WO2018092904A1 - 粘着シート - Google Patents
粘着シート Download PDFInfo
- Publication number
- WO2018092904A1 WO2018092904A1 PCT/JP2017/041673 JP2017041673W WO2018092904A1 WO 2018092904 A1 WO2018092904 A1 WO 2018092904A1 JP 2017041673 W JP2017041673 W JP 2017041673W WO 2018092904 A1 WO2018092904 A1 WO 2018092904A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive sheet
- meth
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
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Classifications
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- C—CHEMISTRY; METALLURGY
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2483/00—Presence of polysiloxane
Definitions
- the present invention relates to an adhesive sheet.
- This application claims priority based on Japanese Patent Application No. 2016-226288 filed on Nov. 21, 2016, the entire contents of which are incorporated herein by reference.
- the pressure-sensitive adhesive sheet is used for the purpose of adhering adherends to each other or fixing an article to the adherends by firmly adhering to the adherends.
- the properties required for the pressure-sensitive adhesive sheet vary depending on the application. For example, a pressure-sensitive adhesive sheet in consideration of re-sticking (reworkability) is required in order to prevent the yield from being lowered due to a sticking error. That is, there is a demand for a pressure-sensitive adhesive sheet that exhibits low adhesive strength at the initial stage of application and exhibits high adhesive strength when the adherend is used.
- Patent Documents 1 to 3 are listed as technical documents related to the pressure-sensitive adhesive sheet having such characteristics.
- the pressure sensitive adhesive sheet having the above-mentioned characteristics that is, the initial low adhesiveness and the strong adhesiveness at the time of use (for example, when fixing a member), mainly relates to the properties and composition of the adhesive.
- the adhesive sheet adheresive sheet with a base material
- the present inventor has attempted to achieve both low initial tackiness and strong tackiness at the time of use with an approach different from the techniques described in Patent Documents 1 to 3 regarding the pressure-sensitive adhesive sheet having a supporting substrate. The present invention has been completed.
- the pressure-sensitive adhesive sheet provided by this specification includes a support base material and a pressure-sensitive adhesive layer laminated on at least one side of the support base material.
- the thickness of the pressure-sensitive adhesive layer may be 3 ⁇ m or more and less than 100 ⁇ m.
- the support substrate has a thickness of 30 ⁇ m or more.
- the relationship between the elastic modulus Et ′ [MPa] of the pressure-sensitive adhesive sheet and the thickness Ts [mm] of the support substrate is as follows: 0.1 [N ⁇ mm] ⁇ Et ′ ⁇ (Ts 3 ) is satisfied.
- the adhesive force N2 after heating the adhesive layer to a stainless steel plate (SUS304BA plate) for 5 minutes at 80 ° C. is 30 at 23 ° C. after the adhesive layer is attached to the stainless steel plate (SUS304BA plate). It is 20 times or more of the adhesive strength N1 after standing for a minute.
- the adhesive strength N1 (hereinafter also referred to as initial adhesive strength) can be suppressed, and the adhesive strength N2 (hereinafter also referred to as post-heating adhesive strength) can be improved.
- the initial low adhesiveness and the strong adhesiveness at the time of use in which the ratio of the adhesive strength N2 to the adhesive strength N1 (that is, N2 / N1; hereinafter also referred to as “adhesive strength increase ratio”) is 20 or more are suitable. It is possible to suitably realize a pressure-sensitive adhesive sheet compatible with the above.
- the adhesive strength N1 is 1.0 N / 20 mm or less, and the adhesive strength N2 is 5.0 N / 20 mm or more.
- Such an adhesive sheet is excellent in the balance between initial low adhesiveness and strong adhesiveness during use.
- the pressure-sensitive adhesive sheet has the pressure-sensitive adhesive force N1 of 0.2 N / 20 mm or greater and 1.0 N / 20 mm or less. Thereby, it is easy to position at the time of sticking even in the adhesive sheet which is hard to bend that Et ′ ⁇ (Ts) 3 is larger than 0.1 N ⁇ mm.
- the elastic modulus Et ′ of the pressure-sensitive adhesive sheet is preferably 1000 MPa or more.
- both the initial low-tackiness and the strong-tackiness during use can be suitably achieved.
- the thickness of the support base material may be 1.1 to 10 times the thickness of the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer can be composed of a pressure-sensitive adhesive containing an adhesive force increase retarder.
- the adhesive force increase retarder refers to a component that exhibits the function of suppressing the adhesive force N1 of the adhesive sheet and improving the adhesive force increase ratio (N2 / N1) by being contained in the adhesive layer.
- the adhesive force increase retarder for example, a polymer containing a monomer unit derived from a monomer having a polyorganosiloxane skeleton or a polymer containing a monomer unit derived from a monomer having a polyoxyalkylene skeleton can be used. .
- the pressure-sensitive adhesive layer may include a siloxane structure-containing polymer Ps.
- the siloxane structure-containing polymer Ps is a copolymer of a monomer having a polyorganosiloxane skeleton and a (meth) acrylic monomer. That is, the siloxane structure-containing polymer Ps includes, as monomer units, a monomer having a polyorganosiloxane skeleton and a (meth) acrylic monomer.
- a polymer having a weight average molecular weight (Mw) of 1 ⁇ 10 4 or more and less than 5 ⁇ 10 4 can be preferably used. According to the siloxane structure-containing polymer Ps having Mw in the above range, an adhesive sheet having a high adhesive force increase ratio is easily realized.
- the pressure-sensitive adhesive layer may include the siloxane structure-containing polymer Ps and an acrylic polymer Pa having a glass transition temperature (Tg) of 0 ° C. or lower.
- Tg glass transition temperature
- the content of the siloxane structure-containing polymer Ps can be 0.1 parts by weight or more and less than 10 parts by weight with respect to 100 parts by weight of the acrylic polymer Pa. When the content falls within the above range, a pressure-sensitive adhesive sheet having a high pressure-sensitive adhesive strength ratio is easily realized.
- FIG. 1 is a sectional view showing typically the composition of the adhesive sheet concerning one embodiment.
- FIG. 2 is a cross-sectional view schematically showing a configuration of an adhesive sheet according to another embodiment.
- acrylic polymer refers to a polymer containing a monomer unit derived from a (meth) acrylic monomer in the polymer structure, and is typically a monomer derived from a (meth) acrylic monomer.
- the (meth) acrylic monomer means a monomer having at least one (meth) acryloyl group in one molecule.
- the “(meth) acryloyl group” means an acryloyl group and a methacryloyl group comprehensively.
- the concept of the (meth) acrylic monomer mentioned here may include both a monomer having an acryloyl group (acrylic monomer) and a monomer having a methacryloyl group (methacrylic monomer).
- (meth) acrylic acid means acrylic acid and methacrylic acid
- (meth) acrylate means acrylate and methacrylate.
- the pressure-sensitive adhesive sheet disclosed herein includes a support base material and a pressure-sensitive adhesive layer laminated on at least one side of the support base material.
- the supporting substrate may be simply referred to as “substrate”.
- the structure of the adhesive sheet which concerns on one Embodiment is typically shown in FIG.
- the pressure-sensitive adhesive sheet 1 includes a sheet-like support base material (for example, a resin film) 10 having a first surface 10A and a second surface 10B, and a pressure-sensitive adhesive layer 21 provided on the first surface 10A side. It is configured as an attached single-sided adhesive sheet.
- the pressure-sensitive adhesive layer 21 is provided on the first surface 10 ⁇ / b> A side of the support base material 10 in a fixed manner, that is, without intention to separate the pressure-sensitive adhesive layer 21 from the support base material 10.
- the pressure-sensitive adhesive sheet 1 is used by attaching a pressure-sensitive adhesive layer 21 to an adherend.
- the pressure-sensitive adhesive sheet 1 before use (that is, before being attached to an adherend) is such that the surface (adhesive surface) 21 ⁇ / b> A of the pressure-sensitive adhesive layer 21 is at least the side facing the pressure-sensitive adhesive layer 21. It can be a component of the pressure-sensitive adhesive sheet 100 with a release liner in a form protected by the release liner 31.
- the release liner 31 for example, a sheet-like base material (liner base material) provided with a release layer made of a release treatment agent on one side so that the one side becomes a release surface can be preferably used.
- the release liner 31 is omitted, and the pressure-sensitive adhesive sheet 21 is wound on the second surface 10B of the support substrate 10 by winding the pressure-sensitive adhesive sheet 1 using the support substrate 10 in which the second surface 10B is the release surface. It may be in the form of contact and protection (roll form).
- FIG. 2 schematically shows the structure of an adhesive sheet according to another embodiment.
- the pressure-sensitive adhesive sheet 2 includes a sheet-like support base material (for example, a resin film) 10 having a first surface 10A and a second surface 10B, a pressure-sensitive adhesive layer 21 fixedly provided on the first surface 10A side, It is comprised as a double-sided adhesive sheet with a base material provided with the adhesive layer 22 fixedly provided in the 2nd surface 10B side.
- the pressure-sensitive adhesive sheet 2 is used by sticking a pressure-sensitive adhesive layer (first pressure-sensitive adhesive layer) 21 and a pressure-sensitive adhesive layer (second pressure-sensitive adhesive layer) 22 to different parts of an adherend.
- the places where the adhesive layers 21 and 22 are affixed may be different places in different members, or different places in a single member.
- the pressure-sensitive adhesive sheet 2 before use has a surface (first pressure-sensitive adhesive surface) 21 ⁇ / b> A of the pressure-sensitive adhesive layer 21 and a surface (second pressure-sensitive adhesive surface) 22 ⁇ / b> A of the pressure-sensitive adhesive layer 22.
- 22 may be a constituent element of the pressure-sensitive adhesive sheet 200 with a release liner in a form protected by release liners 31 and 32 each having a release surface on the side facing 22.
- release liners 31 and 32 for example, a sheet-shaped base material (liner base material) that is configured so that one side becomes a release surface by providing a release layer with a release treatment agent on one side is preferably used. obtain.
- the release liner 32 is omitted, the release liner 31 having both surfaces as release surfaces is used, and this and the adhesive sheet 2 are overlapped and wound in a spiral shape, whereby the second adhesive surface 22A is released into the release liner 31.
- a pressure-sensitive adhesive sheet with a release liner in a form that is in contact with and protected from the back surface (roll form) may be formed.
- the pressure-sensitive adhesive sheet may be in the form of a roll or sheet, and may be cut or punched into an appropriate shape depending on the application or usage.
- the pressure-sensitive adhesive layer in the technology disclosed herein is typically formed continuously, but is not limited thereto, and may be formed in a regular or random pattern such as a dot shape or a stripe shape. Good.
- the relationship between the elastic modulus Et ′ [MPa] of the pressure-sensitive adhesive sheet and the thickness Ts [mm] of the support substrate is expressed by the following formula: 0.1 [N ⁇ mm] ⁇ Et ' ⁇ (Ts) 3 ;
- the initial adhesive strength is a condition in which a pressure is applied to a stainless steel (SUS) plate as an adherend and left in an environment of 23 ° C. and 50% RH for 30 minutes, and then the peeling angle is 180 degrees and the tensile speed is 300 mm / min. It can be evaluated by measuring the peel strength at 180 °.
- the adhesive strength after heating was pressure-bonded to a SUS plate as an adherend and heated at 80 ° C. for 5 minutes, then left in an environment of 23 ° C. and 50% RH for 30 minutes, and then the peel angle was 180 degrees and the tensile speed was Evaluation can be made by measuring the adhesive strength by peeling off 180 ° under the condition of 300 mm / min.
- a SUS304BA plate is used for both initial adhesive strength and post-heating adhesive strength. More specifically, the initial adhesive strength and the post-heating adhesive strength can be measured according to the methods described in Examples described later.
- the pressure-sensitive adhesive surface is bonded by a method such as attaching a thin film (for example, a plastic film having a thickness of about 2 ⁇ m) to the pressure-sensitive adhesive surface on the side not to be measured, or applying appropriate powder. A decrease in workability due to stickiness can be avoided. The same applies to the holding force test described later.
- the value of Et ′ ⁇ (Ts) 3 is proportional to the bending rigidity of the pressure-sensitive adhesive sheet. Therefore, a large value of Et ′ ⁇ (Ts) 3 of the pressure-sensitive adhesive sheet means that the pressure-sensitive adhesive sheet has high bending rigidity, that is, the pressure-sensitive adhesive sheet is difficult to bend.
- the elastic modulus Et ′ of the pressure-sensitive adhesive sheet can be measured using a commercially available dynamic viscoelasticity measuring device. Specifically, a sample to be measured (adhesive sheet) is cut into a strip shape having a length of 30 mm and a width of 5 mm to produce a test piece.
- this test piece was measured in a tensile measurement mode with a distance between chucks of 23 mm, a heating rate of 10 ° C./min, and a frequency.
- the tensile storage elastic modulus in the temperature range of 0 ° C. to 100 ° C. is obtained as a value per cross-sectional area of the substrate under the conditions of 1 Hz and a strain of 0.05%. From the result, the tensile storage elastic modulus per cross-sectional area of the substrate at 25 ° C. can be obtained. This value is defined as the elastic modulus Et ′ of the adhesive sheet.
- the reason why the elastic modulus Et ′ of the pressure-sensitive adhesive sheet is obtained as the value of “per cross-sectional area of the base material” is that the elastic modulus of the pressure-sensitive adhesive is usually small enough to be ignored compared to the elastic modulus of the base material ( If the cross-sectional area of the adhesive layer is included in the cross-sectional area used to calculate the tensile storage elastic modulus (typically less than 1% of the elastic modulus of the base material), it is difficult to grasp the characteristics of the adhesive sheet that meets the purpose of this application. This is because.
- the elastic modulus of the pressure-sensitive adhesive is extremely small as compared with the elastic modulus of the base material as described above, from the viewpoint of solving the problems of the present invention, the elastic modulus (that is, the basis) required by the above method using a pressure-sensitive adhesive sheet as a sample.
- the tensile storage elastic modulus Et ′ per cross-sectional area of the material and the elastic modulus Es ′ of the base material (this Es ′ is Et, except that the base material cut into a strip shape having a length of 30 mm and a width of 5 mm is used as a sample. Measured in the same way as').
- the value of the elastic modulus Es ′ of the base material can be used as an alternative value of the elastic modulus Et ′ of the pressure-sensitive adhesive sheet or at least a practically sufficient approximate value.
- Et ′ and Es ′ in the present specification can be interchanged with each other unless otherwise specified.
- Et ′ ⁇ (Ts) 3 and Es ′ ⁇ (Ts) 3 can be interchanged.
- the pressure-sensitive adhesive sheet disclosed herein can suppress the initial pressure-sensitive adhesive force and improve the pressure-sensitive adhesive force after heating by configuring Et ′ ⁇ (Ts) 3 to be greater than 0.1 N ⁇ mm. . That is, as compared with the pressure-sensitive adhesive sheet having a smaller value of Et ′ ⁇ (Ts) 3 , it is possible to promote the contradictory properties of initial low-tackiness and strong tackiness during use. As a result, the ratio of the adhesive strength after heating to the initial adhesive strength, that is, the adhesive strength increase ratio (N2 / N1) can be increased.
- Et' ⁇ (Ts) 3 values greater than the pressure-sensitive adhesive sheet is, Et' ⁇ (Ts) 3 value is less than the adhesive It is considered that it is less likely to bend than the sheet (high resistance to bending deformation).
- Et' ⁇ (Ts) 3 value is less than the adhesive It is considered that it is less likely to bend than the sheet (high resistance to bending deformation).
- both the force to peel off the adhesive layer from the adherend and the force to bend the substrate work as resistance to peeling. Therefore, it is considered that the adhesive strength is increased in the adhesive sheet that is less likely to bend than the adhesive sheet that is easily bent.
- Et ′ ⁇ (Ts) 3 is configured to be larger than 0.1 N ⁇ mm. It is considered that it is effectively improved (for example, the adhesive force increase ratio is improved).
- the above consideration does not particularly limit the scope of the present invention.
- Et ′ ⁇ (Ts) 3 of the pressure-sensitive adhesive sheet may be 0.25 N ⁇ mm or more, may be 0.30 N ⁇ mm or more, and may be 0.5 N ⁇ mm or more. It may be 0.7 N ⁇ mm or more, or 0.9 N ⁇ mm or more. According to the pressure-sensitive adhesive sheet having a larger Et ′ ⁇ (Ts) 3, the effect of promoting each of the initial low-tackiness and the strong-tackiness during use can be better exhibited.
- the pressure-sensitive adhesive sheet disclosed herein can also be suitably implemented in an embodiment in which Et ′ ⁇ (Ts) 3 is 2.0 N ⁇ mm or more, 3.0 N ⁇ mm or more, or 4.0 N ⁇ mm or more.
- the upper limit of Et ′ ⁇ (Ts) 3 is not particularly limited, but from the viewpoint of the handleability and workability of the pressure-sensitive adhesive sheet, it is usually about 100 N ⁇ mm or less, and about 50 N ⁇ mm or less (for example, 20 N ⁇ mm or less). ) Is preferable.
- the elastic modulus Et ′ of the pressure-sensitive adhesive sheet disclosed herein is not particularly limited, and may be, for example, 300 MPa or more, or 500 MPa or more. In terms of facilitating the achievement of the preferred Et ′ ⁇ (Ts) 3 described above, in some embodiments, the elastic modulus Et ′ of the pressure-sensitive adhesive sheet is preferably 1000 MPa or more, for example, 1500 MPa or more (for example, 2000 MPa or more). It is more preferable that The upper limit of Et ′ is not particularly limited. From the viewpoint of easy availability of the substrate and ease of production, Et ′ is usually suitably 30000 MPa or less, preferably 20000 MPa or less, and more preferably 10,000 MPa or less (for example, 6000 MPa or less). Et ′ can be adjusted by the structure of the base material, the material used, the combination thereof, and the like.
- the ratio of the adhesive strength after heating to the initial adhesive strength can be, for example, 10 or more, or 15 or more. From the viewpoint of achieving both a low initial tackiness and a strong tackiness at the time of use at a higher level, in some embodiments, the ratio of increase in adhesive strength is preferably 20 or more, and may be 30 or more. , 35 or more, 40 or more, or 50 or more.
- the upper limit of the adhesive strength increase ratio is not particularly limited, but may be, for example, 150 or less, 100 or less, or 80 or less (for example, about 20 to 80) from the viewpoint of ease of production of the pressure-sensitive adhesive sheet and economy. Or 70 or less.
- the pressure-sensitive adhesive sheet disclosed herein can be suitably implemented even in an aspect in which the pressure increase ratio is 50 or less.
- the initial pressure-sensitive adhesive force of the pressure-sensitive adhesive sheet may be, for example, 2.0 N / 20 mm or less, and less than 1.5 N / 20 mm. It may be 1.0N / 20mm or less, less than 1.0N / 20mm, 0.8N / 20mm or less, or 0.6N / 20mm or less.
- Et ′ ⁇ (Ts) 3 of the adhesive sheet being larger than a predetermined value tends to be exhibited better.
- a low initial adhesive strength is also preferable from the viewpoint of the reworkability of the adhesive sheet.
- the initial adhesion may be 0.4 N / 20 mm or less.
- the lower limit of the initial adhesive strength is not particularly limited. It can be 0.01 N / 20 mm or more. From the viewpoint of workability for attaching to an adherend, the initial adhesive strength is usually suitably 0.05 N / 20 mm or more. In some embodiments, the initial adhesive strength may be 0.1 N / 20 mm or more, may be 0.2 N / 20 mm or more, for example, 0.3 N / 20 mm or more. That the initial adhesive strength is not too low can be advantageous from the viewpoints of improving the positioning property when sticking to an adhesive sheet that is difficult to bend and adhesion to the adherend surface (for example, surface shape followability). It is preferable that the initial adhesive strength is not too low from the viewpoint of preventing positional displacement after the application and before the adhesive strength increases.
- the pressure-sensitive adhesive force after heating of the pressure-sensitive adhesive sheet may be, for example, 3.0 N / 20 mm or more, and 5.0 N / 20 mm or more. It may be 10N / 20mm or more, 13N / 20mm or more, 15N / 20mm or more, or 17N / 20mm or more.
- a higher post-heating adhesive strength is preferable from the viewpoint of improving the bonding reliability after increasing the adhesive strength (for example, when using the adherend).
- the post-heating adhesive force may be 20 N / 20 mm or more, or 25 N / 20 mm or more.
- the upper limit of the adhesive strength after heating is not particularly limited.
- the pressure-sensitive adhesive strength after heating may be, for example, 50 N / 20 mm or less, or 40 N / 20 mm or less, from the viewpoint of ease of manufacturing the adhesive sheet and economical efficiency.
- the pressure-sensitive adhesive sheet disclosed herein can also be suitably implemented in an embodiment in which the adhesive strength after heating is 30 N / 20 mm or less (for example, 25 N / 20 mm or less, or 20 N / 20 mm or less).
- the pressure-sensitive adhesive force after heating of the pressure-sensitive adhesive sheet disclosed here represents one characteristic of the pressure-sensitive adhesive sheet, and does not limit the use mode of the pressure-sensitive adhesive sheet.
- the usage mode of the pressure-sensitive adhesive sheet disclosed herein is not limited to a mode in which heating is performed at 80 ° C. for 5 minutes, and for example, a room temperature range (usually 20 ° C. to 30 ° C., typically 23 ° C. to 25 ° C. C.) can also be used in an embodiment in which the heat treatment is not particularly performed. Even in such a use mode, the adhesive strength increases over a long period of time, and a strong bonding can be realized.
- the adhesive sheet disclosed here can accelerate
- the heating temperature in such heat treatment is not particularly limited, and can be set in consideration of workability, economy, heat resistance of the base material of the adhesive sheet and the adherend, and the like.
- the heating temperature may be, for example, less than 150 ° C, 120 ° C or less, 100 ° C or less, 80 ° C or less, or 70 ° C or less.
- the said heating temperature can be 35 degreeC or more, 50 degreeC or more, or 60 degreeC or more, for example, may be 80 degreeC or more, and is good also as 100 degreeC or more. With a higher heating temperature, the adhesive force can be increased by a shorter processing time.
- the heating time is not particularly limited, and may be, for example, 1 hour or less, 30 minutes or less, 10 minutes or less, or 5 minutes or less. Or you may perform heat processing for a long period of time in the limit which does not produce remarkable heat deterioration to an adhesive sheet or a to-be-adhered body. Note that the heat treatment may be performed at once or may be performed in a plurality of times.
- the pressure-sensitive adhesive sheet is 40 ° C. 30 minutes after being attached to the bakelite plate with a width of 10 mm and a length of 20 mm.
- a displacement distance in a holding force test in which a load of 500 g is applied in the shear direction along the length and held for 30 minutes may be 1.0 mm or less.
- the deviation distance may be 0.7 mm or less, less than 0.5 mm, or less than 0.3 mm.
- the pressure-sensitive adhesive sheet disclosed herein is suitable, for example, in an aspect where the initial pressure-sensitive adhesive force is 1.0 N / 20 mm or less and the displacement distance in the holding force test is 1.0 mm or less (preferably less than 0.5 mm). Can be implemented. Such a pressure-sensitive adhesive sheet is excellent in position shift prevention because it has good initial re-stickability due to its low adhesive strength in the initial stage after sticking and exhibits good shear shift resistance. More specifically, the holding force test can be performed according to the method described in Examples described later.
- the numerical value of initial adhesive strength (N / 20 mm) (that is, there is no value corresponding to the initial adhesive strength expressed in units of N / 20 mm).
- the product of the number of dimensions) and the numerical value of the deviation distance (mm) in the holding force test (that is, the dimensionless number corresponding to the deviation distance expressed in mm) can be used.
- the product of the numerical value of the initial adhesive force (N / 20 mm) and the numerical value of the displacement distance (mm) may be, for example, 0.25 or less, and 0 20 or less, or 0.15 or less.
- the product value tends to be smaller.
- the lower limit of the value of the product is not particularly limited, but may be, for example, 0.005 or more and 0.01 or more from the viewpoint of curved surface adhesion and the like.
- the thickness of the pressure-sensitive adhesive sheet disclosed herein can be, for example, more than 30 ⁇ m. From the viewpoint of suitably satisfying both the initial low adhesiveness and the strong adhesiveness at the time of use, the thickness of the pressure-sensitive adhesive sheet is usually appropriately 33 ⁇ m or more, for example, 60 ⁇ m or more, and 80 ⁇ m or more. Also good. In some embodiments, the thickness of the pressure-sensitive adhesive sheet may be 100 ⁇ m or more, or 130 ⁇ m or more. The upper limit of the thickness of an adhesive sheet is not specifically limited. The technique disclosed here can be implemented, for example, in an embodiment in which the thickness of the pressure-sensitive adhesive sheet is 5 mm or less (for example, 3 mm or less).
- the thickness of the pressure-sensitive adhesive sheet may be 1000 ⁇ m or less, 600 ⁇ m or less, 350 ⁇ m or less, 250 ⁇ m or less, or 200 ⁇ m or less. In some other embodiments, the thickness of the pressure-sensitive adhesive sheet may be 175 ⁇ m or less, 140 ⁇ m or less, 120 ⁇ m or less, or 100 ⁇ m or less (for example, less than 100 ⁇ m). Reducing the thickness can be advantageous in terms of the handleability and processability of the pressure-sensitive adhesive sheet and the reduction in the thickness of a product formed using the pressure-sensitive adhesive sheet.
- the thickness of an adhesive sheet means the thickness of the part affixed on a to-be-adhered body (process target article).
- the thickness of the release liner 31 refers to the thickness from the pressure-sensitive adhesive surface (the surface to be attached to the object to be processed) 21 ⁇ / b> A to the second surface 10 ⁇ / b> B of the base material 10. Is not included.
- the material of the support base material which comprises the adhesive sheet disclosed here is not specifically limited, It can select suitably according to the intended purpose, usage condition, etc. of this adhesive sheet.
- substrates that can be used include polyolefin films based on polyolefins such as polypropylene and ethylene-propylene copolymers, polyester films based on polyesters such as polyethylene terephthalate and polybutylene terephthalate, Plastic films such as polyvinyl chloride films mainly composed of polyvinyl chloride; foam sheets made of foams such as polyurethane foam, polyethylene foam, polychloroprene foam; various fibrous materials (natural fibers such as hemp and cotton, Synthetic fibers such as polyester and vinylon, semi-synthetic fibers such as acetate, etc.) Woven and non-woven fabrics of single or mixed spinning, etc .; paper such as Japanese paper, fine paper, kraft paper, crepe paper; aluminum foil, Metal foil such as copper foil;
- the base material of the structure which compounded these may be sufficient.
- a composite substrate include a substrate having a structure in which a metal foil and the plastic film are laminated, a plastic substrate reinforced with inorganic fibers such as glass cloth, and the like.
- the film substrate may be a porous substrate such as a foam film or a non-woven sheet, or may be a non-porous substrate, a porous layer and a non-porous layer, May be a base material having a laminated structure.
- a film containing a resin film that can maintain its shape independently (independent or independent) as a base film.
- the “resin film” means a resin film having a non-porous structure and typically containing substantially no bubbles (voidless). Therefore, the said resin film is the concept distinguished from a foam film and a nonwoven fabric.
- the resin film may have a single-layer structure or a multilayer structure having two or more layers (for example, a three-layer structure).
- the resin material constituting the resin film examples include polyester, polyolefin, nylon 6, nylon 66, polyamide (PA) such as partially aromatic polyamide, polyimide (PI), polyamideimide (PAI), and polyetheretherketone (PEEK). ), Polyethersulfone (PES), polyphenylene sulfide (PPS), polycarbonate (PC), polyurethane (PU), ethylene-vinyl acetate copolymer (EVA), polytetrafluoroethylene (PTFE) and other fluororesins, acrylic resins Resins such as polyacrylate, polystyrene, polyvinyl chloride, and polyvinylidene chloride can be used.
- PA polyamide
- PA polyamide
- PES polyphenylene sulfide
- PC polycarbonate
- EVA ethylene-vinyl acetate copolymer
- PTFE polytetrafluoroethylene
- acrylic resins Resins such as polyacrylate, polystyrene
- the resin film may be formed using a resin material containing one kind of such resin alone, or may be formed using a resin material in which two or more kinds are blended. Also good.
- the resin film may be unstretched or stretched (for example, uniaxially stretched or biaxially stretched).
- the resin material constituting the resin film include polyester resins, PPS resins, and polyolefin resins.
- the polyester-based resin refers to a resin containing polyester in a proportion exceeding 50% by weight.
- a PPS resin refers to a resin containing PPS in a proportion exceeding 50% by weight
- a polyolefin-based resin refers to a resin containing a polyolefin in a proportion exceeding 50% by weight.
- polyester resin typically, a polyester resin containing as a main component a polyester obtained by polycondensation of a dicarboxylic acid and a diol is used.
- dicarboxylic acid constituting the polyester examples include phthalic acid, isophthalic acid, terephthalic acid, 2-methyl terephthalic acid, 5-sulfoisophthalic acid, 4,4′-diphenyl dicarboxylic acid, and 4,4′-diphenyl ether dicarboxylic acid.
- Aromatic dicarboxylic acids are preferred because a substrate exhibiting a suitable elastic modulus Es ′ can be easily obtained in the technology disclosed herein.
- preferred dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid.
- 50% by weight or more (for example, 80% by weight or more, typically 95% by weight or more) of the dicarboxylic acid constituting the polyester is terephthalic acid, 2,6-naphthalenedicarboxylic acid, or a combination thereof.
- the dicarboxylic acid may be composed substantially of terephthalic acid, substantially 2,6-naphthalenedicarboxylic acid, or substantially only terephthalic acid and 2,6-naphthalenedicarboxylic acid.
- diol constituting the polyester examples include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,4-butanediol, Aliphatic diols such as 1,6-hexanediol, 1,8-octanediol, polyoxytetramethylene glycol; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4 -Cycloaliphatic dimethylol and other alicyclic diols, xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2-bis (4'-hydroxyphenyl) propane, bis (4-hydroxyphenyl) s Aromatic diols such as phone; and the like.
- aliphatic diols are preferable from the viewpoint of transparency and the like, and ethylene glycol is particularly preferable from the viewpoint of the elastic modulus Es ′ of the substrate.
- the proportion of the aliphatic diol (preferably ethylene glycol) in the diol constituting the polyester is preferably 50% by weight or more (for example, 80% by weight or more, typically 95% by weight or more).
- the diol may be substantially composed only of ethylene glycol.
- polyester resin examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polybutylene naphthalate.
- polyolefin resin one kind of polyolefin can be used alone, or two or more kinds of polyolefins can be used in combination.
- the polyolefin may be, for example, an ⁇ -olefin homopolymer, a copolymer of two or more ⁇ -olefins, a copolymer of one or two or more ⁇ -olefins with other vinyl monomers, and the like.
- PE polyethylene
- PP polypropylene
- PP poly-1-butene
- EPR ethylene propylene rubber
- ethylene-propylene- Examples include butene copolymers, ethylene-butene copolymers, ethylene-vinyl alcohol copolymers, ethylene-ethyl acrylate copolymers, and the like. Both low density (LD) polyolefins and high density (HD) polyolefins can be used.
- LD low density
- HD high density
- polyolefin resin films examples include unstretched polypropylene (CPP) film, biaxially stretched polypropylene (OPP) film, low density polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, and medium density polyethylene (MDPE).
- CPP unstretched polypropylene
- OPP biaxially stretched polypropylene
- LDPE low density polyethylene
- LLDPE linear low density polyethylene
- MDPE medium density polyethylene
- examples thereof include a film, a high density polyethylene (HDPE) film, a polyethylene (PE) film obtained by blending two or more kinds of polyethylene (PE), and a PP / PE blend film obtained by blending polypropylene (PP) and polyethylene (PE).
- Preferred examples from the viewpoint of obtaining Et ′ ⁇ (Ts) 3 suitable for a thinner substrate include PET film, PEN film, PPS film, and PEEK film.
- a PET film and a PPS film are particularly preferable from the viewpoint of availability of the base material, and the PET film is particularly preferable.
- a light stabilizer In the resin film, a light stabilizer, an antioxidant, an antistatic agent, a colorant (dye, pigment, etc.), a filler, a slip agent, an antiblocking agent and the like are known as long as the effect of the present invention is not significantly hindered. These additives can be blended as necessary.
- the compounding quantity of an additive is not specifically limited, According to the use etc. of an adhesive sheet, it can set suitably.
- the method for producing the resin film is not particularly limited.
- conventionally known general resin film forming methods such as extrusion molding, inflation molding, T-die casting, and calendar roll molding can be appropriately employed.
- the base material may be substantially composed of such a base film.
- the base material may include an auxiliary layer in addition to the base film.
- the auxiliary layers include optical property adjusting layers (for example, colored layers and antireflection layers), printed layers and laminate layers for imparting a desired appearance to the substrate, antistatic layers, undercoat layers, and release layers. And the like.
- Such a surface treatment may be a treatment for improving the adhesion between the base material and the pressure-sensitive adhesive layer, in other words, the anchoring property of the pressure-sensitive adhesive layer to the base material.
- the composition of the primer is not particularly limited and can be appropriately selected from known ones.
- the thickness of the undercoat layer is not particularly limited, but is usually about 0.01 ⁇ m to 1 ⁇ m, preferably about 0.1 ⁇ m to 1 ⁇ m.
- a conventionally known surface treatment such as a peeling treatment or an antistatic treatment may be applied to the second surface of the base material as necessary.
- a release treatment agent typically, by providing a release layer with a release treatment agent
- the unwinding force of the pressure-sensitive adhesive sheet in the form of a roll is obtained.
- the release treatment agent silicone release treatment agents, long-chain alkyl release treatment agents, olefin release treatment agents, fluorine release treatment agents, fatty acid amide release treatment agents, molybdenum sulfide, silica powder, and the like can be used. .
- the second surface of the substrate is subjected to treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, and alkali treatment. May be.
- treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, and alkali treatment. May be.
- the second surface of the base material is subjected to the same surface treatment as described above as a surface treatment that can be performed on the first surface of the base material, if necessary. Also good.
- the surface treatment applied to the first surface of the substrate and the surface treatment applied to the second surface may be the same or different.
- the thickness of the base material constituting the pressure-sensitive adhesive sheet disclosed herein can be, for example, more than 25 ⁇ m, and typically 30 ⁇ m or more.
- the thickness of the substrate is preferably 35 ⁇ m or more, 40 ⁇ m or more, 50 ⁇ m or more (for example, more than 50 ⁇ m), 60 ⁇ m or more, or 70 ⁇ m or more. .
- the adhesive sheet which satisfy
- the pressure-sensitive adhesive sheet disclosed herein can also be suitably implemented in an embodiment in which the thickness of the base material is 90 ⁇ m or more, or 100 ⁇ m or more, or 120 ⁇ m or more.
- the upper limit of the thickness of the substrate is not particularly limited.
- the technique disclosed here can be implemented, for example, in a mode in which the thickness of the substrate is 4.5 mm or less (for example, 2.5 mm or less).
- the thickness of the base material may be, for example, 900 ⁇ m or less, 500 ⁇ m or less, 300 ⁇ m or less, or 250 ⁇ m from the viewpoint of the handleability and processability of the pressure-sensitive adhesive sheet. Or 200 ⁇ m or less.
- the thickness of the substrate may be 160 ⁇ m or less, 130 ⁇ m or less, 100 ⁇ m or less, or 90 ⁇ m or less.
- the elastic modulus Es ′ of the substrate is not particularly limited, and may be, for example, 300 MPa or more, or 500 MPa or more.
- the elastic modulus Es ′ of the substrate is preferably 1000 MPa or more, for example, 1500 MPa or more (for example, 2000 MPa or more).
- the upper limit of Es ′ is not particularly limited. From the viewpoint of easy availability of the substrate and ease of production, Es ′ is usually suitably 30000 MPa or less, preferably 20000 MPa or less, and more preferably 10,000 MPa or less (for example, 6000 MPa or less). Es ′ can be adjusted by the structure of the base material, the material used, the combination thereof, and the like.
- the pressure-sensitive adhesive that constitutes the pressure-sensitive adhesive layer is not particularly limited, and a pressure-sensitive adhesive sheet that exhibits desired characteristics (for example, at least one of a pressure increase ratio, an initial pressure-sensitive adhesive force, and a pressure-sensitive adhesive force after heating) It can select suitably so that it may be obtained.
- the pressure-sensitive adhesive is a known acrylic polymer, rubber polymer, polyester polymer, urethane polymer, polyether polymer, silicone polymer, polyamide polymer, fluorine polymer, etc. in a room temperature range.
- One or more of various polymers exhibiting rubber elasticity may be included as a base polymer (that is, a component that occupies 50% by weight or more of the polymer component).
- the pressure-sensitive adhesive layer in the technology disclosed herein can be formed from a pressure-sensitive adhesive composition containing such a base polymer.
- the form of the pressure-sensitive adhesive composition is not particularly limited, and may be various forms of pressure-sensitive adhesive compositions such as a water dispersion type, a solvent type, a hot melt type, and an active energy ray curable type (for example, photocurable type).
- the base polymer preferably has a glass transition temperature (Tg) of less than 0 ° C., more preferably less than ⁇ 10 ° C. (for example, less than ⁇ 20 ° C.).
- Tg glass transition temperature
- the pressure-sensitive adhesive containing the base polymer of Tg is suitable for realizing a pressure-sensitive adhesive sheet having a high pressure-sensitive adhesive strength ratio because it exhibits appropriate fluidity (for example, the mobility of the polymer chain contained in the pressure-sensitive adhesive).
- the Tg of the base polymer may be less than ⁇ 30 ° C. and may be less than ⁇ 40 ° C.
- the lower limit of the Tg of the base polymer is not particularly limited, but a base polymer having a Tg of ⁇ 80 ° C.
- the Tg of the base polymer can be, for example, ⁇ 63 ° C. or higher, ⁇ 55 ° C. or higher, ⁇ 50 ° C. or higher, or ⁇ 45 ° C. or higher.
- the Tg of the base polymer is a nominal value described in literatures, catalogs, or the like, or Tg determined by the Fox equation based on the composition of the monomer component used for the preparation of the base polymer.
- the formula of Fox is a relational expression between Tg of a copolymer and glass transition temperature Tgi of a homopolymer obtained by homopolymerizing each of the monomers constituting the copolymer, as shown below.
- Tg is the glass transition temperature (unit: K) of the copolymer
- Wi is the weight fraction of monomer i in the copolymer (copolymerization ratio based on weight)
- Tgi is the homopolymer of monomer i. Represents the glass transition temperature (unit: K).
- the base polymer is a homopolymer
- the Tg of the homopolymer matches the Tg of the base polymer.
- the glass transition temperature of the homopolymer used for the calculation of Tg the values described in known materials are used. Specifically, the figures are listed in “Polymer Handbook” (3rd edition, John Wiley & Sons, Inc., 1989). The highest value is adopted for the monomers whose values are listed in the Polymer Handbook. As the glass transition temperature of a homopolymer of a monomer not described in the Polymer Handbook, the value obtained by the measurement method described in Japanese Patent Application Publication No. 2007-51271 is used.
- a reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux condenser is charged with 100 parts by weight of monomer, 0.2 part by weight of 2,2′-azobisisobutyronitrile and acetic acid as a polymerization solvent. 200 parts by weight of ethyl is added and stirred for 1 hour while flowing 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. Next, the mixture is cooled to room temperature to obtain a homopolymer solution having a solid concentration of 33% by weight.
- 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 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 by the shear mode at a temperature increase rate of ⁇ 70 ° C. to 150 ° C. and 5 ° C./min, and the temperature corresponding to the peak top temperature of tan ⁇ is defined as Tg of the homopolymer.
- the weight average molecular weight (Mw) of the base polymer is typically about 5 ⁇ 10 4 or more. According to such a base polymer of Mw, it is easy to obtain a pressure-sensitive adhesive exhibiting good cohesiveness.
- the Mw of the base polymer may be, for example, 10 ⁇ 10 4 or more, 20 ⁇ 10 4 or more, or 30 ⁇ 10 4 or more.
- the Mw of the base polymer is usually about 500 ⁇ 10 4 or less.
- Such a base polymer of Mw is suitable for realizing a pressure-sensitive adhesive sheet having a high adhesive force increase ratio because it easily forms a pressure-sensitive adhesive exhibiting moderate fluidity (polymer chain mobility).
- Mw of a base polymer or a siloxane structure-containing polymer described later can be obtained in terms of polystyrene by gel permeation chromatography (GPC). More specifically, Mw can be measured according to the methods and conditions described in the examples described later.
- the pressure-sensitive adhesive sheet disclosed herein can be suitably implemented in a form including a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive containing an acrylic polymer Pa having a Tg of 0 ° C. or less as a base polymer.
- a pressure-sensitive adhesive layer composed of a pressure-sensitive adhesive containing an acrylic polymer Pa having a Tg of 0 ° C. or less as a base polymer.
- the siloxane structure-containing polymer Ps described later is a homopolymer or copolymer containing a monomer unit derived from a (meth) acrylic monomer, good compatibility with the siloxane structure-containing polymer Ps is obtained. Since it is easy to be formed, acrylic polymer Pa can be preferably employed as the base polymer.
- the good compatibility between the base polymer and the siloxane structure-containing polymer Ps is advantageous from the viewpoint of improving the transparency of the pressure-sensitive adhesive layer.
- the improvement in mobility of the siloxane structure-containing polymer Ps in the pressure-sensitive adhesive layer it can contribute to the reduction of the initial pressure-sensitive adhesive force and the improvement of the pressure-sensitive adhesive force after heating.
- the acrylic polymer Pa is, for example, a polymer containing 50 wt% or more of monomer units derived from (meth) acrylic acid alkyl ester, that is, 50 wt% or more of the total amount of monomer components for preparing the acrylic polymer Pa ( It can be a polymer that is a meth) acrylic acid alkyl ester.
- a (meth) acrylic acid alkyl ester having a linear or branched alkyl group having 1 to 20 carbon atoms (namely, C 1-20 ) can be preferably used.
- the proportion of the (meth) acrylic acid C 1-20 alkyl ester in the total amount of the monomer components may be, for example, 50 wt% to 99.9 wt%, preferably 60 wt% to 98 wt%, more preferably 70 wt%. % By weight to 95% by weight.
- Non-limiting specific examples of (meth) acrylic acid C 1-20 alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, ( N-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, (meth) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, (meth ) Decyl acrylate
- the acrylic polymer Pa is a monomer comprising at least one (meth) acrylic acid C 4-12 alkyl ester (preferably an acrylic acid C 4-10 alkyl ester, such as an acrylic acid C 6-10 alkyl ester).
- an acrylic polymer containing one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) is preferred, and an acrylic polymer Pa containing at least 2EHA is particularly preferred.
- Examples of other (meth) acrylic acid C 1-18 alkyl esters that can be preferably used as the monomer component include methyl acrylate, methyl methacrylate (MMA), n-butyl methacrylate (BMA), 2-ethylhexyl methacrylate. (2EHMA) and the like.
- the monomer unit that constitutes the acrylic polymer is composed of (meth) acrylic acid alkyl ester as the main component and, if necessary, another monomer (copolymerizable monomer) copolymerizable with (meth) acrylic acid alkyl ester. May be included.
- a monomer having a polar group for example, a carboxy group, a hydroxyl group, a nitrogen atom-containing ring, etc.
- a monomer having a polar group can serve to introduce a crosslinking point into the acrylic polymer or to increase the cohesive strength of the acrylic polymer.
- a copolymerizable monomer can be used individually by 1 type or in combination of 2 or more types.
- Non-limiting specific examples of the copolymerizable monomer include the following.
- Carboxy group-containing monomer For example, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like.
- Acid anhydride group-containing monomer for example, maleic anhydride, itaconic anhydride.
- Hydroxyl group-containing monomers for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acryl 4-hydroxybutyl acid, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxy Hydroxyalkyl (meth) acrylates such as methylcyclohexyl) methyl (meth) acrylate and the like.
- Monomers containing sulfonic acid groups or phosphoric acid groups for example, styrene sulfonic acid, allyl sulfonic acid, sodium vinyl sulfonate, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfo Propyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid, 2-hydroxyethyl acryloyl phosphate and the like.
- Epoxy group-containing monomers For example, epoxy group-containing acrylates such as glycidyl (meth) acrylate and (meth) acrylic acid-2-ethylglycidyl ether, allyl glycidyl ether, (meth) acrylic acid glycidyl ether, and the like.
- Cyano group-containing monomer For example, acrylonitrile, methacrylonitrile and the like.
- Isocyanate group-containing monomer for example, 2-isocyanatoethyl (meth) acrylate.
- Amide group-containing monomer for example, (meth) acrylamide; N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N-diisopropyl (meth) N, N-dialkyl (meth) acrylamides such as acrylamide, N, N-di (n-butyl) (meth) acrylamide, N, N-di (t-butyl) (meth) acrylamide; N-ethyl (meth) acrylamide N-alkyl (meth) acrylamides such as N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide and Nn-butyl (meth) acrylamide; N-vinylcarboxylic amides such as N-vinylacetamide; In addition, N, N-dimethylaminopropyl (me
- N-vinyl-2-pyrrolidone N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N- Vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N- (meth) acryloyl-2-pyrrolidone, N- (meth) acryloylpiperidine, N- (meth) acryloylpyrrolidine, N-vinylmorpholine, N-vinyl-3 -Morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N-vinyl Thi
- Monomers having a succinimide skeleton for example, N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyhexamethylene succinimide, and the like.
- Maleimides For example, N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide and the like.
- Itaconic imides for example, N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexylitaconimide, N-cyclohexyl leuconconimide, N-lauryl Itacone imide and the like.
- Aminoalkyl (meth) acrylates for example, aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, (meth) acrylic acid t -Butylaminoethyl.
- Alkoxyalkyl (meth) acrylates for example, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate etc.
- Vinyl esters For example, vinyl acetate, vinyl propionate and the like.
- Vinyl ethers For example, vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether.
- Aromatic vinyl compounds for example, styrene, ⁇ -methylstyrene, vinyltoluene and the like.
- Olefin For example, ethylene, butadiene, isoprene, isobutylene and the like.
- (Meth) acrylic acid ester having an alicyclic hydrocarbon group for example, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate and the like.
- (Meth) acrylic acid ester having an aromatic hydrocarbon group for example, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate and the like.
- heterocycle-containing (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, halogen-containing (meth) acrylates such as vinyl chloride and fluorine-containing (meth) acrylate, silicon atoms such as silicone (meth) acrylate (Meth) acrylate, (meth) acrylic acid ester obtained from terpene compound derivative alcohol and the like.
- the amount used is not particularly limited, but it is usually suitably 0.01% by weight or more based on the total amount of monomer components. From the viewpoint of better exhibiting the effect of using the copolymerizable monomer, the amount of the copolymerizable monomer used may be 0.1% by weight or more of the total amount of the monomer components, or 1% by weight or more.
- the amount of the copolymerizable monomer used can be 50% by weight or less, preferably 40% by weight or less, based on the total amount of the monomer components. Thereby, it can prevent that the cohesion force of an adhesive becomes high too much and can improve the tuck feeling in normal temperature (25 degreeC).
- the acrylic polymer Pa is at least one monomer selected from the group consisting of an N-vinyl cyclic amide represented by the following general formula (M1) and a hydroxyl group-containing monomer as described above as a monomer unit: It is preferable to contain.
- R 1 in the general formula (M1) is a divalent organic group.
- N-vinyl cyclic amide examples include N-vinyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3 -Oxazin-2-one, N-vinyl-3,5-morpholinedione and the like. Particularly preferred are N-vinyl-2-pyrrolidone and N-vinyl-2-caprolactam.
- N-vinyl cyclic amide can adjust the cohesive strength and polarity of the adhesive and improve the adhesive strength after heating.
- N-vinyl cyclic amide for improving cohesive strength, the amount of a crosslinking agent (for example, an isocyanate-based crosslinking agent) described later can be suppressed, which is advantageous from the viewpoint of improving the adhesive force increase ratio. Can be.
- the amount of N-vinyl cyclic amide used is not particularly limited, but is usually 0.01% by weight or more (preferably 0.1% by weight or more, for example 0.5% by weight) based on the total amount of monomer components for preparing acrylic polymer Pa. It is appropriate that the weight is not less than% by weight. In some embodiments, the amount of N-vinyl cyclic amide used may be 1% by weight or more, 5% by weight or more, or 10% by weight or more of the total amount of the monomer components.
- the amount of N-vinyl cyclic amide used is usually 40% by weight or less of the total amount of the above monomer components. 30% by weight or less, or 20% by weight or less.
- 2-hydroxyethyl (meth) acrylate As the hydroxyl group-containing monomer, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and the like can be suitably used. Among them, preferred examples include 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA).
- the cohesive force and polarity of the adhesive can be adjusted, and the adhesive strength after heating can be improved.
- the hydroxyl group-containing monomer can provide a reaction point with a cross-linking agent (for example, an isocyanate-based cross-linking agent) described later, and can increase the cohesive force of the pressure-sensitive adhesive by a cross-linking reaction.
- a cross-linking agent for example, an isocyanate-based cross-linking agent
- the amount of the hydroxyl group-containing monomer used is not particularly limited, but is usually 0.01% by weight or more (preferably 0.1% by weight or more, for example 0.5% by weight) of the total amount of monomer components for preparing the acrylic polymer Pa. The above is appropriate. In some embodiments, the amount of the hydroxyl group-containing monomer used may be 1% by weight or more, 5% by weight or more, or 10% by weight or more of the total amount of the monomer components. In addition, from the viewpoint of improving tackiness at room temperature (25 ° C.) and improving flexibility at low temperature, it is appropriate that the amount of the hydroxyl group-containing monomer is usually 40% by weight or less of the total amount of the monomer components. It may be less than or equal to 20% or less than 20% by weight.
- N-vinyl cyclic amide and a hydroxyl group-containing monomer can be used in combination as the copolymerizable monomer.
- the total amount of the N-vinyl cyclic amide and the hydroxyl group-containing monomer can be, for example, 0.1% by weight or more of the total amount of monomer components for preparing the acrylic polymer Pa, and can be 1% by weight or more. Alternatively, it may be 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, or 25% by weight or more.
- the total amount of the N-vinyl cyclic amide and the hydroxyl group-containing monomer can be, for example, 50% by weight or less, preferably 40% by weight or less, based on the total amount of the monomer components.
- the monomer component for preparing the acrylic polymer Pa may contain a polyfunctional monomer as necessary for the purpose of adjusting the cohesive force of the pressure-sensitive adhesive layer.
- the multifunctional monomer 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, Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecane Diol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylo
- trimethylolpropane tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be preferably used.
- a polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types. The amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, etc., but is usually in the range of 0.01% to 3.0% by weight with respect to the total amount of monomer components for preparing the acrylic polymer Pa. And may be 0.02% to 2.0% by weight, or 0.03% to 1.0% by weight.
- the method for obtaining the acrylic polymer is not particularly limited, and various polymerization methods known as synthetic methods for acrylic polymers, such as solution polymerization method, emulsion polymerization method, bulk polymerization method, suspension polymerization method, photopolymerization method, etc. Can be adopted as appropriate.
- a solution polymerization method may be preferably employed.
- the polymerization temperature at the time of performing the solution polymerization can be appropriately selected according to the type of the monomer and solvent to be used, the type of the polymerization initiator, and the like, for example, about 20 ° C. to 170 ° C. (typically 40 ° C. to 140 ° C. C.).
- the initiator used for the polymerization can be appropriately selected from conventionally known thermal polymerization initiators, photopolymerization initiators, and the like according to the polymerization method.
- a polymerization initiator can be used individually by 1 type or in combination of 2 or more types.
- thermal polymerization initiator examples include azo polymerization initiators (for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis ( 2-methylpropionic acid) dimethyl, 4,4′-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2 -(5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethylene) Isobutylamidine) dihydrochloride, etc.); persulfates such as potassium persulfate; peroxide polymerization initiators (eg, dibenzoyl peroxide, t-butyl peroxide) Maleate, lauroyl per
- the amount of the thermal polymerization initiator used is not particularly limited. For example, 0.01 to 5 parts by weight, preferably 0.05 parts by weight to 100 parts by weight of the monomer component used for preparing the acrylic polymer. The amount can be in the range of 3 parts by weight.
- the photopolymerization initiator is not particularly limited, and examples thereof include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, ⁇ -ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactive initiators.
- Oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone photopolymerization initiator, acylphosphine oxide photopolymerization initiator An agent or the like can be used.
- the amount of the photopolymerization initiator used is not particularly limited. For example, 0.01 to 5 parts by weight, preferably 0.05 parts by weight to 100 parts by weight of the monomer component used for preparing the acrylic polymer. The amount can be in the range of 3 parts by weight.
- the acrylic polymer Pa is a partial polymer (acrylic polymer) in which a part of the monomer component is polymerized by irradiating a mixture of the monomer component described above with a polymerization initiator by irradiating ultraviolet rays (UV).
- a polymer syrup may be included in the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive composition containing the acrylic polymer syrup can be applied to a predetermined substrate and irradiated with ultraviolet rays to complete the polymerization. That is, the acrylic polymer syrup can be grasped as a precursor of the acrylic polymer Pa.
- the pressure-sensitive adhesive layer disclosed herein can be formed using, for example, a pressure-sensitive adhesive composition containing the acrylic polymer syrup and a siloxane structure-containing polymer Ps described later.
- siloxane structure-containing polymer Ps Components other than the base polymer (for example, the acrylic polymer Pa) can be contained in the pressure-sensitive adhesive layer in the technology disclosed herein, if necessary.
- a suitable example of such an optional component is a siloxane structure-containing polymer Ps.
- the siloxane structure-containing polymer Ps is defined as a polymer having a siloxane structure (Si—O—Si structure) in the molecule.
- the siloxane structure-containing polymer Ps can function as an adhesive force increase retarder that contributes to suppression of initial adhesive force and improvement of the adhesive force increase ratio due to the low polarity and mobility of the siloxane structure.
- polymer Ps a polymer having a siloxane structure in the side chain can be preferably used.
- the polymer Ps preferably contains a monomer having a polyorganosiloxane skeleton (hereinafter also referred to as “monomer S1”) as a monomer unit.
- the monomer S1 is not particularly limited, and any monomer containing a polyorganosiloxane skeleton can be used.
- Such a polyorganosiloxane skeleton-containing monomer promotes uneven distribution of the polymer Ps on the surface of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet before use (before application to the adherend) due to the low polarity derived from the structure. , Expresses light peelability at the initial stage of bonding.
- the monomer S1 for example, a compound represented by the following general formula (1) or (2) can be used. More specifically, X-22-174ASX, X-22-2426, X-22-2475, KF-2012 and the like are listed as one-end reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. Monomer S1 can be used individually by 1 type or in combination of 2 or more types.
- R 3 in the general formulas (1) and (2) is hydrogen or methyl
- R 4 is a methyl group or a monovalent organic group
- m and n are integers of 0 or more.
- the functional group equivalent of the monomer S1 is, for example, preferably 700 g / mol or more and less than 15000 g / mol, more preferably 800 g / mol or more and less than 10000 g / mol, and more preferably 850 g / mol or more and less than 6000 g / mol. Is more preferable, and particularly preferably 1500 g / mol or more and less than 5000 g / mol.
- the functional group equivalent of the monomer S1 is less than 700 g / mol, the initial adhesive force may not be sufficiently suppressed.
- the functional group equivalent of the monomer S1 is 15000 g / mol or more, the increase in adhesive strength may be insufficient.
- the compatibility for example, compatibility with the base polymer
- mobility in the pressure-sensitive adhesive layer can be easily adjusted to an appropriate range, and the initial low-tackiness and use can be achieved. It becomes easy to realize a pressure-sensitive adhesive sheet that achieves a high level of strong adhesiveness.
- “functional group equivalent” means the weight of the main skeleton (for example, polydimethylsiloxane) bonded per functional group.
- the title unit g / mol is converted to 1 mol of functional group.
- the functional group equivalent of the monomer S1 can be calculated from the spectral intensity of 1 H-NMR (proton NMR) based on nuclear magnetic resonance (NMR), for example.
- the calculation of the functional group equivalent (g / mol) of the monomer S1 based on the spectral intensity of 1 H-NMR is based on a general structural analysis method related to 1 H-NMR spectral analysis. This can be done with reference to the description in Japanese Patent No. 5951153.
- an arithmetic mean value can be used as a functional group equivalent of the monomer S1. That is, the functional group equivalent of the monomer S1 composed of n types of monomers having different functional group equivalents (monomer S1 1 , monomer S1 2 ... Monomer S1 n ) can be calculated by the following formula.
- Functional group equivalent of the monomer S1 (g / mol) (monomer S1 1 functional group equivalent ⁇ monomer S1 1 of the amount + monomer S1 2 functional group equivalent ⁇ monomer S1 2 of the amount + ... + monomer S1 n
- Functional group equivalent ⁇ monomer S1 n blending amount / (monomer S1 1 blending amount + monomer S1 2 blending amount +... + Monomer S1 n blending amount)
- the content of the monomer S1 may be, for example, 5% by weight or more with respect to the total monomer components for preparing the polymer Ps, and is 10% by weight or more from the viewpoint of better exhibiting the effect as an adhesive increase retarder. Preferably, it may be 15% by weight or more. In some embodiments, the content of the monomer S1 may be, for example, 20% by weight or more. Further, the content of the monomer S1 is suitably 60% by weight or less with respect to all monomer components for preparing the polymer Ps from the viewpoint of polymerization reactivity and compatibility, and is 50% by weight or less. Alternatively, it may be 40% by weight or less, or 30% by weight or less. When the content of the monomer S1 is less than 5% by weight, the initial adhesive force may not be sufficiently suppressed. When the content of the monomer S1 is more than 60% by weight, the increase in adhesive strength may be insufficient.
- the monomer component used for the preparation of the polymer Ps may contain, in addition to the monomer S1, a (meth) acrylic monomer or other copolymerizable monomer copolymerizable with the monomer S1, if necessary.
- the compatibility between the polymer Ps and the base polymer for example, the acrylic polymer Pa
- the acrylic polymer Pa can be suitably adjusted by copolymerizing one or more (meth) acrylic monomers and the monomer S1.
- (meth) acrylic-type monomer (meth) acrylic-acid alkylester is mentioned, for example.
- one or more of the above-described monomers can be used as the (meth) acrylic acid alkyl ester that can be used for the acrylic polymer Pa.
- the polymer Ps is a (meth) acrylic acid C 4-12 alkyl ester (preferably a (meth) acrylic acid C 4-10 alkyl ester, such as a (meth) acrylic acid C 6-10 alkyl ester). At least one kind may be contained as a monomer unit.
- the polymer Ps contains at least one methacrylic acid C 1-18 alkyl ester (preferably a methacrylic acid C 1-14 alkyl ester such as a methacrylic acid C 1-10 alkyl ester) as a monomer unit.
- the monomer unit constituting the polymer Ps can include, for example, one or more selected from MMA, BMA, and 2EHMA.
- the (meth) acrylic monomer examples include (meth) acrylic acid ester having an alicyclic hydrocarbon group.
- cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, or the like can be used.
- the polymer Ps may contain as monomer units at least one selected from dicyclopentanyl methacrylate, isobornyl methacrylate, and cyclohexyl methacrylate.
- the amount of the (meth) acrylic acid alkyl ester and the (meth) acrylic acid ester having the alicyclic hydrocarbon group used is, for example, 10% by weight or more and 95% by weight with respect to all monomer components for preparing the polymer Ps. % Or less, 20% to 95% by weight, 30% to 90% by weight, 40% to 90% by weight, 50% It may be not less than 85% by weight.
- the monomer that can be included together with the monomer S1 as the monomer unit constituting the polymer Ps the carboxyl group-containing monomer, the acid anhydride group-containing monomer, and the hydroxyl group-containing monomer exemplified above as the monomer that can be used for the acrylic polymer Pa , Epoxy group-containing monomers, cyano group-containing monomers, isocyanate group-containing monomers, amide group-containing monomers, monomers having a nitrogen atom-containing ring, monomers having a succinimide skeleton, maleimides, itaconimides, aminoalkyl (meth) acrylates, Vinyl esters, vinyl ethers, olefins, (meth) acrylic acid esters having aromatic hydrocarbon groups, heterocycle-containing (meth) acrylates, halogen atom-containing (meth) acrylates, terpene compound derivatives alcohol Obtained from (meth) acrylic acid ester and the like.
- the total amount of the monomer S1 and the (meth) acrylic monomer in the entire monomer component is, for example, 50% by weight or more. It may be 70% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, or substantially 100% by weight.
- the composition of the (meth) acrylic monomer contained in the monomer component can be set such that the glass transition temperature T m1 based on the composition of the (meth) acrylic monomer is higher than 0 ° C., for example.
- the glass transition temperature T m1 based on the composition of the (meth) acrylic monomer is determined by the Fox equation based on the composition of only the (meth) acrylic monomer among the monomer components used for the preparation of the polymer Ps. Refers to the Tg.
- T m1 applies the above-mentioned Fox formula only for the (meth) acrylic monomer among the monomer components used for the preparation of the polymer Ps, and the glass transition temperature of the homopolymer of each (meth) acrylic monomer It can be calculated from the weight fraction of each (meth) acrylic monomer in the total amount of the (meth) acrylic monomer.
- the initial adhesive force is easily suppressed.
- the polymer Ps whose glass transition temperature Tm1 is higher than 0 degreeC an adhesive sheet with a large adhesive force increase ratio is easy to be obtained.
- T m1 may be 10 ° C. or higher, 20 ° C. or higher, 30 ° C. or higher, or 40 ° C. or higher.
- T m1 may be, for example, 50 ° C. or higher, 53 ° C. or higher, 56 ° C. or higher, or 59 ° C. or higher.
- it may be 62 ° C. or higher, 65 ° C. or higher, 68 ° C. or higher, or 70 ° C. or higher.
- T m1 may be, for example, 120 ° C. or less, 110 ° C. or less, 100 ° C. or less, 90 ° C. or less, 85 ° C. or less, 80 ° C. or less, or less than 80 ° C.
- T m1 can be, for example, 75 ° C. or lower, 65 ° C. or lower, or 55 ° C. or lower.
- the technique disclosed herein can be preferably implemented using a polymer Ps having a T m1 in the range of, for example, 10 ° C. to 120 ° C., or 20 ° C. to 110 ° C., or 30 ° C. to 100 ° C.
- the Mw of the polymer Ps is not particularly limited.
- the Mw of the polymer Ps may be 1000 or more, for example, or 5000 or more. Further, the Mw of the polymer Ps may be, for example, 10 ⁇ 10 4 or less, or 7 ⁇ 10 4 or less. In some embodiments, Mw of the polymer Ps can be, for example, be less than 1 ⁇ 10 4 or more 5 ⁇ 10 4, preferably less than 1.2 ⁇ 10 4 or more 5 ⁇ 10 4, 1.5 ⁇ more preferably 10 4 or more 4 ⁇ 10 below 4, more preferably less than 2 ⁇ 10 4 or more 4 ⁇ 10 4. If the Mw of the polymer Ps is less than 1 ⁇ 10 4 , the increase in adhesive strength may be insufficient.
- the initial adhesive force may not be sufficiently suppressed.
- the Mw of the polymer Ps is within the above range, it is easy to adjust the compatibility and mobility in the pressure-sensitive adhesive layer to an appropriate range, and both the initial low-tackiness and the strong-tackiness during use are compatible at a high level. It becomes easy to realize an adhesive sheet.
- the polymer Ps can be prepared, for example, by polymerizing the above-described monomers by a known method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or a photopolymerization method.
- a chain transfer agent can be used to adjust the molecular weight of the polymer Ps.
- the chain transfer agent used include compounds having a mercapto group such as octyl mercaptan, lauryl mercaptan, t-nonyl mercaptan, t-dodecyl mercaptan, mercaptoethanol, ⁇ -thioglycerol; thioglycolic acid, methyl thioglycolate, Ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, ethylene Thioglycolic acid esters
- the amount of the chain transfer agent used is not particularly limited, but is usually 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the monomer. More preferably, it is contained in an amount of 0.2 to 10 parts by weight.
- the polymer Ps with a suitable molecular weight can be obtained by adjusting the addition amount of the chain transfer agent.
- a chain transfer agent can be used individually by 1 type or in combination of 2 or more types.
- the usage-amount of polymer Ps can be 0.1 weight part or more with respect to 100 weight part of base polymers (for example, acrylic polymer Pa), and obtains a higher effect. From the viewpoint, it may be 0.3 parts by weight or more, 0.4 parts by weight or more, or 0.5 parts by weight or more. In some embodiments, the amount of the polymer Ps used relative to 100 parts by weight of the base polymer may be 1 part by weight or more, 2 parts by weight or more, or 3 parts by weight or more.
- the amount of the polymer Ps used relative to 100 parts by weight of the base polymer is usually suitably 25 parts by weight or less, and after higher heating From the viewpoint of obtaining adhesive strength, it is preferably 20 parts by weight or less, may be 17 parts by weight or less, may be 15 parts by weight or less, and may be 10 parts by weight or less.
- the amount of the polymer Ps used relative to 100 parts by weight of the base polymer may be less than 10 parts by weight, may be 8 parts by weight or less, and may be 5 parts by weight or less. Alternatively, it may be less than 5 parts by weight, 4 parts by weight or less, or 3 parts by weight or less.
- the siloxane structure-containing polymer Ps as described above can preferably function as an adhesive force increase retarder by being blended in the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive sheet disclosed herein can be preferably implemented in a mode in which the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains a base polymer and a pressure-sensitive adhesive force increase retarder, and the pressure-sensitive adhesive force increase retarder contains polymer Ps.
- the polymer Ps functions as an adhesive strength increase retarder because the initial adhesive force is suppressed by the polymer Ps present on the surface of the adhesive layer in the adhesive sheet at the initial stage of application before application to the adherend, This is considered to be because the amount of the polymer Ps present on the surface of the pressure-sensitive adhesive layer is reduced and the pressure-sensitive adhesive force is increased due to the flow of the pressure-sensitive adhesive due to aging or heating after pasting. Therefore, as the adhesive force increase retarder in the technology disclosed herein, other materials that can exhibit the same type of function can be used instead of the polymer Ps or in combination with the polymer Ps.
- Non-limiting examples of such materials include polymers having a polyoxyalkylene structure in the molecule (hereinafter also referred to as “polymer Po”).
- the polymer Po can be, for example, a polymer including monomer units derived from a monomer having a polyoxyalkylene skeleton. Specific examples include any one homopolymer or two or more copolymers of monomers having a polyoxyalkylene skeleton as described above, one or more monomers having a polyoxyalkylene skeleton, and others. Copolymers with other monomers (for example, (meth) acrylic monomers) can be used as the polymer Po.
- the usage amount of the monomer having a polyoxyalkylene skeleton is not particularly limited.
- the usage amount of the monomer S1 in the polymer Ps described above may be applied to the usage amount of the monomer having a polyoxyalkylene skeleton in the polymer Po. it can.
- the usage-amount of polymer Po in an adhesive layer is not specifically limited,
- the usage-amount of polymer Ps with respect to the base polymer mentioned above is applicable also to the usage-amount of polymer Po with respect to a base polymer.
- a part of the amount of the polymer Ps used relative to the base polymer described above may be replaced with the polymer Po.
- a crosslinking agent in the pressure-sensitive adhesive layer disclosed herein, can be used for the purpose of adjusting the cohesive force.
- a commonly used crosslinking agent can be used.
- a melamine type crosslinking agent, a metal chelate type crosslinking agent, etc. can be mentioned.
- an isocyanate-based crosslinking agent an epoxy-based crosslinking agent, and a metal chelate-based crosslinking agent can be preferably used.
- a crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
- examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenyl (meth) diisocyanate, hydrogenated diphenyl (meth) diisocyanate. , Tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenyl (meth) triisocyanate, polymethylene polyphenyl isocyanate, and adducts of these with polyols such as trimethylolpropane.
- a compound having at least one isocyanate group and one or more unsaturated bonds in one molecule specifically, 2-isocyanatoethyl (meth) acrylate may be used as an isocyanate-based crosslinking agent.
- 2-isocyanatoethyl (meth) acrylate may be used as an isocyanate-based crosslinking agent.
- Can do These can be used alone or in combination of two or more.
- epoxy crosslinking agent examples include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane tri Glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, etc. Can do. These can be used alone or in combination of two or more.
- metal chelate compound examples include aluminum, iron, tin, titanium and nickel as metal components, and acetylene, methyl acetoacetate and ethyl lactate as chelate components. These can be used alone or in combination of two or more.
- the amount of the crosslinking agent used can be, for example, 0.01 parts by weight or more, preferably 0.05 parts by weight or more, with respect to 100 parts by weight of the base polymer. Higher cohesion tends to be obtained by increasing the amount of the crosslinking agent used.
- the amount of the crosslinking agent used relative to 100 parts by weight of the base polymer may be 0.1 parts by weight or more, 0.5 parts by weight or more, or 1 part by weight or more. Also good.
- the amount of the crosslinking agent used relative to 100 parts by weight of the base polymer is usually suitably 15 parts by weight or less, and may be 10 parts by weight or less.
- the use amount of the crosslinking agent is not too large. It can be advantageous also from the viewpoint of better expressing.
- the technique disclosed herein can be preferably implemented in an embodiment using at least an isocyanate-based crosslinking agent as a crosslinking agent.
- the amount of the isocyanate-based crosslinking agent used relative to 100 parts by weight of the base polymer is, for example, 5 parts by weight or less. 3 parts by weight or less, less than 1 part by weight, 0.7 parts by weight or less, or 0.5 parts by weight or less.
- a crosslinking catalyst may be used in order to make any of the above-described crosslinking reactions proceed more effectively.
- a crosslinking catalyst for example, a tin-based catalyst (particularly dioctyltin dilaurate) can be preferably used.
- the amount of the crosslinking catalyst used is not particularly limited, and can be, for example, about 0.0001 to 1 part by weight with respect to 100 parts by weight of the base polymer.
- the pressure-sensitive adhesive layer can contain a tackifier resin as necessary.
- the tackifying resin is not particularly limited.
- rosin tackifying resin, terpene tackifying resin, phenol tackifying resin, hydrocarbon tackifying resin, ketone tackifying resin, polyamide tackifying resin examples thereof include an epoxy tackifying resin and an elastomer tackifying resin.
- Tackifying resin can be used individually by 1 type or in combination of 2 or more types.
- rosin-based tackifier resins examples include unmodified rosins such as gum rosin, wood rosin and tall oil rosin (raw rosin), and modified rosins modified by polymerization, disproportionation, hydrogenation, etc. Polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin and other chemically modified rosins), and various rosin derivatives.
- rosin derivative examples include: A rosin phenolic resin obtained by thermally polymerizing rosins (unmodified rosin, modified rosin, various rosin derivatives, etc.) by adding phenol with an acid catalyst; Ester compounds of rosin obtained by esterifying unmodified rosin with alcohol (unmodified rosin ester), modified rosins such as polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin, alcohols Rosin ester resins such as modified rosin ester compounds esterified by (polymerized rosin ester, stabilized rosin ester, disproportionated rosin ester, fully hydrogenated rosin ester, partially hydrogenated rosin ester, etc.); An unsaturated fatty acid-modified rosin resin obtained by modifying an unmodified rosin or a modified rosin (polymerized rosin, stabilized rosin, disproportionated rosin,
- terpene-based tackifier resins include terpene resins such as ⁇ -pinene polymers, ⁇ -pinene polymers, and dipentene polymers, and modified terpene resins (phenol modified, aromatic modified, hydrogenated modified). Modified terpene resins such as terpene phenol resins, styrene modified terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, and the like.
- phenolic tackifying resins include condensates of various phenols (eg, phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin, etc.) with formaldehyde (eg, alkylphenolic resin, xyleneformaldehyde). Resin), a resol obtained by addition reaction of the phenols and formaldehyde with an alkali catalyst, and a novolak obtained by condensation reaction of the phenols and formaldehyde with an acid catalyst.
- phenols eg, phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin, etc.
- formaldehyde eg, alkylphenolic resin, xyleneformaldehyde
- Resin a resol obtained by addition reaction of the phenols and formaldehyde with an alkali catalyst
- a novolak obtained by
- hydrocarbon-based tackifying resins examples include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic / aromatic petroleum resins (styrene-olefin copolymers, etc. ), Various hydrocarbon resins such as aliphatic / alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumarone resins, coumarone indene resins, and the like.
- polymerized rosin esters examples include trade names “Pencel D-125”, “Pencel D-135”, “Pencel D-160”, “Pencel KK”, and “Pencel” manufactured by Arakawa Chemical Industries, Ltd. C ”and the like are exemplified, but not limited thereto.
- terpene phenolic resins that can be preferably used include trade names “YS Polystar S-145”, “YS Polystar G-125”, “YS Polystar N125”, and “YS Polystar U-115” manufactured by Yashara Chemical Co., Ltd. Examples include, but are not limited to, trade names “TAMANOL 803L” and “TAMANOL 901” manufactured by Arakawa Chemical Industries, Ltd., and “Sumilite Resin PR-12603” manufactured by Sumitomo Bakelite Co., Ltd.
- the content of the tackifying resin is not particularly limited, and can be set so that appropriate adhesive performance is exhibited according to the purpose and application.
- the content of the tackifying resin with respect to 100 parts by weight of the base polymer (when two or more kinds of tackifying resins are included, the total amount thereof) can be, for example, about 5 to 500 parts by weight.
- the tackifier resin those having a softening point (softening temperature) of about 80 ° C. or more (preferably about 100 ° C. or more, for example, about 120 ° C. or more) can be preferably used. According to the tackifier resin having a softening point equal to or higher than the lower limit value described above, the initial low-tackiness and the strong tackiness during use tend to be effectively improved.
- the upper limit of the softening point is not particularly limited, and can be, for example, about 200 ° C. or lower (typically 180 ° C. or lower).
- the softening point of the tackifier resin can be measured based on the softening point test method (ring ball method) defined in JIS K2207.
- the pressure-sensitive adhesive layer in the technique disclosed herein is a leveling agent, a plasticizer, a softening agent, a colorant (dye, pigment, etc.), a filler, and an antistatic agent as long as the effects of the present invention are not significantly hindered.
- known additives that can be used for the pressure-sensitive adhesive such as an anti-aging agent, an ultraviolet absorber, an antioxidant, a light stabilizer, and a preservative, may be included as necessary.
- the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet disclosed herein can be a cured layer of the pressure-sensitive adhesive composition. That is, the pressure-sensitive adhesive layer can be formed by applying (for example, applying) the pressure-sensitive adhesive composition to an appropriate surface and then appropriately performing a curing treatment. When performing 2 or more types of hardening processes (drying, bridge
- a partially polymerized monomer component acrylic polymer syrup
- pressure-sensitive adhesive composition can be carried out using a conventional coater such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater and the like.
- a conventional coater such as a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater and the like.
- a direct method in which the pressure-sensitive adhesive composition is directly applied to the base material to form the pressure-sensitive adhesive layer may be used.
- a transfer method of transferring the pressure-sensitive adhesive layer formed on the surface having a property (release surface) to the substrate may be used, or these methods may be combined.
- release surface the surface of the release liner, the back surface of the substrate after the release treatment, or the like can be used.
- the gel fraction of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is usually suitably in the range of 20.0% to 99.0%, and 30.0% to 90.90%. It is desirable to be in the range of 0%.
- the gel fraction is measured by the following method.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited, and can be, for example, 1 ⁇ m or more. Normally, good adhesiveness can be realized by setting the thickness of the pressure-sensitive adhesive layer to 3 ⁇ m or more (for example, 5 ⁇ m or more). In some embodiments, the thickness of the pressure-sensitive adhesive layer may be 8 ⁇ m or more, 10 ⁇ m or more, or 13 ⁇ m or more. By increasing the thickness of the pressure-sensitive adhesive layer, it can be easy to improve the adhesive strength after heating. Moreover, the thickness of an adhesive layer can be 200 micrometers or less, for example, may be 150 micrometers or less, and is good also as 100 micrometers or less.
- the thickness of the pressure-sensitive adhesive layer is preferably less than 100 ⁇ m, may be 80 ⁇ m or less, may be 60 ⁇ m or less, may be 50 ⁇ m or less, and may be 40 ⁇ m or less. May be. That the thickness of the pressure-sensitive adhesive layer is not too large can be advantageous from the viewpoint of reducing the thickness of the pressure-sensitive adhesive sheet and preventing cohesive failure of the pressure-sensitive adhesive layer.
- the thickness of the PSA layer described above is the thickness of the PSA layer per side of the substrate.
- Ts / Ta is preferably larger than 1.
- Ts / Ta may be, for example, 1.1 or more, 1.2 or more, 1.5 or more, or 1.7 or more. Also good. Due to the increase in Ts / Ta, there is a tendency that a pressure-sensitive adhesive sheet that achieves a higher level of both low initial adhesiveness and strong adhesiveness during use tends to be realized. In some embodiments, Ts / Ta may be 2 or more (eg, greater than 2), 3 or more, or 4 or more.
- Ts / Ta can be set to 50 or less, for example, or 20 or less. In some embodiments, Ts / Ta may be, for example, 10 or less, or 8 or less from the viewpoint of easily exerting good post-heating adhesive force even if the pressure-sensitive adhesive sheet is thinned.
- the amount of hydroxyl-containing monomer used W OH relative to the amount of isocyanate-based crosslinking agent used W NCO is:
- the amount of W OH / W NCO can be 2 or more on a weight basis.
- W OH / W NCO may be 3 or greater, 5 or greater, 10 or greater, 20 or greater, or 30 or greater. It may be 50 or more.
- the upper limit of W OH / W NCO is not particularly limited. W OH / W NCO may be, for example, 500 or less, 200 or less, or 100 or less.
- the monomer unit common to the monomer unit included in the polymer Ps is also included in the base polymer, whereby the polymer Ps in the pressure-sensitive adhesive layer It is possible to improve the mobility and increase the adhesive strength increase ratio. It is effective that the common monomer unit is a component occupying 5% by weight or more of all monomer units constituting the polymer Ps, and is 10% by weight or more (more preferably 20% by weight or more, for example, 30% by weight or more). It is preferable that it is a component occupying.
- the ratio of the common monomer unit to the total monomer units constituting the base polymer is, for example, 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, and 7% by weight or more. May be.
- the ratio of the common monomer units to all the monomer units constituting the base polymer increases, the effect of improving the compatibility tends to be exhibited better.
- the ratio of the common monomer units to the total monomer units constituting the base polymer may be 50% by weight or less, or 30% by weight or less.
- Non-limiting examples of monomers that can be preferably employed as common monomer units include MMA, BMA, 2EHMA, methyl acrylate (MA), BA, 2EHA, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl. (Meth) acrylate etc. are mentioned.
- the pressure-sensitive adhesive sheet disclosed herein can take the form of a pressure-sensitive adhesive product in which a release liner is bonded to the pressure-sensitive adhesive layer surface for the purpose of protecting the pressure-sensitive adhesive surface. Therefore, this specification can provide a pressure-sensitive adhesive sheet with a release liner (pressure-sensitive adhesive product) including any pressure-sensitive adhesive sheet disclosed herein and a release liner that protects the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet.
- the release liner is not particularly limited.
- a release liner having a release layer on the surface of a liner substrate such as a resin film or paper (which may be a paper laminated with a resin such as polyethylene), or a fluoropolymer.
- a release liner made of a resin film formed of a low-adhesive material such as (polytetrafluoroethylene or the like) or a polyolefin resin (polyethylene, polypropylene or the like) can be used. Since the surface smoothness is excellent, a release liner having a release layer on the surface of a resin film as a liner substrate or a release liner made of a resin film formed of a low adhesive material can be preferably used.
- the resin film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer.
- films polyester films (PET film, PBT film, etc.), polyurethane films, ethylene-vinyl acetate copolymer films, and the like.
- the release layer for example, a silicone release treatment agent, a long-chain alkyl release treatment agent, an olefin release treatment agent, a fluorine release treatment agent, a fatty acid amide release treatment agent, molybdenum sulfide, silica powder, etc.
- a known release treating agent can be used.
- the use of a silicone release treatment agent is particularly preferred.
- the thickness of the release layer is not particularly limited, but is usually about 0.01 ⁇ m to 1 ⁇ m, preferably about 0.1 ⁇ m to 1 ⁇ m.
- the thickness of the release liner is not particularly limited, but is usually about 5 ⁇ m to 200 ⁇ m (for example, about 10 ⁇ m to 100 ⁇ m, preferably about 20 ⁇ m to 80 ⁇ m). When the thickness of the release liner is within the above range, it is preferable because the workability for bonding to the pressure-sensitive adhesive layer and the workability for peeling from the pressure-sensitive adhesive layer are excellent.
- the release liner may be subjected to an antistatic treatment such as a coating type, a kneading type, or a vapor deposition type, if necessary.
- the adhesive sheet disclosed here can satisfy both initial low-adhesiveness and strong adhesiveness at the time of use when Et ′ ⁇ (Ts) 3 is larger than 0.1 N ⁇ mm.
- the adhesive strength is kept low for a while in a room temperature range (for example, 20 ° C. to 30 ° C.), and good reworkability can be exhibited during this time.
- the pressure-sensitive adhesive sheet can greatly increase the pressure-sensitive adhesive force by aging (heating, aging, a combination thereof, or the like), and thereafter can achieve strong bonding.
- the pressure-sensitive adhesive sheet can be firmly adhered to the adherend by heating at a desired timing.
- the pressure-sensitive adhesive sheet disclosed herein is, for example, an aspect that is affixed to members constituting various portable devices (portable devices), fixing, joining, molding, decoration, protection of the members, It can be preferably used for applications such as support.
- “carrying” means that it is not enough to be able to carry it alone, but means that the individual (standard adult) has a level of portability that can be carried relatively easily. To do.
- Examples of mobile devices here include mobile phones, smartphones, tablet computers, notebook computers, various wearable devices, digital cameras, digital video cameras, audio devices (portable music players, IC recorders, etc.), computers ( Calculators, etc.), portable game devices, electronic dictionaries, electronic notebooks, electronic books, in-vehicle information devices, portable radios, portable TVs, portable printers, portable scanners, portable modems, and other portable electronic devices, mechanical watches and pocket watches A watch, flashlight, hand mirror, etc. may be included.
- Examples of members constituting the portable electronic device may include optical films and display panels used in image display devices such as liquid crystal displays and organic EL displays.
- the pressure-sensitive adhesive sheet disclosed herein can be preferably used for applications such as fixing, joining, molding, decoration, protection, and support of members in a mode of being attached to various members in automobiles, home appliances, and the like.
- a pressure-sensitive adhesive sheet comprising a support substrate and a pressure-sensitive adhesive layer laminated on at least one side of the support substrate,
- the thickness of the pressure-sensitive adhesive layer is 3 ⁇ m or more and less than 100 ⁇ m
- the support substrate has a thickness of 30 ⁇ m or more
- the relationship between the elastic modulus Et ′ [MPa] of the pressure-sensitive adhesive sheet and the thickness Ts [mm] of the support substrate satisfies the following formula: 0.1 [N ⁇ mm] ⁇ Et ′ ⁇ (Ts) 3 ;
- the adhesive force N2 after heating the adhesive layer to the stainless steel plate (SUS304BA plate) for 5 minutes at 80 ° C. is 30 at 23 ° C.
- the support substrate includes, as a base film, a resin film formed using a resin material including one or more selected from the group consisting of polyester resins, polyphenylene sulfide resins, and polyolefin resins.
- the above adhesive strength increase retarder is: A siloxane structure-containing polymer Ps containing a monomer having a polyorganosiloxane skeleton as a monomer unit; and a polyoxyalkylene structure-containing polymer Po containing a monomer having a polyoxyalkylene skeleton as a monomer unit;
- the pressure-sensitive adhesive layer contains a siloxane structure-containing polymer Ps, The pressure-sensitive adhesive sheet according to any one of (1) to (8), wherein the siloxane structure-containing polymer Ps is a copolymer of a monomer having a polyorganosiloxane skeleton and a (meth) acrylic monomer. (10) The pressure-sensitive adhesive sheet according to (9), wherein the siloxane structure-containing polymer Ps has a weight average molecular weight of 1 ⁇ 10 4 or more and less than 5 ⁇ 10 4 . (11) The pressure-sensitive adhesive layer contains the siloxane structure-containing polymer Ps and an acrylic polymer Pa having a glass transition temperature of 0 ° C. or less.
- the siloxane structure containing polymer Ps is an adhesive sheet as described in said (9) or (10) which is 0.1 weight part or more and less than 10 weight part with respect to 100 weight part of said acrylic polymer Pa.
- the ratio of the total amount of the hydroxyl group-containing monomer and the N-vinyl cyclic amide in the total amount of monomer components for adjusting the acrylic polymer Pa is 15 wt% or more and 50 wt% or less
- the acrylic polymer Pa and the siloxane structure-containing polymer Ps include at least one monomer selected from the group consisting of MMA, BMA, 2EHMA, MA, BA, and 2EHA as a common monomer unit. ) To (14).
- the pressure-sensitive adhesive layer contains a hydroxyl group-containing monomer as a monomer unit, and the ratio (W OH / W NCO ) of the use amount W OH of the hydroxyl group-containing monomer to the use amount W NCO of the isocyanate-based crosslinking agent is 2 or more.
- a pressure-sensitive adhesive sheet comprising a support substrate and a pressure-sensitive adhesive layer laminated on at least one side of the support substrate,
- the thickness of the pressure-sensitive adhesive layer is 3 ⁇ m or more and less than 100 ⁇ m
- the support substrate has a thickness of 30 ⁇ m or more
- the adhesive force N1 after standing at 23 ° C. for 30 minutes is 1.0 N / 20 mm or less
- the adhesive layer is made of a stainless steel plate (SUS304BA plate).
- a pressure-sensitive adhesive sheet with a release liner comprising a release liner that protects the pressure-sensitive adhesive surface of the pressure-sensitive adhesive sheet.
- the release liner was treated with at least one release agent selected from the group consisting of a silicone release agent, a long-chain alkyl release agent, an olefin release agent, and a fluorine release agent.
- Acrylic polymer A3 40 parts of 2EHA, 40 parts of isostearyl acrylate (ISTA), 18 parts of NVP, 1 part of 4HBA, and 2,2-dimethoxy-1,2-diphenylethane-1-one as a photopolymerization initiator (trade name “Irgacure” manufactured by BASF) 651 ”) and 0.05 part of 1-hydroxycyclohexyl-phenyl-ketone (BASF, trade name” Irgacure 184 ”) are mixed and irradiated with ultraviolet rays in a nitrogen atmosphere to perform partial polymerization.
- Acrylic polymer A3 was prepared in the form of a product (acrylic polymer syrup).
- siloxane structure-containing polymer Ps2 The composition of the monomer components used in the preparation of polymer Ps1 was changed to 50 parts of MMA, 15 parts of BMA, 15 parts of 2EHMA, 8.7 parts of X-22-174ASX, and 11.3 parts of KF-2012. Moreover, 0.8 parts of thioglycerol was used as a chain transfer agent, and ethyl acetate was used as a polymerization solvent. In other respects, a solution of the siloxane structure-containing polymer Ps2 was obtained in the same manner as in the preparation of the polymer Ps1. Mw of this polymer Ps2 was 19700, and T m1 was about 60 ° C.
- Example 1 ⁇ Production of adhesive sheet> (Example 1) In 100 parts of the acrylic polymer A1 contained in the solution, 5 parts of the siloxane structure-containing polymer Ps1 and Pencel D-125 (polymerized rosin ester manufactured by Arakawa Chemical Industries, Ltd.) as a tackifier resin were added to the acrylic polymer A1 solution. 30 parts of a softening point of 120 to 130 ° C. and 3 parts of Coronate L (isocyanate-based crosslinking agent manufactured by Tosoh Corporation) as a crosslinking agent were added and mixed uniformly to prepare an adhesive composition C1. Two types of release liners R1 and R2 were prepared in which one side of the polyester film was a release surface with a silicone release treatment agent.
- Ps1 and Pencel D-125 polymerized rosin ester manufactured by Arakawa Chemical Industries, Ltd.
- Coronate L isocyanate-based crosslinking agent manufactured by Tosoh Corporation
- the release liner R1 a trade name “Diafoil MRF” (thickness: 38 ⁇ m) manufactured by Mitsubishi Plastics, Inc. was used.
- a trade name “Diafoil MRE” (thickness: 38 ⁇ m) manufactured by Mitsubishi Plastics, Inc. was used.
- the pressure-sensitive adhesive composition C1 was applied to the first surface of a 75 ⁇ m-thick polyethylene terephthalate (PET) film (trade name “Lumirror”, manufactured by Toray Industries, Inc.) as a supporting substrate, heated at 110 ° C.
- PET polyethylene terephthalate
- a first adhesive layer having a thickness of 38 ⁇ m was formed, and the release surface of the release liner R1 was bonded to the surface (adhesive surface).
- the pressure-sensitive adhesive composition C1 is applied to the second surface of the support substrate, heated at 110 ° C. for 2 minutes to form a second pressure-sensitive adhesive layer having a thickness of 38 ⁇ m, and a release liner on the surface (pressure-sensitive adhesive surface).
- the release surface of R2 was bonded.
- the double-sided adhesive sheet with a base material which has the 1st, 2nd adhesive layer of thickness 38 micrometers on both surfaces of the support base material of thickness 75 micrometers was obtained.
- This pressure-sensitive adhesive sheet constitutes a pressure-sensitive adhesive sheet with a release liner having release liners R1 and R2 on both pressure-sensitive adhesive surfaces.
- Es ′ ⁇ (Ts) 3 of the pressure-sensitive adhesive sheet according to Example 1 is 0.99 N ⁇ mm, and can be used as the value of Et ′ ⁇ (Ts) 3 as described above.
- Example 2 To the acrylic polymer A2 solution, 5 parts of the siloxane structure-containing polymer Ps1 per 100 parts of the acrylic polymer A2 contained in the solution, Takenate D-110N as a crosslinking agent (isocyanate crosslinking agent manufactured by Mitsui Chemicals) was added and mixed uniformly to prepare an adhesive composition C2.
- a pressure-sensitive adhesive composition C2 was applied to one side of a 125 ⁇ m-thick PET film (trade name “Lumirror”, manufactured by Toray Industries, Inc.) as a supporting substrate, and heated at 110 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 25 ⁇ m.
- release liner R1 (trade name “Diafoil MRF” manufactured by Mitsubishi Plastics, Inc.) was bonded to the adhesive surface. In this way, a single-sided pressure-sensitive adhesive sheet with a substrate according to this example was obtained.
- This pressure-sensitive adhesive sheet constitutes a pressure-sensitive adhesive sheet with a release liner having a release liner R1 on the pressure-sensitive adhesive surface.
- a pressure-sensitive adhesive composition C3 was prepared in the same manner as the pressure-sensitive adhesive composition C2 except that the amount of the crosslinking agent was changed to 1.1 parts.
- a pressure-sensitive adhesive composition C3 was applied to one side of a 75 ⁇ m-thick PET film (trade name “Lumirror” manufactured by Toray Industries, Inc.) as a supporting substrate, and heated at 110 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 15 ⁇ m.
- a single-sided adhesive sheet with a substrate according to this example was obtained.
- Example 4 A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that a PET film having a thickness of 25 ⁇ m (trade name “Lumirror” manufactured by Toray Industries, Inc.) was used as the supporting substrate. Es ′ ⁇ (Ts) 3 of the pressure-sensitive adhesive sheet according to Example 4 is 0.04 N ⁇ mm.
- Example 5 A pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that a 4.5 ⁇ m-thick PET film (trade name “Lumirror” manufactured by Toray Industries, Inc.) was used as the supporting substrate.
- a 4.5 ⁇ m-thick PET film trade name “Lumirror” manufactured by Toray Industries, Inc.
- Example 6 To 100 parts of the acrylic polymer A3 (acrylic polymer syrup) prepared above, 0.2 part of trimethylolpropane triacrylate (trade name “TMP3A” manufactured by Osaka Organic Chemical Industry Co., Ltd.) and 2 parts of a siloxane structure-containing polymer were added. The mixture was added and mixed uniformly to prepare an adhesive composition C4. This pressure-sensitive adhesive composition C4 was applied to the release surface of the release liner R1 so that the final thickness was 100 ⁇ m to form a coating layer. Next, a release liner R2 was placed on the surface of the coating layer such that the release surface was on the coating layer side. Thereby, the coating layer was shielded from oxygen.
- TMP3A trimethylolpropane triacrylate
- This laminated sheet (having a laminated structure of release liner R1 / coating layer / release liner R2) is irradiated with ultraviolet rays having an illuminance of 5 mW / cm 2 for 360 seconds using a chemical light lamp (manufactured by Toshiba Corporation).
- the adhesive layer was formed by curing the coating layer.
- the above illuminance value is a value measured by an industrial UV checker having a peak sensitivity wavelength of about 350 nm (trade name “UVR-T1”, light receiving unit type UD-T36, manufactured by Topcon Corporation).
- the release liner R1 is peeled off from the obtained pressure-sensitive adhesive layer, and a 50 ⁇ m-thick PET film (trade name “Lumirror”, manufactured by Toray Industries, Inc.) as a support substrate is bonded to the exposed adhesive surface.
- a single-sided pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on one side was obtained.
- This pressure-sensitive adhesive sheet constitutes a pressure-sensitive adhesive sheet with a release liner having a release liner R2 on the pressure-sensitive adhesive surface opposite to the side bonded to the support substrate.
- the initial adhesive force of the 1st adhesive surface was measured in the state which bonded the PET film of thickness 2 micrometers to the 2nd adhesive surface.
- the test piece pressure-bonded to the adherend in the same manner as the measurement of the initial adhesive strength N1 was heated at 80 ° C. for 5 minutes and then left in the standard environment for 30 minutes, and then peeled off 180 ° in the same manner to measure the adhesive strength. did.
- the measurement was performed three times, and the average value was shown in the column “After heating (N2)” in Table 1 as the adhesive strength after heating.
- the pressure-sensitive adhesive sheet according to each example was cut into a size having a width of 10 mm and a length of 100 mm together with the release liner to prepare a test piece.
- the above-mentioned size is applied after a 25 ⁇ m thick PET film (trade name “Lumirror S10” manufactured by Toray Industries, Inc.) is bonded to the second pressure-sensitive adhesive surface. Cut to.
- the release liner R1 covering the first adhesive surface of each test piece is peeled off, and the test piece is placed on a bakelite plate (phenol resin plate) as an adherend in an environment of 23 ° C. and 50% RH. With a 20 mm sticking area, a 2 kg roller was reciprocated once and pressed. The adherend to which the test piece was attached in this manner was suspended in an environment of 40 ° C. so that the length direction of the test piece was the vertical direction, and was allowed to stand for 30 minutes. Next, a load of 500 g was applied to the free end of the test piece, and the sample was left in an environment of 40 ° C. for 1 hour in accordance with JIS Z0237 with the load applied.
- a bakelite plate phenol resin plate
- deviated from the initial sticking position was measured.
- the pressure-sensitive adhesive sheets according to Examples 1 to 3 having a large Et ′ ⁇ (Ts) 3 and a high adhesive force increase ratio have a low initial adhesive force and a high adhesive force after heating, and the initial low Adhesiveness and strong adhesiveness at the time of use were combined suitably.
- Et ′ ⁇ (Ts) 3 increases (that is, in the order of Examples 5, 4 and 1), the adhesive strength after heating increases. It can be seen that it is larger and, on the contrary, the initial adhesive strength is smaller.
- the adhesive force raise ratio (N2 / N1) improved greatly compared with the adhesive sheet which concerns on Examples 4 and 5, and the adhesive force raise ratio exceeding 20 was obtained.
- the pressure-sensitive adhesive sheets of Examples 2 and 3 in which the ratio of the thickness of the base material to the value of Et ′ ⁇ (Ts) 3 or the pressure-sensitive adhesive layer was larger than Example 1, a higher increase ratio of the adhesive strength was obtained.
- the pressure-sensitive adhesive sheets according to Examples 1 to 3 clearly good results were obtained in both the low initial pressure-sensitive adhesive strength and the high pressure-sensitive adhesive strength after heating as compared with the pressure-sensitive adhesive sheets of Examples 4 and 5. .
- Example 9 using a siloxane structure-containing polymer having a higher T m1 as compared with Example 8, the initial adhesive strength was suppressed as compared with Example 8, and the adhesive strength increase ratio was improved.
- Adhesive sheet 10
- Support base material 10A 1st surface 10B 2nd surface 21
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Abstract
Description
本出願は、2016年11月21日に出願された日本国特許出願2016-226288に基づく優先権を主張しており、その出願の全内容は本明細書中に参照として組み入れられている。
なお、以下の図面において、同じ作用を奏する部材・部位には同じ符号を付して説明することがあり、重複する説明は省略または簡略化することがある。また、図面に記載の実施形態は、本発明を明瞭に説明するために模式化されており、実際に提供される製品のサイズや縮尺を必ずしも正確に表したものではない。
ここに開示される粘着シートは、支持基材と、上記支持基材の少なくとも片側に積層されている粘着剤層とを含む。以下、支持基材を単に「基材」ということもある。
一実施形態に係る粘着シートの構造を図1に模式的に示す。この粘着シート1は、第一面10Aおよび第二面10Bを有するシート状の支持基材(例えば樹脂フィルム)10と、その第一面10A側に設けられた粘着剤層21とを備える基材付き片面粘着シートとして構成されている。粘着剤層21は、支持基材10の第一面10A側に固定的に、すなわち当該支持基材10から粘着剤層21を分離する意図なく、設けられている。粘着シート1は、粘着剤層21を被着体に貼り付けて用いられる。使用前(すなわち、被着体への貼付け前)の粘着シート1は、図1に示すように、粘着剤層21の表面(粘着面)21Aが、少なくとも粘着剤層21に対向する側が剥離面となっている剥離ライナー31によって保護された形態の剥離ライナー付き粘着シート100の構成要素であり得る。剥離ライナー31としては、例えば、シート状の基材(ライナー基材)の片面に剥離処理剤による剥離層を設けることで該片面が剥離面となるように構成されたものを好ましく使用し得る。あるいは、剥離ライナー31を省略し、第二面10Bが剥離面となっている支持基材10を用い、粘着シート1を巻回することにより粘着面21Aが支持基材10の第二面10Bに当接して保護された形態(ロール形態)であってもよい。
ここに開示される粘着シートは、該粘着シートの弾性率Et’[MPa]と上記支持基材の厚さTs[mm]との関係が、次式:0.1[N・mm]<Et’×(Ts)3;を満たすことによって特徴づけられる。ここで、初期粘着力は、被着体としてのステンレス鋼(SUS)板に圧着して23℃、50%RHの環境で30分間放置した後、剥離角度180度、引張速度300mm/分の条件で180°引きはがし粘着力を測定することにより評価することができる。また、加熱後粘着力は、被着体としてのSUS板に圧着して80℃で5分間加熱し、次いで23℃、50%RHの環境に30分間放置した後に、剥離角度180度、引張速度300mm/分の条件で180°引きはがし粘着力を測定することにより評価することができる。被着体としては、初期粘着力、加熱後粘着力ともに、SUS304BA板が用いられる。初期粘着力および加熱後粘着力は、より具体的には、後述する実施例に記載の方法に準じて測定することができる。なお、両面粘着シートについて測定を行う場合、測定対象ではない側の粘着面に薄いフィルム(例えば、厚さ2μm程度のプラスチックフィルム)を貼り合わせる、適当なパウダーをまぶす等の手法により、該粘着面のべたつきによる作業性の低下を回避することができる。後述する保持力試験についても同様である。
ここに開示される粘着シートを構成する支持基材の材質は特に限定されず、該粘着シートの使用目的や使用態様等に応じて適宜選択することができる。使用し得る基材の非限定的な例としては、ポリプロピレンやエチレン-プロピレン共重合体等のポリオレフィンを主成分とするポリオレフィンフィルム、ポリエチレンテレフタレートやポリブチレンテレフタレート等のポリエステルを主成分とするポリエステルフィルム、ポリ塩化ビニルを主成分とするポリ塩化ビニルフィルム等のプラスチックフィルム;ポリウレタンフォーム、ポリエチレンフォーム、ポリクロロプレンフォーム等の発泡体からなる発泡体シート;各種の繊維状物質(麻、綿等の天然繊維、ポリエステル、ビニロン等の合成繊維、アセテート等の半合成繊維、等であり得る。)の単独または混紡等による織布および不織布;和紙、上質紙、クラフト紙、クレープ紙等の紙類;アルミニウム箔、銅箔等の金属箔;等が挙げられる。これらを複合した構成の基材であってもよい。このような複合基材の例として、例えば、金属箔と上記プラスチックフィルムとが積層した構造の基材、ガラスクロス等の無機繊維で強化されたプラスチック基材等が挙げられる。
ここに開示される技術において、粘着剤層を構成する粘着剤は特に限定されず、所望の特性(例えば、粘着力上昇比、初期粘着力および加熱後粘着力の少なくともひとつ)を示す粘着シートが得られるように適宜選択することができる。
上記ベースポリマーは、ガラス転移温度(Tg)が0℃未満であることが好ましく、-10℃未満(例えば-20℃未満)であることがより好ましい。かかるTgのベースポリマーを含む粘着剤は、適度な流動性(例えば、該粘着剤に含まれるポリマー鎖の運動性)を示すことから、粘着力上昇比の高い粘着シートの実現に適している。いくつかの態様において、ベースポリマーのTgは、-30℃未満であってよく、-40℃未満であってもよい。ベースポリマーのTgの下限は特に制限されないが、材料の入手容易性や粘着剤層の凝集力向上の観点から、通常はTgが-80℃以上のベースポリマーを好適に採用し得る。いくつかの態様において、ベースポリマーのTgは、例えば-63℃以上であってよく、-55℃以上でもよく、-50℃以上でもよく、-45℃以上でもよい。
1/Tg=Σ(Wi/Tgi)
上記Foxの式において、Tgは共重合体のガラス転移温度(単位:K)、Wiは該共重合体におけるモノマーiの重量分率(重量基準の共重合割合)、Tgiはモノマーiのホモポリマーのガラス転移温度(単位:K)を表す。ベースポリマーがホモポリマーである場合、該ホモポリマーのTgとベースポリマーのTgとは一致する。
具体的には、温度計、攪拌機、窒素導入管および還流冷却管を備えた反応器に、モノマー100重量部、2,2’-アゾビスイソブチロニトリル0.2重量部および重合溶媒として酢酸エチル200重量部を投入し、窒素ガスを流通させながら1時間攪拌する。このようにして重合系内の酸素を除去した後、63℃に昇温し10時間反応させる。次いで、室温まで冷却し、固形分濃度33重量%のホモポリマー溶液を得る。次いで、このホモポリマー溶液を剥離ライナー上に流延塗布し、乾燥して厚さ約2mmの試験サンプル(シート状のホモポリマー)を作製する。この試験サンプルを直径7.9mmの円盤状に打ち抜き、パラレルプレートで挟み込み、粘弾性試験機(ティー・エイ・インスツルメント・ジャパン社製、機種名「ARES」)を用いて周波数1Hzのせん断歪みを与えながら、温度領域-70℃~150℃、5℃/分の昇温速度でせん断モードにより粘弾性を測定し、tanδのピークトップ温度に相当する温度をホモポリマーのTgとする。
ここに開示される粘着シートは、Tgが0℃以下のアクリル系ポリマーPaをベースポリマーとして含む粘着剤により構成された粘着剤層を備える形態で好適に実施され得る。特に、後述するシロキサン構造含有ポリマーPsが(メタ)アクリル系モノマーに由来するモノマー単位を含む単独重合体または共重合体である場合には、かかるシロキサン構造含有ポリマーPsとの良好な相溶性が得られやすいことから、ベースポリマーとしてアクリル系ポリマーPaを好ましく採用し得る。ベースポリマーとシロキサン構造含有ポリマーPsとの相溶性が良いことは、粘着剤層の透明性向上の観点から有利である。また、粘着剤層内におけるシロキサン構造含有ポリマーPsの移動性向上を通じて、初期粘着力の低減および加熱後粘着力の向上にも寄与し得る。
カルボキシ基含有モノマー:例えば、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等。
酸無水物基含有モノマー:例えば、無水マレイン酸、無水イタコン酸。
水酸基含有モノマー:例えば、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル、(メタ)アクリル酸2-ヒドロキシブチル、(メタ)アクリル酸3-ヒドロキシプロピル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸6-ヒドロキシヘキシル、(メタ)アクリル酸8-ヒドロキシオクチル、(メタ)アクリル酸10-ヒドロキシデシル、(メタ)アクリル酸12-ヒドロキシラウリル、(4-ヒドロキシメチルシクロへキシル)メチル(メタ)アクリレート等の(メタ)アクリル酸ヒドロキシアルキル等。
スルホン酸基またはリン酸基を含有するモノマー:例えば、スチレンスルホン酸、アリルスルホン酸、ビニルスルホン酸ナトリウム、2-(メタ)アクリルアミド-2-メチルプロパンスルホン酸、(メタ)アクリルアミドプロパンスルホン酸、スルホプロピル(メタ)アクリレート、(メタ)アクリロイルオキシナフタレンスルホン酸、2-ヒドロキシエチルアクリロイルホスフェート等。
エポキシ基含有モノマー:例えば、(メタ)アクリル酸グリシジルや(メタ)アクリル酸-2-エチルグリシジルエーテル等のエポキシ基含有アクリレート、アリルグリシジルエーテル、(メタ)アクリル酸グリシジルエーテル等。
シアノ基含有モノマー:例えば、アクリロニトリル、メタクリロニトリル等。
イソシアネート基含有モノマー:例えば、2-イソシアナートエチル(メタ)アクリレート等。
アミド基含有モノマー:例えば、(メタ)アクリルアミド;N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N,N-ジプロピル(メタ)アクリルアミド、N,N-ジイソプロピル(メタ)アクリルアミド、N,N-ジ(n-ブチル)(メタ)アクリルアミド、N,N-ジ(t-ブチル)(メタ)アクリルアミド等のN,N-ジアルキル(メタ)アクリルアミド;N-エチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-ブチル(メタ)アクリルアミド、N-n-ブチル(メタ)アクリルアミド等のN-アルキル(メタ)アクリルアミド;N-ビニルアセトアミド等のN-ビニルカルボン酸アミド類;その他、N,N-ジメチルアミノプロピル(メタ)アクリルアミド、ヒドロキシエチルアクリルアミド、N-メチロール(メタ)アクリルアミド、N-エチロール(メタ)アクリルアミド、N-メチロールプロパン(メタ)アクリルアミド、N-メトキシメチル(メタ)アクリルアミド、N-メトキシエチル(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド、N-(メタ)アクリロイルモルホリン等。
窒素原子含有環を有するモノマー:例えば、N-ビニル-2-ピロリドン、N-メチルビニルピロリドン、N-ビニルピリジン、N-ビニルピペリドン、N-ビニルピリミジン、N-ビニルピペラジン、N-ビニルピラジン、N-ビニルピロール、N-ビニルイミダゾール、N-ビニルオキサゾール、N-(メタ)アクリロイル-2-ピロリドン、N-(メタ)アクリロイルピペリジン、N-(メタ)アクリロイルピロリジン、N-ビニルモルホリン、N-ビニル-3-モルホリノン、N-ビニル-2-カプロラクタム、N-ビニル-1,3-オキサジン-2-オン、N-ビニル-3,5-モルホリンジオン、N-ビニルピラゾール、N-ビニルイソオキサゾール、N-ビニルチアゾール、N-ビニルイソチアゾール、N-ビニルピリダジン等(例えば、N-ビニル-2-カプロラクタム等のラクタム類)。
スクシンイミド骨格を有するモノマー:例えば、N-(メタ)アクリロイルオキシメチレンスクシンイミド、N-(メタ)アクリロイル-6-オキシヘキサメチレンスクシンイミド、N-(メタ)アクリロイル-8-オキシヘキサメチレンスクシンイミド等。
マレイミド類:例えば、N-シクロヘキシルマレイミド、N-イソプロピルマレイミド、N-ラウリルマレイミド、N-フェニルマレイミド等。
イタコンイミド類:例えば、N-メチルイタコンイミド、N-エチルイタコンイミド、N-ブチルイタコンイミド、N-オクチルイタコンイミド、N-2-エチルへキシルイタコンイミド、N-シクロへキシルイタコンイミド、N-ラウリルイタコンイミド等。
(メタ)アクリル酸アミノアルキル類:例えば、(メタ)アクリル酸アミノエチル、(メタ)アクリル酸N,N-ジメチルアミノエチル、(メタ)アクリル酸N,N-ジエチルアミノエチル、(メタ)アクリル酸t-ブチルアミノエチル。
(メタ)アクリル酸アルコキシアルキル類:例えば、(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エトキシエチル、(メタ)アクリル酸プロポキシエチル、(メタ)アクリル酸ブトキシエチル、(メタ)アクリル酸エトキシプロピル等。
ビニルエステル類:例えば、酢酸ビニル、プロピオン酸ビニル等。
ビニルエーテル類:例えば、例えば、メチルビニルエーテルやエチルビニルエーテル等のビニルアルキルエーテル。
芳香族ビニル化合物:例えば、スチレン、α-メチルスチレン、ビニルトルエン等。
オレフィン類:例えば、エチレン、ブタジエン、イソプレン、イソブチレン等。
脂環式炭化水素基を有する(メタ)アクリル酸エステル:例えば、シクロペンチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート等。
芳香族炭化水素基を有する(メタ)アクリル酸エステル:例えば、フェニル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、ベンジル(メタ)アクリレート等。
その他、(メタ)アクリル酸テトラヒドロフルフリル等の複素環含有(メタ)アクリレート、塩化ビニルやフッ素原子含有(メタ)アクリレート等のハロゲン原子含有(メタ)アクリレート、シリコーン(メタ)アクリレート等のケイ素原子含有(メタ)アクリレート、テルペン化合物誘導体アルコールから得られる(メタ)アクリル酸エステル等。
ここに開示される技術における粘着剤層には、必要に応じて、ベースポリマー(例えばアクリル系ポリマーPa)以外の成分を含有させることができる。このような任意成分の一好適例として、シロキサン構造含有ポリマーPsが挙げられる。シロキサン構造含有ポリマーPsは、分子内にシロキサン構造(Si-O-Si構造)を有するポリマーとして定義される。シロキサン構造含有ポリマーPsは、シロキサン構造の低極性および運動性によって、初期粘着力の抑制および粘着力上昇比の向上に寄与する粘着力上昇遅延剤として機能し得る。シロキサン構造含有ポリマーPs(以下、「ポリマーPs」と略記することがある。)としては、側鎖にシロキサン構造を有するポリマーが好ましく用いられ得る。
モノマーS1の官能基当量(g/mol)=(モノマーS11の官能基当量×モノマーS11の配合量+モノマーS12の官能基当量×モノマーS12の配合量+・・・+モノマーS1nの官能基当量×モノマーS1nの配合量)/(モノマーS11の配合量+モノマーS12の配合量+・・・+モノマーS1nの配合量)
ここに開示される粘着剤層には、凝集力の調整等の目的で、架橋剤が用いられ得る。架橋剤は、通常用いる架橋剤を使用することができ、例えば、エポキシ系架橋剤、イソシアネート系架橋剤、シリコーン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、シラン系架橋剤、アルキルエーテル化メラミン系架橋剤、金属キレート系架橋剤等を挙げることができる。特に、イソシアネート系架橋剤、エポキシ系架橋剤、金属キレート系架橋剤を好適に使用することができる。架橋剤は、1種を単独でまたは2種以上を組み合わせて用いることができる。
粘着剤層には、必要に応じて粘着付与樹脂を含ませることができる。粘着付与樹脂としては、特に制限されないが、例えば、ロジン系粘着付与樹脂、テルペン系粘着付与樹脂、フェノール系粘着付与樹脂、炭化水素系粘着付与樹脂、ケトン系粘着付与樹脂、ポリアミド系粘着付与樹脂、エポキシ系粘着付与樹脂、エラストマー系粘着付与樹脂等が挙げられる。粘着付与樹脂は、1種を単独でまたは2種以上を組み合わせて用いることができる。
上記ロジン誘導体としては、例えば、
ロジン類(未変性ロジン、変性ロジンや、各種ロジン誘導体など)にフェノールを酸触媒で付加させ熱重合することにより得られるロジンフェノール系樹脂;
未変性ロジンをアルコール類によりエステル化したロジンのエステル化合物(未変性ロジンエステル)や、重合ロジン、安定化ロジン、不均化ロジン、完全水添ロジン、部分水添ロジンなどの変性ロジンをアルコール類によりエステル化した変性ロジンのエステル化合物(重合ロジンエステル、安定化ロジンエステル、不均化ロジンエステル、完全水添ロジンエステル、部分水添ロジンエステルなど)などのロジンエステル系樹脂;
未変性ロジンや変性ロジン(重合ロジン、安定化ロジン、不均化ロジン、完全水添ロジン、部分水添ロジンなど)を不飽和脂肪酸で変性した不飽和脂肪酸変性ロジン系樹脂;
ロジンエステル系樹脂を不飽和脂肪酸で変性した不飽和脂肪酸変性ロジンエステル系樹脂;
未変性ロジン、変性ロジン(重合ロジン、安定化ロジン、不均化ロジン、完全水添ロジン、部分水添ロジンなど)、不飽和脂肪酸変性ロジン系樹脂や不飽和脂肪酸変性ロジンエステル系樹脂におけるカルボキシル基を還元処理したロジンアルコール系樹脂;
未変性ロジン、変性ロジンや、各種ロジン誘導体等のロジン系樹脂(特に、ロジンエステル系樹脂)の金属塩などが挙げられる。
ここに開示される粘着シートを構成する粘着剤層は、粘着剤組成物の硬化層であり得る。すなわち、該粘着剤層は、粘着剤組成物を適当な表面に付与(例えば塗布)した後、硬化処理を適宜施すことにより形成され得る。二種以上の硬化処理(乾燥、架橋、重合等)を行う場合、これらは、同時に、または多段階にわたって行うことができる。モノマー成分の部分重合物(アクリル系ポリマーシロップ)を用いた粘着剤組成物では、典型的には、上記硬化処理として、最終的な共重合反応が行われる。すなわち、部分重合物をさらなる共重合反応に供して完全重合物を形成する。例えば、光硬化性の粘着剤組成物であれば、光照射が実施される。必要に応じて、架橋、乾燥等の硬化処理が実施されてもよい。例えば、光硬化性粘着剤組成物で乾燥させる必要がある場合は、乾燥後に光硬化を行うとよい。完全重合物を用いた粘着剤組成物では、典型的には、上記硬化処理として、必要に応じて乾燥(加熱乾燥)、架橋等の処理が実施される。
基材を有する形態の粘着シートでは、基材表面に粘着剤層を設ける方法として、該基材に粘着剤組成物を直接付与して粘着剤層を形成する直接法を用いてもよく、剥離性を有する表面(剥離面)上に形成した粘着剤層を基材に転写する転写法を用いてもよく、これらの方法を組み合わせてもよい。上記剥離面としては、剥離ライナーの表面や、剥離処理された基材背面等を利用し得る。
約0.1gの粘着剤サンプル(重量Wg1)を平均孔径0.2μmの多孔質ポリテトラフルオロエチレン膜(重量Wg2)で巾着状に包み、口をタコ糸(重量Wg3)で縛る。上記多孔質ポリテトラフルオロエチレン膜としては、商品名「ニトフロン(登録商標)NTF1122」(日東電工株式会社、平均孔径0.2μm、気孔率75%、厚さ85μm)またはその相当品を使用する。この包みを酢酸エチル50mLに浸し、室温(典型的には23℃)で7日間保持して粘着剤中のゾル分(酢酸エチル可溶分)を上記膜外に溶出させる。次いで、上記包みを取り出し、外表面に付着している酢酸エチルを拭き取った後、該包みを130℃で2時間乾燥させ、該包みの重量(Wg4)を測定する。各値を以下の式に代入することにより、粘着剤のゲル分率GCを算出することができる。
ゲル分率GC(%)=[(Wg4-Wg2-Wg3)/Wg1]×100
ここに開示される粘着シートは、 粘着面を保護する目的で粘着剤層表面に剥離ライナーが貼り合わされた粘着製品の形態をとり得る。したがって、この明細書により、ここに開示されるいずれかの粘着シートと、該粘着シートの粘着面を保護する剥離ライナーとを含む剥離ライナー付き粘着シート(粘着製品)が提供され得る。
(1) 支持基材と、上記支持基材の少なくとも片側に積層されている粘着剤層と、を含む粘着シートであって、
上記粘着剤層の厚さが3μm以上100μm未満であり、
上記支持基材の厚さが30μm以上であり、
上記粘着シートの弾性率Et’[MPa]と上記支持基材の厚さTs[mm]との関係が、次式:0.1[N・mm]<Et’×(Ts)3;を満たし、
上記粘着剤層をステンレス鋼板(SUS304BA板)に貼り合わせた後に80℃で5分間加熱した後の粘着力N2が、上記粘着剤層をステンレス鋼板(SUS304BA板)に貼り合わせた後に23℃で30分間放置した後の粘着力N1の20倍以上である、粘着シート。
(2) 上記粘着力N1が1.0N/20mm以下であり、かつ上記粘着力N2が5.0N/20mm以上である、上記(1)に記載の粘着シート。
(3) 上記粘着力N1が0.2N/20mm以上1.0N/20mm以下である、上記(1)または(2)に記載の粘着シート。
(4) 上記粘着シートの弾性率Et’が1000MPa以上である、上記(1)~(3)のいずれかに記載の粘着シート。
(5) 上記支持基材の厚さは、上記粘着剤層の厚さの1.1倍以上10倍以下である、上記(1)~(4)のいずれかに記載の粘着シート。
(6) 上記支持基材は、ポリエステル系樹脂、ポリフェニレンサルファイド樹脂およびポリオレフィン系樹脂からなる群から選択される1種または2種以上を含む樹脂材料を用いて形成された樹脂フィルムをベースフィルムとして含む、上記(1)~(5)のいずれかに記載の粘着シート。
(8) 上記粘着力上昇遅延剤は:
ポリオルガノシロキサン骨格を有するモノマーをモノマー単位として含むシロキサン構造含有ポリマーPs;および
ポリオキシアルキレン骨格を有するモノマーをモノマー単位として含むポリオキシアルキレン構造含有ポリマーPo;
からなる群から選択される少なくとも一種を含む、上記(7)に記載の粘着シート。
ここで、上記シロキサン構造含有ポリマーPsは、ポリオルガノシロキサン骨格を有するモノマーと(メタ)アクリル系モノマーとの共重合体である、上記(1)~(8)のいずれかに記載の粘着シート。
(10) 上記シロキサン構造含有ポリマーPsは、重量平均分子量が1×104以上5×104未満である、上記(9)に記載の粘着シート。
(11) 上記粘着剤層は、上記シロキサン構造含有ポリマーPsと、ガラス転移温度が0℃以下のアクリル系ポリマーPaとを含み、
上記シロキサン構造含有ポリマーPsの含有量は、上記アクリル系ポリマーPa100重量部に対して0.1重量部以上10重量部未満である、上記(9)または(10)に記載の粘着シート。
(12) 上記ポリオルガノシロキサン骨格を有するモノマーの官能基当量は700g/mol以上15000g/mol未満である、上記(9)~(11)のいずれかに記載の粘着シート。
(13) 上記アクリル系ポリマーPaは、モノマー単位として、水酸基含有モノマーおよびN-ビニル環状アミドからなる群から選ばれる少なくとも1種のモノマーを含有する、上記(11)または(12)に記載の粘着シート。
(14) 上記アクリル系ポリマーPaを調整するためのモノマー成分全量に占める上記水酸基含有モノマーおよび上記N-ビニル環状アミドの合計量の割合が15重量%以上50重量%以下である、上記(11)~(13)のいずれかに記載の粘着シート。
(15) 上記アクリル系ポリマーPaおよび上記シロキサン構造含有ポリマーPsは、MMA,BMA,2EHMA,MA,BAおよび2EHAからなる群から選択される少なくとも一種のモノマーを共通するモノマー単位として含む、上記(11)~(14)のいずれかに記載の粘着シート。
(17) 上記粘着剤層は、水酸基含有モノマーをモノマー単位として含み、上記イソシアネート系架橋剤の使用量WNCOに対する上記水酸基含有モノマーの使用量WOHの比(WOH/WNCO)が2以上である、上記(16)に記載の粘着シート。
(18) 上記粘着剤層は粘着付与樹脂を含む、上記(1)~(17)のいずれかに記載の粘着シート。
(19) 幅10mm、長さ20mmの貼付け面積でベークライト板に貼り付けてから30分後に、40℃の環境下において上記長さに沿うせん断方向に500gの荷重を付与して30分保持する保持力試験におけるズレ距離が1.0mm以下である、上記(1)~(18)のいずれかに記載の粘着シート。
(20) 上記粘着力N1(N/20mm)の数値と上記保持力試験におけるズレ距離(mm)の数値との積が0.20以下である、上記(19)に記載の粘着シート。
上記粘着剤層の厚さが3μm以上100μm未満であり、
上記支持基材の厚さが30μm以上であり、
上記粘着剤層をステンレス鋼板(SUS304BA板)に貼り合わせた後、23℃で30分間放置後の粘着力N1が1.0N/20mm以下であり、かつ
上記粘着剤層をステンレス鋼板(SUS304BA板)に貼り合わせた後、80℃で5分間加熱後の粘着力N2が5.0N/20mm以上である、粘着シート。
上記粘着シートの粘着面を保護する剥離ライナーと
を含む、剥離ライナー付き粘着シート。
(23) 上記剥離ライナーは、シリコーン系剥離処理剤、長鎖アルキル系剥離処理剤、オレフィン系剥離処理剤およびフッ素系剥離処理剤からなる群から選択される少なくとも一種の剥離処理剤で処理された剥離面を備える、上記(22)に記載の剥離ライナー付き粘着シート。
(アクリル系ポリマーA1の調製)
撹拌羽根、温度計、窒素ガス導入管および冷却器を備えた4つ口フラスコに、2-エチルヘキシルアクリレート(2EHA)30部、n-ブチルアクリレート(BA)70部、アクリル酸(AA)3部、4-ヒドロキシブチルアクリレート(4HBA)0.1部、および重合溶媒としてトルエン150部を仕込み、60℃にて窒素雰囲気下で2時間撹拌した後、熱重合開始剤として2,2’-アゾビスイソブチロニトリル(AIBN)0.1部を投入し、60℃で6時間反応を行って、アクリル系ポリマーAの溶液を得た。このアクリル系ポリマーA1のMwは45万であった。
撹拌羽根、温度計、窒素ガス導入管および冷却器を備えた4つ口フラスコに、2EHA60部、N-ビニル-2-ピロリドン(NVP)15部、メチルメタクリレート(MMA)10部、2-ヒドロキシエチルアクリレート(HEA)15部、および重合溶媒として酢酸エチル200部を仕込み、60℃にて窒素雰囲気下で2時間撹拌した後、熱重合開始剤としてAIBN0.2部を投入し、60℃で6時間反応を行って、アクリル系ポリマーA2の溶液を得た。このアクリル系ポリマーA2のMwは110万であった。
2EHA40部、イソステアリルアクリレート(ISTA)40部、NVP18部、4HBA1部と、光重合開始剤としての2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン(BASF社製、商品名「イルガキュア651」)0.05部および1-ヒドロキシシクロヘキシル-フェニル-ケトン(BASF社製、商品名「イルガキュア184」)0.05部とを混合し、窒素雰囲気下で紫外線を照射することにより、部分重合物(アクリル系ポリマーシロップ)の形態でアクリル系ポリマーA3を調製した。
撹拌羽根、温度計、窒素ガス導入管、冷却器、滴下ロートを備えた4つ口フラスコに、トルエン100部、MMA40部、n-ブチルメタクリレート(BMA)20部、2-エチルヘキシルメタクリレート(2EHMA)20部、官能基当量が900g/molのポリオルガノシロキサン骨格含有メタクリレートモノマー(商品名:X-22-174ASX、信越化学工業株式会社製)8.7部、官能基当量が4600g/molのポリオルガノシロキサン骨格含有メタクリレートモノマー(商品名:KF-2012、信越化学工業株式会社製)11.3部および連鎖移動剤としてチオグリコール酸メチル0.51部を投入した。そして、70℃にて窒素雰囲気下で1時間撹拌した後、熱重合開始剤としてAIBN0.2部を投入し、70℃で2時間反応させた後に、熱重合開始剤としてAIBN0.1部を投入し、続いて80℃で5時間反応させた。このようにしてシロキサン構造含有ポリマーPs1の溶液を得た。このシロキサン構造含有ポリマーPs1の重量平均分子量は22000であった。また、(メタ)アクリル系モノマーの組成に基づくガラス転移温度Tm1は約47℃であった。
ポリマーPs1の調製に使用したモノマー成分の組成を、MMA50部、BMA15部、2EHMA15部、X-22-174ASXを8.7部、およびKF-2012を11.3部に変更した。また、連鎖移動剤としてチオグリセロール0.8部を使用し、重合溶媒として酢酸エチルを使用した。その他の点はポリマーPs1の調製と同様にして、シロキサン構造含有ポリマーPs2の溶液を得た。このポリマーPs2のMwは19700であり、Tm1は約60℃であった。
・サンプル濃度:0.2wt%(テトラヒドロフラン(THF)溶液)
・サンプル注入量:10μl
・溶離液:THF・流速:0.6ml/min
・測定温度:40℃
・カラム:
サンプルカラム;TSKguardcolumn SuperHZ-H(1本)+TSKgel SuperHZM-H(2本)
リファレンスカラム;TSKgel SuperH-RC(1本)
・検出器:示差屈折計(RI)
(例1)
上記アクリル系ポリマーA1の溶液に、該溶液に含まれるアクリル系ポリマーA1の100部当たり、シロキサン構造含有ポリマーPs1を5部、粘着付与樹脂としてペンセルD-125(荒川化学工業社製の重合ロジンエステル、軟化点120~130℃)を30部、架橋剤としてコロネートL(東ソー社製のイソシアネート系架橋剤)を3部添加し、均一に混合して粘着剤組成物C1を調製した。
ポリエステルフィルムの片面がシリコーン系剥離処理剤による剥離面となっている2種類の剥離ライナーR1,R2を用意した。ここで、剥離ライナーR1としては、三菱樹脂株式会社製の商品名「ダイアホイルMRF」(厚さ38μm)を使用した。剥離ライナーR2としては、三菱樹脂株式会社製の商品名「ダイアホイルMRE」(厚さ38μm)を使用した。
支持基材としての厚さ75μmのポリエチレンテレフタレート(PET)フィルム(東レ社製、商品名「ルミラー」)の第一面に粘着剤組成物C1を塗布し、110℃で2分間加熱して、厚さ38μmの第一粘着剤層を形成し、その表面(粘着面)に剥離ライナーR1の剥離面を貼り合わせた。次いで、上記支持基材の第二面に粘着剤組成物C1を塗布し、110℃で2分間加熱して厚さ38μmの第二粘着剤層を形成し、その表面(粘着面)に剥離ライナーR2の剥離面を貼り合わせた。このようにして、厚さ75μmの支持基材の両面に厚さ38μmの第一、第二粘着剤層を有する基材付き両面粘着シートを得た。この粘着シートは、両粘着面上に剥離ライナーR1,R2を有する剥離ライナー付き粘着シートを構成している。なお、例1に係る粘着シートのEs’×(Ts)3は0.99N・mmであり、上述のようにこれをEt’×(Ts)3の値として用いることができる。
上記アクリル系ポリマーA2の溶液に、該溶液に含まれるアクリル系ポリマーA2の100部当たり、シロキサン構造含有ポリマーPs1を5部、架橋剤としてタケネートD-110N(三井化学社製のイソシアネート系架橋剤)を0.25部添加し、均一に混合して粘着剤組成物C2を調製した。
支持基材としての厚さ125μmのPETフィルム(東レ社製、商品名「ルミラー」)の片面に粘着剤組成物C2を塗布し、110℃で2分間加熱して厚さ25μmの粘着剤層を形成し、その粘着面に剥離ライナーR1(三菱樹脂株式会社製の商品名「ダイアホイルMRF」)の剥離面を貼り合わせた。このようにして、本例に係る基材付き片面粘着シートを得た。この粘着シートは、粘着面上に剥離ライナーR1を有する剥離ライナー付き粘着シートを構成している。
架橋剤の使用量を1.1部に変更した他は粘着剤組成物C2の調製と同様にして、粘着剤組成物C3を調製した。支持基材としての厚さ75μmのPETフィルム(東レ社製、商品名「ルミラー」)の片面に粘着剤組成物C3を塗布し、110℃で2分間加熱して厚さ15μmの粘着剤層を形成し、その粘着面に剥離ライナーR1の剥離面を貼り合わせることにより、本例に係る基材付き片面粘着シートを得た。
支持基材として厚さ25μmのPETフィルム(東レ社製、商品名「ルミラー」)を使用した他は例1と同様にして、本例に係る粘着シートを得た。例4に係る粘着シートのEs’×(Ts)3は0.04N・mmである。
支持基材として厚さ4.5μmのPETフィルム(東レ社製、商品名「ルミラー」)を使用した他は例1と同様にして、本例に係る粘着シートを得た。
上記で調製したアクリル系ポリマーA3(アクリル系ポリマーシロップ)100部に対してトリメチロールプロパントリアクリレート(大阪有機化学工業社製、商品名「TMP3A」)0.2部およびシロキサン構造含有ポリマー2部を添加し、均一に混合して粘着剤組成物C4を調製した。
この粘着剤組成物C4を剥離ライナーR1の剥離面に、最終的な厚さが100μmになるように塗布して塗布層を形成した。次いで、上記塗布層の表面に剥離ライナーR2を、その剥離面が上記塗布層側になるようにして被せた。これにより上記塗布層を酸素から遮断した。この積層シート(剥離ライナーR1/塗布層/剥離ライナーR2の積層構造を有する。)に、ケミカルライトランプ((株)東芝製))を用いて照度5mW/cm2の紫外線を360秒間照射することにより、上記塗布層を硬化させて粘着剤層を形成した。なお、上記照度の値は、ピーク感度波長約350nmの工業用UVチェッカー(トプコン社製、商品名「UVR-T1」、受光部型式UD-T36)による測定値である。
得られた粘着剤層から剥離ライナーR1を剥がし、露出した粘着面に支持基材としての厚さ50μmのPETフィルム(東レ社製、商品名「ルミラー」)を貼り合わせることにより、支持基材の片面に粘着剤層を有する片面粘着シートを得た。この粘着シートは、支持基材に貼り合わされた側とは反対側の粘着面上に剥離ライナーR2を有する剥離ライナー付き粘着シートを構成している。
各例に係る粘着シートを剥離ライナーごと20mm幅に裁断したものを試験片とし、トルエンで清浄化したSUS板(SUS304BA板)を被着体として、以下の手順で初期粘着力N1および加熱後粘着力N2を測定した。
(初期粘着力の測定)
すなわち、23℃、50%RHの標準環境下にて、各試験片の粘着面を覆う剥離ライナーを剥がし、露出した粘着面を被着体に、2kgのローラを1往復させて圧着した。このようにして被着体に圧着した試験片を上記標準環境下に30分間放置した後、万能引張圧縮試験機(装置名「引張圧縮試験機、TCM-1kNB」ミネベア社製)を使用して、JIS Z0237に準じて、剥離角度180度、引張速度300mm/分の条件で、180°引きはがし粘着力(上記引張りに対する抵抗力)を測定した。測定は3回行い、それらの平均値を初期粘着力として表1の「初期(N1)」の欄に示した。なお、両面粘着シートの形態の粘着シート(例1,4)については、第二粘着面に厚さ2μmのPETフィルムを貼り合わせた状態で第一粘着面の初期粘着力を測定した。
(加熱後粘着力の測定)
初期粘着力N1の測定と同様にして被着体に圧着した試験片を、80℃で5分間加熱し、次いで上記標準環境下に30分間放置した後に、同様に180°引きはがし粘着力を測定した。測定は3回行い、それらの平均値を加熱後粘着力として表1の「加熱後(N2)」の欄に示した。
例1,4,6に係る粘着シートについて、イソプロピルアルコールで清浄化した厚さ2.0mmのポリカーボネート樹脂(PC)板を被着体に用いた他は上述した対SUS粘着力の測定と同様にして、PCに対する初期粘着力および加熱後粘着力を測定した。結果を表1に示す。なお、表中のNEは未評価であることを表している。
各例に係る粘着シートを剥離ライナーごと幅10mm、長さ100mmのサイズに裁断して試験片を作製した。このとき、両面粘着シートの形態の粘着シート(例1,4)については、第二粘着面に厚さ25μmのPETフィルム(東レ社製、商品名「ルミラーS10」)を貼り合わせた後に上記サイズに裁断した。各試験片の第一粘着面を覆う剥離ライナーR1を剥がし、23℃、50%RHの環境下において、上記試験片を被着体としてのベークライト板(フェノール樹脂板)に、幅10mm、長さ20mmの貼付け面積にて、2kgのローラを1往復させて圧着した。このようにして試験片を貼り付けた被着体を、上記試験片の長さ方向が鉛直方向となるようにして40℃の環境下に垂下し、30分静置した。次いで、上記試験片の自由端に500gの荷重を付与し、JIS Z0237に準じて、該荷重が付与された状態で40℃の環境下に1時間放置した。当該放置後の試験片について、最初の貼付け位置からずれた距離(ズレ距離)を測定した。測定は、各粘着シートにつき3つの試験片を用いて行い(すなわちn=3)、それらの試験片に係るズレ距離の算術平均値を表1の「保持力」の欄に示した。
シロキサン構造含有ポリマーの種類と使用量、および架橋剤の種類と使用量を表2に示すとおりとした他は例2と同様にして、例7~17に係る基材付き片面粘着シートを得た。なお、例14~例17では、イソシアネート系架橋剤として、コロネートHX(東ソー社製、ヘキサメチレンジイソシアネートのイソシアヌレート体)を使用した。
確認された。また、例8に比べてよりTm1の高いシロキサン構造含有ポリマーを用いた例9では、例8に比べて初期粘着力が抑制され、粘着力上昇比が向上した。
10 支持基材
10A 第一面
10B 第二面
21 粘着剤層(第一粘着剤層)
21A 粘着面(第一粘着面)
22 粘着剤層(第二粘着剤層)
22A 粘着面(第二粘着面)
31,32 剥離ライナー
100,200 剥離ライナー付き粘着シート(粘着製品)
Claims (9)
- 支持基材と、前記支持基材の少なくとも片側に積層されている粘着剤層と、を含む粘着シートであって、
前記粘着剤層の厚さが3μm以上100μm未満であり、
前記支持基材の厚さが30μm以上であり、
前記粘着シートの弾性率Et’[MPa]と前記支持基材の厚さTs[mm]との関係が、次式:0.1[N・mm]<Et’×(Ts)3;を満たし、
前記粘着剤層をステンレス鋼板(SUS304BA板)に貼り合わせた後に80℃で5分間加熱した後の粘着力N2が、前記粘着剤層をステンレス鋼板(SUS304BA板)に貼り合わせた後に23℃で30分間放置した後の粘着力N1の20倍以上である、粘着シート。 - 前記粘着力N1が1.0N/20mm以下であり、かつ前記粘着力N2が5.0N/20mm以上である、請求項1記載の粘着シート。
- 前記粘着力N1が0.2N/20mm以上1.0N/20mm以下である、請求項1または2記載の粘着シート。
- 前記粘着シートの弾性率Et’が1000MPa以上である、請求項1から3のいずれか一項に記載の粘着シート。
- 前記支持基材の厚さは、前記粘着剤層の厚さの1.1倍以上10倍以下である、請求項1から4のいずれか一項に記載の粘着シート。
- 前記粘着剤層は、粘着力上昇遅延剤を含む粘着剤により構成されている、請求項1から5のいずれか一項に記載の粘着シート。
- 前記粘着剤層は、シロキサン構造含有ポリマーPsを含み、
ここで、前記シロキサン構造含有ポリマーPsは、ポリオルガノシロキサン骨格を有するモノマーと(メタ)アクリル系モノマーとの共重合体である、請求項1から6のいずれか一項に記載の粘着シート。 - 前記シロキサン構造含有ポリマーPsは、重量平均分子量が1×104以上5×104未満である、請求項7に記載の粘着シート。
- 前記粘着剤層は、前記シロキサン構造含有ポリマーPsと、ガラス転移温度が0℃以下のアクリル系ポリマーPaとを含み、
前記シロキサン構造含有ポリマーPsの含有量は、前記アクリル系ポリマーPa100重量部に対して0.1重量部以上10重量部未満である、請求項7または8に記載の粘着シート。
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| WO2020145188A1 (ja) * | 2019-01-08 | 2020-07-16 | 日東電工株式会社 | 粘着シート |
| WO2020158175A1 (ja) * | 2019-01-29 | 2020-08-06 | 日東電工株式会社 | 積層体 |
| WO2020158176A1 (ja) * | 2019-01-29 | 2020-08-06 | 日東電工株式会社 | 積層体 |
| WO2020162195A1 (ja) * | 2019-02-06 | 2020-08-13 | 日東電工株式会社 | 粘着剤層付き反射防止フィルム、自発光型表示装置およびその製造方法 |
| WO2020262048A1 (ja) * | 2019-06-27 | 2020-12-30 | 日東電工株式会社 | 粘着シート、および粘着シート貼付品の製造方法 |
| JP2021006620A (ja) * | 2019-06-27 | 2021-01-21 | 日東電工株式会社 | 粘着シート、および粘着シート貼付品の製造方法 |
| JP2021042276A (ja) * | 2019-09-06 | 2021-03-18 | 日東電工株式会社 | 粘着シート |
| CN113167964A (zh) * | 2018-12-14 | 2021-07-23 | 日东电工株式会社 | 带粘合剂层的偏振膜 |
| JPWO2020110489A1 (ja) * | 2018-11-30 | 2021-10-14 | 日東電工株式会社 | 粘着シート |
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| JP6605562B2 (ja) * | 2017-11-20 | 2019-11-13 | 日東電工株式会社 | 粘着シート |
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Also Published As
| Publication number | Publication date |
|---|---|
| SG10201900693TA (en) | 2019-02-27 |
| CN110172309A (zh) | 2019-08-27 |
| KR102173316B1 (ko) | 2020-11-03 |
| JP6355874B1 (ja) | 2018-07-11 |
| CN110172308A (zh) | 2019-08-27 |
| KR20190121410A (ko) | 2019-10-25 |
| JP7005431B2 (ja) | 2022-01-21 |
| KR20180087232A (ko) | 2018-08-01 |
| CN108368405B (zh) | 2019-07-12 |
| JP2018172686A (ja) | 2018-11-08 |
| CN108368405A (zh) | 2018-08-03 |
| US20190071589A1 (en) | 2019-03-07 |
| CN110172309B (zh) | 2022-08-16 |
| KR102202222B1 (ko) | 2021-01-13 |
| SG11201801407WA (en) | 2018-06-28 |
| KR102036463B1 (ko) | 2019-10-24 |
| CN110172308B (zh) | 2021-09-21 |
| CN110272691A (zh) | 2019-09-24 |
| KR20190121411A (ko) | 2019-10-25 |
| JPWO2018092904A1 (ja) | 2018-11-15 |
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