CN102993398B - Wet type polyurethane resin, production process and application method thereof - Google Patents
Wet type polyurethane resin, production process and application method thereof Download PDFInfo
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- CN102993398B CN102993398B CN201210395460.XA CN201210395460A CN102993398B CN 102993398 B CN102993398 B CN 102993398B CN 201210395460 A CN201210395460 A CN 201210395460A CN 102993398 B CN102993398 B CN 102993398B
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Abstract
The invention provides a wet type polyurethane resin, a production process and an application method thereof. The production process mainly comprises the following steps: 1, carrying out a soft-segment synthetic reaction on macromolecule dihydric alcohol and diphenyl methane diisocyanate; 2, enabling a first prepolymer to react; 3, adding a chain extender, and carrying out hard-segment synthetic reaction; and 4, adding an auxiliary. The wet type polyurethane resin manufactured by the production process is in form of yellowish transparent and thick viscous fluid, has viscosity of 180,000 to 220,000 (cps/25 DEG C), modulus of 100% under 4.5 to 5.5 MPa, elongation of not less than 550% and strippability of not less than 12.0kg/3cm, the hydrolysis resistance is that 10% of NaOH is hydrated for 24 hours, and the wet type polyurethane resin has texture formation of 50 to 65%. The production process has the advantages that the texture formation, peeling strength and hydrolysis resistance of the wet type polyurethane resin are improved; the auxiliaries are selected before forming the leather, so that the density of the wet type polyurethane resin is improved, the finished artificial leather has washing durability and is high in strippability and full in touch.
Description
Technical field
The present invention relates to a kind of chemical field, particularly a kind of wet polyurethane resin and production technique thereof and using method.
Background technology
At present, imitation leather is all adopt traditional technique to carry out, and the leather that the produced urethane resin of traditional technology is used for being processed to form can not get high separability, becomes muscular good, the characteristic that hydrolysis is good
The size of leather abscess is relevant with the viscosity of leading portion performed polymer, and soft section of traditional technology and hard section are composite reaction, and the bad control of many factors, the leather abscess made is little and regularity is poor, and cause leather to become muscular not good, stripping strength is not high.Scraper number need be improved, increase slurry usage quantity, just can reach relevant one-tenth muscular, to a certain degree add cost.
Such as, low whipping speed is less than normal, and owing to reacting uneven, some places local reaction is fast, and what have is slow, and the product abscess produced like this, with regard to skewness, makes stripping strength not high.When stirring velocity is too fast, the velocity ratio of reacting in production process is very fast, makes the abscess of leather comparatively large, is also unfavorable for the raising of stripping strength.
Equally, traditional technology, in the prepolymerization reaction process of leading portion, make viscosity reach U, and when temperature is low, then speed of response is slow, and the time of production is long, and reaction is also insufficient; When temperature is too high, then the side reaction of reacting generation is many, and speed of response is too fast, and the bubble of generation is irregular, can not get the product of high-density height stripping performance.
In general original urethane resin, mostly adopt polyester polyol to synthesize, polyester polyol is formed by di-carboxylic acid and small molecular alcohol condensation, and reaction formula is as follows:
This reaction is reversible reaction under certain condition, as can be seen from reaction formula, after leather meets water, within a certain period of time, polyester polyol can produce reversed reaction with water, makes product produce degraded, destroy product itself, so its hydrolysis intensity of the product produced by polyester polyol is bad.
Polyether glycol is the oligopolymer of end alkyl, and the alkyl on main chain is connected by ehter bond.Polyether glycol is with the compound of low molecular weight polyols, polyamine or reactive hydrogen for initiator, forms with olefin oxide ring-opening polymerization under catalyst action:
N in formula---the polymerization degree
X---functionality
YH---its beginning agent
R---alkyl or hydrogen
As can be seen from reaction formula, polyether polyol, by being polymerized, is not easily degraded, in PU synthetic leather, introduce polyether glycol, significantly improves the anti-hydrolytic performance of product.But because the ehter bond contained in polyether polyol is little relative to the ester bond polarity in polyester polyol, when using the large polyester type of polarity as soft section, in macromole PU structure, to raising structural regularity with to improve strength ratio more favourable.And soft section of the polyether-type adopting polarity little, just poor in structural regularity and intensity.And polyether polyol contains side chain mostly, these side chains can produce steric effect, and hydrogen bond between PU molecular structure is died down, and crystallinity deterioration, these have direct impact to the stripping strength of product and tensile strength.So in tensile strength and stripping strength index, adjustment hydrolytic resistance, will select the polyether glycol that side chain is few, and the consumption of polyether glycol also needs to control.
Summary of the invention
The object of the present invention is to provide a kind of stripping strength high, become muscular good, the wet polyurethane resin that hydrolysis intensity is high and production technique thereof and using method.
The object of the present invention is achieved like this: it mainly comprises the following steps: 1 macromolecule diol and diphenylmethanediisocyanate (MDI) carry out soft section of building-up reactions, 2 first prepolymer reaction, 3 add chainextender and carry out hard section building-up reactions; 4 add auxiliary agent.
The wet polyurethane resin that the present invention makes: its characteristic is: outward appearance is micro-yellow transparent viscous liquid; Viscosity: 18-22 ten thousand (cps/25 DEG C); 100% modulus 4.5-5.5Mpa; Tensile strength >=35Mpa; Elongation >=550%; Separability: >=12.0 ㎏/3cm; Hydrolytic resistance: 10%NaOH hydrolysis time 24h; Become muscular: 50 ~ 65%.
The method of wet polyurethane resin manufacture of intraocular leather is utilized to comprise weight ratio following: urethane (PU) resin 100 parts, mill base 10 ~ 14 parts, teepol (GB-11) 0.5-1 part, non-ionic surfactant (GB-7) 1 ~ 3 part, DMF45-50 part.
The invention has the advantages that: 1 adjustment diphenylmethanediisocyanate (MDI) and soft section of stirring velocity of reacting in the building-up reactions of macromolecule diol, control suitable stirring velocity, temperature and reaction times.2. promote the first performed polymer viscosity, adjustment reaches reaction times, temperature and the stirring velocity of required viscosity.Improve into muscular and stripping strength.3, in hard section reaction, have employed symmetrical small molecules glycol is chainextender, and improve anti-hydrolytic performance and stripping strength, 4 before leather is formed, and for the selection of auxiliary agent, improves the density of product, makes the feel of the imitation leather of final production fuller.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
It mainly comprises the following steps
It mainly comprises the following steps: 1 macromolecule diol and diphenylmethanediisocyanate (MDI) are carried out soft section of building-up reactions, the product of 2 steps 1 carries out the first prepolymer reaction, 3 and add chainextender and carry out hard section building-up reactions, 4 and add auxiliary agent.
1, so-called soft section synthesizes macromolecule diol and diphenylmethanediisocyanate (MDI) and puts into after solvent DMF (DMF) dissolves and synthesize; Macromolecule diol, diphenylmethanediisocyanate (MDI) and solvent (DMF) mixed weight account for 37 ~ 39% of total formula weight, the reaction stirring velocity of synthesizing than soft section is 30-35 rev/min, temperature controlled at 65-75 DEG C, the time was at 2 ~ 2.5 hours.
Macromolecule diol is: polyether glycol (PTMEG) and poly-hexanodioic acid Isosorbide-5-Nitrae butanediol ester (BA) and polyethylene glycol adipate (EA) in molar ratio example mix for 4:3:3.
2, the solvent product of building-up reactions being added total formula weight 13 ~ 17% carries out the first prepolymer reaction, the reaction stirring velocity of the first prepolymer reaction is 30-35 rev/min, temperature of reaction is 65-75 DEG C, and the reaction times is 1.5 ~ 3 hours, obtains reaction viscosity at 10-15 ten thousand.
3, after the first prepolymer reaction completes, add the solvent of total formula weight 18 ~ 22% in the product and add chainextender small molecules dibasic alcohol, carry out hard section reaction after going forward side by side, hard section synthesizes the synthesis between small molecules dibasic alcohol and diphenylmethanediisocyanate (MDI); The condition of hard section reaction is: below 50 DEG C, add small molecules dibasic alcohol, stirring velocity rises to 40-45 rev/min, stir, add diphenylmethanediisocyanate (MDI), make its slow thermopositive reaction, after temperature rises to 70-80 degree, temperature controlled littlely to run out of up to MDI 70-80 degree reaction 1 ~ 1.5, the weight that wherein chainextender adds accounts for 1.5 ~ 2.5% of formula production gross weight.
Described small molecules dibasic alcohol Isosorbide-5-Nitrae butyleneglycol; The interpolation mol ratio ratio of small molecules dibasic alcohol and macromolecule diol is between 2.0 ~ 3.0:1.
4, the product urethane resin generated through really up to the mark section of reaction adds the solvent of total formula weight 28 ~ 32% and stirs after adding auxiliary agent, and the addition of auxiliary agent is 0.5 ~ 0.8% of total formula weight in urethane resin.
Can be made the product of following character by above-mentioned reaction, outward appearance is micro-yellow transparent viscous liquid; Viscosity: 18-22 ten thousand (cps/25 DEG C); 100% modulus 4.5-5.5Mpa; Tensile strength >=35Mpa; Elongation >=550%; Separability: >=12.0 ㎏/3cm; Hydrolytic resistance: 10%NaOH hydrolysis time 24h; Become muscular: 50 ~ 65%.
Below in conjunction with specific experiment data, the present invention will be described
Case 1
Step is as follows:
1, so-called soft section synthesizes polyether glycol (PTMEG), poly-hexanodioic acid 1,4 butanediol esters (BA) and polyethylene glycol adipate (EA) are put into after solvent DMF dissolves by the mixture of mole 4:3:3 and diphenylmethanediisocyanate (MDI) and are synthesized; Weight after macromolecule diol, diphenylmethanediisocyanate and solvent accounts for 37% of total formula weight, and the reaction stirring velocity of soft section of synthesis is 35 revs/min, and temperature controlled at 75 DEG C, the time was at 2 hours.
2, the solvent product of building-up reactions being added total formula weight 13% carries out the first prepolymer reaction, the reaction stirring velocity of the first prepolymer reaction is 35 revs/min, temperature of reaction is 75 DEG C, and the reaction times is 1.5 hours, obtains the reaction viscosity of soft section 150,000.
3, after the first prepolymer reaction completes, add the solvent of total formula weight 22% in the product and add chainextender small molecules dibasic alcohol, carry out hard section reaction after going forward side by side, hard section synthesizes the synthesis between small molecules dibasic alcohol and diphenylmethanediisocyanate (MDI); The condition of hard section reaction is: below 50 DEG C, add small molecules dibasic alcohol, stirring velocity rises to 45 revs/min, stir, add diphenylmethanediisocyanate (MDI), make its slow thermopositive reaction, after temperature rises to 70 degree, temperature controlled to run out of up to MDI 70 degree of reactions 1 are little, the weight that wherein chainextender adds accounts for 1.5% of reactant production gross weight.
4, the product urethane resin generated through really up to the mark section of reaction adds the solvent of total formula weight 32% and stirs after adding auxiliary agent, and the addition of auxiliary agent is 0.8% of gross weight in urethane resin.
It is as follows that this tests the product property made: outward appearance is micro-yellow transparent viscous liquid; Viscosity: 220,000 (cps/25 DEG C); 100% modulus 4.5Mpa; Tensile strength >=35Mpa; Elongation >=550%; Separability: >=12.0 ㎏/3cm; Hydrolytic resistance: 10%NaOH hydrolysis time 24h; Become muscular: 63%.
Embodiment 2
Step is as follows:
1, so-called soft section synthesizes polyether glycol (PTMEG), poly-hexanodioic acid 1,4 butanediol esters (BA) and polyethylene glycol adipate (EA) are put into after solvent DMF dissolves by the mixture of mole 4:3:3 and diphenylmethanediisocyanate (MDI) and are synthesized; Weight after macromolecule diol, diphenylmethanediisocyanate and solvent accounts for 33% of total formula weight, and the reaction stirring velocity of soft section of synthesis is 30 revs/min, and temperature controls at 65 DEG C, and the time was at 2.5 hours.
2, the solvent product of building-up reactions being added total formula weight 15% carries out the first prepolymer reaction, the reaction stirring velocity of the first prepolymer reaction is 30 revs/min, temperature of reaction is 65 DEG C, and the reaction times is 2.5 hours, obtains the reaction viscosity of soft section 100,000.
3, after the first prepolymer reaction completes, add the solvent of total formula weight 20% in the product and add chainextender small molecules dibasic alcohol, carry out hard section reaction after going forward side by side, hard section synthesizes the synthesis between small molecules dibasic alcohol and diphenylmethanediisocyanate (MDI); The condition of hard section reaction is: below 50 DEG C, add small molecules dibasic alcohol, stirring velocity rises to 40 revs/min, stir, add diphenylmethanediisocyanate (MDI), make its slow thermopositive reaction, after temperature rises to 70 degree, temperature controlled to run out of up to MDI 70 degree of reactions 1.5 are little, the weight that wherein chainextender adds accounts for 2.5% of reactant production gross weight.
4, the product urethane resin generated through really up to the mark section of reaction adds the solvent of total formula weight 28% and stirs after adding auxiliary agent, and the addition of auxiliary agent is 0.5% of gross weight in urethane resin.
It is as follows that this tests the product property made: outward appearance is micro-yellow transparent viscous liquid; Viscosity: 180,000 (cps/25 DEG C); 100% modulus 5.5Mpa; Tensile strength >=35Mpa; Elongation >=550%; Separability: >=12.0 ㎏/3cm; Hydrolytic resistance: 10%NaOH hydrolysis time 24h; Become muscular: 50%.
Embodiment 3
Step is as follows:
1, so-called soft section synthesizes polyether glycol (PTMEG), poly-hexanodioic acid 1,4 butanediol esters (BA) and polyethylene glycol adipate (EA) are put into after solvent DMF dissolves by the mixture of mole 4:3:3 and diphenylmethanediisocyanate (MDI) and are synthesized; Weight after macromolecule diol, diphenylmethanediisocyanate and solvent accounts for 35% of total formula weight, and the reaction stirring velocity of soft section of synthesis is 30 revs/min, and temperature controls at 70 DEG C, and the time was at 2.3 hours.
2, the solvent product of building-up reactions being added total formula weight 15% carries out the first prepolymer reaction, the reaction stirring velocity of the first prepolymer reaction is 30 revs/min, temperature of reaction is 70 DEG C, and the reaction times is 2.0 hours, obtains the reaction viscosity of soft section 120,000.
3, after the first prepolymer reaction completes, add the solvent of total formula weight 20% in the product and add chainextender small molecules dibasic alcohol, carry out hard section reaction after going forward side by side, hard section synthesizes the synthesis between small molecules dibasic alcohol and diphenylmethanediisocyanate (MDI); The condition of hard section reaction is: below 50 DEG C, add small molecules dibasic alcohol, stirring velocity rises to 45 revs/min, stir, add diphenylmethanediisocyanate (MDI), make its slow thermopositive reaction, after temperature rises to 70 degree, temperature is controlled react 1 at 70-80 degree and littlely to run out of up to MDI, the weight that wherein chainextender adds accounts for 1.5% of reactant production gross weight.
4, the product urethane resin generated through really up to the mark section of reaction adds the solvent of total formula weight 30% and stirs after adding auxiliary agent, and the addition of auxiliary agent is 0.56% of gross weight in urethane resin.
It is as follows that this tests the product property made: outward appearance is micro-yellow transparent viscous liquid; Viscosity: 200,000 (cps/25 DEG C); 100% modulus 4.8Mpa; Tensile strength >=35Mpa; Elongation >=550%; Separability: >=12.0 ㎏/3cm; Hydrolytic resistance: 10%NaOH hydrolysis time 24h; Become muscular: 61%.
Use-pattern embodiment about this product is as follows:
Embodiment 4
It is following that it comprises weight ratio: urethane (PU) resin 100 parts, mill base 12 parts, teepol (GB-11) 0.7 part, non-ionic surfactant (GB-7) 2 parts, DMF45 part.
Embodiment 5
It is following that it comprises weight ratio: urethane (PU) resin 100 parts, mill base 10 parts, teepol (GB-11) 1 part, non-ionic surfactant (GB-7) 3 parts, DMF47 part.
Embodiment 6
It is following that it comprises weight ratio: urethane (PU) resin 100 parts, mill base 14 parts, teepol (GB-11) 0.5 part, non-ionic surfactant (GB-7) 1 part, DMF50 part.
By the slurry handled well according to the above ratio, with the painting lining bar in 1.2 millimeters of gaps, be coated on the good non-woven fabrics of impregnation, leave standstill 30 seconds, put into coagulating pan (aqueous solution of about 20% DMF), leave standstill and solidify 15 ~ 20 minutes.Take out the sample solidified, put into washing bath (clear water), repeatedly extrude 8-10 time with pressure roller, till cleaning the DMF in sample.Sample is put into 120 ± 1 degree of air dry ovens, dries (20-30 minute), take out cooling.
Claims (1)
1. a production technique for wet polyurethane resin, is characterized in that: it mainly comprises the following steps:
(1) polyether glycol, poly-hexanodioic acid Isosorbide-5-Nitrae butanediol ester and polyethylene glycol adipate are put into by the mixture of mole 4:3:3 and diphenylmethanediisocyanate carry out soft section after solvent DMF dissolves and synthesize; Weight after macromolecule diol, diphenylmethanediisocyanate and solvent accounts for 37% of total formula weight, and the reaction stirring velocity of soft section of synthesis is 35 revs/min, and temperature controlled at 75 DEG C, the time was at 2 hours;
(2) solvent product of building-up reactions being added total formula weight 13% carries out the first prepolymer reaction, the reaction stirring velocity of the first prepolymer reaction is 35 revs/min, temperature of reaction is 75 DEG C, and the reaction times is 1.5 hours, obtains the reaction viscosity of soft section 150,000;
(3) after the first prepolymer reaction completes, add the solvent of total formula weight 22% in the product and add chainextender small molecules dibasic alcohol, carry out hard section reaction afterwards, hard section synthesizes the synthesis between small molecules dibasic alcohol and diphenylmethanediisocyanate; The condition of hard section reaction is: below 50 DEG C, add small molecules dibasic alcohol, stirring velocity rises to 45 revs/min, stir, add diphenylmethanediisocyanate, make its slow thermopositive reaction, after temperature rises to 70 degree, temperature controlled to run out of up to diphenylmethanediisocyanate 70 degree of reactions 1 are little, the weight that wherein chainextender adds accounts for 1.5% of reactant production gross weight;
(4) the product urethane resin generated through really up to the mark section of reaction adds the solvent of total formula weight 32% and stirs after adding auxiliary agent, and the addition of auxiliary agent is 0.8% of gross weight in urethane resin.
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| CN104961880B (en) * | 2015-07-14 | 2018-08-24 | 福建国邦新材料有限公司 | A kind of TPU membrane fitting polyurethane adhesive resin |
| CN108468228B (en) * | 2018-04-20 | 2020-06-30 | 齐鲁工业大学 | Preparation method of cow hair powder filler modified oil-based polyurethane wet-process bass |
| CN108641062A (en) * | 2018-05-25 | 2018-10-12 | 清远市番亿聚氨酯有限公司 | A kind of middle modulus, the preparation method of high springback wet method resin |
| CN111087566B (en) * | 2019-09-29 | 2021-10-29 | 扬州工业职业技术学院 | Preparation method of polyester modified biomass hydrolysis-resistant high-peel-resistance PU wet resin |
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| CN101054435B (en) * | 2007-04-26 | 2010-05-19 | 上海汇得树脂有限公司 | Wet-type polyamine resin with hydrolyzation resistance and high peeling strength and preparing method thereof |
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Address after: 351117 Fujian city of Putian province high tech Industrial Development Zone, Fujian Guobang resin Co. Ltd. Patentee after: Fujian Guobang New Material Co. Ltd. Address before: 351117 Fujian city of Putian province high tech Industrial Development Zone, Fujian Guobang resin Co. Ltd. Patentee before: Fujian Guobang Resin Co., Ltd. |