CN112513111A - Adhesive composition, adhesive film, laminate and method for producing the same - Google Patents

Adhesive composition, adhesive film, laminate and method for producing the same Download PDF

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Publication number
CN112513111A
CN112513111A CN201980050007.5A CN201980050007A CN112513111A CN 112513111 A CN112513111 A CN 112513111A CN 201980050007 A CN201980050007 A CN 201980050007A CN 112513111 A CN112513111 A CN 112513111A
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China
Prior art keywords
adhesive
monomer
adhesive film
film
base polymer
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Withdrawn
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CN201980050007.5A
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Chinese (zh)
Inventor
黄俊植
郑丞勋
Y·U·裴
俞善我
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3M Innovative Properties Co
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3M Innovative Properties Co
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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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • 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
    • 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
    • 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
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
    • C09J2301/204—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive coating being discontinuous
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer
    • 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
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

The adhesive film according to the present invention may be initially attached to a substrate with low adhesion force to easily remove unnecessary portions, and thereafter the adhesive film may be firmly attached to the substrate by easily increasing the adhesion force of the remaining portion of the film. In particular, the adhesive films of the present invention have a sufficiently low initial adhesion, but a sufficiently high final adhesion, such that the variability of adhesion is very excellent. Accordingly, the adhesive film and the adhesive composition for preparing the same of the present invention can be effectively applied to processes requiring variability of adhesive force, such as the manufacture of OLED display panels.

Description

Adhesive composition, adhesive film, laminate and method for producing the same
Technical Field
The invention relates to an adhesive composition, an adhesive film, a laminate and a method for preparing the same. More particularly, the present invention relates to adhesive films having adhesion variability, methods of making the same, compositions for making the same, and laminates and devices including the same.
Background
Substrates used in display panels and the like generally require an adhesive tape to protect the surface from damage due to external impact or adhesion with other components. For example, in Organic Light Emitting Diode (OLED) panels, adhesive tapes suitable for bonding components to polyimide substrates are used.
Meanwhile, on the display panel, there is a region where the tape is preferably not present for functional reasons, and for example, it is preferable that the tape is not present in a region connected to other terminals. In particular, in a process of manufacturing a curved display panel, which has recently received attention, since an adhesive tape should not exist in an area where the panel is curved, an accurate gluing process is required (see U.S. patent publication 2011-.
In such a process, initially, the adhesive tape may be attached to the substrate with low adhesion force to easily remove unnecessary portions, and thereafter, there is a need for an adhesive tape having adhesive force variability that may be securely attached to the substrate by easily increasing the adhesive force of the remaining portion of the adhesive tape.
Patent document
(patent document 1) U.S. patent publication 2011-
Technical problem
Currently, adhesive films have been developed that achieve variability of adhesive force by mixing various additives with adhesives, but these films in the related art have the following problems: poor compatibility between the adhesive and the additive, insufficient initial adhesion, or insufficient final adhesion.
Accordingly, an object of the present invention is to provide an adhesive film having adhesive force variability capable of exhibiting high performance by solving the problems in the related art, a method of preparing the same, a composition for preparing the same, and a laminate and an apparatus including the same.
Technical solution
According to one aspect of the present invention, there is provided an adhesive composition comprising: a base polymer; a crosslinking agent that reacts with the base polymer; a first monomer that polymerizes after the base polymer and the crosslinking agent react; and an initiator that polymerizes the first monomer. After the base polymer and the crosslinking agent are reacted, the adhesive composition has a first adhesive force before polymerization of the first monomer and a second adhesive force after polymerization of the first monomer, and the second adhesive force is higher than the first adhesive force.
According to another aspect of the present invention, there is provided an adhesive film comprising a reaction product of a base polymer and a crosslinker, wherein the adhesive film comprises a first monomer and an initiator, the first monomer is polymerizable by the initiator, the adhesive film has a first adhesive force before polymerization of the first monomer and a second adhesive force after polymerization of the first monomer, and the second adhesive force is higher than the first adhesive force.
According to another aspect of the present invention, a laminate is provided that includes a substrate and an adhesive film.
According to another aspect of the present invention, there is provided an apparatus comprising a laminate.
According to still another aspect of the present invention, there is provided a display device including: a display panel; and a laminate attached to the display panel.
Advantageous effects
According to the present invention, the adhesive film may be initially attached to the substrate with low adhesion force to facilitate repositioning, and unnecessary portions may be easily removed, and then the film may be securely attached to the substrate by easily increasing the adhesive force of the remaining portions of the film.
In particular, the adhesive film of the present invention is excellent in compatibility between parts, and is more excellent in variability of adhesion because the final adhesion is sufficiently high and the initial adhesion is sufficiently low.
Accordingly, the adhesive film of the present invention and the adhesive composition for preparing the same can be effectively applied to processes requiring variability of adhesive force, such as the manufacture of display panels such as OLEDs.
Drawings
Fig. 1 is a graph illustrating a change in adhesive force according to polymerization of a first monomer of an adhesive composition according to an embodiment.
Fig. 2 is a graph illustrating a change in adhesive force according to the addition of a second monomer of an adhesive composition according to an embodiment.
Fig. 3 is a graph illustrating a change in storage modulus when a base polymer of an adhesive composition is crosslinked according to an embodiment.
Fig. 4 illustrates a cross-sectional view of an adhesive tape including an adhesive film according to an embodiment.
Fig. 5 shows an example of a method of making a laminate according to an embodiment.
Fig. 6A and 6B show the adhesive force before and after UV curing for adhesive compositions 3A to 3F prepared in example 3, respectively.
Detailed Description
The advantages and features of the present invention and methods for accomplishing the same will be more clearly understood from the embodiments described in detail below with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms. That is, the embodiments are provided for completeness of disclosure and to fully announce the scope of the invention to a person skilled in the art to which the invention pertains, and the invention is limited only by the scope of the claims.
Shapes, sizes, ratios, angles, numbers, etc. shown in the drawings for describing the present invention are merely examples, and the present invention is not limited thereto. Like reference numerals refer to like parts throughout the specification. In addition, in describing the present invention, when it is determined that detailed explanation of known related art may unnecessarily obscure the subject matter of the present invention, detailed description thereof will be omitted.
Terms such as "comprising," having, "and" including "as used in this specification are generally intended to allow addition of elements other than the recited details, unless the term is used with" only. When an element is referred to in the singular, any reference to the singular can include the plural unless specifically stated otherwise.
Components are to be construed as including ordinary error ranges even if not explicitly stated.
When terms such as "upper", "above", "below", and "next" are used to describe a positional relationship between two parts, one or more other parts may be positioned between the two parts unless the terms are used with the terms "immediately" or "directly".
The respective features of the embodiments of the invention can be connected or combined with each other partially or entirely and can be technically interlocked or driven in various ways.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The following embodiments are provided as examples to fully convey the substance of the present invention to those skilled in the art. Therefore, the present invention is not limited to the embodiments to be described below and may also be implemented in various forms.
Adhesive composition
According to one aspect of the present invention, an adhesive composition is provided that includes a base polymer, a crosslinking agent, a first monomer, and an initiator.
The base polymer may be reacted with the crosslinking agent prior to polymerization of the first monomer by the initiator. For example, the base polymer can be reacted with the crosslinking agent while retaining the first monomer and the initiator. The adhesion of the adhesive composition after the reaction may be further improved after the polymerization of the first monomer.
An adhesive composition according to one embodiment may comprise: a base polymer; a crosslinking agent that reacts with the base polymer; a first monomer that polymerizes after the base polymer and the crosslinking agent react; and an initiator that polymerizes the first monomer. After the base polymer and the crosslinking agent are reacted, the adhesive composition has a first adhesive force before polymerization of the first monomer and a second adhesive force after polymerization of the first monomer, and the second adhesive force is higher than the first adhesive force.
The first monomer may be polymerized by a photoinitiator or a thermal initiator. In particular, when a photoinitiator is included in the adhesive composition, the first monomer may be polymerized by the photoinitiator after UV irradiation, and when a thermal initiator is included in the adhesive composition, the first monomer may be polymerized by the thermal initiator after heating.
Characteristics of the adhesive composition
Hereinafter, the characteristics of the adhesive composition will be described with reference to the accompanying drawings.
The adhesive composition according to an embodiment includes a first monomer and has a structure different from that before polymerization when the first monomer is polymerized.
Fig. 1 is a graph illustrating a change in adhesive force according to polymerization of a first monomer of an adhesive composition according to an embodiment.
As shown in fig. 1, the adhesive composition has a low adhesive force (e.g., 30gf/in or less) when the first monomer is added, and thereafter, the adhesive force rapidly increases (e.g., 1kgf/in or more) when the first monomer is polymerized.
Thus, the adhesive composition has a first adhesive force before polymerization of the first monomer and the base polymer and a second adhesive force after polymerization of the first monomer, and the second adhesive force is higher than the first adhesive force.
In addition, the adhesive composition may further include a second monomer different from the first monomer, and complexity of the base polymer chain is increased due to the second monomer, so that the adhesive force of the adhesive composition may be further improved.
Fig. 2 is a graph illustrating a change in adhesive force according to the addition of a second monomer of an adhesive composition according to an embodiment.
As shown in fig. 2, in the case where the second monomer is added together, the adhesive force after the polymerization of the monomers is further increased as compared with the case where only the first monomer is added.
Meanwhile, in the case where the second monomer is added together before the polymerization of the monomers, the adhesive composition has lower adhesive force than in the case where only the first monomer is added, so that the adhesive force can be more rapidly increased by the second monomer.
Adhesion on crosslinking of base polymers
In the adhesive composition, the base polymer reacts with (i.e., crosslinks) a crosslinking agent to form a film or the like, and the film formed as above has characteristics different from those of the related art in terms of physical properties such as adhesion.
Therefore, hereinafter, the characteristics of the adhesive composition when the first monomer and the initiator remain after the crosslinking agent reacts with the base polymer will be mainly described.
The adhesive composition has a first adhesion force prior to polymerization of the first monomer (i.e., while retaining the first monomer and the initiator).
The first adhesive force may be 200gf/in or less, 150gf/in or less, 100gf/in or less, 50gf/in or less, or 30gf/in or less.
Specifically, the first adhesive force may be in a range of 1gf/in to 200gf/in, 1gf/in to 100gf/in, or 1gf/in to 30 gf/in.
In the present specification, the adhesive force (first adhesive force, second adhesive force, etc.) may be measured by ASTM D3330, which is a common measurement method in the art, and for example, the adhesive force may be an adhesive force measured for polyimide. More detailed examples of the measurement method are specifically described in the following embodiments.
In addition, the adhesive composition has a second adhesion force after the first monomer is polymerized.
The second adhesive force may be 350gf/in or more, 400gf/in or more, 500gf/in or more, or 1,000gf/in or more.
Specifically, the second adhesive force may be in a range of 350gf/in to 3,000gf/in or 500gf/in to 2,000 gf/in.
For example, the first adhesive force may be 200gf/in or less, and the second adhesive force may be 350gf/in or more.
For another example, the first adhesive force may be 150gf/in or less, and the second adhesive force may be 400gf/in or more.
For another example, the first adhesive force may be in a range of 1gf/in to 30gf/in, and the second adhesive force may be in a range of 500gf/in to 2,000 gf/in.
In the adhesive composition, the second adhesive force is higher than the first adhesive force.
For example, the second adhesive force may be higher than the first adhesive force by 150gf/in or more, 200gf/in or more, 500gf/in or more, or 1,000gf/in or more.
Additionally, the ratio of the second adhesion force to the first adhesion force can be 20 or greater, 30 or greater, 50 or greater, 70 or greater, or 100 or greater.
Further, the ratio of the first adhesive force to the second adhesive force may be 0.06 or less, 0.03 or less, 0.02 or less, or 0.01 or less.
In addition, the base polymer may have an adhesion between the first adhesion and the second adhesion.
When the adhesive composition further includes a second monomer, the second adhesion force may be further improved.
That is, in the case where the second monomer is added together, the second adhesive force is further increased as compared with the case where only the first monomer is added.
On the other hand, in the case where the second monomer is added together before the polymerization of the monomers, the first adhesive force may be further reduced as compared with the case where only the first monomer is added.
Therefore, the difference between the first adhesive force and the second adhesive force may be further increased by the second monomer.
That is, the first adhesive force and the second adhesive force may be adjusted by adjusting the addition amounts of the first monomer and the second monomer.
Characteristics of the base polymer when crosslinked
Fig. 3 illustrates a change in storage modulus when a base polymer is crosslinked in an adhesive composition according to an embodiment. At this time, for comparison, changes in storage modulus of a general acrylic adhesive are shown together.
As shown in FIG. 3, since the crosslinking of the base polymer is performed by increasing the temperature, the storage modulus is lowered and 10 is maintained even in a high temperature region of 100 ℃ or more6Dyne/cm2Or a greater storage modulus, such that adhesive compositions according to embodiments may be advantageous for high temperature processes, such as Chip On Plastic (COP) bonding processes.
At the same time, the user can select the desired position,in the case of a general acrylic adhesive, since crosslinking is performed by raising the temperature, the storage modulus is very low, and even in a high-temperature region of 100 ℃ or more, 10 is exhibited5Dyne/cm2To 106Dyne/cm2Storage modulus of (2). In this case, the initial adhesion of the adhesive is improved, but high temperature durability is deteriorated and the fluidity of the adhesive is increased, so that general acrylic adhesives may not be suitable for a process of passing through a high temperature region.
After polymerization of the first monomer, the adhesive composition may meet the requirements as an optically clear adhesive.
For example, the adhesive composition can have a haze of 5% or less, 2% or less, or 1% or less after polymerization of the first monomer.
Further, the adhesive composition may have a light transmittance of 80% or more, 90% or more, or 95% or more after the polymerization of the first monomer.
The adhesive composition can satisfy the requirement as an optically transparent adhesive even after additionally containing a second monomer and polymerizing it.
For example, when the adhesive composition comprises a first monomer and a second monomer, the haze after polymerization may be 5% or less or 2% or less.
When the adhesive composition includes the first monomer and the second monomer, the light transmittance after polymerization may be 80% or more or 90% or more.
Components of the adhesive composition
An adhesive composition according to an embodiment includes a base polymer, a crosslinking agent, a first monomer, and an initiator.
In addition, the adhesive composition according to an embodiment may further include a second monomer different from the first monomer.
In addition, the adhesive composition according to the embodiment may further include a solvent and other additives.
Hereinafter, each component in the adhesive composition will be described in detail.
Base polymer
The adhesive composition according to an embodiment includes a base polymer.
The base polymer exhibits adhesive properties as a major component of the adhesive composition. Further, the base polymer is reacted with (i.e., crosslinked with) a crosslinking agent to form a film or the like.
The base polymer may be included in a range of 35 wt% to 95 wt%, based on the weight of the adhesive composition. In particular, the base polymer may be included in a range of 40 to 90 wt%, 45 to 85 wt%, or 50 to 80 wt%, based on the weight of the adhesive composition. At this time, the content of the base polymer and the weight of the adhesive composition may be based on the solid content.
The base polymer may comprise functional groups that react with the crosslinking agent. For example, the base polymer may have at least one functional group selected from a carboxyl group, a hydroxyl group, an acryl group, a methacryl group, an acetate group, and a vinyl group.
For example, the base polymer may be an acrylic resin.
In particular, the base polymer may be an acrylic copolymer resin.
For example, the acrylic copolymer resin may be a resin copolymerized with at least two monomers selected from the group consisting of 2-ethylhexyl acrylate (2-EHA), Butyl Acrylate (BA), Methyl Acrylate (MA), vinyl acetate (VAc), Acrylic Acid (AA), and 2-hydroxyethyl acrylate (2-HEA).
As a specific example, the combination of at least two monomers constituting the acrylic copolymer resin may include 2-EHA/MA, BA/MA, AA/2-HEA, MA/2-HEA, BA/2-HEA, MA/AA/2-HEA, and the like.
The base polymer may be a heat-curable resin or a photocurable resin.
For example, the base polymer may be a heat curable resin.
Further, the base polymer may be a Pressure Sensitive Adhesive (PSA) resin.
The base polymer may have a weight average molecular weight (Mw) of 10,000 to 2,000,000. Alternatively, the weight average molecular weight of the base polymer may be 100,000 to 2,000,000.
First monomer
An adhesive composition according to an embodiment includes a first monomer.
The first monomer will polymerize after the base polymer and crosslinker have reacted. That is, the first monomer may be present in an unpolymerized state even after the base polymer and the crosslinking agent are reacted.
The first monomer in an unpolymerized state can reduce the adhesion of the reaction product of the base polymer and the crosslinker. However, after the base polymer and the crosslinking agent are reacted, the first monomer is polymerized as needed, so that the adhesive force of the reaction product can be rapidly increased.
The content of the first monomer in the composition may be 10 parts by weight to 120 parts by weight based on 100 parts by weight of the base polymer. Specifically, the first monomer may be contained in the composition in an amount of 20 to 110 parts by weight, 30 to 100 parts by weight, or 40 to 90 parts by weight, based on 100 parts by weight of the base polymer. At this time, the contents of the base polymer and the first monomer may be based on the solid content.
The molecular weight of the first monomer may be in the range of 50 to 2,000 or 100 to 1,000.
For example, the first monomer may be a monofunctional or difunctional or higher functional compound, such as a monofunctional to trifunctional compound. The first monomer may have at least one functional group selected from the group consisting of an acryl group, a methacryl group, a vinyloxy group, a vinyl group, and a carboxyl group.
The first monomer may have compatibility with the base polymer. In addition, the first monomer may be polymerized by a photoinitiator or a thermal initiator.
For example, the first monomer may be at least one compound represented by the following chemical formula 1.
Figure BDA0002918346340000091
In chemical formula 1, m is an integer of 1 to 5;
R1is straight chain C1-12Alkyl, or C substituted or unsubstituted by phenyl6-10An aryloxy group; and is
RaAnd RbEach independently is hydrogen or acryloyloxymethyl.
According to one embodiment of chemical formula 1, n is an integer of 1 to 3.
According to another embodiment of chemical formula 1, n is an integer of 3 to 5.
According to still another embodiment of chemical formula 1, R1Is straight chain C1-3An alkyl group.
According to still another embodiment of chemical formula 1, R1Is straight chain C6-12An alkyl group.
According to still another embodiment of chemical formula 1, R1Is phenoxy.
According to still another embodiment of chemical formula 1, R1Is phenoxy substituted by phenyl.
According to still another embodiment of chemical formula 1, RaAnd RbAre each hydrogen.
According to still another embodiment of chemical formula 1, RaIs hydrogen, and RbIs an acryloyloxymethyl group.
According to still another embodiment of chemical formula 1, RaAnd RbAre each an acryloyloxymethyl group.
According to still another embodiment of chemical formula 1, R1Is straight chain C1-3An alkyl group; and R isaAnd RbAre each an acryloyloxymethyl group.
According to still another embodiment of chemical formula 1, R1Is straight chain C6-12An alkyl group; and R isaAnd RbAre each hydrogen.
According to still another embodiment of chemical formula 1, R1Is phenoxy; and R isaAnd RbAre each hydrogen.
According to still another embodiment of chemical formula 1, R1Is phenoxy substituted by phenyl; and R isaAnd RbAre respectively provided withIs hydrogen.
As more detailed examples of the above chemical formula 1, trimethylolpropane triacrylate (TMPTA), lauryl acrylate, phenyl (EO) may be included2Acrylates, o-phenylphenol EO acrylates, and the like.
Initiator
The adhesive composition according to an embodiment includes an initiator.
The initiator will polymerize the first monomer.
The initiator may be a photoinitiator or a thermal initiator.
The initiator may be contained in the composition in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of the base polymer. Specifically, the initiator may be contained in the composition in an amount of 0.1 to 5 parts by weight, based on 100 parts by weight of the base polymer. At this time, the contents of the initiator and the base polymer may be based on the solid content.
As the initiator, a general photoinitiator can be used, and for example, as the photoinitiator, at least one selected from ketones (benzophenone, acetophenone, and the like), benzoin ether, benzyl, and benzyl ketal can be used.
For example, the photoinitiator may be a benzoin ether (e.g., benzoin methyl ether or benzoin isopropyl ether) or a substituted benzoin ether.
As another example, the photoinitiator may be a substituted acetophenone, such as 2, 2-diethoxyacetophenone or 2, 2-dimethoxy-2-phenylacetophenone.
As another example, the photoinitiator can be a substituted alpha-ketone (e.g., 2-methyl-2-hydroxypropiophenone), an aromatic sulfonyl chloride (e.g., 2-naphthalenesulfonyl chloride), or a photosensitive oxime (e.g., 1-phenyl-1, 2-propanedione-2- (0-ethoxycarbonyl) oxime).
As another example, the photoinitiator may be 1-hydroxycyclohexyl phenyl ketone, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-benzyl-2-dimethylamino-1-4-morpholinophenyl) butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, or the like.
Examples of commercially available photoinitiators may include the Ciba IRGACURE series from Ciba Specialty Chemicals co., Ltd., the Esacure KIP series from auston, and the like.
As the thermal initiator, a water-soluble or water-insoluble (i.e., oil-soluble) thermal initiator may be selectively used depending on the polymerization method to be used.
As water-soluble initiators, there may be used: persulfates, such as potassium persulfate, ammonium persulfate, sodium persulfate, and mixtures thereof; a redox initiator such as a reaction product of a reducing agent such as a metabisulfite (e.g., sodium metabisulfite) or a bisulfate (e.g., sodium bisulfate) and a persulfate; or 4,4' -azobis (4-cyanopentanoic acid) and soluble salts thereof (e.g., sodium salt, potassium salt), and the like.
As oil-soluble initiators, there may be used: azo such as 2,2' -azobis (2-methylbutyronitrile), 2' -azobis (isobutyronitrile), and 2,2' -azobis (2, 4-dimethylvaleronitrile); or peroxides such as benzoyl peroxide, cyclohexane peroxide and lauroyl peroxide.
Crosslinking agent
The adhesive composition according to an embodiment includes a crosslinking agent.
The crosslinking agent reacts with the base polymer to form a film, etc.
The content of the crosslinking agent in the composition may be 0.1 parts by weight to 20 parts by weight based on 100 parts by weight of the base polymer. Specifically, the content of the crosslinking agent in the composition may be 0.1 to 10 parts by weight or 0.1 to 5 parts by weight based on 100 parts by weight of the base polymer. At this time, the contents of the crosslinking agent and the base polymer may be based on the solid content.
The crosslinking agent may comprise functional groups that react with functional groups of the base polymer.
For example, the crosslinking agent may have one or at least two functional groups selected from an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, an acryl group, a methacryl group, an acetate group, and a vinyl group.
As a specific example, the crosslinking agent may have an epoxy group or an isocyanate group.
The crosslinking agent may be a photocrosslinking agent, a thermal crosslinking agent, or a combination thereof.
As the photocrosslinking agent, a general polyfunctional acrylic compound can be used.
For example, the photo-crosslinking agent may be at least one selected from the group consisting of diacrylates and triacrylates. Specific examples of the photocrosslinking agent may include 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate (HDDA), 1, 9-nonanediol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate.
The thermal crosslinking agent may be an isocyanate-based compound, an epoxy-based compound, or a metal chelate-based compound.
The isocyanate-based compound may be a polyfunctional aromatic or aliphatic isocyanate compound. For example, the isocyanate-based compound may be a trimerized isocyanate, such as a toluene diisocyanate-trimethylolpropane (TDI-TMP) adduct.
The epoxy resin-based compound may have one or at least two epoxy groups, and may have a functional group that reacts with the base polymer.
The metal chelate compound may be a chelate compound having a metal such as Zn, Ni, Mn, Fe, Co, Cr, Al, Ti or Zr.
Examples of commercially available thermal crosslinkers may include the Saivinol hardener series available from Saiden Chemical Industry co.
Second monomer
The adhesive composition according to an embodiment may further include a second monomer different from the first monomer.
The second monomer may form additional bonds when the base polymer reacts with the cross-linking agent. Thus, when the base polymer reacts with the crosslinking agent, the second monomer reacts together to increase the curing density, thereby contributing to the reduction of the first adhesive force.
The content of the second monomer in the composition may be 10 parts by weight to 120 parts by weight based on 100 parts by weight of the base polymer. Specifically, the second monomer may be contained in the composition in an amount of 20 to 110 parts by weight, 30 to 100 parts by weight, or 40 to 90 parts by weight, based on 100 parts by weight of the base polymer.
At this time, the contents of the base polymer and the second monomer may be based on the solid content.
The total content of the first monomer and the second monomer in the composition may be 60 parts by weight or more based on 100 parts by weight of the base polymer. Specifically, the total content of the first monomer and the second monomer in the composition may be 60 parts by weight to 200 parts by weight or 60 parts by weight to 150 parts by weight, based on 100 parts by weight of the base polymer.
At this time, the contents of the base polymer, the first monomer, and the second monomer may be based on the solid content.
When the base polymer reacts with the crosslinking agent, the second monomers may react together to increase the cured density.
In particular, the second monomer can reduce the adhesion of the reaction product of the base polymer and the crosslinker prior to polymerization.
In particular, in the case where both the first monomer and the second monomer are present, the adhesive force of the reaction product of the base polymer and the crosslinking agent is lower before the polymerization of the first monomer, but is higher after the polymerization, as compared to the case where only the first monomer is present, thereby exhibiting a rapid increase in adhesive force.
The molecular weight of the second monomer may be in the range of 50 to 1000 or 100 to 500.
The second monomer may be a monofunctional or a difunctional or higher functional compound, for example a monofunctional to trifunctional compound.
In addition, the second monomer may have at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, an acryl group, a methacryl group, an acetate group, and a vinyl group.
As a specific example, the second monomer may have one functional group at each of both ends.
For example, the second monomer may be at least one compound represented by the following chemical formula 2.
Figure BDA0002918346340000131
In chemical formula 2, n is an integer of 1 to 5.
Specifically, the second monomer may be 2-carboxyethyl acrylate, 2-carboxy (EO) ethyl acrylate, 2-carboxy (EO) acrylate2Ethyl ester, acrylic acid 2-carboxy (EO)3Ethyl ester or carboxyl acrylate (EO)4And (4) ethyl ester.
Solvent(s)
The adhesive composition according to the embodiment may further include a solvent.
Solvents may be used to adjust the viscosity of the adhesive composition.
The type of the solvent is not particularly limited, and may be, for example, at least one selected from the group consisting of toluene, a mixture of hexane/methyl ethyl ketone, xylene, and isopropyl acetate.
The mixing amount of the solvent is not particularly limited, but for example, the solid content of the adhesive composition may be mixed to a range of 40 to 90% by weight or 50 to 80% by weight.
Additive agent
The adhesive composition according to the embodiment may further include other additives as needed.
Specific examples of the additives include tackifiers (e.g., rosin esters, terpenes, phenols and aliphatic synthetic hydrocarbon resins, aromatic synthetic hydrocarbon resins, or mixtures of aliphatic synthetic hydrocarbon resins and aromatic synthetic hydrocarbon resins), surfactants, plasticizers (other than physical blowing agents), nucleating agents (e.g., talc, silica or TiO)2) Fillers (e.g., inorganic and organic), fibers, aging inhibitors, antioxidants, UV absorbers, antistatic agents, lubricants, pigments, dyes, reinforcing agents, hydrophobic or hydrophilic silicas, calcium carbonate, toughening agents, pigments, antioxidants, UV absorbers,Flame retardants, finely ground polymer particles (e.g., polyester, nylon, or polypropylene), stabilizers (e.g., UV stabilizers), and combinations thereof.
The content of the additive is not particularly limited to an appropriate amount capable of obtaining the desired characteristics of the composition, but may be, for example, 0.1 to 10% by weight or 0.1 to 5% by weight, based on the weight of the adhesive composition.
Specific composition examples
The adhesive composition according to the embodiment may be configured such that each component exemplified above has a specific content.
According to one embodiment, the adhesive composition may include 100 parts by weight of a base polymer, 0.1 to 20 parts by weight of a crosslinking agent, 10 to 120 parts by weight of a first monomer, and 0.1 to 10 parts by weight of a photopolymerization initiator.
According to another embodiment, the adhesive composition may include 100 parts by weight of the base polymer, 0.1 to 20 parts by weight of the crosslinking agent, 10 to 120 parts by weight of the first monomer, 10 to 120 parts by weight of the second monomer, and 0.1 to 10 parts by weight of the initiator.
According to yet another embodiment, the adhesive composition may include 100 parts by weight of a Pressure Sensitive Adhesive (PSA) as a base polymer, 0.1 to 20 parts by weight of a thermal crosslinking agent as a crosslinking agent, 10 to 120 parts by weight of the compound of formula 1 as a first monomer, and 0.1 to 10 parts by weight of a photoinitiator as an initiator.
According to yet another embodiment, the adhesive composition may include 100 parts by weight of a Pressure Sensitive Adhesive (PSA) as a base polymer, 0.1 to 20 parts by weight of a thermal crosslinking agent as a crosslinking agent, 10 to 120 parts by weight of the compound of chemical formula 1 as a first monomer, 10 to 120 parts by weight of the compound of chemical formula 2 as a second monomer, and 0.1 to 10 parts by weight of a photoinitiator as an initiator.
At this time, the content of the components in the adhesive composition may be based on the solid content.
Method for preparing adhesive composition
The adhesive composition according to the embodiment may be prepared by mixing the base polymer, the first monomer, the crosslinking agent, and the initiator, and further mixing the solvent and other additives as necessary.
The base polymer can be prepared by a general method such as solution polymerization.
In the preparation of the adhesive composition, the order and conditions for mixing the base polymer, the first monomer, the crosslinking agent, and the initiator are not particularly limited, and the process may be appropriately modified as needed.
Further, the viscosity can be adjusted by using a solvent in each mixing step.
However, the preparation method of the adhesive composition is not particularly limited, and the process conditions may be appropriately modified as needed.
The adhesive composition according to the embodiment may be used to form an adhesive film having variable adhesive force, and thus may be effectively applied to processes requiring variability in adhesive force, such as the manufacture of OLED display panels.
Adhesive film
According to another aspect of the present invention, there is provided an adhesive film formed of the adhesive composition.
The adhesive film has a higher adhesion force after polymerization of the first monomer than before polymerization of the first monomer.
An adhesive film according to one embodiment is an adhesive film comprising a reaction product of a base polymer and a crosslinker, wherein the adhesive film comprises a first monomer and an initiator, the first monomer is polymerizable by the initiator, the adhesive film has a first adhesive force before polymerization of the first monomer and a second adhesive force after polymerization of the first monomer, and the second adhesive force is higher than the first adhesive force.
Components of adhesive film
An adhesive film according to embodiments includes a reaction product of a base polymer and a crosslinker. That is, the adhesive film comprises a crosslinked base polymer.
In addition, the adhesive film comprising the reaction product of the base polymer and the crosslinker comprises a first monomer and an initiator.
For example, the first monomer and the initiator are dispersed in the reaction product of the base polymer and the crosslinking agent.
The first monomer may be compatible with the reaction product of the base polymer and the crosslinker.
Referring back to fig. 1, polymerization of the first monomer may be initiated by the action of an initiator as necessary to improve the adhesive force of the adhesive film.
The specific types and amounts of the base polymer, the crosslinking agent, the first monomer, and the initiator included in the adhesive film are as described above in the adhesive composition.
In addition, the adhesive film according to embodiments may further include a second monomer different from the first monomer, and the second monomer may form an additional bond in the reaction product of the base polymer and the crosslinking agent.
The specific type and amount of the second monomer is as described for the second monomer included in the adhesive composition.
In addition, the adhesive film according to the embodiment may further include other additives, and the specific type and content thereof are as described in the additives included in the adhesive composition.
Characteristics of the adhesive film
Adhesion-before and after polymerization of the first monomer
The adhesive film according to the embodiment has a first adhesive force before the first monomer is polymerized.
The first adhesive force is preferably equal to or lower than a certain level to remove unnecessary portions after attaching the adhesive film to the substrate.
For example, the first adhesive force may be 200gf/in or less, 150gf/in or less, 100gf/in or less, 50gf/in or less, or 30gf/in or less.
Specifically, the first adhesive force may be in a range of 1gf/in to 200gf/in, 1gf/in to 100gf/in, or 1gf/in to 30 gf/in.
In the present specification, the adhesive force (first adhesive force, second adhesive force, etc.) may be measured by ASTM D3330, which is a common measurement method in the art, and for example, the adhesive force may be an adhesive force measured for polyimide. More detailed examples of the measurement method are specifically described in the following embodiments.
The adhesive film according to the embodiment has a second adhesive force after the first monomer is polymerized.
The second adhesive force may be higher than a certain level to fix a remaining portion of the adhesive film to the substrate after removing the unnecessary portion of the adhesive film.
For example, the second adhesive force may be 350gf/in or more, 400gf/in or more, 500gf/in or more, or 1,000gf/in or more.
Specifically, the second adhesive force may be in a range of 350gf/in to 10,000gf/in or 500gf/in to 5,000 gf/in.
The second adhesive force is higher than the first adhesive force.
For example, the second adhesive force may be higher than the first adhesive force by 150gf/in or more, 200gf/in or more, 500gf/in or more, or 1,000gf/in or more.
Additionally, the ratio of the second adhesion force to the first adhesion force can be 3 or greater, 5 or greater, 10 or greater, 12 or greater, or 15 or greater.
Further, the ratio of the first adhesive force to the second adhesive force may be 0.06 or less, 0.03 or less, 0.02 or less, or 0.01 or less.
For example, the first adhesive force may be 200gf/in or less, and the second adhesive force may be 350gf/in or more.
For another example, the first adhesive force may be 150gf/in or less, and the second adhesive force may be 400gf/in or more.
For another example, the first adhesive force may be in a range of 1gf/in to 30gf/in, and the second adhesive force may be in a range of 500gf/in to 5,000 gf/in.
In addition, the adhesive film formed by crosslinking the base polymer not containing the first monomer may have an adhesive force between the first adhesive force and the second adhesive force.
Haze and light transmittance after polymerization of monomer
The adhesive film can satisfy the requirement as an optically transparent adhesive film.
For example, the adhesive film may have a haze of 5% or less, 2% or less, or 1% or less after polymerization of the first monomer.
Further, the adhesive film may have a light transmittance of 80% or more, 90% or more, or 95% or more after the polymerization of the first monomer.
Even when the second monomer is additionally contained, the adhesive film can satisfy the requirement as an optically transparent adhesive film.
For example, when the adhesive film comprises a first monomer and a second monomer, the haze after polymerization may be 5% or less or 2% or less.
Further, when the adhesive film includes the first monomer and the second monomer, the light transmittance after polymerization may be 80% or more or 90% or more.
Thickness of the film
When prepared as a thin film, the thickness of the adhesive film may be in the range of 5 μm to 1000 μm or 10 μm to 100 μm.
Alternatively, when prepared as a thick film, the thickness of the adhesive film may be in the range of 0.1mm to 5mm or 1mm to 3 mm.
Method for producing adhesive film
The adhesive film may be prepared by preparing an adhesive composition to be formed into a film.
A method of preparing an adhesive film according to an embodiment includes: mixing a base polymer, a first monomer, an initiator, and a crosslinking agent; reacting a crosslinking agent with a base polymer to form a film-shaped polymer; and retaining the first monomer and the initiator in the film-shaped polymer to obtain an adhesive film.
The preparation of the adhesive composition may be carried out according to the conditions and procedures described above. The reaction of the base polymer and the crosslinking agent may be carried out by a general thermal curing process. For example, the heat curing temperature may be in the range of 40 ℃ to 150 ℃, 60 ℃ to 120 ℃, or 100 ℃ to 120 ℃, and the heat curing time may be 1 minute to 10 minutes or 2 minutes to 5 minutes, but these heat curing conditions may be adjusted according to the length and number of the curing oven. In addition, after the heat curing, aging may be further performed (for example, aging at about 50 ℃ C. for 3 days).
The heat curing process may be performed while the adhesive composition is coated on the base film. In particular, the adhesive composition may be coated on the base film in an appropriate thickness, and heat curing may be performed in the process. Coating may be performed by methods such as slot bar coating, comma coating, gravure coating, or die coating. Further, the coating rate may be in the range of about 1 to 40m/min or 5 to 30m/min, but the conditions may be adjusted according to the length of the curing oven.
Further, the retention of the first monomer and the initiator in the film-shaped polymer can be performed by suppressing an environment in which the initiator can act on the coated (and thermally cured) film-shaped polymer (e.g., preventing UV light exposure).
Application to adhesive tapes
The adhesive film according to embodiments may be applied as an adhesive tape.
Fig. 4 illustrates a cross-sectional view of an adhesive tape including an adhesive film according to an embodiment.
Referring to fig. 4, an adhesive film 110 according to an embodiment may be formed on one surface of a base film 120 to provide a base-type adhesive tape 100.
In addition, in the adhesive tape, a release film 130 may be laminated on one surface of the adhesive film 110.
Base film
The base film may comprise at least one resin selected from polyester resins, polyurethane resins, and polyolefin (e.g., polyethylene, etc.) resins. Alternatively, the base film may be composed of paper, plastic film, cloth, or metal foil.
In some embodiments, suitable materials for the base film may include, for example, paper (including both flat or smooth paper and textured paper such as creped paper), natural or synthetic polymeric films, natural and/or synthetic fibers and nonwoven fabrics made from combinations thereof, fiber reinforced polymeric films, fiber or yarn reinforced polymeric films or nonwoven fabrics, and multilayer laminate structures.
In addition, the base film may have a thickness in a range of 5 μm to 100 μm or a thickness in a range of 10 μm to 100 μm. For example, the base film may include polyethylene terephthalate and have a thickness of 10 μm to 100 μm.
Such adhesive tapes may be prepared by a method comprising applying an adhesive composition on at least one surface of a base film to form an adhesive film.
In this case, after the adhesive composition is applied, the first monomer in the adhesive film must be prevented from polymerizing before the adhesive tape is used.
Alternatively, the adhesive film according to the embodiment may be provided as a non-base type adhesive tape itself without a base film.
Adhesive film
In the adhesive tape, the adhesive film 110 may be an adhesive film according to the above-described embodiment.
Thus, the adhesive tape may include an adhesive film having the above-described composition and characteristics.
Anti-sticking film
The type of the release film used for the adhesive tape is not particularly limited, but may be, for example, at least one selected from the group consisting of a Polyester (PET) film, a Polyethylene (PE) film, a polypropylene (PP) film, and paper.
In addition, the release film may include a silicone coating on the surface in contact with the adhesive film.
The thickness of the release film may be 5 μm to 100 μm, but may be thinner or thicker as necessary.
Laminate
According to yet another aspect of the present invention, there is provided a laminate comprising a substrate and an adhesive film according to an embodiment.
Component of a laminate
The substrate in the laminate may be made of materials such as metal, glass, polymers, and the like.
Specifically, the material of the substrate may be stainless steel, glass, polyolefin, polyimide, or the like.
More specifically, the substrate may comprise polyimide.
The substrate may be integrally attached with the adhesive film on its surface.
In contrast, the adhesive film may be partially attached to the substrate, and the laminate may have areas where the adhesive film is applied and areas where the adhesive film is not applied.
In the laminate, at least one region to which the adhesive film is applied and at least one region to which the adhesive film is not applied may be included each, and the region to which the adhesive film is applied and the region to which the adhesive film is not applied may form a specific pattern.
The adhesive film in the laminate may be an adhesive film according to the above embodiments. Accordingly, the laminate structure may include an adhesive film having the composition and features described above.
Method for producing laminate
Fig. 5 shows an example of a manufacturing method of the laminate.
Referring to fig. 5, a method of making a laminate may include: applying an adhesive film 110 according to an embodiment to a substrate 200; forming an adhesive film-applied region and an adhesive film-unapplied region on the substrate 200 by removing a portion of the adhesive film 110; and polymerizing the first monomer contained in the adhesive film 111 in the area where the adhesive film is applied by the initiator to improve the adhesive force of the adhesive film 111 in the area where the adhesive film is applied.
In addition, the method of making the laminate may comprise: preparing an adhesive composition according to an embodiment; reacting the base polymer with a crosslinking agent to form an adhesive film that retains the first monomer and the initiator; applying an adhesive film to a substrate; forming an area to which the adhesive film is applied and an area to which the adhesive film is not applied on the substrate by removing a portion of the adhesive film; and polymerizing the first monomer contained in the adhesive film in the area where the adhesive film is applied by an initiator to improve the adhesive force of the adhesive film in the area where the adhesive film is applied.
Accordingly, the adhesive film after polymerization of the first monomer may have improved adhesive force compared to the adhesive film before polymerization of the first monomer.
In the method of producing the laminate, the production of the adhesive composition and the production of the adhesive film may be performed under the above-described conditions.
In addition, the formation of the area to which the adhesive film is applied and the area to which the adhesive film is not applied may be performed on the substrate by removing a part of the adhesive film so that the adhesive film on the obtained area to which the adhesive film is applied has a shape such as a line, a figure, and a pattern.
For example, a cut line in the form of a dotted line is formed along the periphery of a desired region on the surface of an adhesive film applied to a substrate. Then, an adhesive tape or the like may be attached to the area of the adhesive film to be removed and slowly lifted to remove a portion of the adhesive film along the cut line.
In addition, the polymerization of the first monomer may be performed by a general photo-curing or thermal curing process.
Referring to fig. 5, the polymerization of the first monomer may be performed by irradiating UV light 300 to the adhesive film 111 on the area where the adhesive film is applied. The irradiation of UV light can be 500mJ/cm2To 3,000mJ/cm2Under the energy conditions of (1) in the wavelength range of from 250nm to 420 nm.
Device
According to another aspect of the present invention, there is provided an apparatus comprising a laminate.
The specific type of the apparatus is not particularly limited, but may be, for example, a display device.
A display device according to an embodiment includes: a display panel; and a laminate according to an embodiment attached to the display panel.
The display panel may be an Organic Light Emitting Diode (OLED) display panel or a Liquid Crystal Display (LCD) panel.
[ examples of embodiments]
Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are merely to illustrate the present invention, and the present invention is not limited thereto.
Preparation example 1: preparation of the base Polymer
Each base polymer (binder) was prepared by solution polymerization using the components in the table below.
[ Table 1]
Figure BDA0002918346340000211
-2-EHA: 2-ethylhexyl acrylate
-BA: acrylic acid butyl ester
-MA: acrylic acid methyl ester
-VAc: vinyl acetate (VAA)
-AA: acrylic acid
-2-HEA: 2-hydroxyethyl acrylate
-EA: ethyl acetate
Example 1: preparation of adhesive composition
The base polymer (binder a or B) obtained in preparation example 1 was mixed with a UV monomer, a solvent (EA) for adjusting viscosity and other additives were added as needed, and then stirred for 30 minutes to 1 hour to prepare a first solution. Solvent (EA) was added to the photoinitiator in a 1:2 weight ratio to prepare a second solution. The first solution, the second solution and the crosslinking agent are mixed, a solvent (EA) for adjusting viscosity is added as needed, and then stirred for 30 minutes to 1 hour to prepare an adhesive composition.
At this time, the components and contents of the respective materials in the final composition are shown in the following table.
[ Table 2 ]]
Figure BDA0002918346340000221
In the above table, the values in parentheses are parts by weight converted based on 100 parts by weight of binder solids.
-isocyanate-based crosslinking agent: solids content 45%, Saivinol hardener AL, Saiden Chemical Industry Co., Ltd.)
-crosslinking agents based on metal (Al) chelates: solids content 5%, Saivinol hardener M-2, Saiden Chemical industries, Inc. (Saiden Chemical Industry Co., Ltd.)
Lauryl acrylate
Figure BDA0002918346340000222
CibaTMIRGACURE 651
Figure BDA0002918346340000223
Test example 1-1: measurement of adhesion to polyimide
(1) Preparation of samples
The adhesive composition to be tested was coated on a polyethylene terephthalate (PET) film having a thickness of 75 μm at a rate of 1.0 m/min. The coated film was dried in a total 6m oven with three drying zones of length 2m (at temperatures of 40 ℃, 80 ℃ and 120 ℃ respectively). Thus, an adhesive film having a thickness of 13 μm was formed on the PET film, and cut into a size of 1 inch × 12mm to obtain a single-sided tape sample.
(2) Measurement of adhesion before/after UV curing
Polyimide film (manufacturer: SKC Kolon PI) was attached to a rigid acrylic or glass plate using PET double-sided tape. The surface of the polyimide film was washed with isopropyl alcohol/heptane, and the single-sided tape samples prepared above were laminated to obtain a laminate. The preparation of the above laminates was completed within 1 hour to minimize the effect of light during handling.
Subjecting the laminate to UV curing in a UV curing machine (metal halide lamp, wavelength range 250nm to 420nm, dominant wavelength 365nm, energy of 1,000mJ/cm2) And (4) curing. At this time, the 180 ° peel strength between the polyimide films of the single-sided adhesive tape in the laminate was measured for each of the cases before and after UV curing. The peel strength (adhesive force) was measured according to ASTM D3330 using a general-purpose tester (UTM, TA instruments co., Ltd.) at a peel rate of 305mm/min and a load of 2 kgf. The results are shown in the following table.
In addition, for comparison, a single-sided tape sample was prepared using only an adhesive (base polymer), and the adhesive force to the polyimide film was measured under the same conditions and is shown in the following table.
[ Table 3 ]]
Figure BDA0002918346340000231
As shown in the above table, it can be seen that the adhesive composition according to the example has increased adhesive force after UV curing compared to before UV curing, and has lower adhesive force before UV curing than that of the adhesive (base polymer) alone, and has higher adhesive force before UV curing. In particular, it can be seen that when the weight of the first monomer is 60 parts by weight or more based on 100 parts by weight of the solid content of the base polymer, the difference in adhesive force before and after UV curing is significantly increased.
Test examples 1 to 2: measurement of adhesion to various substrates
The same procedure as in test example 1-1 was repeated, and the adhesion of the single-sided tape samples to stainless steel and glass, not to a polyimide film, before and after UV curing was measured, and the results are shown in the following table.
In addition, for comparison, single-sided tape samples were prepared using only an adhesive (base polymer), and adhesion to stainless steel and glass was measured, and the results are shown in the following table.
[ Table 4 ]]
Figure BDA0002918346340000241
[ Table 5 ]]
Figure BDA0002918346340000242
[ Table 6 ]]
Figure BDA0002918346340000243
As shown in the above table, it can be seen that the adhesive composition according to the embodiment has increased adhesive force after UV curing compared to various substrates before UV curing, and in particular, has lower adhesive force before UV curing than that of an adhesive (base polymer) alone, and has higher adhesive force before UV curing.
Test examples 1 to 3: evaluation of static shear
One-sided adhesive tape samples having dimensions of 1 inch × 1 inch were prepared in the same manner as in test example 1-1, and static shear thereof was evaluated. At this time, the evaluation of static shear was performed by measuring a period of time required to break away from adhesion to stainless steel under a condition of 500g load and 60 ℃/90% RH. The results are shown in the following table.
[ Table 7 ]]
Figure BDA0002918346340000251
As shown in the above table, the adhesive composition according to the example has various static shear after UV curing equal to or higher than that of the conventional adhesive.
Example 2: preparation of adhesive composition
The adhesive, the crosslinking agent, the UV monomer and the photoinitiator were mixed with the components and contents shown in the following table under the same conditions as in example 1 to prepare corresponding adhesive compositions.
[ Table 8 ]]
Figure BDA0002918346340000252
In the above table, the values in parentheses are parts by weight converted based on 100 parts by weight of binder solids.
-isocyanate-based crosslinking agent: solids content 45%, Saivinol hardener AL, Saiden Chemical Industry Co., Ltd.)
-crosslinking agents based on epoxy resins: solids content 5%, NA-30, Keda Mei Co (Cosmo Tech Co., Ltd.)
-phenyl (EO)nAcrylic ester (n ═ 2)
Figure BDA0002918346340000261
O-phenylphenol EO acrylate
Figure BDA0002918346340000262
-CibaTMIRGACURE 651
Figure BDA0002918346340000263
Test example 2: adhesion to polyimideMeasurement of
Single-sided tape samples were prepared in the same manner as in test example 1-1 using the respective adhesive compositions 2A to 2H prepared in example 2, the adhesion to the polyimide film before and after UV curing was measured, and the results are shown in the following table. In addition, for comparison, a single-sided tape sample was prepared using only an adhesive (base polymer), and the adhesive force to the polyimide film was measured under the same conditions and is shown in the following table.
[ Table 9 ]]
Figure BDA0002918346340000264
Figure BDA0002918346340000271
As shown in the above table, it can be seen that the adhesive composition according to the embodiment has significantly increased adhesive force after UV curing compared to various substrates before UV curing, and has lower adhesive force before UV curing than that of an adhesive (base polymer) alone, and higher adhesive force before UV curing. In particular, it can be seen that when the weight of the first monomer is 60 parts by weight or more based on 100 parts by weight of the solid content of the base polymer, the difference in adhesive force before and after UV curing is significantly increased.
Example 3: preparation of adhesive composition
The adhesive, the crosslinking agent, the UV monomer and the photoinitiator were mixed with the components and contents shown in the following table under the same conditions as in example 1 to prepare corresponding adhesive compositions.
[ Table 10 ]]
Figure BDA0002918346340000272
In the above table, the values in parentheses are parts by weight converted based on 100 parts by weight of binder solids.
-isocyanate-based crosslinking agent: solids content 45%, Saivinol hardener AL, Saiden Chemical Industry Co., Ltd.)
-crosslinking agents based on epoxy resins: solids content 5%, NA-30, Keda Mei Co (Cosmo Tech Co., Ltd.)
-phenyl (EO)nAcrylate (CAS number 56641-05-5) (n ═ 2)
Figure BDA0002918346340000273
2-Carboxyethyl acrylate (CAS number 56641-05-5)
Figure BDA0002918346340000281
-CibaTMIRGACURE 651
Figure BDA0002918346340000282
Test example 3: measurement of adhesion to polyimide
Single-sided tape samples were prepared in the same manner as in test example 1-1 using the respective adhesive compositions 3A to 3H prepared in example 3, the adhesion to the polyimide film before and after UV curing was measured, and the results are shown in the following table. In addition, changes in adhesive force before and after UV curing according to the content (parts by weight) of 2-carboxyethyl acrylate as an additional UV monomer are illustrated in fig. 6A and 6B, respectively.
[ Table 11]
Figure BDA0002918346340000283
As shown in the above table and fig. 6A and 6B, in the adhesive composition according to the embodiment, even with respect to various substrates, the adhesive force after UV curing is significantly increased compared to before UV curing. In particular, since the content of 2-carboxyethyl acrylate as an additional UV monomer is increased, the adhesive force is reduced before UV curing, and the adhesive force is increased after UV curing.
Example 4: preparation of adhesive composition
The adhesive, the crosslinking agent, the UV monomer and the photoinitiator were mixed with the components and contents shown in the following table under the same conditions as in example 1 to prepare corresponding adhesive compositions.
[ Table 12 ]]
Figure BDA0002918346340000291
In the above table, the values in parentheses are parts by weight converted based on 100 parts by weight of binder solids.
-isocyanate-based crosslinking agent: solids content 45%, Saivinol hardener AL, Saiden Chemical Industry Co., Ltd.)
-crosslinking agents based on epoxy resins: solids content 5%, NA-30, Keda Mei Co (Cosmo Tech Co., Ltd.)
-SA: octadecyl acrylate
Figure BDA0002918346340000292
-HDDA: 1, 6-hexanediol diacrylate
Figure BDA0002918346340000293
-BA: acrylic acid benzyl ester
Figure BDA0002918346340000301
-IBOA: acrylic acid isobornyl ester
Figure BDA0002918346340000302
-2-EHA: 2-ethylhexyl acrylate
Figure BDA0002918346340000303
2-Carboxyethyl (meth) acrylate
Figure BDA0002918346340000304
-CibaTMIRGACURE 651
Figure BDA0002918346340000305
Test example 4: measurement of adhesion to PI film
Using the respective adhesive compositions 4A to 4E prepared in example 4, single-sided tape samples were prepared in the same manner as in test example 1-1, adhesion to a polyimide film before and after UV curing was measured, and the results are shown in the following table.
In addition, the compatibility of the UV monomer with the adhesive in each adhesive composition was evaluated and is shown in the following table.
In addition, for comparison, the results of evaluating physical properties of the adhesive compositions prepared in examples 2 and 3 are shown in the following table.
[ Table 13 ]]
Figure BDA0002918346340000311
[ description of the reference numerals and symbolsMing dynasty]
100: adhesive tape
110: adhesive film according to embodiments
111: adhesive film on the area of application of the adhesive film
120: base film
130: anti-sticking film
200: substrate
300: UV light

Claims (16)

1. An adhesive composition, comprising:
a base polymer;
a crosslinking agent that reacts with the base polymer;
a first monomer that polymerizes after the base polymer and the crosslinking agent react; and
an initiator that polymerizes the first monomer,
wherein after the base polymer and the crosslinker react, the adhesive composition has a first adhesive force prior to polymerization of the first monomer and a second adhesive force after polymerization of the first monomer, and the second adhesive force is higher than the first adhesive force.
2. The adhesive composition of claim 1, wherein the adhesive composition has a haze of 2% or less after polymerization of the first monomer.
3. The adhesive composition of claim 1, wherein the base polymer comprises a functional group that reacts with the crosslinker.
4. The adhesive composition of claim 1, further comprising:
a second monomer different from the first monomer.
5. The adhesive composition of claim 4, wherein the second monomer forms an additional bond upon reaction of the base polymer and the crosslinker.
6. An adhesive film comprising the reaction product of a base polymer and a crosslinker,
wherein the adhesive film comprises a first monomer and an initiator, and the first monomer is capable of polymerizing by the initiator, and
the adhesive film has a first adhesive force before polymerization of the first monomer and a second adhesive force after polymerization of the first monomer, and the second adhesive force is higher than the first adhesive force.
7. The adhesive film of claim 6, wherein the adhesive film has a haze of 2% or less after polymerization of the first monomer.
8. The adhesive film of claim 6, further comprising:
a second monomer different from the first monomer, wherein the second monomer forms an additional bond in the reaction product of the base polymer and the crosslinker.
9. A method of making the adhesive film of claim 6, the method comprising:
mixing a base polymer, a first monomer, an initiator, and a crosslinking agent;
reacting the cross-linking agent with the base polymer to form a film-like polymer; and
retaining the first monomer and the initiator in the film-like polymer to obtain an adhesive film.
10. A laminate comprising a substrate and the adhesive film of claim 6.
11. The laminate of claim 10, wherein the substrate comprises polyimide.
12. The laminate of claim 10, wherein the laminate has areas with an adhesive film applied and areas without an adhesive film applied.
13. A method of making a laminate, the method comprising:
applying the adhesive film of claim 6 to a substrate;
forming an adhesive film-applied region and an adhesive film-unapplied region on the substrate by removing a portion of the adhesive film; and
polymerizing the first monomer contained in the adhesive film in the area where the adhesive film is applied by the initiator to improve the adhesive force of the adhesive film in the area where the adhesive film is applied.
14. A method of making a laminate, the method comprising:
preparing the adhesive composition of claim 1;
reacting the base polymer with the crosslinking agent to form an adhesive film retaining the first monomer and the initiator;
applying the adhesive film to a substrate;
forming an adhesive film-applied region and an adhesive film-unapplied region on the substrate by removing a portion of the adhesive film; and
polymerizing, by the initiator, a first monomer included in the adhesive film in the area where the adhesive film is applied to improve the adhesive force of the adhesive film in the area where the adhesive film is applied.
15. An apparatus comprising the laminate of claim 10.
16. A display device, the display device comprising:
a display panel; and
the laminate of claim 10 attached to the display panel.
CN201980050007.5A 2018-07-27 2019-07-24 Adhesive composition, adhesive film, laminate and method for producing the same Withdrawn CN112513111A (en)

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