JP7175622B2 - Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet - Google Patents

Description

TECHNICAL FIELD The present invention relates to an acrylic pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet.

In general, pressure-sensitive adhesives (also referred to as pressure-sensitive adhesives; hereinafter the same) exhibit a soft solid (viscoelastic) state in a temperature range around room temperature, and have the property of easily adhering to adherends under pressure. Taking advantage of such properties, the adhesive can be used, for example, in the form of a base-attached pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on a supporting base, or in the form of a base-less pressure-sensitive adhesive sheet without a supporting base, for use in smartphones, etc. It is widely used for the purpose of joining, fixing, and protecting members in portable electronic devices. Patent Documents 1 to 4 are cited as technical documents relating to double-sided adhesive tapes used for fixing members of portable electronic devices.

JP 2017-132911 A JP 2013-100485 A JP 2017-002292 A JP 2015-147873 A

The adhesion area for fixing a member in a portable electronic device with an adhesive sheet is usually small due to restrictions on size, weight, and the like. The pressure-sensitive adhesive sheet used for such applications must have adhesive strength that enables good fixation even in a small area, and the required performance is becoming higher due to the demands for weight reduction and miniaturization. ing. In particular, mobile electronic devices equipped with touch panel displays, as typified by smartphones, are becoming smaller and thinner. For these reasons, the pressure-sensitive adhesive used is required to have adhesion and fixation performance under more severe conditions. Specifically, in this application, not only is the bonding area limited, but an elastic member such as a flexible printed wiring board (FPC) is bent and accommodated in the limited internal space of the portable electronic device. , it is precisely positioned with an adhesive sheet and fixed stably. Adhesives used for fixing such members are required to have deformation resistance that can sustainably resist the elastic rebound of the members. In this type of member fixing, a continuous peeling deformation load is applied in the thickness direction (also referred to as the Z-axis direction) of the adhesive sheet. At present, the required performance is achieved by increasing the degree of cross-linking of the pressure-sensitive adhesive to improve its cohesiveness, fixing it by strong pressure bonding, securing sufficient curing time, etc.

On the other hand, in order to improve the productivity and reduce the production cost of products such as electronic devices, reduction in tact time (process work time) is usually considered first. The pressure-sensitive adhesive sheet to be used is required to be easy to apply by light pressure bonding and to exhibit desired performance in a shorter curing time. For that reason, it is necessary to exhibit good adhesive strength immediately after the application. Although it is possible to improve the initial adhesive strength by reducing the degree of cross-linking, a reduction in the degree of cross-linking in the pressure-sensitive adhesive usually accompanies a decrease in cohesive strength, so that the resistance to deformation of the pressure-sensitive adhesive against external force is reduced. In addition, it has a problem of cohesive failure due to being unable to withstand the load in holding applications that require sustained performance. Another option is a method using thermocompression bonding, but high-temperature heating exceeding 60° C. is extremely limited in application. In addition, handling properties tend to be inferior to normal temperature crimping. In short, there is a contradictory relationship between the sustained deformation resistance required for fixing members of recent mobile electronic devices, etc., and the initial adhesiveness for light pressure bonding for reducing the tact time, and it is not easy to achieve both. In applications that require deformation resistance against continuous peeling load in the thickness direction of the adhesive sheet, even if it is applied with light pressure, it exhibits sufficient adhesive performance immediately after pasting (light pressure If a pressure-sensitive adhesive sheet is provided that is resistant to deformation against a sustained peeling load in the thickness direction (has deformation resistance against a sustained load in the Z-axis direction), high performance, It is very meaningful as it leads to the improvement of production efficiency of high-performance products.

The present invention has been made in view of such circumstances, and an acrylic pressure-sensitive adhesive composition capable of achieving both initial adhesiveness for light pressure bonding and resistance to deformation against sustained load in the Z-axis direction without relying on high-temperature thermocompression bonding. The purpose is to provide goods. Another object of the present invention is to provide a pressure-sensitive adhesive sheet that achieves both initial adhesion by light pressure bonding and resistance to deformation against sustained load in the Z-axis direction, without relying on high-temperature thermocompression bonding.

According to the present specification, an acrylic pressure-sensitive adhesive composition is provided. This acrylic pressure-sensitive adhesive composition contains an acrylic polymer as a base polymer and at least one selected from tackifying resins and (meth)acrylic oligomers. Also, the weight average molecular weight of the acrylic polymer is greater than 70×10 ⁴ . Furthermore, the polydispersity (Mw/Mn) of the acrylic polymer is less than 15.

By using an acrylic polymer having a weight-average molecular weight (Mw) of more than 70×10 ⁴ and an Mw/Mn of less than 15 as the base polymer, the cohesiveness due to the relatively uniform high molecular weight is accurately expressed and sustained. Excellent resistance (deformation resistance) to a moderate deformation load can be obtained. Further, in addition to such an acrylic polymer, by using one or more selected from a tackifier resin and a (meth)acrylic oligomer, sufficient adhesive performance is obtained immediately after application even in a mode in which the adhesive is applied by light pressure bonding. express. That is, the pressure-sensitive adhesive composition provides a pressure-sensitive adhesive sheet having both initial adhesiveness under light pressure bonding and resistance to deformation against sustained load in the Z-axis direction. The pressure-sensitive adhesive sheet formed from the above-described pressure-sensitive adhesive composition can fix the elastic adherend in a folded state, and can maintain the fixed state continuously even with light pressure bonding. In addition, since the pressure-sensitive adhesive sheet has excellent initial adhesion after light pressure bonding, it is also advantageous in that it can be easily applied to fragile adherends that may be damaged by normal pressure bonding.

In a preferred embodiment of the technology disclosed herein (including acrylic pressure-sensitive adhesive compositions and pressure-sensitive adhesive sheets; hereinafter the same), the acrylic polymer has an alkyl group having 1 to 6 carbon atoms at the ester end. 50% by weight or more of the alkyl (meth)acrylate is polymerized. By configuring in this way, it is possible to preferably obtain a pressure-sensitive adhesive sheet that has both initial adhesion by light pressure bonding and resistance to deformation against a sustained load in the Z-axis direction.

In a preferred aspect of the technology disclosed herein, the acrylic polymer is copolymerized with an acidic group-containing monomer. The acidic group-containing monomer introduced into the polymer exhibits improved cohesiveness based on its polarity and bonding strength to polar adherends. As a result, even if the pressure-sensitive adhesive is applied by light pressure bonding, it preferably exhibits sufficient adhesive performance immediately after it is applied, and is more deformable against a continuous peeling load in the thickness direction. Hateful. Moreover, the copolymerization ratio of the acidic group-containing monomer in the acrylic polymer is preferably less than 10% by weight. By controlling the copolymerization ratio of the acidic group-containing monomer to be less than 10% by weight, it is possible to appropriately control the effects of the acidic group-containing monomer (cohesiveness, cross-linking points, etc.) and maintain good initial adhesiveness for light pressure bonding. can. Moreover, it is more preferable to use acrylic acid as the acidic group-containing monomer. By using acrylic acid as the acidic group-containing monomer, it is possible to favorably achieve both initial light pressure bonding adhesion and deformation resistance against a sustained load in the Z-axis direction.

In a preferred aspect of the technology disclosed herein, the tackifier resin is contained in a proportion of less than 30 parts by weight with respect to 100 parts by weight of the acrylic polymer. By using a predetermined amount of the tackifier resin, it is possible to preferably improve the initial adhesion by light pressure bonding while ensuring deformation resistance against a continuous load in the Z-axis direction with a high-molecular-weight acrylic polymer.

In a preferred embodiment of the technology disclosed herein, the (meth)acrylic oligomer is contained in a proportion of less than 30 parts by weight with respect to 100 parts by weight of the acrylic polymer. By using a predetermined amount of (meth)acrylic oligomer, it is possible to obtain excellent initial adhesiveness for light pressure bonding, and to withstand a continuous load in the Z-axis direction even in a usage mode exposed to more severe conditions such as strong repulsion. It can exhibit excellent deformation resistance.

A preferred embodiment of the technology disclosed herein includes both the tackifying resin and the (meth)acrylic oligomer. By using a combination of a tackifying resin and a (meth)acrylic oligomer in a composition containing a high-molecular-weight acrylic polymer, it is possible to obtain excellent initial adhesion at light pressure bonding, while also being exposed to severer conditions such as strong repulsion. It can exhibit highly excellent resistance to deformation against a continuous load in the Z-axis direction even in a mode of use.

Further, according to this specification, a pressure-sensitive adhesive sheet comprising an acrylic pressure-sensitive adhesive layer is provided. The acrylic pressure-sensitive adhesive layer contains an acrylic polymer as a base polymer and at least one selected from tackifying resins and (meth)acrylic oligomers. Also, the weight average molecular weight of the acrylic polymer is greater than 70×10 ⁴ . Furthermore, the polydispersity (Mw/Mn) of the acrylic polymer is less than 15. According to the pressure-sensitive adhesive sheet having the above structure, it is possible to achieve both initial adhesion by light pressure bonding and resistance to deformation against continuous load in the Z-axis direction.

Further, according to this specification, a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer is provided. The pressure-sensitive adhesive layer has a storage modulus G' (25°C) of 0.15 MPa or more at 25°C and a storage modulus G' (85°C) of 0.02 MPa or more at 85°C. In addition, the 180 degree peel strength (initial adhesive strength of light pressure bonding at 23°C) measured within 1 minute after pressure bonding under the conditions of 23°C and a pressure load of 0.1 kg, and the pressure bonding under the conditions of 40°C, 0.05 MPa, and 3 seconds. At least one of the 180 degree peel strengths (40°C light pressure bonding initial adhesive strength) measured within 1 minute after the test should be 8 N/20 mm or more.

Since the above pressure-sensitive adhesive layer has storage elastic moduli G' (25°C) and G' (85°C) at 25°C and 85°C of 0.15 MPa or more and 0.02 MPa or more, respectively, It is difficult to deform against the applied load. In addition, at least one of the 23° C. light pressure initial adhesive strength and the 40° C. light pressure initial adhesive strength of the pressure-sensitive adhesive sheet is 8 N/20 mm or more. The pressure-sensitive adhesive sheet having an initial adhesive strength at 23° C. light pressure bonding can exhibit excellent initial adhesiveness to the surface of an adherend by light pressure bonding in a room temperature range. Even if the above 23° C. light pressure bonding initial adhesive strength is not satisfied, as long as the pressure-sensitive adhesive sheet has a 40° C. light pressure initial bonding strength of 8 N/20 mm or more, it can be applied to electronic device applications, for example. Excellent initial adhesion to the surface of the adherend can be exhibited by light pressure bonding using high heat (mild heating below 60°C, typically about 40°C). The pressure-sensitive adhesive sheet having the above-described structure exhibits sufficient adhesive performance immediately after attachment and persists in the thickness direction in a mode in which it is attached by light pressure bonding in a normal temperature range or light pressure bonding using a limited heating temperature. It is difficult to deform against a moderate peeling load. That is, according to the present specification, a pressure-sensitive adhesive sheet is provided that can achieve both initial adhesion by light pressure bonding and resistance to deformation against sustained load in the Z-axis direction, without relying on high-temperature thermocompression bonding. According to such a pressure-sensitive adhesive sheet, it is possible to fix the elastic adherend in a folded state, and to maintain the fixed state continuously even with light pressure bonding. Such a pressure-sensitive adhesive sheet can be preferably produced by using any of the acrylic pressure-sensitive adhesive compositions disclosed herein.

In a preferred aspect of the pressure-sensitive adhesive sheet disclosed herein, the pressure-sensitive adhesive layer has a gel fraction of 40% by weight or more. A pressure-sensitive adhesive having a gel fraction of 40% by weight or more exhibits more favorable deformation resistance against a continuous load in the Z-axis direction.

In a preferred aspect of the pressure-sensitive adhesive sheet disclosed herein, the pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive layer containing an acrylic polymer. By using an acrylic polymer, which has a wide range of molecular design options and is relatively easy to design, a pressure-sensitive adhesive sheet having both initial light pressure adhesion and deformation resistance against a sustained load in the Z-axis direction can be suitably produced. be able to.

In a preferred embodiment of the adhesive sheet disclosed here, the acrylic polymer is crosslinked. By cross-linking the acrylic polymer, the cohesiveness of the pressure-sensitive adhesive increases, and the resistance to deformation against continuous load in the Z-axis direction is exhibited more favorably.

Since the pressure-sensitive adhesive sheet disclosed herein has initial adhesiveness after light pressure bonding, it can reduce the tact time in the manufacture of electronic devices, for example. When the pressure-sensitive adhesive sheet is used for fixing a member in a portable electronic device, it can contribute to improving the productivity of the portable electronic device. Also/or, the pressure-sensitive adhesive sheet disclosed herein has deformation resistance against a continuous load in the Z-axis direction, and is therefore preferably used for fixing elastic adherends such as FPC. According to the pressure-sensitive adhesive sheet, even with light pressure bonding, the elastic adherend can be fixed in a folded state, and the fixed state can be maintained continuously. For example, by using the pressure-sensitive adhesive sheet disclosed herein for fixing an FPC arranged in a portable electronic device, it is possible to simultaneously improve the member accommodation efficiency and production efficiency of the portable electronic device. .

1 is a cross-sectional view schematically showing one configuration example of an adhesive sheet; FIG. FIG. 3 is a cross-sectional view schematically showing another configuration example of the adhesive sheet; FIG. 3 is a cross-sectional view schematically showing another configuration example of the adhesive sheet; FIG. 3 is a cross-sectional view schematically showing another configuration example of the adhesive sheet; FIG. 3 is a cross-sectional view schematically showing another configuration example of the adhesive sheet; FIG. 3 is a cross-sectional view schematically showing another configuration example of the adhesive sheet; It is a schematic diagram explaining the method of a Z-axis direction deformation|transformation resistance test.

Preferred embodiments of the present invention are described below. Matters other than the matters specifically mentioned in the present specification and matters necessary for the implementation of the present invention are based on the teaching of the implementation of the invention described in the present specification and the common general knowledge at the time of filing. can be understood by those skilled in the art. The present invention can be implemented based on the contents disclosed in this specification and common general technical knowledge in the field. Further, in the drawings below, members and portions having the same function may be denoted by the same reference numerals, and redundant description may be omitted or simplified. In addition, the embodiments described in the drawings are schematic for the purpose of clearly explaining the present invention, and do not necessarily accurately represent the size and scale of the pressure-sensitive adhesive sheet of the present invention that is actually provided as a product. .

As used herein, the term “adhesive” refers to a material that exhibits a soft solid (viscoelastic) state in a temperature range around room temperature and has the property of easily adhering to an adherend under pressure, as described above. . The adhesive used herein generally has a complex tensile elastic modulus E ^* (1 Hz) It may be a material having properties satisfying <10 ⁷ dyne/cm ² (typically, a material having the above properties at 25°C).

In this specification, "(meth)acryloyl" is meant to comprehensively refer to acryloyl and methacryloyl. Similarly, "(meth)acrylate" is a generic term for acrylate and methacrylate, and "(meth)acrylic" is a generic term for acrylic and methacrylic.

As used herein, the term "acrylic polymer" refers to a polymer containing monomer units derived from a monomer having at least one (meth)acryloyl group in one molecule as monomer units constituting the polymer. Hereinafter, a monomer having at least one (meth)acryloyl group in one molecule is also referred to as "acrylic monomer". Acrylic polymers in this specification are defined as polymers containing monomeric units derived from acrylic monomers.

The pressure-sensitive adhesive sheet disclosed herein may be a pressure-sensitive adhesive sheet with a substrate having the pressure-sensitive adhesive layer on one or both sides of a substrate (support), and the pressure-sensitive adhesive layer is held by a release liner. It may be a substrate-less pressure-sensitive adhesive sheet, such as a shape. The concept of the adhesive sheet as used herein can include what is called an adhesive tape, an adhesive label, an adhesive film, and the like. The pressure-sensitive adhesive sheet disclosed herein may be roll-shaped or sheet-shaped. Alternatively, it may be a pressure-sensitive adhesive sheet processed into various shapes.

The pressure-sensitive adhesive sheets disclosed herein may have, for example, cross-sectional structures schematically shown in FIGS. 1 to 6. FIG. Among them, FIGS. 1 and 2 show configuration examples of a double-sided pressure-sensitive adhesive sheet with a substrate. The pressure-sensitive adhesive sheet 1 shown in FIG. 1 is provided with pressure-sensitive adhesive layers 21 and 22 on each surface (both of which are non-releasable) of a base material 10, and the pressure-sensitive adhesive layers have at least the pressure-sensitive adhesive layer side as a release surface. It has a structure protected by the release liners 31 and 32, respectively. The pressure-sensitive adhesive sheet 2 shown in FIG. 2 is provided with pressure-sensitive adhesive layers 21 and 22 on each side (both of which are non-releasable) of the substrate 10, and one of the pressure-sensitive adhesive layers 21 has both sides as release surfaces. It has a structure protected by a release liner 31 that is formed. This type of pressure-sensitive adhesive sheet 2 is configured such that the pressure-sensitive adhesive layer 22 is also protected by the release liner 31 by winding the pressure-sensitive adhesive sheet and bringing the other pressure-sensitive adhesive layer 22 into contact with the back surface of the release liner 31. be able to.

FIGS. 3 and 4 show configuration examples of a substrate-less double-sided pressure-sensitive adhesive sheet. The pressure-sensitive adhesive sheet 3 shown in FIG. 3 has a configuration in which both surfaces 21A and 21B of a substrate-less pressure-sensitive adhesive layer 21 are protected by release liners 31 and 32 having release surfaces at least on the pressure-sensitive adhesive layer side, respectively. The adhesive sheet 4 shown in FIG. 4 has a configuration in which one surface (adhesive surface) 21A of a substrate-less adhesive layer 21 is protected by a release liner 31 having release surfaces on both sides. When wound, the other surface (adhesive surface) 21B of the adhesive layer 21 contacts the back surface of the release liner 31, so that the other surface 21B is also protected by the release liner 31.

FIG. 5 and FIG. 6 are configuration examples of a single-sided adhesive type adhesive sheet with a substrate. The adhesive sheet 5 shown in FIG. 5 is provided with an adhesive layer 21 on one surface 10A (non-releasable) of the substrate 10, and the surface (adhesive surface) 21A of the adhesive layer 21 is peelable at least on the adhesive layer side. It has a structure protected by a release liner 31 which is a plane. The adhesive sheet 6 shown in FIG. 6 has a configuration in which an adhesive layer 21 is provided on one surface 10A (non-releasable) of the substrate 10 . The other surface 10B of the base material 10 is a release surface, and when the adhesive sheet 6 is wound, the adhesive layer 21 comes into contact with the other surface 10B, and the surface (adhesive surface) 21B of the adhesive layer becomes the base material. is protected by the other surface 10B.

<Adhesive layer>
The pressure-sensitive adhesive layer disclosed herein can typically have a storage modulus G' (25°C) at 25°C of 0.15 MPa or more. The pressure-sensitive adhesive having the above G' (25°C) can preferably exhibit good resistance to deformation from an early stage after being attached to an adherend. The G′ (25° C.) is preferably 0.17 MPa or higher, more preferably 0.2 MPa or higher, and still more preferably 0.23 MPa or higher. The G′ (25° C.) is particularly preferably 0.25 MPa or more, and may be 0.3 MPa or more, for example. In addition, the above G' (25 ° C.) is usually suitable to be 1.0 MPa or less, preferably 0.6 MPa or less, more preferably 0.6 MPa or less, from the viewpoint of achieving both initial adhesiveness for light pressure bonding and deformation resistance. is 0.4 MPa or less, more preferably 0.35 MPa or less, and may be, for example, 0.3 MPa or less, 0.25 MPa or less, or 0.2 MPa or less.

In addition, the pressure-sensitive adhesive layer disclosed herein generally suitably has a loss elastic modulus G″ (25°C) at 25°C of 2.0 MPa or less. The G″ (25°C) is preferably It is 1.5 MPa or less, more preferably 1.0 MPa or less, still more preferably 0.5 MPa or less. The G″ (25° C.) may be 0.3 MPa or less (for example, 0.25 MPa or less). It is usually suitable that the G″ (25° C.) is 0.01 MPa or more. , from the viewpoint of the wettability to the surface of the adherend and the initial adhesion of light pressure bonding, etc. or more.

In addition, the tan δ (25° C.) at 25° C. of the pressure-sensitive adhesive layer disclosed herein can be appropriately set in consideration of initial light pressure adhesion and deformation resistance at room temperature. Here, the tan δ (loss tangent) of the adhesive (layer) refers to the ratio of the loss elastic modulus G″ to the storage elastic modulus G′ of the adhesive (layer). be. Tan δ (25 ° C.) is, for example, about 0.3 or more, preferably about 0.5 or more, more preferably about 0.7 or more, still more preferably about 0 from the viewpoint of deformation resistance 0.8 or more, particularly preferably about 0.9 or more (eg about 1 or more). In addition, tan δ (25° C.) is, for example, about 3 or less, preferably about 2 or less, more preferably about 1.5 or less, and still more preferably about 1.2 or less from the viewpoint of initial light pressure adhesion. is.

The pressure-sensitive adhesive layer disclosed herein can typically have a storage modulus G' (85°C) at 85°C of 0.02 MPa or more. By having the above G' (85°C), sustained deformation resistance can be preferably obtained. Specifically, G' (85°C) may be 0.022 MPa or more. The G' (85°C) is preferably 0.025 MPa or more, more preferably 0.027 MPa or more. The G'(85°C) is more preferably about 0.03 MPa or more (for example, 0.035 MPa or more), particularly preferably 0.04 MPa or more, and even more preferably 0.05 MPa or more. Also, the above G' (85° C.) is usually suitably 1.0 MPa or less, for example 0.5 MPa or less, typically 0.1 MPa or less. The G' (85° C.) may be 0.05 MPa or less.

In addition, tan δ (85° C.) at 85° C. of the pressure-sensitive adhesive layer disclosed herein can be appropriately set in consideration of sustained deformation resistance. Tan δ (85° C.) is, for example, suitably about 0.1 or more, preferably about 0.2 or more, more preferably 0.22 or more, still more preferably 0.24 or more (for example, 0.25 or more ). Also, tan δ (85° C.) is suitable, for example, about 2 or less, preferably about 1 or less, more preferably about 0.5 or less (for example, about 0.3 or less).

The pressure-sensitive adhesive layer disclosed herein preferably has a storage elastic modulus G'(apply) of 0.6 MPa or less at the temperature (pressure-bonding temperature) at which the pressure-sensitive adhesive sheet is pressure-bonded to the adherend. The pressure-sensitive adhesive having the above G' (apply) can wet the surface of the adherend well and exhibit excellent initial adhesiveness even with light pressure bonding. The G'(apply) is more preferably 0.4 MPa or less, still more preferably 0.35 MPa or less, and may be, for example, 0.3 MPa or less, or 0.25 MPa or less. The G'(apply) may be, for example, 0.2 MPa or less. In addition, from the viewpoint of achieving both initial adhesiveness for light pressure bonding and resistance to deformation, the G'(apply) is suitably larger than 0.12 MPa, preferably 0.15 MPa or more, and more preferably 0.15 MPa or more. It is 17 MPa or more (for example, 0.2 MPa or more), more preferably 0.25 MPa or more, and may be, for example, 0.3 MPa or more. The crimping temperature is selected from a range of more than 0° C. and less than 60° C. from the viewpoint of crimping workability, temperature control, and the like. In the case of pressure-sensitive adhesive sheets used for portable electronic devices, the pressure bonding temperature is selected from the range of 20° C. to 45° C. (typically 25° C. or 40° C., preferably 25° C.) due to temperature restrictions in the application. It is desirable to The pressure bonding in the above temperature range is thermocompression bonding that can be applied to electronic devices and the like, unlike the conventional thermocompression bonding performed at about 100°C.

In the technology disclosed herein, the storage elastic modulus G' (25°C), G' (85°C), G' (apply), loss elastic modulus G" (25°C), tan δ (25°C) of the pressure-sensitive adhesive layer And tan δ (85 ° C.) can be determined by dynamic viscoelasticity measurement.Specifically, the adhesive layer (adhesive sheet in the case of a substrate-less adhesive sheet) to be measured is superimposed A pressure-sensitive adhesive layer with a thickness of about 2 mm is produced by This pressure-sensitive adhesive layer is punched out into a disk shape with a diameter of 7.9 mm, and the sample is sandwiched between parallel plates and fixed. Instrument Co., Ltd., ARES or its equivalent) was subjected to dynamic viscoelasticity measurement under the following conditions, and storage elastic modulus G' (25 ° C.), G' (85 ° C.), G' (apply), loss elasticity Determine the ratios G″ (25° C.), tan δ (25° C.) and tan δ (85° C.).
・Measurement mode: Shear mode ・Temperature range: -70°C to 150°C
・Temperature increase rate: 5°C/min
・Measurement frequency: 1Hz
It is also measured by the above method in the examples described later. The pressure-sensitive adhesive layer to be measured can be formed by applying the corresponding pressure-sensitive adhesive composition in layers and drying or curing.

(Adhesive)
In the technology disclosed herein, the type of adhesive that constitutes the adhesive layer is not particularly limited. Examples include acrylic adhesives, rubber adhesives (natural rubber, synthetic rubber, mixtures of these, etc.), silicone adhesives, polyester adhesives, urethane adhesives, polyether adhesives, and polyamide adhesives. The pressure-sensitive adhesive layer may be composed of one or more pressure-sensitive adhesives selected from various known pressure-sensitive adhesives such as pressure-sensitive adhesives and fluorine-based pressure-sensitive adhesives. Here, the acrylic pressure-sensitive adhesive refers to a pressure-sensitive adhesive containing a (meth)acrylic polymer as a base polymer (the main component in the polymer component, that is, the component contained in an amount exceeding 50% by mass). The same applies to rubber adhesives and other adhesives. Preferred adhesive layers from the viewpoint of transparency, weather resistance, etc. include adhesive layers containing an acrylic adhesive in an amount of 50% by weight or more, more preferably 70% by weight or more, and still more preferably 90% by weight or more. be done. The content of the acrylic pressure-sensitive adhesive may be more than 98% by weight, and the pressure-sensitive adhesive layer may be substantially composed of the acrylic pressure-sensitive adhesive.

(acrylic polymer)
Although not particularly limited, in a preferred embodiment of the technology disclosed herein, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer and the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive include an acrylic polymer as a base polymer. including. The acrylic polymer is preferably a polymer of monomer raw materials containing an alkyl (meth)acrylate as a main monomer and may further contain a sub-monomer copolymerizable with the main monomer. The term "main monomer" as used herein refers to a component that is contained in an amount exceeding 50% by weight in the raw material for the monomer.

As the alkyl (meth)acrylate, for example, a compound represented by the following formula (1) can be preferably used.
_CH2 =C( ^R1 ) ^COOR2 (1)
Here, R ¹ in the above formula (1) is a hydrogen atom or a methyl group. R ² is a chain alkyl group having 1 to 20 carbon atoms (hereinafter, such a range of carbon atoms may be referred to as "C _1-20 "). From the viewpoint of the storage modulus of the adhesive, alkyl (meth)acrylates in which R ² is a C _1-14 chain alkyl group are preferred, and alkyl (meth)acrylates in which R ² is a C _1-10 chain alkyl group. ) acrylates are more preferred, and alkyl (meth)acrylates in which R ² is a butyl group or a 2-ethylhexyl group are particularly preferred.

Examples of alkyl (meth)acrylates in which R ² is a C _1-20 chain alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (Meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate and the like. . These alkyl (meth)acrylates can be used singly or in combination of two or more. Particularly preferred alkyl (meth)acrylates include n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA).

In the technique disclosed herein, the monomer component constituting the acrylic polymer contains at least one of BA and 2EHA, and the total amount of BA and 2EHA in the alkyl (meth)acrylate contained in the monomer component is 75 wt. % or more (usually 85 wt% or more, for example 90 wt% or more, further 95 wt% or more). The technology disclosed herein can be practiced, for example, in a mode in which the alkyl (meth)acrylate contained in the monomer component is BA alone, 2EHA alone, BA and 2EHA, and the like.

When the monomer component contains BA and 2EHA, the weight ratio of BA and 2EHA (BA/2EHA) is not particularly limited, and may be, for example, 1/99 or more and 99/1 or less. In one preferred embodiment, BA/2EHA can be 60/40 or greater (eg 60/40 or greater and 99/1 or less), can be 80/20 or greater, or can be 90/10 or greater (eg more than 99/1 or less).

The technique disclosed herein can be preferably carried out in a mode in which the monomer component constituting the acrylic polymer contains 50% by weight or more of C _1-6 alkyl (meth)acrylate. In other words, the polymerization ratio of C _1-6 alkyl (meth)acrylate in the acrylic polymer is preferably 50% by weight or more. By using C _1-6 alkyl (meth)acrylate as the main monomer in this way, it is possible to preferably design an acrylic polymer capable of achieving deformation resistance against a sustained load in the Z-axis direction. The proportion of C _1-6 alkyl (meth)acrylate in the monomer component (in other words, polymerization proportion) is more preferably greater than 50% by weight, still more preferably 60% by weight or more, and particularly preferably 70% by weight or more (for example, 80% by weight or more, further 85% by weight or more). The upper limit of the ratio of C _1-6 alkyl (meth)acrylate in the monomer component is not particularly limited, and is usually 99% by weight or less. It is suitable that the content is 95% by weight or less. The C _1-6 alkyl (meth)acrylates may be used singly or in combination of two or more. The C _1-6 alkyl (meth)acrylate is preferably a C _1-6 alkyl acrylate, more preferably a C _2-6 alkyl acrylate, and still more preferably a C _4-6 alkyl acrylate. In another aspect, the C _1-6 alkyl (meth)acrylate is preferably a C _1-4 alkyl acrylate, more preferably a C _2-4 alkyl acrylate. A preferred example of the C _1-6 alkyl (meth)acrylate is BA.

In the embodiment using BA as the main monomer, the copolymerization ratio of BA in the acrylic polymer is preferably 50% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, and particularly preferably 70% by weight or more (for example, 80% by weight or more, further 85% by weight or more), more preferably 90% by weight or more (for example, more than 90% by weight). By copolymerizing BA as the main monomer, the pressure-sensitive adhesive can adhere well to the adherend. In addition, the copolymerization ratio of BA in the acrylic polymer is not particularly limited, and is usually 99% by weight or less. % or less, preferably 95% by weight or less.

In a preferred embodiment of the technology disclosed herein, an acidic group-containing monomer is used as a monomer copolymerizable with alkyl (meth)acrylate, which is the main monomer. The acidic group-containing monomer can improve cohesiveness based on its polarity and exhibit good bonding strength to polar adherends. When using a cross-linking agent such as an isocyanate-based or epoxy-based cross-linking agent, the acidic group (typically a carboxyl group) becomes a cross-linking point of the acrylic polymer. Due to these actions, it is possible to suitably achieve deformation resistance against a continuous load in the Z-axis direction. By using the acidic group-containing monomer in a predetermined ratio or more, it is possible to preferably design an acrylic polymer that can achieve initial adhesion at light pressure bonding and resistance to deformation against continuous load in the Z-axis direction.

A carboxy group-containing monomer is preferably used as the acidic group-containing monomer. Examples of carboxy group-containing monomers include ethylenically unsaturated monocarboxylic acids such as acrylic acid (AA), methacrylic acid (MAA), carboxyethyl (meth)acrylate, crotonic acid and isocrotonic acid; maleic acid, itaconic acid and citraconic acid; ethylenically unsaturated dicarboxylic acids such as and anhydrides thereof (maleic anhydride, itaconic anhydride, etc.). The acidic group-containing monomer may also be a monomer having a metal salt (for example, an alkali metal salt) of a carboxy group. Among them, AA and MAA are preferred, and AA is more preferred. When one or two or more acidic group-containing monomers are used, the proportion of AA in the acidic group-containing monomer is preferably 50% by weight or more, more preferably 70% by weight or more, and still more preferably 90% by weight or more. is. In a particularly preferred embodiment, the acidic group-containing monomer consists essentially of AA. AA has multiple effects such as polarity based on its carboxyl group, role as a cross-linking point, and Tg (106 ° C.). It is considered to be the most suitable monomer material for realizing a balance with deformation resistance against sustained load.

In the technology disclosed herein, the content of an acidic group-containing monomer (typically a carboxy group-containing monomer) in the monomer component (in other words, the copolymerization ratio of the acidic group-containing monomer in the acrylic polymer) is usually It is 3% by weight or more, preferably 5% by weight or more. By using a predetermined amount or more of an acidic group-containing monomer, it is preferable to use an acrylic polymer that can achieve both initial adhesiveness for light pressure bonding and resistance to deformation against continuous load in the Z-axis direction, based on the effect of improving cohesion. can be realized. The copolymerization ratio of the acidic group-containing monomer in the acrylic polymer may be, for example, 8% by weight or more, 10% by weight or more, 10% by weight or more, or 11% by weight or more. It may be 12% by weight or more. In the case of obtaining initial adhesion by light pressure bonding by raising the pressure bonding temperature above room temperature, it is possible to further increase the copolymerization ratio of the acidic group-containing monomer in the acrylic polymer. In that case, the copolymerization ratio can be 13% by weight or more, for example, 15% by weight or more. The copolymerization ratio of the acidic group-containing monomer in the acrylic polymer is usually 20% by weight or less, preferably 18% by weight or less from the viewpoint of maintaining the properties of the main monomer. The copolymerization ratio may be 15% by weight or less, for example, 13% by weight or less. In a more preferred embodiment, the copolymerization ratio of the acidic group-containing monomer in the acrylic polymer is approximately 12% by weight or less, more preferably approximately 10% by weight or less, and particularly preferably approximately 8% by weight or less. In an acrylic polymer having a monomer composition containing a large amount of C _1-6 alkyl (meth)acrylate (typically BA), the content of the acidic group-containing monomer (for example, AA) in the monomer component should be within the above range. Effective.

In the monomer component constituting the acrylic polymer disclosed herein, the ratio of the content ratio C _A of the acidic group-containing monomer to the content ratio C _M of the above-described main monomer (typically alkyl (meth)acrylate) (C _A /C _M (%); calculated from C _A /C _M × 100) is usually 3% or more, preferably 5% or more, and 7% or more on a weight basis. is preferred, and may be, for example, 8% or more. By using a predetermined amount or more of an acidic group-containing monomer with respect to the main monomer (typically alkyl (meth) acrylate), based on the adhesion performance of the main monomer and the cohesiveness improvement effect of the acidic group-containing monomer, etc. It is preferable to realize an acrylic polymer that can preferably achieve both initial adhesiveness for light pressure bonding and resistance to deformation against a sustained load in the Z-axis direction. The ratio (C _A /C _M ) may be, for example, 10% or more, 11% or more, or 12% or more. In the case of obtaining initial adhesion by light pressure bonding by raising the pressure bonding temperature above room temperature, it is possible to further increase the copolymerization ratio of the acidic group-containing monomer in the acrylic polymer. In that case, the ratio (C _A /C _M ) can be 15% or more, for example, 18% or more. The ratio (C _A /C _M ) is usually 25% or less, preferably 20% or less from the viewpoint of maintaining the properties of the main monomer. The ratio (C _A /C _M ) may be 15% or less, for example 13% or less. In a more preferred embodiment, the ratio (C _A /C _M ) is about 11% or less, more preferably about 9% or less. In an acrylic polymer having a monomer composition containing a large amount of C _1-6 alkyl (meth)acrylate (typically BA), the content of the acidic group-containing monomer (for example, AA) in the monomer component is particularly within the above range. Effective.

In the technology disclosed herein, a copolymerizable monomer other than the carboxy group-containing monomer can be used as a sub-monomer copolymerizable with the alkyl (meth)acrylate that is the main monomer. As such submonomers, for example, the following functional group-containing monomers can be used.
hydroxyl group-containing monomers: hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; Unsaturated alcohols such as vinyl alcohol and allyl alcohol; polypropylene glycol mono(meth)acrylate;
Amido group-containing monomers: for example (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl(meth)acrylamide;
Amino group-containing monomers: for example aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate.
Monomers with epoxy groups: eg glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, allyl glycidyl ether.
Cyano group-containing monomers: for example acrylonitrile, methacrylonitrile.
Keto group-containing monomers: for example diacetone (meth)acrylamide, diacetone (meth)acrylate, vinylmethylketone, vinylethylketone, allylacetoacetate, vinylacetoacetate.
Monomers having a nitrogen atom-containing ring: such as N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinyl pyrrole, N-vinylimidazole, N-vinyloxazole, N-vinylmorpholine, N-vinylcaprolactam, N-(meth)acryloylmorpholine;
Alkoxysilyl group-containing monomers: such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxy Propylmethyldiethoxysilane.

The functional group-containing monomers may be used singly or in combination of two or more. When the monomer component that constitutes the acrylic polymer contains a functional group-containing monomer, the ratio of the functional group-containing monomer to the monomer component is determined according to the initial adhesiveness for light pressure bonding, deformation resistance against continuous load in the Z-axis direction, and other requirements. Determined appropriately according to performance. The ratio (copolymerization ratio) of the functional group-containing monomer (for example, hydroxyl group-containing monomer) is about 0.01% by weight or more (for example, 0.02% by weight or more, usually 0.03% by weight or more) in the monomer component. Further, it may be about 0.1% by weight or more (for example, 0.5% by weight or more, usually 1% by weight or more). Moreover, the upper limit is preferably about 40% by weight or less (for example, 30% by weight or less, usually 20% by weight or less). In a more preferred embodiment, the proportion of functional group-containing monomers other than the acidic group-containing monomer is, for example, 10% by weight or less, preferably 5% by weight or less, and can be 1% by weight or less. . In a further preferred embodiment, the proportion of functional group-containing monomers (for example, hydroxyl group-containing monomers) other than the acidic group-containing monomer is about 0.5% by weight or less (for example, about 0.2% by weight or less). The monomer component constituting the acrylic polymer may be substantially free of functional group-containing monomers other than the above acidic group-containing monomers.

As the monomer component constituting the acrylic polymer, a copolymer component other than the aforementioned acidic group-containing monomer and other sub-monomers can be used for the purpose of increasing the cohesive strength of the acrylic polymer. Examples of such copolymerization components include vinyl ester monomers such as vinyl acetate, vinyl propionate, and vinyl laurate; aromatic vinyl compounds such as styrene, substituted styrene (α-methylstyrene, etc.) and vinyltoluene; ) acrylate, cyclopentyl (meth)acrylate, cycloalkyl (meth)acrylate such as isobornyl (meth)acrylate; aryl (meth)acrylate (e.g. phenyl (meth)acrylate), aryloxyalkyl (meth)acrylate (e.g. phenoxyethyl (meth)acrylate ) acrylate), aromatic ring-containing (meth)acrylates such as arylalkyl (meth)acrylates (e.g., benzyl (meth)acrylate); olefinic monomers such as ethylene, propylene, isoprene, butadiene, and isobutylene; vinyl chloride, vinylidene chloride chlorine-containing monomers such as; isocyanate group-containing monomers such as 2-(meth)acryloyloxyethyl isocyanate; alkoxy group-containing monomers such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether system monomer; and the like.
The amount of such other copolymerization component may be appropriately selected depending on the purpose and application, and is not particularly limited, but is usually preferably 10% by weight or less of the monomer component. For example, when a vinyl ester monomer (for example, vinyl acetate) is used as another copolymerization component, the content thereof is, for example, about 0.1% by weight or more (usually about 0.5% by weight or more) of the monomer component. It is suitable that the content is about 20% by weight or less (usually about 10% by weight or less).

Acrylic polymers are polyfunctional having at least two polymerizable functional groups (typically radically polymerizable functional groups) having unsaturated double bonds such as (meth)acryloyl groups and vinyl groups as other monomer components. It may contain a monomer. By using a polyfunctional monomer as the monomer component, the cohesive force of the pressure-sensitive adhesive layer can be increased. Polyfunctional monomers can be used as cross-linking agents.

Examples of multifunctional monomers include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, penta Erythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,2-ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1, Polyhydric alcohols such as 6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, and (meth)acryl Esters with acids; allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, and the like. Preferred examples of these include trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate and dipentaerythritol hexa(meth)acrylate. A particularly preferred example is 1,6-hexanediol di(meth)acrylate. A polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types. From the viewpoint of reactivity and the like, polyfunctional monomers having two or more acryloyl groups are usually preferred.

The amount of the polyfunctional monomer used is not particularly limited, and can be appropriately set so as to achieve the intended use of the polyfunctional monomer. From the viewpoint of achieving a good balance between the preferred storage elastic modulus disclosed herein and other adhesive properties or other properties, the amount of the polyfunctional monomer used can be about 3% by weight or less of the monomer component, About 2% by weight or less is preferable, and about 1% by weight or less (for example, about 0.5% by weight or less) is more preferable. The lower limit of the amount used when using a polyfunctional monomer is not particularly limited as long as it is greater than 0% by weight. Usually, by setting the amount of the polyfunctional monomer used to about 0.001% by weight or more (for example, about 0.01% by weight or more) of the monomer component, the effect of using the polyfunctional monomer can be appropriately exhibited.

The composition of the monomer components constituting the acrylic polymer is designed so that the glass transition temperature (Tg) of the acrylic polymer is approximately −15° C. or lower (for example, approximately −70° C. or higher and −15° C. or lower). is appropriate. Here, the Tg of the acrylic polymer refers to the Tg determined by the Fox formula based on the composition of the monomer components. The Fox equation is a relational expression between the Tg of a copolymer and the glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer, as shown below.
1/Tg=Σ(Wi/Tgi)
In the above Fox formula, Tg is the glass transition temperature of the copolymer (unit: K), Wi is the weight fraction of the monomer i in the copolymer (copolymerization ratio based on weight), and Tgi is the content of the monomer i. It represents the glass transition temperature (unit: K) of a homopolymer.

As the glass transition temperature of the homopolymer used for calculating the Tg, the value described in the known materials shall be used. For example, for the monomers listed below, the following values are used as the glass transition temperatures of the homopolymers of the monomers.
2-ethylhexyl acrylate -70°C
n-butyl acrylate -55°C
Ethyl acrylate -22°C
Methyl acrylate 8°C
Methyl methacrylate 105°C
2-hydroxyethyl acrylate -15°C
4-hydroxybutyl acrylate -40°C
Vinyl acetate 32°C
Styrene 100°C
Acrylic acid 106°C
Methacrylic acid 228°C

For the glass transition temperatures of homopolymers of monomers other than those exemplified above, the values described in "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989) shall be used. For monomers for which multiple values are listed in this document, the highest value is adopted.

For monomers for which the glass transition temperatures of homopolymers are not described in the above literature, the values obtained by the following measurement methods are used.
Specifically, a reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser was charged with 100 parts by weight of a monomer, 0.2 parts by weight of 2,2′-azobisisobutyronitrile and acetic acid as a polymerization solvent. 200 parts by weight of ethyl is added, and the mixture is stirred for 1 hour while circulating nitrogen gas. After removing oxygen in the polymerization system in this way, the temperature is raised to 63° C. and the reaction is carried out for 10 hours. Then, it is cooled to room temperature to obtain a homopolymer solution having a solid concentration of 33% by weight. Next, this homopolymer solution is cast-coated on a release liner and dried to prepare a test sample (sheet-like homopolymer) having a thickness of about 2 mm. This test sample is punched out into a disk shape with a diameter of 7.9 mm, sandwiched between parallel plates, and shear strain at a frequency of 1 Hz using a viscoelasticity tester (manufactured by TA Instruments Japan, model name "ARES"). The viscoelasticity is measured in the shear mode at a temperature range of -70°C to 150°C at a heating rate of 5°C/min while giving , and the temperature corresponding to the peak top temperature of tan δ is taken as the homopolymer Tg.

Although not particularly limited, from the viewpoint of adhesiveness, the Tg of the acrylic polymer is advantageously about −25° C. or less, preferably about −35° C. or less, more preferably about −40° C. or less. , more preferably -45°C or lower, for example, it may be -50°C or lower, or -55°C or lower. From the viewpoint of the cohesive strength of the pressure-sensitive adhesive layer, the Tg of the acrylic polymer is usually about -75°C or higher, preferably about -70°C or higher. The technology disclosed herein can be preferably practiced in a mode in which the Tg of the acrylic polymer is approximately −65° C. or higher and approximately −40° C. or lower (for example, approximately −65° C. or higher and approximately −45° C. or lower). In one preferred embodiment, the Tg of the acrylic polymer can be about -55°C or higher and about -45°C or lower. In another aspect, the Tg of the acrylic polymer can be about -65°C or higher and about -55°C or lower. The Tg of the acrylic polymer can be adjusted by appropriately changing the monomer composition (that is, the types and usage ratios of the monomers used in synthesizing the polymer).

Mw of the acrylic polymer is not particularly limited, and may be, for example, about 10×10 ⁴ or more and 500×10 ⁴ or less. From the viewpoint of cohesiveness, the Mw is usually about 30×10 ⁴ or more, and preferably about 45×10 ⁴ or more (for example, about 65×10 ⁴ or more). In a preferred embodiment, Mw of the acrylic polymer is 70×10 ⁴ or more. Also, in a typical aspect of the technology disclosed herein, Mw of the acrylic polymer is suitably larger than 70×10 ⁴ . By using an acrylic polymer with Mw greater than 70×10 ⁴ , due to its cohesiveness, excellent deformation resistance against sustained deformation loads can be obtained. Mw of the acrylic polymer is more preferably about 75×10 ⁴ or more, still more preferably about 90×10 ⁴ or more, and particularly preferably about 95×10 ⁴ or more. In a particularly preferred embodiment, Mw is about 100×10 ⁴ or more (eg about 110×10 ⁴ or more), typically 120×10 ⁴ or more (eg 130×10 ⁴ or more). Also, the above Mw is usually 300×10 ⁴ or less (more preferably about 200×10 ⁴ or less, for example about 150×10 ⁴ or less). Mw of the acrylic polymer may be approximately 140×10 ⁴ or less. For example, acrylic polymers obtained by a solution polymerization method or an emulsion polymerization method preferably have Mw within the above range.

The degree of dispersion (Mw/Mn) of the acrylic polymer disclosed herein is not particularly limited. The dispersity (Mw/Mn) here means the dispersity (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). In a preferred embodiment, the acrylic polymer has a polydispersity (Mw/Mn) of less than 15. For example, in the case of a relatively high-molecular-weight acrylic polymer (typically having an Mw of more than 700,000) obtained by a solution polymerization method or an emulsion polymerization method, it is preferable to set Mw/Mn within the above range. The fact that the Mw/Mn of the acrylic polymer is less than 15 means that when the polymer has a relatively high molecular weight, it contains a considerable amount of a relatively uniform high molecular weight body. It expresses with high accuracy and exhibits excellent resistance (deformation resistance) against sustained deformation loads. The Mw/Mn is preferably less than 12, more preferably less than 10, still more preferably less than 8 (for example, 7.5 or less). The Mw/Mn is theoretically 1 or more, and may be, for example, 2 or more, 3 or more, or 4 or more (typically 5 or more).

In another aspect, the acrylic polymer has a degree of dispersion (Mw/Mn) of 8 or more and 40 or less. The fact that the Mw/Mn of the acrylic polymer is 8 or more and 40 or less can mean that the molecular weight distribution is wide and that the polymer contains considerable amounts of low molecular weight substances and high molecular weight substances. The low-molecular-weight material contributes to the development of initial light-pressure bonding adhesion due to its good wettability with the adherend, and the high-molecular-weight material exhibits resistance to continuous deformation load (deformation resistance) due to its cohesiveness. . When the Mw/Mn is 8 or more, the initial adhesiveness is preferably exhibited. Further, when the Mw/Mn is 40 or less, the molecular weight distribution is preferably restricted within an appropriate range, and stable properties (initial adhesion by light pressure bonding and deformation resistance) can be obtained. The Mw/Mn may be 10 or more, 12 or more, or 15 or more. The Mw/Mn may be 18 or more (for example, 20 or more). Also, the Mw/Mn is preferably 35 or less, more preferably 30 or less, and even more preferably 25 or less.

Mw, Mn and Mw/Mn can be adjusted by polymerization conditions (time, temperature, etc.), use of a chain transfer agent, selection of a polymerization solvent based on the chain transfer constant, and the like. Moreover, Mw and Mn are obtained from values converted to standard polystyrene obtained by GPC (gel permeation chromatography). As the GPC apparatus, for example, model name "HLC-8320GPC" (column: TSKgelGMH-H(S), manufactured by Tosoh Corporation) can be used.

<Adhesive composition>
The pressure-sensitive adhesive layer disclosed herein is a pressure-sensitive adhesive layer containing a monomer component having the composition as described above in the form of a polymer, an unpolymerized product (that is, a form in which the polymerizable functional group is unreacted), or a mixture thereof. can be formed using the agent composition. The pressure-sensitive adhesive composition includes a composition containing a pressure-sensitive adhesive (adhesive component) in an organic solvent (solvent-type pressure-sensitive adhesive composition), and a composition in which the pressure-sensitive adhesive is dispersed in an aqueous solvent (water-dispersed pressure-sensitive adhesive composition), a composition prepared to form an adhesive by curing with active energy rays such as ultraviolet rays and radiation (active energy ray-curable adhesive composition), applied in a heat-melted state, near room temperature It can be in various forms, such as a hot-melt adhesive composition that forms an adhesive when cooled to a temperature. The technology disclosed herein can be particularly preferably implemented in a mode including a pressure-sensitive adhesive layer formed from a solvent-based pressure-sensitive adhesive composition or an active energy ray-curable pressure-sensitive adhesive composition from the viewpoint of adhesive properties and the like.

As used herein, the term "active energy ray" refers to an energy ray having energy capable of causing chemical reactions such as polymerization reaction, cross-linking reaction, and initiator decomposition. Examples of active energy rays here include light such as ultraviolet rays, visible rays, and infrared rays, and radiation such as α rays, β rays, γ rays, electron beams, neutron rays, and X rays.

Typically, the pressure-sensitive adhesive composition contains at least part of the monomer components of the composition (may be part of the types of monomers or may be part of the amount) as a polymer. in the form of The polymerization method for forming the polymer is not particularly limited, and conventionally known various polymerization methods can be appropriately employed. For example, thermal polymerization such as solution polymerization, emulsion polymerization, bulk polymerization (typically performed in the presence of a thermal polymerization initiator); photopolymerization performed by irradiating light such as ultraviolet rays (typically, conducted in the presence of a photopolymerization initiator); radiation polymerization conducted by irradiating radiation such as β-rays and γ-rays; Among them, solution polymerization and photopolymerization are preferred. In these polymerization methods, the mode of polymerization is not particularly limited. , surfactants, etc.) can be selected as appropriate.

For example, in one preferred embodiment, a solution polymerization method can be employed to synthesize the acrylic polymer. According to the above solution polymerization, a polymerization reaction liquid in which the acrylic polymer is dissolved in an organic solvent is obtained. The pressure-sensitive adhesive layer in the technique disclosed herein may be formed from a pressure-sensitive adhesive composition containing an acrylic polymer solution obtained by subjecting the polymerization reaction solution or the reaction solution to appropriate post-treatment. As the above-mentioned acrylic polymer solution, the above-mentioned polymerization reaction solution may be prepared to have an appropriate viscosity (concentration) as necessary. Alternatively, an acrylic polymer solution prepared by synthesizing an acrylic polymer by a polymerization method other than solution polymerization (e.g., emulsion polymerization, photopolymerization, bulk polymerization, etc.) and dissolving the acrylic polymer in an organic solvent may be used. good.

As a method for supplying the monomers when carrying out solution polymerization, a batch charging method for supplying all monomer raw materials at once, a continuous supply (dropping) method, a divided supply (dropping) method, or the like can be appropriately employed. The polymerization temperature can be appropriately selected depending on the type of monomer and solvent used, the type of polymerization initiator, etc., and can be, for example, about 20° C. to 170° C. (usually about 40° C. to 140° C.). . In a preferred embodiment, the polymerization temperature can be about 75° C. or lower (more preferably about 65° C. or lower, for example about 45° C. to 65° C.).

The solvent (polymerization solvent) used for solution polymerization can be appropriately selected from conventionally known organic solvents. For example, aromatic compounds (e.g., aromatic hydrocarbons) such as toluene and xylene; acetic esters such as ethyl acetate and butyl acetate; aliphatic or alicyclic hydrocarbons such as hexane, cyclohexane, and methylcyclohexane; Halogenated alkanes such as ,2-dichloroethane; lower alcohols such as isopropyl alcohol (eg, monohydric alcohols having 1 to 4 carbon atoms); ethers such as tert-butyl methyl ether; ketones such as methyl ethyl ketone and acetone and the like, or a mixed solvent of two or more.

On the other hand, as another aspect of the technology disclosed herein, when employing an active energy ray-curable pressure-sensitive adhesive composition (typically a photocurable pressure-sensitive adhesive composition), the active energy ray-curable pressure-sensitive adhesive From the viewpoint of environmental hygiene, etc., the composition preferably does not substantially contain an organic solvent. For example, a pressure-sensitive adhesive composition having an organic solvent content of about 5% by weight or less (more preferably about 3% by weight or less, such as about 0.5% by weight or less) is preferred. In addition, as described later, the liquid film of the adhesive composition is suitable for forming an adhesive layer in the form of curing between the release surfaces of a pair of release films, so solvents (including organic solvents and aqueous solvents) A PSA composition that does not substantially contain For example, pressure-sensitive adhesive compositions having a solvent content of about 5% by weight or less (more preferably about 3% by weight or less, such as about 0.5% by weight or less) are preferred. Here, the solvent refers to a volatile component that should be removed during the process of forming the pressure-sensitive adhesive layer, that is, a volatile component that is not intended to become a constituent component of the finally formed pressure-sensitive adhesive layer.

In the polymerization, a known or commonly used thermal polymerization initiator or photopolymerization initiator can be used depending on the polymerization method, polymerization mode, and the like. Such polymerization initiators can be used singly or in combination of two or more.

Although the thermal polymerization initiator is not particularly limited, for example, an azo polymerization initiator, a peroxide initiator, a redox initiator obtained by combining a peroxide and a reducing agent, and a substituted ethane initiator. etc. can be used. More specifically, for example, 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis(2-methylpropionamidine) disulfate, 2,2′-azobis(2-amidinopropane ) dihydrochloride, 2,2′-azobis[2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2′-azobis(N,N′-dimethyleneisobutyramidine), 2 , 2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate; persulfates such as potassium persulfate, ammonium persulfate; benzoyl peroxide (BPO); Peroxide initiators such as t-butyl hydroperoxide, hydrogen peroxide; substituted ethane initiators such as phenyl substituted ethane; combinations such as persulfate and sodium bisulfite, peroxide and sodium ascorbate. Redox initiators such as combinations with; and the like, but are not limited to these. Thermal polymerization can be preferably carried out at a temperature of, for example, about 20 to 100°C (typically 40 to 80°C).

Although the photopolymerization initiator is not particularly limited, for example, ketal photopolymerization initiator, acetophenone photopolymerization initiator, benzoin ether photopolymerization initiator, acylphosphine oxide photopolymerization initiator, α- Ketol photoinitiators, aromatic sulfonyl chloride photoinitiators, photoactive oxime photoinitiators, benzoin photoinitiators, benzyl photoinitiators, benzophenone photoinitiators, thioxanthone photoinitiators A polymerization initiator or the like can be used.

Specific examples of ketal photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethan-1-one (eg, trade name “Irgacure 651” manufactured by BASF). Specific examples of acetophenone-based photopolymerization initiators include 1-hydroxycyclohexyl-phenyl-ketone (eg, trade name “Irgacure 184” manufactured by BASF), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (for example, trade name "Irgacure 2959" manufactured by BASF), 2-hydroxy-2 -methyl-1-phenyl-propan-1-one (eg, trade name "Darocure 1173" manufactured by BASF), methoxyacetophenone, and the like.
Specific examples of benzoin ether photoinitiators include benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether, and substituted benzoin ethers such as anisole methyl ether.
Specific examples of acylphosphine oxide-based photopolymerization initiators include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (eg, trade name “Irgacure 819” manufactured by BASF), bis(2,4,6 -trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (for example, trade name "Lucirin TPO" manufactured by BASF), bis(2,6- dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and the like.
Specific examples of α-ketol photopolymerization initiators include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one, and the like. be Specific examples of aromatic sulfonyl chloride photopolymerization initiators include 2-naphthalenesulfonyl chloride and the like. Specific examples of photoactive oxime-based photopolymerization initiators include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime and the like. Specific examples of the benzoin-based photopolymerization initiator include benzoin and the like. Specific examples of benzyl-based photopolymerization initiators include benzyl and the like.
Specific examples of benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexylphenylketone, and the like.
Specific examples of thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, and isopropylthioxanthone. , 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.

The amount of such a thermal polymerization initiator or photopolymerization initiator to be used is not particularly limited, and can be a normal amount to be used according to the polymerization method, polymerization mode, and the like. For example, about 0.001 to 5 parts by weight (typically about 0.01 to 2 parts by weight, for example about 0.01 to 1 part by weight) of a polymerization initiator is used with respect to 100 parts by weight of the monomer to be polymerized. can be done.

(Adhesive composition containing a monomer component in the form of a complete polymer)
A pressure-sensitive adhesive composition according to a preferred embodiment contains the monomer component of the agent composition in the form of a complete polymer. Such adhesive compositions include, for example, a solvent-based adhesive composition containing an acrylic polymer, which is a complete polymerization product of monomer components, in an organic solvent, and a water-dispersed adhesive in which the acrylic polymer is dispersed in an aqueous solvent. It can be in the form of a composition, etc. In the present specification, the term "completely polymerized product" means that the polymerization conversion rate is over 95% by weight.

(Adhesive Composition Containing Polymerized and Unpolymerized Monomer Components)
A preferred pressure-sensitive adhesive composition according to another aspect contains a polymerization reaction product of a monomer mixture containing at least part of the monomer components (raw material monomers) of the composition. Typically, a part of the above monomer components is contained in the form of a polymer, and the remainder is contained in the form of an unpolymerized product (unreacted monomer). The polymerization reaction product of the monomer mixture can be prepared by at least partially polymerizing the monomer mixture.
The polymerization reactant is preferably a partial polymer of the monomer mixture. Such a partial polymer is a mixture of a polymer derived from the monomer mixture and unreacted monomers, and typically exhibits a syrup (viscous liquid). Hereinafter, the partial polymer having such properties is sometimes referred to as "monomer syrup" or simply "syrup".

The polymerization method for obtaining the polymerization reaction product is not particularly limited, and various polymerization methods as described above can be appropriately selected and used. A photopolymerization method can be preferably employed from the viewpoint of efficiency and convenience. According to the photopolymerization, the polymerization conversion rate of the monomer mixture can be easily controlled by the polymerization conditions such as the irradiation amount of light (light amount).

The polymerization conversion rate (monomer conversion) of the monomer mixture in the partially polymerized product is not particularly limited. The polymerization conversion rate can be, for example, about 70% by weight or less, preferably about 60% by weight or less. From the viewpoint of ease of preparation and coating properties of the pressure-sensitive adhesive composition containing the partially polymerized product, the polymerization conversion rate is usually about 50% by weight or less, and about 40% by weight or less (for example, about 35% by weight). % by weight or less) is preferred. Although the lower limit of the polymerization conversion rate is not particularly limited, it is typically about 1% by weight or more, and usually about 5% by weight or more is suitable.

A pressure-sensitive adhesive composition containing a partially polymerized product of the monomer mixture can be easily obtained, for example, by partially polymerizing a monomer mixture containing all of the raw material monomers by an appropriate polymerization method (e.g., photopolymerization method). The pressure-sensitive adhesive composition containing the partial polymer is blended with other components (for example, photopolymerization initiators, polyfunctional monomers, cross-linking agents, (meth)acrylic oligomers described later, etc.) that are used as necessary. obtain. The method of blending such other components is not particularly limited. For example, they may be included in the above monomer mixture in advance, or may be added to the above partial polymer.

Further, in the pressure-sensitive adhesive composition disclosed herein, the complete polymer of the monomer mixture containing some types of monomers among the monomer components (raw material monomers) is dissolved in the remaining types of monomers or partial polymerizations thereof. may be in the form Such a form of pressure-sensitive adhesive composition is also included in examples of pressure-sensitive adhesive compositions containing polymerized and unpolymerized monomer components.

A photopolymerization method can be preferably employed as a curing method (polymerization method) for forming an adhesive from the adhesive composition containing polymerized and unpolymerized monomer components. Adopting a photopolymerization method as a curing method is particularly suitable for a pressure-sensitive adhesive composition containing a polymerization reaction product prepared by a photopolymerization method. Since the polymerization reaction product obtained by the photopolymerization method already contains a photopolymerization initiator, a new photopolymerization initiator is added when the pressure-sensitive adhesive composition containing this polymerization reaction product is further cured to form a pressure-sensitive adhesive. Can be light cured without addition. Alternatively, it may be a pressure-sensitive adhesive composition having a composition obtained by adding a photopolymerization initiator to a polymerization reaction product prepared by a photopolymerization method, if necessary. The additional photoinitiator may be the same as or different from the photoinitiator used to prepare the polymerization reactants. A pressure-sensitive adhesive composition prepared by a method other than photopolymerization can be made photocurable by adding a photopolymerization initiator. A photocurable pressure-sensitive adhesive composition has the advantage that even a thick pressure-sensitive adhesive layer can be easily formed. In a preferred embodiment, photopolymerization when forming the adhesive from the adhesive composition can be performed by UV irradiation. A known high-pressure mercury lamp, low-pressure mercury lamp, metal halide lamp, or the like can be used for ultraviolet irradiation.

(crosslinking agent)
The pressure-sensitive adhesive composition (preferably solvent-based pressure-sensitive adhesive composition) used for forming the pressure-sensitive adhesive layer preferably contains a cross-linking agent as an optional component. The inclusion of a cross-linking agent can advantageously achieve the viscoelastic properties disclosed herein. The pressure-sensitive adhesive layer in the technology disclosed herein contains the cross-linking agent in the form after the cross-linking reaction, the form before the cross-linking reaction, the form in which the cross-linking reaction is partially performed, the intermediate or composite form thereof, or the like. obtain. The above-mentioned cross-linking agent is usually contained in the pressure-sensitive adhesive layer exclusively in the form after the cross-linking reaction.

The type of cross-linking agent is not particularly limited, and can be appropriately selected from conventionally known cross-linking agents. Examples of such cross-linking agents include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, melamine-based cross-linking agents, carbodiimide-based cross-linking agents, hydrazine-based cross-linking agents, amine-based cross-linking agents, Examples include peroxide-based cross-linking agents, metal chelate-based cross-linking agents, metal alkoxide-based cross-linking agents, metal salt-based cross-linking agents, and the like. A crosslinking agent can be used individually by 1 type or in combination of 2 or more types. Examples of cross-linking agents that can be preferably used in the technology disclosed herein include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and oxazoline-based cross-linking agents.

As the epoxy-based cross-linking agent, a compound having two or more epoxy groups in one molecule can be used without particular limitation. An epoxy-based cross-linking agent having 3 to 5 epoxy groups in one molecule is preferred. Epoxy-based cross-linking agents may be used singly or in combination of two or more.

Specific examples of epoxy-based cross-linking agents include, but are not limited to, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl ) cyclohexane, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether and the like. Commercially available epoxy-based cross-linking agents include Mitsubishi Gas Chemical Company's trade name "TETRAD-C" and trade name "TETRAD-X", DIC's trade name "Epiclon CR-5L", and Nagase ChemteX Corp.'s trade name. and "TEPIC-G" manufactured by Nissan Chemical Industries, Ltd. under the trade name of "Denacol EX-512".

In embodiments using an epoxy-based cross-linking agent, the amount used is not particularly limited. The amount of the epoxy-based cross-linking agent used is, for example, more than 0 parts by weight and about 1 part by weight or less (preferably about 0.001 to 0.5 parts by weight) with respect to 100 parts by weight of the acrylic polymer. can. From the viewpoint of suitably exhibiting the effect of improving the cohesive strength, the amount of the epoxy-based cross-linking agent used is usually about 0.002 parts by weight or more per 100 parts by weight of the acrylic polymer, preferably It may be about 0.005 parts by weight or more, for example, about 0.01 parts by weight or more, about 0.02 parts by weight or more, or about 0.03 parts by weight or more. In addition, from the viewpoint of avoiding insufficient adhesion at the initial stage of light pressure bonding due to excessive cross-linking, the amount of the epoxy-based cross-linking agent to be used is usually about 0.2 parts by weight or less per 100 parts by weight of the acrylic polymer. It is preferable that the amount is about 0.1 part by weight or less (for example, 0.05 part by weight or less).

As the isocyanate-based cross-linking agent, a polyfunctional isocyanate (meaning a compound having an average of two or more isocyanate groups per molecule, including those having an isocyanurate structure) can be preferably used. The isocyanate-based cross-linking agents may be used singly or in combination of two or more.

Examples of preferred polyfunctional isocyanates include polyfunctional isocyanates having an average of 3 or more isocyanate groups per molecule. Such tri- or more functional isocyanates are polymers (e.g., dimers or trimers) of di- or tri- or more functional isocyanates, derivatives (e.g., addition reactions of polyhydric alcohols and two or more molecules of polyfunctional isocyanates products), polymers, and the like. For example, dimers and trimers of diphenylmethane diisocyanate, isocyanurate of hexamethylene diisocyanate (trimer adduct of isocyanurate structure), reaction products of trimethylolpropane and tolylene diisocyanate, trimethylolpropane and hexa Polyfunctional isocyanates such as reaction products with methylene diisocyanate, polymethylene polyphenyl isocyanate, polyether polyisocyanate and polyester polyisocyanate can be mentioned. Commercially available polyfunctional isocyanates include "Duranate TPA-100" (trade name) manufactured by Asahi Kasei Chemicals, "Coronate L" (trade name), "Coronate HL", "Coronate HK" (trade name) and "Coronate HK" (trade names) manufactured by Tosoh Corporation. HX", "Coronate 2096", and the like.

In embodiments using an isocyanate-based cross-linking agent, the amount used is not particularly limited. The amount of the isocyanate-based cross-linking agent used can be, for example, about 0.5 parts by weight or more and about 10 parts by weight or less with respect to 100 parts by weight of the acrylic polymer. From the viewpoint of cohesiveness, the amount of the isocyanate cross-linking agent to be used with respect to 100 parts by weight of the acrylic polymer is usually about 0.1 parts by weight or more, and about 0.3 parts by weight or more (for example, 0.3 parts by weight). 5 parts by weight or more). In a more preferred embodiment, the amount of the isocyanate-based cross-linking agent used is approximately 1 part by weight or more, and may be approximately 1.5 parts by weight or more, relative to 100 parts by weight of the acrylic polymer. In addition, the amount of the isocyanate-based cross-linking agent to be used relative to 100 parts by weight of the acrylic polymer is usually about 8 parts by weight or less, and about 5 parts by weight or less (for example, less than about 4 parts by weight). preferable. In a more preferred embodiment, the amount of the isocyanate-based cross-linking agent used is approximately 3 parts by weight or less, for example, 2 parts by weight or less, relative to 100 parts by weight of the acrylic polymer.

As the oxazoline-based cross-linking agent, those having one or more oxazoline groups in one molecule can be used without particular limitation. The oxazoline-based cross-linking agents can be used singly or in combination of two or more. The oxazoline group may be any of 2-oxazoline group, 3-oxazoline group and 4-oxazoline group. Generally, an oxazoline-based cross-linking agent having a 2-oxazoline group can be preferably used. For example, a copolymer obtained by copolymerizing an addition-polymerizable oxazoline with another monomer can be used as an oxazoline-based cross-linking agent. Non-limiting examples of such addition polymerizable oxazolines include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-iso Propenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline.

Examples of oxazoline-based cross-linking agents include cross-linking agents exemplified in JP-A-2009-001673. Specific examples include compounds containing a main chain composed of an acrylic skeleton or a styrene skeleton and having an oxazoline group in the side chain of the main chain. A preferred example is an oxazoline-containing acrylic polymer having a main chain composed of an acrylic skeleton and having oxazoline groups on the side chains of the main chain. Commercially available oxazoline-based cross-linking agents include, for example, Nippon Shokubai Co., Ltd. under the trade names of "Epocross WS-500", "Epocross WS-700", "Epocross K-2010E", "Epocross K-2020E", and "Epocross K- 2030E" and the like.

In embodiments using an oxazoline-based cross-linking agent, the amount used is not particularly limited. The amount of the oxazoline-based cross-linking agent used can be, for example, 0.05 parts by weight or more, 0.1 parts by weight or more, or 0.5 parts by weight or more with respect to 100 parts by weight of the acrylic polymer. In some aspects, the amount of the oxazoline-based cross-linking agent used relative to 100 parts by weight of the acrylic polymer may be 1 part by weight or more, or 1.5 parts by weight or more. Increasing the amount of the oxazoline-based cross-linking agent used tends to make it easier to obtain higher cohesive strength. The amount of the oxazoline-based cross-linking agent to be used is usually, for example, 10 parts by weight or less, 8 parts by weight or less, 5 parts by weight or less, or 3 parts by weight or less with respect to 100 parts by weight of the acrylic polymer.

The technology disclosed herein can be preferably implemented in a mode using at least an epoxy-based cross-linking agent as the cross-linking agent. The epoxy group of the epoxy-based cross-linking agent can react with an acidic group that can be introduced into the acrylic polymer to build a cross-linked structure. This cross-linking reaction increases the cohesiveness of the pressure-sensitive adhesive, and more preferably exerts resistance to deformation against continuous load in the Z-axis direction. Examples of such aspects include an aspect in which an epoxy-based cross-linking agent is used alone and an aspect in which an epoxy-based cross-linking agent and another cross-linking agent are used in combination. In one aspect, the pressure-sensitive adhesive composition contains an epoxy-based cross-linking agent as a cross-linking agent, but does not substantially include an isocyanate-based cross-linking agent.

In another aspect, the pressure-sensitive adhesive composition contains an isocyanate-based cross-linking agent as a cross-linking agent. The isocyanate group of the isocyanate-based cross-linking agent reacts with an acidic group that can be introduced into the acrylic polymer in a reaction mode different from that of the epoxy-based cross-linking agent, and can construct a cross-linked structure. In a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on at least one surface of a base film, it is significant to use an isocyanate-based cross-linking agent from the viewpoint of improving the anchoring property to the base film.

In a particularly preferred embodiment, the pressure-sensitive adhesive composition contains both an epoxy-based cross-linking agent and an isocyanate-based cross-linking agent as cross-linking agents. For example, by using an epoxy-based cross-linking agent and an isocyanate-based cross-linking agent in combination with an acrylic polymer having an acidic group, the deformation resistance against a continuous load in the Z-axis direction can be further improved without impairing the initial adhesion of light pressure bonding. can improve. Specifically, the resistance to deformation in the Z-axis direction can be maintained for a long period of time even under strong repulsion, high temperature, and high humidity conditions, which will be discussed later in Examples. The ratio (C _I /C _E ) of the content C _I of the isocyanate cross-linking agent to the content C _E of the epoxy cross-linking agent is not particularly limited, and is set so as to obtain deformation resistance against a continuous load in the Z-axis direction. properly set. The above ratio (C _I /C _E ) is, for example, greater than 1 and is suitably about 5 or more, preferably about 15 or more, more preferably about 30 or more, still more preferably about 60 or more, and particularly preferably about 60 or more. is about 80 or more (eg, about 100 or more). The ratio (C _I /C _E ) is, for example, approximately 1000 or less, suitably approximately 500 or less, preferably approximately 200 or less, more preferably approximately 150 or less, further preferably approximately 120 or less. (for example, about 80 or less).

The content of the cross-linking agent (total amount of cross-linking agent) in the adhesive composition disclosed herein is not particularly limited. From the viewpoint of cohesiveness, the content of the cross-linking agent is usually about 0.001 parts by weight or more, preferably about 0.002 parts by weight or more, relative to 100 parts by weight of the acrylic polymer. It is preferably about 0.005 parts by weight or more, more preferably about 0.01 parts by weight or more, still more preferably about 0.02 parts by weight or more, and particularly preferably about 0.03 parts by weight or more. In addition, from the viewpoint of avoiding insufficient initial adhesiveness for light pressure bonding, the content of the cross-linking agent in the adhesive composition is usually about 20 parts by weight or less, and about 15 parts by weight or less with respect to 100 parts by weight of the acrylic polymer. It is preferable to make it about 10 parts by weight or less (for example, about 5 parts by weight or less).

(tackifying resin)
In one preferred embodiment, the pressure-sensitive adhesive composition (and thus the pressure-sensitive adhesive layer) contains a tackifying resin. Examples of tackifying resins that can be contained in the pressure-sensitive adhesive composition include phenol-based tackifying resins, terpene-based tackifying resins, modified terpene-based tackifying resins, rosin-based tackifying resins, hydrocarbon-based tackifying resins, and epoxy-based tackifying resins. One or two or more selected from various known tackifying resins such as imparting resins, polyamide-based tackifying resins, elastomer-based tackifying resins, and ketone-based tackifying resins can be used. The use of a tackifying resin improves adhesion, including initial light pressure adhesion.

Examples of phenolic tackifying resins include terpene phenolic resins, hydrogenated terpene phenolic resins, alkylphenolic resins and rosin phenolic resins.
Terpene phenol resin refers to a polymer containing a terpene residue and a phenol residue, a copolymer of terpenes and a phenol compound (terpene-phenol copolymer resin), terpenes or homopolymers or copolymers thereof. It is a concept that includes both phenol-modified coalescence (phenol-modified terpene resin). Preferred examples of terpenes constituting such a terpene phenol resin include monoterpenes such as α-pinene, β-pinene, and limonene (including d-, l- and d/l-forms (dipentene)). are mentioned. A hydrogenated terpene phenol resin refers to a hydrogenated terpene phenol resin having a structure obtained by hydrogenating such a terpene phenol resin. It is sometimes called a hydrogenated terpene phenolic resin.
Alkylphenol resins are resins obtained from alkylphenols and formaldehyde (oily phenolic resins). Examples of alkylphenol resins include novolac and resole types.
Rosin phenolic resins are typically rosins or phenol-modified products of the various rosin derivatives described above (including rosin esters, unsaturated fatty acid-modified rosins, and unsaturated fatty acid-modified rosin esters). Examples of rosin phenol resins include rosin phenol resins obtained by a method of adding phenol to rosins or various rosin derivatives described above with an acid catalyst and thermally polymerizing the mixture.
Among these phenolic tackifying resins, terpene phenol resins, hydrogenated terpene phenol resins and alkylphenol resins are preferred, terpene phenol resins and hydrogenated terpene phenol resins are more preferred, and terpene phenol resins are particularly preferred.

Examples of terpene-based tackifying resins include polymers of terpenes (eg, monoterpenes) such as α-pinene, β-pinene, d-limonene, l-limonene, and dipentene. It may be a homopolymer of one kind of terpenes, or a copolymer of two or more kinds of terpenes. One type of terpene homopolymer includes α-pinene polymer, β-pinene polymer, dipentene polymer and the like.
Examples of modified terpene resins include those obtained by modifying the above terpene resins. Specific examples include styrene-modified terpene resins and hydrogenated terpene resins.

The concept of rosin-based tackifying resins as used herein includes both rosins and rosin derivative resins. Examples of rosins include unmodified rosins (fresh rosins) such as gum rosin, wood rosin and tall oil rosin; homogenized rosin, polymerized rosin, other chemically modified rosins, etc.);

Rosin derivative resins are typically derivatives of rosins as described above. The term "rosin-based resin" as used herein includes derivatives of unmodified rosin and derivatives of modified rosin (including hydrogenated rosin, disproportionated rosin and polymerized rosin). For example, rosin esters such as undenatured rosin esters, which are esters of undenatured rosin and alcohols, and denatured rosin esters, which are esters of denatured rosin and alcohols; Saturated fatty acid-modified rosins; for example, unsaturated fatty acid-modified rosin esters obtained by modifying rosin esters with unsaturated fatty acids; rosin alcohols obtained by reducing the carboxy group of rosin esters modified with fatty acids; for example, rosins or metal salts of the various rosin derivatives described above; Specific examples of rosin esters include methyl esters, triethylene glycol esters, glycerin esters and pentaerythritol esters of unmodified rosins or modified rosins (hydrogenated rosins, disproportionated rosins, polymerized rosins, etc.).

Examples of hydrocarbon tackifying resins include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic/aromatic petroleum resins (styrene-olefin copolymers, etc. ), aliphatic/alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone-based resins, and coumarone-indene-based resins.

The softening point of the tackifying resin is not particularly limited. From the viewpoint of improving cohesive strength, a tackifier resin having a softening point (softening temperature) of about 80° C. or higher (preferably about 100° C. or higher) can be preferably used. For example, a phenol-based tackifying resin (terpene phenol resin, etc.) having such a softening point can be preferably used. In a preferred embodiment, a terpene phenol resin having a softening point of approximately 135° C. or higher (further approximately 140° C. or higher) can be used. There is no particular upper limit for the softening point of the tackifying resin. A tackifying resin having a softening point of about 200° C. or lower (more preferably about 180° C. or lower) can be preferably used from the viewpoint of adhesion to an adherend or base film. The softening point of the tackifying resin can be measured based on the softening point test method (ring and ball method) defined in JIS K2207.

A preferred embodiment includes an embodiment in which the tackifying resin contains one or more phenol-based tackifying resins (eg, terpene phenolic resins). The technology disclosed herein can be preferably practiced, for example, in a mode in which approximately 25% by weight or more (more preferably approximately 30% by weight or more) of the total amount of tackifying resin is a terpene phenolic resin. Approximately 50% by weight or more of the total amount of tackifying resin may be the terpene phenolic resin, and approximately 80% by weight or more (eg, approximately 90% by weight or more) may be the terpene phenolic resin. Substantially all of the tackifying resin (eg, approximately 95% to 100% by weight, or even approximately 99% to 100% by weight) may be a terpene phenolic resin.

The content of the phenolic tackifying resin (eg, terpene phenolic resin) is not particularly limited as long as it satisfies the desired viscoelastic properties. The content of the phenol-based tackifier resin (e.g., terpene phenol resin) is usually about 1 part by weight or more with respect to 100 parts by weight of the acrylic polymer, from the viewpoint of adhesive strength (e.g., initial adhesiveness for light pressure bonding). It is suitable to use 5 parts by weight or more, preferably about 8 parts by weight or more (typically 10 parts by weight or more), more preferably about 12 parts by weight or more (for example, 15 parts by weight or more). From the viewpoint of resistance to deformation, the content of the phenol-based tackifying resin is preferably about 45 parts by weight or less, preferably about 35 parts by weight, with respect to 100 parts by weight of the acrylic polymer. Below, more preferably about 30 parts by weight or less, still more preferably less than 30 parts by weight (for example, 25 parts by weight or less, typically 20 parts by weight or less).

Although not particularly limited, in one aspect of the technology disclosed herein, the tackifying resin may include a tackifying resin having a hydroxyl value higher than 20 mgKOH/g. Among them, a tackifying resin having a hydroxyl value of 30 mgKOH/g or more is preferable. Hereinafter, a tackifying resin having a hydroxyl value of 30 mgKOH/g or more may be referred to as a "high hydroxyl value resin". A tackifying resin containing such a high hydroxyl value resin can realize a pressure-sensitive adhesive layer with high cohesive strength by interacting with a cross-linking agent such as an isocyanate-based cross-linking agent in addition to the pressure-sensitive adhesive strength. In one aspect, the tackifier resin may contain a high hydroxyl value resin having a hydroxyl value of 50 mgKOH/g or more (more preferably 70 mgKOH/g or more). In addition, the above-mentioned high hydroxyl value resin (for example, terpene phenol resin) is preferably used in combination with, for example, an acrylic polymer containing C _1-6 alkyl (meth)acrylate as a main monomer, good adhesive strength.

The upper limit of the hydroxyl value of the high hydroxyl value resin is not particularly limited. From the viewpoint of compatibility with acrylic polymers, etc., the hydroxyl value of the high hydroxyl value resin is usually about 300 mgKOH/g or less, suitably about 200 mgKOH/g or less, preferably about 180 mgKOH/g or less, more preferably about 180 mgKOH/g or less. It is preferably about 160 mgKOH/g or less, more preferably about 140 mgKOH/g or less. The technology disclosed herein can be preferably practiced in a mode in which the tackifying resin contains a high hydroxyl value resin (eg, a phenolic tackifying resin, preferably a terpene phenolic resin) having a hydroxyl value of 30-160 mgKOH/g. In one aspect, a high hydroxyl value resin having a hydroxyl value of 30 to 80 mgKOH/g (eg, 30 to 65 mgKOH/g) can be preferably employed. In another aspect, a high hydroxyl value resin having a hydroxyl value of 70 to 140 mgKOH/g can be preferably employed.

Here, as the value of the hydroxyl value, a value measured by a potentiometric titration method specified in JIS K0070:1992 can be adopted. A specific measuring method is as follows.
[Method for measuring hydroxyl value]
1. Reagent (1) As the acetylation reagent, approximately 12.5 g (approximately 11.8 mL) of acetic anhydride is taken, pyridine is added to bring the total amount to 50 mL, and the mixture is thoroughly stirred and used. Alternatively, take about 25 g (about 23.5 mL) of acetic anhydride, add pyridine to bring the total amount to 100 mL, and use the mixture after thorough stirring.
(2) A 0.5 mol/L potassium hydroxide ethanol solution is used as a measurement reagent.
(3) In addition, prepare toluene, pyridine, ethanol and distilled water.
2. Operation (1) About 2 g of a sample is accurately weighed and collected in a flat-bottomed flask, 5 mL of an acetylation reagent and 10 mL of pyridine are added, and an air cooling tube is attached.
(2) After heating the flask in a bath at 100°C for 70 minutes, allowing it to cool, adding 35 mL of toluene as a solvent from the top of the cooling tube and stirring, then adding 1 mL of distilled water and stirring to obtain acetic anhydride. decompose. Heat again in the bath for 10 minutes for complete decomposition and allow to cool.
(3) Wash the cooling tube with 5 mL of ethanol and remove. Then, 50 mL of pyridine is added as a solvent and stirred.
(4) Add 25 mL of 0.5 mol/L potassium hydroxide ethanol solution using a whole pipette.
(5) Perform potentiometric titration with 0.5 mol/L potassium hydroxide ethanol solution. The inflection point of the obtained titration curve is taken as the end point.
(6) In the blank test, the above (1) to (5) are performed without any sample.
3. Calculation Calculate the hydroxyl value by the following formula.
Hydroxyl value (mgKOH/g) = [(BC) x f x 28.05]/S + D
here,
B: Amount (mL) of 0.5 mol/L potassium hydroxide ethanol solution used in the blank test,
C: Amount (mL) of 0.5 mol/L potassium hydroxide ethanol solution used for the sample,
f: factor of 0.5 mol/L potassium hydroxide ethanol solution,
S: weight of sample (g),
D: acid value,
28.05: ½ of the molecular weight of potassium hydroxide, 56.11;
is.

As the high hydroxyl value resin, among the various tackifier resins described above, those having a hydroxyl value equal to or higher than a predetermined value can be used. High hydroxyl value resin can be used individually by 1 type or in combination of 2 or more types. For example, as the high hydroxyl value resin, a phenolic tackifying resin having a hydroxyl value of 30 mgKOH/g or more can be preferably employed. The terpene phenol resin is convenient because the hydroxyl value can be arbitrarily controlled by the copolymerization ratio of phenol.

Although not particularly limited, a tackifying resin having a hydroxyl value of less than 30 mgKOH/g (for example, less than 20 mgKOH/g) can be used as the tackifying resin in the technique disclosed herein. Hereinafter, a tackifying resin having a hydroxyl value of less than 30 mgKOH/g may be referred to as a "low hydroxyl value resin". The hydroxyl value of the low hydroxyl value resin may be approximately 15 mg KOH/g or less, and may be approximately 10 mg KOH/g or less. The lower limit of the hydroxyl value of the low hydroxyl value resin is not particularly limited, and may be substantially 0 mgKOH/g. Such low hydroxyl value resins (for example, terpene phenolic resins) are preferably used in combination with, for example, acrylic polymers containing _C7-10 alkyl (meth)acrylate as the main monomer, to improve adhesion to adherends. can perform well.

Although not particularly limited, when using a high hydroxyl value resin, the ratio of the high hydroxyl value resin (for example, terpene phenol resin) to the total tackifying resin contained in the adhesive layer is, for example, about 25% by weight or more. about 30% by weight or more is preferable, and about 50% by weight or more (eg, about 80% by weight or more, typically about 90% by weight or more) is more preferable. Substantially all of the tackifying resin (eg, about 95-100 weight percent, or even about 99-100 weight percent) may be a high hydroxyl value resin.

In embodiments using a tackifying resin, the content of the tackifying resin is not particularly limited. The content of the tackifying resin is usually 1 part by weight or more relative to 100 parts by weight of the acrylic polymer, and may be approximately 5 parts by weight or more, and may be approximately 8 parts by weight or more (for example, approximately 10 parts by weight or more). ) is appropriate. The technology disclosed herein can be preferably carried out in a mode in which the content of the tackifier resin is about 12 parts by weight or more (for example, about 15 parts by weight or more) with respect to 100 parts by weight of the acrylic polymer. The upper limit of the content of the tackifying resin is not particularly limited. From the viewpoint of compatibility with the acrylic polymer and deformation resistance, the content of the tackifying resin with respect to 100 parts by weight of the acrylic polymer is appropriately about 70 parts by weight or less, preferably about 55 parts by weight or less. , more preferably about 45 parts by weight or less (eg, about 40 parts by weight or less, typically about 30 parts by weight or less). In a preferred embodiment, the content of the tackifier resin is less than 30 parts by weight, more preferably about 25 parts by weight or less, and even more preferably about 20 parts by weight or less, relative to 100 parts by weight of the acrylic polymer.

((meth)acrylic oligomer)
The pressure-sensitive adhesive composition (and thus the pressure-sensitive adhesive layer) disclosed herein can contain a (meth)acrylic oligomer from the viewpoint of improving adhesive strength and the like. As the (meth)acrylic oligomer, the Tg of the copolymer corresponding to the composition of the monomer component (typically, the Tg of the (meth)acrylic polymer contained in the adhesive formed from the adhesive composition It is preferable to use a polymer having a Tg higher than the Tg. By containing a (meth)acrylic oligomer, the adhesive strength of the pressure-sensitive adhesive can be improved.

The (meth)acrylic oligomer preferably has a Tg of about 0°C to about 300°C, preferably about 20°C to about 300°C, more preferably about 40°C to about 300°C. When Tg is within the above range, the adhesive strength can be favorably improved. In a preferred embodiment, the (meth)acrylic oligomer has a Tg of about 30° C. or higher, more preferably about 50° C. or higher (for example, about 60° C. or higher) from the viewpoint of cohesiveness of the pressure-sensitive adhesive. From the viewpoint of initial adhesiveness, the temperature is preferably about 200° C. or less, more preferably about 150° C. or less, even more preferably about 100° C. or less (for example, about 80° C. or less). The Tg of the (meth)acrylic oligomer is a value calculated based on the Fox formula, like the Tg of the copolymer corresponding to the composition of the monomer components.

The weight average molecular weight (Mw) of the (meth)acrylic oligomer can typically be about 1,000 or more and less than about 30,000, preferably about 1,500 or more and about 20,000 or less, more preferably about 2,000 or more and about 10,000 or less. It is preferable that Mw is within the above range because good adhesive strength and retention properties can be obtained. In a preferred embodiment, the Mw of the (meth)acrylic oligomer is about 2,500 or more (for example, about 3,000 or more) from the viewpoint of deformation resistance against a sustained load in the Z-axis direction, and from the viewpoint of initial light pressure bonding adhesion. , preferably about 7000 or less, more preferably about 5000 or less (eg about 4500 or less, typically about 400 or less). The Mw of the (meth)acrylic oligomer can be measured by gel permeation chromatography (GPC) and calculated as a value in terms of standard polystyrene. Specifically, measurement is performed using HPLC8020 manufactured by Tosoh Corporation, using two TSKgelGMH-H(20) columns, and using tetrahydrofuran as a solvent at a flow rate of about 0.5 ml/min.

Monomers constituting the (meth)acrylic oligomer include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl ( Alkyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate meth)acrylates; esters of (meth)acrylic acid and alicyclic alcohols (alicyclic hydrocarbon group-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate) ) acrylate); aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; (meth)acrylates obtained from terpene compound derivative alcohols; Such (meth)acrylates can be used singly or in combination of two or more.

(Meth)acrylic oligomers include alkyl (meth)acrylates having branched alkyl groups such as isobutyl (meth)acrylate and t-butyl (meth)acrylate; cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; Esters of (meth) acrylic acid and alicyclic alcohol such as dicyclopentanyl (meth) acrylate (alicyclic hydrocarbon group-containing (meth) acrylate); Phenyl (meth) acrylate and benzyl (meth) acrylate The inclusion of an acrylic monomer having a relatively bulky structure, typified by a (meth)acrylate having a cyclic structure such as an aryl (meth)acrylate, as a monomer unit further enhances the adhesiveness of the pressure-sensitive adhesive layer. It is preferable from the viewpoint that it can be improved. In addition, when ultraviolet rays are used when synthesizing a (meth)acrylic oligomer or when producing an adhesive layer, those having a saturated bond are preferable because they are less likely to cause polymerization inhibition, and the alkyl group is branched. An alkyl (meth)acrylate having a structure or an ester with an alicyclic alcohol (alicyclic hydrocarbon group-containing (meth)acrylate) can be suitably used as a monomer constituting the (meth)acrylic oligomer. All of the above branched-chain alkyl (meth)acrylates, alicyclic hydrocarbon group (meth)acrylates, and aryl (meth)acrylates correspond to (meth)acrylate monomers in the technology disclosed herein. Alicyclic hydrocarbon groups can be saturated or unsaturated alicyclic hydrocarbon groups.

The ratio of (meth)acrylate monomer (e.g., alicyclic hydrocarbon group-containing (meth)acrylate) to all monomer components constituting the (meth)acrylic oligomer is typically more than 50% by weight, preferably is 60% by weight or more, more preferably 70% by weight or more (for example, 80% by weight or more, further 90% by weight or more). In a preferred embodiment, the (meth)acrylic oligomer has a monomer composition consisting essentially of (meth)acrylate monomers.

As the constituent monomer component of the (meth)acrylic oligomer, functional group-containing monomers can be used in addition to the above (meth)acrylate monomers. Preferable examples of the functional group-containing monomer include monomers having a nitrogen atom-containing ring (typically a nitrogen atom-containing heterocyclic ring) such as N-vinyl-2-pyrrolidone and N-acryloylmorpholine; N,N-dimethylamino Amino group-containing monomers such as ethyl (meth)acrylate; amide group-containing monomers such as N,N-diethyl (meth)acrylamide; carboxyl group-containing monomers such as AA and MAA; hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate monomer; These functional group-containing monomers can be used singly or in combination of two or more. Among them, carboxyl group-containing monomers are preferred, and AA is particularly preferred.

When all monomer components constituting the (meth)acrylic oligomer contain functional group-containing monomers, the ratio of functional group-containing monomers (for example, carboxyl group-containing monomers such as AA) to all the monomer components is about 1% by weight. or more, preferably 2% by weight or more, more preferably 3% by weight or more, and about 15% by weight or less, preferably 10% by weight or less, more preferably 7% by weight or less.

A (meth)acrylic oligomer can be formed by polymerizing its constituent monomer components. The polymerization method and polymerization mode are not particularly limited, and conventionally known various polymerization methods (eg, solution polymerization, emulsion polymerization, bulk polymerization, photopolymerization, radiation polymerization, etc.) can be employed in an appropriate mode. The type of polymerization initiator that can be used as necessary (e.g., an azo polymerization initiator such as AIBN) is generally as exemplified in the synthesis of the acrylic polymer, and the amount of the polymerization initiator and the arbitrarily used The amount of the chain transfer agent such as n-dodecyl mercaptan, etc., is appropriately set based on common general technical knowledge so as to obtain the desired molecular weight, and therefore detailed description is omitted here.

From the above viewpoint, suitable (meth)acrylic oligomers include, for example, dicyclopentanyl methacrylate (DCPMA), cyclohexyl methacrylate (CHMA), isobornyl methacrylate (IBXMA), isobornyl acrylate (IBXA), In addition to homopolymers of cyclopentanyl acrylate (DCPA), 1-adamantyl methacrylate (ADMA), and 1-adamantyl acrylate (ADA), copolymers of CHMA and isobutyl methacrylate (IBMA), copolymers of CHMA and IBXMA polymers, copolymers of CHMA and acryloylmorpholine (ACMO), copolymers of CHMA and diethylacrylamide (DEAA), copolymers of CHMA and AA, copolymers of ADA and methyl methacrylate (MMA), Examples include a copolymer of DCPMA and IBXMA, a copolymer of DCPMA and MMA, and the like.

When the pressure-sensitive adhesive composition disclosed herein contains a (meth)acrylic oligomer, the content thereof is, for example, 0.1 parts by weight or more (for example, 1 part by weight or more) with respect to 100 parts by weight of the acrylic polymer. It is appropriate to From the viewpoint of better exhibiting the effect of the (meth)acrylic oligomer, the content of the (meth)acrylic oligomer is preferably about 5 parts by weight or more, more preferably about 8 parts by weight or more, and still more preferably about 10 parts by weight or more, particularly preferably about 12 parts by weight or more. From the viewpoint of compatibility with the acrylic polymer, the content of the (meth)acrylic oligomer is preferably less than 50 parts by weight (for example, less than 40 parts by weight), preferably 30 parts by weight. less than, more preferably about 25 parts by weight or less, and even more preferably about 20 parts by weight or less.

In a preferred embodiment, the pressure-sensitive adhesive composition (and thus the pressure-sensitive adhesive layer) contains one or more of the tackifying resins described above and one or more of (meth)acrylic oligomers. By using a combination of a tackifying resin and a (meth)acrylic oligomer in a composition containing a high-molecular-weight acrylic polymer, it is possible to obtain excellent initial adhesiveness at light pressure bonding, while being exposed to severer conditions such as strong repulsion. It can exhibit highly excellent resistance to deformation against a continuous load in the Z-axis direction even in a mode of use. The ratio of the content C _T of the tackifier resin and the content _{C O} of the ₍ meth)acrylic oligomer is not particularly limited. , preferably 2:8 to 8:2, more preferably 3:7 to 7:3, still more preferably 4:6 to 6:4.

The total amount (total amount) of the tackifying resin and (meth)acrylic oligomer contained in the pressure-sensitive adhesive composition (and thus the pressure-sensitive adhesive layer) according to a preferred embodiment is from the viewpoint of preferably exhibiting the effects of the technology disclosed herein. , about 1 part by weight or more, preferably about 10 parts by weight or more, more preferably about 16 parts by weight or more, still more preferably 20 parts by weight or more, particularly preferably 25 parts by weight or more, and It is suitably less than 120 parts by weight (for example, approximately 80 parts by weight or less), preferably less than 60 parts by weight, more preferably approximately 50 parts by weight or less, and even more preferably approximately 40 parts by weight or less.

(Other additives)
In addition to the components described above, the pressure-sensitive adhesive composition may optionally contain a leveling agent, a cross-linking aid, a plasticizer, a softening agent, an antistatic agent, an anti-aging agent, an ultraviolet absorber, an antioxidant, and a light stabilizer. Various additives commonly used in the field of pressure-sensitive adhesives such as As for such various additives, conventionally known ones can be used in a conventional manner, and since they do not particularly characterize the present invention, detailed description thereof will be omitted.

The adhesive layer disclosed here can be formed by a conventionally known method. For example, a method (direct method) of forming an adhesive layer by directly applying (typically applying) an adhesive composition to a non-releasable substrate and drying or curing can be employed. In addition, by applying an adhesive composition to a surface having releasability (release surface) and drying or curing it to form an adhesive layer on the surface, a substrate-less adhesive composition consisting of only an adhesive layer A sheet can be made. Furthermore, a method of transferring the pressure-sensitive adhesive layer formed on the release surface to a non-releasable substrate (transfer method) may be employed. As the release surface, the surface of a release liner, the back surface of a base material subjected to a release treatment, or the like can be used. The pressure-sensitive adhesive layer disclosed herein is typically formed continuously, but is not limited to such a form. It may be a formed pressure-sensitive adhesive layer.

As a method for applying the pressure-sensitive adhesive composition, various conventionally known methods can be used. Specifically, for example, roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, die coater, etc. A method such as an extrusion coating method can be used.

In one aspect of the technology disclosed herein, it is preferable to dry the pressure-sensitive adhesive composition under heating from the viewpoint of promoting the cross-linking reaction, improving production efficiency, and the like. The drying temperature can be, for example, about 40 to 150°C, preferably about 60 to 130°C. After drying the pressure-sensitive adhesive composition, it is further aged for the purpose of adjusting the migration of components in the pressure-sensitive adhesive layer, progressing the cross-linking reaction, relaxing distortion that may exist in the base film and the pressure-sensitive adhesive layer, and the like. good too.

In another aspect, in the pressure-sensitive adhesive sheet disclosed herein, the surface cured on the release surface by drying or curing the liquid film of the pressure-sensitive adhesive composition on the release surface of the release film is the first pressure-sensitive surface. It can be suitably manufactured by a method including forming an adhesive layer. According to this method, the pressure-sensitive adhesive composition (liquid film) in a fluid state is dried or cured in contact with the release surface, thereby improving the smoothness of the surface of the pressure-sensitive adhesive layer formed in contact with the release surface. It can be controlled with high precision. For example, by using a release film having a release surface with appropriate smoothness, the first pressure-sensitive adhesive surface with desired smoothness can be stably produced (with good reproducibility).

The pressure-sensitive adhesive sheet disclosed herein can be preferably produced by a method including drying or curing the liquid film of the pressure-sensitive adhesive composition between the release surfaces of a pair of release films to form a pressure-sensitive adhesive layer. This method is suitable as a method for producing a substrate-less double-sided pressure-sensitive adhesive sheet. Moreover, by laminating the substrate-less double-sided pressure-sensitive adhesive sheet thus obtained to the non-releasing surface of a supporting substrate, it can be preferably applied to the production of a substrate-attached single-sided pressure-sensitive adhesive sheet or a substrate-attached double-sided pressure-sensitive adhesive sheet. . As a method for disposing a liquid film of the adhesive composition between the release surfaces of a pair of release films, a liquid adhesive composition is applied to the release surface of the first release film, and then the liquid of the adhesive composition is applied. A method of covering the membrane with a second release film can be employed. As another method, a first release film and a second release film are supplied between a pair of rolls with their release surfaces facing each other, and a liquid pressure-sensitive adhesive composition is supplied between these release surfaces. are mentioned.

The thickness of the adhesive layer is not particularly limited. The thickness of the pressure-sensitive adhesive layer is usually about 300 μm or less, preferably about 200 μm or less, more preferably about 150 μm or less, and even more preferably about 100 μm or less. In the pressure-sensitive adhesive sheet according to a preferred embodiment, the thickness of the pressure-sensitive adhesive layer is about 70 μm or less (usually 60 μm or less), for example, about 50 μm or less, or about 40 μm or less. The lower limit of the thickness of the pressure-sensitive adhesive layer is not particularly limited, but from the viewpoint of adhesiveness and adherend conformability, it is advantageous to set the thickness to about 3 μm or more, preferably about 6 μm or more, and more preferably about 10 μm or more. (eg, about 15 μm or more), more preferably about 25 μm or more, for example, about 35 μm or more, or about 45 μm or more. The technology disclosed herein can be preferably implemented in the form of a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer with a thickness of, for example, approximately 10 μm or more and approximately 150 μm or less (preferably approximately 15 μm or more and approximately 50 μm or less). A suitable example is a substrate-less double-sided adhesive pressure-sensitive adhesive sheet comprising only a pressure-sensitive adhesive layer having the above thickness.

(Gel fraction)
Although not particularly limited, the gel fraction of the pressure-sensitive adhesive layer disclosed herein can be, for example, 20% or more on a weight basis, and usually 30% or more is suitable. % or more is preferable. By increasing the gel fraction of the pressure-sensitive adhesive layer within an appropriate range, there is a tendency to easily obtain deformation resistance against a sustained load in the Z-axis direction. In the technology disclosed herein, it is more preferable to use an adhesive layer having a gel fraction of 40% or more. The gel fraction is more preferably 45% or higher, particularly preferably 50% or higher. The gel fraction may be, for example, 55% or more. On the other hand, if the gel fraction is too high, the initial adhesiveness for light pressure bonding may tend to be insufficient. From this point of view, the gel fraction of the adhesive layer is preferably 90% or less, more preferably 80% or less, and even more preferably 70% or less (for example, 65% or less).

Here, the "gel fraction of the pressure-sensitive adhesive layer" refers to a value measured by the following method. The gel fraction can be grasped as the weight ratio of ethyl acetate-insoluble matter in the pressure-sensitive adhesive layer.
[Gel fraction measurement method]
An adhesive sample of about 0.1 g (weight Wg ₁ ) is wrapped in a porous polytetrafluoroethylene membrane (weight Wg ₂ ) having an average pore size of 0.2 μm, and the opening is tied with a string (weight Wg ₃ ). As the porous polytetrafluoroethylene (PTFE) membrane, trade name "Nitoflon (registered trademark) NTF1122" available from Nitto Denko Corporation (average pore size 0.2 μm, porosity 75%, thickness 85 μm) or equivalent use the product.
This package was immersed in 50 mL of ethyl acetate and kept at room temperature (typically 23° C.) for 7 days to elute only the sol component in the adhesive layer outside the film. The adhering ethyl acetate is wiped off, the packet is dried at 130° C. for 2 hours, and the weight (Wg ₄ ) of the packet is measured. The gel fraction _FG of the pressure-sensitive adhesive layer is obtained by substituting each value into the following formula. A similar method is adopted in the examples described later.
Gel fraction F _G (%)=[(Wg ₄ -Wg ₂ -Wg ₃ )/Wg ₁ ]×100

<Base material>
In embodiments in which the pressure-sensitive adhesive sheet disclosed herein is in the form of a single-sided pressure-sensitive adhesive type or double-sided pressure-sensitive adhesive type pressure-sensitive adhesive sheet with a substrate, the substrate that supports (backs) the pressure-sensitive adhesive layer may be a resin film, a foam film (foaming substrate), paper, cloth, metal foil, composites thereof, and the like can be used.

The technology disclosed herein can be implemented in the form of a PSA sheet with a substrate having the PSA layer on at least one surface of a substrate film (support). For example, it can be implemented in the form of a double-sided pressure-sensitive adhesive sheet with a substrate having the pressure-sensitive adhesive layer on one surface and the other surface of a substrate film.

As the base film, a base film containing a resin film can be preferably used. The base film is typically an independently shape-maintainable (independent) member. The base film in the technique disclosed here can be substantially composed of such a base film. Alternatively, the base film may contain an auxiliary layer in addition to the base film. Examples of the auxiliary layer include an undercoat layer, an antistatic layer, a colored layer, etc. provided on the surface of the base film.

The resin film is a film containing a resin material as a main component (a component contained in the resin film in an amount exceeding 50% by weight). Examples of resin films include polyolefin resin films such as polyethylene (PE), polypropylene (PP), and ethylene/propylene copolymer; polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and the like. vinyl chloride resin film; vinyl acetate resin film; polyimide resin film; polyamide resin film; fluorine resin film; The resin film may be a rubber-based film such as a natural rubber film or a butyl rubber film. Among them, from the viewpoint of handleability and workability, a polyester film is preferred, and a PET film is particularly preferred. In this specification, the term "resin film" is typically a non-porous sheet, and is a concept distinguished from so-called nonwoven fabrics and woven fabrics (in other words, a concept excluding nonwoven fabrics and woven fabrics). be.

The resin film may have a single-layer structure, or may have a multi-layer structure of two layers, three layers or more. From the viewpoint of shape stability, the resin film preferably has a single-layer structure. In the case of a multilayer structure, at least one layer (preferably all layers) is preferably a layer having a continuous structure of the resin (for example, polyester resin). The method for producing the resin film is not particularly limited, and a conventionally known method may be appropriately adopted. For example, conventionally known general film forming methods such as extrusion molding, inflation molding, T-die casting, and calender roll molding can be employed as appropriate.

In another aspect, paper, cloth, or metal is used as the substrate material. Examples of paper that can be used for the base film include Japanese paper, kraft paper, glassine paper, woodfree paper, synthetic paper, top coat paper, and the like. Examples of fabrics include woven fabrics and non-woven fabrics obtained by spinning various fibrous materials alone or by blending them. Examples of the fibrous substance include cotton, staple fiber, manila hemp, pulp, rayon, acetate fiber, polyester fiber, polyvinyl alcohol fiber, polyamide fiber, and polyolefin fiber. Examples of metal foils that can be used for the base film include aluminum foil and copper foil.

The nonwoven fabric referred to here is a concept that refers to a nonwoven fabric for adhesive sheets that is mainly used in the field of adhesive tapes and other adhesive sheets, and is typically a nonwoven fabric that is produced using a general paper machine. (sometimes referred to as so-called "paper"). The term "resin film" as used herein is typically a non-porous resin sheet, which is distinguished from, for example, non-woven fabrics (that is, does not include non-woven fabrics). The resin film may be a non-stretched film, a uniaxially stretched film, or a biaxially stretched film. In addition, the surface of the substrate on which the pressure-sensitive adhesive layer is to be provided may be subjected to surface treatment such as application of an undercoat, corona discharge treatment, plasma treatment, or the like.

If necessary, the resin film (for example, PET film) may contain fillers (inorganic fillers, organic fillers, etc.), colorants, dispersants (surfactants, etc.), anti-aging agents, antioxidants, ultraviolet Various additives such as absorbents, antistatic agents, lubricants and plasticizers may be added. The blending ratio of various additives is usually less than about 30% by weight (for example, less than about 20% by weight, preferably less than about 10% by weight).

The surface of the substrate film may be subjected to conventionally known surface treatments such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, application of a primer, and the like. Such a surface treatment can be a treatment for improving the adhesion between the base film and the pressure-sensitive adhesive layer, in other words, the anchoring property of the pressure-sensitive adhesive layer to the base film.

The thickness of the base film disclosed herein is not particularly limited. From the viewpoint of avoiding excessive thickness of the pressure-sensitive adhesive sheet, the thickness of the base film (for example, resin film) can be, for example, approximately 200 μm or less, preferably approximately 150 μm or less, and more preferably approximately 100 μm or less. The thickness of the base film may be approximately 70 μm or less, approximately 50 μm or less, or approximately 30 μm or less (for example, approximately 25 μm or less) depending on the intended use and usage mode of the pressure-sensitive adhesive sheet. In one aspect, the thickness of the base film may be about 20 μm or less, about 15 μm or less, or about 10 μm or less (eg, about 5 μm or less). By reducing the thickness of the base film, the thickness of the adhesive layer can be increased even if the total thickness of the adhesive sheet is the same. This can be advantageous from the viewpoint of improving adhesion to the substrate. The lower limit of the thickness of the base film is not particularly limited. The thickness of the base film is usually about 0.5 μm or more (for example, 1 μm or more), preferably about 2 μm or more, for example, about 4 μm or more, from the viewpoint of handleability (handlability) and workability of the pressure-sensitive adhesive sheet. . In one aspect, the thickness of the base film can be approximately 6 μm or greater, can be approximately 8 μm or greater, or can be approximately 10 μm or greater (eg, greater than 10 μm).

<Foam base material>
In another preferred embodiment, a foam substrate is used as the substrate. The foam substrates disclosed herein are substrates with portions having cells (cell structure), typically substrates comprising at least one layer of stratified foam (foam layer). be. The foam substrate may be a substrate composed of one or more foam layers. The foam substrate may be, for example, a substrate substantially composed of only one or two or more foam layers. Although not particularly limited, a preferred example of the foam base material in the technology disclosed herein is a foam base material composed of a single (one) foam layer.

The thickness of the foam base material is not particularly limited, and can be appropriately set according to the strength and flexibility of the pressure-sensitive adhesive sheet, the purpose of use, and the like. From the viewpoint of thinning, the thickness of the foam substrate is usually 1 mm or less, suitably 0.70 mm or less, preferably 0.40 mm or less, and more preferably 0.30 mm or less. The technique disclosed herein is preferably implemented in a mode in which the thickness of the foam substrate is 0.25 mm or less (typically 0.18 mm or less, for example 0.16 mm or less) from the viewpoint of workability. obtain. From the viewpoint of the impact resistance of the adhesive sheet, the thickness of the foam substrate is usually 0.04 mm or more, suitably 0.05 mm or more, preferably 0.06 mm or more, and 0.07 mm. 0.08 mm or more (for example, 0.08 mm or more) is more preferable. The technology disclosed herein is preferably implemented in a mode in which the thickness of the foam substrate is 0.10 mm or more (typically more than 0.10 mm, preferably 0.12 mm or more, for example 0.13 mm or more). obtain. Increasing the thickness of the foam substrate tends to improve impact resistance.

The density of the foam substrate (referring to apparent density; hereinafter the same unless otherwise specified) is not particularly limited, and may be, for example, 0.1 to 0.9 g/cm ³ . From the viewpoint of impact resistance, the density of the foam substrate is suitably 0.8 g/cm ³ or less, preferably 0.7 g/cm ³ or less (for example, 0.6 g/cm ³ or less). In one aspect, the density of the foam substrate may be less than 0.5 g/cm ³ and may be less than 0.4 g/cm ³ (eg, 0.5 g/cm ³ or less). From the viewpoint of impact resistance, the density of the foam substrate is preferably 0.12 g/cm ³ or more, more preferably 0.15 g/cm ³ or more, and 0.2 g/cm ³ or more (for example, 0.3 g/cm 3 or more). /cm ³ or more) is more preferable. In one aspect, the density of the foam substrate may be 0.4 g/cm ³ or greater, 0.5 g/cm ³ or greater (eg, greater than 0.5 g/cm ³ ), or even 0.5 g/cm 3 or greater. 0.55 g/cm ³ or more. The density (apparent density) of the foam substrate can be measured according to JIS K 6767.

Although the average cell diameter of the foam substrate is not particularly limited, it is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 150 μm or less from the viewpoint of stress dispersion. The lower limit of the average bubble diameter is not particularly limited, but from the viewpoint of conformability to unevenness, it is usually appropriate to be 10 μm or more, preferably 20 μm or more, more preferably 30 μm or more, and even more preferably 40 μm or more (for example, 50 μm or more). In one aspect, the average cell diameter may be 55 μm or more, and may be 60 μm or more. In addition, the average cell diameter here refers to the average cell diameter converted to a true sphere obtained by observing the cross section of the foam base material with an electron microscope.

The cell structure of the foam that constitutes the foam substrate disclosed herein is not particularly limited. The cell structure may be an open cell structure, a closed cell structure, or a semi-open and semi-closed cell structure. From the viewpoint of shock absorption, a closed cell structure and a semi-open and semi-closed cell structure are preferable.

The 25% compressive strength C ₂₅ of the foam substrate is not particularly limited, and can be, for example, 20 kPa or more (typically 30 kPa or more, further 40 kPa or more). C ₂₅ is usually suitably 250 kPa or more, preferably 300 kPa or more (for example, 400 kPa or more). A pressure-sensitive adhesive sheet comprising such a foam base material can exhibit good durability against impact such as dropping. For example, tearing of the adhesive sheet due to impact can be better prevented. Although the upper limit of C ₂₅ is not particularly limited, 1300 kPa or less (for example, 1200 kPa or less) is usually appropriate. _In one aspect, C25 may be 1000 kPa or less, 800 kPa or less, even 600 kPa or less (eg, 500 kPa or less), or 360 kPa or less. In another preferred embodiment, the C ₂₅ of the foam substrate can be from 20 kPa to 200 kPa (typically from 30 kPa to 150 kPa, such as from 40 kPa to 120 kPa). A pressure-sensitive adhesive sheet comprising such a foam base material can have excellent cushioning properties. For example, the foam base material absorbs the drop impact, so that the peeling of the pressure-sensitive adhesive sheet can be better prevented.

The 25% compressive strength C ₂₅ of the foam base material is obtained by stacking the foam base material cut into 30 mm squares and stacking them to a thickness of about 2 mm. This is the load when compressed by a thickness corresponding to 25% of the thickness (load at a compression rate of 25%). That is, it refers to the load when the sample to be measured is compressed to a thickness corresponding to 75% of the initial thickness. The compressive strength is measured according to JIS K 6767. As a specific measurement procedure, the measurement sample is set at the center of the pair of flat plates, and the flat plates are continuously compressed to a predetermined compression ratio by narrowing the distance between the flat plates, and the flat plates are stopped for 10 seconds. Measure the load after the passage of time. The compressive strength of the foam substrate can be controlled by, for example, the degree of cross-linking and density of the material forming the foam substrate, the size and shape of cells, and the like.

The tensile elongation of the foam substrate is not particularly limited. For example, a foam substrate having a tensile elongation in the machine direction (MD) of 200% to 800% (more preferably 400% to 600%) can be suitably employed. Further, a foam substrate having a tensile elongation in the width direction (TD) of 50% to 800% (more preferably 200% to 500%) is preferred. The elongation of the foam substrate is measured according to JIS K 6767. The elongation of the foam substrate can be controlled by, for example, the degree of cross-linking, apparent density (expansion ratio), and the like.

The tensile strength (tensile strength) of the foam substrate is not particularly limited. For example, a foam substrate having a tensile strength in the machine direction (MD) of 5 MPa to 35 MPa (preferably 10 MPa to 30 MPa) can be suitably employed. Further, a foam substrate having a tensile strength in the width direction (TD) of 1 MPa to 25 MPa (more preferably 5 MPa to 20 MPa) is preferred. The tensile strength of the foam substrate is measured according to JIS K 6767. The tensile strength of the foam substrate can be controlled by, for example, the degree of cross-linking, apparent density (expansion ratio), and the like.

The material of the foam substrate is not particularly limited. A foam substrate comprising a foam layer formed by a foam of plastic material (plastic foam) is usually preferred. The plastic material (which is meant to include rubber materials) for forming the plastic foam is not particularly limited, and can be appropriately selected from known plastic materials. The plastic material can be used singly or in appropriate combination of two or more.

Specific examples of plastic foams include polyolefin resin foams such as PE foams and PP foams; polyester resin foams such as PET foams, PEN foams, and PBT foams; Polyvinyl chloride resin foam such as polyvinyl chloride foam; vinyl acetate resin foam; polyphenylene sulfide resin foam; aliphatic polyamide (nylon) resin foam, wholly aromatic polyamide (aramid) Amide resin foams such as resin foams; polyimide resin foams; polyether ether ketone (PEEK) foams; styrene resin foams such as polystyrene foams; polyurethane resin foams, etc. urethane-based resin foam; and the like. As the plastic foam, a foam made of rubber-based resin such as a foam made of polychloroprene rubber may be used.

A preferred foam is a polyolefin resin foam (hereinafter also referred to as "polyolefin foam"). As the plastic material (that is, polyolefin resin) constituting the polyolefin foam, various known or commonly used polyolefin resins can be used without particular limitation. Examples thereof include PE such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE), PP, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, and the like. Examples of LLDPE include Ziegler-Natta catalyst linear low density polyethylene, metallocene catalyst linear low density polyethylene and the like. Such polyolefin-based resins can be used singly or in combination of two or more.

A suitable example of the foam base material in the technique disclosed herein is a PE-based foam base material substantially composed of a PE-based resin foam from the viewpoint of impact resistance, waterproofness, dust resistance, etc. and polyolefin foam substrates such as PP foam substrates substantially composed of PP resin foams. Here, the PE resin refers to a resin having ethylene as the main monomer (that is, the main component in the monomer), and in addition to HDPE, LDPE, LLDPE, etc., ethylene- Propylene copolymers, ethylene-vinyl acetate copolymers, and the like may be included. Similarly, a PP-based resin refers to a resin containing propylene as a main monomer. A PE-based foam base material can be preferably employed as the foam base material in the technique disclosed herein.

The method for producing the plastic foam (typically polyolefin foam) is not particularly limited, and various known methods can be appropriately employed. For example, it can be manufactured by a method including a molding step, a cross-linking step and a foaming step of the plastic material or the plastic foam. In addition, a stretching step may be included as necessary.
Examples of the method for cross-linking the plastic foam include a chemical cross-linking method using an organic peroxide, an ionizing radiation cross-linking method using ionizing radiation, and the like, and these methods can be used in combination. Examples of the ionizing radiation include electron beams, α-rays, β-rays, γ-rays, and the like. The dose of ionizing radiation is not particularly limited, and can be set to an appropriate irradiation dose in consideration of the target physical properties (for example, the degree of cross-linking) of the foam substrate.

If necessary, the foam base material may contain fillers (inorganic fillers, organic fillers, etc.), antioxidants, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, flame retardants, Various additives such as surfactants may be blended.

The foam base material in the technique disclosed herein is black or white in order to express desired design properties and optical properties (e.g., light shielding properties, light reflectivity, etc.) in the adhesive sheet provided with the foam base material. etc. may be colored. For this coloring, known organic or inorganic colorants can be used singly or in combination of two or more.

Appropriate surface treatment may be applied to the surface of the foam base material, if necessary. This surface treatment can be, for example, a chemical or physical treatment to enhance adhesion to adjacent materials (eg, adhesive layer). Examples of such surface treatments include corona discharge treatment, chromic acid treatment, ozone exposure, flame exposure, ultraviolet irradiation treatment, plasma treatment, application of a primer, and the like.

<Release liner>
In the technique disclosed herein, a release liner can be used in the formation of the adhesive layer, production of the adhesive sheet, storage of the adhesive sheet before use, distribution, shape processing, and the like. The release liner is not particularly limited. A release liner or the like made of a low-adhesive material such as PP can be used. The release treatment layer may be formed by surface-treating the liner base material with a release treatment agent such as a silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide-based release agent.

<Adhesive sheet>
The pressure-sensitive adhesive sheet disclosed herein has a 180 degree peel strength (initial adhesion strength at 23°C light pressure bonding) measured within 1 minute after pressure bonding under the conditions of 23°C and a pressure load of 0.1 kg, and 40°C, 0.05 MPa At least one of the 180 degree peel strength (40°C light pressure bonding initial adhesive strength) measured within 1 minute after pressure bonding under the conditions of 3 seconds and 3 seconds preferably satisfies 8 N/20 mm or more. A pressure-sensitive adhesive sheet satisfying the above properties can preferably exhibit excellent initial adhesion to the surface of an adherend by light pressure bonding at room temperature or light pressure bonding using a limited heating temperature. Since the pressure-sensitive adhesive sheet can achieve the desired initial light pressure-bonding adhesiveness in the pressure-bonding temperature range, even in applications where heating exceeding 60 ° C. is difficult (for example, for electronic devices), normal temperature or mild heating can be used. It can be preferably used in a sticking mode. Moreover, such a pressure-sensitive adhesive sheet is superior in handleability as compared with conventional thermocompression bonding.

The pressure-sensitive adhesive sheet disclosed herein has a 180 degree peel strength (initial adhesive strength at 23°C light pressure bonding) measured within 1 minute after pressure bonding under the conditions of 23°C and a pressure load of 0.1 kg is 8 N/20 mm or more. is preferred. Satisfying this property can exhibit excellent initial adhesion by light pressure bonding to various adherends (for example, materials used as members of portable electronic devices). In addition, the pressure-sensitive adhesive sheet having excellent initial adhesion after light pressure bonding is advantageous in that it can be easily applied to fragile adherends that may be damaged by normal pressure bonding. The 23° C. light pressure bonding initial adhesive strength is more preferably 10 N/20 mm or more, still more preferably 12 N/20 mm or more, and particularly preferably 14 N/20 mm or more. Although the upper limit of the 23° C. light pressure bonding initial adhesive strength is not particularly limited, it is usually appropriate to be about 30 N/20 mm or less (for example, about 20 N/20 mm or less). The 23° C. light pressure bonding initial adhesive strength is specifically measured by the method described in Examples below.

In addition, the pressure-sensitive adhesive sheet disclosed herein is heat-pressed under the conditions of 40° C., 0.05 MPa, and 3 seconds, and the 180 degree peel strength (40° C. light pressure initial adhesive strength) measured within 1 minute after press-bonding is , 8 N/20 mm or more. Satisfying this property can exhibit excellent initial adhesion at light pressure bonding in thermocompression bonding by heating at about 40° C. (in other words, mild thermocompression bonding). The thermocompression bonding is applicable to electronic devices and the like, unlike the conventional thermocompression bonding performed at about 100°C. The 40° C. light pressure bonding initial adhesive strength is more preferably 10 N/20 mm or more, still more preferably 12 N/20 mm or more, particularly preferably 14 N/20 mm or more, and most preferably 18 N/20 mm or more. Although the upper limit of the 40° C. light pressure bonding initial adhesive strength is not particularly limited, usually about 30 N/20 mm or less (for example, about 25 N/20 mm or less) is suitable. The 40° C. light pressure bonding initial adhesive strength is specifically measured by the method described in Examples below.

In addition, the pressure-sensitive adhesive sheet disclosed herein has a passing level of deformation resistance in the Z-axis direction deformation resistance test (23 ° C. or 40 ° C.) measured using a PET film with a thickness of 75 μm in the examples described later. (that is, no peeling occurs). A pressure-sensitive adhesive sheet satisfying the above properties has excellent light pressure-bonding adhesion and deformation resistance against a peeling load substantially only in the thickness direction (Z-axis direction) of the pressure-sensitive adhesive sheet, and It is difficult to deform against a sustained peeling load of

In addition, in the examples described later, the pressure-sensitive adhesive sheet disclosed herein was measured in a Z-axis direction deformation resistance test using a PET film having a thickness of 125 μm under the conditions of 65 ° C. 90% RH 72 hours. can be less than 1000 μm. A pressure-sensitive adhesive sheet that satisfies the above properties has particularly excellent deformation resistance against a peeling load that is substantially only in the thickness direction (Z-axis direction) of the pressure-sensitive adhesive sheet, and is capable of sustaining deformation in that direction. It is particularly resistant to deformation under peeling loads. In addition, even when the adhesive sheet attached to the adherend (e.g. mobile electronic device or its component module) is exposed to high temperature and high humidity conditions during storage, it exhibits stable deformation resistance. can. The floating height is preferably less than 700 μm, more preferably less than 500 μm, even more preferably less than 300 μm, particularly preferably less than 200 μm (for example less than 150 μm). The floating height is a height including the thickness of the pressure-sensitive adhesive sheet (50 μm in Examples described later).

Moreover, the adhesive sheet disclosed herein preferably has an adhesive strength after curing for 30 minutes measured according to JIS Z 0237:2000 of 8 N/20 mm or more. The pressure-sensitive adhesive sheet having adhesive strength after curing for 30 minutes exhibits good adhesiveness to adherends. The pressure-sensitive adhesive sheet having the above adhesive strength tends to exhibit good adhesiveness to resin materials used in electronic devices, such as polycarbonate (PC) and polyimide (PI). The adhesive strength after curing for 30 minutes is more preferably 10 N/20 mm or more, still more preferably 12 N/20 mm or more, and particularly preferably 14 N/20 mm or more (for example, 18 N/20 mm or more). The upper limit of the adhesive strength after curing for 30 minutes is not particularly limited, but usually about 30 N/20 mm or less (for example, about 25 N/20 mm or less) is suitable. The adhesive strength after curing for 30 minutes is specifically measured by the method described in Examples below.

The pressure-sensitive adhesive sheet according to a preferred embodiment preferably exhibits an initial adhesive strength at 23°C light pressure bonding of more than 50%. The above-mentioned 23°C light pressure initial adhesive strength expression rate can be obtained from the formula: 23°C light pressure initial adhesive strength expression rate (%) = (23°C light pressure initial adhesive strength/adhesive strength after curing for 30 minutes) x 100; can. The initial adhesive strength at 23° C. light pressure bonding and the adhesive strength after curing for 30 minutes have the same unit (typically [N/20 mm]). A pressure-sensitive adhesive sheet exhibiting the above expression rate has a greater initial adhesive strength after curing at 23°C with light pressure bonding, and is therefore preferably used in applications that require good adhesiveness immediately after application by light pressure bonding. The expression rate of the 23° C. light pressure bonding initial adhesive strength is more preferably 55% or more, still more preferably 60% or more, and particularly preferably 65% or more. By combining the techniques disclosed herein, it is possible to increase the expression rate to 70% or more, or even 75% or more. The upper limit of the 23° C. light pressure bonding initial adhesive strength expression rate is ideally 100%, but may be about 90% or less (for example, 85% or less).

The pressure-sensitive adhesive sheet according to another preferred embodiment preferably exhibits an initial adhesive strength at 40°C light pressure bonding of more than 50%. The above-mentioned 40°C light pressure initial adhesive strength expression rate can be obtained from the formula: 40°C light pressure initial adhesive strength expression rate (%) = (40°C light pressure initial adhesive strength/adhesive strength after curing for 30 minutes) x 100; can. The initial adhesive strength at 40° C. light pressure bonding and the adhesive strength after curing for 30 minutes have the same unit (typically (N/20 mm)). By satisfying this property, the pressure-sensitive adhesive sheet can exhibit excellent initial adhesiveness for light pressure bonding in thermocompression bonding by heating at about 40°C. The expression rate of the 40° C. light pressure bonding initial adhesive strength is more preferably 55% or more, still more preferably 60% or more, and particularly preferably 65% or more. By combining the techniques disclosed herein, it is possible to increase the expression rate to 70% or more, or even 75% or more. The upper limit of the 40° C. light pressure bonding initial adhesive strength expression rate is ideally 100%, but may be approximately 90% or less (for example, 85% or less).

Further, when the pressure-sensitive adhesive sheet disclosed herein is a substrate-less pressure-sensitive adhesive sheet consisting essentially of only a pressure-sensitive adhesive layer, the storage elastic modulus G' (25°C) of the pressure-sensitive adhesive sheet at 25°C is 0.25°C. It can be 15 MPa or more. The pressure-sensitive adhesive sheet having the above storage elastic modulus G' (25°C) can preferably exhibit good deformation resistance from an early stage after being attached to an adherend. The G′ (25° C.) is preferably 0.17 MPa or higher, more preferably 0.2 MPa or higher, and still more preferably 0.23 MPa or higher. The G′ (25° C.) is particularly preferably 0.25 MPa or more, and may be 0.3 MPa or more, for example. In addition, the above G' (25 ° C.) is usually suitable to be 1.0 MPa or less, preferably 0.6 MPa or less, more preferably 0.6 MPa or less, from the viewpoint of compatibility between the initial adhesiveness of light pressure bonding and deformation resistance. is 0.4 MPa or less, more preferably 0.35 MPa or less, and may be, for example, 0.3 MPa or less, 0.25 MPa or less, or 0.2 MPa or less.

Further, when the pressure-sensitive adhesive sheet disclosed herein is a substrate-less pressure-sensitive adhesive sheet consisting essentially of only a pressure-sensitive adhesive layer, the storage elastic modulus G' (85°C) of the pressure-sensitive adhesive sheet at 85°C is 0.5°C. 02 MPa or more. Thereby, a pressure-sensitive adhesive sheet having long-lasting deformation resistance can be preferably obtained. The G′ (85° C.) is specifically 0.022 MPa or higher, preferably 0.025 MPa or higher, and more preferably 0.027 MPa or higher. The G'(85°C) is more preferably about 0.03 MPa or more (for example, 0.035 MPa or more), particularly preferably 0.04 MPa or more, and even more preferably 0.05 MPa or more. Also, the above G' (85° C.) is usually suitably 1.0 MPa or less, for example 0.5 MPa or less, typically 0.1 MPa or less. The G' (85° C.) may be 0.05 MPa or less.

Further, when the pressure-sensitive adhesive sheet disclosed herein is a substrate-less pressure-sensitive adhesive sheet consisting essentially of a pressure-sensitive adhesive layer, the pressure-sensitive adhesive sheet is used as an adherend from the viewpoint of the initial adhesion by light pressure bonding. The storage elastic modulus G'(apply) at the temperature (crimping temperature) when crimping may be 0.6 MPa or less. The G'(apply) is preferably 0.4 MPa or less, more preferably 0.35 MPa or less, and may be, for example, 0.3 MPa or less, or may be 0.25 MPa or less. The G'(apply) may be, for example, 0.2 MPa or less. In addition, from the viewpoint of achieving both initial adhesiveness for light pressure bonding and resistance to deformation, the G'(apply) is suitably larger than 0.12 MPa, preferably 0.15 MPa or more, and more preferably 0.15 MPa or more. It is 17 MPa or more (for example, 0.2 MPa or more), more preferably 0.25 MPa or more, and may be, for example, 0.3 MPa or more. The crimping temperature is selected from a range of more than 0° C. and less than 60° C. from the viewpoint of crimping workability, temperature control, and the like. In the case of a pressure-sensitive adhesive sheet used for portable electronic devices, it is desirable to select the pressure bonding temperature from the range of 20° C. to 45° C. (typically 25° C. or 40° C.) due to temperature restrictions in the application.

Further, when the pressure-sensitive adhesive sheet disclosed herein is a substrate-less pressure-sensitive adhesive sheet consisting essentially of a pressure-sensitive adhesive layer, the pressure-sensitive adhesive sheet usually has a loss elastic modulus G″ at 25°C (25°C) of 2.0 MPa or less is suitable. The G″ (25° C.) is preferably 1.5 MPa or less, more preferably 1.0 MPa or less, and still more preferably 0.5 MPa or less. The G″ (25° C.) may be 0.3 MPa or less (for example, 0.25 MPa or less). It is usually suitable that the G″ (25° C.) is 0.01 MPa or more. , from the viewpoint of the wettability to the surface of the adherend and the initial adhesion of light pressure bonding, etc. or more.

Further, when the pressure-sensitive adhesive sheet disclosed herein is a substrate-less pressure-sensitive adhesive sheet consisting essentially of a pressure-sensitive adhesive layer, the tan δ (25°C) of the pressure-sensitive adhesive sheet at 25°C is, for example, about 0.3 or more. From the viewpoint of deformation resistance, it is preferably about 0.5 or more, more preferably about 0.7 or more, still more preferably about 0.8 or more, particularly preferably about 0.9 or more ( For example, about 1 or more). In addition, the above tan δ (25° C.) is suitable, for example, about 3 or less, and from the viewpoint of initial light pressure bonding adhesion, preferably about 2 or less, more preferably about 1.5 or less, and even more preferably about 1.2. It is below.

Further, when the pressure-sensitive adhesive sheet disclosed herein is a substrate-less pressure-sensitive adhesive sheet consisting essentially of a pressure-sensitive adhesive layer, the tan δ (85°C) of the pressure-sensitive adhesive sheet at 85°C is, for example, about 0.1 or more. is preferably about 0.2 or more, more preferably 0.22 or more, and still more preferably 0.24 or more (for example, 0.25 or more). The tan δ (85° C.) is, for example, about 2 or less, preferably about 1 or less, more preferably about 0.5 or less (for example, about 0.3 or less).

The storage elastic modulus G' (25°C), G' (85°C), G' (apply), loss elastic modulus G″ (25°C), tan δ (25°C) and tan δ (85°C) of the adhesive sheet are It can be obtained by the same method as the dynamic viscoelasticity measurement for the adhesive layer.

The pressure-sensitive adhesive sheet according to a preferred embodiment is a substrate-less double-sided adhesive pressure-sensitive adhesive sheet (substrate-less double-sided pressure-sensitive adhesive sheet) substantially composed of only a pressure-sensitive adhesive layer. Since such a substrate-less pressure-sensitive adhesive sheet has excellent conformability, it can adhere well to an adherend having steps, for example, and exhibit excellent adhesion performance. In addition, when the rigid materials are fixed to each other, uneven pressure bonding is less likely to occur, and good adhesive fixation can be easily achieved. Therefore, it can be preferably used for joining members of an electronic device such as a wiring board and a housing in which a rigid member that can have a step is arranged. Since the substrate-less double-sided PSA sheet has a pressure-sensitive adhesive layer over its entire thickness, it can exhibit stronger adhesion (for example, light pressure adhesion) in a space with a limited thickness. Therefore, it can be particularly preferably used for joining members of portable electronic devices.

The total thickness of the PSA sheet (not including the release liner) disclosed herein is not particularly limited. The total thickness of the adhesive sheet can be, for example, about 500 μm or less, usually about 350 μm or less is appropriate, and about 250 μm or less (for example, about 200 μm or less) is preferable. The technology disclosed herein is preferably in the form of a pressure-sensitive adhesive sheet (typically a double-sided pressure-sensitive adhesive sheet) having a total thickness of about 150 μm or less (more preferably about 100 μm or less, still more preferably about 60 μm or less, for example about 55 μm or less). can be implemented. Although the lower limit of the total thickness of the pressure-sensitive adhesive sheet is not particularly limited, it is generally suitable to be about 10 μm or more, preferably about 20 μm or more, and more preferably about 30 μm or more. When the pressure-sensitive adhesive sheet includes a foam base material, the upper limit of the total thickness of the pressure-sensitive adhesive sheet is usually 1.5 mm or less, preferably 1 mm or less, and more preferably 0.5 mm or less. be.

<Application>
The pressure-sensitive adhesive sheet disclosed herein has both initial adhesiveness under light pressure bonding and resistance to deformation against sustained load in the Z-axis direction. Taking advantage of these characteristics, the pressure-sensitive adhesive sheet can be used in various applications that require initial adhesiveness under light pressure bonding and deformation resistance against sustained loads in the Z-axis direction. For example, it can be preferably used for fixing various members by light crimping. Typical examples include applications for fixing members of various electronic devices in which tact time is strictly controlled due to mass production. For example, by using the adhesive sheet disclosed herein for fixing members in various portable devices (portable devices), normal temperature or limited heating (less than 60 ° C., The initial adhesiveness of light pressure bonding based on mild heating (typically about 40° C.) can be used to reduce the tact time in the manufacture of portable electronic devices, which can contribute to the improvement of productivity. Non-limiting examples of the above portable electronic devices include mobile phones, smartphones, tablet computers, notebook computers, various wearable devices (for example, wrist wear type worn on the wrist like a wristwatch, Eyewear type including glasses type (monocular type and binocular type, including head-mounted type), clothes type attached to shirts, socks, hats, etc. in the form of accessories, earphones ear-wear type, etc.), digital cameras, digital video cameras, audio equipment (portable music players, IC recorders, etc.), calculators (calculators, etc.), portable game devices, electronic dictionaries, electronic notebooks, electronic books, vehicle-mounted information equipment, portable radios, portable televisions, portable printers, portable scanners, portable modems, etc. In this specification, the term “portable” means not only being able to be simply carried, but also having a level of portability that allows an individual (a typical adult) to carry it relatively easily. shall mean.

The adhesive sheet disclosed herein (typically a double-sided adhesive sheet) can be used in the form of a bonding material processed into various external shapes to fix members constituting the portable electronic device as described above. Among others, it can be preferably used for portable electronic equipment having a liquid crystal display device. For example, an electronic device (typically a mobile electronic device such as a smartphone) having a display unit such as a touch panel display (which may be the display unit of a liquid crystal display device), and for increasing the screen size etc. The pressure-sensitive adhesive sheet disclosed herein is preferably used for fixing an elastic adherend in a device such as FPC that is folded to accommodate an elastic member in an internal space. By using the pressure-sensitive adhesive sheet disclosed herein, it is possible to fix the elastic adherend in a folded state even with light pressure bonding, and to maintain the fixed state continuously. Thus, the elastic member, which is folded and accommodated in the limited internal space of the portable electronic device, can be accurately positioned and held in a stable fixed state by the adhesive sheet disclosed herein. Moreover, as the material arranged inside the portable electronic device as described above, there are polar and rigid materials such as polycarbonate and polyimide. For this type of material (polar and rigid resin material), the pressure-sensitive adhesive sheet disclosed herein can preferably exhibit initial adhesiveness under light pressure bonding and resistance to deformation against sustained load in the Z-axis direction.

The development of electronic devices (typically, mobile electronic devices such as smartphones and tablet personal computers) having a display unit such as the touch panel display (which may be the display unit of a liquid crystal display device) The trend is toward achieving both high efficiency and high functionality. As for the enlargement of the screen, a countermeasure is taken such that the elastic member such as the FPC as described above is folded and accommodated in the internal space. On the other hand, in terms of high functionality, new functions such as a pressure sensor with more accurate pressure sensing performance and a face authentication unlock function have been embodied, realizing higher performance and higher quality products. For this purpose, high integration of circuits such as FPCs that are responsible for it is indispensable. For example, a double-sided FPC and a multilayer FPC can be cited as means for increasing the degree of circuit integration. It is expected that improved deformation resistance against sustained axial loads will be a required property. A pressure-sensitive adhesive sheet according to a preferred embodiment of the technology disclosed herein exhibits excellent deformation resistance under more severe conditions, such as the Z-axis direction deformation resistance test under strong repulsion, high temperature, and high humidity conditions described later. Therefore, it is more suitable for the above-mentioned next-generation touch panel display-mounted electronic device (typically, a touch panel display-mounted mobile electronic device such as a smartphone) and can be preferably used.

Matters disclosed by this specification include the following.
(1) an acrylic polymer as a base polymer and at least one selected from tackifying resins and (meth)acrylic oligomers,
The weight average molecular weight of the acrylic polymer is greater than 70×10 ⁴ ,
The acrylic pressure-sensitive adhesive composition, wherein the acrylic polymer has a dispersity (Mw/Mn) of less than 15.
(2) The acrylic polymer according to (1) above, wherein the acrylic polymer is polymerized at a rate of 50% by weight or more of an alkyl (meth)acrylate having an alkyl group having 1 to 6 carbon atoms at the ester end. system adhesive composition.
(3) The acrylic pressure-sensitive adhesive composition according to (1) or (2) above, wherein the acrylic polymer is copolymerized with an acidic group-containing monomer.
(4) The pressure-sensitive adhesive sheet according to (3) above, wherein the copolymerization ratio of the acidic group-containing monomer in the acrylic polymer is less than 10% by weight.
(5) The acrylic pressure-sensitive adhesive composition according to any one of (1) to (4), wherein the tackifying resin is contained in a proportion of less than 30 parts by weight with respect to 100 parts by weight of the acrylic polymer. thing.
(6) The acrylic polymer according to any one of (1) to (5), wherein the (meth)acrylic oligomer is contained in a proportion of less than 30 parts by weight with respect to 100 parts by weight of the acrylic polymer. Adhesive composition.
(7) The acrylic pressure-sensitive adhesive composition according to any one of (1) to (6) above, which contains both the tackifying resin and the (meth)acrylic oligomer.

(8) an acrylic pressure-sensitive adhesive layer containing an acrylic polymer as a base polymer and at least one selected from tackifying resins and (meth)acrylic oligomers;
The weight average molecular weight of the acrylic polymer is greater than 70×10 ⁴ ,
The pressure-sensitive adhesive sheet, wherein the acrylic polymer has a degree of dispersion (Mw/Mn) of less than 15.
(9) The adhesive according to (8) above, wherein the acrylic polymer is polymerized with an alkyl (meth)acrylate having an alkyl group having 1 to 6 carbon atoms at the ester end at a rate of 50% by weight or more. sheet.
(10) The adhesive sheet according to (8) or (9) above, wherein the acrylic polymer is copolymerized with an acidic group-containing monomer.
(11) The pressure-sensitive adhesive sheet according to (10) above, wherein the copolymerization ratio of the acidic group-containing monomer in the acrylic polymer is less than 10% by weight.
(12) Any one of (8) to (11) above, wherein in the acrylic pressure-sensitive adhesive layer, the tackifying resin is contained at a rate of less than 30 parts by weight with respect to 100 parts by weight of the acrylic polymer. The adhesive sheet described in .
(13) In the acrylic pressure-sensitive adhesive layer, the (meth)acrylic oligomer is contained in a proportion of less than 30 parts by weight with respect to 100 parts by weight of the acrylic polymer, above (8) to (12) The pressure-sensitive adhesive sheet according to any one of.
(14) The pressure-sensitive adhesive sheet according to any one of (8) to (13) above, wherein the acrylic pressure-sensitive adhesive layer contains both the tackifying resin and the (meth)acrylic oligomer.

(15) The pressure-sensitive adhesive sheet according to any one of (8) to (14) above, wherein the pressure-sensitive adhesive layer has a storage modulus G' (25°C) at 25°C of 0.15 MPa or more.
(16) The pressure-sensitive adhesive sheet according to any one of (8) to (15) above, wherein the pressure-sensitive adhesive layer has a storage modulus G'(85°C) at 85°C of 0.02 MPa or more.
(17) 180 degree peel strength measured within 1 minute after crimping under the conditions of 23 ° C. and a crimping load of 0.1 kg, and 40 ° C., 0.05 MPa, measured within 1 minute after crimping for 3 seconds The pressure-sensitive adhesive sheet according to any one of (8) to (16) above, wherein at least one of the 180 degree peel strengths is 8 N/20 mm or more.
(18) The pressure-sensitive adhesive sheet according to any one of (8) to (17) above, wherein the pressure-sensitive adhesive layer has a gel fraction of 40% by weight or more.
(19) The adhesive sheet according to any one of (8) to (18) above, wherein the acrylic polymer is crosslinked.
(20) The pressure-sensitive adhesive sheet according to any one of (8) to (19) above, wherein the acrylic polymer is copolymerized with n-butyl acrylate at a rate of 50% by weight or more.
(21) Any of the above (8) to (20), wherein the pressure-sensitive adhesive layer contains the tackifying resin, and about 50% by weight or more of the tackifying resin is a phenolic tackifying resin (eg, terpene phenolic resin). The adhesive sheet described in Crab.
(22) The pressure-sensitive adhesive sheet according to (21) above, wherein the phenol-based tackifier resin contains a terpene phenol resin having a hydroxyl value of less than approximately 30 mgKOH/g.
(23) The pressure-sensitive adhesive sheet according to any one of (8) to (22) above, wherein the pressure-sensitive adhesive layer has a loss elastic modulus G″ (25°C) at 25°C of 2.0 MPa or less.
(24) The pressure-sensitive adhesive according to any one of (8) to (23) above, wherein the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer formed from a solvent-based pressure-sensitive adhesive composition or an active energy ray-curable pressure-sensitive adhesive composition. sheet.
(25) The pressure-sensitive adhesive sheet according to any one of (8) to (24) above, which is configured as a substrate-less pressure-sensitive adhesive sheet consisting only of the pressure-sensitive adhesive layer.
(26) The pressure-sensitive adhesive sheet according to any one of (8) to (25) above, which is configured as a double-sided adhesive pressure-sensitive adhesive sheet with a thickness of less than 60 μm.
(27) The pressure-sensitive adhesive sheet according to any one of (8) to (26) above, which exhibits an initial adhesive strength at 23°C light pressure bonding of more than 50%.

(28) A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer,
The pressure-sensitive adhesive layer has a storage modulus G' (25°C) of 0.15 MPa or more at 25°C and a storage modulus G' (85°C) of 0.02 MPa or more at 85°C,
180 degree peel strength measured within 1 minute after crimping under the conditions of 23 ° C. and crimping load of 0.1 kg, and 180 degree peel measured within 1 minute after crimping under the conditions of 40 ° C., 0.05 MPa, 3 seconds A pressure-sensitive adhesive sheet satisfying that at least one of the strengths is 8 N/20 mm or more.
(29) The pressure-sensitive adhesive sheet according to (28) above, wherein the pressure-sensitive adhesive layer has a gel fraction of 40% by weight or more.
(30) The pressure-sensitive adhesive sheet according to (28) or (29) above, wherein the pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive layer containing an acrylic polymer.
(31) The acrylic polymer according to (30) above, wherein an alkyl (meth)acrylate having an alkyl group having 1 to 6 carbon atoms at the ester end is copolymerized at a rate of 50% by weight or more. adhesive sheet.
(32) The pressure-sensitive adhesive sheet according to (30) or (31) above, wherein the acrylic polymer is copolymerized with an acidic group-containing monomer.
(33) The adhesive sheet according to (32) above, wherein the acidic group-containing monomer is acrylic acid.
(34) The pressure-sensitive adhesive sheet according to (32) or (33) above, wherein the copolymerization ratio of the acidic group-containing monomer in the acrylic polymer is less than 10% by weight.
(35) The adhesive sheet according to any one of (30) to (34) above, wherein the acrylic polymer is crosslinked.
(36) The pressure-sensitive adhesive sheet according to any one of (30) to (35) above, wherein the weight average molecular weight (Mw) of the acrylic polymer is greater than 70×10 ⁴ .
(37) The pressure-sensitive adhesive sheet according to any one of (30) to (36) above, wherein the acrylic polymer is copolymerized with n-butyl acrylate at a rate of 50% by weight or more.
(38) Any one of (28) to (37) above, wherein the pressure-sensitive adhesive layer contains a tackifying resin, and about 50% by weight or more of the tackifying resin is a phenol-based tackifying resin (eg, a terpene phenolic resin). The adhesive sheet described in .
(39) The pressure-sensitive adhesive sheet according to (38) above, wherein the phenol-based tackifier resin contains a terpene phenol resin having a hydroxyl value of less than approximately 30 mgKOH/g.
(40) The pressure-sensitive adhesive sheet according to any one of (28) to (39) above, wherein the pressure-sensitive adhesive layer has a loss elastic modulus G″ (25°C) of 2.0 MPa or less at 25°C.
(41) The pressure-sensitive adhesive according to any one of (28) to (40) above, wherein the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer formed from a solvent-based pressure-sensitive adhesive composition or an active energy ray-curable pressure-sensitive adhesive composition. sheet.
(42) The pressure-sensitive adhesive sheet according to any one of (28) to (41) above, which is configured as a substrate-less pressure-sensitive adhesive sheet consisting only of the pressure-sensitive adhesive layer.
(43) The pressure-sensitive adhesive sheet according to any one of (28) to (42) above, which is configured as a double-sided adhesive pressure-sensitive adhesive sheet with a thickness of less than 60 μm.
(44) The pressure-sensitive adhesive sheet according to any one of (28) to (43) above, which exhibits an initial adhesive strength at 23°C light pressure bonding of more than 50%.

(45) The pressure-sensitive adhesive sheet according to any one of (8) to (44) above, which is used for fixing a member in a portable electronic device.
(46) The pressure-sensitive adhesive sheet according to any one of (8) to (45) above, which is used for fixing a flexible printed wiring board.
(47) The pressure-sensitive adhesive sheet according to any one of (8) to (46) above, which is used for fixing a flexible printed wiring board accommodated in a folded state in a portable electronic device.

Several examples relating to the present invention are described below, but the present invention is not intended to be limited to those shown in such examples. In the following description, "parts" and "%" are by weight unless otherwise specified.

≪Experiment 1≫
<Example 1-1>
(Preparation of acrylic polymer solution)
A reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a reflux condenser and a dropping funnel was charged with 90 parts of 2EHA and 10 parts of AA as monomer components, and ethyl acetate and toluene as polymerization solvents were added at a ratio of about 1:1 ( volume ratio), and stirred for 2 hours while introducing nitrogen gas. After removing oxygen from the polymerization system in this manner, 0.2 part of BPO was added as a polymerization initiator, and solution polymerization was performed at 60° C. for 6 hours to obtain an acrylic polymer solution according to this example.

(Preparation of adhesive composition)
To the acrylic polymer solution obtained above, 0.05 part of an epoxy cross-linking agent (trade name “TETRAD-C”, 1,3-bis(N, N-diglycidylaminomethyl)cyclohexane, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 20 parts of a terpene phenol resin (trade name "Tamanol 803L", manufactured by Arakawa Chemical Industries, Ltd., softening point about 145 to 160 ° C., hydroxyl value 1 ~ 20 mg KOH/g) was added and mixed with stirring to prepare a pressure-sensitive adhesive composition according to this example.

(Preparation of adhesive sheet)
As release liner A, a polyester release film (trade name “Diafoil MRV”, thickness 75 μm, manufactured by Mitsubishi Polyester Co., Ltd.) having one side subjected to release treatment to serve as a release surface was used as release liner B, and one side was subjected to release treatment. A polyester release film (trade name “Diafoil MRF”, thickness 38 μm, manufactured by Mitsubishi Polyester Co., Ltd.) was prepared as a release surface. The pressure-sensitive adhesive composition obtained above was applied to the release surface of release liner A and dried at 100° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 50 μm. The exposed adhesive surface of the adhesive layer was covered with a release liner B so that the release surface faced the adhesive layer side to prepare a substrate-less double-sided adhesive adhesive sheet according to this example.

<Example 1-2 to Example 1-5>
A solution of an acrylic polymer according to each example was prepared basically in the same manner as in Example 1-1 except that the monomer composition shown in Table 1 was used. Using the obtained acrylic polymer, a pressure-sensitive adhesive composition according to each example was prepared in the same manner as in Example 1-1, and a substrate-less double-sided adhesive pressure-sensitive adhesive sheet according to each example was produced.

<Example 1-6>
(Preparation of adhesive composition)
2,2-dimethoxy-1,2-diphenylethan-1-one (manufactured by BASF, trade name “Irgacure 651”) is added as a photopolymerization initiator to a monomer mixture obtained by mixing 90 parts of 2EHA and 10 parts of AA as monomer components. 0.05 part and 0.05 part of 1-hydroxycyclohexyl-phenyl-ketone (manufactured by BASF, trade name "Irgacure 184") are mixed, and irradiated with ultraviolet rays (UV) until the viscosity reaches about 15 Pa s. to obtain a partially polymerized product (monomer syrup). 0.1 part of 1,6-hexanediol diacrylate was added to this monomer syrup and uniformly mixed to prepare an adhesive composition. The viscosity was measured using a BH viscometer under the conditions of a rotor (No. 5 rotor), a rotation speed of 10 rpm, and a measurement temperature of 30°C.

(Preparation of adhesive sheet)
Release liners A (thickness: 75 μm) and B (thickness: 38 μm) were prepared in the same manner as in Example 1-1 above, and the pressure-sensitive adhesive composition obtained above was applied to the release surface of release liner A. The coating amount of the pressure-sensitive adhesive composition was adjusted so that the thickness of the finally formed pressure-sensitive adhesive layer was 150 μm. Next, a release liner B was put on the coating film of the pressure-sensitive adhesive composition so that its release surface was in contact with the coating film. In this way, the coating film was shielded from oxygen. Then, from both sides of the coating film of the pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition is irradiated with ultraviolet rays (trade name: “Black Light”, manufactured by Toshiba Corporation) for 3 minutes at an illuminance of 5 mW/cm ² to proceed with the polymerization reaction. The material was cured to form a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet according to this example comprising the pressure-sensitive adhesive layer (that is, the UV-cured product of the coating film) was obtained. The above illuminance values are measured by an industrial UV checker with a peak sensitivity wavelength of about 350 nm (manufactured by Topcon Corporation, trade name "UVR-T1", photodetector model UD-T36).

<Example 1-7>
A substrate-less double-sided adhesive pressure-sensitive adhesive sheet according to this example was produced in basically the same manner as in Example 1-6 except that the monomer composition shown in Table 1 was used.

<Example 1-8>
(Preparation of acrylic polymer solution)
A reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, reflux condenser and dropping funnel was charged with 93 parts of BA, 7 parts of AA and 0.05 part of 4-hydroxybutyl acrylate (4HBA) as a polymerization solvent. of ethyl acetate were charged, and the mixture was stirred for 2 hours while introducing nitrogen gas. After removing oxygen from the polymerization system in this way, 0.1 part of AIBN was added as a polymerization initiator, and solution polymerization was performed at 60° C. for 6 hours to obtain a solution of the acrylic polymer according to this example.

(Preparation of adhesive sheet)
To the acrylic polymer solution obtained above, 1.5 parts of an isocyanate cross-linking agent (trade name "Coronate L", trimethylolpropane/tolylene diisocyanate 3 parts per 100 parts of the acrylic polymer contained in the solution) 75% ethyl acetate solution of the polyadduct, manufactured by Tosoh Corporation) and 0.01 part of an epoxy-based cross-linking agent (trade name “TETRAD-C”, 1,3-bis (N, N-diglycidylaminomethyl) cyclo Hexane, manufactured by Mitsubishi Gas Chemical Co., Ltd.), 15 parts of terpene phenol resin (trade name "YS Polyster S-145" manufactured by Yasuhara Chemical Co., softening point of about 145 ° C., hydroxyl value of 70 to 110 mgKOH / g), and 15 parts and a (meth)acrylic oligomer were added and mixed with stirring to prepare a pressure-sensitive adhesive composition according to this example.
Using the obtained pressure-sensitive adhesive composition, a substrate-less double-sided adhesive pressure-sensitive adhesive sheet according to this example was produced in the same manner as in Example 1-1.
As the (meth)acrylic oligomer, one prepared by the following method was used. Specifically, 95 parts of CHMA and 5 parts of AA, 10 parts of AIBN as a polymerization initiator, and toluene as a polymerization solvent were added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a reflux condenser and a dropping funnel. and stirred in a nitrogen stream for 1 hour to remove oxygen in the polymerization system, then heated to 85° C. and reacted for 5 hours to obtain a (meth)acrylic oligomer having a solid concentration of 50%. Mw of the obtained (meth)acrylic oligomer was 3,600.

<Example 1-9 to Example 1-12>
A solution of an acrylic polymer according to each example was prepared basically in the same manner as in Example 1-1 except that the monomer composition shown in Table 1 was used. Using the obtained acrylic polymer, a pressure-sensitive adhesive composition according to each example was prepared in the same manner as in Example 1-1. In Example 1-11, instead of the epoxy cross-linking agent, 3 parts of an isocyanate cross-linking agent (trade name "Coronate L", trimethylolpropane/tolylene diisocyanate trimer adduct with 75% acetic acid Ethyl solution, manufactured by Tosoh Corporation) was used. Using the resulting pressure-sensitive adhesive composition, substrate-less double-sided adhesive pressure-sensitive adhesive sheets according to Examples 1-9 to 1-12 were produced in the same manner as in Example 1-1.

[Initial adhesive strength at 23°C light pressure bonding]
A sample piece was prepared by cutting the adhesive sheet according to each example into a size of 20 mm in width and 100 mm in length. One adhesive surface of the adhesive sheet is lined with a PET film having a thickness of 50 μm. In addition, the backing film is unnecessary in the measurement of the single-sided pressure-sensitive adhesive sheet with a substrate. Under the environment of 23° C. and 50% RH, the adhesive surface of the sample piece was press-bonded to a stainless steel plate (SUS304BA plate) to prepare a measurement sample. The pressure bonding was performed by reciprocating a 0.1 kg roller once. The peel strength [N/20 mm] of the measurement sample was measured using a tensile tester under the conditions of a tensile speed of 300 mm/min and a peel angle of 180 degrees in an environment of 23° C. and 50% RH. The measurement of the peel strength was performed within 1 minute after attachment to the stainless steel plate. As the tensile tester, "Precision Universal Testing Machine Autograph AG-IS 50N" manufactured by Shimadzu Corporation was used, but equivalent measurement results can be obtained by using an equivalent product.

[Initial adhesive strength at 40°C light pressure bonding]
Sample pieces were prepared by cutting the adhesive sheets according to Examples 1-4, 1-5, and 1-9 to 1-12 into a size of 20 mm in width and 100 mm in length. One adhesive surface of the adhesive sheet is lined with a PET film having a thickness of 50 μm. In addition, the backing film is unnecessary in the measurement of the single-sided pressure-sensitive adhesive sheet with a substrate. In an environment of 23 ° C. and 50% RH, the adhesive surface of the sample piece was crimped to a stainless steel plate (SUS304BA plate) under the conditions of 0.05 MPa and 3 seconds using a press set at a temperature of 40 ° C. A measurement sample was prepared by The peel strength [N/20 mm] of the measurement sample was measured using a tensile tester under the conditions of a tensile speed of 300 mm/min and a peel angle of 180 degrees in an environment of 23° C. and 50% RH. The measurement of peel strength was performed within less than 1 minute after pressure bonding to the stainless steel plate. As the tensile tester, "Precision Universal Testing Machine Autograph AG-IS 50N" manufactured by Shimadzu Corporation was used, but equivalent measurement results can be obtained by using an equivalent product.

[Adhesive strength after curing for 30 minutes]
A sample piece was prepared by cutting the adhesive sheet according to each example into a size of 20 mm in width and 100 mm in length. One adhesive surface of the adhesive sheet is lined with a PET film having a thickness of 50 μm. A backing film is not required in the measurement of the single-sided pressure-sensitive adhesive sheet with a substrate. Under the environment of 23° C. and 50% RH, the adhesive surface of the sample piece was press-bonded to a stainless steel plate (SUS304BA plate) to prepare a measurement sample. The pressure bonding was performed by reciprocating a 2 kg roller once. After leaving the measurement sample in an environment of 23 ° C. and 50% RH for 30 minutes, using a tensile tester, according to JIS Z 0237: 2000, a tensile speed of 300 mm / min and a peel angle of 180 degrees. , the peel strength [N/20 mm] was measured. This value was taken as the adhesive strength after curing for 30 minutes. As the tensile tester, "Precision Universal Testing Machine Autograph AG-IS 50N" manufactured by Shimadzu Corporation was used, but equivalent measurement results can be obtained by using an equivalent product.

[Z-axis deformation resistance test]
As shown in FIG. 7(a), a polycarbonate (PC) plate 50 having a length of 30 mm, a width of 10 mm and a thickness of 2 mm and a PET film 60 having a length of 100 mm, a width of 10 mm and a thickness of 75 μm were prepared, The PC board 50 and the PET film 60 were superimposed so that one end in the longitudinal direction was aligned, and the PC board 50 and the PET film 60 were fixed with the remaining part of the PET film 60 protruding from the other end of the PC board 50. . A commercially available double-sided adhesive tape (“No. 5000NS” manufactured by Nitto Denko Corporation) was used for the fixing.
An adhesive sheet sample piece 70 was prepared by cutting the adhesive sheet according to each example having both adhesive surfaces protected by two release liners into a size of 3 mm in width and 10 mm in length. The surface of the PC board 50 opposite to the fixing surface of the PET film is placed on the upper side, one release liner is peeled off from the adhesive sheet sample piece 70, and the width direction of the PC board 50 and the longitudinal direction of the adhesive sheet sample piece 70 are separated. The adhesive sheet sample piece 70 is attached to the upper surface of the PC board 50 so that both ends of the adhesive sheet sample piece 70 in the width direction are on the lines of 7 mm and 10 mm from the other end on the upper surface of the PC board 50. Fixed. The fixing was performed by reciprocating the upper surface of the adhesive sheet sample piece 70 protected by the other release liner with a 2 kg roller once.
Next, under an environment of 23° C. and 50% RH, the other release liner of the adhesive sheet sample piece 70 attached to the PC board 50 was peeled off, and the PC board 50 was left as shown in FIG. The protruding part (length 70 mm) from the PC board 50 of the PET film 60 fixed to the PC board 50 is folded back to the PC board 50 side, and the adhesive sheet sample piece 70 and the other end (free end) of the PET film 60 are aligned. The other end of the folded PET film 60 was fixed to the upper surface of the PC board 50 via the adhesive sheet sample piece 70 by reciprocating a roller of 0.1 kg over the PET film 60 once. It was observed for 60 minutes whether the PET film 60 was peeled off from the adhesive sheet sample piece 70, and the adhesion holding force of the adhesive sheet sample piece 70 in the adhesive sheet thickness direction based on the elastic rebound of the folded PET film 60 was measured at 23°C. It was evaluated as resistance to deformation in the Z-axis direction. A case where the adhesion state between the adhesive sheet sample piece 70 and the PET film 60 was maintained was judged as "pass", and a case where the PET film 60 was peeled off as shown in FIG. 7(c) was judged as "fail".
The pressure-sensitive adhesive sheets according to Examples 1-4, 1-5, and 1-9 to 1-12 were further evaluated for resistance to deformation in the 40° C. Z-axis direction. In this evaluation method, the PET film 60 and the pressure-sensitive adhesive sheet sample piece 70 are adhered together not by one reciprocation of a 0.1 kg roller, but by using a press set at a temperature of 40° C. under the conditions of 0.05 MPa and 3 seconds. I went with Otherwise, the resistance to deformation in the 40° C. Z-axis direction was evaluated in the same manner as described above.
According to this evaluation method, unlike the conventional repulsion resistance evaluation, it is possible to evaluate the initial light pressure bonding adhesion and deformation resistance against a peeling load substantially only in the thickness direction (Z-axis direction) of the adhesive sheet. It is possible, and continuous deformation resistance can be evaluated by observation over time.

Mw, Mw/Mn of the acrylic polymer according to each example, G' (25 ° C.) [MPa], G' (85 ° C.) [MPa], G' (40 ° C.) [MPa], G" of the adhesive layer (25 ° C) [MPa], gel fraction [%], 23 ° C light pressure initial adhesive strength of adhesive sheet [N / 20 mm], 40 ° C light pressure initial adhesive strength [N / 20 mm], adhesive strength after 30 minutes curing [N/20 mm] and the evaluation results of the Z-axis direction deformation resistance test (23° C. and 40° C.) are shown in Table 1 together with the monomer composition of the acrylic polymer of each example.

As shown in Table 1, the storage elastic modulus G' (25°C) of the adhesive layer is 0.15 MPa or more, G' (85°C) is 0.02 MPa or more, and the initial adhesive strength at 23°C light pressure bonding or 40 ° C. The pressure-sensitive adhesive sheets of Examples 1-1 to 1-8, which had an initial light pressure bonding strength of 8 N/20 mm or more, had initial light pressure bonding adhesiveness at a predetermined pressure bonding temperature, and resistance to deformation in the Z-axis direction. The test was of a passing level. Specifically, the pressure-sensitive adhesive sheets according to Examples 1-1 to 1-3 and Examples 1-6 to 1-8, which had an initial adhesive strength of 8 N/20 mm or more at 23°C light pressure bonding, were applied at 23°C light pressure bonding. It had good initial adhesion at 23° C., and had deformation resistance against continuous load in the Z-axis direction with light pressure bonding at 23°C. In Examples 1-4 and 1-5, the initial light pressure bonding adhesion at 23° C. could not be measured, but the 40° C. light pressure initial adhesion was good, and the Z-axis direction deformation resistance test (40° C.) had an acceptable level of deformation resistance. In Examples 1-4 and 1-5, the backing PET film peeled off both in the measurement of the initial adhesive strength at 40°C light pressure bonding and in the adhesive strength measurement after curing for 30 minutes, and the adhesive strength exceeded 20 N/20 mm. It is thought that In contrast, the pressure-sensitive adhesive sheets according to Examples 1-9 to 1-12 had initial adhesive strengths of 23° C. light pressure bonding and 40° C. initial adhesive strengths of light pressure bonding of less than 8 N/20 mm. The result was that the Z-axis direction deformation resistance test performed by crimping was failed. Examples 1-9 to 1-11, in which the storage elastic modulus G′ (25° C.) was less than 0.15 MPa, had low deformation resistance at the initial stage of attachment, and also failed the Z-axis direction deformation resistance test. This is thought to be one of the reasons why

≪Experiment 2≫
[Evaluation of elastic repulsive force in Z-axis direction deformation resistance test]
For the purpose of further improving deformation resistance against continuous load in the Z-axis direction, the influence of the thickness of the PET film used in the Z-axis direction deformation resistance test was evaluated. Specifically, a PET film having a length of 100 mm, a width of 50 mm and a thickness shown in Table 2 was prepared, and each PET film was subjected to the same Z-axis direction deformation resistance test except that the adhesive sheet was not used. , After being fixed to the PC board, one end (free end) in the longitudinal direction was folded back like a hairpin when viewed from the side to match the other end (fixed end). Then, the free end of the PET film was released from the force holding it down, and the return repulsive force [N/50 mm] at that time was read with a commercially available load cell. Table 2 shows the results.

As shown in Table 2, as the thickness of the PET film increased, the return repulsive force of the PET film folded in a hairpin shape increased. Specifically, when comparing PET films with a thickness of 75 μm and a PET film with a thickness of 125 μm, the repulsive force of the 125 μm thickness was approximately 4.8 times that of the 75 μm thickness.

≪Experiment 3≫
Based on the results of Experiment 2, the test conditions were set more severe than the Z-axis direction deformation resistance test of Experiment 1, and a pressure-sensitive adhesive sheet that could withstand the conditions, that is, exhibit better deformation resistance, was investigated. .

<Example 3-1>
A base-less double-sided adhesive pressure-sensitive adhesive sheet (thickness: 50 μm) according to this example was produced in the same manner as in Example 1-8 of Experiment 1.

<Example 3-2 to Example 3-6>
Using the same acrylic polymer (Mw 1,320,000, Mw / Mn = 5.85) as the acrylic polymer used in Example 3-1, changing the composition of the tackifying resin and the cross-linking agent, basically the same as in Example 3-1 A pressure-sensitive adhesive composition according to each example was prepared in the same manner as in . Using the obtained pressure-sensitive adhesive composition, a substrate-less double-sided adhesive pressure-sensitive adhesive sheet according to each example was produced in the same manner as in Example 3-1.
The (meth)acrylic oligomer used in Examples 3-2 and 3-3 is the same (meth)acrylic oligomer (Mw 3600) used in Example 3-1. In addition, terpene phenol resin A in the table is a trade name "YS Polystar S-145" manufactured by Yasuhara Chemical Co. (softening point about 145 ° C., hydroxyl value 70 to 110 mgKOH / g), and terpene phenol resin B is manufactured by Yasuhara Chemical Co. The trade name is “YS Polystar T-115” (softening point about 115° C., hydroxyl value 30-60 mgKOH/g).

[Z-axis direction deformation resistance test (strong rebound high temperature and high humidity conditions)]
As the PET film to be folded back and fixed with the adhesive sheet sample piece, a PET film having a length of 100 mm, a width of 10 mm, and a thickness of 125 μm was used. After the free end of the PET film was fixed by one reciprocation of a 0.1 kg roller under an environment of 23°C and 50% RH, it was exposed to an environment of 65°C and 90% RH. After exposure to the same environment for 72 hours, it was confirmed whether the adhesion state between the adhesive sheet sample piece and the PET film was maintained. ] was measured using a microscope. Measurements were performed in triplicate and the lowest value was recorded. The floating height is a height including the thickness of the adhesive sheet sample piece.
According to this evaluation method, from the results of Experiment 2, the resistance to repulsive force (deformation resistance) about 4.8 times higher than the resistance to deformation in the Z-axis direction of Experiment 1 was It is possible to evaluate under severe conditions of In this evaluation test, the PET film did not peel off and the floating height was limited. It can be evaluated as exhibiting particularly excellent resistance (deformation resistance) against a sustained peeling load in this direction.

G' (25 ° C.) [MPa], G "(25 ° C.) [MPa], tan δ (25 ° C.) (G "/G'), G' (85 ° C.) [MPa] of the adhesive layer according to each example , tan δ(85° C.) (G″/G′), and Z-axis direction deformation resistance test (strong repulsion, high temperature, high humidity conditions) are shown in Table 3 together with the composition of the adhesive of each example.

selected from acrylic polymers having Mw greater than 70×10 ⁴ and dispersity (Mw/Mn) less than 15, tackifying resins and (meth)acrylic oligomers, as shown in Table 3 The pressure-sensitive adhesive sheets according to Examples 3-1 to 3-5, which are provided with a pressure-sensitive adhesive layer containing at least one of the It had excellent resistance to deformation against sustained axial loading. That is, the above-mentioned pressure-sensitive adhesive sheet achieves both initial adhesion by light pressure bonding and deformation resistance against continuous load in the Z-axis direction, and is excellent even under severe conditions such as high temperature and high humidity due to strong repulsion. It exhibited deformation resistance. Among them, in Examples 3-1 to 3-3 in which the tackifying resin and the (meth)acrylic oligomer were used in combination, the floating height after the Z-axis direction deformation resistance test under strong repulsion, high temperature, and high humidity conditions was 400 μm or less. , and exhibited particularly excellent deformation resistance. On the other hand, the pressure-sensitive adhesive sheet of Example 3-6, in which neither the tackifier resin nor the (meth)acrylic oligomer was used, was subjected to the PET film peeled off and could not withstand the deformation load in the Z-axis direction.

Although specific examples of the present invention have been described in detail above, these are merely examples and do not limit the scope of the claims. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.

1, 2, 3, 4, 5, 6 Adhesive sheet 10 Base materials 21, 22 Adhesive layers 31, 32 Release liner

Claims (16)

comprising an acrylic polymer as a base polymer, a tackifying resin , and a (meth)acrylic oligomer ,
The weight average molecular weight of the acrylic polymer is greater than 70×10 ⁴ ,
The dispersion degree (Mw/Mn) of the acrylic polymer is less than 15,
The (meth)acrylic oligomer has a glass transition temperature of 0° C. or higher and 300° C. or lower,
The content of the tackifying resin is 5 parts by weight or more with respect to 100 parts by weight of the acrylic polymer,
The content of the (meth)acrylic oligomer is 1 part by weight or more relative to 100 parts by weight of the acrylic polymer . The acrylic pressure-sensitive adhesive composition according to claim 1, wherein the acrylic polymer is polymerized with an alkyl (meth)acrylate having an alkyl group having 1 to 6 carbon atoms at the ester end at a rate of 50% by weight or more. thing. The acrylic pressure-sensitive adhesive composition according to claim 1 or 2, wherein the acrylic polymer is copolymerized with an acidic group-containing monomer. 4. The acrylic pressure-sensitive adhesive composition according to claim 3, wherein the copolymerization ratio of said acidic group-containing monomer in said acrylic polymer is less than 10% by weight. The acrylic pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the tackifying resin is contained at a ratio of 5 parts by weight or more and less than 30 parts by weight with respect to 100 parts by weight of the acrylic polymer. thing. The acrylic oligomer according to any one of claims 1 to 5, wherein the (meth)acrylic oligomer is contained in a proportion of 1 part by weight or more and less than 30 parts by weight with respect to 100 parts by weight of the acrylic polymer. Adhesive composition.
An acrylic pressure-sensitive adhesive layer containing an acrylic polymer as a base polymer, a tackifier resin , and a (meth)acrylic oligomer ,
The weight average molecular weight of the acrylic polymer is greater than 70×10 ⁴ ,
The dispersion degree (Mw/Mn) of the acrylic polymer is less than 15 ,
The (meth)acrylic oligomer has a glass transition temperature of 0° C. or higher and 300° C. or lower,
The content of the tackifying resin is 5 parts by weight or more with respect to 100 parts by weight of the acrylic polymer,
The pressure-sensitive adhesive sheet , wherein the content of the (meth)acrylic oligomer is 1 part by weight or more with respect to 100 parts by weight of the acrylic polymer . The pressure-sensitive adhesive layer has a storage modulus G' (25°C) of 0.15 MPa or more at 25°C and a storage modulus G' (85°C) of 0.02 MPa or more at 85°C,
The pressure-sensitive adhesive sheet has a 180 degree peel strength measured within 1 minute after crimping under the conditions of 23° C. and a crimping load of 0.1 kg, and a 180° peel strength measured within 1 minute after crimping under the conditions of 40° C., 0.05 MPa, and 3 seconds. 8. The pressure-sensitive adhesive sheet according to claim 7, wherein at least one of the 180-degree peel strengths is 8 N/20 mm or more. The pressure-sensitive adhesive sheet according to claim 7 or 8 , wherein the pressure-sensitive adhesive layer has a gel fraction of 40% by weight or more. Any one of claims 7 to 9, wherein the acrylic polymer is copolymerized with an alkyl (meth)acrylate having an alkyl group having 1 to 6 carbon atoms at the ester end at a rate of 50% by weight or more. The adhesive sheet described in . The adhesive sheet according to any one of claims 7 to 10, wherein the acrylic polymer is copolymerized with an acidic group-containing monomer. The adhesive sheet according to claim 11 , wherein the acidic group-containing monomer is acrylic acid. The pressure-sensitive adhesive sheet according to claim 11 or 12 , wherein the copolymerization ratio of said acidic group-containing monomer in said acrylic polymer is less than 10% by weight. The adhesive sheet according to any one of claims 7 to 13 , wherein the acrylic polymer is crosslinked. The pressure-sensitive adhesive sheet according to any one of claims 7 to 14 , which is used for fixing members in portable electronic devices. The pressure-sensitive adhesive sheet according to any one of claims 7 to 15 , which is used for fixing a flexible printed wiring board.

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