CN103013417A - Solvent-free double-constituent polyurethane compound adhesive and preparation method for same - Google Patents
Solvent-free double-constituent polyurethane compound adhesive and preparation method for same Download PDFInfo
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- CN103013417A CN103013417A CN201210516688XA CN201210516688A CN103013417A CN 103013417 A CN103013417 A CN 103013417A CN 201210516688X A CN201210516688X A CN 201210516688XA CN 201210516688 A CN201210516688 A CN 201210516688A CN 103013417 A CN103013417 A CN 103013417A
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Abstract
The invention provides a solvent-free double-constituent polyurethane adhesive which is composed of a constituent A and a constituent B, wherein the constituent A is end isocyanate-group polyurethane prepolymer, and the constituent B is carboxyl-containing polyether polyol. The solvent-free polyurethane adhesive is strong in compounding fastness, long in service usage period and wide in suitable base material range; and moreover, the compound film prepared from the adhesive can still keep an excellent appearance and excellent adhesion property after high-temperature sterilization treatment.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of solvent-free dual-component polyurethane adhesive and preparation method thereof.
Technical background
Current, China's food flexible packing is mostly bonding as main take solvent-based adhesive with composite membrane, and it is compound to adopt composite dry process to carry out, because the recombination process energy consumption is high, the VOC discharging is large, the problems such as dissolvent residual is arranged, the serious threat food safety.Solvent-free polyurethane adhesive uses safety, environmental protection because solid content is high, will be the inexorable trend of packing recombining process development.
Solvent-free composite adhesive comprises two types of one-component polyurethane adhesive and dual-component polyurethane adhesives.Because the one's share of expenses for a joint undertaking amount of solventless adhesive is far smaller than solvent-based adhesive, and there are the many factors such as wettability is poor, so when being used for the bonding composite membrane that contains the tinsel such as aluminium foil, after can having High Temperature Sterilization, compound fastness obviously weakens, and the problems such as colloid flavescence impact is attractive in appearance show relatively poor high thermal resistance and weather resistance.In addition, existing dual-component polyurethane adhesive existence viscosity after two kinds of components mix sharply rises, and causes the problem that crawling is even even can't be coated with.
The CN1989217B patent documentation discloses a kind of solvent-free polyurethane adhesive with excellent high temperature resistant and weather resistance, but is applicable to the bonding of the tinsel such as aluminium and plastic film, composite base material narrow range.The CN101503611A patent documentation discloses a kind of double component solvent-free polyurethane adhesive, shown the performance of low water absorbable, low in hydrolysis, high-impact, but its compound fastness is not strong, and its matrix material does not satisfy resistant to elevated temperatures requirement.
Summary of the invention
The technical problem that will solve required for the present invention provides a kind of solvent-free dual-component polyurethane adhesive and preparation method thereof, and its purpose is: the first, and applicable base materials is wide, and compound fastness is strong, is particularly carrying out still keeping good cohesiveness after high-temperature sterilization is processed; The second, eliminate two kinds of components and mix the impact that causes crawling even can't be coated with because of the viscosity height afterwards, prolong the colloid usage period; The 3rd, colloid is inhibited from yellowing, good endurance.
For achieving the above object, the present invention adopts following technical scheme:
Described solvent-free dual-component polyurethane adhesive comprises two components of A, B, and the A component is to generate isocyanate terminated based polyurethanes performed polymer by the small molecules polyether glycol of 50%～75% isocyanic ester and 15%～30% and/or 10%～20% plant oil modified polyol reaction; The B component is to generate carboxylic polyether glycol by 75%～98% micromolecular polyether glycol and 2%～25% anhydride reaction, the retardance catalyzer account for other raw materials in the B component gross weight 0.1%～0.3%.
Isocyanic ester in the described A component is dicyclohexyl vulcabond (HMDI) and/or isophorone diisocyanate (IPDI); The small molecules polyether glycol is the polyoxypropyleneglycol of molecular weight 400 and/or the polyoxytrimethylene triol of molecular weight 300; Plant oil modified polyvalent alcohol is that molecular weight is that 1000 epoxy soybean oil modified polyalcohol (functionality is 2.6) and/or molecular weight are 900 castor oil modified trivalent alcohol (functionality is 2.7).
The preparation method of the isocyanate terminated based polyurethanes performed polymer of above-mentioned A component is: under nitrogen protection, small molecules polyether glycol and/or plant oil modified polyvalent alcohol are heated to 130～150 ℃, under the vacuum tightness 0.266KPa, moisture content is surveyed in sampling behind dehydration 1.5～2h, when water-content ﹤ 0.05%, be cooled to 70 ℃, add isocyanic ester in batches, generate base polyurethane prepolymer for use as at 85～90 ℃ of reaction 2～3h;
Micromolecular polyether glycol in the described B component is the polyoxypropyleneglycol of molecular weight 400 and/or the polyoxytrimethylene triol of molecular weight 300; The acid anhydrides that is used for modification is trimellitic acid 1,2-anhydride; The retardance catalyzer is trolamine.
The preparation method of the carboxylic polyether glycol of above-mentioned B component is: the small molecules polyether glycol is heated to 150～170 ℃, under the vacuum tightness 0.266KPa, water-content is surveyed in sampling behind dehydration 1.5～2h, when water-content ﹤ 0.05%, be cooled to 60 ℃, then add acid anhydrides, under 120～130 ℃, carry out sour modification, add again the retardance catalyzer, obtain carboxylic polyether glycol.
The content of carboxyl is 4%～12% in the carboxylic polyether glycol of above-mentioned B component.
The preparation method of described solvent-free dual-component polyurethane adhesive is: under 30～50 ℃ of temperature, A component and B component are fully mixed by the mol ratio NCO/OH=1.0 of functional group～1.5.
Below be described in further detail technical scheme of the present invention as follows:
A kind of solvent-free dual-component polyurethane adhesive comprises two components of A, B, it is characterized in that, the A component is isocyanate terminated based polyurethanes performed polymer, and the B component is carboxylic polyether glycol; A component and B component are pressed the mol ratio NCO/OH=1.0 of functional group～1.5, preferred NCO/OH=1.3～1.5.
The raw material weight proportioning for preparing solvent-free polyurethane adhesive of the present invention is:
The A component: isocyanic ester 50%～75%,
Small molecules polyether glycol 15%～30%,
Plant oil modified polyvalent alcohol 10%～20%,
The B component: small molecules polyether glycol 75%～98%,
Trimellitic acid 1,2-anhydride 2%～25%,
Retardance catalyzer, its content account for other raw materials in the B component gross weight 0.1%～0.3%.
Preferably, the raw material weight proportioning for preparing solvent-free polyurethane adhesive of the present invention is:
The A component: isocyanic ester 60%～75%,
Small molecules polyether glycol 15%～25%,
Plant oil modified polyvalent alcohol 10%～15%,
The B component: small molecules polyether glycol 75%～95%,
Trimellitic acid 1,2-anhydride 5%～25%,
Retardance catalyzer, its content account for other raw materials in the B component gross weight 0.1%～0.3%.
Isocyanic ester in the A component is dicyclohexyl vulcabond (HMDI) and/or isophorone diisocyanate (IPDI); The small molecules polyether glycol is the polyoxypropyleneglycol of molecular weight 400 and/or the polyoxytrimethylene triol of molecular weight 300; Plant oil modified polyvalent alcohol is that molecular weight is that 1000 epoxy soybean oil modified polyalcohol (functionality is 2.6) and/or molecular weight are 900 castor oil modified trivalent alcohol.
Small molecules polyether glycol in the B component is the polyoxypropyleneglycol of molecular weight 400 and/or the polyoxytrimethylene triol of molecular weight 300; The acid anhydrides that is used for modification is trimellitic acid 1,2-anhydride; The retardance catalyzer is trolamine.
Through a large amount of experimental studies, when the content of carboxyl in the B component is controlled at 4%～12%, be surprised to find that, the compound fastness of solvent-free dual-component polyurethane adhesive of the present invention significantly strengthens, and has effectively eliminated the detrimentally affect that causes crawling to spare even can't be coated with because viscosity is too high after A, B component mix.Be the impact of different carboxyl-contents in the proof B component on the compound fastness of tackiness agent (this test adopts peeling force to measure compound fastness) and viscosity, the contriver has carried out following contrast experiment, and test-results sees Table one.Wherein sample 1 is the prepared tackiness agent of embodiment 11, and sample 2,3,4,5,6,7,8 preparation method are guaranteeing under the constant prerequisite of other raw materials and reaction conditions with reference to the method for embodiment 11, add respectively 10 parts, 12 parts, 14 parts, 22 parts, 41 parts, 55 parts, 58 parts of trimellitic acid 1,2-anhydrides make carboxyl-content and are respectively 3%, 3.5%, 4%, 6%, 10%, 12.5%, 13% polyether glycol, i.e. above-mentioned sample 2-8.
Carboxyl-content is on the impact of compound fastness and viscosity in table one, the B component
The testing data of table one shows, when the content of carboxyl in the B component less than 4% the time, solventless adhesive peeling force of the present invention is little, namely compound fastness is poor; When the content of carboxyl in the B component greater than 12% the time, the peeling force of solventless adhesive of the present invention is large, compound fastness is strong, but the initial viscosity of joining behind the glue is excessive, is difficult to evenly be coated with at substrate surface.Hence one can see that, when the content of carboxyl in the B component 4%～12% the time, prepared solventless adhesive of the present invention satisfies composite demand and modest viscosity, is convenient to even coating, namely satisfies the requirement of performance and technique.
The preparation method of above-mentioned solvent-free dual-component polyurethane adhesive may further comprise the steps:
(1) take by weighing A, B component by the mol ratio NCO/OH of functional group=1.0～1.5, each component takes by weighing raw material by following proportioning:
The A component: isocyanic ester 50%～75%,
Small molecules polyether glycol 15%～30%,
Plant oil modified polyvalent alcohol 10%～20%,
The B component: small molecules polyether glycol 75%～98%,
Trimellitic acid 1,2-anhydride 2%～25%,
Retardance catalyzer, its content account for other raw materials in the B component gross weight 0.1%～0.3%.
(2) preparation A component: under the protection of nitrogen, with the small molecules polyether glycol and (or) plant oil modified polyvalent alcohol is heated to 130～150 ℃, under the vacuum tightness 0.266KPa, moisture content is surveyed in sampling behind dehydration 1.5～2h, when water-content ﹤ 0.05%, be cooled to 70 ℃, add isocyanic ester in batches, generate base polyurethane prepolymer for use as at 85～90 ℃ of reaction 2～3h;
(3) preparation B component: under the protection of nitrogen, the small molecules polyether glycol is heated to 150～170 ℃, under the vacuum tightness 0.266KPa, moisture content is surveyed in sampling behind dehydration 1.5～2h, when water-content ﹤ 0.05%, be cooled to 60 ℃, then add acid anhydrides, under 120～130 ℃, carry out sour modification, obtain carboxylic polyether glycol;
(4) the retardance catalyzer of its raw material gross weight 0.1%～0.3% of adding in the B component;
(5) preparation tackiness agent: A component and B component namely obtain solvent-free polyurethane adhesive in 30～50 ℃ of lower fully mixing of temperature.
The solvent-free dual-component polyurethane adhesive of gained of the present invention can be applicable to comprise the compound of the multiple films such as CPP, PVDC, PE, BOPP, PA, PET, aluminium foil.
Compared with prior art, have following beneficial effect among the present invention:
1. dual-component polyurethane adhesive of the present invention is difficult to the cementability that bonding base material shows excellence to some, such as bonded polyethylene (PE), polypropylene (CPP), aluminium foil etc., and made foil laminated film still keeps good cementability after 121 ℃ of boiling sterilizations are processed.
2. effectively eliminate the detrimentally affect that causes crawling to spare even can't be coated with because viscosity is too high after A, B component mix, prolonged the tackiness agent usage period.
3. colloid is inhibited from yellowing, good endurance.
4. solvent-free discharging in the production process, pollution-free, safe.
5. reduce production costs, because producing without waste gas, so do not need waste gas exhaust device; Do not need drying tunnel just can reach solidification effect, reduce energy consumption, simplified apparatus; Improve production rate, top speed can reach 500m/min, generally about 300m/min.
6. the unit surface glue consumption is little, saves cost.
Specific implementation method:
In order to further specify characteristic of the present invention, be described in further detail below in conjunction with embodiment, but should not be understood as the restriction of protection domain of the present invention.
The preparation of embodiment 1:A-1
Under nitrogen protection; the polyoxytrimethylene triol of the polyoxypropyleneglycol of 65 parts of molecular weight 400,60 parts of molecular weight 300 is heated to 130 ℃; under the vacuum tightness 0.266KPa; water content is surveyed in sampling behind the dehydration 1.5h; when water-content ﹤ 0.05%, be cooled to 70 ℃, add 150 parts of HMDI, 125 parts of IPDI; at 85 ℃ of lower reaction 2h, obtain A component (hereinafter to be referred as A-1).
The preparation of embodiment 2:A-2
Under nitrogen protection; the polyoxytrimethylene triol of 120 parts of molecular weight 300, the soybean oil modified polyvalent alcohol of 80 parts of molecular weight 1000 (functionality 2.6) are heated to 150 ℃; under the vacuum tightness 0.266KPa; water content is surveyed in sampling behind the dehydration 2h; when water-content ﹤ 0.05%, be cooled to 60 ℃, add 150 parts of HMDI, 50 parts of IPDI; at 120 ℃ of lower reaction 2.5h, obtain A component (hereinafter to be referred as A-2).
The preparation of embodiment 3:A-3
Under nitrogen protection; the castor oil modified trivalent alcohol of the polyoxypropyleneglycol of 60 parts of molecular weight 400,40 parts of molecular weight 900 is heated to 140 ℃; under the vacuum tightness 0.266KPa; water content is surveyed in sampling behind the dehydration 2h; when water-content ﹤ 0.05%, be cooled to 70 ℃, add 200 parts of HMDI, 100 parts of IPDI; at 90 ℃ of lower reaction 3h, obtain A component (hereinafter to be referred as A-2).
The preparation of embodiment 4:B-1
Under the protection of nitrogen; the polyoxytrimethylene triol of 40 parts of molecular weight 300, the polyoxypropyleneglycol of 9 parts of molecular weight 400 are joined in the reactor; be heated to 150 ℃ of vacuum hydro-extractions; water content is surveyed in sampling behind the dehydration 1.5h; when water-content ﹤ 0.05%, be cooled to 70 ℃, then add 1 part of trimellitic acid 1,2-anhydride; under 120 ℃, carry out sour modification, obtain B component (hereinafter to be referred as B-1).
The preparation of embodiment 5:B-2
Under the protection of nitrogen; the polyoxytrimethylene triol of 100 parts of molecular weight 300, the polyoxypropyleneglycol of 90 parts of molecular weight 400 are joined in the reactor; be heated to 170 ℃ of vacuum hydro-extractions; water content is surveyed in sampling behind the dehydration 2h; when water-content ﹤ 0.05%, be cooled to 70 ℃, add 10 parts of trimellitic acid 1,2-anhydrides; under 125 ℃, carry out sour modification, add again 0.2 part of trolamine and obtain the B component.Hereinafter to be referred as B-3.
The preparation of embodiment 6:B-3
Under the protection of nitrogen; the polyoxytrimethylene triol of 100 parts of molecular weight 300, the polyoxypropyleneglycol of 50 parts of molecular weight 400 are joined in the reactor; be heated to 170 ℃ of vacuum hydro-extractions; water content is surveyed in sampling behind the dehydration 2h, when water-content ﹤ 0.05%, is cooled to 70 ℃; add 50 parts of trimellitic acid 1,2-anhydrides; under 130 ℃, carry out sour modification, add again 0.6 part of trolamine, obtain the B component.Hereinafter to be referred as B-4.
Embodiment 7: take by weighing A-1, B-1 component by the mol ratio NCO/OH=1.0 of functional group, fully mix under 30 ℃, 50 ℃ respectively, measure the viscosity of its mixing after 2 minutes, 30 minutes, the results are shown in table two.
Embodiment 8: take by weighing A-2, B-1 component by the mol ratio NCO/OH=1.2 of functional group, fully mix under 30 ℃, 50 ℃ respectively, measure the viscosity of its mixing after 2 minutes, 30 minutes, the results are shown in table two.
Embodiment 9: take by weighing A-3, B-1 component by the mol ratio NCO/OH=1.3 of functional group, fully mix under 30 ℃, 50 ℃ respectively, measure the viscosity of its mixing after 2 minutes, 30 minutes, the results are shown in table two.
Embodiment 10: take by weighing A-3, B-2 component by the mol ratio NCO/OH=1.4 of functional group, fully mix under 30 ℃, 50 ℃ respectively, measure the viscosity of its mixing after 2 minutes, 30 minutes, the results are shown in table two.
Embodiment 11: take by weighing A-3, B-3 component by the mol ratio NCO/OH=1.5 of functional group, fully mix under 30 ℃, 50 ℃ respectively, measure the viscosity of its mixing after 2 minutes, 30 minutes, the results are shown in table two.
Table two, 30 ℃, 50 ℃ are joined glue after 2 minutes and the viscosity after 30 minutes
Embodiment 12: (embodiment 8-embodiment 11) prepares respectively two kinds of composite membranes with solvent-free dual-component polyurethane adhesive of the present invention: BON biaxially oriented nylon film (BOPA, 0.015mm)/low-density polyethylene film (LDPE, 0.035mm) and BON biaxially oriented nylon film (BOPA, 0.015mm)/aluminium foil (0.007mm)/polypropylene casting film (CPP, 0.065mm).Be coated with and be compounded under 30 ℃～50 ℃ and carry out, spread is 1.0g/m
2～2.0g/m
2, then after 48 hours, be cooled to room temperature 50 ℃ of lower slakings, composite membrane is cut into wide 15 millimeters, long 200 millimeters test bar is at room temperature measured T-shaped stripping strength with BLD-200 electron detachment trier, and draw speed is 100 in the least m/min.After 30 minutes, measure after the same method more T-shaped stripping strength respectively at 100 ℃, 121 ℃ poach, the results are shown in table three.In addition, above-mentioned composite membrane was observed more than 40 ℃ of lower 4 weeks of placement, composite membrane still keeps good appearance, pears skin, colloid flavescence phenomenon all do not occur.
The splitting power of table three, mensuration composite membrane
As shown in Table 3, the peeling force between the compound CPP/ aluminium foil of the solvent-free polyurethane adhesive of the present invention preparation is 12.5 N/15mm, 121 ℃ of poach after 30 minutes peeling force be 12.0 N/15mm; And the peeling force between the CPP/ aluminium foil is 3 N/15mm among the embodiment 13 of patent CN101280167B, 100 ℃ of poach after 30 minutes peeling force be 2.5N/15mm.Hence one can see that, and the prepared solventless adhesive of the present invention has significantly improved the cementability of colloid, and compound fastness is strong.
Comparative Examples 1: embodiment 7 and embodiment 8,9 difference are not add plant oil modified polyvalent alcohol in the A component of embodiment 7, have only used micromolecular polyether glycol.By can finding that relatively the initial viscosity of embodiment 8,9 in the time of 30 ℃ is lower, and the initial viscosity of embodiment 7 too high be semi-solid state, thereby need in the time of 50 ℃, can join glue, coating, and the colloid initial viscosity is higher.Therefore, when the small molecules polyvalent alcohol cooperates plant oil modified polyvalent alcohol to use, significantly reduced the initial viscosity of solventless adhesive.
Comparative Examples 2: embodiment 9 and embodiment 10,11 difference are that the B component of embodiment 9 does not add the retardance catalyzer, and all add the retardance catalyzer of different ratios among the embodiment 10,11 B component.By relatively can finding, embodiment 9 prepares glue and substantially solidifies in the time of 30 minutes, and embodiment 10,11 still maintenance low viscosity state 30 minutes time the after preparing glue.Further measure, embodiment 10,11 made solvent-free glue have improved the flowability of reaction mass at 45 minutes after fixing, have prolonged the usage period of colloid.
Claims (7)
1. solvent-free dual-component polyurethane adhesive, it is characterized in that, described solvent-free dual-component polyurethane adhesive comprises two components of A, B, the A component be by the small molecules polyether glycol of 50%～75% isocyanic ester and 15%～30% and (or) the isocyanate terminated based polyurethanes performed polymer that generates of 10%～20% plant oil modified polyol reaction; The B component is the carboxylic polyether glycol that the anhydride reaction by 75%～98% micromolecular polyether glycol and 2%～25% generates, the retardance catalyzer account for other raw materials in the B component gross weight 0.1%～0.3%.
2. solvent-free dual-component polyurethane adhesive as claimed in claim 1 is characterized in that, the isocyanic ester in the A component is dicyclohexyl vulcabond (HMDI) and/or isophorone diisocyanate (IPDI); The small molecules polyether glycol is the polyoxypropyleneglycol of molecular weight 400 and/or the polyoxytrimethylene triol of molecular weight 300; Plant oil modified polyvalent alcohol is that molecular weight is that 1000 epoxy soybean oil modified polyalcohol (functionality is 2.6) and/or molecular weight are 900 castor oil modified trivalent alcohol (functionality is 2.7).
3. solvent-free dual-component polyurethane adhesive as claimed in claim 1 or 2; it is characterized in that; the preparation method of the isocyanate terminated based polyurethanes performed polymer of A component is: under nitrogen protection; small molecules polyether glycol and/or plant oil modified polyvalent alcohol are heated to 130～150 ℃, and under the vacuum tightness 0.266KPa, moisture content is surveyed in sampling behind dehydration 1.5～2h; when water-content ﹤ 0.05%; be cooled to 70 ℃, add isocyanic ester in batches, generate base polyurethane prepolymer for use as at 85～90 ℃ of reaction 2～3h.
4. solvent-free dual-component polyurethane adhesive as claimed in claim 1 is characterized in that, the micromolecular polyether glycol in the B component is the polyoxypropyleneglycol of molecular weight 400 and/or the polyoxytrimethylene triol of molecular weight 300; The acid anhydrides that is used for modification is trimellitic acid 1,2-anhydride; The retardance catalyzer is trolamine.
5. such as claim 1 or 4 described solvent-free dual-component polyurethane adhesives, it is characterized in that, the preparation method of the carboxylic polyether glycol of B component is: the small molecules polyether glycol is heated to 150～170 ℃, and under the vacuum tightness 0.266KPa, water-content is surveyed in sampling behind dehydration 1.5～2h, when water-content ﹤ 0.05%, be cooled to 60 ℃, then add acid anhydrides, under 120～130 ℃, carry out sour modification, add again the retardance catalyzer, obtain carboxylic polyether glycol.
6. such as claim 1 or 5 described solvent-free dual-component polyurethane adhesives, it is characterized in that the content of carboxyl is 4%～12% in the carboxylic polyether glycol of B component.
7. such as each described solvent-free dual-component polyurethane adhesive of claim 1～7, it is characterized in that the preparation method of solvent-free dual-component polyurethane adhesive is: A component and B component are fully mixed by the mol ratio NCO/OH=1.0 of functional group～1.5.
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| CN103555429A (en) * | 2013-11-05 | 2014-02-05 | 湖北大学 | Preparation method of carboxylic hydrogenated castor oil polyalcohol |
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| WO2018049672A1 (en) * | 2016-09-19 | 2018-03-22 | Dow Global Technologies Llc | Two-component solventless adhesive compositions and methods of making same |
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| CN115124967A (en) * | 2022-07-12 | 2022-09-30 | 广东天龙油墨有限公司 | Epoxy modified vegetable oil-based bi-component polyurethane laminating adhesive and preparation method and application thereof |
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| CN103555429A (en) * | 2013-11-05 | 2014-02-05 | 湖北大学 | Preparation method of carboxylic hydrogenated castor oil polyalcohol |
| CN103555429B (en) * | 2013-11-05 | 2016-01-20 | 湖北大学 | A kind of preparation method of carboxylic hydrogenated castor oil polyalcohol |
| CN104153204A (en) * | 2014-07-29 | 2014-11-19 | 上海揽胜绿色材料科技有限公司 | Roller coating type preparation method and device for solvent-free two-component polyurethane synthetic leather as well as prepared synthetic leather |
| CN104153204B (en) * | 2014-07-29 | 2016-06-01 | 上海揽胜绿色材料科技有限公司 | The rollon preparation method of a kind of solvent-free double-component polyurethane synthetic leather and the synthetic leather of equipment and preparation |
| CN104497257A (en) * | 2014-12-16 | 2015-04-08 | 山东一诺威聚氨酯股份有限公司 | Preparation method of double-component polyurethane heat insulation casting rubber for aluminum profile |
| CN104497956A (en) * | 2014-12-18 | 2015-04-08 | 北京天山新材料技术有限公司 | Rapidly-cured double-component polyurethane elastic adhesive and preparation method thereof |
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| CN109642012B (en) * | 2016-07-11 | 2022-02-18 | 陶氏环球技术有限责任公司 | Two-part adhesive composition and method for preparing the same |
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| WO2018049672A1 (en) * | 2016-09-19 | 2018-03-22 | Dow Global Technologies Llc | Two-component solventless adhesive compositions and methods of making same |
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| CN107814902A (en) * | 2017-11-06 | 2018-03-20 | 万华化学集团股份有限公司 | A kind of polyurethane aqueous dispersion body of hydroxyl and its production and use |
| CN117651749A (en) * | 2021-07-21 | 2024-03-05 | 大日精化工业株式会社 | Moisture-curable polyurethane hot-melt adhesive |
| CN115124967A (en) * | 2022-07-12 | 2022-09-30 | 广东天龙油墨有限公司 | Epoxy modified vegetable oil-based bi-component polyurethane laminating adhesive and preparation method and application thereof |
| CN115124967B (en) * | 2022-07-12 | 2024-02-27 | 广东天龙油墨有限公司 | Epoxy modified vegetable oil-based bi-component polyurethane laminating adhesive and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103897653B (en) | 2015-12-30 |
| CN103013417B (en) | 2014-05-28 |
| CN103897653A (en) | 2014-07-02 |
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Effective date of registration: 20151214 Address after: 215513 Jiangsu Province Economic and Technological Development Zone of Changshou City Science Park Patentee after: Suzhou Bolaite New Material Co.,Ltd. Address before: 215534 Dong Zhou road, Changshu national economic and Technological Development Zone, Suzhou, Jiangsu Patentee before: Changshu Guohe New Materials Co., Ltd. |