WO2018101335A1 - Double-sided adhesive sheet, and method for producing double-sided adhesive sheet - Google Patents

Double-sided adhesive sheet, and method for producing double-sided adhesive sheet Download PDF

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Publication number
WO2018101335A1
WO2018101335A1 PCT/JP2017/042828 JP2017042828W WO2018101335A1 WO 2018101335 A1 WO2018101335 A1 WO 2018101335A1 JP 2017042828 W JP2017042828 W JP 2017042828W WO 2018101335 A1 WO2018101335 A1 WO 2018101335A1
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WIPO (PCT)
Prior art keywords
sensitive adhesive
double
layer
resin
coating film
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PCT/JP2017/042828
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French (fr)
Japanese (ja)
Inventor
晃司 土渕
高志 阿久津
揮一郎 加藤
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リンテック株式会社
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Publication of WO2018101335A1 publication Critical patent/WO2018101335A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00Adhesives based on unspecified macromolecular compounds

Definitions

  • the present invention relates to a double-sided pressure-sensitive adhesive sheet and a method for producing a double-sided pressure-sensitive adhesive sheet.
  • the double-sided pressure-sensitive adhesive sheet is used for fixing various members such as building materials, electronic parts, and interior materials.
  • a double-sided pressure-sensitive adhesive sheet a baseless double-sided pressure-sensitive adhesive sheet having a configuration in which a single pressure-sensitive adhesive layer is sandwiched between two release sheets without providing a base material (core material), or a base material (core material) ) Is provided with a pressure-sensitive adhesive layer on both surfaces, and a pressure-sensitive adhesive sheet with a substrate having a structure in which a release sheet is laminated on each pressure-sensitive adhesive layer is known.
  • Patent Document 1 as a double-sided pressure-sensitive adhesive sheet without a base material, a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive are respectively formed on the surface and the back surface of a base material pressure-sensitive adhesive formed only with a specific resin used as a pressure-sensitive adhesive.
  • a double-sided pressure-sensitive adhesive sheet comprising only a pressure-sensitive adhesive provided with an agent layer is disclosed.
  • patent document 2 it has a transparent 1st adhesion layer and a 2nd adhesion layer respectively on two surfaces of an optically non-oriented and transparent base material as an adhesive sheet with a base material.
  • a double-sided pressure-sensitive adhesive film in which the thickness of three laminated layers is 55 ⁇ m or less and the internal HAZE is 1 or less is disclosed.
  • the double-sided pressure-sensitive adhesive sheet without a substrate as described in Patent Document 1 is likely to stick out of the adhesive layer from the end during sticking to the adherend or during storage, and may contaminate the adherend or the like. is there. Further, the double-sided pressure-sensitive adhesive sheet without a substrate tends to cause a so-called “crying phenomenon”, which is a phenomenon in which the pressure-sensitive adhesive layer is divided and peeled off along with two release sheets when one release sheet is peeled off. Furthermore, when punching a double-sided pressure-sensitive adhesive sheet without a substrate, problems such as shape deformation and oozing out of the pressure-sensitive adhesive layer are likely to occur, and there is a problem in punchability.
  • the double-sided pressure-sensitive adhesive sheet with a substrate is more effective than the pressure-sensitive adhesive sheet without a substrate in suppressing the sticking-out of the adhesive layer from the edge during sticking to the adherend or storage and the effect of suppressing the tearing phenomenon.
  • the punching process is inferior.
  • the double-sided pressure-sensitive adhesive sheet with a base material described in Patent Document 2 is caused by low interfacial adhesion between the base material and the pressure-sensitive adhesive layer, and is uniformly stretched according to the shape of the adherend. It tends to be difficult to apply.
  • the decrease in interfacial adhesion between the substrate and the pressure-sensitive adhesive layer is caused by the linear lifting parallel to the width direction in the cutting process where the roll product is unwound and the end is cut off and rolled up again. This causes the so-called “tunneling”.
  • the pressure-sensitive adhesive layer is divided and peeled off along with the two release sheets, and the effect of suppressing the tearing phenomenon is high. It aims at providing the manufacturing method of the double-sided adhesive sheet which is excellent, and a double-sided adhesive sheet.
  • the laminate is made of the above three-layer forming material. It has been found that the above-mentioned problems can be solved by sequentially laminating a coating film made of a certain composition and drying it at the same time.
  • a double-sided pressure-sensitive adhesive sheet having a laminate in which a first pressure-sensitive adhesive layer (X1), a base material layer (Y), and a second pressure-sensitive adhesive layer (X2) are directly laminated in this order,
  • the laminate is A coating film (x1 ′) comprising a composition (x1) containing an adhesive resin, which is a material for forming the first adhesive layer;
  • the thickness ratio of the base material layer (Y) to the total thickness 100 of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) is 1 to 100
  • Step (1) a coating film (x1 ′) composed of the composition (x1), a coating film (y ′) composed of the composition (y), and a coating film (x2 ′) composed of the composition (x2)
  • Step (2) The process of drying a coating film (x1 '), a coating film (y'), and a coating film (x2 ') simultaneously, and forming the said laminated body.
  • the double-sided pressure-sensitive adhesive sheet of the present invention has a high effect of suppressing the tearing phenomenon that the pressure-sensitive adhesive layer is divided and peeled off with the two release sheets when peeling one of the release sheets. Due to high interfacial adhesion to the agent layer, it is excellent in punching processability, pasting ability and cutting processability. Moreover, since the manufacturing method of the double-sided adhesive sheet of this invention can reduce the number of processes and improve handling property, the double-sided adhesive sheet which has such a characteristic can improve and can manufacture.
  • Procedure (1) A 20 ⁇ m thick resin layer formed from only the target resin is laminated on the surface of a 50 ⁇ m thick polyethylene terephthalate (PET) film to a size of 300 mm length ⁇ 25 mm width A cut specimen is prepared.
  • Procedure (2) Under an environment of 23 ° C. and 50% RH (relative humidity), the surface of the resin layer exposed on the test piece is attached to a stainless steel plate (SUS304 No. 360 polishing). Leave for 24 hours.
  • Procedure (3) After standing, in an environment of 23 ° C.
  • the adhesive strength was increased at a pulling speed of 300 mm / min by 180 ° peeling method based on JIS Z0237: 2000. taking measurement.
  • the “active ingredient” refers to a component excluding a diluent solvent among components contained in a target composition.
  • a mass average molecular weight (Mw) and a number average molecular weight (Mn) are the values of standard polystyrene conversion measured by a gel permeation chromatography (GPC) method, and are specifically based on the method as described in an Example. Measured value.
  • (meth) acrylic acid indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
  • the lower limit value and upper limit value which were described in steps can be combined independently, respectively.
  • the description “preferably 10 to 90, more preferably 30 to 60”, “preferable lower limit (10)” and “more preferable upper limit (60)” are combined to obtain “10 to 60”. You can also.
  • FIG. 1 is a schematic cross-sectional view of a double-sided PSA sheet showing the configuration of the double-sided PSA sheet of the present invention.
  • the double-sided pressure-sensitive adhesive sheet of the present invention has a first pressure-sensitive adhesive layer (X1) 121, a base material layer (Y) 11, and a second pressure-sensitive adhesive layer (X2) like the double-sided pressure-sensitive adhesive sheet 1 shown in FIG. What is necessary is just to have the laminated body 10 which laminated
  • the above-mentioned “directly laminated” means between the first pressure-sensitive adhesive layer (X1) and the base material layer (Y), and between the base material layer (Y) and the second pressure-sensitive adhesive layer (X2). Between the two, it refers to a configuration in which the two layers are in direct contact with no other layers.
  • the “laminate” of the double-sided pressure-sensitive adhesive sheet of the present invention is composed of the first pressure-sensitive adhesive layer (X1), the base material layer (Y), and the second pressure-sensitive adhesive layer (X2). Other layers (such as a release material, a third pressure-sensitive adhesive layer, and a fourth pressure-sensitive adhesive layer described later) are not included in the configuration of the laminate.
  • a double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention from the viewpoint of handleability, one or both surfaces of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) (in contact with the base material layer) It is preferable that a release material is further provided on the surface (on the opposite side of the surface). That is, as the double-sided pressure-sensitive adhesive sheet of this aspect, the double-sided pressure-sensitive adhesive sheet 2 further having a release material 131 on the sticking surface of the first pressure-sensitive adhesive layer (X1) 121 shown in FIG. The double-sided pressure-sensitive adhesive sheet 3 further having release materials 131 and 132 on the sticking surfaces of the first pressure-sensitive adhesive layer (X1) 121 and the second pressure-sensitive adhesive layer (X2) 122 shown in FIG.
  • the double-sided adhesive sheet 2 shown in FIG.1 (b) it is good also as a double-sided adhesive sheet which has the structure wound in roll shape using the peeling material by which the peeling process was given to both surfaces as the peeling material 131.
  • a double-sided adhesive sheet of 1 aspect of this invention it is the 1st adhesive layer (X1) and one or both sticking surfaces (the side which is contacting the base material layer) of a 2nd adhesive layer (X2). It is good also as a structure which laminated
  • a third pressure-sensitive adhesive layer (X3) 123 is further provided on the sticking surface of the first pressure-sensitive adhesive layer (X1) 121 as shown in FIG.
  • the double-sided pressure-sensitive adhesive sheet 4 in which a fourth pressure-sensitive adhesive layer (X4) 124 is further provided on the adhesive surface of the pressure-sensitive adhesive layer (X2) 122 is mentioned.
  • the first pressure-sensitive adhesive layer (X1) and the third pressure-sensitive adhesive layer (X3) may be formed from compositions that are the same forming material and are different from each other. It may be formed from a composition that is Similarly, the second pressure-sensitive adhesive layer (X2) and the fourth pressure-sensitive adhesive layer (X4) may also be formed from compositions that are the same forming material, and compositions that are different from each other. It is formed from things. However, when 1st adhesive layer (X1) and 3rd adhesive layer (X3) are formed from the composition which is the same formation material, 1st adhesive layer (X1) and 3rd adhesive The layer (X3) is not formed by simultaneously applying and drying the respective compositions, but is formed separately. The same applies to the second pressure-sensitive adhesive layer (X2) and the fourth pressure-sensitive adhesive layer (X4).
  • the laminated body which the double-sided pressure-sensitive adhesive sheet of the present invention has includes a coating film (x1 ′) made of a composition (x1) containing an adhesive resin, which is a material for forming the first pressure-sensitive adhesive layer, and a base material layer (Y).
  • the coating films (x1 ′), (y ′) and (x2 ′) are simultaneously formed. It is formed by drying.
  • the double-sided pressure-sensitive adhesive sheet with a substrate is generally produced by the following method (hereinafter also referred to as “conventional production method”).
  • ⁇ Manufacturing which has a process of applying a pressure-sensitive adhesive composition to both surfaces of a base material already formed into a film or sheet to form a coating film and drying the coating film to form a pressure-sensitive adhesive layer.
  • Method. On the release-treated surface of the release film, the adhesive composition is applied to form a coating film, and two films are prepared by drying the coating film to form an adhesive layer.
  • the manufacturing method which has the process of affixing the adhesive layer formed on the peeling film, respectively on both surfaces of the base material already shape
  • a base material that has already been formed into a film shape or a sheet shape is used, and the pressure-sensitive adhesive layer is on the surface of the base material or the release treatment surface of the release film. Forming. That is, in the conventional manufacturing method, the base material and the pressure-sensitive adhesive layer are generally formed separately.
  • the pressure-sensitive adhesive sheet with a base material obtained by the above-described conventional manufacturing method is such that the base material and the pressure-sensitive adhesive layer are formed separately, so that the interface adhesion between the base material and the pressure-sensitive adhesive layer is Power is low.
  • the pressure-sensitive adhesive sheet with the base material is caused by the difference in mechanical properties between the base material and the pressure-sensitive adhesive layer, and the problem that the punching processability is inferior, and the base sheet and the pressure-sensitive adhesive layer are uniformly extended according to the shape of the adherend. There is a problem that sticking tends to be difficult.
  • so-called “tunneling” occurs in the cutting process of cutting off the end portion while winding the roll product and winding it up again in the form of a roll. .
  • the laminated body which the double-sided adhesive sheet of this invention has is the coating film (x1 ') which consists of each composition which is a formation material of a 1st adhesive layer, a base material layer, and a 2nd adhesive layer, (y ') And (x2') are formed by directly laminating these three coatings “simultaneously” after being directly laminated in this order. Since the laminate was formed as such, it was between the first pressure-sensitive adhesive layer (X1) and the base material layer (Y), and between the base material layer (Y) and the second pressure-sensitive adhesive layer (X2). The interfacial adhesion is much higher than that of the pressure-sensitive adhesive sheet with a substrate obtained by the above-described general production method.
  • the double-sided pressure-sensitive adhesive sheet of the present invention has a tearing phenomenon in which the pressure-sensitive adhesive layer is divided and peeled off along with the two peeling sheets when peeling one release sheet (hereinafter also simply referred to as “crying phenomenon”). ) Is highly effective and can be excellent in punching workability, sticking suitability and cutting workability.
  • the laminated body which a double-sided adhesive sheet has is specified by the manufacturing method as mentioned above, the situation which must be specified by such a manufacturing method exists.
  • a method for prescribing the configuration of the laminate without specifying the manufacturing method for example, the cross section cut in the thickness direction of the laminate using an electron microscope or the like
  • the interface between the base material layer and the adhesive layer In some cases, the interface can be specified by some physical property value.
  • a method for evaluating the interface between the base material layer and the pressure-sensitive adhesive layer for example, a method of measuring the surface roughness can be considered. However, since the roughness of the interface is very small, it cannot be measured accurately, and the difference in the roughness state depending on the region to be observed is very large.
  • the laminate of the double-sided pressure-sensitive adhesive sheet must be specified by the production method as described above.
  • the “coating film” is a film formed from a composition that is a forming material by a known coating method, and the residual ratio of volatile components such as a solvent contained in the film. It refers to those in a state of 10 to 100% by mass with respect to 100% by mass of the total amount of volatile components contained in the composition before coating. That is, in the present specification, the coating films (x1 ′), (y ′), and (x2 ′) contain a certain amount of a volatile component such as a solvent. And the volatile component was removed by drying the coating film of these 3 layers simultaneously, and it comprised from the 1st adhesive layer (X1), the base material layer (Y), and the 2nd adhesive layer (X2). A laminate is formed.
  • a base material layer (Y) since a base material layer (Y) is formed as mentioned above, it becomes an unstretched sheet-like material.
  • the “non-stretched sheet-like material” excludes a sheet-like material obtained by intentionally stretching in a specific direction.
  • a continuous manufacturing process such as using a roll to roll manufacturing apparatus, when the film is stretched by a force forcefully applied in the flow direction, it is not limited to this and may be regarded as a “non-stretched sheet”. it can.
  • composition (x1), (x2) contains a pressure-sensitive adhesive resin.
  • the compositions (x1) and (x2) may be the same or different from each other.
  • the components contained in the compositions (x1) and (x2) can be appropriately adjusted according to the use application of the double-sided pressure-sensitive adhesive sheet of the present invention.
  • the compositions (x1) and (x2) may further contain a tackifier and a crosslinking agent. Moreover, you may contain the additive for adhesives used for a general adhesive.
  • the compositions (x1) and (x2) are also used as materials for forming the third pressure-sensitive adhesive layer (x3) and the fourth pressure-sensitive adhesive layer (x4) included in the double-sided pressure-sensitive adhesive sheet 4 shown in FIG. be able to.
  • adheresive resin means a polymer having adhesiveness by itself and having a mass average molecular weight (Mw) of 10,000 or more.
  • the mass average molecular weight (Mw) of the adhesive resin is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, still more preferably 30,000 to 1,300,000, and still more preferably, from the viewpoint of improving the adhesive strength. Is 100,000 to 1,000,000.
  • Examples of the adhesive resin contained in the compositions (x1) and (x2) include acrylic resins, urethane resins, polyisobutylene resins, polyester resins, and olefin resins. These adhesive resins may be used independently and may use 2 or more types together. In addition, when these adhesive resins are copolymers having two or more kinds of structural units, the form of the copolymer is not particularly limited, and a block copolymer, a random copolymer, and a graft copolymer are not limited. Any of polymers may be used.
  • these pressure-sensitive adhesive resins have polymerizable functional groups. It is preferably an ultraviolet non-curable adhesive resin that does not have.
  • the polymerizable functional group means a group having a carbon-carbon double bond that can be polymerized by radical polymerization, and specifically includes a (meth) acryloyl group, a vinyl group, a vinyl ether group. , Allyl group, allyl ether group and the like.
  • the content of the adhesive resin in the compositions (x1) and (x2) is preferably 30 to 99.99 mass with respect to the total amount (100 mass%) of the active ingredients of the composition (x1) or (x2). %, More preferably 40 to 99.95% by mass, more preferably 50 to 99.90% by mass, still more preferably 55 to 99.80% by mass, and still more preferably 60 to 99.50% by mass.
  • the adhesive resin contained in the compositions (x1) and (x2) preferably contains an acrylic resin from the viewpoint of further improving the interfacial adhesion with the base material layer (Y). .
  • the acrylic resin is more preferably an ultraviolet non-curable resin having no polymerizable functional group.
  • the content of the acrylic resin in the adhesive resin is preferably 30 to 100 mass with respect to the total amount (100 mass%) of the adhesive resin contained in the composition (x1) or (x2). %, More preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, and still more preferably 85 to 100% by mass.
  • acrylic resins that can be used as adhesive resins include polymers containing structural units derived from alkyl (meth) acrylates having linear or branched alkyl groups, and (meth) acrylates having a cyclic structure. Examples thereof include a polymer containing a derived structural unit.
  • the mass average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1,500,000, more preferably 200,000 to 1,300,000, still more preferably 350,000 to 1,200,000, still more preferably 500,000 to 1,100,000. .
  • an acrylic polymer having a structural unit (a1) derived from an alkyl (meth) acrylate (a1 ′) (hereinafter also referred to as “monomer (a1 ′)”) ( A0) is preferable, and together with the structural unit (a1), an acrylic copolymer (A1) having a structural unit (a2) derived from the functional group-containing monomer (a2 ′) (hereinafter also referred to as “monomer (a2 ′)”) ) Is more preferable.
  • the acrylic polymers (A0) and (A1) preferably have no polymerizable functional group.
  • the number of carbon atoms of the alkyl group contained in the monomer (a1 ′) is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, and still more preferably 4 to 6 from the viewpoint of improving adhesive properties. It is.
  • the alkyl group contained in the monomer (a1 ′) may be a linear alkyl group or a branched alkyl group.
  • Examples of the monomer (a1 ′) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl ( Examples include meth) acrylate and stearyl (meth) acrylate. These monomers (a1 ′) may be used alone or in combination of two or more. As the monomer (a1 ′), butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate is more preferable.
  • the content of the structural unit (a1) is preferably 50 to 100% by weight, more preferably based on the total structural unit (100% by weight) of the acrylic polymer (A0) or the acrylic copolymer (A1). It is 60 to 99.9% by mass, more preferably 70 to 99.5% by mass, and still more preferably 80 to 99.0% by mass.
  • the functional group possessed by the monomer (a2 ′) refers to a functional group that reacts with a crosslinking agent to be described later and can serve as a crosslinking starting point or a functional group having a crosslinking accelerating effect.
  • examples of the monomer (a2 ′) include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer. These monomers (a2 ′) may be used alone or in combination of two or more.
  • a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth) )
  • hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate; and unsaturated alcohols such as vinyl alcohol and allyl alcohol.
  • carboxy group-containing monomer examples include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid, and anhydrides thereof.
  • ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid
  • dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid, and anhydrides thereof.
  • the content of the structural unit (a2) is preferably 0.1 to 40% by weight, more preferably 0.3 to 30%, based on the entire structural unit (100% by weight) of the acrylic copolymer (A1). % By mass, more preferably 0.5 to 20% by mass, still more preferably 0.7 to 10% by mass.
  • the acrylic copolymer (A1) may further have a structural unit (a3) derived from another monomer (a3 ′) other than the monomers (a1 ′) and (a2 ′).
  • the content of the structural units (a1) and (a2) is preferably 70 with respect to the total structural units (100% by mass) of the acrylic copolymer (A1).
  • To 100% by mass more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
  • Examples of the monomer (a3 ′) include olefins such as ethylene, propylene, and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene monomers such as butadiene, isoprene, and chloroprene; cyclohexyl (meth) acrylate, It has a cyclic structure such as benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, imide (meth) acrylate, etc.
  • olefins such as ethylene, propylene, and isobutylene
  • halogenated olefins such as vinyl chloride and vinylidene chloride
  • diene monomers such as butadiene, iso
  • the urethane resin that can be used as the adhesive resin is not particularly limited as long as it is a polymer having at least one of a urethane bond and a urea bond in at least one of the main chain and the side chain.
  • Specific examples of the urethane resin include a urethane prepolymer (UX) obtained by reacting a polyol and a polyvalent isocyanate compound.
  • the urethane prepolymer (UX) may be obtained by further subjecting to a chain extension reaction using a chain extender.
  • the mass average molecular weight (Mw) of the urethane resin is preferably 10,000 to 200,000, more preferably 12,000 to 150,000, still more preferably 15,000 to 100,000, and still more preferably 20,000 to 70,000.
  • polyol used as a raw material for the urethane-based prepolymer (UX) examples include polyol compounds such as alkylene type polyols, polyether type polyols, polyester type polyols, polyester amide type polyols, polyester / polyether type polyols, and polycarbonate type polyols. Although it is mentioned, if it is a polyol, it will not specifically limit, Bifunctional diol and a trifunctional triol may be sufficient. These polyols may be used independently and may use 2 or more types together. Among these polyols, diols are preferable and alkylene type diols are more preferable from the viewpoints of availability, reactivity, and the like.
  • alkylene type diol examples include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; ethylene glycol, propylene glycol, And alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polyoxyalkylene glycols such as polytetramethylene glycol; and the like.
  • glycols having a mass average molecular weight of 1000 to 3000 are preferable from the viewpoint of suppressing gelation when the reaction with a chain extender is performed.
  • Examples of the polyvalent isocyanate compound that is a raw material for the urethane prepolymer (UX) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
  • aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2 , 6-Tolylene diisocyanate (2,6-TDI), 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4 ′ -Diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, 1,4-tetramethylxylylene di
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodeca.
  • HMDI hexamethylene diisocyanate
  • pentamethylene diisocyanate 1,2-propylene diisocyanate
  • 2,3-butylene diisocyanate 1,3-butylene diisocyanate
  • dodeca examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
  • Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4- Cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanate) Methyl) cyclohexane and the like.
  • IPDI isophorone diisocyanate
  • IPDI isophorone diisocyanate
  • 1,3-cyclopentane diisocyanate 1,3-cyclohexane diisocyanate
  • polyisocyanate compounds may be a trimethylolpropane adduct type modified product of the above polyisocyanate, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.
  • polyvalent isocyanate compounds 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2, from the viewpoint of obtaining a urethane polymer having excellent adhesive properties.
  • MDI 4,4′-diphenylmethane diisocyanate
  • 2,4-TDI 2,4-tolylene diisocyanate
  • One or more selected from 6-tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) and modified products thereof are preferable. From the viewpoint of weather resistance, at least one selected from HMDI, IPDI, and modified products thereof is more preferable.
  • the isocyanate group content (NCO%) in the urethane-based prepolymer (UX) is preferably 0.5 to 12% by mass, more preferably 1 to 4% by mass, as measured according to JIS K 1603. is there.
  • chain extender a compound having at least one of hydroxyl group and amino group, or a compound having at least three of hydroxyl group and amino group is preferable.
  • the compound having at least one of a hydroxyl group and an amino group is preferably at least one compound selected from the group consisting of aliphatic diols, aliphatic diamines, alkanolamines, bisphenols, and aromatic diamines.
  • aliphatic diol examples include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptanediol.
  • Alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol;
  • the aliphatic diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and the like.
  • the alkanolamine include monoethanolamine, monopropanolamine, isopropanolamine and the like.
  • Examples of bisphenol include bisphenol A and the like.
  • aromatic diamine include diphenylmethanediamine, tolylenediamine, xylylenediamine, and the like.
  • Examples of the compound having at least three hydroxyl groups and amino groups include polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol; 1-amino-2,3-propanediol, 1-methyl And amino alcohols such as amino-2,3-propanediol and N- (2-hydroxypropylethanolamine); ethylene oxide or propylene oxide adducts of tetramethylxylylenediamine;
  • the polyisobutylene resin (hereinafter also referred to as “PIB resin”) that can be used as the adhesive resin is not particularly limited as long as it has a polyisobutylene skeleton in at least one of the main chain and the side chain.
  • the mass average molecular weight (Mw) of the PIB resin is preferably 20,000 or more, more preferably 30,000 to 1,000,000, still more preferably 50,000 to 800,000, and still more preferably 70,000 to 600,000.
  • PIB resin examples include polyisobutylene which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, and these copolymers.
  • examples thereof include halogenated butyl rubber that has been brominated or chlorinated.
  • the structural unit composed of isobutylene is contained in the largest amount among all the structural units.
  • the content of the structural unit composed of isobutylene is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass with respect to all the structural units (100% by mass) of the PIB resin. %.
  • These PIB resins may be used alone or in combination of two or more.
  • a PIB resin with a high mass average molecular weight and a PIB resin with a low mass average molecular weight More specifically, a PIB resin (p1) having a mass average molecular weight of 270,000 to 600,000 (hereinafter also referred to as “PIB resin (p1)”), and a PIB resin having a mass average molecular weight of 50,000 to 250,000 It is preferable to use the resin (p2) (hereinafter also referred to as “PIB resin (p2)”) in combination.
  • the PIB resin (p1) having a high mass average molecular weight it is possible to improve the durability and weather resistance of the pressure-sensitive adhesive layer to be formed, and also improve the adhesive strength. Further, by using the PIB resin (p2) having a low mass average molecular weight, it can be well compatible with the PIB resin (p1), and the PIB resin (p1) can be appropriately plasticized. The wettability of the layer to the adherend can be increased, and the adhesive properties, flexibility, and the like can be improved.
  • the mass average molecular weight (Mw) of the PIB resin (p1) is preferably 270,000 to 600,000, more preferably 290,000 to 480,000, still more preferably 310,000 to 450,000, and even more preferably 320,000 to 400,000. It is.
  • the mass average molecular weight (Mw) of the PIB resin (p2) is preferably 50,000 to 250,000, more preferably 80,000 to 230,000, still more preferably 140,000 to 220,000, and still more preferably 180,000 to 210,000. It is.
  • the content ratio of the PIB resin (p2) to 100 parts by mass of the PIB resin (p1) is preferably 5 to 55 parts by mass, more preferably 6 to 40 parts by mass, still more preferably 7 to 30 parts by mass, and even more.
  • the amount is preferably 8 to 20 parts by mass.
  • polyester resin The polyester-based resin that can be used as the adhesive resin is a copolymer obtained by polycondensation reaction of an acid component and a diol component or a polyol component, and includes a modified product of the copolymer.
  • the polycondensation reaction is performed by a general polyesterification reaction such as a direct esterification method or a transesterification method. These polyester resins may be used alone or in combination of two or more.
  • the acid component examples include terephthalic acid, isophthalic acid, phthalic anhydride, ⁇ -naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid or esters thereof, pimelic acid, suberic acid, and azelain.
  • examples thereof include aliphatic dicarboxylic acids such as acid, sebacic acid, undecylenic acid, dodecanedicarboxylic acid or esters thereof; and alicyclic dicarboxylic acids such as 1,4-cyclohexahydrophthalic anhydride.
  • diol component or polyol component examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methylpentanediol, 2,2,3-trimethylpentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, etc.
  • An aliphatic glycol such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, and an aromatic glycol such as bisphenol A.
  • the olefin resin that can be used as the adhesive resin is not particularly limited as long as it is a polymer having a structural unit derived from an olefin compound such as ethylene or propylene.
  • the said olefin resin may be used independently and may use 2 or more types together.
  • the olefin-based resin examples include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene, polypropylene, copolymers of ethylene and propylene, ethylene and other ⁇ - Copolymers of olefins, copolymers of propylene and other ⁇ -olefins, copolymers of ethylene, propylene and other ⁇ -olefins, copolymers of ethylene and other ethylenically unsaturated monomers Examples thereof include ethylene (vinyl-vinyl acetate copolymer, ethylene-alkyl (meth) acrylate copolymer, etc.) and the like.
  • Examples of the ⁇ -olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like.
  • Examples of the ethylenically unsaturated monomer include vinyl acetate, alkyl (meth) acrylate, vinyl alcohol, and the like.
  • the compositions (x1) and (x2) further contain a tackifier from the viewpoint of making a double-sided PSA sheet with improved adhesive strength.
  • the “tackifier” is a component that assists in improving the adhesive strength of the adhesive resin, and refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000. It is a distinction.
  • the mass average molecular weight (Mw) of the tackifier is preferably 400 to 10000, more preferably 5000 to 8000, and still more preferably 800 to 5000.
  • tackifiers include rosin resins such as rosin resins, rosin ester resins, and rosin-modified phenol resins; hydrogenated rosin resins obtained by hydrogenating these rosin resins; terpene resins, aromatic modified terpene resins, and terpene phenols.
  • Terpene resins such as epoxy resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins; styrene obtained by copolymerizing a styrene monomer such as ⁇ -methylstyrene or ⁇ -methylstyrene with an aliphatic monomer Hydrogenated styrene resins obtained by hydrogenating these styrene resins; C5 systems obtained by copolymerizing C5 fractions such as pentene, isoprene, piperine, 1.3-pentadiene produced by thermal decomposition of petroleum naphtha Petroleum resin and hydrogenated petroleum resin of this C5 petroleum resin; indene and vinyl And C9 petroleum resins obtained by copolymerizing C9 fractions such as toluene and hydrogenated petroleum resins.
  • These tackifiers may be used alone or in combination of two or more different softening points and structures.
  • the softening point of the tackifier is preferably 60 to 170 ° C, more preferably 65 to 160 ° C, and still more preferably 70 to 150 ° C.
  • the “softening point” of the tackifier means a value measured according to JIS K2531.
  • the weighted average of the softening point of these several tackifier belongs to the said range.
  • the content of the tackifier in the compositions (x1) and (x2) is preferably 0.01 to 65 masses with respect to the total amount (100 mass%) of the active ingredients of the composition (x1) or (x2). %, More preferably 0.05 to 55% by mass, more preferably 0.1 to 50% by mass, still more preferably 0.5 to 45% by mass, and still more preferably 1.0 to 40% by mass.
  • the total content of the adhesive resin and the tackifier in the compositions (x1) and (x2) is preferably based on the total amount (100% by mass) of the active ingredients in the composition (x1) or (x2). Is 70% by mass or more, more preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% by mass or more.
  • compositions (x1) and (x2) when the compositions (x1) and (x2) contain an adhesive resin having a functional group such as the acrylic copolymer (A1) described above, the compositions (x1) and (x2) further contain a crosslinking agent. It is preferable to do.
  • the said crosslinking agent reacts with the functional group which the said adhesive resin has, and bridge
  • crosslinking agent examples include: tolylene diisocyanate, hexamethylene diisocyanate, and the like, and isocyanate-based crosslinking agents such as adducts thereof; epoxy-based crosslinking agents such as ethylene glycol glycidyl ether; hexa [1- (2-methyl) -aziridinyl ] Aziridine type crosslinking agents such as triphosphatriazine; Chelate type crosslinking agents such as aluminum chelate; These crosslinking agents may be used independently and may use 2 or more types together. Among these crosslinking agents, an isocyanate-based crosslinking agent is preferable from the viewpoints of increasing cohesive force and improving adhesive force, and availability.
  • content of a crosslinking agent is suitably adjusted with the number of functional groups which adhesive resin has, with respect to 100 mass parts of adhesive resins which have functional groups, such as said acrylic copolymer (A1).
  • the amount is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 7 parts by mass, and still more preferably 0.05 to 4 parts by mass.
  • the compositions (x1) and (x2) are additives for pressure-sensitive adhesives used for general pressure-sensitive adhesives other than a crosslinking agent and a tackifier, as long as the effects of the present invention are not impaired. May be contained.
  • the adhesive additive include an antioxidant, a softener (plasticizer), a rust inhibitor, a pigment, a dye, a retarder, a reaction accelerator (catalyst), and an ultraviolet absorber. These pressure-sensitive adhesive additives may be used alone or in combination of two or more.
  • each pressure-sensitive adhesive additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 100 parts by mass of the adhesive resin. To 10 parts by mass, more preferably 0.005 to 5 parts by mass.
  • the compositions (x1) and (x2) may further contain a diluting solvent together with the various active ingredients described above, and may be in the form of a solution.
  • the dilution solvent may be water or an organic solvent.
  • the organic solvent include toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, t-butanol, s-butanol, acetylacetone, cyclohexanone, n-hexane, and cyclohexane.
  • the dilution solvent contained in composition (x1) and (x2) may be used independently, and may use 2 or more types together.
  • compositions (x1) and (x2) are in the form of a solution containing a diluting solvent
  • active ingredient concentrations of the compositions (x1) and (x2) are each independently preferably preferably 0.1 to 60
  • the mass is more preferably 0.5 to 50 mass%, still more preferably 1.0 to 40 mass%.
  • composition (y) which is a forming material of the base material layer (Y) contains a non-adhesive resin selected from the group consisting of an acrylic urethane resin and an olefin resin.
  • the “non-adhesive resin” means a non-adhesive polymer belonging to acrylic urethane resin or olefin resin and having a mass average molecular weight (Mw) of 10,000 or more.
  • the non-adhesive resin is a copolymer having two or more kinds of structural units
  • the form of the copolymer is not particularly limited, and a block copolymer, a random copolymer, and a graft copolymer Any of them may be combined.
  • the composition (y) it is preferable that the non-adhesive resin contained in is an ultraviolet non-curable resin having no polymerizable functional group.
  • the composition (y) may contain a resin other than an acrylic urethane-based resin and an olefin-based resin as long as the effects of the present invention are not impaired. You may contain the additive for base materials contained in the base material which a sheet
  • the content of the non-adhesive resin in the composition (y) is preferably 50 to 100% by mass, more preferably 65 to 100% by mass with respect to the total amount (100% by mass) of the active ingredients in the composition (y). %, More preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
  • acrylic urethane resin examples include a reaction product of an acrylic polyol compound and an isocyanate compound, and a linear urethane prepolymer having ethylenically unsaturated groups at both ends. Examples thereof include a copolymer obtained by polymerizing a polymer (UY) and a vinyl compound (VY) containing a (meth) acrylic ester.
  • acrylic urethane resin (hereinafter also referred to as “acrylic urethane resin (I)”), which is a reaction product of an acrylic polyol compound and an isocyanate compound, has a main chain of the acrylic resin as a skeleton, and the intermolecular relationship between the molecules. It has a chemical structure that is cured by crosslinking with urethane bonds. Since the acrylic resin that is the main chain is rich in rigidity, it has a structural unit derived from an isocyanate compound that is highly resistant to tensile stress and has a high reactivity, and therefore has the first pressure-sensitive adhesive layer (X1) and the first adhesive layer. It is thought that it is excellent also in adhesiveness with the adhesive resin contained in 2 adhesive layer (X2), and can contribute to the improvement of interface adhesiveness.
  • X1 first pressure-sensitive adhesive layer
  • an acrylic urethane-based resin which is a copolymer obtained by polymerizing a linear urethane prepolymer (UY) having an ethylenically unsaturated group at both ends and a vinyl compound (VY) containing a (meth) acrylic acid ester
  • the “acrylic urethane resin (II)” is a (meth) acrylic acid ester at both ends of the linear urethane prepolymer (UY) with the main chain of the linear urethane prepolymer (UY) as the skeleton. It has a structural unit derived from the vinyl compound (VY) containing.
  • acrylic urethane resin (II) has a portion derived from linear urethane polymer (UY) between acrylic sites in the main chain skeleton, the distance between crosslinking points is longer than that of acrylic urethane resin (I).
  • the molecular structure tends to be a two-dimensional structure (network structure).
  • the urethane prepolymer (UY) of the main chain is linear, the stretching effect is high when an external force is applied.
  • the side chain of the structural unit derived from the vinyl compound (VY) containing the (meth) acrylic acid ester is easily entangled with the adhesive resin in the first adhesive layer (X1) and the second adhesive layer (X2). It has a structure.
  • acrylic urethane resin (II) as the material for forming the base layer (Y) improves the interfacial adhesion with the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2). It is thought that it can contribute to.
  • the mass average molecular weight (Mw) of acrylic urethane resins such as acrylic urethane resins (I) and (II) is preferably 2,000 to 500,000, more preferably 4,000 to 300,000, and even more preferably 5 1,000 to 200,000, and more preferably 10,000 to 150,000.
  • the acrylic urethane resins such as acrylic urethane resins (I) and (II) are preferably ultraviolet non-curable resins having no polymerizable functional group.
  • the acrylic urethane resin (II) is preferably used as the acrylic urethane resin contained in the composition (y) as a non-adhesive resin.
  • the acrylic urethane resins (I) and (II) will be described.
  • (Acrylic urethane resin (I)) As an acrylic polyol compound that is a raw material of the acrylic urethane-based resin (I), a structural unit (b1) derived from an alkyl (meth) acrylate (b1 ′) (hereinafter also referred to as “monomer (b1 ′)”), An acrylic copolymer (B1) having a structural unit (b2) derived from a hydroxyl group-containing monomer (b2 ′) (hereinafter also referred to as “monomer (b2 ′)”) is preferable.
  • the number of carbon atoms of the alkyl group contained in the monomer (b1 ′) is preferably 1 to 12, more preferably 4 to 8, and still more preferably 4 to 6.
  • the alkyl group contained in the monomer (b1 ′) may be a straight chain alkyl group or a branched chain alkyl group.
  • Specific examples of the monomer (b1 ′) include the same monomers as the monomer (a1 ′) described above.
  • a monomer (b1 ') may be used independently and may use 2 or more types together.
  • the monomer (b1 ′) butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate is more preferable.
  • the content of the structural unit (b1) is preferably 60 to 99.9% by mass, more preferably 70 to 99.7% by mass with respect to the total structural unit (100% by mass) of the acrylic copolymer (B1). %, More preferably 80 to 99.5% by mass.
  • a monomer (b2 ') the same thing as the hydroxyl-containing monomer which can be selected as said monomer (a2') is mentioned.
  • a monomer (b2 ') may be used independently and may use 2 or more types together.
  • the content of the structural unit (b2) is preferably 0.1 to 40% by weight, more preferably 0.3 to 30% by weight with respect to the total structural unit (100% by weight) of the acrylic copolymer (B1). %, And more preferably 0.5 to 20% by mass.
  • the acrylic copolymer (B1) may further have a structural unit (b3) derived from another monomer (b3 ′) other than the monomers (b1 ′) and (b2 ′).
  • the monomer (b3 ′) include functional group-containing monomers other than the hydroxyl group-containing monomer that can be selected as the above-mentioned monomer (a2 ′), and the same monomers as the above-mentioned monomer (a3 ′).
  • the content of the structural units (b1) and (b2) is preferably 70 with respect to the total structural units (100% by mass) of the acrylic copolymer (B1).
  • To 100% by mass more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
  • examples of the isocyanate compound used as the raw material for the acrylic urethane resin (I) include the same polyvalent isocyanate compounds used as the raw material for the urethane prepolymer (U1).
  • an isocyanate compound from the viewpoint of stretchability when an external force is applied, an isocyanate compound having no aromatic ring is preferable, and an aliphatic polyisocyanate and an alicyclic polyisocyanate are more preferable.
  • the ratio of the structural unit derived from the acrylic polyol compound to the structural unit derived from the isocyanate compound [acryl polyol compound / isocyanate compound] is preferably 10/90 by mass ratio. Is 90/90, more preferably 20/80 to 80/20, still more preferably 30/70 to 70/30, and still more preferably 40/60 to 60/40.
  • Examples of the linear urethane prepolymer (UY) that is a raw material for the acrylic urethane resin (II) include a reaction product of a diol and a diisocyanate compound.
  • the said diol and diisocyanate compound may be used independently and may use 2 or more types together.
  • the mass average molecular weight of the linear urethane prepolymer (UY) is preferably 1,000 to 300,000, more preferably 3,000 to 200,000, still more preferably 5,000 to 100,000, and still more preferably 10,000 to 80,000, particularly preferably 20,000 to 60,000.
  • diol constituting the linear urethane prepolymer (UY) examples include alkylene glycol, polyether type diol, polyester type diol, polyester amide type diol, polyester / polyether type diol, and polycarbonate type diol. Of these diols, polycarbonate diols are preferred.
  • diisocyanate compound constituting the linear urethane prepolymer (UY) examples include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. From the viewpoint of stretchability when an external force is applied, alicyclic Diisocyanate is preferred.
  • a specific diisocyanate compound what corresponds to a diisocyanate compound is mentioned among the compounds illustrated as a polyisocyanate used as the raw material of the above-mentioned urethane type prepolymer (UX).
  • the linear urethane prepolymer (UY) may be obtained by performing a chain extension reaction using a chain extender together with a diol and a diisocyanate compound.
  • chain extender include the same chain extenders as those exemplified as the chain extender that can be used in the synthesis of the urethane prepolymer (UX).
  • the linear urethane prepolymer (UY) has an ethylenically unsaturated group at both ends.
  • an NCO group at the end of the urethane prepolymer obtained by reacting a diol and a diisocyanate compound, and a hydroxyalkyl (meth) acrylate are used. The method of making it react is mentioned.
  • hydroxyalkyl (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy Examples thereof include butyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
  • the (meth) acrylic acid ester is included as a vinyl compound (VY) used as the raw material of acrylic urethane type resin (II).
  • the (meth) acrylic acid ester is the same as that corresponding to the (meth) acrylic acid ester among the monomers (a1 ′) to (a3 ′) used as the raw material of the above-mentioned acrylic copolymer (A1). Things.
  • the (meth) acrylic acid ester at least one selected from alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate is preferable, and it is more preferable to use alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate together. preferable.
  • the proportion of hydroxyalkyl (meth) acrylate to 100 parts by mass of alkyl (meth) acrylate is preferably 0.1 to 100 parts by mass, The amount is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, and still more preferably 1.5 to 10 parts by mass.
  • the number of carbon atoms in the alkyl group of the alkyl (meth) acrylate is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, and still more preferably 1 to 3.
  • the said alkyl (meth) acrylate the same thing as what was illustrated as a monomer (a1 ') used as the raw material of the above-mentioned acrylic copolymer (A1) is mentioned.
  • hydroxyalkyl (meth) acrylate the same thing as what was illustrated as hydroxyalkyl (meth) acrylate used in order to introduce
  • vinyl compounds other than (meth) acrylic acid esters include aromatic hydrocarbon vinyl compounds such as styrene, ⁇ -methylstyrene, and vinyl toluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate and vinyl propionate.
  • Polar group-containing monomers such as (meth) acrylonitrile, N-vinylpyrrolidone, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and meta (acrylamide). These may be used alone or in combination of two or more.
  • the content of (meth) acrylic acid ester in the vinyl compound (VY) used as the raw material for the acrylic urethane resin (II) is the total amount (100% by mass) of the vinyl compound (VY). Is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, still more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass.
  • the total content of alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate in vinyl compound (VY) used as a raw material for acrylic urethane resin (II) is the vinyl compound (VY). Is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, still more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass with respect to the total amount (100% by mass).
  • the acrylic urethane resin (II) can be obtained by polymerizing a linear urethane prepolymer (UY) as a raw material and a vinyl compound (VY).
  • a radical generator is blended in an organic solvent together with the linear urethane prepolymer (UY) and vinyl compound (VY) as raw materials, and both ends of the linear urethane prepolymer (UY). It can be synthesized by a radical polymerization reaction of a vinyl compound (VY) starting from an ethylenically unsaturated group.
  • the radical generator used include diazo compounds such as azobisisobutyronitrile, benzoyl peroxide, and the like.
  • a chain transfer agent such as a thiol group-containing compound may be added to the solvent to adjust the polymerization degree of acrylic.
  • the content ratio of the structural unit derived from the linear urethane prepolymer (UY) to the structural unit derived from the vinyl compound (VY) [(UY) / (VY)] is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, still more preferably 30/70 to 60/40, still more preferably 35 / 65 to 55/45.
  • the olefin resin contained as the non-adhesive resin in the composition (y) is a polymer having at least a structural unit derived from an olefin monomer.
  • the olefin resin is preferably an ultraviolet non-curable resin having no polymerizable functional group.
  • the olefin monomer is preferably an ⁇ -olefin having 2 to 8 carbon atoms, and specifically includes ethylene, propylene, butylene, isobutylene, 1-hexene and the like. Among these, ethylene and propylene are preferable.
  • olefinic resins for example, ultra low density polyethylene (VLDPE, density: 880 kg / m 3 or more 910 kg / m less than 3), low density polyethylene (LDPE, density: 910 kg / m 3 or more 915 kg / m less than 3 ), Medium density polyethylene (MDPE, density: 915 kg / m 3 or more and less than 942 kg / m 3 ), high density polyethylene (HDPE, density: 942 kg / m 3 or more), linear low density polyethylene, etc .; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin elastomer (TPO); ethylene-vinyl acetate copolymer (EVA); ethylene-propylene- (5-ethylidene-2-norbornene), etc. Olefin terpolymers; and the like.
  • VLDPE ultra low density polyethylene
  • LDPE low density poly
  • the olefin resin may be a modified olefin resin further modified by one or more selected from acid modification, hydroxyl group modification, and acrylic modification.
  • an acid-modified olefin resin obtained by subjecting an olefin resin to acid modification a modified polymer obtained by graft polymerization of the above-mentioned unmodified olefin resin with an unsaturated carboxylic acid or its anhydride.
  • unsaturated carboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth) acrylic acid, maleic anhydride, itaconic anhydride.
  • Glutaconic anhydride citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, and the like.
  • unsaturated carboxylic acid or its anhydride may be used independently and may use 2 or more types together.
  • an acrylic modified olefin resin obtained by subjecting an olefin resin to acrylic modification a modification obtained by graft polymerization of an alkyl (meth) acrylate as a side chain to the above-mentioned unmodified olefin resin as a main chain.
  • a polymer is mentioned.
  • the number of carbon atoms in the alkyl group of the alkyl (meth) acrylate is preferably 1-20, more preferably 1-16, and still more preferably 1-12.
  • said alkyl (meth) acrylate the same thing as the compound which can be selected as said monomer (a1 ') is mentioned, for example.
  • Examples of the hydroxyl group-modified olefin resin obtained by subjecting an olefin resin to hydroxyl group modification include a modified polymer obtained by graft polymerization of a hydroxyl group-containing compound to the above-mentioned unmodified olefin resin, which is the main chain.
  • As said hydroxyl-containing compound the same thing as the hydroxyl-containing monomer which can be selected as said monomer (a2 ') is mentioned.
  • the mass average molecular weight (Mw) of the olefin resin is preferably 2,000 to 1,000,000, more preferably 10,000 to 500,000, still more preferably 20,000 to 400,000, and even more preferably 50,000 to 300,000. is there.
  • the composition (y) may contain a resin other than the acrylic urethane-based resin and the olefin-based resin as long as the effects of the present invention are not impaired.
  • resins include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate.
  • Polyester resin such as phthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; polyurethane not applicable to acrylic urethane resin; polymethylpentene; polysulfone; polyetheretherketone; polyethersulfone; Sulfides; Polyimide resins such as polyetherimide and polyimide; Polyamide resins; Acrylic resins; Fluorine resins and the like.
  • the acrylic urethane-based resin and olefin in the composition (y) The content ratio of the resin other than the resin is preferably as small as possible.
  • the total amount of the non-adhesive resin selected from the group consisting of the acrylic urethane resin and the olefin resin contained in the composition (y) is 100.
  • the amount is preferably less than 30 parts by weight, more preferably less than 20 parts by weight, more preferably less than 10 parts by weight, still more preferably less than 5 parts by weight, and still more preferably less than 1 part by weight with respect to parts by weight.
  • the composition (y) may contain the base material additive contained in the base material which a general adhesive sheet has in the range which does not impair the effect of this invention.
  • base material additives include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, and colorants. These base material additives may be used alone or in combination of two or more. In the case of containing these base material additives, the content of each base material additive is preferably 0.0001 to 20 parts by mass, more preferably 0 to 100 parts by mass of the non-adhesive resin. 0.001 to 10 parts by mass, still more preferably 0.005 to 5 parts by mass.
  • the composition (y) may further contain a diluting solvent together with the various active ingredients described above, and may be in the form of a solution.
  • the dilution solvent may be water or an organic solvent.
  • an organic solvent the same organic solvent used when preparing the above-mentioned composition (x1) and (x2) in the form of a solution is mentioned.
  • the dilution solvent contained in a composition (y) may be used independently, and may use 2 or more types together.
  • the active ingredient concentration of the composition (y) is preferably independently 0.1 to 60% by mass, more preferably 0. It is 5 to 50% by mass, more preferably 1.0 to 40% by mass.
  • the elongation at break of the base material layer (Y) formed from the composition (y) is preferably 100% or more, more preferably 120% or more, still more preferably 200% or more, and still more preferably 350% or more. In addition, it is usually 1000% or less.
  • the breaking strength of the base material layer (Y) formed from the composition (y) is preferably 30 MPa or more, more preferably 60 MPa or more, and usually 300 MPa or less, preferably 200 MPa or less.
  • the breaking elongation and breaking strength of said base material layer (Y) are from the coating film (y ') which consists of a composition (y) on the same application quantity and drying conditions as the case where a double-sided adhesive sheet is manufactured.
  • the formed base material layer (Y) is the object to be measured. The specific measurement method is as described in the examples.
  • the thickness of the laminate of the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention is preferably 2 to 90 ⁇ m, more preferably 4 to 75 ⁇ m, still more preferably 6 to 60 ⁇ m, and still more preferably 8 to 45 ⁇ m.
  • the thicknesses of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) are each independently preferably 0.5 to 50 ⁇ m, more preferably 1 to 40 ⁇ m, still more preferably 2 to 30 ⁇ m. More preferably, the thickness is 3 to 20 ⁇ m.
  • the thickness of the base material layer (Y) is preferably 0.3 to 50.0 ⁇ m, more preferably 0.5 to 30.0 ⁇ m, still more preferably 0.7 to 15.0 ⁇ m, and still more preferably 1.0. -8.0 ⁇ m.
  • the thickness of the laminate is a value measured using a constant pressure thickness measuring instrument based on JIS K6783, Z1702, and Z1709, and specifically measured based on the method described in the examples. Means the value.
  • the thickness of each layer constituting the laminate may be measured by the same method as the thickness of the laminate described above. For example, a cross section of the laminate cut in the thickness direction is observed with a scanning electron microscope. Then, the ratio of the thicknesses of the respective layers may be measured and calculated from the thickness of the laminate measured by the method described above.
  • the thickness ratio of the base material layer (Y) to the total thickness 100 of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) is preferably It is 1 to 100, more preferably 3 to 90, still more preferably 4 to 70, still more preferably 7 to 50, still more preferably 10 to 30, and particularly preferably 11 to 22.
  • the ratio [X1 / X2] of the thickness of the first pressure-sensitive adhesive layer (X1) to the thickness of the second pressure-sensitive adhesive layer (X2) is preferably 10/90 to 90/10, more preferably 20/80 to 80 / 20, more preferably 30/70 to 70/30, still more preferably 40/60 to 60/40.
  • the haze of the laminate of the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention is preferably 5.00% or less, more preferably 4.00% or less, still more preferably 3.00% or less, and still more preferably 2. 00% or less, particularly preferably 1.00% or less.
  • the haze is a value measured according to JIS K 7136: 2000, and specifically, a value measured by the method described in Examples.
  • the total light transmittance of the laminate which the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention has is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
  • the total light transmittance is a value measured in accordance with JIS K7361-1: 1997, and specifically, a value measured by the method described in the examples.
  • each independently preferably 3.0 N / 25 mm or more More preferably, it is 5.0 N / 25 mm or more, More preferably, it is 7.0 N / 25 mm or more, More preferably, it is 10.0 N / 25 mm or more, More preferably, it is 18.0 N / 25 mm or more.
  • the value of said adhesive force means the value measured by the method as described in an Example.
  • the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention may further have a release material on the sticking surface of the pressure-sensitive adhesive layer.
  • pick a laminated body are adjusted so that the difference in peeling force may differ.
  • the release material a release sheet that has been subjected to a double-sided release process, a release sheet that has been subjected to a single-sided release process, or the like is used. Examples include a release material coated on a release material substrate.
  • Examples of the base material for the release material include papers such as high-quality paper, glassine paper, and kraft paper; polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin; and olefins such as polypropylene resin and polyethylene resin.
  • a plastic film such as a resin film;
  • release agent examples include silicone-based resins, olefin-based resins, isoprene-based resins, rubber-based elastomers such as butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.
  • the thickness of the release material is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 25 to 170 ⁇ m, and still more preferably 35 to 80 ⁇ m.
  • the method for producing the double-sided PSA sheet of the present invention is preferably a method having the following steps (1) to (2).
  • Step (1) a coating film (x1 ′) composed of the composition (x1), a coating film (y ′) composed of the composition (y), and a coating film (x2 ′) composed of the composition (x2)
  • Step (2) The process of drying a coating film (x1 '), a coating film (y'), and a coating film (x2 ') simultaneously, and forming the said laminated body.
  • the coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′) for example, after forming the coating film (x1 ′), the coating film (x1 A sequential formation method may be used in which a coating film (y ') is formed on') and a coating film (x2 ') is further formed on the coating film (y'). From the viewpoint of productivity, the coating film ( A method in which x1 ′), (y ′), and (x2 ′) are simultaneously applied is preferable. In addition, from the viewpoint of handleability, the coating film (x1 ′) is preferably formed on the release treatment surface of the release material.
  • Examples of the coater used for sequential formation include a spin coater, a spray coater, a bar coater, a knife coater, a roll coater, a knife roll coater, a blade coater, a gravure coater, a curtain coater, and a die coater.
  • a multilayer coater As the coater used for simultaneous application, a multilayer coater can be mentioned, and specifically, a curtain coater, a die coater and the like can be mentioned. Among these, a die coater is preferable from the viewpoint of operability.
  • a composition (x1), a composition (y), and a composition (x2) contain a dilution solvent further from a viewpoint of making each coating film easy to form and improving productivity.
  • a dilution solvent water or the above-mentioned organic solvent can be used.
  • blending a dilution solvent with each composition is as above-mentioned.
  • the coating amount of the coating film (x1 ') and film (x2') are each independently preferably 0.5 ⁇ 50.0g / m 2, more preferably 1.0 ⁇ 40.0g / m 2, further It is preferably 2.0 to 30.0 g / m 2 , and more preferably 3.0 to 20.0 g / m 2 .
  • the coating amount of the coating film (y ′) is preferably 0.3 to 50.0 g / m 2 , more preferably 0.5 to 30.0 g / m 2 , still more preferably 0.7 to 15.0 g / m. 2 and more preferably 1.0 to 8.0 g / m 2 .
  • the ratio of the coating amount of the coating film (y ′) to the total coating amount 100 of the coating film (x1 ′) and the coating film (x2 ′) is preferably 1 to 100, more preferably 4 to 70, still more preferably. It is 7 to 50, particularly preferably 10 to 30.
  • this process (1) after forming the coating film of 1 layer or more of a coating film (x1 '), a coating film (y'), and a coating film (x2 '), before the process (2), You may perform the predrying process of the grade which does not advance the hardening reaction of a coating film. For example, a pre-drying treatment may be performed each time a coating film (x1 ′), a coating film (y ′), and a coating film (x2 ′) are formed. After forming the two-layer coating film of the coating film (y ′), the coating film (x2 ′) may be formed after performing a pre-drying treatment collectively.
  • the drying temperature at the time of performing the pre-drying treatment is usually appropriately set within a temperature range in which the formed coating film does not cure, but preferably in the step (2).
  • the specific drying temperature indicated by the phrase “below the drying temperature in step (2)” is preferably 10 to 45 ° C., more preferably 10 to 34 ° C., and further preferably 15 to 30 ° C.
  • Step (2) the coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′) are simultaneously dried to form the laminate.
  • a mixed layer is formed at the interface between the coating film (x1 ′) and the coating film (y ′) and at the interface between the coating film (y ′) and the coating film (x2 ′).
  • the first pressure-sensitive adhesive layer (X1) and the base material layer (Y), and the base material layer (Y) and the second pressure-sensitive adhesive layer (X2) are dried and cured in an intertwined state with the non-adhesive resin. It is considered that the interfacial adhesion of the material significantly improves.
  • the drying temperature of the coating film in the step (2) is preferably 60 to 150 ° C, more preferably 70 to 145 ° C, still more preferably 80 to 140 ° C, and still more preferably 90 to 135 ° C.
  • the manufacturing method of the double-sided adhesive sheet which has adhesive layers other than a 1st and 2nd adhesive layer When the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention has a configuration including pressure-sensitive adhesive layers other than the first and second pressure-sensitive adhesive layers, as in the double-sided pressure-sensitive adhesive sheet 4 shown in FIG.
  • a pressure-sensitive adhesive layer other than the two pressure-sensitive adhesive layers may be separately formed and attached to the formed laminate, or may be formed simultaneously with the formation of the laminate.
  • the third pressure-sensitive adhesive layer (X3) and the fourth pressure-sensitive adhesive layer (X4) included in the double-sided pressure-sensitive adhesive sheet 4 shown in FIG. 1 (d) are formed by any of the following (i) and (ii). Can do.
  • the third pressure-sensitive adhesive layer (X3) 123 is formed on the release treatment surface of the release material 131, and the coating film (x1 ′), ( y ′) and (x2 ′) are formed, and these coating films are dried at the same time to form the laminate 10.
  • the second adhesive layer (X2) 122 of the laminate 10 has a Four adhesive layers (X4) 124 are laminated.
  • the 4th adhesive layer (X4) is a coating film which consists of a composition which is a formation material of a 4th adhesive layer (X4) on the sticking surface of a 2nd adhesive layer (X2). May be formed by drying, and a fourth pressure-sensitive adhesive layer (X4) formed on a release-treated surface of a separate release material is applied to the surface of the second pressure-sensitive adhesive layer (X2). May be.
  • a 4th adhesive layer (X4) is the 4th adhesive layer on the sticking surface of the 2nd adhesive layer (X2) 122 of the laminated body 10.
  • the coating film made of the composition which is the forming material of (X4) may be formed by drying, and the fourth pressure-sensitive adhesive layer (X4) formed on the release-treated surface of the release material prepared separately is used as the second pressure-sensitive adhesive. You may affix and form on the sticking surface of an agent layer (X2).
  • the coating film (x3 ′), the coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′) are simultaneously dried,
  • the composition (x1) on which the coating film (x1 ′) is formed is different from each other.
  • the coating film (x1 ′), the coating film (y ′), the coating film (x2 ′), and the coating film (x4 ′) are simultaneously dried, the composition in which the coating film (x4 ′) is formed.
  • the product and the composition (x2) on which the coating film (x2 ′) is formed are different from each other.
  • BA n-butyl acrylate
  • AAc acrylic acid
  • solid content ratio 50 parts by mass (solid content ratio), and as crosslinking agent, isocyanate-based crosslinking agent (product name “Coronate L”, manufactured by Tosoh Corporation), solid content Concentration: 75% by mass) 1.5 parts by mass (solid content ratio) mixed and mixed, further diluted with toluene, stirred uniformly, and a solid content concentration (active ingredient concentration) of 30% by mass Prepare (x-1) .
  • composition (y-1) Non-adhesive resin, acid-modified olefin resin solution (Mitsubishi Chemical Co., Ltd., product name “Unistal H-200”, mass average molecular weight: 145,000, glass transition temperature: ⁇ 53 ° C., dilution solvent : Mixed solvent of methylcyclohexane and methyl ethyl ketone, solid content concentration (active ingredient concentration): 20% by mass) was used as the composition (y-1).
  • composition (y-2) An isocyanate-based crosslinking agent as a crosslinking agent was added to 100 parts by mass (solid content ratio) of the acrylic urethane-based resin solution obtained in (2) above, which is a non-adhesive resin.
  • (Product name “Coronate HL” manufactured by Tosoh Corporation) 6.3 parts by mass (solid content ratio), and 1.4 parts by mass (solid content ratio) of dioctyltin bis (2-ethylhexanoate) as a catalyst
  • a composition (y-2) having a solid content concentration (active ingredient concentration) of 30% by mass.
  • Release film (1) manufactured by Lintec Corporation, product name “SP-PET 382150”, polyethylene terephthalate (PET) film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 ⁇ m.
  • Release film (2) manufactured by Lintec Co., Ltd., product name “SP-PET381031”, a PET film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 ⁇ m.
  • Base film (1) manufactured by Mitsubishi Plastics, product name “Diafoil K-700-6E”, biaxially oriented PET film, thickness: 6.0 ⁇ m.
  • Base film (2) manufactured by Mitsubishi Plastics, product name “Diafoil K100-2.0W”, biaxially stretched PET film, thickness: 2.0 ⁇ m.
  • Examples 1 to 3 Comparative Example 1 (1) Formation of coating film On the release agent layer of the release film (1) as the first release material, the composition (x-1) prepared in Production Example 1, the type of composition described in Table 1, and The composition (x-1) prepared in Production Example 1 was simultaneously applied in this order using a multilayer die coater (width: 250 mm) at a coating speed of 30 m / min. (Y ′) and the coating film (x2 ′) were simultaneously formed in this order.
  • the application quantity of the composition for forming a coating film (x1 '), a coating film (y'), and a coating film (x2 ') is as having described in Table 1.
  • the formed coating film (x1 ′), coating film (y ′), and coating film (x2 ′) are simultaneously dried at a drying temperature of 125 ° C. for 60 seconds to form a release agent layer of the release film (1).
  • a stacked body in which the layer (X1), the layer (Y), and the layer (X2) were directly stacked was formed.
  • the release agent layer of the peeling film (2) which is a 2nd peeling material was laminated
  • Example 4 Formation of coating film A coating film (x1) made of the composition (x-1) prepared in Production Example 1 using an applicator on the release agent layer of the release film (1) as the first release material ') And a coating film (y') comprising the composition (y-2) prepared in Production Example 3 on the coating film (x1 '), and Production Example 1 on the coating film (y').
  • the prepared composition (x-1) was sequentially formed.
  • Drying treatment The formed coating film (x1 ′), coating film (y ′), and coating film (x2 ′) are simultaneously dried at a drying temperature of 110 ° C. for 120 seconds to form a release agent layer of the release film (1).
  • the layer (X1), the layer (Y), and the layer (X2) were directly stacked was formed.
  • the thickness of the formed layer (X1), layer (Y), and layer (X2) was as shown in Table 1.
  • the release agent layer of the peeling film (2) which is a 2nd peeling material was laminated
  • a coating film (x1 ′) made of the composition (x-1) prepared in Production Example 1 is formed and dried at 110 ° C. for 120 seconds. Only the layer (X1) was formed. In addition, the thickness of the formed layer (X1) was as shown in Table 1. And the release agent layer of the peeling film (2) which is a 2nd peeling material was laminated
  • a coating film (x1 ′) made of the composition (x-1) prepared in Production Example 1 is formed and dried at 110 ° C. for 120 seconds.
  • Layer (X1) was formed.
  • a coating film (x2 ′) composed of the composition (x-1) prepared in Production Example 1 was formed on the release agent layer of the release film (2), which is the second release material, at 110 ° C. It was dried for 120 seconds to form a layer (X2).
  • the thickness of the formed layer (X1) and layer (X2) was as shown in Table 1.
  • the base film (1) is laminated in Comparative Example 3
  • the base film (2) is laminated in Comparative Example 4, and the base material is further laminated.
  • a layer (X2) was laminated on the film to form a laminate, and a double-sided PSA sheet was obtained in which the laminate was sandwiched between two release materials.
  • a coating film (x1 ′) made of the composition (x-1) prepared in Production Example 1 is formed and dried at 110 ° C. for 120 seconds.
  • Layer (X1) was formed.
  • a coating film (x2 ′) composed of the composition (x-1) prepared in Production Example 1 was formed on the release agent layer of the release film (2), which is the second release material, at 110 ° C. It was dried for 120 seconds to form a layer (X2).
  • (y-1) prepared in Production Example 2 was used in Comparative Example 5
  • (y-2) prepared in Production Example 3 was used in Comparative Example 6.
  • a coating film was formed and dried at 110 ° C. for 120 seconds to form a layer (Y).
  • the thickness of the formed layer (X1), layer (Y), and layer (X2) was as shown in Table 1. Then, on the surface of the exposed layer (X1), the layer (Y) is laminated, and the release film (2) on the layer (Y) is further removed, and on the surface of the exposed layer (Y).
  • the layer (X2) was laminated to form a laminate, and a double-sided PSA sheet was obtained in which the laminate was sandwiched between two release materials.
  • the thickness of the laminate (the thickness of the layer (X1) in Comparative Example 2) that the double-sided PSA sheets prepared in Examples and Comparative Examples have, and the layer (X1), the layer (Y) constituting the laminate, And the thickness of layer (X2) was measured based on the above-mentioned method. The measurement results are shown in Table 1.
  • the “MD direction” refers to the direction in which the composition was applied when forming the coating film in Examples 1 to 4 and Comparative Examples 5 and 6, and in Comparative Examples 3 and 4, the base used. It refers to the flow direction of the film forming machine when manufacturing the material film.
  • the average value was made into the haze of the target laminated body. Further, the total light transmittance of the laminate was determined by measuring the total light transmittance at three arbitrarily selected points of the test piece in accordance with JIS K7361-1: 1997 using the haze meter, and calculating the average The value was defined as the total light transmittance of the target laminate.
  • the second release material was removed from the double-sided PSA sheets prepared in Examples and Comparative Examples, and a PET film (product name “Diafoil T-100”, manufactured by Mitsubishi Plastics, Inc. 50 ⁇ m) were bonded together and cut into a size of 300 mm long ⁇ 25 mm wide. Then, the first release material was also removed, and a stainless steel plate (SUS306, No. 600 polishing) was applied to the surface of the exposed laminate. After standing for 7 days in an environment of 70 ° C. and dry, further 23 ° C. , And left in an environment of 50% RH (relative humidity) for 1 day.
  • RH relative humidity
  • the state of the peeling interface when the PET film was peeled was observed, and the interfacial adhesion between the layer (Y) and the layers (X1) and (X2) was evaluated according to the following criteria.
  • the double-sided pressure-sensitive adhesive sheets of Examples 1 to 4 had good adhesive strength and resulted in a high effect of suppressing the tearing phenomenon. Moreover, these double-sided PSA sheets are considered to be excellent in punching processability, pasting suitability and cutting processability because of high interfacial adhesion between the base material layer and the PSA layer. On the other hand, the double-sided pressure-sensitive adhesive sheets of Comparative Examples 1 and 2 did not have a base material layer composed of a non-adhesive resin, so that tearing was likely to occur.
  • the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention is useful as a double-sided pressure-sensitive adhesive sheet having a large affixing area used for identification or decoration, coating masking, surface protection of metal plates and the like.

Abstract

Provided is a double-sided adhesive sheet comprising a laminate produced by directly laminating a first adhesive agent layer (X1), a base layer (Y) and a second adhesive agent layer (X2) in this order, wherein the laminate is formed by directly laminating a coating film (x1') made from a composition (x1) that is a material for forming the first adhesive agent layer and contains an adhesive resin, a coating film (y') made from a composition (y) that is a material for forming the base layer (Y) and contains a non-adhesive resin selected from the group consisting of an acrylic urethane resin and an olefin resin, and a coating film (x2') made from a composition (x2) that is a material for forming the second adhesive agent layer and contains an adhesive resin in this order, and then drying the coating films (x1'), (y') and (x2') simultaneously. The double-sided adhesive sheet is highly prevented from the occurrence of an undesired separation phenomenon, i.e., a phenomenon that the adhesive agent layers are divided and torn from each other in conjunction with two release sheets upon the peeling off of one of the release sheets, and the double-sided adhesive sheet also has excellent punching properties, and is excellent in adhesion fitness and cutting processability.

Description

両面粘着シート、及び両面粘着シートの製造方法Double-sided pressure-sensitive adhesive sheet and method for producing double-sided pressure-sensitive adhesive sheet
 本発明は両面粘着シート、及び両面粘着シートの製造方法に関する。 The present invention relates to a double-sided pressure-sensitive adhesive sheet and a method for producing a double-sided pressure-sensitive adhesive sheet.
 両面粘着シートは、建材の固定、電子部品の固定、内装材の固定等の様々な部材の固定用途に使用されている。
 このような両面粘着シートとしては、基材(芯材)を設けずに、2枚の剥離シートで単体の粘着剤層を挟持した構成を有する基材無し両面粘着シートや、基材(芯材)の両面に粘着剤層を設け、それぞれの粘着剤層上に剥離シートを積層した構成を有する基材付き粘着シートが知られている。
The double-sided pressure-sensitive adhesive sheet is used for fixing various members such as building materials, electronic parts, and interior materials.
As such a double-sided pressure-sensitive adhesive sheet, a baseless double-sided pressure-sensitive adhesive sheet having a configuration in which a single pressure-sensitive adhesive layer is sandwiched between two release sheets without providing a base material (core material), or a base material (core material) ) Is provided with a pressure-sensitive adhesive layer on both surfaces, and a pressure-sensitive adhesive sheet with a substrate having a structure in which a release sheet is laminated on each pressure-sensitive adhesive layer is known.
 特許文献1には、基材無し両面粘着シートとして、粘着剤として使用される特定の樹脂のみにより形成された基材粘着剤の表面及び裏面に、それぞれ第一の粘着剤層及び第二の粘着剤層を設けてなる、粘着剤のみによって構成された両面粘着シートが開示されている。 In Patent Document 1, as a double-sided pressure-sensitive adhesive sheet without a base material, a first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive are respectively formed on the surface and the back surface of a base material pressure-sensitive adhesive formed only with a specific resin used as a pressure-sensitive adhesive. A double-sided pressure-sensitive adhesive sheet comprising only a pressure-sensitive adhesive provided with an agent layer is disclosed.
 また、特許文献2には、基材付き粘着シートとして、光学的に無配向で且つ透明な基材の2つの表面に、それぞれ透明な第1の粘着層と第2の粘着層とを有し、積層された3層の厚みが55μm以下で、内部HAZEが1以下である両面粘着フィルムが開示されている。 Moreover, in patent document 2, it has a transparent 1st adhesion layer and a 2nd adhesion layer respectively on two surfaces of an optically non-oriented and transparent base material as an adhesive sheet with a base material. A double-sided pressure-sensitive adhesive film in which the thickness of three laminated layers is 55 μm or less and the internal HAZE is 1 or less is disclosed.
特許第4025405号公報Japanese Patent No. 4025405 特開2007-119562号公報JP 2007-119562 A
 ところで、特許文献1に記載されたような基材無し両面粘着シートは、被着体への貼付時や保管時に、端部から粘着剤層のはみ出し易く、被着体等を汚してしまう場合がある。
 また、基材無し両面粘着シートは、一方の剥離シートを剥離する際に、粘着剤層が2つの剥離シートに伴って分断され引き剥がされるという現象である、いわゆる「泣き別れ現象」が生じ易い。
 さらに、基材無し両面粘着シートに抜き加工を施す際に、形状の変形や粘着剤層の浸み出しといった弊害が生じ易く、抜き加工性に問題がある。
By the way, the double-sided pressure-sensitive adhesive sheet without a substrate as described in Patent Document 1 is likely to stick out of the adhesive layer from the end during sticking to the adherend or during storage, and may contaminate the adherend or the like. is there.
Further, the double-sided pressure-sensitive adhesive sheet without a substrate tends to cause a so-called “crying phenomenon”, which is a phenomenon in which the pressure-sensitive adhesive layer is divided and peeled off along with two release sheets when one release sheet is peeled off.
Furthermore, when punching a double-sided pressure-sensitive adhesive sheet without a substrate, problems such as shape deformation and oozing out of the pressure-sensitive adhesive layer are likely to occur, and there is a problem in punchability.
 一方で、基材付き両面粘着シートは、被着体への貼付時や保管時の端部からの粘着剤層のはみ出しの抑制効果や泣き別れ現象の抑制効果は、基材無し粘着シートに比べると改善し得るが、抜き加工性が劣るという問題を有している。
 また、特許文献2に記載されたような基材付き両面粘着シートは、基材と粘着剤層との界面密着力が低いことに起因し、被着体の形状に合わせて一様に伸ばして貼付することが困難となり易い。また、基材と粘着剤層との界面密着力の低下は、ロール製品を巻き出しながら端部を切り落として再度ロール状に巻き取るという裁断加工工程において、幅方向に平行な直線状の浮き剥がれが生じるといった、いわゆる「トンネリング」の発生の原因となる。
On the other hand, the double-sided pressure-sensitive adhesive sheet with a substrate is more effective than the pressure-sensitive adhesive sheet without a substrate in suppressing the sticking-out of the adhesive layer from the edge during sticking to the adherend or storage and the effect of suppressing the tearing phenomenon. Although it can be improved, it has a problem that the punching process is inferior.
Moreover, the double-sided pressure-sensitive adhesive sheet with a base material described in Patent Document 2 is caused by low interfacial adhesion between the base material and the pressure-sensitive adhesive layer, and is uniformly stretched according to the shape of the adherend. It tends to be difficult to apply. Also, the decrease in interfacial adhesion between the substrate and the pressure-sensitive adhesive layer is caused by the linear lifting parallel to the width direction in the cutting process where the roll product is unwound and the end is cut off and rolled up again. This causes the so-called “tunneling”.
 本発明は、一方の剥離シートを剥離する際に、粘着剤層が2つの剥離シートに伴って分断され引き剥がされるという泣き別れ現象の抑制効果が高く、抜き加工性、貼付適性及び裁断加工適性に優れる両面粘着シート、並びに両面粘着シートの製造方法を提供することを目的とする。 In the present invention, when one release sheet is peeled off, the pressure-sensitive adhesive layer is divided and peeled off along with the two release sheets, and the effect of suppressing the tearing phenomenon is high. It aims at providing the manufacturing method of the double-sided adhesive sheet which is excellent, and a double-sided adhesive sheet.
 本発明者らは、第1粘着剤層、基材層、及び第2粘着剤層をこの順で直接積層した積層体を有する両面粘着シートについて、当該積層体を、上記3層の形成材料である組成物からなる塗膜を順に積層した上で、同時に乾燥して形成したものとすることで、上記課題を解決し得ることを見い出した。 For the double-sided pressure-sensitive adhesive sheet having a laminate in which the first pressure-sensitive adhesive layer, the base material layer, and the second pressure-sensitive adhesive layer are directly laminated in this order, the laminate is made of the above three-layer forming material. It has been found that the above-mentioned problems can be solved by sequentially laminating a coating film made of a certain composition and drying it at the same time.
 すなわち、本発明は、下記[1]~[14]に関する。
[1]第1粘着剤層(X1)、基材層(Y)、及び第2粘着剤層(X2)をこの順で直接積層した積層体を有する両面粘着シートであって、
 前記積層体が、
  第1の粘着剤層の形成材料である、粘着性樹脂を含む組成物(x1)からなる塗膜(x1’)と、
  基材層(Y)の形成材料である、アクリルウレタン系樹脂及びオレフィン系樹脂からなる群から選ばれる非粘着性樹脂を含む組成物(y)からなる塗膜(y’)と、
  第2の粘着剤層の形成材料である、粘着性樹脂を含む組成物(x2)からなる塗膜(x2’)と、
をこの順で直接積層した後、塗膜(x1’)、(y’)及び(x2’)を同時に乾燥して形成されたものである、両面粘着シート。
[2]第1粘着剤層(X1)及び第2粘着剤層(X2)の合計厚さ100に対する、基材層(Y)の厚さ比が、1~100である、上記[1]に記載の両面粘着シート。
[3]前記積層体の厚さが、2~90μmである、上記[1]又は[2]に記載の両面粘着シート。
[4]基材層(Y)の厚さが、0.3~50.0μmである、上記[1]~[3]のいずれか一項に記載の両面粘着シート。
[5]組成物(x1)及び(x2)に含まれる前記粘着性樹脂が、アクリル系樹脂を含む、上記[1]~[4]のいずれか一項に記載の両面粘着シート。
[6]組成物(y)に含まれる前記非粘着性樹脂が、重合性官能基を有しない紫外線非硬化型樹脂である、上記[1]~[5]のいずれか一項に記載の両面粘着シート。
[7]基材層(Y)が、無延伸のシート状物である、上記[1]~[6]のいずれか一項に記載の両面粘着シート。
[8]基材層(Y)の破断伸度が100%以上である、上記[1]~[7]のいずれか一項に記載の両面粘着シート。
[9]基材層(Y)の破断強度が30MPa以上である、上記[1]~[8]のいずれか一項に記載の両面粘着シート。
[10]前記積層体のヘーズが5.00%以下である、上記[1]~[9]のいずれか一項に記載の両面粘着シート。
[11]前記積層体の全光線透過率が80%以上である、上記[1]~[10]のいずれか一項に記載の両面粘着シート。
[12]上記[1]~[11]のいずれか一項に記載の両面粘着シートを製造する方法であって、
 下記工程(1)~(2)を有する、両面粘着シートの製造方法。
・工程(1):組成物(x1)からなる塗膜(x1’)と、組成物(y)からなる塗膜(y’)と、組成物(x2)からなる塗膜(x2’)とをこの順で直接積層して形成する工程。
・工程(2):塗膜(x1’)、塗膜(y’)、及び塗膜(x2’)を同時に乾燥させて前記積層体を形成する工程。
[13]工程(1)において、組成物(x1)、組成物(y)、及び組成物(x2)を同時に塗布する、上記[12]に記載の両面粘着シートの製造方法。
[14]組成物(x1)、組成物(y)、及び組成物(x2)が、さらに希釈溶媒を含有する、上記[12]又は[13]に記載の両面粘着シートの製造方法。
That is, the present invention relates to the following [1] to [14].
[1] A double-sided pressure-sensitive adhesive sheet having a laminate in which a first pressure-sensitive adhesive layer (X1), a base material layer (Y), and a second pressure-sensitive adhesive layer (X2) are directly laminated in this order,
The laminate is
A coating film (x1 ′) comprising a composition (x1) containing an adhesive resin, which is a material for forming the first adhesive layer;
A coating film (y ′) made of a composition (y) containing a non-adhesive resin selected from the group consisting of an acrylic urethane-based resin and an olefin-based resin, which is a forming material of the base material layer (Y);
A coating film (x2 ′) comprising a composition (x2) containing an adhesive resin, which is a material for forming the second adhesive layer;
Are laminated | stacked directly in this order, Then, the double-sided adhesive sheet formed by drying simultaneously a coating film (x1 '), (y'), and (x2 ').
[2] In the above [1], the thickness ratio of the base material layer (Y) to the total thickness 100 of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) is 1 to 100 The double-sided pressure-sensitive adhesive sheet described.
[3] The double-sided pressure-sensitive adhesive sheet according to the above [1] or [2], wherein the thickness of the laminate is 2 to 90 μm.
[4] The double-sided pressure-sensitive adhesive sheet according to any one of [1] to [3], wherein the thickness of the base material layer (Y) is 0.3 to 50.0 μm.
[5] The double-sided pressure-sensitive adhesive sheet according to any one of the above [1] to [4], wherein the adhesive resin contained in the compositions (x1) and (x2) comprises an acrylic resin.
[6] Both sides according to any one of [1] to [5], wherein the non-adhesive resin contained in the composition (y) is an ultraviolet non-curable resin having no polymerizable functional group. Adhesive sheet.
[7] The double-sided pressure-sensitive adhesive sheet according to any one of [1] to [6], wherein the base material layer (Y) is an unstretched sheet-like material.
[8] The double-sided pressure-sensitive adhesive sheet according to any one of [1] to [7], wherein the base layer (Y) has a breaking elongation of 100% or more.
[9] The double-sided pressure-sensitive adhesive sheet according to any one of [1] to [8], wherein the base material layer (Y) has a breaking strength of 30 MPa or more.
[10] The double-sided pressure-sensitive adhesive sheet according to any one of [1] to [9], wherein the laminate has a haze of 5.00% or less.
[11] The double-sided pressure-sensitive adhesive sheet according to any one of [1] to [10], wherein the laminate has a total light transmittance of 80% or more.
[12] A method for producing the double-sided pressure-sensitive adhesive sheet according to any one of [1] to [11] above,
A method for producing a double-sided pressure-sensitive adhesive sheet, comprising the following steps (1) to (2).
Step (1): a coating film (x1 ′) composed of the composition (x1), a coating film (y ′) composed of the composition (y), and a coating film (x2 ′) composed of the composition (x2) A process of directly stacking layers in this order.
-Process (2): The process of drying a coating film (x1 '), a coating film (y'), and a coating film (x2 ') simultaneously, and forming the said laminated body.
[13] The method for producing a double-sided pressure-sensitive adhesive sheet according to [12], wherein in the step (1), the composition (x1), the composition (y), and the composition (x2) are applied simultaneously.
[14] The method for producing a double-sided pressure-sensitive adhesive sheet according to the above [12] or [13], wherein the composition (x1), the composition (y), and the composition (x2) further contain a diluent solvent.
 本発明の両面粘着シートは、一方の剥離シートを剥離する際に、粘着剤層が2つの剥離シートに伴って分断され引き剥がされるという泣き別れ現象の抑制効果が高く、また、基材層と粘着剤層との界面密着性が高いため、抜き加工性、貼付適性及び裁断加工適性に優れる。
 また、本発明の両面粘着シートの製造方法は、このような特性を有する両面粘着シートを、工程数を低減し、ハンドリング性を向上させ得るため、生産性を向上させて製造することができる。
The double-sided pressure-sensitive adhesive sheet of the present invention has a high effect of suppressing the tearing phenomenon that the pressure-sensitive adhesive layer is divided and peeled off with the two release sheets when peeling one of the release sheets. Due to high interfacial adhesion to the agent layer, it is excellent in punching processability, pasting ability and cutting processability.
Moreover, since the manufacturing method of the double-sided adhesive sheet of this invention can reduce the number of processes and improve handling property, the double-sided adhesive sheet which has such a characteristic can improve and can manufacture.
本発明の両面粘着シートの構成の一例を示す、両面粘着シートの断面模式図である。It is a cross-sectional schematic diagram of a double-sided pressure-sensitive adhesive sheet showing an example of the configuration of the double-sided pressure-sensitive adhesive sheet of the present invention.
 本発明において、対象となる樹脂が、「粘着性樹脂」か「非粘着性樹脂」のどちらに属するかの判断は、下記手順(1)~(4)に基づいて行う。
・手順(1):対象となる樹脂のみから形成した厚さ20μmの樹脂層を、厚さ50μmのポリエチレンテレフタレート(PET)フィルムの表面上に積層したものを、縦300mm×横25mmの大きさに切断した試験片を作製する。
・手順(2):23℃、50%RH(相対湿度)の環境下で、当該試験片の表出している樹脂層の表面を、ステンレス板(SUS304 360番研磨)に貼付し、同環境下で24時間静置する。
・手順(3):静置後、23℃、50%RH(相対湿度)の環境下で、JIS Z0237:2000に基づき、180°引き剥がし法により、引っ張り速度300mm/分にて、粘着力を測定する。
・手順(4):測定した粘着力が0.1N/25mm以上であれば、対象となる樹脂は「粘着性樹脂」と判断する。一方、測定した粘着力が0.1N/25mm未満であれば、対象となる樹脂は「非粘着性樹脂」と判断する。
In the present invention, whether the target resin belongs to “adhesive resin” or “non-adhesive resin” is determined based on the following procedures (1) to (4).
Procedure (1): A 20 μm thick resin layer formed from only the target resin is laminated on the surface of a 50 μm thick polyethylene terephthalate (PET) film to a size of 300 mm length × 25 mm width A cut specimen is prepared.
・ Procedure (2): Under an environment of 23 ° C. and 50% RH (relative humidity), the surface of the resin layer exposed on the test piece is attached to a stainless steel plate (SUS304 No. 360 polishing). Leave for 24 hours.
・ Procedure (3): After standing, in an environment of 23 ° C. and 50% RH (relative humidity), the adhesive strength was increased at a pulling speed of 300 mm / min by 180 ° peeling method based on JIS Z0237: 2000. taking measurement.
Procedure (4): If the measured adhesive strength is 0.1 N / 25 mm or more, the target resin is determined as an “adhesive resin”. On the other hand, if the measured adhesive strength is less than 0.1 N / 25 mm, the target resin is determined as a “non-adhesive resin”.
 本明細書において、「有効成分」とは、対象となる組成物に含まれる成分のうち、希釈溶媒を除いた成分を指す。
 また、質量平均分子量(Mw)及び数平均分子量(Mn)は、ゲルパーミエーションクロマトグラフィー(GPC)法で測定される標準ポリスチレン換算の値であり、具体的には実施例に記載の方法に基づいて測定した値である。
In the present specification, the “active ingredient” refers to a component excluding a diluent solvent among components contained in a target composition.
Moreover, a mass average molecular weight (Mw) and a number average molecular weight (Mn) are the values of standard polystyrene conversion measured by a gel permeation chromatography (GPC) method, and are specifically based on the method as described in an Example. Measured value.
 本明細書において、例えば、「(メタ)アクリル酸」とは、「アクリル酸」と「メタクリル酸」の双方を示し、他の類似用語も同様である。
 また、好ましい数値範囲(例えば、含有量等の範囲)について、段階的に記載された下限値及び上限値は、それぞれ独立して組み合わせることができる。例えば、「好ましくは10~90、より好ましくは30~60」という記載から、「好ましい下限値(10)」と「より好ましい上限値(60)」とを組み合わせて、「10~60」とすることもできる。
In the present specification, for example, “(meth) acrylic acid” indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
Moreover, about the preferable numerical range (for example, range of content etc.), the lower limit value and upper limit value which were described in steps can be combined independently, respectively. For example, from the description “preferably 10 to 90, more preferably 30 to 60”, “preferable lower limit (10)” and “more preferable upper limit (60)” are combined to obtain “10 to 60”. You can also.
〔本発明の両面粘着シートの構成〕
 本発明の両面粘着シートは、第1粘着剤層(X1)、基材層(Y)、及び第2粘着剤層(X2)をこの順で直接積層した積層体を有するものであれば、特に限定されない。
 図1は、本発明の両面粘着シートの構成を示す、両面粘着シートの断面模式図である。
[Configuration of the double-sided pressure-sensitive adhesive sheet of the present invention]
If the double-sided pressure-sensitive adhesive sheet of the present invention has a laminate in which the first pressure-sensitive adhesive layer (X1), the base material layer (Y), and the second pressure-sensitive adhesive layer (X2) are directly laminated in this order, It is not limited.
FIG. 1 is a schematic cross-sectional view of a double-sided PSA sheet showing the configuration of the double-sided PSA sheet of the present invention.
 本発明の両面粘着シートは、図1(a)に示す両面粘着シート1のように、第1粘着剤層(X1)121、基材層(Y)11、及び第2粘着剤層(X2)122をこの順で直接積層した積層体10を有するものであればよい。
 ここで、上述の「直接積層した」とは、第1粘着剤層(X1)と基材層(Y)との間、並びに、基材層(Y)と第2粘着剤層(X2)との間に、他の層を有さずに、2層が直接接触している構成を指す。
 また、本発明の両面粘着シートが有する「積層体」とは、第1粘着剤層(X1)、基材層(Y)、及び第2粘着剤層(X2)から構成されたものであり、他の層(後述の剥離材や第3粘着剤層、第4粘着剤層等)は、当該積層体の構成には含まれない。
The double-sided pressure-sensitive adhesive sheet of the present invention has a first pressure-sensitive adhesive layer (X1) 121, a base material layer (Y) 11, and a second pressure-sensitive adhesive layer (X2) like the double-sided pressure-sensitive adhesive sheet 1 shown in FIG. What is necessary is just to have the laminated body 10 which laminated | stacked 122 directly in this order.
Here, the above-mentioned “directly laminated” means between the first pressure-sensitive adhesive layer (X1) and the base material layer (Y), and between the base material layer (Y) and the second pressure-sensitive adhesive layer (X2). Between the two, it refers to a configuration in which the two layers are in direct contact with no other layers.
The “laminate” of the double-sided pressure-sensitive adhesive sheet of the present invention is composed of the first pressure-sensitive adhesive layer (X1), the base material layer (Y), and the second pressure-sensitive adhesive layer (X2). Other layers (such as a release material, a third pressure-sensitive adhesive layer, and a fourth pressure-sensitive adhesive layer described later) are not included in the configuration of the laminate.
 本発明の一態様の両面粘着シートとしては、取扱性の観点から、第1粘着剤層(X1)及び第2粘着剤層(X2)の一方もしくは双方の貼付表面(基材層と接触している側とは反対側の表面)上に、さらに剥離材を有する構成とすることが好ましい。
 つまり、当該態様の両面粘着シートとしては、図1(b)に示す、第1粘着剤層(X1)121の貼付表面上に、更に剥離材131を有する両面粘着シート2や、図1(c)に示す、第1粘着剤層(X1)121及び第2粘着剤層(X2)122の貼付表面上に、それぞれ更に剥離材131、132を有する両面粘着シート3が挙げられる。
As a double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention, from the viewpoint of handleability, one or both surfaces of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) (in contact with the base material layer) It is preferable that a release material is further provided on the surface (on the opposite side of the surface).
That is, as the double-sided pressure-sensitive adhesive sheet of this aspect, the double-sided pressure-sensitive adhesive sheet 2 further having a release material 131 on the sticking surface of the first pressure-sensitive adhesive layer (X1) 121 shown in FIG. The double-sided pressure-sensitive adhesive sheet 3 further having release materials 131 and 132 on the sticking surfaces of the first pressure-sensitive adhesive layer (X1) 121 and the second pressure-sensitive adhesive layer (X2) 122 shown in FIG.
 なお、図1(b)に示す両面粘着シート2においては、剥離材131として、両面に剥離処理が施された剥離材を用いて、ロール状に巻いた構成を有する両面粘着シートとしてもよい。
 また、図1(c)に示す両面粘着シート3においては、泣き別れ現象の抑制効果をより向上させる観点から、剥離材131、132として、互いに剥離力が異なるように設計された2種の剥離材を用いることが好ましい。
In addition, in the double-sided adhesive sheet 2 shown in FIG.1 (b), it is good also as a double-sided adhesive sheet which has the structure wound in roll shape using the peeling material by which the peeling process was given to both surfaces as the peeling material 131. FIG.
Moreover, in the double-sided adhesive sheet 3 shown in FIG.1 (c), from the viewpoint of improving the suppression effect of a tearing-off phenomenon, as the release materials 131 and 132, two types of release materials designed to have different release forces from each other. Is preferably used.
 また、本発明の一態様の両面粘着シートとしては、第1粘着剤層(X1)及び第2粘着剤層(X2)の一方もしくは双方の貼付表面(基材層と接触している側とは反対側の表面)上に、さらに異なる形成材料である組成物から形成した粘着剤層を積層した構成としてもよい。
 そのような態様として、例えば、図1(d)に示すような、第1粘着剤層(X1)121の貼付表面上に、さらに第3粘着剤層(X3)123を設け、また、第2粘着剤層(X2)122の貼付表面上に、さらに第4粘着剤層(X4)124を設けた両面粘着シート4が挙げられる。
Moreover, as a double-sided adhesive sheet of 1 aspect of this invention, it is the 1st adhesive layer (X1) and one or both sticking surfaces (the side which is contacting the base material layer) of a 2nd adhesive layer (X2). It is good also as a structure which laminated | stacked the adhesive layer formed from the composition which is a different formation material on the surface of the other side.
As such an embodiment, for example, a third pressure-sensitive adhesive layer (X3) 123 is further provided on the sticking surface of the first pressure-sensitive adhesive layer (X1) 121 as shown in FIG. The double-sided pressure-sensitive adhesive sheet 4 in which a fourth pressure-sensitive adhesive layer (X4) 124 is further provided on the adhesive surface of the pressure-sensitive adhesive layer (X2) 122 is mentioned.
 なお、両面粘着シート4において、第1粘着剤層(X1)と第3粘着剤層(X3)とは、同じ形成材料である組成物から形成されたものであってもよく、互いに異なる形成材料である組成物から形成されたものであってもよい。また、同様に、第2粘着剤層(X2)と第4粘着剤層(X4)についても、同じ形成材料である組成物から形成されたものであってもよく、互いに異なる形成材料である組成物から形成されたものである。
 ただし、第1粘着剤層(X1)及び第3粘着剤層(X3)が、同じ形成材料である組成物から形成されたものである場合、第1粘着剤層(X1)及び第3粘着剤層(X3)は、各組成物を同時に塗布及び乾燥して形成されたものではなく、別々に形成されたものである。第2粘着剤層(X2)及び第4粘着剤層(X4)についても同様である。
In the double-sided pressure-sensitive adhesive sheet 4, the first pressure-sensitive adhesive layer (X1) and the third pressure-sensitive adhesive layer (X3) may be formed from compositions that are the same forming material and are different from each other. It may be formed from a composition that is Similarly, the second pressure-sensitive adhesive layer (X2) and the fourth pressure-sensitive adhesive layer (X4) may also be formed from compositions that are the same forming material, and compositions that are different from each other. It is formed from things.
However, when 1st adhesive layer (X1) and 3rd adhesive layer (X3) are formed from the composition which is the same formation material, 1st adhesive layer (X1) and 3rd adhesive The layer (X3) is not formed by simultaneously applying and drying the respective compositions, but is formed separately. The same applies to the second pressure-sensitive adhesive layer (X2) and the fourth pressure-sensitive adhesive layer (X4).
〔積層体〕
 本発明の両面粘着シートが有する積層体は、第1の粘着剤層の形成材料である、粘着性樹脂を含む組成物(x1)からなる塗膜(x1’)と、基材層(Y)の形成材料である、アクリルウレタン系樹脂及びオレフィン系樹脂からなる群から選ばれる非粘着性樹脂を含む組成物(y)からなる塗膜(y’)と、第2の粘着剤層の形成材料である、粘着性樹脂を含む組成物(x2)からなる塗膜(x2’)と、をこの順で直接積層した後、塗膜(x1’)、(y’)及び(x2’)を同時に乾燥して形成されたものである。
[Laminate]
The laminated body which the double-sided pressure-sensitive adhesive sheet of the present invention has includes a coating film (x1 ′) made of a composition (x1) containing an adhesive resin, which is a material for forming the first pressure-sensitive adhesive layer, and a base material layer (Y). A coating material (y ′) made of a composition (y) containing a non-adhesive resin selected from the group consisting of acrylic urethane resins and olefin resins, and a forming material for the second adhesive layer And after directly laminating the coating film (x2 ′) made of the composition (x2) containing the adhesive resin in this order, the coating films (x1 ′), (y ′) and (x2 ′) are simultaneously formed. It is formed by drying.
 基材付き両面粘着シートは、下記のような方法(以下、「従来の製造方法」ともいう)で製造されることが一般的である。
・既にフィルム状又はシート状に成形済みの基材の両面に、それぞれ、粘着剤組成物を塗布して塗膜を形成し、その塗膜を乾燥させて粘着剤層を形成する工程を有する製造方法。
・剥離フィルムの剥離処理面上に、粘着剤組成物を塗布して塗膜を形成し、その塗膜を乾燥させて粘着剤層を形成したものを2枚用意し、既にフィルム状又はシート状に成形済みの基材の両面に、それぞれ剥離フィルム上に形成した粘着剤層を貼り付ける工程を有する製造方法。
 上記の従来の製造方法では、いずれも、既にフィルム状又はシート状に成形済みの基材を用いており、また、粘着剤層は、当該基材の表面上もしくは剥離フィルムの剥離処理面上に形成している。つまり、従来の製造方法では、基材及び粘着剤層は、別々に形成することが一般的である。
The double-sided pressure-sensitive adhesive sheet with a substrate is generally produced by the following method (hereinafter also referred to as “conventional production method”).
・ Manufacturing which has a process of applying a pressure-sensitive adhesive composition to both surfaces of a base material already formed into a film or sheet to form a coating film and drying the coating film to form a pressure-sensitive adhesive layer. Method.
・ On the release-treated surface of the release film, the adhesive composition is applied to form a coating film, and two films are prepared by drying the coating film to form an adhesive layer. The manufacturing method which has the process of affixing the adhesive layer formed on the peeling film, respectively on both surfaces of the base material already shape | molded in (1).
In each of the conventional production methods described above, a base material that has already been formed into a film shape or a sheet shape is used, and the pressure-sensitive adhesive layer is on the surface of the base material or the release treatment surface of the release film. Forming. That is, in the conventional manufacturing method, the base material and the pressure-sensitive adhesive layer are generally formed separately.
 しかしながら、上記の従来の製造方法によって得られた基材付き粘着シートは、基材と粘着剤層とが、別々に形成されたものであるため、基材と粘着剤層との間の界面密着力が低い。
 また、当該基材付き粘着シートは、基材と粘着剤層との機械的特性が異なることも起因し、抜き加工性が劣るという問題や、被着体の形状に合わせて一様に伸ばして貼付することが困難となり易いという問題がある。さらに、ロール製品を巻き出しながら端部を切り落として再度ロール状に巻き取るという裁断加工工程において、幅方向に平行な直線状の浮き剥がれが生じるといった、いわゆる「トンネリング」が発生するという問題もある。
However, the pressure-sensitive adhesive sheet with a base material obtained by the above-described conventional manufacturing method is such that the base material and the pressure-sensitive adhesive layer are formed separately, so that the interface adhesion between the base material and the pressure-sensitive adhesive layer is Power is low.
In addition, the pressure-sensitive adhesive sheet with the base material is caused by the difference in mechanical properties between the base material and the pressure-sensitive adhesive layer, and the problem that the punching processability is inferior, and the base sheet and the pressure-sensitive adhesive layer are uniformly extended according to the shape of the adherend. There is a problem that sticking tends to be difficult. Furthermore, there is also a problem that so-called “tunneling” occurs in the cutting process of cutting off the end portion while winding the roll product and winding it up again in the form of a roll. .
 一方で、本発明の両面粘着シートが有する積層体は、第1粘着剤層、基材層、及び第2粘着剤層の形成材料である各組成物からなる塗膜(x1’)、(y’)及び(x2’)を、この順で直接積層した後に、これら3つの塗膜を「同時に」乾燥して形成されたものである。
 積層体がそのように形成されたため、第1粘着剤層(X1)と基材層(Y)との間、並びに、基材層(Y)と第2粘着剤層(X2)との間の界面密着性は、上述の一般的な製造方法によって得られた基材付き粘着シートに比べて、格段に高いものとなる。
 これは、上記3つの塗膜を同時に乾燥する過程で、塗膜(x1’)と塗膜(y’)との界面、及び、塗膜(x1’)と塗膜(y’)との界面で、混層が生じつつ、互いの組成物に含まれる粘着性樹脂の分子鎖と非粘着性樹脂の分子鎖とが絡み合い易くなること推測される。それにより、基材層と粘着剤層との界面密着性が格段に向上するものと考えられる。
 その結果、本発明の両面粘着シートは、一方の剥離シートを剥離する際に、粘着剤層が2つの剥離シートに伴って分断され引き剥がされるという泣き別れ現象(以下、単に「泣き別れ現象」ともいう)の抑制効果が高く、抜き加工性、貼付適性及び裁断加工適性に優れたものとなり得ると考えられる。
On the other hand, the laminated body which the double-sided adhesive sheet of this invention has is the coating film (x1 ') which consists of each composition which is a formation material of a 1st adhesive layer, a base material layer, and a 2nd adhesive layer, (y ') And (x2') are formed by directly laminating these three coatings “simultaneously” after being directly laminated in this order.
Since the laminate was formed as such, it was between the first pressure-sensitive adhesive layer (X1) and the base material layer (Y), and between the base material layer (Y) and the second pressure-sensitive adhesive layer (X2). The interfacial adhesion is much higher than that of the pressure-sensitive adhesive sheet with a substrate obtained by the above-described general production method.
This is the process of simultaneously drying the above three coating films, the interface between the coating film (x1 ′) and the coating film (y ′), and the interface between the coating film (x1 ′) and the coating film (y ′). Thus, it is presumed that the molecular chain of the adhesive resin and the molecular chain of the non-adhesive resin included in each composition are easily entangled while the mixed layer is generated. Thereby, it is thought that the interface adhesiveness of a base material layer and an adhesive layer improves markedly.
As a result, the double-sided pressure-sensitive adhesive sheet of the present invention has a tearing phenomenon in which the pressure-sensitive adhesive layer is divided and peeled off along with the two peeling sheets when peeling one release sheet (hereinafter also simply referred to as “crying phenomenon”). ) Is highly effective and can be excellent in punching workability, sticking suitability and cutting workability.
 なお、本発明において、両面粘着シートが有する積層体を、上述のとおり製造方法にて特定しているが、そのような製造方法による特定をせざるを得ない事情が存在する。
 製造方法による特定をせずに、当該積層体の構成を規定する方法として、例えば、積層体の厚さ方向に切断した断面を電子顕微鏡等を用いて、基材層と粘着剤層との界面に着目し、当該界面を、何らかの物性値により特定するといったことができる場合もある。
 ここで、基材層と粘着剤層との界面の評価方法としては、例えば、表面粗さを測定する方法が考えられる。しかしながら、当該界面の粗さは、微少であるため、正確に測定することができず、また、観察する領域による粗さの状態の相違が非常に大きい。そのため、表面粗さ等の物性値による評価が極めて難しい。
 また、粘着剤層に含まれる粘着性樹脂や、基材層に含まれる非粘着性樹脂の種類によっては、電子顕微鏡等を用いて、基材層と粘着剤層との界面を観察しようとしても、界面が不明瞭となり、そもそも表面粗さの測定自体が困難となる場合がある。
 さらに、積層体の断面を得るために、積層体を厚さ方向に切断する際に、当該積層体は樹脂から形成されたものであるため、基材層と粘着剤層との界面の形状が崩れてしまい、当該界面の状態を正確に評価できないという事情も存在する。
 このような事情から、本発明においては、両面粘着シートが有する積層体を、上述のとおり製造方法による特定をせざるを得ない。
In addition, in this invention, although the laminated body which a double-sided adhesive sheet has is specified by the manufacturing method as mentioned above, the situation which must be specified by such a manufacturing method exists.
As a method for prescribing the configuration of the laminate without specifying the manufacturing method, for example, the cross section cut in the thickness direction of the laminate using an electron microscope or the like, the interface between the base material layer and the adhesive layer In some cases, the interface can be specified by some physical property value.
Here, as a method for evaluating the interface between the base material layer and the pressure-sensitive adhesive layer, for example, a method of measuring the surface roughness can be considered. However, since the roughness of the interface is very small, it cannot be measured accurately, and the difference in the roughness state depending on the region to be observed is very large. For this reason, it is extremely difficult to evaluate by physical property values such as surface roughness.
In addition, depending on the type of adhesive resin contained in the adhesive layer and non-adhesive resin contained in the substrate layer, an electron microscope or the like may be used to observe the interface between the substrate layer and the adhesive layer. In some cases, the interface becomes unclear, and the surface roughness measurement itself may be difficult.
Furthermore, when the laminate is cut in the thickness direction in order to obtain a cross section of the laminate, the laminate is formed from a resin, so that the shape of the interface between the base material layer and the adhesive layer is There is also a situation that the interface state cannot be accurately evaluated.
Under such circumstances, in the present invention, the laminate of the double-sided pressure-sensitive adhesive sheet must be specified by the production method as described above.
 なお、本明細書において、「塗膜」とは、公知の塗布方法によって、形成材料である組成物から形成された膜であって、当該膜中に含まれる溶媒等の揮発成分の残存率が、塗布前の当該組成物中に含まれる揮発成分の全量100質量%に対して、10~100質量%となる状態のものを指す。
 つまり、本明細書において、塗膜(x1’)、(y’)、及び(x2’)には、溶媒等の揮発成分が一定量含まれたものである。そして、これら3層の塗膜を同時に乾燥することで、揮発成分が除去され、第1粘着剤層(X1)、基材層(Y)、及び第2粘着剤層(X2)から構成された積層体が形成される。
In the present specification, the “coating film” is a film formed from a composition that is a forming material by a known coating method, and the residual ratio of volatile components such as a solvent contained in the film. It refers to those in a state of 10 to 100% by mass with respect to 100% by mass of the total amount of volatile components contained in the composition before coating.
That is, in the present specification, the coating films (x1 ′), (y ′), and (x2 ′) contain a certain amount of a volatile component such as a solvent. And the volatile component was removed by drying the coating film of these 3 layers simultaneously, and it comprised from the 1st adhesive layer (X1), the base material layer (Y), and the 2nd adhesive layer (X2). A laminate is formed.
 なお、塗膜(x1’)、(y’)、及び(x2’)を形成する方法、及び形成した塗膜の乾燥条件については、後述の「両面粘着シートの製造方法」の項目の記載のとおりである。 In addition, about the method of forming a coating film (x1 '), (y'), and (x2 '), and the drying conditions of the formed coating film, description of the item of "the manufacturing method of a double-sided adhesive sheet" mentioned later is mentioned. It is as follows.
 なお、基材層(Y)は、上記のようにして形成されるため、無延伸のシート状物となる。
 本明細書において、「無延伸のシート状物」とは、意図的に特定の方向に延伸して得られたシート状物を除外するものである。例えば、Roll to roll製造装置を用いる等の連続的な製造過程で、流れ方向に、不可抗力的にかかる応力によって延伸した場合は、その限りでは無く、「無延伸のシート状物」とみなすことができる。
In addition, since a base material layer (Y) is formed as mentioned above, it becomes an unstretched sheet-like material.
In the present specification, the “non-stretched sheet-like material” excludes a sheet-like material obtained by intentionally stretching in a specific direction. For example, in a continuous manufacturing process such as using a roll to roll manufacturing apparatus, when the film is stretched by a force forcefully applied in the flow direction, it is not limited to this and may be regarded as a “non-stretched sheet”. it can.
<組成物(x1)、(x2)>
 第1粘着剤層(X1)の形成材料である組成物(x1)、及び、第2粘着剤層(X2)の形成材料である組成物(x2)は、双方ともに、粘着性樹脂を含むものである。
 なお、本発明の一態様において、組成物(x1)及び(x2)は、同一のものであってもよく、互いに異なるものであってもよい。組成物(x1)及び(x2)に含まれる成分は、本発明の両面粘着シートの使用用途に応じて、適宜調整可能である。
<Composition (x1), (x2)>
Both the composition (x1) which is a forming material of the first pressure-sensitive adhesive layer (X1) and the composition (x2) which is a forming material of the second pressure-sensitive adhesive layer (X2) contain a pressure-sensitive adhesive resin. .
In one embodiment of the present invention, the compositions (x1) and (x2) may be the same or different from each other. The components contained in the compositions (x1) and (x2) can be appropriately adjusted according to the use application of the double-sided pressure-sensitive adhesive sheet of the present invention.
 本発明の一態様において、粘着力をより向上させた両面粘着シートとする観点から、組成物(x1)及び(x2)は、さらに粘着付与剤や架橋剤を含有してもよく、これら以外にも、一般的な粘着剤に使用される粘着剤用添加剤を含有してもよい。
 なお、組成物(x1)及び(x2)は、図1(d)に示す両面粘着シート4が有する、第3粘着剤層(x3)及び第4粘着剤層(x4)の形成材料としても用いることができる。
In one embodiment of the present invention, from the viewpoint of making a double-sided PSA sheet with improved adhesive strength, the compositions (x1) and (x2) may further contain a tackifier and a crosslinking agent. Moreover, you may contain the additive for adhesives used for a general adhesive.
The compositions (x1) and (x2) are also used as materials for forming the third pressure-sensitive adhesive layer (x3) and the fourth pressure-sensitive adhesive layer (x4) included in the double-sided pressure-sensitive adhesive sheet 4 shown in FIG. be able to.
[粘着性樹脂]
 本発明において、「粘着性樹脂」は、当該樹脂単独で粘着性を有し、質量平均分子量(Mw)が1万以上の重合体を意味する。
 粘着性樹脂の質量平均分子量(Mw)としては、粘着力の向上の観点から、好ましくは1万~200万、より好ましくは2万~150万、更に好ましくは3万~130万、より更に好ましくは10万~100万である。
[Adhesive resin]
In the present invention, “adhesive resin” means a polymer having adhesiveness by itself and having a mass average molecular weight (Mw) of 10,000 or more.
The mass average molecular weight (Mw) of the adhesive resin is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000, still more preferably 30,000 to 1,300,000, and still more preferably, from the viewpoint of improving the adhesive strength. Is 100,000 to 1,000,000.
 組成物(x1)及び(x2)に含まれる粘着性樹脂としては、例えば、アクリル系樹脂、ウレタン系樹脂、ポリイソブチレン系樹脂、ポリエステル系樹脂、及びオレフィン系樹脂等が挙げられる。
 これらの粘着性樹脂は、単独で用いてもよく、2種以上を併用してもよい。
 また、これらの粘着性樹脂が、2種以上の構成単位を有する共重合体である場合、当該共重合体の形態は、特に限定されず、ブロック共重合体、ランダム共重合体、及びグラフト共重合体のいずれであってもよい。
Examples of the adhesive resin contained in the compositions (x1) and (x2) include acrylic resins, urethane resins, polyisobutylene resins, polyester resins, and olefin resins.
These adhesive resins may be used independently and may use 2 or more types together.
In addition, when these adhesive resins are copolymers having two or more kinds of structural units, the form of the copolymer is not particularly limited, and a block copolymer, a random copolymer, and a graft copolymer are not limited. Any of polymers may be used.
 さらに、基材層(Y)と第1粘着剤層(X1)及び第2粘着剤層(X2)との界面密着性をより向上させる観点から、これらの粘着性樹脂は、重合性官能基を有さない紫外線非硬化型粘着性樹脂であることが好ましい。
 なお、本明細書において、重合性官能基とは、ラジカル重合によって重合し得る、炭素-炭素二重結合を有する基を意味し、具体的には、(メタ)アクリロイル基、ビニル基、ビニルエーテル基、アリル基、アリルエーテル基等が挙げられる。
Furthermore, from the viewpoint of further improving the interfacial adhesion between the base material layer (Y), the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2), these pressure-sensitive adhesive resins have polymerizable functional groups. It is preferably an ultraviolet non-curable adhesive resin that does not have.
In the present specification, the polymerizable functional group means a group having a carbon-carbon double bond that can be polymerized by radical polymerization, and specifically includes a (meth) acryloyl group, a vinyl group, a vinyl ether group. , Allyl group, allyl ether group and the like.
 組成物(x1)及び(x2)中の粘着性樹脂の含有量は、組成物(x1)又は(x2)の有効成分の全量(100質量%)に対して、好ましくは30~99.99質量%、より好ましくは40~99.95質量%、より好ましくは50~99.90質量%、更に好ましくは55~99.80質量%、より更に好ましくは60~99.50質量%である。 The content of the adhesive resin in the compositions (x1) and (x2) is preferably 30 to 99.99 mass with respect to the total amount (100 mass%) of the active ingredients of the composition (x1) or (x2). %, More preferably 40 to 99.95% by mass, more preferably 50 to 99.90% by mass, still more preferably 55 to 99.80% by mass, and still more preferably 60 to 99.50% by mass.
 本発明の一態様において、基材層(Y)との界面密着性をより向上させる観点から、組成物(x1)及び(x2)に含まれる粘着性樹脂が、アクリル系樹脂を含むことが好ましい。
 なお、当該アクリル系樹脂は、重合性官能基を有さない紫外線非硬化型樹脂であることがより好ましい。
 粘着性樹脂中のアクリル系樹脂の含有割合としては、上記観点から、組成物(x1)又は(x2)に含まれる粘着性樹脂の全量(100質量%)に対して、好ましくは30~100質量%、より好ましくは50~100質量%、更に好ましくは70~100質量%、より更に好ましくは85~100質量%である。
In one embodiment of the present invention, the adhesive resin contained in the compositions (x1) and (x2) preferably contains an acrylic resin from the viewpoint of further improving the interfacial adhesion with the base material layer (Y). .
The acrylic resin is more preferably an ultraviolet non-curable resin having no polymerizable functional group.
From the above viewpoint, the content of the acrylic resin in the adhesive resin is preferably 30 to 100 mass with respect to the total amount (100 mass%) of the adhesive resin contained in the composition (x1) or (x2). %, More preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, and still more preferably 85 to 100% by mass.
(アクリル系樹脂)
 粘着性樹脂として使用し得る、アクリル系樹脂としては、例えば、直鎖又は分岐鎖のアルキル基を有するアルキル(メタ)アクリレートに由来する構成単位を含む重合体、環状構造を有する(メタ)アクリレートに由来する構成単位を含む重合体等が挙げられる。
(Acrylic resin)
Examples of acrylic resins that can be used as adhesive resins include polymers containing structural units derived from alkyl (meth) acrylates having linear or branched alkyl groups, and (meth) acrylates having a cyclic structure. Examples thereof include a polymer containing a derived structural unit.
 アクリル系樹脂の質量平均分子量(Mw)としては、好ましくは10万~150万、より好ましくは20万~130万、更に好ましくは35万~120万、より更に好ましくは50万~110万である。 The mass average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1,500,000, more preferably 200,000 to 1,300,000, still more preferably 350,000 to 1,200,000, still more preferably 500,000 to 1,100,000. .
 本発明の一態様で用いるアクリル系樹脂としては、アルキル(メタ)アクリレート(a1’)(以下、「モノマー(a1’)」ともいう)に由来する構成単位(a1)を有するアクリル系重合体(A0)が好ましく、構成単位(a1)と共に、官能基含有モノマー(a2’)(以下、「モノマー(a2’)」ともいう)に由来する構成単位(a2)を有するアクリル系共重合体(A1)がより好ましい。
 なお、アクリル系重合体(A0)及び(A1)は、重合性官能基を有さないことが好ましい。
As an acrylic resin used in one embodiment of the present invention, an acrylic polymer having a structural unit (a1) derived from an alkyl (meth) acrylate (a1 ′) (hereinafter also referred to as “monomer (a1 ′)”) ( A0) is preferable, and together with the structural unit (a1), an acrylic copolymer (A1) having a structural unit (a2) derived from the functional group-containing monomer (a2 ′) (hereinafter also referred to as “monomer (a2 ′)”) ) Is more preferable.
The acrylic polymers (A0) and (A1) preferably have no polymerizable functional group.
 モノマー(a1’)が有するアルキル基の炭素数としては、粘着特性の向上の観点から、好ましくは1~24、より好ましくは1~12、更に好ましくは1~8、より更に好ましくは4~6である。
 なお、モノマー(a1’)が有するアルキル基は、直鎖アルキル基であってもよく、分岐鎖アルキル基であってもよい。
The number of carbon atoms of the alkyl group contained in the monomer (a1 ′) is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, and still more preferably 4 to 6 from the viewpoint of improving adhesive properties. It is.
The alkyl group contained in the monomer (a1 ′) may be a linear alkyl group or a branched alkyl group.
 モノマー(a1’)としては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、トリデシル(メタ)アクリレート、ステアリル(メタ)アクリレート等が挙げられる。
 これらのモノマー(a1’)は、単独で用いてもよく、2種以上を併用してもよい。
 モノマー(a1’)としては、ブチル(メタ)アクリレート及び2-エチルヘキシル(メタ)アクリレートが好ましく、ブチル(メタ)アクリレートがより好ましい。
Examples of the monomer (a1 ′) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl ( Examples include meth) acrylate and stearyl (meth) acrylate.
These monomers (a1 ′) may be used alone or in combination of two or more.
As the monomer (a1 ′), butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate is more preferable.
 構成単位(a1)の含有量は、アクリル系重合体(A0)又はアクリル系共重合体(A1)の全構成単位(100質量%)に対して、好ましくは50~100質量%、より好ましくは60~99.9質量%、更に好ましくは70~99.5質量%、より更に好ましくは80~99.0質量%である。 The content of the structural unit (a1) is preferably 50 to 100% by weight, more preferably based on the total structural unit (100% by weight) of the acrylic polymer (A0) or the acrylic copolymer (A1). It is 60 to 99.9% by mass, more preferably 70 to 99.5% by mass, and still more preferably 80 to 99.0% by mass.
 モノマー(a2’)が有する官能基は、後述の架橋剤と反応し、架橋起点となり得る官能基又は架橋促進効果を有する官能基を指し、例えば、水酸基、カルボキシ基、アミノ基、エポキシ基等が挙げられる。
 つまり、モノマー(a2’)としては、例えば、水酸基含有モノマー、カルボキシ基含有モノマー、アミノ基含有モノマー、エポキシ基含有モノマー等が挙げられる。
 これらのモノマー(a2’)は、単独で用いてもよく、2種以上を併用してもよい。
 モノマー(a2’)としては、水酸基含有モノマー及びカルボキシ基含有モノマーが好ましい。
The functional group possessed by the monomer (a2 ′) refers to a functional group that reacts with a crosslinking agent to be described later and can serve as a crosslinking starting point or a functional group having a crosslinking accelerating effect. Can be mentioned.
That is, examples of the monomer (a2 ′) include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer.
These monomers (a2 ′) may be used alone or in combination of two or more.
As the monomer (a2 ′), a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable.
 水酸基含有モノマーとしては、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、3-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート類;ビニルアルコール、アリルアルコール等の不飽和アルコール類等が挙げられる。 Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth) ) And hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate; and unsaturated alcohols such as vinyl alcohol and allyl alcohol.
 カルボキシ基含有モノマーとしては、例えば、(メタ)アクリル酸、クロトン酸等のエチレン性不飽和モノカルボン酸;フマル酸、イタコン酸、マレイン酸、シトラコン酸等のエチレン性不飽和ジカルボン酸及びその無水物、2-(アクリロイルオキシ)エチルサクシネート、2-カルボキシエチル(メタ)アクリレート等が挙げられる。 Examples of the carboxy group-containing monomer include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid, and anhydrides thereof. 2- (acryloyloxy) ethyl succinate, 2-carboxyethyl (meth) acrylate, and the like.
 構成単位(a2)の含有量は、上記アクリル系共重合体(A1)の全構成単位(100質量%)に対して、好ましくは0.1~40質量%、より好ましくは0.3~30質量%、更に好ましくは0.5~20質量%、より更に好ましくは0.7~10質量%である。 The content of the structural unit (a2) is preferably 0.1 to 40% by weight, more preferably 0.3 to 30%, based on the entire structural unit (100% by weight) of the acrylic copolymer (A1). % By mass, more preferably 0.5 to 20% by mass, still more preferably 0.7 to 10% by mass.
 アクリル系共重合体(A1)は、さらにモノマー(a1’)及び(a2’)以外の他のモノマー(a3’)に由来の構成単位(a3)を有していてもよい。
 なお、アクリル系共重合体(A1)において、構成単位(a1)及び(a2)の含有量は、アクリル系共重合体(A1)の全構成単位(100質量%)に対して、好ましくは70~100質量%、より好ましくは80~100質量%、更に好ましくは90~100質量%、より更に好ましくは95~100質量%である。
The acrylic copolymer (A1) may further have a structural unit (a3) derived from another monomer (a3 ′) other than the monomers (a1 ′) and (a2 ′).
In the acrylic copolymer (A1), the content of the structural units (a1) and (a2) is preferably 70 with respect to the total structural units (100% by mass) of the acrylic copolymer (A1). To 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
 モノマー(a3’)としては、例えば、エチレン、プロピレン、イソブチレン等のオレフィン類;塩化ビニル、ビニリデンクロリド等のハロゲン化オレフィン類;ブタジエン、イソプレン、クロロプレン等のジエン系モノマー類;シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、イミド(メタ)アクリレート等の環状構造を有する(メタ)アクリレート;スチレン、α-メチルスチレン、ビニルトルエン、ギ酸ビニル、酢酸ビニル、アクリロニトリル、(メタ)アクリルアミド、(メタ)アクリロニトリル、(メタ)アクリロイルモルホリン、N-ビニルピロリドン等が挙げられる。 Examples of the monomer (a3 ′) include olefins such as ethylene, propylene, and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene monomers such as butadiene, isoprene, and chloroprene; cyclohexyl (meth) acrylate, It has a cyclic structure such as benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, imide (meth) acrylate, etc. (Meth) acrylate; styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acryloyl Ruhorin, N- vinylpyrrolidone and the like.
(ウレタン系樹脂)
 粘着性樹脂として使用し得る、ウレタン系樹脂としては、主鎖及び側鎖の少なくとも一方に、ウレタン結合及び尿素結合の1つ以上を有する重合体であれば、特に制限されない。
 具体的なウレタン系樹脂としては、例えば、ポリオールと多価イソシアネート化合物とを反応して得られるウレタン系プレポリマー(UX)等が挙げられる。
 なお、ウレタン系プレポリマー(UX)は、更に鎖延長剤を用いた鎖延長反応を施して得られたものであってもよい。
(Urethane resin)
The urethane resin that can be used as the adhesive resin is not particularly limited as long as it is a polymer having at least one of a urethane bond and a urea bond in at least one of the main chain and the side chain.
Specific examples of the urethane resin include a urethane prepolymer (UX) obtained by reacting a polyol and a polyvalent isocyanate compound.
The urethane prepolymer (UX) may be obtained by further subjecting to a chain extension reaction using a chain extender.
 ウレタン系樹脂の質量平均分子量(Mw)としては、好ましくは1万~20万、より好ましくは1.2万~15万、更に好ましくは1.5万~10万、より更に好ましくは2万~7万である。 The mass average molecular weight (Mw) of the urethane resin is preferably 10,000 to 200,000, more preferably 12,000 to 150,000, still more preferably 15,000 to 100,000, and still more preferably 20,000 to 70,000.
 ウレタン系プレポリマー(UX)の原料となるポリオールとしては、例えば、アルキレン型ポリオール、ポリエーテル型ポリオール、ポリエステル型ポリオール、ポリエステルアミド型ポリオール、ポリエステル・ポリエーテル型ポリオール、ポリカーボネート型ポリオール等のポリオール化合物が挙げられるが、ポリオールであれば特に限定はされず、2官能のジオール、3官能のトリオールであってもよい。
 これらのポリオールは、単独で用いてもよく、2種以上を併用してもよい。
 これらのポリオールの中でも、入手の容易性、反応性等の観点から、ジオールが好ましく、アルキレン型ジオールがより好ましい。
Examples of the polyol used as a raw material for the urethane-based prepolymer (UX) include polyol compounds such as alkylene type polyols, polyether type polyols, polyester type polyols, polyester amide type polyols, polyester / polyether type polyols, and polycarbonate type polyols. Although it is mentioned, if it is a polyol, it will not specifically limit, Bifunctional diol and a trifunctional triol may be sufficient.
These polyols may be used independently and may use 2 or more types together.
Among these polyols, diols are preferable and alkylene type diols are more preferable from the viewpoints of availability, reactivity, and the like.
 アルキレン型ジオールとしては、例えば、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、ネオペンチルグリコール、1,6-ヘキサンジオール等のアルカンジオール;エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール等のアルキレングリコール;ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール等のポリアルキレングリコール;ポリテトラメチレングリコール等のポリオキシアルキレングリコール;等が挙げられる。
 これらのアルキレン型ジオールの中でも、さらに鎖延長剤との反応を行う際にゲル化を抑制する観点から、質量平均分子量1000~3000のグリコールが好ましい。
Examples of the alkylene type diol include alkane diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol; ethylene glycol, propylene glycol, And alkylene glycols such as diethylene glycol and dipropylene glycol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol; polyoxyalkylene glycols such as polytetramethylene glycol; and the like.
Among these alkylene type diols, glycols having a mass average molecular weight of 1000 to 3000 are preferable from the viewpoint of suppressing gelation when the reaction with a chain extender is performed.
 ウレタン系プレポリマー(UX)の原料となる多価イソシアネート化合物としては、芳香族ポリイソシアネート、脂肪族ポリイソシアネート、脂環式ポリイソシアネート等が挙げられる。
 芳香族ポリイソシアネートとしては、例えば、1,3-フェニレンジイソシアネート、1,4-フェニレンジイソシアネート、4,4’-ジフェニルメタンジイソシアネート(MDI)、2,4-トリレンジイソシアネート(2,4-TDI)、2,6-トリレンジイソシアネート(2,6-TDI)、4,4’-トルイジンジイソシアネート、2,4,6-トリイソシアネートトルエン、1,3,5-トリイソシアネートベンゼン、ジアニシジンジイソシアネート、4,4’-ジフェニルエーテルジイソシアネート、4,4’,4”-トリフェニルメタントリイソシアネート、1,4-テトラメチルキシリレンジイソシアネート、1,3-テトラメチルキシリレンジイソシアネート等が挙げられる。
 脂肪族ポリイソシアネートとしては、例えば、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート(HMDI)、ペンタメチレンジイソシアネート、1,2-プロピレンジイソシアネート、2,3-ブチレンジイソシアネート、1,3-ブチレンジイソシアネート、ドデカメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネート等が挙げられる。
 脂環式ポリイソシアネートとしては、例えば、3-イソシアネートメチル-3,5,5-トリメチルシクロヘキシルイソシアネート(イソホロンジイソシアネート、IPDI)、1,3-シクロペンタンジイソシアネート、1,3-シクロヘキサンジイソシアネート、1,4-シクロヘキサンジイソシアネート、メチル-2,4-シクロヘキサンジイソシアネート、メチル-2,6-シクロヘキサンジイソシアネート、4,4’-メチレンビス(シクロヘキシルイソシアネート)、1,4-ビス(イソシアネートメチル)シクロヘキサン、1,4-ビス(イソシアネートメチル)シクロヘキサン等が挙げられる。
 なお、これらの多価イソシアネート化合物は、上記ポリイソシアネートのトリメチロールプロパンアダクト型変性体、水と反応させたビュウレット型変性体、イソシアヌレート環を含有させたイソシアヌレート型変性体であってもよい。
Examples of the polyvalent isocyanate compound that is a raw material for the urethane prepolymer (UX) include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates.
Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2 , 6-Tolylene diisocyanate (2,6-TDI), 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4 ′ -Diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate and the like.
Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodeca. Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4- Cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanate) Methyl) cyclohexane and the like.
These polyisocyanate compounds may be a trimethylolpropane adduct type modified product of the above polyisocyanate, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.
 これらの多価イソシアネート化合物の中でも、粘着物性に優れたウレタン系ポリマーを得る観点から、4,4’-ジフェニルメタンジイソシアネート(MDI)、2,4-トリレンジイソシアネート(2,4-TDI)、2,6-トリレンジイソシアネート(2,6-TDI)、ヘキサメチレンジイソシアネート(HMDI)、3-イソシアネートメチル-3,5,5-トリメチルシクロヘキシルイソシアネート(IPDI)及びこれらの変性体から選ばれる1種以上が好ましく、耐候性の観点から、HMDI、IPDI及びこれらの変性体から選ばれる1種以上がより好ましい。 Among these polyvalent isocyanate compounds, 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2, from the viewpoint of obtaining a urethane polymer having excellent adhesive properties. One or more selected from 6-tolylene diisocyanate (2,6-TDI), hexamethylene diisocyanate (HMDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) and modified products thereof are preferable. From the viewpoint of weather resistance, at least one selected from HMDI, IPDI, and modified products thereof is more preferable.
 ウレタン系プレポリマー(UX)中のイソシアネート基含有量(NCO%)は、JIS K 1603に準じて測定された値において、好ましくは0.5~12質量%、より好ましくは1~4質量%である。 The isocyanate group content (NCO%) in the urethane-based prepolymer (UX) is preferably 0.5 to 12% by mass, more preferably 1 to 4% by mass, as measured according to JIS K 1603. is there.
 鎖延長剤としては、水酸基及びアミノ基の少なくとも一方を2つ有する化合物、又は、水酸基及びアミノ基の少なくとも一方を3つ以上有する化合物が好ましい。 As the chain extender, a compound having at least one of hydroxyl group and amino group, or a compound having at least three of hydroxyl group and amino group is preferable.
 水酸基及びアミノ基の少なくとも一方を2つ有する化合物としては、脂肪族ジオール、脂肪族ジアミン、アルカノールアミン、ビスフェノール、芳香族ジアミンからなる群より選ばれる少なくとも1種の化合物が好ましい。
 脂肪族ジオールとしては、例えば、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、ネオペンチルグリコール、1,6-ヘキサンジオール、1,7-ヘプタンジオール等のアルカンジオール;エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール等のアルキレングリコール;等が挙げられる。
 脂肪族ジアミンとしては、例えば、エチレンジアミン、1,3-プロパンジアミン、1,4-ブタンジアミン、1,5-ペンタンジアミン、1,6-ヘキサンジアミン等が挙げられる。
 アルカノールアミンとしては、例えば、モノエタノールアミン、モノプロパノールアミン、イソプロパノールアミン等が挙げられる。
 ビスフェノールとしては、例えば、ビスフェノールA等が挙げられる。
 芳香族ジアミンとしては、例えば、ジフェニルメタンジアミン、トリレンジアミン、キシリレンジアミン等が挙げられる。
The compound having at least one of a hydroxyl group and an amino group is preferably at least one compound selected from the group consisting of aliphatic diols, aliphatic diamines, alkanolamines, bisphenols, and aromatic diamines.
Examples of the aliphatic diol include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptanediol. Alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol;
Examples of the aliphatic diamine include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and the like.
Examples of the alkanolamine include monoethanolamine, monopropanolamine, isopropanolamine and the like.
Examples of bisphenol include bisphenol A and the like.
Examples of the aromatic diamine include diphenylmethanediamine, tolylenediamine, xylylenediamine, and the like.
 水酸基及びアミノ基の少なくとも一方を3つ以上有する化合物としては、例えば、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール等のポリオール;1-アミノ-2,3-プロパンジオール、1-メチルアミノ-2,3-プロパンジオール、N-(2-ヒドロキシプロピルエタノールアミン)等のアミノアルコール;テトラメチルキシリレンジアミンのエチレンオキシド又はプロピレンオキシド付加物;等が挙げられる。 Examples of the compound having at least three hydroxyl groups and amino groups include polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol; 1-amino-2,3-propanediol, 1-methyl And amino alcohols such as amino-2,3-propanediol and N- (2-hydroxypropylethanolamine); ethylene oxide or propylene oxide adducts of tetramethylxylylenediamine;
(ポリイソブチレン系樹脂)
 粘着性樹脂として使用し得る、ポリイソブチレン系樹脂(以下、「PIB系樹脂」ともいう)は、主鎖及び側鎖の少なくとも一方にポリイソブチレン骨格を有する樹脂であれば、特に制限はされない。
(Polyisobutylene resin)
The polyisobutylene resin (hereinafter also referred to as “PIB resin”) that can be used as the adhesive resin is not particularly limited as long as it has a polyisobutylene skeleton in at least one of the main chain and the side chain.
 PIB系樹脂の質量平均分子量(Mw)としては、好ましくは2万以上、より好ましくは3万~100万、更に好ましくは5万~80万、より更に好ましくは7万~60万である。 The mass average molecular weight (Mw) of the PIB resin is preferably 20,000 or more, more preferably 30,000 to 1,000,000, still more preferably 50,000 to 800,000, and still more preferably 70,000 to 600,000.
 PIB系樹脂としては、例えば、イソブチレンの単独重合体であるポリイソブチレン、イソブチレンとイソプレンの共重合体、イソブチレンとn-ブテンの共重合体、イソブチレンとブタジエンの共重合体、及びこれら共重合体を臭素化又は塩素化等したハロゲン化ブチルゴム等が挙げられる。 Examples of the PIB resin include polyisobutylene which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, and these copolymers. Examples thereof include halogenated butyl rubber that has been brominated or chlorinated.
 なお、PIB系樹脂が共重合体である場合、イソブチレンからなる構成単位が、全構成単位の中で一番多く含まれているものとする。
 イソブチレンからなる構成単位の含有量は、PIB系樹脂の全構成単位(100質量%)に対して、好ましくは80~100質量%、より好ましくは90~100質量%、更に好ましくは95~100質量%である。
 これらのPIB系樹脂は、単独で用いてもよく、2種以上を併用してもよい。
When the PIB-based resin is a copolymer, it is assumed that the structural unit composed of isobutylene is contained in the largest amount among all the structural units.
The content of the structural unit composed of isobutylene is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass with respect to all the structural units (100% by mass) of the PIB resin. %.
These PIB resins may be used alone or in combination of two or more.
 また、PIB系樹脂を用いる場合、質量平均分子量が高いPIB系樹脂と、質量平均分子量が低いPIB系樹脂とを併用することが好ましい。
 より具体的には、質量平均分子量が27万~60万のPIB系樹脂(p1)(以下、「PIB系樹脂(p1)」ともいう)と、質量平均分子量が5万~25万のPIB系樹脂(p2)(以下、「PIB系樹脂(p2)」ともいう)とを併用することが好ましい。
 質量平均分子量の高いPIB系樹脂(p1)を用いることで、形成される粘着剤層の耐久性及び耐候性を向上させると共に、粘着力を向上させることもできる。
 また、質量平均分子量の低いPIB系樹脂(p2)を用いることで、PIB系樹脂(p1)と良好に相溶して、適度にPIB系樹脂(p1)を可塑化させることができ、粘着剤層の被着体に対する濡れ性を高め、粘着物性、柔軟性等を向上させることができる。
Moreover, when using a PIB resin, it is preferable to use together a PIB resin with a high mass average molecular weight and a PIB resin with a low mass average molecular weight.
More specifically, a PIB resin (p1) having a mass average molecular weight of 270,000 to 600,000 (hereinafter also referred to as “PIB resin (p1)”), and a PIB resin having a mass average molecular weight of 50,000 to 250,000 It is preferable to use the resin (p2) (hereinafter also referred to as “PIB resin (p2)”) in combination.
By using the PIB resin (p1) having a high mass average molecular weight, it is possible to improve the durability and weather resistance of the pressure-sensitive adhesive layer to be formed, and also improve the adhesive strength.
Further, by using the PIB resin (p2) having a low mass average molecular weight, it can be well compatible with the PIB resin (p1), and the PIB resin (p1) can be appropriately plasticized. The wettability of the layer to the adherend can be increased, and the adhesive properties, flexibility, and the like can be improved.
 PIB系樹脂(p1)の質量平均分子量(Mw)は、好ましくは27万~60万、より好ましくは29万~48万、更に好ましくは31万~45万、より更に好ましくは32万~40万である。
 PIB系樹脂(p2)の質量平均分子量(Mw)は、好ましくは5万~25万、より好ましくは8万~23万、更に好ましくは14万~22万、より更に好ましくは18万~21万である。
The mass average molecular weight (Mw) of the PIB resin (p1) is preferably 270,000 to 600,000, more preferably 290,000 to 480,000, still more preferably 310,000 to 450,000, and even more preferably 320,000 to 400,000. It is.
The mass average molecular weight (Mw) of the PIB resin (p2) is preferably 50,000 to 250,000, more preferably 80,000 to 230,000, still more preferably 140,000 to 220,000, and still more preferably 180,000 to 210,000. It is.
 PIB系樹脂(p1)100質量部に対する、PIB系樹脂(p2)の含有割合は、好ましくは5~55質量部、より好ましくは6~40質量部、更に好ましくは7~30質量部、より更に好ましくは8~20質量部である。 The content ratio of the PIB resin (p2) to 100 parts by mass of the PIB resin (p1) is preferably 5 to 55 parts by mass, more preferably 6 to 40 parts by mass, still more preferably 7 to 30 parts by mass, and even more. The amount is preferably 8 to 20 parts by mass.
(ポリエステル系樹脂)
 粘着性樹脂として使用し得る、ポリエステル系樹脂は、酸成分とジオール成分又はポリオール成分とを重縮合反応により得られる共重合体であり、当該共重合体の変性物も含まれる。
 上記重縮合反応は、直接エステル化法、エステル交換法等の一般的なポリエステル化反応によって行われる。
 これらのポリエステル系樹脂は、単独で用いてもよく、2種以上を併用してもよい。
(Polyester resin)
The polyester-based resin that can be used as the adhesive resin is a copolymer obtained by polycondensation reaction of an acid component and a diol component or a polyol component, and includes a modified product of the copolymer.
The polycondensation reaction is performed by a general polyesterification reaction such as a direct esterification method or a transesterification method.
These polyester resins may be used alone or in combination of two or more.
 上記酸成分としては、例えば、テレフタル酸、イソフタル酸、無水フタル酸、α-ナフタレンジカルボン酸、5-ナトリウムスルホイソフタル酸、5-カリウムスルホイソフタル酸又はこれらのエステル類、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデシレン酸、ドデカンジカルボン酸又はこれらのエステル類等の脂肪族ジカルボン酸;1,4-シクロヘキサヒドロ無水フタル酸等の脂環式ジカルボン酸等が挙げられる。 Examples of the acid component include terephthalic acid, isophthalic acid, phthalic anhydride, α-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid or esters thereof, pimelic acid, suberic acid, and azelain. Examples thereof include aliphatic dicarboxylic acids such as acid, sebacic acid, undecylenic acid, dodecanedicarboxylic acid or esters thereof; and alicyclic dicarboxylic acids such as 1,4-cyclohexahydrophthalic anhydride.
 上記ジオール成分又はポリオール成分としては、例えば、エチレングリコール、1,2-プロピレングリコール、1,3-プロピレングリコール、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、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、ネオペンチルグリコール、3-メチルペンタンジオール、2,2,3-トリメチルペンタンジオール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール等の脂肪族グリコール;1,4-シクロヘキサンジオール、1,4-シクロヘキサンジメタノール等の脂環式グリコール;ビスフェノールA等の芳香族グリコール等が挙げられる。 Examples of the diol component or polyol component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, 3-methylpentanediol, 2,2,3-trimethylpentanediol, diethylene glycol, triethylene glycol, dipropylene glycol, etc. An aliphatic glycol such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, and an aromatic glycol such as bisphenol A.
(オレフィン系樹脂)
 粘着性樹脂として使用し得る、オレフィン系樹脂は、エチレン、プロピレン等のオレフィン化合物に由来する構成単位を有する重合体であれば、特に制限はされない。
 当該オレフィン系樹脂は、単独で用いてもよく、2種以上を併用してもよい。
(Olefin resin)
The olefin resin that can be used as the adhesive resin is not particularly limited as long as it is a polymer having a structural unit derived from an olefin compound such as ethylene or propylene.
The said olefin resin may be used independently and may use 2 or more types together.
 具体的なオレフィン系樹脂としては、例えば、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、及び線状低密度ポリエチレン等のポリエチレン、ポリプロピレン、エチレンとプロピレンとの共重合体、エチレンと他のα-オレフィンとの共重合体、プロピレンと他のα-オレフィンとの共重合体、エチレンとプロピレンと他のα-オレフィンとの共重合体、エチレンと他のエチレン性不飽和単量体との共重合体(エチレン-酢酸ビニル共重合体、エチレン-アルキル(メタ)アクリレート共重合体等)等が挙げられる。
 上記のα-オレフィンとしては、例えば、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、4-メチル-1-ペンテン、4-メチル-1-ヘキセン等が挙げられる。
 上記のエチレン性不飽和単量体としては、例えば、酢酸ビニル、アルキル(メタ)アクリレート、ビニルアルコール等が挙げられる。
Specific examples of the olefin-based resin include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene, polypropylene, copolymers of ethylene and propylene, ethylene and other α- Copolymers of olefins, copolymers of propylene and other α-olefins, copolymers of ethylene, propylene and other α-olefins, copolymers of ethylene and other ethylenically unsaturated monomers Examples thereof include ethylene (vinyl-vinyl acetate copolymer, ethylene-alkyl (meth) acrylate copolymer, etc.) and the like.
Examples of the α-olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene and the like.
Examples of the ethylenically unsaturated monomer include vinyl acetate, alkyl (meth) acrylate, vinyl alcohol, and the like.
[粘着付与剤]
 本発明の一態様において、粘着力をより向上させた両面粘着シートとする観点から、組成物(x1)及び(x2)は、さらに粘着付与剤を含有することが好ましい。
 ここで、「粘着付与剤」とは、粘着性樹脂の粘着力を補助的に向上させる成分であって、質量平均分子量(Mw)が1万未満のオリゴマーを指し、上述の粘着性樹脂とは区別されるものである。
 粘着付与剤の質量平均分子量(Mw)は、好ましくは400~10000、より好ましくは5000~8000、更に好ましくは800~5000である。
[Tackifier]
In one embodiment of the present invention, it is preferable that the compositions (x1) and (x2) further contain a tackifier from the viewpoint of making a double-sided PSA sheet with improved adhesive strength.
Here, the “tackifier” is a component that assists in improving the adhesive strength of the adhesive resin, and refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000. It is a distinction.
The mass average molecular weight (Mw) of the tackifier is preferably 400 to 10000, more preferably 5000 to 8000, and still more preferably 800 to 5000.
 粘着付与剤としては、例えば、ロジン樹脂、ロジンエステル樹脂、ロジン変性フェノール樹脂等のロジン系樹脂;これらロジン系樹脂を水素化した水素化ロジン系樹脂;テルペン樹脂、芳香族変性テルペン樹脂、テルペンフェノール系樹脂等のテルペン系樹脂;これらテルペン系樹脂を水素化した水素化テルペン系樹脂;α-メチルスチレン又はβ-メチルスチレン等のスチレン系モノマーと脂肪族系モノマーとを共重合して得られるスチレン系樹脂;これらスチレン系樹脂を水素化した水素化スチレン系樹脂;石油ナフサの熱分解で生成するペンテン、イソプレン、ピペリン、1.3-ペンタジエン等のC5留分を共重合して得られるC5系石油樹脂及びこのC5系石油樹脂の水素化石油樹脂;石油ナフサの熱分解で生成するインデン、ビニルトルエン等のC9留分を共重合して得られるC9系石油樹脂及びこのC9系石油樹脂を水素化石油樹脂;等が挙げられる。
 これらの粘着付与剤は、単独で用いてもよく、軟化点や構造が異なる2種以上を併用してもよい。
Examples of tackifiers include rosin resins such as rosin resins, rosin ester resins, and rosin-modified phenol resins; hydrogenated rosin resins obtained by hydrogenating these rosin resins; terpene resins, aromatic modified terpene resins, and terpene phenols. Terpene resins such as epoxy resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins; styrene obtained by copolymerizing a styrene monomer such as α-methylstyrene or β-methylstyrene with an aliphatic monomer Hydrogenated styrene resins obtained by hydrogenating these styrene resins; C5 systems obtained by copolymerizing C5 fractions such as pentene, isoprene, piperine, 1.3-pentadiene produced by thermal decomposition of petroleum naphtha Petroleum resin and hydrogenated petroleum resin of this C5 petroleum resin; indene and vinyl And C9 petroleum resins obtained by copolymerizing C9 fractions such as toluene and hydrogenated petroleum resins.
These tackifiers may be used alone or in combination of two or more different softening points and structures.
 粘着付与剤の軟化点は、好ましくは60~170℃、より好ましくは65~160℃、更に好ましくは70~150℃である。
 なお、本明細書において、粘着付与剤の「軟化点」は、JIS K 2531に準拠して測定した値を意味する。
 また、2種以上の複数の粘着付与剤を用いる場合、それら複数の粘着付与剤の軟化点の加重平均が、上記範囲に属することが好ましい。
The softening point of the tackifier is preferably 60 to 170 ° C, more preferably 65 to 160 ° C, and still more preferably 70 to 150 ° C.
In the present specification, the “softening point” of the tackifier means a value measured according to JIS K2531.
Moreover, when using 2 or more types of several tackifier, it is preferable that the weighted average of the softening point of these several tackifier belongs to the said range.
 組成物(x1)及び(x2)中の粘着付与剤の含有量は、組成物(x1)又は(x2)の有効成分の全量(100質量%)に対して、好ましくは0.01~65質量%、より好ましくは0.05~55質量%、より好ましくは0.1~50質量%、更に好ましくは0.5~45質量%、より更に好ましくは1.0~40質量%である。 The content of the tackifier in the compositions (x1) and (x2) is preferably 0.01 to 65 masses with respect to the total amount (100 mass%) of the active ingredients of the composition (x1) or (x2). %, More preferably 0.05 to 55% by mass, more preferably 0.1 to 50% by mass, still more preferably 0.5 to 45% by mass, and still more preferably 1.0 to 40% by mass.
 なお、組成物(x1)及び(x2)中の粘着性樹脂及び粘着付与剤の合計含有量は、組成物(x1)又は(x2)の有効成分の全量(100質量%)に対して、好ましくは70質量%以上、より好ましくは80質量%以上、より好ましくは85質量%以上、更に好ましくは90質量%以上、より更に好ましくは95質量%以上である。 The total content of the adhesive resin and the tackifier in the compositions (x1) and (x2) is preferably based on the total amount (100% by mass) of the active ingredients in the composition (x1) or (x2). Is 70% by mass or more, more preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, and still more preferably 95% by mass or more.
[架橋剤]
 本発明の一態様において、組成物(x1)及び(x2)は、上述のアクリル系共重合体(A1)等のような、官能基を有する粘着性樹脂を含有する場合、さらに架橋剤を含有することが好ましい。
 当該架橋剤は、当該粘着性樹脂が有する官能基と反応して、樹脂同士を架橋するものである。
[Crosslinking agent]
In one embodiment of the present invention, when the compositions (x1) and (x2) contain an adhesive resin having a functional group such as the acrylic copolymer (A1) described above, the compositions (x1) and (x2) further contain a crosslinking agent. It is preferable to do.
The said crosslinking agent reacts with the functional group which the said adhesive resin has, and bridge | crosslinks resin.
 架橋剤としては、例えば、トリレンジイソシアネート、ヘキサメチレンジイソシアネート等、及びそれらのアダクト体等のイソシアネート系架橋剤;エチレングリコールグリシジルエーテル等のエポキシ系架橋剤;ヘキサ〔1-(2-メチル)-アジリジニル〕トリフオスファトリアジン等のアジリジン系架橋剤;アルミニウムキレート等のキレート系架橋剤;等が挙げられる。
 これらの架橋剤は、単独で用いてもよく、2種以上を併用してもよい。
 これらの架橋剤の中でも、凝集力を高めて粘着力を向上させる観点、及び入手し易さ等の観点から、イソシアネート系架橋剤が好ましい。
Examples of the crosslinking agent include: tolylene diisocyanate, hexamethylene diisocyanate, and the like, and isocyanate-based crosslinking agents such as adducts thereof; epoxy-based crosslinking agents such as ethylene glycol glycidyl ether; hexa [1- (2-methyl) -aziridinyl ] Aziridine type crosslinking agents such as triphosphatriazine; Chelate type crosslinking agents such as aluminum chelate;
These crosslinking agents may be used independently and may use 2 or more types together.
Among these crosslinking agents, an isocyanate-based crosslinking agent is preferable from the viewpoints of increasing cohesive force and improving adhesive force, and availability.
 架橋剤の含有量は、粘着性樹脂が有する官能基の数により適宜調整されるものであるが、上記アクリル系共重合体(A1)等の官能基を有する粘着性樹脂100質量部に対して、好ましくは0.01~10質量部、より好ましくは0.03~7質量部、更に好ましくは0.05~4質量部である。 Although content of a crosslinking agent is suitably adjusted with the number of functional groups which adhesive resin has, with respect to 100 mass parts of adhesive resins which have functional groups, such as said acrylic copolymer (A1). The amount is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 7 parts by mass, and still more preferably 0.05 to 4 parts by mass.
[粘着剤用添加剤]
 本発明の一態様において、組成物(x1)及び(x2)は、本発明の効果を損なわない範囲で、架橋剤や粘着付与剤以外の一般的な粘着剤に使用される粘着剤用添加剤を含有していてもよい。
 粘着剤用添加剤としては、例えば、酸化防止剤、軟化剤(可塑剤)、防錆剤、顔料、染料、遅延剤、反応促進剤(触媒)、紫外線吸収剤等が挙げられる。
 なお、これらの粘着剤用添加剤は、それぞれ単独で用いてもよく、2種以上を併用してもよい。
 これらの粘着剤用添加剤を含有する場合、それぞれの粘着剤用添加剤の含有量は、粘着性樹脂100質量部に対して、好ましくは0.0001~20質量部、より好ましくは0.001~10質量部、更に好ましくは0.005~5質量部である。
[Additives for adhesives]
In one aspect of the present invention, the compositions (x1) and (x2) are additives for pressure-sensitive adhesives used for general pressure-sensitive adhesives other than a crosslinking agent and a tackifier, as long as the effects of the present invention are not impaired. May be contained.
Examples of the adhesive additive include an antioxidant, a softener (plasticizer), a rust inhibitor, a pigment, a dye, a retarder, a reaction accelerator (catalyst), and an ultraviolet absorber.
These pressure-sensitive adhesive additives may be used alone or in combination of two or more.
When these pressure-sensitive adhesive additives are contained, the content of each pressure-sensitive adhesive additive is preferably 0.0001 to 20 parts by mass, more preferably 0.001 to 100 parts by mass of the adhesive resin. To 10 parts by mass, more preferably 0.005 to 5 parts by mass.
[希釈溶媒]
 本発明の一態様において、組成物(x1)及び(x2)は、上述の各種有効成分と共に、さらに希釈溶媒を含有し、溶液の形態としてもよい。
 当該希釈溶媒は、水であってもよく、有機溶媒であってもよい。
 有機溶媒としては、例えば、トルエン、酢酸エチル、酢酸ブチル、メチルエチルケトン、メチルイソブチルケトン、メタノール、エタノール、イソプロピルアルコール、t-ブタノール、s-ブタノール、アセチルアセトン、シクロヘキサノン、n-ヘキサン、シクロヘキサン等が挙げられる。
 なお、組成物(x1)及び(x2)中に含まれる希釈溶媒は、単独で用いてもよく、2種以上を併用してもよい。
[Diluted solvent]
In one embodiment of the present invention, the compositions (x1) and (x2) may further contain a diluting solvent together with the various active ingredients described above, and may be in the form of a solution.
The dilution solvent may be water or an organic solvent.
Examples of the organic solvent include toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, t-butanol, s-butanol, acetylacetone, cyclohexanone, n-hexane, and cyclohexane.
In addition, the dilution solvent contained in composition (x1) and (x2) may be used independently, and may use 2 or more types together.
 組成物(x1)及び(x2)が希釈溶媒を含有して溶液の形態である場合、組成物(x1)及び(x2)の有効成分濃度としては、それぞれ独立に、好ましくは0.1~60質量%、より好ましくは0.5~50質量%、更に好ましくは1.0~40質量%である。 When the compositions (x1) and (x2) are in the form of a solution containing a diluting solvent, the active ingredient concentrations of the compositions (x1) and (x2) are each independently preferably preferably 0.1 to 60 The mass is more preferably 0.5 to 50 mass%, still more preferably 1.0 to 40 mass%.
<組成物(y)>
 基材層(Y)の形成材料である組成物(y)は、アクリルウレタン系樹脂及びオレフィン系樹脂からなる群より選ばれる非粘着性樹脂を含む。
 本発明において、「非粘着性樹脂」は、アクリルウレタン系樹脂又はオレフィン系樹脂に属し、質量平均分子量(Mw)が1万以上の非粘着性の重合体を意味する。
 また、非粘着性樹脂が、2種以上の構成単位を有する共重合体である場合、当該共重合体の形態は、特に限定されず、ブロック共重合体、ランダム共重合体、及びグラフト共重合体のいずれであってもよい。
 さらに、本発明の一態様において、基材層(Y)と第1粘着剤層(X1)及び第2粘着剤層(X2)との界面密着性をより向上させる観点から、組成物(y)に含まれる前記非粘着性樹脂が、重合性官能基を有しない紫外線非硬化型樹脂であることが好ましい。
<Composition (y)>
The composition (y) which is a forming material of the base material layer (Y) contains a non-adhesive resin selected from the group consisting of an acrylic urethane resin and an olefin resin.
In the present invention, the “non-adhesive resin” means a non-adhesive polymer belonging to acrylic urethane resin or olefin resin and having a mass average molecular weight (Mw) of 10,000 or more.
In addition, when the non-adhesive resin is a copolymer having two or more kinds of structural units, the form of the copolymer is not particularly limited, and a block copolymer, a random copolymer, and a graft copolymer Any of them may be combined.
Furthermore, in one aspect of the present invention, from the viewpoint of further improving the interfacial adhesion between the base material layer (Y), the first pressure-sensitive adhesive layer (X1), and the second pressure-sensitive adhesive layer (X2), the composition (y) It is preferable that the non-adhesive resin contained in is an ultraviolet non-curable resin having no polymerizable functional group.
 また、本発明の一態様において、組成物(y)は、本発明の効果を損なわない範囲で、アクリルウレタン系樹脂及びオレフィン系樹脂以外の樹脂を含有してもよく、また、一般的な粘着シートが有する基材に含まれる基材用添加剤を含有してもよい。 Moreover, in one aspect of the present invention, the composition (y) may contain a resin other than an acrylic urethane-based resin and an olefin-based resin as long as the effects of the present invention are not impaired. You may contain the additive for base materials contained in the base material which a sheet | seat has.
 組成物(y)中の非粘着性樹脂の含有量は、組成物(y)の有効成分の全量(100質量%)に対して、好ましくは50~100質量%、より好ましくは65~100質量%、より好ましくは80~100質量%、更に好ましくは90~100質量%、より更に好ましくは95~100質量%である。 The content of the non-adhesive resin in the composition (y) is preferably 50 to 100% by mass, more preferably 65 to 100% by mass with respect to the total amount (100% by mass) of the active ingredients in the composition (y). %, More preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
(アクリルウレタン系樹脂)
 組成物(y)に非粘着性樹脂として含まれる、アクリルウレタン系樹脂としては、例えば、アクリルポリオール化合物とイソシアネート化合物との反応生成物や、両末端にエチレン性不飽和基を有する直鎖ウレタンプレポリマー(UY)と、(メタ)アクリル酸エステルを含むビニル化合物(VY)とを重合してなる共重合体が挙げられる。
(Acrylic urethane resin)
Examples of the acrylic urethane-based resin contained as the non-adhesive resin in the composition (y) include a reaction product of an acrylic polyol compound and an isocyanate compound, and a linear urethane prepolymer having ethylenically unsaturated groups at both ends. Examples thereof include a copolymer obtained by polymerizing a polymer (UY) and a vinyl compound (VY) containing a (meth) acrylic ester.
 アクリルポリオール化合物とイソシアネート化合物との反応生成物であるアクリルウレタン系樹脂(以下、「アクリルウレタン系樹脂(I)」ともいう)は、アクリル系樹脂の主鎖を骨格としつつ、それらの分子間がウレタン結合によって架橋されて硬化された化学構造を有している。
 主鎖であるアクリル系樹脂が剛性に富むため、引張応力にもよく耐えて伸びにくく、また、反応性に富むイソシアネート化合物に由来の構成単位を有するため、第1粘着剤層(X1)及び第2粘着剤層(X2)に含まれる粘着性樹脂との密着性にも優れており、界面密着性の向上に寄与し得ると考えられる。
An acrylic urethane resin (hereinafter also referred to as “acrylic urethane resin (I)”), which is a reaction product of an acrylic polyol compound and an isocyanate compound, has a main chain of the acrylic resin as a skeleton, and the intermolecular relationship between the molecules. It has a chemical structure that is cured by crosslinking with urethane bonds.
Since the acrylic resin that is the main chain is rich in rigidity, it has a structural unit derived from an isocyanate compound that is highly resistant to tensile stress and has a high reactivity, and therefore has the first pressure-sensitive adhesive layer (X1) and the first adhesive layer. It is thought that it is excellent also in adhesiveness with the adhesive resin contained in 2 adhesive layer (X2), and can contribute to the improvement of interface adhesiveness.
 一方、両末端にエチレン性不飽和基を有する直鎖ウレタンプレポリマー(UY)と(メタ)アクリル酸エステルを含むビニル化合物(VY)とを重合してなる共重合体であるアクリルウレタン系樹脂(以下、「アクリルウレタン系樹脂(II)」ともいう)は、直鎖ウレタンプレポリマー(UY)の主鎖を骨格としつつ、直鎖ウレタンプレポリマー(UY)の両末端に(メタ)アクリル酸エステルを含むビニル化合物(VY)に由来する構成単位を有するものである。
 アクリルウレタン系樹脂(II)は、主鎖骨格におけるアクリル部位間に直鎖ウレタンポリマー(UY)に由来する部位が介されるため、架橋点間距離が、アクリルウレタン系樹脂(I)よりも長くなり、その分子構造が二次元的構造(網状構造)となり易い。
 また、主鎖のウレタンプレポリマー(UY)が直鎖状であるため、外力がかかった時に延伸効果が高い。
 さらに、(メタ)アクリル酸エステルを含むビニル化合物(VY)に由来する構成単位の側鎖が、第1粘着剤層(X1)及び第2粘着剤層(X2)中の粘着性樹脂と絡み易い構造を有している。
 そのために、基材層(Y)の形成材料として、アクリルウレタン系樹脂(II)を用いることで、第1粘着剤層(X1)及び第2粘着剤層(X2)との界面密着性の向上に寄与し得ると考えられる。
On the other hand, an acrylic urethane-based resin, which is a copolymer obtained by polymerizing a linear urethane prepolymer (UY) having an ethylenically unsaturated group at both ends and a vinyl compound (VY) containing a (meth) acrylic acid ester ( Hereinafter, the “acrylic urethane resin (II)” is a (meth) acrylic acid ester at both ends of the linear urethane prepolymer (UY) with the main chain of the linear urethane prepolymer (UY) as the skeleton. It has a structural unit derived from the vinyl compound (VY) containing.
Since acrylic urethane resin (II) has a portion derived from linear urethane polymer (UY) between acrylic sites in the main chain skeleton, the distance between crosslinking points is longer than that of acrylic urethane resin (I). The molecular structure tends to be a two-dimensional structure (network structure).
Further, since the urethane prepolymer (UY) of the main chain is linear, the stretching effect is high when an external force is applied.
Furthermore, the side chain of the structural unit derived from the vinyl compound (VY) containing the (meth) acrylic acid ester is easily entangled with the adhesive resin in the first adhesive layer (X1) and the second adhesive layer (X2). It has a structure.
Therefore, the use of acrylic urethane resin (II) as the material for forming the base layer (Y) improves the interfacial adhesion with the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2). It is thought that it can contribute to.
 アクリルウレタン系樹脂(I)及び(II)等のアクリルウレタン系樹脂の質量平均分子量(Mw)としては、好ましくは2,000~50万、より好ましくは4,000~30万、更に好ましくは5,000~20万、より更に好ましくは1万~15万である。
 また、アクリルウレタン系樹脂(I)及び(II)等のアクリルウレタン系樹脂は、重合性官能基を有さない紫外線非硬化型樹脂であることが好ましい。
The mass average molecular weight (Mw) of acrylic urethane resins such as acrylic urethane resins (I) and (II) is preferably 2,000 to 500,000, more preferably 4,000 to 300,000, and even more preferably 5 1,000 to 200,000, and more preferably 10,000 to 150,000.
The acrylic urethane resins such as acrylic urethane resins (I) and (II) are preferably ultraviolet non-curable resins having no polymerizable functional group.
 なお、本発明の一態様において、組成物(y)に非粘着性樹脂として含まれるアクリルウレタン系樹脂としては、アクリルウレタン系樹脂(II)が好ましい。
 以下、アクリルウレタン系樹脂(I)及び(II)について説明する。
In one embodiment of the present invention, the acrylic urethane resin (II) is preferably used as the acrylic urethane resin contained in the composition (y) as a non-adhesive resin.
Hereinafter, the acrylic urethane resins (I) and (II) will be described.
(アクリルウレタン系樹脂(I))
 アクリルウレタン系樹脂(I)の原料となる、アクリルポリオール化合物としては、アルキル(メタ)アクリレート(b1’)(以下、「モノマー(b1’)」ともいう)に由来する構成単位(b1)と、水酸基含有モノマー(b2’)(以下、「モノマー(b2’)」ともいう)に由来する構成単位(b2)とを有するアクリル系共重合体(B1)が好ましい。
(Acrylic urethane resin (I))
As an acrylic polyol compound that is a raw material of the acrylic urethane-based resin (I), a structural unit (b1) derived from an alkyl (meth) acrylate (b1 ′) (hereinafter also referred to as “monomer (b1 ′)”), An acrylic copolymer (B1) having a structural unit (b2) derived from a hydroxyl group-containing monomer (b2 ′) (hereinafter also referred to as “monomer (b2 ′)”) is preferable.
 モノマー(b1’)が有するアルキル基の炭素数としては、好ましくは1~12、より好ましくは4~8、更に好ましくは4~6である。
 なお、モノマー(b1’)が有するアルキル基は、直鎖アルキル基であってもよく、分岐鎖アルキル基であってもよい。
 具体的なモノマー(b1’)としては、上述のモノマー(a1’)と同じものが挙げられる。
 なお、モノマー(b1’)は、単独で用いてもよく、2種以上を併用してもよい。
 ただし、モノマー(b1’)としては、ブチル(メタ)アクリレート及び2-エチルヘキシル(メタ)アクリレートが好ましく、ブチル(メタ)アクリレートがより好ましい。
The number of carbon atoms of the alkyl group contained in the monomer (b1 ′) is preferably 1 to 12, more preferably 4 to 8, and still more preferably 4 to 6.
The alkyl group contained in the monomer (b1 ′) may be a straight chain alkyl group or a branched chain alkyl group.
Specific examples of the monomer (b1 ′) include the same monomers as the monomer (a1 ′) described above.
In addition, a monomer (b1 ') may be used independently and may use 2 or more types together.
However, as the monomer (b1 ′), butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and butyl (meth) acrylate is more preferable.
 構成単位(b1)の含有量は、アクリル系共重合体(B1)の全構成単位(100質量%)に対して、好ましくは60~99.9質量%、より好ましくは70~99.7質量%、更に好ましくは80~99.5質量%である。 The content of the structural unit (b1) is preferably 60 to 99.9% by mass, more preferably 70 to 99.7% by mass with respect to the total structural unit (100% by mass) of the acrylic copolymer (B1). %, More preferably 80 to 99.5% by mass.
 また、モノマー(b2’)としては、上述のモノマー(a2’)として選択可能な水酸基含有モノマーと同じものが挙げられる。
 なお、モノマー(b2’)は、単独で用いてもよく、2種以上を併用してもよい。
Moreover, as a monomer (b2 '), the same thing as the hydroxyl-containing monomer which can be selected as said monomer (a2') is mentioned.
In addition, a monomer (b2 ') may be used independently and may use 2 or more types together.
 構成単位(b2)の含有量は、アクリル系共重合体(B1)の全構成単位(100質量%)に対して、好ましくは0.1~40質量%、より好ましくは0.3~30質量%、更に好ましくは0.5~20質量%である。 The content of the structural unit (b2) is preferably 0.1 to 40% by weight, more preferably 0.3 to 30% by weight with respect to the total structural unit (100% by weight) of the acrylic copolymer (B1). %, And more preferably 0.5 to 20% by mass.
 また、アクリル系共重合体(B1)は、さらにモノマー(b1’)及び(b2’)以外の他のモノマー(b3’)に由来の構成単位(b3)を有していてもよい。
 モノマー(b3’)としては、上述のモノマー(a2’)として選択可能な水酸基含有モノマー以外の官能基含有モノマーや、上述のモノマー(a3’)と同じものが挙げられる。
The acrylic copolymer (B1) may further have a structural unit (b3) derived from another monomer (b3 ′) other than the monomers (b1 ′) and (b2 ′).
Examples of the monomer (b3 ′) include functional group-containing monomers other than the hydroxyl group-containing monomer that can be selected as the above-mentioned monomer (a2 ′), and the same monomers as the above-mentioned monomer (a3 ′).
 なお、アクリル系共重合体(B1)において、構成単位(b1)及び(b2)の含有量は、アクリル系共重合体(B1)の全構成単位(100質量%)に対して、好ましくは70~100質量%、より好ましくは80~100質量%、更に好ましくは90~100質量%、より更に好ましくは95~100質量%である。 In the acrylic copolymer (B1), the content of the structural units (b1) and (b2) is preferably 70 with respect to the total structural units (100% by mass) of the acrylic copolymer (B1). To 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
 一方、アクリルウレタン系樹脂(I)の原料となる、イソシアネート系化合物としては、上述のウレタン系プレポリマー(U1)の原料となる多価イソシアネート化合物と同じものが挙げられる。
 ただし、イソシアネート系化合物としては、外力がかかった時の延伸性の観点から、芳香族環を有しないイソシアネート系化合物が好ましく、脂肪族ポリイソシアネート及び脂環式ポリイソシアネートがより好ましい。
On the other hand, examples of the isocyanate compound used as the raw material for the acrylic urethane resin (I) include the same polyvalent isocyanate compounds used as the raw material for the urethane prepolymer (U1).
However, as an isocyanate compound, from the viewpoint of stretchability when an external force is applied, an isocyanate compound having no aromatic ring is preferable, and an aliphatic polyisocyanate and an alicyclic polyisocyanate are more preferable.
 アクリルウレタン系樹脂(I)において、アクリルポリオール化合物に由来する構成単位と、イソシアネート系化合物に由来の構成単位との比率〔アクリルポリオール化合物/イソシアネート系化合物〕は、質量比で、好ましくは10/90~90/10、より好ましくは20/80~80/20、更に好ましくは30/70~70/30、より更に好ましくは40/60~60/40である。 In the acrylic urethane resin (I), the ratio of the structural unit derived from the acrylic polyol compound to the structural unit derived from the isocyanate compound [acryl polyol compound / isocyanate compound] is preferably 10/90 by mass ratio. Is 90/90, more preferably 20/80 to 80/20, still more preferably 30/70 to 70/30, and still more preferably 40/60 to 60/40.
(アクリルウレタン系樹脂(II))
 アクリルウレタン系樹脂(II)の原料となる、直鎖ウレタンプレポリマー(UY)としては、ジオールとジイソシアネート化合物との反応物が挙げられる。
 当該ジオール及びジイソシアネート化合物は、単独で用いてもよく、2種以上を併用してもよい。
 直鎖ウレタンプレポリマー(UY)の質量平均分子量としては、好ましくは1,000~30万、より好ましくは3,000~20万、更に好ましくは5,000~10万、より更に好ましく1万~8万、特に好ましくは2万~6万である。
(Acrylic urethane resin (II))
Examples of the linear urethane prepolymer (UY) that is a raw material for the acrylic urethane resin (II) include a reaction product of a diol and a diisocyanate compound.
The said diol and diisocyanate compound may be used independently and may use 2 or more types together.
The mass average molecular weight of the linear urethane prepolymer (UY) is preferably 1,000 to 300,000, more preferably 3,000 to 200,000, still more preferably 5,000 to 100,000, and still more preferably 10,000 to 80,000, particularly preferably 20,000 to 60,000.
 直鎖ウレタンプレポリマー(UY)を構成するジオールとしては、例えば、アルキレングリコール、ポリエーテル型ジオール、ポリエステル型ジオール、ポリエステルアミド型ジオール、ポリエステル・ポリエーテル型ジオール、ポリカーボネート型ジオール等が挙げられる。
 これらのジオールの中でも、ポリカーボネート型ジオールが好ましい。
Examples of the diol constituting the linear urethane prepolymer (UY) include alkylene glycol, polyether type diol, polyester type diol, polyester amide type diol, polyester / polyether type diol, and polycarbonate type diol.
Of these diols, polycarbonate diols are preferred.
 直鎖ウレタンプレポリマー(UY)を構成するジイソシアネート化合物としては、例えば、芳香族ジイソシアネート、脂肪族ジイソシアネート、脂環式ジイソシアネート等が挙げられ、外力がかかった時の延伸性の観点から、脂環式ジイソシアネートが好ましい。
 なお、具体的なジイソシアネート化合物としては、上述のウレタン系プレポリマー(UX)の原料となる多価イソシアネートとして例示された化合物のうち、ジイソシアネート化合物に該当するものが挙げられる。
Examples of the diisocyanate compound constituting the linear urethane prepolymer (UY) include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates. From the viewpoint of stretchability when an external force is applied, alicyclic Diisocyanate is preferred.
In addition, as a specific diisocyanate compound, what corresponds to a diisocyanate compound is mentioned among the compounds illustrated as a polyisocyanate used as the raw material of the above-mentioned urethane type prepolymer (UX).
 また、直鎖ウレタンプレポリマー(UY)は、ジオールとジイソシアネート化合物と共に、鎖延長剤を用いた鎖延長反応を施して得られたものであってもよい。
 当該鎖延長剤としては、上述のウレタンプレポリマー(UX)の合成時に使用し得る鎖延長剤として例示したものと同じものが挙げられる。
Further, the linear urethane prepolymer (UY) may be obtained by performing a chain extension reaction using a chain extender together with a diol and a diisocyanate compound.
Examples of the chain extender include the same chain extenders as those exemplified as the chain extender that can be used in the synthesis of the urethane prepolymer (UX).
 本発明の一態様において、直鎖ウレタンプレポリマー(UY)は、両末端に、エチレン性不飽和基を有するものである。
 ウレタンプレポリマー(UY)の両末端にエチレン性不飽和基を導入する方法としては、ジオールとジイソシアネート化合物とを反応してなるウレタンプレポリマーの末端のNCO基と、ヒドロキシアルキル(メタ)アクリレートとを反応させる方法が挙げられる。
 ヒドロキシアルキル(メタ)アクリレートとしては、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、3-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート等が挙げられる。
In one embodiment of the present invention, the linear urethane prepolymer (UY) has an ethylenically unsaturated group at both ends.
As a method for introducing an ethylenically unsaturated group into both ends of the urethane prepolymer (UY), an NCO group at the end of the urethane prepolymer obtained by reacting a diol and a diisocyanate compound, and a hydroxyalkyl (meth) acrylate are used. The method of making it react is mentioned.
Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy Examples thereof include butyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
 アクリルウレタン系樹脂(II)の原料となる、ビニル化合物(VY)としては、少なくとも(メタ)アクリル酸エステルを含む。
 (メタ)アクリル酸エステルとしては、上述のアクリル系共重合体(A1)の原料として使用しているモノマー(a1’)~(a3’)のうち(メタ)アクリル酸エステルに該当するものと同じものが挙げられる。
 ただし、(メタ)アクリル酸エステルとしては、アルキル(メタ)アクリレート及びヒドロキシアルキル(メタ)アクリレートから選ばれる1種以上が好ましく、アルキル(メタ)アクリレート及びヒドロキシアルキル(メタ)アクリレートを併用することがより好ましい。
As a vinyl compound (VY) used as the raw material of acrylic urethane type resin (II), at least (meth) acrylic acid ester is included.
The (meth) acrylic acid ester is the same as that corresponding to the (meth) acrylic acid ester among the monomers (a1 ′) to (a3 ′) used as the raw material of the above-mentioned acrylic copolymer (A1). Things.
However, as the (meth) acrylic acid ester, at least one selected from alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate is preferable, and it is more preferable to use alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate together. preferable.
 アルキル(メタ)アクリレート及びヒドロキシアルキル(メタ)アクリレートを併用する場合、アルキル(メタ)アクリレート100質量部に対する、ヒドロキシアルキル(メタ)アクリレートの配合割合としては、好ましくは0.1~100質量部、より好ましくは0.5~30質量部、更に好ましくは1.0~20質量部、より更に好ましくは1.5~10質量部である。 When alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate are used in combination, the proportion of hydroxyalkyl (meth) acrylate to 100 parts by mass of alkyl (meth) acrylate is preferably 0.1 to 100 parts by mass, The amount is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, and still more preferably 1.5 to 10 parts by mass.
 当該アルキル(メタ)アクリレートが有するアルキル基の炭素数としては、好ましくは1~24、より好ましくは1~12、更に好ましくは1~8、より更に好ましくは1~3である。
 当該アルキル(メタ)アクリレートとしては、上述のアクリル系共重合体(A1)の原料となるモノマー(a1’)として例示したものと同じものが挙げられる。
The number of carbon atoms in the alkyl group of the alkyl (meth) acrylate is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 8, and still more preferably 1 to 3.
As the said alkyl (meth) acrylate, the same thing as what was illustrated as a monomer (a1 ') used as the raw material of the above-mentioned acrylic copolymer (A1) is mentioned.
 また、ヒドロキシアルキル(メタ)アクリレートとしては、上述のウレタンプレポリマー(UY)の両末端にエチレン性不飽和基を導入するために用いられるヒドロキシアルキル(メタ)アクリレートとして例示したものと同じものが挙げられる。 Moreover, as hydroxyalkyl (meth) acrylate, the same thing as what was illustrated as hydroxyalkyl (meth) acrylate used in order to introduce | transduce an ethylenically unsaturated group into the both ends of the above-mentioned urethane prepolymer (UY) is mentioned. It is done.
 (メタ)アクリル酸エステル以外のビニル化合物としては、例えば、スチレン、α-メチルスチレン、ビニルトルエン等の芳香族炭化水素系ビニル化合物;メチルビニルエーテル、エチルビニルエーテル等のビニルエーテル類;酢酸ビニル、プロピオン酸ビニル、(メタ)アクリロニトリル、N-ビニルピロリドン、(メタ)アクリル酸、マレイン酸、フマル酸、イタコン酸、メタ(アクリルアミド)等の極性基含有モノマー;等が挙げられる。
 これらは単独で用いてもよく、2種以上を併用してもよい。
Examples of vinyl compounds other than (meth) acrylic acid esters include aromatic hydrocarbon vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl acetate and vinyl propionate. Polar group-containing monomers such as (meth) acrylonitrile, N-vinylpyrrolidone, (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, and meta (acrylamide).
These may be used alone or in combination of two or more.
 本発明の一態様において、アクリルウレタン系樹脂(II)の原料として用いるビニル化合物(VY)中の(メタ)アクリル酸エステルの含有量としては、当該ビニル化合物(VY)の全量(100質量%)に対して、好ましくは40~100質量%、より好ましくは65~100質量%、更に好ましくは80~100質量%、より更に好ましくは90~100質量%である。 In one embodiment of the present invention, the content of (meth) acrylic acid ester in the vinyl compound (VY) used as the raw material for the acrylic urethane resin (II) is the total amount (100% by mass) of the vinyl compound (VY). Is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, still more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass.
 本発明の一態様において、アクリルウレタン系樹脂(II)の原料として用いるビニル化合物(VY)中のアルキル(メタ)アクリレート及びヒドロキシアルキル(メタ)アクリレートの合計含有量としては、当該ビニル化合物(VY)の全量(100質量%)に対して、好ましくは40~100質量%、より好ましくは65~100質量%、更に好ましくは80~100質量%、より更に好ましくは90~100質量%である。 In one embodiment of the present invention, the total content of alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate in vinyl compound (VY) used as a raw material for acrylic urethane resin (II) is the vinyl compound (VY). Is preferably 40 to 100% by mass, more preferably 65 to 100% by mass, still more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass with respect to the total amount (100% by mass).
 アクリルウレタン系樹脂(II)は、原料である直鎖ウレタンプレポリマー(UY)と、ビニル化合物(VY)とを、重合することによって得ることができる。
 具体的な重合方法としては、有機溶媒中に、原料である直鎖ウレタンプレポリマー(UY)及びビニル化合物(VY)と共に、ラジカル発生剤を配合し、直鎖ウレタンプレポリマー(UY)の両末端に有するエチレン性不飽和基を起点としたビニル系化合物(VY)のラジカル重合反応によって合成するができる。
 使用するラジカル発生剤としては、例えば、アゾビスイソブチロニトリルのようなジアゾ化合物や、ベンゾイルパーオキサイド等が挙げられる。
 なお、このラジカル重合反応において、チオール基含有化合物等の連鎖移動剤を溶媒中に添加してアクリルの重合度を調製してもよい。
The acrylic urethane resin (II) can be obtained by polymerizing a linear urethane prepolymer (UY) as a raw material and a vinyl compound (VY).
As a specific polymerization method, a radical generator is blended in an organic solvent together with the linear urethane prepolymer (UY) and vinyl compound (VY) as raw materials, and both ends of the linear urethane prepolymer (UY). It can be synthesized by a radical polymerization reaction of a vinyl compound (VY) starting from an ethylenically unsaturated group.
Examples of the radical generator used include diazo compounds such as azobisisobutyronitrile, benzoyl peroxide, and the like.
In this radical polymerization reaction, a chain transfer agent such as a thiol group-containing compound may be added to the solvent to adjust the polymerization degree of acrylic.
 本発明の一態様で用いるアクリルウレタン系樹脂(II)において、直鎖ウレタンプレポリマー(UY)に由来の構成単位と、ビニル化合物(VY)に由来する構成単位との含有量比〔(UY)/(VY)〕としては、質量比で、好ましくは10/90~80/20、より好ましくは20/80~70/30、更に好ましくは30/70~60/40、より更に好ましくは35/65~55/45である。 In the acrylic urethane resin (II) used in one embodiment of the present invention, the content ratio of the structural unit derived from the linear urethane prepolymer (UY) to the structural unit derived from the vinyl compound (VY) [(UY) / (VY)] is preferably 10/90 to 80/20, more preferably 20/80 to 70/30, still more preferably 30/70 to 60/40, still more preferably 35 / 65 to 55/45.
(オレフィン系樹脂)
 組成物(y)に非粘着性樹脂として含まれる、オレフィン系樹脂としては、オレフィンモノマーに由来の構成単位を少なくとも有する重合体である。
 なお、オレフィン系樹脂は、重合性官能基を有さない紫外線非硬化型樹脂であることが好ましい。
 上記オレフィンモノマーとしては、炭素数2~8のα-オレフィンが好ましく、具体的には、エチレン、プロピレン、ブチレン、イソブチレン、1-ヘキセン等が挙げられる。
 これらの中でも、エチレン及びプロピレンが好ましい。
(Olefin resin)
The olefin resin contained as the non-adhesive resin in the composition (y) is a polymer having at least a structural unit derived from an olefin monomer.
The olefin resin is preferably an ultraviolet non-curable resin having no polymerizable functional group.
The olefin monomer is preferably an α-olefin having 2 to 8 carbon atoms, and specifically includes ethylene, propylene, butylene, isobutylene, 1-hexene and the like.
Among these, ethylene and propylene are preferable.
 具体的なオレフィン系樹脂としては、例えば、超低密度ポリエチレン(VLDPE、密度:880kg/m以上910kg/m未満)、低密度ポリエチレン(LDPE、密度:910kg/m以上915kg/m未満)、中密度ポリエチレン(MDPE、密度:915kg/m以上942kg/m未満)、高密度ポリエチレン(HDPE、密度:942kg/m以上)、直鎖状低密度ポリエチレン等のポリエチレン樹脂;ポリプロピレン樹脂(PP);ポリブテン樹脂(PB);エチレン-プロピレン共重合体;オレフィン系エラストマー(TPO);エチレン-酢酸ビニル共重合体(EVA);エチレン-プロピレン-(5-エチリデン-2-ノルボルネン)等のオレフィン系三元共重合体;等が挙げられる。 Specific olefinic resins, for example, ultra low density polyethylene (VLDPE, density: 880 kg / m 3 or more 910 kg / m less than 3), low density polyethylene (LDPE, density: 910 kg / m 3 or more 915 kg / m less than 3 ), Medium density polyethylene (MDPE, density: 915 kg / m 3 or more and less than 942 kg / m 3 ), high density polyethylene (HDPE, density: 942 kg / m 3 or more), linear low density polyethylene, etc .; polypropylene resin (PP); polybutene resin (PB); ethylene-propylene copolymer; olefin elastomer (TPO); ethylene-vinyl acetate copolymer (EVA); ethylene-propylene- (5-ethylidene-2-norbornene), etc. Olefin terpolymers; and the like.
 本発明の一態様において、オレフィン系樹脂は、さらに酸変性、水酸基変性、及びアクリル変性から選ばれる1種以上の変性を施した変性オレフィン系樹脂であってもよい。 In one embodiment of the present invention, the olefin resin may be a modified olefin resin further modified by one or more selected from acid modification, hydroxyl group modification, and acrylic modification.
 例えば、オレフィン系樹脂に対して酸変性を施してなる酸変性オレフィン系樹脂としては、上述の無変性のオレフィン系樹脂に、不飽和カルボン酸又はその無水物を、グラフト重合させてなる変性重合体が挙げられる。
 上記の不飽和カルボン酸又はその無水物としては、例えば、マレイン酸、フマル酸、イタコン酸、シトラコン酸、グルタコン酸、テトラヒドロフタル酸、アコニット酸、(メタ)アクリル酸、無水マレイン酸、無水イタコン酸、無水グルタコン酸、無水シトラコン酸、無水アコニット酸、ノルボルネンジカルボン酸無水物、テトラヒドロフタル酸無水物等が挙げられる。
 なお、不飽和カルボン酸又はその無水物は、単独で用いてもよく、2種以上を併用してもよい。
For example, as an acid-modified olefin resin obtained by subjecting an olefin resin to acid modification, a modified polymer obtained by graft polymerization of the above-mentioned unmodified olefin resin with an unsaturated carboxylic acid or its anhydride. Is mentioned.
Examples of the unsaturated carboxylic acid or anhydride thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, (meth) acrylic acid, maleic anhydride, itaconic anhydride. , Glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, and the like.
In addition, unsaturated carboxylic acid or its anhydride may be used independently and may use 2 or more types together.
 オレフィン系樹脂に対してアクリル変性を施してなるアクリル変性オレフィン系樹脂としては、主鎖である上述の無変性のオレフィン系樹脂に、側鎖として、アルキル(メタ)アクリレートをグラフト重合させてなる変性重合体が挙げられる。
 上記のアルキル(メタ)アクリレートが有するアルキル基の炭素数としては、好ましくは1~20、より好ましくは1~16、更に好ましくは1~12である。
 上記のアルキル(メタ)アクリレートとしては、例えば、上述のモノマー(a1’)として選択可能な化合物と同じものが挙げられる。
As an acrylic modified olefin resin obtained by subjecting an olefin resin to acrylic modification, a modification obtained by graft polymerization of an alkyl (meth) acrylate as a side chain to the above-mentioned unmodified olefin resin as a main chain. A polymer is mentioned.
The number of carbon atoms in the alkyl group of the alkyl (meth) acrylate is preferably 1-20, more preferably 1-16, and still more preferably 1-12.
As said alkyl (meth) acrylate, the same thing as the compound which can be selected as said monomer (a1 ') is mentioned, for example.
 オレフィン系樹脂に対して水酸基変性を施してなる水酸基変性オレフィン系樹脂としては、主鎖である上述の無変性のオレフィン系樹脂に、水酸基含有化合物をグラフト重合させてなる変性重合体が挙げられる。
 上記の水酸基含有化合物としては、上述のモノマー(a2’)として選択可能な水酸基含有モノマーと同じものが挙げられる。
Examples of the hydroxyl group-modified olefin resin obtained by subjecting an olefin resin to hydroxyl group modification include a modified polymer obtained by graft polymerization of a hydroxyl group-containing compound to the above-mentioned unmodified olefin resin, which is the main chain.
As said hydroxyl-containing compound, the same thing as the hydroxyl-containing monomer which can be selected as said monomer (a2 ') is mentioned.
 オレフィン系樹脂の質量平均分子量(Mw)としては、好ましくは2,000~100万、より好ましくは1万~50万、更に好ましくは2万~40万、より更に好ましくは5万~30万である。 The mass average molecular weight (Mw) of the olefin resin is preferably 2,000 to 1,000,000, more preferably 10,000 to 500,000, still more preferably 20,000 to 400,000, and even more preferably 50,000 to 300,000. is there.
(アクリルウレタン系樹脂及びオレフィン系樹脂以外の樹脂)
 本発明の一態様において、組成物(y)は、本発明の効果を損なわない範囲で、アクリルウレタン系樹脂及びオレフィン系樹脂以外の樹脂を含有してもよい。
 そのような樹脂としては、例えば、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリビニルアルコール、エチレン-酢酸ビニル共重合体、エチレン-ビニルアルコール共重合体等のビニル系樹脂;ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂;ポリスチレン;アクリロニトリル-ブタジエン-スチレン共重合体;三酢酸セルロース;ポリカーボネート;アクリルウレタン系樹脂には該当しないポリウレタン;ポリメチルペンテン;ポリスルホン;ポリエーテルエーテルケトン;ポリエーテルスルホン;ポリフェニレンスルフィド;ポリエーテルイミド、ポリイミド等のポリイミド系樹脂;ポリアミド系樹脂;アクリル樹脂;フッ素系樹脂等が挙げられる。
(Resin other than acrylic urethane resin and olefin resin)
In one embodiment of the present invention, the composition (y) may contain a resin other than the acrylic urethane-based resin and the olefin-based resin as long as the effects of the present invention are not impaired.
Examples of such resins include vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate. Polyester resin such as phthalate; polystyrene; acrylonitrile-butadiene-styrene copolymer; cellulose triacetate; polycarbonate; polyurethane not applicable to acrylic urethane resin; polymethylpentene; polysulfone; polyetheretherketone; polyethersulfone; Sulfides; Polyimide resins such as polyetherimide and polyimide; Polyamide resins; Acrylic resins; Fluorine resins and the like.
 ただし、基材層(Y)と第1粘着剤層(X1)及び第2粘着剤層(X2)の界面密着性をより向上させる観点から、組成物(y)中のアクリルウレタン系樹脂及びオレフィン系樹脂以外の樹脂の含有割合は、少ない方が好ましい。
 具体的なアクリルウレタン系樹脂及びオレフィン系樹脂以外の樹脂の含有割合としては、組成物(y)中に含まれるアクリルウレタン系樹脂及びオレフィン系樹脂からなる群から選ばれる非粘着性樹脂の全量100質量部に対して、好ましくは30質量部未満、より好ましくは20質量部未満、より好ましくは10質量部未満、更に好ましくは5質量部未満、より更に好ましくは1質量部未満である。
However, from the viewpoint of further improving the interfacial adhesion between the base material layer (Y), the first pressure-sensitive adhesive layer (X1), and the second pressure-sensitive adhesive layer (X2), the acrylic urethane-based resin and olefin in the composition (y) The content ratio of the resin other than the resin is preferably as small as possible.
As a specific content of the resin other than the acrylic urethane resin and the olefin resin, the total amount of the non-adhesive resin selected from the group consisting of the acrylic urethane resin and the olefin resin contained in the composition (y) is 100. The amount is preferably less than 30 parts by weight, more preferably less than 20 parts by weight, more preferably less than 10 parts by weight, still more preferably less than 5 parts by weight, and still more preferably less than 1 part by weight with respect to parts by weight.
(基材用添加剤)
 本発明の一態様において、組成物(y)は、本発明の効果を損なわない範囲で、一般的な粘着シートが有する基材に含まれる基材用添加剤を含有してもよい。
 そのような基材用添加剤としては、例えば、紫外線吸収剤、光安定剤、酸化防止剤、帯電防止剤、スリップ剤、アンチブロッキング剤、着色剤等が挙げられる。
 なお、これらの基材用添加剤は、それぞれ単独で用いてもよく、2種以上を併用してもよい。
 これらの基材用添加剤を含有する場合、それぞれの基材用添加剤の含有量は、前記非粘着性樹脂100質量部に対して、好ましくは0.0001~20質量部、より好ましくは0.001~10質量部、より更に好ましくは0.005~5質量部である。
(Substrate additive)
1 aspect of this invention WHEREIN: The composition (y) may contain the base material additive contained in the base material which a general adhesive sheet has in the range which does not impair the effect of this invention.
Examples of such base material additives include ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, slip agents, antiblocking agents, and colorants.
These base material additives may be used alone or in combination of two or more.
In the case of containing these base material additives, the content of each base material additive is preferably 0.0001 to 20 parts by mass, more preferably 0 to 100 parts by mass of the non-adhesive resin. 0.001 to 10 parts by mass, still more preferably 0.005 to 5 parts by mass.
(希釈溶媒)
 本発明の一態様において、組成物(y)は、上述の各種有効成分と共に、さらに希釈溶媒を含有し、溶液の形態としてもよい。
 当該希釈溶媒は、水であってもよく、有機溶媒であってもよい。
 有機溶媒としては、上述の組成物(x1)及び(x2)を溶液の形態に調製する際に使用する有機溶媒と同じものが挙げられる。
 なお、組成物(y)中に含まれる希釈溶媒は、単独で用いてもよく、2種以上を併用してもよい。
(Diluted solvent)
In one embodiment of the present invention, the composition (y) may further contain a diluting solvent together with the various active ingredients described above, and may be in the form of a solution.
The dilution solvent may be water or an organic solvent.
As an organic solvent, the same organic solvent used when preparing the above-mentioned composition (x1) and (x2) in the form of a solution is mentioned.
In addition, the dilution solvent contained in a composition (y) may be used independently, and may use 2 or more types together.
 組成物(y)が希釈溶媒を含有して溶液の形態である場合、組成物(y)の有効成分濃度としては、それぞれ独立に、好ましくは0.1~60質量%、より好ましくは0.5~50質量%、更に好ましくは1.0~40質量%である。 When the composition (y) is in the form of a solution containing a diluting solvent, the active ingredient concentration of the composition (y) is preferably independently 0.1 to 60% by mass, more preferably 0. It is 5 to 50% by mass, more preferably 1.0 to 40% by mass.
(組成物(y)から形成された基材層(Y)の物性)
 組成物(y)から形成された基材層(Y)の破断伸度としては、好ましくは100%以上、より好ましくは120%以上、更に好ましくは200%以上、より更に好ましくは350%以上であり、また、通常1000%以下である。
 また、組成物(y)から形成された基材層(Y)の破断強度は、好ましくは30MPa以上、より好ましくは60MPa以上であり、また、通常300MPa以下であり、好ましくは200MPa以下である。
 なお、上記の基材層(Y)の破断伸度及び破断強度は、両面粘着シートを製造する場合と同じ塗布量及び乾燥条件にて、組成物(y)からなる塗膜(y’)から形成した基材層(Y)を測定対象としたものである。具体的な測定方法については、実施例に記載のとおりである。
(Physical properties of the base material layer (Y) formed from the composition (y))
The elongation at break of the base material layer (Y) formed from the composition (y) is preferably 100% or more, more preferably 120% or more, still more preferably 200% or more, and still more preferably 350% or more. In addition, it is usually 1000% or less.
The breaking strength of the base material layer (Y) formed from the composition (y) is preferably 30 MPa or more, more preferably 60 MPa or more, and usually 300 MPa or less, preferably 200 MPa or less.
In addition, the breaking elongation and breaking strength of said base material layer (Y) are from the coating film (y ') which consists of a composition (y) on the same application quantity and drying conditions as the case where a double-sided adhesive sheet is manufactured. The formed base material layer (Y) is the object to be measured. The specific measurement method is as described in the examples.
<積層体の物性>
 本発明の一態様の両面粘着シートが有する積層体の厚さとしては、好ましくは2~90μm、より好ましくは4~75μm、更に好ましくは6~60μm、より更に好ましくは8~45μmである。
<Physical properties of the laminate>
The thickness of the laminate of the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention is preferably 2 to 90 μm, more preferably 4 to 75 μm, still more preferably 6 to 60 μm, and still more preferably 8 to 45 μm.
 第1粘着剤層(X1)及び第2粘着剤層(X2)のそれぞれの厚さは、それそれ独立に、好ましくは0.5~50μm、より好ましくは1~40μm、更に好ましくは2~30μm、より更に好ましくは3~20μmである。 The thicknesses of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) are each independently preferably 0.5 to 50 μm, more preferably 1 to 40 μm, still more preferably 2 to 30 μm. More preferably, the thickness is 3 to 20 μm.
 基材層(Y)の厚さは、好ましくは0.3~50.0μm、より好ましくは0.5~30.0μm、更に好ましくは0.7~15.0μm、より更に好ましくは1.0~8.0μmである。 The thickness of the base material layer (Y) is preferably 0.3 to 50.0 μm, more preferably 0.5 to 30.0 μm, still more preferably 0.7 to 15.0 μm, and still more preferably 1.0. -8.0 μm.
 本明細書において、積層体の厚さはJIS K6783、Z1702、Z1709に準拠した定圧厚さ測定器を用いて測定された値であって、具体的には実施例に記載の方法に基づいて測定された値を意味する。
 また、積層体を構成する各層の厚さは、上述の積層体の厚さと同じ方法で測定してもよく、また、例えば、積層体を厚さ方向に切断した断面を走査型電子顕微鏡で観察して、各層の厚さの比をそれぞれ測定し、上述の方法で測定した積層体の厚さから算出してもよい。
In the present specification, the thickness of the laminate is a value measured using a constant pressure thickness measuring instrument based on JIS K6783, Z1702, and Z1709, and specifically measured based on the method described in the examples. Means the value.
In addition, the thickness of each layer constituting the laminate may be measured by the same method as the thickness of the laminate described above. For example, a cross section of the laminate cut in the thickness direction is observed with a scanning electron microscope. Then, the ratio of the thicknesses of the respective layers may be measured and calculated from the thickness of the laminate measured by the method described above.
 本発明の一態様の両面粘着シートにおいて、第1粘着剤層(X1)及び第2粘着剤層(X2)の合計厚さ100に対する、基材層(Y)の厚さ比としては、好ましくは1~100、より好ましくは3~90、更に好ましくは4~70、より更に好ましくは7~50、より更に好ましくは10~30、特に好ましくは11~22である。 In the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention, the thickness ratio of the base material layer (Y) to the total thickness 100 of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) is preferably It is 1 to 100, more preferably 3 to 90, still more preferably 4 to 70, still more preferably 7 to 50, still more preferably 10 to 30, and particularly preferably 11 to 22.
 第1粘着剤層(X1)の厚さと第2粘着剤層(X2)の厚さとの比〔X1/X2〕は、好ましくは10/90~90/10、より好ましくは20/80~80/20、更に好ましくは30/70~70/30、より更に好ましくは40/60~60/40である。 The ratio [X1 / X2] of the thickness of the first pressure-sensitive adhesive layer (X1) to the thickness of the second pressure-sensitive adhesive layer (X2) is preferably 10/90 to 90/10, more preferably 20/80 to 80 / 20, more preferably 30/70 to 70/30, still more preferably 40/60 to 60/40.
 本発明の一態様の両面粘着シートが有する前記積層体のヘーズは、好ましくは5.00%以下、より好ましくは4.00%以下、更に好ましくは3.00%以下、より更に好ましくは2.00%以下、特に好ましくは1.00%以下である。
 本明細書において、ヘーズは、JIS K 7136:2000に準拠して測定された値であり、具体的には、実施例に記載の方法により測定された値である。
The haze of the laminate of the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention is preferably 5.00% or less, more preferably 4.00% or less, still more preferably 3.00% or less, and still more preferably 2. 00% or less, particularly preferably 1.00% or less.
In the present specification, the haze is a value measured according to JIS K 7136: 2000, and specifically, a value measured by the method described in Examples.
 本発明の一態様の両面粘着シートが有する前記積層体の全光線透過率は、好ましくは80%以上、より好ましくは85%以上、更に好ましくは90%以上である。
 本明細書において、全光線透過率は、JIS K7361-1:1997に準拠して測定された値であり、具体的には、実施例に記載の方法により測定された値である。
The total light transmittance of the laminate which the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention has is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
In this specification, the total light transmittance is a value measured in accordance with JIS K7361-1: 1997, and specifically, a value measured by the method described in the examples.
 なお、本発明の両面粘着シートが有する前記積層体は、上述のとおり、塗膜の乾燥過程で2つの塗膜間で混層が生じ、第1粘着剤層(X1)と基材層(Y)との界面、及び、基材層(Y)と第2粘着剤層(X2)との界面が、消失する程に不明瞭となる傾向にある。
 そのため、各層の形成材料の違いによる屈折率差に起因した光散乱が生じ難く、その結果として、前記積層体は、ヘーズは低く、全光線透過率は高いものになり易い。
In addition, as for the said laminated body which the double-sided adhesive sheet of this invention has as above-mentioned, a mixed layer arises between two coating films in the drying process of a coating film, and a 1st adhesive layer (X1) and a base material layer (Y) And the interface between the base material layer (Y) and the second pressure-sensitive adhesive layer (X2) tend to be unclear enough to disappear.
Therefore, light scattering due to the difference in refractive index due to the difference in the formation material of each layer hardly occurs, and as a result, the laminate is likely to have a low haze and a high total light transmittance.
 本発明の一態様の両面粘着シートの第1粘着剤層(X1)及び第2粘着剤層(X2)のそれぞれの貼付表面における粘着力としては、それぞれ独立に、好ましくは3.0N/25mm以上、より好ましくは5.0N/25mm以上、より好ましくは7.0N/25mm以上、更に好ましくは10.0N/25mm以上、より更に好ましくは18.0N/25mm以上である。
 なお、上記の粘着力の値は、実施例に記載の方法により測定された値を意味する。
As the adhesive force on the respective adhesive surfaces of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) of the double-sided pressure-sensitive adhesive sheet of one aspect of the present invention, each independently, preferably 3.0 N / 25 mm or more More preferably, it is 5.0 N / 25 mm or more, More preferably, it is 7.0 N / 25 mm or more, More preferably, it is 10.0 N / 25 mm or more, More preferably, it is 18.0 N / 25 mm or more.
In addition, the value of said adhesive force means the value measured by the method as described in an Example.
〔剥離材〕
 本発明の一態様の両面粘着シートは、粘着剤層の貼付表面に、さらに剥離材を有していてもよい。
 なお、積層体を挟持する2枚の剥離材は、剥離力の差が異なるように調整されたものであることが好ましい。
 剥離材としては、両面剥離処理をされた剥離シートや、片面剥離処理された剥離シート等が用いられ、剥離材用の基材上に剥離剤を塗布したもの等が挙げられる。
[Release material]
The double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention may further have a release material on the sticking surface of the pressure-sensitive adhesive layer.
In addition, it is preferable that the two peeling materials which hold | pick a laminated body are adjusted so that the difference in peeling force may differ.
As the release material, a release sheet that has been subjected to a double-sided release process, a release sheet that has been subjected to a single-sided release process, or the like is used. Examples include a release material coated on a release material substrate.
 剥離材用基材としては、例えば、上質紙、グラシン紙、クラフト紙等の紙類;ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂等のポリエステル樹脂フィルム、ポリプロピレン樹脂、ポリエチレン樹脂等のオレフィン樹脂フィルム等のプラスチックフィルム;等が挙げられる。 Examples of the base material for the release material include papers such as high-quality paper, glassine paper, and kraft paper; polyester resin films such as polyethylene terephthalate resin, polybutylene terephthalate resin, and polyethylene naphthalate resin; and olefins such as polypropylene resin and polyethylene resin. A plastic film such as a resin film;
 剥離剤としては、例えば、シリコーン系樹脂、オレフィン系樹脂、イソプレン系樹脂、ブタジエン系樹脂等のゴム系エラストマー、長鎖アルキル系樹脂、アルキド系樹脂、フッ素系樹脂等が挙げられる。 Examples of the release agent include silicone-based resins, olefin-based resins, isoprene-based resins, rubber-based elastomers such as butadiene-based resins, long-chain alkyl-based resins, alkyd-based resins, and fluorine-based resins.
 剥離材の厚さは、特に制限ないが、好ましくは10~200μm、より好ましくは25~170μm、更に好ましくは35~80μmである。 The thickness of the release material is not particularly limited, but is preferably 10 to 200 μm, more preferably 25 to 170 μm, and still more preferably 35 to 80 μm.
〔両面粘着シートの製造方法〕
 本発明の両面粘着シートの製造方法としては、下記工程(1)~(2)を有する方法であることが好ましい。
・工程(1):組成物(x1)からなる塗膜(x1’)と、組成物(y)からなる塗膜(y’)と、組成物(x2)からなる塗膜(x2’)とをこの順で直接積層して形成する工程。
・工程(2):塗膜(x1’)、塗膜(y’)、及び塗膜(x2’)を同時に乾燥させて前記積層体を形成する工程。
 以下、各工程について説明する。
[Method for producing double-sided PSA sheet]
The method for producing the double-sided PSA sheet of the present invention is preferably a method having the following steps (1) to (2).
Step (1): a coating film (x1 ′) composed of the composition (x1), a coating film (y ′) composed of the composition (y), and a coating film (x2 ′) composed of the composition (x2) A process of directly stacking layers in this order.
-Process (2): The process of drying a coating film (x1 '), a coating film (y'), and a coating film (x2 ') simultaneously, and forming the said laminated body.
Hereinafter, each step will be described.
<工程(1)>
 工程(1)において、塗膜(x1’)、塗膜(y’)、及び塗膜(x2’)の形成方法としては、例えば、塗膜(x1’)を形成した後、塗膜(x1’)上に塗膜(y’)を形成し、さらに塗膜(y’)上に塗膜(x2’)を形成するといった逐次形成する方法でもよいが、生産性の観点から、塗膜(x1’)、(y’)、及び(x2’)を同時に塗布する方法が好ましい。
 なお、取扱性の観点から、塗膜(x1’)は、剥離材の剥離処理面上に形成することが好ましい。
<Step (1)>
In the step (1), as a method for forming the coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′), for example, after forming the coating film (x1 ′), the coating film (x1 A sequential formation method may be used in which a coating film (y ') is formed on') and a coating film (x2 ') is further formed on the coating film (y'). From the viewpoint of productivity, the coating film ( A method in which x1 ′), (y ′), and (x2 ′) are simultaneously applied is preferable.
In addition, from the viewpoint of handleability, the coating film (x1 ′) is preferably formed on the release treatment surface of the release material.
 逐次形成する際に用いるコーターとしては、例えば、スピンコーター、スプレーコーター、バーコーター、ナイフコーター、ロールコーター、ナイフロールコーター、ブレードコーター、グラビアコーター、カーテンコーター、ダイコーター等が挙げられる。 Examples of the coater used for sequential formation include a spin coater, a spray coater, a bar coater, a knife coater, a roll coater, a knife roll coater, a blade coater, a gravure coater, a curtain coater, and a die coater.
 同時に塗布する際に用いるコーターとしては、多層コーターが挙げられ、具体的には、カーテンコーター、ダイコーター等が挙げられる。これらの中でも、操作性の観点から、ダイコーターが好ましい。 As the coater used for simultaneous application, a multilayer coater can be mentioned, and specifically, a curtain coater, a die coater and the like can be mentioned. Among these, a die coater is preferable from the viewpoint of operability.
 なお、各塗膜を形成し易くし、生産性を向上させる観点から、組成物(x1)、組成物(y)、及び組成物(x2)は、さらに希釈溶媒を含有することが好ましい。
 希釈溶媒としては、水や上述の有機溶媒が使用できる。
 また、各組成物に希釈溶媒を配合して得られる溶液の有効成分濃度は、上述のとおりである。
In addition, it is preferable that a composition (x1), a composition (y), and a composition (x2) contain a dilution solvent further from a viewpoint of making each coating film easy to form and improving productivity.
As a dilution solvent, water or the above-mentioned organic solvent can be used.
Moreover, the active ingredient density | concentration of the solution obtained by mix | blending a dilution solvent with each composition is as above-mentioned.
 塗膜(x1’)及び塗膜(x2’)の塗布量は、それぞれ独立に、好ましくは0.5~50.0g/m、より好ましくは1.0~40.0g/m、更に好ましくは2.0~30.0g/m、より更に好ましくは3.0~20.0g/mである。 The coating amount of the coating film (x1 ') and film (x2') are each independently preferably 0.5 ~ 50.0g / m 2, more preferably 1.0 ~ 40.0g / m 2, further It is preferably 2.0 to 30.0 g / m 2 , and more preferably 3.0 to 20.0 g / m 2 .
 塗膜(y’)の塗布量は、好ましくは0.3~50.0g/m、より好ましくは0.5~30.0g/m、更に好ましくは0.7~15.0g/m、より更に好ましくは1.0~8.0g/mである。 The coating amount of the coating film (y ′) is preferably 0.3 to 50.0 g / m 2 , more preferably 0.5 to 30.0 g / m 2 , still more preferably 0.7 to 15.0 g / m. 2 and more preferably 1.0 to 8.0 g / m 2 .
 塗膜(x1’)及び塗膜(x2’)の合計塗布量100に対する、塗膜(y’)の塗布量の比としては、好ましくは1~100、より好ましくは4~70、更に好ましくは7~50、特に好ましくは10~30である。 The ratio of the coating amount of the coating film (y ′) to the total coating amount 100 of the coating film (x1 ′) and the coating film (x2 ′) is preferably 1 to 100, more preferably 4 to 70, still more preferably. It is 7 to 50, particularly preferably 10 to 30.
 なお、本工程(1)において、塗膜(x1’)、塗膜(y’)、及び塗膜(x2’)の1層以上の塗膜を形成後に、工程(2)の前に、当該塗膜の硬化反応が進行しない程度のプレ乾燥処理を施してもよい。
 例えば、塗膜(x1’)、塗膜(y’)、及び塗膜(x2’)の各塗膜の形成ごとに、その都度プレ乾燥処理を行ってもよく、塗膜(x1’)及び塗膜(y’)の2層の塗膜を形成後に、まとめてプレ乾燥処理を行った後、塗膜(x2’)を形成してもよい。
 本工程(1)における、プレ乾燥処理を行う際の乾燥温度としては、通常は、形成した塗膜の硬化が進行しない程度の温度範囲で適宜設定されるが、好ましくは工程(2)での乾燥温度未満である。
 「工程(2)での乾燥温度未満」との規定が示す具体的な乾燥温度としては、好ましくは10~45℃、より好ましくは10~34℃、更に好ましくは15~30℃である。
In addition, in this process (1), after forming the coating film of 1 layer or more of a coating film (x1 '), a coating film (y'), and a coating film (x2 '), before the process (2), You may perform the predrying process of the grade which does not advance the hardening reaction of a coating film.
For example, a pre-drying treatment may be performed each time a coating film (x1 ′), a coating film (y ′), and a coating film (x2 ′) are formed. After forming the two-layer coating film of the coating film (y ′), the coating film (x2 ′) may be formed after performing a pre-drying treatment collectively.
In this step (1), the drying temperature at the time of performing the pre-drying treatment is usually appropriately set within a temperature range in which the formed coating film does not cure, but preferably in the step (2). Below the drying temperature.
The specific drying temperature indicated by the phrase “below the drying temperature in step (2)” is preferably 10 to 45 ° C., more preferably 10 to 34 ° C., and further preferably 15 to 30 ° C.
<工程(2)>
 工程(2)において、塗膜(x1’)、塗膜(y’)、及び塗膜(x2’)を同時に乾燥させて前記積層体を形成する。
 この乾燥過程において、塗膜(x1’)と塗膜(y’)との界面、及び、塗膜(y’)と塗膜(x2’)との界面で、混層が生じ、粘着性樹脂と非粘着性樹脂との絡み合う状態で乾燥して硬化することで、第1粘着剤層(X1)と基材層(Y)、及び、基材層(Y)と第2粘着剤層(X2)の界面密着性が格段に向上するものと考えられる。
<Step (2)>
In the step (2), the coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′) are simultaneously dried to form the laminate.
In this drying process, a mixed layer is formed at the interface between the coating film (x1 ′) and the coating film (y ′) and at the interface between the coating film (y ′) and the coating film (x2 ′). The first pressure-sensitive adhesive layer (X1) and the base material layer (Y), and the base material layer (Y) and the second pressure-sensitive adhesive layer (X2) are dried and cured in an intertwined state with the non-adhesive resin. It is considered that the interfacial adhesion of the material significantly improves.
 工程(2)における塗膜の乾燥温度としては、好ましくは60~150℃、より好ましくは70~145℃、更に好ましくは80~140℃、より更に好ましくは90~135℃である。 The drying temperature of the coating film in the step (2) is preferably 60 to 150 ° C, more preferably 70 to 145 ° C, still more preferably 80 to 140 ° C, and still more preferably 90 to 135 ° C.
<第1及び第2粘着剤層以外の粘着剤層を有する両面粘着シートの製造方法>
 本発明の一態様の両面粘着シートが、図1(d)に示す両面粘着シート4のように、第1及び第2粘着剤層以外の粘着剤層を備える構成である場合、第1及び第2粘着剤層以外の粘着剤層を、別に形成して、形成した積層体に貼付してなるものであってもよく、積層体の形成と同時に形成してもよい。
 例えば、図1(d)に示す両面粘着シート4が有する第3粘着剤層(X3)及び第4粘着剤層(X4)は、以下の(i)及び(ii)のいずれかによって形成することができる。
<The manufacturing method of the double-sided adhesive sheet which has adhesive layers other than a 1st and 2nd adhesive layer>
When the double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention has a configuration including pressure-sensitive adhesive layers other than the first and second pressure-sensitive adhesive layers, as in the double-sided pressure-sensitive adhesive sheet 4 shown in FIG. A pressure-sensitive adhesive layer other than the two pressure-sensitive adhesive layers may be separately formed and attached to the formed laminate, or may be formed simultaneously with the formation of the laminate.
For example, the third pressure-sensitive adhesive layer (X3) and the fourth pressure-sensitive adhesive layer (X4) included in the double-sided pressure-sensitive adhesive sheet 4 shown in FIG. 1 (d) are formed by any of the following (i) and (ii). Can do.
・(i):剥離材131の剥離処理面上に、第3粘着剤層(X3)123を形成し、第3粘着剤層123の表出している表面に、塗膜(x1’)、(y’)、及び(x2’)を形成し、これらの塗膜を同時に乾燥して積層体10を形成した後、積層体10の第2粘着剤層(X2)122の貼付表面上に、第4粘着剤層(X4)124を積層する。
 なお、上記(i)において、第4粘着剤層(X4)は、第2粘着剤層(X2)の貼付表面上に第4粘着剤層(X4)の形成材料である組成物からなる塗膜を乾燥して形成してもよく、別途用意した剥離材の剥離処理面上に形成した第4粘着剤層(X4)を第2粘着剤層(X2)の貼付表面上に貼付して形成してもよい。
(I): The third pressure-sensitive adhesive layer (X3) 123 is formed on the release treatment surface of the release material 131, and the coating film (x1 ′), ( y ′) and (x2 ′) are formed, and these coating films are dried at the same time to form the laminate 10. Then, the second adhesive layer (X2) 122 of the laminate 10 has a Four adhesive layers (X4) 124 are laminated.
In addition, in said (i), the 4th adhesive layer (X4) is a coating film which consists of a composition which is a formation material of a 4th adhesive layer (X4) on the sticking surface of a 2nd adhesive layer (X2). May be formed by drying, and a fourth pressure-sensitive adhesive layer (X4) formed on a release-treated surface of a separate release material is applied to the surface of the second pressure-sensitive adhesive layer (X2). May be.
・方法(ii):剥離材131の剥離処理面上に、第3粘着剤層(X3)123の形成材料である組成物からなる塗膜(x3’)、塗膜(x1’)、塗膜(y’)、塗膜(x2’)、及び第4粘着剤層(X4)124の形成材料である組成物からなる塗膜(x4’)をこの順で塗布し、これらの塗膜を同時に乾燥して、積層体10の形成と同時に、第3粘着剤層(X3)123及び第4粘着剤層(X4)124を形成する。
 なお、上記(ii)において、第4粘着剤層(X4)は、積層体10を形成した後、積層体10の第2粘着剤層(X2)122の貼付表面上に、第4粘着剤層(X4)の形成材料である組成物からなる塗膜を乾燥して形成してもよく、別途用意した剥離材の剥離処理面上に形成した第4粘着剤層(X4)を、第2粘着剤層(X2)の貼付表面上に貼付して形成してもよい。
 また、少なくとも、塗膜(x3’)、塗膜(x1’)、塗膜(y’)及び塗膜(x2’)を同時に乾燥する場合、塗膜(x3’)を形成した組成物と、塗膜(x1’)を形成した組成物(x1)とは、互いに異なるものである。
 同様に、少なくとも、塗膜(x1’)、塗膜(y’)、塗膜(x2’)及び塗膜(x4’)を同時に乾燥する場合についても、塗膜(x4’)を形成した組成物と、塗膜(x2’)を形成した組成物(x2)とは、互いに異なるものである。
Method (ii): A coating film (x3 ′), a coating film (x1 ′), and a coating film made of a composition that is a material for forming the third pressure-sensitive adhesive layer (X3) 123 on the release treatment surface of the release material 131 (Y '), a coating film (x2'), and a coating film (x4 ') composed of a composition that is a forming material of the fourth pressure-sensitive adhesive layer (X4) 124 is applied in this order, and these coating films are simultaneously applied. It dries and forms the 3rd adhesive layer (X3) 123 and the 4th adhesive layer (X4) 124 simultaneously with formation of the laminated body 10. FIG.
In addition, in said (ii), after forming the laminated body 10, a 4th adhesive layer (X4) is the 4th adhesive layer on the sticking surface of the 2nd adhesive layer (X2) 122 of the laminated body 10. The coating film made of the composition which is the forming material of (X4) may be formed by drying, and the fourth pressure-sensitive adhesive layer (X4) formed on the release-treated surface of the release material prepared separately is used as the second pressure-sensitive adhesive. You may affix and form on the sticking surface of an agent layer (X2).
Further, at least when the coating film (x3 ′), the coating film (x1 ′), the coating film (y ′), and the coating film (x2 ′) are simultaneously dried, The composition (x1) on which the coating film (x1 ′) is formed is different from each other.
Similarly, at least when the coating film (x1 ′), the coating film (y ′), the coating film (x2 ′), and the coating film (x4 ′) are simultaneously dried, the composition in which the coating film (x4 ′) is formed. The product and the composition (x2) on which the coating film (x2 ′) is formed are different from each other.
 本発明について、以下の実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、以下の製造例及び実施例における物性値は、以下の方法により測定した値である。 The present invention will be specifically described with reference to the following examples, but the present invention is not limited to the following examples. In addition, the physical-property value in the following manufacture examples and Examples is a value measured by the following method.
<質量平均分子量(Mw)>
 ゲル浸透クロマトグラフ装置(東ソー株式会社製、製品名「HLC-8020」)を用いて、下記の条件下で測定し、標準ポリスチレン換算にて測定した値を用いた。
(測定条件)
・カラム:「TSK guard column HXL-L」「TSK gel G2500HXL」「TSK gel G2000HXL」「TSK gel G1000HXL」(いずれも東ソー株式会社製)を順次連結したもの
・カラム温度:40℃
・展開溶媒:テトラヒドロフラン
・流速:1.0mL/min
<Mass average molecular weight (Mw)>
Using a gel permeation chromatograph (product name “HLC-8020” manufactured by Tosoh Corporation), measurement was performed under the following conditions, and values measured in terms of standard polystyrene were used.
(Measurement condition)
Column: “TSK guard column HXL-L”, “TSK gel G2500HXL”, “TSK gel G2000HXL”, and “TSK gel G1000HXL” (both manufactured by Tosoh Corporation) Column temperature: 40 ° C.
・ Developing solvent: Tetrahydrofuran ・ Flow rate: 1.0 mL / min
<積層体の厚さの測定>
 株式会社テクロック製の定圧厚さ測定器(型番:「PG-02J」、標準規格:JIS K6783、Z1702、Z1709に準拠)を用いて測定した。
 具体的には、測定対象の両面粘着シートの総厚を測定した上で、予め測定した剥離材の厚みを差し引いた値を「積層体の厚さ」とした。
<Measurement of laminate thickness>
It was measured using a constant pressure thickness measuring instrument (model number: “PG-02J”, standard: conforming to JIS K6783, Z1702, Z1709) manufactured by Teclock Co., Ltd.
Specifically, after measuring the total thickness of the double-sided pressure-sensitive adhesive sheet to be measured, the value obtained by subtracting the thickness of the release material measured in advance was defined as the “thickness of the laminate”.
<各層の厚さの測定>
 走査型電子顕微鏡(日立製作所株式会社製、製品名「S-4700」)を用いて、積層体の厚さ方向における断面を観察し、積層体の厚さに対する、第1粘着剤層(X1)、基材層(Y)及び第2粘着剤層(X2)のそれぞれの厚さ比を測定した。
 そして、各層の厚さ比に基づき、上述の方法により測定した「積層体の厚さ」の実測値から、各層の厚さを算出した。
<Measurement of thickness of each layer>
Using a scanning electron microscope (product name “S-4700”, manufactured by Hitachi, Ltd.), a cross section in the thickness direction of the laminate was observed, and the first pressure-sensitive adhesive layer (X1) with respect to the thickness of the laminate The thickness ratio of each of the base material layer (Y) and the second pressure-sensitive adhesive layer (X2) was measured.
And based on the thickness ratio of each layer, the thickness of each layer was computed from the actual value of the "thickness of a laminated body" measured by the above-mentioned method.
製造例1
(組成物(x-1)の調製)
 粘着性樹脂である、アクリル系共重合体(n-ブチルアクリレート(BA)/アクリル酸(AAc)=98.0/2.0(質量比)からなる原料モノマーに由来の構成単位を有するアクリル系共重合体、質量平均分子量:100万、希釈溶媒:酢酸エチル、固形分濃度:15質量%)100質量部(固形分比)に、粘着付与剤として、ロジン系樹脂(ハリマ化成株式会社製、製品名「ハリエスターTF」、軟化点:75~85℃)50質量部(固形分比)、及び、架橋剤として、イソシアネート系架橋剤(東ソー株式会社製、製品名「コロネートL」、固形分濃度:75質量%)1.5質量部(固形分比)を配合して混合し、さらにトルエンにて希釈し、均一に撹拌して、固形分濃度(有効成分濃度)30質量%の組成物(x-1)を調製した。
Production Example 1
(Preparation of composition (x-1))
An acrylic resin having a structural unit derived from a raw material monomer consisting of an acrylic copolymer (n-butyl acrylate (BA) / acrylic acid (AAc) = 98.0 / 2.0 (mass ratio)) which is an adhesive resin Copolymer, mass average molecular weight: 1 million, dilution solvent: ethyl acetate, solid content concentration: 15% by mass) 100 parts by mass (solid content ratio), as a tackifier, rosin resin (manufactured by Harima Chemical Co., Ltd., Product name “Harry Star TF”, softening point: 75 to 85 ° C. 50 parts by mass (solid content ratio), and as crosslinking agent, isocyanate-based crosslinking agent (product name “Coronate L”, manufactured by Tosoh Corporation), solid content Concentration: 75% by mass) 1.5 parts by mass (solid content ratio) mixed and mixed, further diluted with toluene, stirred uniformly, and a solid content concentration (active ingredient concentration) of 30% by mass Prepare (x-1) .
製造例2
(組成物(y-1)の調製)
 非粘着性樹脂である、酸変性オレフィン系樹脂の溶液(三菱化学株式会社製、製品名「ユニストールH-200」、質量平均分子量:14.5万、ガラス転移温度:-53℃、希釈溶媒:メチルシクロヘキサンとメチルエチルケトンの混合溶媒、固形分濃度(有効成分濃度):20質量%)を組成物(y-1)として用いた。
Production Example 2
(Preparation of composition (y-1))
Non-adhesive resin, acid-modified olefin resin solution (Mitsubishi Chemical Co., Ltd., product name “Unistal H-200”, mass average molecular weight: 145,000, glass transition temperature: −53 ° C., dilution solvent : Mixed solvent of methylcyclohexane and methyl ethyl ketone, solid content concentration (active ingredient concentration): 20% by mass) was used as the composition (y-1).
製造例3
(組成物(y-2)の調製)
(1)ウレタンプレポリマーの合成
 窒素雰囲気下の反応容器内に、質量平均分子量1,000のポリカーボネートジオール100質量部(固形分比)に対して、イソホロンジイソシアネートを、ポリカーボネートジオールの水酸基とイソホロンジイソシアネートのイソシアネート基との当量比が1/1となるように配合し、さらにトルエン160質量部を加え、窒素雰囲気下にて、撹拌しながら、イソシアネート基濃度が理論量に到達するまで、80℃で6時間以上反応させた。
 次いで、2-ヒドロキシエチルメタクリレート(2-HEMA)1.44質量部(固形分比)をトルエン30質量部に希釈した溶液を添加して、両末端のイソシアネート基が消滅するまで、更に80℃で6時間反応させ、質量平均分子量2.9万のウレタンプレポリマー(UY)を得た。
(2)アクリルウレタン系樹脂の合成
 窒素雰囲気下の反応容器内に、上記(1)で得たウレタンプレポリマー100質量部(固形分比)、メチルメタクリレート(MMA)117質量部(固形分比)、2-ヒドロキシエチルメタクリレート(2-HEMA)5.1質量部(固形分比)、1-チオグリセロール1.1質量部(固形分比)、及びトルエン50質量部を加え、撹拌しながら、105℃まで昇温した。
 そして、反応容器内に、さらにラジカル開始剤(株式会社日本ファインケム製、製品名「ABN-E」)2.2質量部(固形分比)をトルエン210質量部で希釈した溶液を、105℃に維持したまま4時間かけて滴下した。
 滴下終了後、105℃で6時間反応させ、質量平均分子量10.5万のアクリルウレタン系樹脂の溶液を得た。
(3)組成物(y-2)の調製
 非粘着性樹脂である、上記(2)で得たアクリルウレタン系樹脂の溶液100質量部(固形分比)に、架橋剤として、イソシアネート系架橋剤(東ソー株式会社製、製品名「コロネートHL」)6.3質量部(固形分比)、及び、触媒として、ジオクチルスズビス(2-エチルヘキサノエート)1.4質量部(固形分比)を配合して混合し、さらにトルエンにて希釈し、均一に撹拌して、固形分濃度(有効成分濃度)30質量%の組成物(y-2)を調製した。
Production Example 3
(Preparation of composition (y-2))
(1) Synthesis of urethane prepolymer In a reaction vessel under a nitrogen atmosphere, isophorone diisocyanate is mixed with the hydroxyl group of polycarbonate diol and isophorone diisocyanate with respect to 100 parts by mass (solid content ratio) of polycarbonate diol having a mass average molecular weight of 1,000. It mix | blends so that the equivalent ratio with an isocyanate group may be set to 1/1, Furthermore, 160 mass parts of toluene is added, and it stirs in nitrogen atmosphere, and it is 6 degreeC at 80 degreeC until an isocyanate group density | concentration reaches | attains theoretical amount. The reaction was continued for more than an hour.
Subsequently, a solution obtained by diluting 1.44 parts by mass (solid content ratio) of 2-hydroxyethyl methacrylate (2-HEMA) in 30 parts by mass of toluene is added, and further at 80 ° C. until the isocyanate groups at both ends disappear. The reaction was performed for 6 hours to obtain a urethane prepolymer (UY) having a mass average molecular weight of 29,000.
(2) Synthesis of acrylic urethane-based resin In a reaction vessel under nitrogen atmosphere, 100 parts by mass (solid content ratio) of urethane prepolymer obtained in (1) above and 117 parts by mass (solid content ratio) of methyl methacrylate (MMA) 2-hydroxyethyl methacrylate (2-HEMA) 5.1 parts by mass (solid content ratio), 1-thioglycerol 1.1 parts by mass (solid content ratio), and toluene 50 parts by mass, The temperature was raised to ° C.
Further, a solution obtained by further diluting 2.2 parts by mass (solid content ratio) of radical initiator (manufactured by Nippon Finechem Co., Ltd., product name “ABN-E”) with 210 parts by mass of toluene in a reaction vessel was heated to 105 ° C. It was dripped over 4 hours, maintaining.
After completion of the dropping, the reaction was carried out at 105 ° C. for 6 hours to obtain a solution of an acrylic urethane resin having a mass average molecular weight of 105,000.
(3) Preparation of composition (y-2) An isocyanate-based crosslinking agent as a crosslinking agent was added to 100 parts by mass (solid content ratio) of the acrylic urethane-based resin solution obtained in (2) above, which is a non-adhesive resin. (Product name “Coronate HL” manufactured by Tosoh Corporation) 6.3 parts by mass (solid content ratio), and 1.4 parts by mass (solid content ratio) of dioctyltin bis (2-ethylhexanoate) as a catalyst Were mixed, further diluted with toluene, and stirred uniformly to prepare a composition (y-2) having a solid content concentration (active ingredient concentration) of 30% by mass.
製造例4
(組成物(y-3)の調整)
 粘着性樹脂である、アクリル系共重合体(n-ブチルアクリレート(BA)/アクリル酸(AAc)=90/10(質量比)からなる原料モノマーに由来の構成単位を有するアクリル系共重合体、質量平均分子量:46万)を、酢酸エチルとトルエンの混合溶媒で希釈し、固形分濃度(有効成分濃度)30質量%の組成物(y-3)を調製した。
Production Example 4
(Adjustment of composition (y-3))
An acrylic copolymer having a structural unit derived from a raw material monomer consisting of an acrylic copolymer (n-butyl acrylate (BA) / acrylic acid (AAc) = 90/10 (mass ratio), which is an adhesive resin, (Mass average molecular weight: 460,000) was diluted with a mixed solvent of ethyl acetate and toluene to prepare a composition (y-3) having a solid content concentration (active ingredient concentration) of 30% by mass.
 以下の実施例及び比較例で使用した、剥離フィルム及び基材フィルムの詳細を以下に示す。
・剥離フィルム(1):リンテック株式会社製、製品名「SP-PET382150」、ポリエチレンテレフタレート(PET)フィルムの片面に、シリコーン系剥離剤から形成した剥離剤層を設けたもの、厚さ:38μm。
・剥離フィルム(2):リンテック株式会社製、製品名「SP-PET381031」、PETフィルムの片面に、シリコーン系剥離剤から形成した剥離剤層を設けたもの、厚さ:38μm。
・基材フィルム(1):三菱樹脂株式会社製、製品名「ダイアホイルK-700-6E」、二軸延伸PETフィルム、厚さ:6.0μm。
・基材フィルム(2):三菱樹脂株式会社製、製品名「ダイアホイルK100-2.0W」、二軸延伸PETフィルム、厚さ:2.0μm。
Details of the release film and the base film used in the following Examples and Comparative Examples are shown below.
Release film (1): manufactured by Lintec Corporation, product name “SP-PET 382150”, polyethylene terephthalate (PET) film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 μm.
Release film (2): manufactured by Lintec Co., Ltd., product name “SP-PET381031”, a PET film provided with a release agent layer formed from a silicone release agent on one side, thickness: 38 μm.
Base film (1): manufactured by Mitsubishi Plastics, product name “Diafoil K-700-6E”, biaxially oriented PET film, thickness: 6.0 μm.
Base film (2): manufactured by Mitsubishi Plastics, product name “Diafoil K100-2.0W”, biaxially stretched PET film, thickness: 2.0 μm.
実施例1~3、比較例1
(1)塗膜の形成
 第1剥離材である剥離フィルム(1)の剥離剤層上に、製造例1で調製した組成物(x-1)、表1に記載の種類の組成物、及び、製造例1で調製した組成物(x-1)をこの順で、多層ダイコーター(幅:250mm)を用いて、塗布速度30m/分で同時塗布し、塗膜(x1’)、塗膜(y’)及び塗膜(x2’)をこの順で同時に形成した。
 なお、塗膜(x1’)、塗膜(y’)及び塗膜(x2’)を形成するための組成物の塗布量は、表1に記載のとおりである。
(2)乾燥処理
 形成した塗膜(x1’)、塗膜(y’)及び塗膜(x2’)を、乾燥温度125℃で60秒間、同時に乾燥させ、剥離フィルム(1)の剥離剤層から順に、層(X1)、層(Y)及び層(X2)を直接積層した積層体を形成した。
 そして、表出している層(X2)の表面上に、第2剥離材である剥離フィルム(2)の剥離剤層を積層させ、両面粘着シートを得た。
Examples 1 to 3, Comparative Example 1
(1) Formation of coating film On the release agent layer of the release film (1) as the first release material, the composition (x-1) prepared in Production Example 1, the type of composition described in Table 1, and The composition (x-1) prepared in Production Example 1 was simultaneously applied in this order using a multilayer die coater (width: 250 mm) at a coating speed of 30 m / min. (Y ′) and the coating film (x2 ′) were simultaneously formed in this order.
In addition, the application quantity of the composition for forming a coating film (x1 '), a coating film (y'), and a coating film (x2 ') is as having described in Table 1.
(2) Drying treatment The formed coating film (x1 ′), coating film (y ′), and coating film (x2 ′) are simultaneously dried at a drying temperature of 125 ° C. for 60 seconds to form a release agent layer of the release film (1). In this order, a stacked body in which the layer (X1), the layer (Y), and the layer (X2) were directly stacked was formed.
And the release agent layer of the peeling film (2) which is a 2nd peeling material was laminated | stacked on the surface of the layer (X2) which has exposed, and the double-sided adhesive sheet was obtained.
実施例4
(1)塗膜の形成
 第1剥離材である剥離フィルム(1)の剥離剤層上に、アプリケータを用いて、製造例1で調製した組成物(x-1)からなる塗膜(x1’)を形成し、塗膜(x1’)上に製造例3で調製した組成物(y-2)からなる塗膜(y’)、及び、塗膜(y’)上に製造例1で調製した組成物(x-1)を逐次形成した。
(2)乾燥処理
 形成した塗膜(x1’)、塗膜(y’)及び塗膜(x2’)を、乾燥温度110℃で120秒間、同時に乾燥させ、剥離フィルム(1)の剥離剤層から順に、層(X1)、層(Y)及び層(X2)を直接積層した積層体を形成した。なお、形成した層(X1)、層(Y)及び層(X2)の厚さは、表1に示すとおりであった。
 そして、表出している層(X2)の表面上に、第2剥離材である剥離フィルム(2)の剥離剤層を積層させ、両面粘着シートを得た。
Example 4
(1) Formation of coating film A coating film (x1) made of the composition (x-1) prepared in Production Example 1 using an applicator on the release agent layer of the release film (1) as the first release material ') And a coating film (y') comprising the composition (y-2) prepared in Production Example 3 on the coating film (x1 '), and Production Example 1 on the coating film (y'). The prepared composition (x-1) was sequentially formed.
(2) Drying treatment The formed coating film (x1 ′), coating film (y ′), and coating film (x2 ′) are simultaneously dried at a drying temperature of 110 ° C. for 120 seconds to form a release agent layer of the release film (1). In this order, a stacked body in which the layer (X1), the layer (Y), and the layer (X2) were directly stacked was formed. In addition, the thickness of the formed layer (X1), layer (Y), and layer (X2) was as shown in Table 1.
And the release agent layer of the peeling film (2) which is a 2nd peeling material was laminated | stacked on the surface of the layer (X2) which has exposed, and the double-sided adhesive sheet was obtained.
比較例2
 第1剥離材である剥離フィルム(1)の剥離剤層上に、製造例1で調製した組成物(x-1)からなる塗膜(x1’)を形成し、110℃で120秒間乾燥させ、層(X1)のみを形成した。なお、形成した層(X1)の厚さは、表1に示すとおりであった。
 そして、表出している層(X1)の表面上に、第2剥離材である剥離フィルム(2)の剥離剤層を積層させ、両面粘着シートを得た。
Comparative Example 2
On the release agent layer of the release film (1) as the first release material, a coating film (x1 ′) made of the composition (x-1) prepared in Production Example 1 is formed and dried at 110 ° C. for 120 seconds. Only the layer (X1) was formed. In addition, the thickness of the formed layer (X1) was as shown in Table 1.
And the release agent layer of the peeling film (2) which is a 2nd peeling material was laminated | stacked on the surface of the layer (X1) exposed, and the double-sided adhesive sheet was obtained.
比較例3~4
 第1剥離材である剥離フィルム(1)の剥離剤層上に、製造例1で調製した組成物(x-1)からなる塗膜(x1’)を形成し、110℃で120秒間乾燥させ、層(X1)を形成した。
 また、別途、第2剥離材である剥離フィルム(2)の剥離剤層上に、製造例1で調製した組成物(x-1)からなる塗膜(x2’)を形成し、110℃で120秒間乾燥させ、層(X2)を形成した。
 なお、形成した層(X1)及び層(X2)の厚さは、表1に示すとおりであった。
 そして、表出している層(X1)の表面上に、層(Y)として、比較例3では基材フィルム(1)を、比較例4では基材フィルム(2)を積層し、さらに基材フィルム上に、層(X2)を積層して積層体を形成し、当該積層体が2枚の剥離材で挟持された両面粘着シートを得た。
Comparative Examples 3-4
On the release agent layer of the release film (1) as the first release material, a coating film (x1 ′) made of the composition (x-1) prepared in Production Example 1 is formed and dried at 110 ° C. for 120 seconds. Layer (X1) was formed.
Separately, a coating film (x2 ′) composed of the composition (x-1) prepared in Production Example 1 was formed on the release agent layer of the release film (2), which is the second release material, at 110 ° C. It was dried for 120 seconds to form a layer (X2).
In addition, the thickness of the formed layer (X1) and layer (X2) was as shown in Table 1.
Then, on the surface of the exposed layer (X1), as the layer (Y), the base film (1) is laminated in Comparative Example 3, the base film (2) is laminated in Comparative Example 4, and the base material is further laminated. A layer (X2) was laminated on the film to form a laminate, and a double-sided PSA sheet was obtained in which the laminate was sandwiched between two release materials.
比較例5~6
 第1剥離材である剥離フィルム(1)の剥離剤層上に、製造例1で調製した組成物(x-1)からなる塗膜(x1’)を形成し、110℃で120秒間乾燥させ、層(X1)を形成した。
 また、別途、第2剥離材である剥離フィルム(2)の剥離剤層上に、製造例1で調製した組成物(x-1)からなる塗膜(x2’)を形成し、110℃で120秒間乾燥させ、層(X2)を形成した。
 さらに別に用意した剥離フィルム(2)の剥離剤層上に、比較例5では製造例2で調製した(y-1)を、比較例6では製造例3で調製した(y-2)を用いて、塗膜を形成し、110℃で120秒間乾燥させ、層(Y)を形成した。
 なお、形成した層(X1)、層(Y)及び層(X2)の厚さは、表1に示すとおりであった。
 そして、表出している層(X1)の表面上に、層(Y)を積層し、さらに層(Y)上の剥離フィルム(2)を除去し、表出した層(Y)の表面上に、層(X2)を積層して積層体を形成し、当該積層体が2枚の剥離材で挟持された両面粘着シートを得た。
Comparative Examples 5-6
On the release agent layer of the release film (1) as the first release material, a coating film (x1 ′) made of the composition (x-1) prepared in Production Example 1 is formed and dried at 110 ° C. for 120 seconds. Layer (X1) was formed.
Separately, a coating film (x2 ′) composed of the composition (x-1) prepared in Production Example 1 was formed on the release agent layer of the release film (2), which is the second release material, at 110 ° C. It was dried for 120 seconds to form a layer (X2).
Furthermore, on the release agent layer of the release film (2) prepared separately, (y-1) prepared in Production Example 2 was used in Comparative Example 5, and (y-2) prepared in Production Example 3 was used in Comparative Example 6. A coating film was formed and dried at 110 ° C. for 120 seconds to form a layer (Y).
In addition, the thickness of the formed layer (X1), layer (Y), and layer (X2) was as shown in Table 1.
Then, on the surface of the exposed layer (X1), the layer (Y) is laminated, and the release film (2) on the layer (Y) is further removed, and on the surface of the exposed layer (Y). The layer (X2) was laminated to form a laminate, and a double-sided PSA sheet was obtained in which the laminate was sandwiched between two release materials.
 実施例及び比較例で作製した両面粘着シートが有する積層体の厚さ(比較例2では層(X1)の厚さ)、並びに、当該積層体を構成する層(X1)、層(Y)、及び層(X2)の厚さを、上述の方法に準拠して測定した。当該測定結果を表1に示す。 The thickness of the laminate (the thickness of the layer (X1) in Comparative Example 2) that the double-sided PSA sheets prepared in Examples and Comparative Examples have, and the layer (X1), the layer (Y) constituting the laminate, And the thickness of layer (X2) was measured based on the above-mentioned method. The measurement results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 実施例及び比較例で作製した両面粘着シートが有する層(Y)及び積層体について、以下に方法に基づき、各種物性を測定した。これらの結果を表2に示す。
 なお、比較例2で作製した両面粘着シートは、層(Y)を有しないため、下記の各種物性の測定は行っていない。
About the layer (Y) and laminated body which the double-sided adhesive sheet produced by the Example and the comparative example has, various physical properties were measured based on the method below. These results are shown in Table 2.
In addition, since the double-sided adhesive sheet produced in the comparative example 2 does not have a layer (Y), the following various physical properties are not measured.
<層(Y)の破断強度、破断伸度>
 剥離フィルム(1)の剥離剤層上に、各実施例及び比較例と同じ条件にて作製した両面粘着シートが有する層(Y)のみを形成した後、剥離フィルム(1)を除去し、縦150mm×横15mmに切断したものを、試験サンプルとした。
 そして、万能材料試験機(株式会社エー・アンド・デイ製、製品名「テンシロン RTG-1225」)を用いて、チャック間距離100mm、引張速度200mm/分にて、試験サンプルのMD方向の破断強度及び破断伸度を測定した。
 なお、「MD方向」とは、実施例1~4及び比較例5、6においては、塗膜を形成する際に組成物を塗布した方向を指し、比較例3、4においては、使用する基材フィルムを製造する際の製膜機の流れ方向を指す。
<Rupture strength and elongation at break of layer (Y)>
On the release agent layer of the release film (1), only the layer (Y) of the double-sided pressure-sensitive adhesive sheet prepared under the same conditions as in each Example and Comparative Example was formed, and then the release film (1) was removed, A sample cut into 150 mm × 15 mm was used as a test sample.
Then, using a universal material testing machine (manufactured by A & D Co., Ltd., product name “Tensilon RTG-1225”), the breaking strength in the MD direction of the test sample at a chuck distance of 100 mm and a tensile speed of 200 mm / min. And the breaking elongation was measured.
The “MD direction” refers to the direction in which the composition was applied when forming the coating film in Examples 1 to 4 and Comparative Examples 5 and 6, and in Comparative Examples 3 and 4, the base used. It refers to the flow direction of the film forming machine when manufacturing the material film.
<積層体のヘーズ、全光線透過率>
 実施例及び比較例で得た両面粘着シートをそれぞれ5cm角に切断し、第1剥離材を除去して、表出した積層体の表面(比較例2では層(X1)の表面)を、ガラス板(日本板硝子株式会社製、ソーダライムガラス板)の表面に貼付した後、第2剥離材も除去したものを試験片とした。
 積層体のヘーズについては、ヘーズメーター(日本電色工業株式会社製、製品名「NDH2000」)を用いて、JIS K7136:2000に準拠して、試験片の任意に選択した3点のヘーズを測定し、その平均値を、対象となる積層体のヘーズとした。
 また、積層体の全光線透過率は、上記ヘーズメーターを用いて、JIS K7361-1:1997に準拠して、試験片の任意に選択した3点での全光線透過率を測定し、その平均値を対象となる積層体の全光線透過率とした。
<Haze of laminate, total light transmittance>
The double-sided PSA sheets obtained in Examples and Comparative Examples were each cut into 5 cm squares, the first release material was removed, and the surface of the exposed laminate (the surface of the layer (X1) in Comparative Example 2) was made of glass. A test piece was prepared by pasting on the surface of a plate (manufactured by Nippon Sheet Glass Co., Ltd., soda lime glass plate) and then removing the second release material.
About haze of a laminated body, the haze of 3 points | pieces arbitrarily selected of the test piece was measured based on JISK7136: 2000 using the haze meter (the Nippon Denshoku Industries Co., Ltd. make, product name "NDH2000"). And the average value was made into the haze of the target laminated body.
Further, the total light transmittance of the laminate was determined by measuring the total light transmittance at three arbitrarily selected points of the test piece in accordance with JIS K7361-1: 1997 using the haze meter, and calculating the average The value was defined as the total light transmittance of the target laminate.
 実施例及び比較例で作製した両面粘着シートについて、以下の試験を行い、各両面粘着シートの性状を評価した。評価結果を表2に示す。
 なお、比較例2で作製した両面粘着シートは、層(Y)を有しないため、界面密着性試験は行っていない。
About the double-sided adhesive sheet produced by the Example and the comparative example, the following tests were done and the property of each double-sided adhesive sheet was evaluated. The evaluation results are shown in Table 2.
In addition, since the double-sided adhesive sheet produced by the comparative example 2 does not have a layer (Y), the interface adhesiveness test is not performed.
<粘着力>
 実施例及び比較例で作製した両面粘着シートの第2剥離材を除去し、表出した積層体の表面に(比較例2では層(X1)の表面に)、PETフィルム(三菱樹脂株式会社製、製品名「ダイアホイルT-100」、厚さ50μm)を貼り合わせ、縦300mm×横25mmの大きさに切断した。
 そして、第1剥離材も除去し、表出した積層体の表面に(比較例2では層(X1)の表面に)、23℃、50%RH(相対湿度)の環境下で、ステンレス板(SUS304、360番研磨)を貼付し、同じ環境下で24時間静置した。
 静置後、JIS Z0237:2000に基づき、180°引き剥がし法により、引っ張り速度300mm/分にて、両面粘着シートの粘着力を測定した。
<Adhesive strength>
The 2nd release material of the double-sided adhesive sheet produced by the Example and the comparative example was removed, and the PET film (Mitsubishi Resin Co., Ltd. product) on the surface of the exposed laminated body (in the comparative example 2 on the surface of a layer (X1)). The product name “Diafoil T-100”, thickness 50 μm) was bonded and cut into a size of 300 mm long × 25 mm wide.
Then, the first release material is also removed, and the stainless steel plate (on the surface of the layer (X1) in Comparative Example 2) is exposed to a stainless steel plate (23 ° C., 50% RH (relative humidity)). SUS304, No. 360) was affixed and allowed to stand for 24 hours in the same environment.
After standing, the adhesive strength of the double-sided pressure-sensitive adhesive sheet was measured at a pulling speed of 300 mm / min by a 180 ° peeling method based on JIS Z0237: 2000.
<泣き別れ試験>
 実施例及び比較例で作製した両面粘着シートを縦300mm×横25mmの大きさに切断した後、第2剥離材側を固定して、第1剥離材を両面粘着シートに対して90°の角度で引き剥がした際に、積層体もしくは粘着剤層が2つの剥離材に伴って分断され引き剥がされるという、泣き別れ現象が生じるか否かを確認した。この操作を20回繰り返し、発生した泣き別れ現象の回数によって、以下の基準により、泣き別れ現象の抑制効果を評価した。
 A:確認した20回のすべてにおいて、泣き別れ現象は発生しなかった。
 B:確認した20回中、泣き別れ現象が1回発生した。
 C:確認した20回中、泣き別れ現象が2回以上発生した。
<Crying breakup test>
After the double-sided pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples are cut into a size of 300 mm long × 25 mm wide, the second release material side is fixed, and the first release material is at an angle of 90 ° with respect to the double-sided pressure-sensitive adhesive sheet. It was confirmed whether or not a tearing phenomenon occurred in which the laminate or the pressure-sensitive adhesive layer was divided and peeled off with the two release materials. This operation was repeated 20 times, and the effect of suppressing the crying phenomenon was evaluated based on the number of times the crying phenomenon occurred.
A: In all of the 20 times confirmed, no crying phenomenon occurred.
B: During the confirmed 20 times, a crying phenomenon occurred once.
C: The tearing phenomenon occurred twice or more during the confirmed 20 times.
<界面密着性試験>
 実施例及び比較例で作製した両面粘着シートを第2剥離材を除去し、表出した積層体の表面に、PETフィルム(三菱樹脂株式会社製、製品名「ダイアホイルT-100」、厚さ50μm)を貼り合わせ、縦300mm×横25mmの大きさに切断した。
 そして、第1剥離材も除去し、表出した積層体の表面に、ステンレス板(SUS306、600番研磨)を貼付し、70℃、dryの環境下で7日間静置した後、さらに23℃、50%RH(相対湿度)の環境下で1日間静置した。
 静置後、PETフィルムを剥離した際の剥離界面の様子を観察し、以下の基準により、層(Y)と層(X1)及び(X2)との界面密着性を評価した。
・A:層(X1)と層(Y)との界面、並びに、層(X2)と層(Y)との界面のいずれにおいても、剥離が確認されず、層(X2)とPETフィルムとの間で剥離された。
・B:層(X1)と層(Y)との界面、並びに、層(X2)と層(Y)との界面の少なくとも一方の界面において、わずかに剥離が確認されたが、全体的には、層(X2)とPETフィルムとの間で剥離された。
・C:層(X1)と層(Y)との界面、並びに、層(X2)と層(Y)との界面の少なくとも一方の界面において、部分的に剥離が確認され、一部分において、層(Y)と層(X1)又は層(X2)との間で剥離された。
・D:層(X1)と層(Y)との界面、並びに、層(X2)と層(Y)との界面の少なくとも一方の界面において、大部分の剥離が確認され、層(Y)と層(X1)又は層(X2)との間で剥離された。
<Interface adhesion test>
The second release material was removed from the double-sided PSA sheets prepared in Examples and Comparative Examples, and a PET film (product name “Diafoil T-100”, manufactured by Mitsubishi Plastics, Inc. 50 μm) were bonded together and cut into a size of 300 mm long × 25 mm wide.
Then, the first release material was also removed, and a stainless steel plate (SUS306, No. 600 polishing) was applied to the surface of the exposed laminate. After standing for 7 days in an environment of 70 ° C. and dry, further 23 ° C. , And left in an environment of 50% RH (relative humidity) for 1 day.
After standing, the state of the peeling interface when the PET film was peeled was observed, and the interfacial adhesion between the layer (Y) and the layers (X1) and (X2) was evaluated according to the following criteria.
A: No peeling was confirmed at any of the interface between the layer (X1) and the layer (Y) and at the interface between the layer (X2) and the layer (Y), and the layer (X2) and the PET film It was peeled between.
B: Slight peeling was confirmed at the interface between the layer (X1) and the layer (Y) and at least one of the interfaces between the layer (X2) and the layer (Y). , Peeled between layer (X2) and PET film.
C: Peeling was partially confirmed at the interface between the layer (X1) and the layer (Y) and at least one of the interfaces between the layer (X2) and the layer (Y). Y) was peeled between layer (X1) or layer (X2).
D: Most of the peeling was confirmed at the interface between the layer (X1) and the layer (Y) and at least one of the interfaces between the layer (X2) and the layer (Y). It peeled between the layer (X1) or the layer (X2).
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
 表2から、実施例1~4の両面粘着シートは、良好な粘着力を有し、泣き別れ現象の抑制効果が高い結果となった。また、これらの両面粘着シートは、基材層と粘着剤層との界面密着性が高いため、抜き加工性、貼付適性及び裁断加工適性に優れると考えられる。
 一方、比較例1~2の両面粘着シートは、非粘着性樹脂から構成された基材層を有しないため、泣き別れが発生し易い結果となった。
 また、比較例3~6の両面粘着シートは、泣き別れ現象の抑制効果は高いものの、基材層と粘着剤層との界面密着性が低く、抜き加工性、貼付適性及び裁断加工適性に問題があると考えられる。
From Table 2, the double-sided pressure-sensitive adhesive sheets of Examples 1 to 4 had good adhesive strength and resulted in a high effect of suppressing the tearing phenomenon. Moreover, these double-sided PSA sheets are considered to be excellent in punching processability, pasting suitability and cutting processability because of high interfacial adhesion between the base material layer and the PSA layer.
On the other hand, the double-sided pressure-sensitive adhesive sheets of Comparative Examples 1 and 2 did not have a base material layer composed of a non-adhesive resin, so that tearing was likely to occur.
In addition, although the double-sided PSA sheets of Comparative Examples 3 to 6 have a high effect of suppressing the tearing-off phenomenon, the interfacial adhesion between the base material layer and the PSA layer is low, and there are problems in the punching processability, sticking suitability, and cutting processability. It is believed that there is.
 本発明の一態様の両面粘着シートは、識別又は装飾用、塗装マスキング用、金属板等の表面保護用等に使用する、貼付面積が大きい両面粘着シートとして有用である。 The double-sided pressure-sensitive adhesive sheet of one embodiment of the present invention is useful as a double-sided pressure-sensitive adhesive sheet having a large affixing area used for identification or decoration, coating masking, surface protection of metal plates and the like.
  1、2、3、4  両面粘着シート
  10  積層体
  11  基材層(Y)
  121  第1粘着剤層(X1)
  122  第2粘着剤層(X2)
  123  第3粘着剤層(X3)
  124  第4粘着剤層(X4)
  131、132  剥離材
 
1, 2, 3, 4 Double-sided adhesive sheet 10 Laminate 11 Base material layer (Y)
121 1st adhesive layer (X1)
122 2nd adhesive layer (X2)
123 3rd adhesive layer (X3)
124 4th adhesive layer (X4)
131, 132 Release material

Claims (14)

  1.  第1粘着剤層(X1)、基材層(Y)、及び第2粘着剤層(X2)をこの順で直接積層した積層体を有する両面粘着シートであって、
     前記積層体が、
      第1の粘着剤層の形成材料である、粘着性樹脂を含む組成物(x1)からなる塗膜(x1’)と、
      基材層(Y)の形成材料である、アクリルウレタン系樹脂及びオレフィン系樹脂からなる群から選ばれる非粘着性樹脂を含む組成物(y)からなる塗膜(y’)と、
      第2の粘着剤層の形成材料である、粘着性樹脂を含む組成物(x2)からなる塗膜(x2’)と、
    をこの順で直接積層した後、塗膜(x1’)、(y’)及び(x2’)を同時に乾燥して形成されたものである、両面粘着シート。
    A double-sided pressure-sensitive adhesive sheet having a laminate in which the first pressure-sensitive adhesive layer (X1), the base material layer (Y), and the second pressure-sensitive adhesive layer (X2) are directly laminated in this order,
    The laminate is
    A coating film (x1 ′) comprising a composition (x1) containing an adhesive resin, which is a material for forming the first adhesive layer;
    A coating film (y ′) made of a composition (y) containing a non-adhesive resin selected from the group consisting of an acrylic urethane-based resin and an olefin-based resin, which is a forming material of the base material layer (Y);
    A coating film (x2 ′) comprising a composition (x2) containing an adhesive resin, which is a material for forming the second adhesive layer;
    Are laminated | stacked directly in this order, Then, the double-sided adhesive sheet formed by drying simultaneously a coating film (x1 '), (y'), and (x2 ').
  2.  第1粘着剤層(X1)及び第2粘着剤層(X2)の合計厚さ100に対する、基材層(Y)の厚さ比が、1~100である、請求項1に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive according to claim 1, wherein the thickness ratio of the base material layer (Y) to the total thickness 100 of the first pressure-sensitive adhesive layer (X1) and the second pressure-sensitive adhesive layer (X2) is 1 to 100. Sheet.
  3.  前記積層体の厚さが、2~90μmである、請求項1又は2に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the laminate has a thickness of 2 to 90 µm.
  4.  基材層(Y)の厚さが、0.3~50.0μmである、請求項1~3のいずれか一項に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein the base material layer (Y) has a thickness of 0.3 to 50.0 µm.
  5.  組成物(x1)及び(x2)に含まれる前記粘着性樹脂が、アクリル系樹脂を含む、請求項1~4のいずれか一項に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 4, wherein the adhesive resin contained in the compositions (x1) and (x2) contains an acrylic resin.
  6.  組成物(y)に含まれる前記非粘着性樹脂が、重合性官能基を有しない紫外線非硬化型樹脂である、請求項1~5のいずれか一項に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 5, wherein the non-sticky resin contained in the composition (y) is an ultraviolet non-curable resin having no polymerizable functional group.
  7.  基材層(Y)が、無延伸のシート状物である、請求項1~6のいずれか一項に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 6, wherein the base material layer (Y) is an unstretched sheet-like material.
  8.  基材層(Y)の破断伸度が100%以上である、請求項1~7のいずれか一項に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 7, wherein the elongation at break of the base material layer (Y) is 100% or more.
  9.  基材層(Y)の破断強度が30MPa以上である、請求項1~8のいずれか一項に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 8, wherein the base material layer (Y) has a breaking strength of 30 MPa or more.
  10.  前記積層体のヘーズが5.00%以下である、請求項1~9のいずれか一項に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 9, wherein the laminate has a haze of 5.00% or less.
  11.  前記積層体の全光線透過率が80%以上である、請求項1~10のいずれか一項に記載の両面粘着シート。 The double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 10, wherein the total light transmittance of the laminate is 80% or more.
  12.  請求項1~11のいずれか一項に記載の両面粘着シートを製造する方法であって、
     下記工程(1)~(2)を有する、両面粘着シートの製造方法。
    ・工程(1):組成物(x1)からなる塗膜(x1’)と、組成物(y)からなる塗膜(y’)と、組成物(x2)からなる塗膜(x2’)とをこの順で直接積層して形成する工程。
    ・工程(2):塗膜(x1’)、塗膜(y’)、及び塗膜(x2’)を同時に乾燥させて前記積層体を形成する工程。
    A method for producing a double-sided pressure-sensitive adhesive sheet according to any one of claims 1 to 11,
    A method for producing a double-sided pressure-sensitive adhesive sheet, comprising the following steps (1) to (2).
    Step (1): a coating film (x1 ′) composed of the composition (x1), a coating film (y ′) composed of the composition (y), and a coating film (x2 ′) composed of the composition (x2) A process of directly stacking layers in this order.
    -Process (2): The process of drying a coating film (x1 '), a coating film (y'), and a coating film (x2 ') simultaneously, and forming the said laminated body.
  13.  工程(1)において、組成物(x1)、組成物(y)、及び組成物(x2)を同時に塗布する、請求項12に記載の両面粘着シートの製造方法。 The manufacturing method of the double-sided adhesive sheet of Claim 12 which apply | coats a composition (x1), a composition (y), and a composition (x2) simultaneously in a process (1).
  14.  組成物(x1)、組成物(y)、及び組成物(x2)が、さらに希釈溶媒を含有する、請求項12又は13に記載の両面粘着シートの製造方法。 The method for producing a double-sided pressure-sensitive adhesive sheet according to claim 12 or 13, wherein the composition (x1), the composition (y), and the composition (x2) further contain a diluent solvent.
PCT/JP2017/042828 2016-11-30 2017-11-29 Double-sided adhesive sheet, and method for producing double-sided adhesive sheet WO2018101335A1 (en)

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WO2020162439A1 (en) * 2019-02-06 2020-08-13 バンドー化学株式会社 Optical transparent adhesive sheet, laminate sheet, and adhered structure

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JP2006063189A (en) * 2004-08-26 2006-03-09 Nitto Denko Corp Optical member with pressure-sensitive adhesive and method for producing the same and image display device
WO2015152359A1 (en) * 2014-04-02 2015-10-08 リンテック株式会社 Adhesive sheet and production method therefor
WO2015152365A1 (en) * 2014-04-02 2015-10-08 リンテック株式会社 Adhesive sheet and adhesive sheet production method

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Publication number Priority date Publication date Assignee Title
JP2006063189A (en) * 2004-08-26 2006-03-09 Nitto Denko Corp Optical member with pressure-sensitive adhesive and method for producing the same and image display device
WO2015152359A1 (en) * 2014-04-02 2015-10-08 リンテック株式会社 Adhesive sheet and production method therefor
WO2015152365A1 (en) * 2014-04-02 2015-10-08 リンテック株式会社 Adhesive sheet and adhesive sheet production method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020162439A1 (en) * 2019-02-06 2020-08-13 バンドー化学株式会社 Optical transparent adhesive sheet, laminate sheet, and adhered structure
JPWO2020162439A1 (en) * 2019-02-06 2021-02-18 バンドー化学株式会社 Optical transparent adhesive sheet, laminated sheet and laminated structure

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