TW202111045A - Adhesive film roll to provide an adhesive sheet roll capable of feeding out an adhesive sheet with excellent appearance - Google Patents

Abstract

The subject of the present invention is to provide an adhesive sheet roll capable of delivering an adhesive sheet having an excellent appearance. The adhesive sheet roll 1 of the solution of the present invention includes a first film 11, a first adhesive layer 12 laminated on one side of the first film 11, and a and laminated on the first adhesive layer 12 The long adhesive sheet 10 formed by the second film 13 on the opposite side of the first film 11 is an adhesive formed by winding the cylindrical or cylindrical core material 20 with the surface on the first film 11 side as the outside In the sheet roll 1, the diameter of the core material 20 is 180 mm or more and 800 mm or less, and the surface on the side of the first adhesive layer 12 of the second film 13 is not peeled off.

Description

Adhesive film roll

The present invention relates to an adhesive sheet having a first film, a first adhesive layer, and a second film. The second film is an adhesive sheet that is not a release sheet and is wound around a core material with the surface on the first film side as the outer side Adhesive film rolls.

Adhesive sheets with at least an adhesive layer are generally manufactured in the form of long strips. Furthermore, the adhesive sheet manufactured in such a long state is usually wound around the core material at the same time as it is manufactured, and is made into the form of an adhesive sheet roll. The adhesive sheet roll thus manufactured is also transported, stored, etc. in this form.

In addition, when manufacturing a predetermined product, an adhesive sheet is sometimes used as a material or an engineering sheet, and the device used for this manufacturing is usually made so that the adhesive sheet can be fed out from the above-mentioned adhesive sheet roll and used for product manufacturing.

An example of using an adhesive sheet roll to manufacture a predetermined product, Patent Document 1 discloses a method for manufacturing an optical display device by sending out a predetermined amount of film from a roll original roll equipped with a polarizing film and a polarizer protective film, an adhesive layer, and a release film. method. [Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5801027

[Problems to be solved by the invention]

However, in the adhesive sheet roll, there may be many appearance problems such as wrinkles in the delivered adhesive sheet. Such an appearance problem of the adhesive sheet not only damages the appearance of the product obtained by using the adhesive sheet, but also sometimes adversely affects the performance of the product.

The present invention has been completed in view of the solid state as described above, and aims to provide an adhesive sheet roll capable of delivering an adhesive sheet having an excellent appearance. [Means for solving problems]

To achieve the above objective, first, the present invention provides an adhesive sheet roll characterized in that it includes a first film, a first adhesive layer laminated on one side of the first film, and a first adhesive layer laminated on the The long adhesive sheet formed by the second film on the side opposite to the first film of the first adhesive layer is wound on a cylindrical or cylindrical core material with the surface on the first film side as the outside In the resulting adhesive sheet roll, the diameter of the core material is 180 mm or more and 800 mm or less, and the surface on the first adhesive layer side of the second film is not peeled off (Invention 1).

In the adhesive sheet roll related to the above invention (Invention 1), by winding the adhesive sheet with a core material having the above-mentioned diameter, it is possible to deliver an adhesive sheet having a good appearance with suppressed wrinkles.

In the above invention (Invention 1), wherein the thickness of the first film is preferably equal to or less than the thickness of the second film (Invention 2).

In the above inventions (Inventions 1 and 2), the peel force when the first film is peeled off from the laminate of the first adhesive layer and the second film is preferably 10mN/25mm or more and 2000mN/25mm or less (Invention 3).

In the above invention (Inventions 1 to 3), wherein the pressure-sensitive adhesive sheet includes: a second pressure-sensitive adhesive layer laminated on the side of the second film opposite to the first pressure-sensitive adhesive layer; and The third film on the side opposite to the above-mentioned second film of the second adhesive layer is preferable (Invention 4).

In the above invention (Invention 4), it is preferable that the adhesion force of the laminate of the third film and the second adhesive layer to the soda lime glass is 0.01 N/25 mm or more and 20 N/25 mm or less (Invention 5).

In the above invention (Inventions 1 to 5), the storage modulus of the first adhesive layer at 23° C. is preferably 0.001 MPa or more and 1.00 MPa or less (Invention 6). [Effects of the invention]

According to the adhesive sheet roll related to the present invention, an adhesive sheet having an excellent appearance can be dispatched.

Hereinafter, embodiments of the present invention will be described. FIG. 1 shows a perspective view of an adhesive sheet roll related to an embodiment of the present invention. As shown in FIG. 1, regarding the adhesive sheet roll 1 of this embodiment, the long adhesive sheet 10 is wound by the cylindrical or cylindrical core material 20. As shown in FIG.

In addition, FIG. 2 shows a cross-sectional view of the adhesive sheet 10 of this embodiment. The adhesive sheet 10 of this embodiment includes: a first film 11; a first adhesive layer 12 laminated on one side of the first film 11, and a first film 11 laminated on the first adhesive layer 12 The second film 13 on the opposite side. In addition, as shown in FIG. 2, the adhesive sheet 10 of this embodiment includes: a second adhesive layer 14 laminated on the side of the second film 13 opposite to the first adhesive layer 12; and The third film 15 on the side opposite to the second film 13 of the second adhesive layer 14 is also preferable.

Here, regarding the adhesive sheet roll 1 of this embodiment, the adhesive sheet 10 is wound around the core material 20 with the surface of the 1st film 11 side as an outer side. In addition, the second film 13 is the surface on the side of the first adhesive layer 12 and has no peeling treatment. That is, in the adhesive sheet roll 1 concerning this embodiment, the 2nd film 13 is not a peeling sheet.

In the adhesive sheet roll 1 of this embodiment, the diameter of the core material 20 is 180 mm or more and 800 mm or less. In this way, in the adhesive sheet roll 1 of the present embodiment, by winding the adhesive sheet 10 around the core material 20 having a relatively large diameter, the adhesive sheet 10 with suppressed wrinkles can be sent out. That is, according to the pressure-sensitive adhesive sheet roll 1 of this embodiment, the pressure-sensitive adhesive sheet 10 having a good appearance can be sent out. In addition, in this specification, when the core material 20 is cylindrical, the diameter of the core material 20 means the outer diameter of this cylinder.

In addition, in this specification, the occurrence of wrinkles in the adhesive sheet sent from the adhesive sheet roll refers to any of the twist wrinkles caused by at least a part of the adhesive sheet and the bending wrinkles caused by the bending of the adhesive sheet.

In addition, the above-mentioned wrinkles are generally presumed to occur in the second film located inside the winding during the production of the adhesive sheet roll or during subsequent storage, and also propagate to the first adhesive layer. However, when the adhesive sheet is sent out from the adhesive sheet roll, the tension of the second film is applied, and the restoring force as a film is also large, so the wrinkles of the second film tend to disappear. In contrast, the wrinkles of the first adhesive layer do not disappear due to the delivery, but tend to remain in the delivered adhesive sheet. In the adhesive sheet roll 1 concerning this embodiment, the wrinkle remaining in the 1st adhesive layer is included, and the occurrence of wrinkles in the adhesive sheet 10 can be suppressed satisfactorily.

The usage of the adhesive sheet 10 of this embodiment is not limited, and the following usages can be mentioned. First, the first film 11 is peeled off from the adhesive sheet 10 sent out from the adhesive sheet roll 1. Then, to the laminated body of the second film 13 and the first adhesive layer 12 thus obtained, the surface on the side of the first adhesive layer 12 is adhered to the adherend. When the adhesive sheet 10 includes the second adhesive layer 14 and the third film 15, these laminates can be used as a protective film for protecting the second film 13. Such a protective film can be peeled from the second film 13 at any timing.

1. The composition of the adhesive film roll (1) The first film Regarding the adhesive sheet roll 1 of this embodiment, the material of the first film 11 is not particularly limited. For example, the first film 11 is composed of a resin-based sheet mainly composed of a resin-based material, or may be composed of a paper-based material.

Regarding the resin component of the resin-based sheet, polyolefins such as polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, ethylene-norbornene copolymers, norbornene resins, and polyolefins and poly Polyesters such as ethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate, polyvinyl chloride, polyvinyl chloride copolymers, polyimine, polyetherimine, Polycarbonate, polyphenylene sulfide, liquid crystal polymer and other resins. The resin sheet may be a sheet composed of a single layer, or a sheet composed of multiple layers of the same species or different species. Among the above, a polyethylene terephthalate film is preferred.

Specific examples when the first film 11 is made of a paper-based material include paper substrates such as cellophane, coated paper, and high-quality paper, and laminated paper in which thermoplastic resins such as polyethylene are laminated on the above-mentioned paper substrate.

The first film 11 is preferably a release sheet obtained by applying a release treatment to one side of a sheet composed of the above-mentioned resin-based sheet or paper-based material (especially the surface in contact with the first adhesive layer 12). Examples of release agents used in the release treatment include alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and wax release agents.

Regarding the adhesive sheet roll 1 of this embodiment, the thickness of the first film 11 is preferably the thickness of the second film 13 or less. In this way, by making the thickness of the first film 11 located on the outer side of the winding the same as the thickness of the second film 13 located on the inner side, or thinner than the thickness of the second film 13, it is easy to alleviate the rolling pressure applied to the second film 13 . As a result, in the adhesive sheet 10 sent out from the adhesive sheet roll 1, the occurrence of wrinkles (especially the occurrence of wrinkles in the second film 13) can be effectively suppressed.

From the viewpoint of easily achieving the above-mentioned thickness relationship between the first film 11 and the second film 13, the thickness of the first film 11 is preferably 20 μm or more, particularly 30 μm or more, and further preferably 40 μm or more. In addition, the thickness of the first film 11 is preferably 150 μm or less, more preferably 100 μm or less, particularly preferably 80 μm or less, and further preferably 70 μm or less.

The Young's modulus of the first film 11 at 23° C. is preferably 0.01 GPa or higher, more preferably 0.1 GPa or higher, particularly preferably 1 GPa or higher, and further preferably 3 GPa or higher. In addition, the Young's modulus is preferably 20 GPa or less, especially 10 GPa or less, and further preferably 5 GPa or less. By making the Young's modulus of the first film 11 at 23° C. above 0.01 GPa, the first film 11 has a predetermined strength, and the handling of the adhesive sheet 10 is more excellent. In addition, by making the Young's modulus of the first film 11 at 23° C. below 20 GPa, during winding, the rolling pressure of the first film 11 to the second film 13 is reduced, and wrinkles of the adhesive sheet 10 are more easily suppressed. In addition, the Young’s modulus in the specification of this case is measured in accordance with JIS K7161:2014. More specifically, a universal tensile tester is used under the conditions of a tensile speed of 200 mm/min under an environment of 23°C and 50% RH. Determination.

(2) The first adhesive layer The adhesive constituting the first adhesive layer 12 of the present embodiment is not particularly limited as long as the desired adhesive force can be achieved, and can be appropriately selected according to the application. For example, the adhesive constituting the first adhesive layer 12 may be an acrylic adhesive, a silicone adhesive, a rubber adhesive, a urethane adhesive, a polyester adhesive, or a polyvinyl ether adhesive. Any of adhesives, etc. In addition, the above-mentioned adhesive may be any of a latex type, a solvent type, or a solvent-free type, and may be either a crosslinked type or a non-crosslinked type. Among these, it is preferable to use an acrylic adhesive as the adhesive constituting the first adhesive layer 12 in the present embodiment from the viewpoint of having sufficient transparency and easily exhibiting the desired adhesive force.

In addition, the adhesive constituting the first adhesive layer 12 may be an active energy ray curable adhesive or an active energy ray non-curable adhesive. The so-called active energy ray-curable adhesive refers to an adhesive with active energy ray-curable at the stage of being used as an adhesive (for example, an adhesive layer composed of the adhesive is attached to the adherend). Agent. In this embodiment, in the state of the adhesive sheet roll 1, the first adhesive layer 12 has active energy ray curability. In addition, the so-called active energy ray curable adhesive refers to the concept of an adhesive in a so-called semi-cured (B-stage) state regardless of whether or not the active energy ray curable adhesive is also included in the stage of manufacturing the adhesive.

On the other hand, the so-called non-curing active energy ray adhesive refers to an adhesive that has completed the active energy ray hardening and has lost the active energy ray hardenability at the stage of being used as an adhesive, or has no activity at the beginning Energy ray hardening adhesive.

Here, the active energy ray-curable adhesive is often lower in cohesive force and softer than the active energy ray non-curable adhesive. Therefore, the active energy ray-curable adhesive has a low resistance to deformation of the second film 13 during roll production, and tends to cause wrinkles. Even when an adhesive with such a high degree of difficulty in suppressing wrinkles is used, as long as it relates to the adhesive sheet roll 1 of this embodiment, the occurrence of wrinkles can be sufficiently suppressed.

In addition, by using an active energy ray-curable adhesive, the adhesive sheet 10 of this embodiment is suitable for sticking to an adherend having a step on the surface. That is, in the adhesive sheet 10 of this embodiment, the first adhesive layer 12 is adhered to the adherend in a relatively soft state with active energy ray curability, so that the first adhesive layer 12 can follow the step well. . After that, by hardening the active energy rays, the cohesive force of the first adhesive layer 12 can be sufficiently high. Thereby, the adhesive sheet 10 can well suppress the occurrence of bubbles, floating, peeling, etc. in the vicinity of the step even when the cured first adhesive layer 12 is placed in a state of being adhered to the adherend under high temperature and high humidity conditions.

Hereinafter, the case where the first adhesive layer 12 of the present embodiment is composed of an active energy ray-curable acrylic adhesive will be described. Such a first adhesive layer 12 can be made of, for example, a first adhesive composition containing (meth)acrylate copolymer (A), crosslinking agent (B), and active energy ray curable component (C) (hereinafter referred to as Sometimes referred to as "the first adhesive composition P1") is an adhesive composition formed by crosslinking (thermal crosslinking). Furthermore, the first adhesive composition P1 may further contain a photopolymerization initiator (D) as desired. In addition, in this specification, the term "(meth)acrylic acid" means both acrylic acid and methacrylic acid. Other similar terms are also the same. Furthermore, "polymer" also includes the concept of "copolymer".

(1-1) (Meth) acrylate copolymer (A) The (meth)acrylate copolymer (A) preferably contains a reactive group-containing monomer having a reactive group that reacts with the crosslinking agent (B) in the molecule as a monomer unit constituting the polymer. This allows the reactive group derived from the reactive group-containing monomer to react with the crosslinking agent (B). By introducing this monomer into the (meth)acrylate copolymer (A), it is easy to adjust the gel fraction or storage modulus of the resulting adhesive.

Examples of the above-mentioned reactive group-containing monomers include monomers having a hydroxyl group in the molecule (hydroxyl group-containing monomer), monomers having a carboxyl group in the molecule (carboxyl group-containing monomer), and amine in the molecule. Monomers (monomers containing amine groups) and the like. Among these, a hydroxyl group-containing monomer that has excellent reactivity with the crosslinking agent (B) and less adverse effects on the adherend is particularly preferable.

Examples of hydroxyl-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Hydroxyalkyl (meth)acrylates such as hydroxybutyl, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and the like. Among them, from the viewpoint of the reactivity between the hydroxyl group of the obtained (meth)acrylate copolymer (A) and the crosslinking agent (B) and the copolymerizability with other monomers, the (meth)acrylic acid 2- Hydroxyethyl or 4-hydroxybutyl (meth)acrylate is preferred. These can be used individually or in combination of 2 or more types.

The (meth)acrylate copolymer (A), from the viewpoint of increasing the gel fraction and storage modulus of the obtained adhesive to a desired level, is the lower limit as the monomer unit constituting the polymer The hydroxyl group-containing monomer is preferably 1% by mass or more, more preferably 5% by mass, particularly 10% by mass or more, and more preferably 12% by mass or more. In addition, the (meth)acrylate copolymer (A), from the viewpoint of reducing the gel fraction and storage modulus of the obtained adhesive to a desired level, is used as the monomer unit constituting the polymer. The limit is preferably 30% by mass or less of hydroxyl-containing monomers, particularly preferably 25% by mass or less, and more preferably 20% by mass or less.

The (meth)acrylate copolymer (A), which contains an alkyl (meth)acrylate alkyl having 1 to 20 carbon atoms as the monomer unit constituting the polymer, can give a relatively high level to the resulting adhesive. Good storage modulus, while showing better adhesion. (Meth) acrylate alkyl esters having 1 to 20 carbon atoms in the alkyl group include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth) ) N-butyl acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-hexyl (meth)acrylate Decyl ester, n-lauryl (meth)acrylate, myristyl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate, and the like. Among them, from the viewpoint of making an appropriate storage modulus and improving adhesiveness, (meth)acrylates having an alkyl group of 4 to 8 carbon atoms are preferred, especially (meth)acrylic acid 2- Ethylhexyl is preferred. In addition, these can be used individually or in combination of 2 or more types.

The (meth)acrylate copolymer (A) preferably contains 40% by mass or more of an alkyl group as a monomer unit constituting the polymer, and a (meth)acrylate alkyl ester having 1 to 20 carbon atoms, especially The content is preferably 50% by mass or more, and more preferably 60% by mass or more. In addition, alkyl (meth)acrylates having a carbon number of 1 to 20 containing 90% by mass or less of alkyl groups are preferred, particularly 80% by mass or less, and more preferably 70% by mass or less.

The (meth)acrylate copolymer (A) preferably contains a monomer having an alicyclic structure in the molecule (alicyclic structure-containing monomer) as a monomer unit constituting the copolymer. The alicyclic structure contains a monomer because it has a large volume, and it can be presumed that by making it exist in the polymer to expand the distance between the polymers, the resulting adhesive can be made excellent in flexibility. The (meth)acrylate copolymer (A) contains an alicyclic structure and contains monomers. When the adhesive sheet 10 of this embodiment is adhered to an adherend with a step on the surface, the first adhesive layer 12 is adhered to Time can follow the gap well.

The carbocyclic ring of the alicyclic structure containing a monomer in the alicyclic structure may have a saturated structure or may have a partially unsaturated bond. In addition, the alicyclic structure may be a monocyclic alicyclic structure, or a polycyclic alicyclic structure such as a bicyclic ring or a tricyclic ring. From the viewpoint of increasing the distance between the obtained (meth)acrylate copolymer (A) and effectively exerting the flexibility of the adhesive, the above-mentioned alicyclic structure is a polycyclic alicyclic structure (polycyclic structure) Better. Furthermore, considering the compatibility of the (meth)acrylate copolymer (A) with other components, the above-mentioned polycyclic structure is particularly preferably bicyclic to tetracyclic. In addition, from the viewpoint of effectively exerting the flexibility of the adhesive as described above, the carbon number of the alicyclic structure (refers to the carbon number of all parts forming the ring, and the total carbon number when the plural rings exist independently), Generally, 5 or more is preferable, and 7 or more is particularly preferable. On the other hand, the upper limit of the carbon number of the alicyclic structure is not particularly limited, but from the viewpoint of the same compatibility as described above, 15 or less is preferable, and 10 or less is particularly preferable.

Examples of the above-mentioned alicyclic structure-containing monomers include cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, ( Dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, etc., among them, dicyclopentyl (meth)acrylate and (meth) Adamantyl acrylate or isobornyl (meth)acrylate is preferred, and isobornyl (meth)acrylate is particularly preferred. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

When the (meth)acrylate copolymer (A) contains an alicyclic structure and contains a monomer as the monomer unit constituting the polymer, the (meth)acrylate copolymer (A) contains 3% by mass or more of the resin The cyclic structure preferably contains monomers, especially 5% by mass or more, and more preferably 8% by mass or more. In addition, the (meth)acrylate copolymer (A) preferably contains 35% by mass or less of alicyclic structure-containing monomer as the monomer unit constituting the polymer, and particularly preferably contains 25% by mass or less It is more preferable to contain 15% by mass or less.

The (meth)acrylate copolymer (A) preferably contains a monomer having a nitrogen atom (nitrogen atom-containing monomer) in the molecule as a monomer unit constituting the polymer. In addition, the reactive group containing a monomer is removed from the nitrogen atom containing monomer. The presence of a monomer containing a nitrogen atom as a constituent unit in the polymer can promote the reaction of the acrylate copolymer (A) and the crosslinking agent (B), impart polarity to the adhesive, and increase the polarity of the adhesive to the glass surface. Surface adhesion.

Examples of the above-mentioned nitrogen atom-containing monomer include a monomer having a tertiary amine group, a monomer having an amide group, a monomer having a nitrogen-containing heterocyclic ring, and the like. Among them, a monomer having a nitrogen-containing heterocyclic ring is good.

As the monomer having a nitrogen-containing heterocycle, for example, N-(meth)acrylomorpholine, N-vinyl-2-pyrrolidone, N-(meth)acryloylpyrrolidone, N-(meth)acryloyl pyrrolidone, N-(meth)acryloyl pyrrolidone, N-(meth)acryloyl morpholine, N-vinyl-2-pyrrolidone, N-(meth)acryloyl pyrrolidone, Yl)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-(meth)acryloylaziridine, aziridinylethyl (meth)acrylate, 2-vinyl Pyridine, 4-vinylpyridine, 2-vinylpyrazine, 1-vinylimidazole, N-vinylcarbazole, N-vinyl phthalimide, etc., plus the polarity to the glass surface, etc. From the standpoint of surface adhesion, which also enhances the cohesive force of the resulting adhesive, and enhances the resistance to foaming, N-(meth)acrylomorpholine is preferred, and N-acrylomorpholine is particularly preferred.

When the (meth)acrylate copolymer (A) contains a nitrogen atom-containing monomer as the monomer unit constituting the polymer, the (meth)acrylate copolymer (A) contains 1% by mass or more of nitrogen atoms Monomers are preferred, especially 2% by mass or more, and more preferably 5% by mass or more. In addition, the (meth)acrylate copolymer (A) preferably contains 40% by mass or less of nitrogen atom-containing monomer as the monomer unit constituting the polymer, particularly preferably 25% by mass or less, and further preferably contains 15% by mass or less is preferable.

The (meth)acrylate copolymer (A) may contain other monomers as monomer units constituting the polymer as desired. As other monomers, monomers that do not contain reactive functional groups are preferred. As the other monomers, for example, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and other alkoxyalkyl (meth)acrylates, vinyl acetate, Styrene and so on. These can be used individually or in combination of 2 or more types.

The polymerization state of the (meth)acrylate copolymer (A) may be a random polymer or a block polymer.

The lower limit of the weight average molecular weight of the (meth)acrylate copolymer (A) is preferably 100,000 or more, especially 200,000 or more, and more preferably 300,000 or more. If the lower limit of the weight average molecular weight of the (meth)acrylate copolymer (A) is above the above, the cohesive force of the obtained adhesive can be improved, and the storage modulus and gel fraction of the adhesive can be prevented from becoming too low , And can prevent the adhesion force from becoming too high. In addition, the upper limit of the weight average molecular weight of the (meth)acrylate copolymer (A) is preferably 1 million or less, particularly 850,000 or less, and further preferably 700,000 or less. The upper limit of the weight average molecular weight of the (meth)acrylate copolymer (A) below the above can prevent the storage modulus and gel fraction of the resulting adhesive from becoming too high. In addition, it can prevent the adhesive force from becoming too high. Too low. In addition, the weight average molecular weight in this specification is a standard polystyrene conversion value measured by a gel permeation chromatography (GPC) method.

In addition, in the first adhesive composition P1, the (meth)acrylate copolymer (A) may be used alone or in combination of two or more.

(1-2) Crosslinking agent (B) The crosslinking agent (B) crosslinks the (meth)acrylate copolymer (A) by heating the first adhesive composition P1 to form a good three-dimensional network structure. Thereby, the cohesive force of the adhesive can be further improved, and the gel fraction and storage modulus can be easily adjusted to appropriate values.

As the above-mentioned crosslinking agent (B), any one capable of reacting with the reactive functional group possessed by the (meth)acrylate copolymer (A) may be used. For example, isocyanate-based crosslinking agents, epoxy-based Cross-linking agent, amine-based cross-linking agent, melamine-based cross-linking agent, aziridine-based cross-linking agent, amine-based cross-linking agent, aldehyde-based cross-linking agent, azoline-based cross-linking agent, metal alkoxide-based Cross-linking agent, metal chelate-based cross-linking agent, metal salt-based cross-linking agent, ammonium salt-based cross-linking agent, etc. Here, as described above, the (meth)acrylate copolymer (A) preferably contains a hydroxyl group-containing monomer as a constituent monomer unit. Therefore, as the crosslinking agent (B), an isocyanate with excellent reactivity with the hydroxyl group is used. The crosslinking agent is better. In addition, the crosslinking agent (B) can be used individually by 1 type or in combination of 2 or more types.

The isocyanate-based crosslinking agent contains at least a polyisocyanate compound. The polyisocyanate compound includes, for example, aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; isophorone diisocyanate , Alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, etc., and such biuret, trimeric isocyanate, and further with ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane , Castor oil and other low-molecular-weight active hydrogen-containing compounds reactant adducts, etc. Among them, from the viewpoint of reactivity with hydroxyl groups, aromatic polyisocyanates modified with trimethylolpropane, particularly toluene diisocyanate modified with trimethylolpropane are preferred.

For the content of the crosslinking agent (B) in the first adhesive composition P1, with respect to 100 parts by mass of the (meth)acrylate copolymer (A), the lower limit is preferably 0.01 parts by mass or more, especially 0.05 It is preferably at least part by mass, and more preferably at least 0.1 part by mass. In addition, the content is preferably 3 parts by mass or less with respect to 100 parts by mass of the (meth)acrylate copolymer (A), particularly preferably 2 parts by mass or less, and further preferably 1 part by mass or less. By setting the content of the crosslinking agent (B) within the above range, it is easy to adjust the gel fraction and storage modulus of the resulting adhesive to appropriate values.

(1-3) Active energy ray sclerosing component (C) By making the first adhesive composition P1 contain the active energy ray curable component (C), the adhesive formed by crosslinking (thermally crosslinking) the first adhesive composition P1 will become active energy ray curable Adhesive. In this adhesive, it is estimated that the active energy ray curable component (C) polymerizes with each other by curing by the active energy ray irradiation after the adherend is adhered, and the polymerized active energy ray curable component (C), and (methyl) ) The crosslinked structure (three-dimensional mesh structure) of the acrylate copolymer (A) is entangled. By forming a high-dimensional structure, it is easy to greatly increase the gel fraction and storage modulus, and at the same time, with the anchoring effect, it is easy to increase the adhesive force.

The active energy ray curable component (C) is not particularly limited as long as it is a component that can be cured by irradiation with active energy rays to obtain the above-mentioned effects, and it may be any of monomers, oligomers, or polymers, or It is a mixture of these. Among them, preferred are polyfunctional acrylate monomers having excellent compatibility with the (meth)acrylate copolymer (A).

Multifunctional acrylate monomers, for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate )Acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxytrimethyl acetate neopentyl glycol di(meth)acrylate, bicyclic Pentyl di(meth)acrylate, caprolactone modified dicyclopentenyl di(meth)acrylate, ethylene oxide modified phosphate di(meth)acrylate (ethylene oxide modified phosphate di(meth) )acrylate), bis(propylene oxyethyl) trimer isocyanate, allylated cyclohexyl di(meth)acrylate, ethoxylated bisphenol A diacrylate, 9,9-bis[4-( 2-propenyloxyethoxy) phenyl] fluorene and other bifunctional types; trimethylolpropane tri(meth)acrylate, dineopentyl erythritol tri(meth)acrylate, propionic acid modification High-quality dineopentaerythritol tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, ginseng (acrylic oxyethylene) Base) trimeric isocyanate, ε-caprolactone modified ginseng-(2-(meth)acryloyloxyethyl) trimer isocyanate, etc. trifunctional type; diglycerol tetra(meth)acrylate, neopentyl tetrakis 4-functional type such as alcohol tetra (meth)acrylate; 5-functional type such as dineopentaerythritol penta(meth)acrylate modified by propionic acid; dineopentaerythritol hexa(meth)acrylate, hexamethylene Lactones are used to modify hexafunctional types such as dineopentaerythritol hexa(meth)acrylate. Among the above, from the viewpoint of the step followability of the resulting adhesive under high-temperature and high-humidity conditions, bis(acryloxyethyl) isocyanate, ginseng (acryloxyethyl) isocyanate, ε- Caprolactone modified ginseng-(2-(meth)acryloyloxyethyl) trimeric isocyanate and other multifunctional acrylate monomers containing a trimeric isocyanate structure in the molecule are preferred. A multifunctional acrylate-based monomer containing a trimeric isocyanate structure in the molecule is more preferable. These can be used individually by 1 type, and can also be used in combination of 2 or more types. In addition, from the viewpoint of compatibility with the (meth)acrylate copolymer (A), the multifunctional acrylate monomer preferably has a molecular weight of less than 1,000.

The content of the active energy ray curable component (C) in the first adhesive composition P1, from the viewpoint of easily increasing the gel fraction and storage modulus, is relative to the (meth)acrylate copolymer ( A) 100 parts by mass, preferably 1 part by mass or more as the lower limit, particularly preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. In addition, the above-mentioned content, with respect to 100 parts by mass of the (meth)acrylate copolymer (A), the upper limit is preferably 50 parts by mass or less, particularly preferably 20 parts by mass or less, and more preferably 10 parts by mass or less .

(1-4) Photopolymerization initiator (D) When ultraviolet rays are used for curing of an adhesive for active energy ray curability, it is preferable that the first adhesive composition P1 further contains a photopolymerization initiator (D). By containing such a photopolymerization initiator (D), the active energy ray curable component (C) can be effectively polymerized, and the polymerization curing time and the irradiation amount of active energy ray can be reduced.

As such a photopolymerization initiator (D), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino Acetophenone, 2,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-benzene Propan-1-one, 1-hydroxycyclohexyl phenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 4-( 2-Hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, Dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone Xanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p- Dimethylaminobenzoic acid ester, oligomeric [2-hydroxy-2-methyl-1[4-(1-methylvinyl)phenyl]acetone], 2,4,6-trimethylbenzyl Aceto-diphenyl-phosphine oxide and the like. Among these, it is preferable to use a phosphine oxide-based photopolymerization initiator to allow sufficient curing by a resin plate containing an ultraviolet absorber. These can be used individually or in combination of 2 or more types.

The content of the photopolymerization initiator (D) in the first adhesive composition P1, with respect to 100 parts by mass of the active energy ray curable component (C), is preferably 0.1 parts by mass or more as the lower limit, and is particularly 1 part by mass or more is preferable. In addition, the upper limit is preferably 30 parts by mass or less, and particularly preferably 15 parts by mass or less.

(1-5) Various additives The first adhesive composition P1 can be added as desired. Various additives commonly used in acrylic adhesives, such as silane coupling agents, ultraviolet absorbers, anti-static agents, adhesion imparting agents, oxidation inhibitors, light stabilizers, and softening agents Agents, fillers, refractive index modifiers, etc. In addition, the polymerization solvent and the dilution solvent mentioned later do not contain the additives which comprise the 1st adhesive composition P1.

Here, the first adhesive composition P1 contains a silane coupling agent, and the resulting adhesive can improve the adhesion to the glass member and the plastic plate.

As the silane coupling agent, an organosilicon compound having at least one alkoxysilyl group in the molecule, which has good compatibility with the (meth)acrylate copolymer (A) and light penetration is preferred .

As the silane coupling agent, for example, vinyl trimethoxy silane, vinyl triethoxy silane, methacryloxypropyl trimethoxy silane, and other polymerizable unsaturated group-containing silicon compounds, 3-shrinkage Silicon compounds with epoxy structure such as glyceryl ether oxypropyl trimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3- The mercapto groups such as mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane, etc. contain silicon compounds, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)- Amino groups such as 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, etc. contain silicon compounds, 3-chloropropyltrimethoxysilane Triethoxysilane, 3-isocyanatopropyltriethoxysilane, or at least one of these, and methyltriethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, ethyltrimethylsilane Alkyl groups such as oxysilane include condensates of silicon compounds and the like. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

The content of the silane coupling agent in the first adhesive composition P1 is preferably 0.01 parts by mass or more, particularly preferably 0.05 parts by mass or more, based on 100 parts by mass of the (meth)acrylate copolymer (A). More preferably, it is 0.1 part by mass or more. In addition, the content is preferably 2 parts by mass or less with respect to 100 parts by mass of the (meth)acrylate copolymer (A), particularly preferably 1 part by mass or less, and further preferably 0.5 parts by mass or less.

(1-6) Manufacturing of the first adhesive composition The first adhesive composition P1 can be produced by manufacturing the (meth)acrylate copolymer (A), and the obtained (meth)acrylate copolymer (A) can be combined with the desired crosslinking agent (B), The active energy ray curable component (C), the photopolymerization initiator (D), and the additives are mixed and manufactured.

The (meth)acrylate copolymer (A) can be produced by polymerizing a mixture of monomers constituting the polymer by a normal radical polymerization method. The polymerization of the (meth)acrylate copolymer (A) can be carried out by a solution polymerization method, using a polymerization initiator as desired. Examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone, etc., and two or more types may be used in combination.

As a polymerization initiator, an azo compound, an organic peroxide, etc. can be mentioned, and 2 or more types can also be used together. Azo compounds, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane Alkane-1-carbonitrile) (1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 4,4'-azobis(4 -Cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] and the like.

Examples of organic peroxides include, for example, benzyl peroxide, t-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, and peroxydicarbonic acid. Di-n-propyl ester, bis(2-ethoxyethyl peroxydicarbonate), t-butyl peroxyneodecanoate, t-butyl peroxypivalate, peroxide ( 3,5,5-Trimethylhexyl), dipropylene peroxide, diacetyl peroxide, etc.

Furthermore, in the above-mentioned polymerization step, by formulating a chain transfer agent such as 2-mercaptoethanol, the weight average molecular weight of the obtained polymer can be adjusted.

To obtain the (meth)acrylate copolymer (A), to the solution of the (meth)acrylate copolymer (A), add a crosslinking agent (B) and an active energy ray curable component (C) as desired 1. The first adhesive composition P1 (coating solution) in which the photopolymerization initiator (D), additives, and diluting solvent are fully mixed and can be diluted with the solvent. Furthermore, when any of the above-mentioned components is used in a solid state, or when precipitation occurs when mixed with other components in an undiluted state, the component may be separately dissolved or diluted with a diluting solvent in advance, and then Mix with other ingredients.

As the above-mentioned dilution solvent, for example, aliphatic hydrocarbons such as hexane, heptane, and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane, vinyl chloride, methanol, ethanol, propanol, etc. can be used. Alcohols such as butanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone and other ketones, ethyl acetate, butyl acetate and other esters, ethyl Cyrosu series solvents such as Kisai Luosu and so on.

The concentration and viscosity of the coating solution prepared in this manner are not particularly limited as long as the coating solution is within a range that can be coated, and can be appropriately selected according to the situation. For example, the first adhesive composition P1 is diluted to a concentration of 10-60% by mass. Furthermore, when the coating solution is obtained, the addition of a dilution solvent or the like is not a necessary condition, and as long as the first adhesive composition P1 has a viscosity that can be coated, the dilution solvent may not be added. At this time, the first adhesive composition P1 becomes a coating solution in which the polymerization solvent of the (meth)acrylate copolymer (A) is directly used as a diluting solvent.

(1-7) Physical properties of the first adhesive layer, etc. The thickness of the first adhesive layer 12 in this embodiment can be appropriately set according to the application of the adhesive sheet 10. For example, the thickness is preferably 100 μm or more, more preferably 140 μm or more, particularly preferably 180 μm or more, and more preferably 200 μm or more. By making the thickness of the first adhesive layer 12 at least 100 μm, it is easy to achieve excellent step followability. In addition, the above-mentioned thickness is preferably 1000 μm or less, particularly 500 μm or less, and more preferably 300 μm or less. By making the thickness of the first adhesive layer 12 below 1000 μm, it is easy to effectively suppress the wrinkles of the adhesive sheet 1. Furthermore, the greater the thickness of the first adhesive layer 12, the greater the rolling pressure of the first film 11 on the second film 13 due to the winding, and the higher the difficulty of suppressing wrinkles.

In the storage modulus of the first adhesive layer 12 of the present embodiment at 23° C., from the viewpoint of reducing the occurrence of wrinkles, 0.001 MPa or more is preferable, especially 0.01 MPa or more, and further 0.05 MPa or more. good. In addition, the storage modulus is preferably 1.00 MPa or less, more preferably 0.5 MPa or less, particularly preferably 0.2 MPa or less, and further preferably 0.09 MPa or less. By setting the storage modulus of the first adhesive layer 12 at 23°C to the above upper limit, even when the adhesive sheet 10 of this embodiment is stuck to an adherend with a step on the surface, the first adhesive is The agent layer 12 can better follow the step difference. Furthermore, when the first adhesive layer 12 of this embodiment is composed of the above-mentioned active energy ray-curable adhesive, the so-called storage modulus, unless otherwise mentioned, means that the first adhesive layer 12 is irradiated The former active energy line. In addition, the test method of the above-mentioned storage modulus is as shown in the test example described later.

When the first adhesive layer 12 of this embodiment is composed of the above-mentioned active energy ray-curable adhesive, the first adhesive layer 12 is stored at 23° C. after the first adhesive layer 12 is irradiated with active energy rays The modulus is preferably 0.01 MPa or more, especially 0.06 MPa or more, and further preferably 0.11 MPa or more. In addition, the storage modulus is preferably 2 MPa or less, more preferably 1 MPa or less, particularly preferably 0.5 MPa or less, and further preferably 0.32 MPa or less. By making the storage modulus of the first adhesive layer 12 at 23° C. after the active energy rays are irradiated in the above range, the step followability of the first adhesive layer 12 under durable conditions can be more excellent. In addition, the test method of the above-mentioned storage modulus is as shown in the test example described later.

In addition, when the first adhesive layer 12 is composed of the active energy ray-curable adhesive, the storage modulus of the first adhesive layer 12 at 23° C. after the active energy ray is irradiated is relative to that before the active energy ray is irradiated The ratio of the storage modulus of the first adhesive layer 12 at 23° C. is preferably 1.1 times or more, especially 1.6 times or more, and more preferably 1.9 times or more. On the other hand, the above ratio is preferably 10 times or less, especially 5 times or less, and further preferably 3 times or less. By making the above ratio within the above range, the step followability of the first adhesive layer 12 under durable conditions can be made more excellent.

The gel fraction of the adhesive constituting the first adhesive layer 12 of this embodiment is preferably 20% or more, particularly preferably 30% or more, and more preferably 40% or more. In addition, the gel fraction is preferably 80% or less, particularly preferably 70% or less, and more preferably 60% or less. By setting the gel fraction of the adhesive constituting the first adhesive layer 12 to the above upper limit, the adhesive can have an appropriate cohesive force. Even when the adhesive sheet 10 of the present embodiment is adhered to an adherend having a step on the surface, the first adhesive layer 12 can follow the step better during the pasting. Furthermore, when the first adhesive layer 12 of the present embodiment is composed of the above-mentioned active energy ray curable adhesive, the so-called gel fraction, unless otherwise mentioned, refers to the first adhesive layer 12 The former is irradiated with active energy rays. In addition, the test method of the above-mentioned gel fraction is as shown in the test example mentioned later.

When the first adhesive layer 12 of this embodiment is composed of the above-mentioned active energy ray curable adhesive, after the active energy ray is irradiated to the first adhesive layer 12, the adhesive of the first adhesive layer 12 is formed The gel fraction is preferably 45% or more, especially 55% or more, and further preferably 65% or more. In addition, the gel fraction is preferably 95% or less, especially 85% or less, and more preferably 75% or less. By setting the gel fraction of the first adhesive layer 12 at 23° C. after the active energy ray irradiation in the above range, the cohesive force of the adhesive after the active energy ray irradiation can be improved well. Thereby, the step followability of the first adhesive layer 12 under durable conditions can be made more excellent. In addition, the test method of the above-mentioned storage modulus is as shown in the test example described later.

(3) The second film In the pressure-sensitive adhesive sheet roll 1 of this embodiment, the second film 13 is not particularly limited as long as the surface on the side of the first pressure-sensitive adhesive layer 12 is not peeled off. For example, the second film 13 may be composed of a resin-based sheet containing a resin-based material as a main component, or may be composed of a paper-based material. Preferred examples of the resin-based sheet and paper-based materials used for the second film 13 include the materials described above as the first film 11.

As described above, in the pressure-sensitive adhesive sheet roll 1 of this embodiment, the thickness of the first film 11 is preferably the thickness of the second film 13 or less. From the viewpoint of easily satisfying such a relationship, the thickness of the second film 13 is preferably 50 μm or more, particularly preferably 75 μm or more, and more preferably 100 μm or more. In addition, the thickness of the second film 13 is preferably 300 μm or less, particularly preferably 200 μm or less, and more preferably 150 μm or less.

The Young's modulus of the second film 13 at 23° C. is preferably 0.01 GPa or higher, more preferably 0.1 GPa or higher, particularly preferably 1 GPa or higher, and further preferably 3 GPa or higher. In addition, the Young's modulus is preferably 20 GPa or less, especially 10 GPa or less, and further preferably 5 GPa or less. By making the Young's modulus of the second film 13 at 23° C. above 0.01 GPa, the shape can be easily maintained against the rolling pressure from the first film 11 during winding, and the wrinkles of the adhesive sheet 10 can be effectively suppressed. In addition, by setting the Young's modulus of the second film 13 at 23° C. to 20 GPa or less, the rigidity does not become too high, and it is easy to wind up.

(4) The second adhesive layer As described above, in the adhesive sheet 10 of this embodiment, the second adhesive layer 14 is laminated on the side of the second film 13 opposite to the first adhesive layer 12; and the second adhesive layer is laminated The third film 15 on the side opposite to the second film 13 of 14 is also preferable. At this time, the laminate of the second adhesive layer 14 and the third film 15 can function as a protective film for protecting the second film 13. Furthermore, in general, when the adhesive sheet further has a laminate of a second adhesive layer and a third film, as a member that can be the starting point of wrinkles, the above-mentioned second film is added, and the third film is also added. Therefore, when there is a laminate of the second adhesive layer and the third film, wrinkles are particularly likely to occur compared to the case without the laminate. However, according to the pressure-sensitive adhesive sheet roll 1 of this embodiment, even when the laminate is provided, the occurrence of wrinkles in the pressure-sensitive adhesive sheet 10 can be suppressed well.

The adhesive constituting the second adhesive layer 14 is not particularly limited, and can be appropriately selected according to the application. In particular, when a laminate of the second adhesive layer 14 and the third film 15 is used as the protective film, the adhesive constituting the second adhesive layer 14 is preferably one that can easily achieve the adhesive force described below and the storage modulus described below.

The adhesive constituting the second adhesive layer 14 may be acrylic adhesive, silicone adhesive, rubber adhesive, urethane adhesive, polyester adhesive, polyvinyl ether adhesive Any one of agents, etc. In addition, the above-mentioned adhesive may be any of a latex type, a solvent type, or a solvent-free type, and may be either a crosslinked type or a non-crosslinked type. Furthermore, the above-mentioned adhesive may be an active energy ray-curable adhesive or an active energy ray non-curable adhesive. Among them, the adhesive constituting the second adhesive layer 14 is preferably an acrylic adhesive that is non-curable with active energy rays from the viewpoint of easily satisfying the adhesive force and the storage modulus described later.

When the adhesive constituting the second adhesive layer 14 of this embodiment is an active energy ray non-curable acrylic adhesive, such a second adhesive layer 14 may be made of, for example, a (meth)acrylate copolymer containing (A) and the second adhesive composition of the crosslinking agent (B) (hereinafter may be referred to as "second adhesive composition P2".) It is an adhesive composition formed by crosslinking (thermal crosslinking).

The (meth)acrylate copolymer (A) contained in the second adhesive composition P2, for example, the same (meth)acrylate copolymer (A) as contained in the first adhesive composition P1 can be used ). In particular, the (meth)acrylate copolymer (A) contained in the second adhesive composition P2, as a monomer unit constituting the polymer, contains: having a crosslinking agent (B) in the molecule The reactive group of the reactive reactive group contains a monomer; and an alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group is preferred. At this time, the obtained second adhesive layer 14 has the desired cohesive force, and at the same time it is easy to exhibit the desired adhesive force.

With regard to the second adhesive composition P2, the above-mentioned reactive group contains monomers and preferred examples of alkyl (meth)acrylates having a carbon number of 1 to 20 with an alkyl group, respectively, and the first adhesive The monomers of composition P1 are the same. In particular, the (meth)acrylate copolymer (A) contained in the second adhesive composition P2 preferably uses 4-hydroxybutyl (meth)acrylate as the reactive group-containing monomer. The alkyl (meth)acrylate having 1-20 carbon atoms is preferably n-butyl (meth)acrylate.

Regarding the (meth)acrylate copolymer (A) of the second adhesive composition P2, as a monomer unit constituting the polymer, the hydroxyl group contains a monomer, preferably at least 0.1% by mass, especially 0.5 It is preferable that the content is at least 1.0% by mass, and it is more preferable to contain 1.0% by mass or more. In addition, in the (meth)acrylate copolymer (A), as a monomer unit constituting the polymer, a hydroxyl group-containing monomer is preferably contained, preferably 30% by mass or less, especially 20% by mass or less, Furthermore, it contains 10 mass% or less.

In addition, regarding the (meth)acrylate copolymer (A) of the second adhesive composition P2, as a monomer unit constituting the polymer, a (methyl) group having 1 to 20 carbon atoms in the alkyl group The alkyl acrylate preferably contains 60% by mass or more, especially 70% by mass or more, and more preferably 80% by mass or more. In addition, in the (meth)acrylate copolymer (A), as a monomer unit constituting the polymer, an alkyl (meth)acrylate having an alkyl group of 1 to 20 carbon atoms is contained so as to contain 99.9% by mass The following is preferable, and it is especially preferable to contain 99.5 mass% or less, and it is more preferable to contain 99.0 mass% or less. Thereby, it is easy to adjust the storage modulus and adhesive force of the obtained second adhesive layer 14 to the ranges described later.

The weight average molecular weight of the (meth)acrylate copolymer (A) contained in the second adhesive composition P2 is preferably 600,000 or more, particularly 900,000 or more, and more preferably 1.1 million or more. In addition, the above-mentioned weight average molecular weight is preferably 2 million or less, particularly preferably 1.7 million or less, and further preferably 1.4 million or less. By setting the weight average molecular weight in the above range, it is easy to adjust the storage modulus of the obtained second adhesive layer 14 and the gel fraction of the adhesive constituting the second adhesive layer 14 within the ranges described later.

The crosslinking agent (B) contained in the second adhesive composition P2 can be, for example, the same as the (meth)acrylate copolymer (A) contained in the first adhesive composition P1. Particularly, as the crosslinking agent (B) included in the second adhesive composition P2, it is preferable to use an isocyanate-based crosslinking agent having excellent reactivity with hydroxyl groups, and especially an aromatic polycarbonate modified with trimethylolpropane. Isocyanate is preferred, and it is further preferred to use trimethylolpropane to modify toluene diisocyanate.

The content of the crosslinking agent (B) in the second adhesive composition P2 is preferably 0.5 parts by mass or more based on 100 parts by mass of the (meth)acrylate copolymer (A), especially 1.0 parts by mass or more Preferably, it is more preferably 2.0 parts by mass or more. In addition, the content is preferably 10 parts by mass or less with respect to 100 parts by mass of the (meth)acrylate copolymer (A), particularly preferably 7 parts by mass or less, and further preferably 5 parts by mass or less. By setting the content of the crosslinking agent (B) within the above range, it is easy to adjust the storage modulus of the second adhesive layer 14 and the gel fraction of the adhesive constituting the second adhesive layer 14 to the ranges described later. .

In addition, in the second adhesive composition P2, similar to the first adhesive composition P1, various additives generally used for acrylic adhesives can be added as desired. As a preferable example of this additive, it is the same as the additive which can be added to the 1st adhesive composition P1.

The second adhesive composition P2 can be prepared by producing a (meth)acrylate copolymer (A), and the obtained (meth)acrylate copolymer (A) can be combined with the desired crosslinking agent (B), Manufactured by mixing with additives. The production of the above-mentioned (meth)acrylate copolymer (A) can be performed in the same manner as the (meth)acrylate copolymer (A) contained in the first adhesive composition P1.

The thickness of the second adhesive layer 14 in this embodiment can be appropriately set according to the application of the adhesive sheet 10. For example, the thickness is preferably 3 μm or more, particularly 5 μm or more, and further preferably 7 μm or more. In addition, the above-mentioned thickness is preferably 40 μm or less, particularly preferably 30 μm or less, and further preferably 20 μm or less. By making the thickness of the second adhesive layer 14 within the above range, it is easy to achieve the desired adhesive force.

In this embodiment, the storage modulus of the second adhesive layer 14 at 23° C. is preferably 0.01 MPa or more, particularly 0.04 MPa or more, and further preferably 0.09 MPa or more. In addition, the storage modulus is preferably 3 MPa or less, particularly preferably 1 MPa or less, and further preferably 0.5 MPa or less. By making the storage modulus of the second adhesive layer 14 at 23° C. in the above range, it becomes easy to suppress the third film 15 from being caused by the rolling pressure of the first film 11 and the second film 13 by the second adhesive layer 14 Deformation, and easy to achieve the desired adhesive force at the same time. In addition, the test method of the above-mentioned storage modulus is as shown in the test example described later.

The gel fraction of the adhesive constituting the second adhesive layer 14 of this embodiment is preferably 60% or more, particularly 80% or more, and more preferably 90% or more. In addition, the gel fraction is preferably 100% or less, particularly preferably 99% or less, and more preferably 95% or less. By making the gel fraction of the adhesive constituting the second adhesive layer 14 within the above range, the adhesive can have good cohesive force. Thereby, while having an appropriate adhesive force, it becomes easy to suppress the third film 15 from being wrinkled due to winding. In addition, the test method of the above-mentioned storage modulus is as shown in the test example described later.

(5) The third film The material of the third film 15 is not particularly limited. Like the first film 11 or the second film 13, it may be composed of a resin-based sheet mainly composed of a resin-based material, or may be composed of a paper-based material. Preferred examples of the resin-based sheet and paper-based materials used for the third film 15 include the materials described above as the first film 11.

Furthermore, as described above, the third film 15 can function as a protective film for protecting the second film 13 together with the second adhesive layer 14. At this time, from the viewpoint of suppressing peeling at the interface between the second adhesive layer 14 and the third film 15, it is preferable that the surface on the second adhesive layer 14 side of the third film 15 does not have a peeling treatment.

The thickness of the third film 15 is preferably 50 μm or more, particularly preferably 75 μm or more, and more preferably 100 μm or more. By setting the thickness of the third film 15 to 50 μm or more, the third film 15 can easily function as a protective film, and at the same time, it is easy to suppress the occurrence of wrinkles. In addition, the thickness of the third film 15 is preferably 300 μm or less, particularly preferably 200 μm or less, and more preferably 150 μm or less. By making the thickness of the third film 15 300 μm or less, the adhesive sheet 10 is easily wound.

The Young's modulus of the third film 15 at 23° C. is preferably 0.01 GPa or higher, more preferably 0.1 GPa or higher, particularly preferably 1 GPa or higher, and further preferably 3 GPa or higher. In addition, the Young's modulus is preferably 20 GPa or less, especially 10 GPa or less, and further preferably 5 GPa or less. By making the Young's modulus of the third film 15 at 23° C. above 0.01 GPa, the occurrence of wrinkles in the adhesive sheet 10 can be effectively suppressed. In addition, by setting the Young's modulus of the third film 15 at 23° C. to 20 GPa or less, it is suppressed that the second film 13 has excessive rigidity and the adhesive sheet 10 is easily wound.

(6) Core material The core material 20 of this embodiment has a cylindrical or cylindrical shape. In addition, the diameter of the core material 20 in this embodiment is 180 mm or more. By setting the diameter of the core material 20 to be 180 mm or more, as described above, the adhesive sheet roll 1 according to the embodiment of the present invention can deliver the adhesive sheet 10 having an excellent appearance. From this point of view, the diameter of the core material 20 is preferably 220 mm or more, particularly preferably 260 mm or more, and further preferably 290 mm or more. On the other hand, the upper limit of the diameter of the core material 20 is 800 mm or less from the viewpoint that the number of rolls of the adhesive sheet 10 can be increased, preferably 600 mm or less, and particularly preferably 400 mm or less.

In addition, in the present embodiment, the length of the core material 20 (the length in the direction of the axis of rotation when the adhesive sheet 10 is wound) is not particularly limited, but it is preferably the same as or larger than the width of the adhesive sheet 10.

The material constituting the core material 20 is not particularly limited as long as it has sufficient strength for winding the adhesive sheet 10, and conventionally known materials can be used. As an example of this material, metal, resin, wood, etc. are mentioned, for example. Among these materials, resins are preferred, polyolefin resins are more preferred, and polypropylene is particularly preferred.

The Young's modulus of the core material 20 at 23° C. is preferably 0.01 GPa or higher, particularly preferably 0.1 GPa or higher, and further preferably 0.3 GPa or higher. In addition, the Young's modulus is preferably 500 GPa or less, more preferably 100 GPa or less, particularly preferably 10 GPa or less, and further preferably 1 GPa or less. By setting the Young's modulus of the core material 20 at 23° C. within the above range, even when the pressure of the adhesive sheet 10 is applied to the core material 20, the shape of the core material 20 can be maintained well. In addition, the Young's modulus of the core material 20 at 23°C is measured in compliance with JIS Z2241:2011.

(7) Other Regarding the adhesive sheet roll 1 of this embodiment, the number of rolls of the adhesive sheet 10 may preferably be 3 weeks or more, and in particular, it may be 10 weeks or more. The inventors found that when the number of rolls is 3 weeks or more, the adhesive sheet 10 sent out from the adhesive sheet roll 1 is prone to wrinkles. However, according to the pressure-sensitive adhesive sheet roll 1 of this embodiment, even when the number of rolls is 3 weeks or more, the occurrence of the above-mentioned wrinkles can be effectively suppressed. Furthermore, the upper limit of the number of rolls mentioned above can be determined by the length of the adhesive sheet 10. The amount and the viewpoint of the operability of the adhesive sheet roll 1 are appropriately set, but for example, it may be 2000 weeks or less, and in particular, it may be 1500 weeks or less.

In addition, regarding the adhesive sheet roll 1 of this embodiment, the width of the adhesive sheet 10 (the length in the direction parallel to the reel axis of the adhesive sheet roll 1) can be appropriately set according to the application. For example, the width may be preferably 100 mm or more, especially Preferably, it may be 500 mm or more, and further it may be 900 mm or more. In addition, the width may be 3000 mm or less, particularly may be 2000 mm or less, and further may be 1500 mm or less.

2. The physical properties of the adhesive sheet In the adhesive sheet 10 of this embodiment, the adhesive force of the laminate of the second film 13 and the first adhesive layer 12 to the soda lime glass can be appropriately set according to the application of the adhesive sheet 10, for example, 1N/25mm or more. Preferably, it is more preferably 15N/25mm or more, and more preferably 40N/25mm or more. In addition, the adhesion is preferably 100N/25mm or less, especially 80N/25mm or less, and further preferably 60N/25mm or less. By setting the adhesive force within the above range, the laminate of the second film 13 and the first adhesive layer 12 can exhibit good adhesion to the adherend. In addition, even when the first adhesive layer 12 is placed in a high-temperature and high-humidity condition in a state of being stuck to the adherend, it is easy to well suppress the occurrence of bubbles, floating, peeling, etc. near the step.

In addition, when the adhesive sheet 10 of the present embodiment includes the second adhesive layer 14 and the third film 15, the adhesive force of the laminate of the third film 15 and the second adhesive layer 14 to the soda lime glass is, for example, 0.01 N /25mm or more is preferable, especially 0.1N/25mm or more is preferable, and 0.5N/25mm or more is more preferable. In addition, the adhesive force is preferably 20N/25mm or less, especially 10N/25mm or less, and further preferably 3N/25mm or less. By setting the adhesive force in the above range, the laminate of the third film 15 and the second adhesive layer 14 is easily adhered to the second film 13 well, and when the laminate is used as a protective film, it is easy to be good To achieve its goals. Especially when the adhesive sheet 10 is wound and sent out, even during use (when the surface of the first adhesive layer 12 opposite to the second film 13 is stuck to the adherend), it is easy to prevent the protective film from not being Intentional peeling. At the same time, at the stage where the above-mentioned protective film is not needed, the adverse effects on the second film 13 and the first adhesive layer 12 can be suppressed, and it is easy to peel off well. Remove.

In addition, the detail of the test method of the above adhesive force is as the test example mentioned later.

In the adhesive sheet 10 of this embodiment, the peeling force when the first film 11 is peeled off from the laminate of the first adhesive layer 12 and the second film 13 is preferably 2000mN/25mm or less, and 1000mN/25mm or less More preferably, it is particularly preferably 500 mN/25mm or less, and further preferably 200 mN/25mm or less. By setting the above-mentioned peeling force to 2000 mN/25 mm or less, the first film 11 can be easily peeled from the adhesive sheet 10. In addition, the above-mentioned peeling force is preferably 10 mN/25mm or more, especially 50 mN/25mm or more, and more preferably 100 mN/25mm or more. By setting the above-mentioned peeling force to 10 mN/25 mm or more, it is easy to suppress unintended peeling of the first film 11.

In addition, when the pressure-sensitive adhesive sheet 10 of the present embodiment includes the second pressure-sensitive adhesive layer 14 and the third film 15, the peeling force of the laminate of the third film 15 and the second pressure-sensitive adhesive layer 14 from the second film 13 is 3000mN/25mm or less is preferred, especially 2000mN/25mm or less, and more preferably 1000mN/25mm or less. By making the above peeling force below 3000mN/25mm, it is easy to separate the third film 15 with the second adhesive The laminated body of the layer 14 is peeled from the adhesive sheet 10. In addition, the above-mentioned peeling ability is preferably 10 mN/25mm or more, especially 100 mN/25mm or more, and more preferably 200 mN/25mm or more. By setting the above-mentioned peeling force to 10 mN/25 mm or more, it is easy to suppress unintended peeling of the laminate of the third film 15 and the second adhesive layer 14.

In addition, the detail of the test method of the above peeling force is as the test example mentioned later.

3. Manufacturing method of adhesive sheet roll Regarding the manufacturing method of the adhesive sheet roll 1 of this embodiment, as long as the first film 11 side of the adhesive sheet 10 is wound around the core material 20 on the outside, a conventionally known method can be adopted without particular limitation.

When the adhesive sheet 10 of this embodiment has a layer structure of the first film 11/the first adhesive layer 12/the second film 13, as an example of the manufacturing method of the adhesive sheet 10, initially, the first film On one side of the film 11 (when there is a peeling process, the peeling process is performed), the coating solution of the above-mentioned first adhesive composition P1 is applied. The obtained coating film is heat-treated to thermally crosslink the first adhesive composition P1 to form the first adhesive layer 12. After that, by laminating one side of the second film 13 on the surface of the first adhesive layer 12 opposite to the first film 11 to form a first film 11/first adhesive layer 12/second film 13 The adhesive sheet 10 is composed of layers. The protection of the first adhesive layer 12 can also be performed as needed. Furthermore, in the above-mentioned manufacturing method, the first film 11 and the second film 13 may be alternated.

In addition, it is difficult to form the first adhesive layer 12 with a desired thickness by one application of the coating solution as described above, the first adhesive layer 12 can also be formed as follows. That is, it is also possible to fabricate a laminate in which an adhesive layer is formed on an engineering sheet, and to adhere the first film 11 and the adhesive layer produced as described above on the surface of the laminate on the side of the adhesive layer. On the adhesive layer side surface of the laminate, the first adhesive layer 12 having a desired thickness is formed. At this time, by sticking the second film 13 to the exposed surface of the first adhesive layer 12 exposed by peeling off the above-mentioned engineering sheet, the adhesive sheet 10 can be obtained. Alternatively, a laminate formed by forming an adhesive layer on one side of the second film 13 may be produced, and the first film 11 produced as described above may be pasted on the adhesive layer side of the laminate. On the adhesive layer side surface of the laminate of adhesive layers, a first adhesive layer 12 having a desired thickness is formed, and a first film 11, a first adhesive layer 12, and a second film 13 are sequentially laminated at the same time成 Adhesive sheet 10.

As a method of applying the coating solution of the first adhesive composition P1, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, and a gravure coating method can be used. Wait.

On the other hand, the adhesive sheet 10 having the layer composition of the first film 11/first adhesive layer 12/second film 13/second adhesive layer 14/third film 15 can be manufactured as follows, for example. First, a laminate having a layer consisting of the first film 11/the first adhesive layer 12/the second film 13 is obtained by the above-mentioned method. In addition, a laminate having a layer configuration of the second adhesive layer 14/third film 15 was obtained. Then, to the surface of the second film 13 side of the laminate of the first film 11/first adhesive layer 12/second film 13 layer, the second adhesive layer 14/third film 15 is attached The surface of the second adhesive layer 14 side of the layered product is manufactured.

The laminate having the layer configuration of the second adhesive layer 14/third film 15 can be manufactured as follows, for example. First, apply the coating solution of the second adhesive composition P2 on the peeling surface of the release sheet, and heat the resulting coating film to thermally crosslink the second adhesive composition P2 to form a second adhesive剂层14。 Agent layer 14. After that, by laminating one side of the third film 15 on the surface of the second adhesive layer 14 on the opposite side of the release sheet, the release sheet is laminated on the second adhesive layer 14 to obtain a second adhesive layer. A laminate of the agent layer 14/the third film 15.

By winding the adhesive sheet 10 manufactured as described above on the core material 20, the adhesive sheet roll 1 can be obtained. In this winding, the surface of the adhesive sheet 10 on the first film 11 side is the outer side, and the adhesive sheet 10 is wound around the core material 20. Furthermore, the manufacture of the adhesive sheet 10 and the winding of the manufactured adhesive sheet 10 may be continuously performed. That is, the lamination of each layer constituting the adhesive sheet 10 is performed upstream in the flow direction, and at the same time, the laminated adhesive sheet 10 is wound up downstream in the flow direction.

At the time of the above-mentioned winding, tension may be applied to the adhesive sheet 10. The tension is preferably 10 N/m or more, especially 50 N/m or more, and more preferably 100 N/m or more. In addition, the tension is preferably 1000 N/m or less, especially 800 N/m or less, and more preferably 500 N/m or less. By winding the adhesive sheet 10 while applying tension in the above-mentioned range, it is easy to manufacture the adhesive sheet roll 1 that is uniformly wound without slack.

4. How to use the adhesive film roll Regarding the adhesive sheet roll 1 of this embodiment, the sent adhesive sheet 10 can be used for a desired application. For example, according to the adhesive sheet roll 1 concerning this embodiment, the adhesive sheet 10 sent out in this way is used as a process sheet, and a predetermined product is manufactured. Or, according to the adhesive sheet roll 1 concerning this embodiment, the adhesive sheet 10 sent out in this way is used as a material, and a predetermined product is manufactured.

The pressure-sensitive adhesive sheet 10 of this embodiment is used for products manufactured as materials, and examples thereof include display devices, semiconductor devices, and the like.

According to the adhesive sheet roll 1 of this embodiment, since the adhesive sheet 10 that suppresses the occurrence of wrinkles can be provided, by using such an adhesive sheet 10, a product with an excellent appearance can be manufactured. In addition, depending on the position where the adhesive sheet 10 is used, etc., the presence or absence of wrinkles not only affects the appearance of the product, but also affects the performance of the product. In such a case, by using the adhesive sheet of this embodiment Volume 1, can manufacture products with excellent performance. From such a viewpoint, the pressure-sensitive adhesive sheet 10 of the present embodiment can be suitably used for the manufacture of a display device. In particular, when a display device has a mini-LED or micro-LED inside, an adhesive sheet that covers the surface or indirectly of the mini-LED or micro-LED, using the adhesive sheet 10 of this embodiment, can be manufactured with excellent performance Mini-LED or micro-LED display device manufacturing.

The specific method of using the adhesive sheet roll 1 of this embodiment is not particularly limited. For example, the adhesive sheet 10 is sent out from the adhesive sheet roll 1, and then the first film 11 is peeled from the adhesive sheet 10 to expose the first adhesive layer The adhesive surface of 12 is stuck to the desired adherend. When the adhesive sheet 10 includes the third film 15 and the second adhesive layer 14, the laminate of the third film 15 and the second adhesive layer 14 is peeled from the second film 13 at a desired timing. Here, when the laminate of the third film 15 and the second adhesive layer 14 is provided as a protective film for protecting the second film 13, it is better to peel off the laminate at a stage where protection is not necessary.

When the first adhesive layer 12 is composed of an active energy ray-curable acrylic adhesive as described above, after the adhesive sheet 10 is adhered to the adherend, the first adhesive layer 12 Irradiating active energy rays can harden the first adhesive layer 12. At this time, even if the first adhesive layer 12 has a step or unevenness on the surface of the adherend, it can fully follow the step or the unevenness to achieve the desired cohesive force. Thereby, even when the adhesive sheet 10 is placed under high temperature and high humidity conditions with the first adhesive layer 12 attached to the adherend, the occurrence of bubbles, floating, peeling, etc. near the step can be well suppressed.

The active energy ray irradiated to the first adhesive layer 12 means that there is an energy quantum in electromagnetic waves or charged particle rays. Specifically, ultraviolet rays, electron rays, and the like can be mentioned. Among the active energy rays, ultraviolet rays, which are easy to operate, are particularly preferred.

The above-mentioned ultraviolet irradiation can be performed by a high-pressure mercury lamp, Fusion H lamp, xenon lamp, etc. The amount of ultraviolet irradiation is preferably 50 mW/cm ² or more and 1000 mW/cm ² or less. Further, the amount of ultraviolet light at 50mJ / cm ² or more preferably, at 80mJ / cm ² or more is more preferred to 200mJ / cm ² or more is particularly preferred, in addition, the amount of ultraviolet light at ² or less 10000mJ / cm preferably to 5000mJ /cm ² or less is more preferable, and 2000 mJ/cm ² or less is particularly preferable. On the other hand, the electron beam irradiation can be performed by an electron beam accelerator or the like, and the irradiation amount of the electron beam is preferably 10 krad or more and 1000 krad or less.

As described above, when the adhesive layer 12 composed of an active energy ray-curable acrylic adhesive is adhered to the first display body constituent member having a step, and the active energy ray is irradiated to harden the adhesive layer 12, The adhesive layer 12 is in a state of well following the step, and the cohesive force of the adhesive layer 12 is improved. Thereby, even when the adhesive layer 12 is placed in a high-temperature and high-humidity condition in a state of being stuck to the adherend, the occurrence of bubbles, floating, peeling, etc. in the vicinity of the step can be well suppressed.

As a preferable method of using the adhesive sheet roll 1 of the present embodiment, the following describes a case where the adhesive sheet roll 1 is used in a manufacturing method of a display device equipped with mini-LEDs.

The above-mentioned manufacturing method includes, for example, after the adhesive sheet 10 is sent out from the adhesive sheet roll 1, the first film 11 is peeled from the adhesive sheet 10, and the exposed surface of the leaked first adhesive layer 12 is pasted on the exposed surface of the first adhesive layer 12 provided with plural mini- Pasting step on LED backlight. Here, the mini-LED is installed on the backlight in a state of being embedded in a predetermined resin.

In addition, the above-mentioned manufacturing method preferably includes a cutting step of cutting the adhesive sheet 10 into a predetermined shape (for example, a shape corresponding to the above-mentioned backlight) before the above-mentioned pasting step.

When the first adhesive layer 12 is made of an active energy ray-curable adhesive, the manufacturing method described above includes after the bonding step, the first adhesive layer 12 is irradiated with active energy rays to make the first adhesive layer 12 Hardening steps are also good.

In addition, when the adhesive sheet 10 includes a laminate of the second adhesive layer 14 and the third film 15, after the pasting step or the curing step, the second adhesive layer 14 and the second adhesive layer 14 are peeled off from the second film 13 The step of peeling off the laminate of the third film 15 is also preferable.

According to the above manufacturing method, a display device with mini-LEDs with excellent performance can be manufactured.

The embodiments described above are described in order to facilitate the understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above-mentioned embodiment includes all design changes or equivalents belonging to the technical scope of the present invention. [Example]

Hereinafter, the present invention will be described more specifically with examples and the like, but the scope of the present invention is not limited to these examples and the like.

[Example 1] 1. Formation of the first layered body 65 parts by mass of 2-ethylhexyl acrylate, 10 parts by mass of 4-propenylmorpholine (N-propenylmorpholine), 10 parts by mass of isobornyl acrylate, and 15 parts by mass of 2-hydroxyethyl acrylate were used as a solution Copolymerization was carried out by a polymerization method to prepare a (meth)acrylate copolymer (A1). As a result of measuring the molecular weight of the (meth)acrylate copolymer (A1) by the method described later, the weight average molecular weight (Mw) was 600,000.

Here, the above-mentioned weight average molecular weight (Mw) is a weight average molecular weight in terms of polystyrene measured (GPC measurement) using gel permeation chromatography (GPC) under the following conditions. <Measurement conditions> . GPC measuring device: made by TOSOH, HLC-8320 . GPC string (pass in the following order): TOSOH company TSK gel superH-H TSK ge1 superHM-H TSK ge1 superH2000 . Determination solvent: tetrahydrofuran . Measuring temperature: 40℃

100 parts by mass of the (meth)acrylate copolymer (A1) obtained as described above (solid content conversion value; the same below) and 0.15 parts by mass of trimethylolpropane as the crosslinking agent (B) are modified toluene diisocyanate , 5.0 parts by mass as the active energy ray curable component (C) ε-caprolactone modified ginseng-(2-propylene oxyethyl) trimeric isocyanate, 0.5 parts by mass as the photopolymerization initiator (D) 2,4,6-Trimethylbenzyl-diphenyl-phosphine oxide and 0.5 parts by mass of 3-glycidyloxypropyltrimethoxysilane as a silane coupling agent were mixed, stirred well, and then mixed with methyl ethyl ketone Dilute to obtain a coating solution of the first adhesive composition.

The coating solution of the first adhesive composition obtained as described above was coated with a knife coater on one side of a long polyethylene terephthalate film that was peeled off with a silicone-based release agent as the first film The peeling surface of the peeling sheet (thickness: 75μm, Young's modulus: 4.6GPa). Then, the obtained coating film was heat-treated at 110° C. for 3 minutes to dry, and the dried coating film was further laminated by transfer to form a first adhesive layer with a thickness of 250 μm.

Next, on the side opposite to the first film on the side of the formed first adhesive layer, a long strip of polyethylene terephthalate (thickness: 100μm, Young's modulus: 4.6 GPa) side. Thereby, the first laminated body composed of the structure of the first film/first adhesive layer/second film is obtained.

2. Formation of the second layered body 99 parts by mass of n-butyl acrylate and 1 part by mass of 4-hydroxybutyl acrylate were copolymerized by a solution polymerization method to prepare a (meth)acrylate copolymer (A2). As a result of measuring the molecular weight of the (meth)acrylate copolymer (A2) by the method described above, the weight average molecular weight (Mw) was 1.3 million.

100 parts by mass of the (meth)acrylate copolymer (A2) obtained as described above (solid content conversion value; the same below) was modified with 2.0 parts by mass of trimethylolpropane as the crosslinking agent (B) The isocyanate is mixed, fully stirred, and diluted with methyl ethyl ketone to obtain a coating solution of the second adhesive composition.

The coating solution of the second adhesive composition obtained as described above was coated with a knife coater on a long polyethylene terephthalate film (thickness: 100 μm, Young's modulus: 4.6) as the third film. GPa) side. Then, the obtained coating film was heat-treated at 110°C for 1 minute to dry it. In addition, on the surface of the coating film opposite to the third film, a peeling sheet on one side of a long polyethylene terephthalate film peeled off with a silicone-based release agent (product made by LINTEC) The peeling-treated surface named "SP-PET752150") is aged at room temperature for 7 days to obtain a second laminate composed of a third film/second adhesive layer (thickness: 5μm)/release sheet. .

3. Manufacture of Adhesive Sheet From the second laminate obtained in step 2 above, the release sheet is peeled off, and the exposed surface of the second adhesive layer thus exposed is stuck on the second film side surface of the first laminate obtained in step 1. In this way, a long adhesive sheet (width: 1080 mm) composed of the first film/first adhesive layer/second film/second adhesive layer/third film is obtained.

4. Manufacture of adhesive film rolls The adhesive sheet obtained in the above step 3 was wound on a cylindrical core material (made of polypropylene, Young's modulus: 0.7 GPa) having a diameter (outer diameter) of 304.8 mm. At this time, the third film side of the pressure-sensitive adhesive sheet was wound inside, and the pressure-sensitive adhesive sheet was wound by applying a tension of 200 N/m in the longitudinal direction. In addition, the length of the wound adhesive sheet is 300m. Thus, the adhesive film roll is obtained.

[Examples 2~8] The thickness of the first film, the first adhesive layer, the second film, the second adhesive layer, and the third film, and the diameter of the core material were changed to those shown in Table 1, and the adhesive was produced in the same manner as in Example 1. Film rolls.

[Example 9] Combine 55 parts by mass of 2-ethylhexyl acrylate, 10 parts by mass of 4-propenylmorpholine (N-propenylmorpholine), 10 parts by mass of isobornyl acrylate and 25 parts by mass of 2-hydroxyethyl acrylate in solution Copolymerization is carried out by a polymerization method to prepare a (meth)acrylate copolymer (A3). As a result of measuring the molecular weight of the (meth)acrylate copolymer (A3) by the method described above, the weight average molecular weight (Mw) was 600,000.

The obtained (meth)acrylate copolymer (A3) was used to prepare a coating solution of the first adhesive composition, and the coating solution was further used to form the first adhesive layer, and an adhesive sheet roll was produced in the same manner as in Example 1. .

[Example 10] Except having changed the thickness of each of the second film and the third film to those shown in Table 1, the pressure-sensitive adhesive sheet roll was produced in the same manner as in Example 1.

[Example 11] Combine 55 parts by mass of 2-ethylhexyl acrylate, 10 parts by mass of 4-propenylmorpholine (N-propenylmorpholine), 10 parts by mass of isobornyl acrylate and 25 parts by mass of 2-hydroxyethyl acrylate in solution Copolymerization is carried out by a polymerization method to prepare a (meth)acrylate copolymer (A4). As a result of measuring the molecular weight of the (meth)acrylate copolymer (A4) by the method described above, the weight average molecular weight (Mw) was 600,000.

100 parts by mass of the obtained (meth)acrylate copolymer (A4), 2.0 parts by mass of trimethylolpropane as a crosslinking agent (B) modified toluene diisocyanate, and 0.5 parts by mass of 3-condensation as a silane coupling agent Glyceryl ether oxypropyl trimethoxysilane is mixed, fully stirred, and diluted with methyl ethyl ketone to obtain a coating solution of the first adhesive composition.

Except that the coating solution of the obtained first adhesive composition was used to form the first adhesive layer, an adhesive sheet roll was produced in the same manner as in Example 1.

[Comparative Example 1] Except having changed the diameter of the core material to what is shown in Table 1, it carried out similarly to Example 1, and produced the adhesive sheet roll.

[Test Example 1] (Measurement of the storage modulus of the adhesive layer) The first adhesive layers produced in the examples and comparative examples were laminated in plural to form a laminate with a thickness of 3 mm. From the obtained laminate of the first adhesive layer, a cylinder with a diameter of 8 mm (height 3 mm) was punched out, and this was used as a sample.

Regarding the above samples, in accordance with JIS K7244-6:1999, a viscoelasticity measuring device (manufactured by REOMETRIC, product name "DYNAMIC ANALYZER") was used to measure the storage modulus (G') (MPa) by the torsion shear method under the following conditions ). The results are shown in Table 1 as the storage modulus of the first adhesive layer before ultraviolet irradiation (before UV irradiation). Measuring frequency: 1Hz Measuring temperature: 23℃

In addition, the sample obtained in the same manner as described above was irradiated with ultraviolet rays under the following conditions to harden the first adhesive layer constituting the sample. For the cured sample, the storage modulus (G') (MPa) was also measured in the same manner as described above. The results are shown in Table 1 as the storage modulus of the first adhesive layer after ultraviolet irradiation (after UV irradiation). <Ultraviolet irradiation conditions>. Use high-pressure mercury lamps. Illumination 200mW/cm ² , light intensity 1000mJ/cm ² . UV illumination. The light meter uses "UVPF-A1" made by EYE GRAPHICS

In addition, the storage modulus (G') (MPa) of the second adhesive layer produced in the examples and comparative examples was measured in the same manner as described above. The results are also shown in Table 1.

[Test Example 2] (Measurement of Gel Fraction) The first laminate (the composition of the first film/the first adhesive layer/the second film) obtained in the examples and comparative examples was cut into a size of 80mm×80mm, and the first adhesive layer was made of polyester mesh ( The mesh size is 200) wrapped, the mass is weighed with a precision balance, and the mass of the net alone is deducted to calculate the mass of only the first adhesive layer. The mass at this time is M1.

Next, the adhesive attached to the above-mentioned polyester mesh was immersed in ethyl acetate at room temperature (23°C) for 24 hours. After that, the adhesive was taken out and dried in an air-dried environment at a temperature of 23°C and a relative humidity of 50% for 24 hours, and further dried in an oven at 80°C for 12 hours. After drying, weigh the mass with a precision balance, deduct the mass of the net alone, and calculate the mass of only the adhesive. The mass at this time is M2.

Substitute the values of the masses M1 and M2 obtained above into the formula of gel fraction (%)=(M2/M1)×100 to calculate the gel fraction (%). The results are shown in Table 1 as the gel fraction (%) of the first adhesive layer before ultraviolet irradiation (before UV irradiation).

In addition, the first adhesive layer was irradiated with ultraviolet rays under the ultraviolet irradiation conditions described in Test Example 1, and the gel fraction (%) was calculated in the same manner as described above for the cured first adhesive layer. The results are shown in Table 1 as the gel fraction of the first adhesive layer after ultraviolet irradiation (after UV irradiation).

In addition, for the second adhesive layers produced in the examples and comparative examples, the gel fraction (%) before ultraviolet irradiation was calculated in the same manner as described above. The result is also shown in 1.

[Test Example 3] (Measurement of Adhesion) The first laminate (the composition of the first film/first adhesive layer/second film) obtained in the examples and comparative examples was cut into a width of 25 mm and a length of 100 mm. Next, the first film was peeled from the first laminate, and the exposed surface of the second adhesive layer was pasted on soda lime glass (manufactured by Nippon Plate Glass Co., Ltd.) in an environment of 23° C. and 50% RH. The autoclave (manufactured by Kurihara Manufacturing Co., Ltd.) was pressurized at 0.5 MPa and 50°C for 20 minutes.

After that, the first adhesive layers of Examples 1 to 10 and Comparative Example 1 were irradiated with ultraviolet rays under the conditions described in Test Example 1 through the PET film to cure them.

Then, after leaving for 24 hours under the conditions of 23°C and 50%RH, the adhesive force was measured using a tensile tester (manufactured by Orientec, product name "Tensilon") at a peeling speed of 300 mm/min and a peeling angle of 180 degrees. (N/25mm). Conditions other than those described here were measured in compliance with JIS Z0237:2009. The results are shown in Table 1.

In addition, about the second laminate (the third film/second adhesive layer/release sheet configuration) obtained in the examples and comparative examples, the adhesive force (N/25mm) was measured in the same manner as described above. However, the surface of the second adhesive layer adhered to the soda lime glass is the exposed surface of the second adhesive layer exposed by peeling off the release sheet from the second laminate. At the same time, the second adhesive layer is not exposed. UV exposure. The results are also shown in Table 1.

[Test Example 4] (Measurement of Peeling Force) The adhesive sheets manufactured in the Examples and Comparative Examples were cut to a length of 100 mm and a width of 25 mm. Next, by fixing the surface of the adhesive sheet on the first film side to a stainless steel plate, a sample for measuring the peeling force was obtained.

For the above-mentioned peeling force measurement sample, in accordance with JIS Z0237:2009, in a standard environment (23°C, 50%RH), a tensile tester (manufactured by Orientec, product name "Tensilon UTM-4-100") was used, and the ° peeling angle and 0.3m/min peeling speed, measure the force when the laminate of the third film and the second adhesive layer is peeled from the second film, and use this as the relation between the second adhesive layer and the second adhesive layer. Peel force of film interface (mN/25mm). The results are shown in Table 1.

Next, from the first film, the laminate of the second film and the first adhesive layer was peeled off in the same manner as above, and the force measured at this time was used as the interface between the first adhesive layer and the first film Peel force (mN/25mm). The results are also shown in Table 1.

[Test Example 5] (Evaluation of the followability of the step difference) On the surface of a glass plate (manufactured by NSG Precision Co., Ltd., product name "Corning Glass EAGLE XG", length 90mm×width 50mm×thickness 0.5mm), UV curable ink (Teikoku Produced by Printing Inks Mfg, product name "POS-911 BLACK"), screen printed into a frame shape with a coating thickness of 10μm (outer shape: vertical 90mm x horizontal 50mm, width 5mm). Next, irradiate ultraviolet rays (80W/cm ² , 2 metal halide lamps, bulb height 15cm, conveyor speed 10~15m/min) to harden the above-mentioned ultraviolet curable ink for printing, and produce a step (step difference) by printing. Height: 10μm) glass plate with steps. Furthermore, a glass plate with a step in which the step height was changed to 5 μm by printing was also produced.

On the other hand, the coating solution of the first adhesive composition prepared in the examples and comparative examples was applied to the polyethylene terephthalate peeled off with a silicone-based release agent using a knife coater. The peeling treatment surface of the first peeling sheet on one side. The obtained coating film was heat-treated at 110°C for 3 minutes to be dried to form a first adhesive layer. The thickness of the first adhesive layer formed at this time is made the same as the thickness of the first adhesive layer of the adhesive sheet rolls of the Examples and Comparative Examples, respectively. Then, on the surface of the formed first adhesive layer opposite to the first release sheet, the second release sheet on the side of the polyethylene terephthalate peeled off with a silicone-based release agent was adhered The treated surface was peeled off to obtain a sample for evaluation.

From the obtained evaluation sample, the first film was peeled off to expose the first adhesive layer to the surface, and a laminating machine (manufactured by FUJiPLA, product name "LPD3214") was used to cover the frame-like printed surface with the first adhesive layer. The two types of glass with step differences obtained as above were laminated separately. Furthermore, the second film is peeled off from each of the first adhesive layers, and the exposed surface of the first adhesive layer is pasted on the side of the glass plate (without printing step).

The thus obtained, a laminated body with a glass plate with a step (step height: 10μm or 5μm)/first adhesive layer/glass plate (with no printing step) is subjected to high pressure under the conditions of 50°C and 0.5MPa The autoclave is treated for 30 minutes and placed for 24 hours under the conditions of normal pressure, 23°C, and 50% RH. Next, the first adhesive layer was irradiated with ultraviolet rays under the same conditions as in Test Example 3 through the above-mentioned glass plate (no print step) to harden the first adhesive layer.

Then, it was stored for 72 hours under high temperature and high humidity conditions of 85° C. and 85% RH (endurance test). After that, the interface with the first adhesive layer after curing was visually observed for the presence or absence of bubbles, floating, and peeling, and the step followability was evaluated based on the following criteria. The results are shown in Table 1. ◎: When the height of the printing step is both 10 μm and 5 μm, no bubbles, floating, and peeling occur. ○: When the height of the printing step is 10 μm, at least one of bubbles, floating, and peeling occurs, but when the height of the printing step is 5 μm, no bubbles, floating, and peeling occur. ×: The height of the printing step is both 10 μm and 5 μm, and at least one of bubbles, floating, and peeling occurs.

[Test Example 6] (Evaluation of the appearance of the adhesive sheet) From the adhesive sheet rolls obtained in the Examples and Comparative Examples 7 days after manufacture, all the adhesive sheets were sent out, and the appearance abnormalities such as bending wrinkles and deformation wrinkles were confirmed visually over the full length (300m). The adhesive sheet was evaluated according to the following criteria Exterior. The results are shown in Table 1. In addition, the "5m" in the following reference refers to a position 5m from the end of the core material side of the adhesive sheet to the delivery direction of the adhesive sheet roll, and the same applies to other similar performances. In addition, the above-mentioned abnormal appearance does not include traces caused by the tape used to fix the adhesive sheet to the core material. ⊚: No abnormal appearance occurs at least from 5m to 300m. ○: Although the appearance abnormality occurred from 0 m to 10 m, no appearance abnormality occurred from 10 m to 300 m. △: Although appearance abnormality occurred from 0m to 30m, no appearance abnormality occurred from 30m to 300m. ×: Abnormal appearance occurred between 30m and 300m.

[Table 1] Thickness (μm) Diameter of core material (mm) Storage modulus (MPa) Gel fraction (%) Adhesion (N/25mm) Peeling force (mN/25mm) Evaluation of the followability of the step difference Appearance evaluation First film First adhesive layer Second membrane Second adhesive layer Third membrane First adhesive layer Second adhesive layer First adhesive layer Second adhesive layer Laminated body of first adhesive layer and second film Laminated body of second adhesive layer and third film The interface between the first adhesive layer and the first film The interface between the second adhesive layer and the second film Before UV irradiation After UV irradiation Before UV irradiation After UV irradiation Example 1 75 250 100 5 100 304.8 0.06 0.12 0.10 50 73 93 50≦ 1 158 280 ◎ ◎ Example 2 75 250 100 5 100 281.2 0.06 0.12 0.10 50 73 93 50≦ 1 153 283 ◎ ○ Example 3 75 250 100 5 100 230.2 0.06 0.12 0.10 50 73 93 50≦ 1 155 285 ◎ △ Example 4 75 150 100 5 100 304.8 0.06 0.12 0.10 50 73 93 50≦ 1 150 290 ○ ◎ Example 5 75 250 100 15 100 304.8 0.06 0.12 0.10 50 73 93 50≦ 2 155 1200 ◎ ◎ Example 6 50 250 100 5 100 304.8 0.06 0.12 0.10 50 73 93 50≦ 1 120 300 ◎ ◎ Example 7 75 250 100 5 75 304.8 0.06 0.12 0.10 50 73 93 50≦ 1 155 240 ◎ ◎ Example 8 75 250 75 5 100 304.8 0.06 0.12 0.10 50 73 93 50≦ 0.8 158 290 ◎ ◎ Example 9 75 250 100 5 100 304.8 0.12 0.35 0.10 55 75 93 40 1 153 285 ○ ◎ Example 10 75 250 50 5 50 304.8 0.06 0.12 0.10 50 73 93 50≦ 0.7 155 215 ◎ △ Example 11 75 250 100 5 100 304.8 0.25 0.25 0.10 85 85 93 20 1 153 280 X ◎ Comparative example 1 75 250 100 5 100 179.4 0.06 0.12 0.10 50 73 93 50≦ 1 150 300 ◎ X

It can be seen from Table 1 that the adhesive sheet rolls obtained in the examples can deliver adhesive sheets with excellent appearance. [Industrial Profitability]

The adhesive sheet roll of the present invention can be well used in, for example, display devices, especially the manufacture of backlights that use mini-LEDs or micro-LEDs as light sources as included in display devices.

1: Adhesive film roll 10: Adhesive sheet 11: The first film 12: The first adhesive layer 13: second film 14: The second adhesive layer 15: The third film 20: core material

[Fig. 1] is a perspective view of an adhesive sheet roll related to an embodiment of the present invention. [Fig. 2] is a cross-sectional view of the adhesive sheet constituting the adhesive sheet roll according to one embodiment of the present invention.

10: Adhesive sheet

11: The first film

12: The first adhesive layer

13: second film

14: The second adhesive layer

15: The third film

Claims (6)

An adhesive sheet roll, characterized in that it is provided with a first film, a first adhesive layer laminated on one side of the first film, and the first adhesive layer laminated with the first film The long adhesive sheet formed by the second film on the side opposite to the first film side is an adhesive sheet roll that is wound on a cylindrical or cylindrical core material with the surface on the first film side as the outer side, The diameter of the above-mentioned core material is 180mm or more and 800mm or less, The surface on the side of the first adhesive layer of the second film was not peeled off. The adhesive sheet roll according to claim 1, wherein the thickness of the first film is less than or equal to the thickness of the second film. The adhesive sheet roll according to claim 1, wherein the peel force when the first film is peeled off from the laminate of the first adhesive layer and the second film is 10 mN/25mm or more and 2000 mN/25mm or less. The adhesive sheet roll according to claim 1, wherein the adhesive sheet includes: a second adhesive layer laminated on the side of the second film opposite to the first adhesive layer; and laminated on the first adhesive layer The third film on the side opposite to the above-mentioned second film of the second adhesive layer. The adhesive sheet roll according to claim 4, wherein the adhesive force of the laminate of the third film and the second adhesive layer to the soda lime glass is 0.01 N/25 mm or more and 20 N/25 mm or less. The adhesive sheet roll according to claim 1, wherein the storage modulus of the first adhesive layer at 23° C. is 0.001 MPa or more and 1.00 MPa or less.

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