級ホスホニウム塩などを挙げることができる。 Catalysts may be added to shorten the reaction time, examples of which include benzyltrimethylammonium chloride (BTMAC), benzyltriethylammonium chloride (BTEAC), benzyltrimethylammonium bromide (BTMAB), benzyltriethylammonium bromide (BTEAB). ), Quaternary ammonium salts such as tetrabutylammonium chloride (TBAC) and tetrabutylammonium bromide (TBAB), and quaternary phosphonium salts such as tetraphenylphosphonium bromide (TPPB).
　触媒としては、塩基触媒を加えてもよく、その例としてはトリエチルアミン、トリメチルアミン、トリプロピルアミン、トリブチルアミン、ジイソプロピルエチルアミン、ピリジン、イミダゾール、Ｎ，Ｎ－ジメチルアミノ－４－ピリジン、１，８－ジアザビシクロ[５．４．０]ウンデセン－７（ＤＢＵ）、１，５－ジアザ－ビシクロ[４．３．０]ノネン－５（ＤＢＮ）などの有機塩基や、アルカリ金属水酸化物、例えば水酸化ナトリウム、水酸化カリウムなど、アルカリ土類金属水酸化物、例えば水酸化カルシウム、水酸化バリウムなど、アルカリ金属炭酸塩、例えば炭酸ナトリウム、炭酸カリウムなど、アルカリ土類金属炭酸塩、例えば炭酸バリウム、炭酸カルシウムなど、アルカリ金属重炭酸塩、例えば炭酸水素ナトリウム、炭酸水素カリウムなど、無機酸のアルカリ金属塩、例えばリン酸２－または３－ナトリウム、リン酸２－または３－カリウムなどの無機塩基が挙げられる。 As the catalyst, a base catalyst may be added, and examples thereof include triethylamine, trimethylamine, tripropylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, N, N-dimethylamino-4-pyridine, 1,8-diazabicyclo Organic bases such as [5.4.0] undecene-7 (DBU), 1,5-diaza-bicyclo [4.3.0] nonene-5 (DBN), alkali metal hydroxides such as sodium hydroxide Alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkaline earth metal carbonates such as barium carbonate and calcium carbonate Alkali metal bicarbonates such as sodium bicarbonate, bicarbonate Alkali metal salts of inorganic acids such as potassium, for example inorganic bases such as 2- or 3-sodium phosphate, 2- or 3-potassium phosphate.
　触媒を添加する場合の添加量は、ＩＡＡまたはＩＡＭの１モルに対し０．００１～１モル使用してもよく、好ましくは０．００５～０．５モル、さらに好ましくは０．０１～０．２モルである。 When the catalyst is added, the amount added may be 0.001 to 1 mol, preferably 0.005 to 0.5 mol, more preferably 0.01 to 0.00 mol per mol of IAA or IAM. 2 moles.
　本反応は、常圧または加圧下で行うことができ、また回分式でも連続式でもよい。 This reaction can be carried out at normal pressure or under pressure, and may be batch or continuous.
　反応後は、析出してくる化合物３の結晶をろ過で取り、テトラヒドロフランまたは酢酸エチル等の溶媒で洗浄すると目的化合物が得られる。このように簡便な方法で目的物を単離することができる点が、本発明の製法の特徴である。 After the reaction, the precipitated compound 3 crystals are collected by filtration and washed with a solvent such as tetrahydrofuran or ethyl acetate to obtain the target compound. A feature of the production method of the present invention is that the target product can be isolated by such a simple method.
　以下に実施例を挙げ、本発明を更に詳しく説明するが、本発明はこれらに限定されるものではない。
　なお、本発明における略号はそれぞれ以下の意味を示す。
ＧＭＡ：グリシジルメタクリレート
２ＨＭ－ＰＡ：２，２－ビス（ヒドロキシメチル）プロピオン酸
ＢＨＴ：２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール
ＢＴＭＡＣ：ベンジルトリメチルアンモニウムクロリド
ＢＴＥＡＣ：ベンジルトリエチルアンモニウムクロリド
ＴＰＰＢ：テトラフェニルホスホニウムブロミド
ＤＭＦ：ジメチルホルムアミド The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
In addition, the symbol in this invention shows the following meaning, respectively.
GMA: glycidyl methacrylate 2HM-PA: 2,2-bis (hydroxymethyl) propionic acid BHT: 2,6-di-tert-butyl-p-cresol BTMAC: benzyltriethylammonium chloride BTEAC: benzyltriethylammonium chloride TPPB: tetraphenyl Phosphonium bromide DMF: dimethylformamide
実施例１：２，２－ビス（ヒドロキシメチル）プロピオン酸　２－ヒドロキシ－３－メタクリロイルオキシプロピルの合成 Example 1: Synthesis of 2,2-bis (hydroxymethyl) propionic acid 2-hydroxy-3-methacryloyloxypropyl
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　窒素気流下中、３ｌ四つ口フラスコに酢酸エチル１２００．０ｇ、ＧＭＡ４００．０ｇ（２．８１mol）及び２ＨＭ－ＰＡ３９６．３ｇ（２．９５mol）、ＢＨＴ４．０ｇ（１８.１５mmol）、ＢＴＥＡＣ６４．０９ｇ（０．２８mol）を室温にて仕込み、マグネチックスターラー攪拌下にて８０℃まで昇温し、２３時間加熱撹拌した。反応液を高速液体クロマトグラフィーにて分析した結果、ＧＭＡが０．５面積％、ＧＭＡ－２ＨＭ－ＰＡＥが６９．５面積％、二種の副生成物がそれぞれ２７．６面積％、１．９面積％であった。
　その後この反応液を室温まで冷却した後、反応液に酢酸エチル２６９８．４ｇを加え、攪拌して均一溶液とした後、続いて純水を４３２．２ｇ加え、分液ロートにて水洗を実施し、水層を廃棄した。この水洗操作を２回繰り返した後、硫酸マグネシウム２６２．２ｇを加え、１時間攪拌後、硫酸マグネシウムをろ過し、ろ液をエバポレーターにて４５℃で完全濃縮し、オイル状物質を５８３．１ｇ（２．１１mol、収率７５．１％）得た。このオイル状物質は、1Ｈ－ＮＭＲ分析結果より、２，２－ビス（ヒドロキシメチル）プロピオン酸　２－ヒドロキシ－３－メタクリロイルオキシプロピル（以下、ＧＭＡ－２ＨＭ－ＰＡＥと称する）であることを確認した。
　化合物［２］の構造は、1Ｈ－ＮＭＲ分析により以下のスペクトルデータを得て確認した。
　1Ｈ－ＮＭＲ（ＣＤＣｌ3）：δ６．０７－６．０５（m，１Ｈ），５．６９（ｓ，１Ｈ），５．２９（ｓ，１Ｈ），５．０３－４．９３（ｍ，１Ｈ），４．６６－４．６０（ｍ，１Ｈ），４．２０－４．００（ｍ，４Ｈ），３．６１－３．３７（ｍ，４Ｈ），１．８９（ｓ，３Ｈ），１．１３－１．０２（ｍ，３Ｈ）. Under a nitrogen stream, 1200.0 g of ethyl acetate, 400.0 g (2.81 mol) of GMA and 396.3 g (2.95 mol) of 2HM-PA, 4.0 g (18.15 mmol) of BHT, 64.09 g of BTEAC (in a nitrogen gas stream) 0.28 mol) was charged at room temperature, heated to 80 ° C. with magnetic stirrer stirring, and heated and stirred for 23 hours. The reaction solution was analyzed by high performance liquid chromatography. As a result, GMA was 0.5 area%, GMA-2HM-PAE was 69.5 area%, and two by-products were 27.6 area% and 1.9, respectively. Area%.
After cooling the reaction solution to room temperature, 2698.4 g of ethyl acetate was added to the reaction solution, and the mixture was stirred to obtain a homogeneous solution. Subsequently, 432.2 g of pure water was added, followed by washing with a separatory funnel. The aqueous layer was discarded. After repeating this washing operation twice, 262.2 g of magnesium sulfate was added, and the mixture was stirred for 1 hour, and then the magnesium sulfate was filtered. The filtrate was completely concentrated at 45 ° C. with an evaporator, and 583.1 g ( 2.11 mol, yield 75.1%). This oily substance was confirmed to be 2,2-bis (hydroxymethyl) propionic acid 2-hydroxy-3-methacryloyloxypropyl (hereinafter referred to as GMA-2HM-PAE) from 1 H-NMR analysis results. did.
The structure of the compound [2] was confirmed by obtaining the following spectral data by 1 H-NMR analysis.
1 H-NMR (CDCl 3 ): δ 6.07-6.05 (m, 1H), 5.69 (s, 1H), 5.29 (s, 1H), 5.03-4.93 (m, 1H), 4.66-4.60 (m, 1H), 4.20-4.00 (m, 4H), 3.61-3.37 (m, 4H), 1.89 (s, 3H) 1.13-1.02 (m, 3H).
実施例２
　水洗操作までは実施例１と同様の操作を実施し、水洗後、以下操作を行った。水洗を２回行った後の有機層にＰＧＭＥ８０３．０ｇ、硫酸マグネシウム２６２．２ｇを加え、１時間攪拌後、硫酸マグネシウムをろ過し、ろ液をエバポレーターにて４５℃、１００Ｔｏｒｒにて溶媒が留去しなくなるまで濃縮し、１１０２．２ｇの溶液を得た。この溶液は、高速液体クロマトグラフィーによる定量分析結果より、ＧＭＡ－２ＨＭ－ＰＡＥの５２．９ｗｔ％溶液であることを確認した。 Example 2
The same operation as Example 1 was implemented until the water washing operation, and the following operation was performed after water washing. 803.0 g of PGME and 262.2 g of magnesium sulfate were added to the organic layer after washing twice, and after stirring for 1 hour, the magnesium sulfate was filtered. The filtrate was distilled off at 45 ° C. with an evaporator at 100 Torr. Concentrate until no more to give 1102.2 g of solution. This solution was confirmed to be a 52.9 wt% solution of GMA-2HM-PAE from the results of quantitative analysis by high performance liquid chromatography.
実施例３
　窒素気流下中、３ｌ四つ口フラスコにＤＭＦ１３５０．０ｇ、ＧＭＡ４５８．２ｇ(３．２２mol)及び２ＨＭ－ＰＡ５２８．８ｇ（３．９４mol）、ＢＨＴ４．６ｇ（２０．８７mmol）、ＢＴＭＡＣ１３．５ｇ（７２．７０mmol）を室温にて仕込み、マグネチックスターラー攪拌下にて８０℃まで昇温し、２４時間加熱撹拌した。ＧＭＡが０．５面積％未満となったことを確認し、ＤＭＦを濃縮した。ＤＭＦ濃縮液へ酢酸エチル４１０１．０ｇを加え、続いて純水を４０５９．０ｇ加え、分液ロートにて水洗を実施し、水層を廃棄した。有機層に硫酸マグネシウム２６２．０ｇを加え、１時間攪拌後、硫酸マグネシウムをろ過し、ろ液をエバポレーターにて４５℃で完全濃縮し、オイル状物質を３７７．２ｇ得た。このオイル状物質は、1Ｈ－ＮＭＲ分析結果より、ＧＭＡ－２ＨＭ－ＰＡＥであることを確認した。 Example 3
Under a nitrogen stream, DMF 1350.0 g, GMA 458.2 g (3.22 mol) and 2HM-PA 528.8 g (3.94 mol), BHT 4.6 g (20.87 mmol), BTMAC 13.5 g (72. 70 mmol) was charged at room temperature, heated to 80 ° C. with magnetic stirring, and stirred for 24 hours. After confirming that GMA was less than 0.5 area%, DMF was concentrated. To the DMF concentrate, 4101.0 g of ethyl acetate was added, followed by 4059.0 g of pure water, washed with water in a separatory funnel, and the aqueous layer was discarded. 262.0 g of magnesium sulfate was added to the organic layer, and after stirring for 1 hour, the magnesium sulfate was filtered. The filtrate was completely concentrated at 45 ° C. with an evaporator to obtain 377.2 g of an oily substance. This oily substance was confirmed to be GMA-2HM-PAE from 1 H-NMR analysis results.
実施例４
　一連の操作は実施例１と同様に実施し、触媒のみＢＴＭＡＣに変更して２１時間加熱撹拌した。反応液を高速液体クロマトグラフィーにて分析した結果、ＧＭＡが０．５面積％以下であることを確認した。 Example 4
A series of operations were carried out in the same manner as in Example 1. Only the catalyst was changed to BTMAC, and the mixture was heated and stirred for 21 hours. As a result of analyzing the reaction solution by high performance liquid chromatography, it was confirmed that GMA was 0.5 area% or less.
実施例５
　一連の操作は実施例１と同様に実施し、触媒のみＴＰＰＢに変更して実施し、２１時間加熱撹拌した。反応液を高速液体クロマトグラフィーにて分析した結果、ＧＭＡが０．５面積％以下であることを確認した。 Example 5
A series of operations were carried out in the same manner as in Example 1. The catalyst was changed to TPPB, and the mixture was heated and stirred for 21 hours. As a result of analyzing the reaction solution by high performance liquid chromatography, it was confirmed that GMA was 0.5 area% or less.
実施例６
　一連の操作は実施例１と同様に実施し、触媒のみＢＴＭＡＣに変更して実施し、触媒量をＧＭＡのモル数に対し０．０２５モル使用した。２１時間後に反応液を高速液体クロマトグラフィーにて分析した結果、ＧＭＡが１７．５面積％残存しており、ＧＭＡが０．５面積％以下であることが確認されたのは４４時間後であった。 Example 6
A series of operations were carried out in the same manner as in Example 1, except that only the catalyst was changed to BTMAC, and the amount of catalyst was 0.025 mol relative to the number of moles of GMA. As a result of analyzing the reaction solution by high performance liquid chromatography after 21 hours, it was confirmed that 17.5 area% GMA remained and GMA was 0.5 area% or less after 44 hours. It was.
Figure JPOXMLDOC01-appb-T000022
 　
Figure JPOXMLDOC01-appb-T000022
 　
＜実施例７および比較例１＞
　ＣＩＮ１：６－ヒドロキシヘキシルオキシけい皮酸メチルエステル <Example 7 and Comparative Example 1>
CIN1: 6-hydroxyhexyloxycinnamic acid methyl ester
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　ＣＩＮ２：３－メトキシ－６－ヒドロキシヘキシルオキシけい皮酸メチルエステル CIN2: 3-methoxy-6-hydroxyhexyloxycinnamic acid methyl ester
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
＜ヒドロキシ基およびカルボキシル基を有するポリマー＞
　ＰＥＰＯ：ポリエステルポリオール重合体 <Polymer having hydroxy group and carboxyl group>
PEPO: Polyester polyol polymer
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
（上記式中、Ｒは、アルキレンを表す。）
＜架橋剤＞
　ＨＭＭ：下記の構造式で表されるメラミン架橋剤 (In the above formula, R represents alkylene.)
<Crosslinking agent>
HMM: Melamine crosslinking agent represented by the following structural formula
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
＜架橋触媒＞
ＰＴＳＡ：パラトルエンスルホン酸 <Crosslinking catalyst>
PTSA: p-toluenesulfonic acid
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
＜ヒドロキシ基およびアクリル基を有する化合物＞
ＧＭＡ－２ＨＭ－ＰＡＥ
Figure JPOXMLDOC01-appb-C000028
 <Compound having a hydroxy group and an acrylic group>
GMA-2HM-PAE
Figure JPOXMLDOC01-appb-C000028
＜溶剤＞
　実施例および比較例の各硬化膜形成組成物は溶剤を含有し、その溶剤として、プロピレングリコールモノメチルエーテル（ＰＭ－Ｐ）と酢酸エチルを用いた。 <Solvent>
Each of the cured film forming compositions of Examples and Comparative Examples contained a solvent, and propylene glycol monomethyl ether (PM-P) and ethyl acetate were used as the solvent.
　表２に示す組成にて実施例７および比較例１の各硬化膜形成組成物を調製した。次に、各硬化膜形成組成物を用い、硬化膜を形成し、得られた硬化膜のそれぞれについて、密着性、配向感度、パターン形成性、および透過率の評価を行った。 Each cured film forming composition of Example 7 and Comparative Example 1 was prepared with the composition shown in Table 2. Next, a cured film was formed using each cured film forming composition, and adhesion, orientation sensitivity, pattern formability, and transmittance were evaluated for each of the obtained cured films.
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000029
［密着性の評価］
　実施例および比較例の各硬化膜形成組成物をＴＡＣフィルム上にバーコータを用いて塗布した後、温度１１０℃で１２０秒間、熱循環式オーブン中で加熱乾燥を行い、硬化膜を形成した。この各硬化膜に３１３ｎｍの直線偏光を垂直に２０ｍＪ／ｃｍ2～４０ｍＪ／ｃｍ2照射した。露光後の基板上の硬化膜の上に、メルク株式会社製の水平配向用重合性液晶溶液ＲＭＳ０３－０１３Ｃを、スピンコータを用いて塗布し、次いで、６０℃で６０秒間ホットプレート上においてプリベークを行い、膜厚１．０μｍの塗膜を形成した。このフィルムを１０００ｍＪ／ｃｍ2で露光し、重合性液晶を重合させて、位相差材を作製した。得られた基板上の位相差材にカッターナイフを用いてクロスカット（１ｍｍ×１ｍｍ×１００マス）を入れ、その後、セロハンテープを貼り付けた。次いで、そのセロハンテープを剥がした時に、基板上の位相差材において、重合した重合性液晶の膜が下層の硬化膜上で剥がれず残っているマス目の個数をカウントした。評価結果は、「初期」とし、（膜が剥がれず残っているマス目の数）／１００の形式で、表２にまとめて示した。膜が剥がれず残っているマス目が９０個以上残っているもの、すなわち、９０／１００～１００／１００の場合を密着性が良好であると判断した。 [Evaluation of adhesion]
Each cured film forming composition of Examples and Comparative Examples was applied on a TAC film using a bar coater, and then heated and dried in a heat circulation oven at a temperature of 110 ° C. for 120 seconds to form a cured film. The linearly polarized light of 313nm was vertically 20mJ / cm 2 ~ 40mJ / cm 2 was irradiated to the cured film. On the cured film on the substrate after the exposure, a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, and then pre-baked on a hot plate at 60 ° C. for 60 seconds. A film having a thickness of 1.0 μm was formed. This film was exposed at 1000 mJ / cm 2 to polymerize the polymerizable liquid crystal to produce a retardation material. A crosscut (1 mm × 1 mm × 100 squares) was put into the retardation material on the obtained substrate using a cutter knife, and then a cellophane tape was attached. Next, when the cellophane tape was peeled off, the number of squares remaining in the retardation material on the substrate where the polymerized polymerizable liquid crystal film was not peeled off on the lower cured film was counted. The evaluation results are “initial” and are shown in Table 2 in the form of (number of cells remaining without peeling off the film) / 100. Adhesiveness was judged to be good when 90 or more squares remained without peeling off the film, that is, 90/100 to 100/100.
［耐久密着性の評価］
　上述の密着性の評価と同様に方法でＴＡＣフィルム上に位相差材を、温度８０℃湿度９０％に設定されたオーブンに入れ、２４時間以上静置した。その後、位相差材を取り出し、上述の密着性の評価と同様に方法で、密着性を評価した。評価結果は、密着耐久性として、表２にまとめて示した。 [Evaluation of durability adhesion]
The retardation material was placed on the TAC film in the same manner as in the above-described evaluation of the adhesiveness in an oven set at a temperature of 80 ° C. and a humidity of 90%, and allowed to stand for 24 hours or more. Thereafter, the phase difference material was taken out, and the adhesion was evaluated by the same method as in the above-described evaluation of adhesion. The evaluation results are shown in Table 2 as adhesion durability.
［配向感度の評価］
　実施例および比較例の各硬化膜形成組成物をアルカリガラス上にスピンコータを用いて２０００ｒｐｍで３０秒間回転塗布した後、温度１１０℃で１２０秒間、熱循環式オーブン中で加熱乾燥を行い、硬化膜を形成した。この各硬化膜に３１３ｎｍの直線偏光を垂直に照射し、配向材を形成した。基板上の配向材の上に、メルク株式会社製の水平配向用重合性液晶溶液ＲＭＳ０３－０１３Ｃを、スピンコータを用いて塗布し、次いで、６０℃で６０秒間ホットプレート上においてプリベークを行い、膜厚１．０μｍの塗膜を形成した。この基板上の塗膜を１０００ｍＪ／ｃｍ2で露光し、位相差材を作製した。作製した基板上の位相差材を一対の偏光板で挟み込み、位相差材における位相差特性の発現状況を観察し、配向材が液晶配向性を示すのに必要な偏光ＵＶの露光量を配向感度とした。評価結果は、後に表２にまとめて示す。実施例１～実施例３および比較例の各硬化膜形成組成物を用いて形成された配向材は、液晶配向性を示すのに必要な偏光ＵＶの露光量がいずれも２０ｍＪ／ｃｍ2～４０ｍＪ／ｃｍ2と低い値であり、良好な配向感度を示した。 [Evaluation of orientation sensitivity]
Each of the cured film forming compositions of Examples and Comparative Examples was spin-coated on an alkali glass at 2000 rpm for 30 seconds using a spin coater, and then heated and dried in a thermal circulation oven at a temperature of 110 ° C. for 120 seconds to obtain a cured film. Formed. Each cured film was vertically irradiated with 313 nm linearly polarized light to form an alignment material. On the alignment material on the substrate, a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, and then pre-baked on a hot plate at 60 ° C. for 60 seconds to obtain a film thickness. A 1.0 μm coating film was formed. The coating film on this substrate was exposed at 1000 mJ / cm 2 to produce a retardation material. The retardation material on the prepared substrate is sandwiched between a pair of polarizing plates, the state of retardation property development in the retardation material is observed, and the exposure amount of polarized UV necessary for the alignment material to exhibit liquid crystal alignment is determined. It was. The evaluation results are summarized in Table 2 later. The alignment materials formed using each of the cured film forming compositions of Examples 1 to 3 and Comparative Example each have an exposure amount of polarized UV necessary to exhibit liquid crystal alignment of 20 mJ / cm 2 to 40 mJ. The value was as low as / cm 2 , indicating good alignment sensitivity.
［パターン形成性の評価］
　実施例および比較例の各硬化膜形成組成物をＴＡＣフィルム上にバーコータを用いて塗布した後、温度１１０℃で１２０秒間、熱循環式オーブン中で加熱乾燥を行い、硬化膜を形成した。この硬化膜に３５０μｍのラインアンドスペースマスクを介し３１３ｎｍの直線偏光を４０ｍＪ／ｃｍ2垂直に照射した。次に、マスクを取り外し、基板を９０度回転させた後、３１３ｎｍの直線偏光を２０ｍＪ／ｃｍ2垂直に照射し、液晶の配向制御方向が９０度異なる２種類の液晶配向領域が形成された配向材を得た。この基板上の配向材の上に、メルク株式会社製の水平配向用重合性液晶溶液ＲＭＳ０３－０１３Ｃを、スピンコータを用いて塗布し、次いで、６０℃で６０秒間ホットプレート上においてプリベークを行い、膜厚１．０μｍの塗膜を形成した。この基板上の塗膜を１０００ｍＪ／ｃｍ2で露光し、異なる位相差特性を有する２種類の領域が規則的に配列されたパターン化位相差材を作製した。作製した基板上のパターン化位相差材を、偏光顕微鏡を用いて観察し、配向欠陥なく位相差パターンが形成されているものを○、配向欠陥が見られるものを×として評価した。評価結果は、後に表３に示す。 [Evaluation of pattern formability]
Each cured film forming composition of Examples and Comparative Examples was applied on a TAC film using a bar coater, and then heated and dried in a heat circulation oven at a temperature of 110 ° C. for 120 seconds to form a cured film. This cured film was irradiated with 313 nm linearly polarized light vertically through a 350 μm line and space mask at 40 mJ / cm 2 . Next, after removing the mask and rotating the substrate by 90 degrees, 313 nm linearly polarized light was irradiated at 20 mJ / cm 2 perpendicularly to form an alignment in which two types of liquid crystal alignment regions differing in the liquid crystal alignment control direction by 90 degrees were formed. I got the material. On the alignment material on the substrate, a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, and then pre-baked on a hot plate at 60 ° C. for 60 seconds to form a film. A coating film having a thickness of 1.0 μm was formed. The coating film on this substrate was exposed at 1000 mJ / cm 2 to prepare a patterned retardation material in which two types of regions having different retardation characteristics were regularly arranged. The patterned phase difference material on the produced substrate was observed using a polarizing microscope, and evaluation was made with ◯ indicating that the phase difference pattern was formed without alignment defects, and × indicating that the alignment defects were observed. The evaluation results are shown later in Table 3.
［光透過率（透明性）の評価］
　実施例および比較例の各硬化膜形成組成物を石英基板上にスピンコータを用いて２０００ｒｐｍで３０秒間回塗布した後、温度１１０℃で１２０秒間ホットプレート上において加熱乾燥ベークを行い膜厚３００ｎｍの硬化膜を形成した。膜厚はＦＩＬＭＥＴＲＩＣＳ社製　Ｆ２０を用いて測定した。この硬化膜を紫外線可視分光光度計（（株）島津製作所製ＳＨＩＭＡＤＺＵ　ＵＶ－２５５０型番）を用いて波長４００ｎｍの光に対する透過率を測定した。 [Evaluation of light transmittance (transparency)]
Each of the cured film forming compositions of Examples and Comparative Examples was applied on a quartz substrate for 30 seconds at 2000 rpm using a spin coater, and then heat-dried and baked on a hot plate at 110 ° C. for 120 seconds to cure to a thickness of 300 nm. A film was formed. The film thickness was measured using F20 manufactured by FILMETRICS. The cured film was measured for transmittance with respect to light having a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SHIMADZU UV-2550 model number, manufactured by Shimadzu Corporation).
［評価の結果］
　以上の評価を行った結果を、上述したように、表３に示す。 [Evaluation results]
The results of the above evaluation are shown in Table 3 as described above.
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030
　実施例７の硬化膜形成組成物を用いて得られた硬化膜は、高温高湿処理しても高い密着性を維持し、優れた密着耐久性を示した。それに対し、比較例１の硬化膜形成組成物を用いて得られた硬化膜は、高温高湿処理後、初期の密着性を維持することが困難であった。 The cured film obtained using the cured film forming composition of Example 7 maintained high adhesion even after high temperature and high humidity treatment, and exhibited excellent adhesion durability. On the other hand, the cured film obtained using the cured film-forming composition of Comparative Example 1 was difficult to maintain the initial adhesion after the high temperature and high humidity treatment.
　実施例７の硬化膜形成組成物を用いて得られた配向材は、比較例の硬化膜形成組成物を用いて得られた配向材と同様に、液晶配向性を示すのに必要な偏光ＵＶの露光量がいずれも２０ｍＪ／ｃｍ2～４０ｍＪ／ｃｍ2と低い値であり、良好な配向感度を示した。 The alignment material obtained using the cured film-forming composition of Example 7 was polarized UV necessary for exhibiting liquid crystal alignment properties, similar to the alignment material obtained using the cured film-forming composition of Comparative Example. the amount of exposure are both a low and 20mJ / cm 2 ~ 40mJ / cm 2, it showed a good alignment sensitivity.
　実施例７の硬化膜形成組成物を用いて得られた配向材は、比較例の硬化膜形成組成物を用いて得られた配向材と同様に、良好なパターン形成性を示した。 The alignment material obtained using the cured film-forming composition of Example 7 showed good pattern-forming properties, similar to the alignment material obtained using the cured film-forming composition of the comparative example.
　実施例７の硬化膜形成組成物を用いて得られた硬化膜は、比較例の硬化膜形成組成物を用いて得られた硬化膜と同様に、波長４００ｎｍの光に対して、１００％の透過率を示し、良好な光透過特性を示した。 The cured film obtained using the cured film-forming composition of Example 7 was 100% of light having a wavelength of 400 nm, similarly to the cured film obtained using the cured film-forming composition of the comparative example. The transmittance was shown and good light transmission characteristics were exhibited.
　以上の実施例と比較例により、本願発明の化合物は、硬化膜形成組成物の密着耐久性を向上させる効果を有しており、また、光透過性やパターン形成性等の特性には影響を与えないことが確認された。 From the above examples and comparative examples, the compound of the present invention has the effect of improving the adhesion durability of the cured film-forming composition, and also affects the properties such as light transmittance and pattern formability. It was confirmed not to give.
実施例８
２－（３－（１，３－ジヒドロキシ－２－（ヒドロキシメチル）プロパン－２－イル）ウレイド）エチルメタクリレートの合成
Figure JPOXMLDOC01-appb-C000031
 　窒素気流下中、ＴＨＦ（テトラヒドロフラン）１００ｍｌ、ＴＨＡＭ（トリスヒドロキシメチルアミノメタン）２．４２ｇ（２０．０mmol）及びＢＨＴ（２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール）３３．０ｍｇ（０．１５０mmol）を２５℃にて仕込み、マグネチックスターラー攪拌下で２－ＩＥＭ（２－イソシアナトエチルメタクリレート）３．２６ｇ（２１．０mmol）を加えた。そのまま２５℃で２４時間攪拌した後、析出した結晶をろ過し、ろ取した結晶をテトラヒドロフラン２０ｍｌで２回洗浄し、結晶を乾燥させて白色固体の２－（３－（１，３－ジヒドロキシ－２－（ヒドロキシメチル）プロパン－２－イル）ウレイド）エチルメタクリレートを得た（２．９９ｇ（１０．８mmol）、収率５４．１％）。この化合物の構造は1Ｈ－ＮＭＲ分析により以下のスペクトルデータを得て確認した。
　1Ｈ－ＮＭＲ（ＣＤＣｌ3）：δ６．６２（ｔ，１Ｈ），６．０８（ｓ，１Ｈ），５．８４（ｓ，１Ｈ），５．７０（ｓ，１Ｈ），５．００（ｔ，３Ｈ），４．０５（ｔ，２Ｈ），３．４３（ｄ，６Ｈ），３．２６（ｍ，２Ｈ），１．８９（ｓ，３Ｈ）. Example 8
Synthesis of 2- (3- (1,3-dihydroxy-2- (hydroxymethyl) propan-2-yl) ureido) ethyl methacrylate
Figure JPOXMLDOC01-appb-C000031
 Under a nitrogen stream, THF (tetrahydrofuran) 100 ml, THAM (trishydroxymethylaminomethane) 2.42 g (20.0 mmol) and BHT (2,6-di-tert-butyl-p-cresol) 33.0 mg (0. 150 mmol) was charged at 25 ° C., and 3.26 g (21.0 mmol) of 2-IEM (2-isocyanatoethyl methacrylate) was added with stirring with a magnetic stirrer. After stirring for 24 hours at 25 ° C., the precipitated crystals were filtered, the collected crystals were washed twice with 20 ml of tetrahydrofuran, and the crystals were dried to give white solid 2- (3- (1,3-dihydroxy- 2- (Hydroxymethyl) propan-2-yl) ureido) ethyl methacrylate was obtained (2.99 g (10.8 mmol), yield 54.1%). The structure of this compound was confirmed by obtaining the following spectral data by 1 H-NMR analysis.
1 H-NMR (CDCl 3 ): δ 6.62 (t, 1H), 6.08 (s, 1H), 5.84 (s, 1H), 5.70 (s, 1H), 5.00 (t , 3H), 4.05 (t, 2H), 3.43 (d, 6H), 3.26 (m, 2H), 1.89 (s, 3H).
参考例９
２－（３－（１，３－ジヒドロキシプロパン－２－イル）ウレイド）エチルメタクリレートの合成
Figure JPOXMLDOC01-appb-C000032
 　窒素気流下中、テトラヒドロフラン４０．０ｍｌ、２－アミノプロパン１，３－ジオール１．８２ｇ（２０．０mmol）、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール２９．５ｍｇ（０．１３４mmol）及びＤＢＵ（ジアザビシクロウンデセン）５８．９ｍｇ（０．３８７mmol）を２５℃にて仕込み、マグネチックスターラー攪拌下で２－イソシアナトエチルメタクリレート２．９５ｇ（１９．０mmol）を加えた。３０分後、白い結晶が析出し、さらにテトラヒドロフラン３０．０ｍｌを加えてそのまま２５℃で４８時間攪拌した。その後ヘキサン１２０ｍｌを加え結晶をろ過し、ろ取した結晶を酢酸エチル１０ｍｌで２回洗浄し、結晶を乾燥させて白色固体の２－（３－（１，３－ジヒドロキシプロパン－２－イル）ウレイド）エチルメタクリレートを得た（２．７０ｇ（１１．０mmol）、収率５７．８％）。この化合物の構造は1Ｈ－ＮＭＲ分析により以下のスペクトルデータを得て確認した。
　1Ｈ－ＮＭＲ（ＣＤＣｌ3）：δ６．２２（ｔ，１Ｈ），６．０８（ｓ，１Ｈ），５．８５（ｄ，１Ｈ），５．７０（ｓ，１Ｈ），４．６７（ｔ，２Ｈ），４．０５（ｔ，２Ｈ），３．５１－３．４３（ｍ，１Ｈ），３．４１－３．２７（ｍ，６Ｈ），１．９０（ｓ，３Ｈ）. Reference Example 9
Synthesis of 2- (3- (1,3-dihydroxypropan-2-yl) ureido) ethyl methacrylate
Figure JPOXMLDOC01-appb-C000032
 Under a nitrogen stream, 40.0 ml of tetrahydrofuran, 1.82 g (20.0 mmol) of 2-aminopropane 1,3-diol, 29.5 mg (0.134 mmol) of 2,6-di-tert-butyl-p-cresol and DBU (diazabicycloundecene) 58.9 mg (0.387 mmol) was charged at 25 ° C., and 2.95 g (19.0 mmol) of 2-isocyanatoethyl methacrylate was added with stirring with a magnetic stirrer. After 30 minutes, white crystals were precipitated, and 30.0 ml of tetrahydrofuran was further added, followed by stirring at 25 ° C. for 48 hours. Thereafter, 120 ml of hexane was added, the crystals were filtered, the collected crystals were washed twice with 10 ml of ethyl acetate, and the crystals were dried to give 2- (3- (1,3-dihydroxypropan-2-yl) ureido as a white solid. ) Ethyl methacrylate was obtained (2.70 g (11.0 mmol), yield 57.8%). The structure of this compound was confirmed by obtaining the following spectral data by 1 H-NMR analysis.
1 H-NMR (CDCl 3 ): δ 6.22 (t, 1H), 6.08 (s, 1H), 5.85 (d, 1H), 5.70 (s, 1H), 4.67 (t , 2H), 4.05 (t, 2H), 3.51-3.43 (m, 1H), 3.41-3.27 (m, 6H), 1.90 (s, 3H).
参考例１０
２－（３－（１，３－ジヒドロキシプロパン－２－イル）ウレイド）エチルアクリレートの合成
Figure JPOXMLDOC01-appb-C000033
 　窒素気流下中、テトラヒドロフラン４０．０ｍｌ、２－アミノプロパン１，３－ジオール１．８２ｇ（２０．０mmol）及び２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール２８．８ｍｇ（０．１３１mmol）を２５℃にて仕込み、マグネチックスターラー攪拌下で２－ＩＥＡ（２－イソシアナトエチルアクリレート）２．８８ｇ（２０．４mmol）を加えた。そのまま２５℃で２４時間攪拌し、ヘキサン１２０ｍｌを加えて析出した結晶をろ過し、ろ取した結晶をヘキサン２０ｍｌで２回洗浄し、結晶を乾燥させて白色固体の２－（３－（１，３－ジヒドロキシプロパン－２－イル）ウレイド）エチルアクリレートを得た（３．４１ｇ（１４．７mmol）、収率７３．４％）。この化合物の構造は1Ｈ－ＮＭＲ分析により以下のスペクトルデータを得て確認した。
　1Ｈ－ＮＭＲ（ＣＤＣｌ3）：δ６．３５（ｄ，１Ｈ），６．２３－６．１４（ｍ，２Ｈ），５．９７（ｄ，１Ｈ），５．８１（ｄ，１Ｈ），４．６３（ｔ，２Ｈ），４．０６（ｔ，２Ｈ），３．５２－３．４３（ｍ，１Ｈ），３．４２－３．３８（ｍ，２Ｈ），３．３６－３．３１（ｍ，２Ｈ），３．３０－３．２４（ｍ，２Ｈ）. Reference Example 10
Synthesis of 2- (3- (1,3-dihydroxypropan-2-yl) ureido) ethyl acrylate
Figure JPOXMLDOC01-appb-C000033
 Under a nitrogen stream, 40.0 ml of tetrahydrofuran, 1.82 g (20.0 mmol) of 2-aminopropane 1,3-diol and 28.8 mg (0.131 mmol) of 2,6-di-tert-butyl-p-cresol were added. The mixture was charged at 25 ° C., and 2.88 g (20.4 mmol) of 2-IEA (2-isocyanatoethyl acrylate) was added with stirring with a magnetic stirrer. The mixture was stirred at 25 ° C. for 24 hours, 120 ml of hexane was added, the precipitated crystals were filtered, the collected crystals were washed twice with 20 ml of hexane, and the crystals were dried to give a white solid 2- (3- (1, 3-Dihydroxypropan-2-yl) ureido) ethyl acrylate was obtained (3.41 g (14.7 mmol), yield 73.4%). The structure of this compound was confirmed by obtaining the following spectral data by 1 H-NMR analysis.
1 H-NMR (CDCl 3 ): δ 6.35 (d, 1H), 6.23-6.14 (m, 2H), 5.97 (d, 1H), 5.81 (d, 1H), 4 .63 (t, 2H), 4.06 (t, 2H), 3.52-3.43 (m, 1H), 3.42-3.38 (m, 2H), 3.36-3.31 (M, 2H), 3.30-3.24 (m, 2H).
実施例１１
２－（３－（１，３－ジヒドロキシ－２－（ヒドロキシメチル）プロパン－２－イル）ウレイド）エチルアクリレートの合成
Figure JPOXMLDOC01-appb-C000034
 　窒素気流下中、テトラヒドロフラン１００ｍｌ、トリスヒドロキシメチルアミノメタン６．０６ｇ（５０．０mmol）を２５℃にて仕込み、マグネチックスターラー攪拌下で２－イソシアナトエチルアクリレート７．４１ｇ（５２．５mmol）を加えた。３０分後、白い結晶が析出し、さらにテトラヒドロフラン１００ｍｌを加えてそのまま２５℃で２４時間攪拌した。析出した結晶をろ過し、ろ取した結晶をテトラヒドロフラン２０ｍｌで２回洗浄し、結晶を乾燥させて白色固体の２－（３－（１，３－ジヒドロキシ－２－（ヒドロキシメチル）プロパン－２－イル）ウレイド）エチルアクリレートを得た（８．３０ｇ（３１．７mmol）、収率６３．３％）。この化合物の構造は1Ｈ－ＮＭＲ分析により以下のスペクトルデータを得て確認した。
　1Ｈ－ＮＭＲ（ＣＤＣｌ3）：δ６．６５（ｔ，１Ｈ），６．３６（ｄ，１Ｈ），６．２１－６．１４（ｍ，１Ｈ），５．９７（ｄ，１Ｈ），５．８４（ｓ，１Ｈ），５．００（ｔ，３Ｈ），４．０７（ｔ，２Ｈ），３．４３（ｄ，６Ｈ），３．３３－３．２４（ｍ，２Ｈ）. Example 11
Synthesis of 2- (3- (1,3-dihydroxy-2- (hydroxymethyl) propan-2-yl) ureido) ethyl acrylate
Figure JPOXMLDOC01-appb-C000034
 In a nitrogen stream, 100 ml of tetrahydrofuran and 6.06 g (50.0 mmol) of trishydroxymethylaminomethane were charged at 25 ° C., and 7.41 g (52.5 mmol) of 2-isocyanatoethyl acrylate was added with stirring with a magnetic stirrer. It was. After 30 minutes, white crystals were precipitated, and 100 ml of tetrahydrofuran was further added, followed by stirring at 25 ° C. for 24 hours. The precipitated crystals were filtered, the collected crystals were washed twice with 20 ml of tetrahydrofuran, and the crystals were dried to give 2- (3- (1,3-dihydroxy-2- (hydroxymethyl) propane-2- Yl) ureido) ethyl acrylate was obtained (8.30 g (31.7 mmol), yield 63.3%). The structure of this compound was confirmed by obtaining the following spectral data by 1 H-NMR analysis.
1 H-NMR (CDCl 3 ): δ 6.65 (t, 1H), 6.36 (d, 1H), 6.21-6.14 (m, 1H), 5.97 (d, 1H), 5 .84 (s, 1H), 5.00 (t, 3H), 4.07 (t, 2H), 3.43 (d, 6H), 3.33-3.24 (m, 2H).
　本発明の化合物は、液晶パネルを用いたテレビ等のディスプレイの分野や、半導体分野において用いられる樹脂組成物に添加することで、得られる硬化膜等の性能を向上させ、透明性等の特性には影響を与えない添加剤等として有用である。 The compound of the present invention improves the performance of a cured film obtained by adding it to a resin composition used in the field of displays such as a television using a liquid crystal panel and in the semiconductor field, and has characteristics such as transparency. Is useful as an additive or the like that does not affect.

Claims (12)

  1. 下記式［１］で表されるヒドロキシル基を有するアクリルまたはメタクリル化合物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ1は水素原子またはメチル基であり、Ｒ2及びＲ3は、互いに独立して水素原子、炭素数１から２０のアルキル基または炭素数１から２０のヒドロキシルアルキル基であり、Ｒ4は、ヒドロキシル基または炭素数１から２０のヒドロキシルアルキル基である。）     An acrylic or methacrylic compound having a hydroxyl group represented by the following formula [1].
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a hydroxyl alkyl group having 1 to 20 carbon atoms, R 4 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms.)
  2. Ｒ2及びＲ3の少なくとも１つが炭素数１から２０のヒドロキシルアルキル基である請求項１に記載のヒドロキシル基を有するアクリルまたはメタクリル化合物。 The acrylic or methacrylic compound having a hydroxyl group according to claim 1, wherein at least one of R 2 and R 3 is a hydroxylalkyl group having 1 to 20 carbon atoms.
  3. 下記式［２］で表されるヒドロキシル基を有するアクリルまたはメタクリル化合物。
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ1は水素原子またはメチル基であり、Ｒ2は、水素原子または炭素数１から２０のアルキル基である。）     An acrylic or methacrylic compound having a hydroxyl group represented by the following formula [2].
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)
  4. 下記式（A）
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ1は水素原子またはメチル基である。）で表されるグリシジルアクリレートあるいはグリシジルメタクリレートと下記式（B）
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｒ2及びＲ3は、互いに独立して水素原子、炭素数１から２０のアルキル基または炭素数１から２０のヒドロキシルアルキル基であり、Ｒ4は、ヒドロキシル基または炭素数１から２０のヒドロキシルアルキル基である。）で表されるヒドロキシル基を有するカルボン酸化合物とを反応させることを特徴とする下記式［１］
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｒ1は水素原子またはメチル基であり、Ｒ2及びＲ3は、互いに独立して水素原子、炭素数１から２０のアルキル基または炭素数１から２０のヒドロキシルアルキル基であり、Ｒ4は、ヒドロキシル基または炭素数１から２０のヒドロキシルアルキル基である。）で表されるヒドロキシル基を有するアクリルまたはメタクリル化合物の製造方法。     Following formula (A)
    Figure JPOXMLDOC01-appb-C000003
     (Wherein R 1 is a hydrogen atom or a methyl group) and glycidyl acrylate or glycidyl methacrylate represented by the following formula (B)
    Figure JPOXMLDOC01-appb-C000004
     (In the formula, R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a hydroxyl alkyl group having 1 to 20 carbon atoms, and R 4 is a hydroxyl group or having 1 to 20 carbon atoms. And a carboxylic acid compound having a hydroxyl group represented by the following formula [1]:
    Figure JPOXMLDOC01-appb-C000005
     (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a hydroxyl alkyl group having 1 to 20 carbon atoms, R 4 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms.) A method for producing an acrylic or methacrylic compound having a hydroxyl group represented by:
  5. Ｒ2及びＲ3の少なくとも１つが炭素数１から２０のヒドロキシルアルキル基である請求項４に記載の製造方法。 The production method according to claim 4, wherein at least one of R 2 and R 3 is a hydroxylalkyl group having 1 to 20 carbon atoms.
  6. Ｒ2が水素原子または炭素数１から２０のアルキル基であり、Ｒ3とＲ4がともにヒドロキシメチル基である請求項４記載の製造方法。 The production method according to claim 4, wherein R 2 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 3 and R 4 are both hydroxymethyl groups.
  7. 反応させる際に重合禁止剤の存在下反応させることを特徴とする請求項４～６のいずれか１項に記載の製造方法。 The production method according to any one of claims 4 to 6, wherein the reaction is carried out in the presence of a polymerization inhibitor.
  8. 反応させる際に触媒の存在下反応させることを特徴とする請求項４～７のいずれか１項に記載の製造方法。 The production method according to any one of claims 4 to 7, wherein the reaction is carried out in the presence of a catalyst.
  9. 下記式［３］で表されるヒドロキシル基を有するアクリルまたはメタクリル化合物。
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ｒ5は水素原子またはメチル基であり、Ｒ6は、ヒドロキシル基または炭素数１から２０のヒドロキシルアルキル基であり、Ｒ7及びＲ8は、炭素数１から２０のヒドロキシルアルキル基であり、Lは炭素数２から２０のアルキレンである。）     An acrylic or methacrylic compound having a hydroxyl group represented by the following formula [3].
    Figure JPOXMLDOC01-appb-C000006
     Wherein R 5 is a hydrogen atom or a methyl group, R 6 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms, and R 7 and R 8 are a hydroxylalkyl group having 1 to 20 carbon atoms. And L is alkylene having 2 to 20 carbon atoms.)
  10. 下記式（C）
    Figure JPOXMLDOC01-appb-C000007
     （式中、Ｒ5は水素原子またはメチル基であり、Lは炭素数２から２０のアルキレンである。）で表されるイソシアネート化合物と下記式（D）
    Figure JPOXMLDOC01-appb-C000008
     （式中、Ｒ6は、ヒドロキシル基または炭素数１から２０のヒドロキシルアルキル基であり、Ｒ7及びＲ8は、炭素数１から２０のヒドロキシルアルキル基である。）で表されるヒドロキシル基を有するアミン化合物とを反応させることを特徴とする下記式［３］
    Figure JPOXMLDOC01-appb-C000009
     （式中、Ｒ5は水素原子またはメチル基であり、Ｒ6は、ヒドロキシル基または炭素数１から２０のヒドロキシルアルキル基であり、Ｒ7及びＲ8は、炭素数１から２０のヒドロキシルアルキル基であり、Lは炭素数２から２０のアルキレンである。）で表されるヒドロキシル基を有するアクリルまたはメタクリル化合物の製造方法。     Following formula (C)
    Figure JPOXMLDOC01-appb-C000007
     (Wherein R 5 is a hydrogen atom or a methyl group, L is an alkylene having 2 to 20 carbon atoms) and the following formula (D)
    Figure JPOXMLDOC01-appb-C000008
     (Wherein R 6 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms, and R 7 and R 8 are hydroxylalkyl groups having 1 to 20 carbon atoms). The following formula [3], wherein the amine compound is reacted with
    Figure JPOXMLDOC01-appb-C000009
     Wherein R 5 is a hydrogen atom or a methyl group, R 6 is a hydroxyl group or a hydroxylalkyl group having 1 to 20 carbon atoms, and R 7 and R 8 are a hydroxylalkyl group having 1 to 20 carbon atoms. And L is alkylene having 2 to 20 carbon atoms.) A method for producing an acrylic or methacrylic compound having a hydroxyl group represented by:
  11. 反応させる際に重合禁止剤の存在下反応させることを特徴とする請求項１０記載の製造方法。 The method according to claim 10, wherein the reaction is carried out in the presence of a polymerization inhibitor.
  12. 反応させる際に触媒の存在下反応させることを特徴とする請求項１０又は１１記載の製造方法。 The production method according to claim 10 or 11, wherein the reaction is carried out in the presence of a catalyst.
PCT/JP2013/078711 2012-10-24 2013-10-23 Acrylic or methacrylic compound having hydroxyl group, and method for producing same WO2014065327A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020157012763A KR20150074059A (en) 2012-10-24 2013-10-23 Acrylic or methacrylic compound having hydroxyl group, and method for producing same
JP2014543325A JPWO2014065327A1 (en) 2012-10-24 2013-10-23 Acrylic or methacrylic compound having hydroxyl group and method for producing the same
CN201380051748.8A CN104718184A (en) 2012-10-24 2013-10-23 Acrylic or methacrylic compound having hydroxyl group, and method for producing same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2012234671 2012-10-24
JP2012-234671 2012-10-24
JP2012234672 2012-10-24
JP2012-234672 2012-10-24

Publications (1)

Publication Number Publication Date
WO2014065327A1 true WO2014065327A1 (en) 2014-05-01

Family

ID=50544702

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/078711 WO2014065327A1 (en) 2012-10-24 2013-10-23 Acrylic or methacrylic compound having hydroxyl group, and method for producing same

Country Status (5)

Country Link
JP (1) JPWO2014065327A1 (en)
KR (1) KR20150074059A (en)
CN (1) CN104718184A (en)
TW (1) TW201434814A (en)
WO (1) WO2014065327A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102555706B1 (en) * 2017-03-27 2023-07-14 닛산 가가쿠 가부시키가이샤 Cured film forming composition, orientation material and phase difference material

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1419634A (en) * 1972-05-15 1975-12-31 Ciba Geigy Ag Method of bonding surfaces together using adhesive compositons
JPS62267258A (en) * 1986-04-30 1987-11-19 イ−ストマン　コダツク　カンパニ− Novel diol monomer and polymer
JP2001125257A (en) * 1999-10-29 2001-05-11 Fuji Photo Film Co Ltd Original plate for planographic printing plate
JP2001166470A (en) * 1999-12-06 2001-06-22 Kansai Paint Co Ltd Photosensitive resin composition for photoresist and resist pattern forming method
JP2006039103A (en) * 2004-07-26 2006-02-09 Fuji Photo Film Co Ltd Polymerizable composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1419634A (en) * 1972-05-15 1975-12-31 Ciba Geigy Ag Method of bonding surfaces together using adhesive compositons
JPS62267258A (en) * 1986-04-30 1987-11-19 イ−ストマン　コダツク　カンパニ− Novel diol monomer and polymer
JP2001125257A (en) * 1999-10-29 2001-05-11 Fuji Photo Film Co Ltd Original plate for planographic printing plate
JP2001166470A (en) * 1999-12-06 2001-06-22 Kansai Paint Co Ltd Photosensitive resin composition for photoresist and resist pattern forming method
JP2006039103A (en) * 2004-07-26 2006-02-09 Fuji Photo Film Co Ltd Polymerizable composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MACROMOLECULAR MATERIALS AND ENGINEERING, vol. 288, no. 10, 2003, pages 751 - 761 *

Also Published As

Publication number Publication date
JPWO2014065327A1 (en) 2016-09-08
TW201434814A (en) 2014-09-16
KR20150074059A (en) 2015-07-01
CN104718184A (en) 2015-06-17

Similar Documents

Publication Publication Date Title
TWI641581B (en) Novel polymeric acrylic compound or methacrylic compound,and production method thereof
TWI421244B (en) A polymerizable liquid crystal compound and a polymerizable liquid crystal composition and an alignment film
KR20110067108A (en) Polymerizable liquid crystal compound, polymerizable liquid crystal composition and oriented film
KR101819061B1 (en) Polymerizable compound, polymerizable liquid crystal composition, polymer and alignment film
KR101988377B1 (en) Polymer, composition containing said polymer, and single-layer-coated horizontally oriented film
TWI521048B (en) A polymerizable liquid crystal compound, a polymerizable liquid crystal composition, and a alignment film
WO2014065327A1 (en) Acrylic or methacrylic compound having hydroxyl group, and method for producing same
JP6516028B2 (en) Composition and single layer coating type horizontal alignment film
JP6879219B2 (en) Liquid crystal composition and single-layer coating type horizontally oriented film
WO2017006922A1 (en) Composition for producing liquid crystal alignment film, liquid crystal alignment film using said composition and production method therefor, and liquid crystal display element having liquid crystal alignment film and production method therefor
JP6425048B2 (en) Compound having polymerizable group and crosslinkable group and method for producing the same
CN108794333A (en) The method for preparing cinnamic acid benzoyl first ester type compound
WO2023223639A1 (en) Polymerizable compound, polymerizable composition, optical film, and display apparatus
KR101641321B1 (en) Modified Triaroylbenzene-Based Polymer
TW201527393A (en) Film forming composition and monolayer coating type horizontal alignment film
JP2017075096A (en) Thiabendazolemono (meth) acrylate compound and method for producing the same
JP2010037243A (en) Method for producing norbornene lactone monomer

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13849453

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014543325

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20157012763

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 13849453

Country of ref document: EP

Kind code of ref document: A1