WO2022181141A1 - 粘着剤組成物および粘着シート - Google Patents
粘着剤組成物および粘着シート Download PDFInfo
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- WO2022181141A1 WO2022181141A1 PCT/JP2022/002272 JP2022002272W WO2022181141A1 WO 2022181141 A1 WO2022181141 A1 WO 2022181141A1 JP 2022002272 W JP2022002272 W JP 2022002272W WO 2022181141 A1 WO2022181141 A1 WO 2022181141A1
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Images
Classifications
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
-
- 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
- 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]
Definitions
- the present invention relates to an adhesive composition and an adhesive sheet. This application claims priority based on Japanese Patent Application No. 2021-030200 filed on February 26, 2021, the entire contents of which are incorporated herein by reference.
- pressure-sensitive adhesives also called pressure-sensitive adhesives; the same applies hereinafter
- pressure-sensitive adhesives exhibit a soft solid (viscoelastic) state in a temperature range around room temperature, and have the property of easily adhering to adherends under pressure.
- pressure-sensitive adhesives are typically used in the form of pressure-sensitive adhesive sheets containing a layer of the pressure-sensitive adhesive in various industrial fields such as home appliances, automobiles, various machines, electrical equipment, and electronic equipment. It is widely used as a joining means with good workability and high reliability of adhesion.
- various adhesives such as acrylic adhesives, rubber adhesives, and polyester adhesives are used according to the purpose of use, the place of use, required properties, and the like.
- Patent Documents 1 to 3 are cited as documents disclosing prior art regarding polyester pressure-sensitive adhesives.
- Adhesive sheets are preferably used, for example, for fixing members in mobile electronic devices such as mobile phones, smartphones, and tablet computers. Due to size, weight, and other limitations, the bonding area for fixing members in a portable electronic device is usually small. Therefore, the pressure-sensitive adhesive sheet used for this application must have adhesion reliability that enables good fixation even in a small area. It has become a thing. In particular, mobile electronic devices equipped with touch panel displays, as typified by smartphones, are becoming smaller and thinner. The pressure-sensitive adhesive to be applied is required to have high adhesion reliability that does not cause peeling even when used under severer conditions. The resistance to peeling can be evaluated, for example, by shear adhesive strength.
- shear adhesion strength evaluates resistance to dynamic load (that is, shear force) that tends to shift the adhesion interface.
- Adhesives with high shear adhesive strength have high resistance to loads in the shear direction that tend to cause delamination when fixing members in portable electronic devices, for example, and effectively prevent delamination. can be a thing.
- acrylic adhesives with acrylic polymers as base polymers are mainly used, and other adhesive sheets include, for example, rubber-based block copolymers such as styrene-butadiene block copolymers.
- rubber-based block copolymers such as styrene-butadiene block copolymers.
- both the above acrylic adhesives and synthetic rubber adhesives are adhesives whose main raw materials are fossil resources such as petroleum. Switching to resources is limited.
- Polyester-based adhesives can be considered as adhesives that can reduce dependence on fossil resource-based materials and that can be expected to have adhesive properties equal to or greater than those of acrylic adhesives and synthetic rubber-based adhesives.
- Polyester-based polymers used in polyester-based pressure-sensitive adhesives can be synthesized using biomass materials (for example, Patent Documents 1 and 2), so by using such polyester-based polymers, the amount of petroleum resource-based materials used can be reduced. can do.
- polyester pressure-sensitive adhesives are excellent in various properties such as chemical resistance, water resistance, durability, and optical properties (transparency), so they can be used in various applications including portable electronic devices.
- Biomass materials are typically materials derived from biological resources (typically plants that perform photosynthesis) that can be sustainably reproduced in the presence of sunlight, water, and carbon dioxide. Say things.
- polyester-based polymers usually have cross-linking points only at the ends of polymer chains, it is difficult to obtain an effective cross-linked structure compared to acrylic-based polymers. Therefore, it is not easy to improve the shear adhesive strength of the polyester pressure-sensitive adhesive. If a polyester-based pressure-sensitive adhesive with high shear adhesive strength can be realized, it will be meaningful to provide an adhesive fixing means with high adhesion reliability that does not cause peeling even when the adhesion area is small while reducing dependence on fossil resource-based materials. is.
- the present invention was created in view of the above circumstances, and aims to provide a pressure-sensitive adhesive composition that is configured to contain a polyester-based polymer synthesized using a biomass material and is capable of exhibiting high shear adhesive strength. aim.
- Another related object is to provide a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing a polyester-based polymer synthesized using a biomass material.
- a pressure-sensitive adhesive composition containing a polyester-based polymer in which 50% or more of the constituent carbon is biomass-derived carbon.
- the adhesive composition further comprises a tackifying resin and a crosslinker.
- the polyester-based polymer contains an aromatic ring
- the tackifying resin also contains an aromatic ring
- the cross-linking agent does not contain an aromatic ring. Since the pressure-sensitive adhesive composition is prepared using a polyester-based polymer in which 50% or more of the constituent carbon is biomass-derived carbon (biogenic rate is 50% or more), dependence on fossil resource-based materials is reduced. can be reduced.
- the polyester-based polymer and the tackifying resin contained in the pressure-sensitive adhesive composition both have aromatic rings, and the cross-linking agent does not contain an aromatic ring, thereby improving the shear adhesive strength. can be made Moreover, according to the pressure-sensitive adhesive composition having the above composition, it is easy to obtain good repulsion resistance.
- the polyester polymer has a weight average molecular weight of 30,000 or more.
- Mw weight-average molecular weight
- shear adhesive strength and repulsion resistance can be preferably improved.
- the use of a polyester-based polymer having Mw equal to or higher than a predetermined value is also preferable from the viewpoint of improving high-temperature holding power.
- the weight average molecular weight of the polyester polymer is greater than 100,000.
- the aromatic ring ratio of the tackifying resin is 20% by weight or more.
- a tackifying resin having a ratio of aromatic rings equal to or higher than a predetermined value it is easy to obtain higher shear adhesive strength and more excellent repulsion resistance.
- the tackifying resin comprises a terpene phenolic resin.
- the effects of the technology disclosed herein are preferably realized.
- an isocyanate-based cross-linking agent is preferably used as the cross-linking agent.
- the isocyanate-based cross-linking agent is particularly preferably an aliphatic isocyanate-based compound.
- a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing a polyester-based polymer in which 50% or more of the constituent carbon is biomass-derived carbon is provided.
- the pressure-sensitive adhesive layer further contains a tackifying resin and a cross-linking agent.
- the polyester-based polymer contains an aromatic ring
- the tackifying resin also contains an aromatic ring
- the cross-linking agent does not contain an aromatic ring. Since the pressure-sensitive adhesive sheet having the above structure uses a polyester-based polymer having a bio rate of 50% or more as the pressure-sensitive adhesive, it is possible to reduce dependence on fossil resource-based materials.
- the pressure-sensitive adhesive sheet has a shear adhesive strength of greater than 100 N/100 mm 2 to a stainless steel plate.
- the pressure-sensitive adhesive sheet having the above-described shear adhesive strength can have high adhesion reliability that prevents peeling even when bonding and fixing with a small adhesion area.
- the pressure-sensitive adhesive sheet disclosed here has high shear adhesive strength and excellent adhesion reliability, so it is suitable for use in portable electronic devices that require high-performance bonding and fixing.
- the use of adhesive sheets with high shear adhesive strength is particularly significant for bonding and fixing in portable electronic devices, since the adhesive area is limited.
- portable electronic devices incorporate heat-generating elements such as batteries in a limited internal space, and when the portable electronic device is used for a long time, the internal temperature rises due to the heat generated by the battery. Due to the repetition of high temperature and normal temperature inside the portable electronic device, internal shrinkage of the material of the adherend occurs. desirable.
- it is generally difficult to obtain an effective crosslinked structure with a polyester-based polymer as compared with an acrylic-based polymer. For example, if you try to increase the amount of cross-linking agent to increase the degree of cross-linking in order to improve the holding power, there is concern that the gel fraction will increase and the flexibility and adhesive strength will decrease, and the impact resistance will decrease. be done.
- a polyester-based adhesive it is difficult to improve the high-temperature holding power using the degree of cross-linking. Since it can have a high temperature holding power, it is also suitable for use in fixing members in portable electronic devices in this respect as well.
- a portable electronic device using any adhesive sheet disclosed herein in other words, a portable electronic device including the adhesive sheet is provided.
- FIG. 1 is a cross-sectional view schematically showing the configuration of a pressure-sensitive adhesive sheet according to one embodiment
- FIG. FIG. 3 is a cross-sectional view schematically showing the configuration of a pressure-sensitive adhesive sheet according to another embodiment
- FIG. 3 is a cross-sectional view schematically showing the configuration of a pressure-sensitive adhesive sheet according to another embodiment
- 1 is a front view schematically showing an example of a portable electronic device including an adhesive sheet
- FIG. It is a schematic diagram explaining the method of a repulsion resistance test.
- the adhesive sheet disclosed here includes an adhesive layer.
- the pressure-sensitive adhesive sheet is, for example, a substrate-less double-sided pressure-sensitive adhesive sheet comprising a first pressure-sensitive adhesive surface configured by one surface of the pressure-sensitive adhesive layer and a second pressure-sensitive adhesive surface configured by the other surface of the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive sheet disclosed herein may be in the form of a substrate-attached pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer is laminated on one or both sides of a supporting substrate.
- the supporting substrate may be simply referred to as "substrate".
- FIG. 1 schematically shows the structure of a pressure-sensitive adhesive sheet according to one embodiment.
- This pressure-sensitive adhesive sheet 1 is configured as a substrate-less double-sided pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer 21 .
- the adhesive sheet 1 has a first adhesive surface 21A configured by one surface (first surface) of the adhesive layer 21 and a second adhesive surface configured by the other surface (second surface) of the adhesive layer 21. 21B are attached to different parts of the adherend.
- the locations where the adhesive surfaces 21A and 21B are attached may be locations on different members or different locations within a single member. As shown in FIG.
- the pressure-sensitive adhesive sheet 1 before use (that is, before being attached to an adherend) has a first pressure-sensitive adhesive surface 21A and a second pressure-sensitive adhesive surface 21B that are peeled off at least on the side facing the pressure-sensitive adhesive layer 21.
- It can be a constituent element of the PSA sheet 100 with a release liner in a form protected by the release liners 31 and 32 which are surfaces.
- the release liners 31 and 32 for example, one having a sheet-like base material (liner base material) provided with a release layer by a release treatment agent on one side so that the one side becomes a release surface is preferably used. obtain.
- the release liner 32 is omitted, and a release liner 31 having release surfaces on both sides is used.
- a release liner-attached pressure-sensitive adhesive sheet in a form (roll form) protected by contacting the back surface of the adhesive sheet may be configured.
- FIG. 2 schematically shows the structure of a pressure-sensitive 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, and a base material provided with an adhesive layer 21 provided on the first surface 10A side. It is configured as a single-sided adhesive sheet with The pressure-sensitive adhesive layer 21 is fixedly provided on the first surface 10A side of the support substrate 10 , that is, without the intention of separating the pressure-sensitive adhesive layer 21 from the support substrate 10 .
- a sheet-like support base material for example, a resin film
- the pressure-sensitive adhesive layer 21 is fixedly provided on the first surface 10A side of the support substrate 10 , that is, without the intention of separating the pressure-sensitive adhesive layer 21 from the support substrate 10 .
- the surface (adhesive surface) 21A of the pressure-sensitive adhesive layer 21 is protected by a release liner 31 having a release surface on at least the side facing the pressure-sensitive adhesive layer 21. It can be a component of the pressure-sensitive adhesive sheet 200 with a release liner. Alternatively, by omitting the release liner 31 and using the supporting substrate 10 whose second surface 10B is the releasing surface, the adhesive sheet 2 is wound so that the adhesive surface 21A becomes the second surface (back surface) of the supporting substrate 10. ) 10B may be in a protected form (roll form).
- Fig. 3 schematically shows the structure of a pressure-sensitive adhesive sheet according to another embodiment.
- This adhesive sheet 3 consists of a sheet-like supporting substrate (for example, a resin film) 10 having a first surface 10A and a second surface 10B, and a first adhesive layer 21 fixedly provided on the first surface 10A side. and a second adhesive layer 22 fixedly provided on the second surface 10B side.
- the pressure-sensitive adhesive sheet 3 before use, as shown in FIG. , 32 can be a component of the pressure-sensitive adhesive sheet 300 with a release liner. Alternatively, the release liner 32 is omitted, and a release liner 31 having release surfaces on both sides is used.
- a release liner-attached pressure-sensitive adhesive sheet in a form (roll form) protected by contacting the back surface of the adhesive sheet may be configured.
- the release liner examples include a release liner having a release treatment layer on the surface of a liner substrate such as a resin film or paper, and a release liner made of a low-adhesive material such as a polyolefin resin (e.g., polyethylene, polypropylene) or a fluororesin.
- a liner or the like can be used.
- the release treatment layer may be formed by surface-treating the liner base material with a release treatment agent such as a silicone-based, long-chain alkyl-based, fluorine-based, or molybdenum sulfide-based release agent.
- a release liner having a release treatment layer on the surface of a resin film or a release liner made of a low-adhesive material is preferable from the viewpoint of avoiding the generation of paper dust.
- the concept of the adhesive sheet can include what is called adhesive tape, adhesive film, adhesive label, and the like.
- the pressure-sensitive adhesive sheet may be in the form of a roll or sheet, or may be cut or punched into an appropriate shape according to the purpose and mode of use.
- the pressure-sensitive adhesive sheet disclosed herein has a pressure-sensitive adhesive layer containing a polyester-based polymer.
- the pressure-sensitive adhesive layer and the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer contain a polyester-based polymer (hereinafter, unless otherwise specified, the matters described for the pressure-sensitive adhesive layer refer to the pressure-sensitive adhesive composition can also be applied to Such adhesives and adhesive compositions containing polyester polymers are also referred to as polyester adhesives and polyester adhesive compositions.
- the above polyester-based polymer is typically contained in the pressure-sensitive adhesive layer as a base polymer.
- the base polymer refers to the main component of the rubber-like polymer (polymer exhibiting rubber elasticity in a temperature range around room temperature) contained in the pressure-sensitive adhesive layer.
- the term "main component” refers to a component contained in an amount exceeding 50% by weight unless otherwise specified.
- the polyester-based polymer refers to a polymer obtained by polycondensation of a dicarboxylic acid and a diol.
- the biomass carbon ratio (also called bio rate) of the polyester polymer is 50% or more.
- the bio-content of the polyester-based polymer is 52% or greater, suitably 55% or greater, and may be, for example, 60% or greater.
- the bio rate of the polyester-based polymer is preferably 70% or higher, more preferably 75% or higher, still more preferably 80% or higher, and may be 85% or higher, or 88% or higher.
- the bio rate of the polyester polymer may be, for example, 95% or less, or even 92% or less when more emphasis is placed on adhesive performance. Well, it may be 90% or less, or 85% or less.
- the bio rate of the polyester-based polymer can be made 50% or more.
- biomass-derived carbon in this specification means carbon derived from biomass materials, that is, materials derived from renewable organic resources (renewable carbon).
- the biomass material is typically a material derived from biological resources (typically photosynthetic plants) that can be sustainably reproduced in the presence of sunlight, water, and carbon dioxide.
- materials derived from fossil resources that are depleted by use after mining are excluded from the concept of biomass materials here.
- the biorate of a polyester-based polymer that is, the ratio of biomass-derived carbon to the total carbon contained in the polyester-based polymer can be estimated from the carbon isotope content with a mass number of 14 measured according to ASTM D6866. The same applies to the examples described later.
- the polyester-based polymer used in the technology disclosed here has an aromatic ring in its polymer molecule.
- shear adhesive strength can be improved. Since the polyester-based polymer contains aromatic rings, the pressure-sensitive adhesive has moderate hardness (elasticity), and the cohesive force is increased due to the interaction ( ⁇ - ⁇ stacking) between the aromatic rings contained in the polyester-based polymer and the tackifying resin. It is thought that this improves the shear adhesive strength. Note that the technology disclosed herein is not limited to the above interpretation. In addition, the use of the aromatic ring-containing polyester polymer tends to provide good repulsion resistance and high-temperature holding power.
- the aromatic ring is introduced into the polymer by using a monomer having an aromatic ring (aromatic dicarboxylic acid or aromatic diol).
- the copolymerization ratio of the aromatic ring-containing monomer is not particularly limited, and it is suitable to be about 1% by weight or more. From the viewpoint of improving the shear adhesive strength, the content is preferably about 3% by weight or more, more preferably about 5% by weight or more, and even more preferably about 7% by weight or more. There is a tendency that the higher the copolymerization ratio of the aromatic ring-containing monomer, the higher the high-temperature holding power.
- the upper limit of the copolymerization ratio of the aromatic ring-containing monomer is, for example, about 30% by weight or less. It is about 12% by weight or less, more preferably about 10% by weight or less, and particularly preferably about 8% by weight or less.
- the weight average molecular weight (Mw) of the polyester polymer is not particularly limited, and is usually about 10,000 or more, for example, about 20,000 or more.
- the Mw of the polyester polymer is 30,000 or more, suitably more than 50,000, preferably more than 60,000, more preferably more than 60,000 from the viewpoint of obtaining better properties. It is more than 70,000, more preferably more than 80,000, particularly preferably more than 90,000, and may be 95,000 or more.
- the use of a polyester-based polymer having a high Mw can improve the holding power and, in turn, the high-temperature holding power.
- the Mw of the polyester-based polymer is greater than 100,000, more preferably greater than 110,000 (e.g., greater than 110,000), more preferably greater than 120,000, and greater than 125,000. may be By using such a high-molecular-weight polyester-based polymer, it is easy to obtain more excellent shear adhesive strength and repulsion resistance.
- the upper limit of the Mw of the polyester-based polymer is usually about 30 ⁇ 10 4 or less, preferably about 20 ⁇ 10 4 or less, more preferably about 15 ⁇ 10 4 from the viewpoint of adhesive strength and the like. or less, and may be, for example, about 12 ⁇ 10 4 or less.
- Mw of a polyester-based polymer refers to a value in terms of standard polystyrene obtained by GPC (gel permeation chromatography).
- GPC gel permeation chromatography
- model name "HLC-8320GPC” column: TSKgelGMH-H(S), manufactured by Tosoh Corporation
- GPC measurement can be performed under the following conditions. It is measured by the same method in the examples described later.
- the glass transition temperature (Tg) of the polyester polymer is advantageously about 15° C. or lower, preferably about 0° C. or lower, more preferably about ⁇ 15° C. or lower, even more preferably about ⁇ 20° C. or lower, especially Preferably, it is about -25°C or lower (eg, about -30°C or lower).
- Tg glass transition temperature
- the adhesive strength can be preferably improved.
- the Tg of the polyester polymer is usually about -80°C or higher, preferably about -60°C or higher, more preferably about -45°C or higher, further preferably about -45°C or higher.
- the Tg of the polyester-based polymer can be adjusted by appropriately changing the monomer composition (that is, the types and usage ratio of the monomers used in synthesizing the polymer).
- the Tg of the polyester polymer is measured by the following method. Specifically, a disc-shaped test piece having a thickness of 2 mm and a diameter of 8 mm is prepared using a polyester-based polymer to be measured. This test piece is sandwiched between parallel plates for a shear test, and a peak of tan ⁇ (loss modulus G''/storage modulus G') is measured at a frequency of 1 Hz using a measuring device (ARES, manufactured by Rheometric Scientific). The temperature of the peak value is defined as Tg (glass transition temperature) [°C]. It is measured by the same method in the examples described later.
- Tg glass transition temperature
- dicarboxylic acid Any of aliphatic dicarboxylic acids, dimer acids, alicyclic dicarboxylic acids, unsaturated dicarboxylic acids, and aromatic dicarboxylic acids can be used as the dicarboxylic acid used for synthesizing the polyester-based polymer.
- dicarboxylic acids include malonic acid, succinic acid, glutaric acid, dimethylglutaric acid, adipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, sebacic acid, and thiodipropionic acid.
- aliphatic dicarboxylic acids such as diglycolic acid; dimer acids obtained by dimerizing fatty acids such as oleic acid and erucic acid; 1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane Alicyclic dicarboxylic acids such as dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, norbornanedicarboxylic acid, adamantanedicarboxylic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid , citraconic acid, dodecenyl succinic anhydride; - aromatic dicarboxylic acids such as dicarboxydiphenyl ether and naphthalenedicarboxylic acid; derivatives thereof;
- the dicarboxylic acid derivatives include derivatives such as carboxylate
- the dicarboxylic acid it is preferable to use a plant-derived dicarboxylic acid from the viewpoint of obtaining a polyester polymer having a bio rate of 50% or more.
- suitable examples of such dicarboxylic acids include sebacic acid derived from plants (eg, castor oil), and dimer acid derived from fatty acids such as oleic acid and erucic acid. Plant-derived dicarboxylic acids can be used singly or in combination of two or more.
- the weight ratio of plant-derived dicarboxylic acids in the total amount (total weight) of dicarboxylic acids as monomer components of polyester polymers should be about 1% by weight or more. is suitable, preferably about 10% by weight or more, more preferably about 50% by weight or more, still more preferably about 70% by weight or more, particularly preferably about 80% by weight or more, and about 90% by weight or more may be about 95% by weight or more (eg, 95 to 100% by weight).
- the upper limit of the weight ratio of the plant-derived dicarboxylic acid is 100% by weight, and from the viewpoint of adhesive properties, about 99% by weight or less is suitable, preferably about 95% by weight or less, and about 90% by weight. % or less.
- a dimer acid is used as the plant-derived dicarboxylic acid.
- a dimer acid By using a dimer acid, the bio rate of the polyester-based polymer can be increased while obtaining good adhesive properties.
- a dimer acid can be used individually by 1 type or in combination of 2 or more types.
- the weight ratio of the dimer acid to the total amount (total weight) of the dicarboxylic acid as the monomer component of the polyester polymer is appropriately and preferably about 1% by weight or more.
- the polymer is about 10% by weight or more, more preferably about 50% by weight or more, more preferably about 70% by weight or more, particularly preferably about 80% by weight or more, and may be about 90% by weight or more, about 95% by weight % or more (for example, 95 to 100% by weight).
- the amount of the dimer acid to be used to a predetermined amount or more, the polymer can be designed based on the properties of the dimer acid.
- the upper limit of the weight ratio of the dimer acid is 100% by weight, and from the viewpoint of adhesive properties such as shear adhesive strength, repulsion resistance, and high temperature holding power, about 99% by weight or less is suitable, preferably about 99% by weight. It is 95% by weight or less, and may be about 90% by weight or less.
- sebacic acid may be used as the plant-derived dicarboxylic acid.
- the use of sebacic acid can also increase the bio-rate of the polyester-based polymer.
- the weight ratio of sebacic acid to the total amount (total weight) of dicarboxylic acids as monomer components of the polyester polymer may be about 1% by weight or more, for example about 10%. It may be at least about 50% by weight, at least about 70% by weight, or at least about 90% by weight (for example, 95 to 100% by weight).
- the weight ratio of the sebacic acid may be approximately 95% by weight or less, or may be approximately 75% by weight or less, or may be approximately 60% by weight or less from the viewpoint of adhesive properties.
- the technology disclosed herein can be practiced in either a mode in which the dicarboxylic acid used as a monomer component for synthesizing the polyester polymer contains sebacic acid or a mode in which sebacic acid is not included.
- the weight percentage of the sebacic acid may be about 50% by weight or less, about 30% by weight or less, about 10% by weight or less, about 3% by weight or less, or even less than 1% by weight.
- the dicarboxylic acid used to synthesize the polyester-based polymer may be substantially free of sebacic acid.
- the molecular weight of the plant-derived dicarboxylic acid is not particularly limited, and is suitably 100 or more, and may be 150 or more.
- the molecular weight of the plant-derived dicarboxylic acid is suitably about 1000 or less from the viewpoint of monomer availability, synthesis, etc., and may be, for example, 800 or less, 700 or less, or 600 or less. good. Suitable examples of dicarboxylic acids having the above molecular weights include dimer acids.
- the molecular weight calculated from the chemical formula is adopted as the molecular weight of the dicarboxylic acid.
- the molecular weight of the dicarboxylic acid for example, the plant-derived dicarboxylic acid
- the weight fraction of each dicarboxylic acid Summation (total value) is adopted.
- aromatic dicarboxylic acids are preferably used as the dicarboxylic acid used for synthesizing the polyester-based polymer disclosed herein.
- Use of a dicarboxylic acid containing an aromatic dicarboxylic acid tends to increase the cohesive strength and improve the shear adhesive strength.
- the use of aromatic dicarboxylic acid is also advantageous in terms of high resistance to repulsion and improvement in holding power at high temperatures.
- an aromatic dicarboxylic acid as the dicarboxylic acid, the amount of the cross-linking agent used can be suppressed, so that it is easy to improve the cohesive force while maintaining or improving the adhesive force.
- Suitable examples of the aromatic dicarboxylic acid include isophthalic acid, terephthalic acid and orthophthalic acid, with terephthalic acid being more preferred. These can be used individually by 1 type or in combination of 2 or more types.
- biomass-derived terephthalic acid and its derivatives may be used as the dicarboxylic acid.
- the method for obtaining the biomass-derived dicarboxylic acid is not particularly limited.
- biomass-derived terephthalic acid is converted to isobutylene after obtaining isobutanol from corn, sugars, and wood, and then dimerizing it to produce isooctene.
- the weight ratio of the aromatic dicarboxylic acid to the total amount (total weight) of the dicarboxylic acid in the monomer component of the polyester polymer is not particularly limited, and is about 1% by weight or more.
- the content is preferably about 3% by weight or more, more preferably about 5% by weight or more, and even more preferably about 7% by weight or more.
- the upper limit of the weight ratio of the aromatic carboxylic acid is not limited to a specific range because it may vary depending on other dicarboxylic acid species, etc., and for example, it is suitable to be about 50% by weight or less. From the viewpoint of adhesion properties, it is preferably about 30% by weight or less, more preferably about 20% by weight or less, even more preferably about 15% by weight or less, and particularly preferably about 10% by weight or less.
- dicarboxylic acids eg, aliphatic dicarboxylic acids
- dicarboxylic acids include dimethylglutaric acid, adipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid.
- adipic acid is preferably used as the aliphatic dicarboxylic acid.
- the dicarboxylic acids (for example, aliphatic dicarboxylic acids) derived from fossil resources may be used singly or in combination of two or more.
- the molecular weight of the dicarboxylic acid used as a monomer component for synthesizing the polyester-based polymer disclosed herein is not particularly limited, and is suitably 100 or more, and may be 150 or more. In some embodiments, the molecular weight of the dicarboxylic acid used may be 200 or greater, 250 or greater, 350 or greater, 450 or greater, or 500 or greater (eg, 530 or greater). On the other hand, the molecular weight of the dicarboxylic acid is suitably about 1,000 or less from the viewpoint of monomer availability, synthesis, etc. below).
- the polyester-based polymer disclosed herein (having an Mw of a predetermined value or more, preferably having a Tg within a predetermined range) is preferably synthesized using a dicarboxylic acid having a molecular weight within the above range.
- diol Any of (poly)alkylene glycols, aliphatic diols, dimer diols, alicyclic diols, aromatic diols, and unsaturated diols can be used as diols used for synthesizing the polyester-based polymer disclosed herein. .
- diol examples include (poly)alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and polytetramethylene glycol; 1,3-propane; diol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl- 2-isobutyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-hexanediol, 2,2,4
- the diol is preferably (poly)alkylene glycols, aliphatic diols or alicyclic diols, more preferably (poly)alkylene glycols or aliphatic diols.
- diols preferably ethylene glycol and aliphatic diols
- dicarboxylic acids preferably dimer acids and aromatic dicarboxylic acids
- Preferred examples include (poly)ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,4 -butanediol, 1,5-pentanediol, 1,6-hexanediol, and from the viewpoint of reactivity, etc., ethylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol. , 1,4-butanediol and 1,6-hexanediol are more preferable. These can be used individually by 1 type or in combination of 2 or more types.
- the (poly)alkylene glycols, aliphatic diols, and alicyclic diols described above may be derived from plants or fossil resources.
- the (poly)ethylene glycol is used in the sense of including ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol.
- the weight ratio of (poly)alkylene glycols, aliphatic diols and alicyclic diols (preferably ethylene glycol and aliphatic diols) in the total amount (total weight) of diols in the monomer component of the polyester polymer is particularly It is not limited, and is suitably about 50% by weight or more, preferably about 70% by weight or more, more preferably about 80% by weight or more, still more preferably about 90% by weight, from the viewpoint of obtaining good adhesive properties. More preferably, it is about 95% by weight or more (for example, 99 to 100% by weight).
- the weight ratio of the (poly)alkylene glycols, the aliphatic diol and the alicyclic diol may be, for example, about 95% by weight or less.
- (poly)ethylene glycol is used as the diol.
- (poly)ethylene glycol in combination with an appropriate dicarboxylic acid, good adhesive properties (shear adhesive strength, etc.) can be preferably obtained.
- the weight ratio of the (poly)ethylene glycol to the total amount (total weight) of the diol as the monomer component of the polyester polymer should be approximately 1% by weight or more. is suitable, preferably about 10% by weight or more, more preferably about 50% by weight or more, still more preferably about 80% by weight or more, and particularly preferably about 90% by weight or more (eg, 95 to 100% by weight).
- the polymer By setting the amount of (poly)ethylene glycol to a predetermined value or more, the polymer can be designed based on the properties of (poly)ethylene glycol. Further, for example, the use of (poly)ethylene glycol facilitates obtaining a pressure-sensitive adhesive layer with low haze. Also, the weight ratio of the (poly)ethylene glycol may be approximately 95% by weight or less, approximately 70% by weight or less, or approximately 50% by weight or less.
- the (poly)ethylene glycol mentioned above may be derived from plants or fossil resources. (Poly)ethylene glycol may be used alone or in combination of two or more.
- a plant-derived diol as the diol from the viewpoint of obtaining a polyester-based polymer with a bio rate of 50% or more.
- examples of such diols include biomass diols obtained from biomass ethanol (e.g., biomass (poly)ethylene glycol), fatty acid esters derived from plants (e.g., castor oil), and fatty acids such as oleic acid and erucic acid. and dimer diol derived from and butanediol produced using glucose. Plant-derived diols can be used singly or in combination of two or more.
- the weight ratio of the plant-derived diol to the total amount (total weight) of diols as monomer components of the polyester-based polymer is about 1% by weight. or more, approximately 10% by weight or more, approximately 50% by weight or more, approximately 80% by weight or more, or approximately 90% by weight or more (eg, 95 to 100% by weight).
- the weight ratio of the plant-derived diol may be approximately 95% by weight or less, approximately 70% by weight or less, or approximately 50% by weight or less.
- a polyester-based polymer can have a bio rate of a predetermined value or higher.
- the weight ratio of the plant-derived diol may be approximately 30% by weight or less, approximately 10% by weight or less, or approximately 3% by weight or less (for example, less than 1% by weight).
- the technology disclosed herein can also be preferably practiced in a mode in which the diol used as the monomer component for synthesizing the polyester-based polymer does not substantially contain a plant-derived diol.
- dimer diol is used as the plant-derived diol.
- the use of dimer diol can also increase the bio-rate of the polyester-based polymer.
- a dimer diol can be used individually by 1 type or in combination of 2 or more types.
- the weight ratio of the dimer diol to the total amount (total weight) of the diol as the monomer component of the polyester polymer may be approximately 1% by weight or more, for example approximately 10% by weight. or more, approximately 50% by weight or more, approximately 70% by weight or more, approximately 80% by weight or more, or approximately 90% by weight or more (eg, 95 to 100% by weight).
- the weight ratio of the dimer diol may be approximately 95% by weight or less, approximately 85% by weight or less, or approximately 60% by weight or less.
- the technology disclosed herein can be practiced in either a mode in which the diol as a monomer component used in the synthesis of the polyester-based polymer contains dimer diol or a mode in which it does not contain dimer diol.
- the weight percentage of the dimer diol may be approximately 50% by weight or less (for example, less than 50% by weight), approximately 30% by weight or less, approximately 10% by weight or less, or approximately 3% by weight or less. It may well be less than 1% by weight, and the diol used in the synthesis of the polyester-based polymer may be substantially free of dimer diol.
- the molecular weight of the diol is not particularly limited.
- the molecular weight of the diol is preferably, for example, 500 or less, may be 300 or less, may be 150 or less, may be 100 or less, or may be 80 or less, from the standpoint of monomer availability and synthesis.
- the molecular weight of the diol is suitably about 50 or more, and may be more than 100, for example.
- a polyester-based polymer capable of exhibiting high shear adhesive strength can be preferably synthesized in an embodiment using a diol having a molecular weight within the above range.
- the molecular weight of the diol derived from fossil resources is suitably 500 or less, and may be 300 or less.
- the molecular weight of the fossil resource-derived diol is suitably about 50 or more, and may be more than 100, for example. Suitable examples of diols having the above molecular weights include ethylene glycol.
- the molecular weight calculated from the chemical formula can be adopted as the molecular weight of the diol.
- the molecular weight of the diol for example, the above-mentioned fossil resource-derived diol
- the weight fraction of each diol total value
- the polyester-based polymer disclosed herein can be substantially composed of the above-described dicarboxylic acid and diol.
- Other copolymerization components other than the dicarboxylic acid and the diol may be copolymerized as long as they do not occur.
- Such other copolymerization components include polyvalent carboxylic acids containing three or four or more carboxy groups (trivalent or higher polycarboxylic acids such as trimellitic acid, pyromellitic acid, adamantanetricarboxylic acid, trimesic acid, and trimeric acid).
- carboxylic acid polyols containing 3 or 4 or more hydroxyl groups in one molecule (pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, trimethylolpropane, trimethylolethane, 1,3,6-hexanetriol, adamantanetriol, etc.), monocarboxylic acids, monoalcohols, hydroxycarboxylic acids, lactones, and the like.
- the above other copolymer components can be used singly or in combination of two or more. These other copolymer components may or may not be derived from plants.
- the ratio of the other copolymerization components in the monomer components of the polyester polymer is, for example, suitably less than 10% by weight, less than 3% by weight, typically less than 1% by weight (furthermore, 0.1% by weight). % by weight).
- the technology disclosed herein can also be preferably carried out in a mode in which the monomer component of the polyester-based polymer does not substantially contain the other copolymer components.
- the total ratio of dicarboxylic acid and diol is appropriately and preferably about 90% by weight or more. is about 95% by weight or more, more preferably about 98% by weight or more, and even more preferably about 99% by weight or more (eg, 99 to 100% by weight).
- the technique disclosed herein is preferably practiced in a mode using a polyester-based polymer substantially synthesized from dicarboxylic acid and diol.
- dimer acid as a dicarboxylic acid and (poly)ethylene glycol as a diol are used together as the monomer component of the polyester polymer.
- a combination of dimer acid and (poly)ethylene glycol it is possible to preferably synthesize a polyester-based polymer that has an Mw of a predetermined value or more and is capable of exhibiting shear adhesive strength.
- the total proportion of dimer acid and (poly)ethylene glycol in the total amount of monomer components of the polyester polymer is suitably about 50% by weight or more, preferably about 60% by weight or more, more preferably about 70% by weight. % or more, more preferably approximately 80% by weight or more, and may be approximately 90% by weight or more (eg, 99 to 100% by weight).
- the method for obtaining the polyester-based polymer disclosed herein is not particularly limited, and polymerization methods known as methods for synthesizing polyester-based polymers can be appropriately employed.
- the monomer raw material used for the synthesis of the polyester-based polymer is, for example, a monomer blended so that 0.95 to 1.05 equivalents (preferably 0.98 to 1.02 equivalents) of dicarboxylic acid is used per equivalent of diol. be able to.
- the dicarboxylic acid and the diol in the above ratio, a high-molecular-weight polyester-based polymer can be easily obtained.
- the polymer can be moderately crosslinked (for example, crosslinked based on reaction with a crosslinking agent such as an isocyanate-based crosslinking agent) to increase the cohesive force.
- the weight ratio of the dicarboxylic acid and the diol as monomer components used for the synthesis of the polyester polymer is not particularly limited. weight ratio can be set.
- the ratio (weight ratio A1/A2) between the weight A1 of the dicarboxylic acid and the weight A2 of the diol used as the monomer component may be 10/90 or more, or 30/70 or more.
- the weight ratio (A1/A2) is approximately 50/50 or greater, more preferably 60/40 or greater, even more preferably 70/30 or greater, and may be 80/20 or greater; It may be 90/10 or more.
- the properties based on the dicarboxylic acid can be favorably expressed.
- the bio rate of the obtained polyester-based polymer can be effectively increased.
- the weight ratio (A1/A2) may be, for example, 95/5 or less, or 85/15 or less.
- the weight ratio (A1/A2) may be 75/25 or less, or 50/50 or less (for example, 30/70 or less), from the viewpoint of favorably expressing diol-based properties. It's okay.
- the above weight ratio allows the polyester polymer to have a high bio-rate.
- a polyester-based polymer having a bio rate of a predetermined value or more can be obtained regardless of the weight ratio of the dicarboxylic acid and the diol.
- the polyester-based polymer in the technology disclosed here can be obtained by polycondensation of a dicarboxylic acid and a diol, like general polyesters. More specifically, the reaction between the carboxyl group of the dicarboxylic acid and the hydroxyl group of the diol is typically allowed to proceed while removing the water produced by the above reaction (produced water) and the like out of the reaction system, thereby producing a polyester system. Polymers can be synthesized. As a method for removing the generated water from the reaction system, an inert gas is blown into the reaction system and the generated water is removed from the reaction system together with the inert gas. A method of dehydration by boiling, a method of distilling off the water produced from the reaction system under reduced pressure (decompression method), and the like can be used.
- the reaction temperature and reaction time when performing the above reaction including esterification and polycondensation), the degree of pressure reduction (pressure in the reaction system) when adopting the pressure reduction method, the desired properties (for example, molecular weight) It can be appropriately set so that the polyester-based polymer can be efficiently obtained.
- the reaction temperature it is usually appropriate for the reaction temperature to be approximately 150° C. or higher (for example, 180° C. to 260° C.). By setting the reaction temperature within the above range, a favorable reaction rate is obtained, productivity is improved, and deterioration of the produced polyester polymer can be easily prevented or suppressed.
- the reaction time is not particularly limited and may be about 3 to 48 hours (eg 10 to 30 hours).
- a decompression method it is not particularly limited, but it is usually appropriate to set the degree of decompression to 10 kPa or less (typically 10 kPa to 0.1 kPa), for example, 4 kPa to 0.1 kPa. be able to.
- 10 kPa or less typically 10 kPa to 0.1 kPa
- 4 kPa to 0.1 kPa be able to.
- a suitable amount of a known or commonly used catalyst can be used for esterification and condensation, as in general polyester synthesis.
- catalysts include various metal compounds such as titanium, germanium, antimony, tin, and zinc; strong acids such as p-toluenesulfonic acid and sulfuric acid; and the like. Since the amount of the catalyst used can be appropriately set according to the reaction rate and the like, detailed description is omitted here.
- a solvent may or may not be used in the process of synthesizing a polyester-based polymer by reacting a dicarboxylic acid and a diol.
- the above synthesis can be carried out substantially without using an organic solvent (for example, this means excluding a mode in which an organic solvent is intentionally used as a reaction solvent during the above reaction). Synthesizing a polyester polymer without substantially using an organic solvent in this way, and preparing a polyester pressure-sensitive adhesive using such a polyester polymer, avoid the use of organic solvents in the manufacturing process. It is preferable because it satisfies the demand.
- the adhesive layers (and adhesive compositions) disclosed herein comprise a tackifying resin.
- a tackifying resin having an aromatic ring in the molecule aromatic ring-containing tackifying resin
- aromatic ring-containing tackifying resin a tackifying resin having an aromatic ring in the molecule
- shear adhesive strength can be improved.
- the use of a tackifying resin containing an aromatic ring makes it easy to obtain good repulsion resistance and high-temperature holding power.
- both the polyester-based polymer and the tackifying resin have an aromatic ring, they are excellent in compatibility and can satisfactorily exhibit desired adhesive properties.
- the aromatic ring-containing tackifier resins may be used singly or in combination of two or more.
- tackifying resins having aromatic rings include phenol-based tackifying resins.
- Phenol-based tackifying resins tend to be more compatible with polyester-based polymers than other tackifying resins (for example, rosin-based tackifying resins).
- examples of phenolic tackifying resins include terpene phenolic resins, hydrogenated terpene phenolic resins, alkylphenolic resins and rosin phenolic resins. Phenolic tackifying resins can be used singly or in combination of two or more.
- the terpene phenol resin refers to a polymer containing a terpene residue and a phenol residue, a copolymer of a terpene and a phenol compound (terpene-phenol copolymer resin), a terpene or a homopolymer thereof.
- it is a concept that includes both a phenol-modified copolymer (phenol-modified terpene resin).
- Preferred examples of terpenes constituting such a terpene phenol resin include monoterpenes such as ⁇ -pinene, ⁇ -pinene, and limonene (including d-, l- and d/l-forms (dipentene)). is mentioned.
- a hydrogenated terpene phenol resin refers to a hydrogenated terpene phenol resin having a structure obtained by hydrogenating such a terpene phenol resin. It is sometimes called a hydrogenated terpene phenolic resin.
- Alkylphenol resins are resins obtained from alkylphenols and formaldehyde (oily phenolic resins). Examples of alkylphenol resins include novolac and resole types. Rosin phenolic resins are typically rosins or phenol-modified products of the various rosin derivatives described above (including rosin esters, unsaturated fatty acid-modified rosins, and unsaturated fatty acid-modified rosin esters). Examples of rosin phenol resins include rosin phenol resins obtained by a method of adding phenol to rosins or various rosin derivatives described above with an acid catalyst and thermally polymerizing the mixture.
- terpene phenol resins terpene phenol resins, hydrogenated terpene phenol resins and alkylphenol resins are preferred, terpene phenol resins and hydrogenated terpene phenol resins are more preferred, and terpene phenol resins are particularly preferred.
- the technology disclosed herein is preferably implemented in a mode in which, for example, approximately 25% by weight or more (more preferably approximately 30% by weight or more) of the total amount of tackifying resin is a phenolic tackifying resin (e.g., terpene phenolic resin). obtain. About 50% by weight or more of the total amount of the tackifying resin may be the phenolic tackifying resin, and about 80% by weight or more (eg, about 90% by weight or more) may be the phenolic tackifying resin. Substantially all of the tackifying resin (for example, approximately 95% by weight or more and 100% by weight or less, further approximately 99% by weight or more and 100% by weight or less) may be a phenolic tackifying resin.
- a phenolic tackifying resin e.g., terpene phenolic resin
- a tackifying resin with a high aromatic ring ratio is preferably used as the tackifying resin having an aromatic ring in the molecule.
- tackifying resins having a phenol structure as an aromatic ring tackifying resins having a high phenol ratio are preferably used.
- a tackifying resin with a high aromatic ring ratio for example, phenol ratio
- more excellent shear adhesive strength is likely to be obtained.
- the aromatic ring ratio (e.g., phenol ratio) of the tackifying resin is, for example, 10% by weight or more, and from the viewpoint of repulsion resistance, etc., is preferably 15% by weight or more, more preferably 20% by weight or more, and still more preferably 25% by weight. % or more, particularly preferably 30% by weight or more.
- the upper limit of the aromatic ring ratio (e.g., phenol ratio) of the tackifier resin is, for example, 65% by weight or less, and from the viewpoint of adhesive strength, etc., it may be 50% by weight or less, 40% by weight or less, or 35% by weight. % or less.
- the aromatic ring ratio (eg, phenol ratio) of the tackifier resin refers to the aromatic ring ratio (eg, phenol ratio) calculated from 1 H-NMR spectrum measured by a nuclear magnetic resonance (NMR) device.
- NMR nuclear magnetic resonance
- the tackifier resin has the chemical structure shown below, in the 1 H-NMR spectrum, the peaks with chemical shifts between 7.5 and 6.3 ppm are derived from the phenol skeleton, and the peaks with chemical shifts between 5.6 and 0.5 ppm are derived from the phenol skeleton. The peaks between 1 ppm are considered to be derived from the pinene skeleton.
- the softening point of the aromatic ring-containing tackifying resin is not particularly limited. From the viewpoint of improving the cohesive strength, in some embodiments, the softening point (softening temperature) of the aromatic ring-containing tackifying resin is suitably about 50 ° C. or higher, and the softening point (softening temperature) is about 80 ° C. or above (preferably about 100° C. or higher, for example about 115° C. or higher). In some preferred embodiments, the softening point of the aromatic ring-containing tackifying resin used may be approximately 120° C. or higher (eg, 135° C. or higher or 145° C. or higher).
- the aromatic ring-containing tackifying resin having the softening point accounts for more than 50% by weight (more preferably more than 70% by weight, for example 90% by weight) of the total tackifying resin contained in the adhesive layer. super) can be preferably implemented in a certain aspect.
- a terpene phenol resin having a softening point of about 120° C. or higher (more preferably 135° C. or higher, for example 145° C. or higher) can be used.
- the softening point of the tackifying resin can be measured based on the softening point test method (ring and ball method) specified in JIS K2207.
- the content of the aromatic ring-containing tackifier resin can be, for example, more than 0 parts by weight with respect to 100 parts by weight of the polyester polymer, and may be about 3 parts by weight or more (for example, about 5 parts by weight or more).
- the content of the aromatic ring-containing tackifying resin relative to 100 parts by weight of the polyester polymer is about 10 parts by weight or more, more preferably about 20 parts by weight or more, and even more preferably about 30 parts by weight or more. and particularly preferably about 35 parts by weight or more.
- the upper limit of the content of the aromatic ring-containing tackifying resin is not particularly limited, and from the viewpoint of compatibility and adhesion with the polyester polymer, in some embodiments, the aromatic ring-containing tackifier is usually added to 100 parts by weight of the polyester polymer.
- the content of the imparting resin is suitably about 120 parts by weight or less, preferably less than 80 parts by weight, more preferably about 70 parts by weight or less (for example, about 50 parts by weight or less).
- the pressure-sensitive adhesive layer disclosed herein optionally contains an aromatic ring-free tackifying resin (aromatic ring-free tackifying resin) in addition to the aromatic ring-containing tackifying resin within a range that does not impair the effects of the invention. may contain.
- aromatic ring-free tackifying resin aromatic ring-free tackifying resin
- Such aromatic ring-free tackifying resins include terpene-based tackifying resins, modified terpene-based tackifying resins, rosin-based tackifying resins, hydrocarbon-based tackifying resins, epoxy-based tackifying resins, polyamide-based tackifying resins, elastomers
- tackifying resins such as tackifying resins and tackifying resins of ketone type can be used.
- a plant-derived tackifying resin (vegetable tackifying resin) is preferably used as the tackifying resin from the viewpoint of improving the bio rate of the entire pressure-sensitive adhesive layer.
- the plant-based tackifying resin is composed of at least a part of the resin derived from plants, and the entire resin may be plant-derived. may be derived from fossil resources.
- Examples of vegetable tackifying resins include the above-described rosin-based tackifying resins, terpene-based tackifying resins, terpene phenolic resins, hydrogenated terpene phenolic resins, rosin phenolic resins, and the like.
- Vegetable tackifying resins can be used singly or in combination of two or more.
- the proportion of the vegetable tackifying resin in the total amount of the tackifying resin contained in the pressure-sensitive adhesive layer is 30% by weight or more (for example, 50% by weight or more, typically 80% by weight or more).
- the ratio of the vegetable tackifying resin to the total amount of tackifying resin may be 90% by weight or more (eg 95% by weight or more, typically 99-100% by weight).
- the technology disclosed herein can be practiced in a manner substantially free of tackifying resins other than vegetable tackifying resins.
- the total amount (total content) of the tackifier resin can be, for example, more than 0 parts by weight with respect to 100 parts by weight of the polyester polymer, and may be about 3 parts by weight or more (for example, about 5 parts by weight or more).
- the total amount of the tackifying resin relative to 100 parts by weight of the polyester polymer is about 10 parts by weight or more, more preferably about 20 parts by weight or more, still more preferably about 30 parts by weight or more, and particularly preferably is about 35 parts by weight or more. The greater the amount of tackifying resin used, the more likely it is that excellent adhesive strength will be obtained.
- the upper limit of the total amount of the tackifying resin is not particularly limited, and from the viewpoint of compatibility and adhesion with the polyester polymer, in some embodiments, the total amount of the tackifying resin is usually about 100 parts by weight of the polyester polymer. It is suitably 120 parts by weight or less, preferably less than 80 parts by weight, and more preferably about 70 parts by weight or less (for example, about 50 parts by weight or less). For example, it is effective to use the tackifying resin in the amount within the above range for a polyester polymer having a Tg of 0° C. or lower.
- the pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer contains, as a cross-linking agent, a cross-linking agent having no aromatic ring (aromatic ring-free cross-linking agent).
- a cross-linking agent having no aromatic ring
- aromatic ring-free cross-linking agent By using a non-aromatic ring-containing cross-linking agent in a composition containing a polyester-based polymer containing an aromatic ring and a tackifying resin, while obtaining a good cross-linked structure (cross-linking reaction), the aromatic contained in the polyester-based polymer and the tackifying resin is reduced. The action of the ring can be favorably exhibited.
- the pressure-sensitive adhesive layer in the technology disclosed herein contains the cross-linking agent in the form after the cross-linking reaction, the form before the cross-linking reaction, the form in which the cross-linking reaction is partially performed, the intermediate or composite form thereof, or the like. obtain.
- the above-mentioned cross-linking agent is usually contained in the pressure-sensitive adhesive layer exclusively in the form after the cross-linking reaction.
- the cross-linking agent used for cross-linking the polyester polymer may also function as a chain extender.
- the type of cross-linking agent is not particularly limited as long as it has a structure that does not contain an aromatic ring, and one that does not contain an aromatic ring can be appropriately selected and used from conventionally known cross-linking agents.
- aromatic ring-free crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, melamine crosslinking agents, and metal chelate crosslinking agents.
- the aromatic ring-free cross-linking agents may be used singly or in combination of two or more. Among them, an isocyanate-based cross-linking agent is preferable.
- the degree of cross-linking can be effectively increased with less hindrance to cross-linking in the pressure-sensitive adhesive composition containing the polyester-based polymer and the tackifying resin.
- isocyanate-based cross-linking agents include polyfunctional isocyanate-based compounds (including those having an isocyanurate structure) having an average of 2 or 3 or more isocyanate groups per molecule.
- polyfunctional isocyanate-based compounds are polymers (e.g., dimers or trimers) of difunctional or trifunctional or more functional isocyanates, derivatives (e.g., addition reactions of polyhydric alcohols and two or more molecules of polyfunctional isocyanates products), polymers, and the like.
- isocyanurate of hexamethylene diisocyanate (trimer adduct of isocyanurate structure), reaction product of trimethylolpropane and hexamethylene diisocyanate, polyether polyisocyanate, polyester polyisocyanate, and other polyfunctional isocyanate compounds are mentioned.
- the above isocyanate-based cross-linking agents may be used singly or in combination of two or more.
- polyfunctional isocyanate-based compounds that do not contain aromatic rings include aliphatic polyisocyanate-based compounds and alicyclic polyisocyanate-based compounds.
- aliphatic polyisocyanate compounds include 1,2-ethylene diisocyanate; tetramethylene diisocyanates such as 1,2-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate and 1,4-tetramethylene diisocyanate; Hexamethylene diisocyanates such as 2-hexamethylene diisocyanate, 1,3-hexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, 1,5-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate and 2,5-hexamethylene diisocyanate ; 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, lysine diisocyanate, and the like.
- alicyclic polyisocyanate compounds include isophorone diisocyanate; cyclohexyl diisocyanates such as 1,2-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate and 1,4-cyclohexyl diisocyanate; 1,2-cyclopentyl diisocyanate, 1, Cyclopentyl diisocyanate such as 3-cyclopentyl diisocyanate; hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and the like.
- Suitable examples of the aromatic ring-free isocyanate include aliphatic isocyanate compounds.
- the technique disclosed herein is particularly preferably implemented in a mode in which an aliphatic isocyanate compound is used as a cross-linking agent in a configuration in which both the polyester-based polymer and the tackifying resin have aromatic rings.
- cross-linking agents preferably isocyanate-based cross-linking agents
- two or more types of cross-linking agents having different numbers of functional groups it is easy to achieve both a plurality of properties (for example, shear adhesive strength, repulsion resistance, etc.) in a well-balanced manner.
- the functional group refers to a cross-linking reactive group, and for example, refers to an isocyanate group in the polyfunctional isocyanate compound described above.
- one or more bifunctional cross-linking agents and one or more tri- or more tri-functional cross-linking agents are used in combination.
- the bifunctional cross-linking agent mainly functions as a chain extender and contributes to the improvement of repulsion resistance by lengthening the chain of the polyester-based polymer when the adhesive composition is cured. It is considered that the cohesive strength is increased and the shear adhesive strength is obtained. Note that the technology disclosed herein is not limited to the above interpretation.
- bi-functional cross-linking agents and tri- or higher functional cross-linking agents can be used without particular limitation.
- an isocyanate compound containing no aromatic ring is preferably used as a bifunctional cross-linking agent and a tri- or more functional cross-linking agent.
- the amount of the bi-functional cross-linking agent used is not particularly limited. From the viewpoint of obtaining the effect, it is appropriate to use about 0.01 parts by weight or more, preferably about 0.1 parts by weight or more, more preferably about 0.5 parts by weight or more, and even more preferably about 0.8 parts by weight. parts or more, may be about 1.5 parts by weight or more, or may be about 3 parts by weight or more. Also, the amount of the bifunctional cross-linking agent to be used relative to 100 parts by weight of the polyester polymer is usually about 10 parts by weight or less, preferably about 7 parts by weight or less, and may be 4 parts by weight or less.
- the amount of the tri- or higher-functional cross-linking agent to be used is not particularly limited. From the viewpoint of obtaining the effect of using a tri- or higher functional cross-linking agent, it is appropriate to use about 0.01 parts by weight or more, preferably about 0.1 parts by weight or more, more preferably about 0.5 parts by weight or more, More preferably about 1 part by weight or more, particularly preferably about 2 parts by weight or more (for example, about 2.5 parts by weight or more). By using an appropriate amount of a tri- or higher functional cross-linking agent, the cohesive force is increased, and excellent properties (shear adhesive strength, etc.) can be easily obtained.
- the amount of tri- or higher functional cross-linking agent to be used is usually about 8 parts by weight or less, preferably about 5 parts by weight or less, and may be 4 parts by weight or less based on 100 parts by weight of the polyester polymer.
- the proportion of the bi-functional cross-linking agent and the tri- or higher functional cross-linking agent is adjusted to achieve the desired multiple adhesive properties (shear adhesive strength, adhesive strength, high-temperature holding power, repulsion resistance, etc.) are appropriately set so as to achieve a good balance, and are not limited to a specific range.
- the ratio (C B /C A ) of the amount C B of the tri- or more functional cross-linking agent to the amount C A of the bi-functional cross-linking agent is, for example, 0.1 or more, and from the viewpoint of improving the cohesive strength, it is preferably 0.3 or more.
- the ratio (C B /C A ) is, for example, 10 or less, preferably 7 or less, more preferably 5 or less, may be 4 or less, or 2.5 or less from the viewpoint of improving repulsion resistance. , or 1.5 or less.
- the amount of the aromatic ring-free cross-linking agent used is not particularly limited. , typically 0.1 parts by weight or more). From the viewpoint of improving the cohesive force, the amount of the aromatic ring-free cross-linking agent used relative to 100 parts by weight of the polyester polymer is usually about 0.5 parts by weight or more, preferably about 1 part by weight or more. , more preferably about 2 parts by weight or more (eg, more than 2 parts by weight), still more preferably 2.5 parts by weight or more. In addition, the amount of the aromatic ring-free cross-linking agent used relative to 100 parts by weight of the polyester polymer is usually about 12 parts by weight or less, for example about 10 parts by weight or less, and preferably about 8 parts by weight or less.
- the content is about 5 parts by weight or less. According to the technique disclosed herein, it is possible to obtain a cohesive force that preferably exhibits high shear adhesive strength, repulsion resistance, etc., with the use amount of the cross-linking agent being limited as described above.
- the amount of the non-aromatic ring-containing cross-linking agent used is more preferably 4 parts by weight or less, more preferably about 3.5 parts by weight or less, relative to 100 parts by weight of the polyester polymer.
- the amount used is not particularly limited.
- the amount of the aromatic ring-free isocyanate cross-linking agent to be used can be, for example, about 0.5 parts by weight or more and about 10 parts by weight or less with respect to 100 parts by weight of the polyester polymer. From the viewpoint of improving the cohesive force, the amount of the aromatic ring-free isocyanate cross-linking agent used relative to 100 parts by weight of the polyester polymer is usually about 1 part by weight or more, preferably about 2 parts by weight or more.
- the amount of the aromatic ring-free isocyanate cross-linking agent used relative to 100 parts by weight of the polyester polymer is usually about 8 parts by weight or less, preferably about 5 parts by weight or less. According to the technology disclosed herein, it is possible to obtain a cohesive force that preferably exhibits shear adhesive strength, repulsion resistance, etc., with the use amount of the aromatic ring-free isocyanate cross-linking agent limited as described above.
- the amount of the aromatic ring-free isocyanate crosslinking agent used relative to 100 parts by weight of the polyester polymer is more preferably 4.5 parts by weight or less, still more preferably about 4.2 parts by weight or less, and particularly preferably 3.8 parts by weight or less. (For example, 3.5 parts by weight or less), and may be about 3.2 parts by weight or less.
- the pressure-sensitive adhesive composition disclosed herein may optionally contain a cross-linking agent containing an aromatic ring (aromatic ring-containing cross-linking agent) in addition to the non-aromatic ring-containing cross-linking agent within a range that does not impair the effects of the invention.
- aromatic ring-containing cross-linking agents are not particularly limited. Those having a ring (eg, aromatic polyisocyanate-based compounds, etc.) can be used.
- the aromatic ring-containing cross-linking agents can be used singly or in combination of two or more.
- the total amount of the cross-linking agent used is not particularly limited. .1 part by weight or more). From the viewpoint of improving the cohesive force, the total amount of the cross-linking agent used relative to 100 parts by weight of the polyester polymer is generally appropriate to be about 0.5 parts by weight or more, preferably about 1 part by weight or more, more preferably about 1 part by weight or more. is about 2 parts by weight or more (eg, more than 2 parts by weight), more preferably 2.5 parts by weight or more. In addition, the total amount of the cross-linking agent used relative to 100 parts by weight of the polyester polymer is usually about 12 parts by weight or less, for example about 10 parts by weight or less, preferably about 8 parts by weight or less. It is preferably 5 parts by weight or less.
- the total amount of the cross-linking agent used with respect to 100 parts by weight of the polyester polymer is more preferably 4 parts by weight or less, and still more preferably about 3.5 parts by weight or less.
- crosslinking catalyst In the technology disclosed herein, it is preferable to use a cross-linking catalyst in addition to the above-described cross-linking agent in order to promote the cross-linking reaction more effectively.
- cross-linking catalysts include zirconium-containing compounds (zirconium-based catalysts) such as zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium ethylacetoacetate, and zirconium octylate compounds; dioctyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, Tin (Sn)-containing compounds (tin-based catalysts) such as dibutyltin diacetylacetonate, tetra-n-butyltin, trimethyltin hydroxide, butyltin oxide; aluminum secondary butoxide, aluminum trisacetylacetonate, aluminum bisethylace
- the cross-linking catalyst does not contain a tin-containing compound from the viewpoint of environmental impact and safety.
- a non-tin-based compound as a cross-linking catalyst, the amount of tin-based compound (typically organic tin) used in the pressure-sensitive adhesive can be reduced.
- the cross-linking catalyst does not include an iron-based catalyst. For example, in a mode of use in which the adhesive is required to have transparency or optical properties, it is desirable to avoid using an iron-based compound that may color the adhesive.
- the amount of cross-linking catalyst used is not particularly limited.
- the amount of the crosslinking catalyst used can be, for example, about 0.001 parts by weight or more, preferably about 0.01 parts by weight or more, and about 0.05 parts by weight or more (for example, 0.10 parts by weight or more). Further, the amount of the cross-linking catalyst used can be, for example, about 3 parts by weight or less, preferably about 1 part by weight or less, and about 0.3 parts by weight or less with respect to 100 parts by weight of the polyester polymer. good too.
- the pressure-sensitive adhesive composition disclosed herein may contain a hydrolysis-resistant agent (also referred to as an anti-hydrolysis agent).
- a hydrolysis-resistant agent also referred to as an anti-hydrolysis agent.
- the hydrolysis-resistant agent is not particularly limited, and known or commonly used hydrolysis-resistant agents can be used. Examples thereof include oxazoline group-containing compounds, epoxy group-containing compounds, carbodiimide group-containing compounds, and the like. Among them, carbodiimide group-containing compounds are preferred.
- the hydrolysis resistant agents can be used singly or in combination of two or more.
- Carbodiimide group-containing compounds include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di- ⁇ -naphthylcarbodiimide, and monofunctional cyclic structures. carbodiimide and the like.
- the monofunctional cyclic structure carbodiimide has one carbodiimide group in the molecular structure, and the carbodiimide group is formed by a bonding group composed of an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof.
- the said bonding group may also contain a hetero atom and a substituent.
- Preferred examples of carbodiimide group-containing compounds include dicyclohexylcarbodiimide, diisopropylcarbodiimide, and monofunctional cyclic structure carbodiimide.
- the amount of the hydrolysis-resistant agent (preferably, a carbodiimide group-containing compound) to be used is not particularly limited, and is about 0.00% per 100 parts by weight of the polyester polymer so that the effect of containing the hydrolysis-resistant agent is preferably exhibited.
- 05 parts by weight or more preferably about 0.1 parts by weight or more, for example, about 0.3 parts by weight or more.
- the upper limit of the amount of the hydrolysis-resistant agent used is, for example, about 5 parts by weight or less, preferably about 3 parts by weight or less, for example, 1 part by weight or less, relative to 100 parts by weight of the polyester polymer. may be
- the pressure-sensitive adhesive composition may optionally contain leveling agents, fillers, plasticizers, softeners, colorants (pigments, dyes, etc.), antistatic agents, anti-aging agents, and ultraviolet absorbers. , antioxidants, light stabilizers, and other additives commonly used in the field of adhesives.
- leveling agents fillers, plasticizers, softeners, colorants (pigments, dyes, etc.), antistatic agents, anti-aging agents, and ultraviolet absorbers.
- antioxidants, light stabilizers, and other additives commonly used in the field of adhesives As for the various additives mentioned above, conventionally known ones can be used in a conventional manner, and since they do not particularly characterize the present invention, detailed description thereof will be omitted.
- the pressure-sensitive adhesive layer (layer made of pressure-sensitive adhesive) disclosed herein is formed from the pressure-sensitive adhesive composition containing the above polyester-based polymer, tackifying resin and cross-linking agent.
- a solvent-type adhesive composition containing an adhesive in an organic solvent is suitable from the viewpoint of adhesive properties and the like.
- Organic solvents such as toluene and ethyl acetate can be used as the organic solvent.
- the present specification provides a pressure-sensitive adhesive composition containing one or more of the components that can be included in the pressure-sensitive adhesive layer disclosed herein.
- the pressure-sensitive adhesive composition contains an aromatic ring-containing polyester polymer in which 50% or more of the constituent carbon is biomass-derived carbon, and further contains an aromatic ring-containing tackifying resin and a non-aromatic ring-containing cross-linking agent. could be.
- the pressure-sensitive adhesive composition may further contain components such as a cross-linking catalyst and an anti-hydrolysis agent. The details of the components that can be contained in the pressure-sensitive adhesive composition are as described for the pressure-sensitive adhesive layer, and redundant description will be omitted.
- a pressure-sensitive adhesive layer can be formed from the pressure-sensitive adhesive composition by a conventionally known method.
- a PSA layer is formed on the surface by applying a PSA composition to the surface having releasability (release surface) and then curing the PSA composition. Forming can form an adhesive sheet.
- a method (direct method) of forming a pressure-sensitive adhesive layer by directly applying (typically applying) a pressure-sensitive adhesive composition to the substrate and curing the composition is preferably adopted. can do.
- a method of applying a pressure-sensitive adhesive composition to a surface having releasability (release surface) and curing the composition to form a pressure-sensitive adhesive layer on the surface and transferring the pressure-sensitive adhesive layer to a substrate may be adopted.
- the release surface the surface of a release liner, the back surface of a base material subjected to a release treatment, or the like can be used.
- curing of the pressure-sensitive adhesive composition can be performed by subjecting the pressure-sensitive adhesive composition to a curing treatment such as drying, crosslinking, polymerization, or cooling. Two or more curing treatments may be performed simultaneously or stepwise.
- the pressure-sensitive adhesive layer disclosed herein is typically formed continuously, but is not limited to such a form, and is formed in a regular or random pattern such as dots or stripes. It may be a pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive composition is carried out using known or commonly used coaters such as gravure roll coaters, reverse roll coaters, kiss roll coaters, dip roll coaters, die coaters, bar coaters, knife coaters, and spray coaters. can be done. Alternatively, the adhesive composition may be applied by impregnation, curtain coating, or the like.
- the pressure-sensitive adhesive composition can be dried at room temperature or under heating. From the viewpoint of promoting the cross-linking reaction, improving production efficiency, etc., it is preferable to dry the pressure-sensitive adhesive composition under heating. The drying temperature can be, for example, about 40 to 150°C, and usually about 40 to 130°C is preferable.
- aging may be performed for the purpose of adjusting migration of components in the pressure-sensitive adhesive layer, progressing the cross-linking reaction, relaxing distortion that may exist in the substrate and the pressure-sensitive adhesive layer, and the like. preferable.
- the aging conditions are not particularly limited, and can be, for example, about 70° C. or lower (typically about 40 to 70° C.) for 1 day or longer (eg, 3 days or longer).
- the thickness of the pressure-sensitive adhesive layer is not particularly limited, and can be appropriately selected depending on the purpose.
- the thickness of the adhesive layer can be, for example, about 2 ⁇ m to 500 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer is usually 3 ⁇ m or more, preferably 5 ⁇ m or more.
- the thickness of the pressure-sensitive adhesive layer may be, for example, 8 ⁇ m or more, preferably 12 ⁇ m or more, and may be 15 ⁇ m or more. It may be 18 ⁇ m or more.
- the thickness of the adhesive layer may be, for example, 200 ⁇ m or less, 150 ⁇ m or less, 100 ⁇ m or less, 70 ⁇ m or less, 50 ⁇ m or less, or 30 ⁇ m or less. good. In an aspect in which thickness reduction is emphasized, the thickness of the pressure-sensitive adhesive layer may be, for example, 25 ⁇ m or less, or 22 ⁇ m or less.
- the pressure-sensitive adhesive sheet disclosed herein is a double-sided pressure-sensitive adhesive sheet having pressure-sensitive adhesive layers on both sides of a substrate, the thickness of each pressure-sensitive adhesive layer may be the same or different.
- Bio rate of adhesive layer Since the technology disclosed herein is implemented using an adhesive containing a polyester-based polymer having a bio rate of 50% or more, the adhesive layer (and the adhesive composition. Unless otherwise specified, the same applies hereinafter. ) has a bio rate greater than or equal to a predetermined value. Although not particularly limited, the bio rate of the adhesive layer may be about 30% or more (for example, more than 30%), suitably about 40% or more, and 50% or more. is preferred.
- a high bio rate of the pressure-sensitive adhesive layer means that the amount of fossil resource-based materials such as petroleum used is small. By designing the pressure-sensitive adhesive layer to have a high bio rate, the pressure-sensitive adhesive layer as a whole can be less dependent on fossil resource-based materials.
- the bio rate of the adhesive layer may be 55% or higher, 60% or higher, 70% or higher, or 75% or higher.
- the upper limit of the bio rate is by definition 100%, in the pressure-sensitive adhesive layer disclosed herein, the bio rate can typically be less than 100% because the ingredients may include materials derived from fossil resources.
- the bio-ratio of the adhesive layer may be, for example, less than 90%, and more emphasis is placed on adhesive performance. It may be less than 80% or less than 70%.
- the biorate of the adhesive layer that is, the ratio of biomass-derived carbon to the total carbon contained in the adhesive layer, can be estimated from the carbon isotope content with a mass number of 14 measured according to ASTM D6866. can.
- the biorate of the base material and the biorate of the pressure-sensitive adhesive sheet, which will be described later, can also be estimated in a similar manner.
- the pressure-sensitive adhesive sheet disclosed herein may be in the form of a pressure-sensitive adhesive sheet with a substrate having a pressure-sensitive adhesive layer on one or both sides of the substrate.
- Various sheet-like substrates can be used as the substrate, and for example, resin films, papers, cloths, rubber sheets, foam sheets, metal foils, composites thereof, and the like can be used.
- substrates that are less likely to generate dust for example, fine fibers or particles such as paper dust
- substrates that do not contain fibrous materials such as paper and cloth are preferable, and for example, resin films, rubber sheets, foam sheets, metal foils, composites thereof, and the like can be preferably used.
- resin films examples include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate; vinyl chloride resin films; polyethylene (PE), polypropylene (PP), ethylene-propylene copolymers, ethylene-butene copolymers, etc. vinylidene chloride resin film; vinyl acetate resin film; polystyrene film; polyacetal film; polyimide film;
- rubber sheets include natural rubber sheets and butyl rubber sheets.
- foam sheets include foamed polyurethane sheets and foamed polyolefin sheets.
- metal foil examples include aluminum foil and copper foil.
- a resin film is preferably used as the base material.
- a resin film is preferably used as a material excellent in dimensional stability, thickness accuracy, economy (cost), workability and tensile strength.
- resin films for example, polyester films such as PET films, which will be described later
- Such recyclable resin films and recycled resin films are also called recycled films.
- Such recyclability of the resin film can also be applied to the resin film used for the release liner described above.
- the term "resin film” is typically a non-porous film, and is a concept distinguished from so-called nonwoven fabrics and woven fabrics.
- a polyester film can be preferably used as the substrate from the viewpoint of strength and workability.
- a polyester resin containing polyester obtained by polycondensation of a dicarboxylic acid and a diol as a main component is typically used.
- dicarboxylic acid constituting the polyester examples include phthalic acid, isophthalic acid, terephthalic acid, 2-methylterephthalic acid, 5-sulfoisophthalic acid, 4,4′-diphenyldicarboxylic acid, and 4,4′-diphenyletherdicarboxylic acid.
- Aromatic dicarboxylic acids such as 6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid; Alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid ; aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanoic acid; unsaturated dicarboxylic acids such as maleic acid, male
- 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 - Alicyclic diols such as cyclohexanedimethylol, xylylene glycol, 4,4'-dihydroxybiphenyl, 2,2-bis(4'-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone and other aromatic diols ; and the
- Aliphatic diols are preferred from the viewpoint of transparency and the like, and ethylene glycol is particularly preferred.
- the ratio of the aliphatic diol (preferably ethylene glycol) to the diols 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 consist essentially of ethylene glycol.
- biomass-derived ethylene glycol typically, biomass ethylene glycol obtained using biomass ethanol as a raw material
- biomass-derived ethylene glycol typically, biomass ethylene glycol obtained using biomass ethanol as a raw material
- the proportion of biomass-derived ethylene glycol in the ethylene glycol constituting the polyester may be, for example, 50% by weight or more, preferably 75% by weight or more, and may be 90% by weight or more, or 95% by weight. % or more. Substantially all of the ethylene glycol may be biomass-derived ethylene glycol.
- polyester resin films include polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polyethylene naphthalate (PEN) film, and polybutylene naphthalate film.
- the polyester film substrate may contain a polymer other than the above polyester in addition to polyester.
- Preferred examples of the polymer other than polyester include those other than polyester among the various polymer materials exemplified as the resin film that can constitute the base material.
- the polyester film substrate disclosed herein contains a polymer other than the polyester in addition to the polyester, the content of the polymer other than the polyester is preferably less than 100 parts by weight per 100 parts by weight of the polyester. 50 parts by weight or less is preferable, 30 parts by weight or less is more preferable, and 10 parts by weight or less is even more preferable.
- the content of the polymer other than polyester may be 5 parts by weight or less, or may be 1 part by weight or less with respect to 100 parts by weight of polyester.
- the technology disclosed herein can be preferably practiced, for example, in a mode in which 99.5 to 100% by weight of the polyester film substrate is polyester.
- a polyolefin film can be preferably used as the substrate from the viewpoint of strength and flexibility.
- a polyolefin film is a film whose main component is a polymer containing ⁇ -olefin as a main monomer (main component among monomer components). The proportion of the polymer is usually 50% by weight or more (eg 80% by weight or more, typically 90-100% by weight).
- Specific examples of polyolefins include those containing ethylene as the main monomer (polyethylene) and those containing propylene as the main monomer (polypropylene).
- the polyethylene may be a homopolymer of ethylene, or a copolymer of ethylene and another olefin (e.g., one or more selected from ⁇ -olefins having 3 to 10 carbon atoms). may be ethylene and monomers other than olefins (e.g., one or more selected from ethylenically unsaturated monomers such as vinyl acetate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate) and may be a copolymer of
- the polypropylene may be a homopolymer of propylene, and propylene and other olefins (for example, one or more selected from ⁇ -olefins having 2,4 to 10 carbon atoms) or a copolymer of propylene and a monomer other than an olefin.
- the substrates disclosed herein may contain only one of the above polyolefins, or may contain two or more polyole
- the polyolefin film substrate may contain a polymer other than the above polyolefin in addition to polyolefin.
- Preferred examples of the polymer other than polyolefin include those other than polyolefin among the various polymer materials exemplified as the resin film that can constitute the base material.
- the content of the polymer other than the polyolefin is preferably less than 100 parts by weight per 100 parts by weight of the polyolefin.
- the content of the polymer other than polyolefin may be 5 parts by weight or less, or may be 1 part by weight or less with respect to 100 parts by weight of polyolefin.
- the technology disclosed herein can be preferably practiced, for example, in a mode in which 99.5 to 100% by weight of the polyolefin film substrate is polyolefin.
- the base material disclosed here preferably contains a biomass material.
- the biomass material that can constitute the base material is not particularly limited, but examples include biomass PET, biomass polyester such as biomass polytrimethylene terephthalate (biomass PTT); polylactic acid; biomass high density polyethylene (biomass HDPE), biomass low density polyethylene.
- biomass LDPE biomass polyethylene such as biomass linear low density polyethylene (biomass LLDPE), biomass polyolefin such as biomass polypropylene (biomass PP); biomass poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) biomass polyamides such as polyhexamethylene sebacamide and poly(xylylene sebacamide); biomass polyurethanes such as biomass polyester ether urethane and biomass polyether urethane; cellulosic resin; These can be used individually by 1 type or in combination of 2 or more types. Among them, biomass PET and biomass PTT are preferred, and biomass HDPE, biomass LDPE, biomass LLDPE, biomass PP and biomass PET are particularly preferred.
- the biomass material described above is a resin material, it can be preferably applied to a configuration in which the substrate is a resin film.
- the amount of fossil resource-based material used can be reduced in the pressure-sensitive adhesive sheet having a resin film (preferably polyolefin film) as a base material.
- the bio rate of the base material is preferably 20% or more, more preferably 35% or more.
- the bio rate of the base material may be, for example, 50% or higher, 70% or higher, 85% or higher, or 90% or higher.
- the upper limit of the bio rate is 100% or less, but in some embodiments, the bio rate of the base material may be, for example, 80% or less, or even 60% or less, in consideration of workability, strength, etc. Well, it may be 40% or less, or it may be less than 20%.
- the base material may have transparency, or may have light shielding or dimming properties.
- the substrate eg, resin film
- the substrate can contain a colorant.
- the light transmittance (light shielding property) of the substrate can be adjusted. Adjusting the light transmittance (for example, normal light transmittance) of the substrate can also help adjust the light transmittance of the substrate and further the light transmittance of the pressure-sensitive adhesive sheet including the substrate.
- coloring agent conventionally known pigments and dyes can be used in the same manner as the coloring agent that can be contained in the adhesive layer.
- the coloring agent is not particularly limited, and may be, for example, black, gray, white, red, blue, yellow, green, yellow-green, orange, purple, gold, silver, pearl color, and the like.
- the substrate may be colored with a colored layer arranged on the surface of the base film (preferably resin film).
- the base film may or may not contain a coloring agent.
- the colored layer may be arranged on either one surface of the base film, or may be arranged on both surfaces. In the configuration in which the colored layers are arranged on both surfaces of the base film, the configurations of the colored layers may be the same or different.
- the color and transparency of the pressure-sensitive adhesive sheet can be adjusted, and desired design properties, light-shielding properties, and hiding properties can be obtained.
- the color of the colored layer is not particularly limited, and various colors can be adopted depending on the purpose.
- the colored layer may be a black layer (eg, black printed layer) formed by, for example, black printing.
- the colored layer can be formed, for example, by applying a colored layer-forming composition containing a coloring agent and a binder to the base film.
- a colored layer-forming composition containing a coloring agent and a binder
- Materials known in the field of coatings or printing can be used as binders without particular limitations. Examples include polyurethane, phenol resin, epoxy resin, urea melamine resin, polymethyl methacrylate, and the like.
- the composition for forming a colored layer may be, for example, a solvent type, an ultraviolet curable type, a heat curable type, or the like.
- the formation of the colored layer can be carried out by adopting means conventionally used for forming the colored layer without particular limitation. For example, a method of forming a colored layer (printed layer) by printing such as gravure printing, flexographic printing, and offset printing can be preferably employed.
- the colored layer may have a single layer structure consisting entirely of one layer, or may have a multilayer structure including two, three or more sub-colored layers.
- a colored layer having a multi-layer structure including two or more sub-colored layers can be formed, for example, by repeatedly applying (for example, printing) a composition for forming a colored layer.
- the colors and blending amounts of the colorants contained in each sub-colored layer may be the same or different. From the viewpoint of preventing the occurrence of pinholes and increasing the reliability of light leakage prevention, it is particularly significant to have a multi-layered structure in the colored layer for imparting light-shielding properties.
- a known pigment or dye can be appropriately selected according to the desired color.
- white pigments include, but are not limited to, titanium dioxide, zinc white, white lead, and the like.
- black pigments include carbon black, acetylene black, pine smoke, graphite and the like. These can be used individually by 1 type or in combination of 2 or more types.
- the content of the colorant is not limited to a specific range because it is set according to the required color tone, light transmittance, etc., but it is suitable to be about 1% by weight or more in the colored layer. and is preferably 2% by weight or more (eg 5% by weight or more), and may be 15% by weight or more.
- the content of the coloring agent is suitably about 65% by weight or less, preferably 30% by weight or less (for example, 15% by weight or less), and may be 8% by weight or less.
- the thickness of the entire colored layer is usually appropriately 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, and more preferably 0.7 ⁇ m or more.
- the thickness of the entire colored layer may be about 0.8 ⁇ m or more, or about 1 ⁇ m or more. In some other embodiments, the thickness of the entire colored layer may be 2 ⁇ m or more (for example, 3 ⁇ m or more) or 4 ⁇ m or more from the viewpoint of obtaining sufficient light shielding properties.
- the thickness of the entire colored layer is usually appropriately 10 ⁇ m or less, preferably 7 ⁇ m or less, and more preferably 5 ⁇ m or less. In some embodiments, the thickness of the entire colored layer can be about 3 ⁇ m or less, or even about 2 ⁇ m or less. In the colored layer including two or more sub-colored layers, the thickness of each sub-colored layer is preferably about 0.5 ⁇ m to 2 ⁇ m.
- the surface of the substrate (for example, resin film, rubber sheet, foam sheet, etc.) on which the adhesive layer is arranged (surface on the adhesive layer side) is subjected to corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, or alkali treatment.
- a known or conventional surface treatment such as formation of an undercoat layer may be applied.
- Such a surface treatment can 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 base material may not be subjected to a surface treatment for improving the anchoring property on the pressure-sensitive adhesive layer side surface.
- the undercoat agent (primer) used for the formation is not particularly limited, and can be appropriately selected from known ones.
- the thickness of the undercoat layer is not particularly limited, and may be, for example, more than 0.01 ⁇ m.
- the thickness of the undercoat layer is preferably less than 1.0 ⁇ m, and may be 0.7 ⁇ m or less, or 0.5 ⁇ m or less. Since primers are generally highly dependent on fossil resource-based materials, not having an excessively large thickness of the undercoat layer can be advantageous from the viewpoint of reducing the bio rate of the pressure-sensitive adhesive sheet, which will be described later.
- the back-treatment agent that can be used to form the back-treatment layer is not particularly limited, and may be a silicone-based back-treatment agent, a fluorine-based back-treatment agent, a long-chain alkyl-based back-treatment agent, or other known or commonly used treatment agents. It can be used depending on the application.
- the back surface treatment agents can be used singly or in combination of two or more.
- the base material may contain fillers (inorganic fillers, organic fillers, etc.), anti-aging agents, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, and plasticizers. , colorants (pigments, dyes, etc.) and other additives may be added.
- the blending ratio of various additives is usually about 30% by weight or less (for example, 20% by weight or less, typically 10% by weight or less).
- a pigment eg, white pigment
- the content is about 0.1 to 10% by weight (eg, 1 to 8% by weight, typically 1 to 5% by weight). Appropriate.
- the thickness of the base material is not particularly limited and can be appropriately selected according to the purpose, but is generally about 1 ⁇ m to 500 ⁇ m. From the standpoint of handleability of the substrate, the thickness of the substrate may be, for example, 1.5 ⁇ m or more, 2 ⁇ m or more, 3 ⁇ m or more, 4 ⁇ m or more, or 4.5 ⁇ m or more. Further, from the viewpoint of thinning the pressure-sensitive adhesive sheet, in some embodiments, the thickness of the substrate may be, for example, 150 ⁇ m or less, 100 ⁇ m or less, 50 ⁇ m or less, 25 ⁇ m or less, or 20 ⁇ m or less. Well, it may be 10 ⁇ m or less, 7 ⁇ m or less, less than 5 ⁇ m, or less than 4 ⁇ m.
- the thickness (total thickness) of the pressure-sensitive adhesive sheet disclosed herein is not particularly limited. It can range from 2 ⁇ m to 1000 ⁇ m. In some aspects, the thickness of the pressure-sensitive adhesive sheet is preferably about 5 ⁇ m to 500 ⁇ m (eg, 10 ⁇ m to 300 ⁇ m, typically 15 ⁇ m to 200 ⁇ m) in consideration of adhesive properties.
- the thickness of the pressure-sensitive adhesive sheet may be 100 ⁇ m or less (eg, 5 ⁇ m to 100 ⁇ m), 70 ⁇ m or less (eg, 5 ⁇ m to 70 ⁇ m), or 45 ⁇ m or less (eg, 5 ⁇ m to 5 ⁇ m). 45 ⁇ m), or 30 ⁇ m or less (for example, 5 ⁇ m to 30 ⁇ m).
- the adhesive sheet disclosed herein is preferably biomass-derived carbon. That is, it is preferable that the adhesive sheet has a bio rate of 30% or more.
- the bio rate of the adhesive sheet is preferably 40% or higher, may be 50% or higher, may be 60% or higher, may be 70% or higher, or may be 75% or higher.
- the upper limit of the bio-rate is 100%. The percentage may be less than 100%.
- the bio rate of the PSA sheet may be, for example, 90% or less, and more emphasis is placed on adhesive performance. In some cases, it may be 80% or less, or 70% or less.
- the bio rate of the pressure-sensitive adhesive layer matches the bio rate of the entire pressure-sensitive adhesive sheet.
- the PSA sheet disclosed herein preferably exhibits a shear adhesive strength exceeding 100 N/100 mm 2 .
- a pressure-sensitive adhesive sheet exhibiting such shear adhesive strength exhibits strong resistance to a dynamic load (i.e., shear force) that tends to shift the adhesive interface, and therefore has excellent adherend holding performance, and is used in portable electronic devices, for example. It can effectively prevent the occurrence of peeling when fixing the inner member.
- the adhesive sheet has a shear adhesive strength of preferably 180 N/100 mm 2 or more, more preferably 220 N/100 mm 2 or more, still more preferably 250 N/100 mm 2 or more, and particularly preferably 280 N/100 mm.
- the shear adhesive strength is not particularly limited, and generally the higher the better.
- the shear adhesive strength is, for example, It may be 700 N/100 mm 2 or less, or 500 N/100 mm 2 or less. The shear adhesive strength is measured by the method described in Examples below.
- the pressure-sensitive adhesive sheet disclosed herein has a passing level of repulsion resistance in a repulsion resistance test measured using a PET film having a thickness of 125 ⁇ m (that is, does not peel off) in Examples described later.
- the pressure-sensitive adhesive sheet with repulsion resistance described above has durability against bending, and exhibits adhesion reliability without lifting or peeling even when used by being attached to a curved surface such as a three-dimensional shape. can.
- the adhesive sheet according to some aspects preferably has a 180-degree peel strength (adhesive strength to SUS) of 10 N/20 mm or more to a stainless steel plate.
- a pressure-sensitive adhesive sheet exhibiting the above properties can be preferably used in a manner in which re-peeling is not intended, typically, because it is strongly bonded to an adherend.
- the adhesive strength may be, for example, 11 N/20 mm or more, preferably 12 N/20 mm or more, 13 N/20 mm or more, 14 N/20 mm or more, or 15 N/20 mm or more. It may be 20 mm or more.
- the upper limit of the adhesive strength is not particularly limited, and in some aspects, the adhesive strength may be, for example, 50 N/20 mm or less, 30 N/20 mm or less, or 25 N/20 mm or less. Specifically, the adhesion to SUS is measured by the method described in Examples below.
- the use of the pressure-sensitive adhesive sheet disclosed herein is not particularly limited, and it can be used for various purposes without limitation.
- the pressure-sensitive adhesive sheet can be used for the purpose of fixing, bonding, reinforcing, etc. of the members in a mode of being attached to the members constituting the electronic device.
- the PSA sheet disclosed herein can be preferably used for fixing or joining members, for example, in the form of a double-sided PSA sheet. In such applications, it is particularly significant that the pressure-sensitive adhesive sheet has good shear adhesion to prevent peeling.
- the double-sided pressure-sensitive adhesive sheet may be substrateless or may have a substrate.
- a substrate-less double-sided PSA sheet or a substrate-attached double-sided PSA sheet using a thin substrate can be preferably employed.
- a thin base material a base material having a thickness of 10 ⁇ m or less (for example, less than 5 ⁇ m) can be preferably used.
- the adhesive sheet disclosed here is suitable for use in fixing members in mobile electronic devices, for example.
- the pressure-sensitive adhesive sheet disclosed herein has high adhesive reliability based on high shear adhesive strength, and is therefore suitable for use in portable electronic devices that require high performance.
- the use of adhesive sheets with high shear adhesive strength is particularly significant for bonding and fixing in portable electronic devices, since the adhesive area is limited.
- Non-limiting examples of the above portable electronic devices include mobile phones, smartphones, tablet computers, notebook computers, various wearable devices (for example, wrist wear type worn on the wrist like a wristwatch, Eyewear type including glasses type (monocular type and binocular type, including head-mounted type), clothes type attached to shirts, socks, hats, etc.
- the pressure-sensitive adhesive sheet disclosed herein can be preferably used, for example, for the purpose of fixing a pressure-sensitive sensor and other members in a portable electronic device having a pressure-sensitive sensor among such portable electronic devices.
- the adhesive sheet includes a device for indicating a position on the screen (typically a pen-type or mouse-type device) and a device for detecting the position.
- a device for indicating a position on the screen typically a pen-type or mouse-type device
- a device for detecting the position In order to fix a pressure sensor and other members in an electronic device (typically a portable electronic device) with a function that allows specifying an absolute position on a (typically touch panel) can be used.
- the term “portable” means not only being able to be simply carried, but also having a level of portability that allows an individual (a typical adult) to carry it relatively easily. shall mean.
- the pressure-sensitive adhesive sheet disclosed herein since the pressure-sensitive adhesive sheet disclosed herein has good repulsion resistance, it exhibits excellent adhesion reliability against bending based on the repulsion resistance, and can be applied to curved surfaces such as three-dimensional shapes. It is preferably used in a mode in which it is attached to a curved surface of a portable electronic device having a shape (for example, a portable electronic device having a display having a curved surface shape).
- the interior of the portable electronic device may include a heat-generating element such as a battery, and thus may be exposed to temperatures of, for example, 40° C. or higher. It is significant to use a pressure-sensitive adhesive sheet with excellent adhesion to obtain adhesion reliability without lifting or peeling even at high temperatures as described above.
- the material (adherend material) to which the pressure-sensitive adhesive sheet disclosed herein is attached is not particularly limited, but examples thereof include metal materials such as copper, iron, aluminum, and stainless steel; plastic materials); inorganic materials such as glass; and the like.
- the resin material include polyimide-based resin, acrylic-based resin, polyethernitrile-based resin, polyethersulfone-based resin, polyester-based resin (PET-based resin, polyethylene naphthalate-based resin, etc.), polyvinyl chloride-based resin, and polyphenylene sulfide.
- the adhesive sheet disclosed herein is preferably used for bonding the metal materials, polyester resins such as PET, polyimide resins, aramid resins, polyphenylene sulfide resins, polycarbonate resins, and the like.
- the above materials may be member materials that constitute products such as portable electronic devices.
- the adhesive sheet disclosed herein can be used by being attached to a member made of the above materials.
- FIG. 4 is an example schematically showing a mobile electronic device (smartphone) using the adhesive sheet disclosed herein.
- a battery (heat generating element) 540 is built inside a housing 520 of the portable electronic device 500 .
- the portable electronic device 500 is configured including an adhesive sheet 550 .
- the adhesive sheet 550 has the form of a double-sided adhesive sheet (double-sided adhesive sheet) for fixing members constituting the portable electronic device 500 .
- the portable electronic device 500 includes a touch panel 570 whose display unit also functions as an input unit.
- the pressure-sensitive adhesive sheet disclosed herein is preferably used as a constituent element (member joining means) of the portable electronic device as described above.
- a portable electronic device A housing and a touch panel whose display unit also functions as an input unit, A heating element (e.g., battery) is built in the housing, At least a first member and a second member among a large number of members constituting the portable electronic device are joined by an adhesive sheet,
- the pressure-sensitive adhesive sheet has a pressure-sensitive adhesive layer containing a polyester-based polymer in which 50% or more of the constituent carbon is biomass-derived carbon,
- the pressure-sensitive adhesive layer further comprises a tackifying resin and a cross-linking agent,
- the portable electronic device wherein the polyester-based polymer contains an aromatic ring, the tackifying resin also contains an aromatic ring, and the cross-linking agent does not contain an aromatic ring.
- a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing a polyester-based polymer in which 50% or more of the constituent carbon is biomass-derived carbon,
- the pressure-sensitive adhesive layer further comprises a tackifying resin and a cross-linking agent,
- a measurement sample is prepared by cutting an adhesive sheet (double-sided adhesive sheet) into a size of 10 mm ⁇ 10 mm. In an environment of 23° C. and 50% RH, each adhesive surface of the measurement sample is superimposed on the surfaces of two stainless steel plates (SUS304BA plates), and pressed by reciprocating a 2 kg roller once. After leaving it under the same environment for 2 days, the shear adhesive strength [N/100 mm 2 ] is measured using a tensile tester under the conditions of a tensile speed of 10 mm/min and a peeling angle of 0 degree. If the shear adhesive strength exceeds 100 N/100 mm 2 , it is evaluated as having high shear adhesive strength.
- a single-sided adhesive sheet (single-sided adhesive sheet)
- the non-adhesive surface of the sheet is fixed to a stainless steel plate with an adhesive or the like, and other than that the measurement is performed in the same manner as described above.
- a tensile tester a universal tension/compression tester (product name “TG-1kN”, manufactured by Minebea Co., Ltd.) can be used.
- a polycarbonate (PC) plate 50 having a length of 30 mm, a width of 10 mm and a thickness of 2 mm and a PET film 60 having a length of 100 mm, a width of 10 mm and a thickness of 125 ⁇ m are prepared, The PC board 50 and the PET film 60 are superimposed so that one end in the longitudinal direction is aligned, and the PC board 50 and the PET film 60 are fixed with the remaining part of the PET film 60 protruding from the other end of the PC board 50.
- a commercially available double-sided adhesive tape (“No. 5000NS” manufactured by Nitto Denko Corporation) is used for the fixing.
- a pressure-sensitive adhesive sheet sample piece 70 is prepared by cutting the pressure-sensitive adhesive sheet according to each example, the pressure-sensitive adhesive surfaces of which are protected by two release liners, into a size of 10 mm ⁇ 10 mm.
- the surface of the PC board 50 opposite to the fixing surface of the PET film is placed on the upper side, one release liner is peeled off from the adhesive sheet sample piece 70, and the other end in the longitudinal direction of the PC board 50 and the adhesive sheet sample piece are attached.
- the adhesive sheet sample piece 70 is attached and fixed to the upper surface of the PC board 50 so that one side of the adhesive sheet sample piece 70 is aligned.
- the fixing is performed by reciprocating the upper surface of the adhesive sheet sample piece 70 protected by the other release liner with a 2 kg roller once. Next, under an environment of 23° C.
- the other release liner of the adhesive sheet sample piece 70 attached to the PC board 50 was peeled off, and the PC board 50 was left as shown in FIG.
- the protruding part (length 70 mm) from the PC board 50 of the PET film 60 fixed to the PC board 50 is folded back to the PC board 50 side, and the adhesive sheet sample piece 70 and the other end (free end) of the PET film 60 are aligned.
- a roller of 0.1 kg is reciprocated once over the PET film 60 to fix the other end of the folded PET film 60 to the upper surface of the PC board 50 via the adhesive sheet sample piece 70 . Whether or not the PET film 60 was peeled off from the adhesive sheet sample piece 70 was observed for 24 hours in an environment of 60° C.
- the adhesive holding power of the adhesive sheet sample piece 70 in the thickness direction of the adhesive sheet is evaluated as repulsion resistance.
- the state of adhesion between the adhesive sheet sample piece 70 and the PET film 60 is indicated as " ⁇ " when the adhesive sheet sample piece 70 and the PET film 60 are maintained in an environment of 60°C and 95% RH for 24 hours, and the adhesive state of the adhesive sheet sample piece 70 and the PET film 60.
- " ⁇ " indicates the case where was held at room temperature for 24 hours, and the case where the PET film 60 was peeled off as shown in FIG. It is judged as "x”. If the result of the repulsion resistance test is ⁇ or ⁇ , it is evaluated to have good repulsion resistance (that is, pass), and if it is ⁇ , the repulsion resistance is evaluated to be insufficient (that is, fail).
- a measurement sample is prepared by cutting the adhesive sheet into a size of 20 mm in width and 150 mm in length. In an environment of 23° C. and 50% RH, the adhesive surface of the measurement sample is exposed, and the adhesive surface is press-bonded to a stainless steel plate (SUS304BA plate) as an adherend by reciprocating a 2-kg rubber roller once. This is left in an environment of 23 ° C. and 50% RH for 30 minutes, and then in accordance with JIS Z0237: 2000 using a tensile tester under the same environment, a peel angle of 180 degrees and a tensile speed of 300 mm / min. The peel strength (adhesive strength to SUS) [N/20 mm] is measured under the conditions.
- SUS304BA plate stainless steel plate
- the tensile tester a universal tensile and compression tester (equipment name “Tensile/compression tester, TCM-1kNB”, manufactured by Minebea Co., Ltd.) can be used.
- the adhesive strength of the object to be measured can be reinforced by applying a suitable backing material.
- the backing material for example, a PET film having a thickness of about 50 ⁇ m can be used, and this backing material was used in the examples.
- Synthesis example 1 A four-necked separable flask was equipped with a stirrer, a thermometer, a nitrogen tube and a water separator, and 100 g of ethylene glycol (manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 62), dimer acid (product name "Pripol 1009", Croda Co., Ltd.) was added.
- ethylene glycol manufactured by Tokyo Kasei Kogyo Co., Ltd., molecular weight 62
- dimer acid product name "Pripol 1009", Croda Co., Ltd.
- polyester polymer (A2) 915 g of molecular weight 567), 0.46 g of di-n-butyltin oxide (manufactured by Kishida Chemical Co., Ltd., molecular weight of 249) as a polymerization catalyst, and 40 g of xylene as a reaction water discharge solvent were charged, and the temperature was raised to 180° C. while stirring in a nitrogen atmosphere. and held at this temperature. After a while, outflow and separation of the reaction water was observed, and the reaction started to progress. The reaction was continued for about 24 hours to obtain a polyester polymer (A2) with a bio rate of 89%.
- This polyester polymer (A2) had an Mw of 100,000 and a glass transition temperature (Tg) of -36°C.
- Example 1 To 100 parts of the polyester polymer (A1), 40 parts of a terpene phenol resin (trade name "YS Polyster S145", manufactured by Yasuhara Chemical Co., Ltd., phenol ratio 22%, hereinafter sometimes referred to as "S145") as a tackifying resin, 3 parts of an isocyanurate form of hexamethylene diisocyanate as a cross-linking agent A (trade name "Coronate HX", manufactured by Tosoh Corporation, containing no aromatic ring, hereinafter also referred to as a "trifunctional cross-linking agent"), and an organic zirconium compound (product name "Orgatics ZC-162", manufactured by Matsumoto Fine Chemical Co., Ltd.) 0.13 parts, and a carbodiimide group-containing compound (trade name "Carbodilite V-03", manufactured by Nisshinbo Chemical Co., Ltd.) as an anti-hydrolysis agent.
- a terpene phenol resin trade name "YS
- an adhesive composition (adhesive solution).
- This adhesive solution was applied to the release-treated surface of a release-treated polyethylene terephthalate (PET) film (trade name “Diafoil MRF #38”, manufactured by Mitsubishi Chemical Corporation) so that the thickness after drying was 20 ⁇ m. , and dried at 120°C for 3 minutes to obtain an adhesive layer.
- the pressure-sensitive adhesive layer was attached to the release-treated surface of a release-treated PET film (trade name “Diafoil MRE #38”, manufactured by Mitsubishi Chemical Corporation), and left to stand at 50° C. for 3 days. A material-less pressure-sensitive adhesive sheet was obtained.
- Example 2 As a cross-linking catalyst, instead of the organic zirconium compound, 0.01 part of an organic tin compound (trade name "dibutyltin dilaurate (IV)", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used in the same manner as in Example 1. A pressure-sensitive adhesive composition according to Example was prepared, and a substrate-less pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1, except that this pressure-sensitive adhesive composition was used.
- an organic tin compound trade name "dibutyltin dilaurate (IV)"
- Example 3 The amount of the cross-linking agent used was changed to 4 parts with respect to 100 parts of the polyester polymer (A1), and as a cross-linking catalyst, an organic aluminum compound (trade name “Nasem Aluminum”, Nippon Kagaku Sangyo Co., Ltd.) was used instead of the organic zirconium compound. (manufactured) 0.13 parts.
- a pressure-sensitive adhesive composition according to this example was prepared in the same manner as in Example 1, and a substrate-less pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that this pressure-sensitive adhesive composition was used.
- Example 4 To 100 parts of polyester polymer (A3), 40 parts of terpene phenol resin (trade name “YS Polystar G150", manufactured by Yasuhara Chemical Co., Ltd., phenol ratio 32%, hereinafter sometimes referred to as "G150") as a tackifying resin, Crosslinking agent A (trade name "Coronate HX", manufactured by Tosoh Corporation) 2 parts, organic zirconium compound (trade name “Orgatics ZC-162", manufactured by Matsumoto Fine Chemical Co., Ltd.) 0.03 parts as a crosslinking catalyst, hydrolysis resistance agent 0.5 part of a carbodiimide group-containing compound (trade name “Carbodilite V-03” manufactured by Nisshinbo Chemical Co., Ltd.) was blended and ethyl acetate was added to prepare an adhesive composition (adhesive solution).
- a substrate-less pressure-sensitive adhesive sheet (thickness: 20 ⁇ m) according to this example was obtained in the same manner as in Example 1, except that
- Example 5 To 100 parts of the polyester polymer (A3), 40 parts of a terpene phenol resin (trade name "YS Polystar S145", manufactured by Yasuhara Chemical Co., Ltd., phenol ratio 22%) as a tackifying resin, a cross-linking agent A (trade name "Coronate HX", Tosoh Co., Ltd.) 3 parts, and 0.01 part of an organic tin compound (trade name "dibutyltin dilaurate (IV), manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as a crosslinking catalyst.
- a substrate-less pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 4, except that the pressure-sensitive adhesive composition was prepared and this pressure-sensitive adhesive composition was used.
- Example 6 To 100 parts of the polyester polymer (A1), 40 parts of a terpene phenol resin (trade name "YS Polystar G150", manufactured by Yasuhara Chemical Co., Ltd., phenol ratio 32%) as a tackifier resin, a cross-linking agent A (trade name “Coronate HX", Tosoh company) and 2 parts of a bifunctional cross-linking agent (trade name “Duranate D101”, manufactured by Asahi Kasei Corporation, containing no aromatic ring), and an organic zirconium compound (trade name “Orgatics ZC-162”, Matsumoto Fine Chemical Co., Ltd.) as a cross-linking catalyst.
- a terpene phenol resin trade name "YS Polystar G150", manufactured by Yasuhara Chemical Co., Ltd., phenol ratio 32%)
- a cross-linking agent A trade name “Coronate HX”, Tosoh company
- 2 parts of a bifunctional cross-linking agent trade name “Duranate D
- a substrate-less pressure-sensitive adhesive sheet (thickness: 20 ⁇ m) according to this example was obtained in the same manner as in Example 1, except that the obtained pressure-sensitive adhesive composition was used.
- Example 7 The polyester polymer (A2) was used instead of the polyester polymer (A1), and the amount of the cross-linking agent used was changed to 5 parts per 100 parts of the polyester polymer (A2).
- a pressure-sensitive adhesive composition according to this example was prepared in the same manner as in Example 2, and a substrate-less pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 2 except that this pressure-sensitive adhesive composition was used.
- Example 8> As a tackifying resin, instead of terpene phenol resin S145 (40 parts), 20 parts of hydrogenated rosin glycerin ester (trade name “Haritac SE10”, manufactured by Harima Chemicals Co., Ltd.) is used, and cross-linking containing an aromatic ring is used as a cross-linking agent. 2 parts of agent B (trade name "Coronate L", 75% ethyl acetate solution of trimethylolpropane/tolylene diisocyanate trimer adduct, manufactured by Tosoh Corporation) were used with respect to 100 parts of the polyester polymer (A1). .
- a pressure-sensitive adhesive composition according to this example was prepared in the same manner as in Example 1, and a substrate-less pressure-sensitive adhesive sheet according to this example was obtained in the same manner as in Example 1 except that the obtained pressure-sensitive adhesive composition was used. .
- the polyester-based polymer and the tackifying resin contain aromatic rings, and the cross-linking agent does not contain an aromatic ring.
- the adhesive according to No. 6 had a high shear adhesive strength exceeding 100 N/100 mm 2 .
- Examples 2 and 4 to 6 passed the repulsion resistance test, and Examples 4 to 6 were particularly excellent in repulsion resistance test results.
- Example 7 using a polyester-based polymer containing no aromatic ring high shear adhesive strength was not obtained.
- Example 8 Even in Example 8, in which a tackifying resin containing no aromatic ring was used and a cross-linking agent containing an aromatic ring was used, high shear adhesive strength was not obtained. From the above results, a polyester-based polymer in which 50% or more of the constituent carbon is biomass-derived carbon, a tackifying resin, and a cross-linking agent are included, the polyester-based polymer and the tackifying resin include an aromatic ring, and the cross-linking agent is aromatic. It can be seen that the ring-free pressure-sensitive adhesive provides high shear adhesion.
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Abstract
Description
本出願は、2021年2月26日に出願された日本国特許出願2021-030200号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、製品として実際に提供される本発明の粘着シートのサイズや縮尺を必ずしも正確に表したものではない。
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、粘着剤層21からなる基材レスの両面粘着シートとして構成されている。粘着シート1は、粘着剤層21の一方の表面(第一面)により構成された第一粘着面21Aと、粘着剤層21の他方の表面(第二面)により構成された第二粘着面21Bとを、被着体の異なる箇所に貼り付けて用いられる。粘着面21A,21Bが貼り付けられる箇所は、異なる部材のそれぞれの箇所であってもよく、単一の部材内の異なる箇所であってもよい。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、第一粘着面21Aおよび第二粘着面21Bが、少なくとも粘着剤層21に対向する側がそれぞれ剥離面となっている剥離ライナー31,32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31,32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32を省略し、両面が剥離面となっている剥離ライナー31を用い、これと粘着シート1とを重ね合わせて渦巻き状に巻回することにより第二粘着面21Bが剥離ライナー31の背面に当接して保護された形態(ロール形態)の剥離ライナー付き粘着シートを構成していてもよい。
(ポリエステル系ポリマー)
ここに開示される粘着シートは、ポリエステル系ポリマーを含む粘着剤層を備える。換言すれば、上記粘着剤層および粘着剤層を形成するための粘着剤組成物は、ポリエステル系ポリマーを含む(以下、特に断りがないかぎり、粘着剤層について説明する事項は、粘着剤組成物にも適用され得る。)。このような、ポリエステル系ポリマーを含む粘着剤や粘着剤組成物は、ポリエステル系粘着剤、ポリエステル系粘着剤組成物ともいう。上記ポリエステル系ポリマーは、典型的にはベースポリマーとして粘着剤層に含まれる。ここで、ベースポリマーとは、粘着剤層に含まれるゴム状ポリマー(室温付近の温度域においてゴム弾性を示すポリマー)の主成分をいう。また、この明細書において「主成分」とは、特記しない場合、50重量%を超えて含まれる成分を指す。また、本明細書においてポリエステル系ポリマーとは、ジカルボン酸とジオールとを重縮合して得られるポリマーをいう。
[GPC測定]
カラム:TSKgelGMH-H(S)
カラム温度:40℃
溶離液:THF(アミン系成分0.1重量%添加)
流速:0.5mL/min
注入量:100μL
検出器:示差屈折計(RI)
標準試料:ポリスチレン(PS)
上記ポリエステル系ポリマーの合成に用いられるジカルボン酸としては、脂肪族ジカルボン酸、ダイマー酸、脂環式ジカルボン酸、不飽和ジカルボン酸、芳香族ジカルボン酸のいずれも使用可能である。ジカルボン酸の具体例としては、例えば、マロン酸、コハク酸、グルタル酸、ジメチルグルタル酸、アジピン酸、トリメチルアジピン酸、ピメリン酸、スベリン酸、アゼライン酸、ドデカン二酸、セバシン酸、チオジプロピオン酸、ジグリコール酸等の脂肪族ジカルボン酸;オレイン酸、エルカ酸等の脂肪酸を二量体化したダイマー酸;1,2-シクロペンタンジカルボン酸、1,2-シクロヘキサンジカルボン酸、1,3-シクロヘキサンジカルボン酸、1,4-シクロヘキサンジカルボン酸、4-メチル-1,2-シクロヘキサンジカルボン酸、ノルボルナンジカルボン酸、アダマンタンジカルボン酸等の脂環式ジカルボン酸;マレイン酸、無水マレイン酸、フマル酸、イタコン酸、シトラコン酸、ドデセニル無水コハク酸等の不飽和ジカルボン酸;イソフタル酸、テレフタル酸、オルソフタル酸、ベンジルマロン酸、2,2’―ビフェニルジカルボン酸、4,4’―ビフェニルジカルボン酸、4,4’―ジカルボキシジフェニルエーテル、ナフタレンジカルボン酸等の芳香族ジカルボン酸;これらの誘導体;等が挙げられる。なお、上記ジカルボン酸の誘導体には、カルボン酸塩、カルボン酸無水物、カルボン酸ハロゲン化物、カルボン酸エステル等の誘導体が含まれる。これらのジカルボン酸の1種または2種以上を適切に選定して用いることで、所望の特性(具体的には、高いせん断接着力、好ましくは、さらに耐反発性、高温保持力等の一つ以上)を発揮し得るポリエステル系ポリマーを得ることができる。
ここに開示されるポリエステル系ポリマーの合成に用いられるジオールとしては、(ポリ)アルキレングリコール類、脂肪族ジオール、ダイマージオール、脂環式ジオール、芳香族ジオール、不飽和ジオールのいずれも使用可能である。上記ジオールの具体例としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等の(ポリ)アルキレングリコール類;1,3-プロパンジオール、2-メチル-1,3-プロパンジオール、2,2-ジメチル-1,3-プロパンジオール(ネオペンチルグリコール)、2-エチル-2-ブチル-1,3-プロパンジオール、2-エチル-2-イソブチル-1,3-プロパンジオール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、3-メチル-1,5-ペンタンジオール、1,6-ヘキサンジオール、2-メチル-1,3-ヘキサンジオール、2,2,4-トリメチル-1,6-ヘキサンジオール、1,8-オクタンジオール、1,9-ノナンジオール、1,10-デカンジオール等の脂肪族ジオール;ダイマージオール(オレイン酸、エルカ酸等の脂肪酸から誘導されるダイマージオール等);1,2-シクロヘキサンジメタノール、1,3-シクロヘキサンジメタノール、1,4-シクロヘキサンジメタノール、スピログリコール、トリシクロデカンジメタノール、アダマンタンジオール、2,2,4,4-テトラメチル-1,3-シクロブタンジオール等の脂環式ジオール;4,4′-チオジフェノール、4,4′-メチレンジフェノール、4,4′-ジヒドロキシビフェニル、o-,m-およびp-ジヒドロキシベンゼン、2,5-ナフタレンジオール、p-キシレンジオールおよびそれらのエチレンオキサイド、プロピレンオキサイド付加体等の芳香族ジオール;等が挙げられる。これらのジオールの1種または2種以上を適切に選定して用いることで、所望の特性(具体的には、高いせん断接着力、好ましくは、さらに耐反発性、高温保持力等の一つ以上)を発揮し得るポリエステル系ポリマーを得ることができる。
ここに開示される粘着剤層(および粘着剤組成物)は粘着付与樹脂を含む。粘着付与樹脂としては、分子内に芳香環を有する粘着付与樹脂(芳香環含有粘着付与樹脂)が用いられる。芳香環を含む粘着付与樹脂を、芳香環を含むポリエステル系ポリマーとともに使用することにより、せん断接着力を向上することができる。また、芳香環を含む粘着付与樹脂の使用により、良好な耐反発性が得られやすく、高温保持力も得られやすい。また、上記ポリエステル系ポリマーと粘着付与樹脂とがともに芳香環を有することで、相溶性に優れ、所望の粘着特性を良好に発現させることができる。芳香環を含む粘着付与樹脂は、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。
アルキルフェノール樹脂は、アルキルフェノールとホルムアルデヒドから得られる樹脂(油性フェノール樹脂)である。アルキルフェノール樹脂の例としては、ノボラックタイプおよびレゾールタイプのものが挙げられる。
ロジンフェノール樹脂は、典型的には、ロジン類または上記の各種ロジン誘導体(ロジンエステル類、不飽和脂肪酸変性ロジン類および不飽和脂肪酸変性ロジンエステル類を包含する。)のフェノール変性物である。ロジンフェノール樹脂の例には、ロジン類または上記の各種ロジン誘導体にフェノールを酸触媒で付加させ熱重合する方法等により得られるロジンフェノール樹脂が含まれる。
モル比率[フェノール骨格:ピネン骨格]=[A/3:B/16]
次に算出したモル比率に、フェノール(分子量94.1)およびピネン(分子量136.2)の分子量をそれぞれ掛けることで、粘着付与樹脂中のフェノール骨格とピネン骨格の重量比率を算出することができる。
重量比率[フェノール骨格:ピネン骨格]=[(A/3)×94.1:(B/16)×136.2]
そして、求められたフェノール骨格の重量比率をa、ピネン骨格の重量比率をbとした場合、以下の式により、上記粘着付与樹脂の芳香環比率(フェノール比率)を算出することができる。
芳香環比率(%)=100×(a/(a+b))
NMR装置としては、例えば機種名「AVANCE III-400」(Bruker Biospin製)を用いることができる。1H-NMRスペクトル測定は、より具体的には、以下の条件で行うことができる。後述の実施例においても同様の方法で測定される。
[1H-NMR測定]
観測周波数:400MHz
測定温度:23℃
測定溶媒:1,1,2,2-テトラクロルエタン-d2(TCE-d2)
測定濃度:33mg/mL
粘着剤層の形成に用いられる粘着剤組成物は、架橋剤として、芳香環を有しない架橋剤(芳香環非含有架橋剤)を含む。芳香環を含むポリエステル系ポリマーおよび粘着付与樹脂を含む組成に芳香環非含有架橋剤を使用することにより、良好な架橋構造(架橋反応)を得つつ、ポリエステル系ポリマーおよび粘着付与樹脂に含まれる芳香環の作用が好適に発揮され得る。ここに開示される技術における粘着剤層は、上記架橋剤を、架橋反応後の形態、架橋反応前の形態、部分的に架橋反応した形態、これらの中間的または複合的な形態等で含有し得る。上記架橋剤は、通常、専ら架橋反応後の形態で粘着剤層に含まれている。なお、ポリエステル系ポリマーの架橋に用いられる架橋剤は、鎖延長剤としても機能するものであり得る。
脂肪族ポリイソシアネート系化合物の具体例としては、1,2-エチレンジイソシアネート;1,2-テトラメチレンジイソシアネート、1,3-テトラメチレンジイソシアネート、1,4-テトラメチレンジイソシアネート等のテトラメチレンジイソシアネート;1,2-ヘキサメチレンジイソシアネート、1,3-ヘキサメチレンジイソシアネート、1,4-ヘキサメチレンジイソシアネート、1,5-ヘキサメチレンジイソシアネート、1,6-ヘキサメチレンジイソシアネート、2,5-ヘキサメチレンジイソシアネート等のヘキサメチレンジイソシアネート;2-メチル-1,5-ペンタンジイソシアネート、3-メチル-1,5-ペンタンジイソシアネート、リジンジイソシアネート、等が挙げられる。
ここに開示される技術においては、架橋反応をより効果的に進行させるために、上記架橋剤に加えて、架橋触媒を用いることが好ましい。架橋触媒としては、ジルコニウムテトラアセチルアセトネート、ジルコニウムモノアセチルアセトネート、ジルコニウムエチルアセトアセテート、オクチル酸ジルコニウム化合物等のジルコニウム含有化合物(ジルコニウム系触媒);ジラウリン酸ジオクチルスズ、ジラウリン酸ジブチルスズ、二酢酸ジブチルスズ、ジブチルスズジアセチルアセトナート、テトラ-n-ブチルスズ、トリメチルスズヒドロキシド、ブチルスズオキシド等のスズ(Sn)含有化合物(スズ系触媒);アルミニウムセカンダリーブトキシド、アルミニウムトリスアセチルアセトネート、アルミニウムビスエチルアセトアセテート、アルミニウムトリスエチルアセトアセテート等のアルミニウム含有化合物(アルミニウム系触媒);ナーセム第二鉄等の鉄含有化合物(鉄系触媒);テトライソプロピルチタネート、テトラ-n-ブチルチタネート、ブチルチタネートダイマー、テトラオクチルチタネート、チタンアセチルアセトネート、チタンテトラアセチルアセトネート、チタンエチルアセトアセテート等のチタン含有化合物(チタン系触媒);等の有機金属触媒が挙げられる。架橋触媒は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。
また、ここに開示される粘着剤組成物は、耐加水分解剤(加水分解防止剤ともいう。)を含んでもよい。耐加水分解剤を添加することにより、粘着剤中での加水分解反応が抑制され、良好な耐久性が得られやすい。耐加水分解剤としては、特に限定されず、公知ないし慣用の耐加水分解剤を用いることができる。例えば、オキサゾリン基含有化合物、エポキシ基含有化合物、カルボジイミド基含有化合物等が挙げられる。なかでも、カルボジイミド基含有化合物が好ましい。耐加水分解剤は、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。
粘着剤組成物には、上述した各成分以外に、必要に応じてレベリング剤、充填剤、可塑剤、軟化剤、着色剤(顔料、染料等)、帯電防止剤、老化防止剤、紫外線吸収剤、酸化防止剤、光安定剤等の、粘着剤の分野において一般的な各種の添加剤が含まれていてもよい。上記各種添加剤については、従来公知のものを常法により使用することができ、特に本発明を特徴づけるものではないので、詳細な説明は省略する。
ここに開示される粘着剤層(粘着剤からなる層)は、上述したポリエステル系ポリマー、粘着付与樹脂および架橋剤を含む粘着剤組成物から形成される。粘着剤組成物としては、粘着特性等の観点から、有機溶媒中に粘着剤を含む形態の溶剤型粘着剤組成物が好適である。有機溶媒としては、トルエンや酢酸エチル等の有機溶媒を用いることができる。
粘着剤組成物からの粘着剤層の形成は、従来公知の方法によって行うことができる。例えば、基材レスの両面粘着シートの場合は、剥離性を有する表面(剥離面)に粘着剤組成物を付与した後、該粘着剤組成物を硬化させることにより該表面上に粘着剤層を形成することで粘着シートが形成され得る。また、基材付きの粘着シートの場合は、該基材に粘着剤組成物を直接付与(典型的には塗布)して硬化させることにより粘着剤層を形成する方法(直接法)を好ましく採用することができる。また、剥離性を有する表面(剥離面)に粘着剤組成物を付与して硬化させることにより該表面上に粘着剤層を形成し、その粘着剤層を基材に転写する方法(転写法)を採用してもよい。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。また、上記粘着剤組成物の硬化は、該粘着剤組成物に乾燥、架橋、重合、冷却等の硬化処理を施すことにより行うことができる。2種以上の硬化処理を同時にまたは段階的に行ってもよい。なお、ここに開示される粘着剤層は、典型的には連続的に形成されるが、かかる形態に限定されるものではなく、例えば点状、ストライプ状等の規則的あるいはランダムなパターンに形成された粘着剤層であってもよい。
粘着剤組成物の乾燥は、常温または加熱下で行うことができる。架橋反応の促進、製造効率向上等の観点から、粘着剤組成物の乾燥は加熱下で行うことが好ましい。乾燥温度は、例えば凡そ40~150℃程度とすることができ、通常は凡そ40~130℃程度とすることが好ましい。粘着剤組成物を乾燥させた後、さらに、粘着剤層内における成分移行の調整、架橋反応の進行、基材や粘着剤層内に存在し得る歪の緩和等を目的としてエージングを行うことが好ましい。エージングの条件は特に限定されず、例えば凡そ70℃以下(典型的には凡そ40~70℃)、1日以上(例えば3日以上)の条件とすることができる。
ここに開示される粘着シートにおいて、粘着剤層の厚さは特に限定されず、目的に応じて適宜選択することができる。粘着剤層の厚さは、例えば2μm~500μm程度とすることができる。被着体に対する接着性の観点から、粘着剤層の厚さは、通常、3μm以上であることが適当であり、5μm以上であることが好ましい。より高いせん断接着力を発揮する粘着シートを実現しやすくする観点から、いくつかの態様において、粘着剤層の厚さは、例えば8μm以上であってよく、12μm以上が好ましく、15μm以上でもよく、18μm以上でもよい。また、粘着シートの薄型化の観点から、粘着剤層の厚さは、例えば200μm以下であってよく、150μm以下でもよく、100μm以下でもよく、70μm以下でもよく、50μm以下でもよく、30μm以下でもよい。より薄型化を重視する態様において、粘着剤層の厚さは、例えば25μm以下であってよく、22μm以下でもよい。ここに開示される粘着シートが基材の両面に粘着剤層を備える両面粘着シートの場合、各粘着剤層の厚さは、同じであってもよく、異なっていてもよい。
ここに開示される技術は、バイオ率が50%以上であるポリエステル系ポリマーを含む粘着剤を用いて実施されることから、粘着剤層(および粘着剤組成物。特に断りがないかぎり以下同じ。)は、所定値以上のバイオ率を有する。特に限定されるものではないが、粘着剤層のバイオ率は凡そ30%以上(例えば30%超)であってもよく、凡そ40%以上であることが適当であり、50%以上であることが好ましい。粘着剤層のバイオ率が高いことは、石油等に代表される化石資源系材料の使用量が少ないことを意味する。粘着剤層のバイオ率が高くなるよう設計することで、粘着剤層全体としての化石資源系材料への依存度を低減することができる。例えば、粘着剤層のバイオ率は、55%以上であってもよく、60%以上でもよく、70%以上でもよく、75%以上でもよい。バイオ率の上限は定義上100%であるが、ここに開示される粘着剤層では、含有成分が化石資源由来の材料を含み得るため、典型的にはバイオ率は100%未満であり得る。携帯電子機器用途に適した性能(例えばせん断接着力)を得やすくする観点から、いくつかの態様において、粘着剤層のバイオ率は、例えば90%未満であってよく、より粘着性能が重視される場合には80%未満でもよく、70%未満でもよい。
ここに開示される粘着シートは、基材の片面または両面に粘着剤層を備える基材付き粘着シートの形態であり得る。基材としては、各種のシート状基材を用いることができ、例えば樹脂フィルム、紙、布、ゴムシート、発泡体シート、金属箔、これらの複合体等を用いることができる。電子機器用の分野においては、塵埃(例えば紙粉等の、微小な繊維または粒子)の発生源となりにくい基材が好ましく用いられ得る。かかる観点から、紙や布等の繊維状物を含まない基材が好ましく、例えば樹脂フィルム、ゴムシート、発泡体シート、金属箔、これらの複合体等を好ましく使用し得る。
ここに開示される粘着シート(粘着剤層を含み、基材付き粘着シートではさらに基材を含むが、剥離ライナーは含まない。)の厚さ(総厚)は、特に限定されず、例えば凡そ2μm~1000μmの範囲とすることができる。いくつかの態様において、粘着シートの厚さは、粘着特性等を考慮して、5μm~500μm(例えば10μm~300μm、典型的には15μm~200μm)程度とすることが好ましい。あるいは、薄型化を重視するいくつかの態様において、粘着シートの厚さは、100μm以下(例えば5μm~100μm)であってよく、70μm以下(例えば5μm~70μm)でもよく、45μm以下(例えば5μm~45μm)でもよく、30μm以下(例えば5μm~30μm)でもよい。
なお、粘着剤層からなる基材レス粘着シートでは、該粘着剤層のバイオ率と粘着シート全体のバイオ率とは一致する。
ここに開示される粘着シートの用途は特に限定されず、各種用途に制限なく用いることができる。例えば、粘着シートは、電子機器を構成する部材に貼り付けられる態様で、例えば部材の固定、接合、補強等の目的で使用することができる。ここに開示される粘着シートは、例えば両面粘着シートの形態で、部材を固定または接合する用途に好ましく利用され得る。かかる用途では、粘着シートが良好なせん断接着力を有し、剥がれを防止することが特に有意義である。上記両面粘着シートは、基材レスでもよく、基材付きでもよい。薄型化の観点から、いくつかの態様において、基材レスの両面粘着シートまたは薄手の基材を用いた基材付き両面粘着シートの形態が好ましく採用され得る。上記薄手の基材としては、厚さが10μm以下(例えば5μm未満)の基材が好ましく用いられ得る。
〔1〕 携帯電子機器であって、
筐体と、表示部が入力部としても機能するタッチパネルと、を備え、
前記筐体の内部には、発熱要素(例えばバッテリー)が内蔵されており、
前記携帯電子機器を構成する多数の部材のうち、少なくとも第1の部材と第2の部材とは粘着シートによって接合されており、
前記粘着シートは、構成炭素の50%以上がバイオマス由来炭素であるポリエステル系ポリマーを含む粘着剤層を有し、
前記粘着剤層は、粘着付与樹脂および架橋剤をさらに含み、
前記ポリエステル系ポリマーは芳香環を含み、前記粘着付与樹脂も芳香環を含み、前記架橋剤は芳香環を含まない、携帯電子機器。
〔2〕 前記ポリエステル系ポリマーの重量平均分子量は30,000以上である、上記〔1〕に記載の携帯電子機器。
〔3〕 前記ポリエステル系ポリマーの重量平均分子量は100,000よりも大きい、上記〔1〕または〔2〕に記載の携帯電子機器。
〔4〕 前記ポリエステル系ポリマーのガラス転移温度は0℃以下である、上記〔1〕~〔3〕のいずれかに記載の携帯電子機器。
〔5〕 前記粘着付与樹脂の芳香環比率は20重量%以上である、上記〔1〕~〔4〕のいずれかに記載の携帯電子機器。
〔6〕 前記粘着付与樹脂は、テルペンフェノール樹脂を含む、上記〔1〕~〔5〕のいずれかに記載の携帯電子機器。
〔7〕 前記粘着剤層は、前記架橋剤として、イソシアネート系架橋剤を含む、上記〔1〕~〔6〕のいずれかに記載の携帯電子機器。
〔8〕 前記粘着剤層は、前記架橋剤として、脂肪族イソシアネート系化合物を含む、上記〔1〕~〔7〕のいずれかに記載の携帯電子機器。
〔9〕 前記粘着剤層における前記架橋剤の含有量は、前記ポリエステル系ポリマー100重量部に対して5重量部以下である、上記〔1〕~〔8〕のいずれかに記載の携帯電子機器。
〔10〕 前記粘着剤層は架橋触媒をさらに含み、該架橋触媒はスズ系化合物を含まない、上記〔1〕~〔9〕のいずれかに記載の携帯電子機器。
粘着付与樹脂および架橋剤をさらに含み、
前記ポリエステル系ポリマーは芳香環を含み、前記粘着付与樹脂も芳香環を含み、前記架橋剤は芳香環を含まない、粘着剤組成物。
〔12〕 前記ポリエステル系ポリマーの重量平均分子量は30,000以上である、上記〔11〕に記載の粘着剤組成物。
〔13〕 前記ポリエステル系ポリマーの重量平均分子量は60,000よりも大きい、上記〔11〕または〔12〕に記載の粘着剤組成物。
〔14〕 前記ポリエステル系ポリマーの重量平均分子量は100,000よりも大きい、上記〔11〕~〔13〕のいずれかに記載の粘着剤組成物。
〔15〕 前記ポリエステル系ポリマーのガラス転移温度は0℃以下である、上記〔11〕~〔14〕のいずれかに記載の粘着剤組成物。
〔16〕 前記粘着付与樹脂の芳香環比率は20重量%以上である、上記〔11〕~〔15〕のいずれかに記載の粘着剤組成物。
〔17〕 前記粘着付与樹脂は、テルペンフェノール樹脂を含む、上記〔11〕~〔16〕のいずれかに記載の粘着剤組成物。
〔18〕 前記架橋剤として、イソシアネート系架橋剤を含む、上記〔11〕~〔17〕のいずれかに記載の粘着剤組成物。
〔19〕 前記架橋剤として、脂肪族イソシアネート系化合物を含む、上記〔11〕~〔18〕のいずれかに記載の粘着剤組成物。
〔20〕 前記架橋剤の含有量は、前記ポリエステル系ポリマー100重量部に対して5重量部以下である、上記〔11〕~〔19〕のいずれかに記載の粘着剤組成物。
〔21〕 架橋触媒をさらに含み、該架橋触媒はスズ系化合物を含まない、上記〔11〕~〔20〕のいずれかに記載の粘着剤組成物。
〔22〕 架橋剤として、2官能架橋剤と、3官能以上の架橋剤とを含む、上記〔11〕~〔21〕のいずれかに記載の粘着剤組成物。
前記粘着剤層は、粘着付与樹脂および架橋剤をさらに含み、
前記ポリエステル系ポリマーは芳香環を含み、前記粘着付与樹脂も芳香環を含み、前記架橋剤は芳香環を含まない、粘着シート。
〔32〕 前記ポリエステル系ポリマーの重量平均分子量は30,000以上である、上記〔31〕に記載の粘着シート。
〔33〕 前記ポリエステル系ポリマーの重量平均分子量は60,000よりも大きい、上記〔31〕または〔32〕に記載の粘着シート。
〔34〕 前記ポリエステル系ポリマーの重量平均分子量は100,000よりも大きい、上記〔31〕~〔33〕のいずれかに記載の粘着シート。
〔35〕 前記ポリエステル系ポリマーのガラス転移温度は0℃以下である、上記〔31〕~〔34〕のいずれかに記載の粘着シート。
〔36〕 前記粘着付与樹脂の芳香環比率は20重量%以上である、上記〔31〕~〔35〕のいずれかに記載の粘着シート。
〔37〕 前記粘着付与樹脂は、テルペンフェノール樹脂を含む、上記〔31〕~〔36〕のいずれかに記載の粘着シート。
〔38〕 前記粘着剤層は、前記架橋剤として、イソシアネート系架橋剤を含む、上記〔31〕~〔37〕のいずれかに記載の粘着シート。
〔39〕 前記粘着剤層は、前記架橋剤として、脂肪族イソシアネート系化合物を含む、上記〔31〕~〔37〕のいずれかに記載の粘着シート。
〔40〕 前記粘着剤層における前記架橋剤の含有量は、前記ポリエステル系ポリマー100重量部に対して5重量部以下である、上記〔31〕~〔39〕のいずれかに記載の粘着シート。
〔41〕 前記粘着剤層は架橋触媒をさらに含み、該架橋触媒はスズ系化合物を含まない、上記〔31〕~〔40〕のいずれかに記載の粘着シート。
〔42〕 前記粘着剤層は、架橋剤として、2官能架橋剤と、3官能以上の架橋剤とを含む、上記〔31〕~〔41〕のいずれかに記載の粘着シート。
〔43〕 ステンレス鋼板に対するせん断接着力が100N/100mm2よりも大きい、上記〔31〕~〔42〕のいずれかに記載の粘着シート。
〔44〕 ステンレス鋼板に対する180度剥離強度が10N/20mm以上である、上記〔31〕~〔43〕のいずれかに記載の粘着シート。
〔52〕 上記〔31〕~〔44〕のいずれかに記載の粘着シートを含む携帯電子機器。
[せん断接着力]
粘着シート(両面粘着シート)を10mm×10mmのサイズにカットして測定サンプルを作製する。23℃、50%RHの環境下にて、上記測定サンプルの各粘着面を2枚のステンレス鋼板(SUS304BA板)の表面にそれぞれ重ねて2kgのローラを1往復させて圧着する。これを同環境下に2日間放置した後、引張試験機を用いて、引張速度10mm/分、剥離角度0度の条件で、せん断接着力[N/100mm2]を測定する。せん断接着力が100N/100mm2を超えれば、高いせん断接着力を有すると評価される。片面接着性の粘着シート(片面粘着シート)の場合は、該シートの非粘着面を接着剤等でステンレス鋼板に固定し、その他は上記と同様にして測定すればよい。引張試験機としては、万能引張圧縮試験機(製品名「TG-1kN」、ミネベア社製)を使用することができる。
図5の(a)に示すように、長さ30mm、幅10mm、厚さ2mmのポリカーボネート(PC)板50と、長さ100mm、幅10mm、厚さ125μmのPETフィルム60と、を用意し、PC板50とPETフィルム60の長手方向の一端を揃えるようにして重ね合わせ、PETフィルム60の残りの部分がPC板50の他端から突出した状態でPC板50とPETフィルム60とを固定する。上記固定には市販の両面粘着テープ(日東電工社製、「No.5000NS」)を使用する。
2枚の剥離ライナーで両粘着面が保護された各例に係る粘着シートを10mm×10mmのサイズにカットして粘着シート試料片70を用意する。PC板50のPETフィルムの固定面とは反対側の表面を上側に設置し、上記粘着シート試料片70から一方の剥離ライナーを剥がして、PC板50の長手方向の他端と粘着シート試料片70の一辺とが一致するようにして粘着シート試料片70をPC板50の上面に貼り付け固定する。上記固定は、粘着シート試料片70のもう一方の剥離ライナーで保護された上面を2kgローラを一往復させることによって行う。
次いで、23℃、50%RHの環境下にて、PC板50に貼り付けた粘着シート試料片70のもう一方の剥離ライナーを剥がして、図5の(b)に示すように、PC板50に固定されたPETフィルム60のPC板50からの突出部分(長さ70mm)をPC板50側に折り返して、粘着シート試料片70とPETフィルム60の他端(自由端)とを一致させて、0.1kgのローラをPETフィルム60上から1往復させることにより、折り曲げられたPETフィルム60の他端を粘着シート試料片70を介してPC板50上面に固定する。PETフィルム60が粘着シート試料片70から剥離するかどうかを、60℃95%RHの環境下および室温(23℃)環境下で、それぞれ24時間観察し、折り曲げられたPETフィルム60の弾性反撥に基づく粘着シート厚さ方向に対する粘着シート試料片70の接着保持力を、耐反発性として評価する。
粘着シート試料片70とPETフィルム60との接着状態が60℃95%RH環境下および室温環境下で24時間保持された場合を「◎」、粘着シート試料片70とPETフィルム60との接着状態が室温環境下で24時間保持された場合を「〇」、60℃95%RH環境下および室温環境下で24時間以内に図5の(c)に示すようにPETフィルム60が剥がれた場合を「×」と判定する。耐反発試験の結果が◎または〇の場合、良好な耐反発性を有し(すなわち合格)、×の場合、耐反発性は不十分(すなわち不合格)であると評価される。
粘着シートを幅20mm、長さ150mmのサイズにカットして測定サンプルを作製する。23℃、50%RHの環境下にて、上記測定サンプルの粘着面を露出させ、その粘着面を被着体としてのステンレス鋼板(SUS304BA板)に2kgのゴムローラを1往復させて圧着する。これを、23℃、50%RHの環境下に30分放置し、次いで同環境下にて引張試験機を使用してJIS Z0237:2000に準じて、剥離角度180度、引張速度300mm/分の条件で剥離強度(対SUS粘着力)[N/20mm]を測定する。引張試験機としては、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)を使用することができる。
なお、対SUS粘着力の測定にあたっては、必要に応じて(例えば、基材レス両面粘着シートの場合や、基材付き粘着シートであって基材が変形しやすい場合等)、測定対象の粘着シートに適切な裏打ち材を貼り付けて補強することができる。裏打ち材としては、例えば厚さ50μm程度のPETフィルムを用いることができ、実施例ではこの裏打ち材を使用した。
(合成例1)
四つ口セパラブルフラスコに攪拌機、温度計、窒素管および水分離管を付し、これにエチレングリコール(東京化成工業社製、分子量62)100g、ダイマー酸(製品名「プリポール1009」、クローダ社製、分子量567)700g、テレフタル酸(東京化成社製、分子量166)63g、重合触媒としてジ-n-ブチルスズオキシド(キシダ化学社製、分子量249)0.46g、反応水排出溶剤としてキシレン40gを仕込み、窒素雰囲気で撹拌しながら180℃まで昇温し、この温度を保持した。しばらくすると反応水の流出分離が認められ、反応が進行しはじめた。約24時間反応を続けて、バイオ率が81%のポリエステル系ポリマー(A1)を得た。このポリエステル系ポリマー(A1)の重量平均分子量(Mw)は10万であり、ガラス転移温度(Tg)は-33℃であった。
四つ口セパラブルフラスコに攪拌機、温度計、窒素管および水分離管を付し、これにエチレングリコール(東京化成工業社製、分子量62)100g、ダイマー酸(製品名「プリポール1009」、クローダ社製、分子量567)915g、重合触媒としてジ-n-ブチルスズオキシド(キシダ化学社製、分子量249)0.46g、反応水排出溶剤としてキシレン40gを仕込み、窒素雰囲気で撹拌しながら180℃まで昇温し、この温度を保持した。しばらくすると反応水の流出分離が認められ、反応が進行しはじめた。約24時間反応を続けて、バイオ率が89%のポリエステル系ポリマー(A2)を得た。このポリエステル系ポリマー(A2)のMwは10万であり、ガラス転移温度(Tg)は-36℃であった。
合成例1における反応時間を約36時間に変更した他は合成例1と同様にして、ポリエステル系ポリマー(A1)よりも高分子量のポリエステル系ポリマー(A3)を得た。このポリエステル系ポリマー(A3)のモノマー組成は、ポリエステル系ポリマー(A1)と同じであり、Mwは13万であった。
ポリエステル系ポリマー(A1)100部に、粘着付与樹脂としてテルペンフェノール樹脂(商品名「YSポリスターS145」、ヤスハラケミカル社製、フェノール比率22%、以下「S145」と表記する場合がある。)40部、架橋剤Aとして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(商品名「コロネートHX」、東ソー社製、芳香環非含有、以下「3官能架橋剤」ともいう。)3部、架橋触媒として有機ジルコニウム化合物(商品名「オルガチックスZC-162」、マツモトファインケミカル社製)0.13部、耐加水分解剤としてカルボジイミド基含有化合物(商品名「カルボジライトV-03」、日清紡ケミカル社製)0.5部を配合し、酢酸エチルを加え、粘着剤組成物(粘着剤溶液)を調製した。この粘着剤溶液を、剥離処理したポリエチレンテレフタレート(PET)フィルム(商品名「ダイアホイルMRF♯38」、三菱ケミカル社製)の剥離処理面に、乾燥後の厚みが20μmになるように塗工し、120℃で3分乾燥させ、粘着剤層を得た。その後、剥離処理したPETフィルム(商品名「ダイアホイルMRE♯38」、三菱ケミカル社製)の剥離処理面に上記粘着剤層を貼り合わせて、さらに50℃3日間放置し、本例に係る基材レス粘着シートを得た。
架橋触媒として、有機ジルコニウム化合物に代えて、有機スズ化合物(商品名「ジラウリン酸ジブチルスズ(IV)」、富士フィルム和光純薬社製)0.01部を使用した他は例1と同様にして本例に係る粘着剤組成物を調製し、この粘着剤組成物を用いた他は例1と同様にして本例に係る基材レス粘着シートを得た。
架橋剤の使用量を、ポリエステル系ポリマー(A1)100部に対して4部に変更し、架橋触媒として、有機ジルコニウム化合物に代えて有機アルミニウム化合物(商品名「ナーセムアルミニウム」、日本化学産業社製)0.13部を使用した。その他は例1と同様にして本例に係る粘着剤組成物を調製し、この粘着剤組成物を用いた他は例1と同様にして本例に係る基材レス粘着シートを得た。
ポリエステル系ポリマー(A3)100部に、粘着付与樹脂としてテルペンフェノール樹脂(商品名「YSポリスターG150」、ヤスハラケミカル社製、フェノール比率32%、以下「G150」と表記する場合がある。)40部、架橋剤A(商品名「コロネートHX」、東ソー社製)2部、架橋触媒として有機ジルコニウム化合物(商品名「オルガチックスZC-162」、マツモトファインケミカル社製)0.03部、耐加水分解剤としてカルボジイミド基含有化合物(商品名「カルボジライトV-03」、日清紡ケミカル社製)0.5部を配合し、酢酸エチルを加え、粘着剤組成物(粘着剤溶液)を調製した。得られた粘着剤組成物を用いた他は例1と同様にして、本例に係る基材レス粘着シート(厚さ20μm)を得た。
ポリエステル系ポリマー(A3)100部に、粘着付与樹脂としてテルペンフェノール樹脂(商品名「YSポリスターS145」、ヤスハラケミカル社製、フェノール比率22%)40部、架橋剤A(商品名「コロネートHX」、東ソー社製)3部、架橋触媒として有機スズ化合物(商品名「ジラウリン酸ジブチルスズ(IV)」、富士フィルム和光純薬社製)0.01部を使用した他は例4と同様にして本例に係る粘着剤組成物を調製し、この粘着剤組成物を用いた他は例4と同様にして本例に係る基材レス粘着シートを得た。
ポリエステル系ポリマー(A1)100部に、粘着付与樹脂としてテルペンフェノール樹脂(商品名「YSポリスターG150」、ヤスハラケミカル社製、フェノール比率32%)40部、架橋剤A(商品名「コロネートHX」、東ソー社製)2部および2官能架橋剤(商品名「デュラネートD101」、旭化成社製、芳香環非含有)2部、架橋触媒として有機ジルコニウム化合物(商品名「オルガチックスZC-162」、マツモトファインケミカル社製)0.03部、耐加水分解剤としてカルボジイミド基含有化合物(商品名「カルボジライトV-03」、日清紡ケミカル社製)0.5部を配合し、酢酸エチルを加え、粘着剤組成物(粘着剤溶液)を調製した。得られた粘着剤組成物を用いた他は例1と同様にして、本例に係る基材レス粘着シート(厚さ20μm)を得た。
ポリエステル系ポリマー(A1)に代えてポリエステル系ポリマー(A2)を使用し、架橋剤の使用量を、ポリエステル系ポリマー(A2)100部に対して5部に変更した。その他は例2と同様にして本例に係る粘着剤組成物を調製し、この粘着剤組成物を用いた他は例2と同様にして本例に係る基材レス粘着シートを得た。
粘着付与樹脂として、テルペンフェノール樹脂S145(40部)に代えて、水添ロジングリセリンエステル(商品名「ハリタック SE10」、ハリマ化成社製)20部を使用し、架橋剤として、芳香環を含む架橋剤B(商品名「コロネートL」、トリメチロールプロパン/トリレンジイソシアネート3量体付加物の75%酢酸エチル溶液、東ソー社製)を、ポリエステル系ポリマー(A1)100部に対して2部使用した。その他は例1と同様にして本例に係る粘着剤組成物を調製し、得られた粘着剤組成物を用いた他は例1と同様にして本例に係る基材レス粘着シートを得た。
上記の結果から、構成炭素の50%以上がバイオマス由来炭素であるポリエステル系ポリマーと、粘着付与樹脂と、架橋剤とを含み、ポリエステル系ポリマーおよび粘着付与樹脂が芳香環を含み、架橋剤が芳香環を含まない粘着剤によると、高いせん断接着力が得られることがわかる。
10 支持基材
10A 第一面
10B 第二面(背面)
21 粘着剤層(第一粘着剤層)
21A 粘着面(第一粘着面)
21B 第二粘着面
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
100,200,300 剥離ライナー付き粘着シート
Claims (14)
- 構成炭素の50%以上がバイオマス由来炭素であるポリエステル系ポリマーを含む粘着剤組成物であって、
粘着付与樹脂および架橋剤をさらに含み、
前記ポリエステル系ポリマーは芳香環を含み、前記粘着付与樹脂も芳香環を含み、前記架橋剤は芳香環を含まない、粘着剤組成物。 - 前記ポリエステル系ポリマーの重量平均分子量は30,000以上である、請求項1に記載の粘着剤組成物。
- 前記ポリエステル系ポリマーの重量平均分子量は100,000よりも大きい、請求項1に記載の粘着剤組成物。
- 前記粘着付与樹脂の芳香環比率は20重量%以上である、請求項1~3のいずれか一項に記載の粘着剤組成物。
- 前記粘着付与樹脂はテルペンフェノール樹脂を含む、請求項1~4のいずれか一項に記載の粘着剤組成物。
- 前記架橋剤として、脂肪族イソシアネート系化合物を含む、請求項1~5のいずれか一項に記載の粘着剤組成物。
- 構成炭素の50%以上がバイオマス由来炭素であるポリエステル系ポリマーを含む粘着剤層を有する粘着シートであって、
前記粘着剤層は、粘着付与樹脂および架橋剤をさらに含み、
前記ポリエステル系ポリマーは芳香環を含み、前記粘着付与樹脂も芳香環を含み、前記架橋剤は芳香環を含まない、粘着シート。 - 前記ポリエステル系ポリマーの重量平均分子量は30,000以上である、請求項7に記載の粘着シート。
- 前記粘着付与樹脂の芳香環比率は20重量%以上である、請求項7または8に記載の粘着シート。
- 前記粘着付与樹脂はテルペンフェノール樹脂を含む、請求項7~9のいずれか一項に記載の粘着シート。
- 前記架橋剤として、脂肪族イソシアネート系化合物を含む、請求項7~10のいずれか一項に記載の粘着シート。
- ステンレス鋼板に対するせん断接着力が100N/100mm2よりも大きい、請求項7~11のいずれか一項に記載の粘着シート。
- 携帯電子機器に用いられる、請求項7~12のいずれか一項に記載の粘着シート。
- 請求項7~13のいずれか一項に記載の粘着シートを含む携帯電子機器。
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JP2007045914A (ja) * | 2005-08-09 | 2007-02-22 | Nippon Synthetic Chem Ind Co Ltd:The | ポリエステル系粘着剤とその粘着シート |
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JP2014196471A (ja) * | 2013-03-05 | 2014-10-16 | 日東電工株式会社 | 両面粘着テープ |
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WO2023140316A1 (ja) * | 2022-01-21 | 2023-07-27 | 日東電工株式会社 | 粘着剤組成物および粘着シート |
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CN117015585A (zh) | 2023-11-07 |
JPWO2022181141A1 (ja) | 2022-09-01 |
JPWO2022181140A1 (ja) | 2022-09-01 |
JP2023107997A (ja) | 2023-08-03 |
CN116867871A (zh) | 2023-10-10 |
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