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WO2020149388A1 - Copolymere sequence reticulable et adhesif thermofusible - Google Patents

Copolymere sequence reticulable et adhesif thermofusible Download PDF

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Publication number
WO2020149388A1
WO2020149388A1 PCT/JP2020/001389 JP2020001389W WO2020149388A1 WO 2020149388 A1 WO2020149388 A1 WO 2020149388A1 JP 2020001389 W JP2020001389 W JP 2020001389W WO 2020149388 A1 WO2020149388 A1 WO 2020149388A1
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Prior art keywords
block copolymer
crosslinkable
meth
spin
polymer
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English (en)
Japanese (ja)
Inventor
章滋 桑原
川端　和裕
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Sekisui Fuller Co Ltd
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Sekisui Fuller Co Ltd
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Priority to JP2020533043A priority Critical patent/JP7289148B2/ja
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    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers

Definitions

  • the present invention relates to a crosslinkable block copolymer and a hot melt adhesive.
  • Acrylic adhesives are used in adhesive tapes and product labels. Further, since the acrylic pressure-sensitive adhesive is excellent in transparency, heat resistance and weather resistance, it is also used for optical displays of electronic devices such as personal computers, smartphones, televisions and digital cameras.
  • solvent-free adhesives are recommended from the viewpoint of improving the usage environment, and even acrylic adhesives are becoming hot-melt.
  • the hot-melt pressure-sensitive adhesive does not require a drying step for removing the solvent in the step of coating the support, and thus does not require equipment for the drying step and contributes greatly to energy saving.
  • Patent Document 1 At least two blocks of a non-elastomeric polymer block A and an elastomeric polymer block B composed of a (meth)acrylate-based polymer are bonded, and the non-elastomeric polymer block A determined by 1 H pulse NMR at 30° C.
  • the elastomer-polymer block A has a spin-spin relaxation time T 2 of 13 to 25 microseconds, its proton component ratio is 0.05 to 0.3, and the melting point or glass transition of the non-elastomeric polymer block A.
  • a reactive hot type which has a main component of a block copolymer having a number average molecular weight of 15,000 to 200,000, which has a proton component ratio of 0 at a temperature of not less than the above, and which is crosslinked or polymerized by heating or irradiation with active energy rays.
  • Melt adhesive compositions are disclosed.
  • the reactive hot-melt pressure-sensitive adhesive composition of Patent Document 1 has a markedly increased viscosity depending on the type and content of the monomers constituting the non-elastomeric polymer block A, which leads to a decrease in coatability and adhesiveness. It also has the problem that it also decreases.
  • the present invention provides a crosslinkable block copolymer having a low melt viscosity, excellent coatability, and excellent adhesive physical properties (particularly peeling resistance) by crosslinking, and a hot melt adhesive using the same. ..
  • the crosslinkable block copolymer is A polymer block A containing a monomer unit having crosslinkability, Having a polymer block B, After cross-linking, when the decay curve obtained by the Solid echo method in 1 H pulsed NMR (20 MHz) at 40° C. was fitted with a two-component relaxation curve using the nonlinear least squares method, the shorter spin-spin relaxation was obtained.
  • the time T 2 (1) is 40 to 90 ⁇ sec, and the component ratio A 1 of the relaxation curve having the spin-spin relaxation time T 2 is 10 to 35%.
  • the crosslinkable block copolymer is a crosslinkable block copolymer having a polymer block A and a polymer block B,
  • the polymer block A contains a monomer unit having crosslinkability
  • After cross-linking the above-mentioned cross-linkable block copolymer when the decay curve obtained by the Solid echo method in 1 H pulse NMR (20 MHz) at 40° C. is subjected to two-component relaxation curve fitting using the nonlinear least squares method
  • the shorter spin-spin relaxation time T 2 (1) is 40 to 90 ⁇ sec, and the component ratio A 1 of the relaxation curve having the above spin-spin relaxation time T 2 (1) is 10 to 35%. Is characterized by.
  • the crosslinkable block copolymer of the present invention has a polymer block A and a polymer block B.
  • the crosslinkable block copolymer is preferably an ABA type triblock copolymer in which the polymer block A is bound to each of both ends of the polymer block B.
  • the monomer constituting the polymer block A of the crosslinkable block copolymer is not particularly limited, and examples thereof include a monomer capable of undergoing a polymerization reaction such as radical polymerization, cationic polymerization, or anionic polymerization.
  • the monomers having are preferred.
  • monomers other than the monomer having crosslinkability described later that is, the monomer having no crosslinkability (hereinafter, referred to as “monomer having no crosslinkable group” or “non-crosslinkable monomer”). May be mentioned)) include, for example, vinyl-based monomers, (meth)acrylic-based monomers, (meth)acrylamide-based monomers, and the like, which have excellent radical polymerization reactivity, and therefore (meth)acrylic-based monomers and (Meth)acrylamide monomers are preferred.
  • (meth)acryl means acryl or methacryl.
  • vinyl monomers examples include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene and 2,4-dimethyl.
  • styrene-based monomers such as p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene.
  • the vinyl monomers may be used alone or in combination of two or more kinds.
  • Examples of the (meth)acrylic monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth).
  • (meth)acrylate is preferable, and saturated aliphatic A (meth)acrylate having a ring structure is more preferable, and isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 3,5,5-trimethylcyclohexyl (meth)acrylate, dicyclopentanyl (Meth)acrylate and adamantyl (meth)acrylate are more preferable, and isobornyl (meth)acrylate, cyclohexyl (meth)acrylate and 4-t-butylcyclohexyl (meth)acrylate are particularly preferable.
  • the (meth)acrylic monomers may be used alone or in combination of two or more.
  • (Meth)acrylate means methacrylate or acrylate.
  • Examples of the (meth)acrylamide-based monomer include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-benzyl.
  • the (meth)acrylamide-based monomers may be used alone or in combination of two or more kinds.
  • the content of the monomer unit having no crosslinkability is preferably 60% by mass or more because the peel resistance after crosslinking of the crosslinkable block copolymer is improved. 90% by mass or more is more preferable, 95% by mass or more is more preferable, and 98% by mass or more is particularly preferable.
  • the content of the monomer unit having no crosslinkability is 99.9% by mass or less because the peel resistance after crosslinking of the crosslinkable block copolymer is improved. Is preferable, 99.8 mass% or less is more preferable, and 99.7 mass% or less is particularly preferable.
  • the polymer block A contains a monomer unit having crosslinkability. Since the polymer block A contains a monomer unit having a crosslinking property, the polymer block A and the polymer block B are made to have different polarities from each other so as to develop a layer separation structure, and at the same time, the polymer block A By positively introducing the crosslinked structure into the crosslinkable block copolymer, the crosslinkable block copolymer has excellent peeling resistance after crosslinking.
  • a monomer having a crosslinkability means irradiation with radiation such as ultraviolet rays and electron beams, heating, reaction with moisture (water), acid, base and/or a crosslinking agent.
  • radiation such as ultraviolet rays and electron beams
  • the crosslinkable monomer is preferably a monomer having a crosslinkable group capable of forming a chemical bond by irradiation with radiation to be crosslinked (hereinafter, may be referred to as “radiation-crosslinkable monomer”), and chemically bonded by irradiation with ultraviolet rays.
  • a monomer having a crosslinkable group capable of forming a group (hereinafter sometimes referred to as “UV crosslinkable monomer”) is more preferable.
  • Crosslinkability means that a chemical bond is formed by a crosslinking treatment such as irradiation with radiation such as ultraviolet rays and electron beams, heating, reaction with moisture (water), acid, base and/or a crosslinking agent to allow crosslinking.
  • the crosslinkable group is not particularly limited, and examples thereof include a hydroxyl group, a thiol group, a carboxyl group, a glycidyl group, an oxetanyl group, a trimethoxysilyl group, an isocyanate group, an amino group, a vinyl group, a (meth)acryloyl group, and a benzophenone group.
  • a benzoin group, a thioxanthone group and the like, a glycidyl group, a benzophenone group, a benzoin group and a thioxanthone group are preferable, and a glycidyl group and a benzophenone group are more preferable.
  • (meth)acryloyl means methacryloyl or acryloyl.
  • (Meth)acryloxy means methacryloxy or acryloxy.
  • the crosslinkable monomer is not particularly limited, and examples thereof include 4-hydroxybutyl acrylate glycidyl ether, 4-(meth)acryloyloxybenzophenone, 4-[2-((meth)acryloyloxy)ethoxy]benzophenone, 4- (Meth)acryloyloxy-4′-methoxybenzophenone, 4-(meth)acryloyloxyethoxy-4′-methoxybenzophenone, 4-(meth)acryloyloxy-4′-bromobenzophenone, 4-(meth)acryloyloxyethoxy- 4′-Bromobenzophenone and the like can be mentioned, and 4-hydroxybutyl acrylate glycidyl ether, 4-(meth)acryloyloxybenzophenone, and 4-[2-((meth)acryloyloxy)ethoxy]benzophenone are preferable.
  • the monomer having a crosslinkable group may be used alone or in combination of two or more kinds.
  • the content of the monomer unit having crosslinkability is preferably 40% by mass or less, because the peel resistance after crosslinking of the crosslinkable block copolymer is improved. 10 mass% or less is more preferable, 5 mass% or less is more preferable, and 2 mass% or less is particularly preferable.
  • the content of the monomer unit having crosslinkability is preferably 0.1% by mass or more because the peel resistance of the crosslinkable block copolymer after crosslinking is improved. 0.2 mass% or more is more preferable, and 0.3 mass% or more is particularly preferable.
  • the preferable content of the monomer unit having crosslinkability is preferably that at least one polymer block A satisfies all the polymer blocks A. It is more preferable that the united block A is filled.
  • the polymer block A is bonded to the polymer block B described later, and preferably is bonded to both ends of the polymer block B.
  • the crosslinkable block copolymer may have a polymer block A and a polymer block B, and preferably has an ABA type triblock structure.
  • the crosslinkable block copolymer has an ABA type triblock structure, the two polymer blocks A bonded to both ends of the polymer block B do not have to be the same and different. May be. That is, in the two polymer blocks A bonded to both ends of the polymer block B, the type and content of the monomer units constituting the two polymer blocks A may be the same or different, The molecular weights may be the same or different.
  • the molecular weight of the polymer constituting the polymer block A is preferably 1000 or more, more preferably 3000 or more, more preferably 5000 or more, and more preferably 5500 or more.
  • the polymer constituting the polymer block A has a molecular weight of preferably 50,000 or less, more preferably 30,000 or less, more preferably 25,000 or less, and further preferably 22,000 or less.
  • the molecular weight of the polymer constituting the polymer block A is 1,000 or more, the peel resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the molecular weight of the polymer constituting the polymer block A is 50,000 or less, the crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability.
  • the ratio of the molecular weights of the two polymer blocks A bonded to both ends of the polymer block B is 2.4 or less. Is preferable, 2.2 or less is more preferable, and 2.0 or less is particularly preferable.
  • the molecular weight ratio is within the above range, a layer separation structure can be satisfactorily formed between the polymer block A and the polymer block B after the crosslinking of the crosslinkable block copolymer, and thus the crosslinkable block.
  • the peel resistance of the copolymer after crosslinking is improved.
  • the ratio of the molecular weights is the value obtained by dividing the large molecular weight by the small molecular weight of the two polymer blocks A and A.
  • the molecular weight of the polymer constituting the polymer block A is determined from the peak top molecular weight of the partial polymer of the polymer block A and the peak top molecular weight of the crosslinkable block copolymer. The value obtained by subtracting the peak top molecular weight of the polymer block B partial polymer.
  • the monomer forming the polymer block B of the crosslinkable block copolymer preferably has no crosslinkability (noncrosslinkability). That is, the monomer forming the polymer block B of the polymer block B is preferably a monomer having no crosslinkable group (non-crosslinkable monomer). When the monomer constituting the polymer block B has no crosslinkability, the peeling resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the monomer constituting the polymer block B of the crosslinkable block copolymer is not particularly limited, and examples thereof include a monomer capable of undergoing a polymerization reaction such as radical polymerization, cationic polymerization or anionic polymerization, and an ethylenically unsaturated bond.
  • the monomers having are preferred.
  • Examples of the monomer constituting the polymer block B include a vinyl-based monomer, a (meth)acrylic-based monomer, a (meth)acrylamide-based monomer, and the like. Since they have excellent radical polymerization reactivity, (meth) Acrylic monomers and (meth)acrylamide monomers are preferred. In addition, (meth)acryl means acryl or methacryl.
  • vinyl monomers examples include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene and 2,4-dimethyl.
  • styrene-based monomers such as p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene.
  • the vinyl monomers may be used alone or in combination of two or more kinds.
  • Examples of the (meth)acrylic monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth).
  • the (meth)acrylic monomers may be used alone or in combination of two or more. 2 or more are preferable and, as for carbon number of the alkyl group of alkyl (meth)acrylate, 4 or more are more preferable. 12 or less is preferable, as for carbon number of the alkyl group of alkyl (meth)acrylate, 10 or less is more preferable, and 8 or less is more preferable.
  • the crosslinkable block copolymer has an appropriate melt viscosity, excellent coatability, and excellent thermal stability. Excellent adhesive properties such as peel resistance.
  • the crosslinkable block copolymer has an appropriate melt viscosity, excellent coatability, and excellent thermal stability. Excellent adhesive properties such as peel resistance.
  • Examples of the (meth)acrylamide-based monomer include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-benzyl.
  • the (meth)acrylamide-based monomers may be used alone or in combination of two or more kinds.
  • the monomer constituting the polymer block B and the non-crosslinking monomer among the monomers constituting the polymer block A may be the same or different.
  • the total content of the polymer block A is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more.
  • the crosslinkable block copolymer has appropriate melt viscosity and excellent coatability, and at the same time, the crosslinkable block copolymer is obtained. Has excellent peeling resistance after crosslinking.
  • the total content of the polymer block A is preferably 39% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.
  • the crosslinkable block copolymer has appropriate melt viscosity and excellent coatability, and at the same time, the crosslinkable block copolymer. Has excellent peeling resistance after crosslinking.
  • the content of the polymer block B is preferably 61% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass or more.
  • the crosslinkable block copolymer has appropriate melt viscosity and excellent coatability, and at the same time, the crosslinkable block copolymer is obtained. Has excellent peeling resistance after crosslinking.
  • the content of the polymer block B is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.
  • the crosslinkable block copolymer has appropriate melt viscosity and excellent coatability, and at the same time, the crosslinkable block copolymer is obtained. Has excellent peeling resistance after crosslinking.
  • the molecular weight of the polymer constituting the polymer block B is preferably 5,000 or more, more preferably 40,000 or more, and even more preferably 50,000 or more.
  • the molecular weight of the polymer constituting the polymer block B is preferably 400000 or less, more preferably 240000 or less, and particularly preferably 150,000 or less.
  • the weight average molecular weight of the polymer constituting the polymer block B is 5,000 or more, the peel resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the molecular weight of the polymer constituting the polymer block B is 400000 or less, the crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability.
  • the molecular weight of the polymer constituting the polymer block B means the value calculated according to the following procedure.
  • the polymer constituting the polymer block B From the peak top molecular weight of the crosslinkable block copolymer, which is a polymer block A-polymer block B partial polymer or AB type diblock copolymer, to the peak of the polymer block A partial polymer. The value obtained by subtracting the top molecular weight.
  • the polymer constituting the polymer block B Is the value obtained by subtracting the peak top molecular weight of the polymer block A partial polymer from the peak top molecular weight of the crosslinkable block copolymer.
  • the ratio of the molecular weight of the polymer block A and the molecular weight of the polymer block B is preferably 0.03 or more, 05 or more is more preferable, and 0.08 or more is more preferable.
  • the ratio of the molecular weight of the polymer block A and the molecular weight of the polymer block B is preferably 0.32 or less, 22 or less is more preferable, and 0.17 or less is particularly preferable.
  • the ratio of the molecular weight of the polymer block A and the molecular weight of the polymer block B is 0.03 or more, the peel resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the ratio of the molecular weight of the polymer block A to the molecular weight of the polymer block B is 0.32 or less, the crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability.
  • the crosslinkable block copolymer contains a plurality of polymer blocks A
  • the molecular weight of the polymer block A means an arithmetic average value of the molecular weights of the plurality of polymer blocks A.
  • the molecular weight of the polymer blocks B means an arithmetic average value of the molecular weights of the plurality of polymer blocks B.
  • the weight average molecular weight (Mw) of the crosslinkable block copolymer is preferably 10,000 or more, more preferably 50,000 or more, more preferably 70,000 or more, particularly preferably 80,000 or more.
  • the weight average molecular weight (Mw) of the crosslinkable block copolymer is preferably 500,000 or less, more preferably 300,000 or less, more preferably 250,000 or less, and particularly preferably 200,000 or less.
  • the weight average molecular weight (Mw) is 10,000 or more, the peeling resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the weight average molecular weight (Mw) is 500000 or less, the crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability.
  • the dispersity (weight average molecular weight Mw/number average molecular weight Mn) of the crosslinkable block copolymer is preferably 3.0 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less. When the dispersity is 3.0 or less, the peeling resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the molecular weight of the polymer constituting the polymer block of the crosslinkable block copolymer, and the weight average molecular weight and number average molecular weight are polystyrene-converted values measured by the GPC (gel permeation chromatography) method. .. Specifically, 0.01 g of the crosslinkable block copolymer was collected, the collected crosslinkable block copolymer was supplied to a test tube, and THF (tetrahydrofuran) was added to the test tube to add the crosslinkable block copolymer. The combined sample is diluted 500 times and filtered to prepare a measurement sample.
  • GPC gel permeation chromatography
  • the molecular weight of the polymer constituting the polymer block of the crosslinkable block copolymer, and the weight average molecular weight Mw and the number average molecular weight Mn of the crosslinkable block copolymer were measured by the GPC method. can do.
  • the molecular weight of the polymer constituting the polymer block of the crosslinkable block copolymer, and the weight average molecular weight Mw and the number average molecular weight Mn of the crosslinkable block copolymer are, for example, in the following measurement device and measurement conditions. Can be measured. Measuring apparatus Waters ACQUITY APC system Measurement conditions Column: Waters HSPgel(TM) HR MB-M Mobile phase: using tetrahydrofuran 0.5 mL/min Detector: RI detector Standard substance: polystyrene SEC temperature: 40°C
  • the shorter one (The spin-spin relaxation time T 2 (1) (hereinafter sometimes referred to simply as “relaxation time T 2 (1)”) of one component) is preferably 35 ⁇ sec or more, more preferably 40 ⁇ sec or more, and 42 ⁇ sec or more. Is more preferable, and 60 ⁇ s or more is more preferable.
  • the spin-spin relaxation time T 2 (1) (hereinafter sometimes referred to simply as “relaxation time T 2 (1)”) of one component is preferably 85 ⁇ sec or less, more preferably 83 ⁇ sec or less, and 81 ⁇ sec or less. Is more preferable, and 75 ⁇ sec or less is more preferable.
  • the spin-spin relaxation time T 2 (1) is 35 ⁇ sec or more, the crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability.
  • the spin-spin relaxation time T 2 (1) is 85 ⁇ sec or less, the peeling resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the relaxation time T 2 (2) of the longer one (second component) of the relaxation times of the two relaxation curves Is preferably 500 ⁇ sec or more, and more preferably 600 ⁇ sec or more.
  • the relaxation time T 2 (2) of the longer one (the second component) of the relaxation times of the above two relaxation curves is preferably 1000 ⁇ sec or less, more preferably 800 ⁇ sec or less.
  • the spin-spin relaxation time T 2 (2) is 500 ⁇ sec or more, the crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability.
  • the spin-spin relaxation time T 2 (2) is 1000 ⁇ sec or less, the peeling resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the decay curve obtained by the Solid echo method at 1 H pulse NMR (20 MHz) at 40° C. is subjected to two-component relaxation using the nonlinear least squares method.
  • the shorter spin-spin relaxation time T 2 (1) is 40 ⁇ sec or longer, preferably 60 ⁇ sec or longer.
  • the decay curve obtained by the Solid echo method at 1 H pulse NMR (20 MHz) at 40° C. is subjected to two-component relaxation using the nonlinear least squares method.
  • the shorter spin-spin relaxation time T 2 (1) is 90 ⁇ sec or less, preferably 75 ⁇ sec or less.
  • the spin-spin relaxation time T 2 (1) is 40 ⁇ sec or more, the crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability.
  • the spin-spin relaxation time T 2 (1) is 90 ⁇ sec or less, the peeling resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the longer spin-spin relaxation time T 2 (2) of the spin-spin relaxation times of the two relaxation curves described above. Is preferably 500 ⁇ sec or more, more preferably 600 ⁇ sec or more.
  • the longer spin-spin relaxation time T 2 (2) of the spin-spin relaxation times of the two relaxation curves described above. ) Is preferably 1000 ⁇ sec or less, more preferably 800 ⁇ sec or less.
  • the relaxation time T 2 (2) is 500 ⁇ sec or more, the crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability.
  • the relaxation time T 2 (2) is 1000 ⁇ sec or less, the peeling resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the rate of change of the relaxation time T 2 (2) is preferably 10% or less, more preferably 6.5% or less, and particularly preferably 5% or less.
  • the rate of change of the relaxation time T 2 (2) is 10% or less, the polymer block A of the crosslinkable block copolymer is more selectively crosslinked, and the peeling resistance of the crosslinkable block copolymer after crosslinking is increased. Is improved.
  • the decay curve obtained by the Solid echo method in 1 H pulsed NMR (20 MHz) at 40° C. was fitted to the two-component relaxation curve spin-spin obtained by fitting as described below.
  • the component ratio A 1 of the relaxation curve having the shorter spin-spin relaxation time T 2 (1) is preferably 6% or more, more preferably 10% or more, and 13% or more. Is more preferable.
  • the component ratio A 1 of the relaxation curve having the shorter spin-spin relaxation time T 2 (1) is preferably 30% or less, preferably 29% or less, and more preferably 28% or less. ..
  • the component ratio A 1 is 6% or more, the peeling resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability.
  • the spin-spin relaxation time of the two-component relaxation curve obtained by fitting the decay curve obtained by the Solid echo method in 1 H pulsed NMR (20 MHz) at 40° C. as described below.
  • the component ratio A 2 of the relaxation curve having the longer spin-spin relaxation time T 2 (2) is preferably 70% or more, more preferably 71% or more, and particularly preferably 72% or more. preferable.
  • the component ratio A 2 of the relaxation curve having the longer spin-spin relaxation time T 2 (2) is preferably 94% or less, more preferably 90% or less, and particularly preferably 87% or less. preferable.
  • the component ratio A 2 is 70% or more, the crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability.
  • the component ratio A 2 is 94% or less, the peeling resistance of the crosslinkable block copolymer after crosslinking is improved.
  • a block copolymer obtained by crosslinking a crosslinkable block copolymer it was obtained by fitting the decay curve obtained by the Solid echo method in 1 H pulse NMR (20 MHz) at 40° C. according to the procedure described below.
  • the component ratio A 1 of the relaxation curve having the shorter spin-spin relaxation time T 2 (1) is 10% or more, 12% or more is preferable and 15% or more is more preferable.
  • the decay curve obtained by the Solid echo method in 1 H pulse NMR (20 MHz) at 40° C. was obtained by fitting 2 as described below.
  • the component ratio A 1 of the relaxation curve having the shorter spin-spin relaxation time T 2 (1) is 35% or less, 33% The following is preferable, and 30% or less is more preferable.
  • the component ratio A 1 is 10% or more, the peeling resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability.
  • the decay curve obtained by the Solid echo method in 1 H pulse NMR (20 MHz) at 40° C. was obtained by fitting 2 as described below.
  • the component ratio A 2 of the relaxation curve having the longer spin-spin relaxation time T 2 (2) is preferably 65% or more, and 67%. The above is more preferable, and 70% or more is particularly preferable.
  • the decay curve obtained by the Solid echo method in 1 H pulse NMR (20 MHz) at 40° C. was obtained by fitting 2 as described below.
  • the component ratio A 2 of the relaxation curve having the longer spin-spin relaxation time T 2 (2) is preferably 90% or less, and 88%. The following is more preferable, and 85% or less is particularly preferable.
  • the crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability.
  • the peeling resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the relaxation time T 2 (1) and the component ratio A 1 of the relaxation curve having the relaxation time T 2 (1) satisfy the above range.
  • the hard component and the soft component are present in a predetermined ratio, the block copolymer obtained by crosslinking the crosslinkable block copolymer, while expressing a good layer separation structure, the hard component Has a suitable hardness, the block copolymer obtained by cross-linking the cross-linkable block copolymer, exhibits excellent peel resistance, and further, the cross-linkable block copolymer is excellent. It has good coatability.
  • the crosslinkable block copolymer contains a polymer block A and a polymer B, and is preferably an ABA type triblock copolymer, and the hard component is a glass of the polymer blocks A and B. While the soft component is mainly composed of the polymer block having a high transition temperature, the soft component is mainly composed of the polymer block having a low glass transition temperature among the polymer blocks A and B.
  • a crosslinkable block copolymer is obtained. It is possible to favorably form a layer separation structure due to the polarity difference between the polymer blocks A and B of the block copolymer obtained by crosslinking the crosslinkable block copolymer while imparting appropriate hardness.
  • the block copolymer obtained by crosslinking the crosslinkable block copolymer can impart excellent peeling resistance, which is preferable.
  • the monomer having no crosslinkability which constitutes the polymer block A a monomer having a saturated aliphatic ring structure (preferably isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 3, 5,5-trimethylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate and adamantyl (meth)acrylate, more preferably isobornyl (meth)acrylate, cyclohexyl (meth)acrylate and 4-t-butylcyclohexyl (meth) ) Acrylate), the hard component can be composed of the polymer block A in a high ratio, and the block copolymer obtained by crosslinking the crosslinkable block copolymer has more excellent peeling resistance.
  • the hard component can be composed of the polymer block A in a high ratio, and the block copolymer obtained by crosslinking the cross
  • a 1 H pulse NMR measuring device is used.
  • the 1 H pulse NMR measurement apparatus irradiates all protons existing in a measurement sample with pulsed radio waves at a low frequency (tens of MHz) by a permanent magnet to cause nuclear magnetic resonance, and its response (spin-spin relaxation time). ) Is a measuring device for observing.
  • each of the cross-linkable block copolymer before cross-linking or the block copolymer after cross-linking is measured at the bottom of the NMR tube, set in a 1 H pulse NMR measuring device, and measured under the following conditions. To obtain the decay curve.
  • a 1 H pulse NMR measuring device a measuring device commercially available from Bruker under the trade name “minispec mq20” can be used.
  • the block copolymer after cross-linking is prepared as follows. A cross-linkable block copolymer before cross-linking is applied onto a release-treated polyethylene terephthalate sheet so as to have a thickness of 20 ⁇ m. Next, the crosslinkable block copolymer is crosslinked so that the gel fraction is 50 to 90% by mass to prepare a crosslinked block copolymer.
  • the crosslinkable block copolymer is irradiated with ultraviolet rays under the conditions of UV-C irradiation intensity of about 48 mW/cm 2 and UV-C integrated light amount of 100 mJ/cm 2 using an ultraviolet irradiation device.
  • the united body is crosslinked to produce a crosslinked block copolymer.
  • an ultraviolet irradiation device for example, an ultraviolet irradiation device commercially available from Heraeus (former Fusion UV Systems) under the trade name "Light Hammer 6" (using H bulb) can be used.
  • the illuminance meter for example, an illuminance meter commercially available from EIT Instrument Markets under the trade name "UV Power Puck II" can be used.
  • the decay curve of the crosslinkable block copolymer before crosslinking or the block copolymer after crosslinking measured in the above manner is decomposed into a two-component relaxation curve.
  • the Weibull coefficient is set to 1 (exponential function), and fitting is performed using the nonlinear least squares method. That is, the spin-spin relaxation time T 2 and the component ratio A in the following formula are calculated.
  • T 2 the spin-spin relaxation time
  • the [err] of [SSR/err] is 0 or 1 and that the data after the two-component fitting is sufficiently close to the measured attenuation curve.
  • " ⁇ " means exponentiation.
  • f(t) A 1 ⁇ exp ⁇ -1/W(1)(t/T 2 (1)) ⁇ W(1) ⁇ + A 2 ⁇ exp ⁇ -1/W(2)(t/T 2 ( 2)) ⁇ W(2) ⁇
  • the shorter spin-spin relaxation time is defined as spin-spin relaxation time T 2 (1)
  • the longer spin-spin relaxation time is defined as spin-spin relaxation time T 2 (2).
  • the relaxation curve component ratio having the spin-spin relaxation time T 2 (1) is A 1
  • the relaxation curve component ratio having the spin-spin relaxation time T 2 (2) is A 2 .
  • W(1) and W(2) be Weibull coefficients (both are 1) of each relaxation curve.
  • analysis software analysis software commercially available from Bruker under the trade name "TD-NMR Analyzer" can be used.
  • the gel fraction of the block copolymer after crosslinking is the value measured according to the following procedure. 0.2 g of the block copolymer after crosslinking is supplied to a glass bottle. 30 g of tetrahydrofuran was supplied to a glass bottle and left at room temperature for 24 hours to swell the cross-linked block copolymer.
  • the higher the glass transition temperature of the monomer constituting the polymer block mainly forming the hard component the shorter the spin-spin relaxation time T 2 becomes. can do.
  • the lower the glass transition temperature of the monomer forming the polymer block mainly forming the hard component the longer the spin-spin relaxation time T 2 can be made.
  • the spin-spin relaxation time T 2 can be shortened as the glass transition temperature of the monomer constituting the polymer block mainly forming the soft component is increased.
  • the lower the glass transition temperature of the monomer forming the polymer block mainly forming the soft component the longer the spin-spin relaxation time T 2 can be made.
  • the component ratio A 1 can be increased as the content of the polymer block mainly forming the hard component is increased.
  • the component ratio A 1 can be lowered as the content of the polymer block mainly forming the soft component is increased.
  • the content of the non-crosslinkable monomer in the polymer block mainly forming the hard component is preferably 10.0% by mass or more, more preferably 14.0% by mass or more, and 16. 0 mass% or more is more preferable.
  • the content of the non-crosslinkable monomer in the polymer block mainly forming the hard component is preferably 29.6% by mass or less, more preferably 25.6% by mass or less, and 23. It is more preferably 6% by mass or less.
  • the crosslinkable block copolymer has improved peeling resistance after crosslinking.
  • the content of the non-crosslinkable monomer in the polymer block that mainly forms the hard component is 29.6% by mass or less, the crosslinkable block copolymer has an appropriate melt viscosity and is excellent in coating. Have sex.
  • the content of the non-crosslinkable monomer in the polymer block mainly forming the soft component is preferably 70.1% by mass or more, more preferably 75.0% by mass or more, and 76. 0 mass% or more is more preferable.
  • the content of the non-crosslinkable monomer in the polymer block mainly forming the soft component is preferably 89.9% by mass or less, more preferably 85.0% by mass or less, and 84. It is more preferably 0% by mass or less.
  • the crosslinkable block copolymer When the content of the non-crosslinkable monomer in the polymer block mainly forming the soft component is 70.1% by mass or more, the crosslinkable block copolymer has an appropriate melt viscosity and is excellent in coating. Have sex. When the content of the non-crosslinkable monomer in the polymer block mainly forming the soft component is 89.9% by mass or less, the crosslinkable block copolymer has improved peeling resistance after crosslinking.
  • the crosslinkable block copolymer can be produced using a general-purpose polymerization method, but it is preferable to produce it using living polymerization.
  • living polymerization examples include living radical polymerization, living cationic polymerization, and living anionic polymerization, but living radical polymerization is preferable from the viewpoint of high versatility and safety of polymerization reaction.
  • Examples of the living radical polymerization method include iniferter polymerization, nitroxide-mediated polymerization (NMP), transition metal-catalyzed atom transfer radical addition polymerization (ATRP), dithioester compound reversible chain transfer polymerization (RAFT), and organic tellurium compound.
  • NMP nitroxide-mediated polymerization
  • ATRP transition metal-catalyzed atom transfer radical addition polymerization
  • RAFT dithioester compound reversible chain transfer polymerization
  • organic tellurium compound organic tellurium compound.
  • Polymerization TERP
  • RTCP reversible transfer catalytic polymerization
  • RCMP reversible coordination-mediated polymerization
  • RAFT reversible chain transfer polymerization
  • monomers (2) does not cause an extreme decrease in reactivity to oxygen and light, and (3) at extremely low or high temperatures. Since the reaction proceeds even without it, it can be carried out in a simple polymerization reaction environment and has high productivity, (4) no poisons such as metals and halogens are used, and (5) a crosslinkable block having a sufficient molecular weight. It is preferable because a copolymer can be produced.
  • the dithioester compound used for carrying out the reversible chain transfer polymerization (RAFT) is not particularly limited as long as it is a dithioester compound having exchange chain reactivity, and examples thereof include a dithiobenzoate compound, a trithiocarbonate compound, Examples thereof include dithiocarbamate compounds and xanthate compounds, with trithiocarbonate compounds being preferred.
  • the trithiocarbonate compound is not particularly limited, and examples thereof include 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, 4- ⁇ [(2-carboxyethyl)sulfanylthiocarbonyl]sulfanyl ⁇ propanoic acid, 4-cyano.
  • a trithiocarbonate compound having only one exchange chain reaction site such as -4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid and 4-[(2-carboxyethylsulfanylthiocarbonyl)sulfanyl]-4-cyanopentanoic acid , S,S-dibenzyltrithiocarbonate, bis ⁇ 4-[ethyl-(2-hydroxyethyl)carbamoyl]benzyl ⁇ trithiocarbonate, etc., such as trithiocarbonate compounds having two exchange chain reaction sites.
  • a trithiocarbonate compound having only one chain reaction site is preferable, and 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid is more preferable.
  • the introduction position of the trithiocarbonate compound residue in the crosslinkable block copolymer differs due to the chemical structure of the trithiocarbonate compound.
  • the trithiocarbonate compound residue is introduced at the end of the polymer block constituting the crosslinkable block copolymer.
  • the trithiocarbonate compound residue is introduced inside the polymer block constituting the crosslinkable block copolymer.
  • a crosslinkable block copolymer produced by reversible chain transfer polymerization (RAFT) using a trithiocarbonate compound having only one exchange chain reaction site decomposes the trithiocarbonate compound residue by heat or light.
  • RAFT reversible chain transfer polymerization
  • the crosslinkable block copolymer structure itself is not decomposed, it is more excellent in thermal stability and UV crosslinking reactivity.
  • the crosslinkable block copolymer is preferably produced by reversible chain transfer polymerization (RAFT) with a dithioester compound.
  • RAFT reversible chain transfer polymerization
  • examples of the reversible chain transfer polymerization (RAFT) polymerization mode include bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, and solution polymerization is preferable.
  • Multistep polymerization is performed to produce a crosslinkable block copolymer.
  • RAFT reversible chain transfer polymerization
  • a monomer constituting the polymer block A is converted into a dithioester compound (dithioester compound). It polymerizes sufficiently (in the presence of a compound) to obtain a polymer block A partial polymer (first stage polymerization).
  • a monomer that constitutes the polymer block B is supplied into the polymerization reaction system and sufficiently polymerized to obtain a polymer block A-polymer block B partial polymer (second-stage polymerization).
  • an ABA type triblock obtained by supplying the monomer constituting the polymer block A into the polymerization reaction system and sufficiently polymerizing it to bond the polymer block A to both ends of the polymer block B.
  • a crosslinkable block copolymer which is a copolymer can be obtained.
  • the above-mentioned first stage polymerization and second stage polymerization may be carried out.
  • RAFT reversible chain transfer polymerization
  • the dithioester compound is used as the monomer constituting the polymer block A.
  • (Below) polymerize sufficiently to obtain polymer block A partial polymer (first stage polymerization).
  • a monomer constituting the polymer block B is supplied into the polymerization reaction system and polymerized (second-stage polymerization) to form a polymer block B in the intermediate part of the polymer block A partial polymer, and A A crosslinkable block copolymer which is a —BA type triblock copolymer can be obtained.
  • the content of the monomer having no crosslinkability is 60% by mass or more because the peel resistance after crosslinking of the crosslinkable block copolymer is improved. 90 mass% or more is more preferable, 95 mass% or more is more preferable, and 98 mass% or more is especially preferable.
  • the content of the monomer having no crosslinkability is 99.9% by mass because the peeling resistance of the crosslinkable block copolymer after crosslinking is improved. The following is preferable, 99.8 mass% or less is more preferable, and 99.7 mass% or less is particularly preferable.
  • the content of the crosslinkable monomer is preferably 40% by mass or less because the peeling resistance of the crosslinkable block copolymer after crosslinking is improved. 10 mass% or less is more preferable, 5 mass% or less is more preferable, and 2 mass% or less is particularly preferable.
  • the content of the crosslinkable monomer is 0.1% by mass or more because the peeling resistance after crosslinking of the crosslinkable block copolymer is improved. Is preferable, 0.2 mass% or more is more preferable, and 0.3 mass% or more is particularly preferable.
  • a crosslinkable block copolymer produced using a dithioester compound may have a coloring derived from its chemical structure or a unique odor derived from a sulfur atom.
  • a treatment for reducing or removing a dithioester compound residue in the crosslinkable block copolymer, and a residual dithioester mixed in the crosslinkable block copolymer It is preferable to perform a compound reduction or removal treatment.
  • the treatment method for reducing or removing the dithioester compound residue or the residual dithioester compound include treatment with heat, treatment with ultraviolet light, treatment with excess radical initiator, treatment with nucleophile or reducing agent, treatment with oxidizing agent.
  • the crosslinkable block copolymer can be suitably used as a hot-melt pressure-sensitive adhesive by adding additives such as a tackifier and a photo-acid generator, if necessary.
  • the hot-melt pressure-sensitive adhesive containing the crosslinkable block copolymer has an appropriate melt viscosity and therefore has excellent coatability.
  • the crosslinkable block copolymer is coated on the adherend and then subjected to a crosslinking treatment to the crosslinkable block copolymer, whereby the crosslinkable monomer units contained in the polymer block A are
  • the crosslinkable group forms a crosslinked structure, and the crosslinked structure is introduced into the polymer block A.
  • the block copolymer having the crosslinked structure introduced exhibits excellent tackiness such as peel resistance.
  • the hot-melt pressure-sensitive adhesive may contain additives such as a tackifier, a UV polymerization initiator, a plasticizer, an antioxidant, a colorant, a flame retardant and an antistatic agent as long as the physical properties of the hot-melt adhesive are not impaired. Good.
  • the crosslinkable block copolymer of the present invention has low viscosity and excellent coatability.
  • the block copolymer obtained by cross-linking the cross-linkable block copolymer of the present invention is excellent in adhesive property, particularly peeling resistance.
  • Example 3 is a graph showing an attenuation curve of the crosslinkable block copolymer obtained in Example 1 and a relaxation curve obtained by fitting the attenuation curve to a two-component relaxation curve.
  • reaction solution After purging the inside of the separable flask with nitrogen gas, the reaction solution was kept at 60° C. using a water bath. Then, 2,2′-azobis(isobutyronitrile) as a polymerization initiator was supplied to the reaction solution in the separable flask in the compounding amounts shown in Tables 1 and 2 to start reversible chain transfer polymerization (RAFT). did.
  • the reaction liquid was kept at 60° C. for 6 hours to obtain a polymer block A partial polymer.
  • the peak top molecular weight and the weight average molecular weight of the polymer block A partial polymer are shown in Tables 1 and 2.
  • a reaction liquid containing the polymer block A partial polymer n-butyl acrylate and 2-ethylhexyl acrylate as non-crosslinkable monomers, 4-acryloyloxybenzophenone as a crosslinkable monomer, and ethyl acetate as a solvent were respectively used in Table 1 and The compounding amounts shown in 2 were supplied.
  • the reaction solution was kept at 60° C. for 6 hours for reversible chain transfer polymerization (RAFT) to obtain a polymer block A-polymer block B partial polymer.
  • RAFT reversible chain transfer polymerization
  • the peak top molecular weight and the weight average molecular weight of the polymer block A-polymer block B partial polymer are shown in Tables 1 and 2.
  • reaction solution containing a polymer block A-polymer block B partial polymer, isobornyl acrylate, cyclohexyl acrylate, 4-t-butylcyclohexyl acrylate and n-butyl acrylate as non-crosslinking monomers and 4 as crosslinkable monomers -Acryloyloxybenzophenone, 4-[2-(acryloyloxy)ethoxy]benzophenone and 4-hydroxybutyl acrylate glycidyl ether, and ethyl acetate as a solvent were supplied in the amounts shown in Tables 1 and 2, respectively.
  • the reaction solution was kept at 60° C.
  • the crosslinkable block copolymer was an ABA type triblock copolymer in which the polymer block A was bound to both ends of the polymer block B.
  • the peak top molecular weight, the weight average molecular weight and the dispersity of the crosslinkable block copolymer are shown in Tables 1 and 2.
  • the contents of polymer blocks A and B in the crosslinkable block copolymer are shown in Tables 1 and 2.
  • the total content of the polymer block A and the content of the polymer block B in the crosslinkable block copolymer are shown in Tables 1 and 2.
  • RAFT reversible chain transfer polymerization
  • Table 3 shows the peak top molecular weight, weight average molecular weight and dispersity of the crosslinkable random copolymer.
  • Example 3 To 100 parts by mass of the crosslinkable block copolymer of Example 3, 2 parts by mass of a triarylsulfonium salt-based photoacid generator (trade name "CPI-200K” manufactured by San-Apro Co.) as a photoacid generator (UV cation generator) was added. The mixture was added and uniformly mixed at 130° C. to obtain a hot melt adhesive.
  • a triarylsulfonium salt-based photoacid generator trade name "CPI-200K” manufactured by San-Apro Co.
  • UV cation generator UV cation generator
  • crosslinkable block copolymers obtained in Examples and Comparative Examples block copolymers obtained by crosslinking this crosslinkable block copolymer, crosslinkable random copolymers and this crosslinkable random copolymer were crosslinked.
  • the decay curve of the random copolymer was measured as described above, and the spin-spin relaxation times T 2 (1) and T 2 (2) and the component ratios A 1 and A 2 were obtained based on the decay curve. ..
  • the rate of change (%) of the relaxation time T 2 (2) was also calculated.
  • the gel fractions of the block copolymer and the random copolymer after crosslinking are shown in Tables 3 to 5.
  • a graph showing an attenuation curve of the crosslinkable block copolymer obtained in Example 1 and a relaxation curve obtained by fitting the attenuation curve to a two-component relaxation curve is shown in FIG.
  • the vertical axis represents the "signal intensity ratio when the maximum intensity of the attenuation curve is 1."
  • the component ratio A 1 of the relaxation curve can be read from the value of the intercept on the Y axis of the relaxation curve having the spin-spin relaxation time T 2 (1).
  • the relaxation curve component ratio A 2 can be read from the value of the intercept on the Y axis of the relaxation curve having the spin-spin relaxation time T 2 (2).
  • the measuring device shown below was prepared. 13 g of the hot melt adhesive was collected and put into an aluminum cylinder mounted in Thermosel. The temperature was set to 130° C. to melt the hot melt adhesive. Melt viscosity measurements were taken over 30 minutes using spindle 4-29. The numerical value after the measurement for 30 minutes was read to obtain the melt viscosity at 130°C. Measuring device: DV-E Viscometer (manufactured by Brookfield) Thermosel (manufactured by Brookfield)
  • melt viscosity was less than 70 Pa ⁇ s.
  • B Melt viscosity was 70 Pa ⁇ s or more and less than 150 Pa ⁇ s.
  • C Melt viscosity was 150 Pa ⁇ s or more.
  • the hot melt adhesive was applied onto a polyethylene terephthalate (PET) film so as to have a thickness of 20 ⁇ m.
  • UV-C irradiation intensity about 48 mW/cm 2
  • UV-C integrated light amount using an ultraviolet irradiation device (Hereus (former Fusion UV Systems), trade name “Light Hammer 6” (H bulb used))
  • UV-C ultraviolet rays
  • a 20 ⁇ m-thick adhesive layer was laminated and integrated on a polyethylene terephthalate film to prepare a test piece.
  • a test film was prepared by cutting the test film into a width of 15 mm and a length of 150 mm.
  • a SUS plate was prepared, the surface of the SUS plate was polished with a #240 water resistant sandpaper, and then wiped with a mixed solvent of hexane and acetone to degrease.
  • test piece bonding surface was installed so as to face downward.
  • the weight of 150 g was hung on the end portion of the test piece not attached to the SUS plate, and the measurement was started in a state where the load was applied so that the test piece was peeled off at an angle of 90 degrees with respect to the SUS surface. The measurement was terminated when the bonded 75 mm was entirely peeled off and the test piece dropped, or when 1 hour passed from the start of the measurement.
  • the peeling distance at which the test piece peeled from the SUS plate was measured.
  • the peeling distance at the time when 1 hour passed from the start of the test was proportionally calculated based on the time required for the test piece to fall from the start of the test. The shorter the peeling distance, the better the peeling resistance.
  • A-PET amorphous polyethylene terephthalate
  • crosslinkable block copolymer having a low melt viscosity, excellent coatability, and excellent adhesive physical properties, particularly peeling resistance, and a hot melt adhesive using the same.

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Abstract

L'invention concerne un copolymère séquencé réticulable, lequel est excellent en termes de faible viscosité et de caractéristiques de revêtement, et lequel présente des propriétés adhésives et de résistance au décollement supérieures. L'invention concerne également un adhésif thermofusible mettant en oeuvre ce copolymère séquencé réticulable. Le copolymère séquencé réticulable selon l'invention possède un bloc polymère A contenant une unité monomère réticulable, et un bloc polymère B. En outre, ce copolymère séquencé réticulable se caractérise en ce que, après réticulation, dans une résonance magnétique (RNM) à impulsion 1H à 40℃ (20MHz) lorsque la courbe de décroissance obtenue à l'aide d'une méthode d'écho solide est ajustée en une courbe de relâchement à deux composants par une méthode de moindres carrés non linéaire, le temps T2 (1) de relaxation transversale court est compris entre 40 et 90 μsecondes, et en ce que le rapport A1 de composants de la courbe de relâchement présentant le temps T2 de relaxation transversale susmentionné est compris entre 10 et 35%.
PCT/JP2020/001389 2019-01-16 2020-01-16 Copolymere sequence reticulable et adhesif thermofusible Ceased WO2020149388A1 (fr)

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