Adhesive sheet and laminate

Abstract

The adhesive sheet has at least a resin layer containing a resin material and a plasticizer having an SP value of 10.0 (cal / cm3)1 / 2 or less, and a polyester-based adhesive layer.

Description

Adhesive sheet and laminate

[0001] The present disclosure relates to a pressure-sensitive adhesive sheet and a laminate.

[0002] Pressure-sensitive adhesive sheets are used in various technical fields (see, for example, Patent Document 1). Pressure-sensitive adhesive sheets generally have a substrate made of a resin material such as a vinyl chloride resin and a pressure-sensitive adhesive layer. Furthermore, when the substrate is made of a vinyl chloride resin, the substrate mainly contains a plasticizer.

[0003] Japanese Patent Application Laid-Open No. 2019-085518

[0004] When a pressure-sensitive adhesive sheet is attached to an adherend and a certain period of time has passed, the adhesive strength may decrease, such as the pressure-sensitive adhesive sheet becoming more easily peeled off from the adherend. One object of the present disclosure is to provide a pressure-sensitive adhesive sheet that can suppress a decrease in adhesive strength even after a certain period of time has passed since the sheet is attached to an adherend.

[0005] The pressure-sensitive adhesive sheet according to the first aspect of the present disclosure is made of a resin material and a pressure sensitive adhesive having an SP value of 10.0 (cal / cm 3 ) 1 / 2 The pressure-sensitive adhesive sheet according to the second aspect of the present disclosure has a base material containing the following plasticizer and a polyester-based pressure-sensitive adhesive layer, and the pressure-sensitive adhesive sheet has a polyester-based pressure-sensitive adhesive layer, and the pressure-sensitive adhesive sheet is made of a resin material and a polyester-based pressure-sensitive adhesive having an SP value of 10.0 (cal / cm 3 ) 1 / 2 The pressure-sensitive adhesive sheet is intended to be attached to an adherend having a portion containing the following plasticizer so that the polyester-based pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet comes into contact with the portion of the adherend.

[0006] According to the present disclosure, there is provided a pressure-sensitive adhesive sheet that can suppress a decrease in adhesive strength even after a certain period of time has passed since it is attached to an adherend.

[0007] Fig. 1 is a schematic cross-sectional view of an embodiment of a pressure-sensitive adhesive sheet, and Fig. 2 is a schematic cross-sectional view of an embodiment of a laminate.

[0008] Generally, the terms "sheet," "film," and "tape" are sometimes used to distinguish between them based on thickness, etc., but in this specification, these terms are used without any particular distinction. In this specification, "adherend" means an object to which the PSA sheet is attached.

[0009] Each of the components described in this specification may be used alone or in combination of two or more.

[0010] In this specification, the numerical range n1 to n2 means n1 or more and n2 or less if n1<n2, and n1>n2 means n2 or more and n1 or less if n1>n2. In this specification, when multiple lower limit values ​​and multiple upper limit values ​​are given in the description of a certain element, a numerical range formed by combining a value arbitrarily selected from the given lower limit value and a value arbitrarily selected from the given upper limit value is also considered to be given.

[0011] [Adhesive Sheet] The adhesive sheet of the first aspect of the present disclosure is a pressure-sensitive adhesive sheet comprising a resin material and an SP value of 10.0 (cal / cm 3 ) 1 / 2 The adhesive film has a substrate containing the following plasticizer and a polyester-based pressure-sensitive adhesive layer.

[0012] The substrate has a first surface and a second surface opposite the first surface.

[0013] The PSA sheet of the first embodiment may be a single-sided PSA sheet having a polyester-based PSA layer on either the first or second surface of the substrate. The PSA sheet of the first embodiment may be a double-sided PSA sheet having a first polyester-based PSA layer on the first surface of the substrate and a second polyester-based PSA layer on the second surface of the substrate, i.e., having a first polyester-based PSA layer, the substrate, and a second polyester-based PSA layer in this order in the stacking direction.

[0014] The pressure-sensitive adhesive sheet according to the second aspect of the present disclosure has a polyester-based pressure-sensitive adhesive layer. The pressure-sensitive adhesive sheet according to the second aspect comprises a resin material and a polyester-based pressure-sensitive adhesive layer having an SP value of 10.0 (cal / cm 3 ) 1 / 2 This sheet is intended to be attached to an adherend having a portion containing the following plasticizer so that the polyester-based adhesive layer of the adhesive sheet comes into contact with the portion of the adherend.

[0015] The pressure-sensitive adhesive sheet of the second embodiment may be a double-sided pressure-sensitive adhesive sheet that does not have a substrate.

[0016] The pressure-sensitive adhesive sheet of the second aspect may further include a substrate containing a resin material. In one embodiment, the substrate in the pressure-sensitive adhesive sheet of the second aspect includes a resin material and a polymer having an SP value of 10.0 (cal / cm 3 ) 1 / 2 The following plasticizers may be included:

[0017] The PSA sheet of the second embodiment may be a single-sided PSA sheet having a polyester-based PSA layer on either the first or second surface of the substrate. The PSA sheet of the second embodiment may be a double-sided PSA sheet having a first polyester-based PSA layer on the first surface of the substrate and a second polyester-based PSA layer on the second surface of the substrate, i.e., having a first polyester-based PSA layer, the substrate, and a second polyester-based PSA layer in this order in the stacking direction.

[0018] Hereinafter, when there is no particular distinction between the adhesive sheet of the first embodiment and the adhesive sheet of the second embodiment, or when describing matters common to the adhesive sheet of the first embodiment and the adhesive sheet of the second embodiment, they will simply be referred to as "adhesive sheet."

[0019] The pressure-sensitive adhesive sheet of the present disclosure may optionally have a release film on the outer side of the polyester-based pressure-sensitive adhesive layer. The release film protects the pressure-sensitive adhesive layer. The pressure-sensitive adhesive sheet may, for example, have a substrate, a polyester-based pressure-sensitive adhesive layer, and a release film in this order in the stacking direction, or a first release film, a first polyester-based pressure-sensitive adhesive layer, a substrate, a second polyester-based pressure-sensitive adhesive layer, and a second release film in this order in the stacking direction, or a first release film, a polyester-based pressure-sensitive adhesive layer, and a second release film in this order in the stacking direction. When using the pressure-sensitive adhesive sheet, for example, the release film is peeled off from the pressure-sensitive adhesive layer, and the exposed pressure-sensitive adhesive layer is attached to the surface of an adherend.

[0020] <Substrate> The substrate contains a resin material. Examples of the resin material include vinyl chloride resins such as polyvinyl chloride and vinyl chloride-vinyl acetate copolymer; other vinyl resins such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and polyvinyl alcohol; polyester resins such as polyethylene terephthalate, polyethylene naphthate, polybutylene terephthalate, and polyethylene terephthalate / isophthalate copolymer; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; cycloolefin resins; polystyrene resins; acrylonitrile-butadiene-styrene copolymers; fluoroethylene resins such as polyvinyl fluoride, polyvinylidene fluoride, and fluorinated polyethylene; polyamide resins such as nylon 6 and nylon 6,6; cellulose resins such as cellulose triacetate and cellophane; (meth)acrylic resins such as polymethyl(meth)acrylate, polyethyl(meth)acrylate, and polybutyl(meth)acrylate; polycarbonate resins; polyarylate resins; and polyimide resins. Among these, polyester resins and vinyl chloride resins are preferred, and polyethylene terephthalate and polyvinyl chloride are more preferred. From the viewpoint of reducing the environmental load, the resin material may be a biomass material obtained using raw materials derived from biomass.

[0021] In one embodiment, the substrate in the pressure-sensitive adhesive sheet of the first aspect comprises a vinyl chloride resin and a cellulose ester having an SP value of 10.0 (cal / cm 3 ) 1 / 2 and a plasticizer as follows: Such a substrate has, for example, rigidity due to the vinyl chloride resin and flexibility due to the plasticizer.

[0022] In this specification, a vinyl chloride resin is a polymer having a structural unit derived from vinyl chloride. The content of the structural unit derived from vinyl chloride in 100% by mass of the structural units derived from polymerizable monomers in a vinyl chloride resin is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more. In this specification, the content of each structural unit in a vinyl chloride resin is measured by a nuclear magnetic resonance (NMR) method. Examples of vinyl chloride resins include a homopolymer of vinyl chloride and a copolymer of vinyl chloride and a comonomer.

[0023] Examples of comonomers include vinylidene chloride, α-olefins such as ethylene and propylene, carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, and fumaric acid, and esters or acid anhydrides thereof, vinyl ester-based monomers such as vinyl acetate and vinyl propionate, styrene-based monomers such as styrene, α-methylstyrene, and vinyltoluene, and (meth)acrylonitrile. One or more types of comonomers may be used.

[0024] The substrate may contain one type of resin material or two or more types of resin materials.

[0025] The content of the resin material in the substrate is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, based on 100% by mass of the substrate. The content of the resin material in the substrate of the pressure-sensitive adhesive sheet of the first aspect is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 91% by mass or less, and particularly preferably 87% by mass or less, based on 100% by mass of the substrate.

[0026] The substrate may further contain additives. Examples of additives include antioxidants, UV absorbers, stabilizers, softeners, antistatic agents, tackifiers, plasticizers, inorganic or organic fillers, metal powders, pigments, and dyes. The substrate may contain one type of additive, or two or more types. The substrate may contain a plasticizer, for example, to improve its flexibility. A substrate containing a vinyl chloride resin preferably contains a plasticizer, for example, to improve its flexibility.

[0027] The substrate in the pressure-sensitive adhesive sheet of the first embodiment has an SP value of 10.0 (cal / cm 3 ) 1 / 2 It contains the following plasticizer. A pressure-sensitive adhesive sheet in which such a substrate is combined with a polyester-based pressure-sensitive adhesive layer can suppress a decrease in adhesive strength even after a certain period of time has passed since it is attached to an adherend (for example, in a high-temperature environment). The reason for this is unclear, but the inventors speculate as follows. In prior art, a plasticizer is sometimes blended into the substrate, for example, to improve the flexibility of the substrate. It is thought that the plasticizer contained in the substrate can migrate into the pressure-sensitive adhesive layer, and this migration reduces the adhesive strength of the pressure-sensitive adhesive layer. The SP value is 10.0 (cal / cm 3 ) 1 / 2 As will be shown in the Examples section below, the following plasticizers have low compatibility with polyester resins. 3 ) 1 / 2 It is presumed that the low compatibility between the following plasticizer and the polyester resin contained in the adhesive layer prevents the plasticizer from migrating from the substrate into the adhesive layer, thereby preventing the adhesive strength of the adhesive layer from being reduced by the plasticizer.

[0028] In this specification, the SP value of a plasticizer refers to a solubility parameter calculated by the Fedors method. Specifically, the SP value of a plasticizer is a value (unit: (cal / cm)) calculated by using the numerical values ​​(heat of vaporization and molar volume at 25°C of atoms or functional groups) described on page 152 (Table 5) of Polymer Engineering and Science, February 1974, Vol. 14, No. 2, pp. 147-154, which describes the Fedors method, according to formula (28) described on page 153 of the same publication. 3 ) 1 / 2 )

[0029] SP value is 10.0 (cal / cm 3 ) 1 / 2 Examples of the plasticizers include phthalates such as diisononyl phthalate, di-2-ethylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, and diisodecyl phthalate; adipic esters such as dimethyl adipate, diisobutyl adipate, di-2-ethylhexyl adipate, diisononyl adipate, and diisodecyl adipate; sebacate esters such as dibutyl sebacate and di-2-ethylhexyl sebacate; azelaic esters such as di-2-ethylhexyl azelate; and trimellitic esters such as tri-2-ethylhexyl trimellitate, and have an SP value of 10.0 (cal / cm 3 ) 1 / 2 Examples of suitable plasticizers include the following compounds: The plasticizer is preferably a mono-, di-, or triester of a di- or tricarboxylic acid, such as phthalic acid, adipic acid, sebacic acid, azelaic acid, or trimellitic acid, with an alcohol. Examples of suitable alcohols include linear or branched alkyl alcohols having 1 to 10 carbon atoms, such as methyl alcohol, n-butyl alcohol, isobutyl alcohol, n-heptyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, isononyl alcohol, and isodecyl alcohol.

[0030] The SP value of the plasticizer (unit: (cal / cm 3 ) 1 / 2) is 10.0 or less, preferably 9.8 or less, more preferably 9.6 or less, even more preferably 9.5 or less, and is preferably 8.0 or more, more preferably 8.5 or more, even more preferably 9.0 or more, for example, 8.0 to 10.0.

[0031] SP value is 10.0 (cal / cm 3 ) 1 / 2 The molecular weight of the following plasticizers is preferably 700 or less, more preferably 600 or less, and even more preferably 500 or less. Plasticizers with such molecular weights tend to have a more excellent plasticizing effect than so-called polymer-type plasticizers.

[0032] The substrate in the pressure-sensitive adhesive sheet of the first embodiment has an SP value of 10.0 (cal / cm 3 ) 1 / 2 Contains at least one of the following plasticizers and has an SP value of 10.0 (cal / cm 3 ) 1 / 2 The substrate in the pressure-sensitive adhesive sheet of the first aspect may contain two or more of the following plasticizers: 3 ) 1 / 2 The plasticizers listed below may be contained, and the SP value is 10.0 (cal / cm 3 ) 1 / 2 From the viewpoint of suppressing the migration of the plasticizer into the polyester-based pressure-sensitive adhesive layer, the substrate in the pressure-sensitive adhesive sheet of the first aspect may further contain a plasticizer having an SP value of 10.0 (cal / cm 3 ) 1 / 2 It is preferred that the composition does not contain more than 100% plasticizer.

[0033] In the substrate of the pressure-sensitive adhesive sheet of the first embodiment, the SP value is 10.0 (cal / cm 3 ) 1 / 2 The content of the following plasticizers is, relative to 100 parts by mass of the resin material contained in the base material, preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, particularly preferably 15 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, even more preferably 40 parts by mass or less, particularly preferably 35 parts by mass or less, for example, 1 to 50 parts by mass.

[0034] In the substrate of the pressure-sensitive adhesive sheet of the first embodiment, the SP value is 10.0 (cal / cm 3 ) 1 / 2 From the viewpoint of suppressing the migration of the plasticizer into the polyester-based adhesive layer, the content of the following plasticizers is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on 100% by mass of the total plasticizer contained in the substrate.

[0035] When the pressure-sensitive adhesive sheet of the second embodiment has a substrate, the substrate has an SP value of 10.0 (cal / cm 3 ) 1 / 2 The following plasticizers may be contained: The substrate may be the same substrate as the substrate in the pressure-sensitive adhesive sheet of the first embodiment.

[0036] The substrate may have a single-layer structure or a multi-layer structure having two or more layers.

[0037] The surface of the substrate on which the polyester-based pressure-sensitive adhesive layer is to be formed may be subjected to a surface treatment in order to improve adhesion between the substrate and the polyester-based pressure-sensitive adhesive layer. Examples of the surface treatment include oxidation treatments by chemical or physical methods such as corona treatment, chromic acid treatment, ozone exposure, flame exposure, high-voltage shock exposure, and ionizing radiation treatment.

[0038] The thickness of the substrate is not particularly limited, but is preferably 1 to 1,000 μm, more preferably 5 to 500 μm, even more preferably 10 to 300 μm, and even more preferably 20 to 200 μm.

[0039] <Polyester-based pressure-sensitive adhesive layer> The polyester-based pressure-sensitive adhesive layer is, for example, a layer formed from a pressure-sensitive adhesive composition containing a polyester resin. The pressure-sensitive adhesive composition may contain one type of polyester resin or two or more types of polyester resin. Details of the polyester resin will be described later.

[0040] The content of the polyester resin in the solid content of the pressure-sensitive adhesive composition is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

[0041] The pressure-sensitive adhesive composition may further contain additives. Examples of additives include crosslinkers, antioxidants, UV absorbers, stabilizers, softeners, antistatic agents, tackifiers, plasticizers, inorganic or organic fillers, metal powders, pigments, and dyes. The pressure-sensitive adhesive composition may contain one type of additive or two or more types of additives.

[0042] When the pressure-sensitive adhesive composition contains an additive, the content of the additive is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, per 100 parts by mass of the polyester resin.

[0043] The pressure-sensitive adhesive composition may further contain a crosslinking agent. Examples of crosslinking agents include isocyanate-based crosslinking agents. Isocyanate-based crosslinking agents are compounds having two or more isocyanate groups per molecule. The number of isocyanate groups per molecule of the isocyanate-based crosslinking agent is preferably 2 to 8, more preferably 2 to 6. Examples of isocyanate-based crosslinking agents include diisocyanate compounds having two isocyanate groups per molecule and isocyanate compounds having three or more isocyanate groups per molecule.

[0044] Examples of diisocyanate compounds include aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates. Examples of aliphatic diisocyanates include aliphatic diisocyanates having 4 to 30 carbon atoms, such as ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, and 2,2,4-trimethyl-1,6-hexamethylene diisocyanate. Examples of alicyclic diisocyanates include alicyclic diisocyanates having 7 to 30 carbon atoms, such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylene diisocyanate. Examples of aromatic diisocyanates include aromatic diisocyanates having 8 to 30 carbon atoms, such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenyl ether diisocyanate, diphenylmethane diisocyanate, and diphenylpropane diisocyanate.

[0045] Examples of the isocyanate compound having three or more isocyanate groups in one molecule include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates, and specific examples include 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, and 4,4',4"-triphenylmethane triisocyanate.

[0046] Examples of the isocyanate crosslinking agent include multimers (e.g., dimers or trimers, biurets, isocyanurates), derivatives (e.g., addition reaction products of polyhydric alcohols with two or more molecules of diisocyanate compounds), and polymers of the above-mentioned isocyanate compounds having two or more isocyanate groups. Examples of the polyhydric alcohols in the derivatives include low-molecular-weight polyhydric alcohols such as trimethylolpropane, glycerin, and pentaerythritol, as well as trivalent or higher alcohols, and high-molecular-weight polyhydric alcohols such as polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, and polyisoprene polyols. Examples of such isocyanate-based crosslinking agents include a trimer of diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, a biuret or isocyanurate of hexamethylene diisocyanate or tolylene diisocyanate, a reaction product of trimethylolpropane and tolylene diisocyanate or xylylene diisocyanate (e.g., a trimolecular adduct of tolylene diisocyanate or xylylene diisocyanate), a reaction product of trimethylolpropane and hexamethylene diisocyanate (e.g., a trimolecular adduct of hexamethylene diisocyanate), polyether polyisocyanate, and polyester polyisocyanate.

[0047] When the pressure-sensitive adhesive composition contains a crosslinking agent, the content of the crosslinking agent is not particularly limited, but is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the polyester resin.

[0048] The thickness of the polyester-based pressure-sensitive adhesive layer is not particularly limited, but is preferably 1 to 500 μm, more preferably 3 to 200 μm, even more preferably 5 to 100 μm, and even more preferably 10 to 50 μm. Such a polyester-based pressure-sensitive adhesive layer tends to have excellent adhesiveness to the adherend. When the pressure-sensitive adhesive sheet has a first polyester-based pressure-sensitive adhesive layer and a second polyester-based pressure-sensitive adhesive layer, the above thickness refers to the thickness of each of the first and second polyester-based pressure-sensitive adhesive layers.

[0049] <Polyester Resin> The polyester resin is, for example, a polycondensation product of a monomer mixture containing a dicarboxylic acid component and a diol component. The polyester resin is obtained, for example, by polycondensing the monomer mixture. The polyester resin has a constitutional unit derived from the dicarboxylic acid component and a constitutional unit derived from the diol component.

[0050] The glass transition temperature (Tg) of the polyester resin is preferably 10°C or lower, more preferably -60 to 5°C, and even more preferably -50 to 0°C. When the Tg is equal to or lower than the upper limit, the pressure-sensitive adhesive layer tends to have excellent adhesiveness and flexibility. When the Tg is equal to or higher than the lower limit, the polyester resin tends to have excellent cohesive strength. The Tg of the polyester resin is a value measured using a differential scanning calorimeter (DSC) at a temperature rise rate of 10°C / min, and details of the measurement conditions are described in the Examples section.

[0051] The weight-average molecular weight (Mw) of the polyester resin is preferably 8,000 to 200,000, more preferably 15,000 to 150,000, and even more preferably 20,000 to 100,000. When the Mw is equal to or greater than the lower limit, the polyester resin tends to have excellent cohesive strength as an adhesive, and excellent heat resistance and mechanical strength. When the Mw is equal to or less than the upper limit, gelation during production of the polyester resin tends to be suppressed. Mw is a polystyrene-equivalent value determined by gel permeation chromatography (GPC), and details of the measurement conditions are described in the Examples section.

[0052] The acid value of the polyester resin is preferably 10 mgKOH / g or less, more preferably 3 mgKOH / g or less, and even more preferably 1 mgKOH / g or less. When the acid value is equal to or less than the upper limit, hydrolysis of the polyester resin can be suppressed. The acid value is a value determined by neutralization titration method in accordance with JIS K 0070:1992.

[0053] (Dicarboxylic Acid Component) A dicarboxylic acid component is used as a raw material monomer for polyester resins. In this specification, the term "dicarboxylic acid component" is used to encompass dicarboxylic acids and dicarboxylic acid derivatives. That is, the term "dicarboxylic acid component" may refer to a dicarboxylic acid, a dicarboxylic acid derivative, or a mixture of a dicarboxylic acid and a dicarboxylic acid derivative. Examples of dicarboxylic acid derivatives include dicarboxylic acid esters such as dicarboxylic acid alkyl esters, dicarboxylic acid anhydrides, dicarboxylic acid salts such as sodium salts and potassium salts, and dicarboxylic acid halides such as dicarboxylic acid chloride. The alkyl group in the dicarboxylic acid alkyl ester preferably has 1 to 15 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 5 carbon atoms. The dicarboxylic acid ester may be a dicarboxylic acid monoester or a dicarboxylic acid diester. The dicarboxylic acid alkyl ester may be a dicarboxylic acid monoalkyl ester or a dialkyl diester. The dicarboxylic acid salt may be a dicarboxylic acid monosalt or a disalt. The dicarboxylic acid halide may be a dicarboxylic acid mono- or dihalide.

[0054] In the production of the polyester resin, one or more dicarboxylic acid components may be used. The polyester resin may have one or more dicarboxylic acid component-derived structural units. From the viewpoint of reducing the environmental load, the dicarboxylic acid component may be a biomass component obtained using a biomass-derived raw material.

[0055] Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids and derivatives thereof, alicyclic dicarboxylic acids and derivatives thereof, and aromatic dicarboxylic acids and derivatives thereof.

[0056] Examples of aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, 3,3-dimethylglutaric acid, adipic acid, 2,2,4-trimethyladipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, diglycolic acid, and 1,9-nonanedicarboxylic acid. Examples of alicyclic dicarboxylic acids include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, and adamantanedicarboxylic acid. Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, benzylmalonic acid, diphenic acid, 4,4'-oxydibenzoic acid, 2,5-furandicarboxylic acid, naphthalenedicarboxylic acids (e.g., 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid), and sulfonate group-containing aromatic dicarboxylic acids.

[0057] The dicarboxylic acid component used in the production of the polyester resin preferably contains at least an aromatic dicarboxylic acid component. When a polyester resin of this type is used, the resulting pressure-sensitive adhesive sheet can further suppress the decrease in adhesive strength after a certain period of time has elapsed, and also tends to have better holding power, as described below. In the above-mentioned monomer mixture, the proportion of the aromatic dicarboxylic acid component in 100 mol% of the dicarboxylic acid component is such that the SP value is 10.0 (cal / cm 3 ) 1 / 2 From the viewpoints of resulting in a polyester resin that has low compatibility with the following plasticizers, being able to further suppress a decrease in adhesive strength after a certain period of time, and achieving even better holding power, which will be described later, the content is preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, still more preferably 50 mol% or more, particularly preferably 60 mol% or more, particularly preferably 70 mol% or more, and is preferably 100 mol% or less, more preferably 99 mol% or less, even more preferably 95 mol% or less, particularly preferably 90 mol%, for example, 20 to 100 mol%.

[0058] In the polyester resin, the content of the constituent units derived from the aromatic dicarboxylic acid component in 100 mol% of the constituent units derived from the dicarboxylic acid component is preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, even more preferably 50 mol% or more, particularly preferably 60 mol% or more, particularly preferably 70 mol% or more, and is preferably 100 mol% or less, more preferably 99 mol% or less, even more preferably 95 mol% or less, particularly preferably 90 mol%, for example, 20 to 100 mol%. In this specification, the content of the constituent units derived from each component in the polyester resin is measured by a nuclear magnetic resonance (NMR) method.

[0059] The dicarboxylic acid component used in the production of the polyester resin preferably contains at least a sulfonate group-containing dicarboxylic acid component. Such a polyester resin has high cohesive strength, and the resulting PSA sheet tends to have even better holding power, as described below. Examples of the sulfonate group-containing dicarboxylic acid component include sulfonate group-containing dicarboxylic acids and their derivatives. Examples of the derivatives include mono- or diesters of dicarboxylic acids, carboxylic acid anhydrides, mono- or di-salts of dicarboxylic acids, and mono- or dihalides of dicarboxylic acids.

[0060] The sulfonate group-containing dicarboxylic acid has two carboxy groups and a sulfonate group in the molecule. Examples of sulfonate groups include metal salts, ammonium salts, and organic amine salts of the sulfonic acid group (—SO3H). Examples of metal atoms that form metal salts include monovalent metal atoms such as alkali metal atoms (e.g., lithium, sodium, and potassium) and divalent metal atoms (e.g., calcium and magnesium). Examples of organic amine salts include alkanolamine salts (e.g., ethanolamine salts, diethanolamine salts, and triethanolamine salts) and triethylamine salts. Examples of sulfonate groups include sodium sulfonate groups, potassium sulfonate groups, magnesium sulfonate groups, calcium sulfonate groups, and ammonium sulfonate groups, with sodium sulfonate groups being particularly preferred.

[0061] The sulfonate group-containing dicarboxylic acid component is preferably a sulfonate group-containing aromatic dicarboxylic acid component, more preferably an aromatic dicarboxylic acid component having a sulfonate group bonded to a benzene ring, and even more preferably phthalic acid, isophthalic acid, or terephthalic acid, each of which has a sulfonate group bonded to a benzene ring.

[0062] Examples of sulfonate group-containing dicarboxylic acid components include sodium 5-sulfoisophthalate, sodium dimethyl 5-sulfoisophthalate, potassium dimethyl 5-sulfoisophthalate, sodium 4-sulfoisophthalate, sodium dimethyl 4-sulfoisophthalate, potassium dimethyl 4-sulfoisophthalate, sodium 2-sulfoterephthalate, potassium 2-sulfoterephthalate, sodium dimethyl 2-sulfoterephthalate, and potassium dimethyl 2-sulfoterephthalate. Of these, sodium dimethyl 5-sulfoisophthalate is preferred.

[0063] In the above-mentioned monomer mixture, the proportion of the sulfonate group-containing dicarboxylic acid component is preferably 1 to 10 mol %, more preferably 2 to 8 mol %, and even more preferably 3 to 7 mol %, based on 100 mol % of the dicarboxylic acid component used in the production of the polyester resin.

[0064] In the polyester resin, the content of the constituent units derived from the sulfonate group-containing dicarboxylic acid component in 100 mol % of the constituent units derived from the dicarboxylic acid component is preferably 1 to 10 mol %, more preferably 2 to 8 mol %, and even more preferably 3 to 7 mol %.

[0065] As a raw material monomer for the polyester resin, a trivalent or higher polycarboxylic acid component may be further used together with the dicarboxylic acid component. Examples of the trivalent or higher polycarboxylic acid component include trivalent or higher polycarboxylic acids and their derivatives. Examples of the trivalent or higher polycarboxylic acid component include trimellitic acid, pyromellitic acid, adamantanetricarboxylic acid, and trimesic acid. By using a trivalent or higher polycarboxylic acid component, for example, it is possible to introduce branching points into the polyester resin.

[0066] In the above-mentioned monomer mixture, the amount of the trivalent or higher polycarboxylic acid component is preferably 20 mol or less, more preferably 10 mol or less, even more preferably 5 mol or less, and particularly preferably 1 mol or less, per 100 mol of the dicarboxylic acid component, from the viewpoint of ease of production of the polyester resin.

[0067] In the polyester resin, the content of structural units derived from trivalent or higher polycarboxylic acid components is preferably 20 mol or less, more preferably 10 mol or less, even more preferably 5 mol or less, and particularly preferably 1 mol or less, per 100 mol of structural units derived from dicarboxylic acid components, from the viewpoint of ease of production of the polyester resin.

[0068] (Diol Component) A diol component (hereinafter also simply referred to as "diol") is used as a raw material monomer for a polyester resin. In producing the polyester resin, one type of diol may be used, or two or more types of diols may be used. The polyester resin may have one type of diol-derived structural unit, or two or more types. From the viewpoint of reducing the environmental load, the diol may be a biomass component obtained using a biomass-derived raw material.

[0069] The diol has two hydroxy groups. Examples of the diol include aliphatic diols, alicyclic diols, and aromatic diols. Other diol components include fatty acid esters derived from castor oil, dimer diols derived from oleic acid or erucic acid, and glycerol monostearate.

[0070] Examples of aliphatic diols include linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, and triethylene glycol; propylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, and 2-methyl-2-propyl-1,3-propanediol; branched diols such as hexanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,3,5-trimethyl-1,3-pentanediol, 2-methyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, and 2,4-dimethyl-2-ethyl-1,3-hexanediol; and ethylene oxide or propylene oxide adducts of these diols.

[0071] Examples of alicyclic diols include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, spiroglycol, tricyclodecane dimethanol, adamantanediol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol; and ethylene oxide or propylene oxide adducts of these diols.

[0072] Examples of aromatic diols include dihydroxybenzene, naphthalenediol, xylenediol, 4,4'-methylenediphenol, and 4,4'-dihydroxybiphenyl; and ethylene oxide or propylene oxide adducts of these diols.

[0073] Among the diols, from the viewpoint of reactivity in the production of polyester resin, aliphatic diols are preferred, aliphatic diols having 2 to 20 carbon atoms are more preferred, and aliphatic diols having 2 to 10 carbon atoms are even more preferred.

[0074] In the above-mentioned monomer mixture, the proportion of the aliphatic diol in 100 mol % of the diol used in the production of the polyester resin is preferably 50 mol % or more, more preferably 60 mol % or more, even more preferably 70 mol % or more, still more preferably 80 mol % or more, and particularly preferably 90 mol % or more, from the viewpoint of ease of production of the polyester resin.

[0075] In the polyester resin, the content of aliphatic diol-derived structural units in 100 mol% of diol-derived structural units is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more, from the viewpoint of ease of production of the polyester resin.

[0076] As a raw material monomer for the polyester resin, a trivalent or higher polyol may be further used together with the diol. The trivalent or higher polyol has three or more hydroxy groups. Examples of trivalent or higher polyols include pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, trimethylolpropane, trimethylolethane, 1,3,6-hexanetriol, and adamantanetriol.

[0077] In the above-mentioned monomer mixture, the amount of trivalent or higher polyol is preferably 20 mol or less, more preferably 10 mol or less, even more preferably 5 mol or less, and particularly preferably 1 mol or less, per 100 mol of diol, from the viewpoint of ease of production of the polyester resin.

[0078] In the polyester resin, the content of the structural units derived from a trivalent or higher polyol per 100 mol of the structural units derived from the diol component is preferably 20 mol or less, more preferably 10 mol or less, even more preferably 5 mol or less, and particularly preferably 1 mol or less, from the viewpoint of ease of production of the polyester resin.

[0079] (Production of Polyester Resin) The polyester resin can be produced, for example, by polycondensation of a dicarboxylic acid component and a diol component by a known method, optionally in the presence of a catalyst. In one embodiment, the esterification reaction is carried out, followed by the polycondensation reaction.

[0080] Regarding the compounding ratio of the dicarboxylic acid component and the diol component in the production of the polyester resin, the amount of the diol component is preferably 1 to 3 mol, more preferably 1.1 to 2.5 mol, per 1 mol of the dicarboxylic acid component.

[0081] A catalyst may be used in the esterification reaction. Examples of the catalyst include titanium-based catalysts such as titanium tetraisopropoxide and titanium tetrabutoxide; antimony-based catalysts such as antimony trioxide; germanium-based catalysts such as germanium dioxide; and catalysts such as zinc acetate, manganese acetate, and dibutyltin oxide. One type of catalyst may be used, or two or more types may be used. The amount of catalyst used is preferably 1.0 × 10 relative to 1 mol of the total of the raw material monomers contained in the monomer mixture. -7 ~1.0 x 10 -3 mol, more preferably 5.0 × 10 -7 ~0.5 x 10 -3 mol, more preferably 1.0 × 10 -6 ~1.0 x 10 -4 mol.

[0082] The reaction temperature in the esterification reaction is preferably 150 to 280°C, more preferably 160 to 260°C, and even more preferably 170 to 240°C.

[0083] A catalyst may be used in the polycondensation reaction. Examples of the catalyst include the catalysts exemplified in the explanation of the esterification reaction. The reaction temperature in the polycondensation reaction is preferably 200 to 300°C, more preferably 220 to 280°C. In the polycondensation reaction, the pressure of the reaction system may be gradually reduced, and the reaction may be finally carried out at 500 Pa or less.

[0084] <Release Film> Examples of the release film include films obtained by subjecting a resin film formed from the resin materials exemplified as components constituting the above-mentioned substrate to a release treatment; foams such as polyurethane foam, vinyl foam, polyethylene foam, and polystyrene foam; metal foils such as aluminum foil, copper foil, stainless steel foil, iron foil, duralumin foil, tin foil, titanium foil, and gold foil; paper; woven fabric; and nonwoven fabric.

[0085] The release treatment may be, for example, a treatment in which a release agent is applied in the form of a layer. Examples of the release agent include silicone-based resins, long-chain alkyl-based resins, fluorine-based resins, and phosphate ester-based surfactants. One type of release agent may be used, or two or more types may be used.

[0086] The thickness of the release film is not particularly limited, but is preferably 1 to 1,000 μm, more preferably 5 to 500 μm, even more preferably 10 to 300 μm, and even more preferably 20 to 200 μm. When the PSA sheet has a first release film and a second release film, the above thickness refers to the thickness of each of the first and second release films.

[0087] <Subject (adherend) to which the pressure-sensitive adhesive sheet of the second embodiment is attached> The pressure-sensitive adhesive sheet of the second embodiment is made of a resin material and a material having an SP value of 10.0 (cal / cm 3 ) 1 / 2 It is applied to an adherend having a portion containing the following plasticizer: The adherend to which the pressure-sensitive adhesive sheet of the second embodiment is applied will be described below.

[0088] The above-mentioned portion of the adherend contains a resin material. Examples of the resin material include vinyl chloride resins such as polyvinyl chloride and vinyl chloride-vinyl acetate copolymer; other vinyl resins such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and polyvinyl alcohol; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polyethylene terephthalate / isophthalate copolymer; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; cycloolefin resins; polystyrene resins; acrylonitrile-butadiene-styrene copolymers; fluoroethylene resins such as polyvinyl fluoride, polyvinylidene fluoride, and fluorinated polyethylene; polyamide resins such as nylon 6 and nylon 6,6; cellulose resins such as cellulose triacetate and cellophane; (meth)acrylic resins such as polymethyl(meth)acrylate, polyethyl(meth)acrylate, and polybutyl(meth)acrylate; polycarbonate resins; polyarylate resins; and polyimide resins. Among these, polyester resins and vinyl chloride resins are preferred, and polyethylene terephthalate and polyvinyl chloride are more preferred. From the viewpoint of reducing the environmental load, the resin material may be a biomass material obtained using raw materials derived from biomass.

[0089] In one embodiment, the above-mentioned portion of the adherend is made of a vinyl chloride resin and a polyurethane having an SP value of 10.0 (cal / cm 3 ) 1 / 2 and a plasticizer as follows: An adherend having such a portion has, for example, rigidity due to the vinyl chloride resin and flexibility due to the plasticizer.

[0090] The above-mentioned portion of the adherend may contain one type of resin material or two or more types of resin materials.

[0091] The content of the resin material in the above-mentioned portion of the adherend is, based on 100% by mass of the above-mentioned portion, preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 91% by mass or less, particularly preferably 87% by mass or less, for example, 50 to 99% by mass.

[0092] The above-mentioned portion of the adherend may further contain an additive. Examples of additives include antioxidants, ultraviolet absorbers, stabilizers, softeners, antistatic agents, tackifiers, plasticizers, inorganic or organic fillers, metal powders, pigments, and dyes. The above-mentioned portion of the adherend may contain one type of additive, or may contain two or more types. The above-mentioned portion of the adherend may contain a plasticizer, for example, to improve its flexibility. The above-mentioned portion containing a vinyl chloride resin preferably contains a plasticizer, for example, to improve its flexibility.

[0093] The polyester-based pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of the second embodiment is a layer formed from a pressure-sensitive adhesive composition containing a polyester resin, and the above-mentioned part of the adherend has an SP value of 10.0 (cal / cm 3 ) 1 / 2 It contains the following plasticizer. Such a pressure-sensitive adhesive sheet can suppress a decrease in adhesive strength even after a certain period of time has passed since it has been attached to an adherend (for example, in a high-temperature environment). The reason for this is unclear, but the inventors speculate as follows. In prior art, for example, a plasticizer is sometimes blended into the above-mentioned part of the adherend in order to improve the flexibility of the above-mentioned part. It is thought that the plasticizer contained in the adherend can migrate into the pressure-sensitive adhesive layer, and this migration reduces the adhesive strength of the pressure-sensitive adhesive layer. The SP value is 10.0 (cal / cm 3 ) 1 / 2 As will be shown in the Examples section below, the following plasticizers have low compatibility with polyester resins. 3 ) 1 / 2It is presumed that the low compatibility between the following plasticizer and the polyester resin contained in the adhesive layer prevents the plasticizer from migrating from the adherend into the adhesive layer, thereby preventing the adhesive strength of the adhesive layer from being reduced by the plasticizer.

[0094] SP value is 10.0 (cal / cm 3 ) 1 / 2 Details of the following plasticizers (for example, specific examples, SP values, and molecular weights) are as described above, and will not be described here.

[0095] The above-mentioned portion of the adherend of the pressure-sensitive adhesive sheet of the second embodiment has an SP value of 10.0 (cal / cm 3 ) 1 / 2 Contains at least one of the following plasticizers and has an SP value of 10.0 (cal / cm 3 ) 1 / 2 The pressure-sensitive adhesive sheet of the second embodiment may contain two or more of the following plasticizers: 3 ) 1 / 2 The plasticizers listed below may be contained, and the SP value is 10.0 (cal / cm 3 ) 1 / 2 From the viewpoint of inhibiting the migration of the plasticizer into the polyester-based pressure-sensitive adhesive layer, the part of the adherend of the pressure-sensitive adhesive sheet of the second aspect may further contain a plasticizer having an SP value of 10.0 (cal / cm 3 ) 1 / 2 It is preferred that the composition does not contain more than 100% plasticizer.

[0096] At the above-mentioned portion of the adherend, the SP value is 10.0 (cal / cm 3 ) 1 / 2 The content of the plasticizer below is, relative to 100 parts by mass of the resin material contained in the above-mentioned portion, preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, particularly preferably 15 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, even more preferably 40 parts by mass or less, particularly preferably 35 parts by mass or less, for example, 1 to 50 parts by mass.

[0097] At the above-mentioned portion of the adherend, the SP value is 10.0 (cal / cm 3 )1 / 2 From the viewpoint of suppressing the migration of the plasticizer into the polyester-based adhesive layer, the content of the following plasticizer is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on 100% by mass of the total plasticizer contained in the above-mentioned portion.

[0098] <Production of Pressure-Sensitive Adhesive Sheet> The pressure-sensitive adhesive sheet of the present disclosure can be produced, for example, by a conventionally known method. For example, the pressure-sensitive adhesive sheet can be produced as follows. A pressure-sensitive adhesive composition containing a polyester resin is prepared. The pressure-sensitive adhesive composition is applied to the first or second surface of a substrate and dried to form a pressure-sensitive adhesive layer, a release film is attached to the surface of the pressure-sensitive adhesive layer, and a curing treatment is performed as necessary. Alternatively, the pressure-sensitive adhesive composition is applied to the surface of a release film and dried to form a pressure-sensitive adhesive layer, a substrate is attached to the surface of the pressure-sensitive adhesive layer, and a curing treatment is performed as necessary. In this way, a pressure-sensitive adhesive sheet having a substrate, a pressure-sensitive adhesive layer, and a release film is obtained.

[0099] For example, a pressure-sensitive adhesive sheet can be produced as follows: A pressure-sensitive adhesive composition containing a polyester resin is prepared. The pressure-sensitive adhesive composition is applied to the surface of a release film and dried to form a pressure-sensitive adhesive layer. Another release film is then laminated to the surface of the pressure-sensitive adhesive layer, and a curing treatment is performed if necessary. In this way, a double-sided pressure-sensitive adhesive sheet without a substrate is obtained.

[0100] The PSA composition may contain a solvent or a dispersion medium. Examples of the solvent or dispersion medium include an organic solvent (organic dispersion medium) and water. The PSA composition may be in the form of, for example, a solution containing a polyester resin and a solvent, or a dispersion containing a polyester resin and a dispersion medium.

[0101] Examples of organic solvents (organic dispersion media) include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, and diphenyl ether; halogenated hydrocarbons such as chloroform, carbon tetrachloride, 1,2-dichloroethane, and chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; and sulfoxides such as dimethyl sulfoxide and sulfolane. Examples of water include tap water, deionized water, and ion-exchanged water. The pressure-sensitive adhesive composition may contain one or more solvents or dispersion media.

[0102] The content of the solvent or dispersion medium in the pressure-sensitive adhesive composition is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and even more preferably 20 to 70% by mass.

[0103] Examples of methods for applying the pressure-sensitive adhesive composition include spin coating, knife coating, roll coating, bar coating, blade coating, die coating, and gravure coating.

[0104] As for the drying conditions after application of the PSA composition, the drying temperature is preferably 50 to 150°C, more preferably 60 to 120°C, and the drying time is preferably 1 to 10 minutes, more preferably 2 to 7 minutes. As for the conditions for the curing treatment, the curing temperature is preferably 5 to 60°C, more preferably 15 to 40°C, and the curing time is preferably 1 to 30 days, more preferably 3 to 20 days.

[0105] <Uses of Pressure-Sensitive Adhesive Sheet> The pressure-sensitive adhesive sheet of the present disclosure can be used for a variety of applications. The material of the portion of the adherend to which the pressure-sensitive adhesive sheet of the first embodiment is attached is not particularly limited. The portion of the adherend to which the pressure-sensitive adhesive sheet of the second embodiment is attached is preferably made of a resin material and a resin having an SP value of 10.0 (cal / cm 3 ) 1 / 2 Contains the following plasticizers:

[0106] The pressure-sensitive adhesive sheet of the present disclosure can be used as, for example, a marking film for display or decoration.The substrate to which the marking film is attached includes, for example, vehicles such as bicycles, motorcycles, automobiles, buses, and trains; household items such as furniture and home appliances; office supplies such as cabinets, desks, and personal computers; buildings such as houses; daily necessities such as mobile phones and mobile phone covers; and their exterior or interior parts.The material of the substrate includes, for example, plastic, glass, and metals such as stainless steel and aluminum.

[0107] The pressure-sensitive adhesive sheet of the present disclosure can be used as, for example, a surface protection sheet.The uses of the surface protection sheet include, for example, a protection sheet for plastic film or glass plate, a protection sheet for optical components, a protection sheet for semiconductor wafer, a protection sheet for electronic components and electronic equipment such as electronic substrates, and a protection sheet for metal plates such as stainless steel and aluminum.Therefore, the adherend to which the surface protection sheet is attached includes, for example, a plastic film, a glass plate, an optical component, a semiconductor wafer, an electronic substrate, and other electronic components and electronic equipment, and a metal plate such as stainless steel and aluminum.

[0108] Examples of optical components include inorganic transparent electrode films such as ITO electrode films, organic transparent electrode films such as polythiophene, polarizing plates, retardation plates, elliptically polarizing plates, light diffusion films, optical compensation films, brightness enhancement films, electromagnetic wave shielding films, near-infrared absorbing films, antireflection films, and antiglare films.

[0109] When the pressure-sensitive adhesive sheet of the present disclosure further comprises an optical member, it can be used, for example, as an optical sheet. The pressure-sensitive adhesive sheet of the present disclosure can also be used as a pressure-sensitive adhesive sheet for optical members used for bonding the optical member.

[0110] Preferred adherends for the PSA sheet of the second embodiment include, for example, vehicle components such as automobiles, buses, and trains, aircraft components, ship components, and building components, and more preferred are vehicle interior materials, aircraft interior materials, ship interior materials, and building interior materials. The PSA sheet of the second embodiment is attached to, for example, the above-mentioned interior materials.

[0111] [Laminate] The laminate of the present disclosure has a first resin layer, a polyester-based pressure-sensitive adhesive layer, and a second resin layer in this order in the lamination direction.

[0112] At least one layer selected from the first resin layer and the second resin layer is made of a resin material and a resin having an SP value of 10.0 (cal / cm 3 ) 1 / 2 In one embodiment, the layer (A) is a layer (hereinafter also referred to as "layer (A)") containing a vinyl chloride resin and a plasticizer having an SP value of 10.0 (cal / cm 3 ) 1 / 2 The resin material contains the following plasticizer: 3 ) 1 / 2 The details of the plasticizer and polyester-based pressure-sensitive adhesive layer are as described above, and therefore will not be described here.

[0113] The content of the resin material in the layer (A) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and is preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 91% by mass or less, particularly preferably 87% by mass or less, for example, 50 to 99% by mass, based on 100% by mass of the layer (A).

[0114] The layer (A) may further contain the additives described above.

[0115] In the layer (A), the SP value is 10.0 (cal / cm 3 )1 / 2 The content of the following plasticizers, relative to 100 parts by mass of the resin material contained in Layer (A), is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, particularly preferably 15 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, even more preferably 40 parts by mass or less, particularly preferably 35 parts by mass or less, for example, 1 to 50 parts by mass.

[0116] In the layer (A), the SP value is 10.0 (cal / cm 3 ) 1 / 2 From the viewpoint of suppressing the migration of the plasticizer into the polyester-based pressure-sensitive adhesive layer, the content of the following plasticizer is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on 100% by mass of the total plasticizer contained in layer (A).

[0117] In one embodiment of the laminate, the first resin layer is in contact with one surface of the polyester-based pressure-sensitive adhesive layer, and the second resin layer is in contact with the other surface of the polyester-based pressure-sensitive adhesive layer.

[0118] In one embodiment of the laminate, one of the first resin layer and the second resin layer is the substrate of the above-mentioned pressure-sensitive adhesive sheet, and the other is a portion of an adherend to which the above-mentioned pressure-sensitive adhesive sheet is attached that comes into contact with the pressure-sensitive adhesive layer. The pressure-sensitive adhesive sheet 1 shown in Fig. 1 has a substrate 10 and a polyester-based pressure-sensitive adhesive layer 20. The laminate 2 shown in Fig. 2 has, in this order, the substrate 10, the polyester-based pressure-sensitive adhesive layer 20, and an adherend 30.

[0119] For example, if either the first resin layer or the second resin layer is made of the resin material in the pressure-sensitive adhesive sheet of the first aspect described above and has an SP value of 10.0 (cal / cm 3 ) 1 / 2 For example, one of the first resin layer and the second resin layer is a substrate containing the following plasticizer, and the other is a portion of an adherend to which the above-mentioned PSA sheet is to be attached, the portion being in contact with the PSA layer. 3) 1 / 2 The part containing the following plasticizers:

[0120] [Examples] The present disclosure relates to the following [1] to

[11] , for example: [1] A resin material and a resin having an SP value of 10.0 (cal / cm 3 ) 1 / 2 A pressure-sensitive adhesive sheet having a substrate containing the following plasticizer and a polyester-based pressure-sensitive adhesive layer. [2] The pressure-sensitive adhesive sheet according to [1], wherein the substrate contains at least a vinyl chloride resin as the resin material. [3] A pressure-sensitive adhesive sheet having a polyester-based pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive sheet is a polyester-based pressure-sensitive adhesive layer containing a resin material and a polyvinyl chloride resin having an SP value of 10.0 (cal / cm 3 ) 1 / 2 A pressure-sensitive adhesive sheet that is to be attached to an adherend having a portion containing the following plasticizer, such that the polyester-based pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is in contact with the portion of the adherend. [4] The pressure-sensitive adhesive sheet according to [3] above, wherein the portion of the adherend contains at least a vinyl chloride resin as the resin material. [5] The pressure-sensitive adhesive sheet according to any of [1] to [4] above, wherein the polyester-based pressure-sensitive adhesive layer is a layer formed from a pressure-sensitive adhesive composition containing a polyester resin having a glass transition temperature of 10°C or less. [6] The SP value of the plasticizer is 8.0 to 9.6 (cal / cm 3 ) 1 / 2[7] The pressure-sensitive adhesive sheet according to any one of [1] to [5] above, wherein the polyester-based pressure-sensitive adhesive layer is a layer formed from a pressure-sensitive adhesive composition containing a polyester resin which is a polycondensate of a monomer mixture containing a dicarboxylic acid component and a diol component, and the polyester resin contains 50 to 100 mol % of structural units derived from an aromatic dicarboxylic acid component, based on 100 mol % of structural units derived from the dicarboxylic acid component. [8] The pressure-sensitive adhesive sheet according to [7] above, wherein the polyester resin contains 1 to 10 mol % of structural units derived from a sulfonate group-containing dicarboxylic acid component, based on 100 mol % of structural units derived from the dicarboxylic acid component. [9] The pressure-sensitive adhesive sheet according to any one of [1] to [5] above, wherein the plasticizer is at least one selected from a phthalate ester, an adipic acid ester, a sebacate ester, an azelaate ester, and a trimellitic acid ester, and wherein the plasticizer has an SP value of 10.0 (cal / cm 3 ) 1 / 2

[10] A pressure-sensitive adhesive sheet according to any one of the above [1] to [8], wherein the compound is the following compound:

[11] A laminate comprising a first resin layer, a polyester-based pressure-sensitive adhesive layer, and a second resin layer in this order in a stacking direction, and at least one layer selected from the first resin layer and the second resin layer is a resin material and a polyester-based pressure-sensitive adhesive layer having an SP value of 10.0 (cal / cm 3 ) 1 / 2

[11] A laminate comprising: at least one layer selected from the first resin layer and the second resin layer; 3 ) 1 / 2 The laminate according to

[10] above,

[0121] The pressure-sensitive adhesive sheet of the present disclosure will be described in more detail below based on production examples, but the pressure-sensitive adhesive sheet of the present disclosure is not limited to these production examples in any way.

[0122] [Methods for measuring various physical properties, etc.] <Content of structural units in polyester resin> The content ratio (amount of structural units) of structural units derived from each raw material monomer in the polyester resin was calculated by nuclear magnetic resonance (NMR) under the following conditions: Measuring device: ECZL-500G (manufactured by JEOL Ltd.) Measuring method: 1 H-NMR Accumulation number: 16 Sample concentration: 10 mg / ml Dilution solvent: dimethyl sulfoxide (DMSO)-d6

[0123] <Glass Transition Temperature (Tg) of Polyester Resin> The polyester resin was placed in a simple hermetic pan and measured using a differential scanning calorimeter (DSC). The temperature was increased from -60°C to 200°C at a rate of 10°C / min under a nitrogen stream, and the thermal change was measured to plot a DSC curve of "endothermal heat generation" versus "temperature." The temperature at the characteristic inflection point observed at this time was taken as Tg. The Tg value was obtained from the DSC curve by the midpoint method.

[0124] <Weight-average molecular weight (Mw) of polyester resin> The weight-average molecular weight (Mw) of the polyester resin, calculated in terms of polystyrene, was determined by gel permeation chromatography (GPC) under the following conditions: Measurement device: HLC-8320GPC (manufactured by Tosoh Corporation) GPC column configuration: the following four columns in series (all manufactured by Tosoh Corporation): (1) TSKgel HxL-H (guard column) (2) TSKgel GMHxL (3) TSKgel GMHxL (4) TSKgel G2500HxL Flow rate: 1.0 mL / min Column temperature: 40°C Sample concentration: 1.5% (w / v) (diluted with tetrahydrofuran) Mobile phase solvent: tetrahydrofuran Standard polystyrene equivalent

[0125] <Compatibility> The polyester resin obtained in the following production example was prepared. 3 ) 1 / 2 Di-2-ethylhexyl phthalate (DOP) and an SP value of 10.5 (cal / cm 3 ) 1 / 2Diethyl phthalate (DEP) of 100 parts by mass of polyester resin and 20 parts by mass of DOP were dissolved in tetrahydrofuran (THF) to prepare a solution with a solids concentration of 30% by mass. Similarly, 100 parts by mass of polyester resin and 20 parts by mass of DEP were dissolved in THF to prepare a solution with a solids concentration of 30% by mass. Each of the obtained solutions was applied to a 50 μm thick polyethylene terephthalate (PET) film so that the thickness after drying was 20 μm, and the film was dried in an environment of 100 ° C for 2 minutes to remove the solvent, forming a pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer after solvent removal was visually inspected and evaluated according to the following criteria.

[0126] A: Cloudiness or bleed-out is observed in the pressure-sensitive adhesive layer. This indicates low compatibility between the polyester resin and the plasticizer. In this case, it is believed that migration of the plasticizer from the layer containing the plasticizer into the polyester-based pressure-sensitive adhesive layer can be effectively suppressed. B: Slight cloudiness is observed in the pressure-sensitive adhesive layer. C: No cloudiness in the pressure-sensitive adhesive layer, and no bleed-out is observed. This indicates high compatibility between the polyester resin and the plasticizer. In this case, it is believed that migration of the plasticizer from the layer containing the plasticizer into the polyester-based pressure-sensitive adhesive layer cannot be sufficiently suppressed.

[0127] [Production Example A1] A flask equipped with a heater, thermometer, stirrer, distillation column, nitrogen inlet tube, and vacuum device was charged with 0.75 mol of isophthalic acid (IPA), 0.2 mol of sebacic acid (SebA), 0.05 mol of 5-dimethylsodium sulfoisophthalate (SIPM), 2 mol of diethylene glycol (DEG), and 0.000035 mol of Orgatix TA-8 (titanium tetraisopropoxide, manufactured by Matsumoto Fine Chemicals) as a polymerization catalyst. The temperature in the flask was gradually increased to 200 ° C while introducing nitrogen, and the esterification reaction was carried out for 3 hours. Thereafter, the temperature in the flask was increased to 250 ° C, and the pressure was reduced to 100 Pa, and the polycondensation reaction was carried out for 3 hours. In this way, polyester resin (1) was obtained. The glass transition temperature of polyester resin (1) was -5 ° C, and the weight average molecular weight was 40,000.

[0128] [Production Examples A2 to A5] Polyester resins (2) to (5) were produced in the same manner as in Production Example A1, except that the amounts of raw material monomers charged were changed as shown in Table 1.

[0129]

[0130] IPA: Isophthalic acid SebA: Sebacic acid SIPM: Sodium dimethyl 5-sulfoisophthalate DEG: Diethylene glycol MPD: 3-methyl-1,5-pentanediol DOP: Di-2-ethylhexyl phthalate DEP: Diethyl phthalate

[0131] [Production Example B1] Polyester resin (1) and THF were charged into a sample bottle to prepare a solution of polyester resin (1) with a solids concentration of 30% by mass. The obtained solution was applied to a 50 μm thick PET film so that the thickness after drying was 20 μm, and dried in a 100 ° C environment for 2 minutes to remove the solvent, forming a pressure-sensitive adhesive layer. A release-treated PET film was attached to the surface of the pressure-sensitive adhesive layer opposite the surface in contact with the PET film. In this way, a pressure-sensitive adhesive sheet having a 50 μm thick PET film, a 20 μm thick pressure-sensitive adhesive layer, and a release-treated PET film was obtained.

[0132] [Production Examples B2 to B5] Pressure-sensitive adhesive sheets were produced in the same manner as in Production Example B1, except that the polyester resin (1) was changed to one of the polyester resins (2) to (5) shown in Table 2.

[0133] [Evaluation] <Adhesive strength> Polyvinyl chloride (PVC) and a plasticizer with an SP value of 9.5 (cal / cm 3 ) 1 / 2 and di-2-ethylhexyl phthalate (DOP) of , and then the obtained mixture was calendered at 170°C to produce a polyvinyl chloride resin film containing 23 mass% of DOP (hereinafter also referred to as "polyvinyl chloride resin film (1)").

[0134] The plasticizer has an SP value of 10.5 (cal / cm 3 ) 1 / 2A polyvinyl chloride resin film (hereinafter also referred to as "polyvinyl chloride resin film (2)") was produced in the same manner as above, except that diethyl phthalate (DEP) of 100 ppm was used.

[0135] The pressure-sensitive adhesive sheet was cut into a size of 20 mm x 100 mm, and the release-treated PET film was peeled off from the pressure-sensitive adhesive layer. The exposed pressure-sensitive adhesive layer was attached to polyvinyl chloride resin film (1) or (2), and a 2 kg roller was rolled back and forth three times to prepare a test piece. Two test pieces were prepared for each test. One test piece was left in a 23°C and 50% RH environment for 20 minutes (referred to as "initial" in Table 2), and the other test piece was left in a 60°C environment for 24 hours (referred to as "60°C x 24 hr" in Table 2). The edge of the pressure-sensitive adhesive sheet was pulled at a speed of 300 mm / min in a 180° direction relative to the surface of the polyvinyl chloride resin film, and the adhesive strength was measured. The larger the ratio of the adhesive strength after 60°C x 24 hr to the initial adhesive strength, the less likely the adhesive strength was to decrease.

[0136] <Holding Power> Under conditions of 23°C and 50% RH, the release-treated PET film of the pressure-sensitive adhesive sheet was peeled off, and the exposed pressure-sensitive adhesive layer was attached to a SUS plate, followed by a pressure-bonding treatment in which a 2 kg roller was rolled back and forth three times. The adhesion area was 25 mm x 25 mm. 20 minutes after application, a 500 g load was applied parallel to the pressure-sensitive adhesive layer surface at 40°C and dry conditions, and the displacement distance (mm) of the pressure-sensitive adhesive sheet from its original position after 1 hour was measured. The smaller the displacement distance of the pressure-sensitive adhesive sheet, the higher the holding power of the pressure-sensitive adhesive sheet.

[0137]

[0138] DESCRIPTION OF SYMBOLS 1... Pressure-sensitive adhesive sheet 2...Laminate 10...Substrate 20...Polyester-based pressure-sensitive adhesive layer 30...Adherend

Claims

1. Resin material and SP value of 10.0 (cal / cm 3 ) 1 / 2 A pressure-sensitive adhesive sheet comprising: a substrate containing the following plasticizer; and a polyester-based pressure-sensitive adhesive layer.

2. The pressure-sensitive adhesive sheet according to claim 1, wherein the base material contains at least a vinyl chloride resin as the resin material.

3. A pressure-sensitive adhesive sheet having a polyester-based pressure-sensitive adhesive layer, the pressure-sensitive adhesive sheet being made of a resin material and having an SP value of 10.0 (cal / cm 3 ) 1 / 2 13. A pressure-sensitive adhesive sheet, which is to be attached to an adherend having a portion containing a plasticizer such that the polyester-based pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is in contact with the portion of the adherend.

4. The pressure-sensitive adhesive sheet according to claim 3, wherein the portion of the adherend contains at least a vinyl chloride resin as the resin material.

5. The pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the polyester-based pressure-sensitive adhesive layer is a layer formed from a pressure-sensitive adhesive composition containing a polyester resin having a glass transition temperature of 10°C or lower.

6. The SP value of the plasticizer is 8.0 to 9.6 (cal / cm 3 ) 1 / 2 The pressure-sensitive adhesive sheet according to any one of claims 1 to 4, 7. The adhesive sheet according to any one of claims 1 to 4, wherein the polyester-based adhesive layer is a layer formed from an adhesive composition containing a polyester resin which is a polycondensate of a monomer mixture containing a dicarboxylic acid component and a diol component, and the polyester resin contains 50 to 100 mol % of structural units derived from an aromatic dicarboxylic acid component, per 100 mol % of structural units derived from the dicarboxylic acid component.

8. The pressure-sensitive adhesive sheet according to claim 7, wherein the polyester resin contains 1 to 10 mol % of structural units derived from a sulfonate group-containing dicarboxylic acid component, relative to 100 mol % of structural units derived from the dicarboxylic acid component.

9. The plasticizer is at least one selected from the group consisting of phthalic acid esters, adipic acid esters, sebacic acid esters, azelaic acid esters, and trimellitic acid esters, and has an SP value of 10.0 (cal / cm 3 ) 1 / 2 The pressure-sensitive adhesive sheet according to claim 1 or 3, wherein the compound is:

10. A laminate comprising a first resin layer, a polyester-based pressure-sensitive adhesive layer, and a second resin layer in this order in a lamination direction, wherein at least one layer selected from the first resin layer and the second resin layer is made of a resin material and has an SP value of 10.0 (cal / cm 3 ) 1 / 2 A laminate comprising the following plasticizer:

11. At least one layer selected from the first resin layer and the second resin layer contains at least a vinyl chloride resin as the resin material, and the SP value of the plasticizer is 8.0 to 9.6 (cal / cm 3 ) 1 / 2 The laminate according to claim 10 ,

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