WO2012043222A1 - 低溶出性エポキシ樹脂及びその部分エステル化エポキシ樹脂、その製造方法、並びにそれを含む硬化性樹脂組成物 - Google Patents

低溶出性エポキシ樹脂及びその部分エステル化エポキシ樹脂、その製造方法、並びにそれを含む硬化性樹脂組成物 Download PDF

Info

Publication number
WO2012043222A1
WO2012043222A1 PCT/JP2011/070916 JP2011070916W WO2012043222A1 WO 2012043222 A1 WO2012043222 A1 WO 2012043222A1 JP 2011070916 W JP2011070916 W JP 2011070916W WO 2012043222 A1 WO2012043222 A1 WO 2012043222A1
Authority
WO
WIPO (PCT)
Prior art keywords
general formula
epoxy resin
epoxy
compound
glycidyl
Prior art date
Application number
PCT/JP2011/070916
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
大晃 臼井
正浩 森本
Original Assignee
協立化学産業株式会社
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 協立化学産業株式会社 filed Critical 協立化学産業株式会社
Priority to CN201180047684.5A priority Critical patent/CN103140535B/zh
Priority to KR1020137011165A priority patent/KR101812832B1/ko
Publication of WO2012043222A1 publication Critical patent/WO2012043222A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3218—Carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a low-elution epoxy resin, a partially esterified epoxy resin, a production method thereof, and a curable resin composition containing the same.
  • the dropping method is a method in which a panel can be formed by directly dropping and bonding liquid crystal in a closed loop of a sealing agent under vacuum and releasing the vacuum.
  • This dripping method has many merits such as a reduction in the amount of liquid crystal used and a time required for injecting the liquid crystal into the panel, and has become the mainstream method for manufacturing a liquid crystal panel using a large substrate.
  • a seal / liquid crystal is applied and bonded together, then a gap is formed, alignment is performed, and the seal is cured mainly by ultraviolet curing.
  • the drawing position of the sealant is completely exposed to light, and it is difficult to produce an uncured portion of the seal and there is no problem of contamination of the liquid crystal.
  • the seal position tends to be closer to the display pixel.
  • contamination from the sealing agent tends to affect the electrical characteristics of the display pixel portion and easily cause display defects.
  • the distance from the display unit to the sealing agent is narrow, and the occurrence of display defects due to contamination is more remarkable.
  • Patent Document 1 a crystalline epoxy resin to reduce elution of the resin into the liquid crystal during the thermosetting process during the production of the liquid crystal panel.
  • an epoxy resin there has been proposed a sealing agent which is a bisphenol S-type, ether-type, thioether-type, and fluorene-type epoxy resin and has a compound having an alkylene oxide unit and which suppresses contamination of liquid crystals (Patent Document 2). ).
  • Patent Document 2 the use of a partially esterified epoxy resin as a raw material for the sealant has been studied.
  • Patent Document 3 It has been proposed to reduce the elution during thermosetting by partially acrylating a trifunctional or tetrafunctional epoxy resin to reduce the proportion of the non-acrylated compound.
  • Patent Document 4 By partially modifying a trifunctional or tetrafunctional phenol novolac type epoxy resin with a (meth) acrylic acid derivative having a carboxyl group, the liquid stability is improved in a blend with an epoxy resin and an acrylic resin, and alignment of liquid crystals It has been proposed to improve the characteristics (Patent Document 4).
  • JP 2006-23583 A Japanese Patent No. 4211942 JP 2008-3260 A JP 2008-179796 A
  • the epoxy resin described in Patent Document 1 is crystalline, in order to be used as a liquid sealant, it may need to be mixed with the liquid resin or may precipitate due to compatibility. is there.
  • the trifunctional and tetrafunctional epoxy resins described in Patent Documents 3 and 4 are often highly viscous or solid, and their use as a sealing agent is limited. Further, in the case of the sealing agent, when the UV irradiation amount is low, the contamination property is insufficient at present. It is an object of the present invention to obtain an epoxy resin and a partially esterified epoxy resin that can be used as an oligomer component of a high-quality sealant that can suppress the contamination of the liquid crystal while suppressing the solubility in the liquid crystal. And
  • the present inventors have made extensive investigations focusing on the contamination of the epoxy resin, which is the main component of the sealing material, to the liquid crystal.
  • the present inventors have found that the solubility and elution property of the oligomer itself in the liquid crystal can be reduced by modifying the structure of the epoxy resin with a certain structure.
  • the present invention relates to the general formula (1): General formula (2): Or, general formula (3): [Where, X is —O—, alkylene having 1 to 4 carbon atoms, or alkylidene having 2 to 4 carbon atoms, Y is alkylene having 1 to 4 carbon atoms-arylene having 6 to 20 carbon atoms-alkylene having 1 to 4 carbon atoms, alkylene having 1 to 4 carbon atoms-arylene having 6 to 20 carbon atoms, or a group : —R 7 — (O—R 7 ) n — (wherein R 7 is alkylene having 1 to 4 carbon atoms, and n is 0 or an integer of 1 to 6), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other hydrogen, glycidyl, or methyl glycidyl; Each R 21 independently of one another is hydrogen or methyl; At least two of R 1 , R 2 , R 3 , R 4 , R
  • the present invention relates to a general formula (4): General formula (5): Or, general formula (6): [Where, X, Y and R 21 are as defined above; R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are hydrogen, glycidyl, methyl glycidyl or a group: —Z—R 8 (Where Z is 2-hydroxypropylene or 2-methyl-2-hydroxypropylene; R 8 is acryloyl or methacryloyl) And At least two of R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are glycidyl, methyl glycidyl, or a group: —ZR 8 ; The ratio of glycidyl and methyl glycidyl to acryloyl and methacryloyl is 10:90 to 90:10] It is related with the partially esterified epoxy resin shown by these.
  • the present invention is a method for producing an epoxy resin, comprising steps (1A) to (1B):
  • (1A) A polyfunctional epoxy compound having two or more epoxy groups in the molecule is reacted with a polyhydroxy compound having two or more hydroxy groups in the molecule in the presence of a metal catalyst, thereby allowing epoxy opening of the polyfunctional epoxy compound.
  • (1B) The process of epoxidizing the hydroxyl group of the epoxy ring-opened product of the polyfunctional epoxy compound obtained in the step (1A).
  • the present invention is a method for producing an epoxy resin as described above for producing an epoxy resin represented by the general formulas (1) to (3) described above, comprising the following steps (2A) to ( 2B): (2A) General formula (7a): General formula (8a): Or, general formula (9a): [Where, X and R 21 are as defined above.] An epoxy compound represented by the following general formula (10) in the presence of a metal catalyst: HO-Y-OH (10) Wherein Y is as defined above.
  • This invention is a manufacturing method of a partially esterified epoxy resin, Comprising: Process (1C): (1C)
  • the present invention relates to a method for producing a partially esterified epoxy resin comprising a step of reacting an epoxy resin obtained by the production method described above with (meth) acrylic acid in the presence of a basic catalyst.
  • the present invention provides a process for producing a partially esterified epoxy resin as described above for producing a partially esterified epoxy resin represented by the general formulas (4) to (6) described above, comprising the steps of: (2C): (2C) General formula (1) obtained by the production method described above: General formula (2): Or, general formula (3): [Where, X, Y, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 21 are as defined above, At least two of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are glycidyl or methyl glycidyl.
  • the present invention includes (a) an epoxy resin represented by the general formula (1), the general formula (2) and the general formula (3) described above, (b) the general formula (4) and the general formula ( 5) and a partially esterified epoxy resin represented by the general formula (6), (c) an epoxy resin obtained by the production method described above, and (d) a partially esterified epoxy resin obtained by the production method described above.
  • the present invention relates to a curable composition containing one or more resins selected from the group consisting of:
  • an epoxy resin and a partially esterified epoxy resin that can be used as an oligomer component of a high-quality sealant that can suppress the solubility of the liquid crystal and prevent the contamination of the liquid crystal.
  • the epoxy resin of this invention is a compound shown by General formula (1), General formula (2), and General formula (3).
  • Examples of the alkylene having 1 to 4 carbon atoms include methylene, ethylene, trimethylene and tetramethylene, and methylene and ethylene are preferable.
  • Examples of the alkylidene having 2 to 4 carbon atoms include ethylidene, propylidene, isopropylidene, methylpropylidene, and butylidene, and ethylidene and isopropylidene are preferable.
  • the arylene having 6 to 20 carbon atoms is a monocyclic or polycyclic aromatic group, and examples thereof include phenylene, naphthylene, and anthracenylene, and preferably phenylene.
  • alkylene having 1 to 4 carbon atoms and arylene having 6 to 20 carbon atoms in alkylene having 1 to 4 carbon atoms-arylene having 6 to 20 carbon atoms are as defined above.
  • Preferred examples of the alkylene having 1 to 4 carbon atoms and the arylene having 6 to 20 carbon atoms include a methylene-phenylene group.
  • the order of bonding to each group in the alkylene having 1 to 4 carbon atoms and the arylene having 6 to 20 carbon atoms may be any.
  • an oxygen atom bonded to R 1 to R 6 may be bonded to an alkylene having 1 to 4 carbon atoms and an alkylene having 6 to 20 carbon atoms in an alkylene having 1 to 4 carbon atoms, Arylene having 6 to 20 carbon atoms may be bonded.
  • alkylene having 1 to 4 carbon atoms-arylene having 6 to 20 carbon atoms-alkylene having 1 to 4 carbon atoms and alkylene having 1 to 4 carbon atoms and arylene having 6 to 20 carbon atoms are given above.
  • Preferred examples of the alkylene having 1 to 4 carbon atoms-arylene having 6 to 20 carbon atoms and alkylene having 1 to 4 carbon atoms include phenylenebis (methylene).
  • R 1 to R 6 are glycidyl or methyl glycidyl.
  • the epoxy group includes both a glycidyl group and a methylglycidyl group.
  • the glycidyl group is a 2,3-epoxypropyl group
  • the methyl glycidyl group is a 2,3-epoxy-2-methylpropyl group.
  • among the R 1 ⁇ R 6, preferably 3 or more is glycidyl or methylglycidyl, among the R 1 ⁇ R 6, and more preferably both are glycidyl or methylglycidyl.
  • glycidyl and methyl glycidyl are present in R 4 , R 5 and R 6 , that is, oxygen atoms bonded to primary carbon atoms, and R 1 to R 6 , that is, primary More preferably, glycidyl and methyl glycidyl are present in the oxygen atom bonded to the secondary carbon atom and the oxygen atom bonded to the secondary carbon atom.
  • the number of glycidyl and methyl glycidyl in the epoxy resins represented by the general formulas (1) to (3) can be calculated by high performance liquid chromatography (HPLC). Specifically, a peak corresponding to the number of glycidyl and methyl glycidyl is obtained by HPLC, and the abundance ratio of the number of glycidyl and methyl glycidyl can be calculated from the respective peak areas. Thereby, the number of glycidyl and methyl glycidyl contained in the compound can be calculated.
  • the epoxy resins represented by the general formulas (1) to (3) are a mixture
  • the number of glycidyl and methyl glycidyl is calculated as an average value of the mixture.
  • the number of epoxy groups can be determined by performing mass spectrometry (LC-MS) at each peak of HPLC, and the average number of epoxy groups in the mixture can be calculated from the abundance ratio of each component in the mixture.
  • the mixture of the epoxy resins represented by the general formula (1) and the general formula (2) includes compounds having 3 and 4 epoxy groups and multimers thereof, and is represented by the general formula (3).
  • the epoxy resin may contain 3, 4, 5 and 6 epoxy groups and multimers thereof.
  • the bonding position of X in the compound represented by the general formula (1) is preferably 4,4′-position, that is, has a bisphenol type epoxy resin skeleton.
  • the bonding position of the naphthalene ring in the compound represented by the general formula (2) is preferably a 1,6-bond.
  • the number average molecular weight of the compounds represented by the general formulas (1) to (3) is preferably 200 to 5,000. If it is such a range, adhesiveness will be favorable and the contamination
  • the number average molecular weight is a number average molecular weight calculated in terms of polystyrene by gel permeation chromatography (GPC).
  • the epoxy equivalent of the epoxy compounds represented by the general formulas (1) to (3) is 100 to 3,000 g / eq. It is preferably 200 to 1,000 g / eq. It is more preferable that If it is such a range, adhesiveness will be favorable and the contamination
  • an epoxy equivalent is calculated
  • an epoxy equivalent is calculated
  • the partially esterified epoxy resin is represented by general formula (4), general formula (5), and general formula (6).
  • the partially esterified epoxy resin represented by the general formula (4) to the general formula (6) at least two of R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are glycidyl, methyl glycidyl, or It is a group represented by —ZR 8 containing a (meth) acryloyl group. That is, the partially esterified epoxy resins represented by the general formulas (4) to (6) of the present invention are glycidyl and a part of methyl glycidyl of the epoxy resins represented by the general formulas (1) to (3). Is a (meth) acryloylated epoxy resin.
  • R 11 to R 16 3 or more are preferably groups represented by —Z—R 8 containing glycidyl, methyl glycidyl, or (meth) acryloyl groups, and among R 11 to R 16 More preferably, all are groups represented by —Z—R 8 containing a glycidyl, methylglycidyl, or (meth) acryloyl group.
  • glycidyl, methylglycidyl and (meth) acryloyl groups are present in R 14 , R 15 and R 16 , that is, the oxygen atom bonded to the primary carbon atom, and R 11 to More preferably, glycidyl, methylglycidyl and (meth) acryloyl groups are present in R 16 , that is, the oxygen atom bonded to the primary carbon atom and the oxygen atom bonded to the secondary carbon atom.
  • the number of glycidyl and methyl glycidyl and the number of (meth) acryloyl groups in the partially esterified epoxy resins represented by the general formulas (4) to (6) can be calculated by HPLC. Specifically, the peak corresponding to the number of each epoxy group and the number of each (meth) acryloyl is obtained by HPLC, and the existence ratio of each number can be calculated from each peak area. Thus, the number of groups represented by —ZR 8 including glycidyl, methylglycidyl, and (meth) acryloyl groups in the partially esterified epoxy resins represented by the general formulas (4) to (6) is obtained. .
  • the number of glycidyl and methyl glycidyl and the number of (meth) acryloyl groups are calculated as the average value of the mixture.
  • the mixture of the partially esterified epoxy resins represented by the general formula (4) and the general formula (5) includes a mixture of the epoxy resins represented by the general formula (1) and the general formula (2) and those epoxy groups.
  • Resins partially including (meth) acryloyl groups are included, and the partially esterified epoxy resin represented by the general formula (6) is a mixture of epoxy resins represented by the general formula (3) and one of those epoxy groups.
  • a resin in which a part is a (meth) acryloyl group is included.
  • the ratio of the glycidyl group and the methyl glycidyl group to the acryloyl group and the methacryloyl group that is, the ratio of the epoxy group to the (meth) acryloyl group is 10:90 to 90:10.
  • the ratio of an epoxy group and a (meth) acryl group can be calculated
  • the degree of esterification can be calculated by measuring the epoxy equivalent of the partially esterified epoxy resin. Further, by performing mass spectrometry (LC-MS) at each peak of HPLC, the molecular weight and the abundance ratio of each component can be determined, and the ratio of the epoxy group and acrylic group for each component can be determined.
  • the number average molecular weight of the partially esterified epoxy resin represented by the general formulas (4) to (6) is preferably 500 to 10,000, and more preferably 800 to 5,000. preferable.
  • the viscosity of the partially esterified epoxy resin represented by the general formulas (4) to (6) at 20 ° C. is preferably 1,000 to 1,000,000 mP ⁇ s, and 40,000 to 600 More preferably, it is 1,000 mP ⁇ s. If it is such a range, when apply
  • the viscosity is a value measured using an E-type viscometer at a cone rotor rotational speed of 2.5 rpm.
  • Manufacturing method of epoxy resin The manufacturing method of the epoxy resin of this invention is demonstrated.
  • epoxidation includes both glycidylation and methylglycidylation.
  • the method for producing an epoxy resin of the present invention includes the following steps (1A) to (1B): (1A) A polyfunctional epoxy compound having two or more epoxy groups in the molecule is reacted with a polyhydroxy compound having two or more hydroxy groups in the molecule in the presence of a metal catalyst, thereby allowing epoxy opening of the polyfunctional epoxy compound. Obtaining a ring; (1B) epoxidizing the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound obtained in step (1A).
  • Step (1A) in the step (1A), in the polyfunctional epoxy compound having two or more epoxy groups in the molecule as the raw material compound, a hydroxy group is formed by ring opening of the epoxy group, and a hydroxy group derived from the polyhydroxy compound includes It is formed.
  • the ring-opened product of the polyfunctional epoxy compound refers to a compound in which all the epoxy groups of the polyfunctional epoxy compound are opened.
  • the polyfunctional epoxy compound is not particularly limited as long as it is an epoxy compound having two or more epoxy groups in one molecule.
  • Examples of the polyfunctional epoxy compound include the following compounds.
  • polyfunctional epoxy compounds polyalkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol, polyhydric alcohols such as dimethylolpropane, trimethylolpropane, spiroglycol and glycerin And an aliphatic polyvalent glycidyl ether compound obtained by reacting chlorohydrin with epichlorohydrin.
  • aromatic diols such as bisphenol A, bisphenol S, bisphenol F, bisphenol AD and the like, and aromatic diols obtained by reacting diols modified with ethylene glycol, propylene glycol, alkylene glycol and epichlorohydrin are used.
  • Valent glycidyl ether compounds are used as the polyfunctional epoxy compound.
  • aromatic polycarboxylic glycidyl ester compounds obtained by reacting aromatic dicarboxylic acids such as adipic acid and itaconic acid with epichlorohydrin, aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid and pyromellitic acid And an aromatic polyvalent glycidyl ester compound obtained by reacting chlorohydrin with epichlorohydrin.
  • polyfunctional epoxy compounds include aromatic polyvalent glycidylamine compounds obtained by reacting aromatic amines such as diaminodiphenylmethane, aniline, and metaxylylenediamine with epichlorohydrin.
  • polyfunctional epoxy compound examples include a hindertoin-type polyvalent glycidyl compound obtained by reacting hydantoin and its derivatives with epichlorohydrin.
  • polyfunctional epoxy compounds include phenol resins derived from phenol or cresol and formaldehyde, phenols obtained by reacting novolac resins and epichlorohydrin, and novolac polyvalent glycidyl ether compounds.
  • Epoxy compounds represented by general formulas (7a) to (9a), which are preferable polyfunctional epoxy compounds of the present invention, are commercially available products such as Epicron 850 (Dainippon Ink Co., Ltd.), Epicoat 828EL, Epicoat 1004.
  • Bisphenol A type epoxy resins such as (Epicoat Resin Co., Ltd.), etc., Bisphenol F type epoxy resins such as Epicoat 806 and Epicoat 4004 (both manufactured by Japan Epoxy Resin Co., Ltd.), Epicron HP4032, and Epicron EXA-4700 Naphthalene type epoxy resins such as Nippon Ink Co., Ltd., and trifunctional epoxy resins such as VG-3101 (Mitsui Petrochemical Co., Ltd.).
  • the polyhydroxy compound having two or more hydroxy groups in the molecule is not particularly limited as long as it is a compound having two or more hydroxy groups in the molecule.
  • Specific examples of the polyhydroxy compound include the following compounds.
  • Examples of compounds having two hydroxy groups in the molecule include monoglycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol.
  • Alkylene glycol and polyalkylene glycol divalent aromatic hydroxy compounds such as catechol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,2-dihydroxyanthraquinone, and 2,3-dihydroxyquinoxaline; benzene-1 , 4-dimethanol, benzene-1,3-dimethanol, benzene-1,4-diethanol and other aromatic alcohols; 4-hydroxymethylphenol, 3-hydroxymethylphenol, 4-hydride Carboxyethyl phenol, and 3-hydroxyethyl-hydroxy alkyl phenols such as phenol and the like.
  • divalent aromatic hydroxy compounds such as catechol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,2-dihydroxyanthraquinone, and 2,3-dihydroxyquinoxaline
  • Examples of compounds having three hydroxy groups in the molecule include glycerin, trimethylolpropane, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2 , 6-hexanetriol, and trihydric alcohols such as 1,1,1-tris (hydroxymethyl) propane; pyrogallol, 3,4,5-trihydroxytoluene, 1,2,4-trihydroxyanthraquinone, gallic acid, And trivalent aromatic polyhydroxy compounds such as gallic acid ester compounds such as methyl gallate, propyl gallate and octyl gallate.
  • Examples of the compound having 4 or more hydroxy groups in the molecule include pentaerythritol, diglycerin, tetramethylolmethane, and alkylene glycoside (methyl glycoside, ethyl glycoside, etc.). Further, tetravalent or higher-valent aromatic polyhydroxy compounds such as 2,3,4,4'-tetrahydroxybenzophenone, ellagic acid, hexahydroxybenzene, tannic acid, and catechol or pyrogallol calixarene compounds may be mentioned.
  • the polyhydroxy compound preferably has 2 to 6 hydroxy groups in the molecule, more preferably 2 to 4 hydroxy groups in the molecule, and the following general formula (10): HO-Y-OH (10) [Wherein Y is as defined in the general formula (1)]
  • the dihydroxy compound represented by the formula is particularly preferred.
  • the dihydroxy compound represented by the general formula (10) is preferably monoalkylene glycol and polyalkylene glycol such as ethylene glycol, propylene glycol, butane-1,4-diol diethylene glycol, triethylene glycol; benzene-1,4-di Aromatic alcohols such as methanol, benzene-1,3-dimethanol and benzene-1,4-diethanol; hydroxyalkylenephenols such as (2-hydroxyphenyl) methanol and (2-hydroxyphenyl) -2-ethanol .
  • Any metal catalyst can be used as long as it is a catalyst used for the ring-opening reaction of an epoxy group.
  • a metal such as copper, zinc, iron, magnesium, silver, calcium, tin, BF 4 ⁇ , SiF, etc.
  • metal catalysts composed of anions such as 6 2- or PF 6 - and CF 3 SO 2- .
  • Preferred is tin borofluoride (Sn (BF 4 ) 2 ).
  • the polyhydroxy compound is used in an amount of 1 to 10 equivalents, preferably 4 to 8 equivalents, based on 1 equivalent of the epoxy group in the polyfunctional epoxy compound.
  • HPLC high performance liquid chromatography
  • all the epoxy groups react with the polyhydroxy compound due to disappearance of the peak of the polyfunctional epoxy compound as a raw material and also the one-end reactant, so that Generation can be confirmed.
  • the one-terminal reactant refers to a reactant in which all of the epoxy groups of the polyfunctional epoxy compound are unopened.
  • one epoxy group I is a compound in which only one or two epoxy groups are opened in the compound represented by the general formula (9a).
  • the metal catalyst is 10 to 1,000 ppm, preferably 20 to 200 ppm, based on the weight of the total reaction mixture.
  • the reaction temperature in the step (1A) is not particularly limited, but is 50 ° C to 130 ° C, preferably 70 ° C to 120 ° C.
  • the reaction in step (1A) can be performed in the presence or absence of an organic solvent.
  • Organic solvents that can be used include aromatic hydrocarbons such as benzene and toluene: cycloaliphatic ketones such as cyclohexanone; and starting dihydroxy compounds.
  • Step (1B) By the step (1B), the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound obtained in the step (1A) is epoxidized. In the step (1B), part or all of the hydroxy groups in the epoxy ring-opened product of the polyfunctional epoxy compound are epoxidized. In the present invention, 50% to 100% of the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound is preferably epoxidized, and more preferably 75% to 100% is epoxidized.
  • the epoxy ring-opened product of the polyfunctional epoxy compound is a raw material compound in the step (1B), and examples thereof include a compound in which all the epoxy groups of the polyfunctional epoxy compound are opened.
  • the following general formula (7b) which is an epoxy ring-opened product of an epoxy compound represented by the general formula (7a) to the general formula (9a):
  • epoxidation can be performed by using a known reaction for epoxidizing a hydroxy group, for example, epichlorohydrin method and oxidation method, preferably epichlorohydrin method.
  • an epoxy ring-opened product of the polyfunctional epoxy compound obtained in step (1A) is reacted with epichlorohydrin or methyl epichlorohydrin in the presence of a phase transfer catalyst.
  • This is a method of epoxidizing a hydroxy group of an epoxy ring-opened product of an epoxy compound.
  • epichlorohydrin or methyl epichlorohydrin can be reacted in the number of moles corresponding to the desired number of epoxy groups.
  • the amount of epichlorohydrin or methyl epichlorohydrin is 0.5 to 5 mol, preferably 0.5 to 2.5 mol, based on 1 mol of the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound. .
  • the amount of epichlorohydrin or methyl epichlorohydrin is 2 to 20 with respect to 1 mol of the compounds represented by the general formula (7b) and the general formula (8b) having four hydroxy groups in the molecule. Mol, preferably 2 to 10 mol.
  • the amount of epichlorohydrin or methyl epichlorohydrin is 3 to 30 mol, preferably 3 to 15 mol, per 1 mol of the compound represented by the general formula (9b) having 6 hydroxy groups in the molecule. It is.
  • Phase transfer catalysts include quaternary ammonium salts such as methyltrioctylammonium chloride, tetraalkylammonium chloride such as methyltridecylammonium chloride and tetramethylammonium chloride, and aralkyltrialkylammonium chloride such as benzyltrimethylammonium chloride. And benzyltrimethylammonium chloride is preferred.
  • the amount of phase transfer catalyst used is 0.1 to 5% by weight, more preferably 0.5 to 2.0% by weight, based on the total weight of the reactants.
  • the reaction can be carried out in the presence of a solvent such as hydrocarbons such as hexane and pentane; ethers such as diethyl ether, t-butyl methyl ether and diisopropyl ether; or ketones such as acetone and methyl ethyl ketone, but the solvent is excess It is also possible to use epichlorohydrin and methyl epichlorohydrin.
  • the reaction temperature may be 30 to 90 ° C, preferably 40 to 65 ° C, and most preferably a temperature in the range of about 50 to about 55 ° C.
  • the oxidation method includes a step of allylating the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound obtained in the step (1A) to obtain a diallyl ether compound, an allyl group of the diallyl ether compound or 2-methyl-2-propenyl Oxidizing the group.
  • allylation of a hydroxy group includes making the hydroxy group an allyl group or a 2-methyl-2-propenyl group.
  • the step of obtaining a diallyl ether compound comprises the step of reacting an epoxy ring-opened product of a polyfunctional epoxy compound with an allyl halide or 2-methyl-2-propenyl halide, thereby causing an epoxy ring-opened product of the polyfunctional epoxy compound.
  • the hydroxy group is converted to an allyl group or a 2-methyl-2-propenyl group.
  • quaternary ammonium salt is added, and an aqueous alkaline solution is dropped while maintaining the reaction temperature at 40 ° C. or lower, and the dropping is completed. Thereafter, the reaction is carried out at 30 to 40 ° C. for about 6 hours.
  • Halides in allyl halide and 2-methyl-2-propenyl halide include chlorine and bromine.
  • the addition amount of allyl halide and 2-methyl-2-propenyl halide is preferably 3 to 30 mol with respect to 1 mol of the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound.
  • the quaternary ammonium salt examples include tetraalkylammonium halides such as tetrabutylammonium bromide and tetraarylammonium halides such as tetraphenylammonium chloride.
  • the addition amount of the quaternary ammonium salt is preferably 0.001 mol to 0.1 mol with respect to 1 mol of the epoxy ring-opened product of the polyfunctional epoxy compound.
  • alkaline aqueous solution examples include calcium hydroxide, potassium hydroxide, and sodium hydroxide.
  • the amount of the alkali metal used is preferably 2 to 8 equivalents relative to 1 equivalent of the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound.
  • the step of oxidizing the allyl group or 2-methyl-2-propenyl group of the diallyl ether compound is a step of reacting the diallyl ether compound with hydrogen peroxide in the presence of potassium carbonate.
  • a diallyl ether compound obtained by allylating the hydroxy group of an epoxy ring-opened product of a polyfunctional epoxy compound is added with a solvent such as an alcohol such as methanol or ethanol, or a nitrile such as acetonitrile or benzonitrile, and potassium carbonate.
  • a solvent such as an alcohol such as methanol or ethanol, or a nitrile such as acetonitrile or benzonitrile
  • potassium carbonate Under stirring, 5 to 40%, preferably 30 to 35% hydrogen peroxide solution is added dropwise, and after completion of the addition, an oxidation reaction is carried out for 0.5 to 10 hours, preferably 1 to 6 hours.
  • the addition amount of the hydrogen peroxide solution is preferably 5 to 15 mol per 1 mol of the diallyl ether compound in which the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound is allylated.
  • the reaction temperature is, for example, 45 ° C. or less, preferably 20 to 40 ° C.
  • the method for producing an epoxy resin of the present invention is preferably a method for producing an epoxy resin represented by the general formula (1) to the general formula (3) of the present invention, comprising the following steps (2A) to (2B): (2A)
  • HO-Y-OH (10) [Wherein Y is as defined in the general formula (1)]
  • the method for producing a partially esterified epoxy resin of the present invention includes step (1C): (1C) a step of reacting an epoxy resin obtained by the production method including the steps (1A) to (1B) with (meth) acrylic acid in the presence of a basic catalyst.
  • Step (1C) the glycidyl group and methyl glycidyl group of the epoxy resin obtained by the production method including the steps (1A) to (1B) are (meth) acryloylated.
  • the epoxy resin obtained by the production method including the steps (1A) to (1B) is preferably an epoxy resin represented by the general formula (1) to the general formula (3).
  • (Meth) acrylic acid is not particularly limited, and for example, commercially available acrylic acid or methacrylic acid can be used.
  • the epoxy obtained by the production method including steps (1A) to (1B) with (meth) acrylic acid in the step of reacting the epoxy resin obtained by the production method including steps (1A) to (1B) with (meth) acrylic acid, the epoxy obtained by the production method including steps (1A) to (1B)
  • the (meth) acrylic acid to be reacted with respect to 1 equivalent of the epoxy group of the resin is preferably 10 to 90 equivalent%, more preferably 20 to 80 equivalent%, still more preferably 30 to 70 equivalent%, Particularly preferred is 40-60 equivalent%.
  • the reaction of glycidyl group and methyl glycidyl group with (meth) acrylic acid proceeds quantitatively, so the esterification rate of the obtained partially esterified epoxy resin is estimated from epoxy equivalent You can also
  • the basic catalyst a known basic catalyst used by a reaction between an epoxy resin and (meth) acrylic acid can be used.
  • a polymer-supported basic catalyst in which a basic catalyst is supported on a polymer can also be used.
  • the basic catalyst is preferably a trivalent organic phosphorus compound and / or an amine compound.
  • the basic atom of the basic catalyst is phosphorus and / or nitrogen.
  • trivalent organic phosphorus compound examples include alkylphosphines such as triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine and salts thereof, triphenylphosphine, tri-m-tolylphosphine, tris- (2 Arylphosphines such as, 6-dimethoxyphenyl) phosphine and salts thereof, phosphorous acid triesters such as triphenyl phosphite, triethyl phosphite and tris (nonylphenyl) phosphite and salts thereof.
  • alkylphosphines such as triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine and salts thereof
  • triphenylphosphine tri-m-tolylphosphine
  • tris- (2 Arylphosphines such as, 6-dime
  • amine compounds include secondary amines such as diethanolamine, tertiary amines such as triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, trisdiethylaminomethylphenol, 1,5,7-triazabicyclo [4.
  • dec-5-ene TBD
  • 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene Me-TBD
  • 1,8-diazabicyclo DBU
  • 6-dibutylamino-1,8-diazabicyclo [5.4.0] undec-7-ene 1,5-diazabicyclo [4.3.0]
  • Examples include strongly basic amines such as non-5-ene (DBN) and 1,1,3,3-tetramethylguanidine and salts thereof. Of these, 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) is preferable.
  • the salt of the amine compound include benzyltrimethylammonium chloride and benzyltriethylammonium chloride.
  • the polymer for supporting the basic catalyst is not particularly limited, and a polymer obtained by crosslinking polystyrene with divinylbenzene, a polymer obtained by crosslinking acrylic resin with divinylbenzene, or the like is used.
  • These polymers are solvents (for example, methyl ethyl ketone, methyl isobutyl ketone, toluene, etc.) used for the reaction between the epoxy resin obtained by the production method including steps (1A) to (1B) and (meth) acrylic acid, raw materials, Insoluble in objects.
  • a polymer-supported basic catalyst is obtained by chemically bonding a basic catalyst to an insoluble polymer or introducing a basic catalyst into a monomer, polymerizing the monomer, and then three-dimensionally crosslinking with a crosslinking monomer such as divinylbenzene.
  • a crosslinking monomer such as divinylbenzene.
  • polymer-supported basic catalyst examples include diphenylphosphinopolystyrene, 1,5,7-triazabicyclo [4.4.0] dec-5-enepolystyrene, N, N- (diisopropyl) aminomethylpolystyrene. N- (methylpolystyrene) -4- (methylamino) pyridine and the like. These polymer-supported basic catalysts may be used alone or in combination of two or more.
  • polymer-supported basic catalyst a commercially available one may be used.
  • examples of commercially available polymer-supported basic catalysts include PS-PPh 3 (diphenylphosphinopolystyrene, manufactured by Biotage), PS-TBD (1,5,7-triazabicyclo [4.4.0] deca-5 -Enpolystyrene, manufactured by Biotage Corporation).
  • the polymer-supported basic catalyst is used in an amount of 0.5 to 5.0 milliequivalents of the polymer-supported basic catalyst with respect to 1 equivalent of epoxy of the epoxy resin obtained by the production method including steps (1A) to (1B). And is more preferably 1.0 to 3.0 milliequivalents. It is preferable from the viewpoint of reaction rate, reaction time, and catalyst cost that the ratio of the polymer-supported basic catalyst is within the above range.
  • the temperature in the reaction step of the epoxy resin obtained by the production method comprising steps (1A) to (1B) and (meth) acrylic acid is preferably 60 to 120 ° C., more preferably 80 to 120. ° C, more preferably 90-110 ° C.
  • the reaction between the epoxy resin obtained by the production method including steps (1A) to (1B) and (meth) acrylic acid is because the partially esterified epoxy resin obtained by this reaction is cured by active energy rays such as ultraviolet rays. It is desirable to perform the reaction in a container that shields from ultraviolet rays.
  • the reaction between the epoxy resin obtained by the production method including steps (1A) to (1B) and (meth) acrylic acid is a reflux that exhibits good solvent properties with respect to the epoxy resin in order to prevent gas phase polymerization. Although it may be carried out in the presence of a solvent, in this case, since it is necessary to remove the solvent after completion of the reaction, it is preferably carried out without a solvent. Examples of the reflux solvent include acetone and methyl ethyl ketone.
  • the partially esterified epoxy resin comprises a polymer-supported basic catalyst. It is obtained by removing.
  • a method for removing the polymer-supported basic catalyst it is preferable to use filtration or centrifugation.
  • Examples of the method of filtering the polymer-supported basic catalyst include a method of filtering the polymer-supported basic catalyst using a nylon mesh NY-10HC (manufactured by Sefar, Switzerland) having a mesh size of 10 ⁇ m.
  • Examples of the method of centrifuging the polymer-supported basic catalyst include a method of removing the polymer-supported basic catalyst by solid-liquid separation using a centrifuge.
  • the method for producing a partially esterified epoxy resin of the present invention is preferably a partial ester as described above for producing the partially esterified epoxy resin represented by the general formulas (4) to (6).
  • a process for producing a epoxidized epoxy resin, the step (2C): (2C) The epoxy resin represented by the general formula (1), the general formula (2) or the general formula (3) obtained by the production method including the steps (2A) to (2B) is used as a basic catalyst.
  • a method for producing a partially esterified epoxy resin comprising a step of reacting with (meth) acrylic acid in the presence to obtain partially esterified epoxy resins represented by general formulas (4) to (6).
  • Curable composition (a) Epoxy resin represented by general formula (1), general formula (2) and general formula (3), (b) general formula (4), general formula (5) and general formula of the present invention Partially esterified epoxy resin represented by (6), (c) epoxy resin obtained by a production method comprising steps (1A) to (1B), and (d) partial ester obtained by a production method comprising step (1C)
  • the curable composition containing 1 or more types of resin selected from the group which consists of a chlorinated epoxy resin is demonstrated.
  • resin used as the base oligomer component contained in curable resin is 1 or more types of resin selected from the group which consists of the epoxy resin of this invention, and the partially esterified epoxy resin of this invention.
  • an epoxy resin represented by general formula (1), general formula (2) or general formula (3), or partially esterified epoxy represented by general formula (4), general formula (5) or general formula (6) The resin may be used alone, or an epoxy resin represented by the general formula (1), the general formula (2), or the general formula (3), or the general formula (4), the general formula (5), or the general formula (6). Two or more of the partially esterified epoxy resins represented by) may be mixed and used.
  • components contained in the curable composition of the present invention include a curing agent, a polymerization initiator, a filler, and a coupling agent in addition to the epoxy resin and the partially esterified epoxy resin of the present invention.
  • the curing agent is not particularly limited, and a known compound can be used as the curing agent.
  • the curing agent include amine-based curing agents such as organic acid dihydrazide compounds, imidazole and its derivatives, dicyandiamide, aromatic amines, epoxy-modified polyamines, and polyaminoureas.
  • VDH (1,3- Bis (hydrazinocarboethyl) -5-isopropylhydantoin), ADH (adipic acid dihydrazide), UDH (7,11-octadecadiene-1,18-dicarbohydrazide) and LDH (octadecane-1,18-dicarboxylic acid) Dihydrazide)
  • curing agents may be used alone or in combination.
  • the blending amount of the initiator is preferably 1 to 25 parts by weight, and more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the epoxy resin and the partially esterified epoxy resin.
  • the polymerization initiator means a compound that is activated by absorbing light energy and generates radicals.
  • a polymerization initiator is not specifically limited, A well-known compound can be used as a polymerization initiator.
  • As polymerization initiators benzoins, acetophenones, benzophenones, thioxanthones, ⁇ -acyloxime esters, phenylglyoxylates, benzyls, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, benzoins And polymerization initiators of benzoin ethers and anthraquinones, preferably having a reactive group that has low solubility in liquid crystals and that itself does not gasify the decomposition product upon light irradiation.
  • EY Resin KR-2 manufactured by KS M. Co., Ltd.
  • the blending amount of the polymerization initiator is preferably 0.1 to 5 parts by weight and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin and the partially esterified epoxy resin.
  • the filler is added for the purpose of improving the adhesive reliability of the curable composition by controlling the viscosity of the curable composition, improving the strength of the cured product obtained by curing the curable composition, or suppressing the linear expansion.
  • known inorganic fillers and organic fillers used for compositions containing epoxy resins can be used.
  • inorganic fillers calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and silicon nitride Is mentioned.
  • organic filler examples include polymethyl methacrylate, polystyrene, a copolymer obtained by copolymerizing a monomer constituting these and another monomer, polyester fine particles, polyurethane fine particles, and rubber fine particles.
  • inorganic fillers such as silicon dioxide and talc are particularly preferable.
  • the blending amount of the filler is preferably 2 to 40 parts by weight, and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin and the partially esterified epoxy resin.
  • the coupling agent is added for the purpose of further improving the adhesion to the liquid crystal display substrate.
  • the coupling agent is not particularly limited, and examples thereof include ⁇ -aminopropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane.
  • These silane coupling agents may be used alone or in combination of two or more.
  • the blending amount of the silane coupling agent is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of the epoxy resin and the partially esterified epoxy resin. .
  • the curable composition of the present invention is cured by applying heat by irradiation with energy rays such as ultraviolet rays or by applying heat after irradiation with energy rays such as ultraviolet rays.
  • energy rays such as ultraviolet rays
  • the method of curing the curable composition containing the epoxy resin and partially esterified epoxy resin of the present invention irradiates the curable composition containing the epoxy resin and partially esterified epoxy resin of the present invention with energy rays such as ultraviolet rays.
  • the epoxy resin and partially esterified epoxy resin of the present invention have extremely low elution properties for liquid crystals.
  • the liquid crystal display element using the curable composition containing the epoxy resin and the partially esterified epoxy resin of the present invention has good liquid crystal orientation even when the UV irradiation amount is low, and display failure occurs. Therefore, it is useful as a sealing agent for liquid crystals.
  • the mixture was then heated to about 50-55 ° C. with stirring under a high vacuum of 70 torr to vigorously reflux epichlorohydrin. 185 g of 48% solution NaOH (Kanto Chemical Co.) was slowly added to the mixture over 2 hours. As soon as the azeotrope was formed, stirring was continued while returning epichlorohydrin to the reaction system in the water / epichlorohydrin mixture. Stirring was continued for 4 hours after the addition. The reaction mixture was then cooled to room temperature, 1 L dichloromethane was added and washed 6 times with 1 L water.
  • the solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 233 g of a glycidyl ether (compound 2b) as a yellow transparent viscous product. From HPLC, the number of epoxy groups in the molecule was 3.6.
  • the reaction mixture was cooled to room temperature, 1 L of dichloromethane was added, and the mixture was washed 6 times with 1 L of water.
  • the solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 190 g of a yellow viscous ring-opened product.
  • Comparative Synthesis Example 1 (5-1) Synthesis of Comparative Compound 5c (Partially Methacrylated Epoxy Resin of Bisphenol A Type Epoxy Resin Used in Synthesis Example 1) 320.2 g of bisphenol A type epoxy resin (EXA850CRP, manufactured by DIC Corporation) was added to methacrylic acid ( 90.4 g (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.5 g PS-PPh 3 (manufactured by Biotage) and 100 mg BHT were mixed and stirred at 100 ° C. for 6 hours. After completion of the reaction, the catalyst was removed by filtration to obtain a partially methacrylated epoxy resin (Comparative Compound 5c).
  • EXA850CRP manufactured by DIC Corporation
  • Type A epoxy resin (Comparative Compound 1a), naphthalene type epoxy resin (Comparative Compound 3a), which is the raw material compound used in Synthesis Example 3, and trifunctional type epoxy resin (Techmore VG3101L (purine), which is the raw material compound used in Synthesis Example 4 Tech.), Comparative Compound 4a), and each oligomer of the partially methacrylated epoxy resin (Comparative Compound 5c) of the bisphenol A type epoxy resin produced in Comparative Synthesis Example 1 were subjected to an elution test as follows.
  • the elution property to the liquid crystal was evaluated by changing the Ni point (Nematic-Isotropic point) which is the phase transition temperature of the liquid crystal and directly quantifying the elution amount to the liquid crystal by HPLC (high performance liquid chromatography).
  • the Ni point of the liquid crystal is determined by the mixed composition of each component of the liquid crystal and is a unique value for each formulation. Generally, it is known that the Ni point is lowered when some impurities (other components) are mixed in the liquid crystal, and the impurity mixing state can be evaluated from the Ni point.
  • a differential scanning calorimeter (DSC, manufactured by PerkinElmer, Inc., Pyris 6) was used to measure the Ni point.
  • a 10 mg liquid crystal sample for evaluation was sealed in an aluminum sample pan, and the measurement was performed under the condition of a heating rate of 5 ° C./min.
  • the resin composition thus obtained was rubbed with a seal dispenser at a cross-sectional area of 4000 ⁇ m 2 on an ITO glass substrate (60 mm ⁇ 70 mm ⁇ 0.7 mmt) with an alignment film (Sunever SE-7492, manufactured by Nissan Chemical Industries, Ltd.). ) was dispensed. Thereafter, liquid crystal (TN liquid crystal, MLC-11900-080, manufactured by Merck) is dropped on the substrate, and the upper and lower substrates are bonded together by a liquid crystal dropping method (ODF method), and ultraviolet rays (UV irradiation device: UVX-01224S1, Ushio Electric).
  • ODF method liquid crystal dropping method
  • UV irradiation device UVX-01224S1, Ushio Electric
  • illuminance and radiation time for 1000mJ, 100mW / cm 2 / 365nm at 10 sec, in the case of 50mJ was cured by irradiation with 1 second) 50mW / cm 2 / 365nm, thereafter 120 ° C. hot air oven Thermal curing was performed for 1 hour to prepare a test cell for the orientation test.
  • illuminance of 0 mJ with a light-shielding mask after bonding, the liquid crystal and the sealant are not irradiated with ultraviolet rays, and then heat-cured in a hot air oven at 120 ° C. for 1 hour to provide a test cell for the orientation test.
  • Initiator EY resin, KR-2 (manufactured by KS Corporation) Curing agent: adipic acid dihydrazide (Otsuka Chemical Co., Ltd.) Filler: Silicon dioxide spherical fine particles, Seahoster KE-C50HG (manufactured by Nippon Shokubai Co., Ltd.) Coupling agent: 3-glycidoxypropyltrimethoxysilane, KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • the epoxy resin and partially esterified epoxy resin of the present invention are useful as a raw material for a sealing agent that can maintain high reliability by either active energy rays such as ultraviolet rays or heat because of its low solubility and elution in liquid crystals. It is.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Epoxy Compounds (AREA)
PCT/JP2011/070916 2010-10-01 2011-09-14 低溶出性エポキシ樹脂及びその部分エステル化エポキシ樹脂、その製造方法、並びにそれを含む硬化性樹脂組成物 WO2012043222A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201180047684.5A CN103140535B (zh) 2010-10-01 2011-09-14 低溶出性环氧树脂及其部分酯化环氧树脂、它们的制造方法以及含有它们的固化性树脂组合物
KR1020137011165A KR101812832B1 (ko) 2010-10-01 2011-09-14 저용출성 에폭시 수지 및 그의 부분 에스테르화 에폭시 수지, 그의 제조 방법, 및 그것을 포함하는 경화성 수지 조성물

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-223842 2010-10-01
JP2010223842A JP5736613B2 (ja) 2010-10-01 2010-10-01 低溶出性エポキシ樹脂及びその部分エステル化エポキシ樹脂、その製造方法、並びにそれを含む硬化性樹脂組成物

Publications (1)

Publication Number Publication Date
WO2012043222A1 true WO2012043222A1 (ja) 2012-04-05

Family

ID=45892693

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/070916 WO2012043222A1 (ja) 2010-10-01 2011-09-14 低溶出性エポキシ樹脂及びその部分エステル化エポキシ樹脂、その製造方法、並びにそれを含む硬化性樹脂組成物

Country Status (5)

Country Link
JP (1) JP5736613B2 (zh)
KR (1) KR101812832B1 (zh)
CN (2) CN103140535B (zh)
TW (2) TWI588173B (zh)
WO (1) WO2012043222A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106796376A (zh) * 2015-05-08 2017-05-31 积水化学工业株式会社 液晶显示元件用密封剂、上下导通材料及液晶显示元件
CN111560111A (zh) * 2020-06-22 2020-08-21 陕西科技大学 一种bpa-ga酚醛环氧树脂及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5979972B2 (ja) 2012-05-17 2016-08-31 協立化学産業株式会社 エステル化エポキシ樹脂、その製造方法、及びそれを含む硬化性組成物
JP6445780B2 (ja) * 2013-05-09 2018-12-26 積水化学工業株式会社 液晶滴下工法用シール剤、上下導通材料、及び、液晶表示素子
CN109789782B (zh) 2016-09-26 2021-10-29 富士胶片株式会社 投影型显示装置、投影显示方法、及存储介质
JP6601634B2 (ja) * 2017-03-31 2019-11-06 協立化学産業株式会社 変性樹脂及びそれを含む硬化性樹脂組成物

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5417999A (en) * 1977-07-06 1979-02-09 Ciba Geigy Ag Glycidyl and hydroxyl grouppcontaining linear polyether resin and preparation thereof
JPH06157712A (ja) * 1992-11-27 1994-06-07 Nippon Kayaku Co Ltd 変性エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
JP2001310927A (ja) * 2000-04-28 2001-11-06 Nippon Shokubai Co Ltd 不飽和基含有カルボン酸化合物
JP2006063227A (ja) * 2004-08-27 2006-03-09 Sakamoto Yakuhin Kogyo Co Ltd 熱硬化性エポキシ樹脂組成物
JP2008179796A (ja) * 2006-12-26 2008-08-07 Mitsui Chemicals Inc （メタ）アクリロイル基およびグリシジル基を有する化合物、および当該化合物を含む重合性組成物
JP2010202790A (ja) * 2009-03-04 2010-09-16 Dic Corp 繊維強化複合材料用樹脂組成物、その硬化物、プリント配線基板用樹脂組成物、繊維強化複合材料、繊維強化樹脂成形品、及びその製造方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5936361B2 (ja) * 1976-08-03 1984-09-03 三菱電機株式会社 マイカ薄葉材
JP4813647B2 (ja) * 2000-09-28 2011-11-09 三井化学株式会社 低臭気樹脂組成物およびそれを含む被覆材およびそれを用いた被覆工法
JP4524083B2 (ja) * 2003-01-22 2010-08-11 阪本薬品工業株式会社 活性エネルギー線硬化性樹脂組成物
JP4117838B2 (ja) * 2003-02-14 2008-07-16 三井化学株式会社 エポキシ部分エステル化物の製造方法
JP4524127B2 (ja) * 2004-03-18 2010-08-11 阪本薬品工業株式会社 新規なエポキシ樹脂およびそれを含む硬化性樹脂組成物
JP4779362B2 (ja) * 2005-01-06 2011-09-28 三菱化学株式会社 水素化エポキシ樹脂及びエポキシ樹脂組成物
JP2009185116A (ja) * 2008-02-04 2009-08-20 Air Water Inc カルボキシル基含有エポキシアクリレート樹脂、それを含有するアルカリ現像可能な光硬化性・熱硬化性樹脂組成物およびその硬化物
CN101747594B (zh) * 2009-12-11 2014-03-05 上海新天和树脂有限公司 环氧丙烯酸预聚体树脂及其制法和在光固化涂料中的应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5417999A (en) * 1977-07-06 1979-02-09 Ciba Geigy Ag Glycidyl and hydroxyl grouppcontaining linear polyether resin and preparation thereof
JPH06157712A (ja) * 1992-11-27 1994-06-07 Nippon Kayaku Co Ltd 変性エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
JP2001310927A (ja) * 2000-04-28 2001-11-06 Nippon Shokubai Co Ltd 不飽和基含有カルボン酸化合物
JP2006063227A (ja) * 2004-08-27 2006-03-09 Sakamoto Yakuhin Kogyo Co Ltd 熱硬化性エポキシ樹脂組成物
JP2008179796A (ja) * 2006-12-26 2008-08-07 Mitsui Chemicals Inc （メタ）アクリロイル基およびグリシジル基を有する化合物、および当該化合物を含む重合性組成物
JP2010202790A (ja) * 2009-03-04 2010-09-16 Dic Corp 繊維強化複合材料用樹脂組成物、その硬化物、プリント配線基板用樹脂組成物、繊維強化複合材料、繊維強化樹脂成形品、及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106796376A (zh) * 2015-05-08 2017-05-31 积水化学工业株式会社 液晶显示元件用密封剂、上下导通材料及液晶显示元件
CN111560111A (zh) * 2020-06-22 2020-08-21 陕西科技大学 一种bpa-ga酚醛环氧树脂及其制备方法

Also Published As

Publication number Publication date
TWI534170B (zh) 2016-05-21
KR101812832B1 (ko) 2017-12-27
CN103140535A (zh) 2013-06-05
CN105131251A (zh) 2015-12-09
TW201229081A (en) 2012-07-16
TWI588173B (zh) 2017-06-21
KR20130118324A (ko) 2013-10-29
JP5736613B2 (ja) 2015-06-17
TW201619231A (zh) 2016-06-01
CN103140535B (zh) 2015-09-02
JP2012077202A (ja) 2012-04-19
CN105131251B (zh) 2017-08-04

Similar Documents

Publication Publication Date Title
JP5184361B2 (ja) 液晶シール剤、およびそれを用いた液晶表示パネルの製造方法、ならびに液晶表示パネル
JP4211942B2 (ja) 液晶シール剤およびそれを用いた液晶表示セル
JP5979972B2 (ja) エステル化エポキシ樹脂、その製造方法、及びそれを含む硬化性組成物
JP5736613B2 (ja) 低溶出性エポキシ樹脂及びその部分エステル化エポキシ樹脂、その製造方法、並びにそれを含む硬化性樹脂組成物
TWI662055B (zh) 具有優良硬化後柔軟性的硬化性樹脂、（甲基）丙烯酸硬化性樹脂、及液晶密封劑組成物
JP5172321B2 (ja) 液晶シール剤
TWI782991B (zh) 含有酸基之（甲基）丙烯酸酯樹脂及阻焊用樹脂材料
JP6471620B2 (ja) エポキシ化合物、部分エステル化エポキシ化合物及びそれらを含む硬化性組成物
JP6310852B2 (ja) グリシジルエーテル系化合物、液晶シール剤及びグリシジルエーテル系化合物の製造方法
JP5645765B2 (ja) 液晶シール剤及びそれを用いた液晶表示セル
JP5897679B2 (ja) 低溶出性エポキシ樹脂及びその部分エステル化エポキシ樹脂、その製造方法、並びにそれを含む硬化性樹脂組成物
JP6461721B2 (ja) エポキシ化合物及びその部分エステル化エポキシ化合物、その製造方法、並びにそれを含む硬化性組成物
JP5748273B2 (ja) 液晶シール剤及びそれを用いた液晶表示セル
JP7484459B2 (ja) エポキシ（メタ）アクリレート樹脂、硬化性樹脂組成物、硬化物及び物品
WO2007074781A1 (ja) 液晶シール剤およびこれを用いた液晶パネルの製造方法
WO2013042614A1 (ja) 新規ヒドラジド化合物及びそれを用いた樹脂組成物
JP2009037008A (ja) カラーフィルター保護膜用樹脂組成物およびカラーフィルター

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180047684.5

Country of ref document: CN

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

Ref document number: 11828782

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20137011165

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 11828782

Country of ref document: EP

Kind code of ref document: A1