CN103235493A - Adhesive composition for ink powder and preparation method of adhesive composition - Google Patents
Adhesive composition for ink powder and preparation method of adhesive composition Download PDFInfo
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Abstract
The invention discloses an adhesive composition for ink powder for printers and copying machines. The composition is prepared from 85-99% by mass of mixed liquid and 1-15% by mass of wax-modified crystalline polyester, wherein the mixed liquid is mainly prepared from styrene, butyl methacrylate, crylic acid hexyl, crylic acid and ethylene glycol monomers. The invention further discloses a preparation method of the adhesive composition for the ink powder for the printers and the copying machines. The adhesive composition disclosed by the invention is added into the ink powder applied to electromagnetic induction heating devices, so that the ink powder has excellent low-temperature fixation property, high-temperature anti-excursion property and storability.
Description
Technical field
The present invention relates to a kind of ink powder adhesive composition and preparation method thereof, specifically a kind of ink powder adhesive composition and preparation method thereof that is applicable to electromagnetic induction heating photographic fixing mode.
Background technology
In recent years, along with fast development of information technology, the degree of office automation is more and more higher, and the use of duplicating machine, printer more and more widely, and is also more and more higher to the requirement of duplicating machine, printer capability.Generally speaking, the course of work of duplicating machine and printer is to form electrostatic latent image at photoreceptor earlier, adsorbs ink powder then to its video picture, and image is transferred on the paper, utilizes hot pressing photographic fixing mode to carry out.For the preheating time and the raising print speed that shorten printer, heater block is also improving gradually and is upgrading in the hot fixing, has occurred fluorescent tube heat form, ceramic heat form, electromagnetic induction heating form etc. successively.Therefore the performance for ink powder has also had further requirement, and ink powder should have excellent low-temperature fixing.And as the performance of the adhesive composition of ink powder principal ingredient the performance of ink powder has been played leading role.
The traditional fuser of laser printer is the lamp tube type heating, last roll assembly mainly can be made up of by rotating metal top roll the heating fluorescent tube that is fixed on internal layer and outside, the outside surface of metal top roll has been covered with the thin layer (being generally fluorine coating) of buffer action, and lower roll is made up of the metal roller core that the surface is coating the soft rubber layer.For the preheating time and the raising print speed that shorten laser printer, some printer adopts two fluorescent tubes heating, even the heating of three fluorescent tubes.
For under energy-conservation condition, shorten the preheating time of laser printer, released the potsherd directional heater afterwards.Different with traditional fixing roller type of heating, the last roll assembly of the directed type of heating of potsherd uses the film (photographic fixing film) of the not enough 0.1mm of a thickness to replace original aluminium base top roll, and its rotation also relies on lower roll that its friction is obtained.
On this basis, occurred the fuser of electromagnetic induction form heating again, its essential structure is except well heater itself, with the heating component basically identical of the directed heat form of potsherd.Except the intrinsic advantage that keeps the directed heating of potsherd, preheating time is shorter, has realized " preheating in zero second " basically.
For mentioning in a lot of patents of ink powder that are applied to electromagnetic induction heating photographic fixing mode.Jap.P. JPH11-344830 mentions and uses a kind of strong magnetic material and a kind of resin, and wherein the Tg of resin is 45-65 ℃, and softening point is 80-140 ℃.JP2001-235893 mentions a kind of ink powder that contains styrene-acrylic resin and polyolefin-wax.JP2001-272812 mentions a kind of vibrin that contains the dynamic viscoelastic of regular heat absorption wax peak and rule.
The principal ingredient that patent ZL03138486.2 ink powder is mentioned with adhesive composition and ink powder is vibrin and segmented copolymer, the adhesive composition molecular weight distribution of preparation is narrower, though the low temperature development is better, storage characteristics is relatively poor, and especially high-temp resisting high-humidity resisting is poor.
The adhesive composition for preparing in the above-mentioned patent is applied in the electromagnetic induction heating device, can satisfy good low-temperature fixing, but anti-skew simultaneously, storage characteristics decrease to some degree.
Summary of the invention
The problem that can not take into account at low-temperature fixing in the prior art and anti-skew, storage characteristics, the invention provides a kind of ink powder adhesive composition, specifically, the invention provides in low-temperature fixing, the anti-skew of high temperature, reach all ink powder adhesive compositions and preparation method thereof of excellence of storage characteristics each side.
Specific implementation method is as follows:
A kind of ink powder adhesive composition is got by mixed liquor and wax modification crystal type polyester;
Described mixed liquor mainly is equipped with by styrene, butyl methacrylate, Hexyl 2-propenoate, acrylic acid, glycol monomethyl system.
Further, a kind of ink powder adhesive composition is got by mixed liquor and the 1-15 quality % wax modification crystal type polyester of 85-99 quality %.
Further, described adhesive composition, it is that 5000～30000, Mw is that 150000～1400000, PDI is 30～70 that tetrahydrofuran (THF) soluble part is estimated Mn with gel permeation chromatography (GPC), glass transition temperature is 45～80 ℃.
Further, described wax modification crystal type polyester is to put in the reactor by the reactant liquor that acid, alcohol, catalyzer, wax are formed, purge with nitrogen, displace whole air in the still, progressively be warming up to 200-230 ℃, reacted 6-8 hour, be evacuated to 0.9kPa reaction 1 hour, use the nitrogen pressure discharging, be cooled to room temperature, pulverizing, fine powder, sieving prepares.
Acid constituents described in the preparation of wax modification crystalline polyester can be saturated dicarboxylic acid or unsaturated dicarboxylic acid among the present invention, as fumaric acid, maleic acid, itaconic acid, glutaconic acid, oxalic acid, malonic acid, succinic acid, 1,4-succinic acid, 1, the 6-hexane diacid, 1,8-suberic acid, 1, the 10-decanedioic acid, 1,12-dodecanedioic acid, 1,18-octadecane diacid and their derivant.
Alkoxide component described in the preparation of wax modification crystalline polyester can be the saturated fat dibasic alcohol among the present invention, as 1,4-butylene glycol, ethylene glycol, 1,2-propylene glycol, 1, ammediol, neopentyl glycol, 1, the 4-butylene glycol, 1,6-hexanediol, 1,8-ethohexadiol, 1,10-decanediol, 1,12-dodecanediol and their derivant.
Catalyzer described in the preparation of wax modification crystalline polyester can use known esterification catalyst or polymerization inhibitor among the present invention, as molecular sieve, heteropoly acid, solid super-strong acid, metal-organic complex, organic acid, inorganic salts etc.
Further, described wax is one or more in paraffin, microcrystalline wax, Brazil wax, fischer-tropsch wax, smart wax, ceresine, the natural wax.
Further, described reactant liquor consists of the acid of 40-60 part, 30-50 part alcohol, 1-3 part catalyzer, 3-8 part wax.
Further, described wax modification crystalline polyester, it is that 2000～5000, Mw is that 10000～30000, PDI is 3～7 that tetrahydrofuran (THF) soluble part is estimated Mn with gel permeation chromatography (GPC), fusing point is 60-110 ℃.
Ink powder is put into the dimethylbenzene of 100-300 part in the reactor with the preparation method of adhesive composition, purge with nitrogen then, displace whole air in the still, progressively be warming up to 130-140 ℃, under the refluxing xylene state, splash into the mixed liquor of being formed by styrene, butyl methacrylate, Hexyl 2-propenoate, acrylic acid, ethylene glycol, initiating agent, crosslinking chemical, catalyzer, dripped 3-6 hour; Get wax modification crystalline polyester 10-16 part, being higher than fusion under the temperature of its fusing point, then it is added drop-wise in the reaction system, be incubated 2-4 hour, carry out vacuum extraction to negative pressure 0.08MPa, keep emptying in 2 hours, use the nitrogen pressure discharging; Be cooled to room temperature, pulverizing, fine powder, sieve, obtain adhesive composition.
Ink powder of the present invention refers to contain in the molecule compound of a plurality of functional groups or a plurality of unsaturated double-bonds with the crosslinking chemical among the preparation method of adhesive composition, as organic dibasic acid, polyvalent alcohol, divinylbenzene, diisocyanate, N, N-methylene-bisacrylamide etc.These initiating agents can use separately, also can two or more be used in combination.
Ink powder of the present invention can use all to can be used as the material of radical polymerization initiator usually with the initiating agent among the preparation method of adhesive composition, as 1,1 '-azo two (1-cyclohexane nitrile), 2, azo-initiators such as 2 '-azobis isobutyronitrile, ABVN; Organic peroxy class initiating agents such as cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, bytyry superoxide, oxidation diisopropylbenzene (DIPB), di-t-butyl peroxide, dimethoxy isopropyl peroxide two carbonic esters.These initiating agents can use separately, also can two or more be used in combination.Its kind and consumption can be selected according to temperature of reaction, monomer concentration etc.
Ink powder of the present invention can use known esterification catalyst or polymerization inhibitor with the catalyzer among the preparation method of adhesive composition, as molecular sieve, heteropoly acid, solid super-strong acid, metal-organic complex, organic acid, inorganic salts etc.
Further, described mixed liquor consists of 60-80 part styrene, 8-14 part butyl methacrylate, 9-15 part Hexyl 2-propenoate, 5-10 part acrylic acid, 4-8 part ethylene glycol, 0.2-0.8 part initiating agent, 0.3-0.6 part crosslinking chemical, 0.1-0.3 part catalyzer.
Wax modification crystalline polyester after chemical reaction of the present invention is handled, again by in course of reaction, being added drop-wise in the mixed liquor with molten state, added ethylene glycol in the mixed liquor, increased the compatibility of potpourri and wax modification crystalline polyester, make the ink powder that uses adhesive composition of the present invention have the excellent anti-skew of low-temperature fixing, high temperature and good storage characteristics, can be widely used in various printers, duplicating machine, can fully adapt to the electromagnetic induction heating device high speed, the requirement that low-temperature fixing etc. improve in recent years has excellent storage simultaneously.
Embodiment
Following embodiment specifies the present invention, and the present invention is not limited to these embodiment.In addition, if no special instructions, following " part " all refers to mass parts.
Wax modification crystalline polyester prepares 1
With 40 part 1,10-decanedioic acid, 50 part 1,8-ethohexadiol, 2 parts of catalyzer, 8 parts of paraffin are put in the reactor, purge with nitrogen, displace whole air in the still, progressively be warming up to 200 ℃, reacted 6 hours, be evacuated to 0.9kPa reaction 1 hour, use the nitrogen pressure discharging, be cooled to room temperature, pulverizing, fine powder, sieve, obtain wax modification crystalline polyester 1.
Wax modification crystalline polyester prepares 2
With 50 parts of maleic acids, 40 part 1,10-decanediol, 3 parts of catalyzer, 7 parts of smart waxes are put in the reactor, purge with nitrogen, displace whole air in the still, progressively be warming up to 215 ℃, reacted 7 hours, be evacuated to 0.9kPa reaction 1 hour, use the nitrogen pressure discharging, be cooled to room temperature, pulverizing, fine powder, sieve, obtain wax modification crystalline polyester 2.
Wax modification crystalline polyester prepares 3
With 55 part 1,18-octadecane diacid, 41 part 1,12-dodecanediol, 1 part of catalyzer, 3 parts of microcrystalline waxes are put in the reactor, purge with nitrogen, displace whole air in the still, progressively be warming up to 230 ℃, reacted 6 hours, be evacuated to 0.9kPa reaction 1 hour, use the nitrogen pressure discharging, be cooled to room temperature, pulverizing, fine powder, sieve, obtain wax modification crystalline polyester 3.
Wax modification crystalline polyester prepares 4
With 60 part 1,8-suberic acid, 30 part 1,10-decanediol, 3 parts of catalyzer, 5 parts of smart waxes are put in the reactor, purge with nitrogen, displace whole air in the still, progressively be warming up to 220 ℃, reacted 8 hours, be evacuated to 0.9kPa reaction 1 hour, use the nitrogen pressure discharging, be cooled to room temperature, pulverizing, fine powder, sieve, obtain being wax modification crystalline polyester 4.
Wax modified poly ester test index sees Table 1.
Table 1. wax modification crystalline polyester test index
Adopt the GPC method to measure number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of wax modification crystalline polyester, in the mensuration with commercially available single decentralized standard polystyrene as standard, carry out under the following conditions:
Detecting device: Waters2414Refractive Index Detector
Solvent: tetrahydrofuran
Chromatographic column: WAT044207WAT044210WAT044213 serial connection
Flow velocity: 0.1ml/ minute
Sample: 0.25%THF solution
Wherein the reliability of Ce Dinging can be utilized under these conditions, by the NBS760 polystyrene sample (Mw=288,000, Mn=137,000, Mw/Mn Mw/Mn=2.11) reaches 2.11 ± 0.01 and is confirmed.
Mn: number-average molecular weight, Mn is preferred 2000～5000, if Mn is lower than 2000, the anti-skew of the high temperature of ink powder is poor; If Mn is higher than 5000, the low-temperature fixing of ink powder is poor.
Mw: weight-average molecular weight, Mw is preferred 10000～30000, if Mw is lower than 10000, the anti-skew of the high temperature of ink powder is poor, if Mw is higher than 30000, the low-temperature fixing of ink powder is poor.
PDI:Mw/Mn, molecular weight distribution, PDI is preferred 3～7, if PDI is lower than 3, ink powder oil resistant China ink contaminative deficiency, if PDI is higher than 7, fixing toner is poor.
Embodiment 1
100 parts dimethylbenzene is put in the reactor, purge with nitrogen then, displace whole air in the still, progressively be warming up to 138 ℃, under the refluxing xylene state, splash into mixed liquor (60 parts of styrene of the composition of mixed liquor, 12 parts of butyl methacrylates, 12 parts of Hexyl 2-propenoates, 6 parts of acrylic acid, 5 parts of ethylene glycol, 0.6 part of initiating agent, 0.3 part of crosslinking chemical, 0.1 part of catalyzer), Dropwise 5 hour.Get 1,17 part of wax modification crystalline polyester, being higher than fusion under the temperature of its fusing point, then it is added drop-wise in the reaction system, be incubated 3 hours, carry out vacuum extraction to negative pressure 0.08MPa, keep emptying in 2 hours, use the nitrogen pressure discharging.Be cooled to room temperature, pulverizing, fine powder, sieve, obtain adhesive composition 1.
Embodiment 2
200 parts dimethylbenzene is put in the reactor, purge with nitrogen then, displace whole air in the still, progressively be warming up to 138 ℃, under the refluxing xylene state, splash into mixed liquor (65 parts of styrene of the composition of mixed liquor, 8 parts of butyl methacrylates, 9 parts of Hexyl 2-propenoates, 10 parts of acrylic acid, 8 parts of ethylene glycol, 0.3 part of initiating agent, 0.6 part of crosslinking chemical, 0.1 part of catalyzer), Dropwise 5 hour.Get 2,10 parts of wax modification crystalline polyesters, being higher than fusion under the temperature of its fusing point, then it is added drop-wise in the reaction system, be incubated 3 hours, carry out vacuum extraction to negative pressure 0.08MPa, keep emptying in 2 hours, use the nitrogen pressure discharging.Be cooled to room temperature, pulverizing, fine powder, sieve, obtain adhesive composition 2.
Embodiment 3
300 parts dimethylbenzene is put in the reactor, purge with nitrogen then, displace whole air in the still, progressively be warming up to 138 ℃, under the refluxing xylene state, splash into mixed liquor (55 parts of styrene of the composition of mixed liquor, 10 parts of butyl methacrylates, 10 parts of Hexyl 2-propenoates, 10 parts of acrylic acid, 10 parts of ethylene glycol, 0.5 part of initiating agent, 0.4 part of crosslinking chemical, 0.1 part of catalyzer), Dropwise 5 hour.Get 3,7 parts of wax modification crystalline polyesters, being higher than fusion under the temperature of its fusing point, then it is added drop-wise in the reaction system, be incubated 3 hours, carry out vacuum extraction to negative pressure 0.08MPa, keep emptying in 2 hours, use the nitrogen pressure discharging.Be cooled to room temperature, pulverizing, fine powder, sieve, obtain adhesive composition 3.
Embodiment 4
300 parts dimethylbenzene is put in the reactor, purge with nitrogen then, displace whole air in the still, progressively be warming up to 138 ℃, under the refluxing xylene state, splash into mixed liquor (60 parts of styrene of the composition of mixed liquor, 14 parts of butyl methacrylates, 14 parts of Hexyl 2-propenoates, 6 parts of acrylic acid, 5 parts of ethylene glycol, 0.4 part of initiating agent, 0.5 part of crosslinking chemical, 0.1 part of catalyzer), Dropwise 5 hour.Get 4,2 parts of wax modification crystalline polyesters, being higher than fusion under the temperature of its fusing point, then it is added drop-wise in the reaction system, be incubated 3 hours, carry out vacuum extraction to negative pressure 0.08MPa, keep emptying in 2 hours, use the nitrogen pressure discharging.Be cooled to room temperature, pulverizing, fine powder, sieve, obtain adhesive composition 4.
Comparison example 1(does not add wax modification crystalline polyester)
300 parts dimethylbenzene is put in the reactor, purge with nitrogen then, displace whole air in the still, progressively be warming up to 138 ℃, under the refluxing xylene state, splash into mixed liquor (60 parts of styrene of the composition of mixed liquor, 14 parts of butyl methacrylates, 10 parts of Hexyl 2-propenoates, 6 parts of acrylic acid, 5 parts of ethylene glycol, 0.5 part of initiating agent, 0.3 part of crosslinking chemical), Dropwise 5 hour, be incubated 3 hours, carry out vacuum extraction to negative pressure 0.08MPa, keep emptying in 2 hours, use the nitrogen pressure discharging.Be cooled to room temperature, pulverizing, fine powder, sieve, obtain adhesive composition.
The test index of embodiment 1～embodiment 4 and comparison example sees Table 2.
Table 2. embodiment 1-4 test index
Tg: glass transition temperature, the corresponding temperature of amorphous phase generation glass transition in amorphous polymer or the partially crystalline polymer.Be that the macroscopic view that the macromolecule forms of motion changes embodies, it directly has influence on usability and the shop characteristic of material.
Glass transition temperature among the present invention (Tg) is measured with METTLERTOLEDO DSC1 device according to differential scanning calorimetry (DSC).With 10 ℃ of/minute speed about 10 milligrams of samples are warmed up to 120 ℃ from 0 ℃, obtain Tg by the intersection point of the baseline that obtains curve and endothermic peak oblique line.
T1/2: softening point characterizes the resin flow performance.
Softening point (T among the present invention
1/2) test, with MLW-400 type observing and controlling intelligent constant-voltage formula capillary rheometer determining.30 ℃ of initial temperatures, negative pressure 200N obtains temperature---compressing rod displacement curve figure with 6 ℃/min intensification, reads T
1/2Data.
Adopt 100 parts of the adhesive compositions of ink powder that make in the above-mentioned embodiment of being 1-4 and the comparison example respectively, 5 parts of carbon blacks, 1 part of Tissuemat E, 1 part of charge controling agent, the use Henschel mixer mixes, and utilizes the twin-screw mixer machine mixing then, and melting temperature is 150～200 ℃.Then, cooling, pulverizing, classification obtain about 7 microns ink powder.Get 100 parts of above-mentioned ink powders and add 0.5 part of aerosil.Get 4 parts of these ink powders and 97 parts of carriers mixing, form the two-component magnetic ink powder.Utilize the electromagnetic induction heating copier, estimate.The ink powder The performance test results sees Table 3.
Table 3. ink powder performance evaluation result
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparison example |
| Low-temperature fixing | Excellent | Excellent | Excellent | Very | Difference |
| Anti-skew | Excellent | Excellent | Very | Excellent | Excellent |
| Storage characteristics | Very | Excellent | Excellent | Excellent | Difference |
Remarks: evaluation effect is divided into excellent, good, difference Three Estate.
Low-temperature fixing evaluation foundation: if minimum fixing temperature≤160 ℃ are excellent; Minimum fixing temperature is poor greater than 190 ℃; Other minimum fixing temperatures are good.
Anti-skew evaluation foundation: if the highest anti-offset temperatures≤200 ℃ for poor; The highest anti-offset temperatures＞230 ℃ is excellent, and other anti-skews are good.
Storage characteristics is estimated foundation: 50 ℃ of test condition temperature, humidity 80%, standing time 96h.If caking rate 〉=30% is for poor; If caking rate＜5% is excellent, other storage characteristics are good.
From evaluation result as can be seen ink powder of the present invention can be used for electromagnetic induction heating copier ink powder with adhesive composition, they are all very excellent aspect low-temperature fixing, the anti-skew of high temperature, storge quality.
Above example is for the embodiment of this patent being described, not conduct restriction in application.
Claims (10)
1. an ink powder adhesive composition is characterized in that, is got by mixed liquor and wax modification crystal type polyester;
Described mixed liquor mainly is equipped with by styrene, butyl methacrylate, Hexyl 2-propenoate, acrylic acid, glycol monomethyl system.
2. a kind of ink powder adhesive composition according to claim 1 is characterized in that, described composition is got by mixed liquor and the 1-15 quality % wax modification crystal type polyester of 85-99 quality %.
3. according to claim 1 or the described a kind of ink powder adhesive composition of 2 arbitrary claims, it is characterized in that, described adhesive composition, it is 5000～30000 that the tetrahydrofuran soluble part is estimated Mn with gel permeation chromatography, Mw is 150000～1400000, PDI is 30～70, and glass transition temperature is 45～80 ℃.
4. according to claim 1 or the described a kind of ink powder adhesive composition of 2 arbitrary claims, it is characterized in that, described wax modification crystal type polyester is to put in the reactor by the reactant liquor that acid, alcohol, catalyzer, wax are formed, and purges with nitrogen, displaces whole air in the still, progressively be warming up to 200-230 ℃, reacted 6-8 hour, and be evacuated to 0.9kPa reaction 1 hour, use the nitrogen pressure discharging, be cooled to room temperature, pulverizing, fine powder, sieving prepares.
5. according to asking profit to require 4 described a kind of ink powder adhesive compositions, it is characterized in that described wax is one or more in paraffin, microcrystalline wax, Brazil wax, fischer-tropsch wax, smart wax, ceresine, the natural wax.
6. a kind of ink powder adhesive composition according to claim 4 is characterized in that, described reactant liquor consist of the acid of 40-60 part, 30-50 part alcohol, 1-3 part catalyzer, 3-8 part wax.
7. according to claim 1 or the described a kind of ink powder adhesive composition of 2 arbitrary claims, it is characterized in that, described wax modification crystalline polyester, it is 2000～5000 that the tetrahydrofuran soluble part is estimated Mn with gel permeation chromatography, Mw is 10000～30000, PDI is 3～7, and fusing point is 60-110 ℃.
8. one kind prepares the method that the described ink powder of claim 1 is used adhesive composition, it is characterized in that, the dimethylbenzene of 100-300 part is put in the reactor, purge with nitrogen then, displace whole air in the still, progressively be warming up to 130-140 ℃, under the refluxing xylene state, splash into the mixed liquor of being formed by styrene, butyl methacrylate, Hexyl 2-propenoate, acrylic acid, ethylene glycol, initiating agent, crosslinking chemical, catalyzer, dripped 3-6 hour; Get wax modification crystalline polyester 10-16 part, being higher than fusion under the temperature of its fusing point, then it is added drop-wise in the reaction system, be incubated 2-4 hour, carry out vacuum extraction to negative pressure 0.08MPa, keep emptying in 2 hours, use the nitrogen pressure discharging; Be cooled to room temperature, pulverizing, fine powder, sieve, obtain adhesive composition.
According to Claim 8 the described ink powder for preparing with the method for adhesive composition, it is characterized in that described mixed liquor consists of 60-80 part styrene, 8-14 part butyl methacrylate, 9-15 part Hexyl 2-propenoate, 5-10 part acrylic acid, 4-8 part ethylene glycol, 0.2-0.8 part initiating agent, 0.3-0.6 part crosslinking chemical, 0.1-0.3 part catalyzer.
10. an ink powder wherein contains the described ink powder adhesive composition of claim 1 at least.
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| CN107304238A (en) * | 2016-04-20 | 2017-10-31 | 天津市有为印刷包装有限公司 | A kind of printing ink powder adhesive composition and preparation method thereof |
| CN107312297A (en) * | 2017-08-07 | 2017-11-03 | 天津市合成材料工业研究所有限公司 | A kind of ink powder composite resin emulsion and preparation method thereof |
| CN109976114A (en) * | 2019-03-05 | 2019-07-05 | 湖北雨田科技有限公司 | A kind of printing shelf-stable color toner and preparation method thereof |
| CN110561828A (en) * | 2019-09-15 | 2019-12-13 | 安徽佰特包装制品有限公司 | Pressure-resistant corrugated carton and production process thereof |
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Address after: 300220 Tianjin city Hexi District Dongting Road No. 29 Patentee after: TIANJIN INSTITUTE OF SYNTHETIC MATERIALS INDUSTRY CO.,LTD. Address before: 300220 Tianjin city Hexi District Dongting Road No. 29 Patentee before: Tianjin Synthetic Material Research Institute |
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Application publication date: 20130807 Assignee: Gold Value (China) Financial Leasing Co.,Ltd. Assignor: Tianjin Synthetic Materials Industry Research Institute Co.,Ltd. Binhai New Branch Office Contract record no.: X2022110000017 Denomination of invention: A kind of binder composition for toner and preparation method thereof Granted publication date: 20150114 License type: Exclusive License Record date: 20220920 |