CN105085869B - The liquid crystal panel encapsulant that drips - Google Patents
The liquid crystal panel encapsulant that drips Download PDFInfo
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- CN105085869B CN105085869B CN201510484603.8A CN201510484603A CN105085869B CN 105085869 B CN105085869 B CN 105085869B CN 201510484603 A CN201510484603 A CN 201510484603A CN 105085869 B CN105085869 B CN 105085869B
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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
- C08G59/14—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
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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Abstract
The present invention provides the liquid crystal panel encapsulant that drips, its comprising can using fairly simple means by catalyst residue except going to below certain value, the manufacture method of bin stability and the excellent partial esterification epoxy resin of electrical characteristics, partial esterification epoxy resin and its use.The present invention relates to the manufacture method of partial esterification epoxy resin, it is included：Make the process of polyfunctional epoxy resin and (methyl) propylene acid reaction in the presence of polymer carrying base catalyst；Polymer carrying base catalyst is removed, the process for obtaining partial esterification epoxy resin.In addition, the present invention relates to partial esterification epoxy resin, it in the presence of carrying base catalyst in polymer by making (methyl) acrylic acid be reacted with polyfunctional epoxy resin, polymer carrying base catalyst is removed and obtained, the content that the basic atom of base catalyst is carried from polymer is below 50ppm.
Description
The present invention is the divisional application of the application of Application No. 201080059035.2, and parent application day is in December, 2010
20 days, entitled " partial esterification epoxy resin and its manufacture method " of female case.
Technical field
The present invention relates to make polyfunctional epoxy resin and (methyl) propylene in the presence of polymer carrying base catalyst
Obtained from acid reaction, partial esterification epoxy resin and its manufacture method.
Background technology
Partial esterification epoxy resin, can be polymerize using ultraviolet isoreactivity energy line, heat or the means of both, even if
It is not fully cured, mechanical strength is also played at normal temperatures.Therefore, partial esterification epoxy resin, can effectively serve as processing work
The raw material of the encapsulant of the product of in sequence it needs to be determined that position etc..Specifically, as the encapsulant of liquid crystal panel, electrical part
The raw material of the coating of part etc. is used.
Particularly as the encapsulant used in the manufacturing procedure that the precision of units of micrometers is required as liquid crystal panel
Raw material, partial esterification epoxy resin can be effectively utilized.Contain partial esterification epoxy resin as the encapsulant of raw material, energy
Position during enough minimally limitation processing is deviateed, and forms liquid crystal panel.
But, if in large quantities containing urging for being used in the manufacture of partial esterification epoxy resin in partial esterification epoxy resin
The impurity such as agent residue, then due to the catalyst of remaining, solidification is carried out at leisure, produces thickening, gelation, bin stability drop
It is low.
In order to remove the catalyst of remaining, it is proposed that using organic solvents such as methanol, partial esterification epoxy resin is carried out
The method (patent document 1) of carrying out washing treatment.
In addition, in order to improve bin stability, it is proposed that by catalyst oxidation remaining in partial esterification epoxy resin
Carry out the method (patent document 2,3) of inactivationization.
Propose using strong-acid ion exchange resin to remaining by tertiary phosphine derivative structure in partial esterification epoxy resin
Into the method (patent document 4) that is handled of catalyst.
In addition, it is also proposed that by using tertiary amine as catalyst, polymerization inhibitor is added, so as to improve partial esterification asphalt mixtures modified by epoxy resin
The method (patent document 5) of the bin stability of fat.
Patent document 1：Japanese Unexamined Patent Publication 5-295087 publications
Patent document 2：Japanese Unexamined Patent Publication 5-320312 publications
Patent document 3：Japanese Unexamined Patent Publication 2002-145984 publications
Patent document 4：Japanese Unexamined Patent Publication 11-12345 publications
Patent document 5：Japanese Unexamined Patent Publication 2004-244543 publications
The content of the invention
The invention problem to be solved
But, for as described in Patent Document 1 by washing the method that the catalyst that will be used when manufacturing is removed, it is necessary to anti-
The multiple carrying out washing treatment for carrying out that solvent has been used for multiple times, even if so, from the viewpoint of electrical characteristics described later, to obtain purity foot
Enough high partial esterification epoxy resin is also difficult.
In addition, for catalyst is aoxidized and the method for inactivationization as patent document 2~3, in partial esterification epoxy
The catalyst of inactivation is still remaining in resin, for coloring the problem of, electrical characteristics reduce the problem of do not improved.
Method for as described in Patent Document 4 being removed catalyst using strong-acid ion exchange resin, in order to efficient
Rate catalyst is removed, it is necessary to using secondary solvents such as dimethyl diethylene glycol (DEG)s, exist to remove solvent and manufacturing cost
Surging the problem of, and from the viewpoint of electrical characteristics, to obtain the sufficiently high partial esterification epoxy resin of purity still just difficult.
In addition, the method for adding polymerization inhibitor as described in Patent Document 5, due to being inactivated in partial esterification epoxy resin
The catalyst and polymerization inhibitor of change are still remaining, therefore the problem of reduced for electrical characteristics, are not improved.
These on bin stability, achieve considerable degree of success, also product, but in liquid in the prior art
In field of the crystal panel with the encapsulant that drips, along with the higher image quality of liquid crystal display in recent years, high performance, to above-mentioned
Characteristic required by encapsulant is also increasingly strict.
The present inventor is conceived to as sealing material to improve to the liquid crystal panel characteristic dripped required by encapsulant
The electrical characteristics of the partial esterification epoxy resin of the principal component of material have made intensive studies, and as a result find：Wish partial esterification epoxy
The electrical characteristics of resin and raw material epoxy resin do not change as far as possible, are that this must come from remaining in partial esterification epoxy resin
The impurity of base catalyst is removed, and completes the present invention.
In manufacture method using the liquid crystal panel for engineering method of dripping, encapsulant is contacted with liquid crystal in the uncured state,
UV solidifications are carried out in this state, be heating and curing.Therefore, if in partial esterification epoxy resin catalyst residue, inhibition
The impurity such as agent remaining, then during solidification, impurity from catalyst etc. is from encapsulant to liquid crystal panel dissolution and expansion
Dissipate, as the electrical characteristics for making liquid crystal panel deteriorate will be because.
The driving frequency of liquid crystal panel is 30~120Hz now, and the liquid of the driving frequency using 240Hz is being developed recently
Crystal panel.So, liquid crystal panel due to be electric field drive device, therefore from encapsulant to the miscellaneous of liquid crystal panel dissolution
Matter, as from direct current region in the case of the electric field response material that can be responded in the range of 240Hz, to the spy of liquid crystal panel
Property produce big influence.
The change of the characteristic of liquid crystal panel, is greatly classified into and is showed with the version of electrical characteristics and display characteristic.
The change of the electrical characteristics of liquid crystal panel can be confirmed by the change of the voltage retention relevant with power consumption.Voltage retention with
The leakage current of liquid crystal panel is relevant, changes because of the presence of the charged particles such as the ionic species to liquid crystal panel dissolution.
The change of the display characteristic of liquid crystal panel for example, by the liquid crystal panel relevant with response speed brightness irregularities
Deng performance.Brightness irregularities of liquid crystal panel etc. and the distinctive association of characteristics of liquid crystal with dielectric anisotropy, threshold voltage
And produce, influenceed by the presence of the charged particles such as the ionic species to liquid crystal panel dissolution and dielectric substance dipole etc..
The electrical characteristics and display characteristic of such liquid crystal panel, can be evaluated by determining dielectric property.Such as fruit part
Impurity in acrylated epoxy turns into electric field response material (dielectric substance material and charged particle) and existed, then from direct current region
When changing frequency in the range of 240Hz, change dielectric property (impedance, electric capacity and phase angle θ).
Dielectric property middle impedance represents the resistance for AC signal, in other words represents the flowing easiness of electric current, impedance
Reduction be the increased result of leakage current, represent voltage retention decline.
Electric capacity represents static capacity in dielectric property, in other words represents the delay easiness of electricity.Electric capacity is depended on by electrode
The interfacial polarization and orientation polarization of the dielectric material of clamping, the change of the numerical value of electric capacity represent the holding capacity of liquid crystal cells
Change, represent liquid crystal panel characteristic fluctuation.
Phase angle θ represents the phase difference of voltage and electric current in dielectric property.The feelings that phase angle is deviateed from -90 ° to 0 ° direction
Under condition, expression generates energy loss, and the change of phase angle θ can show as decline, the delay of response speed of voltage retention.
The change of the dielectric property of such liquid crystal panel, the portion that can be used by the raw material determined as encapsulant
Divide the dielectric property (impedance, electric capacity and phase angle θ) of acrylated epoxy and predict.
Partial esterification epoxy resin, due to being the structure with vinyl, ester bond, hydroxyl etc., therefore polarity rises, and is surveying
Decline, the rising of electric capacity, the skew of phase angle θ of impedance are produced in the case that constant temperature degree is high.Therefore, as the portion of measure object
The dielectric property (impedance, electric capacity and phase angle θ) of point acrylated epoxy, can by a temperature of various measure with raw material tree
Fat, the dielectric property of pure partial esterification epoxy resin are compared and confirm it and change.Relative to the raw material tree as benchmark
The dielectric property of fat, pure partial esterification epoxy resin, is used as the dielectric property (resistance of the partial esterification epoxy resin of comparison other
Anti-, electric capacity and phase angle θ) change it is small in the case of, be able to confirm that it is the excellent partial esterification epoxy resin of electrical characteristics.
In order to obtain the partial esterification epoxy resin that electrical characteristics are excellent, it is desirable to manufacture purity and significantly larger than use conventional side
The partial esterification epoxy resin for the product that method is obtained.In order to realize this point, the inventors discovered that make polyfunctional epoxy resin with
In method of (methyl) the propylene acid reaction to manufacture part acrylated epoxy, base catalyst is carried by using polymer,
Polymer carrying base catalyst is filtered after reaction, centrifuged and is removed, so as to obtain the excellent high-purity of electrical characteristics
Partial esterification epoxy resin, even and if do not add polymerization inhibitor especially, bin stability is also excellent, so as to complete this hair
It is bright.
Means for solving the problems
That is, the present invention is as described below.
[1] a kind of manufacture method of partial esterification epoxy resin, it is characterised in that including：Urged in polymer carrying alkalescence
Make the process of polyfunctional epoxy resin and (methyl) propylene acid reaction in the presence of agent；Base catalyst is carried with by polymer
Remove, the process for obtaining partial esterification epoxy resin.
[2] manufacture method of the partial esterification epoxy resin described in above-mentioned [1], wherein, polymer carrying base catalyst
Base catalyst be trivalent organic phosphorus compound and/or amines.
[3] manufacture method of the partial esterification epoxy resin described in above-mentioned [1] or [2], wherein, make multi-functional epoxy tree
Fat is with the process of (methyl) propylene acid reaction, relative to the equivalent of epoxy radicals 1 of polyfunctional epoxy resin, making 10~90 equivalent %
(methyl) propylene acid reaction.
[4] manufacture method of the partial esterification epoxy resin described in any one of above-mentioned [1]~[3], wherein, by polymer
Carry in the process that base catalyst is removed, using filtering or centrifugation.
[5] a kind of partial esterification epoxy resin, it is characterised in that in the presence of carrying base catalyst in polymer
(methyl) acrylic acid is reacted with polyfunctional epoxy resin, polymer carrying base catalyst is removed and obtained, carrys out auto polymerization
The content of the basic atom of thing carrying base catalyst is below 50ppm.
[6] a kind of solidification compound, it includes the partial esterification epoxy resin described in above-mentioned [5].
The effect of invention
According to the present invention, polymer carrying base catalyst is removed by using relatively more easy physical means, can
There is provided electrical characteristics excellent, even and if without polymerization inhibitor, the manufacture of bin stability also excellent partial esterification epoxy resin
Method, partial esterification epoxy resin and its solidification compound is used.
Brief description of the drawings
Fig. 1 is to represent the measure frequency at 25 DEG C of material resin and partial esterification epoxy resin (embodiment 1, comparative example 1)
The coordinate diagram of rate and the relation of impedance.
Fig. 2 is to represent the measure frequency at 25 DEG C of material resin and partial esterification epoxy resin (embodiment 1, comparative example 1)
The coordinate diagram of rate and the relation of electric capacity.
Fig. 3 is to represent the measure frequency at 25 DEG C of material resin and partial esterification epoxy resin (embodiment 1, comparative example 1)
The coordinate diagram of rate and the relation of phase angle θ.
Fig. 4 is to represent the measure frequency at 50 DEG C of material resin and partial esterification epoxy resin (embodiment 1, comparative example 1)
The coordinate diagram of rate and the relation of impedance.
Fig. 5 is to represent the measure frequency at 50 DEG C of material resin and partial esterification epoxy resin (embodiment 1, comparative example 1)
The coordinate diagram of rate and the relation of electric capacity.
Fig. 6 is to represent the measure frequency at 50 DEG C of material resin and partial esterification epoxy resin (embodiment 1, comparative example 1)
The coordinate diagram of rate and the relation of phase angle θ.
Fig. 7 is to represent the measure frequency at 80 DEG C of material resin and partial esterification epoxy resin (embodiment 1, comparative example 1)
The coordinate diagram of rate and the relation of impedance.
Fig. 8 is to represent the measure frequency at 80 DEG C of material resin and partial esterification epoxy resin (embodiment 1, comparative example 1)
The coordinate diagram of rate and the relation of electric capacity.
Fig. 9 is to represent the measure frequency at 80 DEG C of material resin and partial esterification epoxy resin (embodiment 1, comparative example 1)
The coordinate diagram of rate and the relation of phase angle θ.
Figure 10 is the coordinate diagram of the relation for the content and electric capacity for representing phosphorus atoms contained in each resin under each frequency.
Figure 11 is the coordinate of the relation for the content and phase angle θ for representing phosphorus atoms contained in each resin under each frequency
Figure.
Embodiment
Of the invention is preferred embodiment illustrated below.
The present invention is the manufacture method of partial esterification epoxy resin, and it is included：Depositing for base catalyst is carried in polymer
Make the process of polyfunctional epoxy resin and (methyl) propylene acid reaction under；Next, polymer carrying base catalyst is removed
Go, the process for obtaining partial esterification epoxy resin.
Polyfunctional epoxy resin, as long as having the epoxy resin of more than 2 epoxy radicals in 1 molecule, is not particularly limited,
As polyfunctional epoxy resin, following compound can be enumerated.
As polyfunctional epoxy resin, can enumerate makes ethylene glycol, diethylene glycol (DEG), triethylene glycol, propane diols, DPG, 3 third
The polyalcohols such as the polyalkylene glycols such as glycol, dihydroxy methylpropane, trimethylolpropane, the spiroglycol, glycerine and table chlorine
Aliphatic polybasic glycidyl ether compound obtained from alcohol reaction.
As polyfunctional epoxy resin, can enumerate make the aromatic series diphenols such as bisphenol-A, bisphenol S, Bisphenol F, bisphenol-A D and
They aromatic series obtained from ethylene glycol, propane diols, the glycols of alkylen glycol-modified and epichlorohydrin react is subjected to many
First glycidyl ether compound.
As polyfunctional epoxy resin, can enumerate make the aromatic dicarboxylic acids such as adipic acid, itaconic acid and epichlorohydrin react and
Obtained aliphatic polybasic epihydric alcohol ester compound, makes the aromatic series such as M-phthalic acid, terephthalic acid (TPA), Pyromellitic Acid two
Carboxylic acid and aromatic polyvalent epihydric alcohol ester compound obtained from epichlorohydrin reaction.
Can enumerate makes the aromatic amines such as diaminodiphenyl-methane, aniline, m-xylene diamine and epichlorohydrin react and obtain
Aromatic polyvalent glycidol amines.
As polyfunctional epoxy resin, it can enumerate obtained from making hydantoins and its derivative and epichlorohydrin reaction in second
The polynary glycidyl compound of uride type.
As polyfunctional epoxy resin, can enumerate makes by phenol or cresols and the phenolic resin of formaldehyde-derived, novolaks
Resin and phenolic aldehyde, the polynary glycidyl ether compound of phenolic varnish type obtained from epichlorohydrin reaction.
As (methyl) acrylic acid, it is not particularly limited, for example commercially available acrylic or methacrylic acid can be used.
In the process for making polyfunctional epoxy resin and (methyl) propylene acid reaction, relative to the epoxy of polyfunctional epoxy resin
The equivalent of base 1 and react (methyl) acrylic acid, preferably 10~90 equivalent %, more preferably 20~80 equivalent %, further it is excellent
Elect 30~70 equivalent %, particularly preferably 40~60 equivalent % as.
If the equivalent of epoxy radicals 1 relative to polyfunctional epoxy resin makes (methyl) acrylic acid react within the above range,
Result in following partial esterification epoxy resin：During the once polymerization for only reacting unsaturated group, obtain for interim fixed
Good resin properties, will not occur phase separation etc. and can form the partial esterification epoxy of the polymer of homogeneous during after polymerization
Resin.
So-called polymer carries base catalyst, refers to by the work of polyfunctional epoxy resin and (methyl) propylene acid reaction
The base catalyst used in sequence is carried on product obtained by polymer.
It is used as the organic phosphorus compound and/or amines of base catalyst, preferably trivalent.The alkalescence of base catalyst
Atom is phosphorus and/or nitrogen.
As the organic phosphorus compound of trivalent, triethyl phosphine, three n-propyl phosphines, alkyl as tri-n-butyl phosphine can be enumerated
Aryl phosphine and its salt, the Asia such as phosphine and its salt, triphenylphosphine, three-m- tolylphosphine, three (2,6- Dimethoxyphenyl) phosphines
The tris phosphite classes and its salt etc. such as triphenyl phosphate, triethyl phosphite, phosphorous acid three (nonyl phenyl) ester.It is used as trivalent
The salt of organic phosphorus compound, can enumerate triphenylphosphine bromic ether, triphenylphosphine butyl bromide, triphenylphosphine n-octyl bromide, three
Phenylphosphine decyl bromide, triphenylphosphine isobutyl bromide, triphenylphosphine propyl chloride, triphenylphosphine amyl chloride, triphenyl
Phosphine hexyl bromide etc..Wherein, triphenylphosphine.
As amines, the secondary amine such as diethanol amine, triethanolamine, dimethyl benzyl amine, three (dimethylaminos can be enumerated
Methyl) tertiary amine, 1,5,7- tri- azabicyclo [4.4.0] decyl- 5- alkene (TBD), 7- such as phenol, three (diethylamino methyl) phenol
Methyl isophthalic acid, 5,7- tri- azabicyclo [4.4.0] decyl- 5- alkene (Me-TBD), the carbon -7- alkene of 1,8- diazabicyclos [5.4.0] 11
(DBU), 6- dibutylaminos -1,8- diazabicyclo [5.4.0] hendecane -7- alkene, 1,5- diazabicyclos [4.3.0] nonyl-
Strong basicity amine and its salt such as 5- alkene (DBN), 1,1,3,3- TMG.Wherein, preferably 1,5,7- tri- azabicyclos [4.4.0]
Decyl- 5- alkene (TBD).As the salt of amines, benzyltrimethylammonium chloride, benzyltriethylammoinium chloride can be enumerated.
As the polymer for carrying base catalyst, it is not particularly limited, can be used polystyrene divinyl
The polymer of benzene crosslinking, by polymer of acrylic resin divinyl benzene crosslinked etc..These polymer are in multifunctional ring
The solvent (such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene) that is used in the reaction of oxygen tree fat and (methyl) acrylic acid and
It is insoluble in raw material, product.
Polymer carries base catalyst, by being chemically bonded base catalyst and insoluble polymer, or by alkali
Property catalyst import monomer after, monomer is polymerize, then, carried out with cross-linking monomers such as divinylbenzenes it is three-dimensional cross-linked, so as to
Enough manufacture polymer carrying base catalyst insoluble in methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene equal solvent.
Base catalyst is carried as polymer, specifically, diphenylphosphine base polystyrene, 1,5,7- tri- azepines can be enumerated
Bicyclic [4.4.0] decyl- 5- alkene polystyrene, N, N- (diisopropyl) aminomethylpolystyre.e, N- (methylated polystyrene) -4-
(methylamino) pyridine etc..These polymer carrying base catalyst can be used alone, and also two or more may be used.
Commercially available product can be used in polymer carrying base catalyst.Base catalyst is carried as commercially available polymer,
Such as PS-PPh can be enumerated3(diphenylphosphine base polystyrene, BIOTAGE company systems), PS-TBD (1,5,7- tri- azabicyclos
[4.4.0] decyl- 5- alkene polystyrene, BIOTAGE company systems).
Polymer carries the use ratio of base catalyst, relative to the equivalent of epoxy 1 of polyfunctional epoxy resin, preferably gathers
The base catalyst of compound carrying base catalyst is 0.5~5.0 milliequivalent, more preferably 1.0~3.0 milliequivalents.Polymer
The use ratio of base catalyst is carried if in above range, from the viewpoint of reactivity, reaction time and catalyst cost
It is preferred to set out.
In the manufacture method of the present invention, polyfunctional epoxy resin and temperature in the reaction process of (methyl) acrylic acid are preferred
For 60~120 DEG C, more preferably 80~120 DEG C, more preferably 90~110 DEG C.
In the case of making polyfunctional epoxy resin and (methyl) propylene acid reaction in the presence of a catalyst, in order to prevent gel
Change, it is necessary to suitably keep the oxygen concentration of the gas phase in reaction system and in reaction system.For example, energetically being sprayed into reaction system
In the case of air, due to causing the oxidation of catalyst sometimes, cause the reduction of activity, it is therefore necessary to note.
The reaction of polyfunctional epoxy resin and (methyl) acrylic acid, due to the partial esterification asphalt mixtures modified by epoxy resin obtained by the reaction
Fat is by ultraviolet isoreactivity energy line curing, and it is desirable to reacted in the container of masking ultraviolet.In addition, multifunctional
The reaction of epoxy resin and (methyl) acrylic acid, in order to prevent gas-phase polymerization, can show good solvent for epoxy resin
Carried out in the presence of reflux solvent, in this case, due to that after the completion of reaction must remove solvent, therefore preferably solvent-free
It is lower to carry out.As reflux solvent, acetone, methyl ethyl ketone etc. can be enumerated.
In the manufacture method of the present invention, make polyfunctional epoxy resin with after (methyl) propylene acid reaction, polymer is carried
Base catalyst is removed.The method that base catalyst is removed is carried as by polymer, it is preferred to use filtering is centrifuged.
The method that base catalyst is carried as filtered polymeric, can enumerate the nylon wire NY- for example using 10 μm of mesh
The method that 10HC (Swiss Sefar company systems) leaching polymer carries base catalyst.
The method that base catalyst is centrifuged is carried as by polymer, can enumerate and be carried out by using centrifugal separator
Separation of solid and liquid, so that polymer is carried into the method that base catalyst is removed.
Manufacturing method according to the invention, is adopted by the way that polymer is carried into base catalyst as filtering or centrifuge
Removed with fairly simple method, so as to obtain being practically free of polymer carrying base catalyst, high-purity part ester
Change epoxy resin.
Manufacturing method according to the invention, due to polymer carrying base catalyst being compared using filtering, centrifugation etc.
More easy physical method is removed, therefore the polymerization inhibitor with conventional use washer solvent, for making catalyst deactivation
Method etc. is compared, and can reduce manufacturing cost.
The partial esterification epoxy resin of the present invention, is to make multi-functional epoxy in the presence of polymer carrying base catalyst
Resin and (methyl) propylene acid reaction, polymer carrying base catalyst is removed and formed, base catalysis is carried from polymer
The content of the basic atom of agent is below 50ppm.
The partial esterification epoxy resin of the present invention, the content of the basic atom from polymer carrying base catalyst is low to be reached
Below 50ppm, compared with the partial esterification epoxy resin obtained using conventional method, electrical characteristics are excellent.In addition, the present invention
Partial esterification epoxy resin, content as little as below the 50ppm of the basic atom of base catalyst is carried from polymer, although not
Must add polymerization inhibitor in reaction process, but with order that remaining catalyst deactivation and with the addition of the partial esterification of polymerization inhibitor
Epoxy resin is compared, and bin stability is also excellent.
Partial esterification epoxy resin, preferably impurity are few, and the content of the basic atom of base catalyst is carried from polymer,
Preferably below 40ppm, more preferably below 30ppm, more preferably below 20ppm, particularly preferably below 10ppm.
The basic atom of base catalyst, in particular phosphorus or nitrogen etc. are carried from polymer.By determining partial esterification
The content of these contained basic atoms in epoxy resin, can speculate the polymer carrying alkalescence in the acrylated epoxy of part
The remaining quantity of catalyst residue.The basic atom of polymer carrying base catalyst can be luminous using inductively coupled plasma
Analytic approach (ICP/AES) is determined.
The solidification compound of the present invention includes partial esterification epoxy resin, and the partial esterification epoxy resin is in polymer
(methyl) acrylic acid is reacted with polyfunctional epoxy resin in the presence of carrying base catalyst, polymer is carried into base catalysis
Agent is removed and formed, and the content that the basic atom of base catalyst is carried from polymer is below 50ppm.
Above-mentioned solidification composition filling, polymerize it by ultraviolet Isoenergetical line or heat, can obtain solidfied material.
The solidification compound of the present invention, the content of the basic atom comprising polymer carrying base catalyst is low to be reached
Below 50ppm, the partial esterification epoxy resin for being practically free of polymer carrying base catalyst residue and polymerization inhibitor, therefore will not
Oxidation product caused by catalyst residue and polymerization inhibitor is produced, electrical characteristics and bin stability are excellent.Therefore, it is of the invention to consolidate
The property changed composition can be suitable as electrical characteristics, the painting of liquid crystal panel of the pollution as problem drip encapsulant, electric component
Material etc. is used.
Embodiment
The specific embodiment of the present invention is described in more detail followed by embodiment, but the present invention is not by this
A little embodiments are limited.
[embodiment 1]
Prepare the 500ml glass system four-hole boiling flasks with agitator, thermometer, the cooling tube that flows back, by bisphenol type epoxy tree
Fat：EPICLON EXA850CRP [DIC societies system] 340g (2.0 equivalents/epoxy radicals), methacrylic acid 90.4g (1.0 equivalent),
PS-PPh3(diphenylphosphine base polystyrene, 2.0mmol/g) [BIOTAGE company systems] 750mg (1.5 milliequivalents/TPP (triphens
Base phosphine) catalytic amount (g)) mix, the stirring reaction at 100 DEG C is until acid number reaches below 1.0KOHmg/g.Reaction solution is cold
But to 60 DEG C, with the nylon wire NY-10HC (Swiss Sefar societies system) of 10 μm of mesh by the PS-PPh of catalyst3Remove, obtain
Partial esterification epoxy resin (PR-1).The epoxide equivalent of obtained resin is 468g/eq.In addition, by resin (PR-1) wet type
After decomposition, using containing for the phosphorus atoms in the resin (PR-1) of inductively coupled plasma luminescence analysis (ICP/AES) measure
Measure as below 2ppm.
[embodiment 2]
Except having used bisphenol-A D-ring oxygen tree fat：EPOMIK R1710 [Printec company systems] 326g (2.0 equivalents/ring
Epoxide) beyond, partial esterification epoxy resin (PR-2) has been obtained similarly to Example 1.The epoxy of obtained resin (PR-2)
Equivalent is 450g/eq.The content of phosphorus atoms in the resin (PR-2) determined similarly to Example 1 is below 2ppm.
[embodiment 3]
Prepare the 500ml glass system four-hole boiling flasks with agitator, thermometer, the cooling tube that flows back, by bisphenol type epoxy tree
Fat：EPICLON EXA850CRP [DIC societies system] 340g (2.0 equivalents/epoxy radicals), PS-PPh3(2.0mmol/g)[BIOTAGE
Company system] 750mg (1.5 milliequivalents/TPP [triphenylphosphine] catalytic amount (g)), PS-TBD (1,5,7- tri- azabicyclos
[4.4.0] decyl- 5- alkene polystyrene, 1.40mmol/g) [BIOTAGE company systems] 1.07g (1.5 milliequivalents/amine catalyst amount
(g)) mix, stirred at 100 DEG C, while reacting it when slowly adding acrylic acid 76.0g (1.0 equivalent) with 6 hours.
The addition of acrylic acid is completed, and then stirring makes its reaction until acid number reaches below 1.0KOHmg/g at 100 DEG C.By reaction solution
60 DEG C are cooled to, with the nylon wire NY-10HC (Swiss Sefar societies system) of 10 μm of mesh by the PS-PPh of catalyst3And PS-
TBD is removed, and has obtained partial esterification epoxy resin (PR-3).The epoxide equivalent of obtained resin (PR-3) is 461g/eq.With reality
The content for applying the phosphorus atoms in the resin (PR-3) that example 1 is similarly determined is below 2ppm.
[comparative example 1]
Prepare that there is agitator, air leading-in conduit, thermometer, the 500ml glass system four-hole boiling flasks for the cooling tube that flows back, will be double
Phenol A type epoxy resin：EPICLON EXA850CRP [DIC societies system] 340g (2.0 equivalents/epoxy radicals), methacrylic acid 90.4g
(1.0 equivalent), TPP (triphenylphosphine) [Tokyo chemical conversion society system] 0.5g (1.9 milliequivalent), the quinhydrones 25mg as polymerization inhibitor and right
Metoxyphenol 100mg is mixed, and stirring makes its reaction until acid number reaches below 1.0KOHmg/g at 100 DEG C.Reaction terminates
Afterwards, while blowing air into liquid, while carrying out 2 hours oxidation processes at 80 DEG C, partial esterification epoxy resin (KR- has been obtained
1).The epoxide equivalent of obtained resin (KR-1) is 465g/eq.Phosphorus in the resin (KR-1) determined similarly to Example 1
The content of atom is 290ppm.
[comparative example 2]
In addition to without quinhydrones 25mg, p methoxy phenol 100mg, reacted in the same manner as comparative example 1, but
The midway gelation of reaction.
For embodiment 1~4 and the partial esterification epoxy resin of comparative example 1, thermal-stable examination has been proceeded as described below
Test and promote to test with heating under reduced pressure.
[thermal-stable experiment]
Load the 50g of each several part acrylated epoxy in 100ml brown polyethylene can, sealed with embolism, with appearance
Device is positioned in 60 DEG C of baking oven together, was being taken out after 20 hours, 200 hours, 500 hours, for content, is being used E
Type viscosimeter (Dong Ji industries society RE105U), viscosity is determined under the rotary speed 2.5rpm of cone rotor.According to the following formula (1)
Obtain the rate of change when viscosity after firm manufacture is set into 100.Show the result in table 1.
Rate of change in viscosity=(viscosity after measure viscosity/just manufacture after certain time) (1)
[heating under reduced pressure promotes experiment]
Load the 50g of each several part acrylated epoxy in 100ml brown polyethylene can, embolism is not sealed, with appearance
Device is stored in 50 DEG C, is depressurized in 100Pa vacuum drying oven together, is being taken out after 20 hours, 200 hours, 500 hours,
Using E types viscosimeter (Dong Ji industries society RE105U), viscosity is determined under the rotary speed 2.5rpm of cone rotor.According to upper
Formula (1) obtains the rate of change when viscosity after firm manufacture is set into 100.Show the result in table 1.
[table 1]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | |
| Partial esterification epoxy resin | PR-1 | PR-2 | PR-3 | KR-1 |
| Thermal-stable result of the test | ||||
| 60 DEG C/after 20 hours | 1.00 | 1.00 | 1.00 | 1.10 |
| 60 DEG C/after 200 hours | 1.00 | 1.00 | 1.02 | 1.25 |
| 60 DEG C/after 500 hours | 1.00 | 1.00 | 1.05 | 2.05 |
| Heating under reduced pressure promotes result of the test (100Pa) | ||||
| 50 DEG C/after 20 hours | 1.00 | 1.00 | - | 1.18 |
| 50 DEG C/after 200 hours | 1.00 | 1.01 | - | 1.39 |
| 50 DEG C/after 500 hours | 1.04 | 1.05 | - | Gelation |
As shown in table 1, the partial esterification epoxy resin of embodiment 1~3 is able to confirm that, is passed through at a temperature of 60 DEG C
500 hours are spent, viscosity also hardly changes, bin stability is also excellent under heat run.
On the other hand, the partial esterification epoxy resin of comparative example 1, after 500 hours viscosity substantially change 2 times of left sides
The right side, thermal-stable reduction.
In addition, as shown in table 1, be able to confirm that the partial esterification epoxy resin of embodiment 1~3, even in 50 DEG C,
Also hardly change by 500 hours viscosity under 100Pa decompression, bin stability is also excellent under heating under reduced pressure experiment.
On the other hand, the partial esterification epoxy resin of comparative example 1 is in the gelation after 500 hours.
Next, determining the dielectric property of the partial esterification epoxy resin of embodiment 1 and comparative example 1 using following methods.
[measure of dielectric property]
As benchmark, the bisphenol A type epoxy resin as raw material has been used：EPICLON EXA850CRP [DIC societies system].
Use dielectric substance measurement system 126096W types [Solartron company systems] and liquid electrode SR-C1R (cell capabilities：2pF, electricity
Anode-cathode distance：1mm) [TOYO Corporation systems], using FRA methods, determines material resin (benchmark), embodiment 1 and compares
The partial esterification epoxy resin of example 1 makes frequency 1.0 × 10-2Hz~1.0 × 106At 25 DEG C, 50 DEG C, 80 DEG C when Hz changes
Dielectric property (impedance, electric capacity, phase angle θ)., can be in resin by the dielectric property for the resin for evaluating its uncured state
Impurity produce influence semidefinite quantify.Show the result in Fig. 1~9.It should be noted that in figure, such as " 1.0E-02 "
Token represents 1.0 × 10-2Implication.
As illustrated in figures 1-3, at 25 DEG C the partial esterification epoxy resin of embodiment 1 dielectric property (impedance, electric capacity and
Phase angle θ) substantially it is equal with the dielectric property of the material resin as benchmark, it is able to confirm that in the absence of partial esterification epoxy resin
In impurity produce influence, with excellent electrical characteristics.
On the other hand, as illustrated in figures 1-3, the dielectric property of the partial esterification epoxy resin of comparative example 1 is relative to raw material
The dielectric property of resin is changed.I.e., as shown in fig. 1, relative to the impedance of material resin, under the impedance of comparative example 1
Drop, thus, it is possible to confirm that the voltage retention of partial esterification epoxy resin of comparative example 1 is reduced.In addition, as shown in Figure 2,
Relative to the electric capacity of material resin, the electric capacity of comparative example 1 is changed, the partial esterification ring thus, it is possible to confirm comparative example 1
The holding capacity fluctuation of oxygen tree fat.In addition, as shown in Figure 3, relative to the phase angle θ of material resin, the phase angle of comparative example 1
θ is offset from -90 ° to 0 ° of direction, thus, it is possible to confirm that the partial esterification epoxy resin of comparative example 1 produces energy loss, is produced
Delay of response speed etc. etc..So, the dielectric property reduction of the partial esterification epoxy resin of comparative example 1, the dielectric property
Reduce caused by the influence of impurity contained in the partial esterification epoxy resin of comparative example 1.
As shown in Fig. 4~9, if determining temperature rises to 50 DEG C, 80 DEG C, the partial esterification epoxy resin of embodiment 1
Dielectric property (impedance, electric capacity and phase angle θ), relative to the dielectric property of the material resin as benchmark, there occurs a little
Change, but speculate because because temperature rises, contained vinyl, ester structure and hydroxyl etc. in partial esterification epoxy resin
Caused by the influence of the intermolecular interaction of generation.On the other hand, as shown in Fig. 4~9, the partial esterification epoxy of comparative example 1
The dielectric property of resin, temperature more rises, and relative to the dielectric property of material resin, significantly changes, electrical characteristics reduction.
It is able to confirm that by the result shown in Fig. 1~9, the dielectric property (resistance of the partial esterification epoxy resin of embodiment 1
Anti-, electric capacity and phase angle θ), it is roughly the same degree with the dielectric property of material resin, due to being practically free of impurity, therefore
It is the partial esterification epoxy resin with excellent electrical characteristics in the absence of the change of dielectric property caused by the influence of impurity.
[embodiment 4]
Except having used PS-PPh3(diphenylphosphine base polystyrene, 2.0mmol/g) [BIOTAGE company systems] 500mg
(1.33 milliequivalents/TPP (triphenylphosphine) catalytic amount (g)) and TPP (triphenylphosphine) 160mg [Northeast chemistry society system] (0.61
Milliequivalent/TPP (triphenylphosphine) catalytic amount (g)) as catalyst beyond, partial esterification has been obtained similarly to Example 1
Epoxy resin (PR-4).The epoxide equivalent of obtained resin is 458g/eq.The resin (PR-4) determined similarly to Example 1
In phosphorus atoms content be 100ppm.
[embodiment 5]
Except having used PS-PPh3(diphenylphosphine base polystyrene, 2.0mmol/g) [BIOTAGE company systems] 650mg
(1.73 milliequivalents/TPP (triphenylphosphine) catalytic amount (g)) and TPP (triphenylphosphine) 80mg [Northeast chemistry society system] (0.31 milli
Equivalent/TPP (triphenylphosphine) catalytic amount (g)) as catalyst beyond, partial esterification ring has been obtained similarly to Example 1
Oxygen tree fat (PR-5).The epoxide equivalent of obtained resin is 466g/eq.In the resin (PR-5) determined similarly to Example 1
Phosphorus atoms content be 48ppm.
[embodiment 6]
Except having used PS-PPh3(diphenylphosphine base polystyrene, 2.0mmol/g) [BIOTAGE company systems] 700mg
(1.87 milliequivalents/TPP (triphenylphosphine) catalytic amount (g)) and TPP (triphenylphosphine) 40mg [Northeast chemistry society system] (0.15 milli
Equivalent/TPP (triphenylphosphine) catalytic amount (g)) as catalyst, in addition, partial esterification ring has been obtained similarly to Example 1
Oxygen tree fat (PR-6).The epoxide equivalent of obtained resin is 456g/eq.In the resin (PR-6) determined similarly to Example 1
Phosphorus atoms content be 26ppm.
[comparative example 3]
After terminating except reaction, carried out at 80 DEG C beyond 2 hours oxidation processes, portion has been obtained in the same manner as comparative example 1
Divide acrylated epoxy (KR-2).The epoxide equivalent of obtained resin (KR-2) is 465g/eq.Added in 300 parts of the resin
Ion exchange resin (AMBERLYST15DRY (ion exchange resin that benzene sulfonic acid is carried in main chain), Organo company systems) 15
Part, stir process 3 hours at 80 DEG C.Reaction solution is cooled to 60 DEG C, with 10 μm of nylon wire NY-10HC (Swiss of mesh
Sefar societies system) ion exchange resin is removed, obtain partial esterification epoxy resin (KR-3).Determine similarly to Example 1
Resin (KR-2 and KR-3) in the contents of phosphorus atoms be respectively 300ppm, 250ppm.It is able to confirm that by the result, even if making
In the case of ion exchange resin with highly acid, also contain more in obtained part ester epoxy resin and carry out self-catalysis
The impurity (phosphorus atoms) of agent, makes the effect of the impurity reduction from catalyst small.
For the partial esterification epoxy resin (PR-1 of embodiment 1：The content of phosphorus atoms：Below 2ppm), the portion of embodiment 4
Divide acrylated epoxy (PR-4：The content of phosphorus atoms：100ppm), the partial esterification epoxy resin (PR-5 of embodiment 5：Phosphorus is former
The content of son：48ppm), the partial esterification epoxy resin (PR-6 of embodiment 6：The content of phosphorus atoms：26ppm) with comparative example 3
Partial esterification epoxy resin (KR-2：The content of phosphorus atoms：300ppm), surveyed respectively by the measure of above-mentioned dielectric property
Determine to determine frequency 10mHz~100Hz electric capacity, frequency 50Hz~10KHz phase angle under temperature 50 C.Represented in Figure 10 each
Institute in each resin under each frequency is represented in each resin under frequency in the content and the relation of electric capacity of contained phosphorus atoms, Figure 11
The content of the phosphorus atoms contained and the relation of phase angle θ.
As shown in Figure 10, it is able to confirm that if the content of impurity, i.e. phosphorus atoms contained in partial esterification epoxy resin
It is below 50ppm for flex point, then being changed significantly for electric capacity (holding capacity) diminishes.If especially in below frequency 200mHz
Determined under low frequency, compared with the situation determined at high frequencies, the voltage change of low-frequency situation is slow, therefore electric capacity (is protected
Hold capacity) show with being changed significantly.Therefore, as shown in Figure 10, it is able to confirm that if in below frequency 200mHz
Determined under low frequency, then the content of phosphorus atoms is that below 50ppm partial esterification epoxy resin and the content of phosphorus atoms exceed
50ppm partial esterification epoxy resin is compared, and being changed significantly for electric capacity (holding capacity) is small, and dielectric property is not fluctuated.
As shown in Figure 11, the content for being able to confirm that phosphorus atoms is i.e. below the 50ppm of flex point partial esterification epoxy resin
In, the change from the phase angle θ of -90 ° to 0 ° direction skew is small, and the decline of voltage retention, the delay of response speed are small, have
Excellent dielectric property.Especially, if direct current region (the 0Hz) -240Hz applied in recent years in liquid crystal panel low frequency
Determined in the region (such as shown in Figure 11,50Hz-200Hz region) of rate, the content for being able to confirm that phosphorus atoms is 50ppm
Following partial esterification epoxy resin with phosphorus atoms content exceed 50ppm partial esterification epoxy resin compared with, phase angle θ
It is changed significantly small, therefore does not produce energy loss, with excellent dielectric property.
Utilization possibility in industry
The partial esterification epoxy resin obtained using the manufacture method of the present invention is stable, can preserve for a long time, reduced pressure
Under stability and electrical characteristics it is also excellent, can as can using ultraviolet isoreactivity energy line, heat any one be polymerize
The raw material of composition use, therefore can be used as the raw material of the coating of the encapsulant of liquid crystal panel, electric component etc..
Claims (3)
1. a kind of liquid crystal panel encapsulant that drips, it is characterised in that include partial esterification epoxy resin, the partial esterification
In the presence of epoxy resin in polymer by carrying base catalyst and make (methyl) acrylic acid and many without polymerization inhibitor
Functional epoxy resins are reacted, then polymer carrying base catalyst is removed and obtained, and base catalyst is carried from polymer
Basic atom content be below 50ppm,
The base catalyst of polymer carrying base catalyst is the organic phosphorus compound of trivalent.
2. the liquid crystal panel encapsulant that drips as claimed in claim 1, wherein, make polyfunctional epoxy resin and (methyl) third
In the process of olefine acid reaction, relative to the equivalent of epoxy radicals 1 of polyfunctional epoxy resin, make 10~90 equivalent % (methyl) propylene
Acid reaction.
3. the liquid crystal panel encapsulant that drips as claimed in claim 1 or 2, wherein, polymer is carried into base catalyst
In the process of removing, using filtering or centrifugation.
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| JP2009-293765 | 2009-12-25 | ||
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| JPH03296568A (en) * | 1990-04-16 | 1991-12-27 | Dainippon Ink & Chem Inc | Production of aqueous resin dispersion |
| CA2055833C (en) * | 1990-11-20 | 2001-04-24 | Katsue Nishikawa | Preparation of unsaturated epoxy ester resin and carboxylated unsaturated epoxy ester resin and photosensitive composition comprising the same |
| JPH1112345A (en) * | 1997-06-26 | 1999-01-19 | Kyoeisha Chem Co Ltd | Production of partially (meth)acrylated resin excellent in preservation stability and having photosensitivity |
| GB9913627D0 (en) | 1999-06-12 | 1999-08-11 | Ciba Geigy Ag | Process for the preparation of reaction products of cycloaliphatic epoxides with multifunctional hydroxy compounds |
| JP4117838B2 (en) * | 2003-02-14 | 2008-07-16 | 三井化学株式会社 | Method for producing epoxy partial esterified product |
| JP4682340B2 (en) | 2003-07-25 | 2011-05-11 | 昭和電工株式会社 | Method for producing photosensitive resin |
| JP2010185002A (en) * | 2009-02-12 | 2010-08-26 | Hitachi Chem Co Ltd | METHOD FOR PRODUCING alpha,beta-UNSATURATED CARBOXYLIC ACID ESTER OF EPOXY RESIN |
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| "Recoverable Catalysts and Reagents Using Recyclable Polystyrene-Based Supports";Catherine A. McNamara, et al.;《Chemical Reviews》;20021009;第102卷(第10期);3275-3300 * |
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