JP2019108499A - Adhesive for repeatedly bending device, adhesive sheet, repeatedly bending laminate member, and repeatedly bending device - Google Patents

Abstract

To provide an adhesive for repeatedly bending device and an adhesive sheet, when being applied to a repeatedly bending device and being repeatedly bent and being in a long-term bent state, releasing the bent state, suppressing deformation of an adhesive layer, and being able to alleviate an influence of the repeated bending and the bent state of the repeating bending device.SOLUTION: There is provided an adhesive for repeatedly bending device in which a relaxation elastic modulus variation ΔlogG(t) is 0.85 or less, which is calculated from a maximum relaxation elastic modulus G(t)max (MPa) measured according to JIS K 7244-1 when the adhesive is distorted by 10% and a minimum relaxation elastic modulus G(t)(MPa) measured while the adhesive is continuously distorted by 10% after 3,757 seconds from the measurement and from Expression (I): ΔlogG(t)=logG(t)-logG(t).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet for a device that is repeatedly bent, and a repeated bending laminate member and a repeated bending device.

  In recent years, a bendable display has been proposed as a display of an electronic device, which is a type of device. Such flexible displays are expected to find a wide range of uses, for example, for stationary displays that are curved and installed on cylindrical columns, or for mobile displays that can be folded, folded, rolled, and carried.

  Examples of the flexible display include an organic electroluminescent (organic EL) display, an electrophoretic display (electronic paper), and a liquid crystal display using a plastic film as a substrate.

  In the flexible display as described above, it is general to bond one bendable member (flexible member) constituting the flexible display with another flexible member by the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet. It is considered to be Here, as an adhesive sheet for the conventional display which can not be bent, what is shown by patent documents 1 and 2 is known, for example.

  The flexible display may be repeatedly bent (folded) as described in Patent Document 3, instead of being curved on one time. Moreover, in such a repeatedly bendable display, it may be fixed in a bent state for a long time. When a conventional pressure-sensitive adhesive sheet is used for a repetitively flexible display for such a purpose, deformation of the pressure-sensitive adhesive layer occurs even after release from the bent state, and the flexible display remains largely bent and solidifies in the bent state I had a problem.

JP, 2015-174907, A JP, 2016-774, A JP, 2016-2764, A

  The present invention has been made in view of the above-described circumstances, and is applied to a bending device repeatedly, and when it is repeatedly bent and placed in a bent state for a long time, adhesion is released after releasing from the bent state. Adhesive and pressure-sensitive adhesive sheet for repetitive bending devices capable of suppressing the deformation of the agent layer and reducing the influence of repeated bending devices and the effects of being placed in the bending state, and the case and length of the repetitive bending It is an object of the present invention to provide a repeated bending laminate member and a repeated bending device capable of alleviating the influence of repeated bending and the effect of being placed in a bending state after being released from the bending state when placed in a bending state for a period of time. To aim.

In order to achieve the above object, first, the present invention is an adhesive for a repetitive bending device for bonding one flexible member and another flexible member constituting a device to be repeatedly bent, The maximum relaxation elastic modulus value measured when 10% of the pressure-sensitive adhesive is distorted in accordance with JIS K7244-1 is the maximum relaxation elastic modulus G (t) max (MPa), and the maximum relaxation elastic modulus Continue to distort the adhesive by 10% until 3757 seconds after the rate G (t) max is measured, and the minimum relaxation elastic modulus value measured during that time is the minimum relaxation elastic modulus G (t) _min (MPa) And a relaxation elastic modulus fluctuation value Δlog G (t) calculated from the following formula (I) is 0.85 or less, to provide a pressure-sensitive adhesive for a repetitive bending device (Invention 1).
Δlog G (t) = log G (t) _max −log G (t) _min (I)

  In the above invention (Invention 1), the pressure-sensitive adhesive layer is released after being released from the bent state when the material is repeatedly applied to the bending device to be repeatedly bent and when it is placed in the bent state for a long time by satisfying the above physical properties. It is difficult for the deformation of the bending device to occur and the solidification of the bending device in the large bending state is suppressed, thereby alleviating the influence of the repeated bending of the bending device and the influence of being placed in the bending state.

  In the said invention (invention 1), it is preferable that the storage elastic modulus (G ') in 25 degreeC is 0.01 or more and 0.25 MPa or less (invention 2).

  In the above inventions (Inventions 1 and 2), the loss elastic modulus (G ′ ′) at 25 ° C. is preferably 0.005 MPa or more and 0.10 MPa or less (Invention 3).

  In the above inventions (Inventions 1 to 3), the pressure-sensitive adhesive is a pressure-sensitive adhesive formed by crosslinking a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester polymer (A) and a crosslinking agent (B). It is preferable that there exist (invention 4).

  Secondly, the present invention is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer for bonding one flexible member and another flexible member constituting a device to be repeatedly bent, wherein the pressure-sensitive adhesive layer is The pressure-sensitive adhesive sheet is characterized in that the pressure-sensitive adhesive for the repeated bending device (inventions 1 to 4) is provided (invention 5).

  In the said invention (invention 5), the said adhesive sheet is equipped with two peeling sheets, and the said adhesive layer is clamped by the said peeling sheet so that the peeling surface of the said two peeling sheets may be contacted. Is preferred (invention 6).

  Third, according to the present invention, an adhesive layer which bonds one flexible member and another flexible member constituting the device to be repeatedly bent, and the one flexible member and the other flexible member to each other. And the pressure-sensitive adhesive layer is the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (Inventions 5 and 6) (Invention 7).

  In the said invention (invention 7), it is preferable that at least one of the said one flexible member and said other flexible member is a display element (invention 8).

  Fourthly, the present invention provides a repeated bending device (invention 9) comprising the above-mentioned repeated bending laminated members (inventions 7 and 8).

  The pressure-sensitive adhesive and pressure-sensitive adhesive sheet for repetitive bending devices according to the present invention is a pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer after being released from the bending state when it is repeatedly applied to the bending device to be repeatedly bent and placed in a long-time bending state. The deformation is unlikely to occur, and the effects of repeated bending of the repeated bending device and the effects of being placed in a bent state can be mitigated. In addition, the repeated bending laminate member and the repeating bending device according to the present invention are subjected to repeated bending and placed in the bending state after being released from the bending state when repeatedly bent and placed in the long-time bending state. Can reduce the impact of

It is sectional drawing of the adhesive sheet which concerns on one Embodiment of this invention. It is sectional drawing of the repetition bending laminated member which concerns on one Embodiment of this invention. It is explanatory drawing (side view) explaining a static bending | flexion test. It is explanatory drawing (side view) explaining the deformation amount of the test piece as a test result of a bending | flexion test. It is explanatory drawing (side view) explaining a dynamic bending | flexion test.

Hereinafter, embodiments of the present invention will be described.
[Pressure-sensitive adhesive for repeated bending devices]
The pressure-sensitive adhesive for repetitive bending device according to the present embodiment (hereinafter sometimes simply referred to as “pressure-sensitive adhesive”) is used to bond one flexible member and another flexible member constituting the repetitive bending device. Is an adhesive. The repetitive bending device and the flexible member will be described later.

The pressure-sensitive adhesive according to this embodiment is the maximum relaxation elastic modulus value G (t) max (maximum relaxation elastic modulus value measured when the pressure-sensitive adhesive is distorted by 10% in accordance with JIS K7244-1). The pressure-sensitive adhesive is continuously deformed by 10% until 3757 seconds after the maximum relaxation elastic modulus G (t) max is measured, and the minimum relaxation elastic modulus value measured during that time is the minimum relaxation elastic modulus. Assuming that G (t) _min (MPa), the relaxation elastic modulus fluctuation value Δlog G (t) calculated from the following formula (I) is 0.85 or less.
Δlog G (t) = log G (t) _max −log G (t) _min (I)
In addition, the detail of the measuring method of relaxation elastic modulus G (t) is as showing to the test example mentioned later.

  In the pressure-sensitive adhesive according to the present embodiment, since the relaxation elastic modulus fluctuation value is small as described above, the property close to a perfect elastic body is increased, and the stress fluctuation when distorted by a predetermined amount is small, that is, originally It is easy to hold the power to return. Therefore, when unloading, deformation is easy to return. Therefore, the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive adheres even after being released from the bending state when the repetitive bending device to which the pressure-sensitive adhesive layer is applied is repeatedly bent and placed in a bent state for a long time It is difficult for deformation of the agent layer to occur, and the repeated bending device is prevented from solidifying in a largely bent state, so that the influence of the repeated bending of the repeated bending device and the influence of being placed in the bent state can be alleviated. Hereinafter, this effect may be referred to as “a bending state relaxation effect of the repeated bending device”. In addition, as an index of the number of times of the above-mentioned repetitive bending, 30,000 times are illustrated as an example.

  From the viewpoint of the bending state relaxation effect of the repeated bending device, the relaxation elastic modulus fluctuation value Δlog G (t) needs to be 0.85 or less, preferably 0.82 or less, and particularly preferably 0.75 or less Is preferably, and further preferably 0.50 or less. The lower limit value of the relaxation elastic modulus fluctuation value is not particularly limited, but usually, it is preferably 0.10 or more, and particularly preferably 0.15 or more.

The maximum relaxation elastic modulus G (t) _max of the pressure-sensitive adhesive according to this embodiment is preferably 1.0 MPa or less, particularly preferably 0.95 MPa or less, and further preferably 0.9 MPa or less as an upper limit value. Is preferred. When the upper limit value of the maximum relaxation elastic modulus G (t) _max is as described above, the relaxation elastic modulus fluctuation value Δlog G (t) can easily satisfy the value described above. The lower limit value of the maximum relaxation elastic modulus G (t) _max is not particularly limited, but is usually preferably 0.05 MPa or more, particularly preferably 0.10 MPa or more, and further preferably 0.15 MPa or more Is preferred.

In addition, the minimum relaxation elastic modulus G (t) _min of the pressure-sensitive adhesive according to the present embodiment is preferably 0.005 MPa or more, particularly preferably 0.01 MPa or more, as a lower limit, and more preferably 0. It is preferable that it is 02 Mpa or more. When the lower limit value of the minimum relaxation elastic modulus G (t) _min is as described above, the relaxation elastic modulus fluctuation value Δlog G (t) can easily satisfy the value described above. The upper limit value of the minimum relaxation elastic modulus G (t) _min is not particularly limited, but generally, it is preferably 0.50 MPa or less, particularly preferably 0.45 MPa or less, and further preferably 0.40 MPa or less Is preferred.

  The type of pressure-sensitive adhesive according to the present embodiment is not particularly limited as long as the above-described physical properties are satisfied, and, for example, acrylic pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, polyurethane-based pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives It may be either. Further, the pressure-sensitive adhesive may be any of an emulsion type, a solvent type or a non-solvent type, and may be any of a crosslinking type or a non-crosslinking type. Among them, acrylic pressure-sensitive adhesives which are easy to satisfy the above-mentioned physical properties and are excellent in adhesion physical properties, optical properties and the like are preferable.

  The acrylic pressure-sensitive adhesive may be an active energy ray curable one, an active energy ray non-curable one, or a heat crosslinkable one. It may be non-crosslinkable or a combination thereof, but in order to obtain good flexibility, it is preferable to be non-curable with active energy rays. As the acrylic pressure-sensitive adhesive which is not curable with active energy rays, in particular, a crosslinking type adhesive is preferable, and a thermal crosslinking type adhesive is more preferable.

  The pressure-sensitive adhesive according to the present embodiment may be particularly referred to as a pressure-sensitive adhesive composition (hereinafter referred to as “pressure-sensitive composition P”) containing (meth) acrylic acid ester polymer (A) and a crosslinking agent (B) It is preferable that it is an adhesive formed by bridge | crosslinking. With such a pressure-sensitive adhesive, the above-mentioned physical properties can be easily satisfied, and good adhesion and predetermined cohesion can be obtained, so that the durability is also excellent. In the present specification, (meth) acrylic acid means both acrylic acid and methacrylic acid. Other similar terms are also the same. The term "polymer" also includes the concept of "copolymer".

(1) Component (-1) of adhesive composition P (meth) acrylic acid ester polymer (A)
The (meth) acrylic acid ester polymer (A) is a (meth) acrylic acid alkyl ester as a monomer unit constituting the polymer, and a monomer having a reactive functional group in the molecule (reactive functional group-containing monomer) It is preferable to contain and.

  The (meth) acrylic acid ester polymer (A) can express preferable adhesiveness by containing (meth) acrylic acid alkyl ester as a monomer unit which comprises the said polymer. The (meth) acrylic acid alkyl ester is preferably a (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group. The alkyl group may be linear or branched, or may have a cyclic structure.

  As the (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group, one having a glass transition temperature (Tg) as a homopolymer of -40 ° C. or lower (hereinafter sometimes referred to as "low Tg alkyl acrylate" Is preferably contained. By containing such a low Tg alkyl acrylate as a constituent monomer unit, the flexibility of the resulting adhesive can be improved.

  As low Tg alkyl acrylate, for example, n-butyl acrylate (Tg-55 ° C), n-octyl acrylate (Tg-65 ° C), isooctyl acrylate (Tg-58 ° C), 2-ethylhexyl acrylate (Tg) -70 ° C), isononyl acrylate (Tg-58 ° C), isodecyl acrylate (Tg-60 ° C), isodecyl methacrylate (Tg-41 ° C), n-lauryl methacrylate (Tg-65 ° C), tridecyl acrylate Preferred examples include (Tg-55 ° C.) and tridecyl methacrylate (Tg-40 ° C.). Among them, from the viewpoint of more effectively improving the flexibility, it is more preferable that the Tg of the homopolymer is −45 ° C. or less as the low Tg alkyl acrylate, and is −50 ° C. or less Is particularly preferred. Specifically, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred. These may be used alone or in combination of two or more.

  The (meth) acrylic acid ester polymer (A) preferably contains, as a lower limit, 50% by mass or more, particularly 55% by mass or more, of a low Tg alkyl acrylate as a monomer unit constituting the polymer. It is more preferable to contain 60 mass% or more. By containing 50% by mass or more of the low Tg alkyl acrylate, the glass transition temperature (Tg) of the (meth) acrylic acid ester polymer (A) can be easily set in the above-described range.

  On the other hand, the (meth) acrylic acid ester polymer (A) preferably contains the above-mentioned low Tg alkyl acrylate as a monomer unit constituting the polymer in an upper limit of 99.9% by mass, particularly 99% by mass It is preferable to contain below, and also it is preferable to contain 98 mass% or less. Introducing a suitable amount of another monomer component (in particular, a reactive functional group-containing monomer) into the (meth) acrylic acid ester polymer (A) by containing 99.9% by mass or less of the low Tg alkyl acrylate Can.

  Moreover, the case where the glass transition temperature (Tg) as a homopolymer exceeds 0 degreeC as a (meth) acrylic-acid alkylester whose carbon number of the said alkyl group is 1-20 is a case called the following "high Tg alkyl acrylate" May be included. By containing such a high Tg alkyl acrylate as a constituent monomer unit, the relaxation elastic modulus fluctuation value of the obtained adhesive may easily satisfy the value described above.

  When the (meth) acrylic acid ester polymer (A) contains a high Tg alkyl acrylate as a monomer unit constituting the polymer, its content is preferably 5% by mass or more, particularly 10% by mass The above content is preferably, and more preferably 15% by mass or more. In addition, the content is preferably 30% by mass or less, particularly preferably 25% by mass or less, and further preferably 20% by mass or less.

  Examples of the high Tg alkyl acrylate include methyl acrylate (Tg 10 ° C.), methyl methacrylate (Tg 105 ° C.), ethyl methacrylate (Tg 65 ° C.), n-butyl methacrylate (Tg 20 ° C.), isobutyl methacrylate (Tg 48 ° C. ), T-butyl methacrylate (Tg 107 ° C), n-stearyl acrylate (Tg 30 ° C), n-stearyl methacrylate (Tg 38 ° C), cyclohexyl acrylate (Tg 15 ° C), cyclohexyl methacrylate (Tg 66 ° C), methacrylic acid Benzyl (Tg 54 ° C.), isobornyl acrylate (Tg 94 ° C.), isobornyl methacrylate (Tg 180 ° C.), adamantyl acrylate (Tg 115 ° C.), adamantyl methacrylate (Tg 141 ° C.), morpholine acrylate (Tg 145 ° C.), etc. And the like. Among the above, methyl acrylate, methyl methacrylate and isobornyl acrylate are preferable from the viewpoint of cohesion. These may be used alone or in combination of two or more.

  The (meth) acrylic acid ester polymer (A) contains a reactive functional group-containing monomer as a monomer unit constituting the polymer, so that the reactive functional group derived from the reactive functional group-containing monomer is They react with a crosslinking agent (B) described later, whereby a crosslinked structure (three-dimensional network structure) is formed, and a pressure-sensitive adhesive having a desired cohesive strength can be obtained.

  As a reactive functional group-containing monomer which the (meth) acrylic acid ester polymer (A) contains as a monomer unit constituting the polymer, a monomer having a hydroxyl group in the molecule (hydroxyl group-containing monomer), carboxy in the molecule Preferred are monomers having a group (carboxy group-containing monomers) and monomers having an amino group in the molecule (amino group-containing monomers). One of these reactive functional group-containing monomers may be used alone, or two or more thereof may be used in combination.

  Among the above reactive functional group-containing monomers, hydroxyl group-containing monomers and carboxy group-containing monomers are preferable, and in particular, hydroxyl group-containing monomers are preferable. Since the hydroxyl group-containing monomer has a relatively low glass transition temperature (Tg) as a homopolymer, the flexibility of the resulting (meth) acrylic acid ester polymer (A) can be easily maintained at a high level, and the carboxyl group-containing monomer can be obtained The adhesion of the (meth) acrylic acid ester polymer (A) can be increased.

  Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth And (iii) hydroxyalkyl esters of (meth) acrylic acid such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate. Among them, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferable from the viewpoint of the flexibility of the (meth) acrylate polymer (A) to be obtained. These may be used alone or in combination of two or more.

  Examples of carboxy group-containing monomers include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid and the like. Among them, acrylic acid is preferable from the viewpoint of the adhesion of the (meth) acrylic acid ester polymer (A) to be obtained. These may be used alone or in combination of two or more.

  When the (meth) acrylate polymer (A) contains a hydroxyl group-containing monomer as a monomer unit constituting the polymer, the content of the hydroxyl group-containing monomer is preferably 0.1% by mass or more. And particularly preferably 0.3% by mass or more. The content of the hydroxyl group-containing monomer is preferably 30% by mass or less, and particularly preferably 25% by mass or less. On the other hand, when the (meth) acrylic acid ester polymer (A) contains a carboxy group-containing monomer as a monomer unit constituting the polymer, the content of the carboxy group-containing monomer is 0.5% by mass or more. The content is preferably 1% by mass or more. In addition, the content of the carboxy group-containing monomer is preferably 10% by mass or less, particularly preferably 7% by mass or less, and further preferably 5% by mass or less. The content of the hydroxyl group-containing monomer and the carboxyl group-containing monomer is respectively as described above, whereby the flexibility and adhesiveness of the (meth) acrylic acid ester polymer (A) obtained become better, and the pressure-sensitive adhesive layer obtained The flexed state relaxation effect of the repeated flexing device is achieved at a higher level.

  The (meth) acrylic acid ester polymer (A) may contain a nitrogen atom-containing monomer as a monomer unit constituting the polymer. As a nitrogen atom containing monomer, the monomer which has an amino group, the monomer which has an amide group, the monomer which has a nitrogen containing heterocyclic ring etc. are mentioned, The monomer which has a nitrogen containing heterocyclic ring is especially preferable.

  As a monomer having a nitrogen-containing heterocycle, for example, N- (meth) acryloyl morpholine, N-vinyl-2-pyrrolidone, N- (meth) acryloyl pyrrolidone, N- (meth) acryloyl piperidine, N- (meth) acryloyl Pyrrolidine, N- (meth) acryloyl aziridine, aziridinyl ethyl (meth) acrylate, 2-vinylpyridine, 4-vinylpyridine, 2-vinylpyrazine, 1-vinylimidazole, N-vinylcarbazole, N-vinylphthalimide, etc. Among them, N- (meth) acryloyl morpholine which exerts more excellent adhesive strength is preferable, and N-acryloyl morpholine is particularly preferable. These may be used alone or in combination of two or more.

  When the (meth) acrylic acid ester polymer (A) contains a nitrogen atom-containing monomer as a monomer unit constituting the polymer, the content of the nitrogen atom-containing monomer is preferably 1% by mass or more And particularly preferably 3% by mass or more. In addition, the content of the nitrogen atom-containing monomer is preferably 20% by mass or less, particularly preferably 15% by mass or less, and further preferably 10% by mass or less.

  The (meth) acrylic acid ester polymer (A) may optionally contain other monomers as monomer units constituting the polymer. As the other monomers, monomers which do not contain a reactive functional group are preferable in order not to inhibit the above-mentioned effects of the reactive functional group-containing monomer. Examples of such a monomer include (meth) acrylic acid alkoxyalkyl esters such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylic acid, vinyl acetate and styrene. These may be used alone or in combination of two or more.

  The polymerization mode of the (meth) acrylic acid ester polymer (A) may be a random copolymer or a block copolymer.

  The lower limit value of the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is preferably 100,000 or more, particularly preferably 300,000 or more, and further preferably 500,000 or more. When the lower limit value of the weight average molecular weight of the (meth) acrylate polymer (A) is above, the durability of the pressure-sensitive adhesive becomes more excellent. In addition, the weight average molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.

  The upper limit value of the weight average molecular weight of the (meth) acrylic acid ester polymer (A) is preferably 1.5 million or less, particularly preferably 1.2 million or less, and further preferably 1 million or less. preferable. The softness | flexibility of the adhesive obtained as the upper limit of the weight average molecular weight of a (meth) acrylic acid ester polymer (A) is the above becomes more excellent.

  In the adhesive composition P, as the (meth) acrylic acid ester polymer (A), one type may be used alone, or two or more types may be used in combination.

(1-2) Crosslinking agent (B)
The crosslinking agent (B) crosslinks the (meth) acrylic acid ester polymer (A) with the heating of the adhesive composition P containing the crosslinking agent (B) as a trigger to form a three-dimensional network structure . Thereby, the cohesion of the obtained adhesive improves, and the adhesive layer becomes excellent in durability.

  As the crosslinking agent (B), any crosslinking agent may be used as long as it reacts with the reactive group possessed by the (meth) acrylic acid ester polymer (A). For example, an isocyanate crosslinking agent, an epoxy crosslinking agent, an amine crosslinking agent Melamine based crosslinking agent, Aziridine based crosslinking agent, Hydrazine based crosslinking agent, Aldehyde based crosslinking agent, Alkaline based crosslinking agent, Metal alkoxide based crosslinking agent, Metal chelate based crosslinking agent, Metal salt based crosslinking agent, Ammonium salt based crosslinking agent, etc. Can be mentioned. Among the above, it is preferable to use an isocyanate-based crosslinking agent excellent in the reactivity with the reactive functional group-containing monomer, particularly the hydroxyl group-containing monomer. In addition, a crosslinking agent (B) can be used individually by 1 type or in combination of 2 or more types.

  The isocyanate crosslinking agent contains at least a polyisocyanate compound. Examples of polyisocyanate compounds include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. And biuret bodies thereof, isocyanurate bodies, and adducts which are reaction products with low molecular weight active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil and the like. Among them, from the viewpoint of reactivity with a hydroxyl group, trimethylolpropane-modified aromatic polyisocyanates, particularly trimethylolpropane-modified tolylene diisocyanate and trimethylolpropane-modified xylylene diisocyanate are preferable.

  The content of the crosslinking agent (B) in the adhesive composition P is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A), particularly preferably 0. The content is preferably 5 parts by mass or more, and more preferably 1.0 parts by mass or more. Further, the content is preferably 10 parts by mass or less, particularly preferably 8 parts by mass or less, and further preferably 5 parts by mass or less. When the content of the crosslinking agent (B) is in the above range, the cohesion of the obtained adhesive becomes appropriate, and the bending state alleviating effect of the repeated bending device of the obtained adhesive layer is achieved at a high level Ru.

(1-3) Various Additives In the adhesive composition P, various additives generally used in acrylic pressure-sensitive adhesives, for example, silane coupling agents, ultraviolet absorbers, antistatic agents, and tackifiers, as desired. Additives, antioxidants, light stabilizers, softeners, fillers, refractive index modifiers and the like can be added. In addition, the below-mentioned polymerization solvent and dilution solvent shall not be contained in the additive which comprises the adhesive composition P.

(2) Production of Adhesive Composition P The adhesive composition P produces a (meth) acrylic acid ester polymer (A), and the obtained (meth) acrylic acid ester polymer (A) and a crosslinking agent It can be produced by mixing with (B) and optionally adding an additive.

  The (meth) acrylic acid ester polymer (A) can be produced by polymerizing a mixture of monomers constituting the polymer by a conventional radical polymerization method. The polymerization of the (meth) acrylic acid ester polymer (A) is preferably carried out by a solution polymerization method using a polymerization initiator, if desired. As a polymerization solvent, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, acetone, hexane, methyl ethyl ketone etc. are mentioned, for example, You may use 2 or more types together.

  As a polymerization initiator, an azo compound, an organic peroxide, etc. are mentioned, You may use 2 or more types together. As an azo compound, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methyl propionate) 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2- (2-imidazolin-2-yl) Propane] and the like.

  As the organic peroxide, for example, benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxy dicarbonate, di-n-propyl peroxy dicarbonate, di (2-ethoxyethyl) peroxy Dicarbonate, t-butyl peroxy neodecanoate, t-butyl peroxy bivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like can be mentioned.

  In addition, in the said superposition | polymerization process, the weight average molecular weight of the polymer obtained can be adjusted by mix | blending chain transfer agents, such as 2-mercapto ethanol.

  When the (meth) acrylic acid ester polymer (A) is obtained, the crosslinking agent (B) and optionally additives and dilution solvents are added to the solution of the (meth) acrylic acid ester polymer (A), and sufficient The mixture is mixed with the solvent to obtain a tacky composition P (coating solution) diluted with a solvent.

  In addition, when using a solid thing in any of said each component, or producing precipitation when it mixes with other components in the undiluted state, the component is independently made into the dilution solvent beforehand. It may be dissolved or diluted and then mixed with other components.

  Examples of the dilution solvent include aliphatic hydrocarbons such as hexane, heptane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol, butanol, Alcohols such as 1-methoxy-2-propanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone, esters such as ethyl acetate and butyl acetate, and cellosolve solvents such as ethyl cellosolve are used.

  The concentration / viscosity of the coating solution prepared in this manner is not particularly limited as long as it can be coated, and can be appropriately selected depending on the situation. For example, it dilutes so that the density | concentration of the adhesive composition P may be 10-60 mass%. In addition, when obtaining a coating solution, addition of a dilution solvent etc. is not a necessary condition, and if viscosity etc. which the adhesive composition P can coat, it is not necessary to add a dilution solvent. In this case, the adhesive composition P is a coating solution in which the polymerization solvent of the (meth) acrylic acid ester polymer (A) is used as a dilution solvent as it is.

(3) Production of Pressure-Sensitive Adhesive The pressure-sensitive adhesive according to this embodiment is preferably formed by crosslinking the pressure-sensitive adhesive composition P. Crosslinking of the adhesive composition P can usually be carried out by heat treatment. In addition, this heat processing can also serve as the drying processing at the time of volatilizing a dilution solvent etc. from the coating film of adhesive composition P apply | coated to the desired target object.

  It is preferable that the heating temperature of heat processing is 50-150 degreeC, and it is preferable that it is especially 70-120 degreeC. The heating time is preferably 10 seconds to 10 minutes, and more preferably 50 seconds to 2 minutes.

  After the heat treatment, if necessary, a curing period of about 1 to 2 weeks may be provided at normal temperature (for example, 23 ° C., 50% RH). When this curing period is necessary, after the curing period, when the curing period is unnecessary, an adhesive is formed after the heat treatment is completed.

  By the above heat treatment (and curing), the (meth) acrylic acid ester polymer (A) is sufficiently crosslinked via the crosslinking agent (B) to form a crosslinked structure, whereby a pressure-sensitive adhesive is obtained. Such a pressure-sensitive adhesive has a predetermined cohesion.

(4) Physical Properties of Adhesive The storage elastic modulus (G ′) at 25 ° C. of the adhesive according to this embodiment is preferably 0.01 MPa or more as a lower limit value. The upper limit of the storage elastic modulus (G ′) is preferably 0.25 MPa or less, and particularly preferably 0.20 MPa or less.

  In addition, the loss elastic modulus (G ′ ′) at 25 ° C. of the pressure-sensitive adhesive according to the present embodiment is preferably 0.005 MPa or more as a lower limit, and particularly preferably 0.01 MPa or more. The upper limit value of the loss elastic modulus (G ′ ′) is preferably 0.1 MPa or less, and particularly preferably 0.08 MPa or less.

  Furthermore, the loss tangent (tan δ) at 25 ° C. of the pressure-sensitive adhesive according to the present embodiment is preferably 0.25 or more, particularly preferably 0.28 or more, as the lower limit value. The upper limit of the loss tangent (tan δ) is preferably 0.85 or less, and particularly preferably 0.80 or less.

  When the storage elastic modulus (G ′), loss elastic modulus (G ′ ′) and loss tangent (tan δ) of the pressure-sensitive adhesive according to this embodiment are respectively in the above ranges, the adhesive force to the flexible member becomes good, The durability of the repeated bending device is improved The methods of measuring the storage elastic modulus (G ′), loss elastic modulus (G ′ ′) and loss tangent (tan δ) are as described in the test examples described later.

[Adhesive sheet]
The pressure-sensitive adhesive sheet according to the present embodiment has a pressure-sensitive adhesive layer for bonding one bending member constituting another bending device to another bending member, and the pressure-sensitive adhesive layer is the pressure-sensitive adhesive described above. It consists of

The specific structure as an example of the adhesive sheet which concerns on this embodiment is shown in FIG.
As shown in FIG. 1, the pressure-sensitive adhesive sheet 1 according to one embodiment includes the two release sheets 12 a and 12 b and the two release sheets 12 a and 12 b so as to be in contact with the release surfaces of the two release sheets 12 a and 12 b. , 12b, and the adhesive layer 11. In addition, the peeling surface of the peeling sheet in this specification means the surface which has peelability in a peeling sheet, and includes both the surface which performed peeling processing, and the surface which shows peeling even if it does not perform peeling processing. .

(1) Component (1-1) Pressure-Sensitive Adhesive Layer The pressure-sensitive adhesive layer 11 is formed of the pressure-sensitive adhesive according to the embodiment described above, and is preferably formed of the pressure-sensitive adhesive formed by crosslinking the pressure-sensitive adhesive composition P. .

  The thickness (value measured according to JIS K7130) of the pressure-sensitive adhesive layer 11 in the pressure-sensitive adhesive sheet 1 according to the present embodiment is preferably 2 μm or more as a lower limit value, particularly preferably 5 μm or more, and more preferably It is preferable that it is 10 micrometers or more. It is easy to exhibit desired adhesive force as the lower limit of the thickness of the adhesive layer 11 is the above, and it is possible to effectively suppress the occurrence of floating or peeling at the time of repeated bending. The thickness of the pressure-sensitive adhesive layer 11 is preferably 150 μm or less as an upper limit value, more preferably 100 μm or less, particularly preferably 70 μm or less, and further preferably 50 μm or less. When the upper limit value of the thickness of the pressure-sensitive adhesive layer 11 is the above, it is possible to prevent the pressure-sensitive adhesive or the component constituting the pressure-sensitive adhesive from exuding from the pressure-sensitive adhesive layer due to repeated bending. The pressure-sensitive adhesive layer 11 may be formed as a single layer, or may be formed by laminating a plurality of layers.

(1-2) Release Sheet The release sheets 12a and 12b protect the adhesive layer 11 until the adhesive sheet 1 is used, and are peeled off when the adhesive sheet 1 (adhesive layer 11) is used. In the pressure-sensitive adhesive sheet 1 according to the present embodiment, one or both of the release sheets 12a and 12b are not necessarily required.

  As the release sheets 12a and 12b, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene Terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene (meth) acrylic acid copolymer film, ethylene (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluorine A resin film or the like is used. Moreover, these crosslinked films are also used. Furthermore, these laminated films may be sufficient.

  It is preferable that the peeling process is performed to the peeling surface (especially the surface which contact | connects the adhesive layer 11) of said peeling sheet 12a, 12b. Examples of the release agent used for the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based and wax-based release agents. Among the release sheets 12a and 12b, it is preferable that one release sheet be a heavy release type release sheet having a large release force, and the other release sheet be a light release type release sheet having a small release force.

  Although there is no restriction | limiting in particular about the thickness of peeling sheet 12a, 12b, Usually, it is about 20-150 micrometers.

(2) Production of Pressure-Sensitive Adhesive Sheet As one production example of the pressure-sensitive adhesive sheet 1, the case where the above-mentioned pressure-sensitive adhesive composition P is used will be described. A coating solution of the adhesive composition P is applied to the release surface of one release sheet 12a (or 12b), and heat treatment is performed to thermally crosslink the adhesive composition P to form an application layer, and then the application layer is applied. The release surface of the other release sheet 12b (or 12a) is superimposed on the layer. When the curing period is necessary, the application period becomes the pressure-sensitive adhesive layer 11 as it is by setting the curing period, and when the curing period is unnecessary. Thus, the pressure-sensitive adhesive sheet 1 is obtained. The heat treatment and curing conditions are as described above.

  As another manufacturing example of the adhesive sheet 1, the coating liquid of the adhesive composition P is apply | coated to the peeling surface of one peeling sheet 12a, heat processing is performed, the adhesive composition P is thermally crosslinked, and an application layer is carried out. To obtain a release sheet 12a with a coating layer. Moreover, the coating liquid of the said adhesive composition P is apply | coated to the peeling surface of the other peeling sheet 12b, heat processing are performed, the adhesive composition P is thermally crosslinked, an application layer is formed, and an application layer is attached. The release sheet 12b of Then, the release sheet 12a with the application layer and the release sheet 12b with the application layer are pasted together so that the two application layers are in contact with each other. When the curing period is required, the curing period is kept, and when the curing period is unnecessary, the laminated coated layer becomes the pressure-sensitive adhesive layer 11 as it is. Thus, the pressure-sensitive adhesive sheet 1 is obtained. According to this production example, even when the pressure-sensitive adhesive layer 11 is relatively thick, stable production can be achieved.

  As a method of apply | coating the coating liquid of the said adhesive composition P, the bar-coat method, the knife coat method, the roll coat method, the blade coat method, the die coat method, the gravure coat method etc. can be utilized, for example.

[Repeatedly bent laminated member]
As shown in FIG. 2, the repeated bending and laminating member 2 according to this embodiment includes a first bending member 21 (one bending member) and a second bending member 22 (another bending member). And a pressure-sensitive adhesive layer 11 located between them and bonding the first flexible member 21 and the second flexible member 22 to each other.

  The pressure-sensitive adhesive layer 11 in the repeated bending and laminating member 2 is the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1 described above.

  The repeated bending laminate member 2 is a repeated bending device itself or a member constituting a part of the repeated bending device. The repetitive bending device is preferably, but not limited to, a display capable of repetitive bending (including bending). As such a repetitive bending device, for example, an organic electroluminescence (organic EL) display, an electrophoretic display (electronic paper), a flexible printed substrate, a liquid crystal display using a plastic substrate (film) as a substrate, a foldable display, etc. It may be a touch panel.

  The first flexible member 21 and the second flexible member 22 are members that can be repeatedly bent (including bent), and for example, a cover film, a barrier film, a polarizing film, a polarizer, a retardation film, Viewing angle compensation film, brightness enhancement film, contrast enhancement film, diffusion film, semi-transmissive reflective film, electrode film, transparent conductive film, metal mesh film, film sensor, liquid crystal polymer film, light emitting polymer film, film-like liquid crystal module, organic Examples include an EL module (organic EL film), an electronic paper module (film-like electronic paper), and the like.

  Among the above, at least one of the first flexible member 21 and the second flexible member 22 is a display element which can be repeatedly bent, specifically, a liquid crystal polymer film, a light emitting polymer film, a film-like liquid crystal module, an organic It is preferably an EL module (organic EL film) or an electronic paper module (film-like electronic paper).

  The Young's modulus of each of the first flexible member 21 and the second flexible member 22 is preferably 0.1 to 10 GPa, particularly preferably 0.5 to 7 GPa, and further preferably 1.0 to It is preferably 5 GPa. When the Young's modulus of the first flexible member 21 and the second flexible member 22 falls within such a range, it becomes easy to repeatedly bend each flexible member.

  The thickness of each of the first flexible member 21 and the second flexible member 22 is preferably 5 to 3000 μm, more preferably 10 to 1000 μm, and further preferably 10 to 500 μm. . When the thicknesses of the first flexible member 21 and the second flexible member 22 are in such a range, it becomes easy to repeatedly bend each flexible member.

  In order to manufacture the above-mentioned repeated bending layered member 2, as an example, one exfoliation sheet 12a of adhesive sheet 1 is exfoliated, adhesive layer 11 of adhesive sheet 1 is exposed to one side of the 1st flexible member 21. Paste on the face of

  Thereafter, the other release sheet 12b is peeled off from the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1, and the exposed pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1 and the second flexible member 22 are bonded to each other. Get Moreover, you may replace the bonding order of the 1st flexible member 21 and the 2nd flexible member 22 as another example.

[Repetitive bending device]
The repeated bending device according to the present embodiment is provided with the above-mentioned repeated bending laminate member 2, and may be formed only of the repeated bending laminate member 2, or one or more repeated bending laminate members 2 and the other And a flexible member. When laminating one repetitive bending laminate member 2 and another repetitive bending laminate member 2 or laminating the repetitive bending laminate member 2 and another flexible member, the pressure-sensitive adhesive layer 11 of the adhesive sheet 1 described above is used. It is preferable to laminate through.

  In the repetitive bending device according to the present embodiment, since the adhesive layer is made of the above-mentioned adhesive, it is repeatedly bent (for example, 30,000 times) and placed in a bent state for a long time (for example, at least 24 hours or more) In the above, after releasing from the bending state, the repeated bending device is suppressed from being solidified in the largely bent state, and the influence of the repeated bending and the influence of being placed in the bending state are alleviated. The bending state relaxation effect of such a repeated bending device can be evaluated, for example, by the amount of static bending deformation by a static bending test and the amount of dynamic bending deformation by a dynamic bending test.

  In the static bending test, it is a laminate formed by sandwiching an adhesive layer (thickness: 12 μm) between two polyethylene terephthalate films (thickness: 12 μm), which is 200 mm × 50 mm in size Be a piece. As shown in FIG. 3, the test piece S is held for 24 hours in a bent state between holding plates P consisting of two glass plates erected in an environment of 23 ° C. and 50% RH. . At this time, the distance between the two holding plates P is set to 6 mm (bending diameter of the test piece S: 6 mmφ), and the approximate center of the long side (200 mm) of the test piece S becomes a bending portion. Hold the test piece S so that both short sides (50 mm) of S are on the upper side. After the static bending test is performed, the test piece S is taken out from between the two holding plates P, and as shown in FIG. 4, the test piece S is placed on a flat plate so that the convex direction of the bent portion is on the upper side. Place on Then, immediately after the test, 30 minutes after the test, and 24 hours after the test, the height h from the flat plate surface to the top of the bent portion (deformed portion) is measured as a static bending deformation amount. The static bending deformation amount can be used as a test result of the static bending test, and the bending state relaxation effect can be evaluated based on the static bending deformation amount.

  Immediately after the test, the static bending deformation amount by the static bending test is preferably 3 mm or less, particularly preferably 1 mm or less, and further preferably 0.5 mm or less. Moreover, after 30 minutes of a test, it is preferable that it is 1 mm or less, and it is preferable that it is especially 0.5 mm or less. Moreover, it is preferable that it is 0.5 mm or less after test 24 hours, and it is preferable that it is especially 0.3 mm or less. In any static bending deformation amount, the lower limit is preferably 0 mm.

  On the other hand, in the dynamic bending test, it is a laminate formed by sandwiching an adhesive layer (thickness: 12 μm) between two polyethylene terephthalate films (thickness: 12 μm), and having a size of 150 mm × 50 mm As a test piece. As shown in FIG. 5, this test piece S is held between two holding plates P of a surface state no-load U-shaped stretching tester under an environment of 23 ° C. and 50% RH. One of the two holding plates P maintains a parallel relationship with the other holding plate P, and can move back and forth toward and away from the other holding plate P. The distance between the two holding plates P is changed from 86 mm to 6 mm (bending diameter of the test piece S: 6 mm, stroke: 80 mm). The test piece S is fixed to the holding plate P such that a substantially central portion of its long side (150 mm) is a bend and both short sides (50 mm) of the test piece S are positioned on the upper side. In that state, the test piece S is bent 30,000 times at a bending speed (reciprocating movement speed of the holding plate P) of 30 rpm. After this dynamic bending test is performed, the test piece S is taken out from between the two holding plates P, and as shown in FIG. 4, the test piece S is placed on a flat plate so that the convex direction of the bending portion is on the upper side. Place it. Then, immediately after the test and 24 hours after the test, the height h from the flat plate surface to the top of the bent portion (deformed portion) is measured as a dynamic bending deformation amount. This dynamic bending deformation amount can be used as a test result of a dynamic bending test, and the bending state relaxation effect can be evaluated based on the dynamic bending deformation amount.

  Immediately after the test, the dynamic bending deformation amount by the dynamic bending test is preferably 3 mm or less, particularly preferably 1 mm or less, and further preferably 0.5 mm or less. Moreover, after 24 hours of test, it is preferable that it is 1 mm or less, and it is preferable that it is especially 0.5 mm or less. In any dynamic bending deformation amount, the lower limit is preferably 0 mm.

  The embodiments described above are described to facilitate the understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents that fall within the technical scope of the present invention.

  For example, one or both of the release sheets 12a and 12b in the adhesive sheet 1 may be omitted, and a desired flexible member may be laminated instead of the release sheets 12a and / or 12b.

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

Example 1
1. Preparation of (Meth) Acrylate Polymer (A) 47.8 parts by mass of 2-ethylhexyl acrylate, 47.8 parts by mass of n-butyl acrylate, 4 parts by mass of acrylic acid and 2-hydroxypropyl acrylate 0.4 The parts by mass were copolymerized by a solution polymerization method to prepare a (meth) acrylic acid ester polymer (A). When the molecular weight of this (meth) acrylic acid ester polymer (A) was measured by the method mentioned later, it was 600,000 of weight average molecular weight (Mw).

2. Preparation of adhesive composition 100 parts by mass of the (meth) acrylic acid ester polymer (A) obtained in the above step 1 (in terms of solid content; the same shall apply hereinafter) and trimethylolpropane-modified trimer as the crosslinking agent (B) 3.5 parts by mass of diisocyanate (manufactured by Toyo Chem Co., Ltd., product name "BHS 8515"), mixed thoroughly with stirring, and diluted with toluene to obtain a coating solution of the adhesive composition (solid content concentration: 30. 0 mass%) was obtained.

3. Production of Pressure-Sensitive Adhesive Sheet Peeling of a heavy release type release sheet (Lintech Co., Ltd., product name "SP-PET 382150") obtained by release-treating one side of a polyethylene terephthalate film with a coating solution of the obtained adhesive composition using a silicone release agent. The treated surface was coated with a comma coater (registered trademark). Then, the applied layer was heat-treated at 90 ° C. for 1 minute to form an applied layer.

  Next, a light release type release sheet (Lintec Co., Ltd., product name "SP-PET 381031") in which the coated layer on the heavy release type release sheet obtained above and one side of the polyethylene terephthalate film were release treated with a silicone release agent. And the light-peelable release sheet in such a manner that the release-treated side of the light-release type release sheet is in contact with the coating layer, followed by curing for 7 days under conditions of 23 ° C. and 50% RH. A pressure-sensitive adhesive sheet was produced, that is, a pressure-sensitive adhesive sheet having a structure of a heavy release type release sheet / pressure-sensitive adhesive layer (thickness: 12 μm) / light release type release sheet. The thickness of the pressure-sensitive adhesive layer is a value measured according to JIS K7130 using a constant-pressure thickness measuring device (product name “PG-02” manufactured by Techlock Co., Ltd.).

Example 2
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1, except that the amount of the crosslinking agent (B) was changed to 6.56 parts by mass.

[Example 3]
60 parts by mass of 2-ethylhexyl acrylate, 20 parts by mass of methyl methacrylate and 20 parts by mass of 2-hydroxyethyl acrylate were copolymerized by a solution polymerization method to prepare a (meth) acrylate polymer (A). When the molecular weight of this (meth) acrylic acid ester polymer (A) was measured by the method mentioned later, it was 600,000 of weight average molecular weight (Mw).

  100 parts by mass of the (meth) acrylic acid ester polymer (A) obtained above and 1.88 mass of trimethylolpropane modified tolylene diisocyanate as a crosslinking agent (B) (product name "BHS 8515" manufactured by Toyo Chem Co., Ltd.) The resulting solution was mixed with a mixture, sufficiently stirred, and diluted with methyl ethyl ketone (MEK) to obtain a coating solution (solids concentration: 30.0 mass%) of the adhesive composition. A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 using the coating solution of the obtained tacky composition.

Example 4
60 parts by mass of butyl acrylate, 20 parts by mass of methyl acrylate and 20 parts by mass of 2-hydroxyethyl acrylate were copolymerized by a solution polymerization method to prepare a (meth) acrylic acid ester polymer (A). When the molecular weight of this (meth) acrylic acid ester polymer (A) was measured by the method mentioned later, it was 600,000 of weight average molecular weight (Mw).

  100 parts by mass of the (meth) acrylic acid ester polymer (A) obtained above and 1.88 mass of trimethylolpropane modified tolylene diisocyanate as a crosslinking agent (B) (product name "BHS 8515" manufactured by Toyo Chem Co., Ltd.) The resulting solution was mixed with a portion, sufficiently stirred, and diluted with MEK to obtain a coating solution (solids concentration: 30.0 mass%) of a tacky composition. A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 using the coating solution of the obtained tacky composition.

[Example 5]
(Meth) acrylic acid ester copolymerized by solution polymerization using 65 parts by mass of 2-ethylhexyl acrylate, 5 parts by mass of N-acryloyl morpholine, 15 parts by mass of isobonyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate Combine (A) was prepared. When the molecular weight of this (meth) acrylic acid ester polymer (A) was measured by the method mentioned later, it was 500,000 of weight average molecular weight (Mw).

  100 parts by mass of the (meth) acrylic acid ester polymer (A) obtained above and 1.20 mass of trimethylolpropane modified tolylene diisocyanate as a crosslinking agent (B) (product name "BHS 8515" manufactured by Toyo Chem Co., Ltd.) The resulting solution was mixed with a portion, sufficiently stirred, and diluted with MEK to obtain a coating solution (solids concentration: 30.0 mass%) of a tacky composition. A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 using the coating solution of the obtained tacky composition.

[Example 6]
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the (meth) acrylic acid ester polymer (A) prepared in Example 3 was used, and the amount of the crosslinking agent (B) was changed to 0.47 parts by mass. Made.

[Example 7]
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the (meth) acrylic acid ester polymer (A) prepared in Example 3 was used, and the compounding amount of the crosslinking agent (B) was changed to 0.94 parts by mass. Made.

Example 8
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the (meth) acrylic acid ester polymer (A) prepared in Example 4 was used, and the amount of the crosslinking agent (B) was changed to 0.47 parts by mass. Made.

[Example 9]
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the (meth) acrylic acid ester polymer (A) prepared in Example 4 was used, and the compounding amount of the crosslinking agent (B) was changed to 0.94 parts by mass. Made.

[Example 10]
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the (meth) acrylic acid ester polymer (A) prepared in Example 5 was used, and the amount of the crosslinking agent (B) was changed to 0.60 parts by mass. Made.

Comparative Example 1
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the compounding amount of the crosslinking agent (B) was changed to 0.94 parts by mass.

Comparative Example 2
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the (meth) acrylic acid ester polymer (A) prepared in Example 3 was used, and the amount of the crosslinking agent (B) was changed to 0.23 parts by mass. Made.

Comparative Example 3
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the (meth) acrylic acid ester polymer (A) prepared in Example 4 was used, and the amount of the crosslinking agent (B) was changed to 0.23 parts by mass. Made.

Comparative Example 4
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the (meth) acrylic acid ester polymer (A) prepared in Example 5 was used, and the compounding amount of the crosslinking agent (B) was changed to 0.15 parts by mass. Made.

Comparative Example 5
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the (meth) acrylic acid ester polymer (A) prepared in Example 5 was used, and the compounding amount of the crosslinking agent (B) was changed to 0.30 parts by mass. Made.

Comparative Example 6
15 parts by mass of isobutylene-isoprene copolymer (manufactured by Nippon Butyl Co., product name "Butyl 365") and 3 parts by mass of a tackifier (manufactured by Nippon Zeon Co., product name "Quinton A100") are mixed and sufficiently stirred Then, by diluting with toluene, a coating solution (solid content concentration: 15% by mass) of a tacky composition as butyl rubber was obtained. A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the heat treatment temperature was set to 100 ° C., using the coating solution of the obtained adhesive composition.

In Table 1, the composition of the (meth) acrylic acid ester polymer (A) and the blending amount of the crosslinking agent (B) in each example and comparative example (100 mass of (meth) acrylic acid ester polymer (A) Describe parts by mass). The abbreviations in Table 1 are as follows.
2EHA: 2-ethylhexyl acrylate BA: n-butyl acrylate AA: acrylic acid 2 HPA: 2-hydroxypropyl acrylate MMA: methyl methacrylate HEA: 2-hydroxyethyl acrylate MA: methyl acrylate ACMO: N-acryloyl morpholine IBXA: Isobornyl Acrylate

[Test Example 1] (Measurement of Relaxation Modulus)
A plurality of pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheet produced in the example and the comparative example were laminated to form a laminate having a thickness of 0.5 mm. A cylindrical body (0.5 mm in height) having a diameter of 8 mm was punched out of the laminate of the obtained pressure-sensitive adhesive layer and used as a sample.

For the above sample, in accordance with JIS K7244-1, using a visco-elasticity measuring apparatus (manufactured by Anton paar, product name "MCR302"), the adhesive is continuously deformed by 10% under the following conditions, and the relaxation elastic modulus G (T) (MPa) was measured. From the measurement results, the maximum relaxation modulus G (t) _max (MPa) is derived, and the minimum relaxation modulus G measured up to 3757 seconds after the measurement of the maximum relaxation modulus G (t) _max (T) _min (MPa) was derived.
Measurement temperature: 25 ° C
Measurement point: 1000 points (logarithmic plot)

From the obtained maximum relaxation elastic modulus G (t) _max (MPa) and the minimum relaxation elastic modulus G (t) _min (MPa), based on the following formula (I), the relaxation elastic modulus fluctuation value Δlog G (t) Calculated. The results are shown in Table 1.
Δlog G (t) = log G (t) _max −log G (t) _min (I)

[Test Example 2] (Measurement of elastic modulus)
A plurality of pressure-sensitive adhesive layers of the pressure-sensitive adhesive sheet produced in the example and the comparative example were laminated to form a laminate having a thickness of about 0.5 mm. A cylindrical body (0.5 mm in height) having a diameter of 8 mm was punched out of the laminate of the obtained pressure-sensitive adhesive layer and used as a sample.

The dynamic viscoelasticity of the above sample was measured under the following conditions using a viscoelasticity measuring apparatus (product name: "MCR302" manufactured by Anton paar) in accordance with JIS K7244-1, and the storage elastic modulus at 25 ° C. (G ′) (MPa), loss modulus (G ′ ′) (MPa) and loss tangent (tan δ) were observed. The results are shown in Table 1.
Measurement frequency: 1 Hz
Measurement temperature range: -20 to 150 ° C

[Test Example 3] (Static bending test)
The light-peelable release sheet was peeled off from the pressure-sensitive adhesive sheet prepared in Examples and Comparative Examples under an environment of 23 ° C. and 50% RH, and the exposed pressure-sensitive adhesive layer was S10 mirror ", thickness: 12 μm) was bonded to one side. Next, the heavy release type release sheet was peeled off, and the exposed pressure-sensitive adhesive layer was bonded to one surface of another polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name "S10 mirror", thickness: 12 μm). Then, after pressure was applied for 20 minutes at 50 MPa and 0.5 MPa in an autoclave manufactured by Kurihara Seisakusho Co., Ltd., it was left for 24 hours under conditions of 23 ° C. and 50% RH. Thus, the laminated body which consists of a PET film / adhesive layer / PET film obtained was cut | judged to 200 mm x 50 mm, and this was made into the test piece.

The obtained test piece was bent at an environment of 23 ° C. and 50% RH as shown in FIG. 3 between holding plates (distance between each other: 6 mm) consisting of two glass plates erected. It was kept in the state for 24 hours. After performing this static bending test, as shown in FIG. 4, the test piece is placed on a flat plate, and immediately after the test, 30 minutes after the test and 24 hours after the test, the flat portion to the bent portion (deformed portion) The height h to the top was measured as a static bending deformation. Based on the measured static bending deformation amount, static bending was evaluated according to the following criteria. Moreover, in the test piece after a test, it was visually confirmed whether there is any peeling in the interface of an adhesive layer and a to-be-adhered body. The results are shown in Table 1.
:: The amount of deformation immediately after the bending test is 1 mm or less ○: The amount of deformation immediately after the bending test is 1 mm or more and 3 mm or less, the amount of deformation 30 minutes after the test is 1 mm or less Δ: The amount of deformation immediately after the bending test is 3 mm or more and 6 mm or less The deformation after 30 minutes of test is 5 mm or less, and the deformation after 24 hours of test is 1 mm or less. ×: Other than the above

[Test Example 4] (Dynamic bending test)
A laminate composed of PET film / pressure-sensitive adhesive layer / PET film obtained in the same manner as in Test Example 3 was cut into 150 mm × 50 mm and used as a test piece. As shown in FIG. 5, both ends of the obtained test piece were fixed to two holding plates of a surface state no-load U-shaped stretch tester (product name “DDLDHH-FS” manufactured by Yuasa System Instruments Co., Ltd.). Then, the test piece was bent 30,000 times at a bending diameter of 6 mmφ, a stroke of 80 mm, and a bending speed of 30 rpm in an environment of 23 ° C. and 50% RH.

After the above-mentioned dynamic bending test is performed, as shown in FIG. 4, the test piece is placed on a flat plate, and immediately after the test and 24 hours after the test, from the flat plate surface to the apex of the bending portion (deformed portion) The height h was measured as a dynamic bending deformation. Based on the measured amount of dynamic bending deformation, dynamic flexibility was evaluated according to the following criteria. Moreover, in the test piece after a test, it was visually confirmed whether there is any peeling in the interface of an adhesive layer and a to-be-adhered body. The results are shown in Table 1.
:: The amount of deformation immediately after the bending test is 0 mm
:: The amount of deformation immediately after the bending test is 1 mm or less, and the amount of deformation after 24 hours of the test is 0 mm
Δ: Deformation amount immediately after bending test is more than 1 mm, 3 mm or less, deformation amount after 24 hours of test is 1 mm or less ×: Other than the above

  As can be seen from Table 1, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the example is excellent in the flexed state alleviating effect when two flexible members are bonded and repeatedly flexed and when placed in a flexed state for a long time .

  The present invention is suitable for bonding one flexible member (for example, various films) constituting another bending device to another flexible member (for example, display element).

DESCRIPTION OF SYMBOLS 1 ... Adhesive sheet 11 ... Adhesive layer 12a, 12b ... Peeling sheet 2 ... Repeating bending laminated member 21 ... 1st flexible member 22 ... 2nd flexible member S ... Test piece P ... Holding plate

Claims (9)

A pressure-sensitive adhesive for a repetitive bending device, for bonding one flexible member and another flexible member constituting a device to be repeatedly bent,
The maximum relaxation elastic modulus value measured when 10% of the pressure-sensitive adhesive is distorted in accordance with JIS K7244-1 is the maximum relaxation elastic modulus G (t) max (MPa), and the maximum relaxation elastic modulus Continue to distort the adhesive by 10% until 3757 seconds after G (t) max is measured, and let the minimum relaxation elastic modulus value measured during that time be the minimum relaxation elastic modulus G (t) _min (MPa) The relaxation elastic-modulus fluctuation value Δlog G (t) calculated from the following formula (I) is 0.85 or less.
Δlog G (t) = log G (t) _max −log G (t) _min (I)   The storage elastic modulus (G ') at 25 ° C. is 0.01 MPa or more and 0.25 MPa or less, The pressure-sensitive adhesive for a repetitive bending device according to claim 1, characterized in that   The pressure-sensitive adhesive for a repetitive bending device according to claim 1 or 2, wherein a loss elastic modulus (G ′ ′) at 25 ° C. is 0.005 MPa or more and 0.1 MPa or less.   The pressure-sensitive adhesive according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive is a pressure-sensitive adhesive formed by crosslinking a pressure-sensitive adhesive composition containing a (meth) acrylic acid ester polymer (A) and a crosslinking agent (B). The adhesive for repeated bending devices according to any one of the preceding claims. A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer for bonding one flexible member and another flexible member constituting a device to be repeatedly bent,
The pressure-sensitive adhesive sheet, wherein the pressure-sensitive adhesive layer is made of the pressure-sensitive adhesive for repeated bending devices according to any one of claims 1 to 4. The pressure-sensitive adhesive sheet is provided with two release sheets,
The pressure-sensitive adhesive sheet according to claim 5, wherein the pressure-sensitive adhesive layer is sandwiched by the release sheet so as to be in contact with the release surfaces of the two release sheets. One flexible member and another flexible member that constitute a device that is repeatedly bent;
A repeated bending laminate member comprising: a pressure-sensitive adhesive layer for bonding the one flexible member and the other flexible member to each other,
The said adhesive layer is an adhesive layer of the adhesive sheet of Claim 5 or 6, The repeatedly bending laminated member characterized by the above-mentioned.   8. The repeatedly bending laminate member according to claim 7, wherein at least one of the one flexible member and the other flexible member is a display element.   A repetitive bending device comprising the repetitive bending laminate member according to claim 7 or 8.

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