CN101941804A - Cracking auxiliary agent-containing paste composition - Google Patents

Cracking auxiliary agent-containing paste composition Download PDF

Info

Publication number
CN101941804A
CN101941804A CN 201010287206 CN201010287206A CN101941804A CN 101941804 A CN101941804 A CN 101941804A CN 201010287206 CN201010287206 CN 201010287206 CN 201010287206 A CN201010287206 A CN 201010287206A CN 101941804 A CN101941804 A CN 101941804A
Authority
CN
China
Prior art keywords
oxide
slurry
usefulness
tensile strength
mixing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 201010287206
Other languages
Chinese (zh)
Other versions
CN101941804B (en
Inventor
冯殿润
廖德超
陈豪升
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nan Ya Plastics Corp
Original Assignee
Nan Ya Plastics Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nan Ya Plastics Corp filed Critical Nan Ya Plastics Corp
Priority to CN2010102872069A priority Critical patent/CN101941804B/en
Publication of CN101941804A publication Critical patent/CN101941804A/en
Application granted granted Critical
Publication of CN101941804B publication Critical patent/CN101941804B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

A kind of paste compound that contains the cracking auxiliary agent
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 glass fibre destarch efficient especially.
Background technology
The manufacture method 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 be through the melten glass cream of fusion processes, mouthful flow down by 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 glass fibre 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, antioxidant, colorant and water etc.
The surface of glass fibre 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 be prevented to cause broken yarn, thereby improves weaving efficiency and promote fabric quality.
After fabric was finished, the slurry of fiberglass surfacing had not had effect, for guaranteeing the original high physical strength of glass fibre, carried out slurry to be 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, in 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, the expanded method of No. 4932108 a kind of glass fibre of patent disclosure of the U.S. is coated a kind of thermoplastic material at fiberglass surfacing, and its composition comprises starch, wax, softening agent, emulsifying agent, cationic lubricant and wetting agent.
The size composition (sizingcomposition) of No. 4530876 a kind of glass fibre of patent disclosure of another piece U.S., its composition comprise polyvinyl alcohol polymer, secondary membrane-forming agent, spermaceti, contain the straight chain fatty acid of 12-32 carbon atom and through hydroxylated derivative 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 for for the glass fibre 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, described 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
Paste compound disclosed in this 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; Described 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.Described paste is preferably corn and/or yam starch.
2. finish accounts for the 1.0-3.0wt% of pulp solution; Described finish is selected from a kind of independent use or two or more mixing and the usefulness in modified hydrogenated Semen Maydis oil, soybean oil, adipocere and the plant oil.Finish is preferably modified hydrogenated soybean oil and/or adipocere.
3 tensio-active agents account for the 0.2-0.5wt% of pulp solution; Described 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; Described 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, described amine is preferably primary amine; Described cationic derivative is preferably acid amides.
5. cracking auxiliary agent accounts for the 0.005-5.0wt% of pulp solution; Described cracking auxiliary agent is used to impel the starch cracking, and it comprises:
A) metal oxide 0.005-5wt%;
B) superoxide 0-5wt%; And
C) sensitizing agent 0-5wt%.
Paste compound disclosed in this invention, the purpose of adding cracking auxiliary agent comprises:
One, metal oxide has highly active characteristic, adds nano-metal-oxide in the slurry and can effectively reduce the tensio-active agent in the slurry and the initial cracking temperature of tenderizer, reaches the effect of low temperature pyrolyzer.
A kind of independent use in the optional self-alumina of described metal oxide, silicon-dioxide, germanium oxide, nickel oxide, zinc oxide, cupric oxide, cobalt oxide, ferric oxide, manganese oxide, chromic oxide, titanium oxide, magnesium oxide, calcium oxide, Tungsten oxide 99.999, zirconium white, stannic oxide and the gallium oxide or two or more mixing and usefulness, or select 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 free radical by the superoxide cracking and promote the slurry cracking, can reduce the slurry final residual amount after glasscloth passes through the high temperature destarch.Described superoxide is selected from 2, a kind of independent use in 5-2, ditertiary butyl peroxide, dicumyl peroxide, dibenzoyl peroxide, 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 dicumyl peroxide 18H 22O 2, English name dicumyl peroxide is called for short DCP;
The molecular formula C of dibenzoyl peroxide 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, by 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) benzophenone, 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 by following examples and comparative example, but scope of the present invention is not limited to these examples.
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 that the glasscloth impregnation is allocated, press suction with running roller;
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 glass fibre destarch efficient;
9. according to ASTM D638 test method, 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 metal oxide (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 1 that does not add any auxiliary agent 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 metal oxide 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 metal oxide.
3. can find out from the embodiment 2 and the result of comparative example 1, add metal oxide (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 1 that does not add any auxiliary agent; 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 metal oxide, and synergy is arranged.
4. embodiment 3 adds metal oxide (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 better than 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 metal oxide collocation use, synergy is arranged.
6. behind the formula of size of glasscloth impregnation embodiment 1 to 7, slurry burns the mistake rate all below 0.05% after tested, compare with comparative example 1 to 4, suffice to show that in the formula of size only need to add metal oxide 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 ℃, the formula of size of glasscloth impregnation embodiment 1 to 7 is through the tensile strength after calcining after tested, 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 metal oxide 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, the formula of size of glass cloth impregnation embodiment 1 to 7 is through the tensile strength after calcining after tested, all higher with 42 hours tensile strength of 380 ℃ of calcinings, suffice to show that in the formula of size only need to add metal oxide 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
Figure BSA00000277379900101
Illustrate: (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 (7)

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, soybean oil, adipocere and the plant oil;
(c) tensio-active agent accounts for the 0.2-0.5wt% of pulp solution; And be selected from a kind of independent use or two or more mixing and usefulness in polyoxyethylene glycol Sorbitol Powder and the 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 amine, oxyethylene group amine, quaternary ammonium salts and the cationic derivative;
(e) cracking auxiliary agent accounts for the 0.005-5.0wt% of pulp solution.
2. paste compound according to claim 1, wherein, described cracking assistant packet containing metal oxide compound 0.005-5wt%, superoxide 0-5wt% and sensitizing agent 0-5wt%.
3. paste compound according to claim 2, wherein, described metal oxide is selected from a kind of independent use or two or more mixing and the usefulness in aluminum oxide, silicon-dioxide, germanium oxide, nickel oxide, zinc oxide, cupric oxide, cobalt oxide, ferric oxide, manganese oxide, chromic oxide, titanium oxide, magnesium oxide, calcium oxide, Tungsten oxide 99.999, zirconium white, stannic oxide and the gallium oxide.
4. paste compound according to claim 2, wherein, described metal oxide is the two or more sinters behind high temperature co-firing in aluminum oxide, silicon-dioxide, germanium oxide, nickel oxide, zinc oxide, cupric oxide, cobalt oxide, ferric oxide, manganese oxide, chromic oxide, titanium oxide, magnesium oxide, calcium oxide, Tungsten oxide 99.999, zirconium white, stannic oxide and the gallium oxide.
5. according to claim 3 or 4 described paste compounds, wherein, the primary particle size of described metal oxide is 3-200nm.
6. paste compound according to claim 2, wherein, described superoxide is selected from 2, a kind of independent use in 5-2, ditertiary butyl peroxide, dicumyl peroxide, dibenzoyl peroxide, t-tutyl cumyl peroxide and the peroxidized t-butyl perbenzoate or two or more mixing and usefulness.
7. paste compound according to claim 2, wherein, described sensitizing agent is 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-.
CN2010102872069A 2010-09-16 2010-09-16 Cracking auxiliary agent-containing paste composition Expired - Fee Related CN101941804B (en)

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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010102872069A CN101941804B (en) 2010-09-16 2010-09-16 Cracking auxiliary agent-containing paste composition

Publications (2)

Publication Number Publication Date
CN101941804A true CN101941804A (en) 2011-01-12
CN101941804B CN101941804B (en) 2012-08-22

Family

ID=43434044

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010102872069A Expired - Fee Related CN101941804B (en) 2010-09-16 2010-09-16 Cracking auxiliary agent-containing paste composition

Country Status (1)

Country Link
CN (1) CN101941804B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106567249A (en) * 2016-10-18 2017-04-19 建滔(连州)玻璃纤维有限公司 Novel electronic grade glass fiber cloth pulp and production method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4530876A (en) * 1983-08-12 1985-07-23 Ppg Industries, Inc. Warp sizing composition, sized warp strands and process
CN1325369A (en) * 1998-10-30 2001-12-05 欧文斯科尔宁格公司 Sizing for glass fibres having low nonionic and cationic lubricant content
CN1605575A (en) * 2003-06-12 2005-04-13 国家淀粉及化学投资控股公司 Glass adhesion promoter
CN101531472A (en) * 2009-03-13 2009-09-16 珠海富华复合材料有限公司 Slurry composition of glass fiber yarn and method for preparing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4530876A (en) * 1983-08-12 1985-07-23 Ppg Industries, Inc. Warp sizing composition, sized warp strands and process
CN1325369A (en) * 1998-10-30 2001-12-05 欧文斯科尔宁格公司 Sizing for glass fibres having low nonionic and cationic lubricant content
CN1605575A (en) * 2003-06-12 2005-04-13 国家淀粉及化学投资控股公司 Glass adhesion promoter
CN101531472A (en) * 2009-03-13 2009-09-16 珠海富华复合材料有限公司 Slurry composition of glass fiber yarn and method for preparing same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106567249A (en) * 2016-10-18 2017-04-19 建滔(连州)玻璃纤维有限公司 Novel electronic grade glass fiber cloth pulp and production method thereof

Also Published As

Publication number Publication date
CN101941804B (en) 2012-08-22

Similar Documents

Publication Publication Date Title
CN101941804B (en) Cracking auxiliary agent-containing paste composition
EP2372018B1 (en) Aqueous dispersion for treatment of fibers
US4009317A (en) Glass fiber coated with a size comprising emulsified clad particles of poly(methyl methacrylate)
US20230322636A1 (en) Sagger for sintering lithium composite transition metal oxide and preparation method thereof
JP3197851U (en) One kind of core spun yarn and hollow fiber made from it, air core fabric, hollow towel
DE602006000280T2 (en) Curable composition
WO2017024423A1 (en) Environmentally-friendly anti-yellowing dacron dty oiling agent and preparation method therefor
EP0099053A1 (en) Fiber-reinforced hydraulically setting materials
DE10304958A1 (en) Use of aqueous binders in the manufacture of abrasive materials
TWI400206B (en) A slurry composition containing a cleavage aid
CN104693366B (en) Core shell structure ACR latex, modified resin powder and preparation method thereof
CN110295414A (en) A kind of environment-friendly and energy-efficient rubber latex thread product and preparation method thereof
NO742334L (en)
US20030162879A1 (en) Preparation of an aqueous polymer dispersion curable thermally
EP0950684A2 (en) Process for recycling a polyamide material which contains silicon resin
CN109629030A (en) A kind of polyvinyl and preparation method thereof
CN101851504A (en) Low-temperature type fluorescent pigment and preparation method thereof
CN106120473A (en) High intensity aviation refuse bag and preparation method thereof
EP2912223B1 (en) Composition and process for weigthing silk
GB1584921A (en) Glass fibre size composition
JP2002146028A (en) Modified lignosulfonate and application
CN108708193A (en) A kind of terylene compounding converted starch printing gum and preparation method thereof
CN1167730A (en) Process for preparing superfine zinc borate flame retardant
CN110983825A (en) Water-based acrylate printing paste for gold stamping
CN102558411A (en) Preparation method of ether ester copolymer water reducer

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120822

Termination date: 20200916