CN114350289B - Adhesive, composition and application thereof - Google Patents
Adhesive, composition and application thereof Download PDFInfo
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- CN114350289B CN114350289B CN202111603011.5A CN202111603011A CN114350289B CN 114350289 B CN114350289 B CN 114350289B CN 202111603011 A CN202111603011 A CN 202111603011A CN 114350289 B CN114350289 B CN 114350289B
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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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
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- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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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
- C09J2453/00—Presence of 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The application relates to the field of adhesives, in particular to an adhesive composition, an adhesive containing or obtained from the composition and application of the adhesive. The adhesive composition includes an a-component and a B-component; wherein the A component comprises one or more triblock copolymers with an X-Y-X structure, wherein the X block is a styrene segment and the Y block is an isoprene segment; the component B comprises one or more resin compounds with softening points of 80-150 ℃. The adhesive prepared by the adhesive composition has excellent cohesiveness and excellent rebound resistance under high-temperature and high-humidity conditions, can effectively absorb continuous stress brought by a bending state of a substrate structural member when being used for bonding curved surfaces, and has wide application prospect, for example, can be used for bonding the lasting curved surfaces of a scroll screen display assembly.
Description
Technical Field
The application relates to the field of adhesives, in particular to an adhesive composition, an adhesive containing or obtained from the composition and application of the adhesive.
Background
In recent years, displays of electronic devices have exhibited concepts and trends of large size, curved (curved) surface, etc., and this type of electronic device has received strong reflection from the consumer market and has been widely expected, for example, as a scroll display. The scroll display can realize contraction, curling, expansion and the like of the display assembly by using the scroll device in the assembly, so that a larger display size is obtained, and meanwhile, the edge part of the display module also has a certain curved surface radian. The bonding inside the curved display module requires bonding of the adhesive sheet.
However, the bonding sheets between CPI and substrate structural components currently developed for use in OLED screens are designed for planar bonding and these sheets perform poorly when used for curved surface bonding; the adhesive sheets with few special functions which are studied at present can only realize short-term curved surface adhesion at normal temperature, and cannot be used in scroll display components which need lasting curved surface adhesion. The rebound resistance is an important property affecting the durability of the curved surface bonding, and the existing adhesive sheet is not ideal in rebound resistance and is not enough to meet the higher and higher requirements of curved surface display components.
It is therefore very important to develop an adhesive with good anti-rebound properties and maintaining good adhesion properties.
Disclosure of Invention
The present application aims to overcome the above problems of the prior art and to provide an adhesive composition, an adhesive containing or obtainable from the composition and the use of the adhesive. The adhesive prepared by the adhesive composition has good cohesiveness and rebound resistance, can effectively absorb continuous stress brought by a bending state of a substrate structural member when being used for bonding curved surfaces, has wide application prospect, and can be used for bonding the lasting curved surfaces of a scroll screen display assembly.
In order to achieve the above object, the first aspect of the present application provides an adhesive composition comprising an a-component and a B-component; wherein the A component comprises one or more triblock copolymers with an X-Y-X structure, wherein the X block is a styrene segment and the Y block is an isoprene segment; the component B comprises one or more resin compounds with softening points of 80-150 ℃.
The inventors of the present application found that in order to achieve a longer-lasting curved surface state, it is generally required that the adhesive sheet has a relatively high storage modulus, however, in order to increase the storage modulus, the adhesion of the adhesive sheet is often lowered to cause adhesion failure instead, so that finding a better balance between the storage modulus and the adhesion is a key to achieving a better curved surface adhesive property.
The inventors of the present application have found that the combination of a specific triblock copolymer with a specific resin can provide the resulting adhesive with both excellent adhesion and anti-rebound properties. The application can realize better effect compared with the prior art by matching the component A with the component B. The composition may further be subjected to one or more of the following preferred embodiments in order to obtain a better combination of adhesion and rebound resistance.
According to one embodiment, the triblock copolymer is a styrene segment (S) -isoprene segment (I) -styrene segment (S) triblock copolymer, abbreviated herein as SIS.
In the present application, the X block and the Y block may be a single structural unit or may be a polymerized structural unit composed of a plurality of structural units, for example, the X block may be a styrene segment or a polystyrene segment composed of a plurality of styrenes.
The weight ratio of the X block to Y block in the triblock copolymer is referred to herein as the "block ratio X/Y".
The block ratio of the triblock copolymer may be selected in a wide range, and the inventors of the present application found that, in order to exert a good synergistic effect in the specific combination of the present application, it is preferable that the block ratio X/Y of the triblock copolymer is (10-35)/(90-65), more preferably (15-30)/(85-70).
In the present application, the range of the block ratio X/Y is represented as (X1-X2)/(Y1-Y2), and the expression will be described as follows: the values of the x content and the y content are not independent values, but are interrelated, and the sum of the x content and the y content is 100%; for example, when the x content is x1, the y content can be taken as y1 added thereto to be 100.
In order to further improve the overall properties of the resulting adhesive, the triblock copolymer preferably has a weight average molecular weight of 10 to 30 Da, more preferably 15 to 25 Da.
Preferably, the triblock copolymer has a tensile strength of 10 to 35MPa, more preferably 15 to 25MPa.
Preferably, the triblock copolymer has a hardness of 20 to 65 Shore A, more preferably 30 to 60 Shore A.
The triblock copolymer, such as SIS, can be star-shaped or linear, and can be used for achieving better effect in the application. Further preferably, the triblock copolymer is a linear structure SIS.
The triblock copolymer may contain therein a diblock copolymer having an X-Y structure due to the influence of the preparation process. When a diblock copolymer is contained, each physical and chemical parameter in the triblock copolymer, for example, the block ratio X/Y, is detected by integrating the diblock copolymer and the triblock copolymer contained therein.
In the present application, the triblock copolymer may optionally contain the diblock copolymer, and may or may not contain the diblock copolymer.
In a preferred embodiment, the combination a comprises at least one triblock copolymer comprising a diblock copolymer. The inventors of the present application have found that when a triblock copolymer containing an appropriate amount of a diblock copolymer is used, the adhesive properties and anti-rebound properties of the resulting adhesive can be specifically improved; in a preferred embodiment, by controlling the content of the diblock copolymer, an adhesive having more excellent adhesive properties and anti-rebound properties can be obtained.
Preferably, the diblock copolymer is present in the triblock copolymer in an amount of 10 to 30 weight percent.
Preferably, the a component comprises at least one class a triblock copolymer having a block ratio X/Y of (15-25): (85-75), the content of the diblock copolymer being 15-20% by weight.
According to a first embodiment, the a-component consists of one or more class a triblock copolymers.
According to a second embodiment, the A component comprises a triblock copolymer of type a and a triblock copolymer of type b, the block ratio X/Y of the triblock copolymer of type b being (28-35)/(72-65) and the content of diblock copolymer being 10-25%; the weight ratio of the a-type triblock copolymer to the b-type triblock copolymer is (65-98): (35-2); more preferably (85-95): (15-5).
In some embodiments, the a component may also include triblock copolymers according to the present application other than the class a and class b triblock copolymers, and other triblock copolymers that do not conform to the classes a and b may be referred to as class c triblock copolymers for ease of description. The content of the c-type triblock copolymer in the component A is preferably 10% by weight or less.
In this document, when the range defining means is expressed as a ratio between two ranges, both means that there is a relationship of "addition to 100" between two factors, that is, the two ranges before and after are not independent values, but are required to satisfy "addition=100".
The adhesive composition of the application also comprises a B component which is a resin compound, and the proportion of the A component and the B component can be selected in a large range.
Preferably, the content of the B component is 10 to 50 parts by weight, more preferably 15 to 40 parts by weight, still more preferably 20 to 30 parts by weight, relative to 100 parts by weight of the a component.
Preferably, the softening point of the resin compound is 100 to 150 ℃.
The resin compound may be selected from various types of resin compounds on the premise of satisfying the aforementioned softening point.
The inventors of the present application found that, in order to achieve a better synergistic effect, preferably, the resin compound is selected from one or more of rosin resins, terpene phenol resins, and petroleum resins.
According to a preferred embodiment, the resin compound is a terpene resin and/or a terpene phenol resin.
According to a preferred embodiment, the resin compound comprises a first resin compound having a softening point of 80 to 120 ℃ and a second resin compound having a softening point of 120 to 150 ℃ in a weight ratio (0.2 to 2): 1, and the difference between the softening points of the first resin compound and the second resin compound is greater than 20 ℃, preferably 20-40 ℃. The inventors of the present application have found that the adhesive properties and the anti-rebound properties of the resulting adhesive can be further improved by specifying a combination of different softening points.
Wherein the first resin compound and the second resin compound are each independently selected from one or more of rosin resin, terpene phenol resin, and petroleum resin, more preferably terpene resin and/or terpene phenol resin.
According to a preferred embodiment, the first resin compound is a terpene resin and the second resin compound is a terpene phenol resin.
Various additives conventional in the art, such as one or more selected from antioxidants, curing agents, fillers and viscosity modifiers, may also be included in the adhesive composition.
In one example, an antioxidant is further included in the adhesive composition in an amount of 0.5 to 2.5 parts by weight, preferably 1 to 1.5 parts by weight, relative to 100 parts by weight of the a-component. The antioxidant is preferably selected from one or more of hindered phenol antioxidants and phosphite antioxidants, preferably the hindered phenol antioxidants and the phosphite antioxidants in a weight ratio of (1.5-2.5): 1.
In one example, the adhesive composition further includes a curing agent in an amount of 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the a-component. The curing agent is preferably an isocyanate-based curing agent.
In the present application, the parts by weight refer to dry weight.
According to one mode of application, the composition is prepared by hot-melt or the like without the addition of an organic solvent when used to prepare the adhesive.
According to another mode of application, the composition requires the addition of an additional organic solvent when used to prepare the adhesive, in which case the adhesive composition may also include an organic solvent. The organic solvent is selected from, for example, one or more of ethyl acetate, toluene, n-heptane, cyclohexane and tetrahydrofuran. According to a preferred embodiment, the organic solvent is toluene and n-heptane in a volume ratio of 1: (0.5-1.5) mixing the obtained mixed solvent.
The first aspect of the application claims a composition wherein the individual components may be stored individually or in a mixture of several or all components, selected and adapted for storage, transportation, marketing, production, etc. It will be appreciated that the composition may be free of the organic solvent for ease of storage, transportation, and sale, and that the purchaser may add the organic solvent during the manufacturing process.
And it is understood that although the foregoing has been given the proportions of the components in the composition, these proportions are all carried out for the purpose of directly producing the adhesive, in other words, these proportions can be regarded as the proportions of the components contained in the adhesive or the proportions added during the preparation of the adhesive. In contrast, since the purchaser can purchase the composition according to the lack of the raw materials, the composition does not need to strictly follow the above-described ratio, and therefore the above-described ratio does not necessarily limit the composition.
In a second aspect, the present application provides an adhesive comprising the adhesive composition of the first aspect of the present application or prepared from the adhesive composition.
The adhesive may be obtained from the adhesive composition according to the first aspect of the application by simple mixing or may be prepared by a preparation process. The content or amount of each component in the adhesive composition is as defined in the first aspect of the present application, and will not be described here.
The adhesive obtained by the composition has excellent adhesive property and excellent rebound resistance.
The adhesive according to the second aspect of the application may be prepared by conventional methods. Preferably, the preparation method comprises the following steps: heating the mixture containing the adhesive composition according to the first aspect at a temperature of 50-150 ℃ for 1-10min.
Preferably, the temperature of the heating treatment is 70-120 ℃ and the time is 2-5min.
According to a preferred embodiment, the heating treatment comprises a first stage and a second stage carried out sequentially; the temperature of the first stage is 70-80 ℃ and the time is 2-4min; the temperature of the second stage is 100-120 ℃ and the time is 1-3min.
Preferably, the method further comprises a stabilization treatment stage performed after the heating treatment, the conditions of the stabilization treatment comprising: and standing the heated material at 15-30deg.C and 30-70% RH for 1-5 days.
Thus, an adhesive having excellent adhesive properties and anti-rebound properties can be prepared, and the resulting adhesive has the same properties as the adhesive according to the second aspect of the present application, and will not be described in detail herein.
A third aspect of the present application provides the use of one or more of the adhesive composition of the first aspect and/or the adhesive of the second aspect in curved surface bonding.
The adhesive of the present application can exhibit excellent anti-rebound performance and can exhibit durable adhesive force when used for curved surface adhesion.
By means of the technical scheme, the composition obtained by the composition has at least the following advantages compared with the prior art:
(1) The adhesive has excellent bonding performance;
(2) The adhesive has excellent rebound resistance, and is particularly suitable for bonding curved surfaces;
(3) The adhesive can effectively absorb continuous stress brought by the bending state of the substrate structural member, and realizes durable curved surface bonding;
(4) The adhesive can resist high-temperature and high-humidity environments;
(5) The adhesive of the application has wide application prospect, for example, can be used for bonding scroll screen display components.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Detailed Description
The present application will be described in detail by examples. The described embodiments of the application are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The following examples illustrate the preparation process and application of the adhesive by way of example of an adhesive sheet, and it should be noted that the adhesive of the present application can be used in various application modes not limited to an adhesive sheet, which does not limit the present application.
In the following examples, 1 part by weight means 1g.
Example 1
(1) Preparation of the composition
And (3) a component A: 100 parts by weight of a triblock copolymer a1 (block ratio: 22/78, diblock content: 15%, tensile strength: 20MPa, hardness: 45 Shore A, linear structure), 10 parts by weight of a triblock copolymer a2 (block ratio: 15/85, diblock content: 19%, tensile strength: 21MPa, hardness: 32 Shore A, linear structure);
and the component B comprises the following components: 25 parts by weight in total, comprising 15 parts by weight of a terpene phenol resin (softening point about 150 ℃ C.) and 10 parts by weight of a terpene resin (softening point about 120 ℃ C.);
an antioxidant: 1.5 parts by weight of a total comprising 1 part by weight of an antioxidant HPA (hindered phenols) and 0.5 part by weight of a second antioxidant PPA (phosphites);
curing agent: 1 part by weight of an isocyanate curing agent ICA;
organic solvent: toluene and n-heptane in a volume ratio of 1: 1.
(2) Preparation of the adhesive
Mixing the prepared composition, stirring to dissolve each component in organic solvent to obtain adhesive glue solution;
coating the adhesive glue solution on the stripping surface of the heavy stripping force stripping sheet by using a scraper coater, firstly heating the coating layer at 70 ℃ for 3 minutes, and then heating the coating layer at 110 ℃ for 2 minutes to form a coating layer A;
coating the stripping surface of the stripping sheet with light stripping force, and repeating the two-stage heating treatment process to obtain a coating layer B;
the coating layer a and the coating layer B were respectively stuck on both sides of the PET substrate, thereby producing an adhesive sheet having a composite layer structure of a heavy peel force release sheet-adhesive layer (50 μm) -PET substrate (12 μm) -adhesive layer (50 μm) -light peel force release sheet.
Example 2
(1) Preparation of the composition
And (3) a component A: 100 parts by weight in total, comprising 100 parts by weight of triblock copolymer a1 (same as in example 1);
and the component B comprises the following components: 20 parts by weight in total, comprising 12 parts by weight of a terpene phenol resin (softening point about 140 ℃) and 8 parts by weight of a terpene resin (softening point about 110 ℃);
an antioxidant: 1 part by weight of the total composition comprises 0.7 part by weight of antioxidant HPA (hindered phenols) and 0.3 part by weight of second antioxidant PPA (phosphites);
curing agent: 1 part by weight of an isocyanate curing agent ICA;
organic solvent: toluene and n-heptane in a volume ratio of 1: 1.
(2) Preparation of the adhesive
Mixing the prepared composition, stirring to dissolve each component in organic solvent to obtain adhesive glue solution;
coating the adhesive glue solution on the stripping surface of the heavy stripping force stripping sheet by using a scraper coater, firstly heating the coating layer at 70 ℃ for 3 minutes, and then heating the coating layer at 110 ℃ for 2 minutes to form a coating layer A;
coating the stripping surface of the stripping sheet with light stripping force, and repeating the two-stage heating treatment process to obtain a coating layer B;
the coating layer a and the coating layer B were respectively stuck on both sides of the PET substrate, thereby producing an adhesive sheet having a composite layer structure of a heavy peel force release sheet-adhesive layer (50 μm) -PET substrate (12 μm) -adhesive layer (50 μm) -light peel force release sheet.
Example 3
(1) Preparation of the composition
And (3) a component A: 100 parts by weight of the total composition comprising 95 parts by weight of triblock copolymer a1 (same as in example 1) and 5 parts by weight of triblock copolymer a2 (same as in example 1);
and the component B comprises the following components: 25 parts by weight in total, comprising 10 parts by weight of a first terpene resin (softening point about 160 ℃) and 15 parts by weight of a second terpene resin (softening point about 120 ℃);
an antioxidant: 1.5 parts by weight of a total comprising 1 part by weight of an antioxidant HPA (hindered phenols) and 0.5 part by weight of a second antioxidant PPA (phosphites);
curing agent: 1 part by weight of an isocyanate curing agent ICA;
organic solvent: toluene and n-heptane in a volume ratio of 1: 1.
(2) Preparation of the adhesive
Mixing the prepared composition, stirring to dissolve each component in organic solvent to obtain adhesive glue solution;
coating the adhesive glue solution on the stripping surface of the heavy stripping force stripping sheet by using a scraper coater, firstly heating the coating layer at 70 ℃ for 3 minutes, and then heating the coating layer at 110 ℃ for 2 minutes to form a coating layer A;
coating the stripping surface of the stripping sheet with light stripping force, and repeating the two-stage heating treatment process to obtain a coating layer B;
the coating layer a and the coating layer B were respectively stuck on both sides of the PET substrate, thereby producing an adhesive sheet having a composite layer structure of a heavy peel force release sheet-adhesive layer (50 μm) -PET substrate (12 μm) -adhesive layer (50 μm) -light peel force release sheet.
Example 4 group
This set of examples is intended to illustrate the effect of varying the mode of combination of triblock copolymers in the A-component.
This set of examples is carried out with reference to example 1, except that the proportions in the A-component (keeping the total amount at 100 parts by weight) and/or the choice of the specific materials are varied, respectively; specifically:
example 4a, component A was changed to 50 parts by weight of triblock copolymer a2 and 50 parts by weight of triblock copolymer b1 (block ratio 30/70, diblock content 17%, tensile strength 21MPa, hardness 59 Shore A, linear structure);
example 4b, component A was changed to 100 parts by weight of triblock copolymer b1;
example 4c: changing the component A into 100 parts by weight of triblock copolymer c1 (with a block ratio of 15/85, a diblock content of 59%, a tensile strength of 4MPa, a hardness of 23 Shore A, a linear structure);
example 4d: changing the A component into 80 parts by weight of a triblock copolymer c1 and 20 parts by weight of a triblock copolymer b1;
finally, the adhesive sheets were obtained, respectively.
Example 5 group
This set of examples is intended to illustrate the effect of varying the amount of resin in the B component, the manner of combination and the properties.
This set of examples was carried out as in example 1, except that the amount of the B component and/or the choice of the particular material was varied separately; specifically:
example 5a, changing the total weight of the component B to 10 parts by weight, and keeping the specific materials and the internal proportions unchanged;
example 5B, changing the total weight of component B to 45 parts by weight, and keeping the specific materials and internal proportions unchanged;
example 5c, a single component B component is used, specifically the B component is all the terpene resin used in example 1;
example 5d, replacing a first terpene resin with the same weight of rosin resin having a softening point of about 150 ℃, and replacing a second terpene resin with the same weight of petroleum resin having a softening point of about 120 ℃;
finally, the adhesive sheets were obtained, respectively.
Comparative example 1
Reference is made to example 1 except that no B component is added.
Finally, an adhesive sheet was obtained.
Comparative example 2
Reference was made to example 1, except that the A component was 100 parts by weight of a styrene-butadiene-styrene (SBS, block ratio 28/72, diblock content 16% by weight) triblock copolymer.
Finally, an adhesive sheet was obtained.
Comparative example 3
Commercially available adhesive sheets of the acrylic glue type having a higher adhesive rank are available.
Test case
The adhesive sheets obtained in examples and comparative examples were each subjected to the following test:
(1) Determination of anti-rebound of 85 ℃/85% RH (D85) curved-surface steel sheet
The test case is an acceleration test under severe conditions, and can reflect the actual use condition to a certain extent; it is generally believed that maintaining for 2 days at 85 ℃/85% rh environment corresponds to approximately 1 year of use in a daily environment.
The light peel force release sheets were peeled from the pressure sensitive adhesive sheets produced in examples and comparative examples, and the exposed pressure sensitive adhesive layer was bonded to a PI film (thickness 100 μm) for simulating a CPI module, and rolled at a speed of 300mm/min by a 2kg roller for 2 back and forth, to obtain a laminate of heavy peel force release sheet/pressure sensitive adhesive layer (50 μm)/PET substrate (12 μm)/pressure sensitive adhesive layer (50 μm)/PI film (100 μm). The laminate was cut into pieces of 140mm long and 10mm wide, and then the laminate was peeled off with a heavy peel force, the adhesive layer was laminated on the edge of the curved steel sheet (radian R10) at the arc side, the resultant was rolled with a 2kg roller at a speed of 300mm/min for 2 rounds to prepare a combination of the curved steel sheet (radian R10)/adhesive layer (50 μm)/PET substrate (12 μm)/adhesive layer (50 μm)/PI film (100 μm), and after the combination was left to stand at a temperature of 23.+ -. 2 ℃ and a relative humidity of 50.+ -. 5% for 24 hours, whether the combination was sprung off was observed, and if not, the combination was placed in a 85 ℃ C./85% RH high temperature high humidity loop test box, whether the PI film (100 μm) was sprung off was observed at fixed time, and the time required for the sprung-off of the PI film (100 μm) and the failure mode were recorded, and the results are shown in Table 1.
The test was performed for a period of 10 days, and if the spring-off phenomenon occurred within 10, the specific days were recorded in Table 1, and if the spring-off was not occurred within 10 days, the test was recorded as ". Gtoreq.10" in Table 1.
(2) Failure type
Failure interfaces of the sprung-out examples were observed to determine whether they belonged to cohesive failure or interfacial failure, and the results are reported in table 1.
The failure mode is described as follows:
cohesive failure: the cohesive force of the adhesive layer is poor, the separation between the adhesive layers is shown, and the adhesive residue exists on the adhered object;
interface failure: the adhesive layer has poor adhesion, and is characterized in that the adhesive is separated from the object to be adhered, and no adhesive remains on the object to be adhered.
(2) Stripping force (N/25 mm)
The light release force release sheet was released from the adhesive sheet, and the exposed adhesive layer was bonded to a PET film (thickness 25 μm) to obtain a laminate of a heavy release force release sheet/adhesive layer (50 μm)/PET substrate (12 μm)/adhesive layer (50 μm)/PET film (25 μm). The obtained laminate was cut into a sheet of 25mm width and 300mm length, and the heavy release force release sheet was peeled off from the laminate at a temperature of 23.+ -. 2 ℃ and a relative humidity of 50.+ -. 5%, and the exposed adhesive layer was attached to SUS steel plate (roughness 50.+ -. 25nm, manufactured by Guangdong Co., ltd.). The adhesion (N/25 mm) of the laminate was measured from SUS steel plates using a peel strength tester (KJ-1065A, manufactured by Guangdong Co., ltd.) with GB/T2792-2014 as a standard, and the results are shown in Table 1.
(3) Primary adhesion (N)
The laminate obtained in the adhesion test was cut to a width of 25mm and a length of 170mm, and the heavy peel force release sheet was peeled off from the laminate under an atmosphere of a relative humidity of 50.+ -. 5% at a temperature of 23.+ -. 2 ℃ and the laminate was clamped to a jig of an annular initial adhesion tester (YL-1106E, manufactured by Guangdong cross-section), and the initial adhesion (N) of the laminate to SUS steel sheets (roughness of 50.+ -. 25nm, manufactured by Guangdong cross-section) was measured on the basis of GB/T31125-2014 and the results were shown in Table 1.
(4) Storage modulus (kPa)
The adhesive layers of the adhesive sheets produced in the examples and comparative examples were laminated to produce a laminate having a thickness of 1 mm. The resulting laminate of the adhesive layers was punched out into a cylinder (height 1 mm) of 8mm in diameter, which was taken as a sample. For the above samples, the storage modulus (kPa) was measured by a torsional shear method using a rotary rheometer (MCR 102, manufactured by An Dongpa Anton-Paar), and the storage modulus results at 85℃are shown in Table 1.
TABLE 1
As can be seen from table 1, the resulting adhesive of the examples of the present application has a suitable range of storage modulus at 85 ℃ and better adhesion and initial adhesion relative to the comparative examples, can be kept for a significantly longer time without failure under severe testing of 85 ℃/85% rh curved surface adhesion, and can be well applied in the requirements of curved surface adhesion, such as in the adhesion of a scroll screen display assembly.
The preferred embodiments of the present application have been described in detail above, but the present application is not limited thereto. Within the scope of the technical idea of the application, a number of simple variants of the technical solution of the application are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the application, all falling within the scope of protection of the application.
Claims (9)
1. An adhesive composition, characterized in that the adhesive composition comprises an a-component and a B-component; wherein the A component comprises one or more triblock copolymers with an X-Y-X structure, wherein the X block is a styrene segment and the Y block is an isoprene segment; the component B comprises one or more resin compounds with softening points of 80-150 ℃;
the A component comprises at least one triblock copolymer containing a diblock copolymer; the A component comprises the a-type triblock copolymer and a b-type triblock copolymer, wherein the block ratio X/Y of the a-type triblock copolymer is (15-25): (85-75) a diblock copolymer content of 15-20 wt.%; the block ratio X/Y of the class b triblock copolymer is (28-35)/(72-65), and the content of the diblock copolymer is 10-25%; the weight ratio of the a-type triblock copolymer to the b-type triblock copolymer is (65-98): (35-2); the weight average molecular weight of the triblock copolymer is 10 ten thousand-30 ten thousand Da;
the content of the component B is 10 to 50 parts by weight relative to 100 parts by weight of the component A;
the resin compound comprises a first resin compound with a softening point of 80-120 ℃ and a second resin compound with a softening point of 120-150 ℃ in a weight ratio of (0.2-2): 1, and the difference between the softening points of the first resin compound and the second resin compound is 20-40 ℃;
wherein the first resin compound is a terpene resin and the second resin compound is a terpene phenol resin.
2. The adhesive composition of claim 1, wherein the triblock copolymer is a linear structure or a star structure.
3. The adhesive composition of claim 2 wherein the triblock copolymer is a linear structure.
4. The adhesive composition of claim 1, wherein the weight ratio of the class a triblock copolymer to the class b triblock copolymer is (85-95): (15-5).
5. The adhesive composition of any of claims 1-4, wherein the adhesive composition further comprises an additive selected from one or more of an antioxidant, a curing agent, a filler, and a viscosity modifier.
6. The adhesive composition of claim 5, wherein the antioxidant is a hindered phenolic antioxidant and a phosphite antioxidant in a weight ratio of (1.5-2.5): 1.
7. The adhesive composition of claim 5, wherein the adhesive composition further comprises an organic solvent selected from one or more of ethyl acetate, toluene, n-heptane, cyclohexane, and tetrahydrofuran.
8. An adhesive comprising the adhesive composition of any one of claims 1-7, or prepared from said adhesive composition.
9. Use of the adhesive composition according to any one of claims 1-7 and/or the adhesive according to claim 8 for curved adhesion.
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