CN85106028A - The unsaturated polyester that is used for cathode-ray tube - Google Patents
The unsaturated polyester that is used for cathode-ray tube Download PDFInfo
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- CN85106028A CN85106028A CN85106028.5A CN85106028A CN85106028A CN 85106028 A CN85106028 A CN 85106028A CN 85106028 A CN85106028 A CN 85106028A CN 85106028 A CN85106028 A CN 85106028A
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Abstract
A kind of unsaturated polyester, it consists of (I) a kind of unsaturated polyester, at least a polymerisable unsaturated compound of (II) styrene monomer and/or its derivative and (III), for example, vinyl cyanide, methylene-succinic acid, methyl-maleic acid acid anhydride, a kind of monoesters of unsaturated dibasic acid or dibasic acid esters, vinylformic acid, methacrylic acid etc.Component (I) is dissolved in component (II) and (III) by predetermined proportion.With this sizing material cathode-ray tube, can obtain one deck binding property excellence, and not have the transparent film of solidification internal stress.
Description
The present invention relates to a kind of unsaturated polyester that is used for cathode-ray tube.
Owing to be in high vacuum in the cathode tube, broken danger is arranged during collision, i.e. implosion easily, therefore, and the dispersing of glass fragment when preventing implosion, cathode tube must be through explosion-proof processing.
The method that is used for explosion-proof processing is a lot.For example, the explosion-proof as shown in drawings facture of structure is effective.This method is with a kind of resin sizing material retaining glass to be adhered on the window of tube of cathode tube.Thin speech, this method is retaining glass 3 parcels and closely is fixed on the window of tube 2 of cathode tube that the curvature of retaining glass 3 is identical with the window of tube 2 of tape insulation band 4 with size, insulating tape is very near from window of tube, fills gap 5 for explosion-proof with the resin sizing material.Made explosion-proof cathode tube 6 thus.
The resin sizing material that has been used for explosion-proof processing before this has Resins, epoxy, unsaturated polyester resin and analogue thereof.Yet their existing advantages also have shortcoming, under reality, are not also obtaining the satisfied resin sizing material that is used for explosion-proof processing aspect characteristic and the plasticity-.
For example, during application of epoxy, it has higher adhesion strength, and this helps bonding retaining glass on window of tube, still, As time goes on it has the character of band look, therefore, when Resins, epoxy was used for cathode tube, the band look just became important problem, as, the sharpness and the brightness of band look cathode tube all can descend.In addition, compare with unsaturated polyester resin, in a single day Resins, epoxy mixes viscosity with solidifying agent and increases immediately, and not only the usage period is short and deaeration is poor, and needs to mix and injection device.Therefore, but its application property is not good.
On the other hand, when using unsaturated polyester resin, its viscosity generally can be low to moderate several pools, and viscosity no longer increases until condensing before, therefore, mixes with solidifying agent easily, and is injected into the window of tube of cathode tube easily and keeps off in the gap between the glass and going.In addition, because its viscosity is low, thereby working life can regulated at will, mixes or easy deaeration etc. when injecting.These all are their advantages.But, if solidifying agent is different with predetermined condition to the per-cent of resin, in some cases, can cause local deformaton during curing.This distortion can cause lens effect, like this, when opening cathode tube, surface imperfection can occur on window of tube, if any the figure of striped, luminous point etc.Because these surface imperfection influence the effect of cathode tube, so must the careful blending ratio of grasping solidifying agent.Surface imperfection, for example, striated pattern, luminous point etc. also may be because the rapid heating of curing oven or temperature be uneven causes, and therefore, the unusual grasp condition of cure of carefulness is as temperature condition etc.
The surface imperfection that exists in the technology before the objective of the invention is to eliminate, this is to use the great advantage of unsaturated polyester resin, and aim to provide a kind of unsaturated polyester that is used for cathode-ray tube, this compound viscosity is low, and transparency and bond strength height, and the surface imperfection that does not cause by curing deformation etc.
The invention provides a kind of liquid unsaturated polyester resin sizing material that is used for cathode-ray tube, it is composed as follows:
(I) acid its mainly to form be a kind of unsaturated dibasic acid and/or its acid anhydrides, with the alcohol prepared unsaturated polyester that reacts, the molecular weight of every mole of unsaturated group is 500-8000.
(II) styrene monomer and/or its derivative.
(III) at least a polymerisable unsaturated compound, this compound is selected from:
(ⅰ) vinyl cyanide, methylene-succinic acid and methyl-maleic acid acid anhydride.
(ⅱ) monoesters of unsaturated dibasic acid and dibasic acid esters.
(ⅲ) vinylformic acid, methacrylic acid and derivative thereof.
Scope according to (b)/((a)+(c))=1/10-10/1 is dissolved in component (I) in component (II) and (III),
(a) is the mole number of unsaturated group in the component (I) in the formula; (b) be the mole number of unsaturated group in the component (II); (c) be the mole number of unsaturated group in the component (III).
Accompanying drawing is the partial schematic diagram of explosion-proof cathode tube.
Chief component-unsaturated dibasic acid and/or its acid anhydrides for the preparation of the acid constituents of unsaturated polyester (UP) (I) comprise maleic acid, fumaric acid, methylene-succinic acid, methyl-maleic acid, maleic anhydride etc. These compositions can two kinds or multiple mixing use.
If need, acid constituents can comprise polyacid. The example of polyacid has: phthalic acid, phthalic anhydride, M-phthalic acid, terephthalic acid (TPA), trimellitic acid, trimellitic anhydride, succinic acid, azelaic acid, adipic acid, decanedioic acid, tetrahydrophthalic acid, tetrabydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, carbic anhydride, anthracene-maleic acid adduct, rosin-maleic acid anhydride adduct, HET acid and acid anhydrides thereof, the chlorination polyacid, for example, tetrachlorophthalic acid, tetrachlorophthalic tetrachlorophthalic anhydrid and analog, the bromination polyacid, for example, tetrabromophthalate, tetrabromophthalic anhydride, etc., above compound can use by mixture.
In addition, acid constituents also can comprise 3,6-endo-methylene group-1,2,3,6-tetrabydrophthalic anhydride, or 3,6-endo-methylene group-1,2,3,6-tetrahydrophthalic acid.
Dicyclopentadiene is cyclopentadiene in 170 ° of-180 ℃ of pyrolysis, reacts 2 hours through Diels-Alder at 20 °-40 ℃ with maleic anhydride then, obtains 3,6-endo-methylene group-1,2,3, the 6-tetrabydrophthalic anhydride. This compound can have been bought in market, and commodity are called the HIMIC acid anhydrides, are made by Hitachi chemical Co., Ltd.
Replace above-mentioned maleic anhydride can make 3,6-endo-methylene group-1,2,3 with maleic acid, the 6-tetrahydrophthalic acid.
The alkoxide component of preparation unsaturated polyester (UP) (I) can be used dihydroxylic alcohols, for example, and ethylene glycol, tirethylene glycol, propane diols, two contracting propane diols, 1,3-BDO, BDO, 2,3-butanediol, 1,5-PD, 1,6-hexylene glycol, triethylene glycol, the analogs such as neopentyl glycol; Trihydroxylic alcohol, for example, glycerine, trimethylolethane, the analogs such as trimethylolpropane; Tetrahydroxylic alcohol, for example, pentaerythrite and analog; Etc..
Also can use halohydrin, for example, the chloride of above-mentioned various alcohol, bromide and analog.
By the process that unsaturated polyester is produced in above-mentioned acid constituents and the reaction of above-mentioned alkoxide component, mainly undertaken by the condensation reaction and the elimination reaction of this serial low-molecular weight compound.
Implementing the reactor of this reaction selects a kind of to acid constituents inert reactor, for example, glass reactor, the reactor of stainless steel reactor or analogous material, preferably select a kind of reactor that stirring is housed, boil off with water alcohol azeotrope, a fractionation plant should be arranged in order to prevent alkoxide component, be the heating unit that reaction system heats up, the temperature-control circuit of heating unit and the device or the allied equipment that blast nitrogen.
About reaction conditions, this reaction is preferably in 150 ℃ or higher temperature to be carried out, enough high in this temperature range speed of response.When preventing high temperature because oxidation and painted, temperature of reaction be controlled at 160 ℃-210 ℃ better.
Reaction is paid in oxidation when preventing high temperature, and this synthetic being preferably under the situation that feeds nitrogen, carbonic acid gas or similar rare gas element is carried out.
The system of forming by the mixture of heating acid constituents and alkoxide component, and from system, remove the low-molecular weight compound such as the condensation water of generation, promote the carrying out of this reaction.Preferably rare gas element is spontaneous to steam or underpressure distillation promotion reaction elimination reaction by importing.Steam high boiling low-molecular weight compound, need use high vacuum.
In addition,, also can add a kind of solvent in order to quicken to steam low-molecular weight compound such as condensation water, as toluene, dimethylbenzene or analogue in reaction system, as azeotropic component so that its spontaneous steaming.
The reaction degree of carrying out generally can know, for example, and the amount of the distillate that produces by assaying reaction, quantitative assay functional end-group, or the viscosity of assaying reaction system.
The molecular weight 500-8000 of every mole of unsaturated group of unsaturated polyester that the present invention is used, preferably 1000-4000.
Adopt usual method,, just can obtain such unsaturated polyester by regulating the blending ratio of raw material.
When the molecular weight of every mole of unsaturated group of unsaturated polyester less than 500 the time, the cross-linking density of gained cured resin product can increase.Therefore, the contraction percentage of this resin can increase, and the resin solidification product becomes rigidity, and flexibility reduces, so, because heat or collision will cause from the retaining glass or the window of tube of cloudy cathode tube to come off, and, time product can not be reclaimed.
When the molecular weight of every mole of unsaturated group of unsaturated polyester surpasses 8000, when resin solidification, can not produce enough degree of crosslinking, prolong set time, and plasticity-reduces, and number of spots increases.In addition, also can cause vinylbenzene and/or its derivative and polymerisable unsaturated compound, as vinylformic acid, the copolymerization of methacrylic acid and/or its derivative, the perhaps only copolymerization of vinyl monomer causes the solidified resin to become White-opalescent, can not be re-used as the cathode tube commodity.
In addition, owing to there are not enough crosslinked generations, (80 ℃ 90%R.H.), can cause the reduction of bonding strength between the retaining glass of cathode tube and the window of tube, and cause coming off under hot and humid condition.
Unsaturated polyester (I) by styrene monomer and/or its derivative (II) make dissolves in vinylbenzene, chlorostyrene, dichlorobenzene ethene, p-methylstyrene, neighbour-vinyl toluene, Vinyl toluene, Vinylstyrene etc.These compounds can use or mix use separately.
Used polymerizable unsaturated compound (III) is selected from the following compound at least.(ⅰ) vinyl cyanide, methylene-succinic acid and methyl-maleic acid acid anhydride.
Also can adopt the monoesters of (ⅱ) unsaturated dibasic acid and at least one compound in the dibasic acid esters as polymerizable unsaturated compound (III).
Monoesters and dibasic acid esters as unsaturated dibasic acid can be various esters, for example, and the FUMARIC ACID TECH GRADE mono-methyl, dimethyl fumarate, monomethyl cis-butenedioic acid, dimethyl maleate, single-ethyl fumarate, diethyl fumarate, cis-butenedioic acid mono ethyl maleate, diethyl maleate, the single propyl ester of FUMARIC ACID TECH GRADE, FUMARIC ACID TECH GRADE dipropyl, maleic acid list propyl ester, maleic acid ester, the FUMARIC ACID TECH GRADE mono, dibutyl fumarate, FUMARIC ACID TECH GRADE mono octyl ester, dioctyl fumarate, the methylene-succinic acid mono-methyl, methylene-succinic acid dimethyl ester, methylene-succinic acid diethyl ester, the methylene-succinic acid mono ethyl ester, the methylene-succinic acid mono, methylene-succinic acid dibutylester, methylene-succinic acid list propyl ester, the methylene-succinic acid dipropyl, or the like.
Above ester compound can use or mix use separately.
Polymerisable unsaturated compound (III) also can be selected from (ⅲ) vinylformic acid, at least a compound in methacrylic acid and the derivative thereof.
The derivative of adaptable vinylformic acid and methacrylic acid.For example, vinylformic acid allyl ester, vinylformic acid benzyl ester, butyl acrylate, ethyl propenoate, methyl acrylate, propyl acrylate, Hydroxyethyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, propyl methacrylate, allyl methacrylate, the methacrylic acid benzyl ester, hydroxyethyl methylacrylate, lauryl methacrylate, Octyl methacrylate, the methacrylic acid pentyl ester, or the like.
The mole number of supposing the unsaturated group of unsaturated polyester (I) in the present invention is (a), the mole number of the unsaturated group of styrene monomer and/or its derivative (II) is (b), the mole number of the unsaturated group of polymerisable unsaturated compound (III) is (c), so, the unsaturated polyester that is dissolved in styrene monomer and/or its derivative (II) and the polymerisable unsaturated compound (III) is in the following scope:
（b）/〔（a）+（c）〕＝1/10-10/1
When polymerisable unsaturated compound was (ⅰ), preferably scope was:
（b）/〔（a）+（c）〕＝5/10-10/1
When (b)/((a)+(c)) surpassed 10/1, luminous point increased, and caused the surface imperfection ratio to increase.When (b)/((a)+(c)) less than 5/10 the time, viscosity increases, so that deaeration reduction and cure period prolongs greatly, therefore, plasticity-reduces greatly owing to bubble, resin spills, and injects deficiency etc., has strengthened the tendency of surface imperfection.
At polymerisable unsaturated compound is under the situation of (ⅱ), when (b)/((a)+(c)) greater than 10/1 the time, predetermined condition when the ratio of mixture of solidifying agent is different from unsaturated polyester curing, owing to solidify the furnace temperature inequality when solidifying, and contain the temperature difference between the retaining glass seat of the unsaturated polyester of solidifying agent and cathode tube, cause curing deformation easily, the sizing material of injection comes off easily.Therefore, striated pattern or luminous point on window of tube, occur, lose commodity value.
On the other hand, when (b)/((a)+(c)) less than 1/10 the time, the viscosity reduction effect of styrene monomer and/or its derivative forfeiture, therefore, plasticity-reduces.For example, it is very difficult that the casting of unsaturated polyester becomes, and is difficult to deaeration when mixing or casting solidifying agent.(b)/((a)+(c)) good again scope only is 1/2-5/1.Under the situation of above-mentioned (ⅱ), though unsaturated polyester (I) is dissolvable in water in the mixture of the monoesters of styrene monomer and/or its derivative (II) and unsaturated dibasic acid and/or dibasic acid esters, but also can be dissolved in unsaturated polyester in styrene monomer and/or its derivative in advance, and then add the monoesters and/or the dibasic acid esters of unsaturated dibasic acid.In addition, also can be dissolved in unsaturated polyester earlier in the monoesters and/or dibasic acid esters of unsaturated dibasic acid, add vinylbenzene and/or its a kind of derivative then.
Under the situation of above-mentioned (ⅲ), although unsaturated polyester (I) is dissolvable in water vinylbenzene and/or its derivative (II) and vinylformic acid, in the mixture of methacrylic acid or derivatives thereof, but also can be dissolved in unsaturated polyester in vinylbenzene and/or its derivative earlier, and then adding vinylformic acid, the methacrylic acid or derivatives thereof can be dissolved in vinylformic acid to unsaturated polyester earlier again, in the methacrylic acid or derivatives thereof, and then add vinylbenzene and/or its derivative.
If desired, the unsaturated polyester that so makes can contain stopper, for example, quinhydrones, pyrocatechol, 2,6-di-tert-butyl cresols, right-benzoquinones, di-tert-butyl pyrocatechol, hydroquinone monomethyl ether, t-butyl catechol, monotert-butyl quinhydrones or the like, though add stopper amount be not very strict, the unsaturated polyester sizing material of preferably per 100 parts of weight adds the stopper of 0-0.03 part weight.
Solidify the used organo-peroxide of resin sizing material of the present invention and comprise, first (base) second (base) ketone peroxide for example, cycloethanone peroxide, cumene hydroperoxide, dicumyl peroxide, diacetone peroxide, benzoyl peroxide, dilauroyl peroxide, cumene peroxide etc.These chemical combination compounds can be used alone or as a mixture.Though the amount of the organo-peroxide that adds is not very strict, preferably is controlled at per 100 parts of weight unsaturated polyesters and adds superoxide 0.1-2 part.In addition, if desired, can in this resin sizing material, add curing catalyst.Curing catalyst decomposes organo-peroxide by redox reaction or similar reaction, promotes living radical to produce.Curing catalyst can be used the metallic soap class, cobalt naphthenate for example, naphthenic acid vanadium, cobalt octoate etc.; Quaternary ammonium salt, for example dimethyl benzyl ammonium chloride etc.; Beta-diketon class, for example methyl ethyl diketone etc.; Amine, xylidine for example, Diethyl Aniline, Tolylamine, the N-ethyl--Tolylamine, trolamine and analogue thereof; Or the like,
Unsaturated polyester of the present invention also can be used the light curing catalyst, diphenyl disulfide for example, benzoin methyl ether, Benzoin ethyl ether, the st-yrax positive propyl ether, benzoin isopropyl ether, the secondary butyl ether of st-yrax, st-yrax-2-amyl ether, st-yrax hexamethylene ether, dimethyl benzyl ketal or analogue.
Above-mentioned organo-peroxide and these high curing catalysts can use simultaneously.
If desired, resin sizing material of the present invention can contain dyestuff, softening agent, UV light absorber etc.
Unsaturated polyester of the present invention can be cast in the retaining glass and the gap between the window of tube of cathode tube into, for example, the picture tube of televisor, the typotron of computer etc., and in the gap, solidify.Curing comprises ultraviolet curing, and is infrared ray cured, electrocuring, and thermofixation, cold-curing, or the like.These methods can be used separately, perhaps combined utilization.
The present invention further illustrates by following example.Unless indicate in addition, per-cent and umbers all in the example all are meant weight.
Reference example 1
Under nitrogen atmosphere, 15 moles of MALEIC ANHYDRIDE, 50 moles of hexanodioic acids, 35 moles of Tetra Hydro Phthalic Anhydrides, 60 moles of glycol ethers and 45 moles of propylene glycol obtained a kind of unsaturated polyester (I in 12 hours in 220 ℃ of reactions
1), the molecular weight of its every mole unsaturated group is 1400, acid value is 28.In containing 25 parts of styrene monomers of 0.01 part of quinhydrones, dissolve 75 parts of unsaturated polyester (I
1), add 0.1 part 6% cobalt naphthenate then, obtain a kind of unsaturated polyester (A
1).
Example 1
Unsaturated polyester (A at 93 parts of reference example 1 gained
1) in, dissolve 7 parts of vinyl cyanide and obtain a kind of unsaturated polyester (B
1).
Example 2
At 95 parts of reference examples, 1 gained unsaturated polyester (A
1) in, 5 parts of methylene-succinic acids of heating for dissolving obtain a kind of unsaturated polyester (C
1).
Example 3
At 95 parts of reference examples, 1 resulting unsaturated polyester (A
1) in, 5 parts of methyl-maleic acid acid anhydrides of heating for dissolving.Obtain unsaturated polyester (D
1).
Example 4
In containing 20 parts of styrene monomers of 0.01 part of quinhydrones, dissolve 80 parts of unsaturated polyester (I by reference example 1 gained
1), dissolve 10 parts of vinyl cyanide then, obtain a kind of unsaturated polyester (E
1).
Comparative Examples 1
Under nitrogen atmosphere, 50 moles of MALEIC ANHYDRIDE, 50 moles of Tetra Hydro Phthalic Anhydrides, 60 moles of propylene glycol and 50 moles of ethylene glycol, in 200 ℃ of down reactions 10 hours, obtain a kind of acid value and be 35 and the molecular weight of every mole of unsaturated group be 400 unsaturated polyester.In containing 30 parts of styrene monomer solution of 0.02 part of quinhydrones and 0.1 part of cobalt naphthenate, dissolve 70 parts of gained unsaturated polyesters, obtain a kind of unsaturated polyester (F
1).
Get respectively by reference example 1, example 1 is to the unsaturated polyester (A of example 4 and Comparative Examples 1 gained
1), (B
1), (C
1), (D
1), (E
1) and (F
1) 100 parts, respectively adding 1 part 55% methylethyl ketone peroxide, in the 3mm gap between not explosion-proof cathode ray tube screen of gained sizing material impouring and the retaining glass, this cathode tube has installed retaining glass and preheating by accompanying drawing, solidifies 2 hours in 80 ℃.After the cooling, the spot number that visual valuation forms.
After the luminous point evaluation is intact, in 149 ℃ of heated cathode x ray tubes 48 hours, the visual observation dropping situations.Gained the results are shown in table 1.
Luminous point is estimated
◎: the spot number 0-10 of formation
Zero: the spot number 11-20 of formation
△: the spot number 21-50 of formation
X: the spot number of formation is more than 50
148 ℃ of heating are after 48 hours, and evaluation comes off
Zero: nothing comes off
X: come off
Just as demonstrated in Table 1, when selecting vinyl cyanide, methylene-succinic acid, when at least a compound is as polymerisable unsaturated compound in the methyl-maleic acid acid anhydride, the resulting unsaturated polyester that is used for the explosion-proof processing of cathode tube, the luminous point that former technology forms can be reduced to 1/10 or still less, treating processes can shorten greatly in cathode tube.
Example 5
Under nitrogen atmosphere, 0.15 mole MALEIC ANHYDRIDE, 0.85 mole 3,6-endo-methylene group-1,2,3, (commodity are called the HIMIC acid anhydrides to the 6-Tetra Hydro Phthalic Anhydride, by Hitachi chemical company limited preparation) and 1.1 moles of glycol ethers, reacted 10 hours down in 205 ℃ of stirrings, obtain a kind of acid value and be 24 and the molecular weight of every mole of unsaturated group be 2530 unsaturated polyester (I
2).
At 75 parts of unsaturated polyester (I
2) 25 parts of vinylbenzene of middle dissolving, add 0.005 part of quinhydrones and 0.05 part of cobalt naphthenate (by the preparation of Dainippon company, metal content 6%) again, obtain a kind of unsaturated polyester (A
2), its viscosity is 6.2 pools (2.5 ℃, the Gardner-Holdt air bubble viscosimeter).At 92 parts of gained unsaturated polyester (A
2) 8 parts of diethyl fumarates of middle dissolving, obtain a kind of unsaturated polyester (B
2), its viscosity is 3.8 pools (25 ℃, the Gardner-Holdt air bubble viscosimeter).And then add the prepared sizing material of 1 part of methylethyl ketone peroxide (is the mixture of 55% methylethyl ketone peroxide and 45 ℃ of % dimethyl phthalates by Nippon grease company limited preparation), by connect an opening at its edge at the cathode tube top, pour into not explosion-proof cathode ray tube screen 2(14 inch shown in the accompanying drawing) and the 3mm gap of retaining between the glass 3 in, solidified 2 hours in 80 ℃.
After the cooling, the visual valuation spot number.After the luminous point evaluation, in 149 ℃ of heated cathode x ray tubes 48 hours, the visual observation dropping situations.The result is as shown in table 2.
Example 6
At 90 parts of examples, 5 gained unsaturated polyester (A
2) 10 parts of monomethyl cis-butenedioic acids of middle dissolving, obtain a kind of unsaturated polyester (C
2), its viscosity is 3.0 pools (25 ℃, the Gardner-Holdt air bubble viscosimeter).This sizing material solidifies and check with the method for example 5.Gained the results are shown in table 2.
Example 7
Under nitrogen atmosphere, 0.1 mole FUMARIC ACID TECH GRADE, 0.7 mole 3,6-endo-methylene group-1,2,3, the 6-tetrahydrophthalic acid, 0.2 mole hexanodioic acid and 1.15 mole of two propylene glycol that contracts, in 205 ℃ of stirrings reaction 13 hours down, obtain a kind of acid value and be 20 and the molecular weight of every mole of unsaturated group be 2890 unsaturated polyester (I
3).
At 80 parts of unsaturated polyester (I
3) 20 parts of vinylbenzene of middle dissolving, then, add 0.02 part of t-butyl catechol and 0.03 part of octylenic acid cobalt (preparation of Dainippon company limited, containing metal 6%), obtain a kind of unsaturated polyester (D
2), its viscosity is 7.1 pools (25 ℃, the Gardner-Holdt air bubble viscosimeter).At 92 parts of gained unsaturated polyester resin (D
2) 8 parts of diethyl fumarates of middle dissolving, obtain a kind of unsaturated polyester (E
2), its viscosity is 4.9 pools (25 ℃, the Gardner-Holdt air bubble viscosimeter).This sizing material solidifies and check with example 5 same methods.It the results are shown in table 2.
Example 8
At 90 parts of examples, 7 gained unsaturated polyester (D
2) 10 parts of monomethyl cis-butenedioic acids of middle dissolving, obtain a kind of unsaturated polyester (F
2), its viscosity is 3.7 pools (25 ℃, the Gardner-Holdt air bubble viscosimeter).This sizing material solidifies and check with example 5 same methods.It the results are shown in table 2.
Comparative Examples 2 and Comparative Examples 3
Unsaturated polyester (the A of example 5 gained
2) and the unsaturated polyester (O of example 7 gained
2), solidify with example 5 same methods respectively.The former as a comparison case 2, the latter as a comparison case 3, the results are shown in table 2.
Comparative Examples 4 and Comparative Examples 5
Under nitrogen atmosphere, 0.50 mole Tetra hydro Phthalic anhydride, 0.15 mole MALEIC ANHYDRIDE, 0.35 mole hexanodioic acid, 0.3 mole ethylene glycol and 0.8 mole of glycol ether, in 200 ℃ of following stirring reactions 11 hours, obtain a kind of acid value and be 28 and every mole of unsaturated group molecular weight be 2180 unsaturated polyester (I
8).
At 75 parts of unsaturated polyester (I
3) 25 parts of vinylbenzene of middle dissolving, then, add 0.005 part of quinhydrones and 0.05 part of cobalt naphthenate (containing metal 6%), obtain a kind of unsaturated polyester (G
2), its viscosity is 9.0 pools (25 ℃, the Gardner-Holdt air bubble viscosimeter).Solidify this unsaturated polyester (G with example 5 same methods
2), as a comparison case 4, it the results are shown in table 2.
At 92 parts of unsaturated polyester (G
2) 8 parts of diethyl fumarates of middle dissolving, obtain a kind of unsaturated polyester (H
2), its viscosity is 6 pools (25 ℃, the Gardner-Holdt air bubble viscosimeter).Solidify this sizing material with example 5 same methods.As a comparison case 5, with the same methods check of example 5.It the results are shown in table 2.
Just as demonstrated in Table 2, in order to prepare unsaturated polyester, when acid constituents with 3,6-endo-methylene group-1,2,3,6-Tetra Hydro Phthalic Anhydride or 3,6-endo-methylene group-1,2,3, the 6-tetrahydrophthalic acid, when polymerisable unsaturated compound is used at least one compound of unsaturated dibasic acid monoesters or dibasic acid esters, the unsaturated polyester of gained cathode-ray tube, the luminous point that forms in cathode tube can reduce 1/10, even still less.This sizing material has improved tackiness to glass.
Example 9 and example 10
At one stirring rod is housed, prolong in 3 liters of four-hole boiling flasks of nitrogen ingress pipe and thermometer, adds following raw material:
1166 parts of glycol ethers
584 parts of hexylene glycols
740 parts of adjacent benzene two benzoic anhydrides
116 parts of FUMARIC ACID TECH GRADE
When this flask slowly imports nitrogen, in 1.5 hours, be warming up to 150 ℃ with electric mantle.In 4 hours, further be warming up to 200 ℃ and keep this temperature.Obtain a kind of acid value after about 10 hours and be 34 unsaturated polyester (A
3).Temperature drops to 100 ℃ again, adds 1 part of stopper-quinhydrones, then, this is mixed with the unsaturated polyester (A of quinhydrones
3) in stainless steel cask of impouring, room temperature is placed cooling.Gained unsaturated polyester (A
3) molecular weight of every mole of unsaturated group is 2440.
This unsaturated polyester can be dissolved in the mixing solutions of vinylbenzene and dibutyl fumarate by prescription shown in the table 3.
Per 200 parts of gained unsaturated polyesters add 0.05 part of octylenic acid cobalt (Dainippon printing ink chemical company preparation, containing metal 6% by weight) and 2 parts of methylethyl ketone peroxides (preparation of Nippon grease company limited).
On the other hand, a 3mm(is thick) * 250mm * 250mm silicone sheet, stay the silicone resin square frame after diging up 240mm * 240mm with razor from the centre, open a slit in its somewhere, then, it is thick that this silicone resin square frame is placed on a 3mm() * 250mm * 250mm clear plate glass on, 3mm(is thick for another piece) * 250mm * 250mm clear plate glass is placed on this silicone resin square frame, two blocks of sheet glass are tightly fixing with clip, become a mold.Above-mentioned unsaturated polyester pours into this mold from the slit aperture of silicone resin square frame.Then, this mold is placed in the electric oven, in 80 ℃ of resin solidifications 30 minutes, so obtain a unsaturated polyester resin moulding plate.
The characteristic of gained moulding plate is shown in table 3.
As Comparative Examples 6 and Comparative Examples 7, with front example 9 and example 10 described unsaturated polyester (A
3), the sizing material that makes according to filling a prescription shown in the table 3 and the characteristic of moulding plate thereof are by above-mentioned same method evaluation.
Under the situation of example 9 and example 10, curing deformation does not take place during curing.And, both do not had bar graph not have luminous point to be observed yet.Yet, under the situation of Comparative Examples 6 and Comparative Examples 7, but observed bar graph and luminous point.
In table 3, curing deformation is the result of visual observation: check whether bar graph exists, and spot number is to obtain with counting process.Dropping situations also is visual observation, the area that whether takes place and come off (being equally applicable to table 4).
Bond strength is to represent in order to the value that following method is obtained.The sheet glass of two 20mm * 15mm * 3mm, one is placed on another piece, the two is not exclusively overlapping, so that the adjusting contact area is 15mm * 15mm, they are bonded together (condition of cure: 1% methylethyl ketone peroxide by weight, solidified 5 hours) with unsaturated polyester, fix this subassembly from both sides in 80 ℃, the load of exerting pressure up and down, the longitudinal shear power of gluing of surfaces destroy whole bonding plane.
Example 11,12 and 13
Be equipped with in 3 liters of four-hole boiling flasks as example 8 described equipment, add following raw material:
Two contract 1474 parts of propylene glycol
1241 parts of hexanodioic acids
147 parts of MALEIC ANHYDRIDE
When this flask slowly feeds nitrogen, in 1 hour, be warming up to 150 ℃ with electric mantle.In 4 hours, continue to be warming up to 200 ℃, keep this temperature.After about 12 hours, obtain a kind of acid value and be 25 unsaturated polyester (B
3).
When temperature drops to 100 ℃, add 0.5 part of stopper-quinhydrones, then, will be added with the unsaturated polyester (B of quinhydrones
3) in stainless steel cask of impouring, place and be cooled to room temperature.
Unsaturated polyester (the B that obtains like this
3) molecular weight of every mole of unsaturated group is 1710.
This unsaturated polyester (B
3) be dissolved in the mixing solutions of vinylbenzene and diethyl fumarate by prescription shown in the table 4.
Table 4 provides by example 9 and example 10 same quadrat methods, the characteristic of solidifying every kind of unsaturated polyester gained cast panel.
In example 11,12 and 13, do not observe the curing deformation phenomenon.
Example 14
In 3 liters of four-hole boiling flasks that example 9 same equipment are housed, add following raw material:
1166 parts of glycol ethers
1509 parts of bridge methylene Tetra Hydro Phthalic Anhydrides (trade(brand)name HIMIC acid anhydrides, the limited chemical corporate system of Hitachi is equipped with)
93 parts of FUMARIC ACID TECH GRADE
Heat up by example 9 the same manners, remain in 200 ℃ then.After 8 hours, obtain a kind of acid value and be 24 unsaturated polyester.The molecular weight that calculates every mole of unsaturated group from the ratio of mixture for preparing the unsaturated polyester raw material is 3240.
Unsaturated polyester is cooled to 120 ℃, gets 2000 parts and is dissolved in by 400 parts of vinylbenzene, in the solution that 400 parts of dibutyl fumarates and 1.5 parts of quinhydrones are made.
The unsaturated polyester resin that obtains mixes with 0.05 part of octylenic acid cobalt and 1.5 parts of methylethyl ketone peroxides, by at not explosion-proof cathode tube top and the opening that communicates with the edge, in the 3mm gap between gained resin sizing material this cathode ray tube screen of impouring and the retaining glass.This cathode tube is 20 inches cathode tubes, structure as shown in drawings and retaining glass is housed, this cathode tube is preheating to 60 ℃ before the casting resin sizing material, solidified one hour in 60 ℃ the casting back.
From baking oven, take out cathode tube, be chilled to room temperature, start then, do not observe bar graph and luminous point, also do not come off.
The cathode tube that this handled in 150 ℃ of placements 48 hours, uses then, curing deformation had not both taken place also do not come off.Even in 85 ℃ and relative humidity are 90% environment, placed 72 hours, do not observe curing deformation yet and come off.
Example 15
As the same unsaturated polyester that is mixed with octylenic acid cobalt and methylethyl ketone peroxide used in example 14, under room temperature, be cast in the not explosion-proof cathode tube with example 14 same methods, this cathode tube is placed in 80 ℃ of baking ovens then, solidifies 2 hours
Cathode tube taken out from baking oven be chilled to room temperature, use then, do not observe curing deformation.
The result of table 3 and table 4 and example 14 and example 15 confirms, when choosing a kind of unsaturated dibasic acid monoesters and dibasic acid esters at least and make polymerisable unsaturated compound, superiority according to the used unsaturated polyester of the present invention is, the curing deformation that it causes when common unsaturated polyester is solidified reduces greatly, there is not crackle, bonding fabulous to sheet glass, do not come off.
Example 16,17 and 18
Stirring rod is housed, and prolong in 3 liters of four-hole boiling flasks of nitrogen ingress pipe and thermometer, adds following raw material:
1166 parts of glycol ethers
584 parts of hexanodioic acids
740 parts of Tetra hydro Phthalic anhydrides
116 parts of FUMARIC ACID TECH GRADE
When slowly importing nitrogen, in 1.5 hours, be warming up to 150 ℃ with electric mantle.Then, in 4 hours, be warming up to 400 ℃ and keep this temperature.Obtain a kind of acid value after about 10 hours and be 34 unsaturated polyester (A
4).Add 0.3 part of quinhydrones stopper after temperature drops to 100 ℃ again, then, in the impouring stainless steel cask, place and be cooled to room temperature.The molecular weight of every mole of unsaturated group of gained unsaturated polyester is 2440.
This unsaturated polyester is dissolved in the mixing solutions of vinylbenzene and methyl methacrylate, its proportioning is as shown in table 5.
Per 200 parts of gained unsaturated polyesters add 0.1 part of octylenic acid cobalt (Dainippon ink chemistry company preparation, metal content is 6% by weight) and 2 parts of methylethyl ketone peroxides (preparation of Nippon grease company limited).
On the other hand, thick at a 3mm() * 250mm * 250mm silicone sheet center, dig up 240mm * 240mm with razor, stay next silicone resin square frame, open a slit in its somewhere, then, it is thick that this silicone resin square frame is placed on a 3mm() * 250mm * 250mm clear plate glass on, 3mm(is thick another piece) * 250mm * 250mm clear plate glass is placed on this silicone resin square frame again, and two blocks of sheet glass are tightly fixing with clip, become a mold.Above-mentioned unsaturated polyester pours into mold from the gap opening of silicone resin square frame.This mold is placed in the electric oven, and sizing material obtains a unsaturated polyester resin cast panel in 80 ℃ of curing 30 minutes.
The characteristic of gained cast panel is shown in Table 5.
Comparative Examples 8 and Comparative Examples 9 used sizing materials are application examples 16,17 and 18 described unsaturated polyester (A
4), make according to prescription shown in the table 5.The cast panel characteristic is with the evaluation of above-mentioned same side's method.
Under the situation of example 16,17 and 18, curing deformation does not take place during curing, bar graph and luminous point are not all observed.
Yet, under the situation of Comparative Examples 8 and Comparative Examples 9, though do not observe bar graph, luminous point has appearred.
In table 5, curing deformation is the visual observation result: whether bar graph exists, and calculates number of spots (being equally applicable to table 6).
Example 19,20 and 21
Be equipped with in 3 liters of four-hole boiling flasks of example 16 same equipment, add following raw material:
Two contract 1474 parts of propylene glycol
1241 parts of hexanodioic acids
147 parts of MALEIC ANHYDRIDE
When in flask, slowly importing nitrogen,, be warming up to 150 ℃ in 1 hour with the electric mantle heating.Then, in 4 hours, be warming up to 400 ℃ and keep this temperature.After 12 hours, obtain a kind of acid value and be 25 unsaturated polyester (B
4).
After temperature drops to 100 ℃, add 0.3 part of quinhydrones stopper, then, in stainless steel cask of impouring, place and be cooled to room temperature.
Gained unsaturated polyester (B
4) molecular weight of every mole of unsaturated group is 1710.
This unsaturated polyester is dissolved in vinylbenzene and the butyl acrylate mixing solutions for prescription according to table 6.
With the same method of example 16, the characteristic of the cast panel made from each unsaturated polyester of top gained is shown in Table 6.
In example 19,20 and 21, do not observe curing deformation.
Result shown in table 5 and the table 6 confirms, vinylformic acid, at least a during in methacrylic acid and their derivative as polymerisable unsaturated compound, unsaturated polyester of the present invention can reduce the curing deformation when solidifying greatly, luminous point particularly, and this class curing deformation often betides in the common unsaturated polyester, and therefore, it is suitable for dealing with the resin sizing material of cathode tube.
Claims (10)
1, a kind of liquid unsaturated polyester resin sizing material that is used for cathode-ray tube is characterized in that being made up of following:
(I) by a kind of acid constituents, it is mainly formed is unsaturated dibasic acid and/or its acid anhydrides, a kind of unsaturated polyester that obtains with a kind of alkoxide component reaction.The molecular weight of every mole of unsaturated group of this unsaturated polyester is 500～8000;
(II) styrene monomer and/or its derivative;
(III) chooses a kind of polymerisable unsaturated compound of doing at least from following compound;
(i) vinyl cyanide, methylene-succinic acid and methyl-maleic acid acid anhydride
The (ii) monoesters of unsaturated dibasic acid and dibasic acid esters
(iii) vinylformic acid, methacrylic acid and their derivative
In the scope of (b)/[(a)+(c)]=1/10-10/1, component (I) is dissolved in component (II) and (III), and (a) is the mole number of unsaturated group in the component (I) in the formula; (b) be the mole number of unsaturated group in the component (II); (c) be the mole number of unsaturated group in the component (III).
2, according to the sizing material of claim 1 regulation, it is characterized in that polymerisable unsaturated compound should be from vinyl cyanide, choose a kind of compound at least in methylene-succinic acid and the methyl-maleic acid acid anhydride.
3,, it is characterized in that the acid constituents for preparing unsaturated polyester is one or more unsaturated dibasic acids and/or its acid anhydrides and one or more polyprotonic acids according to the sizing material of claim 1 regulation; Polymerisable unsaturated compound should be from vinyl cyanide, chooses a kind of compound at least in methylene-succinic acid and the methyl-maleic acid acid anhydride.
4,, it is characterized in that the acid constituents for preparing unsaturated polyester is one or more unsaturated dibasic acids and/or its acid anhydrides and 3,6-endo-methylene group-1,2 according to the sizing material of claim 1 regulation, 3,6-Tetra Hydro Phthalic Anhydride or 3,6-endo-methylene group-1,2,3, the 6-tetrahydrophthalic acid; Polymerisable unsaturated compound should be chosen a kind of compound at least from unsaturated dibasic acid monoesters and dibasic acid esters.
5,, it is characterized in that polymerisable unsaturated compound should choose a kind of compound at least from unsaturated dibasic acid monoesters and dibasic acid esters according to the sizing material of claim 1 regulation.
6,, it is characterized in that the acid constituents for preparing unsaturated polyester is one or more unsaturated dibasic acids and/or their acid anhydrides and one or more polyprotonic acids according to the sizing material of claim 1 regulation; Polymerisable unsaturated compound should be chosen a kind of compound at least from unsaturated dibasic acid monoesters and dibasic acid esters.
7, according to the sizing material of claim 1 regulation, it is characterized in that polymerisable unsaturated compound should be from vinylformic acid, choose a kind of compound at least in methacrylic acid and their derivative.
8,, it is characterized in that the acid constituents for preparing unsaturated polyester is one or more unsaturated dibasic acids and/or their acid anhydrides and one or more polyprotonic acids according to the sizing material of claim 1 regulation; Polymerisable unsaturated compound should be from vinylformic acid, chooses a kind of compound at least in methacrylic acid and their derivative.
9, according to the sizing material of claim 2 regulation, it is characterized in that (b)/ratio of ((a)+(c)) is in the 5/10-10/1 scope.
10, according to the sizing material of claim 3 regulation, it is characterized in that (b)/ratio of ((a)+(c)) is in the 5/10-10/1 scope.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP271188/84 | 1984-12-21 | ||
| JP59271188A JPS61148263A (en) | 1984-12-21 | 1984-12-21 | Unsaturated polyester resin composition for treating cathode ray tube |
| JP271189/84 | 1984-12-21 | ||
| JP59271189A JPS61148264A (en) | 1984-12-21 | 1984-12-21 | Unsaturated polyester resin composition for treating cathode ray tube |
| JP60010687A JPS61168658A (en) | 1985-01-22 | 1985-01-22 | Unsaturated polyester resin composition for treatment of cathode ray tube |
| JP10687/85 | 1985-01-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85106028A true CN85106028A (en) | 1986-07-09 |
| CN1006225B CN1006225B (en) | 1989-12-27 |
Family
ID=27279052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85106028.5A Expired CN1006225B (en) | 1984-12-21 | 1985-08-10 | Unsaturated polyester for cathode-ray tube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1006225B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103045055A (en) * | 2012-12-12 | 2013-04-17 | 澳达树熊涂料(惠州)有限公司 | High-hardness unsaturated polyester full-bright top-coat paint and preparation method thereof |
| CN104789097A (en) * | 2015-05-08 | 2015-07-22 | 南通天燕纺织器材有限公司 | Wear-resistant textile shuttle |
-
1985
- 1985-08-10 CN CN85106028.5A patent/CN1006225B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103045055A (en) * | 2012-12-12 | 2013-04-17 | 澳达树熊涂料(惠州)有限公司 | High-hardness unsaturated polyester full-bright top-coat paint and preparation method thereof |
| CN104789097A (en) * | 2015-05-08 | 2015-07-22 | 南通天燕纺织器材有限公司 | Wear-resistant textile shuttle |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1006225B (en) | 1989-12-27 |
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