CN106147674B - A kind of compound film adhesive and preparation method thereof - Google Patents
A kind of compound film adhesive and preparation method thereof Download PDFInfo
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- CN106147674B CN106147674B CN201510201513.3A CN201510201513A CN106147674B CN 106147674 B CN106147674 B CN 106147674B CN 201510201513 A CN201510201513 A CN 201510201513A CN 106147674 B CN106147674 B CN 106147674B
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Abstract
The invention discloses a kind of compound film adhesive and preparation method thereof, the compound film adhesive includes matrix resin, tackifying resin, auxiliary agent and solvent, wherein, matrix resin is that one end has amido, the other end has tri- sections of embedding copolymers of SBS of carboxyl, the compound film adhesive has good fluidity, cohesive force is strong, the characteristics of ink-receptive is good, it is bad to the affinity of ink layer to overcome existing SBS adhesive, when laminating adhesive paper is stripped, ink is difficult to throw off, easily there is the defects of " light film " phenomenon, and compound film adhesive environmental protection, cost is low, meet the requirement of industrial production and application.
Description
Technical field
The present invention relates to a kind of compound film adhesive and preparation method thereof, belongs to composite high-molecular material field.
Background technology
Laminating adhesive be by the plastic sheeting after coating binder, with paper printed matter it is heated, pressurization after be bonded together, shape
Into the product of paper unification, it is one of paper printed matter post-press finishing technique common at present.By the printed matter of laminating adhesive, by
One layer of thin, transparent plastic sheeting more than the surface, surface is more smooth bright, not only increase printed matter glossiness and
Fastness, extends the service life of printed matter, while plastic sheeting plays waterproof, antifouling, wear-resisting, folding, resistant to chemical etching again
Deng protective effect.At present, common paper-plastic lamination packaging product has carton, carton, handbag, fertilizer bag, seed packet, adhesive sticker
Label etc..Laminating adhesive is different by chemical composition, can be divided into polyurethane adhesive, polyacrylic acid ester gum, EVA glue and the major class of SBS glue 4, its
Middle EVA glue and SBS glue sales volume is maximum.
It is all that SBS adhesive has that the shallow transparent, frost resistance of color and puncture are excellent, manufacture craft is simple and cost is low etc.
More advantages.But SBS compound film adhesives are mostly solvent-borne type at present, although cementability is good, substantial amounts of organic solvent meeting in operation
Directly it evaporate into air, causes environmental pollution, murder by poisoning is produced to human body.People have found that SBS glue is also present in use
Weak point：(1) peel strength of laminating adhesive paper declines very fast；(2) viscosity is larger, poor fluidity, application difficulties；(3) to ink
The affinity of layer is bad, and when laminating adhesive paper is stripped, ink is difficult to throw off, and " light film " phenomenon easily occurs.
The content of the invention
The defects of existing for SBS adhesive of the prior art, the purpose of the present invention are to be to provide a kind of mobility
The good, compound film adhesive that cohesive force is strong, ink-receptive is good, environmentally friendly during the compound film adhesive use, use cost is low, meets
Commercial Application requirement.
Another object of the present invention be to provide a kind of simple to operate, cost it is low prepare the compound film adhesive
Method.
The invention provides a kind of compound film adhesive, including matrix resin, tackifying resin, auxiliary agent and solvent, described base
Body resin is the modified SBS with the structure of formula 1；
Wherein,
R1And R2It is each independently selected from C1~C4 alkyl；
Modified SBS molecular weight is 20000~200000；
Modified SBS is the quality of styrene/butadiene/styrene block copolymers, butadiene block and styrene block
Than for 15/85~45/65.
More preferably modified SBS molecular weight is 70000~150000 in compound film adhesive；More preferably 80000~
120000。
More preferably the mass ratio of butadiene block and styrene block enters one for 17/83~40/60 in compound film adhesive
Step is preferably 20/80~30/70.
More preferably compound film adhesive includes following parts by weight of component：1~8 part of modified SBS；3~25 parts of tackifying resin；Water
15~40 parts；2~15 parts of organic solvent；0.5~5 part of emulsifying agent.
Further preferred compound film adhesive, including following parts by weight of component：2~6 parts of modified SBS；Tackifying resin 5~
20 parts；20~30 parts of water；5~12 parts of organic solvent；1~3 part of emulsifying agent；2~8 parts of thickener.
The R of preferable compound film adhesive Chinese style 11And R2It is each independently selected from methyl, ethyl, propyl group, isopropyl, butyl
Or isobutyl group.
Preferable tackifying resin is included with the resin of polystyrene block compatible in modified SBS and/or with gathering in modified SBS
The compatible resin of butadiene midblock.Resin with polystyrene block compatible be preferably inden resin, poly- methyl-indene resin,
At least one of polystyrene resin, α-methylstyrene resin, polyphenylene oxide.The resin compatible with polybutadiene mid block
Preferably C5 hydrocarbon resins, hydrogenation C5 hydrocarbon resins, phenylethene modified C5 resins, C5/C9 Petropols, terpene resin, styrene change
Property terpene resin, completely at least one of hydrogenation or part hydrogenation C9 hydrocarbon resins, rosin resin, rosin derivative.More preferably
Tackifying resin be terpene resin, rosin resin, C5/C9 resins.In view of the characteristics of modified SBS of the present invention, most preferably terpenes
Resin and rosin resin compound resin system.
Preferable emulsifying agent can be cationic emulsifier, anion emulsifier, nonionic emulsifier and its composite emulsifying
Agent.The present invention is more preferably cationic emulsifier, such as selects cationic emulsifier 1227,1631, at least one of 1831, especially
It is optimal with 1831 cationic emulsifiers.
Preferable solvent is toluene, ethyl acetate, dichloromethane, gasoline, C6 oil, hexamethylene, acetone, chloroform, acetic acid fourth
At least one of ester.Solvent plays an important role in Laminating adhesive, and suitable solvent can reduce the viscosity of adhesive, make it
It is easy to be coated with, and the wettability of Laminating adhesive and the mobility of molecule can be increased, so as to improve bonding force, and solvent can
The levelability of Laminating adhesive is improved, avoids glue-line became uneven.Solvent should be less toxic or nontoxic.And it also requires consider the present invention
Modified SBS, tackifying resin it is not soluble in water, need to be dissolved with appropriate solvent, can be just emulsified.
Preferable thickener is at least one of cellulose, amylan, polyvinyl alcohol, EVA.
The compound film adhesive of the present invention can also include other adjuvant components.
Present invention also offers the preparation method of described compound film adhesive, the preparation method is by modified SBS, thickening tree
Liposoluble adds emulsifying agent after organic solvent, adds water, emulsion dispersion, obtains water and milk compound film adhesive.
The coating of the compound film adhesive of the present invention can use chilling roller to be coated with.
Tackifying resin, organic solvent, emulsifying agent and the thickener that the present invention uses all are conventional commercial preparation.
The modified SBS that the present invention uses can be prepared by the following method to obtain, it is necessary to illustrate, the present invention is modified
SBS can also use other any methods to prepare, and illustrate below for example purposes only：
Amido is contained in modified SBS one end of the present invention, and the other end contains carboxyl.In anionic SBS block copolymer
When, using the alkyl amine group lithium of the structure of formula 2 as initiator, blocked after the completion of polymerization by acid anhydrides, be acidified, that is, obtain the knot of formula 1
The modified SBS of structure.
Specific reaction scheme is as follows：
1st, the synthesis of alkyl amine group lithium：
2nd, polymerization is triggered：By monomer order of addition, monomer adding proportion can strictly control polystyrene in polymer
With the mass ratio of polybutadiene block, while can strictly be controlled by the addition and monomer addition of alkyl amine group lithium poly-
The molecular weight of compound：
3rd, block, be acidified：Carboxyl can be introduced in end group by anhydride reaction；Acid anhydrides can use phthalic anhydride, maleic two
Acid anhydrides, the needs based on technical solution of the present invention modified SBS as compound film adhesive material, optimal end-blocking acid anhydrides is maleic
Dicarboxylic anhydride；After end capping reaction, polymer glue is acidified under the conditions of diluted acid (PH=5~6 when), and diluted acid can be salt
The aqueous solution of acid, sulfuric acid or phosphoric acid, and carbon dioxide and water are passed through, other any suitable acid can also be used.
Compared with the prior art, the beneficial effect that technical solution of the present invention is brought：1st, compound film adhesive of the invention have compared with
Good mobility, coating is easy, avoids using a large amount of organic solvents, overcomes a large amount of solvent volatilizations of solvent-borne type SBS adhesive,
The defects of causing environmental pollution；2nd, compound film adhesive of the invention has preferable ink-receptive, with non-polar material affinity
Strengthen, overcome that existing SBS adhesive is bad to the affinity of ink layer, and ink is difficult to throw off when laminating adhesive paper is stripped, easily
There is the defects of " light film " phenomenon；3rd, compound film adhesive cementitiousness of the invention greatly improves, and overcomes existing SBS adhesive
In use, the peel strength of laminating adhesive paper declines the defects of very fast.4th, compound film adhesive of the invention need not heat dry when in use
Dry, tack is good, and bonding force is strong, and appearance of film is highly polished.5th, it is few using organic solvent amount, cost is significantly reduced, really
Nontoxic, pollution-free, inexpensive, easy to use and function admirable is accomplished.
Embodiment
Following examples are intended to further illustrate present invention, rather than limiting the scope of the present invention.Implement
Example 1
The modified SBS of table 1 is compounded according to the compound film adhesive formula of table 2, modified SBS is added in a reservoir, increases
After viscosity resin and organic solvent, fully dissolving, emulsifying agent is added, deionized water is added, is emulsified, obtained with high-shear emulsion machine
To water and milk compound film adhesive.Obtained water and milk compound film adhesive performance is as shown in table 3 below.
The characterisitic parameter of the modified SBS of table 1
| Sample number into spectrum | Counter sample |
| 1# | S/B=3/7, Mn=8.9 ten thousand |
| 2# | S/B=3/7, Mn=10.8 ten thousand |
| 3# | S/B=3/7, Mn=12.7 ten thousand |
| 4# | S/B=2/8, Mn=8.2 ten thousand |
| 5# | S/B=2/8, Mn=10.4 ten thousand |
| 6# | S/B=4/6, Mn=8.3 ten thousand |
| 7# | S/B=4/6, Mn=10.5 ten thousand |
The formula composition of the modified SBS water and milk Laminating adhesive of table 2
| Component | Parts by weight |
| Modified SBS | 2 parts |
| Terpene resin | 5 parts |
| Rosin resin | 5 parts |
| Emulsifying agent 1831 | 1 part |
| Butyl acetate | 3 parts |
| 200# gasoline | 3 parts |
| Deionized water | 30 parts |
| Other (thickeners etc.) | 5 parts |
The performance of the modified SBS water and milk Laminating adhesive of table 3
Embodiment 2
Except modified SBS using the 5# and emulsifying agent of table 1 using anion and nonionic emulsifier combination (SDBS+OP-10)
Outside, it is other identical with example 1.Gained laminating adhesive latex solution is white uniformity emulsion, and pH is that 6.7,25 DEG C of viscosity are 265, is peeled off strong
Degree is 25, and film is without foaming, tabula rasa.
Comparative example 1
It is other with the phase of embodiment 2 except outside 796 (S/B=2/8, the Mn=10.1 ten thousand) that modified SBS is changed into Ba Ling petrochemical industry
Together.Gained laminating adhesive latex solution is white uniformity emulsion, but is easily layered after placing a period of time, and pH is that 6.5,25 DEG C of viscosity are 235,
Peel strength is 19, and foaming, tabula rasa phenomenon occurs in film.
From comparative example as can be seen that using modified SBS of the invention, emulsion is more stable, improves foaming, the light of film
Plate phenomenon.
Although disclosed herein is embodiments of the invention, it should be understood, however, that the present invention is not limited to shown reality
Example is applied, those skilled in the art can carry out various change and change to the present invention, and without departing from institute of the present invention
The scope of attached claims and its suitable content provided.
Claims (13)
1. a kind of compound film adhesive, including matrix resin, tackifying resin, auxiliary agent and solvent, it is characterised in that described matrix tree
Fat is the modified SBS with the structure of formula 1；
Wherein,
R1And R2It is each independently selected from C1~C4 alkyl；
Modified SBS molecular weight is 20000~200000；
Modified SBS is styrene/butadiene/styrene block copolymers, and the mass ratio of butadiene block and styrene block is
15/85~45/65.
2. compound film adhesive according to claim 1, it is characterised in that modified SBS molecular weight is 70000~150000.
3. compound film adhesive according to claim 2, it is characterised in that modified SBS molecular weight is 80000~120000.
4. compound film adhesive according to claim 1, it is characterised in that the mass ratio of butadiene block and styrene block
For 17/83~40/60.
5. compound film adhesive according to claim 1, it is characterised in that the mass ratio of butadiene block and styrene block
For 20/80~30/70.
6. according to the compound film adhesive described in any one of Claims 1 to 5, it is characterised in that including following parts by weight of component：
1~8 part of modified SBS；
3~25 parts of tackifying resin；
15~40 parts of water；
2~15 parts of organic solvent；
0.5~5 part of emulsifying agent.
7. compound film adhesive according to claim 6, it is characterised in that including following parts by weight of component：
2~6 parts of modified SBS；
5~20 parts of tackifying resin；
20~30 parts of water；
5~12 parts of organic solvent；
1~3 part of emulsifying agent；
2~8 parts of thickener.
8. compound film adhesive according to claim 7, it is characterised in that described tackifying resin is inden resin, poly- first
Base indene resin, polystyrene resin, α-methylstyrene resin, polyphenylene oxide, C5 hydrocarbon resins, hydrogenation C5 hydrocarbon resins, styrene change
Property C5 resins, C5/C9 Petropols, terpene resin, styrenated terpene resins, completely hydrogenation or part hydrogenation C9 hydrocarbon trees
At least one of fat, rosin resin, rosin derivative.
9. compound film adhesive according to claim 8, it is characterised in that described tackifying resin is terpene resin and rosin
The compound resin of resin.
10. compound film adhesive according to claim 7, it is characterised in that described emulsifying agent is cationic emulsifier
1227th, 1631, at least one of 1831.
11. compound film adhesive according to claim 7, it is characterised in that described thickener be cellulose, amylan,
At least one of polyvinyl alcohol.
12. compound film adhesive according to claim 7, it is characterised in that described organic solvent is toluene, acetic acid second
At least one of ester, dichloromethane, gasoline, C6 oil, hexamethylene, acetone, chloroform, butyl acetate.
13. the preparation method of the compound film adhesive described in claim 6, it is characterised in that be dissolved in modified SBS, tackifying resin
After organic solvent, it is added in the solution containing emulsifying agent, emulsion dispersion, obtains water and milk compound film adhesive.
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| CN201510201513.3A CN106147674B (en) | 2015-04-24 | 2015-04-24 | A kind of compound film adhesive and preparation method thereof |
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| CN106147674A CN106147674A (en) | 2016-11-23 |
| CN106147674B true CN106147674B (en) | 2018-02-27 |
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| CN110157365A (en) * | 2019-04-15 | 2019-08-23 | 安徽绿谷新材料有限公司 | A kind of rubber glue and preparation method thereof that volatility is low |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006093051A1 (en) * | 2005-03-04 | 2006-09-08 | Bridgestone Corporation | Rubber composition and tire using same |
| CN1923870A (en) * | 2006-08-10 | 2007-03-07 | 大连海事大学 | Synthesis for copolymer of terminal amino and carboxyl styrene/butadiene and method of preparing storage stabilized modified asphalt |
| CN101338175A (en) * | 2008-08-28 | 2009-01-07 | 华南师范大学 | Water-emulsion type paper-plastic composite adhesive and method for preparing same |
| CN103483475A (en) * | 2013-09-30 | 2014-01-01 | 北京化工大学 | Method for preparing terminal carboxyl group polymer through active anionic polymer termination |
-
2015
- 2015-04-24 CN CN201510201513.3A patent/CN106147674B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006093051A1 (en) * | 2005-03-04 | 2006-09-08 | Bridgestone Corporation | Rubber composition and tire using same |
| CN1923870A (en) * | 2006-08-10 | 2007-03-07 | 大连海事大学 | Synthesis for copolymer of terminal amino and carboxyl styrene/butadiene and method of preparing storage stabilized modified asphalt |
| CN101338175A (en) * | 2008-08-28 | 2009-01-07 | 华南师范大学 | Water-emulsion type paper-plastic composite adhesive and method for preparing same |
| CN103483475A (en) * | 2013-09-30 | 2014-01-01 | 北京化工大学 | Method for preparing terminal carboxyl group polymer through active anionic polymer termination |
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