CN104672437B - A kind of high index of refraction waterborne polyester and preparation thereof - Google Patents
A kind of high index of refraction waterborne polyester and preparation thereof Download PDFInfo
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- CN104672437B CN104672437B CN201510092454.0A CN201510092454A CN104672437B CN 104672437 B CN104672437 B CN 104672437B CN 201510092454 A CN201510092454 A CN 201510092454A CN 104672437 B CN104672437 B CN 104672437B
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Abstract
The present invention relates to a kind of high index of refraction waterborne polyester and preparation method thereof, described high index of refraction waterborne polyester strand contains A, B, M, N repetitive, wherein A is aromatic acid or aromatic acid ester units, B is aromatic acid sulfonate or aromatic dicarboxylic acid ester sulfonates unit, and M is C2~12Glycol unit, N is the glycol unit of sulfur atom-containing.The high index of refraction waterborne polyester that the present invention obtains has enhanced water resistance, higher surface tension, high adhesion force and the refractive index of 1.58 ~ 1.63 simultaneously, has wide application in optical polyester film bottom field.
Description
Technical field
The present invention relates to mylar technical field, spy is standby is optics and printing, decoration caking property mylar.
Technical background
In recent years, polyethylene terephthalate (PET), as excellent film-forming resin, was protected at electronic product
It is used widely in the fields such as film, decorating film, optical thin film.For display and Dicoration base material, to use before it
A kind of stacking electron ray, ultraviolet or hardcoat film of heat cure system resin composition on clear PET film, in order to improve
Hard conating and the adhesive force of mylar base material, and to suppress the rainbow stricture of vagina caused when arbitrarily angled observation because of reflection light
With the phenomenon such as dazzle, one layer of adhesive layer will be set in centre as pre-priming operation, this pre-priming operation first has to ask as carrier
Polyester film surface formed high refractive index layer, the most also require be laminated with the strongest adhesive force and humidity resistance with other.
For solving the refractive index (acrylic resin of the refractive index (PET is 1.62) due to substrate polyester thin film and coating
Be 1.49) the rainbow stricture of vagina that produces greatly of difference, high index of refraction polyester is studied by many patent documentations.High index of refraction optics
The kind of resin is a lot, the group introduced according to preparation high index of refraction optical resin or the characteristic group of resin itself, is divided into
Sulfur optical resin, multi-ring optical resin, inorganic nano combined optical resin and several important kind of silicone photonic resin.
Chinese patent 20048002379.8 provides a kind of by waterborne polyester (A), water-soluble titanium chelate, water-soluble titanium
In acyl compound, water-soluble zirconium chelate or water solublity zirconyl compound, at least one (B) is as the main structure of resin combination
Become composition, prepare a kind of gumminess mylar suppressing rainbow stricture of vagina, but, waterborne polyester uses several titaniferous and zirconium
The chelate of element, can make production process complicated and product cost increases, and loss of adhesion to functional layer.
Japan Patent JP200749097 synthesizes a kind of PEN with high index of refraction, be by
Strand introduces bisphenol S and the addition product of oxirane and realizes, the oxirane involved by this invention have instability,
Difficult store, inflammable, poisonous, the performance such as zest, bring potential danger to preparation technology, and, during preparing latex,
Employ organic solvent tetrahydrofuran and environment can be caused certain pollution.
Chinese patent 201180011802.7 proposes a kind of polyester based resin, the manufacture method of polyester based resin and gathers
Ester system resin waterborne liquid, in this patent in resin combination containing specified quantitative, to have ad hoc structure fluorenes based compound many
Unit's alcohol and carboxylic acid composition, owing to fluorenes based compound has hydrophobicity, can make surface of polyester tension force less, be difficult to carry out on surface merit
Coating can be changed process, this shortcoming will be improved, need to add different types of surfactant, and surfactant is the most residual
Stay in film layer after coating, cause resistance to water to be deteriorated.
Summary of the invention
Present invention aim at providing a kind of high index of refraction waterborne polyester, this waterborne polyester has enhanced water resistance, relatively simultaneously
High surface tension, high adhesion force and high index of refraction, this height refraction waterborne polyester environmental friendliness when preparing emulsion.
Another object of the present invention is to provide the preparation method of a kind of high index of refraction waterborne polyester.
Technical problem of the present invention is achieved through the following technical solutions:
A kind of high index of refraction waterborne polyester, described high index of refraction waterborne polyester strand contains A, B, M, N repetitive,
Wherein A is aromatic acid or aromatic acid ester units, and B is aromatic acid sulfonate or aromatic dicarboxylic acid esters
Sulfonate salt units, M is C2～12Glycol unit, N is the glycol unit of sulfur atom-containing；
Described A with M or N is connected by ester bond, and described B with M or N is connected,
The intrinsic viscosity of described high index of refraction waterborne polyester is 0.3～1.2dl/g, and the refractive index of described waterborne polyester is
1.58～1.63, glass transition temperature is 53～67 DEG C.
Above-mentioned high index of refraction waterborne polyester, the ratio of the molal quantity of described A and B and the molal quantity of M and N, i.e. (A+B)/(M+
N) it is (1.0:1.0)～(2.5～1.0).
Above-mentioned high index of refraction waterborne polyester, described A is p-phthalic acid, M-phthalic acid or a combination thereof thing；Between described B is
Phthalic acid-5-sodium sulfonate.
Above-mentioned high index of refraction waterborne polyester, described M is ethylene glycol, neopentyl glycol or a combination thereof thing；
Above-mentioned high index of refraction waterborne polyester, described N is bisphenol derivatives, bisphenol-a derivative or a combination thereof thing.
Above-mentioned high index of refraction waterborne polyester, the mol ratio of described A and B is 85～99:1～15.
Above-mentioned high index of refraction waterborne polyester, the mol ratio of described M and N is 80～99:1～20.
Above-mentioned high index of refraction waterborne polyester, described N is one or more in following structural:
Described N1For the derivant of bisphenol S, N2And N3For the derivant of dihydroxy diphenyl sulfide, N4Deriving for bisphenol-A
Thing, wherein m represents the integer of 1～10, and n represents the integer of 1～10.
A kind of high index of refraction waterborne polyester preparation method, preparation process is:
1) by A, B and M, N and catalyst, after value of calculation precise, 30L polymerization reaction kettle is added in the lump；2) carry out
In still, nitrogen is replaced 3～4 times, starts stirring, and the while that control reaction system being carried out under the conditions of 220～250 DEG C, in still, pressure exists
200Kpa～300Kpa, esterification 2～5 hours；3) temperature rises to 250～270 DEG C, reaction system be gradually decompressed to 1000～
30Pa, after 1～3 hour, terminates decompression, is slowly introducing nitrogen after closing heating system, and sticky polymers is melted by discharging of pressurizeing
Body runs through cold water cooling, pelletizing, available high index of refraction waterborne polyester section.
Above-mentioned preparation method, described catalyst is the one in zinc acetate, antimony acetate, antimony oxide, butyl titanate
Or two kinds, catalyst amount and A and B mol ratio are 10-6: 1.0～10-3:1.0。
The invention have the advantages that
The high index of refraction waterborne polyester of the present invention overcomes in above-mentioned prior art and has problems, and is not introducing rigidity base
Under conditions of group's naphthalene nucleus, strand introduces phenols and the derivant of diphenyl sulfide and hydrophilic group monomer, the water obtained
Property polyester has enhanced water resistance, higher surface tension, high adhesion force and the high index of refraction of 1.58～1.63 simultaneously.
This height refraction waterborne polyester, when being applied to film substrate coating fluid, does not use tetrahydrofuran solvent, to environment friend
Good；And owing to the refractive index of this waterborne polyester reaches more than 1.58, the refractivity between the priming coat and the mylar that obtain is relatively
Little, effectively inhibit the generation of rainbow stricture of vagina；The surface tension of priming coat can reach more than 52mN/m, and can keep not for a long time
Decline, eliminate the shortcoming reduced after corona method improves surface tension, also abandoned and carved with resorcinol or other organic solvent
Erosion mylar improves environmental pollution and the method for infringement workmen's health that surface tension is brought；The bottom formed, cements
Degree height, and can improve to binding agent, ink, etc. the adhesive force of other functional coating.
Detailed description of the invention
High index of refraction waterborne polyester prepared by the present invention, introduces special groups, and involved group has aromatic rings, sulfone
Base, thioether, sulfonic group etc..Wherein, in order to give polyester, there is hydrophilic, in strand import hydroxyl, carboxyl, sulfonic group,
The hydrophilic groups such as ether, in above-mentioned hydrophilic group, consider from performance and the adhesive force of film, preferably sulfonic group.It addition, from power
Learn performance and thermally-stabilised angle is set out, also select containing ehter bond, the monomer of aromatic rings.
The aromatic acid being suitable in the present invention or aromatic dicarboxylic acid esters composition A, for p-phthalic acid, isophthalic diformazan
Acid, phthalic acid, PMA, trimellitic anhydride, trimesic acid, aliphatic polybasic acids have adipic acid, dodecanedioic acid, 1,
4-cyclohexyl dicarboxylic acid, dimethyl terephthalate (DMT), dimethyl isophthalate, dimethyl phthalate, preferably terephthaldehyde
Acid, M-phthalic acid.
The aromatic acid sulfonate being suitable in the present invention or aromatic dicarboxylic acid ester sulfonates composition B, for isophthalic two
Formic acid-5-sodium sulfonate, M-phthalic acid-5-potassium sulfonate, Sodium Dimethyl Isophthalate-5-sulfonate, dimethyl isophthalate-
5-potassium sulfonate, preferably 5-sodium sulfo isophthalate, Sodium Dimethyl Isophthalate-5-sulfonate.The mol ratio of described A and B
It is 85～99:1～15.Aromatic acid sulfonate or aromatic dicarboxylic acid ester sulfonates monomer are in the A and B component of polyester
Occupying molar percentage is 1～15%.When molar percentage is less than 1%, polyester will not show hydrophilic, is just difficult to obtain water
Property emulsion, then can not get the pre-priming operation of homogeneous transparent；When sulfonic group content of monomer exceedes molar percentage 15%, moisture-proof
Hot property is greatly reduced.
In the present invention be suitable for glycol component M be ethylene glycol, diglycol ethylene, 1,2-propylene glycol, 1,3-propylene glycol, 1,
The less glycol of carbon atom such as 4-butanediol, neopentyl glycol, 1,5-PD, most preferably ethylene glycol, diglycol ethylene, sulfur generation two
Glycol, neopentyl glycol.
Sulfur atom-containing glycol component N being suitable in the present invention relates to containing aromatic rings, hydroxyl reactive group, ehter bond, fat
Fat segment, its structural formula is expressed as:
N1: the derivant of bisphenol S, N2And N3: the derivant of dihydroxy diphenyl sulfide, N4: the derivant of bisphenol-A, wherein m
Representing the integer of 1～10, n represents the integer that the integer of 1～10, preferably m are 2～6, and n is the integer of 2～6.
The mol ratio of described M and N is 80～99:1～20.In the present invention, N is sulfur atom-containing, aromatic rings, hydroxyl activity
Group, ehter bond, the fat segment glycol component i.e. derivant of bisphenol S, the derivant of dihydroxy diphenyl sulfide, the spreading out of bisphenol-A
Biology, the mol ratio of M and N is 80～99:1～20.When the content of N is too small, and waterborne polyester can not embody the effect improving refractive index
Really；When N content of monomer is too much, owing to such strand is longer so that polyester molecule chain in polycondensation process, too early end-blocking,
It is unable to reach anticipated molecular weight, thus causes mechanical properties decrease.
The catalyst being suitable in the present invention is the one in zinc acetate, antimony acetate, antimony oxide, butyl titanate or two
Kind, preferably antimony acetate, butyl titanate or a combination thereof thing, its whole consumptions are the 10 of A and B total mole number-6～10-3.Work as catalysis
Agent is more than 10-3Time, it is no matter that the polycondensation reaction in ester exchange, esterification or later stage all can be carried out with two-forty, causes molecular weight to divide
Cloth is uneven, and the reasonable layout of influencing characterisitic group eventually affects mechanical property and the optical property of polyester；If catalyst is less than
10-6Then react more slow, cause reaction system to be maintained at high temperature high vacuum state for a long time, do not only result in polyester portion oxidation
And turn yellow, colour raises also time consumption and energy consumption.
Preparation method:
By above-mentioned preferred dihydroxylic alcohols and binary acid, antimony acetate and the tetrabutyl titanate catalyst mentioned, accurate by value of calculation
After weighing, add 30L polymerization reaction kettle in the lump；In carrying out still, nitrogen is replaced 3-4 time, starts stirring, controls reaction system 220
～carry out under the conditions of 250 DEG C, in still, pressure is at 200Kpa～300Kpa simultaneously, and esterification 2～5 hours, then temperature rises to
250～270 DEG C, carrying out polycondensation reaction under conditions of catalyst, reaction system is gradually decompressed to 1000～30Pa, 1～3 hour
After, terminating decompression, after closing heating system, be slowly introducing inert nitrogen gas, discharging of pressurizeing, by fast for sticky polymers molten mass
Speed is cooled down by cold water, and crosses pelleter, available light yellow polyester slice.It is designated as P-x (x is embodiment numbering) polyester.So
Test polyester inherent viscosity with Ubbelohde viscometer afterwards, measure glass transition temperature with TG-DSC thermal analyzer.
Describe the present invention in detail below in conjunction with embodiment, but the present invention is not limited to below example.Additionally, the present invention
In to resin property test evaluation methodology as follows.
1, intrinsic viscosity: carry out intrinsic viscosity test according to GB/T14190-2008 standard.
2, glass transition temperature
Use Nai Chi company release STA 449F3Jupiter synchronize TG-DSC thermal analyzer, make 10mg resin sample with
The speed of 10 DEG C/min heats up within the temperature range of 25～150 DEG C, temperature the extrapolation glass transition that will be obtained by DSC curve
Degree is as glass transition temperature.
3, refractive index: polyester slice is hot pressed into, by vulcanizer, the resin sheet that thickness is 0.5mm, exists with Abbe refractometer
Test under conditions of room temperature 25 DEG C.
Embodiment 1:
By 60 moles of ethylene glycol, 10 moles of Thiodiglycols, 21 moles of neopentyl glycol mixing, as polyol component C and 7
The derivatives monomer N of mole of dihydroxy diphenyl sulfide2, the derivatives monomer N of 2 moles of bisphenol A4Mixing；
By 63 moles terephthalic acid, 27 moles of M-phthalic acids, 10 moles of sodiosulfoisophthalic acid mixing；
With 10-4Molar acetate antimony and 10-5Mole tetrabutyl titanate catalyst, adds 30L polymerization reaction kettle in the lump；Then
In carrying out still, nitrogen is replaced 3 times, starts stirring, and controlling reaction system is 240 DEG C, and in still, pressure is at 200Kpa simultaneously, and esterification is anti-
Answering 4 hours, then temperature rises to 270 DEG C, carries out polycondensation reaction under conditions of catalyst, and reaction system is gradually decompressed to
50Pa, after 3 hours, terminates decompression, is slowly introducing inert nitrogen gas after closing heating system, and thickness is polymerized by discharging of pressurizeing
Thing molten mass runs through cold water cooling, and crosses pelleter, available high index of refraction waterborne polyester.It is designated as P-1 polyester.Use Ubbelohde
Viscometer test polyester inherent viscosity be 0.48dl/g, with TG-DSC thermal analyzer measure glass transition temperature be 65 DEG C, use Ah
Refractive index measured by shellfish refractometer is 1.58.
In addition to raw material and monomer difference, as the polyester synthesis step in embodiment 1, complete embodiment P-2～
The synthesis of P-10 polyester, each raw material usage and test result, sum up in the following Table 1.
Table 1
Embodiment 11
By above-described embodiment 4 gained high index of refraction waterborne polyester (P-4) 1Kg and distilled water 3Kg, load and there is band stirring
In machine, reflowable 5L glass container, being stirred, heated by conduction oil, in system, temperature is maintained at 90～95 DEG C,
Stir 2 hours, obtain the aqueous emulsion that solid content is 25%.It is 5% by the aqueous emulsion distilled water diluting obtained to solid content
Coating fluid, by silk rod coating to mylar one side, 130 DEG C are dried 1 minute.Gained coating bottom test result such as table 2.
The performance test of table 2. high index of refraction waterborne polyester emulsion coating film forming layer
In thin film industrial applicability:
The high index of refraction waterborne polyester of the present invention, its intrinsic viscosity is at 0.3-1.2dl/g, and refractive index is more than 1.58, main
Functional compartments is wanted to reduce the refractivity between gained priming coat and optics polyester base material thin film, effectively suppression or elimination optics polyester
Rainbow stricture of vagina, interference that thin film produces have relatively strong adhesive force, and make optical polyester film top layer have between stricture of vagina, and optical polyester film
High surface tension and can persistently existing, can be as other functional coating such as binding agent, ink at optics polyester base material thin film table
The bottom in face, high index of refraction waterborne polyester is environmentally friendly, easy large-scale production.
Claims (8)
1. a high index of refraction waterborne polyester, it is characterised in that described high index of refraction waterborne polyester strand contains A0、B0、M0、N0
Repetitive, wherein A0From aromatic acid or the unit of aromatic dicarboxylic ester compound (being designated as A), B0From virtue
Fragrant race's binary acid sulfonate or the unit of aromatic dicarboxylic acid ester sulfonates compound (B), M0Binary from C2～12 is refined
The unit of compound (M), N0From bisphenol-a derivative or the unit of dihydroxy diphenyl sulfide derivant (N)；Its structural formula is as follows:
Wherein, N2And N3For the derivant of dihydroxy diphenyl sulfide, N4For the derivant of bisphenol-A, m represents the integer of 1～10, n table
Show the integer of 1～10；
The intrinsic viscosity of described high index of refraction waterborne polyester is 0.3dl/g～1.2dl/g, and the refractive index of described waterborne polyester is
1.58～1.63, glass transition temperature is 53 DEG C～67 DEG C.
High index of refraction waterborne polyester the most according to claim 1, it is characterised in that described A and the molal quantity of described B and M
It is (1.0:1.0)～(1.0:2.5) with the ratio of molal quantity of N, i.e. (A+B)/(M+N).
High index of refraction waterborne polyester the most according to claim 2, it is characterised in that described A is p-phthalic acid, isophthalic two
Formic acid or a combination thereof thing；Described B is 5-sodium sulfo isophthalate.
High index of refraction waterborne polyester the most according to claim 3, it is characterised in that described M be ethylene glycol, neopentyl glycol or
A combination thereof thing.
High index of refraction waterborne polyester the most according to claim 4, it is characterised in that the mol ratio of described A and described B is 85
～99:1～15.
High index of refraction waterborne polyester the most according to claim 5, it is characterised in that the mol ratio of described M and N be 80～
99:1～20.
7. prepare the method for high index of refraction waterborne polyester as described in any one of claim 1-6 for one kind, it is characterised in that preparation is pressed
Following steps are carried out:
1) by A, B and M, N and catalyst, after value of calculation precise, 30L polymerization reaction kettle is added in the lump；
2) carry out nitrogen in still to replace 3～4 times, start stirring, control reaction system 220 DEG C～250 DEG C, pressure exists in still
Esterification 2～5 hours under conditions of 200KPa～300KPa；
3) temperature rises to 250 DEG C～270 DEG C, and reaction system is gradually decompressed to 1000Pa～30Pa, after 1～3 hour, terminates subtracting
Pressure, is slowly introducing nitrogen after closing heating system, discharging of pressurizeing, and sticky polymers molten mass runs through cold water cooling, cuts
Grain, available high index of refraction waterborne polyester.
Preparation method the most according to claim 7, it is characterised in that described catalyst includes zinc acetate, antimony acetate, three oxygen
Change in two antimony, butyl titanate one or both, catalyst amount and A and B mol ratio are 10-6: 1～10-3:1。
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| CN106318145B (en) * | 2016-08-28 | 2019-02-01 | 中国乐凯集团有限公司 | A kind of polyester-type water-based emulsion, preparation method and applications |
| CN106493387B (en) * | 2016-11-05 | 2018-08-28 | 中国乐凯集团有限公司 | The preparation method of micron ping-pong ball |
| JP6741078B2 (en) * | 2017-09-22 | 2020-08-19 | 東洋紡株式会社 | Easy-adhesive polyester film |
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| CN1333792A (en) * | 1998-12-03 | 2002-01-30 | 伊斯曼化学公司 | Terephthalate-based sulfopolyesters |
| JP5377830B2 (en) * | 2007-02-28 | 2013-12-25 | 竹本油脂株式会社 | POLYESTER RESIN, POLYESTER RESIN AQUEOUS LIQUE |
| CN102076498B (en) * | 2008-04-30 | 2014-12-17 | 东洋纺织株式会社 | Substrate film with modified adhesiveness and hard coat film |
| CN102604062B (en) * | 2012-04-11 | 2013-11-06 | 山东巨业精细化工有限公司 | Water-soluble polyester for textile size and preparation method of water-soluble polyester |
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