CN112789338B - Reinforced film - Google Patents

Reinforced film Download PDF

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Publication number
CN112789338B
CN112789338B CN201980063830.XA CN201980063830A CN112789338B CN 112789338 B CN112789338 B CN 112789338B CN 201980063830 A CN201980063830 A CN 201980063830A CN 112789338 B CN112789338 B CN 112789338B
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meth
adhesive layer
acrylic
acrylate
pressure
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CN112789338A (en
Inventor
仲野武史
片冈贤一
米川雄也
藤山雄士
安江智广
池上贤真
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Soken Chemical and Engineering Co Ltd
Nitto Denko Corp
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Soken Chemical and Engineering Co Ltd
Nitto Denko Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J147/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Adhesives based on derivatives of such polymers
    • 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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their 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
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained 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
    • C09J7/20—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]
    • 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
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The reinforcing film (10) is provided with a pressure-sensitive adhesive layer (2) which is fixedly laminated on a film base material (1). The adhesive layer is a photocurable composition comprising a (meth) acrylic base polymer, (meth) acrylic oligomer, and a polyfunctional compound. It is preferable that: when the pressure-sensitive adhesive layer is trisected in the thickness direction and the region farthest from the substrate side is defined as the surface region, the amount of the polyfunctional compound present in the surface region is 50% or more of the amount of the polyfunctional compound present in the entire thickness direction, and the amount of the (meth) acrylic oligomer present in the surface region is 31% or less of the amount of the (meth) acrylic oligomer present in the entire thickness direction.

Description

Reinforced film
Technical Field
The present invention relates to a reinforcing film to be stuck to surfaces of various apparatuses and the like.
Background
For the purpose of protecting the surface, imparting impact resistance, and the like, an adhesive film may be attached to the surface of optical equipment and electronic equipment such as a display. Such an adhesive film is generally adhered to a device surface via an adhesive layer, which is fixedly laminated on a main surface of a film base.
In a state before use such as assembly, processing, transportation of equipment, damage or breakage of an adherend can be suppressed by temporarily adhering an adhesive film to the surface of the equipment or an equipment component. Such adhesive films are engineered materials that are peeled off and removed prior to use of the device. As described in patent document 1, an adhesive film used as an engineering material is required to have low adhesiveness, be easily peelable from an adherend, and not cause adhesive residue on the adherend.
Patent document 2 discloses an adhesive film which is used in a state of being stuck to a surface of a device when the device is used, in addition to assembly, processing, transportation, and the like of the device. Such an adhesive film has a function of reinforcing a device by dispersing an impact on the device, imparting rigidity to a flexible device, or the like while protecting the surface.
When an adhesive film is attached to an adherend, attachment defects such as mixing of air bubbles and displacement of the attachment position may occur. When the adhesion failure occurs, an operation (rework) of peeling the adhesive film from the adherend and adhering another adhesive film is performed. The pressure-sensitive adhesive film used as a construction material is designed on the premise of being peeled from an adherend, and therefore, can be easily reworked. On the other hand, the reinforcing film is not generally supposed to be peeled off from the device, and is firmly adhered to the surface of the device, so that it is difficult to perform rework.
Patent document 3 discloses a pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) designed to have low adhesiveness and to increase the adhesiveness with time immediately after the pressure-sensitive adhesive sheet is attached to an adherend. The pressure-sensitive adhesive film having such a pressure-sensitive adhesive layer fixedly laminated on a film base material is easily peeled from an adherend immediately after the pressure-sensitive adhesive film is adhered to the adherend, and is strongly adhered to the adherend after a predetermined time has elapsed.
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open publication No. 2013-185007
Patent document 2: japanese patent laid-open publication No. 2017-132977
Patent document 3: WO2015/163115 pamphlet
Disclosure of Invention
Problems to be solved by the invention
It is difficult to say that a reinforcing film whose adhesive strength to an adherend changes with time is sufficiently adaptable to lead time (lead time) of a process. For example, a reinforcing film having a pressure-sensitive adhesive layer with an increased adhesive strength over time needs to be inspected for the state of adhesion and reworked within a predetermined time after the reinforcing film is adhered to an adherend and before the adhesive strength increases. In addition, when a reinforcing film is attached to the entire surface of a device or a device component and then the reinforcing film is removed from a partial region, it is necessary to perform processing until the adhesive strength increases.
In view of the above circumstances, an object of the present invention is to provide a reinforcing film which can be easily reworked immediately after being attached to an adherend, can arbitrarily set the time until the adhesive strength is improved after the attachment to the adherend, and can be firmly attached to the adherend by improving the adhesive strength.
Means for solving the problems
The reinforced film of the present invention includes an adhesive layer fixedly laminated on one main surface of a film base. The adhesive layer is formed from a photocurable composition comprising a (meth) acrylic base polymer and a polyfunctional compound. The weight average molecular weight of the (meth) acrylic matrix polymer is preferably 10 ten thousand or more. The (meth) acrylic base polymer preferably contains a hydroxyl group-containing monomer as a monomer unit. It is preferable that a crosslinked structure is introduced into the (meth) acrylic base polymer. The polyfunctional compound is a compound containing 2 or more polymerizable functional groups, and is preferably a polyfunctional (meth) acrylate.
The photocurable composition for forming the adhesive layer comprises a (meth) acrylic base polymer, a polyfunctional compound, and a (meth) acrylic oligomer having a weight average molecular weight of 1000 to 50000. The adhesive layer preferably contains 3 to 30 parts by weight of a (meth) acrylic oligomer and 0.5 to 30 parts by weight of a polyfunctional compound per 100 parts by weight of the (meth) acrylic base polymer.
When the pressure-sensitive adhesive layer is trisected in the thickness direction and the region farthest from the substrate side is defined as the surface region, the amount of the polyfunctional compound present in the surface region is 50% or more of the amount of the polyfunctional compound present in the entire thickness direction. The amount of the (meth) acrylic oligomer present in the surface region is 31% or less of the amount of the (meth) acrylic oligomer present in the entire thickness direction.
ADVANTAGEOUS EFFECTS OF INVENTION
In the reinforcing film of the present invention, the pressure-sensitive adhesive layer is formed from the photocurable composition, and the polyfunctional compound is present in a slightly larger amount in the surface layer region, so that the pressure-sensitive adhesive layer has a small adhesive strength before photocuring and is easily peeled from an adherend. Further, the adhesive layer shows high adhesion to an adherend after photocuring, and thus contributes to the enhancement of the device and the improvement of reliability.
Drawings
Fig. 1 is a sectional view showing a laminated structure of a reinforcing film.
Fig. 2 is a sectional view showing a laminated structure of the reinforcing film.
Detailed Description
FIG. 1 is a cross-sectional view illustrating one embodiment of a reinforced membrane. The reinforcing film 10 includes an adhesive layer 2 on one main surface of a film substrate 1. The pressure-sensitive adhesive layer 2 is fixedly laminated on one main surface of the base film 1. The pressure-sensitive adhesive layer 2 is a photocurable pressure-sensitive adhesive formed of a photocurable composition, and is cured by irradiation with active light such as ultraviolet light, whereby the adhesive strength with an adherend is increased.
Fig. 2 is a cross-sectional view of a reinforcing film in which a separator 5 is temporarily bonded to a main surface of an adhesive layer 2. The reinforcing film 10 is attached to the surface of the adherend by peeling and removing the separator 5 from the surface of the pressure-sensitive adhesive layer 2 and attaching the exposed surface of the pressure-sensitive adhesive layer 2 to the adherend. In this state, the pressure-sensitive adhesive layer 2 is in a state in which the reinforcing film 10 (pressure-sensitive adhesive layer 2) is temporarily bonded to an adherend before photocuring. By photo-curing the pressure-sensitive adhesive layer 2, the adhesive strength at the interface between the adherend and the pressure-sensitive adhesive layer 2 increases, and the adherend is fixed to the reinforcing film 10.
"fixed" means that the two laminated layers are firmly bonded and cannot be peeled off or hardly peeled off at the interface between the two layers. The term "temporary bonding" means a state in which the adhesion between the two stacked layers is small and the layers can be easily peeled off from each other at the interface between the two layers.
In the reinforcing film shown in fig. 2, the film base 1 is fixed to the pressure-sensitive adhesive layer 2, and the separator 5 is temporarily bonded to the pressure-sensitive adhesive layer 2. When the separator 5 is peeled off, peeling occurs at the interface between the pressure-sensitive adhesive layer 2 and the separator 5, and the state in which the pressure-sensitive adhesive layer 2 is fixed to the film base 1 is maintained. No adhesive remains on the release film 5 after peeling.
[ film base ]
As the film substrate 1, a plastic film is used. In order to fix the film base 1 and the pressure-sensitive adhesive layer 2, the surface of the film base 1 on which the pressure-sensitive adhesive layer 2 is provided is preferably not subjected to release treatment.
The film base material has a thickness of about 4 to 500 μm, for example. The thickness of the film base 1 is preferably 20 μm or more, more preferably 30 μm or more, and further preferably 45 μm or more, from the viewpoint of reinforcing the device by imparting rigidity, relaxing impact, and the like. From the viewpoint of providing flexibility to the reinforcing film and improving the handling properties, the thickness of the film base 1 is preferably 300 μm or less, more preferably 200 μm or less.
Examples of the plastic material constituting the film base 1 include polyester resin, polyolefin resin, polyamide resin, and polyimide resin. In a reinforcing film for optical devices such as displays, the film base 1 is preferably a transparent film. When the pressure-sensitive adhesive layer 2 is photo-cured by irradiation with actinic light from the film substrate 1 side, the film substrate 1 is preferably transparent to actinic light used for curing the pressure-sensitive adhesive layer. Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate are suitably used in view of achieving both mechanical strength and transparency.
[ adhesive layer ]
A reinforced film is obtained by providing an adhesive layer 2 on a film base 1. The pressure-sensitive adhesive layer 2 may be formed directly on the film base 1, or a pressure-sensitive adhesive layer formed in a sheet form on another base may be transferred onto the film base 1.
The adhesive layer 2 is formed of a photocurable composition. The pressure-sensitive adhesive layer 2 has a small adhesive force with an adherend such as a device or a device member before photocuring, and therefore can be easily reworked. Since the pressure-sensitive adhesive layer 2 has improved adhesion to an adherend by photocuring, the reinforcing film is less likely to peel off from the surface of the device even when the device is used, and the adhesion reliability is excellent.
The thickness of the adhesive layer 2 is, for example, about 1 to 300 μm. The adhesive property to an adherend tends to be improved as the thickness of the pressure-sensitive adhesive layer 2 is increased. On the other hand, when the thickness of the pressure-sensitive adhesive layer 2 is too large, the fluidity before photocuring is high, and handling may be difficult. Therefore, the thickness of the adhesive layer 2 is preferably 5 to 100 μm, more preferably 8 to 50 μm, still more preferably 10 to 40 μm, and particularly preferably 13 to 30 μm.
When the reinforcing film is used for an optical device such as a display, the total light transmittance of the pressure-sensitive adhesive layer 2 is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. The haze of the pressure-sensitive adhesive layer 2 is preferably 2% or less, more preferably 1% or less, further preferably 0.7% or less, and particularly preferably 0.5% or less.
The adhesive composition (photocurable composition) constituting the adhesive layer 2 contains a (meth) acrylic base polymer, a (meth) acrylic oligomer, and a polyfunctional compound. The pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer 2 preferably contains a photopolymerization initiator from the viewpoint of improving the efficiency of curing by irradiation with active light.
The (meth) acrylic base polymer is a main component of the adhesive composition, and is a main factor that determines the adhesive strength of the adhesive. In view of preventing adhesive residue on an adherend by facilitating peeling when the reinforcing film is peeled from the adherend before photocuring of the pressure-sensitive adhesive layer 2, it is preferable to introduce a crosslinked structure into the (meth) acrylic base polymer.
The polyfunctional compound has 2 or more polymerizable functional groups in 1 molecule. The polyfunctional compound has the effect of improving the cohesive property of the pressure-sensitive adhesive after photocuring and improving the adhesion to an adherend. Further, by making the amount of the polyfunctional compound present in the surface region 2a of the pressure-sensitive adhesive layer 2 before photocuring larger than the amount of the polyfunctional compound present in the other regions 2b, 2c in the thickness direction, the adhesive strength between the pressure-sensitive adhesive 2 before photocuring and the adherend is appropriately reduced, and the releasability of the reinforcing sheet from the adherend tends to be improved.
The (meth) acrylic oligomer has a function of adjusting the adhesive force of the adhesive before and after photocuring by providing a composition in the thickness direction of the adhesive layer 2 before photocuring with a distribution. In particular, when the amount of the (meth) acrylic oligomer present in the surface region 2a of the pressure-sensitive adhesive layer 2 before photocuring is smaller than the amount of the (meth) acrylic oligomer present in the intermediate region 2b and the substrate-side region 2c, the following tendency is present: the adhesive strength before photocuring is small, the peelability is excellent, the adhesive strength is greatly improved by photocuring, and the adhesion reliability is improved.
Hereinafter, the psa layer 2 is trisected in the thickness direction, and the region 1/3 on the surface layer side (the region farthest from the film substrate 1) is referred to as the "surface region", the region 1/3 at the center in the thickness direction is referred to as the "middle region", and the region 1/3 on the film substrate 1 side is referred to as the "substrate-side region".
When the composition distribution of the pressure-sensitive adhesive layer 2 is measured from the surface layer side toward the film base material side by Secondary Ion Mass Spectrometry (SIMS) with respect to the pressure-sensitive adhesive layer 2, the presence ratio of each component in the surface layer region 2a, the presence ratio in the intermediate layer region 2b, and the presence ratio in the base material side region 2c have a distribution with respect to 100% of the total amount. In the case where the pressure-sensitive adhesive layer does not have a composition distribution in the thickness direction, the ratio of each component present in the surface layer region 2a, the intermediate layer region 2b, and the substrate side region 2c is about 33%. In contrast, in the pressure-sensitive adhesive layer 2 of the reinforced film of the present invention, the ratio of the polyfunctional compound present in the surface region 2a is 50% or more, and the ratio of the (meth) acrylic oligomer present in the surface region 2a is 31% or less. In the present specification, the "presence ratio of the polyfunctional compound in the surface region" means: the presence ratio of the polyfunctional compound in the surface region to 100% of the total amount of the polyfunctional compounds contained in the adhesive layer, "(meth) acrylic oligomer presence ratio in the surface region" means: the presence ratio of the (meth) acrylic oligomer in the surface layer region to 100% of the total amount of the (meth) acrylic oligomer contained in the adhesive layer.
The presence ratio of the (meth) acrylic oligomer in the surface layer region 2a is preferably 30% or less, more preferably 29% or less, further preferably 28% or less, and particularly preferably 27.5% or less. The ratio of the (meth) acrylic oligomer present in the surface region 2a is usually 15% or more, and from the viewpoint of improving the transparency of the adhesive, is preferably 20% or more, more preferably 23% or more, and still more preferably 25% or more.
The presence ratio of the polyfunctional compound in the surface region 2a is preferably 55% or more, more preferably 60% or more, further preferably 63% or more, and particularly preferably 65% or more. The presence ratio of the polyfunctional compound in the surface region 2a is usually 95% or less, and is preferably 93% or less, more preferably 90% or less, and even more preferably 87% or less, from the viewpoint of improving the adhesion of the pressure-sensitive adhesive layer 2 to an adherend after photocuring.
There is a tendency that: the smaller the amount of the (meth) acrylic oligomer present in the surface layer region 2a, the larger the amount of the polyfunctional compound present in the surface layer region 2a, and the higher the adhesive strength of the pressure-sensitive adhesive layer 2 to the adherend after photocuring. On the other hand, if the amount of the polyfunctional compound present in the surface layer region 2a is too large, the adhesive strength after photocuring may not be sufficiently increased.
Preferred embodiments of the components constituting the pressure-sensitive adhesive composition will be described below in order.
[ meth (acrylic) base Polymer ]
The (meth) acrylic base polymer is a polymer containing an alkyl (meth) acrylate as a main monomer component and having a weight average molecular weight of 10 ten thousand or more. In the present specification, "(meth) acrylic acid" means acrylic acid and/or methacrylic acid.
As the alkyl (meth) acrylate, alkyl (meth) acrylates in which the alkyl group has 1 to 20 carbon atoms are suitably used. The alkyl group of the alkyl (meth) acrylate may be linear or branched. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, isotridecyl (meth) acrylate, tetradecyl (meth) acrylate, dodecyl (meth) acrylate, and the like, Isotetradecyl (meth) acrylate, pentadecyl (meth) acrylate, cetyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, isostearyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, and the like.
The content of the alkyl (meth) acrylate is preferably 40% by weight or more, more preferably 50% by weight or more, and still more preferably 55% by weight or more, based on the total amount of the monomer components constituting the (meth) acrylic base polymer.
The (meth) acrylic base polymer preferably contains a monomer component having a crosslinkable functional group as a copolymerization component. Examples of the monomer having a crosslinkable functional group include a hydroxyl group-containing monomer and a carboxyl group-containing monomer. Among these, the (meth) acrylic base polymer preferably contains a hydroxyl group-containing monomer as a copolymerization component. The hydroxyl group and the carboxyl group of the (meth) acrylic base polymer serve as reactive sites with a crosslinking agent described later. By introducing a crosslinked structure into the (meth) acrylic base polymer, the cohesive force is improved, the adhesiveness of the pressure-sensitive adhesive layer 2 is improved, and the fluidity of the pressure-sensitive adhesive is lowered, so that the residual adhesive on the adherend during reprocessing tends to be reduced.
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, and 4- (hydroxymethyl) cyclohexylmethyl (meth) acrylate. Examples of the carboxyl group-containing monomer include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
In addition to the above, as the comonomer component, a monomer containing an acid anhydride group, a caprolactone adduct of acrylic acid, a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, or the like can be used for the (meth) acrylic base polymer. Further, as the modifying monomer, vinyl monomers such as vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methyl vinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, N-vinylcarboxylic acid amides, styrene, α -methylstyrene, and N-vinylcaprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; (meth) acrylamide monomers such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl acrylamide, and N-isopropyl (meth) acrylamide; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; glycol-based acrylate monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate; and (meth) acrylate monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine-containing (meth) acrylate, silicone (meth) acrylate, and 2-methoxyethyl acrylate.
The ratio of the comonomer component in the (meth) acrylic base polymer is not particularly limited, and for example, when a hydroxyl group-containing monomer and a carboxyl group-containing monomer are used as the comonomer component for the purpose of introducing a crosslinking point, the total content of the hydroxyl group-containing monomer and the carboxyl group-containing monomer is preferably about 1 to 20% by weight, more preferably 2 to 15% by weight, based on the total amount of the monomer components constituting the (meth) acrylic base polymer.
The (meth) acrylic base polymer is obtained by polymerizing the above monomer components by various known methods such as solution polymerization, emulsion polymerization, bulk polymerization, and the like. From the viewpoints of balance of properties such as adhesion and holding power of the adhesive, cost, and the like, the solution polymerization method is preferable. As a solvent for solution polymerization, ethyl acetate, toluene, or the like can be used. The concentration of the solution is usually about 20 to 80 wt%. As the polymerization initiator, various known polymerization initiators such as azo-based polymerization initiators and peroxide-based polymerization initiators can be used. In order to adjust the molecular weight, a chain transfer agent may be used. The reaction temperature is usually 50-80 ℃ and the reaction time is usually 1-8 hours.
From the viewpoint of imparting an appropriate holding force to the pressure-sensitive adhesive layer 2, the weight average molecular weight of the (meth) acrylic base polymer is preferably 10 ten thousand or more. From the viewpoint of processability, transparency, and the like of the pressure-sensitive adhesive layer 2, the weight average molecular weight of the (meth) acrylic base polymer is preferably 200 ten thousand or less. The weight average molecular weight of the (meth) acrylic base polymer is preferably 20 to 150 ten thousand, and more preferably 40 to 120 ten thousand. The weight average molecular weight is a molecular weight in terms of polystyrene measured by Gel Permeation Chromatography (GPC). When a crosslinked structure is introduced into the matrix polymer, the molecular weight of the (meth) acrylic matrix polymer before the introduction of the crosslinked structure is preferably in the above range.
In order to obtain the pressure-sensitive adhesive layer 2 having appropriate adhesiveness to an adherend in a normal temperature environment, the glass transition temperature (Tg) of the (meth) acrylic base polymer in terms of Fox formula is preferably 0 ℃ or lower. The Tg of the (meth) acrylic matrix polymer is preferably from-80 to-10 ℃, more preferably from-75 to-20 ℃, and still more preferably from-70 to-20 ℃.
< crosslinking agent >
From the viewpoint of providing a moderate cohesive force to the pressure-sensitive adhesive, it is preferable to introduce a crosslinked structure into the (meth) acrylic base polymer. For example, a crosslinking structure is introduced by adding a crosslinking agent to a solution after polymerization of a (meth) acrylic base polymer and heating the solution as necessary. Examples of the crosslinking agent include an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, an oxazoline-based crosslinking agent, an aziridine-based crosslinking agent, a carbodiimide-based crosslinking agent, and a metal chelate-based crosslinking agent. These crosslinking agents react with functional groups such as hydroxyl groups introduced into the (meth) acrylic base polymer to form a crosslinked structure.
The crosslinking agent is preferably a polyisocyanate having 2 or more isocyanate groups in 1 molecule, because a crosslinked structure can be introduced into the (meth) acrylic base polymer by heating. Examples of the polyisocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; aromatic isocyanates such as 2, 4-tolylene diisocyanate, 4' -diphenylmethane diisocyanate, and xylylene diisocyanate; trimethylolpropane/tolylene diisocyanate trimer adduct (e.g., "CORONATE L" manufactured by Tosoh corporation), trimethylolpropane/hexamethylene diisocyanate trimer adduct (e.g., "CORONATE HL" manufactured by Tosoh corporation), and xylylene diisocyanate trimethylolpropane adduct (e.g., "TAKENATE D110N" manufactured by Mitsui chemical corporation and isocyanurate of hexamethylene diisocyanate (e.g., "CORONATE HX" manufactured by Tosoh corporation and "Y-75" manufactured by Suchoy chemical corporation), and the like.
The amount of the crosslinking agent to be used may be appropriately adjusted depending on the composition, molecular weight, and the like of the (meth) acrylic base polymer. The amount of the crosslinking agent is 0.1 to 10 parts by weight, preferably 0.2 to 7 parts by weight, more preferably 0.3 to 5 parts by weight, and still more preferably 1 to 4 parts by weight, based on 100 parts by weight of the (meth) acrylic base polymer.
To promote the formation of a crosslinked structure, a crosslinking catalyst may be used. Examples of the crosslinking catalyst include metallic crosslinking catalysts (particularly tin crosslinking catalysts) such as tetra-n-butyl titanate, tetra-isopropyl titanate, ferrous NACEM, butyltin oxide, dibutyltin acetate, dibutyltin dilaurate, dioctyltin diacetate, dioctyltin distearate and dioctyltin dilaurate. The crosslinking catalyst is generally used in an amount of 0.05 parts by weight or less based on 100 parts by weight of the (meth) acrylic base polymer.
< polyfunctional Compound >
As the polyfunctional compound, a photocurable monomer or a photocurable oligomer can be used. The polyfunctional compound is preferably a compound having 2 or more ethylenically unsaturated bonds in 1 molecule.
From the viewpoint of high affinity with the (meth) acrylic base polymer, it is preferable to use a polyfunctional (meth) acrylate as the polyfunctional compound. Examples of the polyfunctional (meth) acrylate include esters of a glycol and a (meth) acrylic acid such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate; esters of (meth) acrylic acid and a polyhydric alcohol having 3 or more hydroxyl groups such as pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, bis (trimethylolpropane) tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; and compounds having a (meth) acryloyl group and a polymerizable functional group other than the (meth) acryloyl group, such as urethane (meth) acrylate, epoxy (meth) acrylate, butadiene (meth) acrylate, and isoprene (meth) acrylate.
As the polyfunctional compound, an ester of a (meth) acryloyl group and a modified product of a polyhydric alcohol based on an alkylene oxide such as formaldehyde, ethylene oxide, or propylene oxide can be used. Examples of the ester of the alkylene oxide-modified product of the polyhydric alcohol and the (meth) acryloyl group include esters in which 1 or more oxyalkylene groups are inserted between the polyhydric alcohol and the (meth) acryloyl group. By inserting an oxyalkylene group, the functional group equivalent of the polyfunctional compound becomes large (that is, the number of functional groups per unit molecular weight becomes small), and the polarity of the molecule also changes. Furthermore, the compatibility of the polyfunctional compound with the (meth) acrylic base polymer and the (meth) acrylic oligomer changes by the insertion of the oxyalkylene group, and the composition distribution in the thickness direction in the pressure-sensitive adhesive layer before photocuring, the adhesiveness of the pressure-sensitive adhesive after photocuring, and the like may change accordingly.
From the viewpoint of improving the adhesion after photocuring, the functional group equivalent (g/eq) of the polyfunctional compound is preferably 500 or less, more preferably 450 or less. On the other hand, if the photo-crosslinking density is excessively increased, the viscosity of the adhesive may be decreased, and the adhesive strength may be decreased. Therefore, the functional group equivalent of the polyfunctional compound is preferably 100 or more, more preferably 130 or more, and further preferably 150 or more. When the functional group equivalent of the polyfunctional compound is small, the interaction between the (meth) acrylic base polymer and the polyfunctional compound is strong, and the adhesive strength of the pressure-sensitive adhesive layer 2 before photocuring increases, and peeling from an adherend may be difficult. From the viewpoint of maintaining the adhesion between the pressure-sensitive adhesive layer 2 before photocuring and an adherend within an appropriate range, it is also preferable that the functional group equivalent of the polyfunctional compound is within the above range. The molecular weight of the polyfunctional compound is preferably 100 to 1000.
The content of the polyfunctional compound in the adhesive composition is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, and still more preferably 2 to 15 parts by weight, based on 100 parts by weight of the (meth) acrylic base polymer. By containing 0.5 parts by weight or more of the polyfunctional compound, the polyfunctional compound tends to be present in the surface layer portion 2a in the pressure-sensitive adhesive layer 2 before photocuring, and the adhesive strength with the adherend tends to be lowered appropriately. On the other hand, if the content of the polyfunctional compound in the pressure-sensitive adhesive composition is excessively increased, the transparency may be reduced due to bleeding of the polyfunctional compound, and the viscosity of the pressure-sensitive adhesive after photocuring may be reduced, thereby failing to obtain sufficient adhesive strength. Since the polyfunctional compound is contained in the composition in an uncured state, it is preferable to add the polyfunctional compound after polymerizing the (meth) acrylic base polymer.
[ meth (acrylic) oligomer ]
The adhesive layer 2 contains a (meth) acrylic oligomer. The (meth) acrylic oligomer functions as a thickener and contributes to improvement of adhesion of the pressure-sensitive adhesive after photocuring to an adherend. In the present invention, the adhesive composition further contains a (meth) acrylic oligomer in addition to the matrix polymer and the polyfunctional compound, and thus has a function of providing a distribution in the composition in the thickness direction of the adhesive layer 2 and adjusting the adhesive force of the adhesive before and after photocuring.
The (meth) acrylic oligomer is a polymer containing a (meth) acrylic monomer, and is a component having a weight average molecular weight smaller than that of the (meth) acrylic matrix polymer. The weight average molecular weight of the (meth) acrylic oligomer is 1000 to 50000. From the viewpoint of having a moderate affinity with the (meth) acrylic base polymer and the polyfunctional compound and maintaining the transparency of the pressure-sensitive adhesive layer 2, the weight average molecular weight of the (meth) acrylic oligomer is preferably 30000 or less, more preferably 10000 or less, and still more preferably 8000 or less.
The (meth) acrylic oligomer contains an alkyl (meth) acrylate as a main monomer component. The content of the alkyl (meth) acrylate is 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more, based on the total amount of the monomer components constituting the (meth) acrylic oligomer. In a preferred embodiment, the (meth) acrylic oligomer contains substantially only an alkyl (meth) acrylate as a monomer component. The (meth) acrylic oligomer may contain 2 or more monomer components.
The monomer component constituting the (meth) acrylic oligomer preferably does not form a crosslinked structure with the crosslinking agent. That is, the monomer component constituting the (meth) acrylic oligomer preferably does not contain a hydroxyl group or a carboxyl group.
Examples of the monomer component constituting the (meth) acrylic oligomer include alkyl (meth) acrylates having a straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms, which have been exemplified above as the monomer component constituting the (meth) acrylic base polymer. Other than these, alicyclic group-containing (meth) acrylates such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate; (meth) acrylates having an aromatic ring-or heterocyclic ring-containing group such as benzyl (meth) acrylate, 2-naphthyl (meth) acrylate, pentamethylpiperidine (meth) acrylate, and 2-phenoxyethyl (meth) acrylate; monomer components such as methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl methacrylate, and the like are also suitable as monomer components constituting the (meth) acrylic oligomer.
< photoinitiator >
The adhesive layer 2 preferably contains a photoinitiator. The photoinitiator generates an active species by irradiation of an active ray, and accelerates a curing reaction of the polyfunctional compound. As the photoinitiator, a photo cation initiator (photo acid generator), a photo radical initiator, a photo anion initiator (photo base generator), or the like can be used depending on the kind of the polyfunctional compound or the like. When a polyfunctional acrylate is used as the polyfunctional compound, a photo radical initiator is preferably used. Examples of the photo radical initiator include hydroxyketones, benzildimethylketals, aminoketones, acylphosphine oxides, benzophenones, trichloromethyl group-containing triazine derivatives, and the like. The photo radical generators may be used alone or in combination of 2 or more. The content of the photopolymerization initiator in the adhesive layer 2 is preferably 0.001 to 10 parts by weight, and more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the total amount of the adhesive layer 2.
< other additives >
The adhesive composition may contain additives such as a silane coupling agent, a tackifier, a plasticizer, a softening agent, an anti-deterioration agent, a filler, a colorant, an ultraviolet absorber, an antioxidant, a surfactant, and an antistatic agent in addition to the above-exemplified components within a range not to impair the characteristics of the present invention.
< formation of adhesive layer >
The above adhesive composition comprising a (meth) acrylic base polymer, a polyfunctional compound and a (meth) acrylic oligomer is coated on a substrate by roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, die coating or the like, and dried to remove the solvent as necessary, thereby forming an adhesive layer. As the drying method, an appropriate method can be suitably employed. The heating and drying temperature is preferably 40 to 200 ℃, more preferably 50 to 180 ℃, and still more preferably 70 to 170 ℃. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 15 minutes, and further preferably 10 seconds to 10 minutes.
When the adhesive composition contains a crosslinking agent, crosslinking is preferably performed by heating or curing at the same time as or after drying of the solvent. The heating temperature and the heating time are appropriately set depending on the kind of the crosslinking agent to be used, and the crosslinking is usually performed by heating at 20 to 160 ℃ for about 1 minute to 7 days. The heating for drying off the solvent may double as the heating for crosslinking.
By introducing a crosslinked structure into the (meth) acrylic base polymer, the gel fraction of the pressure-sensitive adhesive layer 2 tends to increase. The higher the gel fraction of the pressure-sensitive adhesive layer 2 is, the harder the pressure-sensitive adhesive becomes, and when the reinforcing film is peeled from the adherend by reworking or the like, the adhesive residue on the adherend tends to be suppressed. The gel fraction of the pressure-sensitive adhesive layer 2 before photocuring is preferably 20% or more, more preferably 30% or more, and still more preferably 40% or more. If the gel fraction of the pressure-sensitive adhesive layer 2 before photocuring is too large, the anchoring force to an adherend may be reduced, and the adhesive strength may be insufficient. Therefore, the gel fraction of the pressure-sensitive adhesive layer 2 before photocuring is preferably 95% or less, more preferably 90% or less, still more preferably 85% or less, and particularly preferably 80% or less. The gel fraction can be determined as an insoluble component in a solvent such as ethyl acetate, specifically, as a weight fraction (unit: weight%) of an insoluble component after the pressure-sensitive adhesive layer is immersed in ethyl acetate at 23 ℃ for 7 days with respect to the sample before immersion. Generally, the gel fraction and the degree of crosslinking of a polymer are equal, and the more the crosslinking portion in the polymer, the larger the gel fraction becomes.
The polyfunctional compound is also left unreacted after the crosslinking structure is introduced into the (meth) acrylic base polymer by the crosslinking agent. When a (meth) acrylic oligomer having no reactive functional group with the crosslinking agent is used, the (meth) acrylic oligomer is present in the pressure-sensitive adhesive layer 2 in a state of not forming a chemical bond with the (meth) acrylic matrix polymer.
When the pressure-sensitive adhesive layer 2 is formed on the film base 1, the separator 5 is preferably provided on the pressure-sensitive adhesive layer 2 for the purpose of, for example, protecting the pressure-sensitive adhesive layer 2. The release film 5 may be attached to the adhesive layer 2 and then crosslinked. When the pressure-sensitive adhesive layer 2 is formed on another substrate, the pressure-sensitive adhesive layer 2 is transferred to the film substrate 1 after drying the solvent, thereby obtaining a reinforced film. The substrate for forming the adhesive layer may be used directly as the separator 5.
As the separator 5, a plastic film such as polyethylene, polypropylene, polyethylene terephthalate, or polyester film is preferably used. The thickness of the separator is usually 3 to 200 μm, preferably 10 to 100 μm. The surface of the separator 5 in contact with the pressure-sensitive adhesive layer 2 is preferably subjected to a release treatment with a silicone-based, fluorine-based, long-chain alkyl-based, or fatty acid amide-based release agent, or with silica powder or the like. By performing the release treatment on the surface of the separator 5, when the film base 1 and the separator 5 are peeled off, peeling occurs at the interface between the pressure-sensitive adhesive layer 2 and the separator 5, and the state in which the pressure-sensitive adhesive layer 2 is fixed to the film base 1 is maintained.
As described above, the pressure-sensitive adhesive layer 2 before photocuring has a composition distribution in the thickness direction, the ratio of the polyfunctional compound present in the surface layer region 2a is 50% or more, and the ratio of the (meth) acrylic oligomer present in the surface layer region 2a is 31% or less. That is, the amount of the polyfunctional compound present in the surface region (interface to be adhered to an adherend) is larger than that in the intermediate region and the substrate-side region, and the amount of the (meth) acrylic oligomer present is smaller.
It can be considered that: by making the polyfunctional compound of low molecular weight be present in the surface Layer region 2a with a slight weight, an adhesion-inhibiting Layer (WBL) is formed at the adhesion interface with the adherend, and the pressure-sensitive adhesive Layer 2 before photocuring has strong liquid properties at the adhesion interface with the hardness as a main component, and thus has a small adhesion force to the adherend. Further, it is considered that: since the polyfunctional compound is present in the surface region 2a serving as the adhesion interface with the adherend, the increase in the cohesive force at the adherend interface due to the photocuring becomes significant. By increasing the cohesive force of the pressure-sensitive adhesive layer after photocuring at the adherend interface, the adhesive strength to the adherend is greatly increased, and the adhesion reliability of the reinforcing film is improved.
It can be considered that: the composition distribution in the thickness direction depends on the compatibility of the three components of the (meth) acrylic base polymer, the polyfunctional compound and the (meth) acrylic oligomer. The compatibility of the (meth) acrylic base polymer with the polyfunctional compound is mainly affected by the structure of the compound. The structure and compatibility of the compounds can be assessed, for example, by Hansen (Hansen) solubility parameters.
The Hansen Solubility Parameter (HSP) is the splitting of the solubility parameter delta of Hildebrand into a dispersion term deltadPolar term δpAnd hydrogen bond term δhThe three components, and the parameter, δ, expressed in three-dimensional space2＝δd 2+δp 2+δh 2The relationship of (1) is true. Dispersion term deltadIndicating the effect based on the dispersion force, the polarity term δpRepresenting the effect based on the force between dipoles, the hydrogen bond term deltahIndicating the effect based on hydrogen bonding force. The distance Ra of HSP of two substances is determined by the difference Delta of dispersion terms between the two substancesdThe difference of the polarity terms deltapDifference of the hydrogen bond term Δ δhBy Ra ═ {4 Δ δd 2+Δδp 2+Δδh 2}1/2The smaller the Ra, the higher the compatibility, and the larger the Ra, the lower the compatibility.
Details of Hansen Solubility Parameters are described in Charles m.hansen, Hansen Solubility Parameters: a Users Handbook (CRC Press, 2007) was calculated for unknown substances such as literature values using computer software Handsen Solubility Parameters In Practice (HSPiP).
It can be considered that: the presence of a bias in the surface region of the polyfunctional compound depends on the compatibility of the (meth) acrylic base polymer as a main component of the adhesive composition with the polyfunctional compound. Namely, it can be considered that: by using a polyfunctional compound having a moderately large HSP distance from the (meth) acrylic base polymer, the presence of a predominant amount of the polyfunctional compound in the surface region can be promoted.
When the compatibility of the (meth) acrylic oligomer with the polyfunctional compound is low, the presence ratio of the (meth) acrylic oligomer having low compatibility with the polyfunctional compound in the surface region decreases as the polyfunctional compound is present in a different weight in the surface region. It can therefore be considered that: by using a (meth) acrylic oligomer having a moderately large HSP distance from the polyfunctional compound, the pressure-sensitive adhesive layer 2 having a relatively small (e.g., 31% or less) ratio of the (meth) acrylic oligomer present in the surface region can be formed. Further, it can be considered that: compatibility with the (meth) acrylic matrix polymer as a main component of the adhesive composition also becomes a factor affecting the amount of the (meth) acrylic oligomer present in the surface layer region.
In view of these, by selecting a combination of the (meth) acrylic base polymer, the polyfunctional compound, and the (meth) acrylic oligomer constituting the adhesive composition, it is possible to form an adhesive layer which has a small amount of the (meth) acrylic oligomer present in the surface region and exhibits high adhesiveness by photocuring.
[ sticking and photocuring of reinforcing sheet to adherend ]
The reinforcing film of the present invention is used by being attached to a component (semi-finished product) of various apparatuses and the completed apparatuses. In the manufacturing process of the device, when the reinforcing film is attached to the semi-finished product, the reinforcing film may be attached to the large-sized semi-finished product before being cut into the product size. The reinforcing film may be stuck by roll-to-roll on a main roll of an apparatus manufactured by a roll-to-roll process. The reinforcing film may be attached to the entire surface of the adherend, or may be selectively attached only to a portion to be reinforced. In addition, after the reinforcing film is attached to the entire surface of the adherend, the reinforcing film in the portion where reinforcement is not necessary may be cut, and the reinforcing film may be peeled off and removed.
Since the adhesive layer has a low adhesion to the adherend before photocuring of the adhesive and the reinforcing film is temporarily adhered to the surface of the adherend, the reinforcing film can be easily peeled and removed from the surface of the adherend, and the reworkability is excellent. As described above, by making the polyfunctional compound be present more heavily in the surface layer region of the pressure-sensitive adhesive layer 2, the adhesiveness before photocuring tends to be small.
The adhesion strength between the pressure-sensitive adhesive layer 2 before photocuring and the adherend is preferably 1N/25mm or less, more preferably 0.8N/25mm or less, and even more preferably 0.6N/25mm or less, from the viewpoint of facilitating peeling from the adherend and preventing adhesive residue on the adherend after peeling the reinforcing film. On the other hand, the adhesion strength between the pressure-sensitive adhesive layer 2 before photocuring and the adherend is preferably 0.01N/25mm or more, more preferably 0.05N/25mm or more, further preferably 0.15N/25mm or more, and particularly preferably 0.1N/25mm or more, from the viewpoint of preventing the reinforcing sheet from peeling from the adherend during storage and handling. The adhesive strength was evaluated by a 180 ° peel test at a tensile rate of 300 mm/min using a SUS304 plate as an adherend.
After the reinforcing film is attached to the adherend, the pressure-sensitive adhesive layer 2 is irradiated with active light to photocure the pressure-sensitive adhesive layer. Examples of the active rays include ultraviolet rays, visible light, infrared rays, X-rays, α -rays, β -rays, and γ -rays. The active light is preferably ultraviolet light because curing of the pressure-sensitive adhesive layer in a storage state can be suppressed and curing is easy. The irradiation intensity and the irradiation time of the active light may be appropriately set depending on the composition, thickness, and the like of the pressure-sensitive adhesive layer.
From the viewpoint of adhesion reliability in actual use of equipment, the adhesion force between the pressure-sensitive adhesive layer after photocuring and an adherend is preferably 5N/25mm or more, more preferably 8N/25mm or more, and still more preferably 10N/25mm or more. The adhesion strength between the pressure-sensitive adhesive layer after photocuring and the adherend is preferably 10 times or more, more preferably 15 times or more, and still more preferably 20 times or more the adhesion strength between the pressure-sensitive adhesive layer 2 before photocuring and the adherend.
As described above, in the pressure-sensitive adhesive layer 2 before photocuring, when the presence ratio of the (meth) acrylic oligomer in the surface layer region is small, the adhesive strength tends to increase greatly by photocuring. Even when the pressure-sensitive adhesive layer 2 before photocuring has a composition distribution in the thickness direction, the ratio of the (meth) acrylic oligomer present in the pressure-sensitive adhesive layer after photocuring is often substantially uniform in the thickness direction. It can be presumed from the fact that: the movement of the (meth) acrylic oligomer existing in the substrate-side region and the interlayer region before photocuring to the surface region with photocuring is associated with the improvement of the adhesive strength.
When the polymerization of the polyfunctional compound is carried out by photocuring, the liquid properties of the polyfunctional compound existing in the surface region are weakened, WBL disappears, and the compatibility between the (meth) acrylic matrix polymer and the polyfunctional compound is increased. Accordingly, the compatibility of the (meth) acrylic oligomer with other components in the surface region is substantially equal to the compatibility of the (meth) acrylic oligomer with other components in the middle layer region and the substrate side region. As the photocuring proceeds, the factor of the distribution of the existence ratio of the (meth) acrylic oligomer in the thickness direction is eliminated, and the concentration of the (meth) acrylic oligomer in the surface region becomes high. As described above, when the pressure-sensitive adhesive layer is photocured, the cohesive force in the surface layer region increases due to the polymerization of the polyfunctional compound existing in a heavier manner before photocuring. On this basis, it can be considered that: the increased concentration of the (meth) acrylic oligomer functioning as a thickener in the surface layer region also contributes to an improvement in the adhesion of the pressure-sensitive adhesive layer after photocuring to an adherend.
Since the reinforcing film can be attached to impart rigidity to the adherend, bending, warping, deflection, and the like due to stress, self weight, and the like are suppressed, and the handling property is improved. Therefore, by attaching the reinforcing thin film to the semi-finished product in the device manufacturing process, it is possible to prevent the defects and discomfort in the conveyance and processing. In addition, even when an external force is accidentally applied due to the drop of the device, the placement of a heavy object on the device, the impact of a flying object on the device, or the like during the use of the completed device, the reinforcing film can be attached to prevent the device from being damaged. The reinforcing film obtained by photocuring the adhesive is firmly bonded to the device, and therefore, even if the reinforcing film is used for a long time, the reinforcing film is difficult to peel off, and the reliability is excellent.
The pressure-sensitive adhesive layer 2 in the reinforcing film of the present invention is photocurable, and the timing of curing can be set arbitrarily. Since the treatment such as the reworking or the processing of the reinforcing film can be performed at any timing during the period from the time when the reinforcing film is attached to the adherend to the time when the pressure-sensitive adhesive is photocured, the time required for the pre-production of the device manufacturing process can be flexibly coped with.
Examples
The present invention is not limited to the following specific examples, but the present invention will be further described by way of examples of producing a reinforcing film comprising a pressure-sensitive adhesive composition in various proportions.
[ (production of (meth) acrylic acid-based matrix Polymer ]
< matrix Polymer A >
95.9 parts by weight of 2-ethylhexyl acrylate (2EHA), 4 parts by weight of 2-hydroxyethyl acrylate (2HEA), 0.1 part by weight of Acrylic Acid (AA), 0.2 part by weight of azobisisobutyronitrile as a polymerization initiator, and 200 parts by weight of ethyl acetate as a solvent were charged into a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas introduction tube, and nitrogen gas was exchanged for about 1 hour while stirring while flowing nitrogen gas. Thereafter, the mixture was heated to 70 ℃ and allowed to react for 6 hours to obtain a solution of the matrix polymer A. The weight average molecular weight of the matrix polymer a was 49.4 ten thousand.
< matrix polymers B to H >
Solutions of the matrix polymers B to H were obtained in the same manner as in the polymerization of the matrix polymer a except that the monomer charge amounts were changed as shown in table 1.
The charge monomer ratios of the matrix polymers a to H, the glass transition temperatures (Tg) of the polymers, the weight average molecular weights (Mw), and the molecular weight distributions (Mw/Mn) are shown in table 1. In table 1, the monomer components are described below for short.
2 EHA: 2-ethylhexyl acrylate (Tg of homopolymer: -70 ℃ C.)
2 HEA: 2-hydroxyethyl acrylate (Tg of homopolymer: -15 ℃ C.)
BA: butyl acrylate (Tg of homopolymer: -55 ℃ C.)
AM: acrylamide (Tg of homopolymer: 165 ℃ C.)
AA: acrylic acid (Tg of homopolymer: 106 ℃ C.)
The Tg of the (meth) acrylic matrix polymer is calculated from the Tg of the homopolymer of each monomer component and the compounding ratio of the monomers by the Fox formula. Mw (in terms of polystyrene) of the (meth) acrylic base polymer was measured by the following conditions using GPC ("HLC-8220 GPC" manufactured by Tosoh Co., Ltd.).
Sample concentration: 0.2 wt% (tetrahydrofuran solution)
Sample injection amount: 10 μ L
Eluent: THF
Flow rate: 0.6 ml/min
Measuring temperature: 40 deg.C
Sample column: TSK guard column SuperHZ-H (1 root) + TSKgel SuperHZM-H (2 roots)
Reference column: TSKgel SuperH-RC (1 root)
A detector: RI (Ri)
[ Table 1]
Figure BDA0002995228970000201
[ production of reinforcing film ]
< preparation of adhesive composition >
In the matrix polymer solution obtained by the production of the (meth) acrylic matrix polymer, 5 parts by weight of a (meth) acrylic oligomer, 10 parts by weight of a polyfunctional compound, 2 parts by weight of a crosslinking agent, and 0.1 part by weight of a photopolymerization initiator were added to and uniformly mixed with 100 parts by weight of the solid content of the (meth) acrylic matrix polymer, respectively, to prepare adhesive compositions of formulation ratios 1 to 39 shown in table 2. As the thermal crosslinking agent, a trimethylolpropane adduct of xylylenediisocyanate (75% ethyl acetate solution, "TAKENATE D110N" available from Mitsui chemical Co., Ltd.) was used. As the photopolymerization initiator, 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by BASF) was used.
As the (meth) acrylic oligomer, a polymer of tetrahydrofurfuryl methacrylate (THFMA), a polymer of n-butyl methacrylate (nBMA), or a polymer of isobornyl methacrylate (IBXMA) is used. The weight average molecular weights were all about 3000.
As the polyfunctional compound, trimethylolpropane triacrylate (TMPTA) or trimethylolpropane (EO) is used3Triacrylate (TMP (EO)3TA) or trimethylolpropane (EO)6Triacrylate (TMP (EO)6TA)。TMP(EO)3TA is a compound having an average of 1 (an average of 3 in 1 molecule) ethylene oxide interposed between a hydroxymethyl group and an acryloyl group, TMP (EO)6TA is a compound having an average of 2 (6 in 1 molecule) ethylene oxides inserted between a methylol group and an acryloyl group.
In the compositions 40 and 41, the adhesive composition was prepared without using the (meth) acrylic oligomer. In the compounding ratios 42 to 44, the adhesive composition is prepared without using a polyfunctional compound and a photopolymerization initiator.
< coating and crosslinking of adhesive solution >
The adhesive composition was applied to a polyethylene terephthalate film (manufactured by Toray corporation, as "Lumiror S10") having a thickness of 75 μm without surface treatment, using a spray roller so that the thickness after drying was 25 μm. After drying at 130 ℃ for 1 minute to remove the solvent, a release-treated surface of a separator (a polyethylene terephthalate film having a thickness of 25 μm and a surface subjected to silicone release treatment) was attached to the coated surface of the adhesive. Thereafter, the cured film was cured at 25 ℃ for 4 days and crosslinked to obtain a reinforced film in which a photocurable adhesive sheet was fixedly laminated on a substrate and a separator was temporarily bonded thereto.
[ evaluation ]
< thickness distribution of composition >
The composition of the adhesive layer in the depth direction was analyzed by secondary ion mass spectrometry while sputtering the adhesive layer from the front surface side using TOF-SIMS "TRIFT V nano TOF" equipped with an Ar-GCIB gun manufactured by ULVAC-PHI. The measurement conditions and sputtering conditions are as follows.
(measurement conditions)
Primary ion: bi3 ++
Acceleration voltage: 30kV
Ion current: about 2nA (in DC)
Analysis area: 100 μm × 100 μm
Analysis time: about 15 seconds/period
Detecting ions: positive/negative ions
Neutralizing: using electron guns
(sputtering conditions)
Sputtering ions: ar2500+
Acceleration voltage: 20kV
Ion current: about 8nA
Sputtering area: 400 μm.times.400 μm
Sputtering time: 30 seconds/period
For each of the (meth) acrylic base polymer, the (meth) acrylic oligomer, and the polyfunctional compound, a depth curve was prepared, and the area ratio of the surface layer region (region from the surface to 1/3 indicating the total thickness) to the total area (the integral value of the amount of secondary ions) was used as the presence ratio of the component in the surface layer region.
< adhesion >
The release film was peeled off from the surface of the reinforcing film cut to a width of 25mm × length of 100mm, and the film was adhered to the surface of SUS304 plate by a hand roller to prepare a test sample before photocuring. A sample obtained by irradiating ultraviolet rays from the reinforcing film side (polyethylene terephthalate film side) of the test sample before photocuring to photocure the adhesive layer was used as the test sample after photocuring. Using these test samples, the end of the polyethylene terephthalate film of the reinforcing film was held by a jig, and 180 ℃ peeling of the reinforcing film was performed at a stretching speed of 300 mm/min to measure the peel strength.
Table 2 shows the results of measuring the compounding ratio of the pressure-sensitive adhesive composition of each reinforcing sheet (the types of the (meth) acrylic base polymer, the polyfunctional compound, and the (meth) acrylic oligomer), the presence ratio of the polyfunctional compound and the (meth) acrylic oligomer in the surface region, and the adhesion before and after photocuring.
[ Table 2]
Figure BDA0002995228970000231
As shown in table 2, in the photocurable adhesive layer containing the (meth) acrylic base polymer, the polyfunctional compound, and the (meth) acrylic oligomer in the formulation ratios of 1 to 39, the polyfunctional compound was present in a high proportion in the surface region, and the adhesive force with the adherend (SUS304 plate) before photocuring was small, and good reworkability was exhibited. Furthermore, it can be seen that: even if the (meth) acrylic base polymer and the polyfunctional compound are the same in type, if the (meth) acrylic oligomer is different in type, the amount of the (meth) acrylic oligomer present in the surface region changes, and accordingly, the amount of the polyfunctional compound present in the surface region changes.
For example, in the case of the compositions 7 to 9, the presence ratio of the (meth) acrylic base polymer in the surface region was 33.7% with respect to the presence ratio of the (meth) acrylic oligomer in the surface region, while the presence ratio was 27.2% in the case of the composition 8, although the same applies to the (meth) acrylic base polymer and the polyfunctional compound. In the formulation 8, the (meth) acrylic oligomer is present in a small amount in the surface region, and the polyfunctional compound is present in a large amount in the surface region, so that the adhesive strength to an adherend after photocuring of the adhesive is greatly increased.
For the other examples of table 2, the following trends were observed: the smaller the ratio of the (meth) acrylic oligomer present in the surface region, the higher the ratio of the polyfunctional compound present in the surface region, and the adhesion strength is greatly increased by photocuring. From these results, it can be seen that: in a photocurable adhesive composition containing a (meth) acrylic oligomer in addition to a (meth) acrylic base polymer and a polyfunctional compound, depending on the compatibility of these three components, the polyfunctional compound can be present in the vicinity of the surface layer in a biased manner, so that the adhesion strength after photocuring can be greatly increased, and the adhesion reliability can be improved.

Claims (3)

1. A reinforcing film comprising a film base and an adhesive layer fixedly laminated on one main surface of the film base,
the adhesive layer is formed from a photocurable composition,
the photocurable composition comprises a (meth) acrylic base polymer having a weight average molecular weight of 10 ten thousand or more, a (meth) acrylic oligomer having a weight average molecular weight of 1000 to 50000, and a polyfunctional acrylate,
comprising 3 to 30 parts by weight of the (meth) acrylic oligomer and 0.5 to 30 parts by weight of the polyfunctional acrylate per 100 parts by weight of the (meth) acrylic base polymer,
when the adhesive layer is trisected in the thickness direction and the region farthest from the substrate side is defined as the surface layer region,
the amount of the multifunctional acrylate existing in the surface layer region is 50% or more of the amount of the multifunctional acrylate existing in the entire thickness direction, and
the amount of the (meth) acrylic oligomer present in the surface region is not more than 31% of the amount of the (meth) acrylic oligomer present in the entire thickness direction.
2. The reinforced film according to claim 1, wherein a crosslinked structure is introduced into the (meth) acrylic matrix polymer.
3. The reinforced film according to claim 1 or 2, wherein the (meth) acrylic base polymer contains a hydroxyl group-containing monomer as a monomer unit.
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