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WO2018174085A1 - Composition durcissable, feuille et stratifié produits par utilisation de cette dernière, et dispositif d'affichage d'image - Google Patents

Composition durcissable, feuille et stratifié produits par utilisation de cette dernière, et dispositif d'affichage d'image Download PDF

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Publication number
WO2018174085A1
WO2018174085A1 PCT/JP2018/011170 JP2018011170W WO2018174085A1 WO 2018174085 A1 WO2018174085 A1 WO 2018174085A1 JP 2018011170 W JP2018011170 W JP 2018011170W WO 2018174085 A1 WO2018174085 A1 WO 2018174085A1
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acrylate
sheet
mass
polymer
curable composition
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English (en)
Japanese (ja)
Inventor
大樹 田畑
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to CN201880019382.9A priority Critical patent/CN110431174A/zh
Priority to KR1020197030832A priority patent/KR20190124318A/ko
Publication of WO2018174085A1 publication Critical patent/WO2018174085A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08J2323/22—Copolymers of isobutene; butyl rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical

Definitions

  • the present invention relates to a sheet having adhesive strength, holding power, transparency and water vapor barrier property, and further relates to a curable composition for producing this sheet.
  • OCA transparent optical adhesive
  • a polymer (referred to as “isobutylene polymer”) containing isobutene as a polymerization component and a copolymerization component can be given.
  • the isobutylene polymer has a feature that the water vapor barrier property is particularly high as a general-purpose soft resin, but the cohesive force is too small to be applied to the resin composition, so that the adhesive residue, low-temperature flow, insufficient holding power, etc. There was a problem.
  • Non-Patent Document 1 discloses a composition having a semi-IPN structure consisting of a network of isobutylene polymer and polycyclohexyl methacrylate (PCHMA), which is a monofunctional acrylate, and this composition has a low temperature flow. It is disclosed that the water vapor barrier property inherent in the isobutylene polymer is suppressed.
  • PCHMA polycyclohexyl methacrylate
  • Patent Document 1 discloses a pressure-sensitive adhesive composition containing a sealing resin such as an isobutylene polymer, a polyfunctional acrylate, and a specific silane compound, and a pressure-sensitive adhesive film obtained from this pressure-sensitive adhesive composition has an excellent water vapor content. It describes that it has barrier properties and transparency.
  • a sealing resin such as an isobutylene polymer, a polyfunctional acrylate, and a specific silane compound
  • the pressure-sensitive adhesive sheet composed of the isobutylene polymer and the polyfunctional acrylate disclosed in Patent Document 1 can have excellent water vapor barrier properties, the glass transition temperature is too low to obtain a sufficient pressure-sensitive adhesive force. I had a problem that I could't.
  • a method of increasing the glass transition temperature a method of blending a large amount of a tackifier such as petroleum resin is known, and even in Example 1 of Patent Document 1, about 25% by mass of a hydrogenated DCPD-based tackifier is present. It has been added.
  • the glass transition temperature can be increased, but the holding power as a property capable of maintaining the adhesion state for a long period of time is lowered.
  • the isobutylene polymer / DCPA-based composition containing tricyclodecane dimethanol diacrylate (DCPA) exemplified in the example of Patent Document 1 described above has a refractive index of the cured product equal to the refractive index of the isobutylene polymer. Since it is very close, the transparency of the composition can be maintained to some extent.
  • TEM transmission electron microscope
  • the compatibility of the isobutylene polymer and DCPA is not good, and a DCPA cured product having a size of 1 ⁇ m or more is dispersed. In such a state, there is a possibility that a problem occurs in holding power and transparency.
  • Non-Patent Document 1 when the content ratio of the isobutylene polymer is large, the characteristics of the isobutylene polymer appear remarkably, and it is difficult to obtain a pressure-sensitive adhesive sheet having sufficient adhesion and holding power. there were.
  • the present invention provides a sheet having good adhesive strength, good holding power, excellent transparency, and excellent water vapor barrier properties, and further a curable composition for producing this sheet. To do.
  • the present invention is a sheet comprising an isobutylene polymer (A) and an acrylate polymer (B), wherein the acrylate polymer (B) has a unit structure represented by the following formula (1) as a structural unit.
  • Each of the sheet has a functional acrylate unit and a polyfunctional acrylate unit, and the sheet has at least one maximum point of loss tangent (tan ⁇ ) in shear measurement at a frequency of 1 Hz in a range of ⁇ 30 ° C. to 30 ° C., and has a haze.
  • a sheet that is 2.0% or less is proposed.
  • R represents a hydrocarbon group
  • R ′ represents hydrogen (H) or a methyl group (CH 3 ), respectively).
  • the present invention also provides a curable composition containing 5 parts by mass or more and less than 100 parts by mass of an acrylate monomer with respect to 100 parts by mass of the isobutylene polymer (A), and the monofunctional acrylate monomer and the polyfunctional acrylate are used as the acrylate monomer.
  • the present invention proposes a curable composition having a monomer and containing the polyfunctional acrylate in the curable composition in an amount of 0.5% by mass or more and less than 10% by mass.
  • the curable composition proposed by the present invention can be cured to produce the sheet proposed by the present invention.
  • the sheet proposed by the present invention contains a monofunctional acrylate unit having a unit structure represented by the above formula (1) as a structural unit and an acrylate polymer (B) having a polyfunctional acrylate unit, A semi-IPN (interpenetrating polymer network) structure can be formed between the isobutylene polymer (A) and the acrylate polymer (B), and both water vapor barrier properties and transparency can be achieved.
  • at least one maximum point of loss tangent (tan ⁇ ) in shear measurement at a frequency of 1 Hz is in the range of ⁇ 30 ° C.
  • FIG. 6 is a graph showing loss tangents (tan ⁇ ) of sheets (samples) obtained in Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-2, that is, sheets (samples) after curing treatment. It is the photograph which observed the sheet
  • a sheet according to an example of an embodiment of the present invention is a sheet including an isobutylene polymer (A) and an acrylate polymer (B).
  • the isobutylene polymer (A) constituting this sheet is a polymer having an isobutylene skeleton in the main chain or side chain, and has a structural unit of the following formula (2).
  • the isobutylene polymer (A) has a function of improving the water vapor barrier property of the sheet.
  • isobutylene polymer (A) an isobutylene polymer which is a homopolymer of isobutylene, a copolymer of isobutylene and isoprene, a copolymer of isobutylene and n-butene, a copolymer of isobutylene and butadiene, and these copolymers And halogenated butyl rubber obtained by bromination or chlorination.
  • These polymers can be used singly or in combination of two or more.
  • the isobutylene polymer (A) may be an isobutylene polymer, an isobutylene / isoprene copolymer, or a combination thereof. Is preferred.
  • the isobutylene / isoprene copolymer has, in its molecule, a repeating unit derived from isobutylene [—CH 2 —C (CH 3 ) 2 —] and a repeating unit derived from isoprene [—CH 2 —C (CH 3 ) ⁇ CH.
  • the content of repeating units derived from isoprene in the isobutylene / isoprene copolymer is usually from 0.1 to 99 mol%, preferably from 0.5 to 50 mol%, more preferably from all repeating units. 1 to 10 mol%. If the repeating unit derived from isoprene in the isobutylene / isoprene copolymer is in the above range, it is preferable because this sheet having excellent moisture resistance can be obtained.
  • the type of isobutylene / isoprene copolymer is not particularly limited. Examples thereof include regenerated isobutylene / isoprene copolymer and synthetic isobutylene / isoprene copolymer. Among these, a synthetic isobutylene / isoprene copolymer is preferable.
  • Examples of the method for synthesizing the isobutylene polymer include a method in which a monomer component such as isobutylene is polymerized in the presence of a Lewis acid catalyst such as aluminum chloride or boron trifluoride. Moreover, a commercial item can also be used as an isobutylene polymer (A). Examples of commercially available products include Vistanex (manufactured by Exxon Chemical Co.), Hycar (manufactured by Goodrich), Oppanol (manufactured by BASF), Tetrax (manufactured by JXTG), Nippon Polybutene (manufactured by JXTG), and the like. .
  • the weight average molecular weight (Mw) of the isobutylene polymer (A) is preferably 1,000 to 2,000,000 g / mol, more preferably 1,500 g / mol or more or 1,500,000 g / mol or less. Among them, it is more preferably 2,000 g / mol or more and 1,000,000 g / mol or less, especially 50,000 g / mol or more, especially 100,000 g / mol or more, especially 120,000 g / mol or more.
  • the isobutylene polymer weight average molecular weight (Mw) is an isobutylene polymer (A) having a molecular weight of 1,000 g / mol or more, the fluidity of the curable composition forming the sheet becomes appropriate, and the sheet shape It becomes easy to hold the shape after molding. Moreover, a uniform structure
  • the weight average molecular weight (Mw) is a value measured by gel permeation chromatography using tetrahydrofuran as a solvent (GPC analysis) and converted to standard polystyrene.
  • the isobutylene polymer (A) can also be used in combination of two or more types of isobutylene polymers (A) having different average molecular weights.
  • an isobutylene polymer having a weight average molecular weight of less than 100,000 g / mol and an isobutylene polymer having a weight average molecular weight of 100,000 g / mol or more are used in combination as an isobutylene polymer having a bimodal molecular weight distribution. be able to.
  • the weight average molecular weight of the whole isobutylene polymer (A) is 1,000 to 2,000,000 g / mol, more preferably 1,500 to 1,500,000. 000 g / mol, more preferably 2,000 to 1,000,000 g / mol.
  • Examples of commercially available products having a weight average molecular weight of less than 100,000 g / mol include trade name: Tetrax (JXTG), trade name: Nisseki Polybutene (JXTG), and trade name: Hymor (JXTG).
  • trade name: Opanol (BASF) can be mentioned.
  • the acrylate polymer (B) constituting the sheet includes, as structural units, a monofunctional acrylate unit having a unit structure represented by the following formula (1) (also simply referred to as “monofunctional acrylate”) and a polyfunctional acrylate unit (simply Those having “polyfunctional acrylate”) are preferred.
  • R represents a hydrocarbon group
  • R ′ represents hydrogen (H) or a methyl group (CH 3 ), respectively).
  • the acrylate polymer (B) preferably has at least two types of monofunctional acrylates.
  • the number of carbon atoms in the side chain becomes uneven, and the Tg of the sheet can be lowered.
  • the Tg of the sheet is about -2 ° C, while isostearyl (iso-C18) acrylate and cetyl (n When C16) acrylate is blended at a mass ratio of 1: 1, the Tg of the sheet can be reduced to around -20 ° C.
  • the monofunctional acrylate is preferably a monofunctional acrylate having a long-chain alkyl chain having 10 or more carbon atoms from the viewpoint of compatibility with the isobutylene polymer (A).
  • a monofunctional acrylate having a long-chain alkyl chain having 10 or more carbon atoms a monofunctional aliphatic acrylate which is an acrylate having one (meth) acryloyloxy group and having a long-chain alkyl chain having 10 or more carbon atoms
  • the structure is shown in the following formula (3).
  • R represents a long-chain alkyl group having 10 or more carbon atoms.
  • R ′ is hydrogen (H) or a methyl group (CH 3 ).
  • the long chain alkyl group (R) having 10 or more carbon atoms is an alkyl group having 10 or more carbon atoms in the main chain.
  • the carbon number of the main chain in the long chain alkyl group (R) is preferably 20 or less, particularly 18 or less. If the number of carbon atoms is 18 or less, crystallization between monofunctional aliphatic acrylates hardly occurs, and transparency due to low haze and high total light transmittance is easily exhibited. On the other hand, if the main chain has 10 or more carbon atoms, the long-chain alkyl group (R) may have a branched alkyl group. In general, a branched alkyl group is less likely to be crystallized in a normal temperature region than a straight chain alkyl group, and transparency is easily exhibited.
  • the long-chain alkyl group (R) is composed of two or more different combinations, crystallization can be suppressed and transparency can be improved.
  • the acrylate polymer (B) preferably contains a monofunctional acrylate in the range of 60 to 90% by mass, more preferably 70% by mass or more and 90% by mass or less. By setting it as such a range, creep resistance can also be improved, maintaining the transparency of this sheet
  • the content of the monofunctional acrylate with respect to the entire sheet is preferably 3% by mass or more.
  • seat can be improved because it is 3 mass% or more.
  • the content of the monofunctional acrylate with respect to the entire sheet is more preferably 5% by mass or more, and more preferably 10% by mass or more.
  • about the upper limit it is preferable that content of monofunctional acrylate is 50 mass% or less.
  • the content of the monofunctional acrylate is more preferably 40% by mass or less, and among them, 35% by mass or less, particularly 30% by mass or less, and particularly preferably 25% by mass or less.
  • the acrylate polymer (B) contains at least one monofunctional acrylate which is a branched alkyl group as R in the above formula (1) from the viewpoint of lowering the crystallinity of the side chain and improving the transparency. Is preferred.
  • the Hansen solubility parameter (HSP) distance between the isobutylene polymer (A) and the monofunctional acrylate of the acrylate polymer (B) is preferably 5.0 or less, more preferably 4.5 or less. Further, it is particularly preferably 3.8 or less. If the Hansen solubility parameter (HSP) distance between the isobutylene polymer (A) and the monofunctional acrylate of the acrylate polymer (B) is 5.0 or less, the isobutylene polymer (A) and the acrylate polymer (B ), And the deterioration of transparency due to bleed out and increased dispersion diameter can be suppressed.
  • the HSP of the monofunctional acrylate is preferably at a position where the HSP distance to the isobutylene polymer (A) is 5.0 or less, and more preferably at a position of 4.5 or less.
  • monofunctional acrylates having an HSP distance of 5.0 or less with the isobutylene polymer (A) include, for example, isostearyl acrylate, isohexadecyl acrylate, stearyl acrylate, hexadecyl acrylate, isotetradecyl acrylate, tetradecyl acrylate , Isododecyl acrylate, dodecyl acrylate, isodecyl acrylate, and the like.
  • HSP hansen solubility parameter
  • the dispersion term ⁇ D indicates the effect due to the dispersion force
  • the polar term ⁇ P indicates the effect due to the dipole force
  • the hydrogen bond term ⁇ H indicates the effect due to the hydrogen bond force
  • ⁇ D Energy derived from intermolecular dispersion force
  • ⁇ P Energy derived from intermolecular polar force
  • ⁇ H Energy derived from intermolecular hydrogen bonding force (Here, each unit is MPa 0.5 .)
  • HSP HSP The definition and calculation of HSP are described in the following documents. Charles M. Hansen, Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007).
  • the dispersion term reflects the van der Waals force
  • the polar term reflects the dipole moment
  • the hydrogen bond term reflects the action of water, alcohol, etc.
  • Those having similar vectors by HSP can be determined to have high solubility, and the similarity of vectors can be determined by the distance of the Hansen solubility parameter (HSP distance).
  • Hansen's solubility parameter can be an index not only for determining solubility, but also for determining how much a certain substance is likely to exist in another certain substance, that is, how good the dispersibility is.
  • HSP [ ⁇ D, ⁇ P, ⁇ H]
  • HSPiP computer software Hansen Solubility Parameters in Practice
  • Y-MB method implemented in HSPiP
  • the chemical structure is obtained by the sphere method implemented in HSPiP from the result of the dissolution test using a plurality of solvents.
  • HSP distance (Ra) is to example solute HSP of (acrylate polymer in the present invention (B)) ( ⁇ D 1, ⁇ P 1, ⁇ H 1) and, HSP solvent (isobutylene polymer in the present invention (A)) the ( ⁇ D 2, ⁇ P 2, ⁇ H 2) when formed into a can be calculated by the following equation.
  • HSP distance (Ra) ⁇ 4 ⁇ ( ⁇ D 1 - ⁇ D 2) 2 + ( ⁇ P 1 - ⁇ P 2) 2 + ( ⁇ H 1 - ⁇ H 2) 2 ⁇ 0.5
  • the network of the acrylate polymer (B) can be adjusted, and as a result, the plateau elastic modulus of the sheet can be adjusted.
  • the plateau elastic modulus can be increased as the addition amount of the polyfunctional acrylate is increased, and the plateau elastic modulus can be decreased as the molecular weight of the polyfunctional acrylate is increased.
  • the polyfunctional acrylate is an acrylate having two or more (meth) acryloyloxy groups, and at least (meth) acryloyloxy groups are bonded via a hydrocarbon group.
  • the structure of the bifunctional aliphatic acrylate is shown in the following formula (4).
  • R is hydrogen (H) or methyl group (CH 3).
  • X is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.
  • the HSP of the polyfunctional acrylate is preferably at a position where the HSP distance from the isobutylene polymer (A) is 9.0 or less, and more preferably at a position of 8.0 or less.
  • the aliphatic hydrocarbon group or alicyclic hydrocarbon group (X) is preferably a hydrocarbon group that does not contain multiple bonds from the viewpoint of long-term stability of the sheet.
  • polyfunctional acrylate examples include diacrylates having a linear alkyl group such as 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, hydrogenated polybutadiene acrylate; tricyclodecanediol diacrylate, tricyclode Examples thereof include diacrylates having an alicyclic skeleton such as candimethanol diacrylate. However, it is not limited to these.
  • Polyfunctional urethane acrylate can also be used as the polyfunctional acrylate.
  • a urethane acrylate having an aliphatic polymer such as polybutadiene in the skeleton is preferable.
  • commercially available urethane acrylate include trade name: CN9014 NS (Sartomer), trade name: BAC-45 (manufactured by Osaka Organic Chemical Co., Ltd., polybutadiene-terminated diacrylate), and the like. Since such a polymer-based polyfunctional acrylate has an effect of lowering the plateau elastic modulus of the sheet, the acrylate polymer (B) constituting the sheet contains the polyfunctional acrylate. It can be suitably used for folding displays and impact resistant applications.
  • the polyfunctional acrylate is not limited to the bifunctional acrylate, and may be a polyfunctional acrylate having 3, 4, or 4 (meth) acryloyl groups. However, from the viewpoint of long-term stability of the sheet and easy availability of the acrylate, a bifunctional acrylate is preferable.
  • polyfunctional acrylate may be only one type or two or more types.
  • the polyfunctional acrylate is preferably contained in the sheet in a proportion of 0.5% by mass or more and less than 10% by mass, particularly 0.7% by mass or more or less than 9% by mass, of which 1.0% by mass or more, or 8 More preferably, it is contained in a proportion of less than 0.0% by mass. Bleed out can be reduced by setting the polyfunctional acrylate content to less than 10% by mass. On the other hand, transparency can be expressed by making content of polyfunctional acrylate into 0.5 mass% or more.
  • the acrylate polymer (B) is preferably contained in a proportion of 5 parts by mass or more and less than 100 parts by mass with respect to 100 parts by mass of the isobutylene polymer (A). If content of an acrylate polymer (B) is 5 mass parts or more, the cohesion force of this curable composition can be improved effectively. Moreover, if content of an acrylate polymer (B) is 100 mass parts or less, the dispersion diameter of the (B) component in this sheet
  • the content of the acrylate polymer (B) is preferably 5 parts by mass or more and less than 100 parts by mass with respect to 100 parts by mass of the isobutylene polymer (A), and more preferably 8 parts by mass or more or 90 parts by mass. Or less, more preferably 10 parts by mass or more or 80 parts by mass or less.
  • the thickness of the sheet is not particularly limited. For example, it is 0.01 mm or more, more preferably 0.03 mm or more, still more preferably 0.05 mm or more.
  • the upper limit is preferably 1 mm or less, more preferably 0.7 mm or less, and still more preferably 0.5 mm or less. If the thickness is 0.01 mm or more, the handleability is good, and if the thickness is 1 mm or less, it can contribute to the thinning of the laminate.
  • a lump with a maximum diameter of 1 ⁇ m or more is not observed means that the sheet is dyed with ruthenium tetroxide or the like and then frozen with a cryomicrotome or the like, and the sheet is perpendicular to or parallel to the sheet surface.
  • TEM transmission electron microscope
  • the “lumps having a maximum diameter of 1 ⁇ m or more” are lumps composed of the acrylate polymer (B).
  • the fact that a lump having a maximum diameter of 1 ⁇ m or more is not observed means that the isobutylene polymer (A) and the acrylate polymer (B) are highly compatible with each other. As shown in FIGS. 2 to 5, the isobutylene polymer (A) and the acrylate polymer (B) have a co-continuous structure in which they are uniformly dispersed.
  • the acrylate monomer which is the precursor of the acrylate polymer (B), is uniformly mixed with the isobutylene polymer (A), and the acrylate monomer in the mixture is polymerized. Can take.
  • At least one maximum point of loss tangent (tan ⁇ ) in shearing at a frequency of 1 Hz is in a range of ⁇ 30 to 30 ° C.
  • the maximum point of the loss tangent (tan ⁇ ) is in the range of ⁇ 30 to 30 ° C.
  • a sheet having good adhesion and holding power can be obtained.
  • the maximum point of loss tangent (tan ⁇ ) can be adjusted.
  • the maximum point of loss tangent can be adjusted within the range of ⁇ 30 to 30 ° C. by adding a tackifier described later. However, it is not limited to such a method.
  • the maximum value of the loss tangent (tan ⁇ ) at a shear frequency of 1 Hz is within a range of ⁇ 30 to 30 ° C., and the maximum value of the loss tangent at a frequency of 1 Hz is 0.5 or more. From the viewpoint of ensuring adhesion, it is more preferably 0.55 or more, and even more preferably 0.6 or more.
  • the loss tangent (tan ⁇ ) at 100 ° C. of the sheet is preferably 0.6 or less, and more preferably 0.5 or less. When the loss tangent (tan ⁇ ) is 0.6 or less, sufficient high-temperature holding power can be expressed.
  • a polyfunctional acrylate may be blended with the acrylate polymer and sufficiently polymerized. However, it is not limited to this method.
  • the sheet preferably has a single glass transition temperature (Tg). It is rare for a multicomponent system consisting of at least the component (A) and the component (B) to have a single glass transition temperature (Tg) like a single material. However, in this sheet, since the compatibility of the component (A) and the component (B) is good, the glass transition temperature (Tg) can be made single. When the glass transition temperature is single, the transparency of the sheet can be increased.
  • the “glass transition temperature” refers to the temperature at which the main dispersion peak of loss tangent (tan ⁇ ) appears. Therefore, when only one maximum point of loss tangent (tan ⁇ ) in shearing at a frequency of 1 Hz is observed, it can be considered that the glass transition temperature (Tg) is single.
  • This sheet preferably has a total light transmittance of 85% or more, more preferably 88% or more, and further preferably 90% or more.
  • the sheet preferably has a haze of 2.0% or less, more preferably less than 1.0%, and particularly preferably less than 0.9%. When the haze is 2.0% or less, the sheet can be used for a display device depending on the application.
  • the sheet is required to have a water vapor transmission rate as low as possible in order to suppress deterioration of the light emitting element due to water and improve the life of the display device.
  • the water vapor transmission rate in an environment of a temperature of 40 ° C. and a relative humidity of 90% RH in terms of 100 ⁇ m thickness (when the thickness is 100 ⁇ m) of the sheet is preferably 20 g / m 2 ⁇ 24 h or less, It is more preferably 15 g / m 2 ⁇ 24 h or less, and particularly preferably 10 g / m 2 ⁇ 24 h or less.
  • the lower limit is not particularly limited, but is generally 0.5 g / m 2 ⁇ 24 h or more.
  • the isobutylene polymer (A) is contained in an appropriate amount as the present sheet.
  • the water vapor transmission rate can be measured according to JIS K7129B.
  • the thickness is A ⁇ m and the water vapor transmission rate is Bg / (m 2 ⁇ day)
  • the water vapor transmission rate in terms of 100 ⁇ m thickness is obtained by applying the formula B ⁇ A / 100. be able to.
  • the present sheet can be obtained by curing an uncured sheet made of the present curable composition described later.
  • a known method such as dry lamination, extrusion casting method using a T die, extrusion lamination method, calendar method, inflation method or the like can be employed.
  • a melt molding method such as an extrusion casting method and an extrusion lamination method is preferable.
  • the present curable composition for melt molding has a storage elastic modulus (G ′) at a shear frequency of 1 Hz in an uncured state of 1,000 Pa at 20 ° C. As mentioned above, it is especially preferable that it is 50,000 Pa or more and 160 Pa or less and 10,000 Pa or less. If G ′ at 20 ° C. is in the above range, the shape can be maintained at room temperature after molding. If G ′ at 160 ° C. is in the above range, molding can be performed without entraining bubbles.
  • G ′ storage elastic modulus
  • the molding temperature at the time of melt molding is preferably adjusted as appropriate depending on the flow characteristics, film forming properties, and the like.
  • the temperature is preferably 0 to 230 ° C., more preferably 80 ° C. or more, and particularly preferably 90 ° C. or more or 160 ° C. or less.
  • the thickness of the sheet can be appropriately adjusted by the lip gap of the T die, the sheet take-up speed, and the like.
  • a cured product can be produced by irradiating and curing the present curable composition with heat and / or active energy rays.
  • the sheet can be produced by irradiating the curable composition formed into a sheet with heat and / or active energy rays.
  • active energy rays to be irradiated ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, neutron rays, electron rays, ultraviolet rays, visible rays, and the like can be mentioned. Ultraviolet rays are preferred from the viewpoint of reaction control.
  • the present curable composition described later can be dissolved in an appropriate solvent, and various coating techniques can be used. However, in this embodiment, it is necessary to consider in terms of manufacturing cost such as solvent recovery.
  • the coating technique is used, the present sheet can be obtained by heat curing in addition to the above active energy ray irradiation curing.
  • a cured composition is easily obtained by thermal curing, and when it is a thermosetting composition, it has a decomposition temperature higher than the drying temperature of the solvent.
  • a polymerization initiator is selected.
  • the thickness of the sheet can be adjusted by the coating thickness and the solid content concentration of the coating solution.
  • this laminate can be cured by irradiation with heat and / or active energy rays to obtain a laminate in which a release film is laminated on at least one surface of the sheet. it can. If necessary, embossing and various irregularities (conical, pyramidal, hemispherical, etc.) processing may be performed. Further, various surface treatments such as corona treatment, plasma treatment and primer treatment may be performed on the surface for the purpose of improving adhesion to various adherends.
  • the curable composition examples include a curable composition containing an isobutylene polymer (A) and an acrylate monomer.
  • the “curable composition” means a composition having a property capable of being cured.
  • the present curable composition can be formed into a sheet and cured to produce the present sheet.
  • seat is not limited to the said method.
  • the isobutylene polymer (A) constituting the present curable composition may be the isobutylene polymer (A) described in the present sheet.
  • the acrylate monomer constituting the curable composition includes a monofunctional acrylate monomer (also referred to as “monofunctional acrylate”) and a polyfunctional acrylate monomer (also referred to as “polyfunctional acrylate”), respectively. It is preferable to have.
  • the monofunctional acrylate monomer and the polyfunctional acrylate monomer in the acrylate monomer may be the monofunctional acrylate and polyfunctional acrylate described in this sheet, respectively.
  • the acrylate monomer preferably contains two or more types of the monofunctional acrylate from the viewpoint of controlling the Tg after curing and suppressing crystallization.
  • the acrylate monomer preferably contains a monofunctional acrylate having a long alkyl chain having 10 or more carbon atoms.
  • the acrylate monomer contains a monofunctional acrylate having a long alkyl chain having 10 or more carbon atoms, the entanglement between the isobutylene polymer (A) and the acrylate polymer (B) is further increased.
  • the present curable composition which selectively contains a long-chain alkyl acrylate having 10 or more carbon atoms, greatly affects the higher-order structure of the present curable composition, and is a two-component curable composition. Can exhibit very good transparency.
  • the polyfunctional acrylate is preferably contained in the curable composition in an amount of 0.5% by mass or more and less than 10% by mass, and more preferably 0.7% by mass or more or less than 9% by mass, of which 1.0% by mass or more. Or it is more preferable to contain in less than 8.0 mass%. Bleed out can be reduced by setting the polyfunctional acrylate content to less than 10% by mass. On the other hand, transparency can be expressed by making content of polyfunctional acrylate into 0.5 mass% or more.
  • the content ratio of the acrylate monomer is preferably 5 parts by mass or more and less than 100 parts by mass with respect to 100 parts by mass of the isobutylene polymer (A), and more preferably 8 parts by mass or more or 90 parts by mass or less. More preferably, it is 10 mass parts or more or 80 mass parts or less.
  • a preferable curable composition is a curable composition containing 5 parts by mass or more and less than 100 parts by mass of an acrylate monomer with respect to 100 parts by mass of the isobutylene polymer (A), and as the acrylate monomer, A curable composition having a monofunctional acrylate monomer and a polyfunctional acrylate monomer, and containing the polyfunctional acrylate in the curable composition in an amount of 0.5% by mass or more and less than 10% by mass is given. be able to.
  • the curable composition preferably contains a polymerization initiator in order to obtain curability.
  • the polymerization initiator is not particularly limited as long as it is a polymerization initiator that can be used for the polymerization reaction of acrylate.
  • those activated by heat and those activated by active energy rays can be used. Any of those that generate radicals to cause radical reactions and those that generate cations and anions to cause addition reactions can be used.
  • a preferred polymerization initiator is a photopolymerization initiator, and generally the selection of the photopolymerization initiator depends at least in part on the specific components used in the curable composition and the desired cure rate.
  • the photopolymerization initiator examples include acetophenone such as phenyl or diphenylphosphine oxide, ketone, and acridine, benzoin, benzophenone, benzoyl compound, anthraquinone, thioxanthone, and phosphine oxide.
  • acetophenone such as phenyl or diphenylphosphine oxide, ketone, and acridine
  • benzoin benzophenone
  • benzoyl compound anthraquinone
  • thioxanthone thioxanthone
  • phosphine oxide phosphine oxide
  • LUCIRIN BASF
  • DAROCUR Ciba Specialty Chemicals
  • IRGACURE Ciba Specialty Chemicals
  • ethyl-2,4,6-trimethylbenzoyldiphenyl phosphinate available as LUCIRIN TPO
  • a photoinitiator can be mentioned.
  • photopolymerization initiator one having an excitation wavelength region of 400 nm or more can be selected and used.
  • Specific photopolymerization initiators include, for example, ⁇ -diketones such as camphorquinone and 1-phenyl-1,2-propanedione; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6 Acylphosphine oxides such as -trimethylbenzoyl) -phenylphosphine oxide; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- (4-methylthiophenyl) ⁇ -aminoalkylphenones such as -2-morpholinopropan-1-one; or bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) -1-yl) phenyl) titanium and other titanocen
  • ⁇ -diketones and acylphosphine oxides are preferable from the viewpoint of good polymerization activity and low harm to the living body, and camphorquinone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are more preferable. preferable.
  • thermal polymerization initiator can be used in addition to the photopolymerization initiator to form a crosslinked structure.
  • thermal polymerization initiators include azo compounds, quinine, nitro compounds, acyl halides, hydrazones, mercapto compounds, pyrylium compounds, imidazoles, chlorotriazines, benzoins, benzoin alkyl ethers, diketones, phenones, and dilauroyl peroxide and NOF. Co. And organic peroxides such as 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane available as PERHEXA TMH.
  • the polymerization initiator is often used at a concentration of about 0.01 to about 10% by weight, particularly about 0.01 to about 5% by weight, based on the total weight of the curable composition.
  • a mixture of polymerization initiators may be used.
  • the curable composition may further contain a tackifier in order to increase the adhesiveness.
  • the isobutylene resin composition contains a large amount of a tackifier.
  • the content of the tackifier is preferably less than 10% by mass in order to prevent problems such as a decrease in high-temperature cohesion due to the addition of the tackifier and yellowing. By setting it as this range, it can be set as the present curable composition excellent in high temperature cohesive force.
  • the tackifier may be any compound or mixture of compounds that enhance the adhesion of the curable composition.
  • the tackifier examples include an aliphatic hydrocarbon tackifier represented by a terpene tackifier, an aromatic hydrocarbon tackifier represented by a phenol tackifier, and a rosin tackifier.
  • Representative alicyclic hydrocarbon tackifiers, tackifiers composed of these hydrocarbon copolymers, epoxy tackifiers, polyamide tackifiers, ketone tackifiers, and hydrogens thereof An additive etc. are mentioned.
  • an aliphatic hydrocarbon tackifier, an aromatic hydrocarbon tackifier, an alicyclic hydrocarbon tackifier, and a tack made of these hydrocarbon copolymers An imparting agent is preferred.
  • Particularly preferred are aliphatic hydrocarbon tackifiers. These tackifiers can be used alone or in combination of two or more.
  • the present curable composition may contain a softening agent.
  • the softening agent can adjust the viscosity of the composition in order to improve processability, for example.
  • the softening agent examples include petroleum hydrocarbons such as aromatic, paraffin, and naphthene, petroleum jelly, petroleum asphalt, and the like. However, it is not limited to these. In embodiments that use a softener, a single softener or a combination of softeners can be used.
  • the liquid isobutylene polymer is treated as the isobutylene polymer (A).
  • the present curable composition may be a filler, a rust inhibitor, an acrylamide, a curing accelerator, a filler, a silane coupling agent, an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant, a stabilizer, or some of them. May be added to the curable composition.
  • the amount of these additives is typically preferably selected so as not to adversely affect the curing of the curable composition or to adversely affect the physical properties of the curable composition.
  • the state and form of the curable composition are arbitrary. For example, it may be liquid, gel, solid, or other state.
  • the present curable composition may be in various forms such as a sheet shape, a rod shape, a hollow shape, and other shapes.
  • a sheet shape such as a sheet shape, a rod shape, a hollow shape, and other shapes.
  • an unstretched sheet used as an adhesive sheet can be given.
  • the thickness is not particularly limited. For example, it is 0.01 mm or more, more preferably 0.03 mm or more, still more preferably 0.05 mm or more.
  • the upper limit is preferably 1 mm or less, more preferably 0.7 mm or less, and still more preferably 0.5 mm or less.
  • Method for producing the present curable composition Hereinafter, the manufacturing method of this curable composition is demonstrated.
  • the following description is an example of a method for producing the present curable composition, and the present curable composition is not limited to those produced by such a production method.
  • the curable composition contains, for example, an isobutylene polymer (A) (also referred to as “component (A)”) and an acrylate monomer containing a monofunctional acrylate (also referred to as “component (B)”). Preparing the composition, polymerizing the component (B) using the monofunctional acrylate, curing the curable composition, and preparing the curable composition by appropriately processing as necessary. Can do. However, it is not limited to such a manufacturing method.
  • the component (A), an acrylate monomer containing a monofunctional acrylate, a polymerization initiator, and an optional component are mixed into a kneading machine (for example, a single screw extruder, a twin screw extruder, a planetary mixer, a twin screw mixer). , A pressure kneader or the like) to prepare a curable composition that is a precursor of the present curable composition.
  • a kneading machine for example, a single screw extruder, a twin screw extruder, a planetary mixer, a twin screw mixer.
  • a pressure kneader or the like to prepare a curable composition that is a precursor of the present curable composition.
  • various additives such as silane coupling agents and antioxidants may be blended with the resin in advance and then supplied to the extruder. All materials may be supplied after being melt-mixed, or a master batch in which only the additive is previously concentrated in the resin may be prepared and supplied.
  • melt forming method As a method for forming the present curable composition into a sheet, a known method such as an extrusion casting method using a T die, an extrusion laminating method, a calendar method, an inflation method, or the like can be employed. Among these, from the viewpoint of handling properties, productivity, and the like, a melt molding method such as an extrusion casting method and an extrusion lamination method is preferable.
  • the present curable composition for melt molding has a storage elastic modulus (G ′) at a shear frequency of 1 Hz in an uncured state of 50,000 Pa at 20 ° C. As mentioned above, it is preferable that it is 10,000 Pa or less at 160 degreeC. If G ′ at 20 ° C. is in the above range, the shape can be maintained at room temperature after molding. If G ′ at 160 ° C. is in the above range, molding can be performed without entraining bubbles.
  • G ′ storage elastic modulus
  • the molding temperature at the time of melt molding is appropriately adjusted depending on flow characteristics, film forming properties, etc., but is preferably 80 to 230 ° C., more preferably 90 to 160 ° C.
  • the thickness of the sheet can be appropriately adjusted by the lip gap of the T die, the sheet take-up speed, and the like.
  • a laminate in which a release film is laminated on at least one surface of a sheet obtained by sheet-molding the present curable composition produced as described above is preferable.
  • at least one surface of the sheet may be embossed or processed with various irregularities (such as a cone, a pyramid shape, or a hemispherical shape).
  • various surface treatments such as corona treatment, plasma treatment and primer treatment may be performed on the surface for the purpose of improving adhesion to various adherends.
  • the sheet can be produced by irradiating a heat and / or active energy ray on the sheet obtained by molding the curable composition produced as described above.
  • active energy rays to be irradiated ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, neutron rays, electron rays, ultraviolet rays, visible rays, and the like can be mentioned.
  • Ultraviolet rays are preferred from the viewpoint of reaction control.
  • a polymerization initiator should be activated and acrylate should just be polymerized.
  • a curable composition when the viscosity of the curable composition is sufficiently low as a result of adding paraffin or isoparaffin as a softening agent, a curable composition can be formed by solventless coating on the film using a die coater or a comma coater. You may get
  • the curable composition can be dissolved in an appropriate solvent, and various coating techniques can be used. However, in this embodiment, it is necessary to consider in terms of manufacturing cost such as solvent recovery.
  • the coating technique is used, the present curable composition can also be obtained by heat curing in addition to the above active energy ray irradiation curing.
  • thermosetting in addition to active energy ray curing, it is easy to obtain a cured composition that is thermosetting, and in the case of a thermosetting composition, from the drying temperature of the solvent A polymerization initiator having a high decomposition temperature is selected.
  • the thickness of the sheet can be adjusted by the coating thickness and the solid content concentration of the coating solution.
  • this foldable sheet a sheet having a foldable property (referred to as “this foldable sheet”) will be described.
  • the demand for optical adhesive (OCA) for foldable (foldable) displays is increasing.
  • the conventional acrylic adhesive having a glass transition temperature (Tg) near 0 ° C. causes a problem that buckling occurs at the bonding interface. This is influenced by the dynamic viscoelasticity of the adhesive in the frequency range that humans bend. Therefore, it is preferable to further lower the glass transition temperature (Tg) of the adhesive and lower the elastic modulus in the low temperature region.
  • the glass transition temperature (Tg) of the foldable sheet is preferably ⁇ 15 ° C. or lower, and more preferably ⁇ 20 ° C. or lower.
  • the glass transition temperature (Tg) of the glass transition temperature (Tg) of the foldable sheet is preferably ⁇ 30 ° C. or higher.
  • At least one maximum point of loss tangent (tan ⁇ ) in shearing at a frequency of 1 Hz is in a range of ⁇ 30 ° C. to ⁇ 15 ° C.
  • the maximum point of the loss tangent (tan ⁇ ) is in the range of ⁇ 30 to ⁇ 15 ° C.
  • the acrylate polymer (B) has at least two types of monofunctional acrylate components having different R in the above formula (1), so that the maximum point of loss tangent (tan ⁇ ) is ⁇ 30 ° C. to ⁇ 30 ° C. It becomes easy to make it the range of 15 degreeC.
  • the maximum point of loss tangent (tan ⁇ ) can be appropriately adjusted by selecting the kind of acrylate constituting the isobutylene polymer (A) and the acrylate polymer (B) and the composition ratio thereof.
  • the maximum point of loss tangent can be adjusted within the range of ⁇ 30 to ⁇ 15 ° C. by adding a tackifier described later. However, it is not limited to such a method.
  • the acrylate polymer (B) is an acrylate having an acrylate unit structure having an ester part having a large number of carbon atoms (for example, 12 or more carbon atoms) from the viewpoint of compatibility with the isobutylene polymer (A). It is preferable that it is a polymer. Therefore, the curable composition and the foldable sheet containing a monofunctional acrylate having a hydrocarbon group having 12 or more carbon atoms as the acrylate monomer of the curable composition are preferably used.
  • the monofunctional acrylate has a characteristic that its glass transition temperature (Tg) is relatively higher than that of a general monofunctional acrylate, and can increase the Tg of the present curable composition and the present foldable sheet.
  • the Tg of a homopolymer of a monofunctional acrylate having a hydrocarbon group having 12 or more carbon atoms on the market is specifically shown. It can be seen that the larger the carbon number, the higher the Tg, and in all cases, the Tg is higher than ⁇ 15 ° C. Thus, the Tg of the homopolymer comprising the component is shown as “polymer Tg” below.
  • the Tg of the homopolymer is lower than that of the straight chain having the same carbon number, but the Tg of the commercially available branched alkyl acrylate shown below is still -15.
  • Tg over °C. Isostearyl acrylate (C18 branched, polymer Tg: 15 ° C. (DMA))
  • polyfunctional acrylates and the like can be added to the curable composition or the foldable sheet for crosslinking.
  • the polyfunctional acrylate from the viewpoint of compatibility with the isobutylene polymer (A), an acrylate having the following hydrocarbon group is selected, and the Tg of the resulting curable composition is further increased.
  • Tg of the acrylate copolymer (B) is obtained using the following FOX formula.
  • Formula of FOX: 1 / Tg W1 / T1 + W2 / T2 +... Wn / Tn
  • Tg is the theoretical glass transition temperature (K)
  • W1, W2... Wn is the mass fraction of each monomer
  • T1, T2... Tn are the measured glass transition temperatures (K) of each monomer. It is.
  • the maximum point of the loss tangent in shearing at a frequency of 1 Hz of the curable composition is ⁇
  • the actual situation is that the temperature exceeds 15 ° C., and it has been difficult to adjust it to ⁇ 15 ° C. or lower.
  • the acrylate polymer (B) contains at least two types of monofunctional acrylates, whereby the Tg of the curable composition can be dramatically reduced. This is considered to be due to a change in the interaction between the side chains composed of the long-chain hydrocarbon group of the acrylate polymer (B). As a result, a special phenomenon showing a Tg significantly lower than the Tg predicted from the FOX equation can be obtained.
  • the present curable composition having at least one maximum point of loss tangent (tan ⁇ ) in shear at a frequency of 1 Hz in the range of ⁇ 30 ° C. to ⁇ 15 ° C. can be produced and buckled by bending. Therefore, the present foldable sheet can be realized, and a curable composition having excellent adhesion, holding power, and water vapor barrier properties can be obtained.
  • the acrylate polymer (B) in the foldable sheet preferably contains a monofunctional acrylate in a proportion of 60 parts by mass or more with respect to 100 parts by mass of the acrylate polymer (B), especially 70 parts by mass or more. More preferably, it is contained in a proportion of 80 parts by mass or more.
  • the monofunctional acrylate is 60 parts by mass or more, the cohesive force of the sheet is effectively improved, and the good adhesive force and holding force of the curable composition are exhibited.
  • R is not particularly limited in the above formula (1) of the acrylate polymer (B).
  • the R is preferably a hydrocarbon group having a restricted carbon number of 12 to 30 from the viewpoint of adhesiveness and holding power.
  • R may contain a double bond, a triple bond, or an aromatic ring, and is preferably a hydrocarbon group that does not contain a double bond, a triple bond, or an aromatic ring from the viewpoint of long-term stability. .
  • R include, for example, a decyl group (C 10 ), an undecyl group (C 11 ), a dodecyl group (C 12 ), a tridecyl group (C 13 ), a tetradecyl group (C 14 ), and a pentadecyl group (C 15 ). , Hexadecyl group (C 16 ), heptadecyl group (C 17 ), octadecyl group (C 18 ), nonadecyl group (C 19 ) and the like.
  • the acrylate polymer (B) preferably includes at least two types of the monofunctional acrylate components having Rs having different carbon numbers in the above formula (1).
  • the acrylate polymer (B) preferably contains two types of acrylates having different R in the formula (1), and may contain three or more types.
  • the acrylate polymer (B) constituting the sheet preferably contains at least one monofunctional acrylate component which is a branched alkyl group as R in the above formula (1).
  • the optical adhesive can be folded (foldable) for a display. Further, it has an advantage that it is difficult to crystallize in a normal temperature region and transparency is easily developed. If it is a branched alkyl group, there will be no restriction
  • Preferred examples include branched alkyl groups such as a group (C 16 ), an isoheptadecyl group (C 17 ), an isooctadecyl (isostearyl) group (C 18 ), and an isonononadecyl group (C 19 ).
  • the branched alkyl group may be either secondary or tertiary, and the position of branching and the number of branches are not particularly limited as long as they can exist chemically and stably.
  • the content of the monofunctional acrylate component in which R in the above formula (1) is a branched alkyl group 30 monofunctional acrylate components in which R is a branched alkyl group with respect to 100 parts by mass of the acrylate polymer (B).
  • the amount is preferably from 80 parts by mass to 80 parts by mass, more preferably from 35 parts by mass to 75 parts by mass. If the content is 30 parts by mass or more, it becomes easy to express the transparency of the foldable sheet. On the other hand, if it is 80 parts by mass or less, the maximum point of the loss tangent (tan ⁇ ) of the foldable sheet can be easily set in the range of ⁇ 30 ° C. to ⁇ 15 ° C.
  • a monofunctional acrylate that becomes an acrylate polymer (B) by the curing reaction is shown in the following formula (3).
  • R represents a hydrocarbon group
  • R ′ represents hydrogen (H) or a methyl group (CH 3 ), respectively).
  • the HSP of the monofunctional acrylate is preferably located at a position where the HSP distance to the isobutylene polymer (A) is 5.0 or less, more preferably 4.5 or less.
  • monofunctional acrylates having an HSP distance of 5.0 or less with the isobutylene polymer (A) include isostearyl acrylate, isohexadecyl acrylate, stearyl acrylate, hexadecyl acrylate, isotetradecyl acrylate, tetradecyl acrylate, Examples thereof include isododecyl acrylate, dodecyl acrylate, and isodecyl acrylate.
  • At least one kind of R in the formula (3) is a branched alkyl group.
  • the maximum point of loss tangent (tan ⁇ ) of the foldable sheet can be easily set in the range of ⁇ 30 ° C. to ⁇ 15 ° C.
  • an optical adhesive for a foldable display can be obtained.
  • the branched alkyl group may be secondary or tertiary, and the position of the branch and the number of branches are not particularly limited as long as they can exist chemically and stably.
  • curable composition 60% of the monofunctional acrylate having the unit structure of the above formula (3) is used with respect to 100 parts by weight of the acrylate in the precursor composition before curing (hereinafter referred to as “curable composition”). It is preferably contained in an amount of at least part by mass, more preferably at least 70 parts by mass, and even more preferably at least 80 parts by mass.
  • the polyfunctional acrylate is an acrylate having two or more acryloyloxy groups and having at least acryloyloxy groups bonded via a hydrocarbon group.
  • the structure of a bifunctional aliphatic acrylate monomer is shown in the following formula (4).
  • R is hydrogen (H) or a methyl group (CH 3 ).
  • the content of the polyfunctional acrylate is preferably 0.5% by mass or more and less than 10% by mass with respect to the foldable sheet, more preferably 1% by mass or more or less than 9% by mass, and more preferably 2% by mass or more or 8%. More preferably, it is less than mass%.
  • the HSP of the polyfunctional acrylate used in the foldable sheet is preferably located at a position where the HSP distance to the isobutylene polymer (A) is 9.0 or less, and more preferably at a position of 8.0 or less.
  • X is preferably an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.
  • the polyfunctional acrylate used in this foldable sheet includes diacrylates having a linear alkyl group such as 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, hydrogenated polybutadiene acrylate; Examples thereof include, but are not limited to, diacrylates having an alicyclic skeleton such as decanediol diacrylate and tricyclodecane dimethanol diacrylate.
  • X may be a hydrocarbon group containing multiple bonds.
  • polyfunctional acrylates include trade name: BAC-45 (manufactured by Osaka Organic Chemical Co., Ltd., polybutadiene-terminated diacrylate).
  • polyfunctional urethane acrylate can also be used as polyfunctional acrylate.
  • a urethane acrylate having an aliphatic polymer such as polybutadiene in the skeleton is preferable.
  • brand name: CN9014 NS (Sartomer company) etc. can be mentioned.
  • X is preferably a hydrocarbon group consisting of a single bond.
  • the polyfunctional acrylate is not limited to a bifunctional acrylate, and a polyfunctional acrylate having 3, 4, or more than 4 (meth) acryloyl groups may be used. Among these, a bifunctional acrylate is preferable from the viewpoint of long-term stability of the sheet and ease of lowering the Tg of the curable composition.
  • polyfunctional acrylate only one type of polyfunctional acrylate may be used, or several types may be used in combination.
  • image display device By laminating the image display device constituting member on at least one surface of the sheet, an image display device constituting laminate can be formed, and the image display device can be configured using the image display device constituting laminate. it can.
  • At least one side of the sheet has a configuration in which any one or more members selected from the group consisting of a touch panel, an image display panel, a surface protection panel, a retardation film, a polarizing film, a color filter, and a flexible substrate are laminated. It can be set as the laminated body for image display apparatuses.
  • An image display device can be constituted by using the laminate for constituting an image display device composed of any one kind or a combination of two or more kinds.
  • the present sheet may be an image display device provided on the display surface side and / or the non-display surface side as the image display device constituent member.
  • a light emitting layer is formed on a resin substrate such as polyimide, and the light emitting layer side is a display surface, but by disposing the sealing material on the non-display surface side of the resin substrate, Intrusion of water from the non-display surface side and moisture absorption of polyimide can be prevented, which can contribute to extending the life of the OLED. Further, the influence of the deformation of the display surface and external force can be suppressed.
  • This foldable sheet can be suitably used as a constituent member of a foldable image display device.
  • acrylate is synonymous with acrylate and includes methacrylate unless otherwise specified.
  • Example 1 First, compounds and materials used in Examples 1-1 to 1-2 and Comparative Examples 1-1 to 1-4 are shown below. Next, production methods in each Example and Comparative Example are shown, and then evaluated. A method will be described.
  • HSP distance (Ra) HSP the acrylate (B) ( ⁇ D 1, ⁇ P 1, ⁇ H 1) and then, isobutylene polymer HSP of (A) ( ⁇ D 2, ⁇ P 2, ⁇ H 2) when the following It was calculated by the following formula.
  • HSP distance (Ra) ⁇ 4 ⁇ ( ⁇ D 1 - ⁇ D 2) 2 + ( ⁇ P 1 - ⁇ P 2) 2 + ( ⁇ H 1 - ⁇ H 2) 2 ⁇ 0.5
  • Table 1 shows the distances between the HSPs obtained by the Y-MB method of several components (b-1) and (b-2) and typical isobutylene polymers (A).
  • Total light transmittance, haze Further, the total light transmittance and haze were obtained by pasting the release film on one side to the measurement hole, peeling off the other release film, and using a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.). The total light transmittance was measured according to JIS K7361-1, and the haze was measured according to JIS K7136.
  • the release film on both sides of the sheet obtained from the composition was peeled off, and a plurality of sheets were stacked to prepare a sheet having a thickness of about 2 mm, and punched into a circle with a diameter of 20 mm.
  • a rheometer manufactured by Eiko Seiki Co., Ltd., MARS
  • the storage elastic modulus (G ′), loss elastic modulus (G ′′), and loss tangent (tan ⁇ ) in the cured state were obtained.
  • the uncured sheet is cured by irradiating ultraviolet rays with a high-pressure mercury lamp so that the integrated light quantity at 365 nm is 2000 mJ / cm 2, and 23 ° C. and 50% RH.
  • the cured sheet was obtained by curing for 15 hours or longer.
  • the thickness of the cured sheet is A ⁇ m
  • a value in terms of 100 ⁇ m was obtained by applying the formula A ⁇ B / 100.
  • the uncured sheets obtained in Examples 1-1 and 1-2 had excellent transparency with low haze and high total light transmittance. Further, cured sheets obtained by curing these uncured sheets also had excellent transparency with low haze and high total light transmittance. Furthermore, the cured sheet obtained in Example 1-3 also had low haze, high total light transmittance, and excellent transparency.
  • the cured sheet of Example 1-1 is excellent in impact energy absorption during high-speed deformation because the peak of loss tangent (tan ⁇ ) at a frequency of 1 Hz has a maximum value of 0.3 at ⁇ 35 ° C. Also, the water vapor permeability in terms of 100 ⁇ m was as good as 20 g / m 2 ⁇ 24 h or less.
  • the cured sheet of Example 1-2 is excellent in impact energy absorption during high-speed deformation because the peak of loss tangent (tan ⁇ ) at a shear frequency of 1 Hz has a peak value of 0.4 at ⁇ 38 ° C. Also, the water vapor permeability in terms of 100 ⁇ m was as good as 20 g / m 2 ⁇ 24 h or less.
  • the cured sheets of Comparative Examples 1-1 to 1-3 using only the monofunctional aliphatic acrylate (b-1) as the acrylate had high haze and poor transparency. This is considered to be because the polymer produced and the isobutylene polymer were phase-separated on the order of micrometers by the polymerization proceeding only with the monofunctional acrylate.
  • the cured sheet of Comparative Example 1-4 using only the polyfunctional alicyclic acrylate (b-2) as the acrylate bleeding out was confirmed in an uncured state, and haze was not preferable in the uncured sheet. Further, the transparency of the cured sheet obtained by curing this uncured sheet also deteriorated.
  • Example 2 The compounds and materials used in Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3 are shown below, followed by the production methods in each Example and Comparative Example, and then the evaluation method Will be described.
  • [Tackifier] (C) -1 YS resin PX800 (manufactured by Yasuhara Chemical Co., Ltd., terpene resin)
  • a molten curable composition is supplied between two sheets of polyethylene terephthalate film (Mitsubishi Chemical Corporation, Diafoil MRF38, thickness: 38 ⁇ m) that has been subjected to a release treatment, and between two heating rolls.
  • the obtained sheet-like curable composition is irradiated with ultraviolet rays using a high-pressure mercury lamp so that the integrated light quantity at 365 nm is 2000 mJ / cm 2 in a state where a release film is laminated, and 23 ° C. and 50% RH.
  • the obtained sheet (sample) was dyed with ruthenium tetroxide and freeze-cut perpendicularly to the sheet surface using a Leica microtome EM UC7 to produce a plurality of sections having a thickness of about 80 nm. 3 sections were randomly extracted from the sample, and using a Hitachi transmission electron microscope “H-7650”, the section of each section was randomly set to 10 times at an acceleration voltage of 100 kv at a magnification of 1000 to 5000 times. Observation was made to confirm the dispersion state.
  • each of the three slices observed was randomly observed in 10 fields of view, and if no “lumps with a maximum diameter of 1 ⁇ m” were observed in any field of view, it was judged as “none”.
  • “a lump having a maximum diameter of 1 ⁇ m or more” was observed in the field of view, it was judged as “present”.
  • the electron micrograph of the sheet (sample) obtained in Example 2-1 is shown in FIGS. 2 and 3
  • the electron micrograph of the sheet (sample) obtained in Example 2-3 is shown in FIGS.
  • Electron micrographs of the sheets (samples) obtained in 2-1 and 2-2 are shown in FIGS. 6 and 7, respectively.
  • Adhesion test One release film of the obtained sheet (sample) was peeled off, and a 50 ⁇ m polyethylene terephthalate film (manufactured by Mitsubishi Plastics, Diafoil T100, thickness 50 ⁇ m) was bonded as a backing film to prepare a laminate. After the laminated product was cut into a length of 150 mm and a width of 10 mm, the remaining release film was peeled off, and the exposed adhesive surface was roll-bonded to soda lime glass. The bonded product was subjected to autoclave treatment (60 ° C., gauge pressure 0.2 MPa, 20 minutes) and finished and bonded to prepare a sample for measuring adhesive strength.
  • autoclave treatment 60 ° C., gauge pressure 0.2 MPa, 20 minutes
  • the haze is obtained by using a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.) in a state where glass is bonded to both sides of a sheet (sample), and the total light transmittance according to JIS K7361-1, Each haze was measured accordingly.
  • the results for each of the obtained curable compositions are shown in Table 3.
  • the curable compositions obtained in Examples 2-1 and 2-3 are highly compatible with the isobutylene polymer (A) and the acrylate polymer.
  • a lump having a maximum diameter of 1 ⁇ m or more in other words, a dispersed phase composed of an acrylate polymer (B) having a maximum diameter of 1 ⁇ m or more was not recognized.
  • the curable composition obtained in Example 2-2 that is, the sheet (sample)
  • a lump having a maximum diameter of 1 ⁇ m or more, that is, a dispersed phase was not observed.
  • the curable compositions obtained in Examples 2-1 to 2-3 that is, the sheets (samples), as can be seen from the results in Table 3 and FIG. 1, have good adhesive strength, good holding power, high It had transparency and was excellent in water vapor barrier properties.
  • the curable compositions or sheets (samples) obtained in Comparative Examples 2-1 and 2-2 do not have a maximum point of loss tangent in the shear at a frequency of 1 Hz in the range of ⁇ 20 to 20 ° C. Therefore, it was inferior to the adhesive strength when it was made into a sheet.
  • Example 3 The compounds and materials used in Examples 3-1 to 3-6 and Comparative Examples 3-1 to 3-5 are shown below, followed by the production methods in each Example and Comparative Example, and then the evaluation method Will be described.
  • Multifunctional acrylate (B) -4: CD595 (Sartomer, 1.10-decanediol diacrylate, HSP distance from component (A): 6.65) (B) -5: A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecane dimethanol diacrylate, HSP distance from component (A): 7.77) (B) -6: CN9014NS (manufactured by Sartomer, polybutadiene bifunctional urethane acrylate)
  • ⁇ Preparation method of sheet-like curable composition In the formulations shown in Tables 4 and 5, the isobutylene polymer, monofunctional acrylate, polyfunctional acrylate, tackifier, and polymerization initiator are mixed until uniform, and the precursor of the curable composition of the present invention. A curable composition was obtained. Subsequently, a curable composition was developed between two sheets of polyethylene terephthalate film (Mitsubishi Chemical Corporation, Diafoil MRF38, thickness: 38 ⁇ m) that had been subjected to a release treatment. A sheet-like curable composition having a thickness of about 100 ⁇ m was obtained.
  • polyethylene terephthalate film Mitsubishi Chemical Corporation, Diafoil MRF38, thickness: 38 ⁇ m
  • the obtained sheet-like curable composition is irradiated with ultraviolet rays using a high-pressure mercury lamp so that the integrated light quantity at 365 nm is 2000 mJ / cm 2 in a state where a release film is laminated, and 23 ° C. and 50% RH.
  • Adhesion test One release film of the obtained sheet (sample) was peeled off, and a 50 ⁇ m polyethylene terephthalate film (manufactured by Mitsubishi Plastics, Diafoil T100, thickness 50 ⁇ m) was bonded as a backing film to prepare a laminate. After the laminated product was cut into a length of 150 mm and a width of 10 mm, the remaining release film was peeled off, and the exposed adhesive surface was roll-bonded to soda lime glass. The bonded product was subjected to autoclave treatment (60 ° C., gauge pressure 0.2 MPa, 20 minutes) and finished and bonded to prepare a sample for measuring adhesive strength.
  • autoclave treatment 60 ° C., gauge pressure 0.2 MPa, 20 minutes
  • the haze is obtained by applying a total light transmittance to JIS K7136 according to JIS K7361-1, using a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.) in a state where glass is bonded to both sides of the sheet (sample). The haze was measured accordingly.
  • the results for the obtained curable compositions are shown in Tables 6 and 7.
  • Example 3-1 ⁇ Production example using solvent>
  • the isobutylene polymer, monofunctional acrylate, polyfunctional acrylate, tackifier, and polymerization initiator were uniformly mixed to obtain a curable composition as a precursor. Obtained. 100 parts by mass of the obtained curable composition was transferred to a light-shielding container, and 200 parts by mass of heptane was added and dissolved to obtain a uniform coating solution. Subsequently, the coating liquid was developed using an applicator on the release surface side of the polyethylene terephthalate film (Mitsubishi Chemical Corporation, Diafoil MRF38, thickness: 38 ⁇ m) subjected to the release treatment, and a dryer at 120 ° C.
  • the polyethylene terephthalate film Mitsubishi Chemical Corporation, Diafoil MRF38, thickness: 38 ⁇ m
  • the sheets obtained in Examples 3-1 to 3-6 all have a maximum point of loss tangent (tan ⁇ ) in a shear of 1 Hz in the range of ⁇ 30 ° C. to ⁇ 15 ° C., and excellent adhesion It has strength, holding power, bendability and water vapor barrier properties.
  • Examples 3-1 to 3-5 were more significant in terms of holding power compared to Example 3-6.
  • Examples 3-1 to 3-4 were more significant in terms of haze (transparency) than Example 3-5. However, even the haze of Example 3-5 is practical.
  • Comparative Examples 3-1 to 3-3 and Comparative Example 3-5 have a maximum point of loss tangent (tan ⁇ ) in a shear at a frequency of 1 Hz in a range of ⁇ 30 ° C. to ⁇ 15 ° C. No buckling was observed at the time of evaluation of the bendability.
  • Comparative Example 3-4 using an acrylate polymer composed only of a polyfunctional acrylate was inferior in adhesive strength and holding power, and was observed after flow at the time of evaluation of bending property.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une feuille pouvant présenter une bonne adhésivité et une bonne aptitude à la rétention, une transparence élevée et des propriétés de barrière à la vapeur d'eau, et contenant un polymère d'isobutylène (A) et un polymère (B) à base d'acrylate, le polymère (B) à base d'acrylate contenant un motif acrylate monofonctionnel et un motif acrylate polyfonctionnel en tant que motifs structuraux, au moins l'un des points maximaux de la tangente de l'angle de perte (tanδ), lors d'une mesure du cisaillement de la feuille à une fréquence de 1 Hz, tombant dans la gamme de -30 °C à 30 °C, et le voile de la feuille étant de 2,0 % ou moins.
PCT/JP2018/011170 2017-03-22 2018-03-20 Composition durcissable, feuille et stratifié produits par utilisation de cette dernière, et dispositif d'affichage d'image Ceased WO2018174085A1 (fr)

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WO2020101000A1 (fr) * 2018-11-14 2020-05-22 デンカ株式会社 Composition
JP2020164619A (ja) * 2019-03-29 2020-10-08 三菱ケミカル株式会社 粘着シート、それを用いた積層シート及び画像表示装置
CN113330046A (zh) * 2019-03-26 2021-08-31 积水化学工业株式会社 树脂组合物及有机el显示元件用周边密封剂
CN113557280A (zh) * 2019-03-29 2021-10-26 三菱化学株式会社 粘合片、层叠片、图像显示装置
WO2021235406A1 (fr) * 2020-05-21 2021-11-25 デンカ株式会社 Composition

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WO2019189404A1 (fr) * 2018-03-29 2019-10-03 三菱ケミカル株式会社 Feuille adhésive, feuille stratifiée et dispositif d'affichage d'image les utilisant
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WO2020101000A1 (fr) * 2018-11-14 2020-05-22 デンカ株式会社 Composition
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JP2023021436A (ja) * 2019-03-29 2023-02-10 三菱ケミカル株式会社 粘着シート、それを用いた積層シート及び画像表示装置
JP7497748B2 (ja) 2019-03-29 2024-06-11 三菱ケミカル株式会社 粘着シート、それを用いた積層シート及び画像表示装置
CN113557280A (zh) * 2019-03-29 2021-10-26 三菱化学株式会社 粘合片、层叠片、图像显示装置
JP2020164619A (ja) * 2019-03-29 2020-10-08 三菱ケミカル株式会社 粘着シート、それを用いた積層シート及び画像表示装置
JPWO2021235406A1 (fr) * 2020-05-21 2021-11-25
EP4148096A4 (fr) * 2020-05-21 2023-11-01 Denka Company Limited Composition
WO2021235406A1 (fr) * 2020-05-21 2021-11-25 デンカ株式会社 Composition
JP7522188B2 (ja) 2020-05-21 2024-07-24 デンカ株式会社 組成物
US12480025B2 (en) 2020-05-21 2025-11-25 Denka Company Limited Composition

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