CN103849100A - Preparation of carrier styrene-isoprene block copolymer composition and adhesive for plaster or patch - Google Patents

Preparation of carrier styrene-isoprene block copolymer composition and adhesive for plaster or patch Download PDF

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Publication number
CN103849100A
CN103849100A CN201210510238.XA CN201210510238A CN103849100A CN 103849100 A CN103849100 A CN 103849100A CN 201210510238 A CN201210510238 A CN 201210510238A CN 103849100 A CN103849100 A CN 103849100A
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styrene
block
isoprene
preparation
molecular weight
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CN201210510238.XA
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袁煜艳
周燎原
何林
佘振银
滕儒超
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China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention discloses preparation of a carrier styrene-isoprene block copolymer composition and adhesive for plaster or patch. The composition comprises the following ingredients in percentage by weight: 80%-90% of styrene-isoprene-styrene tri-block, i.e., S-I-S, and 10%-20% of styrene-isoprene di-block, i.e., S-I, wherein a block ratio S:I of the styrene-isoprene-styrene tri-block is (14-17):(83-86), and molecular weight is 0.11 million to 0.14 million; the block ratio S:I of the styrene-isoprene di-block is (8-12):(88-92), and the molecular weight is 0.055 million-0.075 million. The preparation disclosed by the invention adopts 100 parts of SIS composition, 70-80 parts of plasticizer and 140-150 parts of tackfiying resin to prepare plaster or patch carrier hot-melt pressure-sensitive adhesive which is high in drug loading capacity, low in drug adding temperature, lower in release force and good in holding power.

Description

A kind of carrier styrene-isoprene block copolymer composition for plaster or patch and the preparation of tackiness agent
Technical field
The present invention relates to a kind of carrier styrene-isoprene block copolymer composition (SIS) for plaster or patch and the preparation of tackiness agent, belong to adhesive area.
Background technology
The synthetic method of styrene-isoprene block copolymer SIS comprise the reinforced method of three steps and two steps reinforced after with coupler coupling method.The reinforced method of three steps first adds vinylbenzene reaction, then adds isoprene reaction, then adds vinylbenzene reaction, obtains the SIS of linear structure, does not contain two block SI in the SIS of this structure; After two steps are reinforced, first add vinylbenzene reaction with coupler coupling method, add again isoprene reaction, after having reacted, add coupler to carry out linked reaction, obtain the SIS of hub-and-spoke configuration, if coupler functional group is 2, the SIS that is still linear structure in fact obtaining, more or less contains two block SI in the SIS of this structure, also can pass through the add-on control two block content of coupler.
Plaster or patch normally join functional medicine in relevant tackiness agent, and then applying glue is on by film, non-woven fabrics or the carrier of making of weaving cotton cloth and make.At present, domestic plaster or patch used carrier tackiness agent are natural rubber, because the plaster of preparing take natural rubber as supported adhesive or patch exist many-sided not enough, the neutral protease that particularly natural rubber contains makes part population easily produce anaphylaxis, and the tackiness agent that therefore a lot of technician or have studied take SIS as matrix resin in the industry replaces the supported adhesive of natural rubber for plaster or patch.
Summary of the invention
The object of the present invention is to provide a kind of styrene-isoprene block copolymer composition for high content of dispersion plaster or patch carrier.
The object of the present invention is to provide a kind of with above-mentioned composition preparation have high drug load, low dosing temperature and peeling force lower, hold plaster that viscous force is good or the method for patch carrier hot-melt pressure sensitive adhesive.
The styrene-isoprene block copolymer composition that the invention provides a kind of plaster or patch carrier, mass component comprises:
Styrene-isoprene-phenylethene three blocks, i.e. S-I-S 80 ~ 90%;
Styrene-isoprene two blocks, i.e. S-I 10 ~ 20%;
The block of described styrene-isoprene-phenylethene three blocks is 14 ~ 17:83 ~ 86 than S:I, and molecular weight is 11 ~ 140,000; The block of described styrene-isoprene two blocks is 8 ~ 12:88 ~ 92 than S:I, and molecular weight is 5.5 ~ 7.5 ten thousand.
In composition of the present invention, styrene-isoprene-phenylethene three block mass content are preferably 85%, and block is preferably 15:85 than S:I, and molecular weight is preferably 12 ~ 130,000.
In composition of the present invention, styrene-isoprene two block mass content are preferably 15%, and block is preferably 10:90 than S:I, and molecular weight is preferably 6.5 ~ 70,000.
The present invention also provides a kind of method of preparing hot melt moulding stick with above-mentioned composition, specifically: by weight by styrene-isoprene block copolymer composition of the present invention, 100 parts; Softening agent, 70 ~ 80 parts; Tackifying resin, 140 ~ 150 parts; Add in reactor, under nitrogen protection and oxidation inhibitor existence condition, make through 160 ~ 190 ℃ of high-temperature stirring meltings.
Described in the inventive method, softening agent comprises: phthalic acid two pungent (fourth) ester, mineral oil, naphthenic oil, vegetables oil or whiteruss; Be preferably naphthenic oil; More preferably naphthenic oil KN-4010.
Tackifying resin described in the inventive method comprises: Gum Rosin, terpine resin or synthesizing petroleum resin; Be preferably synthesizing petroleum resin; Most preferably be C 5petroleum resin or hydrogenation C 5petroleum resin.
1010,1076,168 oxidation inhibitor described in the inventive method comprises: one or more, in AC or DLTP; Be preferably one or both in 1076 or 1010.
0.1 ~ 0.5wt% that in the inventive method, the consumption of oxidation inhibitor is whole tackiness agent.
Principle of the present invention: composition S-I-S tri-blocks of the present invention and S-I diblock are at industrial synthetic three block SIS and the two block SI respectively of adopting, and the way then two kinds of products being mixed in proportion in glue tank realizes the production of the determined SIS of the present invention.Contriver finds that through great many of experiments the technical parameter of SIS is that block is very larger to the performance impact of SIS hot-fusible pressure-sensitive adhesive than (S/I), molecular weight, two block SI content etc.The in the situation that in other parameter of SIS, identical and application formula being identical, if block than increasing within the specific limits, the initial bonding strength of SIS hot-fusible pressure-sensitive adhesive reduces, holds that viscous force increases, softening temperature increases; If molecular weight increases within the specific limits, SIS hot-fusible pressure-sensitive adhesive hold that viscous force increases, softening temperature increases; Two block SI content increase, and the initial bonding strength of SIS hot-fusible pressure-sensitive adhesive increases, holds that viscous force reduces, softening temperature reduces.Because two block SI almost do not contribute the force of cohesion of SIS, the block that reduces by two block SI in SIS but can reduce the softening temperature of SIS hot-fusible pressure-sensitive adhesive than the force of cohesion that can not affect SIS hot-fusible pressure-sensitive adhesive, reach reduction dosing temperature object, thereby improve the drug loading of its hot-fusible pressure-sensitive adhesive.
The present invention has outstanding effect: the prepared hot-fusible pressure-sensitive adhesive softening temperature of SIS of the present invention is lower, force of cohesion is better, its dosing temperature is usually less than 100 ℃, be generally 85 ~ 95 ℃, its coating temperature is usually less than 90 ℃, be generally 75 ~ 85 ℃, the initial bonding strength of pressure sensitive adhesive is generally greater than 32# ball (rolling ball method), hold viscous force and be greater than 24 hours, stripping strength is less than 1.5 Ns/millimeter, and at chemical feeding quantity up to 25% time, the plaster of making after dosing or patch initial bonding strength reach 30# ball, hold viscous force and be greater than 0.5 hour, stripping strength is less than 1.5 Ns/millimeter, meet the requirement of plaster or patch supported adhesive.
Embodiment
For making those skilled in the art understand better the present invention, enumerate following specific embodiment, but do not limit the present invention in any way.
Embodiment 1
Hot-fusible pressure-sensitive adhesive application formula is: 100 parts of mass parts SIS, 75 parts of naphthenic oils, hydrogenation C 5145 parts of petroleum resin, antioxidant 1010 0.2%.SIS is synthesized by professional and technical personnel, and the technical parameter of SIS is: linear structure, the block ratio of three block SIS is 15/85, the block ratio of molecular weight 12.5 ten thousand, two block SI is 10/90, molecular weight 70,000, content 15%.At 180 ℃, stir melting and make hot-fusible pressure-sensitive adhesive, and then dosing coating, plaster made.Add the pain-relieving plaster for injury and rheumatism magistral medicines that medicine provides for Beijing antelope is sharp, adding drug ratios is 25%.Relevant performance is as follows:
Figure BDA00002516948200031
Embodiment 2
The technical parameter of application formula and SIS is identical with embodiment 1.Just adding drug ratios is 23%.Relevant performance is as follows:
Figure BDA00002516948200032
Embodiment 3
The technical parameter of application formula and SIS is identical with embodiment 1.Just adding drug ratios is 20%.Relevant performance is as follows:
Figure BDA00002516948200033
Above embodiment explanation, the hot-fusible pressure-sensitive adhesive that adopts the determined SIS of the present invention to make under certain formula, its dosing temperature is lower than 100 ℃, add after the medication amount that is no more than 25% initial bonding strength of gained ointment table good, peeling force is lower, particularly force of cohesion better, hold viscous force and be greater than 30 minutes, can meet the service requirements of ointment.
Comparative example 1
The SIS trade mark used is the SIS-1106(of Ba Ling petro-chemical corporation line style, block than 15/85, molecular weight 12-13 ten thousand, two block content 17%, two block blocks than 15/85, molecular weight 6-7 ten thousand).By 100 parts of application prescription quality part SIS, 75 parts of naphthenic oils, 145 parts of hydrogenation C5 petroleum resin, antioxidant 1010 0.2% stirs melting and makes hot-fusible pressure-sensitive adhesive at 180 ℃, and dosing coating, make plaster.Add the pain-relieving plaster for injury and rheumatism magistral medicines that medicine provides for Beijing antelope is sharp, adding drug ratios is 25%.Relevant performance is as follows:
Figure BDA00002516948200041
Comparative example 2
Hot-fusible pressure-sensitive adhesive application formula is formula used in comparative example 1, but the technical parameter of SIS used is: three block SIS blocks than 15/85, molecular weight 120,000, two block SI blocks than 15/85, molecular weight 70,000, two block content are 20%, after making hot-fusible pressure-sensitive adhesive, dosing is coated with, make plaster, add the pain-relieving plaster for injury and rheumatism magistral medicines that medicine provides for Beijing antelope is sharp, adding drug ratios is 20%.Relevant performance is as follows:
Comparative example 3
On the basis of comparative example 2, will add drug ratios and improve 23%.
Relevant performance is as follows:
Figure BDA00002516948200043
Comparative example 4
On the basis of comparative example 2, will add drug ratios and bring up to 25%.

Claims (13)

1. a carrier styrene-isoprene block copolymer composition for plaster or patch, is characterized in that, mass component comprises:
Styrene-isoprene-phenylethene three blocks, i.e. S-I-S 80 ~ 90%;
Styrene-isoprene two blocks, i.e. S-I 10 ~ 20%;
The block of described styrene-isoprene-phenylethene three blocks is 14 ~ 17:83 ~ 86 than S:I, and molecular weight is 11 ~ 140,000; The block of described styrene-isoprene two blocks is 8 ~ 12:88 ~ 92 than S:I, and molecular weight is 5.5 ~ 7.5 ten thousand.
2. composition as claimed in claim 1, is characterized in that, styrene-isoprene-phenylethene three block mass content are 85%, and block is 15:85 than S:I, and molecular weight is 12 ~ 130,000.
3. composition as claimed in claim 1, is characterized in that, styrene-isoprene two block mass content are 15%, and block is 10:90 than S:I, and molecular weight is 6.5 ~ 70,000.
4. a method of preparing hot melt moulding stick with composition as claimed in claim 1, is characterized in that, by weight by styrene-isoprene block copolymer composition of the present invention, 100 parts; Softening agent, 70 ~ 80 parts; Tackifying resin, 140 ~ 150 parts; Add in reactor, under nitrogen protection and oxidation inhibitor existence condition, make through 160 ~ 190 ℃ of high-temperature stirring meltings.
5. preparation method as claimed in claim 4, is characterized in that, described softening agent comprises: phthalic acid two pungent (fourth) ester, mineral oil, naphthenic oil, vegetables oil or whiteruss.
6. preparation method as claimed in claim 5, is characterized in that, described softening agent comprises naphthenic oil.
7. preparation method as claimed in claim 6, is characterized in that, described softening agent comprises naphthenic oil KN-4010.
8. preparation method as claimed in claim 4, is characterized in that, described tackifying resin comprises: Gum Rosin, terpine resin or synthesizing petroleum resin.
9. preparation method as claimed in claim 8, is characterized in that, described tackifying resin comprises synthesizing petroleum resin.
10. preparation method as claimed in claim 9, is characterized in that, described tackifying resin comprises C 5petroleum resin or hydrogenation C 5petroleum resin.
1010,1076,168 11. preparation methods as claimed in claim 4, is characterized in that, described oxidation inhibitor comprises: one or more, in AC or DLTP.
12. preparation methods as claimed in claim 11, is characterized in that, described oxidation inhibitor comprises one or both in 1076 or 1010.
13. preparation methods as described in claim 4 ~ 12 any one, is characterized in that 01 ~ 03wt% that the consumption of oxidation inhibitor is whole tackiness agent.
CN201210510238.XA 2012-12-03 2012-12-03 Preparation of carrier styrene-isoprene block copolymer composition and adhesive for plaster or patch Pending CN103849100A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105663468A (en) * 2016-02-17 2016-06-15 北京乳凝创智生物技术研发中心(有限合伙) Hydrophilic and oleophilic gel eye pad with eye fatigue relieving function and eye care function and preparation method thereof
CN106085305A (en) * 2016-06-23 2016-11-09 大连理工大学 A kind of natural rubber base hot-fusible pressure-sensitive adhesive and preparation method thereof
CN107619571A (en) * 2016-07-15 2018-01-23 中国石油化工股份有限公司 A kind of polystyrene b polyisoprene/tackifying resin compounded rubber particle and its preparation method and application
CN113416508A (en) * 2021-04-06 2021-09-21 巢进化学(上海)有限公司 Hot-melt pressure-sensitive adhesive and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1424908A (en) * 2000-04-18 2003-06-18 久光制药株式会社 Patch containing anti-inflammatory agent
CN101966339A (en) * 2009-12-22 2011-02-09 侯玉庆 Thermoplastic elastomer styrene-isoprene-styrene (SIS) framework material extruded and coated by extruder

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1424908A (en) * 2000-04-18 2003-06-18 久光制药株式会社 Patch containing anti-inflammatory agent
CN101966339A (en) * 2009-12-22 2011-02-09 侯玉庆 Thermoplastic elastomer styrene-isoprene-styrene (SIS) framework material extruded and coated by extruder

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105663468A (en) * 2016-02-17 2016-06-15 北京乳凝创智生物技术研发中心(有限合伙) Hydrophilic and oleophilic gel eye pad with eye fatigue relieving function and eye care function and preparation method thereof
CN105663468B (en) * 2016-02-17 2020-01-14 北京乳凝创智生物技术研发中心(有限合伙) Amphiphilic gel eye patch with dual effects of relieving visual fatigue and nursing around eyes and preparation method thereof
CN106085305A (en) * 2016-06-23 2016-11-09 大连理工大学 A kind of natural rubber base hot-fusible pressure-sensitive adhesive and preparation method thereof
CN106085305B (en) * 2016-06-23 2017-12-26 大连理工大学 A kind of natural rubber base hot-fusible pressure-sensitive adhesive and preparation method thereof
CN107619571A (en) * 2016-07-15 2018-01-23 中国石油化工股份有限公司 A kind of polystyrene b polyisoprene/tackifying resin compounded rubber particle and its preparation method and application
CN107619571B (en) * 2016-07-15 2021-01-05 中国石油化工股份有限公司 Polystyrene-b-polyisoprene/tackifying resin composite rubber particles and preparation method and application thereof
CN113416508A (en) * 2021-04-06 2021-09-21 巢进化学(上海)有限公司 Hot-melt pressure-sensitive adhesive and preparation method thereof

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Application publication date: 20140611