CN114634778B - Adhesive resin composition and self-adhesive protective film - Google Patents

Adhesive resin composition and self-adhesive protective film Download PDF

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Publication number
CN114634778B
CN114634778B CN202111293886.XA CN202111293886A CN114634778B CN 114634778 B CN114634778 B CN 114634778B CN 202111293886 A CN202111293886 A CN 202111293886A CN 114634778 B CN114634778 B CN 114634778B
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adhesive
block copolymer
styrene block
resin composition
weight
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CN114634778A (en
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刘威
邵雪
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Zhangjiagang Kangdexin Optronics Material Co Ltd
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Zhangjiagang Kangdexin Optronics Material Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02Vinyl aromatic monomers and conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14Protective coatings, e.g. hard coatings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/08Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Abstract

The invention provides an adhesive resin composition and a self-adhesive protective film, wherein the adhesive resin composition comprises 5-20 parts by weight of a styrene block copolymer, 5-15 parts by weight of a tackifying resin and 100 parts by weight of a maleic anhydride grafted styrene block copolymer. The adhesive resin composition improves the compatibility of the styrene block copolymer and tackifying resin by introducing the maleic acid oversrafted styrene block copolymer, thereby obtaining the self-restorative prism sheet protective film with high initial adhesion and reducing surface pollution.

Description

Adhesive resin composition and self-adhesive protective film
Technical Field
The invention relates to the field of protective films, in particular to an adhesive resin composition and a self-adhesive protective film.
Background
For the prism sheet with high self-recovery, the protective film with low initial adhesion is easy to float after being attached. In addition, in the prism sheet manufacturing process, in order to detach the prism sheet from the mold, a stripper is usually added and transferred to the prism sheet, so that the surface tension of the prism sheet is high and the prism sheet is difficult to attach.
CN 103620450A proposes to improve the adhesion of the protective film by adding a terpene phenol resin which cannot be phenol content. The excessive addition of terpene phenolic resin is not mentioned to cause surface contamination of the prism sheet. The prism sheet protective film disclosed in CN 102292655A reduces unwinding, fails to significantly improve initial adhesion, and is not easy to attach to a self-restorative prism sheet. The invention disclosed in CN 104837946A is prepared into a PET base material protective film in a coating mode, and the influence of the addition amount of terpene phenolic resin on paste residue and surface pollution is specified. The protective film for a prism sheet proposed in CN 106459684A mainly solves the problem of end peeling, and fails to effectively improve the initial adhesion.
Therefore, it is necessary to provide an adhesive resin composition and a self-adhesive protective film to solve the problems of low initial adhesion of the protective film to the prism sheet and contamination of the protective film to the prism sheet in the prior art.
Disclosure of Invention
The invention provides an adhesive resin composition and a self-adhesive protective film, and aims to improve the initial adhesion of the self-adhesive protective film to a prism sheet and reduce pollution of the protective film to the prism sheet.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
an adhesive resin composition comprises 5-20 parts by weight of a styrene block copolymer, 5-15 parts by weight of a maleic anhydride grafted styrene block copolymer, and a tackifying resin based on 100 parts by weight of the styrene block copolymer.
Further, the styrene block copolymer is a copolymer of styrene and an olefin or a hydride thereof.
Further, the styrene block copolymer is one or more of a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer, a styrene-ethylene-propylene-styrene block copolymer, or a hydride thereof.
Further, the tackifying resin is selected from one or more of petroleum resin, rosin resin, terpene phenolic resin, preferably, the tackifying resin is selected from one or more of terpene phenolic resin.
Further, the maleic anhydride grafted styrene block copolymer is selected from one or more of maleic anhydride grafted SEBS and maleic anhydride grafted SEPS.
Further, the grafting rate of the maleic anhydride in the maleic anhydride grafted styrene block copolymer is 0.5-2%.
Further, a phenoxy resin is included in an amount of 0.5 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the styrene block copolymer.
Further, the phenoxy resin has a molecular weight of 2×10 4 ~5*10 4
The invention also provides a self-adhesive protective film which comprises an adhesive layer, an intermediate layer and a surface layer, wherein the adhesive layer comprises the adhesive resin composition.
Further, the self-adhesive protective film is attached to the prism face, and the adhesive force between the self-adhesive protective film and the prism face is more than or equal to 5g/25mm.
The adhesive resin composition improves the compatibility of the styrene block copolymer and tackifying resin by introducing the maleic acid oversrafted styrene block copolymer, thereby obtaining the self-restorative prism sheet protective film with high initial adhesion and reducing surface pollution.
Meanwhile, the polarity and the viscosity of the adhesive resin composition are improved by adding the macromolecular and high-polarity phenoxy resin, the interaction force with the prism sheet is enhanced, and the precipitation risk is avoided.
Detailed Description
The present invention will be described in detail with reference to embodiments. These embodiments are not intended to limit the invention and structural, methodological, or functional modifications of these embodiments that may be made by one of ordinary skill in the art are included within the scope of the invention.
As described in the prior art, the conventional protective film is attached to the prism sheet with low initial adhesion, and the protective film is easy to pollute the prism sheet. The present inventors have studied on the above problems and have proposed an adhesive resin composition comprising a styrene block copolymer, a tackifying resin and a maleic anhydride-grafted styrene block copolymer, wherein the tackifying resin is 5 to 20 parts by weight and the maleic anhydride-grafted styrene block copolymer is 5 to 15 parts by weight based on 100 parts by weight of the styrene block copolymer. When the adhesive resin composition with the proportion is used for a self-adhesive protective film, the adhesive resin composition has stronger adhesive force to a coated object, especially a prism sheet, and the adhesive force is more than or equal to 5g/25mm. At the same time, the adhesive resin composition is not easy to precipitate, and can not cause pollution on the surface of a coating object such as a prism sheet.
In the present invention, the above-mentioned styrene block copolymer is a copolymer of styrene and an olefin or a hydride thereof. For example, it may be one or more of a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer, a styrene-ethylene-propylene-styrene block copolymer, or a hydride thereof.
In a preferred embodiment, the styrene block copolymer of the present invention is selected from one or more of the group consisting of a hydride of a styrene-butadiene-styrene block copolymer (SEBS) and a hydride of a styrene-isoprene-styrene block copolymer (SEPS).
For the self-restorative prism sheet, the protective film made of the styrene block copolymer is not satisfied with the bonding condition, and a sufficient amount of tackifying resin is required to be added. In the present invention, the tackifying resin composition comprises 5 to 20 parts by weight of the tackifying resin per 100 parts by weight of the styrene block copolymer, and if the tackifying resin is less than 5 parts by weight, the adhesive force of the adhesive layer is not changed even if the tackifying resin is compounded, and the desired adhesive force cannot be obtained; if the content of the tackifying resin exceeds 20 parts, there is a possibility that significant surface contamination may be brought about because of poor compatibility of the styrene block copolymer with the tackifying resin. Preferably, the tackifier resin is 10 to 20 parts.
The tackifying resin is one or more selected from petroleum resin, rosin resin and terpene phenolic resin.
In a preferred embodiment, the tackifying resin is selected from one or more of terpene phenolic resins such as UH115 of the Anyuan chemistry, S145 of the Anyuan chemistry, and the like. Since the terpene phenolic resin contains phenolic hydroxyl groups and has high polarity, the initial tackiness is excellent, but the presence of phenolic hydroxyl groups changes the compatibility of the tackifying resin with the styrene block copolymer, thereby causing surface contamination.
According to the invention, the maleic anhydride grafted styrene block copolymer is added, so that the compatibility of the styrene block copolymer and the terpene phenolic resin is improved, and the self-restorative prism sheet protective film with high initial adhesion is obtained. The maleic anhydride grafted styrene block copolymer is one or more selected from maleic anhydride grafted SEBS and maleic anhydride grafted SEPS.
In the invention, the grafting rate of the maleic anhydride in the maleic anhydride grafted styrene block copolymer is 0.5-2%. The maleic anhydride grafted styrene block copolymer with different grafting rates can improve the compatibility of the maleic anhydride grafted styrene block copolymer and the maleic anhydride grafted styrene block copolymer, and reduce the incidence rate of surface pollution. If the grafting ratio is less than 0.5%, the compatibility of the styrene block copolymer and the terpene phenolic resin cannot be effectively improved; if the grafting ratio is more than 2%, polymerization of the maleic anhydride-grafted styrene block copolymer is not facilitated.
In order to further improve the initial tackiness of the tacky resin composition and prevent the contamination thereof to a coating material, in a preferred embodiment of the present invention, the tacky resin composition further contains a phenoxy resin in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the styrene block copolymer, and if the phenoxy resin content is less than 0.5 parts by weight, no significant effect is exerted on the improvement of the initial tackiness; if the phenoxy resin content is more than 10 parts by weight, the adhesive resin composition becomes hard, and the improvement of the initial tackiness is also disadvantageous. Preferably, the phenoxy resin is 0.5 to 5 parts by weight.
The molecular weight of the phenoxy resin is 2 x 10 4 ~5*10 4 The phenoxy resin is used as a high-polarity macromolecular material and also contains hydroxyl or carboxyl, so that the polarity of the adhesive resin composition can be obviously improved, the overall viscosity is increased, and the interaction force with the prism sheet is enhanced.
The adhesive resin composition is prepared into adhesive layer master batch by a double-screw melting technology through an underwater pelletizing mode. The self-adhesive protective film is prepared by three layers of coextrusion of an adhesive layer, an intermediate layer and a surface layer.
The self-adhesive protective film has proper adhesive property even if the surface of the coated object is in a prism structure, the adhesive force between the self-adhesive protective film and the prism surface is more than or equal to 5g/25mm, and the self-adhesive protective film has no pollution to the prism sheet.
The advantageous effects of the present invention will be further described below with reference to examples and comparative examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The adhesive resin composition included 100 parts by weight of a styrene block copolymer H1221 (Asahi chemical), 5 parts by weight of a terpene phenol resin UH115 (Anyuan chemical), 5 parts by weight of a maleic anhydride grafted styrene block copolymer M1943 (Asahi chemical).
The adhesive resin composition is prepared into adhesive layer master batch by a double-screw melting technology through an underwater pelletizing mode. The self-adhesive protective film is prepared by three layers of coextrusion of an adhesive layer, a middle layer and a surface layer.
Example 2
The adhesive resin composition included 100 parts by weight of styrene block copolymer H1221 (rising chemical), 10 parts by weight of terpene phenolic resin UH115 (ampoul chemical), 10 parts by weight of maleic anhydride-grafted styrene block copolymer M1943 (rising chemical).
The adhesive resin composition is prepared into adhesive layer master batch by a double-screw melting technology through an underwater pelletizing mode. The self-adhesive protective film is prepared by three layers of coextrusion of an adhesive layer, a middle layer and a surface layer.
Example 3
The adhesive resin composition included 100 parts by weight of styrene block copolymer H1221 (rising chemical), 20 parts by weight of terpene phenolic resin UH115 (ampoul chemical), 15 parts by weight of maleic anhydride-grafted styrene block copolymer M1943 (rising chemical).
The adhesive resin composition is prepared into adhesive layer master batch by a double-screw melting technology through an underwater pelletizing mode. The self-adhesive protective film is prepared by three layers of coextrusion of an adhesive layer, a middle layer and a surface layer.
Example 4
The adhesive resin composition included 100 parts by weight of a styrene block copolymer H1221 (Asahi chemical), 20 parts by weight of a terpene phenolic resin S145 (Anyuan chemical), 15 parts by weight of a maleic anhydride-grafted styrene block copolymer M1911 (Asahi chemical).
The adhesive resin composition is prepared into adhesive layer master batch by a double-screw melting technology through an underwater pelletizing mode. The self-adhesive protective film is prepared by three layers of coextrusion of an adhesive layer, a middle layer and a surface layer.
Example 5
The adhesive resin composition included 100 parts by weight of a styrene block copolymer H1221 (Asahi chemical), 15 parts by weight of a terpene phenol resin UH115 (Anyuan chemical), 1 part by weight of a phenoxy resin PKHH (carbon company), 10 parts by weight of a maleic anhydride-grafted styrene block copolymer M1943 (Asahi chemical).
The adhesive resin composition is prepared into adhesive layer master batch by a double-screw melting technology through an underwater pelletizing mode. The self-adhesive protective film is prepared by three layers of coextrusion of an adhesive layer, a middle layer and a surface layer.
Example 6
The adhesive resin composition included 100 parts by weight of a styrene block copolymer H1221 (Asahi chemical), 15 parts by weight of a terpene phenol resin UH115 (Anyuan chemical), 5 parts by weight of a phenoxy resin PKHH (carbon company), and 15 parts by weight of a maleic anhydride-grafted styrene block copolymer M1943 (Asahi chemical).
The adhesive resin composition is prepared into adhesive layer master batch by a double-screw melting technology through an underwater pelletizing mode. The self-adhesive protective film is prepared by three layers of coextrusion of an adhesive layer, a middle layer and a surface layer.
Comparative example 1
The adhesive resin composition included 100 parts by weight of styrene block copolymer H1221 (asahi chemical), 3 parts by weight of terpene phenolic resin UH115 (angyuan chemical).
The adhesive resin composition is prepared into adhesive layer master batch by a double-screw melting technology through an underwater pelletizing mode. The self-adhesive protective film is prepared by three layers of coextrusion of an adhesive layer, a middle layer and a surface layer.
Comparative example 2
The adhesive resin composition included 100 parts by weight of styrene block copolymer H1221 (asahi chemical), 25 parts by weight of terpene phenolic resin UH115 (angyuan chemical).
The adhesive resin composition is prepared into adhesive layer master batch by a double-screw melting technology through an underwater pelletizing mode. The self-adhesive protective film is prepared by three layers of coextrusion of an adhesive layer, a middle layer and a surface layer.
The components and parts by weight of the adhesive resin composition in each example are shown in the following table.
H1221 UH115 S145 PKHH M1943 M1911
Example 1 100 5 5
Example 2 100 10 10
Example 3 100 20 15
Example 4 100 20 15
Example 5 100 15 1 10
Example 6 100 15 5 15
Comparative example 1 100 3
Comparative example 2 100 25
The prism sheets are respectively attached to different examples and comparative examples, initial adhesion is tested, normal temperature 5kg weight is placed for testing time-dependent adhesion, surface pollution of the prism structure is observed under the light after the prism structure is placed for 7 days at 50 ℃ 5kg weight, and test data are as follows:
from comparative examples 1 and 2, it was found that the addition amount of the terpene phenolic resin was small, it was difficult to satisfy the adhesive force requirement, and if the terpene phenolic resin was added in a sufficient amount, the protective film obtained could satisfy the adhesive force required for the prism structure, but the surface contamination was slightly inferior. By controlling the addition amount of the terpene phenolic resin and adding a small amount of phenoxy resin, the adhesive force of the protective film can be obviously improved, and the surface pollution performance is better.
It should be noted that the specific embodiments are merely illustrative of the technical solutions of the present invention, and should not be construed as limiting the technical solutions of the present invention, and any embodiments that use the essential inventive content of the present invention and only partially change the essential inventive content of the present invention should still fall within the protection scope of the present invention.

Claims (11)

1. The adhesive resin composition is characterized by comprising 5-20 parts by weight of a styrene block copolymer, 5-15 parts by weight of a tackifying resin, and 0.5-10 parts by weight of a phenoxy resin, based on 100 parts by weight of the styrene block copolymer.
2. The adhesive resin composition according to claim 1, wherein the styrene block copolymer is a copolymer of styrene and an olefin or a hydride thereof.
3. The adhesive resin composition according to claim 2, wherein the styrene block copolymer is one or more of a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer, a styrene-ethylene-propylene-styrene block copolymer, or a hydride thereof.
4. The adhesive resin composition according to claim 1, wherein the tackifying resin is one or more selected from the group consisting of petroleum resins, rosin resins, terpene phenolic resins.
5. The tackifying resin composition of claim 4 wherein the tackifying resin is selected from terpene phenolic resins.
6. The tackifying resin composition of claim 1 wherein the maleic anhydride grafted styrene block copolymer is selected from one or more of maleic anhydride grafted SEBS, maleic anhydride grafted SEPS.
7. The adhesive resin composition according to claim 1, wherein the grafting ratio of maleic anhydride in the maleic anhydride-grafted styrene block copolymer is 0.5% to 2%.
8. The adhesive resin composition according to claim 1, wherein the phenoxy resin is 0.5 to 5 parts by weight.
9. The adhesive resin composition according to claim 8, wherein the phenoxy resin has a molecular weight of 2 x 10 4 ~5*10 4
10. A self-adhesive protective film comprising an adhesive layer, an intermediate layer and a surface layer, characterized in that the material of the adhesive layer comprises the adhesive resin composition according to any one of claims 1 to 9.
11. The self-adhesive protective film according to claim 10, wherein the self-adhesive protective film is attached to the prism face, and the adhesive force between the self-adhesive protective film and the prism face is more than or equal to 5g/25mm.
CN202111293886.XA 2021-11-03 2021-11-03 Adhesive resin composition and self-adhesive protective film Active CN114634778B (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1977017A (en) * 2004-06-29 2007-06-06 东赛璐株式会社 Laminated film using adhesive composition therein and its application, and the adhesive composition
CN101313044A (en) * 2005-10-24 2008-11-26 克莱顿聚合物研究有限公司 Protective films and pressure sensitive adhesives
CN102277112A (en) * 2011-05-23 2011-12-14 波士胶芬得利(中国)粘合剂有限公司 Wax-containing hot melt adhesive and disposable absorbent product
CN102775944A (en) * 2011-01-30 2012-11-14 苏州尚善新材料科技有限公司 Sealing joint strip and application method thereof
CN108165205A (en) * 2016-12-08 2018-06-15 北京橡胶工业研究设计院有限公司 A kind of hot-melt adhesive composition and its application method
CN109266228A (en) * 2018-08-20 2019-01-25 河北省同创交通工程配套产品产业技术研究院 Superpower chemistry reactive polymer self-adhering rubber waterstop and preparation method thereof
CN111662662A (en) * 2020-07-23 2020-09-15 佛山南宝高盛高新材料有限公司 Antistatic hot melt adhesive and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1977017A (en) * 2004-06-29 2007-06-06 东赛璐株式会社 Laminated film using adhesive composition therein and its application, and the adhesive composition
CN101313044A (en) * 2005-10-24 2008-11-26 克莱顿聚合物研究有限公司 Protective films and pressure sensitive adhesives
CN102775944A (en) * 2011-01-30 2012-11-14 苏州尚善新材料科技有限公司 Sealing joint strip and application method thereof
CN102277112A (en) * 2011-05-23 2011-12-14 波士胶芬得利(中国)粘合剂有限公司 Wax-containing hot melt adhesive and disposable absorbent product
CN108165205A (en) * 2016-12-08 2018-06-15 北京橡胶工业研究设计院有限公司 A kind of hot-melt adhesive composition and its application method
CN109266228A (en) * 2018-08-20 2019-01-25 河北省同创交通工程配套产品产业技术研究院 Superpower chemistry reactive polymer self-adhering rubber waterstop and preparation method thereof
CN111662662A (en) * 2020-07-23 2020-09-15 佛山南宝高盛高新材料有限公司 Antistatic hot melt adhesive and preparation method thereof

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