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CN103140535B - Low stripping property epoxy resin and partial esterification epoxy resin thereof, they manufacture method and containing their curable resin composition - Google Patents

Low stripping property epoxy resin and partial esterification epoxy resin thereof, they manufacture method and containing their curable resin composition Download PDF

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Publication number
CN103140535B
CN103140535B CN201180047684.5A CN201180047684A CN103140535B CN 103140535 B CN103140535 B CN 103140535B CN 201180047684 A CN201180047684 A CN 201180047684A CN 103140535 B CN103140535 B CN 103140535B
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general formula
epoxy resin
compound
epoxy
carbonatoms
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CN103140535A (en
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臼井大晃
森本正浩
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Kyoritsu Chemical and Co Ltd
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Kyoritsu Chemical and Co Ltd
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    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Epoxy Compounds (AREA)

Abstract

The object of the invention is to obtain solvability in liquid crystal be suppressed and the pollution of liquid crystal can be prevented, the oligopolymer of the sealing agent that can be used as high-quality becomes to assign to the epoxy resin that uses and partial esterification epoxy resin.The invention provides and a kind ofly by certain specific structure, modification is carried out to the structure of epoxy resin and the new epoxy resin obtained and the partial esterification epoxy resin making the esterification of epoxy resin generating portion and obtain and their manufacture method.

Description

Low stripping property epoxy resin and partial esterification epoxy resin thereof, they manufacture method and containing their curable resin composition
Technical field
The present invention relates to low stripping property epoxy resin and partial esterification epoxy resin thereof, they manufacture method and containing their curable resin composition.
Background technology
In the manufacture method of liquid crystal display device, technique of dripping a kind ofly makes it fit by directly being dripped in the closed loop of sealing agent by liquid crystal under vacuo, and it is open to carry out vacuum, thus makes the technique of panel.This technique of dripping have reduce liquid crystal consumption, shorten the many merits such as injection length of liquid crystal to panel, as the manufacture method of liquid crystal panel using large substrate at present, become main flow.Drip in the method for technique comprising, coating sealing agent/liquid crystal, makes it fit, and then carries out gap formation, position adjustment, carries out the solidification of sealing agent mainly through ultraviolet curing.
At present, the position of drawing of sealing agent is in the position that light irradiates completely, and therefore present situation seals not easily to produce uncured part, thus there is not the problem polluting liquid crystal, but in recent years along with the needs on narrow limit, sealing station is in the trend closer to display pixel.Therefore, owing to carrying out the pollution of self-sealing substance, the electrical characteristic in display pixel portion are impacted so be in and easily cause the bad trend of display.Particularly in small panel, narrow to the distance of sealing agent from display part, the bad generation of the display caused because of contaminative is more obvious.Thus, the sealing agent few to liquid crystal pollution is needed.
Up to the present, as the method reduced the contaminative of liquid crystal, various research has been carried out.
Propose by using Cristalline epoxy resin, thus be reduced in the scheme (patent documentation 1) of the resin in curing process when making liquid crystal panel to the stripping in liquid crystal.
As epoxy resin, having in the compound of epoxy alkane unit for bisphenol S type, ether type, thioether-type and fluorenes type epoxy resin, propose the sealing agent (patent documentation 2) of the contaminative that inhibit liquid crystal.
In addition, as the raw material of sealing agent, be investigated the situation using partial esterification epoxy resin.
The epoxy resin generating portion proposing the epoxy resin or 4 officials energy by making 3 officials' energy is acrylated, thus reduces the ratio that acrylated compound does not occur, the scheme (patent documentation 3) of stripping during reduction thermofixation.
Propose by utilizing (methyl) acrylic acid derivative with carboxyl to make the phenol novolak type epoxy resin of 3 officials' energy or the phenol novolak type epoxy resin generating portion modification of 4 officials energy, thus improve liquid stability with the title complex of epoxy resin and acrylic resin, improve the scheme (patent documentation 4) of the orientation characteristic of liquid crystal.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-23583 publication
Patent documentation 2: Japanese Patent No. 4211942 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2008-3260 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2008-179796 publication
Summary of the invention
Invent problem to be solved
But, because the epoxy resin recorded in patent documentation 1 is crystalline, so exist to be used as possibility that liquid sealant and needing mixes with liquid resin or the possibility separated out occurring because of intermiscibility.
The epoxy resin of 3 officials' energy recorded in patent documentation 3 and 4 and the epoxy resin of 4 officials energy are high viscosity, or are solids as a rule, and the use thus as sealing agent is limited.
In addition, with regard to sealing agent, when UV irradiation dose is low, relevant contaminative is not enough under existing conditions.
The object of the invention is to obtain solvability in liquid crystal be suppressed and the pollution of liquid crystal can be prevented, the oligopolymer that can be used as high-quality sealing agent becomes to assign to the epoxy resin that uses and partial esterification epoxy resin.
For solving the means of problem
The present inventor etc. are in order to improve the liquid crystal panel characteristic of dripping required by sealing material, be conceived to epoxy resin as the main component of sealing material to the contaminative of liquid crystal, conduct in-depth research, found that, by carrying out modification with certain ad hoc structure to the structure of the epoxy resin as main component, thus the solvability/stripping property of oligopolymer in liquid crystal itself can be reduced, thus complete the present invention.
That is, the present invention relates to a kind of epoxy resin, described epoxy resin is represented by general formula (1), general formula (2) or general formula (3),
In general formula (1), general formula (2) and general formula (3),
X is-O-, the alkylene base of carbonatoms 1 ~ 4 or the alkylidene of carbonatoms 2 ~ 4,
Y be the alkylene base of the arylidene-carbonatoms 1 ~ 4 of the alkylene base-carbonatoms 6 ~ 20 of carbonatoms 1 ~ 4, the alkylene base-carbonatoms 6 ~ 20 of carbonatoms 1 ~ 4 arylidene or by-R 7-(O-R 7) n-represent group (in formula, R 7for the alkylene base of carbonatoms 1 ~ 4, n is the integer of 0 or 1 ~ 6),
R 1, R 2, R 3, R 4, R 5and R 6be hydrogen, glycidyl or methylglycidyl independently of each other,
Each R 21be hydrogen or methyl independently of each other separately,
R 1, R 2, R 3, R 4, R 5and R 6in at least 2 be glycidyl or methylglycidyl.
The present invention relates to a kind of partial esterification epoxy resin, described partial esterification epoxy resin is represented by general formula (4), general formula (5) or general formula (6),
In general formula (4), general formula (5) and general formula (6),
X, Y and R 21as described in above-mentioned definition,
R 11, R 12, R 13, R 14, R 15and R 16for hydrogen, glycidyl, methylglycidyl or by-Z-R 8(in formula, Z is 2-hydroxyl trimethylene base or 2-methyl-2-hydroxyl trimethylene base to the group represented, R 8for acryloxy or methacryloxy),
R 11, R 12, R 13, R 14, R 15and R 16in at least 2 be glycidyl, methylglycidyl or by-Z-R 8the group represented,
Glycidyl and methylglycidyl, ratio with acryl and methacryloyl, that is, glycidyl+methylglycidyl/with acryl+methacryloyl, be 10: 90 ~ 90: 10.
The present invention relates to a kind of manufacture method of epoxy resin, the manufacture method of described epoxy resin comprises operation (1A) ~ (1B),
Operation (1A): make the multi-functional epoxy compound of the epoxy group(ing) in molecule with more than 2 under the existence of metal catalyst with molecule in there is the hydroxyl of more than 2 polyol react, obtain the operation of the epoxy addition body of multi-functional epoxy compound, and
Operation (1B): make the hydroxyl of the epoxy addition body of the multi-functional epoxy compound obtained in operation (1A) that epoxidised operation occur.
The present invention relates to the manufacture method according to epoxy resin described above, it is the method for the manufacture of the above-mentioned epoxy resin represented by general formula (1) ~ general formula (3), comprises following operation (2A) ~ (2B),
Operation (2A): the epoxy compounds represented by general formula (7a), general formula (8a) or general formula (9a) is reacted with the dihydroxy compound represented by following general formula (10) under the existence of metal catalyst, obtain the operation of the epoxy addition body represented by general formula (7b), general formula (8b) or general formula (9b)
In general formula (7a), general formula (8a) and general formula (9a),
X and R 21as described in above-mentioned definition,
HO-Y-OH (10)
In general formula (10), Y as described in above-mentioned definition,
In general formula (7b), general formula (8b) and general formula (9b), X, Y and R 21as described in above-mentioned definition; With
Operation (2B): the hydroxyl initial ring of the epoxy addition body represented by general formula (7b) ~ general formula (9b) obtained in operation (2A) is oxidized, obtains the operation of the epoxy resin represented by general formula (1) ~ general formula (3).
The present invention relates to a kind of manufacture method of partial esterification epoxy resin, the manufacture method of described partial esterification epoxy resin comprises operation (1C),
Operation (1C): make the operation that the epoxy resin obtained by above-mentioned manufacture method is reacted with (methyl) vinylformic acid under the existence of basic catalyst.
The present invention relates to the manufacture method according to partial esterification epoxy resin described above, it is the method for the manufacture of the above-mentioned partial esterification epoxy resin represented by general formula (4) ~ general formula (6), comprises operation (2C),
Operation (2C): the epoxy resin represented by general formula (1), general formula (2) or general formula (3) by above-mentioned manufacture method is obtained is reacted with (methyl) vinylformic acid under the existence of basic catalyst, obtain the operation of the partial esterification epoxy resin represented by general formula (4) ~ general formula (6)
In general formula (1), general formula (2) and general formula (3),
X, Y, R 1, R 2, R 3, R 4, R 5, R 6, R 21as described in above-mentioned definition,
R 1, R 2, R 3, R 4, R 5and R 6in at least 2 be glycidyl or methylglycidyl.
The present invention relates to a kind of solidification compound, described solidification compound contains and is selected from (a) above-mentioned epoxy resin represented by general formula (1), general formula (2) and general formula (3), (b) above-mentioned partial esterification epoxy resin represented by general formula (4), general formula (5) and general formula (6), c () is by the obtained epoxy resin of above-mentioned manufacture method, and the resin of more than a kind in (d) partial esterification epoxy resin of being obtained by above-mentioned manufacture method.
The effect of invention
According to the present invention, the solvability that can obtain in liquid crystal be suppressed and liquid crystal pollution can be prevented, the oligopolymer that can be used as high-quality sealing agent becomes to assign to the epoxy resin that uses and partial esterification epoxy resin.
Accompanying drawing explanation
Fig. 1 is the microscope figure of the orientation of the corner part of the liquid crystal represented under illumination 1000mJ.
Fig. 2 is the microscope figure of the orientation of the line part of the liquid crystal represented under illumination 1000mJ.
Fig. 3 is the microscope figure of the orientation of the corner part of the liquid crystal represented under illumination 50mJ.
Fig. 4 is the microscope figure of the orientation of the line part of the liquid crystal represented under illumination 50mJ.
Fig. 5] be the microscope figure of the orientation of the corner part of the liquid crystal represented under illumination 0mJ.
Fig. 6 is the microscope figure of the orientation of the line part of the liquid crystal represented under illumination 0mJ.
Embodiment
Below suitable embodiment of the present invention is described.
Epoxy resin of the present invention is the compound represented by general formula (1), general formula (2) and general formula (3).
The alkylene base of carbonatoms 1 ~ 4 can list methylene radical, ethylene group, trimethylene base and fourth support group, is preferably methylene radical and ethylene group.
The alkylidene of carbonatoms 2 ~ 4 can list ethidine, propylidene base, isopropylidene, methyl propylidene base and fourth fork base, is preferably ethidine and isopropylidene.
The arylidene of carbonatoms 6 ~ 20 is aryl of monocycle or many rings, can list phenylene, naphthylidene and anthrylene, is preferably phenylene.
The illustration of the alkylene base of the carbonatoms 1 ~ 4 in the arylidene of the alkylene base-carbonatoms 6 ~ 20 of carbonatoms 1 ~ 4 and the arylidene of carbonatoms 6 ~ 20 is as described in above-mentioned definition.As the arylidene of the alkylene base-carbonatoms 6 ~ 20 of carbonatoms 1 ~ 4, preferably methylene-phenylene can be listed.In the present invention, can be optional with the bonding order of each group in the arylidene of the alkylene base-carbonatoms 6 ~ 20 of carbonatoms 1 ~ 4.Such as, for being bonded to R 1~ R 6sauerstoffatom, can with the alkylene base bonding of the carbonatoms 1 ~ 4 in the arylidene of the alkylene base-carbonatoms 6 ~ 20 of carbonatoms 1 ~ 4, can also with the arylidene bonding of carbonatoms 6 ~ 20.
The illustration of the alkylene base of the carbonatoms 1 ~ 4 in the alkylene base of the arylidene-carbonatoms 1 ~ 4 of the alkylene base-carbonatoms 6 ~ 20 of carbonatoms 1 ~ 4 and the arylidene of carbonatoms 6 ~ 20 is as described in above-mentioned definition.As the alkylene base of the arylidene-carbonatoms 1 ~ 4 of the alkylene base-carbonatoms 6 ~ 20 of carbonatoms 1 ~ 4, phenylene two (methylene radical) preferably can be listed.
In the present invention, R 1~ R 6in at least 2 be glycidyl or methylglycidyl.In the present invention, so-called epoxy group(ing) comprises both glycidyl and methylglycidyl.Here, glycidyl is 2,3-epoxypropyl, and methylglycidyl is 2,3-epoxy group(ing)-2-methyl-propyl.In the present invention, preferred R 1~ R 6among more than 3 be glycidyl or methylglycidyl, more preferably R 1~ R 6among be all glycidyl or methylglycidyl.In addition, in the present invention, preferred glycidyl and methylglycidyl are present in and R 4, R 5and R 6on the Sauerstoffatom of i.e. primary carbon atom bonding, more preferably glycidyl and methylglycidyl are present in and R 1~ R 6on the Sauerstoffatom of i.e. primary carbon atom and secondary carbon(atom) bonding.
In the present invention, the glycidyl in the epoxy resin represented by general formula (1) ~ general formula (3) and the quantity of methylglycidyl calculate by high performance liquid chromatography (HPLC).Specifically, obtaining the peak corresponding with the number of glycidyl and methylglycidyl by HPLC, there is ratio in what calculate the number of glycidyl and methylglycidyl according to respective peak area.The number of glycidyl and the methylglycidyl contained in compound can be calculated thus.In addition, when being mixture by the epoxy resin that general formula (1) ~ (3) represent, the quantity of glycidyl and methylglycidyl can calculate with the form of the mean value of mixture.That is, with regard to the quantity of epoxy group(ing), judge molecular weight by the mass analysis (LC-MS) carrying out each peak of HPLC, calculate the average quantity of the epoxy group(ing) in mixture according to the existence ratio of each composition in mixture.Such as, exist in the mixture of epoxy resin represented by general formula (1) and general formula (2) and comprise the compound and polymer thereof that epoxy group(ing) is 3 and 4, in the epoxy resin represented by general formula (3), comprise compound and polymeric situation thereof that epoxy group(ing) is 3,4,5 and 6.
The bonding position of the X of the compound represented by general formula (1) is preferably 4,4 '-position, in other words, is the compound with bisphenol-type epoxy resin skeleton.In addition, the bonding position of the naphthalene nucleus in the compound represented by general formula (2) is preferably 1,6-bonding.
In the present invention, the number-average molecular weight of the compound represented by general formula (1) ~ general formula (3) is preferably 200 ~ 5,000.If in such scope, then cementability is good, and is inhibited further to the contaminative of liquid crystal.In the present invention, number-average molecular weight is the number-average molecular weight adopting gel permeation chromatography (GPC) to be calculated by polystyrene conversion.
In the present invention, the epoxy equivalent (weight) of the epoxy compounds represented by general formula (1) ~ general formula (3) is preferably 100 ~ 3,000g/eq., is more preferably 200 ~ 1,000g/eq..If in such scope, then cementability is good, and is inhibited further to the contaminative of liquid crystal.In the present invention, when epoxy resin is mixture, epoxy equivalent (weight) can be obtained with the form of the mean value of mixture.In the present invention, epoxy equivalent (weight) can be obtained according to JIS K 7236:2001 (corresponding ISO3001:1999).
In the present invention, partial esterification epoxy resin is represented by general formula (4), general formula (5) and general formula (6).In the partial esterification epoxy resin represented by general formula (4) ~ general formula (6), R 11, R 12, R 13, R 14, R 15and R 16in at least 2 be glycidyl, methylglycidyl or containing (methyl) acryl by-Z-R 8the group represented.That is, the epoxy resin by the partial esterification epoxy resin that general formula (4) ~ general formula (6) represents being the glycidyl of the epoxy resin represented by general formula (1) ~ general formula (3) and a part for methylglycidyl and being obtained by (methyl) polyacryl of the present invention.
In the present invention, preferred R 11~ R 16among more than 3 be glycidyl, methylglycidyl or containing (methyl) acryl by-Z-R 8the group represented, more preferably R 11r 16among be glycidyl, methylglycidyl or containing (methyl) acryl by-Z-R 8the group represented.In addition, in the present invention, preferred glycidyl, methylglycidyl and (methyl) acryl are present in and R 14, R 15and R 16on the Sauerstoffatom of i.e. primary carbon atom bonding, more preferably glycidyl, methylglycidyl and (methyl) acryl are present in and R 11~ R 16on the Sauerstoffatom of i.e. primary carbon atom and secondary carbon(atom) bonding.
The quantity of the glycidyl in the partial esterification epoxy resin represented by general formula (4) ~ general formula (6) and the quantity of methylglycidyl and (methyl) acryl calculates by HPLC.Specifically, obtaining the peak corresponding with the quantity of the quantity of each epoxy group(ing) and each (methyl) acryl by HPLC, there is ratio in what calculate respective number according to respective peak area.Obtain thus the glycidyl in the partial esterification epoxy resin represented by general formula (4) ~ general formula (6), methylglycidyl, containing (methyl) acryl by-Z-R 8the number of the group represented.In addition; when the partial esterification epoxy resin represented by general formula (4) ~ (6) is mixture, the quantity of glycidyl and methylglycidyl and (methyl) acryl can calculate with the form of the mean value of mixture.Such as; there is in the mixture of partial esterification epoxy resin represented from general formula (4) and general formula (5) resin that the mixture of epoxy resin that comprises and represented from general formula (1) and general formula (2) and a part for their epoxy group(ing) become (methyl) acryl, a part for mixture and their epoxy group(ing) that the partial esterification epoxy resin represented from general formula (6) comprises the epoxy resin represented from general formula (3) becomes the situation of the resin of (methyl) acryl.
In the partial esterification epoxy resin represented by general formula (4) ~ general formula (6); the ratio of glycidyl and methylglycidyl and acryl and methacryloyl; that is, the ratio of epoxy group(ing) and (methyl) acryl, is 10: 90 ~ 90: 10.Here, epoxy group(ing) is obtained by HPLC and epoxy equivalent (weight) with the ratio of (methyl) acryl.Specifically, the part that the epoxy equivalent (weight) due to the epoxy resin as raw material has only reduced by partial esterification, so the epoxy equivalent (weight) by measuring part acrylated epoxy, thus calculates which kind of degree of esterified one-tenth.In addition, by carrying out the mass analysis (LC-MS) at each peak of HPLC, and obtain the molecular weight of various composition and there is ratio, thus obtaining the epoxy group(ing) of various composition and the ratio of acryl.
In the present invention, the number-average molecular weight of the partial esterification epoxy resin represented by general formula (4) ~ general formula (6) is preferably 500 ~ 10,000, is more preferably 800 ~ 5,000.In addition, the partial esterification epoxy resin represented by general formula (4) ~ general formula (6) is preferably 1,000 ~ 1,000,000mPs the viscosity of 20 DEG C, is more preferably 40,000 ~ 600,000mPs.If in such scope, then not easily flow when coating liquid crystal, the pollution to liquid crystal can be suppressed.It should be noted that, in the present invention, viscosity uses E type viscometer, the value recorded under the rotating speed of bell-shaped rotor is 2.5rpm.
The manufacture method of epoxy resin
The manufacture method of epoxy resin of the present invention is described.In the manufacture method of epoxy resin of the present invention, comprise following operation: based on the open loop operation of the epoxy group(ing) of the multi-functional epoxy compound carried out as the multi-functional epoxy compound of raw material and the reaction of polyol, and the hydroxyl of the epoxy addition body generated by the open loop of epoxy group(ing) and be derived from the epoxidation process of hydroxyl of polyol.In the present invention, epoxidation comprises both Glycidyl and methylglycidyl.
The manufacture method of epoxy resin of the present invention comprises following procedures (1A) ~ (1B):
(1A) make the multi-functional epoxy compound of the epoxy group(ing) in molecule with more than 2 under the existence of metal catalyst with molecule in there is the hydroxyl of more than 2 polyol react, obtain the operation of the epoxy addition body of multi-functional epoxy compound, and
(1B) make the hydroxyl of the epoxy addition body of the multi-functional epoxy compound obtained in operation (1A) that epoxidised operation occur.
Operation (1A)
In operation (1A), the multi-functional epoxy compound as the epoxy group(ing) in the molecule of starting compound with more than 2 forms hydroxyl by the open loop of epoxy group(ing), and forms the hydroxyl being derived from polyol.Here, the open loop body of so-called multi-functional epoxy compound refers to the whole open loop of the epoxy group(ing) of multi-functional epoxy compound and the compound obtained.
As long as have the epoxy compounds of the epoxy group(ing) of more than 2 in multi-functional epoxy compound 1 molecule, just without particular determination.As multi-functional epoxy compound, following compound can be listed.
As multi-functional epoxy compound, many alkylene glycols classes such as ethylene glycol of sening as an envoy to, glycol ether, triglycol, propylene glycol, dipropylene glycol, tripropylene glycol can be enumerated, the aliphatic polybasic glycidyl ether compound that the polyalcohols such as dihydroxy methylpropane, TriMethylolPropane(TMP), the spiroglycol, glycerine and Epicholorohydrin react and obtain.
As multi-functional epoxy compound, the aromatic diol classes such as dihydroxyphenyl propane of sening as an envoy to, bisphenol S, Bisphenol F, dihydroxyphenyl propane D can be enumerated and ethylene glycol is carried out to them, aromatic polyvalent glycidyl ether compound that propylene glycol, alkylene glycol modification and the glycols obtained and Epicholorohydrin react and obtain.
As multi-functional epoxy compound, the aliphatic polybasic glycidyl ether compound that the send as an envoy to aromatic dicarboxylic acid such as hexanodioic acid, methylene-succinic acid and Epicholorohydrin react and obtain can be enumerated, make the aromatic polyvalent epihydric alcohol ester compound that the aromatic dicarboxylic acids such as m-phthalic acid, terephthalic acid, pyromellitic acid and Epicholorohydrin react and obtain.
As multi-functional epoxy compound, the aromatic polyvalent Racemic glycidol amine compound that the aromatic amines such as diaminodiphenyl-methane of sening as an envoy to, aniline, m-xylene diamine and Epicholorohydrin react and obtain can be enumerated.
As multi-functional epoxy compound, the polynary glycidyl compound of glycolylurea type that send as an envoy to glycolylurea and derivative and Epicholorohydrin thereof react and obtain can be enumerated.
As multi-functional epoxy compound, the polynary glycidyl ether compound of phenolic, the polynary glycidyl ether compound of phenolic varnish type that phenol resins, novolac resin and Epicholorohydrin that can enumerate sends as an envoy to is gone out by phenol or cresols and formaldehyde-derived react and obtain.
In the present invention, as multi-functional epoxy compound, the epoxy compounds preferably represented by following general formula (7a), general formula (8a) or general formula (9a),
In general formula (7a), general formula (8a) and general formula (9a),
X and R 21as described in define in general formula (1).
As preferred multi-functional epoxy compound's of the present invention, the epoxy compounds represented by general formula (7a) ~ general formula (9a), EPICLON 850 (DAINIPPON INK & CHEMICALS is include, for example out as commercially available product, INC manufactures), EPIKOTE 828EL, EPIKOTE 1004 (is JAPAN EPOXY RESIN CO., LTD. manufacture) etc. bisphenol A type epoxy resin, EPIKOTE 806, EPIKOTE 4004 (is JAPAN EPOXY RESIN CO., LTD. manufacture) etc. bisphenol f type epoxy resin, EPICLON HP4032, EPICLON EXA-4700 (is DAINIPPON INK & CHEMICALS, INC manufacture) etc. naphthalene type epoxy resin, 3 functional epoxy resins such as VG-3101 (Mitsui Petrochemical Ind., Ltd.'s manufacture).
In the present invention, as long as have the compound containing the hydroxyl of more than 2 in the polyol molecule of the hydroxyl of more than 2 in molecule, just without particular determination.As the concrete example of polyol, following compound can be listed.
As the compound in molecule with 2 hydroxyls, ethylene glycol can be listed, glycol ether, triglycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1, 4-butyleneglycol and 1, single alkylene glycol and many alkylene glycols such as 6-hexylene glycol, pyrocatechol, 1, 2-dihydroxy naphthlene, 2, 3-dihydroxy naphthlene, 1, 2-dihydroxyanthraquinone and 2, the aromatic hydroxy compound of 3-dihydroxyl quinoxaline etc. 2 yuan, benzene-1, 4-dimethanol, benzene-1, 3-dimethanol, benzene-1, the aromatic alcohols such as 4-di-alcohol, 4-methylolphenol, 3-methylolphenol, the hydroxyalkyl phenol such as 4-hydroxyethyl phenol and 3-hydroxyethyl phenol.
As the compound in molecule with 3 hydroxyls, glycerine, TriMethylolPropane(TMP), 2-methyl-2-methylol-1 can be listed, ammediol, 2,4-dihydroxyl-3-methylol pentane, 1,2,6-hexane triol and 1,1,3 yuan of alcohol such as 1-tri-(methylol) propane, pyrogallol, 3,4,5-trihydroxytoluenes, 1, the aromatic polyhydroxy compounds of the gallic acid ester cpds such as 2,4-trihydroxyanthraquinone, gallic acid and methyl gallate, Tenox PG and Stabilizer GA 8 etc. 3 yuan.
As the compound of hydroxyl in molecule with more than 4, tetramethylolmethane, diglycerol, tetramethylol methane, alkylene glycosides (methyl glucoside, ethyl glycosides etc.) can be listed.In addition, the aromatic polyhydroxy compounds of calixarene compound of 2,3,4,4'-Tetrahydroxybenzophenone, ellagic acid, hexahydroxybenzene, tannic acid and pyrocatechol or pyrogallol etc. more than 4 yuan can be listed.
In the present invention, there is in the preferred molecule of polyol the polyol of the hydroxyl of 2 ~ 6, more preferably there is in molecule the polyol of the hydroxyl of 2 ~ 4, the dihydroxy compound particularly preferably for being represented by following general formula (10),
HO-Y-OH (10)
In general formula (10), as described in Y definition as middle in general formula (1).
As the dihydroxy compound represented by general formula (10), can preferably list ethylene glycol, propylene glycol, butane-1, single alkylene glycol and many alkylene glycols such as 4-glycol glycol ether, triglycol, benzene-1,4-dimethanol, benzene-1, the aromatic alcohols such as 3-dimethanol, benzene-Isosorbide-5-Nitrae-di-alcohol, the hydroxyl alkylene base phenol such as (2-hydroxy phenyl) methyl alcohol, (2-hydroxy phenyl)-2-ethanol.
As long as metal catalyst is for the catalyzer of the ring-opening reaction of epoxy group(ing), just optionally can use, include, for example out by metal and BF such as copper, zinc, iron, magnesium, silver, calcium, tin 4 -, SiF 6 2-or PF 6 -, CF 3sO 2 -deng the metal catalyst that negatively charged ion is formed.Be preferably stannous fluoboric acid (Sn (BF 4) 2).
In the present invention, relative to the epoxy group(ing) in the polyfunctional epoxy compound of 1 equivalent, the consumption of polyol is 1 equivalent ~ 10 equivalent, is preferably 4 equivalent ~ 8 equivalents.In the present invention, high performance liquid chromatography (HPLC) can be adopted, by the disappearance at the peak of the multi-functional epoxy compound in raw material and single end reaction thing, thus confirm that all epoxy group(ing) and polyol react and generate epoxy addition body.Here, so-called single end reaction thing refers to the reactant of the non-open loop of whole epoxy group(ing) of multi-functional epoxy compound, such as the compound of only 1 epoxy group(ing) generation open loop in the compound represented by general formula (7a) and (8a), and the compound of only 1 or 2 epoxy group(ing) generation open loop in the compound represented by general formula (9a).
In the present invention, metal catalyst is 10 ~ 1,000ppm for the weight of complete reaction mixture, is preferably 20 ~ 200ppm.
Operation (1A) although in temperature of reaction without particular restriction, be 50 DEG C ~ 130 DEG C, preferably 70 DEG C ~ 120 DEG C.Reaction in operation (1A) can be carried out in presence of organic solvent or under not having organic solvent.As spendable organic solvent, the aromatic hydrocarbons as Benzene and Toluene and so on can be listed, the ring type aliphatic ketone of such as pimelinketone and so on, and the dihydroxy compound in starting raw material.
Operation (1B)
By operation (1B), the hydroxyl initial ring of the epoxy addition body of the multi-functional epoxy compound obtained in operation (1A) is oxidized.In operation (1B), part or all initial ring oxidation of the hydroxyl in the epoxy addition body of multi-functional epoxy compound.In the present invention, 50% ~ 100% initial ring oxidation of the hydroxyl of the epoxy addition body of preferred multi-functional epoxy compound, more preferably 75% ~ 100% initial ring oxidation.
The epoxy addition body of multi-functional epoxy compound is the starting compound in operation (1B), can list the whole open loop of epoxy group(ing) of above-mentioned multi-functional epoxy compound and the compound obtained.Preferably as the epoxy compounds represented by general formula (7a) ~ general formula (9a) epoxy addition body, the epoxy addition body of multi-functional epoxy compound that represented by following general formula (7b), general formula (8b) or general formula (9b)
In formula, X, Y and R 21as described in above-mentioned definition.
In operation (1B), epoxidation can adopt and known epoxidised for hydroxyl reaction be include, for example out Epicholorohydrin method and oxidation style, is preferably Epicholorohydrin method.
Epicholorohydrin method is a kind of by making the epoxy addition body of the multi-functional epoxy compound obtained in operation (1A) react with Epicholorohydrin or methyl epichlorohydrin under the existence of alternate transfer catalyst, thus by the hydroxyl process for epoxidation of the epoxy addition body of multi-functional epoxy compound.
In Epicholorohydrin method, Epicholorohydrin or methyl epichlorohydrin reaction can be made to reach the mole number of required epoxy group(ing) quantity.The hydroxyl of the epoxy addition body of the multi-functional epoxy compound relative to 1 mole, the amount of Epicholorohydrin or methyl epichlorohydrin is 0.5 ~ 5 mole, is preferably 0.5 ~ 2.5.Such as, have the compound represented by general formula (7b) and general formula (8b) of 4 hydroxyls in the molecule relative to 1 mole, the amount of Epicholorohydrin or methyl epichlorohydrin is 2 ~ 20 moles, preferably 2 ~ 10 moles.Have the compound represented by general formula (9b) of 6 hydroxyls in molecule relative to 1 mole, the amount of Epicholorohydrin or methyl epichlorohydrin is 3 ~ 30 moles, preferably 3 ~ 15 moles.
Alternate transfer catalyst can list the tetra-alkyl ammonium chloride as methyl tricapryl ammonium chloride, methyl three decyl ammonium chloride and tetramethyl ammonium chloride and so on, and as the quaternary ammonium salt such as aralkyltrialkylphosphonium ammonium chloride of benzyl trimethyl ammonium chloride and so on, preferred benzyl trimethyl ammonium chloride.The consumption of alternate transfer catalyst is 0.1 ~ 5 % by weight based on the gross weight of reactant, is more preferably 0.5 ~ 2.0 % by weight.
Reaction can at the such as hydrocarbon such as hexane and pentane, the ethers such as diethyl ether, t-butyl methyl ether and diisopropyl ether, or carries out under the existence of the solvent of the ketone such as acetone and methylethylketone and so on, but also can use excessive Epicholorohydrin and methyl epichlorohydrin as solvent.Temperature of reaction is 30 ~ 90 DEG C, preferably 40 ~ 65 DEG C, most preferably can react at the temperature of about 50 to about 55 DEG C of scopes.
Oxidation style is a kind of method comprising following operation, be about to the hydroxyl in addition allylation of the epoxy addition body of multi-functional epoxy compound obtained in operation (1A), obtain the operation of diallyl ether compound, and by operation that the allyl group of diallyl ether compound or 2-methyl-2-propenyl are oxidized.In the present invention, the allylation of hydroxyl comprises and makes conversion of hydroxyl be allyl group or 2-methyl-2-propenyl.
In the present invention, the operation obtaining diallyl ether compound is a kind of by making the epoxy addition body of multi-functional epoxy compound and allyl halide or 2-methyl-2-propenyl halide reaction, thus is the operation of allyl group or 2-methyl-2-propenyl by the conversion of hydroxyl of the epoxy addition body of multi-functional epoxy compound.Specifically, after the epoxy addition body of multi-functional epoxy compound and allyl halide are dissolved in dimethyl sulfoxide (DMSO), add quaternary ammonium salt, while temperature of reaction being remained on below 40 DEG C, drip alkali aqueous solution, after dropping terminates, carry out the reaction of about 6 hours in 30 ~ 40 DEG C.
As the halogen in allyl halide and 2-methyl-2-propenyl halogenide, chlorine and bromine can be listed.The hydroxyl of the epoxy addition body of the multi-functional epoxy compound relative to 1 mole, allyl halide and the halid addition of 2-methyl-2-propenyl are preferably 3 ~ 30 moles.
As quaternary ammonium salt, include, for example out the four aryl ammonium halides such as the quaternary alkylammonium halides such as Tetrabutyl amonium bromide or tetraphenylphosphonichloride chloride ammonium.The epoxy addition body of the multi-functional epoxy compound relative to 1 mole, the addition of quaternary ammonium salt is preferably 0.001 mole ~ 0.1 mole.
As alkali aqueous solution, calcium hydroxide, potassium hydroxide and sodium hydroxide can be listed.Relative to the hydroxyl of the epoxy addition body of the multi-functional epoxy compound of 1 equivalent, the alkali-metal consumption used is preferably 2 ~ 8 equivalents.
The operation be oxidized allyl group or the 2-methyl-2-propenyl of diallyl ether compound is a kind of operation that diallyl ether compound is reacted with aquae hydrogenii dioxidi in the presence of potassium carbonate.Specifically, in the hydroxyl allylation and in the diallyl ether compound obtained in addition of the epoxy addition body by multi-functional epoxy compound, add the alcohol such as methyl alcohol, ethanol or the nitrile such as acetonitrile, benzonitrile equal solvent and salt of wormwood, under agitation drip the aquae hydrogenii dioxidi of 5 ~ 40%, preferably 30 ~ 35%, after dropping terminates, carry out 0.5 ~ 10 hour, the preferred oxidizing reaction of 1 ~ 6 hour.
The addition of aquae hydrogenii dioxidi is added into 5 ~ 15 moles preferably relative to 1 mole for the hydroxyl of the epoxy addition body of multi-functional epoxy compound in addition allylation and the diallyl ether compound obtained.Temperature of reaction is such as less than 45 DEG C, preferably 20 ~ 40 DEG C.
The manufacture method of epoxy resin of the present invention is preferably the manufacture method of the epoxy resin represented by general formula (1) ~ general formula (3) of the present invention, and the manufacture method of described epoxy resin comprises following operation (2A) ~ (2B):
(2A) by making the epoxy compounds represented by general formula (7a), general formula (8a) or general formula (9a) react with the dihydroxy compound represented by following general formula (10) under the existence of metal catalyst, thus obtain the operation of the epoxy addition body represented by following general formula (7b), general formula (8b) or general formula (9b)
In general formula (7a), general formula (8a) and general formula (9a),
X and R 21as described in define in general formula (1),
HO-Y-OH (10)
In general formula (10), as described in Y definition as middle in general formula (1),
In general formula (7b), general formula (8b) and general formula (9b),
X, Y and R 21as described in above-mentioned definition; With
(2B) make the hydroxyl initial ring of the epoxy addition body represented by general formula (7b) ~ general formula (9b) obtained in operation (2A) be oxidized, obtain the operation of the epoxy resin represented by general formula (1) ~ general formula (3).
The manufacture method of partial esterification epoxy resin
Then, the manufacture method of partial esterification epoxy resin of the present invention is described.The manufacture method of partial esterification epoxy resin of the present invention comprises operation (1C):
(1C) operation that the epoxy resin manufacture method by comprising above-mentioned operation (1A) ~ (1B) being obtained reacts with (methyl) vinylformic acid under the existence of basic catalyst.
Operation (1C)
In operation (1C), there is (methyl) polyacryl in the glycidyl of the epoxy resin that the manufacture method by comprising above-mentioned operation (1A) ~ (1B) is obtained and methylglycidyl.As the epoxy resin that the manufacture method by comprising operation (1A) ~ (1B) is obtained, the epoxy resin preferably represented by general formula (1) ~ general formula (3).
As (methyl) vinylformic acid, without particular determination, such as, can use commercially available acrylic or methacrylic acid.
In the present invention, in the operation making the obtained epoxy resin of the manufacture method by comprising operation (1A) ~ (1B) and (methyl) vinylformic acid react, for the epoxy group(ing) of the epoxy resin obtained by the manufacture method comprising operation (1A) ~ (1B) of 1 equivalent, (methyl) vinylformic acid reacted is preferably 10 ~ 90 equivalent %, be more preferably 20 ~ 80 equivalent %, more preferably 30 ~ 70 equivalent %, are particularly preferably 40 ~ 60 equivalent %.In the manufacture method of partial esterification epoxy resin, because glycidyl and methylglycidyl and (methyl) acrylic acid reaction are carried out, quantitatively so the esterification yield of the partial esterification epoxy resin obtained also can be inferred according to epoxy equivalent (weight).
Relative to the epoxy group(ing) of the epoxy resin obtained by the manufacture method comprising operation (1A) ~ (1B) of 1 equivalent, if make (methyl) vinylformic acid react in above-mentioned scope, then can obtain partial esterification epoxy resin, this partial esterification epoxy resin temporarily obtains good resin properties regularly when the once polymerization only enabling unsaturated group react, and can not producing when after polymerization is separated etc. just forms the partial esterification epoxy resin of uniform polymkeric substance.
As basic catalyst, the known basic catalyst used based on epoxy resin and (methyl) acrylic acid reaction can be used.In addition, also can use and basic catalyst is equipped on polymkeric substance and the Polymer Supported type basic catalyst obtained.
As basic catalyst, be preferably organo phosphorous compounds and/or the amine compound of 3 valencys.The basic atom of basic catalyst is phosphorus and/or nitrogen.
As the organo phosphorous compounds of 3 valencys, the alkylphosphines class as triethyl phosphine, three n-propyl phosphines, tri-n-butyl phosphine and so on and salt thereof can be listed, triphenylphosphine, three tolylphosphine, three-(2,6-Dimethoxyphenyl) aryl phosphine class and the salt thereof such as phosphine, tris phosphite class and the salt etc. thereof such as triphenyl phosphite, triethyl-phosphite, tricresyl phosphite (nonyl phenyl ester).As the salt of the organo phosphorous compounds of 3 valencys, ethyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide phosphine, octyl group triphenylphosphinebromide, decyl triphenylphosphinebromide, isobutyl-triphenylphosphinebromide, propyl group triphenyl phosphine dichloride, amyl group triphenyl phosphine dichloride, hexyltriphenylphosphonium bromide phosphine etc. can be listed.Wherein, triphenylphosphine is preferably.
As amine compound, the secondary amine such as diethanolamine can be listed, trolamine, dimethyl benzylamine, three (dimethylaminomethyl) phenol, the tertiary amines such as three (diethylamino methyl) phenol, 1, 5, 7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene (TBD), 7-methyl isophthalic acid, 5, 7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene (Me-TBD), 1, 8-diazabicyclo [5.4.0] 11 carbon-7-alkene (DBU), 6-dibutylamino-1, 8-diazabicyclo [5.4.0] 11 carbon-7-alkene, 1, 5-diazabicyclo [4.3.0]-5-in ninth of the ten Heavenly Stems alkene (DBN), 1, 1, 3, strong basicity amine and the salt thereof such as 3-tetramethyl guanidine.Wherein, preferred 1,5,7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene (TBD).As the salt of amine compound, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride can be listed.
As the polymkeric substance supporting basic catalyst, without particular determination, can use and by Vinylstyrene, polystyrene is cross-linked and the polymkeric substance obtained or the polymkeric substance etc. by Vinylstyrene, acrylic resin being cross-linked and obtaining.These polymkeric substance are insoluble in the solvent (such as methylethylketone, methyl iso-butyl ketone (MIBK), toluene etc.) that uses in the obtained epoxy resin of the manufacture method by comprising operation (1A) ~ (1B) with (methyl) acrylic acid reaction and raw material, resultant.
Polymer Supported type basic catalyst is by making basic catalyst and insoluble polymer generation chemical bonding, or be then dimensionally cross-linked by cross-linking monomers such as Vinylstyrenes by monomer polymerization after basic catalyst is imported monomer, thus the Polymer Supported type basic catalyst being insoluble to methylethylketone, methyl iso-butyl ketone (MIBK), toluene equal solvent can be manufactured.
As Polymer Supported type basic catalyst, specifically, diphenylphosphine base polystyrene, 1 can be listed, 5,7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene polystyrene, N, N-(di-isopropyl) aminomethylpolystyre.e, N-(methylated polystyrene)-4-(methylamino) pyridine etc.These Polymer Supported type basic catalysts can be used alone or share two or more and use.
Polymer Supported type basic catalyst can use commercially available product.As commercially available Polymer Supported type basic catalyst, include, for example out PS-PPh 3(diphenylphosphine base polystyrene, BIOTAGE JAPAN LTD. manufactures), PS-TBD (1,5,7-tri-azabicyclo [4.4.0]-5-in last of the ten Heavenly stems alkene polystyrene, BIOTAGE JAPAN LTD. manufactures).
The usage ratio of Polymer Supported type basic catalyst is, for the epoxy group(ing) of the epoxy resin obtained by the manufacture method comprising operation (1A) ~ (1B) of 1 equivalent, Polymer Supported type basic catalyst is preferably 0.5 ~ 5.0 milliequivalent, is more preferably 1.0 ~ 3.0 milliequivalents.If the usage ratio of Polymer Supported type basic catalyst is in above-mentioned scope, then from the viewpoint of reactivity, reaction times and catalyzer cost preferably.
In manufacture method of the present invention, the epoxy resin obtained by the manufacture method comprising operation (1A) ~ (1B) is preferably 60 ~ 120 DEG C with the temperature in (methyl) acrylic acid reaction process, be more preferably 80 ~ 120 DEG C, more preferably 90 ~ 110 DEG C.
When the epoxy resin making the manufacture method by comprising operation (1A) ~ (1B) obtain in the presence of a catalyst and (methyl) vinylformic acid react, for preventing gelation, need the oxygen concn suitably ensureing the gas phase in reaction system and in reaction system.Such as, active reduction is caused owing to causing the oxidation of catalyzer sometimes when being blown into air energetically in reaction system, so should be noted that.
With regard to the epoxy resin obtained with regard to the manufacture method by comprising operation (1A) ~ (1B) and (methyl) acrylic acid reaction, because by this reaction, the partial esterification epoxy resin that obtain solidifies because of ultraviolet isoreactivity energy-ray, so hope is reacted covering in ultraviolet container.In addition, for preventing vapour phase polymerization, carry out under the epoxy resin obtained by the manufacture method comprising operation (1A) ~ (1B) and (methyl) acrylic acid reaction also can be existed at reflux solvent epoxy resin being presented to good solvent, but owing to needing after the completion of reaction except desolventizing in the case, so preferably carry out under solvent-free.As reflux solvent, acetone, methylethylketone etc. can be listed.
In manufacture method of the present invention, after the epoxy resin obtained in the manufacture method made by comprising operation (1A) ~ (1B) and (methyl) vinylformic acid reacts, obtain partial esterification epoxy resin by removing Polymer Supported type basic catalyst.As the method for removing Polymer Supported type basic catalyst, preferably adopt and filter or centrifugation.
As the method for the loaded basic catalyst of filtered polymeric, include, for example use aperture is the method that the nylon mesh NY-10HC (manufacture of Sefar company of Switzerland) of 10 μm filters out Polymer Supported type basic catalyst.
As the method by the in addition centrifugation of Polymer Supported type basic catalyst, can list by using separating centrifuge to carry out solid-liquid separation, thus the method for removing Polymer Supported type basic catalyst.
Thus, the manufacture method of partial esterification epoxy resin of the present invention is preferably the manufacture method of partial esterification epoxy resin described above, it is the method for the manufacture of the partial esterification epoxy resin represented by general formula (4) ~ general formula (6), comprises operation (2C):
(2C) making the manufacture method of the operation by comprising operation (2A) ~ (2B) and the epoxy resin represented by general formula (1), general formula (2) or general formula (3) that obtains reacts with (methyl) vinylformic acid under the existence of basic catalyst, obtaining the operation of the partial esterification epoxy resin represented by general formula (4) ~ general formula (6).
Solidification compound
Solidification compound of the present invention is described, described curable resin contains the epoxy resin being selected from (a) and being represented by general formula (1), general formula (2) and general formula (3), b partial esterification epoxy resin that () is represented by general formula (4), general formula (5) and general formula (6), c () is by comprising the manufacture method of operation (1A) ~ (1B) and the epoxy resin obtained, and (d) is by comprising the manufacture method of operation (1C) and the resin of more than a kind in the partial esterification epoxy resin obtained.In the present invention, the resin as the matrix oligopolymer composition contained in curable resin is selected from the resin of more than a kind in epoxy resin of the present invention and partial esterification epoxy resin of the present invention.Such as, the epoxy resin represented by general formula (1), general formula (2) or general formula (3) or the partial esterification epoxy resin represented by general formula (4), general formula (5) or general formula (6) can be used alone, or can by used in combination for two or more of the epoxy resin represented by general formula (1), general formula (2) or general formula (3) or the partial esterification epoxy resin represented by general formula (4), general formula (5) or general formula (6).
As the composition contained in solidification compound of the present invention, except epoxy resin of the present invention and partial esterification epoxy resin, also solidifying agent, polymerization starter, weighting agent, coupling agent can be listed.
As solidifying agent, without particular determination, solidifying agent can be used as and known compound.As solidifying agent, amine system solidifying agent can be listed, such as organic acid dihydrazide compound, imidazole and its derivants, Dyhard RU 100, aromatic amine, epoxide modified polyamines and poly-Urea,amino-etc., particularly preferably as the VDH (1 of organic acid dihydrazide, two (Hydrazinocarbonyl the ethyl)-5-sec.-propyl glycolylurea of 3-), ADH (adipic dihydrazide), UDH (7,11-octadecane diene-1,18-two (Hydrazinocarbonyl)) and LDH (octadecane-1,18-diformazan acid dihydrazide).These solidifying agent can be used alone or share multiple.For the epoxy resin of 100 weight parts and partial esterification epoxy resin, the use level of initiator is preferably 1 ~ 25 weight part, is more preferably 5 ~ 15 weight parts.
Polymerization starter refers to by light absorbing energy and activates, thus produces the compound of free radical.Polymerization starter, without particular determination, can be used as polymerization starter and known compound.As polymerization starter, bitter almond oil camphor class can be listed, acetophenones, benzophenone, thioxanthene ketone, α-acyl group oxime ester class (α-ア シ ロ キ シ system エ ス テ Le Class), oxoethanoic acid phenyl ester class (Off エ ニ Le グ リ オ キ シ レ mono-ト Class), benzil class, Azo, diphenyl sulfide based compound, acylphosphine oxide based compound, bitter almond oil camphor class, benzoin ethers and Anthraquinones polymerization starter, the solvability be preferably in liquid crystal is low, and himself there is the polymerization starter of when the rayed resolvent not reactive group of generating gasification.As preferred polymerization starter of the present invention, include, for example out EY resin KR-2 (KSM CO., LTD. manufacture) etc.For the epoxy resin of 100 weight parts and partial esterification epoxy resin, the use level of polymerization starter is preferably 0.1 ~ 5 weight part, is more preferably 1 ~ 5 weight part.
The intensity of cured article that weighting agent makes solidification compound solidify with the viscosity or raising that control solidification compound and obtain, or improved by suppression linear expansion for the purpose of the Cohesion reliability of solidification compound etc. and add.Weighting agent can use the known inorganic filler and organic filler that use for the composition containing epoxy resin.As inorganic filler, calcium carbonate, magnesiumcarbonate, barium sulfate, magnesium sulfate, pure aluminium silicate, titanium oxide, aluminum oxide, zinc oxide, silicon-dioxide, kaolin, talcum, granulated glass sphere, sericite activated clay, wilkinite, aluminium nitride and silicon nitride can be listed.As organic filler, polymethylmethacrylate, polystyrene can be listed, make their monomer of formation and other monomer copolymerization and the multipolymer, polyester micropartical, polyurethane particulate and the rubber particle that obtain.In the present invention, particularly preferably inorganic filler, such as silicon-dioxide and talcum.For the epoxy resin of 100 weight parts and partial esterification epoxy resin, the use level of weighting agent is preferably 2 ~ 40 weight parts, is more preferably 5 ~ 30 weight parts.
Coupling agent by make more good with the cohesiveness of liquid crystal display substrate for the purpose of and add.As coupling agent, without particular determination, include, for example out gamma-amino propyl trimethoxy silicane, γ mercaptopropyitrimethoxy silane, γ-isocyanate group propyl trimethoxy silicane and 3-glycidoxypropyltrime,hoxysilane etc.These silane coupling agents can be used alone or share two or more and use.For the epoxy resin of 100 weight parts and partial esterification epoxy resin, the use level of silane coupling agent is preferably 0.1 ~ 10 weight part, is more preferably 0.5 ~ 2 weight part.
Solidification compound of the present invention is by irradiation ultraviolet radiation homenergic ray, by heating or pass through to solidify at irradiation ultraviolet radiation homenergic ray post-heating.The cured article of solidification compound of the present invention can be obtained thus.Therefore, the method that solidification compound containing epoxy resin of the present invention and partial esterification epoxy resin is cured comprises: to the solidification compound irradiation ultraviolet radiation homenergic ray containing epoxy resin of the present invention and partial esterification epoxy resin, heat, or after irradiation ultraviolet radiation homenergic ray, carry out the operation that heats.
Epoxy resin of the present invention and the stripping property of partial esterification epoxy resin in liquid crystal extremely low.In addition, with regard to employing the liquid crystal display device of the solidification compound containing epoxy resin of the present invention and partial esterification epoxy resin, even if when UV irradiation dose is low, the orientation of liquid crystal is still good, do not produce display bad, therefore, can be used as liquid crystal sealing agent.
Embodiment
Next, by embodiment, the specific embodiment of the present invention is described in detail, but the present invention is not limited to the examples.
The manufacture of [synthesis example 1] compound 1c
(1-1) (the ethylene glycol open loop body of bisphenol A type epoxy resin is that X is isopropylidene in the general formula (7b), the bonding position of X is 4,4 '-position, R to compound 1a 21be hydrogen, Y be the compound of ethylene group) synthesis
The ethylene glycol (Tokyo changes into company and manufactures) of 500g, 45% stannous fluoboric acid (II) aqueous solution (manufacture of Sen Tian chemical industrial company) of 1.0g are added in eggplant type flask.While stirring the bisphenol A type epoxy resin (EXA850CRP, Dainippon Ink Chemicals manufactures) of 340g, hold it in 80 DEG C, slowly added with 1 hour, stir 1 hour at 80 DEG C from interpolation end.Reaction mixture is cooled to room temperature, adds the methylene dichloride of 1L, with the water washing 6 times of 1L.By the solvent of the organic phase of underpressure distillation removing gained, obtain the open loop body (compound 1a) of the water white transparency dope of 410g.It should be noted that, by high performance liquid chromatography (HPLC), according to the epoxy resin in raw material and only 1 epoxy group(ing) there occurs the disappearance at the peak of the compound of open loop, thus confirm that all epoxy group(ing) all open loop occur.
(1-2) (in general formula (1), X is isopropylidene to compound 1b, and the bonding position of X is 4,4 '-position, R 21be hydrogen, Y is ethylene group, R 1, R 2, R 4and R 5among 3.8 be the compound of glycidyl) synthesis
The Epicholorohydrin (manufacturing with Guang Chun medicine company) of the compound 1a (EXA850CRP-ethylene glycol open loop body) of 232g, 590g, the benzyl trimethyl ammonium chloride (Tokyo changes into company and manufactures) of 50g are joined in the three neck round-bottomed flasks of 2 liters that are provided with mechanical stirrer, thermometer, thermoswitch, condenser, Dean-Stark water trap and dropping funnel.Then, be heated to about 50 to 55 DEG C while being stirred under the high vacuum of 70 holders (torr) by mixture, make Epicholorohydrin vigorous reflux.The 48% solution NaOH (manufacture of Northeast chemical company) of 160g was slowly added in mixture with 2 hours.After generating azeotrope, among water/Epicholorohydrin mixture, send Epicholorohydrin back to reaction system, meanwhile continue to stir.After interpolation terminates, continue stirring 3 hours.Then, reaction mixture is cooled to room temperature, adds the methylene dichloride of 1L, with the water washing 6 times of 1L.Removed the solvent of the organic phase obtained by underpressure distillation, obtain the glycidyl ether body (compound 1b) of the pale yellow transparent dope of 245g.According to HPLC, the epoxy group(ing) in molecule is 3.8.
(1-3) (be in general formula (4), X is isopropylidene to compound 1c, and the bonding position of X is 4,4 '-position, R 21be hydrogen, Y is ethylene group, R 11, R 12, R 14and R 15among 1.9 be glycidyl and methacryloyl, the ratio of glycidyl and methacryloyl is the compound of 50: 50) synthesis
By the methacrylic acid (Tokyo changes into company and manufactures) of compound 1b, 88.7g of 210g, the PS-PPh of 4.7g 3the PS-TBD (BIOTAGE JAPAN LTD. manufactures) of (BIOTAGE JAPAN LTD. manufactures), 10.3g, the BHT mixing of 100mg, stir 6 hours in 100 DEG C.After the completion of reaction, by Filtration of catalyst, obtain part methyl acrylated epoxy resins.
The manufacture of [synthesis example 2] compound 2c
(2-1) (2-(4-hydroxy phenyl) the ethanol open loop body of bisphenol A type epoxy resin is that X is isopropylidene in the general formula (7b), the bonding position of X is 4,4 '-position, R to compound 2a 21for hydrogen, Y are the compound of methylene-phenylene) synthesis
By the bisphenol A type epoxy resin (EXA850CRP, Dainippon Ink Chemicals manufactures) of 170g, 2-(4-hydroxy phenyl) ethanol (Tokyo changes into company and manufactures) of 138g, the PS-PPh of 2.3g 3the PS-TBD (BIOTAGE JAPAN LTD. manufactures) of (BIOTAGE JAPAN LTD. manufactures), 4.2g, the toluene of 500ml join in eggplant type flask, stir 24 hours in 100 DEG C.Reaction solution being cooled to room temperature, removing catalyzer by filtering.Removed the solvent of the mixture obtained by underpressure distillation, obtain the open loop body of the pale yellow transparent dope of 285g.
(2-2) (be that X is isopropylidene in general formula (1), the bonding position of X is 4 to compound 2b, 4 '-position, R 21be hydrogen, Y is methylene-phenylene, R 1, R 2, R 4and R 5among 3.6 be the compound of glycidyl) synthesis
The Epicholorohydrin (manufacturing with Guang Chun medicine company) of the compound 2a (EXA850CRP-2-(4-hydroxy phenyl) ethanol open loop body) of 185g, 590g, the benzyl trimethyl ammonium chloride (Tokyo changes into company and manufactures) of 22g are joined and be provided with in the 2L tri-neck round-bottomed flask of mechanical stirrer, thermometer, thermoswitch, condenser, Dean-Stark water trap and dropping funnel.Then, be heated to about 50 to 55 DEG C while being stirred under the high vacuum of 70 holders (torr) by mixture, make Epicholorohydrin vigorous reflux.The 48% solution NaOH (manufacture of Northeast chemical company) of 185g was slowly added in mixture with 2 hours.After generating azeotrope, among water/Epicholorohydrin mixture, continue to stir while sending Epicholorohydrin back to reaction system.After interpolation terminates, continue stirring 4 hours.Then, reaction mixture is cooled to room temperature, adds the methylene dichloride of 1L, with the water washing 6 times of 1L.Removed the solvent of the organic phase obtained by underpressure distillation, obtain the glycidyl ether body (compound 2b) of the yellow transparent dope of 233g.According to HPLC, the epoxy group(ing) in molecule is 3.6.
(2-3) (be that X is isopropylidene in general formula (4), the bonding position of X is 4 to compound 2c, 4 '-position, R 21be hydrogen, Y is methylene-phenylene, R 1, R 2, R 4and R 5among 1.8 be glycidyl and methacryloyl, the ratio of glycidyl and methacryloyl is the compound of 50: 50) synthesis
By the methacrylic acid (Tokyo changes into company and manufactures) of compound 2b, 36g of 180g, the PS-PPh of 1.9g 3the PS-TBD (BIOTAGE JAPAN LTD. manufactures) of (BIOTAGE JAPAN LTD. manufactures), 8.3g, BHT (manufacturing with the Guang Chun medicine company) mixing of 85mg, stir 6 hours in 100 DEG C.After the completion of reaction, removing catalyzer by filtering, obtaining part methyl acrylated epoxy resins.
The manufacture of [synthesis example 3] compound 3c
(3-1) (the ethylene glycol open loop body of naphthalene type epoxy resin is R in general formula (8b) to compound 3a 21for hydrogen, Y be ethylene group, the bonding position of naphthalene nucleus is the compound of 1,6-position) synthesis
The ethylene glycol (Tokyo changes into company and manufactures) of 500g, 45% stannous fluoboric acid (II) aqueous solution (manufacture of Sen Tian chemical industrial company) of 1.0g are added in eggplant type flask.Naphthalene type epoxy resin (HP-4032D, Dainippon Ink Chemicals manufactures) 282g is remained on 100 DEG C while stirring, slowly added with 1 hour, arise from 100 DEG C from interpolation end and stir 3 hours.Reaction mixture is cooled to room temperature, adds the methylene dichloride of 1L, with the water washing 6 times of 1L.Removed the solvent of the organic phase obtained by underpressure distillation, obtain the open loop body (compound 3a) of the yellow transparent dope of 390g.
(3-2) compound 3b (is R in general formula (2) 21be hydrogen, Y is ethylene group, and the bonding position of naphthalene nucleus is 1,6-position, R 1, R 2, R 4and R 5among 3.9 be the compound of glycidyl) synthesis
The Epicholorohydrin (manufacturing with Guang Chun medicine company) of the compound 3a (HP4032D-ethylene glycol open loop body) of 112g, 590g, the benzyl trimethyl ammonium chloride (Tokyo changes into company and manufactures) of 21g are joined in the three neck round-bottomed flasks of 2 liters that are provided with mechanical stirrer, thermometer, thermoswitch, condenser, Dean-Stark water trap and dropping funnel.Then, mixture is stirred under 70 holder (torr) high vacuum, is meanwhile heated to about 50 to 55 DEG C, makes Epicholorohydrin vigorous reflux.The 48% solution NaOH (manufacture of Northeast chemical company) of 188g was slowly added in mixture through 2 hours.After generating azeotrope, among water/Epicholorohydrin mixture, continue to stir while sending Epicholorohydrin back to reaction system.After interpolation terminates, continue stirring 4 hours.Then, reaction mixture is cooled to room temperature, adds the methylene dichloride of 1L, with the water washing 6 times of 1L.Removed the solvent of the organic phase obtained by underpressure distillation, obtain the glycidyl ether body (compound 3b) of the pale yellow transparent dope of 179g.According to HPLC, the epoxy group(ing) in molecule is 3.9.
(3-3) compound 3c (is R in general formula (5) 21be hydrogen, Y is ethylene group, and the bonding position of naphthalene nucleus is 1,6-position, R 11, R 12, R 14and R 15among 1.9 be glycidyl and methacryloyl, the ratio of glycidyl and methacryloyl is the compound of 50: 50) synthesis
By the methacrylic acid (Tokyo changes into company and manufactures) of compound 3b, 11.8g of 50g, the PS-PPh of 154mg 3the PS-TBD (BIOTAGE JAPAN LTD. manufactures) of (BIOTAGE JAPAN LTD. manufactures), 341mg, the BHT mixing of 12mg, stir 6 hours in 100 DEG C.After the completion of reaction, removing catalyzer by filtering, obtaining part methyl acrylated epoxy resins (compound 3c).
The manufacture of [synthesis example 4] compound 4c
(4-1) (the propylene glycol open loop body of VG3101L is R in general formula (9b) to compound 4a 21be hydrogen, Y be the compound of propylidene) synthesis
The propylene glycol (manufacture of Northeast chemical company) of the TECHMORE VG3101L (PRINTEC CORPORATION manufactures) of 148g, 456g, 45% stannous fluoboric acid (II) aqueous solution (manufacture of Sen Tian chemical industrial company) of 130mg are added in eggplant type flask, stirs 20 hours in 100 DEG C.Reaction mixture is cooled to room temperature, adds the methylene dichloride of 1L, with the water washing 6 times of 1L.Removed the solvent of the organic phase obtained by underpressure distillation, obtain the open loop body of the clear yellow viscous thing of 190g.
(4-2) compound 4b (is R in general formula (3) 21be hydrogen, Y is propylidene, R 1~ R 6among 5.8 be the compound of glycidyl) synthesis
The Epicholorohydrin (manufacturing with Guang Chun medicine company) of the compound 4a (VG3101L-propylene glycol open loop body) of 160g, 590g, the benzyl trimethyl ammonium chloride (Tokyo changes into company and manufactures) of 22g are joined in the three neck round-bottomed flasks of 2 liters that are provided with mechanical stirrer, thermometer, thermoswitch, condenser, Dean-Stark water trap and dropping funnel.Then, be heated to about 50 to 55 DEG C while being stirred under the high vacuum of 70 holders (torr) by mixture, make Epicholorohydrin vigorous reflux.The 48% solution NaOH (manufacture of Northeast chemical company) of 117g was slowly added in mixture with 2 hours.After generating azeotrope, among water/Epicholorohydrin mixture, continue to stir while sending Epicholorohydrin back to reaction system.After interpolation terminates, continue stirring 4 hours.Then, reaction mixture is cooled to room temperature, adds the methylene dichloride of 1L, with the water washing 6 times of 1L.Removed the solvent of the organic phase obtained by underpressure distillation, obtain the glycidyl ether body (compound 4b) of the clear yellow viscous thing of 207g.According to HPLC, the epoxy group(ing) in molecule is 5.8.
(4-3) compound 4c (is R in general formula (6) 21be hydrogen, Y is propylidene, R 11r 16among 5.8 be glycidyl and methacryloyl, the ratio of glycidyl and methacryloyl is the compound of 75: 25) synthesis
By the methacrylic acid (Tokyo changes into company and manufactures) of compound 4b, 3.2g of 34g, the PS-PPh of 41mg 3the PS-TBD (BIOTAGE JAPAN LTD. manufactures) of (BIOTAGE JAPAN LTD. manufactures), 75mg, the BHT mixing of 10mg, stir 6 hours at 100 DEG C.After the completion of reaction, removing catalyzer by filtering, obtaining part methyl acrylated epoxy resins.
[comparing synthesis example 1]
(5-1) synthesis of comparative compound 5c (the part methyl acrylated epoxy resins of the bisphenol A type epoxy resin used in synthesis example 1)
By the bisphenol A type epoxy resin (EXA850CRP, Dainippon Ink Chemicals manufactures) of 320.2g, the methacrylic acid (Tokyo changes into company and manufactures) of 90.4g, the PS-PPh of 1.5g 3the BHT mixing of (BIOTAGE JAPAN LTD. manufactures), 100mg, stirs 6 hours in 100 DEG C.After the completion of reaction, removing catalyzer by filtering, obtaining part methyl acrylated epoxy resins (comparative compound 5c).
By the epoxy addition body obtained in synthesis example 1 ~ 4, epoxy resin and part (methyl) acrylated epoxy resins, the viscosity that uses E type viscometer (Dong Ji industry companies manufactures RE105U) to measure viscosity under the rotating speed of bell-shaped rotor is 2.5rpm to obtain, the epoxy equivalent (weight) recorded according to JIS K 7236:2001 and acryloyl rate are shown in Table 1.Here, acryloyl rate calculates according to the equivalence ratio of used epoxy equivalent (weight) and methacrylic acid equivalent.
[table 1]
Compound 1a 1b 1c 2a 2b 2c
Viscosity (mPas) Dope 27,600 209,400 Dope 94,800 240,000
Epoxy equivalent (weight) (g/eq.) - 206 590 - 220 490
Acryloyl rate (%) - - 50 - - 50
Compound 3a 3b 3c 4a 4b 4c
Viscosity (mPas) Dope 15,000 121,200 Dope 212,400 559,200
Epoxy equivalent (weight) (g/eq.) - 181 420 - 225 280
Acryloyl rate (%) - - 50 - - 25
For epoxy resin (the compound 1b manufactured in synthesis example 1 ~ 4, 2b, 3b and 4b) and partial esterification epoxy resin (compound 1c, 2c, 3c and 4c) and synthesis example 1 in use the bisphenol A type epoxy resin as starting compound (comparative compound 1a), the naphthalene type epoxy resin (comparative compound 3a) as starting compound used in synthesis example 3, (the TECHMORE VG3101L (PRINTEC CORPORATION manufactures) of the 3 functional-type epoxy resin as starting compound used in synthesis example 4, comparative compound 4a) and compare the various oligopolymer of part methyl acrylated epoxy resins (comparative compound 5c) of the bisphenol A type epoxy resin manufactured in synthesis example 1, carry out stripping property test as follows.
[stripping property test]
The evaluation of the stripping property in liquid crystal is by the change of the Ni point (Nematic-Isotropic point) of the transformation temperature as liquid crystal and utilize the direct quantitative of the stripping quantity in liquid crystal of HPLC (high performance liquid chromatography) to carry out.The Ni point of liquid crystal is made up of the mixing of the various compositions in liquid crystal and decides, and is intrinsic value under various cooperation.Generally speaking, known Ni point reduces because these are mixed into some impurity (other composition) in liquid crystal, evaluates impurity be mixed into situation by Ni point.[making of measurement sample]
In ampoule, add the oligopolymer of 0.1g, add the liquid crystal (MLC-11900-080, MERCK & CO., INC. manufacture) of 1g.This bottle to be dropped in 120 DEG C of baking ovens 1 hour, after this leave standstill in room temperature, take out lcd segment afterwards returning to room temperature (25 DEG C), with 0.2 μm of metre filter, make evaluation liquid crystal sample.
[mensuration of Ni point]
The mensuration of Ni point uses differential scanning calorimeter (DSC, PERKIN ELMER INC. manufactures, Pyris6).Being sealing in aluminium platter by the evaluation liquid crystal sample of 10mg, is measure under the condition of 5 DEG C/min at heat-up rate.
[calculating of stripping quantity]
The meltage of the oligopolymer in liquid crystal uses HPLC to measure.HPLC measurement sample uses the sample liquid crystal dilution in acetonitrile to 100 times of taking out obtained.In addition, the calibration curve of the quantitative peak area according to each compound of stripping quantity calculates.The result of the viscosity and each test that are used for the compound of each test is shown in table 2 and table 3.
[table 2]
[table 3]
Then, use the partial esterification epoxy resin (compound 1c and 2c) manufactured in synthesis example 1 and 2 and partial esterification epoxy resin (the comparative compound 5c comparing manufacture in synthesis example 1, the part methyl acrylated epoxy resins of bisphenol A type epoxy resin), make resin combination with proportioning as shown in table 4, carry out the evaluation of the liquid crystal aligning in test element.
[orientation evaluation]
The compound (compound 1c, 3c and 5c) that synthesis example 1 and 3 and comparing is obtained in synthesis example 1 respectively with EY resin KR-2 (KSM CO.; LTD. manufacture), after SEAHOSTAR KE-C50HG (Japanese catalyst Co. manufacture), adipic dihydrazide (manufactures of great Zhong chemical company) and KBM-403 (silane coupling agent: SHIN-ETSU HANTOTAI's chemical industry manufacture) mix by use level as shown in table 4; use 3 rollers fully to carry out mixing, obtain various resin combination (embodiment 9, embodiment 10 and comparative example 5).The resin combination sealing obtained like this is dripped device at 4000 μm 2sectional area in drip be coated on the alignment films (SUNEVERSE-7492, Nissan Chemical Industries company manufacture) after milled processed ito glass substrate on (60mm × 70mm × 0.7mmt).Then, substrate drips liquid crystal (TN liquid crystal, MLC-11900-080, MERCK & CO., INC. manufacture), by liquid crystal dripping process (ODF technique), upper and lower base plate is bonded, irradiation ultraviolet radiation (UV irradiating unit: UVX-01224S1, USHIO INC. manufactures, illumination and irradiation time: the 100mW/cm when 1000mJ 2/ 365nm, 10 seconds, the 50mW/cm when 50mJ 2/ 365nm, 1 second) make it solidification, in the hot-air oven of 120 DEG C, then carry out the thermofixation of 1 hour, make be used for orientation test test element.In addition, when illumination is 0mJ, forms the state of ultraviolet not irradiating liquid crystal and sealing agent after bonding by shadow mask, in the hot-air oven of 120 DEG C, carry out the thermofixation of 1 hour, make the test element being used for orientation test.
For the panel obtained, the confirmation of the state of orientation of liquid crystal when sealing.Confirm to be undertaken by opticmicroscope, polaroid is clamped test element with the state of Nicol crossed (Network ロ ス ニ コ Le), is observed by transmission.The microphotograph of the corner part of liquid crystal under display 1000mJ, 50mJ and 0mJ illumination and the state of orientation of line part is shown in Fig. 1 ~ Fig. 6.It should be noted that, Fig. 1 ~ Fig. 6 is the scale of vertical 900 μm × horizontal 1200 μm.The judgement criteria of the orientation of liquid crystal judges with or without orientation disorder according to during sealing.The situation being less than 50 μm by orientation disorder during sealing counts "○", counts "×" by there being the situation of larger orientation disorder.Show the result in table 4.It should be noted that, the content in table 4 is weight part.
[table 4]
Coordinate (weight part) Embodiment 9 Embodiment 10 Comparative example 5
Compound 1c 100
Compound 3c 100
Comparative compound 5c 100
Initiator 2 2 2
Solidifying agent 10 10 10
Weighting agent 10 10 10
Coupling agent 1 1 1
Orientation (0mJ) ○ ○ ×
Orientation (50mJ) ○ ○ ×
Orientation (1000mJ) ○ ○ ○
Stripping property (Ni point) ○ ○ ×
Initiator: EY resin KR-2 (KSM CO., LTD. manufacture)
Solidifying agent: adipic dihydrazide (manufacture of great Zhong chemical company)
Weighting agent: the spherical particulate of silicon-dioxide, SEAHOSTAR KE-C50HG (Japanese catalyst Co. manufacture)
Coupling agent: 3-glycidoxypropyltrime,hoxysilane, KBM-403 (manufacture of chemical industrial company of SHIN-ETSU HANTOTAI)
Result according to such as table 2 and table 4 can confirm: epoxy resin of the present invention and the solvability of partial esterification epoxy resin in liquid crystal significantly reduce.In addition, the result of the orientation test according to such as table 4 and Fig. 1 ~ Fig. 6, even if the liquid crystal aligning that the partial esterification epoxy resin showing to employ epoxy resin of the present invention does not produce when UV irradiation dose is low irradiation dose as the bad reason of display is yet disorderly, the known oligopolymer composition availability as the technique liquid crystal sealing agent that drips is high.On the other hand, when using the composition of comparative example 5, under the illumination of 50mJ, produce the liquid crystal aligning disorder of about 200 μm at corner part because of the stripping of solidification compound, under the illumination of this external 0mJ, all produce the liquid crystal aligning disorder of 500 ~ 800 μm at corner part and line part because of the stripping of solidification compound.
Utilizability in industry
Epoxy resin of the present invention and partial esterification epoxy resin due to the solvability to liquid crystal, stripping property low, so can be used as the raw material that all can be maintained the sealing agent of high reliability by both ultraviolet isoreactivity energy-ray and heat.

Claims (7)

1. an epoxy resin, it is the epoxy resin represented by general formula (1), general formula (2) or general formula (3),
In general formula (1), general formula (2) and general formula (3),
X is-O-, the alkylene base of carbonatoms 1 ~ 4 or the alkylidene of carbonatoms 2 ~ 4,
Y be the alkylene base of the arylidene-carbonatoms 1 ~ 4 of the alkylene base-carbonatoms 6 ~ 20 of carbonatoms 1 ~ 4, the alkylene base-carbonatoms 6 ~ 20 of carbonatoms 1 ~ 4 arylidene or by-R 7-(O-R 7) nthe group of-expression, described by-R 7-(O-R 7) nin the group of-expression, R 7for the alkylene base of carbonatoms 1 ~ 4, n is the integer of 0 or 1 ~ 6,
R 1, R 2, R 3, R 4, R 5and R 6be hydrogen, glycidyl or methylglycidyl independently of each other,
Each R 21be hydrogen or methyl independently of each other separately,
In general formula (1) and general formula (2), R 1, R 2, R 4and R 5in more than 3 be glycidyl or methylglycidyl,
In general formula (3), R 1, R 2, R 3, R 4, R 5and R 6in at least 2 be glycidyl or methylglycidyl.
2. a partial esterification epoxy resin, it is the epoxy resin represented by general formula (4), general formula (5) or general formula (6),
In general formula (4), general formula (5) and general formula (6),
X is-O-, the alkylene base of carbonatoms 1 ~ 4 or the alkylidene of carbonatoms 2 ~ 4,
Y be the alkylene base of the arylidene-carbonatoms 1 ~ 4 of the alkylene base-carbonatoms 6 ~ 20 of carbonatoms 1 ~ 4, the alkylene base-carbonatoms 6 ~ 20 of carbonatoms 1 ~ 4 arylidene or by-R 7-(O-R 7) nthe group of-expression, described-R 7-(O-R 7) n-in, R 7for the integer that the alkylene base of carbonatoms 1 ~ 4, n are 0 or 1 ~ 6,
Each R 21be hydrogen or methyl independently of each other separately,
R 11, R 12, R 13, R 14, R 15and R 16for hydrogen, glycidyl, methylglycidyl or by-Z-R 8the group represented, described by-Z-R 8in the group represented, Z is 2-hydroxyl trimethylene base or 2-methyl-2-hydroxyl trimethylene base, R 8for acryloxy or methacryloxy,
In general formula (4) and general formula (5), R 11, R 12, R 14and R 15in more than 3 be glycidyl, methylglycidyl or by-Z-R 8the group represented,
In general formula (6), R 11, R 12, R 13, R 14, R 15and R 16in at least 2 be glycidyl, methylglycidyl or by-Z-R 8the group represented,
Glycidyl and methylglycidyl, ratio with acryloxy and methacryloxy, that is, glycidyl+methylglycidyl/acryloxy+methacryloxy, is 10: 90 ~ 90: 10.
3. a manufacture method for epoxy resin, it comprises operation (1A) ~ (1B),
Operation (1A): make the multi-functional epoxy compound of the epoxy group(ing) in molecule with more than 2 under the existence of metal catalyst with molecule in there is the hydroxyl of more than 2 polyol react, obtain the operation of the epoxy addition body of multi-functional epoxy compound, and
Operation (1B): make the hydroxyl of the epoxy addition body of the multi-functional epoxy compound obtained in operation (1A) that epoxidised operation occur.
4. the manufacture method of epoxy resin according to claim 3, it is the method for the manufacture of the epoxy resin represented by general formula (1) ~ general formula (3) according to claim 1, comprise following operation (2A) ~ (2B)
Operation (2A): the epoxy compounds represented by general formula (7a), general formula (8a) or general formula (9a) is reacted with the dihydroxy compound represented by following general formula (10) under the existence of metal catalyst, thus obtain the operation of the epoxy addition body represented by general formula (7b), general formula (8b) or general formula (9b)
In general formula (7a), general formula (8a) and general formula (9a), X and R 21as described in define in claim 1,
HO-Y-OH (10)
In general formula (10), Y as in claim 1 definition as described in,
In general formula (7b), general formula (8b) and general formula (9b), X, Y and R 21as described in define in claim 1;
Operation (2B): the hydroxyl initial ring of the epoxy addition body represented by general formula (7b) ~ general formula (9b) obtained in operation (2A) is oxidized, obtains the operation of the epoxy resin represented by general formula (1) ~ general formula (3).
5. a manufacture method for partial esterification epoxy resin, it comprises operation (1C),
Operation (1C): make the operation that the epoxy resin obtained by manufacture method according to claim 3 is reacted with (methyl) vinylformic acid under the existence of basic catalyst.
6. the manufacture method of partial esterification epoxy resin according to claim 5, it is the method for the manufacture of the partial esterification epoxy resin represented by general formula (4) ~ general formula (6) according to claim 2, comprise operation (2C)
Operation (2C): the epoxy resin represented by general formula (1), general formula (2) or general formula (3) by manufacture method according to claim 4 is obtained is reacted with (methyl) vinylformic acid under the existence of basic catalyst, obtain the operation of the partial esterification epoxy resin represented by general formula (4) ~ general formula (6)
In general formula (1), general formula (2) and general formula (3),
X, Y, R 1, R 2, R 3, R 4, R 5, R 6, R 21as described in define in claim 1,
In general formula (1) and general formula (2), R 1, R 2, R 4and R 5in more than 3 be glycidyl or methylglycidyl,
In general formula (3), R 1, R 2, R 3, R 4, R 5and R 6in at least 2 be glycidyl or methylglycidyl.
7. a solidification compound, it contains and is selected from (a) epoxy resin represented by general formula (1), general formula (2) and general formula (3) according to claim 1, (b) partial esterification epoxy resin represented by general formula (4), general formula (5) and general formula (6) according to claim 2, c () is by the obtained epoxy resin of manufacture method according to claim 4, and the resin of more than a kind in (d) partial esterification epoxy resin of being obtained by manufacture method according to claim 6.
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CN110366571B (en) * 2017-03-31 2020-09-18 协立化学产业株式会社 Modified resin and curable resin composition containing the same

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CN105131251A (en) 2015-12-09
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