CN103540281B - A kind of quick-setting rubber-type PUR - Google Patents
A kind of quick-setting rubber-type PUR Download PDFInfo
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- CN103540281B CN103540281B CN201310494944.4A CN201310494944A CN103540281B CN 103540281 B CN103540281 B CN 103540281B CN 201310494944 A CN201310494944 A CN 201310494944A CN 103540281 B CN103540281 B CN 103540281B
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Abstract
The invention discloses a kind of quick-setting rubber-type PUR, its component and percentage by weight be: thermoplastic elastomer: 25 40%, tackifying resin: 35 65%, plasticizer: 5 20%, curing rate conditioning agent: more than 0 and no more than 10%, antioxidant: 0 3%.The rubber-type PUR prepared not only has the polyamide-based flanging general with prior art and has identical or close curing rate, and there is better adhesive property, the base material used is more extensive, it is more suitable for the machine flanging of automation, advantage that is additionally simultaneously the best with ageing-resistant performance, that save energy consumption and extension device service life.
Description
Technical field
The invention belongs to macromolecule product manufacture field, be specifically related to a kind of quick-setting rubber-type PUR.
Background technology
In the manufacture production process of vamps of sport shoes, usual PUR at high temperature (130 DEG C ~ 180 DEG C), by heat seeling coating to spare and accessory parts, carries out temporarily fixing before sewing machine to these spare and accessory parts.PUR is generally used for the following main portions of vamps of sport shoes: 1, the combination of the repeatedly sewing machine spare and accessory parts before instep formation is fixed, and these spare and accessory parts materials are adhesive-bonded fabric, leatheret, Animal Skin or EVA and PU foam material etc.；2, middle base plate is fixed with the temporary transient of shoe last, and the general material at this position is fiber sheet and plastic cement shoe last or aluminum last head；3, the flanging before vamp spare and accessory parts sewing machine is fixed, and these spare and accessory parts materials are adhesive-bonded fabric, leatheret, Animal Skin etc..For the 1st kind of above-mentioned application site, it is generally required to pressure-sensitive type or half pressure-sensitive type PUR, it is desirable to the open hour are long, solidify slow；For the 2nd kind of above-mentioned application site, it is generally required to the EVA type PUR of relatively low bonding force；For the 3rd kind of above-mentioned application site, it is desirable to curing rate fast (open hour 3s or within), bonding force strong (after flanging, material does not flicks) should have certain pliability, and some vamp also requires color inhibition grade more than 3.8 grades simultaneously.Therefore, flanging field before vamp spare and accessory parts sewing machine a kind of be different from that pressure-sensitive type or half pressure-sensitive type PUR and middle base plate and shoe last temporarily fix EVA type PUR can be with quick-setting rubber-type PUR.
At present, being applied to the PUR kind of flanging before vamp spare and accessory parts sewing machine, how based on polyamide hot, the feature of this hot melt adhesive is quick solidifying, good to leather bonding force, and shortcoming is that to be suitable for material more single, and poor in flexibility, yellowing resistance are poor；In addition, domestic also having been reported that is modified the flanging field before vamp spare and accessory parts sewing machine for TPO PUR, but it is unable to reach preferable curing rate (open hour 3s or within) all the time, thus, this area needs a kind of deficiency that can make up above two type PUR with quick-setting rubber-type PUR, ensure bonding force and flexible its curing rate that simultaneously improves, also to ensure coating performance when it is used for flanging gumming machine.
Summary of the invention
The purpose of the present invention is overcoming above-mentioned deficiency of the prior art, a kind of quick-setting rubber-type PUR is provided, described PUR has good adhesive property to adhesive-bonded fabric and leather, curing rate fast (open hour 3s or within), has good pliability and coating performance simultaneously.
The above-mentioned purpose of the present invention is achieved by following technical solution:
A kind of quick-setting rubber-type PUR, its component and percentage by weight be:
Thermoplastic elastomer: 25-40%, tackifying resin: 35-65%, plasticizer: 5-20%, curing rate conditioning agent: more than 0 and no more than 10%, antioxidant: 0-3%；
Described thermoplastic elastomer is one or more mixtures in A-B-A triblock copolymer, A-B diblock copolymer, A-C-B-A Tetrablock copolymer, A-B-AB-A-B segmented copolymer, star block copolymer or its graft modification product selected from version, wherein A is styrene, C is ethene, and B is butadiene, isoprene or pentadiene；Described thermoplastic elastomer when selecting a kind of melt index more than 8g/10 minute；
Described curing rate conditioning agent is selected from aliphatic hydrocarbon, including one or more mixtures in paraffin, microcrystalline wax, synthesis paraffin, low molecular weight polyethylene wax, Fischer-Tropsch wax, polypropylene wax；The molecular weight of described curing rate conditioning agent is more than 350.
Preferably, component and the percentage by weight of described rubber-type PUR is: thermoplastic elastomer: 25-35%, tackifying resin: 40-55%, plasticizer: 5-12%, curing rate conditioning agent: 3-8%, antioxidant: 0.2-1.5%.
It is furthermore preferred that described thermoplastic elastomer when selecting a kind of melt index more than 8g/10 minute.
Preferably, described thermoplastic elastomer is A-B-A triblock copolymer, and wherein A is styrene, and C is ethene, and B is butadiene, isoprene or pentadiene.
Described tackifying resin is selected from aliphatic hydrocarbon, clicyclic hydrocarbon, aromatic hydrocarbon, modified hydrocarbon resins and hydrogenated derivatives, terpenes and hydrogenated derivatives thereof, rosin, modified rosin and hydrogenated derivatives thereof etc., and the mixture of above-claimed cpd.
Tackifying resin of the present invention is specifically selected from C5 Petropols, C9 Petropols, C5/C9 Petropols, terpene resin, rosin, rosin ester etc., and the hydrogenation of above-mentioned resin or modifier.Preferably, tackifying resin is hydrogenation or semihydrogenation C5 Petropols, C5/C9 Petropols, and melt Gardner's colorimetric is less than the terpene resin of No. 3 looks, Terpene styron and rosin ester；Preferably, the ring and ball softening point of described tackifying resin is between 100 DEG C-120 DEG C, and the percentage by weight preferred amounts of described tackifying resin is 40%-55%.
Described plasticizer is selected from mineral base hydrocarbon-type oil, petroleum base hydrocarbon-type oil, polybutene, polyisobutene liquid tackifiers resin, liquid elastomer, the oil of functionalization, fat oil etc., and the mixture of above-claimed cpd.
Described plasticizer includes olefines oligomer and low polymer, also vegetable oil and animal oil and derivative thereof, and adoptable petroleum derivative contains the higher boiling point materials of very small scale aromatic hydrocarbon (preferably ＜ 15% weight ratio).On the other hand, plasticizer can be entirely non-aromatic.Suitably oligomer includes polypropylene that mean molecule quantity is 350 ~ 10000, polybutene, polyisoprene, polybutadiene, polyisobutene or the like, and liquid tackifying resin.Preferably, described plasticizer percentage by weight preferred amounts is 5%-12%.Plasticizer of the present invention is specifically selected from KN4010, KN4008, KN4012 etc. of Kelamayi company.
Preferably, one or more mixtures during described curing rate conditioning agent is synthesis paraffin, low molecular weight polyethylene wax or Fischer-Tropsch wax.As one most preferably scheme, described curing rate conditioning agent is most preferably Fischer-Tropsch wax.
Described antioxidant is selected from hindered phenol or the hindered phenol being combined with aid anti-oxidants.
Preferably, described antioxidant percentage by weight preferred amounts is 0.2% ~ 1.5%, and antioxidant of the present invention is specifically selected from the antioxidant 1010 and 1076 of Ciba company.Antioxidant of the present invention can be used alone, it is also possible to is used in conjunction with phosphite ester, the sulfuration aid anti-oxidants such as dipropionic acid distearate.
Described thermoplastic elastomer includes Kraton D and the G series polymer obtained from U.S. Shell Chemical Co, and described polymer can be used alone, or uses as a mixture.The molecular weight of described thermoplastic elastomer typically characterizes by testing its melt index, and the melt index of rubber is the biggest, shows that its molecular weight is the least, and fluidity of molten is good, and vice versa.
According to actual needs, the PUR of the present invention can add do not affect other compounds of its physical and chemical performance.These compounds include increasing the pigment of color, fluorescer, compound, UV absorbers and the filler etc. of any coverage smell.
The present invention selects the thermoplastic elastomer of specific melt index to compound under the conditions of specified weight percentage with tackifying resin, plasticizer, curing rate conditioning agent and antioxidant, the PUR prepared viscosity when 175 DEG C is less than 13000 centipoises, it is ensured that the good coating performance at a temperature of 150 DEG C of flangings；And under this coating temperature, open hour≤3S, the flanging machine flanging being suitable for automation uses.The PUR prepared under the conditions of optimum ratio of the present invention viscosity when 175 DEG C uses less than 10000 centipoises, open hour about 2S, the flanging machine flanging being applicable to more advanced automation.The most described PUR curing rate is fast, and adhesive property is good, is suitable for multiple base material, including leather, middle bottom edgefold, adhesive-bonded fabric flanging, and above-mentioned base material analog etc..
Compared with prior art, there is advantages that
The invention discloses a kind of quick-setting rubber-type PUR, not only there is the polyamide-based flanging general with prior art and have identical or close curing rate, and there is better adhesive property, the base material used is more extensive, it is more suitable for the machine flanging of automation, advantage that is additionally simultaneously the best with ageing-resistant performance, that save energy consumption and extension device service life.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further explained, but embodiments of the present invention is not limited in any way.Unless stated otherwise, involved in embodiment reagent, method are reagent commonly used in the art and method.
Present invention the following step prepares sample:
Thermoplastic elastomer, antioxidant are joined together with plasticizer in the paddle mixer of temperature control about 160 DEG C, by each material mix and blend until uniformly, it is then slowly added into tackifying resin, add rear mix and blend 15-25 minute, add curing rate conditioning agent, mix and blend 10-15 minute, vacuumizes froth breaking simultaneously.Then pour into melting uniform PUR completely in the box folded by release liners, and be cooled to room temperature.
Selective thermoplastic elastomer is listed in table 1.
Table 1
| Thermoplastic elastomer | Melt index, g/10 minute | Kind |
| VectorD-4411 | 33 | SIS |
| KratonD-1155 | 14 | SBS |
| KratonG-1726 | 50 | SEBS |
| VectorG-1652 | 2 | SEBS |
| YH-792 | 1.5 | SBS |
| YH-1209 | 10 | SIS |
Selective tackifying resin is listed in table 2.
Table 2
| Resin title | Type | Softening point DEG C | Gardner's colorimetric | Supplier |
| SU-130 | Hydrogenation C5 Petropols | 130 | ＜ 1 | Kolon company of Korea S |
| E-5600 | Hydrogenation C5/C9 Petropols | 100 | ＜ 1 | Exxon Neftegas Limited |
| PER-100L | Pale rosin pentaerythritol ester | 100 | ＜ 2 | Wuzhou day becomes forest chemical |
Curing rate conditioning agent is the Fischer-Tropsch wax PX-105 of Shell company.
PUR is carried out the mensuration of following performance: brookfield viscosity, ring and ball softening point, open hour, the peel strength to adhesive-bonded fabric, the peel strength to leather.
Brookfield viscosity: viscosity test is carried out in 175 DEG C in Brookfield viscosimeter, unit cps(centipoise) represent.
Softening point: carry out with ring and ball softening point tester, controls programming rate 5 DEG C/min.
Open hour: carry out by HG/T 3716-2003 standard, use the s(second) represent.
To adhesive-bonded fabric and the peel strength of leather: under the melt adhesive temperature of 150 DEG C, PUR is carried out flanging with adhesive-bonded fabric or leather and is combined by the automatic edge folding provided with Ju Long company, controlling glue-spread is 40g/ square meter, the composite sample of above-mentioned preparation is cooled down about 30 minutes at normal temperatures, carry out peel strength test by GB2792-1998 standard, be broked into standard reaching material.
Embodiment
1
The present embodiment prepares thermoplastic elastomer according to the formula of table 3, and test result is shown in Table 3.
Table 3
| Formula | I-1 | I-2 | I-3 |
| KN4010 | 8 | 8 | 8 |
| YH792 | 15 | 15 | |
| KratonD-1155 | 15 | 30 | |
| VectorD-4411 | 15 | ||
| PX-105 | 5 | 5 | 5 |
| E-5600 | 56.5 | 56.5 | 56.5 |
| Irganox1010 | 0.2 | 0.2 | 0.2 |
| Irganox1076 | 0.3 | 0.3 | 0.3 |
| Formula test result | I-1 | I-2 | I-3 |
| 175 DEG C of viscosity, cps | 13000 | 11500 | 11200 |
| Softening point, DEG C | 115 | 115 | 113 |
| Open hour, S | 2.5 | 2.5 | 3 |
| To adhesive-bonded fabric/leather peel strength | Material breaks | Material breaks | Material breaks |
Three above formula is all the rapid curing rubber-type PUR going for automatic machinery flanging, I-1Thermoplastic elastomer melt index owing to selecting is the most on the low side, and viscosity is bigger than normal, and coating performance is general,I-2、I-3Owing to having selected the thermoplastic elastomer of higher melting index, viscosity drops to about 11000, and coating performance improves substantially, and the most crucial curing rate and adhesive property two indices change little.
Embodiment
2
The present embodiment prepares thermoplastic elastomer according to the formula of table 4, and test result is shown in Table 4.
Table 4
| Formula | Ⅱ -1 | Ⅱ -2 |
| White oil (as plasticizer) | 8 | 8 |
| YH1209 | 20 | |
| KratonG-1726 | 10 | 20 |
| VectorG-1652 | 10 | |
| PX-105 | 5 | 5 |
| SU-130 | 56.5 | 56.5 |
| Irganox1010 | 0.2 | 0.2 |
| Irganox1076 | 0.3 | 0.3 |
| Formula test result | Ⅱ -1 | Ⅱ -2 |
| 175 DEG C of viscosity, cps | 9000 | 10500 |
| Softening point, DEG C | 115 | 118 |
| Open hour, S | 3 | 2.5 |
| To adhesive-bonded fabric/leather peel strength | Material breaks | Material breaks |
| Yellowing resistance (UV xanthochromia grade) | 3.8 | 4.0 |
VectorG-1652 with KratonG-1726 is used to mix the anti-yellowing property that can improve product, but cost is higher, the coating performance of product is affected little, the most crucial curing rate and adhesive property two indices change little, it is also possible to make the rapid curing rubber-type PUR being applicable to automatic machinery flanging.
Embodiment
3
The present embodiment prepares thermoplastic elastomer according to the formula of table 5, and test result is listed in Table 5 below.
Table 5
| Formula | Ⅲ -1 | Ⅲ -2 |
| KN4010 | 8 | 8 |
| YH792 | 10 | |
| Kraton D-1155 | 20 | 10 |
| VectorD-4411 | 10 | 10 |
| PX-105 | 5 | 5 |
| PER-100L | 56.5 | 56.5 |
| Irganox1010 | 0.2 | 0.2 |
| Irganox1076 | 0.3 | 0.3 |
| Formula test result | Ⅲ -1 | Ⅲ -2 |
| 175 DEG C of viscosity, cps | 9000 | 10500 |
| Softening point, DEG C | 105 | 106 |
| Open hour, S | 3 | 3 |
| To adhesive-bonded fabric/leather peel strength | Material breaks | Material breaks |
| Yellowing resistance (UV xanthochromia grade) | 4.0 | 3.8 |
The product yellowing resistance using YH792 to replace part Kraton D-1155 to obtain can be slightly worse, but cost is reduced, the coating performance of product is affected little, the most crucial curing rate and adhesive property two indices change little, it is also possible to make the rapid curing rubber-type PUR being applicable to automatic machinery flanging.
Claims (1)
1. a quick-setting rubber-type PUR, it is characterised in that its component and percentage by weight be:
White oil 8%, KratonG-1726 20%, VectorG-1652 10%, PX-105 5%, SU-130 56.5%, Irganox1010 0.2%, Irganox1076 0.3%；
Described KratonG-1726 be melt index be the SEBS thermoplastic elastomer of 50g/10 minute, described VectorG-1652 is SEBS thermoplastic elastomer that melt index is 2g/10 minute, described PX-105 is Fischer-Tropsch wax, and described SU-130 is the hydrogenation C5 Petropols of softening point 130 DEG C.
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