TWI784008B - Reinforcing membrane - Google Patents

Abstract

The present invention provides a reinforced film with both initial low adhesiveness and strong adhesiveness during use with improved and stabilized performance. The invention provides a reinforcing film, which comprises a support substrate having a first surface and a second surface, and an adhesive layer laminated on the first surface of the support substrate. The above-mentioned support substrate includes a resin film as a base film. The second surface of the adhesive layer is fixed to the first surface of the support substrate, and the first surface of the adhesive layer is in contact with a peelable surface with a water contact angle of 100 degrees or more. The said pressure-sensitive adhesive layer contains the polymer A whose Tg is less than 0 degreeC, and the polymer B which is a copolymer of the monomer which has a polyorganosiloxane frame|skeleton, and a (meth)acrylic-type monomer. The adhesive force N2 of the reinforcing film after being attached and heated at 80°C for 5 minutes and then placed at 23°C for 30 minutes is more than 10 times the adhesive force N1 after being placed at 23°C for 30 minutes after attaching.

Description

Reinforcing membrane

The present invention relates to a reinforced membrane. This application claims priority based on Japanese Patent Application No. 2017-222777 filed on November 20, 2017 and Japanese Patent Application No. 2018-107849 filed on June 5, 2018, and these applications The entire content is incorporated into this manual as a reference.

The adhesive sheet is used for the purpose of bonding adherends, fixing articles to adherends, and reinforcing adherends by firmly adhering to adherends. Conventionally, for such a purpose, an adhesive sheet exhibiting high adhesive force from the initial stage of attachment has been used. Moreover, recently, as shown in patent documents 1-3, the adhesive sheet which can show low adhesive force at the initial stage of sticking to an adherend and can raise adhesive force significantly after that is proposed. According to the adhesive sheet having such characteristics, it is possible to exert the repositioning property (secondary processability) useful for suppressing the decrease in the yield rate caused by the wrong or damaged adhesive sheet before the adhesive force increases, and the adhesive After the force is increased, it will exhibit strong adhesiveness suitable for the original purpose of the adhesive sheet. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2014-224227 [Patent Document 2] Japanese Patent No. 5890596 [Patent Document 3] Japanese Patent No. 5951153

[Problem to be solved by the invention]

In Patent Documents 1 to 3, studies are mainly made on the properties or composition of the adhesive for an adhesive sheet having the above characteristics, ie low initial adhesiveness and strong adhesiveness during use. On the other hand, there is still room for research on an adhesive sheet provided with a support substrate for supporting the adhesive (adhesive sheet with substrate). As one form of the adhesive sheet with the base material having the above characteristics, the present inventors focused on the reinforcement film used for the purpose of reinforcement, which is composed of a resin film as the support base material, and improved the performance of the reinforcement film and The present invention has been accomplished through studies on stabilization. [Technical means to solve the problem]

According to the specification, there is provided a reinforcing film comprising a support substrate having a first surface and a second surface, and an adhesive layer laminated on the first surface of the support substrate. The above-mentioned support substrate includes a resin film as a base film. The second surface of the adhesive layer is fixed on the first surface of the support substrate, and the first surface of the adhesive layer is in contact with the peelable surface. Here, the water contact angle of the peelable surface is 100 degrees or more. The said adhesive layer contains the polymer A whose glass transition temperature (Tg) is less than 0 degreeC, and the polymer B which is a copolymer of the monomer which has a polyorganosiloxane frame|skeleton, and a (meth)acrylic-type monomer. Regarding the above-mentioned reinforcing film, the adhesive force N2 after bonding the above-mentioned first surface of the above-mentioned adhesive layer to a stainless steel plate, heating at 80°C for 5 minutes, and then standing at 23°C for 30 minutes is the above-mentioned first surface of the above-mentioned adhesive layer After one side is pasted on the stainless steel plate, the adhesive force N1 is more than 10 times after being placed at 23°C for 30 minutes.

The reinforcing film of this structure is constructed in such a way that the adhesive force N2 (hereinafter also referred to as "adhesion after heating") becomes 10 times or more than the adhesive force N1 (hereinafter also referred to as "initial adhesive force"), so it can take care of the initial stage of use Good secondary processability with low adhesiveness, and high reinforcement performance with strong adhesion to the adherend when using the adherend. In addition, by making the first surface of the adhesive layer (the surface on the side attached to the adherend, hereinafter also referred to as "adhesive surface") contact the peelable surface with a water contact angle of 100 degrees or more, it can effectively Reduce the influence of the storage conditions of the reinforced membrane on the performance of the reinforced membrane. For example, even if the reinforced film before use (i.e., before being attached to the adherend) is stored in a temperature region higher than room temperature, the reinforced film after storage can still properly exhibit the initial low adhesiveness and the adherend can be used Strong adhesiveness of time. Moreover, since the above-mentioned second surface of the adhesive layer (the surface on the opposite side to the adhesive surface, hereinafter also referred to as the back surface) is fixed to the first surface of the supporting substrate, it is difficult for the adhesive layer to remain on the adherend. The peeling of the support substrate from the adhesive layer (grip failure) can effectively maintain the integrity of the adherend and the support substrate.

In addition, hereinafter, the ratio of the adhesive force after heating to the initial adhesive force, that is, N2/N1 may be referred to as "adhesive force increase ratio". In addition, the first surface of the support substrate, that is, the surface on which the adhesive layer is fixed is sometimes referred to as the "front surface", and the second surface of the support substrate is referred to as the "back surface". In addition, the releasable surface may be simply referred to as a "releasable surface".

In some aspects of the reinforcing film disclosed here, the surface of the release layer containing silicon (Si) can be favorably utilized as the release surface. According to the reinforcing film having the adhesive surface in contact with the peelable surface of such a composition, it is possible to better suppress the increase of the initial adhesive force caused by storage at a temperature region higher than room temperature. As a typical example of the silicon-containing release layer, a release layer formed with a silicone-based release treatment agent is mentioned.

In some other aspects of the reinforcing film disclosed here, the surface of the peeling layer formed with a long-chain alkyl-based peeling treatment agent can be used as the peelable surface. In the reinforced film formed by the long-chain alkyl-based peeling treatment agent, the peelable surface with a water contact angle of 100 degrees or more is in contact with the adhesive surface, which can effectively inhibit the damage caused by storage at a temperature higher than room temperature. The increase in the initial adhesion force caused by the area.

The thickness of the above-mentioned support substrate is preferably 30 μm or more. A good reinforcing effect can be easily obtained with a reinforcing film in which an adhesive layer is fixed to a supporting substrate of such thickness.

In some aspects of the reinforcing film disclosed here, the thickness of the above-mentioned support substrate may be not less than 1.1 times and not more than 10 times the thickness of the above-mentioned adhesive layer. According to the reinforcing sheet having such a constitution, it is easy to obtain a good reinforcing effect.

In some aspects, as said polymer B, what has a weight average molecular weight (Mw) of 10000 or more and 50000 or less can be used favorably. According to the polymer B whose Mw is within the above-mentioned range, it is easy to realize a reinforced film with a relatively high increase in adhesion.

In some aspects, content of the said polymer B in the said adhesive agent layer can be made into the range of 0.05 weight part or more and 20 weight part or less with respect to 100 weight part of said polymer A. According to the content in the above range, it is easy to realize a reinforced film with a relatively high increase in adhesion.

In some aspects of the reinforcing film disclosed herein, the releaseable surface may be the surface of a release liner. The reinforcing film of this aspect can make good balance between the initial low adhesiveness and the adherend by peeling the above-mentioned release liner from the adhesive surface to expose the above-mentioned adhesive surface, and attaching the adhesive surface to the adherend. Strong adhesiveness when used.

In several other aspects of the reinforcing film disclosed here, the above-mentioned peelable surface may also be the second surface (back surface) of the supporting substrate. That is, the reinforcing film disclosed here may be a form in which the back surface of the supporting substrate is a detachable surface with a water contact angle of 100 degrees or more, and an adhesive surface is in contact with the back surface. The reinforcement film of this aspect exposes the above-mentioned adhesive surface by peeling the back of the support base material from the adhesive surface, and attaches the adhesive surface to the adherend, so that the initial low adhesiveness and the adherend can be well balanced. Strong adhesiveness when used.

Furthermore, an appropriate combination of the above-mentioned elements can also be included in the scope of the invention claimed in this Japanese patent application.

Hereinafter, preferred embodiments of the present invention will be described. Matters other than those specifically mentioned in this specification and necessary for the implementation of the present invention can be understood by the trader based on the instructions on implementation of the invention described in this specification and the technical knowledge at the time of filing. The present invention can be implemented based on the contents disclosed in this specification and common technical knowledge in this field. In addition, in the following drawings, members and parts that perform the same functions may be described with the same symbols, and overlapping descriptions may be omitted or simplified. In addition, the embodiments described in the drawings are schematic for clearly explaining the present invention, and do not necessarily represent the dimensions or scales of actually provided products accurately.

In addition, in this specification, "acrylic polymer" refers to a polymer containing a monomer unit derived from a (meth)acrylic monomer in the polymer structure, and typically refers to a polymer containing more than 50% by weight Ratio Polymers containing monomer units derived from (meth)acrylic monomers. Moreover, a (meth)acryl-type monomer means the monomer which has at least one (meth)acryl group in 1 molecule. Here, "(meth)acryl" includes both acryl and methacryl. Therefore, the concept of the so-called (meth)acrylic monomers here may include both monomers with acryl groups (acrylic monomers) and monomers with methacryl groups (methacrylic monomers). By. Similarly, in this specification, "(meth)acrylic acid" includes the meaning of acrylic acid and methacrylic acid, and "(meth)acrylate" includes the meaning of acrylate and methacrylate.

<Structure Example of Reinforcement Film> The reinforcement film disclosed here includes at least a support substrate having a first surface and a second surface, and an adhesive layer laminated on the first surface of the support substrate. As a supporting base material, what contains a resin film as a base film is used. Hereinafter, the supporting substrate may also be simply referred to as "substrate".

The structure of the reinforcing film of one embodiment is schematically shown in FIG. 1 . The reinforcing film 1 is constituted as a single-sided adhesive sheet with a base material, and the single-sided adhesive sheet with a base material has a sheet shape having a first surface (front surface) 10A and a second surface (back surface) 10B. The support substrate 10 and the adhesive layer 21 that are fixed on the first surface 10A and laminated. The adhesive layer 21 contains at least a polymer A and a polymer B described below. In addition, the adhesive layer 21 has a first surface (adhesive surface) 21A and a second surface (back surface) 21B.

The reinforcement film 1 attached in front of the adherend is such that the adhesive surface 21A is in contact with a peelable surface (peelable surface) having a water contact angle of 100 degrees or more. As the release surface, for example, as shown in FIG. 1 , the release surface of release liner 31 having at least the surface 31A facing the adhesive layer 21 as a release surface with a water contact angle of 100 degrees or more can be used. The reinforcement film 1 in which the adhesive surface 21A is in contact with the release surface 31A of the release liner 31 can also be understood as a component of the release liner-attached reinforcement film 100 including the reinforcement film 1 and the release liner 31 . As the release liner 31, for example, one configured such that one side of a sheet base (liner base) is provided with a release layer formed with a release treatment agent and becomes the above-mentioned release surface can be preferably used. .

When attaching the reinforcing film 1 to the adherend, the release liner 31 is peeled off from the adhesive surface 21A, and the exposed adhesive surface 21A is pressure-bonded to the adherend. The reinforcement film 1 is constructed so that the adhesion increase ratio becomes 10 or more. Therefore, it can exhibit good secondary workability at the initial stage of attaching to the adherend, and can be attached through the adhesive layer 21 after the adhesion is increased. The support substrate 10 is firmly fixed to the adherend to reinforce the adherend. Here, the back surface 21B of the adhesive layer 21 is fixed to the front surface 10A of the support substrate 10 to prevent peeling (grip failure) of the interface between the adhesive layer 21 and the support substrate 31 . Thereby, the integrity of the adherend and the support base material 10 can be maintained reliably, and a high reinforcing effect can be exhibited.

Moreover, in the reinforcement film 1 shown in FIG. 1, the 2nd surface (back surface) 10B of the support base material 10 can also be utilized as a peeling surface with which the adhesive surface 21A abuts. For example, by winding the reinforcing film 1, the adhesive surface 21A may be in contact with the back surface 10B of the supporting base material 10 to be protected (roll form), or may be in contact with the back surface 10B of the reinforcing film 1. The form of the adhesive surface 21A of the next reinforcing film 1, and the form of laminating a plurality of reinforcing films 1, etc.

The structure of the reinforcing film of another embodiment is schematically shown in FIG. 2 . The reinforcing film 2 is constituted as a double-sided adhesive sheet with a base material. The double-sided adhesive sheet with a base material has a sheet-shaped support base material 10 having a first surface 10A and a second surface 10B. An adhesive layer (first adhesive layer) 21 laminated on the first surface 10A, and an adhesive layer (second adhesive layer) 22 laminated on the second surface 10B. The first adhesive layer 21 contains at least a polymer A and a polymer B described below. The reinforcing film 2 is fixed on the first surface of the support substrate with the second surface (back surface) 21B of the first adhesive layer 21, and the adhesive force of the surface (first adhesive surface) 21A of the first adhesive layer 21 increases The ratio becomes 10 or more and is comprised. In this way, both good secondary processability and high reinforcing effect can be taken into account. The reinforcement film 2 is used by attaching the first adhesive layer 21 and the second adhesive layer 22 to different parts of the adherend. The parts where the adhesive layers 21 and 22 are attached may be parts of different members, or may be different parts in a single member. Moreover, the composition of the 2nd adhesive agent layer 22, and the adhesive force raising ratio of the surface (2nd adhesive surface) 22A of the 2nd adhesive agent layer 22 are not specifically limited.

As shown in FIG. 2 , the reinforcing film 2 attached in front of the adherend can be the first adhesive surface 21A and the second adhesive surface 22A abutting at least on the side opposite to the adhesive layers 21 and 22 to form the peeling surface 31A respectively. The components of the reinforcing film 200 with a release liner in a form protected by the release liners 31 and 32 of . Alternatively, the release liner 32 may also be omitted, and a release liner 31 whose both sides are the release surfaces 31A and 31B may be used, and the second adhesive surface 22A may be abutted by overlapping the reinforcing film 2 and winding it in a spiral shape. A reinforcing film with a release liner in a form (roll form) in which the back surface 31B of the liner 31 is protected. In either case, among the peeling surfaces 31A and 32A, at least the peeling surface 31A abutting against the first adhesive surface 21A is a peeling surface with a water contact angle of 100 degrees or more.

<Adhesive Layer> The reinforcing film disclosed here has an adhesive layer on the first surface of the support substrate, and the adhesive layer contains a polymer A having a Tg of less than 0° C. and polymer A having a polyorganosiloxane skeleton. Polymer B of a copolymer of a monomer and a (meth)acrylic monomer. Such an adhesive layer may be formed from an adhesive composition containing polymer A or its precursor and polymer B. The form of the adhesive composition is not particularly limited, and may be in various forms such as water dispersion type, solvent type, hot melt type, active energy ray curing type (such as photocuring type), and the like.

(Polymer A) As the polymer A, acrylic polymers, rubber-based polymers, polyester-based polymers, urethane-based polymers, polyether-based polymers, Polysiloxane-based polymers, polyamide-based polymers, and fluorine-based polymers are one or more of various polymers that exhibit rubber elasticity at room temperature.

The Tg of the polymer A is typically less than 0°C, preferably less than -10°C, more preferably less than -20°C. The adhesive containing polymer A whose Tg is less than 0° C. shows moderate fluidity (such as the mobility of polymer chains contained in the adhesive), and is therefore suitable for realizing a reinforced film with a relatively high increase in adhesive force. In some aspects, the Tg of the polymer A may be less than -30°C, less than -40°C, less than -50°C, or less than -60°C, for example. When the Tg of the polymer A becomes lower, there is a tendency that the adhesive force after sticking to the adherend is increased easily. The lower limit of Tg of the polymer A is not particularly limited. In general, polymer A having a Tg of -80° C. or higher can be favorably used from the viewpoint of the ease of acquisition of the material and the improvement of the cohesive force of the adhesive layer.

Here, in this specification, the Tg of a polymer refers to a nominal value described in a document or a catalog, or the Tg obtained by Fox's formula based on the composition of the monomer components used in the preparation of the polymer. The formula of Fox refers to the relationship between the Tg of the copolymer and the glass transition temperature Tgi of the homopolymer obtained by homopolymerizing the monomers constituting the copolymer, as shown below. 1/Tg=Σ(Wi/Tgi) In the above formula of Fox, Tg represents the glass transition temperature (unit: K) of the copolymer, and Wi represents the weight fraction of the monomer i in the copolymer (copolymerization based on weight Ratio), Tgi represents the glass transition temperature (unit: K) of the homopolymer of monomer i. When the target polymer of Tg is a homopolymer, the Tg of the homopolymer coincides with the Tg of the target polymer.

As the glass transition temperature of the homopolymer used for the calculation of Tg, a value described in a known data is used. Specifically, the numerical value in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989) can be mentioned. For monomers with plural values described in the above-mentioned polymer handbook, the highest value is adopted.

The glass transition temperature of the homopolymer which is a monomer which is not described in the said polymer handbook shall use the value obtained by the following measuring method. Specifically, 100 parts by weight of monomers, 0.2 parts by weight of 2,2'-azobisisobutyronitrile, and ethyl acetate as a polymerization solvent were put into a reactor equipped with a thermometer, a stirrer, a nitrogen gas introduction pipe, and a reflux cooling pipe. 200 parts by weight, stirring for 1 hour while flowing nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature was raised to 63° C., and the reaction was performed for 10 hours. Then, it cooled to room temperature, and obtained the homopolymer solution of 33 weight% of solid content concentration. Next, this homopolymer solution was cast-coated on a release liner and dried to prepare a test sample (sheet-shaped homopolymer) having a thickness of about 2 mm. The test sample was punched into a disc shape with a diameter of 7.9 mm and clamped by parallel plates. While applying a shear strain at a frequency of 1 Hz using a viscoelasticity testing machine (manufactured by TA Instruments Japan, model name "ARES"), Viscoelasticity was measured in the temperature range -70°C to 150°C with a heating rate of 5°C/min by shear mode, and the temperature corresponding to the peak temperature of tanδ was defined as the Tg of the homopolymer.

The weight-average molecular weight (Mw) of the polymer A is usually preferably about 5×10 ⁴ or more, but it is not particularly limited. According to the polymer A of this Mw, the adhesive agent which shows favorable cohesiveness can be obtained easily. In several aspects, the Mw of the polymer A may be, for example, not less than 10×10 ⁴ , not less than 20×10 ⁴ , or not less than 30×10 ⁴ . In addition, the Mw of the polymer A is usually preferably about 500×10 ⁴ or less. The polymer A of this Mw is easy to form an adhesive exhibiting moderate fluidity (mobility of the polymer chain), and thus is suitable for realizing a reinforced film with a relatively high increase in adhesive force.

In addition, in this specification, Mw of polymer A and polymer B can be calculated|required by polystyrene conversion by gel permeation chromatography (GPC). More specifically, Mw can be measured according to the methods and conditions described in the following examples.

As the polymer A in the reinforcing film disclosed here, an acrylic polymer can be suitably used. When an acrylic polymer is used as the polymer A, good compatibility with the polymer B tends to be easily obtained. Good compatibility between polymer A and polymer B can help reduce the initial adhesive force and improve the adhesive force after heating by increasing the mobility of polymer B in the adhesive layer, so it is preferable.

The acrylic polymer can be, for example, a polymer containing more than 50% by weight of monomer units derived from alkyl (meth)acrylate, that is, 50% by weight of the total amount of monomer components used to prepare the acrylic polymer. More than % is a polymer of alkyl (meth)acrylate. As the alkyl (meth)acrylate, an alkyl (meth)acrylate having a straight-chain or branched alkyl group having 1 to 20 carbon atoms (that is, C _1-20 ) can be preferably used. In terms of easily obtaining a balance of properties, the ratio of the C _1-20 alkyl (meth)acrylate in the total amount of monomer components may be, for example, 50% by weight or more, 60% by weight or more, or 50% by weight or more. More than 70% by weight. For the same reason, the ratio of C _1-20 alkyl (meth)acrylate in the total amount of monomer components may be, for example, 99.9% by weight or less, 98% by weight or less, or 95% by weight or less . In several aspects, the ratio of the C _1-20 alkyl (meth)acrylate in the total amount of monomer components may be, for example, 90% by weight or less, 85% by weight or less, or 80% by weight or less .

As non-limiting specific examples of C _1-20 alkyl (meth)acrylates, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylate, Base) isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, (meth)acrylic acid Pentyl, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate base) isooctyl acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate ester, lauryl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, (meth) cetyl acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, (meth)acrylate base) eicosyl acrylate, etc.

Among them, it is preferable to use at least C _1-18 alkyl (meth)acrylate, and it is more preferable to use at least C _1-14 alkyl (meth)acrylate. In several aspects, the acrylic polymer may contain a group selected from C _4-12 alkyl (meth)acrylates (preferably C _4-10 alkyl acrylates, such as C _6-10 alkyl acrylates) At least one of them is used as a monomer unit. For example, an acrylic polymer containing one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) is preferred, and an acrylic polymer containing at least 2EHA is particularly preferred. Examples of other C _1-18 alkyl (meth)acrylates that can be used well include methyl acrylate, methyl methacrylate (MMA), n-butyl methacrylate (BMA), methyl 2-ethylhexyl acrylate (2EHMA), isostearyl acrylate (ISTA), etc.

The monomer unit constituting the acrylic polymer may contain alkyl (meth)acrylate as a main component and, if necessary, other monomers (copolymerizable monomers) capable of copolymerizing with alkyl (meth)acrylate . As a copolymerizable monomer, the monomer which has a polar group (for example, a carboxyl group, a hydroxyl group, a ring containing a nitrogen atom, etc.) can be used suitably. The monomer having a polar group functions to introduce crosslinking points into the acrylic polymer or to increase the cohesion of the acrylic polymer. A copolymerizable monomer can be used individually by 1 type or in combination of 2 or more types.

The following are mentioned as a non-limiting specific example of a copolymerizable monomer. Carboxyl group-containing monomers: such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, methacrylic acid, and the like. Anhydride group-containing monomers: such as maleic anhydride and itaconic anhydride. Hydroxyl-containing monomers: such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, 6-Hydroxyhexyl (meth)acrylate, 8-Hydroxyoctyl (meth)acrylate, 10-Hydroxydecyl (meth)acrylate, 12 (meth)acrylate -Hydroxylauryl (meth)acrylate, hydroxyalkyl (meth)acrylate, such as (4-hydroxymethylcyclohexyl) methyl (meth)acrylate, etc. Monomers containing sulfonic acid groups or phosphoric acid groups: such as styrenesulfonic acid, allylsulfonic acid, sodium vinylsulfonate, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (methyl ) acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloxynaphthalenesulfonic acid, 2-hydroxyethylacryloyl phosphate, etc. Epoxy-containing monomers: epoxy-containing acrylates such as glycidyl (meth)acrylate or 2-ethyl glycidyl (meth)acrylate, allyl glycidyl ether, (methyl) Glycidyl acrylate, etc. Cyano-containing monomers: such as acrylonitrile, methacrylonitrile, etc. Isocyanato group-containing monomers: for example, 2-isocyanatoethyl (meth)acrylate and the like. Amino group-containing monomers: e.g. (meth)acrylamide; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N- Dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di (Tertiary butyl)(meth)acrylamide and other N,N-dialkyl(meth)acrylamide; N-ethyl(meth)acrylamide, N-isopropyl(methyl) Acrylamide, N-butyl(meth)acrylamide, N-n-butyl(meth)acrylamide, etc. N-alkyl(meth)acrylamide; N-vinylacetamide, etc. -Vinylcarboxamides; monomers with hydroxyl and amido groups, such as N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide Amide, N-(1-hydroxypropyl)(meth)acrylamide, N-(3-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(methyl) Acrylamide, N-(3-hydroxybutyl)(meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, etc. N-hydroxyalkyl(meth)acrylamide ; Monomers with alkoxy and amide groups, such as N-methoxymethyl (meth)acrylamide, N-methoxyethyl (meth)acrylamide, N-butoxymethyl N-alkoxyalkyl(meth)acrylamide such as N-alkoxyalkyl(meth)acrylamide; in addition, N,N-dimethylaminopropyl(meth)acrylamide, N-(methyl) ) Acrylyl 𠰌line, etc. Monomers with rings containing nitrogen atoms: such as N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinyl Pyrimidine, N-vinylpyrrole, N-vinylpyrrole, N-vinylpyrrole, N-vinylimidazole, N-vinylpyrazole, N-(meth)acryl-2-pyrrolidone , N-(meth)acrylpiperidine, N-(meth)acrylpyrrolidine, N-vinyl 𠰌line, N-vinyl-3-𠰌linone, N-vinyl-2- Caprolactamin, N-vinyl-1,3-㗁𠯤-2-ketone, N-vinyl-3,5-𠰌linedione, N-vinylpyrazole, N-vinylisoxazole, N - Vinylthiazole, N-vinylisothiazole, N-vinylpyrrole, etc. (for example, lactams such as N-vinyl-2-caprolactam). Monomers with succinimide skeleton: such as N-(meth)acryloxymethylene succinimide, N-(meth)acryl-6-oxyhexamethylene butane diimide, N-(meth)acryloyl-8-oxyhexamethylenesuccinimide, and the like. Maleimides: such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-benzene Maleic imide, etc. Iconimides: such as N-methyl iconimide, N-ethyl iconimide, N-butyl iconimide, N-octyl iconimide, N- 2-Ethylhexyl iconimide, N-cyclohexyl iconimide, N-lauryl iconimide, etc. Aminoalkyl (meth)acrylates: such as aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethacrylate Ethylaminoethyl ester, tert-butylaminoethyl (meth)acrylate. Alkoxy-containing monomers: e.g. 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (methyl) ) propoxy ethyl acrylate, butoxy ethyl (meth) acrylate, ethoxy propyl (meth) acrylate and other alkoxy alkyl (meth) acrylates; methoxy (meth) acrylate Alkoxyalkylene glycol (meth)acrylates such as ethylene glycol esters, methoxypolypropylene glycol (meth)acrylates, etc. Vinyl esters: such as vinyl acetate, vinyl propionate, etc. Vinyl ethers: vinyl alkyl ethers such as methyl vinyl ether or ethyl vinyl ether. Aromatic vinyl compounds: such as styrene, α-methylstyrene, vinyltoluene, etc. Olefins: such as ethylene, butadiene, isoprene, isobutylene, etc. (Meth)acrylates with alicyclic hydrocarbon groups: e.g. cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, iso(meth)acrylate, dicyclopentyl (meth)acrylate Wait. (Meth)acrylate having an aromatic hydrocarbon group: for example, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, etc. In addition, (meth)acrylates containing heterocycles such as tetrahydrofurfuryl methyl (meth)acrylate, (meth)acrylates containing halogen atoms such as vinyl chloride or (meth)acrylates containing fluorine atoms, polysiloxane Silicon atom-containing (meth)acrylates such as (meth)acrylates, (meth)acrylates obtained from terpene compound derivative alcohols, etc.

When such a copolymerizable monomer is used, the usage amount thereof is not particularly limited, but usually it is suitably set at 0.01% by weight or more of the total amount of the monomer components. From the viewpoint of exerting the effect produced by the use of the copolymerizable monomer better, the usage amount of the copolymerizable monomer can be set to 0.1% by weight or more of the total amount of the monomer components, and can also be set to 1% by weight above. Moreover, the usage-amount of a copolymerizable monomer can be made into 50 weight% or less of the monomer component total amount, Preferably it is made into 40 weight% or less. Thereby, the cohesive force of the adhesive can be prevented from becoming too high, and the adhesive feeling at room temperature (25° C.) can be improved.

In several aspects, the acrylic polymer preferably contains N-vinyl cyclic amides and hydroxyl-containing monomers (monomers with hydroxyl and other functional groups) represented by the following general formula (M1) , for example, at least one monomer from the group consisting of a monomer having a hydroxyl group and an amide group) may be used as a monomer unit.

此處，上述通式(M1)中之R¹ 為二價有機基。[chemical 1]

Here, R ¹ in the above general formula (M1) is a divalent organic group.

By using N-vinyl cyclic amide, the cohesion or polarity of the adhesive can be adjusted, and the adhesive force after heating can be improved. Specific examples of N-vinyl cyclic amides include: N-vinyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-3-alphalinone, N -Vinyl-2-caprolactam, N-vinyl-1,3-methan-2-ketone, N-vinyl-3,5-methanolactone, etc. Especially preferred are N-vinyl-2-pyrrolidone and N-vinyl-2-caprolactam.

The usage amount of N-vinyl cyclic amide is not particularly limited, and it is generally suitably set at 0.01% by weight or more (preferably 0.1% by weight or more, such as 0.5% by weight) of the total amount of monomer components used to prepare acrylic polymers. %above). In several aspects, the amount of N-vinyl cyclic amide used may be 1% by weight or more, 5% by weight or more, or 10% by weight or more of the total amount of the above-mentioned monomer components. In addition, from the viewpoint of improving the stickiness at normal temperature (25°C) or improving the flexibility at low temperature, the amount of N-vinyl cyclic amide used is usually suitably set at 40% by weight of the total amount of the above-mentioned monomer components. Below, it may be 30 weight% or less, and may be 20 weight% or less.

By using hydroxyl-containing monomers, the cohesion or polarity of the adhesive can be adjusted, and the adhesive force after heating can be improved. In addition, the hydroxyl-containing monomer system provides a reaction point with the following crosslinking agent (such as isocyanate crosslinking agent), and the cohesion of the adhesive can be improved through the crosslinking reaction.

As the hydroxyl group-containing monomer, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, N-(2-hydroxyethyl base) (meth)acrylamide, etc. Among them, 2-hydroxyethyl acrylate (HEA), 4-hydroxybutyl acrylate (4HBA), and N-(2-hydroxyethyl)acrylamide (HEAA) are mentioned as preferable examples.

The usage amount of the hydroxyl group-containing monomer is not particularly limited, and it is generally suitably set at 0.01% by weight or more (preferably 0.1% by weight or more, such as 0.5% by weight or more) of the total amount of monomer components used to prepare the acrylic polymer. In several aspects, the usage-amount of a hydroxyl-containing monomer can be 1 weight% or more, 5 weight% or more, or 10 weight% or more of the total amount of the said monomer component. In addition, from the viewpoint of improving the stickiness at normal temperature (25° C.) or improving the flexibility at low temperature, the usage amount of the hydroxyl group-containing monomer is usually preferably 40% by weight or less of the total amount of the above-mentioned monomer components. 30% by weight or less, may be 20% by weight or less, may be 10% by weight or less, or 5% by weight or less.

In several aspects, N-vinyl cyclic amide and a hydroxyl group-containing monomer can be used together as a copolymerizable monomer. In this case, the total amount of the N-vinyl cyclic amide and the hydroxyl-containing monomer can be, for example, 0.1% by weight or more, or 1% by weight, of the total amount of monomer components used to prepare the acrylic polymer. The above may be 5% by weight or more, may be 10% by weight or more, may be 15% by weight or more, may be 20% by weight or more, and may be 25% by weight or more. In addition, the total amount of N-vinyl cyclic amide and hydroxyl group-containing monomer may be, for example, 50% by weight or less, preferably 40% by weight or less, of the total amount of monomer components.

The method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as acrylic polymer synthesis methods, such as solution polymerization, emulsion polymerization, block polymerization, suspension polymerization, and photopolymerization, can be suitably used. . In several aspects, solution polymerization can be advantageously employed. The polymerization temperature during solution polymerization can be appropriately selected according to the type of monomers and solvents used, the type of polymerization initiator, etc., for example, it can be set at about 20°C to 170°C (typically about 40°C to 140°C) .

The initiator used for the polymerization can be appropriately selected from previously known thermal polymerization initiators, photopolymerization initiators, and the like according to the polymerization method. A polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

Examples of thermal polymerization initiators include: azo-based polymerization initiators (such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2, 2'-Azobis(2-methylpropionate) dimethyl ester, 4,4'-azobis-4-cyanopentanoic acid, azobisisovaleronitrile, 2,2'-azobis( 2-amidinopropane) dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'- Nitrobis(2-methylpropionamidine) disulfate, 2,2'-azobis(N,N'-dimethyleneisobutylamidine) dihydrochloride, etc.); potassium persulfate and other persulfates Salts; peroxide-based polymerization initiators (such as dibenzoyl peroxide, tert-butyl peroxymaleate, lauryl peroxide, etc.); redox-based polymerization initiators, etc. In several aspects, an azo-type polymerization initiator can be favorably used. The amount of the thermal polymerization initiator used is not particularly limited, for example, it can be set at 0.01 to 5 parts by weight, preferably 0.05 to The amount within the range of 3 parts by weight.

系光聚合起始劑、醯基氧化膦系光聚合起始劑等。光聚合起始劑之使用量並無特別限制，例如相對於丙烯酸系聚合物之製備所使用之單體成分100重量份，可設為0.01重量份～5重量份、較佳為0.05重量份～3重量份之範圍內之量。The photopolymerization initiator is not particularly limited, and for example, benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, α-ketol-based photopolymerization initiators, aromatic sulfonyl chlorides, Photopolymerization initiator, photoactive oxime photopolymerization initiator, benzoin photopolymerization initiator, benzoyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator Polymerization initiator, 9-oxosulfur

A photopolymerization initiator, acyl phosphine oxide photopolymerization initiator, etc. The amount of the photopolymerization initiator used is not particularly limited. For example, it can be set at 0.01 to 5 parts by weight, preferably 0.05 to 5 parts by weight relative to 100 parts by weight of the monomer components used in the preparation of the acrylic polymer. The amount within the range of 3 parts by weight.

In several aspects, the acrylic polymer can be a partial polymer (acrylic acid) that is obtained by irradiating ultraviolet rays (UV) to a mixture obtained by preparing a polymerization initiator in the above-mentioned monomer components to polymerize a part of the monomer components. It is contained in the adhesive composition for forming the adhesive layer in the form of polymer slurry). The adhesive composition containing the acrylic polymer slurry can be applied to a specific object to be coated, and can be irradiated with ultraviolet rays to complete polymerization. That is, the above-mentioned acrylic polymer syrup can be understood as a precursor of an acrylic polymer. The adhesive layer disclosed here can be formed using the adhesive composition containing the above-mentioned acrylic polymer slurry and the polymer B, for example.

(Polymer B) Polymer B in the technology disclosed here is a copolymer of a monomer having a polyorganosiloxane skeleton (hereinafter also referred to as "monomer S1") and a (meth)acrylic monomer. The low polarity and mobility of the polyorganosiloxane structure derived from the monomer S1 of the polymer B can function as an adhesion increase retarder that helps to suppress the initial adhesion force and increase the increase ratio of the adhesion force. The monomer S1 is not particularly limited, and any monomer having a polyorganosiloxane skeleton can be used. Monomer S1 promotes the segregated presence of polymer B on the surface of the adhesive layer in the reinforcing film before use (before it is attached to the adherend) due to the low polarity derived from its structure, showing the lightness at the initial stage of lamination. Peelability (low adhesion). As the monomer S1, those having a structure having a polymerizable reactive group at one end (that is, one with single-end reactivity) can be favorably used. By copolymerizing such a monomer S1 and a (meth)acrylic monomer, a polymer B having a polyorganosiloxane skeleton in a side chain is formed. Polymer B with this structure tends to have a relatively low initial adhesive force and a relatively high increase in adhesive force due to the mobility and ease of movement of the side chains. The technique disclosed here can be well implemented in a state in which most of the monomer S1 used (for example, 70% by weight or more, 85% by weight or more, or 95% by weight or more) is single-terminal reactive. Substantially all (for example, 98 to 100% by weight) of the monomer S1 may be single-terminal reactive.

[化3]

此處，上述通式(1)、(2)中之R³ 為氫或甲基，R⁴ 為甲基或一價有機基，m及n為0以上之整數。As the monomer S1, for example, a compound represented by the following general formula (1) or (2) can be used. More specifically, X-22-174ASX, X-22-2426, X-22-2475, KF-2012 and the like are exemplified as single-end reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. Monomer S1 can be used individually by 1 type or in combination of 2 or more types. [Chem 2]

[Chem 3]

Here, R ³ in the above general formulas (1) and (2) is hydrogen or methyl, R ⁴ is methyl or a monovalent organic group, and m and n are integers of 0 or more.

The functional group equivalent weight of monomer S1 is, for example, preferably 700 g/mol or more and less than 15000 g/mol, more preferably 800 g/mol or more and less than 10000 g/mol, and more preferably 850 g/mol or more and It is less than 6000 g/mol, preferably more than 1500 g/mol and less than 5000 g/mol. If the functional group equivalent of the monomer S1 is less than 700 g/mol, it may not be possible to sufficiently suppress the initial adhesive force. When the functional group equivalent of monomer S1 is 15000 g/mol or more, the increase of adhesive force may become insufficient. If the functional group equivalent of monomer S1 is within the above range, it is easy to adjust the compatibility (such as compatibility with polymer A) or mobility in the adhesive layer within an appropriate range, and it is easy to achieve high-level Reinforcing film with both initial low adhesiveness and strong adhesiveness when the adherend is in use.

Here, the "functional group equivalent" means the weight of the main skeleton (for example, polydimethylsiloxane) bonded to one functional group. Regarding the marking unit g/mol, it is converted into 1 mol of functional group. The functional group equivalent of the monomer S1 can be calculated from the spectral intensity of ¹ H-NMR (proton NMR) based on nuclear magnetic resonance (NMR), for example. The calculation of the functional group equivalent (g/mol) of the monomer S1 based on the spectral intensity of ¹ H-NMR can be based on a general structure analysis method related to ¹ H-NMR spectral analysis, referring to the records of Japanese Patent No. 5951153 as necessary. conduct.

In addition, when using two or more monomers with different functional group equivalents as monomer S1, an arithmetic mean value can be used as the functional group equivalent of monomer S1. That is, the functional group equivalent of monomer S1 including n kinds of monomers (monomer S1 ₁ , monomer S1 ₂ ... monomer S1 _n ) having different functional group equivalents can be calculated by the following formula. Functional group equivalent of monomer S1 (g/mol) = (functional group equivalent of monomer S1 ₁ × compounding amount of monomer S1 ₁ + functional group equivalent of monomer S1 ₂ × compounding amount of monomer S1 ₂ +・・・＋The functional group equivalent of the monomer S1 _n ×the compounding amount of the monomer S1 _n )/(the compounding amount of the monomer S1 _{1 +} the compounding amount of the monomer S1 2+・・・+the compounding amount of the monomer S1 _n )

The content of the monomer S1 can be, for example, 5% by weight or more with respect to all the monomer components used to prepare the polymer B, and it is preferably set to 10% by weight or more, may be 15% by weight or more, or may be 20% by weight or more. In addition, the content of the monomer S1 is preferably 60% by weight or less, and may be 50% by weight or less, based on the total monomer components used to prepare the polymer B from the viewpoint of polymerization reactivity or compatibility. It may be 40 weight% or less, and may be 30 weight% or less. When content of monomer S1 is less than 5 weight%, initial stage adhesive force may not be fully suppressed. When the content of the monomer S1 is more than 60% by weight, the increase of the adhesive force may become insufficient.

The monomer component used in the preparation of the polymer B contains not only the monomer S1, but also a (meth)acrylic monomer that can be copolymerized with the monomer S1. By copolymerizing one or two or more (meth)acrylic monomers with the monomer S1, the mobility of the polymer B in the adhesive layer can be well adjusted. Copolymerizing the monomer S1 with the (meth)acrylic monomer can also help to improve the compatibility of the polymer B and the polymer A (such as an acrylic polymer).

As a (meth)acrylic-type monomer, an alkyl (meth)acrylate is mentioned, for example. For example, as an alkyl (meth)acrylate that can be used when the polymer A is an acrylic polymer, one or two or more of the monomers exemplified above can be used as a copolymerization component of the polymer B. In several aspects, polymer B may contain a C _4-12 alkyl (meth)acrylate (preferably a C _4-10 alkyl (meth)acrylate, such as a C _{6- 10} alkyl esters) as a monomer unit. In several other aspects, polymer B may contain a C _1-18 alkyl methacrylate (preferably a C _1-14 alkyl methacrylate, such as a C _1-10 alkyl methacrylate) At least one of them is used as a monomer unit. The monomer unit constituting polymer B may contain, for example, one or two or more selected from MMA, BMA, and 2EHMA.

As another example of the said (meth)acryl-type monomer, the (meth)acrylate which has an alicyclic hydrocarbon group is mentioned. For example, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, iso(meth)acrylate, dicyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, Esters etc. In several aspects, the polymer B may contain at least one selected from dicyclopentanyl methacrylate, isomethacrylate, and cyclohexyl methacrylate as a monomer unit.

The amount of the above-mentioned alkyl (meth)acrylate and the above-mentioned (meth)acrylate having an alicyclic hydrocarbon group can be, for example, 10% by weight or more and 95% by weight relative to the total monomer components used to prepare the polymer B. % or less, 20% by weight to 95% by weight, 30% by weight to 90% by weight, 40% by weight to 90% by weight, or 50% by weight to 85% by weight the following. From the viewpoint of easiness of raising the adhesive force by heating, it may become advantageous to use an alkyl (meth)acrylate. In several aspects, the amount of (meth)acrylate having an alicyclic hydrocarbon group may not reach the total amount of (meth)acrylic monomers contained in the monomer components used to prepare polymer B, for example. The amount of 50% by weight may be less than 30% by weight, less than 15% by weight, less than 10% by weight, or less than 5% by weight. A (meth)acrylate having an alicyclic hydrocarbon group may not be used.

As other examples of the monomer that can be contained together with the monomer S1 in the monomer unit constituting the polymer B, the above-mentioned exemplified monomers that can be used when the polymer A is an acrylic polymer can be mentioned. Carboxyl-containing monomers, acid anhydride-containing monomers, hydroxyl-containing monomers, epoxy-containing monomers, cyano-containing monomers, isocyanate-containing monomers, amide-containing monomers, monomers with rings containing nitrogen atoms Monomers, monomers having a succinimide skeleton, maleimides, itaconimides, (meth)aminoalkyl acrylates, vinyl esters, vinyl ethers, olefins (meth)acrylates with aromatic hydrocarbon groups, (meth)acrylates containing heterocycles, (meth)acrylates containing halogen atoms, (meth)acrylates obtained from terpene compound derivative alcohols Acrylic etc.

Still other examples of the monomer that can be contained together with the monomer S1 in the monomer units constituting the polymer B include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate , triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate ) acrylate and other oxyalkylene di(meth)acrylates; monomers with a polyoxyalkylene skeleton, such as (methyl) at one end of a polyoxyalkylene chain such as polyethylene glycol or polypropylene glycol ) a polymerizable functional group such as acryl group, vinyl group, allyl group, etc., and a polymerizable polyoxyalkylene ether having an ether structure (alkyl ether, aryl ether, aryl alkyl ether, etc.) at the other end; ( Methoxyethyl methacrylate, Ethoxyethyl (meth)acrylate, Propoxyethyl (meth)acrylate, Butoxyethyl (meth)acrylate, Ethoxy(meth)acrylate Alkoxyalkyl (meth)acrylate such as propyl ester; salt such as alkali metal (meth)acrylate; poly(meth)acrylate such as trimethylolpropane tri(meth)acrylate: partial di Vinyl chloride, 2-chloroethyl (meth)acrylate and other halogenated vinyl compounds; 2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropene Monomers containing oxazoline groups such as 2-oxazoline; monomers containing aziridine groups such as (meth)acryl aziridine, (meth)acrylic acid-2-aziridinyl ethyl ester, etc. 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, adducts of lactones and 2-hydroxyethyl (meth)acrylate, etc. fluorine-substituted alkyl (meth)acrylate and other fluorine-containing vinyl monomers; 2-chloroethyl vinyl ether, vinyl monochloroacetate and other vinyl monomers containing reactive halogens; such as vinyl trimethyl Oxysilane, γ-(Meth)acryloxypropyltrimethoxysilane, Allyltrimethoxysilane, Trimethoxysilylpropylallylamine, 2-Methoxyethoxytrimethoxy Silicone-containing vinyl monomers of silanes; in addition, macromonomers having a radically polymerizable vinyl group at the end of a monomer that polymerizes vinyl groups, etc. may be mentioned. These can be copolymerized with the monomer S1 alone or in combination.

In several aspects, the mobility of the polymer B in the adhesive layer can be improved by making the monomer unit common to the monomer unit contained in the polymer B also contained in the polymer A, and the adhesion can be improved. Force rise ratio. The common monomer unit is effective when it occupies 5% by weight or more of all the monomer units constituting the polymer B, preferably 10% by weight or more (more preferably 20% by weight or more, for example, 30% by weight or more). Element. The ratio of the above-mentioned common monomer units in all the monomer units constituting the polymer A may be, for example, 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, or 7% by weight %above. When the ratio of the common monomer unit to all the monomer units constituting the polymer A increases, the effect of improving the compatibility tends to be exhibited more favorably. In addition, considering the balance with other characteristics, the ratio of the common monomer unit to all the monomer units constituting the polymer A may be 50% by weight or less, or may be 30% by weight or less. Non-limiting examples of monomers that can be favorably used as common monomer units include MMA, BMA, 2EHMA, methacrylate (MA), BA, 2EHA, cyclohexyl (meth)acrylate, Iso(meth)acrylate, dicyclopentanyl (meth)acrylate, etc.

The Mw of the polymer B is not particularly limited. Mw of polymer B may be 1000 or more, for example, and may be 5000 or more. When the Mw of the polymer B is too low, the increase of the adhesive force may become insufficient. In several preferred aspects, the Mw of the polymer B may be, for example, not less than 10000, not less than 12000, not less than 15000, not less than 17000, or not less than 20000. In addition, the Mw of the polymer B may be, for example, 100,000 or less, or may be 70,000 or less. When the Mw of the polymer B is too high, it may not be possible to sufficiently suppress the initial adhesive force. In some preferred aspects, the Mw of the polymer B may be less than 50,000, may be less than 50,000, may be less than 40,000, may be less than 35,000, may be less than 30,000, may be less than 28,000, or may be less than 25,000 . If the Mw of the polymer B is within the range of any one of the above-mentioned upper limit and lower limit, it is easy to adjust the compatibility or mobility in the adhesive layer to an appropriate range, and it is easy to achieve a high level of compatibility with the initial stage. Reinforcing film with low adhesiveness and strong adhesiveness when used on adherends.

Polymer B can be produced, for example, by polymerizing the aforementioned monomers by known methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and photopolymerization. The initiator used for the polymerization of the polymer B can be appropriately selected from previously known thermal polymerization initiators, photopolymerization initiators, and the like according to the polymerization method. A polymerization initiator can be used individually by 1 type or in combination of 2 or more types. The above-mentioned thermal polymerization initiator and the above-mentioned photopolymerization initiator can be selected from the same materials as those exemplified for the polymerization of the polymer A. In several aspects, an azo-type polymerization initiator can be favorably used.

In order to adjust the molecular weight of polymer B, chain transfer agents can be used. Examples of the chain transfer agent used include: octyl mercaptan, lauryl mercaptan, tertiary nonyl mercaptan, tertiary (dodecyl) mercaptan, mercaptoethanol, α-thioglycerol, etc. Mercapto compounds; thioglycolic acid; methyl thioglycolate, ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, tertiary butyl thioglycolate, thioglycolic acid 2-ethylhexyl ester, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, thioglycolate of ethylene glycol, neopentyl Thioglycolic acid esters such as glycol thioglycolate and pentaerythritol thioglycolic acid ester; α-methylstyrene dimer, etc. In several aspects, as chain transfer agents, thioglycolic acid esters can be favorably used.

There is no particular limitation on the amount of the chain transfer agent used. Generally, 0.05 to 20 parts by weight of the chain transfer agent is contained relative to 100 parts by weight of the monomer, preferably 0.1 to 15 parts by weight, and more preferably 0.2 parts by weight. Parts by weight to 10 parts by weight. By adjusting the addition amount of the chain transfer agent in this way, polymer B with a better molecular weight can be obtained. In addition, a chain transfer agent can be used individually by 1 type or in combination of 2 or more types.

The usage-amount of polymer B is 0.1 weight part or more with respect to the usage-amount of polymer A of 100 weight part, for example, and can be 0.3 weight part or more from a viewpoint of obtaining a higher effect, and can be 0.4 weight part or more. It may be at least 0.5 parts by weight, but it is not particularly limited. In several aspects, the usage-amount of the polymer B with respect to 100 weight part of polymer A may be 1 weight part or more, 2 weight part or more, or 3 weight part or more. Moreover, the usage-amount of the polymer B with respect to 100 weight part of polymer A may be 75 weight part or less, 60 weight part or less, or 50 weight part or less, for example. From the viewpoint of avoiding an excessive decrease in the cohesive force of the adhesive layer, in several aspects, the amount of polymer B used relative to 100 parts by weight of polymer A can be set to 40 parts by weight or less, and can also be set to 35 parts by weight. Parts by weight or less, 30 parts by weight or less, or 25 parts by weight or less. From the viewpoint of obtaining a higher adhesive force after heating, in some aspects, the amount of the polymer B used may be 20 parts by weight or less, may be 17 parts by weight or less, or may be 15 parts by weight 10 parts by weight or less, or 10 parts by weight or less. In several aspects of the reinforced film disclosed here, the amount of polymer B used relative to 100 parts by weight of polymer A may be less than 10 parts by weight, but may be less than 8 parts by weight, or less than 5 parts by weight. Or less than 5 parts by weight, may be 4 parts by weight or less, or may be 3 parts by weight or less.

The adhesive layer may contain polymers (arbitrary polymers) other than polymer A and polymer B as needed within the range that does not greatly impair the performance of the reinforced film disclosed herein. The usage-amount of such an arbitrary polymer is normally suitably made into 20 weight% or less of the whole polymer component contained in an adhesive layer, and may be 15 weight% or less, and may be 10 weight% or less. In some aspects, the amount of the above-mentioned optional polymer used may be 5% by weight or less, 3% by weight or less, or 1% by weight or less of the entire polymer component. An adhesive layer that does not substantially contain polymers other than polymer A and polymer B may also be used.

(Crosslinking agent) In the adhesive layer, a crosslinking agent may be used as necessary for the purpose of adjusting cohesive force or the like. As the cross-linking agent, known cross-linking agents in the field of adhesives can be used, for example, epoxy-based cross-linking agents, isocyanate-based cross-linking agents, polysiloxane-based cross-linking agents, oxazoline-based cross-linking agents, Aziridine-based cross-linking agents, silane-based cross-linking agents, alkyl etherified melamine-based cross-linking agents, metal chelate-based cross-linking agents, etc. In particular, isocyanate-based crosslinking agents, epoxy-based crosslinking agents, and metal chelate-based crosslinking agents can be used favorably. A crosslinking agent can be used individually by 1 type or in combination of 2 or more types.

Specifically, examples of isocyanate-based crosslinking agents include toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diisocyanate, Phenyl (methane) diisocyanate, hydrogenated diphenyl (methane) diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenyl (methane) triisocyanate, polymethylene polyphenyl isocyanate, And these adducts with trimethylolpropane and other polyols. Alternatively, compounds having at least one isocyanate group and one or more unsaturated bonds in one molecule, specifically, 2-isocyanatoethyl (meth)acrylate, etc., can also be used as isocyanate-based crosslinkers. agent. These can be used individually by 1 type or in combination of 2 or more types.

Examples of epoxy-based crosslinking agents include bisphenol A, epichlorohydrin-type epoxy-based resins, ethylidene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, and glycerin triglycidyl ether. ether, 1,6-hexanediol glycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl meta Xylylenediamine and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, etc. These can be used individually by 1 type or in combination of 2 or more types.

Examples of metal chelate compounds include aluminum, iron, tin, titanium, nickel, etc. as metal components, and acetylene, acetyl methyl acetate, ethyl lactate, etc., as chelate components. These can be used individually by 1 type or in combination of 2 or more types.

The usage-amount in the case of using a crosslinking agent is not specifically limited, For example, it can be made into the quantity exceeding 0 weight part with respect to 100 weight part of polymer A. Moreover, the usage-amount of a crosslinking agent can be made into 0.01 weight part or more with respect to 100 weight part of polymer A, for example, Preferably it is 0.05 weight part or more. By increasing the amount of cross-linking agent used, there is a tendency to obtain higher cohesion. In several aspects, the usage-amount of the crosslinking agent with respect to 100 weight part of polymer A may be 0.1 weight part or more, 0.5 weight part or more, and may be 1 weight part or more. On the other hand, from the viewpoint of avoiding a decrease in viscosity due to an excessive increase in cohesion, the amount of the crosslinking agent used is usually preferably 15 parts by weight or less per 100 parts by weight of polymer A, and may be 10 parts by weight. 5 parts by weight or less, or 5 parts by weight or less. It may also be advantageous from the viewpoint of expressing the use effect of the polymer B better by utilizing the fluidity of the adhesive that the usage-amount of the crosslinking agent is not too much.

The technique disclosed here can be implemented favorably in the form of using at least an isocyanate-based crosslinking agent as a crosslinking agent. From the point of view of easy realization of a reinforced film with high cohesive force after heating and a relatively large increase in adhesion force, in several aspects, the usage amount of the isocyanate crosslinking agent can be set to 5, for example, relative to 100 parts by weight of polymer A. The weight part or less may be 4 weight parts or less, may be 3 weight parts or less, may be less than 1 weight part, may be 0.7 weight part or less, and may be 0.5 weight part or less. Moreover, in some correspondences, the usage-amount of the said isocyanate crosslinking agent may be 0.1 weight part or more, 0.3 weight part or more, 0.5 weight part or more, or 1.0 weight part or more.

When an isocyanate-based cross-linking agent is used in the adhesive layer containing a hydroxyl-containing monomer as a monomer unit, the amount of the hydroxyl-containing monomer W _OH relative to the amount of the isocyanate-based cross-linking agent W _NCO is by weight On the basis of the basis, W _OH /W _NCO may be set to an amount of 2 or more, but it is not particularly limited. Thus, by increasing the usage-amount of a hydroxyl-containing monomer with respect to an isocyanate type crosslinking agent, the crosslinking structure suitable for the improvement of an adhesive force increase ratio can be formed. In some aspects, W _OH /W _NCO may be 3 or more, 5 or more, 10 or more, 20 or more, 30 or more, or 50 or more. The upper limit of W _OH /W _NCO is not particularly limited. W _OH /W _NCO may be, for example, 500 or less, 200 or less, or 100 or less.

A crosslinking catalyst may also be used in order to carry out any of the above crosslinking reactions more efficiently. As a crosslinking catalyst, a tin-based catalyst (especially dioctyltin dilaurate) can be used suitably, for example. The usage-amount of a crosslinking catalyst is not specifically limited, For example, it can set it as about 0.0001-1 weight part with respect to 100 weight part of polymer A.

A polyfunctional monomer may be used in an adhesive layer as needed. By using the multifunctional monomer instead of the above-mentioned crosslinking agent or in combination with the crosslinking agent, it can contribute to the adjustment of cohesive force and the like. For example, a polyfunctional monomer can be favorably used in an adhesive layer formed from a photocurable adhesive composition. Examples of polyfunctional monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate Acrylates, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol di(meth)acrylate ) acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, four Methylolmethane tri(meth)acrylate, Allyl (meth)acrylate, Vinyl (meth)acrylate, Divinylbenzene, Epoxy acrylate, Polyester acrylate, Urethane acrylate, Butanediol (meth)acrylate, hexanediol di(meth)acrylate, etc. Among them, trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and dipentaerythritol hexa(meth)acrylate can be preferably used. A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.

The usage-amount of a polyfunctional monomer changes with its molecular weight, the number of functional groups, etc., Usually, it is suitable to set it as the range of about 0.01-3.0 weight part with respect to 100 weight part of polymer A. In several aspects, the usage-amount of a polyfunctional monomer may be 0.02 weight part or more with respect to 100 weight part of polymer A, and may be 0.03 weight part or more, for example. By increasing the amount of polyfunctional monomer used, there is a tendency to obtain higher cohesion. On the other hand, from the viewpoint of avoiding a decrease in viscosity due to an excessive increase in cohesive force, the amount of the polyfunctional monomer used may be 2.0 parts by weight or less, or 1.0 parts by weight with respect to 100 parts by weight of Polymer A. It may be less than or equal to 0.5 parts by weight. It may also be advantageous from the viewpoint of expressing the use effect of the polymer B better by utilizing the fluidity of the adhesive that the usage-amount of the polyfunctional monomer is not too much.

(Adhesive Imparting Resin) The adhesive agent layer may contain an adhesive agent resin as needed. The tackifying resin is not particularly limited, and examples thereof include rosin-based tackifying resins, terpene-based tackifying resins, phenol-based tackifying resins, hydrocarbon-based tackifying resins, ketone-based tackifying resins, and polyamide-based tackifying resins. Imparting resins, epoxy-based adhesion-imparting resins, elastic-based adhesion-imparting resins, etc. The tack-imparting resin may be used alone or in combination of two or more.

Examples of rosin-based tackifying resins include unmodified rosins (raw rosins) such as rosin gum, wood rosin, and tall oil rosin, or those modified by polymerization, disproportionation, hydrogenation, and the like. Modified rosins (polymerized rosins, stabilized rosins, disproportionated rosins, fully hydrogenated rosins, partially hydrogenated rosins, or other chemically modified rosins, etc.), and various rosin derivatives are also listed. Examples of the aforementioned rosin derivatives include: abietol obtained by adding phenol to rosins (unmodified rosin, modified rosin, or various rosin derivatives, etc.) under an acid catalyst and thermally polymerizing rosin ester compound (unmodified rosin ester), or polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin, etc. Rosin ester resins such as modified rosin ester compounds (polymerized rosin esters, stabilized rosin esters, disproportionated rosin esters, fully hydrogenated rosin esters, partially hydrogenated rosin esters, etc.) that are esterified with permanent rosin; Rosin or modified rosin (polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin, etc.) Saturated fatty acid modified rosin ester resin; unmodified rosin, modified rosin (polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin, etc.), unsaturated fatty acid modified rosin resin or unsaturated Fatty acid-modified rosin ester-based resins in which carboxyl groups have been reduced; metal salts of rosin-based resins (especially rosin-based resins) such as unmodified rosin, modified rosin, or various rosin derivatives.

Examples of terpene-based tackifier resins include terpene-based resins such as α-pinene polymers, β-pinene polymers, and dipentene polymers, or modified (phenol-modified) terpene-based resins. properties, aromatic modification, hydrogenation modification, hydrocarbon modification, etc.) of modified terpene resins (such as terpene phenolic resins, styrene terpene-based resins, etc.), etc.

Examples of phenolic tackifying resins include condensates of various phenols (such as phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcinol, etc.) and formaldehyde (such as alkyl phenolic resins, xylene formaldehyde resins, etc.), resole resins obtained by addition reaction of the above-mentioned phenols and formaldehyde with an alkaline catalyst, or condensation reactions of the above-mentioned phenols and formaldehyde with an acid catalyst The obtained novolac resin and the like.

Examples of hydrocarbon-based tackifying resins include: aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic-aromatic petroleum resins (styrene-olefin copolymers, etc.) Various hydrocarbon resins such as aliphatic-alicyclic petroleum resins, hydrogenated hydrocarbon resins, lavender-based resins, and lavender-based resins.

Examples of commercially available polymerized rosin esters that can be favorably used include: "Pensel D-125", "Pensel D-135", "Pensel D-160", "Pensel KK", "Pensel C", etc., but not limited to these.

Examples of commercially available terpene phenolic resins that can be favorably used include: Yasuhara Chemical Co., Ltd. product names "YS Polystar S-145", "YS Polystar G-125", "YS Polystar N125", "YS Polystar U-115", trade name "Tamanol 803L" manufactured by Arakawa Chemical Industry Co., Ltd., "Tamanol 901", trade name "Sumilite resin PR-12603" manufactured by Sumitomo Bakelite Co., Ltd., etc., but not limited for such.

The content of the tack-imparting resin is not particularly limited, and can be set so as to exhibit appropriate tack performance according to the purpose or use. The content of the tackifier resin relative to 100 parts by weight of the polymer A (when two or more kinds of tackifier resins are contained, the total amount thereof) can be, for example, about 5 to 500 parts by weight.

As the tackifying resin, one having a softening point (softening temperature) of about 80° C. or higher (preferably about 100° C. or higher, for example, about 120° C. or higher) can be preferably used. The tack-imparting resin having a softening point equal to or higher than the above-mentioned lower limit tends to be effective in improving initial low tack and strong tack at the time of use of an adherend. The upper limit of the softening point is not particularly limited, and may be, for example, about 200°C or lower (typically, 180°C or lower). In addition, the softening point of the tack-providing resin can be measured based on the softening point test method (ring and ball method) stipulated in JIS K2207.

In addition, the adhesive layer in the technology disclosed here may also contain leveling agents, plasticizers, softeners, colorants (dyes, pigments, etc.), fillers, etc. Known additives that can be used in adhesives such as antistatic agents, antiaging agents, ultraviolet absorbers, antioxidants, light stabilizers, and preservatives.

The adhesive layer constituting the reinforced film disclosed herein may be the hardened layer of the adhesive composition. That is, the adhesive layer can be formed by applying (for example, coating) an adhesive composition such as a water dispersion type, solvent type, photocurable type, or hot melt type to an appropriate surface, and then appropriately performing a hardening treatment. When two or more hardening treatments (drying, crosslinking, polymerization, cooling, etc.) are performed, these can be performed simultaneously or in multiple stages. In an adhesive composition using a partial polymer (acrylic polymer syrup) of a monomer component, typically, the final copolymerization reaction is performed as the curing treatment described above. That is, a part of the polymer is subjected to further copolymerization to form a complete polymer. For example, in the case of a photocurable adhesive composition, light irradiation is performed. Hardening treatments such as crosslinking and drying may be performed as necessary. For example, when it is necessary to dry with a photocurable adhesive composition, photocuring may be performed after drying. In an adhesive composition using a complete polymer, typically, drying (heat drying), crosslinking, and other treatments are performed as the above-mentioned hardening treatment, if necessary.

For the coating of the adhesive composition, for example, a gravure roll coater, reverse roll coater, touch roll coater, dip roll coater, rod coater, knife coater, spray coater, etc. can be used It is carried out with commonly used coating machines.

The thickness of the adhesive layer is not particularly limited, and may be, for example, 1 μm or more. In some aspects, the thickness of the adhesive layer can be, for example, 3 μm or more, 5 μm or more, 8 μm or more, 10 μm or more, 15 μm or more, or 20 μm or more. More than 20 μm. By increasing the thickness of the adhesive layer, the adhesive force tends to increase after heating. This may be advantageous from the viewpoint of firmly integrating the adherend and the support base to exhibit a high reinforcing function. Also, in several aspects, the thickness of the adhesive layer may be, for example, 300 μm or less, 200 μm or less, 150 μm or less, 100 μm or less, 70 μm or less, or 50 μm or less , can also be 40 μm or less. The thickness of the adhesive layer is not too large, which may be advantageous from the viewpoints of reducing the thickness of the reinforcing film and preventing coagulation failure of the adhesive layer. Furthermore, in the case where the reinforcing film of the first adhesive layer and the second adhesive layer is provided on the first surface and the second surface of the base material, the thickness of the above-mentioned adhesive layer can be applied at least to the first adhesive layer. thickness. The thickness of the second adhesive layer can also be selected from the same range.

The gel fraction of the adhesive constituting the adhesive layer is usually suitably in the range of 20.0% to 99.0%, more preferably in the range of 30.0% to 90.0%, but it is not particularly limited. By setting the gel fraction within the above-mentioned range, it is easy to realize a reinforced film that satisfies both initial low adhesiveness and strong adhesiveness when the adherend is used at a high level. The gel fraction was measured by the following method.

[Measurement of Gel Fraction] About 0.1 g of the adhesive sample (weight Wg ₁ ) was wrapped into a purse with a porous polytetrafluoroethylene membrane (weight Wg ₂ ) with an average pore size of 0.2 μm, and was wrapped with a kite string (weight Wg Wg ₃ ) Tighten the mouth. As the porous polytetrafluoroethylene membrane, the trade name "Nitoflon (registered trademark) NTF1122" (Nitto Denko Co., Ltd., average pore diameter 0.2 μm, porosity 75%, thickness 85 μm) or its equivalent was used. The package was immersed in 50 mL of ethyl acetate, and kept at room temperature (typically 23° C.) for 7 days to dissolve the sol component (soluble in ethyl acetate) in the adhesive to the outside of the film. Then, the above-mentioned package was taken out, and after wiping off the ethyl acetate adhering to the outer surface, the package was dried at 130° C. for 2 hours, and the weight (Wg ₄ ) of the package was measured. By substituting each value into the following formula, the gel fraction G _C of the adhesive can be calculated. Gel fraction G _C (%)=[(Wg ₄ -Wg ₂ -Wg ₃ )/Wg ₁ ]×100

The reinforcing film disclosed here can be favorably produced, for example, by a method comprising the steps of: bringing a liquid adhesive composition into contact with a first surface of a substrate; and combining the above-mentioned adhesive on the first surface. The substance hardens to form an adhesive layer. The hardening of the above-mentioned adhesive composition may be accompanied by one or more of drying, cross-linking, polymerization, cooling, etc. of the adhesive composition. According to the method of forming the adhesive layer by hardening the liquid adhesive composition on the first surface of the base material in this way, and attaching the hardened adhesive layer to the first surface of the base material to form the adhesive layer on the first surface of the base material Compared with the method of arranging an adhesive layer on one side, the gripping property of the adhesive layer to the substrate can be improved. Utilizing this fact, it is possible to favorably manufacture a reinforcing film in which an adhesive layer is fixed to the first surface of the base material.

In several aspects, as a method of bringing the liquid adhesive composition into contact with the first surface of the substrate, a method of directly coating the above-mentioned adhesive composition on the first surface of the substrate may be used. By making the first side (adhesive side) of the adhesive layer hardened on the first side of the substrate abut against the peeling side, the second side of the adhesive layer can be fixed to the first side of the substrate and The first surface of the adhesive layer abuts against the reinforcing film formed by the peeling surface. As the above-mentioned release surface, the surface of a release liner, the back surface of a base material subjected to release treatment, or the like can be used.

Also, for example, in the case of using a light-curable adhesive composition of a partial polymer (acrylic polymer syrup) of the monomer component, for example, after applying the adhesive composition on the peeling surface, the The coated adhesive composition coats the first surface of the substrate, whereby the uncured adhesive composition is in contact with the first surface of the substrate, and in this state, it is sandwiched between the first surface of the substrate The adhesive composition between the release surface and the peeling surface is irradiated with light to harden, thereby forming an adhesive layer.

Furthermore, the methods exemplified above do not limit the method of manufacturing the reinforcing film disclosed here. In the manufacture of the reinforcement film disclosed here, one kind of appropriate method capable of fixing the second surface of the adhesive layer to the first surface of the substrate can be used alone or in combination of two or more. For example, when the grip of the adhesive layer to the substrate can be sufficiently improved by providing a primer layer on the first surface of the substrate, the hardened adhesive layer can also be bonded to the substrate. The reinforcement film is manufactured by the method of the first surface of the base material.

<Support base material> As a support base material of the reinforcement film disclosed here, what contains various resin films as a base film can be used. The term "resin film" here refers to a non-porous structure, and typically refers to a resin film substantially free of bubbles (non-porous). Therefore, the concept of the above-mentioned resin film is different from that of a foam film or a nonwoven fabric. As said resin film, what can maintain a shape independently (self-supporting type, or non-dependency) can be used favorably. The above-mentioned resin film may have a single-layer structure, or may have a multi-layer structure of two or more layers (for example, a three-layer structure).

As the resin material constituting the resin film, for example, polyester, polyolefin, nylon 6, nylon 66, polyamide (PA), polyimide (PI), polyamide amide, etc. Imine (PAI), polyetheretherketone (PEEK), polyethersulfide (PES), polyphenylene sulfide (PPS), polycarbonate (PC), polyurethane (PU), ethylene-vinyl acetate Ester copolymer (EVA), polytetrafluoroethylene (PTFE) and other fluorine resins, acrylic resins, polyacrylates, polystyrene, polyvinyl chloride, polyvinylidene chloride and other resins. The above-mentioned resin film may be formed using a resin material containing one of such resins alone, or may be formed using a resin material in which two or more types are blended. The aforementioned resin film may be unstretched or stretched (for example, uniaxially stretched or biaxially stretched).

Preferred examples of the resin material constituting the resin film include polyester-based resins, polyimide-based resins, PPS resins, and polyolefin-based resins. Here, the polyester-based resin refers to a resin containing polyester in a ratio of more than 50% by weight. Similarly, a polyimide-based resin refers to a resin containing polyimide in a ratio exceeding 50% by weight, a PPS resin refers to a resin containing PPS in a ratio exceeding 50% by weight, and a polyolefin-based resin refers to a resin containing polyimide in a ratio exceeding 50% by weight. A resin containing polyolefin in a ratio of 50% by weight.

As the polyester-based resin, typically, a polyester-based resin containing, as a main component, a polyester obtained by polycondensing a dicarboxylic acid and a diol is used.

Examples of the dicarboxylic acid constituting the polyester include: phthalic acid, isophthalic acid, terephthalic acid, 2-methylterephthalic acid, 5-sulfoisophthalic acid, 4,4 '-Diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl ketone dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid and other aromatic Alicyclic dicarboxylic acids; 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids; malonic acid, succinate aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid; maleic acid, maleic anhydride, trans Unsaturated dicarboxylic acids such as butenedioic acid; their derivatives (for example, lower alkyl esters of the above-mentioned dicarboxylic acids such as terephthalic acid, etc.), etc. These can be used individually by 1 type or in combination of 2 or more types. From the viewpoints of strength and the like, aromatic dicarboxylic acids are preferred. Among these, terephthalic acid and 2,6-naphthalene dicarboxylic acid are mentioned as preferable dicarboxylic acid. For example, it is preferable that 50% by weight or more (for example, 80% by weight or more, typically 95% by weight or more) of the dicarboxylic acids constituting the polyester is terephthalic acid, 2,6-naphthalene dicarboxylic acid, or a combination thereof. and use. The above-mentioned dicarboxylic acid may consist substantially only of terephthalic acid, substantially only of 2,6-naphthalene dicarboxylic acid, or substantially only of terephthalic acid and 2,6-naphthalene dicarboxylic acid.

Examples of diols constituting the polyester include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,5-pentanediol, neopentyl glycol, Diol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, polyoxytetramethylene glycol and other aliphatic diols; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol and other alicyclic diols, benzenedimethanol, 4,4'-dihydroxy Aromatic diols such as biphenyl, 2,2-bis(4'-hydroxyphenyl)propane, bis(4-hydroxyphenyl)pyridine, etc. These can be used individually by 1 type or in combination of 2 or more types. Among these, aliphatic diols are preferred, and ethylene glycol is particularly preferred from the viewpoint of transparency and the like. The ratio of the aliphatic diol (preferably ethylene glycol) to the diol constituting the polyester is preferably 50% by weight or more (for example, 80% by weight or more, typically 95% by weight or more). The above-mentioned diol may consist essentially only of ethylene glycol.

Specific examples of polyester-based resins include: polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene naphthalate Butylene formate, etc.

As the polyolefin resin, one kind of polyolefin may be used alone, or two or more kinds of polyolefins may be used in combination. The polyolefin can be, for example, a homopolymer of α-olefin, a copolymer of two or more α-olefins, a copolymer of one or more α-olefins and other vinyl monomers, and the like. Specific examples include ethylene-propylene copolymers such as polyethylene (PE), polypropylene (PP), poly-1-butene, poly-4-methyl-1-pentene, and ethylene-propylene rubber (EPR). , Ethylene-propylene-butene copolymer, ethylene-butene copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer, etc. Either low density (LD) polyolefins or high density (HD) polyolefins may be used. Examples of polyolefin resin films include unstretched polypropylene (CPP) films, biaxially stretched polypropylene (OPP) films, low-density polyethylene (LDPE) films, and linear low-density polyethylene (LLDPE) films. , medium density polyethylene (MDPE) film, high density polyethylene (HDPE) film, polyethylene (PE) film blended with two or more polyethylene (PE), blended with polypropylene (PP) and polyethylene (PE) PP/PE blended film, etc.

Examples of commercially available polyimide resin films include: Mitsubishi Gas Chemical Co., Ltd.'s product name "Neopulim" (S grade, H grade, R grade, etc.), Toray-Dupont company's product name "Kapton" (H type, V type, VN type, etc.), Ube Industries' trade name "Upilex" (S type, RN type, etc.), Kaneka's trade name "Apical" (AH type, NPH type, etc.), The trade name "Kapton 100H" manufactured by Toray Co., Ltd. and the like.

Specific examples of the resin film that can be favorably used as the base film of the reinforcing film disclosed here include PET films, PEN films, PPS films, PEEK films, CPP films, and OPP films. Examples of preferred base films from the viewpoint of strength and dimensional stability include PET films, PEN films, PPS films, and PEEK films. From the viewpoint of the ease of acquisition of the substrate, etc., PET films and PPS films are particularly preferred, and PET films are particularly preferred.

In the resin film, light stabilizers, antioxidants, antistatic agents, colorants (dyes, pigments, etc.), fillers, slip agents, antisticking agents, etc. Known additives such as linking agents. The compounding quantity of an additive is not specifically limited, It can set suitably according to the use etc. of a reinforcement film.

The manufacturing method of a resin film is not specifically limited. For example, conventionally known general resin film molding methods such as extrusion molding, inflation molding, T-die die casting molding, and calender roll molding can be suitably used.

The aforementioned base material may substantially include such a base film. Alternatively, the base material may also include an auxiliary layer in addition to the base film. Examples of the above-mentioned auxiliary layer include: an optical characteristic adjustment layer (such as a colored layer, an antireflection layer), a printing layer or a laminated layer for imparting a desired appearance to a base material, an antistatic layer, a primer layer, Surface treatment layer such as peeling layer.

The thickness of the base material constituting the reinforcing film disclosed herein may exceed 25 μm, typically 30 μm or more. The thickness of the base material is preferably more than 35 μm, can be more than 40 μm, can be more than 50 μm (for example, more than 50 μm), can be more than 60 μm, or can be more than 70 μm. According to the thicker base material, there is a tendency to exert higher reinforcing performance. The reinforcing film disclosed here can also be implemented well in the form that the thickness of the base material is 90 μm or more, or 100 μm or more, or 120 μm or more. The upper limit of the thickness of the substrate is not particularly limited. In some aspects, the thickness of the base material may be, for example, 500 μm or less, 300 μm or less, 250 μm or less, or 200 μm or less from the viewpoint of the handleability or processability of the reinforcement film . From the viewpoint of miniaturization or weight reduction of products to which the reinforcing film is applied, in some aspects, the thickness of the base material may be, for example, 160 μm or less, 130 μm or less, 100 μm or less, or 90 μm. μm or less, may be 75 μm or less, or may be 60 μm or less.

If necessary, corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, primer coating and other previously known surfaces can be applied to the first surface of the substrate. deal with. Such surface treatment can be used to improve the grip of the adhesive layer on the substrate. That is, the above-mentioned surface treatment can help to easily obtain the reinforcing film on the second surface of the adhesive layer fixed on the first surface of the base material. The above surface treatments may be applied alone or in combination. The composition of the primer used for the formation of the primer layer is not particularly limited, and can be appropriately selected from known ones. The thickness of the undercoat layer is not particularly limited, and it is generally suitable to be about 0.01 μm to 1 μm, preferably about 0.1 μm to 1 μm. Examples of other treatments that may be performed on the first surface of the substrate as necessary include antistatic layer forming treatment, colored layer forming treatment, printing treatment, and the like.

When the reinforcing film disclosed here is in the form of a single-sided adhesive sheet with an adhesive layer only on the first side of the base material, the second side of the base material can also be subjected to peeling treatment or antistatic treatment if necessary. Previously known surface treatments. For example, in a reinforcing film in a form (roll form, laminated form, etc.) that uses the second surface of the substrate as the peeling surface that is in contact with the adhesive surface, in order to adjust the water contact angle of the second surface to 100 degrees or more , or in a more preferred range disclosed in this specification, the above-mentioned second surface may be subjected to a peeling treatment. As a typical example of the above-mentioned release treatment, a process of forming a release layer obtained by using a release treatment agent on the second surface of the base material is mentioned. In addition, in the form of a reinforcing film in which the release surface of the release liner different from the base material is used as the release surface abutting against the adhesive surface, the printing property to the second surface can be improved, the light reflectivity can be reduced, and the overlap can be improved. For the purpose of adhesion, etc., corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment and other treatments are carried out on the second surface of the substrate.

When the reinforcing film disclosed here is in the form of a double-sided adhesive sheet having a first adhesive layer on the first surface of the substrate and a second adhesive layer on the second surface of the substrate, it can also be viewed as The second surface of the substrate needs to be subjected to the same surface treatment as that exemplified above as the surface treatment that can be applied to the first surface of the substrate. The surface treatment may be a surface treatment for improving the grip of the second adhesive layer on the substrate. Furthermore, the surface treatment performed on the first surface of the substrate may be the same as or different from the surface treatment performed on the second surface.

<Reinforcing Film> The reinforcing film disclosed here fixes the second surface of the adhesive layer to the first surface of the substrate. The above-mentioned fixation means that in the reinforced film whose adhesive force increases after being attached to the adherend, the adhesive layer will not damage the use of the above-mentioned reinforcement due to the peeling of the interface between the adhesive layer and the supporting substrate. The degree of reinforcing function acquired by the film shows sufficient grip. Even if the adhesive strength of the adhesive surface to the adherend increases after the reinforcing film is attached to the adherend, in the reinforcing film with insufficient grip of the adhesive layer to the support substrate, the adherend cannot be connected to the support. The base material is firmly integrated, and it is easy to damage the reinforcing performance of the adherend obtained by using the reinforcing film. The reinforcement film on the second surface of the adhesive layer fixed on the first surface of the base material can effectively contribute to the reinforcement of the adherend. As one of the preferred examples of the reinforcement film on the second surface with the adhesive layer fixed on the first surface of the base material, the following reinforcement film can be cited, that is, after being attached to the adherend, it exhibits at least 5 N/ 25 mm, preferably 10 N/25 mm or more, more preferably 15 N/25 mm or more (180° peel adhesion measured at a peel angle of 180 degrees and a tensile speed of 300 mm/min) , and no peeling (grip failure) between the second surface of the adhesive layer and the first surface of the support substrate occurs when peeling from the above-mentioned adherend. For example, a reinforced film with an adhesive force of 15 N/25 mm or more after heating and which does not cause grasping failure during the measurement of the adhesive force after heating belongs to the second film with an adhesive layer fixed on the first surface of the substrate. A better example of the reinforcement film on the surface.

As a method of obtaining a reinforcing film on the second surface of the substrate with the adhesive layer fixed on the first surface, it is possible to cite the formation of a liquid adhesive composition that is hardened on the first surface of the substrate as described above. The method of the adhesive layer, or the method of applying surface treatment to the first surface of the base material to improve the grip of the adhesive layer, etc. By selecting the material of the base material or the composition of the adhesive, the gripping property of the adhesive layer on the base material can also be improved. Also, by applying a temperature higher than room temperature to the reinforcing film having the adhesive layer on the first surface of the substrate, the grip of the adhesive layer to the substrate can be improved. The temperature for improving the grip property may be, for example, about 35°C to 80°C, about 40°C to 70°C or higher, or about 45°C to 60°C.

The reinforcing film disclosed here has a form in which the first surface (adhesive surface) of the adhesive layer abuts against the peeling surface with a water contact angle of 100 degrees or more. In this way, the influence of the preservation conditions of the reinforced membrane on the performance of the reinforced membrane can be effectively reduced. It is considered that since the peeling surface with a water contact angle of 100 degrees or more has low polarity, by storing the reinforcing film in a state where the peeling surface is in contact with the adhesive surface, no matter what the storage conditions are (for example, even when it is attached to an adherend Stored in a temperature region where the adhesive force will rise in the state of the adhesive), it also promotes or maintains the bias of the polymer B on the surface of the adhesive layer, showing the light peeling property (low adhesiveness) at the initial stage of lamination. In addition, it is considered that after the adhesive surface of the reinforcing film is separated from the above-mentioned peeling surface and attached to the adherend, that is, in the state where the adhesive surface is in contact with the adherend, the polarity of the adherend is generally higher than that of the above-mentioned peeling surface. Therefore, the presence of polymer B on the surface of the adhesive decreases due to heat or material movement or molecular movement in the adhesive layer over time, thereby greatly increasing the adhesive force. However, the scope of the present invention is not limited thereto.

The above-mentioned water contact angle may be measured in accordance with JIS R 3257: 1999 using a commercially available contact angle measuring device (drop method). For example, the water contact angle can be measured under the following conditions. The measurement is preferably carried out 5 times, and the average value (n=5) is used. The same method was also adopted for the following examples. [Water contact angle measurement conditions] Measuring device: Contact angle measuring device DropMaster DM700 (manufactured by Kyowa Interface Science Co., Ltd.) Measuring environment: 23°C, 50%RH Measuring liquid: Distilled water Measuring time: 1500 ms after the drop

In some aspects, the water contact angle of the peeling surface abutting against the adhesive surface may exceed 100 degrees, 102 degrees or more, or 105 degrees or more. The upper limit of the water contact angle of the peeling surface is not particularly limited, but from the viewpoint of the availability of materials, for example, it may be 130 degrees or less, 120 degrees or less, 115 degrees or less, or 110 degrees or less. For example, a peeling surface having a water contact angle of not less than 100° and not more than 110° can be preferably used.

In some aspects of the reinforcing film disclosed herein, the release surface may be the surface of a release liner different from the support substrate. The release liner is not particularly limited, and for example, a release liner having a release layer on the surface of a liner substrate such as a resin film or paper (it may be paper laminated with a resin such as polyethylene), or a release liner containing a material such as Fluoropolymer (PTFE, etc.) or polyolefin-based resin (polyethylene, polypropylene, etc.) low-adhesion materials for the release liner of the resin film, etc. A release liner having a release layer on the surface of the liner base is preferred in terms of easily obtaining a release surface with a large water contact angle. In terms of excellent surface smoothness, a resin film is preferable as the spacer base material. For example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyester film (PET film, PBT film, etc.), polyurethane film, ethylene-vinyl acetate copolymer film and other resin films have a release liner with a release layer on the surface.

The reinforcement film whose release surface abutting against the adhesive surface is the surface of the release liner can be understood as a constituent element of a release liner-attached reinforcement film including this reinforcement film and a release liner providing the above-mentioned releasable surface. Therefore, according to the present specification, it is possible to provide a reinforcing film with a release liner comprising any of the reinforcing films disclosed herein, and a release liner having a release surface abutting against the adhesive surface of the reinforcing film.

The thickness of the release liner is not particularly limited, but usually it is suitably about 5 μm to 200 μm. When the thickness of the release liner is within the above-mentioned range, it is preferable because the bonding workability to the adhesive layer and the peeling workability from the adhesive layer are excellent. In several aspects, the thickness of the release liner may be, for example, more than 10 μm, more than 20 μm, more than 30 μm, or more than 40 μm. In addition, the thickness of the release liner may be, for example, 100 μm or less, or may be 80 μm or less from the viewpoint of facilitating peeling from the adhesive layer. The release liner may be subjected to known antistatic treatment such as coating type, kneading type, vapor deposition type, etc. if necessary.

In several aspects of the reinforcement film disclosed herein, the above-mentioned peeling surface may be the second surface of the supporting substrate. For example, the second surface of the supporting substrate whose water contact angle is adjusted to be 100 degrees or more by providing a release layer on the surface of the above-mentioned base film can be used as the release surface that abuts on the adhesive surface.

For the formation of the peeling layer, for example, known peeling agents such as silicone-based peeling agents, long-chain alkyl-based peeling agents, olefin-based peeling agents, fluorine-based peeling agents, and fatty acid amide-based peeling agents can be used. . Among them, a silicone-based peeling treatment agent is preferable. According to the peeling layer formed by the silicone-based peeling agent, compared with the peeling layer formed by other peeling agents, it is possible to suppress the reinforcement before use (before sticking to the adherend) at a higher level The increase of initial adhesion caused by the film being stored in a temperature region higher than room temperature. For example, even if the reinforced film before use is stored at a higher temperature and/or at a temperature region higher than room temperature for a longer period of time, the initial adhesive force can be suppressed to be low.

The elemental ratio (atomic%) of silicon atoms (Si) on the surface of the release layer can be calculated by measuring the surface of the release layer formed with a polysiloxane release treatment agent by X-ray photoelectron spectroscopy (ESCA) . In several aspects, the element ratio of Si on the surface of the release layer may be, for example, 10 atomic% or more, 15 atomic% or more, or 20 atomic% or more. In addition, the element ratio of the above-mentioned Si is usually suitably 40 atomic% or less, may be 30 atomic% or less, and may be 25 atomic% or less. In the reinforcing film disclosed here, as the peeling surface to be brought into contact with the adhesive surface, a peeling surface having a peeling layer having a surface Si element ratio (atomic%) of 20 atomic% or more and 25 atomic% or less can be preferably used. . The measurement of the elemental ratio of Si on the surface of the peeling layer by ESCA can be performed by the method described in the following examples.

In addition, in some aspects, the above-mentioned release layer may be a release layer formed using a non-polysiloxane-based release treatment agent. The peeling surface having such a peeling layer can be favorably used as, for example, a peeling surface abutting against an adhesive surface of a reinforcing film used in a field where adhesion of an uncured silicone-based peeling treatment agent to an adherend is concerned. Specific examples of the non-silicone-based release treatment agent include long-chain alkyl-based release treatment agents, olefin-based release treatment agents, and fluorine-based release treatment agents. Examples of preferable non-silicone-based release treatment agents include long-chain alkyl-based release treatment agents and olefin-based release treatment agents. Among them, long-chain alkyl-based peeling treatment agents are preferred.

The reinforced film disclosed here can be used regardless of the storage conditions of the reinforced film by abutting its adhesive surface on the peeling surface with a water contact angle of 100 degrees or more, for example, even if it is stored in a temperature region higher than room temperature. The peeling force of the above-mentioned adhesive surface from the above-mentioned peeling surface (hereinafter also referred to as "liner peeling force" or simply "peeling force") is kept low. If the above-mentioned peeling force becomes too high, there may be problems such as an increase in the workload when the reinforcing film is attached to the adherend, or a decrease in the surface roughness of the adhesive surface due to peeling the adhesive surface from the peeling surface. By bringing the peeling surface with a water contact angle of 100 degrees or more into contact with the adhesive surface, the increase in the peeling force during storage of the reinforced film can be effectively suppressed. Depending on the peeling surface having a peeling layer formed with a silicone-based peeling treatment agent, there is a tendency to exhibit a particularly excellent effect of suppressing an increase in peeling force.

The thickness of the peeling layer is not particularly limited, and it is usually suitably about 0.01 μm to 1 μm, preferably about 0.1 μm to 1 μm. The method for forming the release layer is not particularly limited, and a known method corresponding to the type of the release treatment agent to be used can be appropriately employed.

The thickness of the reinforcing film disclosed herein may exceed 30 μm, for example. From the viewpoint of enhancing the reinforcing effect, in some aspects, the thickness of the reinforcing film can be, for example, 50 μm or more, 60 μm or more, 80 μm or more, 100 μm or more, or 130 μm above. The upper limit of the thickness of the reinforcing film is not particularly limited. The thickness of the reinforcing film may be, for example, 1000 μm or less, 600 μm or less, 350 μm or less, or 250 μm or less. From the perspective of miniaturization, weight reduction, and thinning of products to which the reinforcing film is applied, the thickness of the reinforcing film may be, for example, 200 μm or less, 175 μm or less, or 140 μm or less in several forms. It may be 120 μm or less, may be 100 μm or less (for example, less than 100 μm), or may be 80 μm or less. Furthermore, the thickness of the reinforcing film refers to the thickness of the part attached to the adherend. For example, in the reinforcement film 1 having the structure shown in FIG. 1 , it refers to the thickness from the adhesive surface 21A of the reinforcement film 1 to the second surface 10B of the substrate 10 , excluding the thickness of the release liner 31 .

The reinforcing film disclosed here can be well implemented in a state where the thickness Ts of the support substrate is greater than the thickness Ta of the adhesive layer. That is, Ts/Ta is preferably larger than 1. Ts/Ta may be, for example, 1.1 or more, 1.2 or more, 1.5 or more, or 1.7 or more, but it is not particularly limited. By increasing Ts/Ta, it tends to be easy to exhibit good reinforcing performance even if the reinforcing film is thinned. In several aspects, Ts/Ta may be 2 or more (for example, greater than 2), may be 3 or more, or may be 4 or more. Moreover, Ts/Ta may be set to 50 or less, for example, and may be set to 20 or less. Ts/Ta may be, for example, 10 or less, or may be 8 or less from the viewpoint of easily exhibiting high post-heating adhesive force even if the reinforcing film is thinned.

<Characteristics of the reinforced film> The reinforced film disclosed here has a ratio of the adhesive force N2 (adhesion after heating) to the adhesive force N1 (initial adhesive force), that is, the increase ratio of the adhesive force (N2/N1), which is 10 or more. It can exhibit low adhesiveness at the initial stage, and exert strong adhesiveness to the adherend when the adherend is used. In this way, good secondary processability and high reinforcement performance can be well balanced. From the viewpoint of obtaining a higher effect, in some aspects, the adhesion strength increase ratio is preferably 15 or more, may be 18 or more, may be 20 or more, and may be 25 or more. The upper limit of the adhesion increase ratio is not particularly limited, and may be, for example, 100 or less, 80 or less, or 60 or less from the viewpoint of ease of manufacture of the reinforcing film or economical efficiency. The reinforcing film disclosed here can be implemented favorably in the form of an adhesive strength increase ratio of, for example, 10 to 80, or 15 to 60.

The above adhesion increase ratio is defined in the form of the ratio of the adhesion after heating [N/25 mm] to the initial adhesion [N/25 mm]. The initial adhesion is obtained by The stainless steel (SUS) plate as the adherend was placed in an environment of 23°C and 50% RH for 30 minutes, and the 180° peel adhesion was measured under the conditions of a peeling angle of 180° and a tensile speed of 300 mm/min. Also, the adhesive force after heating [N/25 mm] was obtained by crimping the SUS plate as the adherend and heating at 80°C for 5 minutes, and then in an environment of 23°C and 50%RH After standing in the air for 30 minutes, measure the 180° peel adhesion under the conditions of a peel angle of 180° and a tensile speed of 300 mm/min. As the adherend, SUS304BA board is used for both the initial adhesion and the adhesion after heating. The methods for measuring the initial adhesive force and the adhesive force after heating can be applied to any one of the first adhesive surface and the second adhesive surface. More specifically, the initial adhesive force and the adhesive force after heating can be measured according to the method described in the following examples.

In several forms of the reinforced film disclosed here, the initial adhesive force of the reinforced film may be, for example, less than 2.0 N/25 mm, less than 1.5 N/25 mm, less than 1.2 N/25 mm, or less than 1.2 N/25 mm. It may be 1.0 N/25 mm or less, and may be 0.8 N/25 mm or less, but it is not particularly limited. Lower initial adhesion is also preferable from the viewpoint of secondary processability. The lower limit of the initial adhesion force is not particularly limited, for example, it may be 0.01 N/25 mm or more. From the standpoint of attaching workability to the adherend or preventing positional shift before the adhesive force increases, the initial adhesive force is usually more than 0.1 N/25 mm. In some aspects, the initial adhesion force may be, for example, not less than 0.2 N/25 mm, not less than 0.3 N/25 mm, not less than 0.4 N/25 mm, or not less than 0.5 N/25 mm.

In several aspects of the reinforced film disclosed here, the adhesive force of the reinforced film after heating may be, for example, not less than 5.0 N/25 mm, not less than 7.0 N/25 mm, or not less than 10 N/25 mm, It may be 13 N/25 mm or more, 15 N/25 mm or more, or 17 N/25 mm or more, but it is not particularly limited. It is preferable to exhibit higher adhesive force after heating from the viewpoint of improving reinforcing performance. The upper limit of the adhesive force after heating is not particularly limited. From the standpoint of ease of manufacture or economical efficiency of the reinforcing film, in some aspects, the adhesive force after heating can be, for example, 50 N/25 mm or less, 40 N/25 mm or less, and 35 N/25 mm or less. 25 mm or less, or 30 N/25 mm or less.

Furthermore, the adhesive force after heating of the reinforced film disclosed here is a characteristic of the reinforced film, and does not limit the usage of the reinforced film. In other words, the use of the reinforced film disclosed here is not limited to the state of heating at 80°C for 5 minutes, for example, it can also be used in a region where it is not specially heated to room temperature (usually 20°C to 30°C, typically It is a state of treatment at 23°C to 25°C). In this mode of use, the adhesive force can also be increased for a long time to achieve a firm joint. In addition, the reinforcing film disclosed here can promote the increase of adhesive force by performing heat treatment at any time after attachment. The heating temperature in this heat treatment is not particularly limited, and can be set in consideration of workability, economical efficiency, the heat resistance of the substrate of the reinforcing film, the adherend, and the like. The above-mentioned heating temperature may be, for example, less than 150°C, may be 120°C or lower, may be 100°C or lower, may be 80°C or lower, and may be 70°C or lower. In addition, the above heating temperature may be, for example, 35°C or higher, 50°C or higher, or 60°C or higher, may be 80°C or higher, or may be 100°C or higher. Based on the higher heating temperature, the adhesion can be increased by shorter treatment time. The heating time is not particularly limited, and may be, for example, 1 hour or less, 30 minutes or less, 10 minutes or less, or 5 minutes or less. Alternatively, the heat treatment may be performed for a longer time within the limit that the reinforcing film or the adherend does not undergo significant thermal deterioration. In addition, heat processing may be performed once, and may be divided into plural times and performed.

In several aspects, the peeling force of the adhesive surface of the reinforcing film from the peeling surface is generally suitable to be 1.5 N/25 mm or less, preferably 1.0 N/25 mm or less, more preferably 0.5 N/25 mm or less, and even more preferably Preferably it is less than 0.3 N/25 mm. A low peeling force is preferable from the viewpoint of reducing the workload when peeling the peeling surface from the adhesive surface or maintaining the smoothness of the adhesive surface. In several aspects, the above-mentioned peeling force may be, for example, less than 0.2 N/25 mm, less than 0.1 N/25 mm, less than 0.08 N/25 mm, or less than 0.06 N/25 mm. In addition, from the viewpoint of suppressing the phenomenon that the adhesive surface unintentionally bulges from the peeling surface before the reinforcing film is attached to the adherend, the above-mentioned peeling force may be, for example, 0.005 N/25 mm or more, and may be 0.01 N/25 mm or more. mm, or more than 0.015 N/25 mm.

According to the technology disclosed here, it is possible to provide a reinforced film which, after being stored at 60°C and 90%RH for 7 days (hereinafter also referred to as "storage based on condition 1"), has no peeling of the adhesive surface from the peeling surface. The force is 2.0 N/25 mm or less. In several aspects, the peeling force after storage based on the above condition 1 may be, for example, 1.5 N/25 mm or less, 1.0 N/25 mm or less, 0.5 N/25 mm or less, or 0.3 N/25 mm or less. 25 mm or less, may be 0.1 N/25 mm or less, or 0.08 N/25 mm or less. In addition, the peel force after storage based on the above condition 1 may be, for example, 0.005 N/25 mm or more, 0.01 N/25 mm, or 0.015 N/25 mm or more. The reinforcing film whose peeling force after storage based on condition 1 is relatively small compared to the peeling force before storage is preferable because there is little change in peeling performance due to storage.

The peeling force after storage based on the above-mentioned condition 1 is preferably 5 times or less (for example, 0.5 times or more and 5 times or less) of the peeling force before storage, more preferably 3 times or less. In several aspects, the peeling force after storage based on the above condition 1 may be 3 times or less, 2 times or less, 1.5 times or less, or 1.3 times or less the peeling force before storage. In addition, the difference between the peel force after storage and the peel force before storage based on the above-mentioned condition 1 is preferably 1.0 N/25 mm or less, and may be 0.5 N/25 mm or less, 0.1 N/25 mm or less, 0.05 N/25 mm or less, or 0.05 N/25 mm or less. 25 mm or less than 0.03 N/25 mm. The reinforcing film having a small difference between the peeling force after storage and the peeling force before storage based on the above-mentioned condition 1 is preferable because there is little change in peeling performance due to storage.

According to the technology disclosed here, it is possible to provide a reinforced film whose peeling force from the adhesive surface is 2.0 N after being stored at 85°C for 7 days (hereinafter also referred to as "storage based on condition 2") /25 mm or less. In several aspects, the peeling force after storage based on the above condition 2 may be, for example, 1.5 N/25 mm or less, 1.0 N/25 mm or less, 0.5 N/25 mm or less, or 0.3 N/25 mm or less. 25 mm or less, may be 0.1 N/25 mm or less, or 0.08 N/25 mm or less. In addition, the peeling force after storage based on the above condition 2 may be, for example, 0.005 N/25 mm or more, 0.01 N/25 mm, or 0.015 N/25 mm or more. The reinforcing film whose peeling force after storage based on condition 2 is relatively small compared to the peeling force before storage is preferable because there is little change in peeling performance due to storage.

The peeling force after storage based on the above condition 2 is preferably 5 times or less (for example, 0.5 times or more and 5 times or less) of the peeling force before storage, more preferably 3 times or less. In several aspects, the peeling force after storage based on the above condition 2 may be 3 times or less, 2 times or less, 1.5 times or less, or 1.3 times or less the peeling force before storage. In addition, the difference between the peeling force after storage and the peeling force before storage based on the above-mentioned condition 2 is preferably 1.0 N/25 mm or less, may be 0.5 N/25 mm or less, may be 0.1 N/25 mm or less, or may be 0.05 N/25 mm or less than 0.03 N/25 mm. The reinforcing film having a small difference between the peeling force after storage and the peeling force before storage based on the above-mentioned condition 2 is preferable because there is little change in peeling performance due to storage.

According to several aspects of the technology disclosed here, a reinforced film can be provided which, after storage based on the above-mentioned condition 1, has an increase ratio of adhesion force of 10 times or more, or satisfies any other preferred increase ratio of adhesion force mentioned above. The adhesion increase ratio of the reinforced film after storage based on the above-mentioned condition 1 may be, for example, about 0.8 to 3 times, about 1.0 to 2.5 times, or about 1.1 to 2.5 times the increase ratio of the adhesion before storage. , It can also be about 1.2 times to 2.0 times.

According to several aspects of the technology disclosed here, a reinforced film can be provided, which, after storage based on the above-mentioned condition 2, has an increase ratio of adhesion force of 10 times or more, or satisfies any other preferred increase ratio of adhesion force mentioned above. The adhesion increase ratio of the reinforced film after storage based on the above-mentioned condition 2 may be, for example, about 0.8 to 3 times, about 1.0 to 2.5 times, or about 1.1 to 2.5 times the increase ratio of the adhesion before storage. , It can also be about 1.2 times to 2.0 times.

The reinforcing film disclosed here is a reinforcing film having a first adhesive layer disposed on a first surface of a substrate and a second adhesive layer disposed on a second surface of the substrate (i.e. double-sided adhesive reinforcement) In the case of the form of a film), the first adhesive layer and the second adhesive layer may have the same configuration or different configurations. When the composition of the first adhesive layer and the second adhesive layer are different, the difference may be, for example, a difference in composition or a difference in structure (thickness, surface roughness, formation range, formation pattern, etc.). As long as at least the second side of the first adhesive layer is fixed on the first side of the support substrate, the first side (first adhesive side) of the first adhesive layer is in contact with water. The peeling surface with an angle of 100 degrees or more, and the adhesive strength increase ratio of the above-mentioned first adhesive surface is 10 or more, and the characteristics of the second adhesive layer side are not particularly limited. For example, the second adhesive layer may also be an adhesive layer not containing the polymer B. In addition, the adhesive strength increase ratio of the surface of the second adhesive layer (second adhesive surface) may be less than 10, may be less than 5, or may be less than 2.

<Applications> For example, after the reinforced film provided by this manual is pasted on the adherend, the adhesive force can be suppressed to be low in a short period of time in the room temperature region (such as 20°C to 30°C), and a good secondary performance can be exerted during the period. Processability, therefore, can contribute to the suppression of yield and the improvement of the quality of products including the reinforced film. Moreover, the above-mentioned reinforcing film can greatly increase the adhesive force by curing (heating, time, a combination of these, etc.), and then can perform well by firmly integrating the support base material and the adherend. The reinforcing effect. For example, by heating at a desired timing, the reinforcing film can be firmly attached to the adherend, and the support base and the adherend can be firmly integrated. In addition, the above-mentioned reinforced film is excellent in storage stability, for example, it can stably exhibit desired performance even if it is stored in a temperature region higher than room temperature. Utilizing such characteristics, the reinforcing film disclosed herein can be used in various fields to reinforce components contained in various products.

For example, with regard to optical components used in optical products, or electronic components used in electronic products, a high degree of integration, miniaturization, light weight, and thinning continue to develop, and multiple thinner optical components with different linear expansion coefficients or thicknesses can be laminated. /Electronic components. Appropriate rigidity can be imparted to the above-mentioned optical member/electronic member by affixing a reinforcing film to such a member. Thereby, in the manufacturing process and/or the manufactured product, it is possible to suppress curling or bending caused by stress that may be generated between the above-mentioned plural members having different coefficients of linear expansion or different thicknesses.

Also, in the manufacturing process of optical products/electronic products, when performing shape processing such as cutting processing on thin optical members/electronic members as described above, it is processed by attaching a reinforcing film to the member , can alleviate the local stress concentration of optical components/electronic components accompanying processing, and can reduce the risk of cracks, cracks, and peeling off of laminated components. The operation of attaching a reinforcing member to an optical member/electronic member can also help alleviate the local stress concentration during the transfer, lamination, rotation, etc. of the member, or the bending or bending caused by the member's own weight. Inhibition etc.

Furthermore, when devices such as optical products or electronic products including the above-mentioned reinforcing film are put on the market for consumer use, even if the device is dropped, placed under a heavy object, or hit by a flying object, etc. When an unexpected stress is applied, the stress applied to the device can also be relaxed by including a reinforcing film in the device. Therefore, by including the reinforcing film in the above-mentioned device, the durability of the device can be improved.

The reinforcement film disclosed here can be used favorably, for example, in the form of being attached to members constituting various portable devices (portable devices). The so-called "carrying" here does not only refer to being able to carry, but refers to the degree of portability that can be carried relatively easily by an individual (standard adult). Also, examples of the so-called portable devices here may include: mobile phones, smart phones, tablet personal computers, notebook personal computers, various portable devices, digital cameras, digital video cameras, audio equipment (portable music players) , recorder, etc.), computers (calculators, etc.), portable game devices, electronic dictionaries, electronic notebooks, electronic books, information equipment for vehicles, portable radios, portable TVs, portable printers, portable scanners Portable electronic equipment such as instruments, portable modems, etc. In addition, it may also include mechanical watches or pocket watches, flashlights, magnifying glasses, etc. Examples of members constituting the aforementioned portable electronic equipment include optical films or display panels used in image display devices such as thin-layer displays such as liquid crystal displays or film-type displays. The reinforcing film disclosed here can also be used well in the form of being attached to various components in automobiles, home appliances, and the like.

Matters disclosed in this specification include the following. (1) A reinforcing film comprising: a supporting substrate having a first surface and a second surface; and an adhesive layer laminated on the first surface of the supporting substrate; the supporting substrate comprising a resin film as The base film; the above-mentioned second surface of the above-mentioned adhesive layer is fixed on the above-mentioned first surface of the above-mentioned support substrate; the above-mentioned first surface of the above-mentioned adhesive layer is abutted against the peelable surface; the water contact angle of the above-mentioned peelable surface is 100 degrees or more; the above-mentioned adhesive layer contains polymer A whose glass transition temperature (Tg) is less than 0 ℃, and polymerized as a copolymer of a monomer having a polyorganosiloxane skeleton and a (meth)acrylic monomer Object B; and the adhesive force N2 after attaching the first surface of the above-mentioned adhesive layer to the stainless steel plate, heating at 80°C for 5 minutes and then placing it at 23°C for 30 minutes is the above-mentioned first surface of the above-mentioned adhesive layer The adhesive strength N1 is more than 10 times of the adhesive force N1 after the surface is pasted on the stainless steel plate and placed at 23°C for 30 minutes. (2) The reinforcing film as described in (1) above, wherein the peelable surface is a surface of a peeling layer containing silicon (Si). (3) The reinforcing film as described in said (2) whose atomic ratio of Si of the said peelable surface is 15 atomic% or more and 30 atomic% or less. (4) The reinforcing film as described in said (1) whose said peelable surface is the surface of the peeling layer formed with the long-chain alkyl system peeling agent. (5) The reinforcing film described in any one of (1) to (4) above, wherein the thickness of the supporting base material is 30 μm or more. (6) The reinforcing film described in any one of (1) to (5) above, wherein the thickness of the support substrate is 1.1 times to 10 times the thickness of the adhesive layer. (7) The reinforced film as described in any one of said (1)-(6) whose weight average molecular weight of the said polymer B is 1000-30000. (8) The reinforcing film described in any one of the above (1) to (7), wherein the content of the polymer B in the adhesive layer is 0.05 parts by weight or more based on 100 parts by weight of the polymer A and 20 parts by weight or less. (9) The reinforcing film according to any one of (1) to (8) above, wherein the releaseable surface is the surface of a release liner. (10) The reinforcing film according to any one of (1) to (9) above, wherein the release liner has a thickness of 30 μm or more and 100 μm or less. (11) The reinforced film described in any one of (1) to (10) above, wherein the adhesive layer has a thickness of 3 μm to 100 μm (for example, 20 μm to 50 μm). (12) The reinforcing film described in any one of (1) to (11) above, wherein the base film is a polyester film having a thickness of 35 μm or more (for example, a thickness of 35 μm or more and 500 μm or less). (13) The reinforcing film described in the above (12), wherein the base film is a PET film having a thickness of 50 μm or more (for example, a thickness of 50 μm or more and 200 μm or less). (14) The reinforced film according to any one of (1) to (13) above, wherein the polymer A is an acrylic polymer. (15) The reinforcing film according to the above (14), wherein the acrylic polymer contains N-vinyl cyclic amide and a hydroxyl group-containing monomer as monomer units. (16) The reinforced film according to any one of (1) to (15) above, wherein the adhesive layer contains an isocyanate-based crosslinking agent. (17) The reinforcing film according to any one of (1) to (16) above, wherein the adhesive force N2 is 15 N/25 mm or more. (18) The reinforcing film described in any one of the above (1) to (17), wherein after storing for 7 days under the conditions of 60°C and 90%RH, the above-mentioned first side of the above-mentioned adhesive layer is pasted Adhesive force N2 after being bonded to a stainless steel plate, heated at 80°C for 5 minutes, and then placed at 23°C for 30 minutes is after the above-mentioned first side of the above-mentioned adhesive layer is attached to a stainless steel plate and placed at 23°C for 30 minutes The adhesive force of N1 is more than 10 times. (19) A reinforcing film with a release liner, comprising the reinforcing film described in any one of (1) to (18) above, and a release liner having the above-mentioned release liner. (20) A member with a reinforcing film, which includes a member, and the reinforcing film as described in any one of the above (1) to (18) attached to the member with the above-mentioned adhesive surface. (21) The member with a reinforcing film as described in the above (20), wherein the member is an optical member or an electronic member. (22) A device comprising the member with a reinforcing film as described in (20) or (21) above. (23) A method for producing a reinforced film, which is a method for producing the reinforced film described in any one of (1) to (18) above, and sequentially includes: making a liquid adhesive composition and a support substrate contacting the first surface; and hardening the adhesive composition on the first surface to form the adhesive layer. [Example]

Hereinafter, some examples of the present invention will be described, but the present invention is not intended to be limited to those shown in the specific examples. In addition, "part" and "%" in the following description are based on weight unless otherwise specified.

(Preparation of Polymer A1) In a four-neck flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube and a cooler, add 60 parts of 2EHA, 15 parts of N-vinyl-2-pyrrolidone (NVP), methyl methacrylate 10 parts of ester (MMA), 15 parts of 2-hydroxyethyl acrylate (HEA), and 200 parts of ethyl acetate as a polymerization solvent, stirred at 60°C for 2 hours under a nitrogen atmosphere, and then put in as a thermal polymerization initiator 0.2 part of AIBN was reacted at 60° C. for 6 hours to obtain a solution of polymer A1. The Mw of the polymer A1 was 1.1 million.

(Preparation of Polymer B1) In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen inlet tube, a cooler, and a dropping funnel, 100 parts of toluene, 40 parts of MMA, 20 parts of n-butyl methacrylate (BMA), 20 parts of 20 parts of 2-ethylhexyl methacrylate (2EHMA), a methacrylate monomer containing a polyorganosiloxane skeleton with a functional group equivalent of 900 g/mol (trade name: X-22-174ASX, Shin-Etsu Chemical Industrial Co., Ltd.) 8.7 parts, methacrylate monomer having a polyorganosiloxane skeleton with a functional group equivalent of 4600 g/mol (trade name: KF-2012, manufactured by Shin-Etsu Chemical Co., Ltd.) 11.3 parts And 0.51 parts of methyl thioglycolate as a chain transfer agent. Then, after stirring for 1 hour at 70°C under a nitrogen atmosphere, put in 0.2 parts of AIBN as a thermal polymerization initiator, and after reacting at 70°C for 2 hours, put in 0.1 part by weight of AIBN as a thermal polymerization initiator , and then allowed to react at 80° C. for 5 hours. A solution of polymer B1 is thus obtained. The polymer B1 has a Mw of 22,000.

In addition, the weight average molecular weight of each said polymer was measured using the GPC apparatus (manufactured by Tosoh, HLC-8220GPC) under the following conditions, and was calculated|required by polystyrene conversion.・Sample concentration: 0.2 wt% (tetrahydrofuran (THF) solution) ・Sample injection volume: 10 μl ・Eluent: THF, flow rate: 0.6 ml/min ・Measurement temperature: 40℃ ・Column: Sample column; TSKguardcolumn SuperHZ -H (1 piece) + TSKgel SuperHZM-H (2 pieces) Reference column; TSKgel SuperH-RC (1 piece) ・Detector: Differential refractometer (RI)

(Preparation of Adhesive Composition C1) To the above polymer A1 solution, 2.5 parts of polymer B1 and 2.5 parts of isocyanate-based crosslinking agent ( Trade name: Takenate D110N, trimethylolpropane xylylene diisocyanate, manufactured by Mitsui Chemicals Corporation), were uniformly mixed to prepare adhesive composition C1.

<Preparation of a reinforcing film with a release liner> (Example 1) A polyethylene terephthalate (PET) film (manufactured by Toray, trade name "Lumirror"; The adhesive composition C1 was directly coated on the first surface called "support substrate A", and dried by heating at 110° C. for 2 minutes, thereby forming an adhesive layer with a thickness of 25 μm. By bonding the peeling surface of the peeling liner R1 to the surface (adhesive surface) of the adhesive layer, a reinforcing film with a peeling liner in a form in which the peeling surface is in contact with the peeling surface is obtained. As the release liner R1, MRQ50T100 (a release liner having a release layer formed of a silicone-based release treatment agent on one side of a polyester film, thickness 50 μm) manufactured by Mitsubishi Chemical Co., Ltd. was used.

(Examples 2-6) Except having used release liner R2-R6 instead of release liner R1, the reinforcement film with the release liner of Examples 2-6 was produced in the same manner as Example 1, respectively. As the release liners R2 to R6, the following were used. [Release liner R2] 100 parts of a silicone-based release agent (manufactured by Shin-Etsu Chemical, KS-847H) and 3.3 parts of a silicone curing catalyst (manufactured by Shin-Etsu Chemical, CAT-PL-50T) were prepared using toluene ( Idemitsu Petrochemical), n-hexane (Maruzen Petrochemical) and methyl ethyl ketone (Idemitsu Kosan) with a weight ratio of 1:2:1 was diluted to 0.3% to prepare silicone-based peeling treatment agent. This release treatment agent was applied to one side of a 50 μm-thick PET film (Mitsubishi Plastics, Diafoil T100C50) and dried at 130° C. for 1 minute to prepare a release liner R2. [Release liner R3] 92 parts of a polysiloxane-based release agent containing vinyl (manufactured by Shin-Etsu Chemical, KS-3703), 8 parts of a release control agent (manufactured by Shin-Etsu Chemical, KS-3800) and a platinum catalyst ( Shin-Etsu Chemical Co., Ltd., CAT-PL-50T) 3 parts were mixed with 680 parts of toluene and 680 parts of n-hexane as a diluting solvent to prepare a silicone-based release treatment agent. This release treatment agent was applied to one side of a 50 μm-thick PET film (Mitsubishi Plastics, Diafoil T100C50) and dried at 130° C. for 1 minute to prepare a release liner R3. [Release liner R4] 80 parts of a polysiloxane-based release agent containing vinyl (manufactured by Shin-Etsu Chemical, KS-3703), 20 parts of a release control agent (manufactured by Shin-Etsu Chemical, KS-3800) and a platinum catalyst ( Shin-Etsu Chemical Co., Ltd., CAT-PL-50T) 3 parts were mixed with 680 parts of toluene and 680 parts of n-hexane as a diluting solvent to prepare a silicone-based release treatment agent. This release treatment agent was applied to one side of a PET film (Mitsubishi Plastics, Diafoil T100C50) having a thickness of 50 μm, and dried at 130° C. for 1 minute to prepare a release liner R4. [Peel-off liner R5] 200 parts of xylene (manufactured by Sun Chemical Co., Ltd., Xylol) and 600 parts of octadecyl isocyanate (manufactured by Ohara paragium chemical Co., Ltd., R-NCO) were added to a reaction vessel equipped with a cooler , stirring while heating. From the time when xylene started to reflux, 100 parts of polyvinyl alcohol (manufactured by Kuraray, Kuraray Poval 205) was gradually added in small amounts, and the addition was continued for 2 hours at intervals of 10 minutes. After the addition of polyvinyl alcohol was completed, the reaction was further refluxed for 2 hours to complete the reaction. After cooling the reaction mixture to about 80°C, it was added to methanol, and the reaction product was precipitated as a white precipitate. The precipitate was separated by filtration, 140 parts of xylene was added, heated to dissolve it completely, and methanol was added again to precipitate. After repeating this operation several times, the precipitate was washed with methanol and dried and pulverized. The obtained powder was diluted to 0.3% with water to prepare a long-chain alkyl-based peeling treatment agent. This release treatment agent was applied to one side of a PET film (Mitsubishi Plastics, Diafoil T100C50) having a thickness of 50 μm, and dried at 130° C. for 1 minute to prepare a release liner R5. [Release liner R6] In a reaction container equipped with a cooler, 100 parts of acrylonitrile (manufactured by Showa Denko Co., Ltd.), 62.5 parts of stearyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd., SMA), methacrylate Acrylic acid (manufactured by Mitsubishi Rayon Co., Ltd.) 18 parts, 1-dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd., 1-dodecanethiol) 1.8 parts, benzoyl peroxide (NOF Co., Ltd. Manufactured by the company, Nyper BW) 0.55 parts, diluted to 24% with toluene (manufactured by Idemitsu Petrochemical), and reacted at 70° C. for 7 hours under a nitrogen stream. The obtained liquid was diluted to 0.3% with toluene to prepare a long-chain alkyl-based peeling treatment agent. This release treatment agent was applied to one side of a PET film (Mitsubishi Plastics, Diafoil T100C50) having a thickness of 50 μm, and dried at 130° C. for 1 minute to prepare a release liner R6.

The water contact angles of the release liners R1 to R6 were measured by the above method. The results are shown in Table 1.

[15 kV，25 W] 光電子掠出角：相對於試樣表面為45°In addition, measurement by X-ray photoelectron spectroscopy (ESCA) was performed on the release surfaces (surfaces of the release layers) of the release liners R1 to R6 above under the following conditions to measure the elemental ratio of Si. The results are shown in Table 1. Device: PHI Quantera SXM manufactured by ULVAC PHI X-ray source: Monochromatic AlKα X-ray setting (XRay Setting): 100 μm

[15 kV, 25 W] Photoelectron grazing angle: 45° relative to the sample surface

(Storage conditions) The reinforcement film with a release liner of each example was left to stand for 4 days in an environment of 23° C. and 50% RH as a sample of the initial state (before storage) of the reinforcement film with a release liner. The reinforcement film with release liner in the above initial state was further preserved for 7 days under conditions of 60° C. and 90% RH as samples after preservation based on Condition 1. The reinforcement film with a release liner in the above initial state was further stored at 85° C. for 7 days as a sample after storage based on Condition 2. The following evaluation tests were performed on each of the samples before storage, after storage under Condition 1, and after storage under Condition 2. In addition, the samples after storage based on conditions 1 and 2 were used for each evaluation test after returning to the environment of 23 degreeC and 50%RH from the environment of each condition and leaving it still for 30 minutes.

<Measurement of Liner Peeling Force> The reinforcing film with release liner of each example was cut into a width of 25 mm together with the release liner, and these were used as test pieces. Under the environment of 23°C and 50%RH, the above-mentioned test piece was set in a universal tensile compression testing machine (device name "tensile compression testing machine, TCM-1kNB" manufactured by Minebea Co., Ltd.), and stretched at a peeling angle of 180 degrees. Peel the release liner from the adhesive surface at a speed of 300 mm/min, and measure the 180° peel adhesive force at this time (relative to the above tensile resistance). The measurement was performed three times, and the average value thereof is shown in Table 1 as the liner peeling force (N0) [N/25 mm].

<Measurement of Adhesion to SUS> The reinforcement film of each example was cut into 25 mm width together with the release liner, and these were used as test pieces, and the SUS board (SUS304BA board) cleaned with toluene was used as the adherend, The initial adhesive force N1 and the post-heating adhesive force N2 were measured in the following procedure. (Measurement of Initial Adhesion) Under the standard environment of 23°C and 50%RH, the release liner covering the adhesive surface of each test piece was peeled off, and the exposed adhesive surface was bonded by making a 2 kg roller reciprocate once. on the adherend. Put the test piece crimped on the adherend in the above-mentioned standard environment for 30 minutes, and use a universal tensile compression testing machine (device name "tensile compression testing machine, TCM-1kNB" manufactured by Minebea Co., Ltd.), according to JIS Z0237 , under the conditions of a peeling angle of 180 degrees and a tensile speed of 300 mm/min, the 180° peeling adhesion (relative to the resistance of the above stretching) was measured. The measurement was performed three times, and the average value thereof is shown in Table 1 as the initial adhesion force (N1) [N/25 mm]. (Measurement of Adhesive Force after Heating) Heat the test piece bonded to the adherend by the same method as the initial adhesive force measurement at 80°C for 5 minutes, and then leave it in the above-mentioned standard environment for 30 minutes, similarly Measure the 180° peel adhesion. The measurement was carried out three times, and the average value thereof is shown in Table 1 as the adhesive force after heating (N2) [N/25 mm]. In addition, it was confirmed that the reinforced films of Examples 1 to 6 were not seized in the measurement of the adhesive force after heating in any of the samples before storage, after storage under condition 1, and after storage under condition 2. destroy.

[Table 1]

As shown in Table 1, the reinforced films of Examples 1 to 5 prepared in the form of a reinforced film with a release liner whose adhesive surface is in contact with the peeling surface with a water contact angle of 100 degrees or more, even after storage based on Condition 1, Good performance of the initial low adhesiveness and strong adhesiveness during use that are equal to or higher than those before storage. According to the reinforcing films of Examples 1 to 4 in which the above-mentioned peeling surface is a peeling surface formed by using a silicone-based peeling treatment agent, better results were obtained. That is, it was confirmed that the reinforced films of Examples 1 to 4 exhibited good initial low adhesiveness and strong adhesiveness during use even after storage under the more severe condition 2. In addition, the reinforcing films of Examples 1 to 5 were all easily peeled from the peeling surface after storage based on Conditions 1 and 2. In the reinforced films of Examples 1 to 4, the difference between the liner peeling force after storage and before storage based on conditions 1 and 2 was particularly small, and the stability of the liner peeling force was excellent.

On the other hand, the reinforcement film of Example 6 prepared in the form of a reinforcement film with a release liner in which the adhesive surface is in contact with the release surface with a water contact angle of less than 100 degrees is compared with that before storage after storage based on condition 1. , the initial adhesion was significantly higher. Also, the liner peeling force of the reinforcing film of Example 6 was greatly increased by storage under Condition 1. After storage under Condition 2, the release force of the liner increased significantly, and the ease of removal of the release liner decreased.

(Examples 7-8) In Examples 1 and 6, a polyimide resin film manufactured by Mitsubishi Gas Chemical Co., Ltd. (thickness 50 μm, trade name "Neopulim S-100"; hereinafter also referred to as support substrate B) was used instead Support Substrate A. Regarding other aspects, the reinforcing films with release liners of Examples 7 and 8 were obtained in the same manner as in Examples 1 and 6, respectively.

The same evaluation as Examples 1-6 was performed about the reinforcement film with a release liner of Examples 7 and 8. The results are shown in Table 2.

[Table 2]

As shown in Table 2, in Example 7 using the release liner R1, even after storage under conditions 1 and 2, the release force of the liner was low, and the initial low adhesiveness and the strong adhesiveness during use were well exhibited. On the other hand, in Example 8 using the release liner R6, the initial adhesive force and liner peeling force tended to increase due to storage. Thus, also in the structure using the support base material B, the same tendency as the structure using the support base material A was confirmed.

(Examples 9-12) In Examples 7 and 8, a polyimide resin film manufactured by Kaneka Co., Ltd. (thickness: 50 μm, trade name "Kapton 200H"; hereinafter also referred to as support substrate C) was used instead of support substrate B . Regarding other aspects, the reinforcing films with release liners of Examples 9 and 10 were obtained in the same manner as in Examples 7 and 8, respectively.

(Examples 11-12) In Examples 7 and 8, a polyimide resin film manufactured by Ube Industries (thickness 50 μm, trade name "Upilex 50S"; hereinafter also referred to as support substrate D) was used instead of the support base Material B. Regarding other points, the reinforcing films with release liners of Examples 11 and 12 were obtained in the same manner as in Examples 7 and 8, respectively.

Regarding the reinforcing film with a release liner of Examples 9 to 12, changes in release performance due to storage were evaluated in the same manner as in Examples 1 to 6. The results are shown in Table 3.

[table 3]

As shown in Table 3, the same tendency as that of the configuration using the supporting base material B was also confirmed in the configurations using the supporting base materials C and D. That is, in Examples 9 and 11 using the release liner R1, the stability of the liner peeling force was excellent compared with Examples 10 and 12 using the release liner R6.

As mentioned above, although the specific example of this invention was demonstrated in detail, these are only illustrations, and do not limit the scope of claims. The technologies described in the claims include various modifications and changes of the specific examples exemplified above.

1‧‧‧Reinforcing film 2‧‧‧Reinforcing film 10‧‧‧Supporting substrate 10A‧‧‧First surface 10B‧‧‧Second surface 21‧‧‧Adhesive layer (first adhesive layer) 21A‧‧ ‧First side (adhesive surface, first adhesive surface) 21B ‧‧‧Release liner 31A‧‧‧Releasable surface (release surface) 31B‧‧‧Releasable surface 32‧‧‧Release liner 32A‧‧‧Releasable surface (release surface) 100‧‧‧with release liner Reinforcement film 200‧‧‧Reinforcement film with release liner

Fig. 1 is a cross-sectional view schematically showing the configuration of a reinforcing film according to an embodiment. Fig. 2 is a cross-sectional view schematically showing the configuration of a reinforcing film according to another embodiment.

1‧‧‧Reinforcing film

10‧‧‧Support substrate

10A‧‧‧first side

10B‧‧‧Second side

21‧‧‧adhesive layer (first adhesive layer)

21A‧‧‧first side (adhesive surface, first adhesive surface)

21B‧‧‧Second side (back)

31‧‧‧Release liner

31A‧‧‧Releasable Surface (Releasable Surface)

100‧‧‧Reinforcing film with release liner

Claims (8)

A reinforcing film, comprising: a supporting substrate having a first surface and a second surface; and an adhesive layer laminated on the first surface of the supporting substrate; the supporting substrate includes a resin film as a base film; The second surface of the above-mentioned adhesive layer is fixed on the above-mentioned first surface of the above-mentioned support substrate; the first surface of the above-mentioned adhesive layer is in contact with the peelable surface; the water contact angle of the above-mentioned peelable surface is 100 degrees or more; the above-mentioned The adhesive layer contains a polymer A having a glass transition temperature of less than 0°C, and a polymer B which is a copolymer of a monomer having a polyorganosiloxane skeleton and a (meth)acrylic monomer; and the above adhesive The above-mentioned first surface of the layer is pasted on the stainless steel plate, and the adhesive force N2 after heating at 80°C for 5 minutes and then standing at 23°C for 30 minutes is the adhesive force N2 after the above-mentioned first surface of the above-mentioned adhesive layer is pasted on the stainless steel plate. The adhesive force after being placed at 23°C for 30 minutes is more than 10 times that of N1. The reinforcing film according to claim 1, wherein the peelable surface is the surface of a peeling layer containing silicon (Si). The reinforced film according to claim 1, wherein the peelable surface is the surface of a peeling layer formed by a long-chain alkyl-based peeling treatment agent. The reinforced film according to any one of claims 1 to 3, wherein the thickness of the above-mentioned support substrate is 30 μm or more. The reinforced film according to any one of claims 1 to 3, wherein the thickness of the above-mentioned supporting substrate is 1.1 times or more and 10 times or less of the thickness of the above-mentioned adhesive layer. The reinforced film according to any one of claims 1 to 3, wherein the polymer B has a weight average molecular weight of 10,000 to 50,000. The reinforced film according to any one of claims 1 to 3, wherein the content of the polymer B in the adhesive layer is 0.05 parts by weight to 20 parts by weight relative to 100 parts by weight of the polymer A. The reinforcing film according to any one of claims 1 to 3, wherein the above-mentioned releasable surface is a surface of a release liner.

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