CN103773293A - Low temperature coated styrene thermoplastic elastomer-based hot-melt pressure-sensitive adhesive - Google Patents
Low temperature coated styrene thermoplastic elastomer-based hot-melt pressure-sensitive adhesive Download PDFInfo
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- CN103773293A CN103773293A CN201410001593.3A CN201410001593A CN103773293A CN 103773293 A CN103773293 A CN 103773293A CN 201410001593 A CN201410001593 A CN 201410001593A CN 103773293 A CN103773293 A CN 103773293A
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Abstract
The invention relates to a low temperature coated styrene thermoplastic elastomer-based hot-melt pressure-sensitive adhesive, belonging to the technical field of hot-melt pressure-sensitive adhesives. The adhesive is characterized in that a linetype or star-shaped SIS (styrene isoprene styrene) or SBS (styrene butadiene styrene) thermoplastic elastomer provides the system with enough physical cross linking points and cohesion strength through a long styrene block, and the glass-transition temperature and the processing temperature of the system are regulated through the length and proportion of a short styrene block. The adhesive has the beneficial effect that the SIS or SBS based hot-melt pressure-sensitive adhesive with excellent properties, which can be fused at 60-85 DEG C and coated, is prepared by matching tackifying resin and using a little or non softener.
Description
Technical field
The invention belongs to hot-fusible pressure-sensitive adhesive technical field, relate to a kind of polystyrene thermoplastic elastomer base hot-fusible pressure-sensitive adhesive that can be low temperature coated.
Background technology
At present, conventional polystyrene thermoplastic elastomer mainly comprises styrene-butadiene-styrene block copolymer (SBS), styrene isoprene styrene block copolymer (SIS) (SIS) and their hydrogenation modified form segmented copolymer (SEBS, SEPS).They are elastomer materials that a class can be carried out melt-processed, and it one of is mainly applied is to be equipped with the composition such as tackifying resin, softening agent, the hot-fusible pressure-sensitive adhesive of processability excellence, and Application Areas is extensive.Wherein, polydiolefin block not only provides good viscoelasticity for thermoplastic elastomer, and provides immersional wetting and voltage-dependent characteristic for hot-fusible pressure-sensitive adhesive.Styrene block is assembled becomes microcell, be distributed in diene hydrocarbon phase, under use temperature, form physics cross-linking set, play the effect of " sulfuration " and reinforcement, melt-flowable under processing temperature, for system provides good processing characteristics, its second-order transition temperature has determined the lower limit temperature of system melt-processed.At present, the vinylbenzene of commercially available SIS or SBS has higher second-order transition temperature (between 90～110 ℃) mutually, thereby make the melt coating temperature of its hot-fusible pressure-sensitive adhesive higher than 120 ℃, cause the application of corresponding hot-fusible pressure-sensitive adhesive in some fields to be extremely restricted, as external use plaster hot-fusible pressure-sensitive adhesive, most drug higher processing temperature (being greater than 100 ℃) is lower cannot stable existence and lost efficacy.For can be at lower temperature processing treatment, Chinese patent CN100420726C adopts SIS, tackifier and tenderizer (softening agent) etc. to prepare medical hot melt pressure sensitive adhesive, and that described hot-fusible pressure-sensitive adhesive has is transparent, docile, without allergic, environmental protection, the plurality of advantages such as anti-aging, drug loading is large.But the use of a large amount of tenderizers obviously reduces the performance of sticking of hot-fusible pressure-sensitive adhesive, and easily remain in skin or substrate surface removing hot-fusible pressure-sensitive adhesive in process.In addition, some Application Areass, as hygienic articles hot-fusible pressure-sensitive adhesive, not only require it to have lower melt processing temperature, but also require it to have the higher performance of sticking.
Summary of the invention
Object of the present invention is just to provide a kind of polystyrene thermoplastic elastomer base hot-fusible pressure-sensitive adhesive that can be low temperature coated.
The present invention adopt can watery fusion the line style of processing or star-like SIS or SBS block polymer replace commercially available SIS or SBS block polymer, be equipped with tackifying resin and oxidation inhibitor, prepare a kind of polystyrene thermoplastic elastomer base hot-fusible pressure-sensitive adhesive that can be low temperature coated.Line style SIS used or SBS block polymer have by two ends the mixture that the thermoplastic elastomer of long styrene block, thermoplastic elastomer that two ends have short styrene block and two ends styrene block thermoplastic elastomer different in size form.The mixture that the brachium that star-like SIS used or SBS block polymer are made up of the two blocks of phenylethylene-dialkene and the different multiarm polymers of structure form.
Hot-fusible pressure-sensitive adhesive prepared by the present invention comprises following main component:
(a) line style of 30-100 parts by weight or star-like SIS or SBS block polymer, the number-average molecular weight of the long styrene block of described block polymer is 1 × 10
4～2 × 10
4, the number-average molecular weight of short styrene block is 1 × 10
2～1 × 10
4, the second-order transition temperature of vinylbenzene phase is between 30～80 ℃, and the number-average molecular weight of diene block is 2 × 10
4～5 × 10
4.
(b) tackifying resin of 50-120 parts by weight, described tackifier are selected from petroleum resin, terpine resin, rosin or its composition.
(c) softening agent of 0-50 parts by weight, described softening agent is selected from mineral oil, whiteruss, white oil or its composition.
(d) oxidation inhibitor of 0.5-3.0 parts by weight, described oxidation inhibitor is selected from N, N-dibutylamino dithio zinc formate, rubber accelerator or its composition.
SIS provided by the invention or SBS base hot-fusible pressure-sensitive adhesive, its preparation method concrete operations comprise the following steps: be full of N
2encloses container in, by 0.5～3.0 parts by weight oxidation inhibitor, 0～50 parts by weight softening agent and 50～120 parts by weight tackifier melting mixing 5～20 minutes at 120 ℃～150 ℃ temperature, afterwards, progressively add SIS or the SBS block polymer of 30～100 parts by weight, and melting mixing 10～20 minutes, SIS or the SBS base hot-fusible pressure-sensitive adhesive of preparation are cooled to 60 ℃～85 ℃, directly melt coating.
The preferred 60-80 parts by weight of described line style or star-like SIS or SBS block polymer, the preferred 80-90 parts by weight of described tackifying resin, the preferred 0-35 parts by weight of described softening agent, the preferred 1-2 parts by weight of described oxidation inhibitor.
Described tackifying resin is selected from petroleum resin, terpine resin, rosin or its composition, the preferred petroleum resin of tackifying resin; Described softening agent is selected from whiteruss, white oil or its composition, the preferred white oil of softening agent; Described anti-aging agent is selected from N, N-dibutylamino dithio zinc formate, rubber accelerator or its composition, anti-aging agent preferred rubber promotor.
Feature of the present invention is that line style or star-like SIS or SBS thermoplastic elastomer provide by long styrene block physical crosslinking point and the cohesive strength that system is enough, and the length by short styrene block and ratio regulate the processing temperature of its second-order transition temperature and system.Effect of the present invention and benefit are to use a small amount of tenderizer or even without tenderizer in the situation that, be equipped with tackifying resin, and can prepare can be at the SIS of the excellent performance of 60～85 ℃ of scope melt coating or SBS base hot-fusible pressure-sensitive adhesive.
Accompanying drawing explanation
Fig. 1 is the temperature variant flow curve figure of commercially available SIS hot-fusible pressure-sensitive adhesive.
Fig. 2 is the temperature variant flow curve figure of line style SIS hot-fusible pressure-sensitive adhesive.
Fig. 3 is the temperature variant flow curve figure of star-like SIS hot-fusible pressure-sensitive adhesive.
Embodiment
Describe specific embodiments of the invention in detail below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
Test, is directly used commercially available SIS resin for SIS hot-fusible pressure-sensitive adhesive in contrast, specific as follows: to be full of N
2encloses container in, by 1～2 parts by weight N, N-dibutylamino dithio zinc formate, 0～35 parts by weight mineral oil and 80～90 parts by weight petroleum resin melting mixing 5～20 minutes at 120 ℃～150 ℃ temperature, afterwards, progressively add the commercially available SIS resin of 60～80 parts by weight, and melting mixing 10～20 minutes, the SIS hot-fusible pressure-sensitive adhesive of preparation is cooled to 60 ℃～85 ℃, directly melt coating, its adhesion property adopts national standard (GB/T4851-1998) test, its melt coating temperature and stick performance and the results are shown in Table 1.Accompanying drawing 1 is the prepared temperature variant flow curve figure of SIS hot-fusible pressure-sensitive adhesive, its test conditions: material thickness is 1mm, and normal force is 5N, rotation frequency is 6.28rad/s, carries out temperature scanning 40～180 ℃ of scopes.
Show the melt coating temperature of 1SIS hot-fusible pressure-sensitive adhesive and stick performance
Embodiment 2
Use line style SIS resin for SIS hot-fusible pressure-sensitive adhesive, specific as follows: to be full of N
2encloses container in, by 1～2 parts by weight N, N-dibutylamino dithio zinc formate, 0～35 parts by weight mineral oil and 80～90 parts by weight petroleum resin melting mixing 5～20 minutes at 120 ℃～150 ℃ temperature, afterwards, progressively add the line style SIS resin of 60～80 parts by weight, and melting mixing 10～20 minutes, the SIS hot-fusible pressure-sensitive adhesive of preparation is cooled to 60 ℃～85 ℃, directly melt coating, its adhesion property adopts national standard (GB/T4851-1998) test, its melt coating temperature and stick performance and the results are shown in Table 1.Accompanying drawing 2 is prepared temperature variant flow curve figure of SIS hot-fusible pressure-sensitive adhesive, its test conditions: material thickness is 1mm, and normal force is 5N, rotation frequency is 6.28rad/s, carries out temperature scanning 40～180 ℃ of scopes.
Embodiment 3
Use star-like SIS resin for SIS hot-fusible pressure-sensitive adhesive, specific as follows: to be full of N
2encloses container in, by 1～2 parts by weight N, N-dibutylamino dithio zinc formate, 0～35 parts by weight mineral oil and 80～90 parts by weight petroleum resin melting mixing 5～20 minutes at 120 ℃～150 ℃ temperature, afterwards, progressively add the star-like SIS resin of 60～80 parts by weight, and melting mixing 10～20 minutes, the SIS hot-fusible pressure-sensitive adhesive of preparation is cooled to 60 ℃～85 ℃, directly melt coating, its adhesion property adopts national standard (GB/T4851-1998) test, its melt coating temperature and stick performance and the results are shown in Table 1.Accompanying drawing 3 is prepared temperature variant flow curve figure of SIS hot-fusible pressure-sensitive adhesive, its test conditions: material thickness is 1mm, and normal force is 5N, rotation frequency is 6.28rad/s, carries out temperature scanning 40～180 ℃ of scopes.
Claims (5)
1. a polystyrene thermoplastic elastomer base hot-fusible pressure-sensitive adhesive that can be low temperature coated, is characterized in that comprising following main component:
(a) line style of 30-100 parts by weight or star-like SIS or SBS block polymer, the number-average molecular weight of the long styrene block of described block polymer is 1 × 10
4～2 × 10
4, the number-average molecular weight of short styrene block is 1 × 10
2～1 × 10
4, the second-order transition temperature of vinylbenzene phase is between 30～80 ℃, and the number-average molecular weight of diene block is 2 × 10
4～5 × 10
4;
(b) tackifying resin of 50-120 parts by weight, described tackifier are selected from petroleum resin, terpine resin, rosin or its composition;
(c) softening agent of 0-50 parts by weight, described softening agent is selected from mineral oil, whiteruss, white oil or its composition;
(d) oxidation inhibitor of 0.5-3.0 parts by weight, described oxidation inhibitor is selected from N, N-dibutylamino dithio zinc formate, rubber accelerator or its composition.
One kind can be low temperature coated polystyrene thermoplastic elastomer base hot-fusible pressure-sensitive adhesive, it is characterized in that, line style SIS used or SBS block polymer have by two ends the mixture that the thermoplastic elastomer of long styrene block, thermoplastic elastomer that two ends have short styrene block and two ends styrene block thermoplastic elastomer different in size form; The mixture that the brachium that star-like SIS used or SBS block polymer are made up of the two blocks of phenylethylene-dialkene and the different multiarm polymers of structure form.
3. a kind of polystyrene thermoplastic elastomer base hot-fusible pressure-sensitive adhesive that can be low temperature coated according to claim 1, is characterized in that, the number-average molecular weight of the long styrene block of described line style or star-like SIS or SBS block polymer is 1 × 10
4～2 × 10
4, the number-average molecular weight of short styrene block is 1 × 10
2～1 × 10
4, the second-order transition temperature of vinylbenzene phase is between 30～80 ℃, and the number-average molecular weight of diene block is 2 × 10
4～5 × 10
4.
4. a kind of polystyrene thermoplastic elastomer base hot-fusible pressure-sensitive adhesive that can be low temperature coated according to claim 1, is characterized in that, concrete operations comprise the following steps: be full of N
2encloses container in, by 0.5～3.0 parts by weight oxidation inhibitor, 0～50 parts by weight softening agent and 50～120 parts by weight tackifier melting mixing 5～20 minutes at 120 ℃～150 ℃ temperature, afterwards, progressively add SIS or the SBS block polymer of 30～100 parts by weight, and melting mixing 10～20 minutes, SIS or the SBS base hot-fusible pressure-sensitive adhesive of preparation are cooled to 60 ℃～85 ℃, directly melt coating; Wherein, the preferred 60-80 parts by weight of described line style or star-like SIS or SBS block polymer, the preferred 80-90 parts by weight of described tackifying resin, the preferred 0-35 parts by weight of described softening agent, the preferred 1-2 parts by weight of described oxidation inhibitor.
5. a kind of polystyrene thermoplastic elastomer base hot-fusible pressure-sensitive adhesive that can be low temperature coated according to claim 1, is characterized in that, tackifying resin used is selected from petroleum resin, terpine resin, rosin or its composition, the preferred petroleum resin of tackifying resin; Softening agent used is selected from whiteruss, white oil or its composition, the preferred white oil of softening agent; Anti-aging agent used is selected from N, N-dibutylamino dithio zinc formate, rubber accelerator or its composition, anti-aging agent preferred rubber promotor.
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|---|---|---|---|
| CN201410001593.3A CN103773293A (en) | 2014-01-02 | 2014-01-02 | Low temperature coated styrene thermoplastic elastomer-based hot-melt pressure-sensitive adhesive |
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| CN201410001593.3A CN103773293A (en) | 2014-01-02 | 2014-01-02 | Low temperature coated styrene thermoplastic elastomer-based hot-melt pressure-sensitive adhesive |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017524A (en) * | 2014-05-29 | 2014-09-03 | 浙江固特热熔胶有限公司 | Novel environmental-friendly middle- and low- temperature pressure-sensitive adhesive used for hygienic products and preparing method thereof |
| CN104559860A (en) * | 2014-10-10 | 2015-04-29 | 竹林伟业科技发展（天津）股份有限公司 | Low-temperature hot melt adhesive |
| CN106281153A (en) * | 2016-08-31 | 2017-01-04 | 如皋市嘉好热熔胶有限公司 | A kind of ornament materials glue and preparation method thereof |
| CN106906572A (en) * | 2017-03-15 | 2017-06-30 | 大连理工大学 | A kind of preparation method of the electrospun fibers film that adhesion structure is formed in micro-nano size |
| CN107700075A (en) * | 2017-11-13 | 2018-02-16 | 大连理工大学 | A kind of preparation method of the electrospun fibers film with self-crosslinking structure |
| CN110205093A (en) * | 2019-05-07 | 2019-09-06 | 深圳日高胶带新材料有限公司 | A kind of low temperature coated modification hot-fusible pressure-sensitive adhesive and preparation method thereof |
| CN110699021A (en) * | 2019-10-24 | 2020-01-17 | 江苏嘉好热熔胶股份有限公司 | Special hot-melt pressure-sensitive adhesive for surgical hole towel and preparation method thereof |
| CN113930198A (en) * | 2021-11-23 | 2022-01-14 | 佛山市本嘉新材料科技有限公司 | Oil-filled star-shaped rubber hot melt adhesive and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017524A (en) * | 2014-05-29 | 2014-09-03 | 浙江固特热熔胶有限公司 | Novel environmental-friendly middle- and low- temperature pressure-sensitive adhesive used for hygienic products and preparing method thereof |
| CN104559860A (en) * | 2014-10-10 | 2015-04-29 | 竹林伟业科技发展（天津）股份有限公司 | Low-temperature hot melt adhesive |
| CN104559860B (en) * | 2014-10-10 | 2017-08-22 | 竹林伟业科技发展（天津）股份有限公司 | A kind of low-temperature hot melt adhesive |
| CN106281153A (en) * | 2016-08-31 | 2017-01-04 | 如皋市嘉好热熔胶有限公司 | A kind of ornament materials glue and preparation method thereof |
| CN106906572A (en) * | 2017-03-15 | 2017-06-30 | 大连理工大学 | A kind of preparation method of the electrospun fibers film that adhesion structure is formed in micro-nano size |
| CN107700075A (en) * | 2017-11-13 | 2018-02-16 | 大连理工大学 | A kind of preparation method of the electrospun fibers film with self-crosslinking structure |
| CN107700075B (en) * | 2017-11-13 | 2019-08-09 | 大连理工大学 | A kind of preparation method of the electrospun fibers film with self-crosslinking structure |
| CN110205093A (en) * | 2019-05-07 | 2019-09-06 | 深圳日高胶带新材料有限公司 | A kind of low temperature coated modification hot-fusible pressure-sensitive adhesive and preparation method thereof |
| CN110699021A (en) * | 2019-10-24 | 2020-01-17 | 江苏嘉好热熔胶股份有限公司 | Special hot-melt pressure-sensitive adhesive for surgical hole towel and preparation method thereof |
| CN113930198A (en) * | 2021-11-23 | 2022-01-14 | 佛山市本嘉新材料科技有限公司 | Oil-filled star-shaped rubber hot melt adhesive and preparation method thereof |
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Application publication date: 20140507 |