CN104652166B - A kind of preparation method of fire retardant papers of water-tolerant - Google Patents
A kind of preparation method of fire retardant papers of water-tolerant Download PDFInfo
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Abstract
The invention belongs to the preparation method of the fire retardant papers of a kind of water-tolerant of field of papermaking. The method be with the compound of N-hexamethylol amino ring triphosphine nitrile (HHMAPT) and part methyl-etherified melamine resin (HMMM) be that fire retardant is prepared fire retardant papers. Detailed process is by spraying process, the mixture aqueous solution of HHMAPT and HMMM to be sprayed to equably on paper or by infusion process paper is flooded to 5min in the mixture aqueous solution of HHMAPT and HMMM, then by the cardboard of processing airing 1～2h in natural environment, be placed on paper with in drier, prior to the dry 1h in 105 DEG C of left and right, then at 140～150 DEG C, solidify about 10min. The addition of HHMAPT is 5%～9% of paper quality, and the addition that is preferably 6%, HMMM is paper quality 6%～22%, is preferably 10%. In the time that the addition of HHMAPT and HMMM is respectively 6% and 10%, the fire retardant papers making not only has good anti-flammability and intensity, and water-tolerant, washed the LOI of sample still up to 33.5%, still difficult combustion rank, the afterflame time of vertical combustion is 4.8s, the time of burning is 0s, average char length is 12mm, and fire-retardant rank is still qualified.
Description
Technical field
That the present invention relates to is a kind of preparation method of fire retardant papers of water-tolerant, specificallyBy the amino ring of N-hexamethylol triphosphine nitrile (HHMAPT) and part methyl-etherified melamine firstThe compound of urea formaldehyde (HMMM) is the method that fire retardant is prepared fire retardant papers, belongs to papermaking neckTerritory.
Background technology
Paper and paper products are generally to be manufactured paper with pulp and formed by inflammable string, their useOften can cause the generation of fire. Along with the pay attention to day by day of people to fire safety evaluating, to made of paperThe fire-retardant requirement of product also grow with each passing day [Li Chao, Hui Lanfeng, Liu Zhong. the Development Status of fire retardant papersAnd trend [J]. Chinese paper industry, 2010,23:62-66].
Adding fire retardant is to reduce the combustible main path of paper products. The kind of fire retardant veryMany, but be applicable to paper fire-retardant and few. The fire retardant that is usually used at present paper products comprisesMetal hydroxides, metal oxide and halogen system, phosphorus system and nitrogenated flame retardant etc. Metallic hydrogenAlthough oxide, metal oxide based flame retardant and compound thereof have certain flame retardant effect andPress down cigarette ability, but flame retarding efficiency is low, obtain good flame retardant effect, addition generally existsMore than 50%, thus the processing characteristics of paper and physical property significantly decline [Zhao Qiang, Deng Guilin.The application [J] of fire retardant in paper industry. Chinese paper industry, 2006, (6): 58-61; Liu YueArmy, Hao Zongxian, Liu Yiwu. polynary layer dihydroxy composite oxide of metal is as fire-retardant fillerPreparation fire retardant papers [J]. Chinese papermaking, 2012, (7): 17-21]. In addition, this based flame retardant is manyNumber is hydroaropic substance, and fiber surface great majority are hydroxyls, and it has disturbed between fiber and has dividedThe formation of hydrogen bond between son, thus limited this based flame retardant addition [Wang Hu, Liu Jiping.Halogen-free flame retardants current situation and trend [C]. Chinese fire-retardant association, Chinese fire-retardant in 2011Art annual meeting proceeding. Chinese fire-retardant association, 2011-5]. In papermaking, conventional halogen is fire-retardantAgent mainly contains organohalogen compounds, Halogen amino-acid salt and Halogen macromolecule etc., and mostly is chlorine systemAnd bromide fire retardant. Its outstanding advantage is to have high flame retardant, and antioxygen index is high, but halogen systemFire retardant is because existing environmental issue and burning time can generate Toxic, particularly carcinogenic substance, because ofAnd its use be more and more restricted [ChristopherM, PrestonL,AmarasingheG，etal.Evaluationofpolarethylenecopolymersasfireretardantnanocompositematrices[J].PolymerDegradationandStability, 2004,84:533-544]. Be used forThe fire-retardant phosphorus flame retardant of paper mainly contains phosphate, APP and phosphate etc. The resistance of phosphorus systemCombustion agent not only overcome halogen containing flame-retardant combustion fumes large, emit poisonous and corrosive gasShortcoming, has overcome again inorganic combustion inhibitor addition large simultaneously, has a strong impact on the physical machine of materialThe shortcoming of tool performance, has high flame retardant, low cigarette, low toxicity, non-corrosiveness γ-ray emission etc.Advantage. But the poor water resistance such as phosphate and APP using at present, little molecular phosphorus acid estersFire retardant great majority are liquid, have the shortcomings such as volatility is high, poor heat resistance. For paperFire-retardant nitrogenated flame retardant is mainly melamine and derivative thereof, dicyandiamide salt, amine saltDeng. Nitrogenated flame retardant have low toxicity, corrosion-free, to heat and UV stable, inexpensive etc. excellentPoint, but use separately flame retarding efficiency not high, do not reach some field the special of fire retardant papers wantedAsk. Phosphorus, the general compound use of nitrogenated flame retardant, because both have synergistic function [public affairsDimension light, Gao Yujie. the progress [J] of papermaking fire retardant. papermaking chemical product, 2002,(3): 26-28; Pan Quanli, Xu Chengcheng, Liu Mingyou etc. the application of fire retardant in papermaking withDevelopment [J]. Chinese papermaking, 2006, (5): 39-42].
As a whole, all there are some shortcomings with fire retardant, paper flame-retarded technology in paper at presentEnter a new developing stage, following paper base material fire-retardant towards efficient, warpJi, environmental protection future development.
Phosphonitrile is that a class forms with phosphorus, nitrogen element alternative arrangement, has stable phosphorus nitrogen skeletonThe compound of structure. Its unique phosphorus, nitrogen hybrid structure and high phosphorus, nitrogen content make it toolThere are good heat endurance and anti-flammability. Phosphonitrile has few, the resistance of Halogen, when burning amount of being fumingFuel efficiency rate is high, do not produce the advantages such as poisonous and corrosive gas and be considered to have before development mostWay a based flame retardant, be fire retardant from now on developing direction [Bao Dongmei, Liu Jiping. phosphonitrileThe application study progress of compounds in fire proofing. China is fire-retardant, and 2011, (3): 15-19; Qian Lijun. the researching and developing status of current phosphorus flame retardant. China is fire-retardant, and 2011,(3)：2-4；Allen,C.W.TheuseofphosphazenesasfireresistantMaterials.J.FireSci.1993,11,320-328; Cai Zhe, Zhang Hong, He Hongwu. organophosphorFire retardant New research progress [J]. fine-chemical intermediate, 2010,40 (4): 6-13].
HHMAPT is one of business-like phosphonitrile fire retardant few in number. Some document reportsRoad, this fire retardant not only has good flame retardant effect to textile, and washable [HebeishA,WalyA,Abou-OkeilA.M.Flameretardantcotton[J].FireandMaterials,1999,23(3):117-123；KubotaShizuo，Fireproofingmethodoffibersbyaminophosphazenederivatives[P],JP0104074A2,1989-2-10; Higher-dimension is complete, Tang Shujuan, Sun De etc. synthesizing of hydroxyl ring three phosphazene derivative fire retardantsAnd performance study [J]. dyeing and finishing technique, 2008,30 (9): 11-14]. Based on paper products with spinThe fibrous similitude of fabric, this fire retardant also should have good to paper and paper productsFlame retardant effect. For this reason, inventor of the present invention is studied HHMAPT fire retardant papers, sends outNow this fire retardant has extraordinary flame retardant effect to paper, when its consumption is paper quality 3%Time, by GB/T14656-2009 (1.3mm) standard method test, vertical combustion reachesQualified requirement. When the consumption of this fire retardant is paper quality 4% time, the flame retardant rating of paper reachesTo one-level, i.e. carbonization length is less than 50mm, and ember is less than 1s, after dust 1min, does not deposit. This achievement applied for Chinese patent [how be Liu Yujia, Wang Yong etc. a kind of fire retardant papersPreparation method [P], CN103866648A, 2014-06-18]. But in test, find to use this resistanceThe cardboard poor water resistance that combustion agent makes, after washing, the anti-flammability of paper significantly declines, fire-retardant paperIntensity also decreases. This explanation HHMAPT is scattered in paper in the mode of physics,Produce the less of chemical bonding with paper cellulose molecule. Fire retardant papers must have certain water-fastProperty, otherwise can cause after paper experience exposes to the sun and rain, its fire resistance declines thereupon.
Melamine resin is conventional wet strengthening agents for papermaking, the N-CH in its molecule2OHOr N-CH2OR can with paper cellulose molecule-there is etherificate or ether exchange reaction in OH, therebyMake paper cellulose molecule occur crosslinked and improve paper intensity [Wang Zhiyan. conventional wet strength agent for papermakingThe mechanism of action and present Research [J], Heilungkiang papermaking, 2009,37 (1): 25-28]. FromTheoretically, the N-CH of melamine resin2OH or N-CH2OR also can be withN-CH in HHMAPT molecule2OH or N-CH2OCH2There is etherificate or ether exchange reaction in N, formsHybrid resin, and occur to be cross-linked with paper cellulose molecule, thereby make HHMAPT chemical bondingIn paper cellulose molecule, improve thus resistance to water and the intensity of fire retardant papers. In addition, as frontState, melamine and derivative thereof are conventional nitrogenated flame retardants, it and phosphorus flame retardant toolThere is good cooperative flame retardant effect. Therefore, melamine resin and HHMAPT can to paperCan there is cooperative flame retardant effect. According to above analysis, this patent has been invented one and has been passed throughHHMAPT and HMMM composite flame-proof paper and make resistance to water and the side of the fire retardant papers that intensity is goodMethod.
Summary of the invention
Inventor of the present invention has furtherd investigate HHMAPT and HMMM does the cooperative flame retardant of paperWith. Found that, HHMAPT and HMMM not only have good cooperative flame retardant to paper and doWith, and can significantly improve resistance to water and the intensity of fire retardant papers. As HHMAPT and HMMMAddition be respectively paper quality 6% and 10% time, before and after fire retardant papers washing, all have goodAnti-flammability, washed the LOI of sample still up to 33.5%, difficult combustion rank, vertical combustionAfterflame time is 4.8s, and the time of burning is 0s, and average char length is 12mm, meetsGB/T14656-2009 requirement, fire-retardant rank is still qualified, and the tearing strength of paper andTensile strength significantly improves.
This patent HHMAPT used by patent [how be Liu Yujia, Wang Yong etc. a kind of fire-retardantThe preparation method [P] of paper, CN103866648A, 2014-06-18] the method preparation described.
This patent HMMM bibliography used [coating process editorial board. coating process [M] (onVolume), P553-555. Beijing: Chemical Industry Press, 1997] the method preparation described. SpecificallyProcess is as follows: by 116.0g36.55% formaldehyde, and 16.53g95% paraformaldehyde and 160.0g firstAlcohol drops in 1000mL there-necked flask, regulates with the NaOH solution of several 20%PH=8.0～9.0, are warming up to 50 DEG C of insulations transparent to system, add 44.9g melamine, riseTemperature, to 60 DEG C, adds 64.4g methyl alcohol after being incubated 4～5h at 60 DEG C again, lowers the temperature and uses denseSulfuric acid regulates pH=3.0～4.0, transparent to system to insulation at 35 DEG C, with 10%NaOH solution regulates pH=9.0～10.0, and vacuum is steamed except volatile matter, until 70 DEG C,Under 93Kpa vacuum pressure, no liquid steams, and obtains product 151.86g, and wherein HMMM quality is dividedNumber is 75.04%.
The preparation process of fire retardant papers is: synthetic as stated above product configuration is become to HHMAPTMass fraction be 12% and the mass fraction of the HMMM mixed aqueous solution that is 20%, this is moltenLiquid is evenly sprayed onto on paper, or with the mass fraction of HHMAPT be 16% and the quality of HMMM divideNumber is 10% the about 5min of mixed aqueous solution impregnated paper, paper water suction is reached capacity and (in experiment, send outThe saturated water adsorptive value of existing paper approximately equates with paper sole mass), make HHMAPT and HMMMAddition is respectively 6% and 10% fire retardant papers, then by the cardboard of processing at natural environmentMiddle airing 1～2h, is placed on paper with in drier, prior to the dry 1h in 105 DEG C of left and right, thenAt 140～150 DEG C, solidify about 10min.
Compound use HHMAPT and HMMM are not only high to the flame retarding efficiency of paper, make with themFire retardant papers have the fiery char area of chance little, without residual flame, the advantage such as do not glow, and makeFire retardant papers there is extraordinary resistance to water and intensity, be many fire retardant papers institute on the market at presentInaccessiable.
Detailed description of the invention
Below the preferred embodiments of the present invention are described, should be appreciated that described hereinPreferred embodiment only for description and interpretation the present invention, be not intended to limit the present invention.
Except as otherwise noted, the percentage adopting in the present invention is mass percent.
Embodiment 1
Spraying process
The anti-flammability of paper measures by limited oxygen index and vertical combustion tests to evaluate. The limitOxygen index (OI) (LOI) is according to GB/T2406-80, and vertical combustion is according to GB/T14656-2009Method test. Sample cardboard is many on pressure gauge by body paper (Canadian dolphin needlebush paper)Layer unipress makes (Tian Feng papermaking Co., Ltd provides by Qingdao). Limited oxygen index testSpecimen size is 100 × 6.5 × 1.3mm, and instrument is Jiangning county's analytical instrumentThe JF-3 type oxygen index measurer that factory produces; Vertical combustion experimental sample is of a size of210 × 70 × 1.3mm, instrument is that analytical instrument factory of Jiangning county producesCZF-3 type horizontal vertical burning analyzer. Spraying process sprays on paper equably with sprayerUpper a certain amount of retardant solution, makes the addition of fire retardant in fire retardant papers reach required amount,Then by the cardboard of processing airing 1～2h in natural environment, be placed on paper drierIn, prior to the dry 1h in 105 DEG C of left and right, then at 140～150 DEG C, solidify about 10min. ToolGymnastics is done as follows, when requiring 6.0% He that the addition of HHMAPT in fire retardant papers is paper qualityThe addition of HMMM be paper quality 10.0% time, HHMAPT and HMMM are mixed with to contentBe respectively 12.0% and 20.0% mixed aqueous solution, the amount on paper of being sprayed on is paper quality oneHalf, then by the paper of processing above airing 1～2h in natural environment, be placed on paper and useIn drier, prior to the dry 1h in 105 DEG C of left and right, then solidify approximately at 140～150 DEG C10min, just can make desired fire retardant papers. By that analogy, HHMAPT and HMMM are joinedMake concentration and be respectively 12% and 36% solution, the amount being sprayed on paper is also paper self matterOne half of amount, the addition that just can make HHMAPT and HMMM is respectively 6.0% He18.0% fire retardant papers.
The Water Resistance Test of fire retardant papers
According to GB/T14656-2009 (1.3mm) standard method, fire retardant papers is washed to examinationTest, first pattern to be washed is put into 2000mL beaker, the glass tube that is 6mm by internal diameter is insertedTo beaker bottom, go to injecting 24.5 DEG C continuously in beaker with 12L/h speed by glass tubeIonized water, continues 1h, after injection, takes out sample from beaker, wipes table with paper handkerchiefFace moisture, is placed in drier in 105 DEG C of dry 1h by sample level. Dried patternFor the fire-retardant resistance to water of test paper.
Under the addition of different HHMAPT and HMMM, the oxygen index (OI) before and after fire retardant papers washingMensuration and vertical combustion experimental result are as shown in table 1.
The impact of the addition of table 1HHMAPT and HMMM on paper fire resistance
In table 1, data show, in the time that the addition of HHMAPT is 6%, add HMMM simultaneouslyLess on not washing the fire resistance impact of fire retardant papers, with the increase of HMMM addition, LOI slightlyHave increase, after flame time slightly reduces, and burns time and char length without significant change. ButAdd HMMM larger on the fire resistance impact of washing fire retardant papers, with HMMM addition simultaneouslyIncrease, LOI significantly increases, after flame time and char length significantly reduce, when HMMM addsWhen dosage >=10%, the LOI that washed sample is greater than 33.5%, difficult combustion rank, vertical combustionAfterflame time be less than 4.8s, the time of burning is 0s, average char length is less than 12mm,Meet GB/T14656-2009 requirement, fire-retardant rank is qualified. That is to say, whenWhen the addition of HHMAPT and HMMM is respectively 6% and 10%, the fire retardant papers making has goodGood resistance to water, has reached the requirement of water-resistant type fire retardant papers. Experiment is also found, is worked as HHMAPTAddition while being less than 6%, composite HMMM is difficult to prepare water-resistant type fire retardant papers, as worked asThe addition of HHMAPT and HMMM is respectively 5% and while being 22%, and the LOI that does not wash sample is45.6%, reach and do not fire rank, the afterflame time of vertical combustion is 1.6s, the time of burning is0s, average char length is 5.9mm, fire-retardant rank is qualified. But the LOI of sample after washingBe 31.5%, difficult combustion rank, the afterflame time of vertical combustion is 36.9s, the time of burning is0s, average char length is 55mm, not exclusively meets GB/T14656-2009 requirement, resistanceCombustion rank is defective.
Embodiment 2
Infusion process
When requiring adding of 6.0% and HMMM that the addition of HHMAPT in fire retardant papers is paper qualityDosage be paper quality 10.0% time, can be made into HHMAPT and HMMM content is respectively 6.0% He10.0% mixed solution floods paper about 5min in this solution, and paper water suction is reached capacity(soakage approximates paper sole mass), subsequently by the paper of processing above at natural environmentMiddle airing 1～2h, is placed on paper with in drier, prior to the dry 1h in 105 DEG C of left and right, thenAt 140～150 DEG C, solidify about 10min. After tested, the result of spraying process and dippingThe no significant difference of method.
Comparative example 1
The fire retardancy test of HHMAPT to paper
Press spraying process, independent use HHMAPT fire retardant papers is tested. Spraying and washingProcess is not except adding HMMM, and other is identical with embodiment 1. In the interpolation of different HHMAPTUnder amount, the limiting oxygen index determination before and after fire retardant papers washing and vertical combustion experimental result are as table 2Show. In table 2, data show, HHMAPT has good fire retardation to paper. Do not add resistanceThe LOI of the body paper of combustion agent is 22.1%, and in vertical combustion experiment, paper completing combustion becomes ash alsoProduce a large amount of cigarettes; In the time that HHMAPT addition is only 4.5%, the LOI of sample is34.9%, difficult combustion rank, the afterflame time of vertical combustion is 3.2s, the time of burning is0s, average char length is 6mm, all meets GB/T14656-2009 requirement, flame retardant gradeWei be unqualified; In the time that HHMAPT addition is 6.0%, the LOI of sample is up to 47.5%, forDo not fire rank, the afterflame time of vertical combustion is only 1.5s, and average char length is only4.5mm. The fire retardant papers of only adding HHMAPT is not water-fastness, and after washing, anti-flammability is remarkableDecline, as in the time that the addition of HHMAPT is 6.0%, after washing, the LOI of sample is only24.9%, in vertical combustion experiment, sample completing combustion becomes ash, is inflammable rank, evenHHMAPT addition is up to 9.0%, and after washing, the LOI of sample is only also 27.6%, just reachesDifficult combustion rank, but in vertical combustion experiment, average after flame time is 24s, does not reach GB/T14656-2009 requirement, fire-retardant rank is defective. That is to say, add separately HHMAPTBe difficult to prepare water-resistant type fire retardant papers.
The impact of the addition of table 2HHMAPT on paper anti-flammability
Comparative example 2
The fire retardancy test of HMMM to paper
Press spraying process, independent use HMMM fire retardant papers is tested. Spray and washedJourney is not except adding HHMAPT, and other is identical with embodiment 1. At the addition of different HMMMUnder, the limiting oxygen index determination of fire retardant papers and vertical combustion experimental result are as shown in table 3. In table 3Data show, HMMM is very poor to the fire retardation of paper, with the increase of HMMM, fire retardant papersLOI slightly increases, and afterflame time and the time of burning obviously increase, even but the interpolation of HMMMAmount is up to 22%, and in vertical combustion experiment, also very fast completing combustion one-tenth is grey for cardboard.
The impact of the addition of table 3HMMM on paper fire resistance
Embodiment 3
Measuring physical properties
Choose is quantitatively 70g/m2Individual layer body paper be sample, analyzed with HHMAPT andHMMM composite flame-proof (both additions be respectively paper quality 6% and 10%) is to paperThe impact of folding strength, tearability and tensile strength.
The ZZD-25B type paper that the folding strength of paper adopts Changchun small-scale test machine factory to produce is resistance toFolding degree analyzer is measured, and sample standard size is 120 × 15mm, and individual is measured, each sampleMeasure 8 times, remove after maximum and minimum of a value, average.
Paper tear degree adopts the paper of the Changchun moon bright small-scale test machine Co., Ltd productionOpen tearability instrument and measure, sample standard size is 76 × 63mm, and otch 20mm, by formulaF=16N/n calculates (N: tear needed power, the mN of unit; N: the number of plies, n=2), everyIndividual sample is measured 8 times, removes after maximum and minimum of a value, averages.
The TTM electricity that paper tensile strength adopts Hangzhou Autotek S. r. l. of Boke to produceBrain tensile testing machine is measured, and sample standard size is 90 × 15mm, and individual is measured, eachSample is measured 8 times, removes after maximum and minimum of a value, averages.
Preparation process for the washing paper of strength detection is: by paper in deionized water in oftenTemperature is soaked 4h, then by the paper of processing above airing 1～2h in natural environment, thenIn papermaking dry device, toast 1h in 100～105 DEG C.
Body paper, washing paper, spray coated flame retardant paper, spraying washing fire retardant papers, dipping fire retardant papers andThe intensity data of dipping washing fire retardant papers is listed in table 4.
Table 4 paper strength test result
As shown in Table 4: adopt HHMAPT and HMMM composite flame-proof, slightly reduced the resistance to of paperFolding intensity, affects not quite the tearability of not washing paper, but has obviously improved tearing of washing paperDegree of splitting, has obviously improved the tensile strength of paper. Generally, improved the intensity of paper.
Finally it should be noted that: the foregoing is only embodiments of the invention, and need notIn restriction the present invention, although the present invention is had been described in detail with reference to previous embodiment,For a person skilled in the art, it still can be recorded aforementioned each embodimentTechnical scheme is modified, or part technical characterictic is wherein equal to replacement. AllWithin the spirit and principles in the present invention, any amendment of doing, be equal to replacement, improvement etc.,Within all should being included in protection scope of the present invention.
Claims (5)
1. a preparation method for the fire retardant papers of water-tolerant, the method is to prepare the method for fire retardant papers by infusion process or spraying process with the compound of N-hexamethylol amino ring triphosphine nitrile (HHMAPT) and HMMM.
2. preparation method according to claim 1, the addition of HHMAPT used is paper quality 5%～9%.
3. preparation method according to claim 1, the addition of HMMM used is paper quality 6%～22%.
4. preparation method according to claim 1, the addition manner of described compound is spraying process, with sprayer be 12%～18% and the HMMM mass fraction mixture aqueous solution that is 12%～44% toward spraying equably a certain amount of HHMAPT mass fraction on paper, then airing 1～2h in natural environment, be placed on paper with in drier, prior to the dry 1h in 105 DEG C of left and right, then at 140～150 DEG C, solidify about 10min.
5. preparation method according to claim 1, the addition manner of described compound is infusion process, by paper HHMAPT mass fraction be 6%～9% and the HMMM mass fraction mixture aqueous solution that is 6%～22% in flood about 5min, paper water suction is reached capacity, then airing 1～2h in natural environment, be placed on paper with in drier, prior to the dry 1h in 105 DEG C of left and right, then at 140～150 DEG C, solidify about 10min.
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| TW445276B (en) * | 1998-08-13 | 2001-07-11 | Otsuka Chemical Co Ltd | Crosslinked phenoxyphosphazene compounds, process for the preparation thereof, flame retardants, flame-retardant resin compositions, and moldings of flame-retardant resins |
| WO2003085039A1 (en) * | 2002-04-10 | 2003-10-16 | Ciba Specialty Chemicals Holding Inc. | Flame retardant coatings |
| CN100344697C (en) * | 2002-05-28 | 2007-10-24 | 旭化成株式会社 | Flame retardant composition |
| CN100482757C (en) * | 2005-08-15 | 2009-04-29 | 上海化工研究院 | Flame resisting agent with no halogen in series of crylic acid in use for pressure sensitive adhesive tape, and prepartion method |
| CN101746102B (en) * | 2008-12-18 | 2012-06-27 | 建滔积层板（昆山）有限公司 | Compound base copper-clad laminate and manufacturing method thereof |
| CN103866648A (en) * | 2014-04-02 | 2014-06-18 | 青岛科技大学 | Preparation method of flame-resistant paper |
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Application publication date: 20150527 Assignee: New Mstar Technology Ltd in Shandong Assignor: Shandong Brother Sci. & Tech. Co., Ltd. Contract record no.: 2018370000019 Denomination of invention: Method for preparing flame retardant paper with high water resistance Granted publication date: 20160504 License type: Common License Record date: 20180620 Application publication date: 20150527 Assignee: Shandong brotherhood flame retardant new materials Co., Ltd. Assignor: Shandong Brother Sci. & Tech. Co., Ltd. Contract record no.: 2018370000020 Denomination of invention: Method for preparing flame retardant paper with high water resistance Granted publication date: 20160504 License type: Common License Record date: 20180620 |
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Assignee: Shandong brotherhood flame retardant new materials Co., Ltd. Assignor: SHANDONG BROTHER SCI.&TECH. Co.,Ltd. Contract record no.: 2018370000020 Date of cancellation: 20200424 |
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