CN114634778A - Adhesive resin composition and self-adhesive protective film - Google Patents
Adhesive resin composition and self-adhesive protective film Download PDFInfo
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- CN114634778A CN114634778A CN202111293886.XA CN202111293886A CN114634778A CN 114634778 A CN114634778 A CN 114634778A CN 202111293886 A CN202111293886 A CN 202111293886A CN 114634778 A CN114634778 A CN 114634778A
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- block copolymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives 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
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Adhesives Or Adhesive Processes (AREA)
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 tackifying resin and 5-15 parts by weight of maleic anhydride grafted styrene block copolymer in terms of 100 parts by weight of styrene block copolymer. The adhesive resin composition improves the compatibility of the styrene block copolymer and tackifying resin by introducing the maleic acid over-grafted styrene block copolymer, thereby obtaining the self-recoverable prism sheet protective film with high initial adhesion and reducing surface pollution.
Description
Technical Field
The present invention relates to the field of protective films, and particularly to an adhesive resin composition and a self-adhesive protective film.
Background
The prism sheet having high self-recovery properties is likely to float after the protective film having low initial adhesion is attached. In addition, in order to peel off the prism sheet from the mold, the prism sheet is usually transferred to a stripper, which causes the prism sheet to have a large surface tension and to be difficult to adhere.
CN 103620450 a proposes to improve the adhesion of the protective film by adding a terpene phenol resin with a non-phenol content. It is not mentioned that excessive addition of terpene-phenolic resin causes surface contamination of the prism sheet. The prism sheet protective film disclosed in CN 102292655 a reduces unwinding, fails to significantly improve initial adhesion, and is not easy to adhere to a self-recoverable prism sheet. The invention disclosed in CN 104837946 a is a PET substrate protective film prepared by coating, which details the influence of the addition of terpene phenolic resin on paste residue and surface contamination. The protective film for prism sheets proposed in CN 106459684 a mainly solves the problem of edge peeling, and fails to effectively improve initial adhesion.
Therefore, there is a need for 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 a prism sheet attached with the self-adhesive protective film and reduce the pollution of the protective film to the prism sheet.
In order to achieve the purpose, the invention adopts the following technical scheme:
the viscous resin composition comprises a styrene block copolymer, 5-20 parts by weight of tackifying resin and 5-15 parts by weight of maleic anhydride grafted styrene block copolymer in terms of 100 parts by weight of styrene block copolymer.
Further, the styrene block copolymer is a copolymer of styrene and olefin or a hydrogenated product 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 hydrogenated product thereof.
Further, the tackifying resin is selected from one or more of petroleum resin, rosin resin and terpene phenolic resin, and 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%.
The styrene block copolymer further comprises 0.5-10 parts by weight of phenoxy resin, preferably 0.5-5 parts by weight of phenoxy resin, based on 100 parts by weight of the styrene block copolymer.
Further, the molecular weight of the phenoxy resin is 2 x 104～5*104。
The invention also provides a self-adhesive protective film which comprises an adhesive layer, an intermediate layer and a surface layer, wherein the material of the adhesive layer comprises the adhesive resin composition.
Furthermore, the self-adhesive protective film is attached to the surface of the prism, and the adhesive force between the self-adhesive protective film and the surface of the prism is more than or equal to 5g/25 mm.
The adhesive resin composition improves the compatibility of the styrene block copolymer and tackifying resin by introducing the maleic acid over-grafted styrene block copolymer, thereby obtaining the self-recoverable prism sheet protective film with high initial adhesion and reducing surface pollution.
Meanwhile, the polarity and viscosity of the adhesive resin composition are improved by adding the phenoxy resin with macromolecules and high polarity, the interaction force with the prism sheet is enhanced, and the risk of precipitation is avoided.
Detailed Description
The present invention will be described in detail below with reference to embodiments. These embodiments are not intended to limit the present invention, and structural, methodological, or functional changes in accordance with the embodiments are within the scope of the present invention.
As described in the prior art, the conventional protective film has a low initial adhesion to the prism sheet, and the protective film easily contaminates the prism sheet. The present inventors have made studies to solve the above problems and have proposed a tackifier resin composition comprising 5 to 20 parts by weight of a tackifier resin and 5 to 15 parts by weight of a maleic anhydride-grafted styrene block copolymer, based on 100 parts by weight of a styrene block copolymer. When the adhesive resin composition with the proportion is used for the self-adhesive protective film, the adhesive resin composition has strong adhesive force to a coated object, particularly a prism sheet, and the adhesive force is more than or equal to 5g/25 mm. Meanwhile, the viscous resin composition is not easy to precipitate, and cannot cause pollution on the surface of coated objects such as a prism sheet and the like.
In the present invention, the styrene block copolymer is a copolymer of styrene and an olefin or a hydrogenated product 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 hydrogenated product thereof.
In a preferred embodiment, the styrene block copolymer of the present invention is selected from one or more of a hydrogenated product of styrene-butadiene-styrene block copolymer (SEBS) or a hydrogenated product of styrene-isoprene-styrene block copolymer (SEPS).
For the self-recoverable prism sheet, the protective film made of the styrene block copolymer does not meet the bonding condition, and a sufficient amount of tackifying resin needs to be added. In the present invention, the tackifier resin is 5 to 20 parts by weight based on 100 parts by weight of the styrene block copolymer, and if the tackifier resin is less than 5 parts by weight, the tackifier resin does not contribute to the change of the adhesive force of the adhesive layer even when compounded, and the desired adhesive force cannot be obtained; if the tackifier resin content exceeds 20 parts, significant surface contamination may occur due to poor compatibility of the styrene block copolymer with the tackifier resin. Preferably, the tackifier resin is 10 to 20 parts.
The tackifying resin is selected from one or more of 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 in amp chemistry, S145 in amp chemistry, and the like. The terpene-phenolic resin has a phenolic hydroxyl group and has high polarity, so that the initial tack performance is excellent, but the existence of the phenolic hydroxyl group changes the compatibility of the tackifying resin and the styrene block copolymer, thereby causing surface pollution.
The compatibility of the styrene block copolymer and terpene phenolic resin is improved by adding the maleic anhydride grafted styrene block copolymer, so that the self-recoverable prism sheet protective film with high initial adhesion is obtained. The maleic anhydride grafted styrene block copolymer is selected from one or more of 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 ratios can improve the compatibility of the maleic anhydride grafted styrene block copolymer and reduce the occurrence rate of surface pollution. If the grafting rate is less than 0.5%, the compatibility of the styrene block copolymer and the terpene phenolic resin cannot be effectively improved; if the graft ratio is more than 2%, the polymerization of the maleic anhydride-grafted styrene block copolymer is not favored.
In order to further improve the initial adhesion of the adhesive resin composition and prevent the coating from being polluted, in a preferred embodiment of the invention, the adhesive resin composition further comprises a phenoxy resin, wherein the phenoxy resin accounts for 0.5-10 parts by weight based on 100 parts by weight of the styrene block copolymer, and if the content of the phenoxy resin is less than 0.5 part by weight, the phenoxy resin has no obvious effect on improving the initial adhesion; if the phenoxy resin content is more than 10 parts by weight, the adhesive resin composition becomes hard, and the initial tack is also disadvantageously improved. Preferably, the phenoxy resin is 0.5 to 5 parts by weight.
The molecular weight of the phenoxy resin is 2 x 104～5*104The 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 layer master batch is prepared from the adhesive resin composition by a twin-screw melting technology in an underwater grain cutting mode. The self-adhesive protective film is prepared by three layers of adhesive layers, an intermediate layer and a surface layer through co-extrusion.
The self-adhesive protective film has proper adhesive property even if the surface of a coated object with a prism structure is provided, 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 is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
The adhesive resin composition comprises 100 parts by weight of a styrene block copolymer H1221 (Asahi chemical composition), 5 parts by weight of a terpene phenolic resin UH115 (Anyuan chemical composition), and 5 parts by weight of a maleic anhydride-grafted styrene block copolymer M1943 (Asahi chemical composition).
The adhesive layer master batch is prepared from the adhesive resin composition by a twin-screw melting technology in an underwater grain cutting mode. The self-adhesion protective film is prepared by three layers of adhesive layer, middle layer and surface layer through co-extrusion.
Example 2
The adhesive resin composition comprises 100 parts by weight of a styrene block copolymer H1221 (Asahi chemical composition), 10 parts by weight of a terpene phenolic resin UH115 (Ancheng chemical), 10 parts by weight of a maleic anhydride-grafted styrene block copolymer M1943 (Asahi chemical composition).
The adhesive layer master batch is prepared from the adhesive resin composition by a twin-screw melting technology in an underwater grain cutting mode. The self-adhesion protective film is prepared by three layers of adhesive layers, a middle layer and a surface layer through co-extrusion.
Example 3
The adhesive resin composition comprises 100 parts by weight of a styrene block copolymer H1221 (Asahi chemical composition), 20 parts by weight of a terpene phenolic resin UH115 (Ancheng chemical), and 15 parts by weight of a maleic anhydride-grafted styrene block copolymer M1943 (Asahi chemical composition).
The adhesive layer master batch is prepared from the adhesive resin composition by a twin-screw melting technology in an underwater grain cutting mode. The self-adhesion protective film is prepared by three layers of adhesive layer, middle layer and surface layer through co-extrusion.
Example 4
The adhesive resin composition comprises 100 parts by weight of a styrene block copolymer H1221 (Asahi chemical composition), 20 parts by weight of a terpene-phenolic resin S145 (Ancheng chemical), and 15 parts by weight of a maleic anhydride-grafted styrene block copolymer M1911 (Asahi chemical composition).
The adhesive layer master batch is prepared from the adhesive resin composition by a twin-screw melting technology in an underwater grain cutting mode. The self-adhesion protective film is prepared by three layers of adhesive layer, middle layer and surface layer through co-extrusion.
Example 5
The adhesive resin composition comprises 100 parts by weight of a styrene block copolymer H1221 (asahi chemical), 15 parts by weight of a terpene phenolic resin UH115 (anyuan chemical), 1 part by weight of a phenoxy resin PKHH (allied carbon), 10 parts by weight of a maleic anhydride-grafted styrene block copolymer M1943 (asahi chemical).
The adhesive resin composition is prepared into the bonding layer master batch by a double-screw melting technology in an underwater grain cutting mode. The self-adhesion protective film is prepared by three layers of adhesive layer, middle layer and surface layer through co-extrusion.
Example 6
The adhesive resin composition comprises 100 parts by weight of a styrene block copolymer H1221 (asahi chemical), 15 parts by weight of a terpene phenolic resin UH115 (anyuan chemical), 5 parts by weight of a phenoxy resin PKHH (allied carbon), and 15 parts by weight of a maleic anhydride-grafted styrene block copolymer M1943 (asahi chemical).
The adhesive layer master batch is prepared from the adhesive resin composition by a twin-screw melting technology in an underwater grain cutting mode. The self-adhesion protective film is prepared by three layers of adhesive layer, middle layer and surface layer through co-extrusion.
Comparative example 1
The tackifying resin composition comprises 100 parts by weight of a styrene block copolymer H1221 (asahi chemical), 3 parts by weight of a terpene phenolic resin UH115 (angen chemical).
The adhesive layer master batch is prepared from the adhesive resin composition by a twin-screw melting technology in an underwater grain cutting mode. The self-adhesion protective film is prepared by three layers of adhesive layer, middle layer and surface layer through co-extrusion.
Comparative example 2
The tackifying resin composition comprises 100 parts by weight of a styrene block copolymer H1221 (asahi chemical), 25 parts by weight of a terpene phenolic resin UH115 (angen chemical).
The adhesive layer master batch is prepared from the adhesive resin composition by a twin-screw melting technology in an underwater grain cutting mode. The self-adhesion protective film is prepared by three layers of adhesive layer, middle layer and surface layer through co-extrusion.
The components and parts by weight of the adhesive resin compositions in the examples 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 |
Different examples and comparative examples are respectively attached with the prism sheet, the initial adhesive force is tested, the adhesive force is tested after the test of placing under 5kg weight at normal temperature for time, the surface pollution of the prism structure is observed under the light after the placing under 5kg weight at 50 ℃ for 7 days, and the test data is as follows:
it is found from comparative examples 1 and 2 that the adhesion requirement is difficult to satisfy when the terpene-phenolic resin is added in a small amount, and that the adhesion required for the prism structure can be satisfied when a protective film prepared by adding a sufficient amount of terpene-phenolic resin is added, but the surface contamination is 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 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 modifications that adopt the spirit of the present invention and are only partially changed should still fall within the scope of the present invention.
Claims (10)
1. The adhesive resin composition is characterized by comprising 5-20 parts by weight of tackifying resin and 5-15 parts by weight of maleic anhydride grafted styrene block copolymer based on 100 parts by weight of 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 hydrogenated product 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 hydrogenated product thereof.
4. The adhesive resin composition according to claim 1, wherein the tackifying resin is selected from one or more of petroleum resins, rosin resins, terpene phenolic resins, preferably from terpene phenolic resins.
5. The adhesive resin composition according to claim 1, wherein the maleic anhydride grafted styrene block copolymer is selected from one or more of maleic anhydride grafted SEBS and maleic anhydride grafted SEPS.
6. The adhesive resin composition according to claim 1, wherein the maleic anhydride-grafted styrene block copolymer has a grafting ratio of maleic anhydride of 0.5 to 2%.
7. The adhesive resin composition according to claim 1, further comprising a phenoxy resin 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.
8. The adhesive resin composition according to claim 7, wherein the phenoxy resin has a molecular weight of 2 x 104～5*104。
9. A self-adhesive protective film comprising an adhesive layer, an intermediate layer and a surface layer, wherein the material of the adhesive layer comprises the adhesive resin composition according to any one of claims 1 to 8.
10. The self-adhesive protective film according to claim 9, wherein the self-adhesive protective film is attached to the surface of the prism, and the adhesive force between the self-adhesive protective film and the surface of the prism is not less than 5g/25 mm.
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| CN202111293886.XA CN114634778B (en) | 2021-11-03 | 2021-11-03 | Adhesive resin composition and self-adhesive protective film |
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| CN202111293886.XA CN114634778B (en) | 2021-11-03 | 2021-11-03 | Adhesive resin composition and self-adhesive protective film |
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| CN114634778B CN114634778B (en) | 2023-09-22 |
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| 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 |
-
2021
- 2021-11-03 CN CN202111293886.XA patent/CN114634778B/en active Active
Patent Citations (7)
| 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 |
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