WO2023068009A1 - Matériau adhésif sensible à la pression et feuille adhésive sensible à la pression - Google Patents

Matériau adhésif sensible à la pression et feuille adhésive sensible à la pression Download PDF

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WO2023068009A1
WO2023068009A1 PCT/JP2022/036455 JP2022036455W WO2023068009A1 WO 2023068009 A1 WO2023068009 A1 WO 2023068009A1 JP 2022036455 W JP2022036455 W JP 2022036455W WO 2023068009 A1 WO2023068009 A1 WO 2023068009A1
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meth
molecular weight
less
group
adhesive
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PCT/JP2022/036455
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English (en)
Japanese (ja)
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健太 山本
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大塚化学株式会社
東山フイルム株式会社
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Priority to JP2023516748A priority Critical patent/JP7282288B1/ja
Publication of WO2023068009A1 publication Critical patent/WO2023068009A1/fr

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    • 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
    • C09J133/04Homopolymers or copolymers of esters
    • 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
    • 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
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]

Definitions

  • the present invention relates to an adhesive material and an adhesive sheet, and more particularly to an adhesive material and an adhesive sheet used for bonding one flexible member and another flexible member.
  • Adhesive materials are generally used to join the components that make up various displays and touch panels for televisions, mobile phones, smartphones, etc.
  • the adhesive material is provided, for example, in the form of a substrate-attached adhesive sheet having an adhesive layer on a supporting substrate, or a substrate-less adhesive sheet having no supporting substrate, and the members are bonded together.
  • Flexible displays include a foldable display that can be folded, a rollable display that can be rolled into a cylindrical shape, etc., and are expected to be used in mobile terminals such as smartphones and tablet terminals, and stationary displays that can be stored.
  • Patent Document 1 discloses one side of an adhesive layer and the other side of the adhesive layer. The ratio of shear stress 60 seconds after 1000% displacement to the maximum shear stress when the surfaces are displaced 1000% in opposite directions, and the gel fraction are controlled within a predetermined range. is disclosed (see Patent Document 1 (claim 1)).
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an adhesive material that has excellent adhesiveness, excellent flexibility, and excellent restorability.
  • the pressure-sensitive adhesive of the present invention which has solved the above problems, is a pressure-sensitive adhesive containing a polymer (X) having a cross-linked structure, a shear storage modulus at a temperature of 25 ° C. of 0.15 MPa or less, and a glass transition temperature of is 0° C. or less, the gel fraction is 50% to 95% by mass, and the differential molecular weight distribution curve of the sol component satisfies the requirements (1), (2) and (3).
  • the ratio (W1) of the peak area with a molecular weight of 10,000 or more and less than 100,000 to the peak area with a molecular weight of 10,000 to 30,000,000 is 20% or less.
  • the ratio (W2) of the peak area with a molecular weight of 100,000 or more and less than 560,000 to the peak area with a molecular weight of 10,000 to 30,000,000 is 40% or more.
  • the ratio (W3) of the peak area with a molecular weight of 560,000 or more to the peak area with a molecular weight of 10,000 to 30,000,000 is 40% or less.
  • the adhesive material of the present invention has excellent adhesiveness and excellent flexibility and restorability. Therefore, by using the adhesive material of the present invention for bonding the flexible member, even if the flexible member is repeatedly bent, it is possible to suppress the occurrence of lifting or peeling at the interface between the adhesive material and the flexible member at the bent portion.
  • (Meth)acrylic means “at least one of acrylic and methacrylic”.
  • (Meth)acrylate means “at least one of acrylate and methacrylate”.
  • (Meth)acryloyl means “at least one of acryloyl and methacryloyl”.
  • a “vinyl monomer” refers to a monomer having a radically polymerizable carbon-carbon double bond in the molecule.
  • a “structural unit derived from a vinyl monomer” refers to a structural unit in which a radically polymerizable carbon-carbon double bond of a vinyl monomer is polymerized to form a carbon-carbon single bond.
  • the “structural unit derived from (meth)acrylate” refers to a structural unit in which the radically polymerizable carbon-carbon double bond of (meth)acrylate is polymerized to form a carbon-carbon single bond.
  • a “structural unit derived from a (meth)acrylic monomer” refers to a structural unit in which a radically polymerizable carbon-carbon double bond of a (meth)acrylic monomer is polymerized to form a carbon-carbon single bond.
  • the adhesive material of the present invention is an adhesive material containing a polymer (X) having a crosslinked structure, and has a shear storage modulus at a temperature of 25 ° C. of 0.15 MPa or less, a glass transition temperature of 0 ° C. or less, and a gel fraction of 50% by mass to 95% by mass.
  • the shear storage modulus of the adhesive material at a temperature of 25°C is preferably 0.15 MPa or less, more preferably 0.10 MPa or less, and still more preferably 0.08 MPa or less. If the shear storage elastic modulus is 0.15 MPa or less, the flexibility of the adhesive material is improved and the followability to deformation is increased. and peeling can be suppressed.
  • the shear storage elastic modulus of the adhesive material at a temperature of 25° C. is preferably 0.01 MPa or more, more preferably 0.02 MPa or more. When the shear storage elastic modulus is 0.01 MPa or more, the adhesive holding power when the adhesive sheet and the adherend are laminated together can be increased.
  • the glass transition temperature (Tg) of the adhesive is preferably 0°C or lower, more preferably -20°C or lower, and even more preferably -30°C or lower. If the glass transition temperature is 0° C. or lower, the adhesion of the formed adhesive material to the adherend is enhanced, peeling is suppressed at low temperatures, and durability is improved. Although the lower limit of the glass transition temperature of the adhesive is not particularly limited, it is usually -50°C.
  • the gel fraction of the adhesive material is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, and further Preferably, it is 80% by mass or less. If the gel fraction is 50% by mass or more and 95% by mass or less, it is possible to form an adhesive material with excellent flexibility and restorability.
  • the gel fraction can be controlled by the content of the first crosslinkable group, the type of the crosslinker, the blending amount, etc. in the composition described later.
  • the adhesive contains a sol component.
  • the sol component is a component eluted into the solvent when the adhesive material is extracted with ethyl acetate at 25° C. for 72 hours.
  • the pressure-sensitive adhesive is characterized in that the differential molecular weight distribution curve of the sol component satisfies the requirements (1), (2) and (3).
  • a differential molecular weight distribution curve is created from a chromatograph obtained by GPC (gel permeation chromatography). Specifically, an integral molecular weight distribution curve is created by plotting the molecular weight (logarithmic value) on the horizontal axis and the integrated value of the concentration fraction on the vertical axis. Next, the slope (differential value) of the curve at each molecular weight is obtained. Finally, a differential molecular weight distribution curve is created by plotting the molecular weight (logarithmic value) on the horizontal axis and the differential value on the vertical axis.
  • the ratio (W1) of the peak area with a molecular weight of 10,000 or more and less than 100,000 to the peak area with a molecular weight of 10,000 to 30,000,000 is 20% or less.
  • the ratio (W2) of the peak area with a molecular weight of 100,000 or more and less than 560,000 to the peak area with a molecular weight of 10,000 to 30,000,000 is 40% or more.
  • the ratio (W3) of the peak area with a molecular weight of 560,000 or more to the peak area with a molecular weight of 10,000 to 30,000,000 is 40% or less.
  • the W1 is preferably 15% or less, more preferably 10% or less, and even more preferably 7% or less. If the W1 is 15% or less, it is possible to suppress the decrease in adhesiveness due to the plasticizing effect of the sol component.
  • W1 is preferably 0%, it may be greater than 0%. In this case, W1 is preferably 1.0% or more, more preferably 1.6% or more, and still more preferably 1.8% or more. When the W1 is 1.0% or more, the wettability of the interface with the adherend is improved by the sol component of the adhesive, resulting in good adhesiveness.
  • the W2 is preferably 50% or more, more preferably 60% or more, and still more preferably 70% or more. When W2 is 50% or more, an adhesive material having excellent adhesiveness can be formed.
  • the W2 is preferably 100%, but may be less than 100%. In this case, W2 is preferably 98% or less, more preferably 95.4% or less, still more preferably 88.2% or less.
  • the W3 is preferably 30% or less, more preferably 25% or less, and even more preferably 20% or less. If the W3 is 30% or less, the entanglement effect of the sol components can be suppressed, and the resilience after repeated bending is improved.
  • the W3 is preferably 0%, but may be greater than 0%. In this case, W3 is preferably 0.5% or more, more preferably 1.0% or more, still more preferably 3.0% or more, and particularly preferably 10% or more. When the W3 is 0.5% or more, the cohesive force of the adhesive is improved and the adhesiveness is improved.
  • the ratio of W1 to W3 is preferably 0.07 or more, more preferably 0.10 or more, still more preferably 0.15 or more, and preferably 26.0 or less, more preferably 6 It is preferably 0.5 or less, more preferably 5.5 or less, and particularly preferably 4.0 or less.
  • the ratio (W1/W3) is 0.07 or more, the wettability of the interface between the adhesive material and the flexible member by the sol component is improved, resulting in good adhesion. It is possible to suppress the decrease in adhesiveness due to the plasticizing effect.
  • the pressure-sensitive adhesive preferably has a differential molecular weight distribution curve of the sol component that further satisfies the requirements (2a) and (2b).
  • (2a) The ratio (W2a) of the peak area with a molecular weight of 100,000 or more and less than 150,000 to the peak area with a molecular weight of 10,000 to 30,000,000 is 15% or more.
  • (2b) The ratio (W2b) of the peak area with a molecular weight of 150,000 or more and less than 560,000 to the peak area with a molecular weight of 10,000 to 30,000,000 is 20% or more.
  • the W2a is preferably 20% or more, more preferably 25% or more, still more preferably 30% or more, particularly preferably 35% or more, preferably 46% or less, more preferably 45.4% or less, further preferably 44.9% or less.
  • the W2a is 20% or more, the entanglement effect of the sol components is suppressed, and excellent flexibility and restorability are exhibited. .
  • the W2b is preferably 25% or more, more preferably 30% or more, still more preferably 35% or more, and preferably 52% or less, more preferably 50% or less, further preferably 43.3% or less.
  • W2b is 25% or more, the cohesive force of the sol component is improved, resulting in excellent adhesiveness.
  • the ratio of W2 to W2a is preferably 0.30 or more, more preferably 0.35 or more, still more preferably 0.45 or more, and preferably 0.60 or less, more preferably 0 0.55 or less, more preferably 0.53 or less.
  • the highest peak molecular weight (Mp) at a molecular weight of 10,000 to 30,000,000 is preferably 100,000 or more, preferably 500,000 or less, more preferably 300,000 or less, and further It is preferably 200,000 or less. If the peak molecular weight (Mp) is within this range, there is a tendency to form a highly adhesive adhesive.
  • the weight average molecular weight of the sol component is preferably 100,000 or more, more preferably 150,000 or more, still more preferably 200,000 or more, and preferably 560,000 or less, more preferably 450,000 or less, further preferably 400,000 or less. is. If the weight-average molecular weight is within this range, an excellent adhesive can be formed.
  • the molecular weight distribution (Mw/Mn) of the sol component is preferably 6.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less. If the molecular weight distribution is 6.0 or less, the content of substances with large or small molecular weights is low compared to the designed polymer molecular weight, and an adhesive material with excellent adhesiveness, flexibility and restorability can be obtained.
  • the molecular weight distribution is 1.0 or more. The smaller the molecular weight distribution, the narrower the width of the molecular weight distribution. When the value is 1.0, the width of the molecular weight distribution is the narrowest.
  • the molecular weight distribution is a value calculated by (weight average molecular weight (Mw))/(number average molecular weight (Mn)), and methods for measuring Mw and Mn will be described later.
  • the adhesive contains a polymer (X) having a crosslinked structure.
  • the polymer (X) having a crosslinked structure is an adhesive composition containing a polymer component containing a polymer having a first reactive group and a crosslinkable component having a second reactive group that reacts with the first reactive group. It is obtained by cross-linking a substance.
  • the polymer (X) having a crosslinked structure is a (meth)acrylic polymer (A) having a first reactive group having a weight average molecular weight of 600,000 or more and 3,000,000 or less (hereinafter simply referred to as "(meth)acrylic polymer (A)”), a (meth)acrylic polymer (B) having a weight average molecular weight (Mw) of 100,000 or more and 800,000 or less (hereinafter simply “(meth)acrylic polymer (B) ) and a cross-linking agent having a second reactive group that reacts with the first reactive group.
  • the difference (MwA-MwB) between the weight average molecular weight (MwA) of the (meth)acrylic polymer (A) and the weight average molecular weight (MwB) of the (meth)acrylic polymer (B) is preferably 500,000 or more. , more preferably 700,000 or more, more preferably 1,000,000 or more, preferably 2,900,000 or less, more preferably 2,500,000 or less, still more preferably 2,200,000 or less.
  • the difference (MwA-MwB) is 500,000 or more, even if the (meth)acrylic polymer (B) has a first reactive group, the cross-linking agent having a second reactive group and the (meth) )
  • the acrylic polymer (A) can be selectively reacted, and if it is 2.9 million or less, the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B) are uniformly dispersed during coating. can be mixed.
  • the ratio (MwA/MwB) of the weight average molecular weight (MwA) of the (meth)acrylic polymer (A) to the weight average molecular weight (MwB) of the (meth)acrylic polymer (B) is 1.9 or more. It is preferably 3.6 or more, still more preferably 6.0 or more, and preferably 18.0 or less, more preferably 15.0 or less, and still more preferably 13.0 or less.
  • the ratio (MwA/MwB) is 1.9 or more, even if the (meth)acrylic polymer (B) has a first reactive group, the cross-linking agent having a second reactive group and the ( The meth)acrylic polymer (A) can be selectively reacted, and if it is 18.0 or less, the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B) are mixed during coating. It can be mixed uniformly.
  • the (meth)acrylic polymer (B) may or may not have a first reactive group. That is, the combination of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B) is a (meth)acrylic polymer having a first reactive group having a weight average molecular weight of 600,000 or more and 3,000,000 or less.
  • a combination with (B) can be mentioned.
  • the (meth)acrylic polymer (A) and the cross-linking agent are mainly components that form a cross-linked structure.
  • the sol component includes a component that was not crosslinked during the crosslinking reaction in the (meth)acrylic polymer (A), a component that has a low degree of crosslinking and can be extracted with a solvent, and the like.
  • the (meth)acrylic polymer (B) having no first reactive group mainly becomes a sol component.
  • components in the (meth)acrylic polymer (B) that were not crosslinked during the crosslinking reaction, or components that have a low degree of crosslinking and can be extracted with a solvent components, etc. are included in the sol component.
  • the (meth)acrylic polymer (A) has a structural unit derived from a (meth)acrylic monomer as a main component (50% by mass or more).
  • the (meth)acrylic polymer (A) may be used alone or in combination of two or more.
  • the (meth)acrylic polymer (A) can contain a structural unit derived from a vinyl monomer other than the (meth)acrylic monomer.
  • the content of structural units derived from (meth)acrylic monomers in the (meth)acrylic polymer (A) is preferably 80% by mass or more, more preferably 90% by mass or more, based on 100% by mass of the polymer.
  • the (meth)acrylic polymer (A) may be composed only of structural units derived from (meth)acrylic monomers.
  • the (meth)acrylic polymer (A) is preferably a (meth)acrylate copolymer.
  • the (meth)acrylate copolymer may be a copolymer having a structural unit derived from (meth)acrylate as a main component (50% by mass or more), and is derived from a vinyl monomer other than (meth)acrylate. It can contain structural units.
  • the (meth)acrylate is an ester compound in which the hydrogen atom of the carboxy group of (meth)acrylic acid is substituted with an organic group.
  • the content of structural units derived from (meth)acrylate in the (meth)acrylic polymer (A) is preferably 80% by mass or more, more preferably 90% by mass or more, based on 100% by mass of the polymer.
  • the (meth)acrylic polymer (A) has a first reactive group.
  • the first reactive group is a functional group having reactivity with a second reactive group of a cross-linking agent, which will be described later.
  • Functional groups that can be the first reactive group include reactive functional groups.
  • the first reactive group includes a hydroxy group, a carboxy group, an epoxy group and the like, preferably a hydroxy group and/or a carboxy group.
  • the amount of the first reactive group of the (meth)acrylic polymer (A) is preferably 0.002 mmol/g or more, more preferably 0.005 mmol/g or more, still more preferably 0.010 mmol/g or more, It is preferably 1.0 mmol/g or less, more preferably 0.8 mmol/g or less, still more preferably 0.7 mmol/g or less.
  • the amount of the first reactive group is 0.002 mmol/g or more, the adhesive material formed is appropriately crosslinked and exhibits suitable restorability, and when the amount is 1.0 mmol/g or less, the adhesive material formed is improved.
  • the distance between cross-linking points is sufficiently long and the flexibility is excellent.
  • the (meth)acrylic polymer (A) When the (meth)acrylic polymer (A) has a hydroxyl group as the first reactive group, it preferably further has a carboxy group as a functional group other than the first reactive group.
  • the amount of carboxy groups in the (meth)acrylic polymer (A) is preferably 0.08 mmol/g or more, more preferably 0.16 mmol/g or more, still more preferably 0.32 mmol/g or more, It is preferably 1.3 mmol/g or less, more preferably 0.8 mmol/g or less, still more preferably 0.6 mmol/g or less.
  • the unit mass of the (meth)acrylic polymer (A) is preferably 4 or more, more preferably 8 or more, still more preferably 16 or more, preferably 60 or less, more preferably 40 or less, More preferably, it is 30 or less. If the molar ratio (carboxy group/hydroxy group) is within the above range, the adhesive layer has high restorability and a suitable balance between adhesiveness and flexibility.
  • the (meth)acrylic polymer (A) preferably has a hydroxy group as a functional group other than the first reactive group when the carboxy group is the first reactive group.
  • the amount of hydroxy groups in the (meth)acrylic polymer (A) is preferably 0.01 mmol/g or more, more preferably 0.02 mmol/g or more, still more preferably 0.04 mmol/g or more, It is preferably 0.25 mmol/g or less, more preferably 0.20 mmol/g or less, still more preferably 0.15 mmol/g or less.
  • the unit mass of the (meth)acrylic polymer (A) is preferably 3.0 or more, more preferably 3.5 or more, still more preferably 4.0 or more, and 30.0 or less. It is preferably 25.0 or less, still more preferably 20.0 or less. If the molar ratio (carboxy group/hydroxy group) is within the above range, the adhesive layer has high restorability and a suitable balance between adhesiveness and flexibility.
  • the (meth)acrylic polymer (A) may be a random copolymer, a block copolymer, or a graft copolymer, preferably a random copolymer.
  • the weight average molecular weight (MwA) of the (meth)acrylic polymer (A) is preferably 600,000 or more, more preferably 750,000 or more, still more preferably 900,000 or more, particularly preferably 1,000,000 or more, and particularly preferably 1,000,000 or more. The following is preferable, more preferably 2.8 million or less, and still more preferably 2.6 million or less.
  • MwA weight average molecular weight
  • the molecular weight distribution (Mw/Mn) of the (meth)acrylic polymer (A) is 3.0 or less, preferably 2.7 or less, more preferably 2.5 or less, and still more preferably 2.5. 1 or less.
  • Mw/Mn the narrower the width of the molecular weight distribution is and the more uniform the molecular weight of the polymer becomes.
  • Mw/Mn 3.0 or less, the content of low molecular weight and high molecular weight polymers is low compared to the molecular weight of the designed polymer, and an adhesive material with excellent adhesiveness and restorability can be obtained.
  • the glass transition temperature (Tg) of the (meth)acrylic polymer (A) is preferably ⁇ 70° C. or higher, more preferably ⁇ 60° C. or higher, and preferably 0° C. or lower, more preferably ⁇ 10° C. or lower. More preferably -20°C or lower. If the Tg is -70°C or higher, the adhesive is provided with sufficient cohesive strength, and the durability of the formed adhesive is improved. Peeling at low temperature is suppressed, and durability is improved.
  • the Tg of the (meth)acrylic polymer (A) is a value calculated by the following FOX formula (formula (1)).
  • Tg represents the glass transition temperature (°C) of the polymer.
  • Tgi indicates the glass transition temperature (°C) when the vinyl monomer i forms a homopolymer.
  • i is a natural number from 1 to n.
  • the (meth)acrylic polymer (B) has a structural unit derived from a (meth)acrylic monomer as a main component (50% by mass or more).
  • the (meth)acrylic polymer (B) may be one kind, or two or more kinds.
  • the (meth)acrylic polymer (B) can contain a structural unit derived from a vinyl monomer other than the (meth)acrylic monomer.
  • the content of structural units derived from (meth)acrylic monomers in the (meth)acrylic polymer (B) is preferably 80% by mass or more, more preferably 90% by mass or more, based on 100% by mass of the polymer.
  • the (meth)acrylic polymer (B) may be composed only of structural units derived from (meth)acrylic monomers.
  • the (meth)acrylic polymer (B) is preferably a (meth)acrylate copolymer.
  • the (meth)acrylate copolymer may be a copolymer having a structural unit derived from (meth)acrylate as a main component (50% by mass or more), and is derived from a vinyl monomer other than (meth)acrylate. It can contain structural units.
  • the content of structural units derived from (meth)acrylate in the (meth)acrylic polymer (B) is preferably 80% by mass or more, more preferably 90% by mass or more, based on 100% by mass of the polymer.
  • the (meth)acrylic polymer (B) may be a random copolymer, a block copolymer, or a graft copolymer, preferably a random copolymer.
  • the weight average molecular weight (MwB) of the (meth)acrylic polymer (B) is preferably 100,000 or more, more preferably 130,000 or more, still more preferably 150,000 or more, and preferably 800,000 or less, more preferably It is less than 600,000, more preferably 500,000 or less, particularly preferably 400,000 or less. If the MwB of the (meth)acrylic polymer (B) is within this range, there is a tendency to form an adhesive material with excellent adhesiveness.
  • the molecular weight distribution (Mw/Mn) of the (meth)acrylic polymer (B) is preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.0 or less, and particularly preferably 2.5 or less. be.
  • Mw/Mn is 5.0 or less, the content of low molecular weight and high molecular weight polymers is low compared to the designed polymer, and an adhesive material with excellent adhesiveness can be obtained.
  • the glass transition temperature (Tg) of the (meth)acrylic polymer (B) is preferably ⁇ 70° C. or higher, more preferably ⁇ 60° C. or higher, and preferably 0° C. or lower, more preferably ⁇ 10° C. or lower. More preferably -20°C or lower. If the Tg is -70 ° C. or higher, the adhesive material is given sufficient cohesive strength, and the durability of the formed adhesive material is improved. As a result, peeling at low temperatures is suppressed, and durability is improved.
  • the amount of the (meth)acrylic polymer (B) blended with respect to 100 parts by mass of the (meth)acrylic polymer (A) is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and further It is preferably 70 parts by mass or more, preferably 300 parts by mass or less, more preferably 250 parts by mass or less, and even more preferably 200 parts by mass or less.
  • the amount of the (meth)acrylic polymer (B) is 30 parts by mass or more, an adhesive material having excellent flexibility can be formed. can be formed.
  • the (meth)acrylic polymer (B) may or may not have a first reactive group.
  • a polymer having the first reactive group and a polymer not having the first reactive group may be used in combination.
  • the first reactive group includes a hydroxy group, a carboxy group, an epoxy group and the like, preferably a hydroxy group and/or a carboxy group.
  • the amount of the first reactive group of the (meth)acrylic polymer (B) is preferably 0.002 mmol/g or more, more preferably is 0.005 mmol/g or more, more preferably 0.010 mmol/g or more, preferably 1.0 mmol/g or less, more preferably 0.8 mmol/g or less, still more preferably 0.7 mmol/g or less .
  • the amount of the first reactive group is 0.002 mmol/g or more, the adhesive material formed is appropriately crosslinked and exhibits suitable restorability, and when the amount is 1.0 mmol/g or less, the adhesive material formed is improved.
  • the distance between cross-linking points is sufficiently long and the flexibility is excellent.
  • the (meth)acrylic polymer (B) When the (meth)acrylic polymer (B) has a first reactive group, the (meth)acrylic polymer (B) in the total mass of the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B)
  • the total amount of the first reactive groups possessed by the acrylic polymer (A) and the (meth)acrylic polymer (B) is preferably 0.002 mmol/g or more, more preferably 0.005 mmol/g or more, still more preferably 0 010 mmol/g or more, preferably 1.0 mmol/g or less, more preferably 0.8 mmol/g or less, and even more preferably 0.7 mmol/g or less.
  • the adhesive material formed is appropriately crosslinked and exhibits suitable restorability, and when the amount is 1.0 mmol/g or less, the adhesive material formed is improved.
  • the distance between cross-linking points is sufficiently long and the flexibility is excellent.
  • the (meth)acrylic polymer (B) preferably has a carboxy group when the hydroxyl group is the first reactive group.
  • the (meth)acrylic polymer (B) having a carboxyl group exhibits excellent adhesiveness.
  • the amount of carboxy groups in the (meth)acrylic polymer (B) is preferably 0.002 mmol/g or more, more preferably 0.005 mmol/g or more, still more preferably 0.010 mmol/g or more, It is preferably 1.0 mmol/g or less, more preferably 0.8 mmol/g or less, still more preferably 0.7 mmol/g or less.
  • the adhesive composition may contain polymer components other than the (meth)acrylic polymer (A) and (meth)acrylic polymer (B).
  • the total content of the (meth)acrylic polymer (A) and (meth)acrylic polymer (B) in the polymer component contained in the adhesive composition is preferably 70% by mass or more, more preferably 80% by mass or more, More preferably, it is 90% by mass or more.
  • the adhesive composition may contain only the (meth)acrylic polymer (A) and the (meth)acrylic polymer (B) as polymer components.
  • the (meth)acrylic polymer (A) has a first reactive group. That is, the (meth)acrylic polymer (A) contains a structural unit (a-1) having a first reactive group in its structure.
  • the (meth)acrylic polymer (B) may or may not contain the structural unit (a-1) having the first reactive group in its structure.
  • the structural unit (a-1) having the first reactive group may be of only one type, or may be of two or more types.
  • the first reactive group is a structural unit derived from a (meth)acrylic monomer (preferably a (meth)acrylate monomer and/or (meth)acrylic acid), or a structural unit derived from a vinyl monomer other than the (meth)acrylic monomer. You may have it in any of That is, the structural unit (a-1) having the first reactive group is derived from (meth)acrylic monomer (preferably (meth)acrylate monomer and/or (meth)acrylic acid) having the first reactive group or a structural unit derived from a vinyl monomer other than a (meth)acrylic monomer having a first reactive group.
  • the content of the structural unit derived from the vinyl monomer having the first reactive group in the (meth)acrylic polymer (A) is 100% of the polymer component. In mass%, it is preferably 0.03% by mass or more, more preferably 0.09% by mass or more, still more preferably 0.15% by mass or more, and preferably 6% by mass or less, more preferably 4% by mass or less. , more preferably 3% by mass or less.
  • the vinyl monomer having the first reactive group includes vinyl monomers other than the (meth)acrylic monomer having the first reactive group and the (meth)acrylic monomer having the first reactive group.
  • the structural unit (first reaction) is preferably 0.03% by mass or more, more preferably 0.09% by mass or more, and still more preferably 0.15% by mass in 100% by mass of the polymer component. % by mass or more, preferably 6% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
  • the vinyl monomer having the first reactive group includes vinyl monomers other than the (meth)acrylic monomer having the first reactive group and the (meth)acrylic monomer having the first reactive group.
  • Examples of the (meth)acrylic monomer include (b1) a (meth)acrylic monomer having no functional group capable of serving as the first reactive group, and (b2) a (meth)acrylic monomer having a functional group capable of serving as the first reactive group. is mentioned. These monomers may be used alone or in combination of two or more.
  • As the (b1) (meth)acrylic monomer (b1-1) a (meth)acrylate monomer having no functional group capable of serving as a first reactive group is preferable.
  • Examples of the (b2) (meth)acrylic monomer include (b2-1) a (meth)acrylate monomer having a functional group capable of serving as a first reactive group, and (meth)acrylic acid.
  • the (b1) (meth)acrylic monomer having no functional group that can be the first reactive group includes (meth)acrylate having a linear alkyl group, (meth)acrylate having a branched alkyl group, alkoxy group-containing (meth)acrylates, alicyclic hydrocarbon group-containing (meth)acrylates, aromatic group-containing (meth)acrylates, tertiary amino group-containing (meth)acrylates, (meth)acrylamides, and the like. be done.
  • (meth)acrylates having a linear alkyl group (meth)acrylates having a branched alkyl group, (meth)acrylates having an alicyclic hydrocarbon group, and (meth)acrylates having an aromatic group and (meth)acrylamides are preferred.
  • the (meth)acrylate having a straight-chain alkyl group is preferably a (meth)acrylate having a straight-chain alkyl group having 1 to 20 carbon atoms in the straight-chain alkyl group.
  • (Meth)acrylates having a straight-chain alkyl group with a number of 1 to 15 are more preferred, and (meth)acrylates having a straight-chain alkyl group with a straight-chain alkyl group having a carbon number of 1 to 12 are even more preferred. and (meth)acrylates having a straight-chain alkyl group having 4 to 12 carbon atoms in the straight-chain alkyl group are more preferred.
  • Examples of (meth)acrylates having a linear alkyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and n-hexyl (meth)acrylate. , n-octyl (meth)acrylate, n-nonyl (meth)acrylate, n-decyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate and other linear alkyl (meth)acrylates esters.
  • the (meth)acrylate having a branched-chain alkyl group is preferably a (meth)acrylate having a branched-chain alkyl group having 3 to 20 carbon atoms in the branched-chain alkyl group.
  • (Meth)acrylates having a branched-chain alkyl group having a number of 3 to 12 are more preferred, and (meth)acrylates having a branched-chain alkyl group having a branched-chain alkyl group having a carbon number of 3 to 10 are even more preferred. .
  • Examples of (meth)acrylates having a branched alkyl group include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, 2 - (meth)acrylic acid branched chain alkyl esters such as ethylhexyl (meth)acrylate, isononyl (meth)acrylate and isodecyl (meth)acrylate.
  • (meth)acrylates having an alkoxy group examples include (meth)acrylic acid alkoxyalkyl esters such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate.
  • Examples of (meth)acrylates having an alicyclic hydrocarbon group include (meth)acrylates having a cyclic alkyl group and (meth)acrylates having a polycyclic structure.
  • the (meth)acrylate having a cyclic alkyl group is preferably a (meth)acrylate having a cyclic alkyl group having 6 to 12 carbon atoms.
  • the cyclic alkyl group includes a cyclic alkyl group having a monocyclic structure (for example, a cycloalkyl group), and may have a chain portion.
  • (meth)acrylates having a cyclic alkyl group having a monocyclic structure include (meth)acrylic acid cyclic alkyl esters such as cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, and cyclododecyl (meth)acrylate. be able to.
  • the (meth)acrylate having a polycyclic structure is preferably a (meth)acrylate having a polycyclic structure with 6 to 12 carbon atoms.
  • the polycyclic structure includes cyclic alkyl groups having a bridged ring structure (eg, adamantyl group, norbornyl group, isobornyl group), and may have a chain portion.
  • (meth)acrylates having a polycyclic structure include bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 2-methyl-2- adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, norbornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) Acrylate, dicyclopentenyloxyethyl (meth)acrylate and the like can be mentioned.
  • the (meth)acrylate having an aromatic group is preferably a (meth)acrylate having an aromatic group having 6 to 12 carbon atoms.
  • the aromatic group include an aryl group, and may have a chain portion such as an alkylaryl group, an araryl group, an aryloxyalkyl group, and the like.
  • the (meth)acrylate having an aromatic group include a compound in which an aryl group is directly bonded to a (meth)acryloyloxy group, a compound in which an aralkyl group is directly bonded to a (meth)acryloyloxy group, and a (meth)acryloyloxy group.
  • a compound having an alkylaryl group directly bonded thereto may be mentioned.
  • the aryl group preferably has 6 to 12 carbon atoms.
  • the aralkyl group preferably has 6 to 12 carbon atoms.
  • the alkylaryl group preferably has 6 to 12 carbon atoms.
  • (Meth)acrylates having an aromatic group include benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate and the like.
  • Examples of (meth)acrylates having a tertiary amino group include 2-(dimethylamino)ethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate.
  • Examples of the (meth)acrylamides include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, (meth)acrylamide, N-methyl(meth) Acrylamide, N-ethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, N-octyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl ( meth)acrylamide, N-propoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, diacetoneacrylamide, 4-(meth)acryloylmorpholine and the like.
  • the (meth)acrylamides are (meth)acryl monomers, but are not included in (meth)acrylate monomers.
  • the (b2) (meth)acrylic monomer having a functional group capable of serving as a first reactive group includes a (meth)acrylic monomer having a hydroxy group (preferably a (meth)acrylate monomer) and a (meth)acrylic monomer having a carboxy group.
  • Monomers preferably (meth)acrylic acid), epoxy group-containing (meth)acrylic monomers (preferably (meth)acrylate monomers), and the like can be mentioned.
  • a (meth)acrylic monomer having a hydroxy group and/or a (meth)acrylic monomer having a carboxy group are preferred, and a (meth)acrylic monomer having a hydroxy group is more preferred.
  • Examples of the (meth)acrylic monomer having a hydroxy group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6 - hydroxyalkyl (meth)acrylates such as hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate; (4-hydroxymethylcyclohexyl) hydroxyalkylcycloalkyl (meth)acrylates such as methyl (meth)acrylate; and caprolactone adducts of hydroxyalkyl (meth)acrylates.
  • hydroxyalkyl (meth)acrylates are preferred, and (meth)acrylates having a hydroxyalkyl group having 1 to 5 carbon atoms are more preferred.
  • Examples of the (meth)acrylic monomer having a carboxy group include carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, 2 - Monomers obtained by reacting (meth)acrylates having a hydroxy group such as (meth)acryloyloxyethyl phthalate with acid anhydrides such as maleic anhydride, succinic anhydride, and phthalic anhydride (e.g., 2-acryloyloxy hydrogen succinate) Ethyl, 2-methacryloyloxyethyl hydrogen succinate, 2-(acryloyloxy)ethyl hydrogen hexahydrophthalate, 2-(methacryloyloxyethyl) hydrogen hexahydrophthalate, 1-(2-acryloyloxyethyl) phthalate, phthalate acid 1-(2-methacryl
  • Examples of the (meth)acrylic acid ester having an epoxy group include glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate.
  • Examples of the vinyl monomer other than the (meth)acrylic monomer include (b3) a vinyl monomer other than the (meth)acrylic monomer which does not have a functional group that can be the first reactive group, and (b4) a functional group that can be the first reactive group.
  • Examples include vinyl monomers other than (meth)acrylic monomers having a group. These monomers may be used alone or in combination of two or more.
  • Examples of (b3) vinyl monomers other than (meth)acrylic monomers having no functional group that can be the first reactive group include aromatic vinyl monomers, heterocyclic vinyl monomers, vinyl carboxylates, and tertiary amino groups. and vinyl monomers, vinyl amides, ⁇ -olefins, dienes, halogenated vinyl monomers, and the like.
  • Examples of the aromatic vinyl monomers include styrene, ⁇ -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene and 1-vinylnaphthalene.
  • Examples of the vinyl monomer containing the heterocycle include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 2-vinylpyridine, 4-vinylpyridine and the like.
  • Examples of the vinyl carboxylate include vinyl acetate, vinyl pivalate, and vinyl benzoate.
  • Examples of vinyl monomers containing a tertiary amino group include N,N-dimethylallylamine.
  • Examples of the vinylamides include N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinyl- ⁇ -caprolactam and the like.
  • Examples of the ⁇ -olefin include 1-hexene, 1-octene, 1-decene and the like.
  • Examples of the dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, and 7-methyl-1,6-octadiene.
  • halogenated vinyl monomers examples include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, tetrafluoropropylene, vinylidene chloride, vinyl chloride, 1-chloro-1-fluoro Examples include ethylene, 1,2-dichloro-1,2-difluoroethylene, and the like.
  • Vinyl monomers other than the (b4) (meth)acrylic monomer having a functional group capable of serving as the first reactive group include vinyl monomers having a hydroxy group, vinyl monomers having a carboxy group, vinyl monomers containing an epoxy group, and the like. mentioned.
  • Examples of vinyl monomers having a hydroxy group include p-hydroxystyrene and allyl alcohol.
  • vinyl monomers having a carboxyl group include crotonic acid, maleic acid, itaconic acid, citraconic acid, and cinnamic acid.
  • Examples of vinyl monomers containing epoxy groups include 2-allyloxirane, glycidyl vinyl ether, 3,4-epoxycyclohexyl vinyl ether, and the like.
  • the content of structural units derived from a (meth)acrylate having an alkyl group having 1 to 12 carbon atoms is preferably 70% by mass or more, more preferably 80% by mass. % by mass or more, more preferably 90% by mass or more, preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 96% by mass or less.
  • Examples of (meth)acrylates having an alkyl group having 1 to 12 carbon atoms include (meth)acrylates having a linear alkyl group having 1 to 12 carbon atoms, and (meth)acrylates having a branched alkyl group having 1 to 12 carbon atoms. ) acrylates are preferred.
  • a polymerization method for polymerizing the monomer composition either a free radical polymerization method or a living radical polymerization method can be employed.
  • the method for polymerizing the (meth)acrylic polymer (A) is preferably living radical polymerization. That is, the (meth)acrylic polymer (A) is preferably polymerized by living radical polymerization.
  • the method of polymerizing the (meth)acrylic polymer (B) is preferably living radical polymerization. That is, the (meth)acrylic polymer (B) is preferably polymerized by living radical polymerization.
  • the living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method. It is preferable in terms of precise control of , and easy production of a polymer having a uniform composition.
  • Living radical polymerization methods include methods using compounds that can generate nitroxide radicals (nitrooxide method; NMP method); A method of living polymerization from the polymerization initiation compound (ATRP method); a method of using a dithiocarboxylic acid ester or a xanthate compound (RAFT method); a method of using an organic tellurium compound (TERP method); A method using an organic iodine compound (ITP method); a method using an iodine compound as a polymerization initiator compound and an organic compound such as a phosphorus compound, a nitrogen compound, an oxygen compound, or a hydrocarbon as a catalyst (reversible transfer catalyst polymerization; RTCP method, reversible catalyst-mediated polymerization; RCMP method).
  • TERP method it is preferable to use the TERP method from the viewpoint of the diversity of usable monomers, molecular weight control in the high molecular region, uniform composition, or coloring.
  • the TERP method is a method of polymerizing a radically polymerizable compound (vinyl monomer) using an organic tellurium compound as a chain transfer agent. 2004/072126 and methods described in WO 2004/096870.
  • Specific polymerization methods for the TERP method include the following (a) to (d).
  • R 1 is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group.
  • R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • R 4 is an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amido group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group.
  • R 1 is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group.
  • Specific examples of the organic ditelluride compound represented by formula (2) include dimethyl ditelluride, dibutyl ditelluride, and the like.
  • the azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization.
  • ADVN ,2′-azobis(2,4-dimethylvaleronitrile)
  • ACBN 1,1′-azobis(1-cyclohexanecarbonitrile)
  • V-70 2,2′-azobis(4-methoxy-2,4- dimethylvaleronitrile)
  • the polymerization step is carried out in a vessel substituted with an inert gas, with a vinyl monomer and an organic tellurium compound of formula (1) for the purpose of promoting the reaction, controlling the molecular weight and molecular weight distribution depending on the type of the vinyl monomer, and further adding an azo A polymerization initiator and/or an organic ditelluride compound of formula (2) are mixed.
  • the inert gas include nitrogen, argon, and helium. Argon and nitrogen are preferred.
  • the amount of the vinyl monomer used in (a), (b), (c) and (d) may be appropriately adjusted according to the physical properties of the desired polymer.
  • the polymerization reaction can be carried out without a solvent, it may be carried out by using an aprotic or protic solvent generally used in radical polymerization and stirring the mixture.
  • Aprotic solvents that can be used are, for example, acetonitrile, methyl ethyl ketone, anisole, benzene, toluene, propylene glycol monomethyl ether acetate, ethyl acetate, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), acetone, dioxane, chloroform, carbon tetrachloride and the like.
  • protic solvents examples include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, diacetone alcohol and the like.
  • a solvent may be used individually and may use 2 or more types together.
  • the amount of the solvent to be used may be appropriately adjusted, and is preferably 0.01 ml to 50 ml per 1 g of the vinyl monomer.
  • the reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the polymer component to be obtained, but the mixture is usually stirred at 0°C to 150°C for 1 minute to 100 hours.
  • the pressure is usually normal pressure, but may be pressurized or reduced.
  • the desired polymer can be separated from the resulting reaction mixture by removing the used solvent, residual vinyl monomer, etc., by a conventional separation and purification means.
  • the growing terminal of the polymer obtained by the polymerization reaction is in the form of —TeR 1 (wherein R 1 is the same as above) derived from the tellurium compound, and is deactivated by an operation in air after the completion of the polymerization reaction.
  • TeR 1 (wherein R 1 is the same as above) derived from the tellurium compound
  • tellurium atoms may remain. Since a polymer having a tellurium atom remaining at the end thereof is colored or has poor thermal stability, it is preferable to remove the tellurium atom.
  • Examples of the method for removing tellurium atoms include a radical reduction method; a method of adsorption with activated carbon or the like; a method of adsorbing a metal with an ion exchange resin or the like; these methods can also be used in combination.
  • the other end of the polymer obtained by the polymerization reaction (the end opposite to the growing end) is -CR 2 R 3 R 4 derived from a tellurium compound (wherein R 2 , R 3 and R 4 are represented by the formula ( 1) are the same as R 2 , R 3 and R 4 in ).
  • Free radical polymerization method A conventionally known method may be adopted for the free radical polymerization method.
  • Polymerization initiators used in free radical polymerization include azo polymerization initiators, peroxide polymerization initiators, and the like.
  • the azo polymerization initiator include 2,2′-azobis(isobutyronitrile) (AIBN), 2,2′-azobis(2-methylbutyronitrile) (AMBN), 2,2′- azobis(2,4-dimethylvaleronitrile) (ADVN), 1,1′-azobis(1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4 '-azobis(4-cyanovaleric acid) (ACVA), 1,1'-azobis(1-acetoxy-1-phenylethane), 2,2'-azobis(2-methylbutyramide), 2,2'- Azobis(4-methoxy-2,4-dimethylvaleronitrile
  • the polymerization reaction can be carried out without a solvent, it may be carried out by using an aprotic or protic solvent generally used in radical polymerization and stirring the mixture.
  • Aprotic solvents that can be used are, for example, acetonitrile, anisole, benzene, toluene, N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), acetone, 2-butanone.
  • protic solvents include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol and diacetone alcohol.
  • the amount of the solvent to be used may be adjusted as appropriate. For example, it is preferably 0.01 ml or more, more preferably 0.05 ml or more, still more preferably 0.1 ml or more, and 50 ml or less per 1 g of the vinyl monomer. It is preferably 10 ml or less, more preferably 1 ml or less.
  • the reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the resulting polymer component, but the mixture is usually stirred at 0°C to 150°C for 1 minute to 100 hours. At this time, the pressure is usually normal pressure, but may be pressurized or reduced.
  • the intended polymer composition can be separated from the resulting reaction mixture by removing the used solvent, residual vinyl monomer, etc., by a conventional separation and purification means.
  • the adhesive composition contains a cross-linking agent.
  • the cross-linking agent is a compound having two or more second reactive groups in one molecule that react with the first reactive groups of the (meth)acrylic polymer.
  • the cross-linking agent is not particularly limited, and examples thereof include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, aziridine-based cross-linking agents, metal chelate-based cross-linking agents, melamine resin-based cross-linking agents, and urea resin-based cross-linking agents.
  • the said crosslinking agent may be used individually by 1 type, and may use 2 or more types together. Among these, isocyanate-based cross-linking agents and epoxy-based cross-linking agents are preferred.
  • the average number of second reactive groups in one molecule of the cross-linking agent is 2 or more, preferably 8 or less, and more preferably 6 or less.
  • the molecular weight of the cross-linking agent is preferably 200 or more, more preferably 300 or more, still more preferably 400 or more, and preferably 1500 or less, more preferably 1000 or less, still more preferably 700 or less.
  • the content of the second reactive group in the cross-linking agent is preferably 1.5 mmol/g or more, more preferably 3 mmol/g or more, still more preferably 3.7 mmol/g or more, and preferably 10 mmol/g or less. Preferably, it is 8 mmol/g or less. If the content of the second reactive group of the cross-linking agent is within this range, the valence of the cross-linking agent will be low, the cross-linking points will be evenly distributed in the adhesive, and the average distance between cross-linking points will be long. Therefore, the resulting adhesive material has a low initial stress and exhibits high restorability.
  • Examples of the combination of the first reactive group possessed by the (A) (meth)acrylic polymer and (B) the (meth)acrylic polymer and the second reactive group possessed by the cross-linking agent include the following combinations: mentioned.
  • the second reactive group of the cross-linking agent is an isocyanate group
  • the first reactive group may be a hydroxy group.
  • the second reactive group of the cross-linking agent is an epoxy group
  • the first reactive group may be a carboxy group.
  • first reaction a combination in which the reactive group is a hydroxy group and the second reactive group is an isocyanate group; (2) a combination in which the first reactive group is a carboxy group and the second reactive group is an epoxy group; is preferred.
  • the isocyanate-based cross-linking agent is a compound having two or more isocyanate groups (including isocyanate-regenerative functional groups in which the isocyanate groups are temporarily protected by a blocking agent or quantization) as the second reactive groups in one molecule.
  • the isocyanate-based cross-linking agents may be used alone or in combination of two or more.
  • Isocyanate-based cross-linking agents include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, adducts of these with various polyols, polyfunctionalized with isocyanurate bonds, biuret bonds, allophanate bonds, etc. polyisocyanate, and the like.
  • a compound having two isocyanate groups including an isocyanate-regenerative functional group in which the isocyanate group is temporarily protected by a blocking agent or quantification
  • a compound having three isocyanate groups including an isocyanate regenerative functional group temporarily protected by a blocking agent or a quantization, etc.
  • an isocyanate group Compounds (hexafunctional isocyanate-based cross-linking agents) having 6 in one molecule (including isocyanate regenerative functional groups in which isocyanate groups are temporarily protected by blocking agents or quantification) are exemplified.
  • Diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds can be mentioned as bifunctional isocyanate-based cross-linking agents, and adducts of these diisocyanate compounds and diol compounds can also be used.
  • the diol compound is a compound represented by the general formula "HO-Y-OH" (Y is a divalent aliphatic group, a divalent alicyclic group, a divalent aromatic group, etc.). .
  • aliphatic diisocyanate compounds include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, 2,2,4- Examples include trimethyl-1,6-hexamethylene diisocyanate, among which aliphatic diisocyanate compounds having 4 to 30 carbon atoms are preferred, and aliphatic diisocyanate compounds having 4 to 10 carbon atoms are more preferred.
  • alicyclic diisocyanate compound examples include isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate and the like, among which 7 carbon atoms. ⁇ 30 alicyclic diisocyanate compounds are preferred.
  • aromatic diisocyanate compounds include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenylether diisocyanate, diphenylmethane diisocyanate, diphenylpropane diisocyanate, etc., and aromatic diisocyanate compounds having 8 to 30 carbon atoms are preferred.
  • diol compound examples include 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-ethyl-2 -Butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol and other aliphatic diol compounds, among which 3 to 10 carbon atoms is preferred.
  • Examples of the trifunctional isocyanate cross-linking agent and the hexafunctional isocyanate cross-linking agent include the adduct of the diisocyanate compound, the biuret of the diisocyanate compound, the isocyanurate of the diisocyanate compound (cyclic multimer of diisocyanate compounds), and the like. be done.
  • the isocyanate-based cross-linking agent preferably does not have an aromatic ring.
  • the isocyanate-based cross-linking agent includes an aliphatic diisocyanate compound, and a bifunctional isocyanate-based cross-linking agent selected from the group consisting of an adduct of an aliphatic diisocyanate compound and an aliphatic diol compound; Trifunctional or hexafunctional isocyanate-based cross-linking agents selected from the group consisting of adducts, biurets of aliphatic diisocyanate compounds, and isocyanurate compounds of aliphatic diisocyanates are preferred.
  • epoxy cross-linking agent refers to a compound having two or more epoxy groups in one molecule as a second reactive group.
  • the epoxy-based cross-linking agents may be used alone or in combination of two or more.
  • Epoxy-based cross-linking agents include aliphatic epoxy compounds, alicyclic epoxy compounds, aromatic epoxy compounds, heterocyclic epoxy compounds, and the like.
  • Examples of the aliphatic epoxy compounds include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane polyglycidyl ether, diglycidylamine, neopentyl glycol diglycidyl ether, propylene glycol diglycidyl ether, Polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, polyglycerol polyglycidyl ether, adipic acid diglycidyl ester, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane and
  • Examples of the alicyclic epoxy compounds include 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, N,N,N',N'-tetraglycidyl- and m-xylylenediamine.
  • aromatic epoxy compound examples include bisphenol A epichlorohydrin type epoxy resin, diglycidylaniline, o-diglycidyl phthalate, resorcin diglycidyl ether, and bisphenol-S-diglycidyl ether.
  • heterocyclic epoxy compounds examples include triglycidyl-tris(2-hydroxyethyl) isocyanurate, 1,3,5-tris-(2,3-epoxybutyl)-isocyanurate, 1,3,5-tris- (3,4-epoxybutyl)-isocyanurate, 1,3,5-tris-(4,5-epoxypentyl)-isocyanurate, sorbitan polyglycidyl ether and the like.
  • the epoxy-based cross-linking agent a compound having two epoxy groups in one molecule (bifunctional epoxy-based cross-linking agent), a compound having three epoxy groups in one molecule (tri-functional epoxy-based cross-linking agent) or an epoxy group A compound having four in one molecule (tetrafunctional epoxy-based cross-linking agent) is preferred.
  • the cross-linking agent is a bifunctional epoxy cross-linking agent, a tri-functional epoxy cross-linking agent or a tetra-functional epoxy cross-linking agent, the cross-linking points will be evenly distributed in the adhesive material and the average distance between cross-linking points will be long. Therefore, the resulting adhesive material has a low initial stress and exhibits high restorability.
  • the adhesive composition preferably contains only an isocyanate-based cross-linking agent or only an epoxy-based cross-linking agent as a cross-linking agent.
  • an isocyanate-based cross-linking agent is contained as a cross-linking agent, a bifunctional isocyanate-based cross-linking agent having two isocyanate groups in one molecule, a trifunctional isocyanate-based cross-linking agent having three isocyanate groups in one molecule, or one It is preferable to contain only a hexafunctional isocyanate-based cross-linking agent having 6 isocyanate groups in the molecule.
  • a bifunctional epoxy-based cross-linking agent having two epoxy groups in one molecule a trifunctional epoxy-based cross-linking agent having three epoxy groups in one molecule, or , preferably contains only a tetrafunctional epoxy-based cross-linking agent having four epoxy groups in one molecule.
  • the content of the cross-linking agent in the adhesive composition is preferably 0.05 parts by mass or more, more preferably 0.07 parts by mass or more, and preferably 0.4 parts by mass or less with respect to the total 100 parts by mass of the polymer components. , more preferably 0.3 parts by mass or less. If the content of the cross-linking agent is within the above range, the flexibility and resilience will be in a suitable range.
  • the molar ratio of the second reactive group possessed by the cross-linking agent to the first reactive group possessed by the (meth)acrylic polymer in the polymer component is 1 or more, preferably 1.5 or more, more preferably 2.0 or more, preferably 80 or less, more preferably 50 or less, still more preferably 30 or less, and particularly preferably 20 or less.
  • the cross-linking agent reacts just enough, the second reactive group does not surplus, and high flexibility is exhibited. express.
  • additives In addition to the polymer component and the cross-linking agent, other additives may be added to the adhesive composition.
  • Other additives include cross-linking accelerators, cross-linking retarders, tackifying resins (tackifiers), polymerizable compounds, photopolymerization initiators, silane coupling agents, plasticizers, softeners, release aids, dyes, and pigments.
  • dyes include dyes, fluorescent brighteners, antistatic agents, wetting agents, surfactants, thickeners, antifungal agents, preservatives, oxygen absorbers, ultraviolet absorbers, antioxidants, near-infrared absorbers, water-soluble quenchers agents, fragrances, metal deactivators, nucleating agents, alkylating agents, flame retardants, lubricants, processing aids, and the like.
  • Cross-linking accelerator A cross-linking accelerator may be added to the adhesive composition as necessary.
  • cross-linking accelerators include organic tin compounds and metal chelate compounds.
  • the cross-linking accelerators may be used alone, or two or more of them may be used in combination.
  • organic tin compounds examples include dibutyltin dilaurate, dioctiolstin dilaurate, and dibutyltin dioctylate.
  • the metal chelate compound is a complex in which a ligand having two or more coordinating atoms forms a ring and is bound to a central metal.
  • the content of the cross-linking accelerator in the adhesive composition is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and still more preferably 0.04 parts by mass or more with respect to 100 parts by mass of the polymer component. , preferably 0.5 parts by mass or less, more preferably 0.4 parts by mass or less, and even more preferably 0.3 parts by mass or less.
  • Cross-linking retarder A cross-linking retarder may be added to the adhesive composition as necessary.
  • the cross-linking retarder is a compound capable of suppressing an excessive increase in viscosity of the pressure-sensitive adhesive composition by blocking the functional group of the cross-linking agent in the pressure-sensitive adhesive composition containing the cross-linking agent.
  • cross-linking retarder is not particularly limited, but for example, ⁇ -diketones such as acetylacetone, hexane-2,4-dione, heptane-2,4-dione, octane-2,4-dione; ⁇ -ketoesters such as methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate and stearyl acetoacetate; benzoylacetone and the like can be used.
  • the cross-linking retarder one capable of acting as a chelating agent is preferable, and ⁇ -diketones and ⁇ -ketoesters are preferable.
  • the content of the cross-linking retarder that can be blended in the adhesive composition is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and still more preferably 0.1 part by mass or more, relative to 100 parts by mass of the polymer component. It is 5 parts by mass or more, preferably 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, and even more preferably 1.5 parts by mass or less.
  • tackifier resin A tackifier resin other than the polymer component may be blended in the adhesive composition, if necessary.
  • the tackifier resin is not particularly limited, and examples thereof include rosin-based tackifier resins, terpene-based tackifier resins, phenol-based tackifier resins, and hydrocarbon-based tackifier resins.
  • rosin-based tackifying resins examples include unmodified rosins (fresh rosins) such as gum rosin, wood rosin, tall oil rosin, and modified rosins obtained by modifying these unmodified rosins by polymerization, disproportionation, hydrogenation, etc. rosin, stabilized rosin, disproportionated rosin, completely hydrogenated rosin, partially hydrogenated rosin, and other chemically modified rosins), as well as various rosin derivatives.
  • fresh rosins fresh rosins
  • modified rosins obtained by modifying these unmodified rosins by polymerization, disproportionation, hydrogenation, etc.
  • rosin stabilized rosin, disproportionated rosin, completely hydrogenated rosin, partially hydrogenated rosin, and other chemically modified rosins
  • rosin derivative examples include rosin phenolic resins obtained by adding phenol to rosins (unmodified rosin, modified rosin) with an acid catalyst and thermally polymerizing them; Ester compounds (unmodified rosin esters) and denatured rosin ester compounds obtained by esterifying denatured rosin with alcohols (polymerized rosin esters, stabilized rosin esters, disproportionated rosin esters, completely hydrogenated rosin esters, partially hydrogenated rosin rosin ester-based resins such as esters); unsaturated fatty acid-modified rosin-based resins obtained by modifying unmodified rosin or modified rosin with unsaturated fatty acids; unsaturated fatty acid-modified rosin ester-based resins obtained by modifying rosin ester-based resins with unsaturated fatty acids ; unmodified rosin, modified rosin, rosin alcohol resin obtained by reducing the carboxyl group in unsaturated
  • Terpene-based tackifying resins include, for example, ⁇ -pinene polymer, ⁇ -pinene polymer, terpene-based resins such as dipentene polymer, and modification of these terpene-based resins (phenol modification, aromatic modification, hydrogenation modification, hydrocarbon-modified) modified terpene-based resins (for example, terpene-phenolic resins, styrene-modified terpene-based resins, aromatic modified terpene-based resins, hydrogenated terpene-based resins).
  • phenol modification, aromatic modification, hydrogenation modification, hydrocarbon-modified terpene-based resins for example, terpene-phenolic resins, styrene-modified terpene-based resins, aromatic modified terpene-based resins, hydrogenated terpene-based resins.
  • phenol-based tackifying resins include condensation products of various phenols (e.g., phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcinol) and formaldehyde (e.g., alkylphenol-based resins, xylene-formaldehyde-based resins), resoles obtained by addition reaction of the above phenols and formaldehyde with an alkali catalyst, and novolaks obtained by condensation reaction of the above phenols and formaldehyde with an acid catalyst.
  • phenols e.g., phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcinol
  • formaldehyde e.g., alkylphenol-based resins, xylene-formaldehyde-based resins
  • resoles obtained by addition reaction of the above phenols and formaldehyde with an alkali
  • hydrocarbon-based tackifying resins include, for example, aliphatic hydrocarbon resins [olefins and dienes having 4 to 5 carbon atoms (olefins such as butene-1, isobutylene, pentene-1; butadiene, Dienes such as 1,3-pentadiene and isoprene), etc.], aliphatic cyclic hydrocarbon resins [so-called “C4 petroleum fraction” and “C5 petroleum fraction” are cyclized dimers Alicyclic hydrocarbon resins polymerized after solidification, polymers of cyclic diene compounds (cyclopentadiene, dicyclopentadiene, ethylidenenorbornene, dipentene, etc.) or hydrogenated products thereof, aromatic hydrocarbon resins such as the following Alicyclic hydrocarbon resins obtained by hydrogenating aromatic rings of aliphatic/aromatic petroleum resins], aromatic hydrocarbon resins [vinyl group-containing
  • the content of the tackifying resin that can be blended in the adhesive composition is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more with respect to 100 parts by mass of the polymer component. It is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 40 parts by mass or less.
  • the adhesive composition may contain a polymerizable compound. Flexibility can be imparted to the adhesive by blending the polymerizable compound and polymerizing the polymerizable compound in the adhesive.
  • Examples of the polymerizable compound include compounds having two or more polymerizable groups in one molecule.
  • Examples of polymerizable groups include ethylenically unsaturated groups.
  • the said polymerizable compound can be used individually or in combination of 2 or more types.
  • Examples of the polymerizable compound include compounds having two or more (meth)acryloyl groups, and polyfunctional monomers and polyfunctional oligomers are preferred.
  • the number of ethylenically unsaturated groups in one molecule of the polymerizable compound is preferably 2 or more, preferably 4 or less, and more preferably 3 or less.
  • Examples of the compound having two or more (meth)acryloyl groups include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, and (poly)propylene glycol.
  • the content of the polymerizable compound is preferably 0.1 parts by mass or more, more preferably 2.5 parts by mass or more, relative to 100 parts by mass of the polymer component. , preferably 100 parts by mass or less, more preferably 50 parts by mass or less.
  • photopolymerization Initiator When the polymerizable compound is cured with an active energy ray, it is preferable to add a photopolymerization initiator to the adhesive composition. By blending a photopolymerization initiator, the reaction during active energy ray irradiation can be stabilized.
  • the photopolymerization initiator is not particularly limited as long as it generates radicals by the action of light. is mentioned. These photopolymerization initiators can be used alone or in combination of two or more. Among these photopolymerization initiators, photopolymerization initiators of hydrogen abstraction type benzophenones and intramolecular cleavage type acetophenones are preferable from the viewpoint of efficient intermolecular or intramolecular crosslinking.
  • the content of the photopolymerization initiator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polymer component. , more preferably 0.5 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 2 parts by mass or less.
  • the content of the photopolymerization initiator is within the above range, the curing speed is improved, and insufficient curing can be suppressed.
  • the adhesive composition may contain an auxiliary agent for the photopolymerization initiator.
  • auxiliary agent include triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoate, and ethyl 4-dimethylaminobenzoate.
  • silane coupling agent A silane coupling agent may be added to the adhesive composition as necessary.
  • the silane coupling agent include, but are not limited to, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Epoxy group-containing silane coupling agents such as 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3- Amino group-containing silane coupling agents such as triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl- ⁇ -aminopropyltrimethoxysilane; 3-acryloxypropyltrimethoxysilane, 3- Examples thereof include (meth)acryl
  • the content of the silane coupling agent that can be blended in the adhesive composition is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, relative to 100 parts by mass of the polymer component. parts by mass or less, more preferably 0.8 parts by mass or less, and even more preferably 0.6 parts by mass or less.
  • the adhesive composition may contain a plasticizer, if necessary.
  • plasticizer include, but are not limited to, oils such as paraffin oil and process oil; liquid rubbers such as liquid polyisoprene, liquid polybutadiene, and liquid ethylene-propylene rubber; tetrahydrophthalic acid, azelaic acid, benzoic acid, and phthalate.
  • Acids trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citric acid and their derivatives; dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl adipate, adipine diisononyl acid (DINA), isodecyl succinate, and the like.
  • the said plasticizer may be used individually by 1 type, and may use 2 or more types together. Among these, liquid rubber is preferred.
  • the weight average molecular weight (Mw) of the liquid rubber is preferably 5,000 or more, more preferably 10,000 or more, and preferably 60,000 or less, more preferably 50,000 or less.
  • Mw weight average molecular weight
  • the content of the plasticizer is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more based on 100 parts by mass of the polymer component. It is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.
  • the adhesive composition can be produced by mixing the polymer component, the cross-linking agent, and other optional additives.
  • the adhesive composition may contain a solvent derived from the production of the polymer component, or may be a solution diluted to a suitable viscosity for forming an adhesive layer by adding a suitable solvent. There may be.
  • the solvent examples include aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; acetone, methyl ethyl ketone, 2-pentanone, isophorone, and cyclohexanone. esters such as ethyl acetate and butyl acetate; cellosolve solvents such as ethyl cellosolve; and glycol ether solvents such as propylene glycol monomethyl ether. These solvents may be used singly or in combination of two or more.
  • the amount of the solvent used may be appropriately adjusted so that the adhesive composition has a viscosity suitable for coating, and is not particularly limited, but from the viewpoint of coatability, for example, 1% by mass to 90% by mass is preferable. , more preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass.
  • the adhesive material of the present invention can be formed by applying and drying the adhesive composition. Moreover, the coating film may be heated, if necessary, in order to promote the formation of the crosslinked structure.
  • the pressure-sensitive adhesive sheet of the present invention comprises a base sheet and a pressure-sensitive adhesive layer formed on at least one surface of the base sheet, wherein the pressure-sensitive adhesive layer is the pressure-sensitive adhesive.
  • the adhesive layer is formed on at least one side or at least a part of the base sheet.
  • the adhesive layer may be a single layer or may have a multilayer structure.
  • sheet is defined in JIS as a flat product that is thin and generally has a small thickness relative to its length and width.
  • a thin flat product with an extremely small thickness and an arbitrarily limited maximum thickness usually supplied in the form of a roll (Japanese Industrial Standard JIS K6900).
  • a thickness of 100 ⁇ m or more is called a sheet, and a thickness of less than 100 ⁇ m is sometimes called a film.
  • the boundary between a sheet and a film is not clear, and there is no need to distinguish between the two in the present invention. But "sheet” is included.
  • the base sheet can be appropriately selected and used according to the application of the pressure-sensitive adhesive sheet.
  • Polyimide resin such as polyethylene terephthalate (PET) resin and polyethylene naphthalate (PEN) resin; polycarbonate resin; poly(meth)acrylate resin; polystyrene resin; polyamide resin;
  • Polyolefin resins such as polyethylene resins, polycycloolefin resins, cycloolefin copolymer resins; polyphenylene sulfide resins; polysulfone resins; polyether sulfone resins; polyether ether ketone resins; (TAC) resin, cellulose resin such as diacetyl cellulose resin; polyvinyl chloride resin; polyvinylidene chloride resin; polyvinyl alcohol resin; polyvinyl acetate resin;
  • the polymeric materials may be used alone or in combination of two or more.
  • PET resin is preferable in terms of excellent mechanical strength and dimensional stability.
  • a polyimide resin is preferable in that it is excellent in heat resistance.
  • the base sheet is preferably a PET sheet (especially a biaxially stretched PET sheet) or a polyimide sheet.
  • the thickness of the base sheet is not particularly limited and may be appropriately selected, but is generally preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, still more preferably 20 ⁇ m or more, and preferably 200 ⁇ m or less, more preferably 100 ⁇ m. 50 ⁇ m or less, more preferably 50 ⁇ m or less. If the thickness is less than 5 ⁇ m, the strength of the base sheet will be insufficient, and problems such as tearing of the sheet will occur when peeled off. Further, if the thickness of the base sheet is thicker than 200 ⁇ m, problems such as the sheet itself becoming expensive occur.
  • one side or both sides of the base sheet can be surface-treated by an oxidation method, a roughening method, or the like, if desired.
  • the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone/ultraviolet irradiation treatment, and the like.
  • the roughening method include a sandblasting method and a solvent treatment method.
  • the thickness of the adhesive material (adhesive layer) formed on the base sheet can be appropriately set according to, for example, the adhesive force required for the adhesive sheet.
  • the thickness of the adhesive layer is generally preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, still more preferably 10 ⁇ m or more, and preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less, still more preferably 50 ⁇ m or less.
  • the method for forming the adhesive layer is not particularly limited, and includes, for example, a method of applying an adhesive composition and drying it, as in the following methods (1) and (2).
  • (1) A method of applying an adhesive composition to one or both sides of a substrate sheet using various coating devices, removing the solvent by drying, and curing as necessary.
  • (2) Using various coating devices, the adhesive composition was applied to the release surface of the release sheet whose surface was subjected to release treatment, the solvent was removed by drying, and the adhesive composition was transferred to one or both sides of the base sheet. After that, how to cure as needed.
  • Examples of the coating apparatus include reverse roll coaters, gravure coaters, forward roll coaters, knife coaters, wire bar coaters, doctor blade coaters, slot die coaters, curtain coaters, and dip coaters.
  • the drying temperature for removing the solvent by drying is preferably 40°C or higher, more preferably 60°C or higher, and preferably 150°C or lower, more preferably 140°C or lower, and still more preferably 130°C or lower.
  • the drying time is preferably 5 seconds to 20 minutes, more preferably 10 seconds to 10 minutes. Drying means include hot air, near-infrared rays, infrared rays, high-frequency waves, and the like. Further, the curing conditions include, for example, 30° C. to 60° C. for 3 to 7 days.
  • the pressure-sensitive adhesive sheet may have a release sheet (separator) on the surface of the pressure-sensitive adhesive layer until it is used.
  • a release layer is provided on the opposite side of the adhesive layer laminated surface of the base sheet without using a separate release sheet, and the surface of the release layer is wound in a roll so that the exposed surface side of the adhesive layer is in contact. , or may be stacked in a stack.
  • the release sheet is used as a protective material for the adhesive layer, and is peeled off when the adhesive sheet of the present invention is attached to an adherend.
  • the release sheet examples include paper such as glassine paper, coated paper, laminated paper, and various plastic sheets coated with a release agent such as silicone resin.
  • the plastic sheet used for the release sheet the ones listed as the base sheet can be appropriately used.
  • the thickness of the release sheet is not particularly limited, it is usually 10 ⁇ m to 150 ⁇ m.
  • the adhesive material of the present invention is preferably used for an adhesive layer (adhesive material) used in a flexible display that can be repeatedly bent and stretched.
  • an adhesive layer adhesive material
  • Examples of the flexible display that can be used by repeatedly bending and stretching include a foldable display that can be folded and a rollable display that can be rolled into a cylindrical shape.
  • Flexible displays are expected to be used for mobile terminals such as smartphones and tablet terminals, and stationary displays that can be stored.
  • Adhesive materials for flexible displays As the adhesive material for flexible displays, it is suitable as an adhesive material for flexible displays for bonding one flexible member and another flexible member constituting a flexible display.
  • the adhesive sheet for a flexible display includes an adhesive layer used for bonding one flexible member and another flexible member constituting a flexible display, and a flexible sheet member attached to at least one surface of the adhesive layer. wherein the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive material.
  • the configuration of the pressure-sensitive adhesive sheet for a flexible display includes an embodiment having an adhesive layer and a first flexible sheet member adhered to one side of the pressure-sensitive adhesive layer; and a second flexible sheet member attached to the other surface of the adhesive layer.
  • FIG. 1 An example of the adhesive sheet for flexible displays of the present invention is shown in FIG.
  • the flexible display adhesive sheet 10 of FIG. 1 is composed of an adhesive layer 12, a first flexible sheet member 14 sandwiching the adhesive layer 12, and a second flexible sheet member 16. As shown in FIG. The adhesive layer 12 is in contact with the releasable surfaces of the first flexible sheet member 14 and the second flexible sheet member 16 .
  • the adhesive layer is formed from the adhesive material.
  • the thickness of the adhesive layer is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, and even more preferably 10 ⁇ m or more, from the viewpoint of ensuring sufficient adhesion to the adherend.
  • the thickness of the adhesive layer is preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less, and even more preferably 50 ⁇ m or less from the viewpoint of suppressing the protrusion of the adhesive layer.
  • the flexible sheet members include flexible base sheets and release sheets.
  • the base sheet is a sheet member that supports the adhesive layer, and this sheet member may be a functional sheet member.
  • the functional sheet members include cover films, barrier films, polarizing films, retardation films, optical compensation films, brightness enhancement films, diffusion films, and antireflection films.
  • the release sheet protects the adhesive layer until the adhesive layer is adhered to the adherend, and is peeled off from the adhesive layer before the adhesive layer is adhered to the adherend.
  • the flexible sheet members include polymeric material sheets and glass sheets.
  • the thickness of the flexible sheet member is not particularly limited, it is preferably 2 ⁇ m to 500 ⁇ m, more preferably 2 ⁇ m to 200 ⁇ m from the viewpoint of excellent handleability.
  • Polyimide resin polyester resin such as polyethylene terephthalate resin and polyethylene naphthalate resin; polycarbonate resin; poly(meth)acrylate resin; polystyrene resin; polyamide resin; Polyolefin resins such as cycloolefin resins and cycloolefin copolymer resins; polyphenylene sulfide resins; polyvinyl chloride resins; polyvinylidene chloride resins; The polymeric materials may be used alone or in combination of two or more.
  • the flexible sheet member may be composed of a single layer comprising a layer containing one or more of the polymeric materials, or a layer containing one or more of the polymeric materials and a layer containing the polymeric material. It may be composed of two or more layers, such as a layer containing one or more polymeric materials different from the layer.
  • the flexible sheet member is preferably a release sheet whose surface in contact with the adhesive layer is subjected to release treatment.
  • Release agents used in the release treatment include, for example, silicone-based, fluorine-based, alkyd-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents.
  • the adhesive sheet for a flexible display has a first flexible sheet member attached to one surface of the adhesive layer and a second flexible sheet member attached to the other surface of the adhesive layer,
  • the first flexible sheet member is the first release sheet
  • the second flexible sheet member is the second release sheet
  • the first release sheet and the second release sheet are adhered so that the respective release surfaces are in contact with the adhesive layer. It is preferable that When the adhesive layer is sandwiched between two release sheets, one of the release sheets should be a heavy release type release sheet with a large release force, and the other release sheet should be a light release type release sheet with a small release force. is preferred.
  • the pressure-sensitive adhesive sheet for flexible displays can be produced, for example, by applying the above-described pressure-sensitive adhesive composition onto a flexible sheet member and, if necessary, curing it by a drying heat treatment to form an pressure-sensitive adhesive layer.
  • a reverse gravure coating method for example, a reverse gravure coating method, a direct gravure coating method, a die coating method, a bar coating method, a wire bar coating method, a roll coating method, a spin coating method, a dip coating method, a spray coating method, a knife
  • Various coating methods such as coating method and kiss coating method; inkjet method; various printing methods such as offset printing, screen printing and flexo printing can be employed.
  • the surface of the release sheet may be subjected to surface treatment such as corona treatment, plasma treatment, hot air treatment, ozone treatment, and ultraviolet treatment.
  • the drying and heating step is not particularly limited as long as the solvent or the like used in the adhesive composition can be removed and cured, but it is preferable to carry out at a temperature of 60°C to 150°C for about 20 seconds to 600 seconds.
  • the heating temperature is preferably 100°C to 150°C.
  • the adhesive composition is applied to the first flexible sheet member, and the adhesive layer is formed on the first flexible sheet member. is formed, the second flexible sheet member may be adhered to this adhesive layer. Furthermore, the adhesive layer may be cured as necessary.
  • the curing conditions include, for example, 60° C. for about 3 to 7 days.
  • a flexible laminated member of the present invention is a flexible laminated member comprising a first flexible member, a second flexible member, and an adhesive layer for bonding the first flexible member and the second flexible member together,
  • the adhesive layer is made of the adhesive material. Since the adhesive layer of the flexible laminated member is formed from the adhesive material, even when the flexible laminated member is repeatedly bent, appearance defects such as wavy appearance at the bent portion are suppressed.
  • the flexible laminated member 20 of FIG. 2 includes a first flexible member 22, a second flexible member 24, and an adhesive layer between the first flexible member 22 and the second flexible member 24 for bonding these flexible members together. 12.
  • the configuration of the flexible laminated member includes, for example, a configuration in which both the first flexible member and the second flexible member are constituent members of the flexible device;
  • a configuration that is a functional sheet member bonded to a flexible device may be mentioned.
  • the flexible device include a foldable display that can be folded and a rollable display that can be rolled into a cylinder.
  • the functional sheet members include cover films, barrier films, polarizing films, retardation films, optical compensation films, brightness enhancement films, diffusion films, antireflection films, transparent conductive films, metal mesh films, cushion films, and the like. be done.
  • the first flexible member and the second flexible member are members that can be repeatedly bent or bent for use.
  • Examples of the first flexible member and the second flexible member include flexible substrate materials, functional sheet members, and display elements (organic EL modules, electronic paper modules, etc.). At least one of the first flexible member and the second flexible member is preferably a display element.
  • the flexible laminate member can be used in flexible displays.
  • the method for producing the flexible laminated member of the present invention is not particularly limited, and examples thereof include the following methods (1) to (4).
  • the release sheet attached to one surface of the adhesive sheet is peeled off, the exposed adhesive layer is attached to the first flexible member, and then the release sheet is attached to the other surface of the adhesive sheet. is peeled off, and the exposed adhesive layer and the second flexible member are adhered to obtain a flexible laminated member.
  • the adhesive layer After coating the adhesive composition on one surface of the first flexible member and curing it by drying and heat treatment as necessary to form an adhesive layer, the adhesive layer has the releasability of a release sheet. Affix the surface. Then, the adhesive layer exposed by peeling off the release sheet is attached to the second flexible member to obtain a flexible laminated member.
  • the order of using the first flexible member and the second flexible member may be changed.
  • the adhesive layer can be formed using various coating methods and various printing methods similar to those used in the production of the adhesive sheet, and the same applies to the drying and heating process. Moreover, you may cure as needed.
  • the release sheet used for manufacturing the flexible laminated member may be the same as the release sheet used for the pressure-sensitive adhesive sheet.
  • EHA 2-ethylhexyl acrylate
  • LA n-lauryl acrylate
  • HA n-hexyl acrylate
  • BA n-butyl acrylate
  • VP N-vinyl-2-pyrrolidone
  • ACMO acryloyl morpholine
  • AA acrylic acid
  • HBA 4-hydroxybutyl acrylate
  • AIBN azobisisobutyronitrile
  • AcOEt ethyl acetate
  • Polystyrene as a standard substance 10,200, 2,630, 440 was used to prepare a calibration curve (calibration curve), and the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured. A molecular weight distribution (Mw/Mn) was calculated from this measured value.
  • the thickness of the adhesive material is obtained by measuring the total thickness of the entire adhesive sheet using a thickness measuring machine ("TH-104" manufactured by Tester Sangyo Co., Ltd.) and subtracting the thickness of the release sheet from this total thickness. rice field.
  • the adhesive layers (adhesive material) constituting the adhesive sheet were laminated together using a hand roller to prepare a laminate having a thickness of 600 ⁇ m, which was used as a test piece.
  • the measurement was performed using a dynamic viscoelasticity measuring device (manufactured by Anton Paar, MCR702) by sandwiching the sample between parallel plates with a diameter of 8 mm.
  • the measurement conditions were a temperature range of ⁇ 60° C. to 150° C., a temperature increase rate of 3° C./min, and a frequency of 1 Hz.
  • the strain is changed stepwise according to the elastic modulus, from the start of measurement to 0.1% up to 10 MPa, 0.2% up to 0.5 MPa, 0.5% up to 0.09 MPa, 1.5% up to 0.05 MPa, 3% at less than 0.05 MPa.
  • Glass transition temperature Tg Glass transition temperature
  • Tg glass transition temperature
  • Shear storage modulus G' The shear storage modulus G' at 25°C was read from the dynamic viscoelasticity measurement results.
  • the molecular weight at which the molecular weight distribution curve reaches a maximum was defined as the peak top molecular weight (Mp).
  • Mp peak top molecular weight
  • W1 the ratio of the peak area with a molecular weight of 10,000 or more to less than 100,000 with respect to the peak area with a molecular weight of 10,000 to 30,000,000
  • W2a the ratio of peak area of molecular weight of 150,000 or more to less than 560,000 to the peak area of the molecular weight of 10,000 to 30,000,000
  • W2b The ratio of the peak area of less than 10,000 (W2a) and the ratio of the peak area of the molecular weight of 150,000 or more to less than 560,000 to the peak area of the molecular weight of 10,000 to 30,000,000
  • the adhesive layers (adhesive material) constituting the adhesive sheet were laminated together using a hand roller to prepare a laminate having a thickness of 600 ⁇ m, which was used as a test piece.
  • the measurement was performed using a viscoelasticity measuring device (MCR302, manufactured by Anton Paar), sandwiching the sample between 8 mm diameter parallel plates (the bonding surface was roughened with No. 240 sandpaper) and performed in an atmosphere of 25°C.
  • the test piece was compressed with an axial force of 1 N and left to stand for 10 minutes, then the axial force was changed to 0.05 N, and shear stress was immediately applied to strain the specimen up to 400% strain.
  • the strain was kept at 400% for 10 minutes, and the change in shear stress was measured to measure the stress relaxation time.
  • the shear stress was released (0 kPa) and left for 10 minutes, and the final strain after 10 minutes was measured to obtain the recovery rate.
  • the stress relaxation time was the time required for the shear stress to become 0.368 times the initial stress after the strain reached 400%.
  • the shear stress value 0.1 seconds after the start of shear stress application was defined as the initial stress.
  • the adhesive layers (adhesive material) constituting the adhesive sheet were laminated together using a hand roller to prepare a laminate having a thickness of 600 ⁇ m, which was used as a test piece.
  • the measurement was performed using a viscoelasticity measuring device (MCR302, manufactured by Anton Paar), sandwiching the sample between 8 mm diameter parallel plates (the bonding surface was roughened with No. 240 sandpaper) and performed in an atmosphere of 25°C.
  • the release sheet is peeled off from the adhesive layer, and the adhesive layer surface is covered with a polyimide (PI) film (Kapton (registered trademark) 100V: manufactured by Toray DuPont, thickness 25 ⁇ m), or white plate glass (S9112, Matsunami Glass Industry 1.0 to 1.2 mm in thickness) was crimped by reciprocating a 2 kg roller twice.
  • the sample pressure-bonded to the polyimide (PI) film was further autoclaved at 60° C., 5 atm, and 30 minutes.
  • Tables 1 and 2 show the polymerization conditions for each polymer.
  • the amount of carboxyl groups, the amount of hydroxy groups and the glass transition temperature were calculated from the charging ratio and polymerization rate of the monomers used in the polymerization reaction.
  • Adhesive composition No. 1 Polymer No. obtained in Synthesis Example 1; 1 solution (polymer component 100 parts by mass), polymer No. 1 obtained in Synthesis Example 11; 0.222 parts by mass of a cross-linking agent (Duranate (registered trademark) D101) and butyl acetate were added to the solution of No. 11 (100 parts by mass of the polymer component), and stirred to give an adhesive composition No. 11 having a solid content of 24% by mass. got 1.
  • Adhesive composition No. 2 to 35 Adhesive composition no. Adhesive composition No. 1 was prepared in the same manner as in 1. 2-35 were made. The amount of the cross-linking agent shown in Tables 3 to 5 is the amount in terms of solid content. A solid content is a component other than a solvent. Adhesive composition no. In Nos. 2 to 24 and 30 to 35, the first reactive group possessed by the (meth)acrylic polymer (A) is a hydroxy group, and the second reactive group possessed by the cross-linking agent is an isocyanate group. Adhesive composition no. In Nos. 25 to 29, the first reactive group possessed by the (meth)acrylic polymer (A) is a carboxy group, and the second reactive group possessed by the cross-linking agent is an epoxy group.
  • Cross-linking agent A Duranate (registered trademark) D101 (manufactured by Asahi Kasei, isocyanate-based cross-linking agent (hexamethylene diisocyanate-1,6-hexanediol adduct, number of functional groups: 2, solid content concentration: 100% by mass, NCO content: 4.7 mmol/g (Solid content conversion)))
  • Cross-linking agent B D178NL (manufactured by Mitsui Chemicals, isocyanate-based cross-linking agent (hexamethylene diisocyanate allophanate, functional group number 2, solid content concentration 100% by mass, NCO amount 4.6 mmol / g (solid content conversion))
  • Cross-linking agent C Duranate (registered trademark) TPA-100 (manufactured by Asahi Kasei, isocyanate-based cross-linking agent (hexamethylene diisocyanate cyclic trimer, number of functional groups 3, solid content concentration
  • Adhesive No. 1 to 29 have a shear storage modulus of 0.15 MPa or less at a temperature of 25° C., a glass transition temperature of 0° C. or less, a gel fraction of 50% to 95% by mass, and a differential molecular weight distribution curve of the sol component. satisfies the requirements of (1), (2) and (3). These adhesive no. 1 to 29 were good in both the recovery rate after being distorted to 400% strain and the amount of strain when a shear stress of 20 kPa was applied. Also, the adhesive strength was good for both glass and PI film.
  • Adhesive No. 30 is a case where the gel fraction exceeds 95% by mass and the content of the sol component is too small. This adhesive No. 30 had poor adhesion to both glass and PI film. Adhesive No. 31 and 32 are cases where the gel fraction is less than 50% mass. These adhesive no. Nos. 31 and 32 were inferior in both the recovery rate after being distorted to 400% strain and the recovery rate when a shear stress of 20 kPa was applied.
  • Adhesive No. No. 33 is the case where the shear storage modulus at a temperature of 25° C. exceeds 0.15 MPa. This adhesive No. No. 33 had a poor recovery rate after straining up to 400% strain.
  • Adhesive No. 34 and 35 are cases where the differential molecular weight distribution curve of the sol component does not satisfy the requirements (2) and (3). These adhesive no. Nos. 34 and 35 had poor recovery rates when a shear stress of 20 kPa was applied, and had poor adhesion to both glass and PI film.
  • the present invention includes the following aspects.
  • the ratio (W1) of the peak area with a molecular weight of 10,000 or more and less than 100,000 to the peak area with a molecular weight of 10,000 to 30,000,000 is 20% or less.
  • the ratio (W2) of the peak area with a molecular weight of 100,000 or more and less than 560,000 to the peak area with a molecular weight of 10,000 to 30,000,000 is 40% or more.
  • the ratio (W3) of the peak area with a molecular weight of 560,000 or more to the peak area with a molecular weight of 10,000 to 30,000,000 is 40% or less.
  • the ratio (W2a/W2) of the peak area ratio (W2) having a molecular weight of 100,000 or more and less than 560,000 to the peak area ratio (W2a) having a molecular weight of 100,000 or more and less than 150,000 is The pressure-sensitive adhesive according to aspect 2, which is 0.30 to 0.60.
  • the polymer (X) having a crosslinked structure is a (meth)acrylic polymer (A) having a first reactive group having a weight average molecular weight of 600,000 or more and 3,000,000 or less, and a weight average molecular weight (Mw) of 100,000 or more. 800,000 or less (meth)acrylic polymer (B), and a pressure-sensitive adhesive composition containing a cross-linking agent having a second reactive group that reacts with the first reactive group, obtained by cross-linking reaction.
  • the adhesive material according to any one of aspects 1 to 5.
  • the combination of the first reactive group and the second reactive group is a combination in which the first reactive group is a hydroxy group and the second reactive group is an isocyanate group, or the first reactive group
  • the adhesive material according to any one of .
  • An adhesive material for a flexible display characterized by:
  • a pressure-sensitive adhesive sheet for a flexible display comprising: a pressure-sensitive adhesive layer used for bonding one flexible member and another flexible member constituting a flexible display; and a flexible sheet member adhered to at least one surface of the pressure-sensitive adhesive layer. and A pressure-sensitive adhesive sheet for a flexible display, wherein the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive material according to any one of claims 1 to 10.
  • the adhesive sheet has a first flexible sheet member attached to one surface of the adhesive layer and a second flexible sheet member attached to the other surface of the adhesive layer, and the first flexible sheet member is attached to the other surface of the adhesive layer.
  • the sheet member is a first release sheet
  • the second flexible sheet member is a second release sheet
  • the first release sheet and the second release sheet are attached such that the release surfaces of the first release sheet and the second release sheet are in contact with the adhesive layer.
  • a flexible laminated member comprising a first flexible member, a second flexible member, and an adhesive layer for bonding the first flexible member and the second flexible member together, wherein the adhesive layer comprises: 11.
  • a flexible laminated member comprising the adhesive material according to any one of items 1 to 10.
  • Adhesive sheet 12 Adhesive layer 14: First flexible sheet member 16: Second flexible sheet member 20: Flexible laminate member 22: First flexible member 24: Second flexible member

Abstract

L'invention concerne un matériau adhésif sensible à la pression présentant une excellente adhésivité sensible à la pression, une excellente flexibilité et une excellente aptitude à la restauration. Le matériau adhésif sensible à la pression est caractérisé en ce qu'il comprend un polymère (X) qui présente une structure réticulée et présentant un module de conservation en cisaillement à 25 °C de 0,15 MPa ou moins, une température de transition vitreuse de 0 °C ou moins, et une teneur en gel comprise entre 50 et 95 % en masse, et en ce qu'il comprend un constituant sol donnant une courbe de distribution de poids moléculaire différentiel qui satisfait aux exigences suivantes : (1) la proportion (W1) de l'aire des pics apparaissant à des poids moléculaires de 10 000 et plus mais inférieurs à 100 000 à l'aire des pics apparaissant à des poids moléculaires de 10 000 à 30 000 000 est de 20 % ou moins ; (2) la proportion (W2) de l'aire des pics apparaissant à des poids moléculaires de 100 000 et plus mais inférieurs à 560 000 à l'aire des pics apparaissant à des poids moléculaires de 10 000 à 30 000 000 est de 40 % ou plus ; et (3) la proportion (W3) de l'aire des pics apparaissant à des poids moléculaires de 560 000 et plus à l'aire des pics apparaissant à des poids moléculaires de 10 000 à 30 000 000 est de 40 % ou moins.
PCT/JP2022/036455 2021-10-18 2022-09-29 Matériau adhésif sensible à la pression et feuille adhésive sensible à la pression WO2023068009A1 (fr)

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WO2013183563A1 (fr) * 2012-06-05 2013-12-12 日本カーバイド工業株式会社 Composition adhésive pour des plaques de polarisation, plaque de polarisation ayant un adhésif et dispositif d'affichage
WO2020095870A1 (fr) * 2018-11-06 2020-05-14 三菱ケミカル株式会社 Couche adhésive sensible à la pression, composition adhésive sensible à la pression, composition adhésive sensible à la pression sans solvant, adhésif sensible à la pression et feuille adhésive sensible à la pression
WO2021049229A1 (fr) * 2019-09-12 2021-03-18 住友化学株式会社 Corps stratifié optique et dispositif d'affichage
WO2021111995A1 (fr) * 2019-12-06 2021-06-10 大塚化学株式会社 Matériau adhésif, feuille adhésive et élément stratifié flexible
WO2021172017A1 (fr) * 2020-02-28 2021-09-02 東山フイルム株式会社 Matériau adhésif, feuille adhésive et élément stratifié flexible
JP7108165B1 (ja) * 2021-05-27 2022-07-28 東洋インキScホールディングス株式会社 粘着剤、粘着シート、積層体、およびフレキシブルディスプレイ
WO2022181355A1 (fr) * 2021-02-26 2022-09-01 大塚化学株式会社 Composition adhésive pour écrans souples, matériau adhésif et feuille adhésive
JP2022132137A (ja) * 2021-02-26 2022-09-07 大塚化学株式会社 フレキシブルディスプレイ用粘着組成物、粘着材および粘着シート

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011231189A (ja) * 2010-04-26 2011-11-17 Nippon Carbide Ind Co Inc 偏光板用粘着剤組成物、並びにそれを用いた粘着剤付偏光板及び液晶表示装置
WO2013183563A1 (fr) * 2012-06-05 2013-12-12 日本カーバイド工業株式会社 Composition adhésive pour des plaques de polarisation, plaque de polarisation ayant un adhésif et dispositif d'affichage
WO2020095870A1 (fr) * 2018-11-06 2020-05-14 三菱ケミカル株式会社 Couche adhésive sensible à la pression, composition adhésive sensible à la pression, composition adhésive sensible à la pression sans solvant, adhésif sensible à la pression et feuille adhésive sensible à la pression
WO2021049229A1 (fr) * 2019-09-12 2021-03-18 住友化学株式会社 Corps stratifié optique et dispositif d'affichage
WO2021111995A1 (fr) * 2019-12-06 2021-06-10 大塚化学株式会社 Matériau adhésif, feuille adhésive et élément stratifié flexible
WO2021172017A1 (fr) * 2020-02-28 2021-09-02 東山フイルム株式会社 Matériau adhésif, feuille adhésive et élément stratifié flexible
WO2022181355A1 (fr) * 2021-02-26 2022-09-01 大塚化学株式会社 Composition adhésive pour écrans souples, matériau adhésif et feuille adhésive
JP2022132137A (ja) * 2021-02-26 2022-09-07 大塚化学株式会社 フレキシブルディスプレイ用粘着組成物、粘着材および粘着シート
JP7108165B1 (ja) * 2021-05-27 2022-07-28 東洋インキScホールディングス株式会社 粘着剤、粘着シート、積層体、およびフレキシブルディスプレイ

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