WO2016140285A1 - Film décoratif - Google Patents

Film décoratif Download PDF

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Publication number
WO2016140285A1
WO2016140285A1 PCT/JP2016/056490 JP2016056490W WO2016140285A1 WO 2016140285 A1 WO2016140285 A1 WO 2016140285A1 JP 2016056490 W JP2016056490 W JP 2016056490W WO 2016140285 A1 WO2016140285 A1 WO 2016140285A1
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WO
WIPO (PCT)
Prior art keywords
meth
unit
group
acrylic acid
substituent
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PCT/JP2016/056490
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English (en)
Japanese (ja)
Inventor
英明 武田
雅洋 川崎
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株式会社クラレ
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Priority to JP2017503702A priority Critical patent/JP6615178B2/ja
Publication of WO2016140285A1 publication Critical patent/WO2016140285A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • 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
    • C09J133/00—Adhesives 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
    • 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

Definitions

  • the present invention relates to a decorative film containing a modified acrylic block copolymer.
  • the decorative film generally consists of a decorative layer and an adhesive layer.
  • Patent Documents 1 and 2 propose a laminated film using an acrylic block copolymer as a material for an adhesive layer.
  • a phase separation structure composed of a polymer block having a high glass transition temperature and a polymer block having a low glass transition temperature is formed, of which a high glass transition temperature is formed.
  • the polymer block having the above becomes a physical cross-linking point and develops cohesive force.
  • the crosslinking point melts under high temperature conditions, and sufficient cohesive force cannot be obtained, and adhesive residue on the adherend due to cohesive failure may occur.
  • An object of the present invention is to provide a decorative film excellent in adhesive strength and adhesion durability at high temperatures.
  • a polymer block (A) comprising a thermoplastic resin layer and an adhesive layer, wherein the adhesive layer has (meth) acrylic acid ester units (a), and (meth) acrylic acid units (b) and N-substituted
  • the polymer block (B) having a (meth) acrylamide unit (c), and the number of moles of the (meth) acrylic acid unit (b) relative to 100 mol in total of the units constituting the polymer block (B) [b ],
  • the number of moles of the N-substituted (meth) acrylamide unit (c) [c] is 5 ⁇ ([b] + [c]) ⁇ 80; and 0.01 ⁇ [c] / [b] ⁇ 0.
  • the polymer block (B) further has a (meth) acrylic acid ester unit (d),
  • N-substituted (meth) acrylamide unit (c) is a unit represented by the formula (Ia) or (Ib);
  • R 1 , R 2 and R 3 each independently represents an alkyl group which may have a substituent, a silyl group, an amino group which may have a substituent, A silanyl group, an alicyclic group that may have a substituent, a heterocyclic group that may have a substituent, or an aromatic ring group that may have a substituent, and R 1 and R 2 together And may form a ring together with the nitrogen atom to which they are bonded.
  • R 4 each independently represents a hydrogen atom or a methyl group.
  • each R 3 may independently have an alkyl group, silyl group, amino group that may have a substituent, silanyl group, or substituent that may have a substituent.
  • R 5 and R 6 each independently represent a hydrogen atom or a methyl group; .
  • a block copolymer (D) having (B ′) and a (meth) acrylic acid ester unit (a) having a structure different from the (meth) acrylic acid ester unit (b ′) is converted to an amine compound (
  • the decorative film according to any one of [1] to [6], which is obtained by reacting in the presence of E);
  • thermoplastic resin layer is an amorphous resin or a crystalline resin having a heat of crystal fusion of 5 J / g or less;
  • thermoplastic resin is an acrylic resin
  • the decorative film according to the present invention includes a thermoplastic resin layer and a modified acrylic block copolymer layer.
  • thermoplastic resin A well-known thermoplastic resin can be used.
  • acrylic resin ABS resin (acrylonitrile-butadiene-styrene resin), AS resin (acrylonitrile-styrene resin), PVC resin (polyvinyl chloride resin), polystyrene resin, polycarbonate resin, polyester resin, polyamide resin, polyolefin resin, etc.
  • an amorphous resin such as an acrylic resin, an ABS resin, a PVC resin, and a polycarbonate, or a crystalline resin having a crystal heat of fusion of 5 J / g or less is preferable.
  • An acrylic resin is more preferable from the viewpoint of weather resistance.
  • the rubber can be added to impart toughness.
  • the rubber is preferably a block copolymer or a modified acrylic block copolymer, which will be described later, because it has little influence on the appearance when stretched.
  • the modified acrylic block copolymer of the adhesive layer according to the present invention has a polymer block (A) and a polymer block (B).
  • the polymer block (A) has a (meth) acrylic acid ester unit (a).
  • the (meth) acrylic acid ester unit (a) is a unit formed by an addition polymerization reaction of (meth) acrylic acid ester.
  • Such (meth) acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, s-butyl acrylate, Acrylic acid alkyl esters such as 2-ethylhexyl acrylate; Acrylic acid cycloalkyl esters such as cyclohexyl acrylate and isobornyl acrylate; Acrylic acid aryl esters such as phenyl acrylate; Acrylic acid aralkyl esters such as benzyl acrylate; Acrylic Glycidyl acrylate, allyl acrylate, 2-meth
  • (meth) acrylic acid ester unit (a) (meth) acrylic acid alkyl ester units other than the (meth) acrylic acid methyl unit are preferable, and (meth) acrylic acid ethyl ester and (meth) acrylic acid n -Butyl, 2-ethylhexyl (meth) acrylate is more preferred.
  • the amount of the (meth) acrylic acid ester unit (a) is preferably 95 mol% or more, more preferably 99 mol% or more in the polymer block (A).
  • Examples of monomer units other than the (meth) acrylate unit (a) that may be contained in the polymer block (A) include aromatic vinyl units such as styrene, ⁇ -olefin units such as ethylene and propylene, butadiene, Examples thereof include conjugated diene units such as isoprene.
  • the number average molecular weight of the polymer block (A) is not particularly limited, but is preferably 500 to 500,000.
  • the polymer block (B) has a (meth) acrylic acid unit (b).
  • the (meth) acrylic acid unit (b) is a unit having the same structure as the unit considered to be formed by the addition polymerization reaction of (meth) acrylic acid.
  • (meth) acrylic acid is a monomer that is difficult to undergo an addition polymerization reaction by a living anion polymerization method, which is a general method for producing a block copolymer described later.
  • the polymer block (B) may further have an N-substituted (meth) acrylamide unit (c).
  • the N-substituted (meth) acrylamide unit (c) in the polymer block (B) is a unit having the same structure as a unit thought to be formed by an addition polymerization reaction of N-substituted (meth) acrylamide.
  • N-substituted (meth) acrylamide is a monomer that is difficult to undergo an addition polymerization reaction by a living anion polymerization method, which is a general method for producing a block copolymer described later.
  • the N-substituted (meth) acrylamide unit (c) is preferably a unit represented by the formula (Ia) or (Ib).
  • R 1 , R 2 and R 3 each independently represents an alkyl group which may have a substituent, a silyl group, an amino group which may have a substituent, or silanyl.
  • R 4 each independently represents a hydrogen atom or a methyl group.
  • Examples of the amino group that may have a substituent include monoalkylamino groups such as NH 2 group (unsubstituted amino group), methylamino group, and ethylamino group, and dialkylamino groups such as dimethylamino group and diethylamino group. And cyclic amino groups such as 1-pyrrolidinyl group and 1-piperidinyl group.
  • Examples of the alicyclic group which may have a substituent include a cyclopentanyl group, a cyclohexyl group, a bicyclo [2.2.1] heptanyl group, and a tricyclo [5.2.1.0 2,6 ] deca- A 3-enyl group, a 2-ethenylbicyclo [2.2.1] heptanyl group, an N, N-dimethylamino-cyclohexyl group, a t-butyl-cyclohexyl group, and the like can be given.
  • aromatic ring group examples include a phenyl group, a naphthyl group, a 4-methylphenyl group, and a 4-ethenylphenyl group.
  • Examples of the ring formed together with the nitrogen atom to which R 1 and R 2 are bonded together include, for example, pyrrolidin-1-yl group, piperidin-1-yl group, 4-methyl-4-allyl-piperidine- 1-yl group, 4- (3-buten-1-yl) -piperidin-1-yl group, 4-aminomethyl-piperidin-1-yl group, morpholin-4-yl group, 2-oxo-pyrrolidin-1 And -yl group.
  • the polymer block (B) may further have a (meth) acrylic acid ester unit (d).
  • (Meth) acrylate unit (d) is a unit formed by addition polymerization reaction of (meth) acrylate.
  • the (meth) acrylic acid ester include the same ones shown in the description of the (meth) acrylic acid ester unit (a).
  • the (meth) acrylic acid ester unit (d) is preferably a unit having a different structure from the (meth) acrylic acid ester unit (a).
  • a (meth) acrylic acid alkyl ester unit is preferable, and a (meth) acrylic acid methyl unit is more preferable.
  • the polymer block (B) may further have an N-substituted bis ((meth) acryl) amide unit (e).
  • the N-substituted bis ((meth) acryl) amide unit (e) is a unit having the same structure as a unit thought to be formed by an addition polymerization reaction of N-substituted bis ((meth) acryl) amide.
  • the N-substituted bis ((meth) acryl) amide unit (e) may have a form in which a ring is formed adjacently in one molecular chain, or between two molecular chains or one You may have in the form which bridge
  • N-substituted bis ((meth) acryl) amide is a monomer that is difficult to undergo an addition polymerization reaction by a living anion polymerization method, which is a general method for producing a block copolymer described later.
  • the N-substituted bis ((meth) acryl) amide unit (e) is preferably a unit represented by the formula (II).
  • each R 3 may independently have an alkyl group that may have a substituent, a silyl group, an amino group that may have a substituent, a silanyl group, or a substituent.
  • An alicyclic group, a heterocyclic group that may have a substituent, or an aromatic ring group that may have a substituent, R 5 and R 6 each independently represent a hydrogen atom or a methyl group.
  • the total amount in the polymer block (B) is preferably 95 mol% or more, more preferably 99 mol% or more.
  • 1 mole of the N-substituted bis ((meth) acryl) amide unit (e) is regarded as 2 moles. To calculate.
  • monomer units other than (meth) acryl) amide units (e) include aromatic vinyl units such as styrene, ⁇ -olefin units such as ethylene and propylene, and conjugated diene units such as butadiene and isoprene. .
  • the number average molecular weight of the polymer block (B) is not particularly limited, but is preferably 500 to 500,000.
  • the modified acrylic block copolymer (C) comprises a (meth) acrylic acid unit (b), an N-substituted (meth) acrylamide unit (c), a (meth) acrylic acid ester unit ( d) and a total of 100 moles of N-substituted bis ((meth) acryl) amide unit (e), (meth) acrylic acid unit (b), N-substituted (meth) acrylamide unit (c), And the total amount of N-substituted bis ((meth) acryl) amide units (e) is preferably 0.1 mol or more and 100 mol or less, more preferably 0.1 mol or more and less than 100 mol, and still more preferably 0.1 mol Mol to 95 mol.
  • the modified acrylic block copolymer (C) according to another embodiment of the present invention comprises (meth) acrylic acid units (b) with respect to a total of 100 moles of units constituting the polymer block (B).
  • the number of moles [b] and the number of moles [c] of the N-substituted (meth) acrylamide unit (c) are 5 ⁇ ([b] + [c]) ⁇ 80; and 0.01 ⁇ [c] / [b ] ⁇ 0.075 ⁇ ([b] + [c]) + 4 Satisfy the relationship.
  • the modified acrylic block copolymer according to the present invention has a tendency that when [b] + [c] is small, the adhesive strength and the adhesive durability at high temperature tend to be lowered, and when [b] + [c] is large, it is softened. There is a tendency for the adhesive strength to decrease because the temperature increases. In the modified acrylic block copolymer according to the present invention, when [c] / [b] becomes too large, the adhesive force tends to decrease.
  • the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually 1.0 to 1.5, preferably 1.0. ⁇ 1.3.
  • the modified acrylic block copolymer according to the present invention is not particularly limited by the molecular weight, but the number average molecular weight is preferably 1,000 to 1,000,000.
  • the weight average molecular weight and number average molecular weight are molecular weights in terms of standard polystyrene measured by GPC (gel permeation chromatography).
  • the mass ratio (A / B) of the polymer block (A) to the polymer block (B) is preferably 20 to 0.5, more preferably 9 to 1. It is.
  • the modified acrylic block copolymer (C) according to the present invention is not particularly limited depending on the bonding form of the polymer block (A) and the polymer block (B).
  • an AB diblock copolymer a linear block copolymer such as A- (BA) n, B- (AB) n, (AB-) mX, (B- A-) mX and the like, and star-type block copolymers such as Ag-B, and the like.
  • A represents a polymer block (A).
  • B represents a polymer block (B).
  • g represents a graft bond.
  • X represents a coupling agent residue.
  • n is the number of repeating polymer block structures in parentheses.
  • the acrylic block copolymer according to the present invention preferably has one or more polymer blocks (A) and two or more polymer blocks (B), and is a triblock copolymer consisting of BAB. Coalescence is more preferred.
  • the method for producing the modified acrylic block copolymer (C) according to the present invention comprises a polymer block (A) having a (meth) acrylic acid ester unit (a) and a (meth) acrylic acid ester unit (d ′).
  • a part or all of the (meth) acrylic acid ester unit (d ′) is converted into a (meth) acrylic acid unit (b) and an N-substituted (meth) acrylamide unit.
  • (Meth) acrylate unit (d ′) is a unit formed by addition polymerization reaction of (meth) acrylate.
  • Examples of the (meth) acrylic acid ester include the same ones shown in the description of the (meth) acrylic acid ester unit (a).
  • the block copolymer (D) is not particularly limited by its production method, but a living polymerization method is preferable in that a block copolymer having a narrow molecular weight distribution suitable for the present invention can be obtained.
  • An anionic polymerization method can be used.
  • an organic alkali metal compound is used as a polymerization initiator, and anionic polymerization is performed in the presence of an organoaluminum compound. This is more preferable because a block copolymer with a small amount can be produced.
  • a (meth) acrylic acid ester (d ′) is first supplied to the polymerization system to produce the living polymer, and then (meth) acrylic acid ester (a) is supplied to the active anion terminal of the living polymer.
  • a diblock copolymer comprising a polymer block (B ′) and a polymer block (A) can be produced by linking polymerization. Even if the polymerization is carried out by first supplying the (meth) acrylic acid ester (a) and then the polymerization is performed by supplying the (meth) acrylic acid ester (d ′), the polymer block (A)- A diblock copolymer comprising the polymer block (B ′) can be produced.
  • a (meth) acrylic acid ester (d ′) is first supplied to the polymerization system to form the living polymer, and then a (meth) acrylic acid ester (a) is supplied to the active anion of the living polymer.
  • a diblock copolymer consisting of a polymer block (B ′) and a polymer block (A) (a living polymer having an active anion terminal on the block A side) is formed by linking and polymerizing at the terminal, and (meth) acrylic is further formed.
  • a triblock copolymer comprising (A) -polymer block (B ′) can be produced.
  • the polymer block (A) A triblock copolymer comprising a polymer block (B ′) and a polymer block (A) can be produced.
  • the number of sequential (alternate) feedings of (meth) acrylic acid ester (a) and (meth) acrylic acid ester (d ′) to the polymerization system is 4 or more, and four or more polymerization steps are sequentially performed.
  • the tetrablock copolymer consisting of polymer block (A) -polymer block (B ')-polymer block (A) -polymer block (B'), polymer block (A) and A block copolymer of pentablock or more in which five or more polymer blocks (B ′) are alternately bonded in total can be produced.
  • the block copolymer (D) is not particularly limited by the molecular weight of each polymer block and the entire molecular weight of the block copolymer (D).
  • the molecular weight and the like of the block copolymer (D) can be appropriately set according to the use of the modified acrylic block copolymer.
  • the number average molecular weight of the polymer block (A) is 500 to 500,000
  • the number average molecular weight of the polymer block (B ′) is 500 to 500,000
  • the block copolymer (D) is not particularly limited by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), but the Mw / Mn of the modified acrylic block copolymer is In order to make the above range, Mw / Mn of the block copolymer (D) is preferably 1.0 to 1.5, and more preferably 1.0 to 1.4.
  • the mixture of the block copolymer (D) and the amine compound (E) is brought to a temperature equal to or higher than the softening point of the block copolymer (D). Is preferably performed.
  • the mixture of the block copolymer (D) and the amine compound (E) may contain a solvent that can dissolve both, if necessary. In order to obtain a temperature equal to or higher than the softening point, melt kneading, heat compression, or the like can be performed.
  • a known kneader such as a single screw extruder, a twin screw extruder, a kneader, or a Banbury mixer can be used.
  • a twin screw extruder that has a large shearing force during kneading and can be operated continuously.
  • the melt kneading time is preferably 30 seconds to 100 minutes.
  • the modified acrylic block copolymer (C) and another resin are mixed in a molten state or a solution state.
  • a method of reacting the amine compound (E) after mixing the block copolymer (D) with another resin in a molten state or a solution state can be used.
  • the amount of the amine compound (E) used may be appropriately determined, and is preferably 1 to 300 mol, more preferably 2 to 100 mol, per 100 mol of the (meth) acrylic acid ester unit (d ′). Further, the rate of conversion reaction (modification rate) with the amine compound (E) can be confirmed using H-NMR, FT-IR, or the like.
  • the temperature during the reaction is preferably 150 to 400 ° C., more preferably 170 to 300 ° C., and even more preferably 180. ⁇ 280 ° C.
  • a part or all of the (meth) acrylic acid ester (d ′) is converted into (meth) acrylic acid units (b), N-substituted (meta ) Converted into at least one selected from the group consisting of acrylamide units (c) and N-substituted bis ((meth) acryl) amide units (e).
  • the structure of the N-substituted (meth) acrylamide unit (c) or the N-substituted bis ((meth) acryl) amide unit (e) depends on the structure of the amine compound (E) to be reacted. Therefore, for example, by using an amine compound (E) having a functional group such as a hydroxyl group, an allyl group, an amino group, or an epoxy group, these functional groups can be introduced into the block copolymer (D).
  • the amine compound (E) used in the reaction is preferably a primary amine or a secondary amine, more preferably a primary amine represented by the formula (III) or a secondary amine represented by the formula (IV).
  • conversion to (meth) acrylic acid units (b) is dominant, conversion to N-substituted (meth) acrylamide units (c) and conversion to (meth) acrylic acid units (b).
  • the ratio [c] / [b] with the rate decreases.
  • the amount of the acrylic acid unit (b) contained in the polymer block (B) may be adjusted using a general esterifying agent.
  • R 1 , R 2 and R 3 are each independently an alkyl group which may have a substituent, a silyl group, an amino group which may have a substituent, A silanyl group, an alicyclic group that may have a substituent, a heterocyclic group that may have a substituent, or an aromatic ring group that may have a substituent, and R 1 and R 2 together And may form a ring with the nitrogen atom to which they are attached.
  • amine compound (E) examples include 6-hydroxyhexylamine, cyclohexylamine, N-methylcyclohexylamine, 4- (N, N-dimethylamine) -cyclohexylamine, allylamine, 4-allyl-4-methyl.
  • Piperidine 4- (3-buten-1-yl) -piperidine, 4-aminomethylpiperidine, morpholine, 2-oxopyrrolidine, piperidine, pyrrolidine, 4-t-butylcyclohexylamine, 2- (isopropylamino) ethanol, Examples include 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 3-aminopropyltriethoxysilane.
  • the method for producing a decorative film of the present invention includes, for example, a method of forming a laminated film by coextrusion of a thermoplastic resin and an acrylic block copolymer by a T-die film molding method, a method of laminating each film by thermal lamination, Alternatively, a method of applying a solution of an acrylic block copolymer to the thermoplastic resin layer can be applied. Among these, the coextrusion method is preferable from the viewpoint of productivity.
  • the decorative film of the present invention preferably has a total light transmittance of 0 to 20% from the viewpoint of the design properties of the decorative molded body after the decorative decoration.
  • the total light transmittance is more preferably 0 to 15%, and most preferably 0 to 10%.
  • Examples of the method for adjusting the total light transmittance of the decorative film for molding of the present invention to 0 to 20% include a method of containing a colorant in the thermoplastic resin layer, a method of laminating a colored layer, and a metal layer. .
  • the colorant contained in the thermoplastic resin layer and the colorant contained in the colored layer are required not to cause discoloration, discoloration, and coloration in processing steps such as a drying step and a molding step.
  • pigments are preferably used, and any of inorganic pigments and organic pigments can be used.
  • phthalocyanine blue, metal-free phthalocyanine blue, and green pigment include chrome green, chromium oxide, pigment green B, and malachite green lake.
  • metallic pigments include metal powder pigments (aluminum, bronze, etc.), metal foil pigments (aluminum, bronze, etc.), and metal vapor-deposited foil pigments (pulverized films such as plastics on which aluminum, bronze, etc. are deposited). It is done.
  • the pearl pigment include pearl pigments (obtained by pulverizing natural pearls, flaky substances such as mica, aluminum, and glass coated with titanium oxide, iron oxide, etc.).
  • black pigments such as carbon black and black iron oxide
  • white pigments such as titanium oxide, barium sulfate, zinc white, and zinc sulfate
  • metal-like pigments such as metal powder pigments, metal foil pigments, and metal-deposited foil pigments have excellent concealability. Therefore, when the total light transmittance is controlled by the colorant, the thermoplastic resin layer and the color layer contain 5% by mass to 30% by mass of the colorant in 100% by mass of the total components of the respective layers. Is preferred.
  • a masterbatch method in which the colorant is melt-kneaded at a high concentration in advance with the thermoplastic resin used as a raw material so that a predetermined concentration is obtained with the diluted resin during film formation.
  • the masterbatch method is a method of freeze-pulverizing resin at low temperature, adding a predetermined colorant to the powdered form, mixing it uniformly, and then supplying it to a vent type twin screw extruder to melt it. Knead.
  • the colored and kneaded resin is extruded into a strand shape, cooled and solidified in water, and then cut into a desired size with a cutter to obtain a master batch.
  • the metal layer is made of a thermoplastic resin film or sheet by using a metal such as aluminum, chromium, gold, silver, copper, nickel, cobalt, zinc, brass, and stainless steel by a method such as vacuum deposition, sputtering, or wet plating. Formed on top. Further, a metal foil-like material can be used by being laminated through an adhesive layer or by heat fusion or the like.
  • a hard coat layer, antistatic layer, antifouling layer, antireflection layer, adhesive layer, adhesive layer, antistatic layer, antifouling layer, antireflection layer, etc. are provided on the outermost surface of the decorative film. It may be provided.
  • the decorative film is used by being bonded to a decorative object.
  • a bonding method pressure forming, vacuum pressure forming, film insert injection forming, or the like can be used.
  • the resin used as the resin molded body is not particularly limited, and examples thereof include polyester resins, polyamide resins, polyacetal resins, polyolefin resins such as polyethylene resins and polypropylene resins, polystyrene resins, acrylic resins, polyurethane resins, chlorinated polyethylene resins, Chlorinated polypropylene resin, aromatic and aliphatic polyketone resin, fluorine resin, polyphenylene sulfide resin, polyether ketone resin, polyimide resin, thermoplastic starch resin, AS resin, ABS resin, polyvinyl chloride resin, polyvinylidene chloride resin , Vinyl ester resin, MS resin, polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene oxide resin, poly-4-methyl Pentene-1, polyetherimide resin,
  • the decorative film of the present invention is excellent in adhesiveness and adhesive durability at high temperatures, it is not only decorative for mobile phones, personal computer enclosures, air conditioners, TVs, refrigerators, and automotive interior applications, but also moisture and heat resistance of automotive exteriors, etc. It can also be used in harsh applications where high durability is required.
  • a proton (OC-1H) bonded to a carbon atom bonded to an oxygen atom of an oxy group in a methyl methacrylate unit and a nitrogen in an N-substituted (meth) acrylamide unit A signal corresponding to a proton bonded to the carbon atom bonded to the atom (NC-1H) appears at 3.6 ppm, and the proton bonded to the carbon atom bonded to the oxygen atom of the oxy group in the n-butyl acrylate unit.
  • the amount of N-substituted (meth) acrylamide unit and N-substituted bis ((meth) acryl) amide unit was calculated from the integrated value of each signal and the result of quantification of (meth) acrylic acid unit described later.
  • the amount of N-substituted bis ((meth) acryl) amide unit was calculated assuming that 1 mol of N-substituted bis ((meth) acryl) amide unit was 2 mol.
  • a sheet having a thickness of 0.5 mm was cut to produce a strip having a width of 5 mm. This was used for dynamic viscoelasticity measurement.
  • the dynamic viscoelasticity was measured using a viscoelasticity analyzer (“DVE-V4” manufactured by Rheology) under the condition of a frequency of 1 Hz.
  • a test piece having a width of 25 mm and a length of 10 mm was cut out from the obtained sample, and the adhesive force between the adhesive layer and the ABS sheet was measured by peeling at 90 degrees using a peel tester (manufactured by Shimadzu Corporation, AGS-X). .
  • polymethyl methacrylate blocks PMMA block [b1] having Mw 9900 and Mw / Mn 1.08 were formed.
  • the temperature of the reaction solution was set to ⁇ 25 ° C., and 384 g (3.0 mol) of n-butyl acrylate was added dropwise over 2 hours to cause a polymerization reaction.
  • an n-butyl acrylate block PnBA block [a] connected to the end of the PMMA block [b1] was formed.
  • the triblock copolymer (D) composed of PMMA block [b1] -PnBA block [a] -PMMA block [b2].
  • the triblock copolymer (D) has an Mw of 62000, an Mw / Mn of 1.19, a PMMA block [b1] of 7.3% by mass (9.0 mol%), and a PnBA block [a] of 85. 4 mass% (82 mol%) and PMMA block [b2] had a ratio of 7.3 mass% (9.0 mol%).
  • the block copolymer (D) was dissolved in tetrahydrofuran. This solution was cast at room temperature. Then, it heated for 30 minutes at 220 degreeC with the compression molding machine. The sheet was taken out from the compression molding machine and vacuum dried at 100 ° C. overnight to obtain a sheet having a thickness of 0.5 mm. The dynamic viscoelasticity of this sheet was measured. A peak of loss modulus considered to be derived from the PnBA block [a] was observed at -44 ° C. Moreover, the temperature of the reduced part of the loss elastic modulus considered to be derived from PMMA blocks [b1] and [b2] was 144 ° C.
  • a block copolymer (D) is supplied from a hopper to a twin-screw extruder (manufactured by Parker Corporation) at 0.6 kg / h, and cyclohexylamine is added from the middle of the cylinder to the methyl methacrylate unit in the block copolymer (D).
  • a modified acrylic block copolymer (1) was obtained by supplying in an amount of 25 mol per 100 mol, and melt-kneading at a cylinder temperature (reaction temperature) of 240 ° C. and a screw rotation speed of 200 rpm. The ratio of the monomer unit in the modified acrylic block copolymer (1) was analyzed. The results are shown in Table 1.
  • the modified acrylic block copolymer (1) was dissolved in tetrahydrofuran. This solution was cast at room temperature. Then, it heated for 30 minutes at 220 degreeC with the compression molding machine. The sheet was taken out from the compression molding machine and vacuum dried at 100 ° C. overnight to obtain a sheet having a thickness of 0.5 mm. The dynamic viscoelasticity of this sheet was measured. A peak of loss modulus considered to be derived from the PnBA block [a] was observed at -44 ° C. Moreover, the temperature of the fall part of the loss elastic modulus considered to originate in PMMA blocks [b1] and [b2] was 164 degreeC.
  • the temperature of the portion where the loss elastic modulus is lowered is considered to be derived from the PMMA blocks [b1] and [b2] which are hard segments.
  • the peak position of the loss modulus considered to be derived from the PnBA block [a], which is a soft segment, has not changed. From this result, it is understood that the amine compound (E) reacts only with the PMMA blocks [b1] and [b2].
  • a block copolymer (D) is supplied from a hopper to a twin-screw extruder (manufactured by Parker Corporation) at 0.6 kg / h, and cyclohexylamine is added from the middle of the cylinder to the methyl methacrylate unit in the block copolymer (D). It was supplied in an amount of 80 mol per 100 mol, and melt-kneaded at a cylinder temperature (reaction temperature) of 240 ° C. and a screw rotation speed of 200 rpm to obtain a modified acrylic block copolymer (2). The ratio of the monomer unit in the modified acrylic block copolymer (2) was analyzed. The results are shown in Table 1.
  • the modified acrylic block copolymer (2) was dissolved in tetrahydrofuran. This solution was cast at room temperature. Then, it heated for 30 minutes at 220 degreeC with the compression molding machine. The sheet was taken out from the compression molding machine and vacuum dried at 100 ° C. overnight to obtain a sheet having a thickness of 0.5 mm. The dynamic viscoelasticity of this sheet was measured. A peak of loss modulus considered to be derived from the PnBA block [a] was observed at -44 ° C. Moreover, the temperature of the reduced part of the loss elastic modulus considered to be derived from the PMMA blocks [b1] and [b2] was 194 ° C.
  • Table 2 shows the results of evaluation of adhesive strength and adhesion durability at high temperatures using the block copolymer (D) and the modified acrylic block copolymer shown in Table 1 as an adhesive layer.

Abstract

L'invention concerne un film décoratif qui comprend une couche de résine thermoplastique et une couche adhésive, et dans lequel : un copolymère à blocs acrylique de la couche adhésive possède un bloc polymère (A) ayant une unité d'ester d'acide (méth)acrylique (a) et un bloc polymère (B) ayant une unité d'acide (méth)acrylique (b) et une unité de (méth)acrylamide N-substitué (c) ; le nombre de moles [b] de l'unité d'acide (méth)acrylique (b) et le nombre de moles [c] de l'unité de (méth)acrylamide N-substitué (c), par rapport à 100 moles du total des unités qui constituent le bloc polymère (B), satisfont les expressions relationnelles 5 < ([b] + [c]) < 80 et 0,01 < [c]/[b] < 0,075 × ([b] + [c]) + 4 ; le rapport du poids moléculaire moyen en poids (Mw) au poids moléculaire moyen en nombre (Mn), c'est-à-dire (Mw)/(Mn), est de 1,0 à 1,5.
PCT/JP2016/056490 2015-03-03 2016-03-02 Film décoratif WO2016140285A1 (fr)

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JP2016160362A (ja) * 2015-03-03 2016-09-05 株式会社クラレ 湿気硬化型樹脂組成物
WO2020138498A1 (fr) 2018-12-28 2020-07-02 株式会社クラレ Film de base pour film décoratif et film décoratif le comprenant
WO2021261585A1 (fr) * 2020-06-26 2021-12-30 東亞合成株式会社 Composition adhésive pour film décoratif et son utilisation

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CN113784839A (zh) * 2019-04-26 2021-12-10 日东电工株式会社 粘合剂和粘合带

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JP2006500433A (ja) * 2002-07-26 2006-01-05 アルケマ 少なくとも一つの親水性ブロックを含むブロックコポリマーをベースにした湿った媒体用接着剤組成物
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WO2020138498A1 (fr) 2018-12-28 2020-07-02 株式会社クラレ Film de base pour film décoratif et film décoratif le comprenant
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WO2021261585A1 (fr) * 2020-06-26 2021-12-30 東亞合成株式会社 Composition adhésive pour film décoratif et son utilisation

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