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
  • C08G59/14—Polycondensates modified by chemical after-treatment
  • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
  • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
  • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
• • 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
  • C08L63/10—Epoxy resins modified by unsaturated compounds
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1339—Gaskets; Spacers; Sealing of cells

Definitions

• the present invention relates to an esterified epoxy resin excellent in liquid stability, a method for producing the same, and a curable composition containing the esterified epoxy resin.
• the dropping method is a method in which a panel can be formed by directly dropping and bonding liquid crystal into 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.
• Patent Documents 1 to 3 It has been studied to use an esterified epoxy resin with (meth) acrylic acid as a raw material for the sealing agent.
• reaction of a compound having an epoxy group with (meth) acrylic acid is described as a method for converting an epoxy group into a (meth) acryloyl group. It is described that the (meth) acrylic esterified epoxy resin described in Patent Document 3 is particularly excellent in liquid crystal resistance.
• the object of the present invention is to improve the liquid stability of the sealing agent and reduce the viscosity while maintaining the liquid crystal resistance, which is an advantage of the sealing agent containing the esterified epoxy resin with conventional (meth) acrylic acid.
• Patent Document 3 for example, the following formula: The resin composition containing the esterification epoxy resin by methacrylic acid shown by this is described, and it is described that this epoxy resin composition is excellent in liquid crystal resistance.
• the hydroxyl group present in the esterified epoxy resin with (meth) acrylic acid deteriorates the liquid stability of the sealant and increases the viscosity of the sealant due to intermolecular hydrogen bonding.
• the present invention is as follows.
• R 21 independently of one another is hydrogen or methyl;
• R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently of each other hydrogen, glycidyl, methyl glycidyl, (meth) acryloyl, alkyl, acyl, silyl, acetal, or a group: —CH 2 —CH (OR ′) — CH 2 —O—R 8 or group: —CH 2 —C (CH 3 ) (OR ′) — CH 2 —O—R 8
• R ′ is hydrogen, (meth) acryloyl, alkyl, acyl, silyl, or acetal
• R 8 is (meth) acryloyl, Group: —CH 2 —CH (OR ′) — CH 2 —O—R 8 out of R ′ present on average is less than 0.8 on average.
• R 11 , R 12 , R 14 and R 15 present in the general formulas (1) and (2), glycidyl, methyl glycidyl and a group: —CH 2 —CH (OR ′) — CH 2 —O—R 8
• the sum of the groups: —CH 2 —C (CH 3 ) (OR ′) — CH 2 —O—R 8 on average is 2 or more, and the average number of glycidyl and methylglycidyl and groups: —CH 2 —
• the ratio of the average number of CH (OR ′) — CH 2 —O—R 8 and the group: —CH 2 —C (CH 3 ) (OR ′) — CH 2 —O—R 8 is 10:90 to 90 : 10,
• R 11 , R 12 , R 13 , R 14 , R 15 and R 16 present in the general formula (3), glycidyl, methyl glycidyl and a group: —CH 2
• R 21 independently of one another is hydrogen or methyl;
• R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently of each other hydrogen, glycidyl, methyl glycidyl, (meth) acryloyl, or a group: —CH 2 —CH (OR ′) — CH 2 —O—R 8 or group: —CH 2 —C (CH 3 ) (OR ′) — CH 2 —O—R 8 Wherein R ′ is hydrogen or (meth) acryloyl; R 8 is (meth) acryloyl, Group: —CH 2 —CH (OR ′) — CH 2 —O—R 8 out of R ′ present on average is less than 0.8 on average) In R 11 , R 12 , R 14 and R 15 present in the general formulas (1a) and (2a), glycidyl, methyl glycidyl and a group: —CH 2 —CH (OR
• (1B) The step of epoxidizing the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound obtained in step (1A) to obtain an epoxy resin and the (1C) epoxy resin obtained in step (1B) are (meth) The manufacturing method of esterified epoxy resin including the process made to react with an acrylic anhydride.
• Each R 21 independently of one another is hydrogen or methyl;
• R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, glycidyl, or methyl glycidyl, At least two of R 1 , R 2 , R 4 and R 5 present in the general formulas (4) and (5) are glycidyl or methyl glycidyl; At least two of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 present in the general formula (6) are glycidyl or methyl glycidyl.
• the method for producing an esterified epoxy resin according to the above (2) which comprises reacting a compound with (meth) acrylic anhydride.
• An epoxy resin comprising the resin represented by any one of the general formulas (4) to (6) described in the above (4) and optionally a multimerized product thereof is prepared by the following steps (2A) to (2B): (2A) General formula (7a): General formula (8a): Or, general formula (9a): [In each formula, X and R 21 are as defined in (4) above] An epoxy compound represented by the following general formula (10) in the presence of a metal catalyst: HO-Y-OH (10) (Where Y is as defined in (4) above) Is reacted with a dihydroxy compound represented by the general formula (7b): An epoxy ring-opened product comprising a resin represented by the formula (1) and optionally a multimer thereof, or the general formula (8b): Or an epoxy ring-opened product comprising a multimer of the resin represented by the general formula (9b): And a step of obtaining an epoxy ring-opened product consisting of a resin represented by the following and optionally a multimer thereof (wherein X, Y and R
• (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.
• step (1B) The step of epoxidizing the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound obtained in step (1A) to obtain an epoxy resin and the (1C ′) epoxy resin obtained in step (1B) (meta )
• the manufacturing method of esterified epoxy resin including the process made to react with an agent or an acetalizing agent.
• Each R 21 independently of one another is hydrogen or methyl;
• R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently of each other hydrogen, glycidyl, methyl glycidyl, or a group: —CH 2 —CH (OH) —CH 2 —O—R 8 Wherein R 8 is acryloyl or methacryloyl.
• R 11 , R 12 , R 14 and R 15 present in the general formulas (1 ′) and (2 ′) are glycidyl, methyl glycidyl, or a group: —CH 2 —CH (OH) —CH 2 —O—R 8 or group: —CH 2 —C (CH 3 ) (OH) —CH 2 —O—R 8 , the average number of glycidyl and methyl glycidyl and groups: —CH 2 —CH (OH)
• the ratio of —CH 2 —O—R 8 and the group: —CH 2 —C (CH 3 ) (OH) —CH 2 —O—R 8 to the average number is 10:90 to 90:10
• At least two of R 11 , R 12 , R 13 , R 14 , R 15 and R 16 present in the general formula (3 ′) are glycidyl, methyl glycidyl, or a group: —CH 2 —CH (
• a partially esterified epoxy resin comprising a resin represented by any one of the general formulas (1 ′) to (3 ′) described in (7) above and optionally a multimerized product thereof is prepared by the following step (2A) ⁇ (2C): (2A)
• An epoxy compound represented by the following general formula (10) in the presence of a metal catalyst: HO-Y-OH (10) (Where Y is as defined in (7) above) Is reacted with a dihydroxy compound represented by the general formula (7b):
• An epoxy ring-opened product comprising a resin represented by the formula (1) and optionally a multimer thereof, or the general formula (8b):
• An epoxy ring-opened product (wherein X, Y and R 21 are as defined above) consisting of
• Each R 21 independently of one another is hydrogen or methyl;
• R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently hydrogen, glycidyl, or methyl glycidyl, At least two of R 1 , R 2 , R 4 and R 5 present in the general formulas (4) and (5) are glycidyl or methyl glycidyl; At least two of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 present in general formula (6) are glycidyl or methyl glycidyl] (2C) Step (2B) A method comprising reacting the obtained resin represented by any one of the general formulas (4) to (6) and optionally an epoxy resin comprising a multimer thereof with (meth) acrylic acid The method for producing an esterified epoxy resin according to the above (7), which is produced by
• a curable composition comprising an esterified epoxy resin obtained by the production method according to any one of (3) to (8) above.
• the present invention it is possible to reduce the viscosity of the sealing agent and improve the liquid stability of the sealing agent while suppressing the solubility in the liquid crystal and preventing the contamination of the liquid crystal.
• the present invention relates to the general formulas (1) to (3) wherein X is —O—, alkylene having 1 to 4 carbon atoms, or alkylidene having 2 to 4 carbon atoms, and Y is carbon An alkylene having 1 to 4 atoms-an arylene having 6 to 20 carbon atoms-an alkylene having 1 to 4 carbon atoms, an alkylene having 1 to 4 carbon atoms-an 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), and each R 21 is Independently of each other, hydrogen or methyl, and R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently of one another hydrogen, glycidyl, methyl glycidyl, (meth)
• R 11 , R 12 , R 13 , R 14 , R 15 and R 16 glycidyl, methyl glycidyl and a group: —CH 2 —CH (OR ′) — CH 2 —O—R 8 and a group: —CH 2 —
• the sum total of C (CH 3 ) (OR ′) — CH 2 —O—R 8 is 2 or more on average, and the average number and group of glycidyl and methylglycidyl: —CH 2 —CH (OR ′) —
• the ratio of the average number of CH 2 —O—R 8 and the group: —CH 2 —C (CH 3 ) (OR ′) — CH 2 —O—R 8 is 10:90 to 90:10]
• optionally included multimer may be dimer, trimer, tetramer, pentamer or higher.
• the multimer of the general formula (1) is Indicated by The multimers of the general formulas (2) and (3) can be expressed in the same manner as the multimer of the general formula (1). The amount of multimer can vary.
• alkylene having 1 to 4 carbon atoms examples include methylene, ethylene, trimethylene and tetramethylene, preferably methylene and ethylene.
• alkylidene having 2 to 4 carbon atoms examples include ethylidene, propylidene, isopropylidene, methylpropylidene, and butylidene, preferably ethylidene and isopropylidene.
• 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).
• alkyl examples include methyl, ethyl, propyl, allyl, benzyl, p-methoxybenzyl, trityl and the like.
• acyl examples include acetyl, pivaloyl, benzoyl, t-butoxycarbonyl and the like.
• silyl examples include trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, triisopropylsilyl, t-butyldiphenylsilyl and the like.
• acetal examples include methoxymethyl, ethoxyethyl, tetrahydropyranyl, benzyloxymethyl, methoxyethoxymethyl, methylthiomethyl and the like.
• R 11 to R 16 it is preferable that hydrogen out of R 11 to R 16 is as small as possible.
• the average number of hydrogen is preferably 1 or less, more preferably 0.5 or less, still more preferably 0.1 or less, and most preferably 0.
• the total of —CH 2 —O—R 8 is preferably 3 or more on average, more preferably 3.8 or more in the case of formulas (1) and (2), In the case of the formula (1) and (2), the number is 4 or more, and in the case of the formula (3), the number is 6 or more.
• Average number and group of glycidyl and methyl glycidyl —CH 2 —CH (OR ′) — CH 2 —O—R 8 and group: —CH 2 —C (CH 3 ) (OR ′) — CH 2 —O—
• the ratio of the average number of R 8 is 10:90 to 90:10.
• R ′ present in the group: —CH 2 —CH (OR ′) — CH 2 —O—R 8 , hydrogen is preferably 0.7 or less on average, more preferably 0.5 or less, More preferably, it is 0.3 or less, and most preferably 0.
• the number of glycidyl and methyl glycidyl and the number of (meth) acryloyl groups in the esterified epoxy resin 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.
• a group containing glycidyl, methylglycidyl, (meth) acryloyl group: —CH 2 —CH (OR ′) — CH 2 —O—R 8 and group: —CH 2 —C (CH 3 ) ( OR ′) — CH 2 —O—R 8 is determined.
• the esterified epoxy resin is a mixture
• 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 esterified epoxy resin is a mixture of the epoxy resins represented by the general formula (4) and the general formula (5) described later and those
• a partially esterified epoxy resin represented by the general formula (3) includes a mixture of epoxy resins represented by the following general formula (6) and a resin having a (meth) acryloyl group as a part thereof. Resins in which some of these epoxy groups are (meth) acryloyl groups may be included.
• the bonding position of X in the general formula (1) is preferably 4,4′-position, that is, having 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 ratio of glycidyl group and methyl glycidyl group to acryloyl group and methacryloyl group can be determined from HPLC and epoxy equivalent. Specifically, since the epoxy equivalent of the raw material epoxy resin is increased by the amount of esterification, the degree of esterification can be calculated by measuring the epoxy equivalent of the esterified epoxy resin. Further, by performing mass spectrometry (LC-MS) at each peak of HPLC, the molecular weight and the existence ratio of each component can be obtained, and the ratio of the epoxy group and the acrylic group for each component can be obtained.
• LC-MS mass spectrometry
• the number average molecular weight of the esterified epoxy resin of the present invention is preferably 500 to 10,000, and more preferably 800 to 5,000.
• the viscosity of the esterified epoxy resin at 25 ° C. is preferably 1,000 to 600,000 mPa ⁇ s, more preferably 1,000 to 100,000 mPa ⁇ s, and 1,000 to 50, Most preferably, it is 000 mPa ⁇ s. If it is such a range, more hardening
• the viscosity is a value measured using an E-type viscometer.
• the esterified epoxy resin of the present invention represented by the general formula (1) is preferably, for example, (In the formula, R is (meth) acryloyl, Me, Et or the like) Furthermore, it can also contain multimers such as hexamethacrylate, octamethacrylate, dimer and trimer.
• the present invention further relates to general formulas (1a) to (3a) wherein R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently of each other hydrogen, glycidyl, methyl glycidyl, (Meth) acryloyl, or group: —CH 2 —CH (OR ′) — CH 2 —O—R 8 or group: —CH 2 —C (CH 3 ) (OR ′) — CH 2 —O—R 8 ( Wherein R ′ is hydrogen or (meth) acryloyl, and R 8 is (meth) acryloyl), which is the same as in general formulas (1) to (3)] It is an esterified epoxy resin comprising the indicated resin and optionally its multimer.
• the method for producing the esterified epoxy resin of the present invention comprises steps (1A) to (1C):
• (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 step of epoxidizing the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound obtained in step (1A) to obtain an epoxy resin and the (1C) epoxy resin obtained in step (1B) are (meth) A step of reacting with acrylic anhydride.
• 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 chloroquine with epichlorohydrin.
• polyfunctional epoxy compound it is obtained by reacting aromatic diols such as bisphenol A, bisphenol S, bisphenol F, bisphenol AD and the like, and diols modified with ethylene glycol, propylene glycol, alkylene glycol, and epichlorohydrin.
• aromatic diols such as bisphenol A, bisphenol S, bisphenol F, bisphenol AD and the like
• diols modified with ethylene glycol, propylene glycol, alkylene glycol, and epichlorohydrin An aromatic polyvalent glycidyl ether compound is mentioned.
• an aromatic polycarboxylic glycidyl ester compound obtained by reacting an aromatic dicarboxylic acid such as adipic acid or itaconic acid with epichlorohydrin, an aromatic such as isophthalic acid, terephthalic acid or pyromellitic acid
• 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 resin such as (Epicoat Resin Co., Ltd.), bisphenol F type epoxy resin such as Epicoat 806 and Epicoat 4004 (both manufactured by Japan Epoxy Resin Co., Ltd.), Epicron HP4032, and Epicron EXA-4700 (all large 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 above]
• 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. 6 2- or PF 6 -, CF 3 SO 2 - metal catalyst comprising anions and the like.
• 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-end reactant refers to a reactant in which a part of the epoxy group of the polyfunctional epoxy compound is unopened.
• one epoxy It is a compound in which only a group is opened
• the compound represented by the general formula (9a) it means a compound in which only one or two epoxy groups are opened.
• the amount of the metal catalyst used 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) the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound obtained in the step (1A) is epoxidized.
• step (1B) part or all of the hydroxy groups in the epoxy ring-opened product of the polyfunctional epoxy compound are epoxidized.
• 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): An epoxy ring-opened product comprising a resin represented by the formula (1) and optionally a multimer thereof, or the general formula (8b): Or an epoxy ring-opened product comprising a multimer of the resin represented by the general formula (9b): An epoxy ring-opened product comprising the resin represented by the above and optionally a multimer thereof (wherein X, Y and R 21 are as defined above).
• 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 mol to 20 mol, preferably 0.5 to 10 mol, relative to 1 mol of the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound.
• 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 3.0% 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.
• alkaline aqueous solution examples include calcium hydroxide, potassium hydroxide, and sodium hydroxide.
• the amount of the alkali metal used is preferably 0.5 to 2.0 equivalents relative to 1 equivalent of the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound.
• 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 polyallyl ether compound, an allyl group of the polyallyl ether compound or 2-methyl-2 Oxidizing the propenyl group.
• allylation of a hydroxy group includes making the hydroxy group an allyloxy group or a 2-methyl-2-propenyloxy group.
• the step of obtaining a polyallyl 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 the epoxy ring-opening of the polyfunctional epoxy compound.
• This is a step of converting the hydroxy group of the body into an allyloxy group or a 2-methyl-2-propenyloxy 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 polyallyl ether compound is a step of reacting the polyallyl ether compound with hydrogen peroxide in the presence of potassium carbonate.
• a polyallyl ether compound in which the hydroxy group of an epoxy ring-opened product of a polyfunctional epoxy compound is allylated a solvent such as an alcohol such as methanol or ethanol, or a nitrile such as acetonitrile or benzonitrile, and potassium carbonate.
• 5 to 40%, preferably 30 to 35% aqueous hydrogen peroxide is added dropwise with stirring, and after completion of the addition, an oxidation reaction is performed 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 with respect to 1 mol of the polyallyl 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 epoxy resin obtained in the step (1B) is preferably a compound represented by the general formulas (4), (5) and (6) from the general formulas (7b) to (9b).
• Examples of the epoxy resin component represented by the general formula (4) include: In addition, in some cases, a multimer such as a dimer or a trimer may be included.
• 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.
• the numbers of glycidyl and methylglycidyl in the general formulas (4) to (6) 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 resin is 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 (4) and the general formula (5) may include a compound having 3 and 4 epoxy groups, and a multimer thereof.
• the epoxy resins shown may include compounds with 3, 4, 5, and 6 epoxy groups and multimers thereof.
• the bonding position of X in the compound represented by the general formula (4) 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 (5) is preferably a 1,6-bond.
• the number average molecular weight of the epoxy resin is preferably 200 to 5,000.
• 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 resin is 100 to 3,000 g / eq. It is preferably 150 to 1,000 g / eq. It is more preferable that In this invention, an epoxy equivalent is calculated
• step (1C) the glycidyl group, methyl glycidyl group and hydroxyl group of the epoxy resin obtained by the production method including the steps (1A) to (1B) are (meth) acryloylated with (meth) acrylic anhydride.
• the epoxy resin obtained by the production method including the steps (1A) to (1B) is preferably an epoxy resin comprising a resin represented by the general formula (4) to the general formula (6) and, optionally, a multimer thereof. .
• (Meth) acrylic anhydride is not particularly limited, and for example, commercially available anhydrides of acrylic acid or methacrylic acid can be used.
• the epoxy resin obtained by the production method including the steps (1A) to (1B) is reacted with (meth) acrylic anhydride
• it is obtained by the production method including the steps (1A) to (1B).
• the (meth) acrylic anhydride to be reacted with respect to 1 equivalent of the epoxy group of the epoxy resin is preferably 10 to 90 equivalent%, more preferably 20 to 80 equivalent%, particularly preferably 25 to 75 equivalent%. It is.
• the reaction of glycidyl group and methylglycidyl group with (meth) acrylic anhydride proceeds quantitatively, so the esterification rate of the obtained esterified epoxy resin is estimated from the epoxy equivalent You can also
• the above reaction can be carried out in the presence of a phase transfer catalyst or a basic catalyst.
• the phase transfer catalyst may be selected from the aforementioned catalysts, with benzyltrimethylammonium chloride being preferred.
• the amount of phase transfer catalyst used is 0.001 to 5% by weight, more preferably 0.001 to 2.0% by weight, based on the total weight of the reactants.
• 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.
• a polymer-supported basic catalyst in which a basic catalyst is supported on a polymer can also be used.
• 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 include solvents (for example, methyl ethyl ketone, methyl isobutyl ketone, toluene, etc.) and raw materials used in the reaction of the epoxy resin obtained by the production method including steps (1A) to (1B) with (meth) acrylic anhydride. Insoluble in the product.
• 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 10.0 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). It is preferable that it is 1.0 to 5.0 milliequivalent. It is preferable from the viewpoint of the reaction rate, reaction time, and catalyst cost that the proportion 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 anhydride is preferably 60 to 130 ° C., more preferably 80 -130 ° C, more preferably 90-120 ° C.
• the reaction system and on the reaction system are used to prevent gelation. It is necessary to maintain an appropriate oxygen concentration in the gas phase. For example, when air is actively blown into the reaction system, it is necessary to be careful because it may cause oxidation of the catalyst and cause a decrease in activity.
• a polymerization inhibitor may be added, and examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, BHT (dibutylhydroxytoluene) and the like, and these may be used alone or in combination. Absent. The addition amount is preferably 50 to 1000 ppm based on the weight of the reaction system.
• the reaction between the epoxy resin obtained by the production method including steps (1A) to (1B) and (meth) acrylic anhydride is that the esterified epoxy resin obtained by this reaction is cured by active energy rays such as ultraviolet rays. Therefore, 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 the steps (1A) to (1B) and (meth) acrylic anhydride has good solvent properties with respect to the epoxy resin in order to prevent gas phase polymerization.
• the reaction may be performed in the presence of the refluxing solvent shown, but in this case, since it is necessary to remove the solvent after completion of the reaction, it is preferably performed without a solvent. Examples of the reflux solvent include acetone and methyl ethyl ketone.
• the esterified epoxy resin can be obtained by removing the polymer-supported basic catalyst.
• a method for removing the polymer-supported basic catalyst it is preferable to use filtration or centrifugation.
• Examples of the method for 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.
• the method for centrifuging the polymer-supported basic catalyst includes a method of removing the polymer-supported basic catalyst by solid-liquid separation using a centrifuge.
• the method for producing an esterified epoxy resin of the present invention is preferably for producing an esterified epoxy resin comprising a resin represented by the general formulas (1) to (3) and, optionally, a multimer thereof.
• the method for producing an esterified epoxy resin described above which is obtained by the production method including the steps (2C): steps (2A) to (2B), represented by the general formulas (4) to (6):
• a resin represented by any of the above and optionally an epoxy resin comprising a multimer is reacted with (meth) acrylic anhydride to obtain a resin represented by the general formulas (1a) to (3a)
• It is a manufacturing method of esterified epoxy resin including the process of obtaining the esterified epoxy resin which consists of a quantification body.
• the production method of the esterified epoxy resin of the present invention includes steps (1A), (1B), (1C ′) and (1D): (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.
• step (1B) The step of epoxidizing the hydroxy group of the epoxy ring-opened product of the polyfunctional epoxy compound obtained in step (1A) to obtain an epoxy resin and the (1C ′) epoxy resin obtained in step (1B) (meta )
• Steps (1A) and (1B) are as described above.
• the glycidyl group and the methyl glycidyl group of the epoxy resin obtained by the production method including the steps (1A) to (1B) are partially (meth) acryloylated.
• the epoxy resin obtained by the production method including the steps (1A) to (1B) is preferably an epoxy resin comprising a resin represented by the general formula (4) to the general formula (6) and, optionally, a multimer thereof. .
• (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 described above or a polymer-supported basic catalyst in which a basic catalyst is supported on a polymer can be used for the reaction between an epoxy resin and (meth) acrylic acid.
• 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 gas in the reaction system and on the reaction system is prevented in order to prevent gelation. It is necessary to keep the oxygen concentration of the phase proper. For example, when air is actively blown into the reaction system, it is necessary to be careful because it may cause oxidation of the catalyst and cause a decrease in activity.
• a polymerization inhibitor may be added, and examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, BHT, etc., and these may be used alone or in combination. The addition amount is preferably 50 to 1000 ppm based on the weight of the reaction system.
• 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 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. As described above, filtration or centrifugation is preferably used as a method for removing the polymer-supported basic catalyst.
• the partially esterified epoxy resin obtained in the step (1C ′) is represented by the general formula (1 ′), the general formula (2 ′) and the general formula (3 ′) produced from the general formulas (4) to (6).
• the general formula (1 ′) is represented by the general formula (1 ′), the general formula (2 ′) and the general formula (3 ′) produced from the general formulas (4) to (6).
• at least two of R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are glycidyl, methyl glycidyl.
• the partially esterified epoxy resins represented by the general formulas (1 ′) to (3 ′) of the present invention are glycidyl and methyl glycidyl represented by the general formulas (4) to (6). Some are epoxy resins that are (meth) acryloylated.
• R 11 to R 16 include a glycidyl, methylglycidyl, or (meth) acryloyl group: —CH 2 —CH (OH) —CH 2 —O—R 8 or a group: —CH 2 —C (CH 3 ) (OH) —CH 2 —O—R 8 is preferred, and R 11 to R 16 are represented by the general formula (1 ′ ) And (2 ′) are groups containing 3.8 or more, and in formula (3 ′) 5.8 or more containing a glycidyl, methylglycidyl or (meth) acryloyl group: —CH 2 —CH (OH) — More preferably, it is CH 2 —O—R 8 or a group: —CH 2 —C (CH 3 ) (OH) —CH 2 —O—R 8 , and all of R 11 to R 16 , that is
• the number of glycidyl and methyl glycidyl and the number of (meth) acryloyl groups 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.
• a group containing a glycidyl, methylglycidyl, (meth) acryloyl group —CH 2 —CH (OH) —CH 2 —O—R 8 or a group : The number of —CH 2 —C (CH 3 ) (OH) —CH 2 —O—R 8 is determined.
• the partially esterified epoxy resins represented by the general formulas (1 ′) to (3 ′) are a mixture, the number of glycidyl and methyl glycidyl and a group containing a (meth) acryloyl group: —CH 2 —CH
• the number of (OH) —CH 2 —O—R 8 or group: —CH 2 —C (CH 3 ) (OH) —CH 2 —O—R 8 is calculated as the average value of the mixture.
• a mixture of partially esterified epoxy resins may include a mixture of epoxy resins and a resin in which some of the epoxy groups are (meth) acryloyl groups.
• a group containing a glycidyl group, a methylglycidyl group, an acryloyl group and a methacryloyl group —CH 2 —CH (OH) —CH 2 —O—R 8 and a group: —CH 2 —C (CH 3 ) (OH) —CH 2 —O—R 8 is preferably 20:80 to 80:20, more preferably 25:75 to 75:25.
• 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.
• LC-MS mass spectrometry
• the number average molecular weight of the partially esterified epoxy resin is preferably 500 to 10,000, and more preferably 800 to 5,000.
• the partially esterified epoxy resin represented by the general formula (1 ′) is, for example, as a dimethacrylate compound, In addition, it may also contain multimers such as monomethacrylates, trimethacrylates, tetramethacrylates, dimerizations and trimerizations thereof.
• Step 1D is a step of reacting the partially esterified epoxy resin obtained in step (1C ′) with a (meth) acryloylating agent, an alkylating agent, an acylating agent, a silylating agent, or an acetalizing agent.
• Examples of the (meth) acryloylating agent include (meth) acrylic acid chloride, (meth) acrylic acid halides such as (meth) acrylic acid bromide, or (meth) acrylic anhydride, or (meth) acrylic acid methyl, It may be a (meth) acrylic ester such as ethyl (meth) acrylate or propyl (meth) acrylate.
• Examples of the alkylating agent include alkyl halides such as alkyl chloride, alkyl bromide, and alkyl iodide.
• acylating agent examples include acyl halides such as acyl chloride and acyl bromide, acid anhydrides, and esters.
• the silylating agent can be, for example, a trialkylsilyl halide such as trialkylsilyl chloride or trialkylsilyl bromide.
• acetalizing agent may include alkoxymethyl halides such as methoxymethyl chloride and ethoxymethyl chloride, or alkyl vinyl ethers such as tetrahydropyran and ethyl vinyl ether.
• reaction between the partially esterified epoxy resin and the (meth) acryloylating agent, alkylating agent, silylating agent or acetalizing agent can be carried out by a conventional method.
• Step 1D preferably, partially esterified epoxy resin composed of a resin represented by the general formulas (1 ′) to (3 ′) and optionally a multimerized product thereof is used as the partially esterified epoxy resin.
• An esterified epoxy resin comprising a resin represented by the general formulas (1) to (3) and optionally a multimer thereof by reacting with an acryloylating agent, alkylating agent, acylating agent, silylating agent or acetalizing agent.
• the curable composition of the present invention contains one or more esterified epoxy resins that can be produced by any of the above-described esterified epoxy resins or the aforementioned methods.
• the curable composition may be a liquid crystal sealant, particularly a liquid crystal sealant for a dropping method.
• 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 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, organic acid dihydrazide compounds, imidazole and its derivatives, dicyandiamide, aromatic amines, epoxy-modified polyamines, polyaminoureas, and the like.
• VDH (1,3-bis is an organic acid dihydrazide.
• the blending amount of the curing agent 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 when irradiated with light.
• EY Resin KR-2 manufactured by KS M. Co.
• 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. Or applying heat after applying energy rays such as ultraviolet rays.
• the esterified epoxy resin of the present invention has a low viscosity and is excellent in liquid stability when mixed with a latent curing agent, while maintaining the property of extremely low elution to liquid crystals. Useful as.
• esterified epoxy resin A in the general formula (1a), X is isopropylidene, the bonding position of X is 4,4′-position, R 21 is all hydrogen, Y is ethylene, R ′ present in the group: —CH 2 —CH (OR ′) — CH 2 —O—R 8 has an average of 0.3 or less hydrogen, and R 11 , R 12 , R 14 and R 15
• the average number of hydrogen atoms and the average number of glycidyl groups and the average number of groups: —CH 2 —CH (OR ′) — CH 2 —O—R 8 is 75:25.
• Example 2 Synthesis of Esterified Epoxy Resin B In the same manner as in Example 1 except that 13.6 g (0.0886 equivalent) of methacrylic anhydride was used, esterified epoxy resin B was obtained as a yellow viscous product. 57 g was obtained.
• esterified epoxy resin B in the general formula (1a), X is isopropylidene, the bonding position of X is 4,4′-position, R 21 is all hydrogen, Y is ethylene, R ′ present in the group: —CH 2 —CH (OR ′) — CH 2 —O—R 8 has an average of 0.3 or less hydrogen, and R 11 , R 12 , R 14 and R 15 The average number of hydrogen atoms and the average number of glycidyl groups and the average number of groups: —CH 2 —CH (OR ′) — CH 2 —O—R 8 is 65:35.
• Example 3 Synthesis of esterified epoxy resin C In Example 1, except that 20.5 g (0.133 equivalents) of methacrylic anhydride was used, esterified epoxy resin C was obtained as a yellow viscous product. 63 g was obtained.
• X is isopropylidene
• the bonding position of X is 4,4′-position
• R 21 is all hydrogen
• Y is ethylene
• R ′ present in the group: —CH 2 —CH (OR ′) — CH 2 —O—R 8 has an average of 0.3 or less hydrogen
• R 11 , R 12 , R 14 and R 15 The average number of hydrogen atoms and the average number of glycidyl groups and the average number of groups: —CH 2 —CH (OR ′) — CH 2 —O—R 8 is 50:50.
• R ′ present in the group: —CH 2 —CH (OR ′) — CH 2 —O—R 8
• the average number of hydrogen is 1.0 on average
• R 11 , R 12 , R 14 And R 15 the average number of hydrogen atoms is approximately zero
• the average number of glycidyl groups and the average number of groups —CH 2 —CH (OR ′) — CH 2 —O—R 8
• the target ratio was 50:50.
• Partially esterified epoxy resin B A partially esterified bisphenol A type epoxy resin (manufactured by Daicel UCB) that was 50% acrylated was used.
• the bisphenol A-type glycidyl epoxy resin is a bifunctional epoxy resin, of which a monofunctional epoxy is methacrylated with methacrylic acid.
• the partially esterified epoxy resin B has the following formula: (In the formula, R is glycidyl or a group: —CH 2 —CHOH—CH 2 —O—CO—C (CH 3 ) ⁇ CH 2 , and the average number and group of glycidyl: group: —CH 2 —CHOH— The theoretical ratio of the average number of CH 2 —O—CO—C (CH 3 ) ⁇ CH 2 is 50:50).
• 5 parts by weight of partially esterified epoxy resin A is 0.84 parts by weight of Amicure VDH
• 5 parts by weight of esterified epoxy resin A is 1.25 parts by weight of Amicure VDH
• 5 parts of esterified epoxy resin B 1.10 parts by weight of Amicure VDH with respect to parts by weight, 0.71 parts by weight of Amicure VDH with respect to 5 parts by weight of esterified epoxy resin C, and Amicure VDH with respect to 5 parts by weight of partially esterified epoxy resin B was used in an amount of 0.92 parts by weight.
• the measurement results are shown in Tables 1 and 2.
• Esterified epoxy resin D 50 g of epoxy resin A (0.266 equivalent / epoxy group), 10.25 g (0.0665 equivalent) of methacrylic anhydride, PS-TBD (polystyrene-1,5,7-triazabicyclo [4.4. 0] Dec-5-ene) and BT mg of BHT in a 12 mg eggplant type flask were stirred at 100 ° C. for 5 hours. The solid content was separated by filtration to obtain 50 g of esterified epoxy resin D as a yellow viscous substance.
• esterified epoxy resin D in the general formula (1a), X is isopropylidene, the bonding position of X is 4,4′-position, R 21 is all hydrogen, Y is ethylene, R ′ present in the group: —CH 2 —CH (OR ′) — CH 2 —O—R 8 has an average of 0.3 or less hydrogen, and R 11 , R 12 , R 14 and R 15 The average number of hydrogen atoms and the average number of glycidyl groups and the average number of groups: —CH 2 —CH (OR ′) — CH 2 —O—R 8 is 75:25.
• Esterified epoxy resin E 50 g of epoxy resin A (0.266 equivalent / epoxy group), 10.25 g (0.0665 equivalent) of methacrylic anhydride, 434 mg of PS-TPP (polystyrene-triphenylphosphine), and 12 mg of BHT in an eggplant type flask The mixture was stirred at 100 ° C. for 7 hours. Solid content was separated by filtration to obtain 50 g of esterified epoxy resin E as a yellow viscous substance.
• epoxy resin A 0.266 equivalent / epoxy group
• PS-TPP polystyrene-triphenylphosphine
• esterified epoxy resin E in the general formula (1a), X is isopropylidene, the bonding position of X is 4,4′-position, R 21 is all hydrogen, Y is ethylene, R ′ present in the group: —CH 2 —CH (OR ′) — CH 2 —O—R 8 has an average of 0.3 or less hydrogen, and R 11 , R 12 , R 14 and R 15 The average number of hydrogen atoms and the average number of glycidyl groups and the average number of groups: —CH 2 —CH (OR ′) — CH 2 —O—R 8 is 75:25.
• Table 2 shows the measurement results of the esterified epoxy resins D and E obtained in Examples 4 and 5.
• the esterified epoxy resin of the present invention can reduce the viscosity of the sealant and improve the liquid stability of the sealant while maintaining low solubility and elution in the liquid crystal. It is useful as a blending raw material.

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