CN101941804B - Cracking auxiliary agent-containing paste composition - Google Patents
Cracking auxiliary agent-containing paste composition Download PDFInfo
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- CN101941804B CN101941804B CN2010102872069A CN201010287206A CN101941804B CN 101941804 B CN101941804 B CN 101941804B CN 2010102872069 A CN2010102872069 A CN 2010102872069A CN 201010287206 A CN201010287206 A CN 201010287206A CN 101941804 B CN101941804 B CN 101941804B
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Abstract
The invention discloses a cracking auxiliary agent-containing paste composition. The past composition comprises 1.5 to 4.0 weight percent of paste, 1.0 to 3.0 weight percent of oiling agent, 0.2 to 0.5 weight percent of surfactant, 0.1 to 0.5 weight percent of softening agent, and 0.005 to 5.0 weight percent of cracking auxiliary agent. Compared with the formula of conventional glass fiber yarn paste, the cracking auxiliary agent is added into the paste composition, which can improve the desizing efficiency of a glass fiber fabric, reduce a secondary desizing temperature, reduce desizing time and reduce ignition loss and improve the strength of the glass fiber fabric.
Description
Technical field
The present invention relates to a kind of paste compound, refer to a kind of paste compound that contains the cracking auxiliary agent and be applicable to raising spun glass destarch efficient especially.
Background technology
The method of manufacture of glass fiber yarn is divided into frit fusion, melt-spinning and three processes of twisted filament processing.In the melt-spinning process; Comprise reel off raw silk from cocoons, starching and batch step, will pass through the melten glass cream of fusion processes, mouthful flow down through platinum the spinning of box of reeling off raw silk from cocoons according to the freely falling body principle; Through the moment cooling of spray water xi spray cloth; Process starching device makes and by buncher hundreds of spun glass single fiber boundlings is become thigh by the conventional glass fiber yarn slurry (following this paper is called for short starching) of fiberglass surfacing impregnation, becomes fiberglass spinning cake via batching the device high speed wind-up again.
Described glass fiber yarn slurry has lubricant and cakingagent effect, and its composition comprises: paste, finish, coupling agent, tensio-active agent, static inhibitor, inhibitor, colorant and water etc.
The surface of spun glass is through after the starching impregnation slurry, and slurry can prevent mutual wearing and tearing by the protective glass fiber.In the glass fiber yarn forming process or when utilizing glass fiber warps to become fabric with weft weaving, the slurry on glass fiber yarn surface can be reduced friction and prevented to cause broken yarn, thereby improves weaving efficiency and promote fabric quality.
After fabric was accomplished, the slurry of fiberglass surfacing had not had effect, for guaranteeing the original high physical strength of spun glass, carried out must slurry being removed (following this paper is called for short destarch) before cloth cover is handled at fabric.
Glasscloth is to utilize the high temperature destarch, is divided into desizing twice, and destarch for the first time is a continuous processing, under temperature 360-380 ℃ and linear speed 40-90m/min condition, with cloth cover 80-90% slurry burn off.After destarch for the first time, with batch mode glasscloth is sent into the sultry destarch of secondary destarch stove again, remove the residual slurry of residue, make cloth cover burn the mistake rate and reduce to below 0.05%, almost completely remove.But destarch for the second time must be removed residual slurry in 36-65 hour with high temperature 360-380 ℃ of burning, not only expended the energy and influenced glass fiber strength.
In patent documentation, the several pieces of patents of invention relevant with the glass fiber yarn slurry are arranged, but do not add the cracking auxiliary agent in the composition of slurry.
For example, No. 4932108 patent of the U.S. discloses a kind of expanded method of spun glass, coats a kind of thermoplastic material at fiberglass surfacing, and its composition comprises starch, wax, softening agent, emulsifying agent, cationic lubricant and wetting agent.
No. 4530876 patent of another piece U.S. discloses a kind of size composition (sizingcomposition) of spun glass, and its composition comprises polyvinyl alcohol polymer, secondary membrane-forming agent, spermaceti, contain the straight chain fatty acid of 12-32 carbon atom and through hydroxylated verivate and composition thereof.
Summary of the invention
In view of this; For improving and break through the characteristic of existing glass fiber yarn slurry, the invention discloses a kind of paste compound that contains the cracking auxiliary agent, it is used to supply the spun glass starching; And after the glass fiber yarn that utilizes the said composition starching is woven into fabric; Can improve the destarch efficient of glasscloth, comprise that the destarch second time temperature that makes glasscloth reduces, shortens the destarch time, reduces slurry burning mistake rate (LOI, Loss on Ignition) to below 0.05%; And the saving energy, and can improve the intensity 10～50% of glasscloth.
Paste compound of the present invention, the solid composition accounts for aqueous slurry solution 4.0-8.0wt%, and comprises following ingredients:
1. paste accounts for the 1.5-4.0wt% of pulp solution;
2. finish accounts for the 1.0-3.0wt% of pulp solution;
3. tensio-active agent accounts for the 0.2-0.5wt% of pulp solution;
4. tenderizer accounts for the 0.1-0.5wt% of pulp solution;
5. cracking auxiliary agent accounts for the 0.005-5.0wt% of pulp solution;
Wherein, said cracking assistant packet containing metal oxide compound 0.005-5wt%, superoxide 0-5wt% and sensitizing agent 0-5wt%.
Compare with existing glass fiber yarn formula of size, add the cracking auxiliary agent in the paste compound of the present invention, can improve the destarch efficient of glasscloth; Reduce the temperature of destarch for the second time, reduce the destarch time and reduce the mistake rate of burning; And can improve the intensity of glasscloth, that is to say, under the katalysis of cracking auxiliary agent; Destarch was for the second time burnt 12～60 hours down by burning down to be improved as in 36-65 hour at 300～380 ℃ at 360-380 ℃ originally, and it burns the mistake rate is below 0.05%.
Embodiment
The disclosed paste compound of the present invention is a kind of slurry that contains the cracking auxiliary agent, and wherein the solid composition accounts for pulp solution 4.0-8.0wt%, and it comprises following composition:
1. paste accounts for the 1.5-4.0wt% of pulp solution; Said paste is selected from a kind of independent use or two or more mixing and the usefulness in starch, vinyl emulsification and the polycondensation emulsification.Wherein, starch comprises corn, wheat or yam starch; The vinyl emulsification comprises polyvinyl acetate, acrylic or polyvinyl proprionate; The polycondensation emulsification comprises epoxy polymer or polyester polymers.Said paste is preferably corn and/or yam starch.
2. finish accounts for the 1.0-3.0wt% of pulp solution; Said finish is selected from a kind of independent use or two or more mixing and the usefulness in modified hydrogenated Semen Maydis oil, VT 18, adipocere and the plant oil.Finish is preferably modified hydrogenated VT 18 and/or adipocere.
3 tensio-active agents account for the 0.2-0.5wt% of pulp solution; Said tensio-active agent is selected from a kind of independent use or two above the mixing and usefulness in polyoxyethylene glycol Sorbitol Powder and the polyoxyethylene, is preferably the polyoxyethylene glycol Sorbitol Powder.
4. tenderizer accounts for the 0.1-0.5wt% of pulp solution; Said tenderizer is selected from a kind of independent use or two or more mixing and the usefulness in amine, oxyethylene group amine, quaternary ammonium salts and the cationic derivative.Wherein, said amine is preferably primary amine; Said cationic derivative is preferably acid amides.
5. cracking auxiliary agent accounts for the 0.005-5.0wt% of pulp solution; Said cracking auxiliary agent is used to impel the starch cracking, and it comprises:
A) MOX 0.005-5wt%;
B) superoxide 0-5wt%; And
C) sensitizing agent 0-5wt%.
The disclosed paste compound of the present invention, the purpose of adding cracking auxiliary agent comprises:
One, MOX has highly active characteristic, adds nano-metal-oxide in the slurry and can effectively reduce tensio-active agent and the initial cracking temperature of tenderizer in the slurry, reaches the effect of low temperature pyrolyzer.
A kind of independent use in the optional self-alumina of said MOX, silicon-dioxide, germanium oxide, nickel oxide, zinc oxide, cupric oxide, powder blue, red stone, manganese oxide, chromic oxide, titanium oxide, Natural manganese dioxide, quicklime, Tungsten oxide 99.999, zirconium white, White tin oxide and the gallium oxide or two or more mixing and usefulness; Or select the two or more sinters behind high temperature co-firing in the aforementioned metal oxide compound for use; And its primary particle size is preferably 3-200nm; Its surface-area is bigger, reaches good low temperature pyrolyzer effect.
Two, add superoxide and nano-metal-oxide in the slurry, except having the low temperature pyrolyzer effect, produce radical through the superoxide cracking and promote the slurry cracking, can reduce the slurry final residual amount after glasscloth passes through the high temperature destarch.Said superoxide is selected from 2; A kind of independent use in 5-2, ditertiary butyl peroxide, Di Cumyl Peroxide 99, BPO, t-tutyl cumyl peroxide and the peroxidized t-butyl perbenzoate or two or more mixing and usefulness.
Wherein, 2,5-dimethyl--2, the molecular formula C of 5-bis(t-butylperoxy) hexane
16H
34O
4, trade(brand)name Trigonox 101, English name 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane;
The molecular formula C of ditertiary butyl peroxide
8H
18O
2, trade(brand)name Trigonox B, English name tert-butyl peroxide;
The molecular formula C of Di Cumyl Peroxide 99
18H
22O
2, English name dicumyl peroxide is called for short DCP;
The molecular formula C of BPO
14H
10O
4, English name dibenzoyl peroxide is called for short BPO;
The molecular formula C of t-tutyl cumyl peroxide
13H
20O
2, English name t-butylcumyl peroxide is called for short TBCP;
The molecular formula C of peroxidized t-butyl perbenzoate
11H
14O
3, English name tert-butylperoxybenzoate is called for short TBPB.
Three, add sensitizing agent and nano-metal-oxide in the slurry; Or add superoxide again; Except having the low temperature pyrolyzer effect; Through having the sensitizing agent of resonance structure, send energy to slurry with the resonance form, with the slurry final residual amount after promoting the slurry cracking and reducing the destarch of glasscloth process high temperature.Sensitizing agent is selected from 4,4 '-azo two (4-cyanopentanoic acid), 2,2-azo two (2,4, the 4-trimethylpentane), N-phenylglycines, tetraethyl-michaelis ketone and 1, a kind of independent use or two or more mixing and usefulness in two (9-acridyl) heptane of 7-.
Wherein, 4,4 '-the molecular formula C of azo two (4-cyanopentanoic acid)
12H
16N
4O
4, trade(brand)name V-501, English name 4,4 '-Azobis (4-cyanopentanoic Acid);
2, the molecular formula C of 2-azo two (2,4, the 4-trimethylpentane)
16H
34N
2, trade(brand)name VR-110, English name 2,2-Azobis (2,4,4-trimethylpentane) or Azo-tert-octane;
The molecular formula C of N-phenylglycine
8H
9NO
2, English name N-phenyl glycine is called for short NPG;
The molecular formula C of tetraethyl-michaelis ketone
21H
28N
2O, claim 4,4 again '-two (diethylamino) UVNUL MS-40, English name 4,4 '-bis (dliethylamino) benzophenone;
1, the molecular formula C of two (9-acridyl) heptane of 7-
33H
30N
2, trade(brand)name CHEMCURE-96, English name 1,7-bis (9-acridinyl) heptane.
The characteristic of paste compound of the present invention further specifies through following examples and comparative example, but scope of the present invention is not limited to these instances.
The formula of size of following examples and comparative example; To make after the glasscloth impregnation; Burn mistake rate (Loss on Ignition according to the destarch of following test procedure assessment glasscloth again; LOI%), last again according to ASTM D638 measurement of test method glasscloth in length and breadth to (MD, CD) tensile strength:
1. press the paste compound prescription of table 1 allotment embodiment 1-7 and comparative example 1-4;
2. in the slurry of the glasscloth impregnation being allocated, press with running roller and to inhale;
3. after pressing suction, dried 1 minute down at 160 ℃;
4. be converted into square sample;
5. High Temperature Furnaces Heating Apparatus calcining is respectively at 380 ℃ of 55 hours, 380 ℃ of calcinings, 42 hours, 350 ℃ of calcinings calcinings 55 hours down down down;
6. according to the different test conditions of preceding step after calcining, weigh (W1);
7. High Temperature Furnaces Heating Apparatus is warming up to 625 ℃ of calcinings and weighs (W2) after 30 minutes, and the mixed slurry of impregnation this moment all burnouts and only remains glasscloth;
8. calculate and burn mistake rate (LOI%)=(W1-W2)/W1 * 100%;
Destarch burning mistake rate (LOI%) is lower, represents the prescription of slurry more can improve spun glass destarch efficient;
9. according to ASTM D638 TP, use instrument Zwick1474, under the condition of 23 ℃ of test temperatures and draw speed 20mm/min, the glasscloth of test completing steps 7 destarch in length and breadth to (MD, CD) tensile strength.
Embodiment 1
Press table 1 enchashment shape raw yarn slurry 100 grams, add the aluminum oxide 1 gram uniform mixing form slurry of particle diameter 10nm.Burning mistake rate (LOI%) according to the destarch of above-mentioned testing method assessment glasscloth reaches in length and breadth to (MD, CD) tensile strength.
Test result is as shown in table 1, calcines 55 hours down in 380 ℃, burns mistake rate 0.038%, and the MD/CD tensile strength is 21.6/13.6kg/cm
2Calcined 42 hours down in 380 ℃, burn mistake rate 0.047%, the MD/CD tensile strength is 22.2/13.8kg/cm
2Calcined 55 hours down in 350 ℃, burn mistake rate 0.049%, the MD/CD tensile strength is 28.4/18.4kg/cm
2
Slurry burns the mistake rate all below 0.05%, and the tensile strength of calcining after 55 hours is the highest down at 350 ℃, shows that calcining temperature is low more, and tensile strength is just high more.
Embodiment 2
Press table 1 enchashment shape raw yarn slurry 100 grams, add aluminum oxide 1 gram and the superoxide DCP 3 gram uniform mixing form slurry of particle diameter 10nm.
Test result such as table 1 were calcined 55 hours down in 380 ℃, and slurry burns mistake rate 0.035%, and the MD/CD tensile strength is 21.8/13.7kg/cm
2Calcined 42 hours down in 380 ℃, slurry burns mistake rate 0.045%, and the MD/CD tensile strength is 22.3/13.9kg/cm
2Calcined 55 hours down in 350 ℃, slurry burns mistake rate 0.048%, and the MD/CD tensile strength is 29.3/18.6kg/cm
2
Slurry burns the mistake rate all below 0.05%, and the tensile strength of calcining after 55 hours is the highest down at 350 ℃, shows that calcining temperature is low more, and tensile strength is just high more.
Embodiment 3
Press table 1 enchashment shape raw yarn slurry 100 grams, add aluminum oxide 1 gram and the sensitizing agent NPG 1 gram uniform mixing form slurry of particle diameter 10nm.
Test result such as table 1 were calcined 55 hours down in 380 ℃, and slurry burns mistake rate 0.038%, and the MD/CD tensile strength is 21.7/13.6kg/cm
2Calcined 42 hours down in 380 ℃, slurry burns mistake rate 0.047%, and the MD/CD tensile strength is 22.4/14.2kg/cm
2Calcined 55 hours down in 350 ℃, slurry burns mistake rate 0.049%, and the MD/CD tensile strength is 28.4/18.7kg/cm
2
Slurry burns the mistake rate all below 0.05%, and the tensile strength of calcining after 55 hours is the highest down at 350 ℃, shows that calcining temperature is low more, and tensile strength is just high more.
Embodiment 4
Press table 1 enchashment shape raw yarn slurry 100 grams, add aluminum oxide 1 gram, sensitizing agent NPG 1 gram and the superoxide DCP 3 gram uniform mixing form slurry of particle diameter 10nm.
Test result is as shown in table 1, calcines 55 hours down in 380 ℃, burns mistake rate 0.031%, and the MD/CD tensile strength is 21.9/13.8kg/cm
2Calcined 42 hours down in 380 ℃, burn mistake rate 0.038%, the MD/CD tensile strength is 22.5/13.9kg/cm
2In 350 ℃ of calcinings 55 hours, burn mistake rate 0.045%, the MD/CD tensile strength is 30.8/19.3kg/cm
2
The slurry of present embodiment burns the mistake rate all below 0.045%, and is lower than the slurry burning mistake rate of embodiment 1-3.And present embodiment is 30.8/19.3kg/cm in the MD/CD tensile strength of 350 ℃ of calcinings after 55 hours
2, higher than embodiment 1-3.
Embodiment 5
Press table 1 enchashment shape raw yarn slurry 100 grams, add zirconium white 1 gram, sensitizing agent CHEMCURE961 gram and the superoxide TBCP 3 gram uniform mixing form slurry of particle diameter 10nm.
Test result is as shown in table 1, calcines 55 hours down in 380 ℃, burns mistake rate 0.033%, and the MD/CD tensile strength is 21.6/13.4kg/cm
2Calcined 42 hours down in 380 ℃, burn mistake rate 0.045%, the MD/CD tensile strength is 22.6/13.8kg/cm
2Calcined 55 hours down in 350 ℃, burn mistake rate 0.047%, the MD/CD tensile strength is 29.5/18.2kg/cm
2
Slurry burns the mistake rate all below 0.05%, and the tensile strength of calcining after 55 hours is the highest down at 350 ℃, shows that calcining temperature is low more, and tensile strength is just high more.
Embodiment 6
Press table 1 enchashment shape raw yarn slurry 100 grams, add aluminum oxide and silicon oxide compound 1 gram, sensitizing agent EAB 1 gram and the superoxide TBP 3 gram uniform mixing form slurry of particle diameter 10～20nm.
Test result is as shown in table 1, calcines 55 hours down in 380 ℃, burns mistake rate 0.035%, and the MD/CD tensile strength is 21.7/13.2kg/cm
2Calcined 42 hours down in 380 ℃, burn mistake rate 0.046%, the MD/CD tensile strength is 22.4/13.7kg/cm
2Calcined 55 hours down in 350 ℃, burn mistake rate 0.048%, the MD/CD tensile strength is 29.3/18.9kg/cm
2
Slurry burns the mistake rate all below 0.05%, and the tensile strength of calcining after 55 hours is the highest down at 350 ℃, shows that calcining temperature is low more, and tensile strength is just high more.
Embodiment 7
Press table 1 enchashment shape raw yarn slurry 100 grams, add aluminum oxide 0.5 gram of particle diameter 10nm, zirconium white 0.5 gram, sensitizing agent EAB 1 gram and the superoxide BPO 3 gram uniform mixing form slurry of particle diameter 10nm.
Test result is as shown in table 1, calcines 55 hours down in 380 ℃, burns mistake rate 0.034%, and the MD/CD tensile strength is 21.5/13.6kg/cm
2Calcined 42 hours down in 380 ℃, burn mistake rate 0.043%, the MD/CD tensile strength is 22.3/13.9kg/cm
2Calcined 55 hours down in 350 ℃, burn mistake rate 0.046%, the MD/CD tensile strength is 28.4/18.3kg/cm
2
Slurry burns the mistake rate all below 0.05%, and the tensile strength of calcining after 55 hours is the highest down at 350 ℃, shows that calcining temperature is low more, and tensile strength is just high more.
Comparative example 1
Press table 1 enchashment shape raw yarn slurry 100 grams, the uniform mixing form slurry.
Test result is as shown in table 1, calcines 55 hours down in 380 ℃, burns mistake rate 0.050%, and the MD/CD tensile strength is 21.6/13.3kg/cm
2Calcined 42 hours down in 380 ℃, burn mistake rate 0.072%, the MD/CD tensile strength is 22.1/13.8kg/cm
2Calcined 55 hours down in 350 ℃, burn mistake rate 0.081%, the MD/CD tensile strength is 28.4/18.3kg/cm
2
Slurry burns the calcining under 380 ℃ of mistake rate and just can reach below 0.05% in 55 hours, but reduction temperature or shortening time fail to reach below 0.050%.The tensile strength of calcining after 55 hours is the highest down at 350 ℃.
Comparative example 2
Press table 1 enchashment shape raw yarn slurry 100 grams, add conventional particle diameter 3～5 μ m aluminum oxide 1.0 gram uniform mixing form slurry.
Test result is as shown in table 1, calcines 55 hours down in 380 ℃, burns mistake rate 0.052%, and the MD/CD tensile strength is 21.5/13.0kg/cm
2Calcined 42 hours down in 380 ℃, burn mistake rate 0.078%, the MD/CD tensile strength is 21.9/13.7kg/cm
2Calcined 55 hours down in 350 ℃, burn mistake rate 0.085%, the MD/CD tensile strength is 28.2/18.1kg/cm
2
Slurry burns the calcining under 380 ℃ of mistake rate and reached 0.052% in 55 hours, reduces temperature or shortening time and fails to reach below 0.050%.
Comparative example 3
Press table 1 enchashment shape raw yarn slurry 100 grams, add sensitizing agent NPG 1 gram uniform mixing form slurry.
Test result is as shown in table 1, calcines 55 hours down in 380 ℃, burns mistake rate 0.049%, and the MD/CD tensile strength is 21.3/13.2kg/cm
2Calcined 42 hours down in 380 ℃, burn mistake rate 0.070%, the MD/CD tensile strength is 22.013.8kg/cm
2Calcined 55 hours down in 350 ℃, burn mistake rate 0.076%, the MD/CD tensile strength is 28.6/18.9kg/cm
2
Slurry burn the mistake rate 380 ℃ down calcining just can reach below 0.05% in 55 hours, its result is suitable with the comparative example 1 of adding assistant not, shows to add sensitizing agent NPG poor effect separately.The tensile strength of calcining after 55 hours is the highest down at 350 ℃ equally.
Comparative example 4
Press table 1 enchashment shape raw yarn slurry 100 grams, add superoxide DCP 3 gram uniform mixing form slurry.
Test result is as shown in table 1, calcines 55 hours down in 380 ℃, burns mistake rate 0.049%, and the MD/CD tensile strength is 21.4/13.3kg/cm
2Calcined 42 hours down in 380 ℃, burn mistake rate 0.061%, the MD/CD tensile strength is 22.2/13.9kg/cm
2Calcined 55 hours down in 350 ℃, burn mistake rate 0.072%, the MD/CD tensile strength is 28.9/18.7kg/cm
2
Slurry burns the calcining under 380 ℃ of mistake rate and just can reach below 0.05% in 55 hours.The tensile strength of calcining after 55 hours is the highest down at 350 ℃ equally.
The result
Behind the result through embodiment 1-7 shown in the comparison sheet 1 and comparative example 1-4, can obtain to draw a conclusion:
1. can find out from the embodiment 1 and the result of comparative example 1, add MOX (aluminum oxide of 10nm), in the time of 380 ℃ * 55 hours, burning mistake rate (LOI%) is 0.038% at calcination condition, and 0.05% the condition of reaching than the comparative example that does not add any auxiliary agent 1 is better; Even calcination time was reduced to 42 hours by 55 hours, 0.047% the burning mistake rate (LOI%) of embodiment 1 still is lower than 0.072% burning mistake rate of comparative example 1; Kept calcination time 55 hours and reduce calcining temperature and reduce to 350 ℃ by 380 ℃, it burns mistake rate (LOI%) is 0.049%, compares with 0.081% of comparative example 1 better, and the demonstration nano-metal-oxide helps lytic effect.
2. embodiment 1 all adds MOX with comparative example 2, can be found out by the result, adds nano-metal-oxide (aluminum oxide of 10nm), under three kinds of calcination conditions, burns mistake rate (LOI%) and is much better than conventional particle diameter MOX.
3. can find out from the embodiment 2 and the result of comparative example 1; Add MOX (aluminum oxide 1 gram of 10nm), superoxide (DCP 3 grams); Under 380 ℃ * 55hr of calcination condition, burning mistake rate (LOI%) is 0.035%, better than 0.05% burning mistake rate of the comparative example that does not add any auxiliary agent 1; Even calcination time was reduced to 42 hours by 55 hours, 0.045% burning mistake rate (LOI%) still is lower than 0.072% of comparative example 1; Kept calcination time 55 hours and reduce calcining temperature and reduce to 350 ℃ by 380 ℃, it burns mistake rate (LOI%) is 0.047%, compares with 0.081% of comparative example 1 better, shows the use of arranging in pairs or groups of superoxide DCP and MOX, and synergy is arranged.
4. embodiment 3 adds MOX (aluminum oxide 1 gram of 10nm), sensitizing agent (NPG 1 gram), and a little higher than embodiment 2 of mistake rate (LOI%) is burnt in the calcining back, but is superior to the not comparative example 1 of adding assistant.
5. the formula of size of embodiment 4 is a most preferred embodiment of the present invention, and slurry burns the mistake rate all below 0.045% under three kinds of calcination conditions, and glasscloth is the highest in the tensile strength of calcining after 55 hours under 350 ℃.Show sensitizing agent and superoxide DCP and MOX collocation use, synergy is arranged.
6. behind the formula of size of glasscloth impregnation embodiment 1 to 7; Burn the mistake rate all below 0.05% through testing size; Compare with comparative example 1 to 4; Suffice to show that in the formula of size only need to add MOX or add again sensitizing agent or superoxide wherein one or more, can reduce slurry really and burn the mistake rate, keep good tensile strength and improve the destarch efficient of glasscloth.
7. under 55 hours condition of calcining under 380 ℃ and 350 ℃; Tensile strength after the formula of size process calcining of tested glass cloth impregnation embodiment 1 to 7; 55 hours tensile strength of calcining is all higher down at 350 ℃; Suffice to show that in the formula of size only need to add MOX or add again sensitizing agent or superoxide wherein one or more, can reduce the destarch temperature of glasscloth really and save the energy.
8. at 380 ℃ down under the condition of calcining 42 hours and 55 hours; Tensile strength after the formula of size process calcining of test glass cloth impregnation embodiment 1 to 7; All higher with 42 hours tensile strength of 380 ℃ of calcinings; Suffice to show that in the formula of size only need to add MOX or add again sensitizing agent or superoxide wherein one or more, can shorten the destarch time of glasscloth really and save the energy.
The formula of size of table 1 embodiment and comparative example and physicals table
Explain: (1) aluminum oxide particle diameter is 10nm.
(2) the zirconium white particle diameter is 10nm.
(3) aluminum oxide and silicon oxide compound, particle diameter is 10～20nm.
(4) the aluminum oxide particle diameter is 3～5 μ m.
(5) the NPG commodity of CHEMBRIDGE INTL.CORP. manufacturing.
(6) CHEMCURE 96 commodity of CHEMBRIDGE INTL.CORP. manufacturing.
(7) the EAB commodity of HODOGAYA CHEMICAL CO. manufacturing.
(8) the TBCP commodity of AKZO NOBEL CO. manufacturing, name of an article Trigonox T.
(9) the DCP commodity of AKZO NOBEL CO. manufacturing, name of an article Perkadox BC-FF.
(10) the TBP commodity of AKZO NOBEL CO. manufacturing, name of an article Trigonox C.
(11) the BPO commodity of AKZONOBELCO. manufacturing, name of an article PerkadoxL-50S.
(12) composition of raw yarn slurry comprises paste, finish, tensio-active agent, tenderizer and water.
Claims (6)
1. paste compound that contains the cracking auxiliary agent, the solid composition accounts for the 4.0-8.0wt% of aqueous slurry solution, and comprises following composition:
(a) paste accounts for the 1.5-4.0wt% of pulp solution; And be selected from a kind of independent use or two or more mixing and usefulness in starch, vinyl emulsification and the polycondensation emulsification;
(b) finish accounts for the 1.0-3.0wt% of pulp solution; And be selected from a kind of independent use or two or more mixing and usefulness in modified hydrogenated Semen Maydis oil, VT 18 and the adipocere;
(c) tensio-active agent accounts for the 0.2-0.5wt% of pulp solution; And be polyoxyethylene;
(d) tenderizer accounts for the 0.1-0.5wt% of pulp solution; And be selected from a kind of independent use or two or more mixing and usefulness in oxyethylene group amine and the quaternary ammonium salt;
(e) cracking auxiliary agent accounts for the 0.005-5.0wt% of pulp solution, and wherein, said cracking auxiliary agent comprises nano-metal-oxide 0.005-5wt%, superoxide 0-5wt% and sensitizing agent 0-5wt%.
2. paste compound according to claim 1, wherein, the primary particle size of said nano-metal-oxide is 3-200nm.
3. paste compound according to claim 2; Wherein, said nano-metal-oxide is selected from a kind of independent use or two or more mixing and the usefulness in aluminum oxide, germanium oxide, nickel oxide, zinc oxide, cupric oxide, powder blue, red stone, manganese oxide, chromic oxide, titanium oxide, Natural manganese dioxide, quicklime, Tungsten oxide 99.999, zirconium white, White tin oxide and the gallium oxide.
4. paste compound according to claim 2; Wherein, said nano-metal-oxide is the two or more sinters behind high temperature co-firing in aluminum oxide, germanium oxide, nickel oxide, zinc oxide, cupric oxide, powder blue, red stone, manganese oxide, chromic oxide, titanium oxide, Natural manganese dioxide, quicklime, Tungsten oxide 99.999, zirconium white, White tin oxide and the gallium oxide.
5. paste compound according to claim 2; Wherein, Said superoxide is selected from 2; A kind of independent use in 5-2, ditertiary butyl peroxide, Di Cumyl Peroxide 99, BPO, t-tutyl cumyl peroxide and the peroxidized t-butyl perbenzoate or two or more mixing and usefulness.
6. paste compound according to claim 2; Wherein, said sensitizing agent be selected from 4,4 '-azo two (4-cyanopentanoic acid), 2; 2 '-azo two (2; 4,4-trimethylpentane), N-phenylglycine, tetraethyl-michaelis ketone or 1, a kind of independent use or two or more mixing and usefulness in two (9-acridyl) heptane of 7-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102872069A CN101941804B (en) | 2010-09-16 | 2010-09-16 | Cracking auxiliary agent-containing paste composition |
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| CN102733193A (en) * | 2011-04-07 | 2012-10-17 | 建滔（连州）玻璃纤维有限公司 | Novel energy-saving size for electronic grade glass fabric |
| CN102926183A (en) * | 2012-10-31 | 2013-02-13 | 上海宏和电子材料有限公司 | Application of assistant agent in electronic-grade glass fiber cloth desizing and desizing process thereof |
| CN106567249B (en) * | 2016-10-18 | 2017-12-26 | 建滔（连州）玻璃纤维有限公司 | A kind of novel electron grade fiberglass cloth slurry and preparation method thereof |
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| US4530876A (en) * | 1983-08-12 | 1985-07-23 | Ppg Industries, Inc. | Warp sizing composition, sized warp strands and process |
| US6228281B1 (en) * | 1998-10-30 | 2001-05-08 | Owens Corning Fiberglas Technology | Sizing for glass fibers having low nonionic and cationic lubricant content |
| US7270853B2 (en) * | 2003-06-12 | 2007-09-18 | National Starch And Chemical Investment Holding Corporation | Glass adhesion promoter |
| CN101531472B (en) * | 2009-03-13 | 2011-04-27 | 珠海富华复合材料有限公司 | Slurry composition of glass fiber yarn and method for preparing same |
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