WO2020149386A1 - Copolymere sequence reticulable, son procede de fabrication ainsi qu'adhesif thermofusible - Google Patents

Copolymere sequence reticulable, son procede de fabrication ainsi qu'adhesif thermofusible Download PDF

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WO2020149386A1
WO2020149386A1 PCT/JP2020/001387 JP2020001387W WO2020149386A1 WO 2020149386 A1 WO2020149386 A1 WO 2020149386A1 JP 2020001387 W JP2020001387 W JP 2020001387W WO 2020149386 A1 WO2020149386 A1 WO 2020149386A1
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polymer
crosslinkable
meth
polymer block
monomer
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PCT/JP2020/001387
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Japanese (ja)
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章滋 桑原
川端　和裕
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積水フーラー株式会社
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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, a method for producing the same, 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. And the thermal stability is also low.
  • the present invention has a low melt viscosity, excellent coatability and thermal stability, and exhibits excellent adhesive physical properties (particularly peeling resistance) by crosslinking, and a crosslinkable block copolymer excellent in ultraviolet curability and A hot melt adhesive using the same is provided.
  • the crosslinkable block copolymer comprises a polymer block B, And a polymer block A containing a benzyl (meth)acrylate-based monomer unit and a UV-crosslinkable monomer unit, each of which is bonded to both ends of the polymer block B.
  • the crosslinkable block copolymer is an ABA type triblock copolymer in which the polymer block A is bound to both ends of the polymer block B,
  • the polymer block A is characterized by containing a benzyl (meth)acrylate-based monomer unit and a UV-crosslinkable monomer unit.
  • the crosslinkable block copolymer of the present invention is an ABA type triblock copolymer in which the polymer block A is bound to both ends of the polymer block B.
  • a benzyl (meth)acrylate-based monomer and a UV crosslinkable monomer may be contained.
  • the (meth)acrylate means methacrylate or acrylate.
  • the polymer block A contains a monomer unit having an ultraviolet crosslinking property. Since the polymer block A contains a monomer unit having an ultraviolet-crosslinking property, the polymer block A and the polymer block B have different polarities from each other, thereby exhibiting a layer separation structure, and at the same time, the polymer block By positively introducing a crosslinked structure into A, the crosslinkable block copolymer has excellent peel resistance after crosslinking.
  • Ultraviolet crosslinkable monomer refers to a monomer having an ultraviolet crosslinkable group that forms a chemical bond upon irradiation with ultraviolet rays.
  • the "ultraviolet ray crosslinkability" means that a chemical bond is formed by irradiation of ultraviolet rays and thus the compound can be crosslinked.
  • the ultraviolet crosslinkable group is not particularly limited, and examples thereof include a thiol group, a glycidyl group, an oxetanyl group, a vinyl group, a (meth)acryloyl group, 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, a glycidyl group and a benzophenone group are more preferable, and a benzophenone group is particularly preferable.
  • (meth)acryloyl means methacryloyl or acryloyl.
  • (Meth)acryloxy means methacryloxy or acryloxy.
  • the UV-crosslinkable monomer is not particularly limited, and examples thereof include glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 4-(meth)acryloyloxybenzophenone, and 4-[2-((meth)acryloyloxy.
  • the UV-crosslinkable group-containing monomer may be used alone or in combination of two or more kinds.
  • (meth)acryloyloxy means methacryloyloxy or acryloyloxy.
  • the content of the UV-crosslinkable monomer unit 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, and 2 mass% or less is particularly preferable.
  • the content of the monomer unit having an ultraviolet crosslinking property is preferably 1% by mass or more because the ultraviolet curability of the crosslinkable block copolymer is improved.
  • a monomer having no ultraviolet crosslinking property (hereinafter referred to as "monomer having no ultraviolet crosslinking group” or “ultraviolet light”). Sometimes referred to as “non-crosslinkable monomer”).
  • monomer having no UV crosslinking property include a monomer capable of undergoing a polymerization reaction such as radical polymerization, cationic polymerization or anionic polymerization, and a monomer having an ethylenically unsaturated bond is preferable.
  • Examples of the monomer having no UV crosslinking property include a vinyl-based monomer, a (meth)acrylic-based monomer, and a (meth)acrylamide-based monomer, which have excellent radical polymerization reactivity. And (meth)acrylamide-based 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)acryl-based monomer include benzyl (meth)acrylate-based monomer, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate and isobutyl (meth).
  • the crosslinkable block copolymer has an appropriate melt viscosity and is excellent.
  • Benzyl (meth)acrylate-based monomers are preferred because they have good coatability and excellent thermal stability, and also have excellent adhesive properties such as peeling resistance after crosslinking, and benzyl (meth)acrylate is preferred.
  • Acrylate is more preferred, and benzyl acrylate is particularly preferred.
  • the (meth)acrylic monomers may be used alone or in combination of two or more.
  • Examples of the (meth)acrylamide-based monomer include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylamide, N- Phenyl(meth)acrylamide, N-benzyl(meth)acrylamide, N-isobornyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-3,5,5-trimethylcyclohexyl(meth)acrylamide, N-dicyclopenta Examples thereof include nyl(meth)acrylamide, N-dicyclopentenyl(meth)acrylamide, N-adamantyl(meth)acrylamide, N,N-diphenyl(meth)acrylamide and the like.
  • the (meth)acrylamide-based monomers may be used alone or in combination of two or more kinds.
  • the crosslinkable block copolymer contains a benzyl (meth)acrylate-based monomer unit as a monomer unit having no UV crosslinkability in the monomer unit constituting the polymer block A.
  • the crosslinkable block copolymer has excellent coating properties and thermal stability, and also has excellent adhesiveness such as peeling resistance and It has excellent curability.
  • the benzyl (meth)acrylate-based monomer has the following structural formula.
  • the benzyl (meth)acrylate-based monomers may be used alone or in combination of two or more.
  • R 1 is a hydrogen atom or a methyl group
  • R 2 to R 6 are each independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms.
  • R 2 to R 6 may be the same or different.
  • R 2 to R 6 examples include methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group. , Hexadecyl group, eicosyl group and the like.
  • R 1 is preferably a hydrogen atom or a methyl group
  • R 2 to R 6 are preferably hydrogen atoms
  • R 1 to R 6 are more preferably hydrogen atoms. .. That is, the benzyl (meth)acrylate-based monomer is preferably benzyl (meth)acrylate, and more preferably benzyl acrylate.
  • the content of the benzyl (meth)acrylate-based monomer unit is preferably 60% by mass or more, more preferably 90% by mass or more, and particularly preferably 98% by mass or more.
  • the content of the benzyl (meth)acrylate-based monomer is more preferably 99% by mass or less.
  • the content of the monomer unit having no ultraviolet crosslinking property 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, and 98 mass% or more is particularly preferable. In the monomer units constituting the polymer block A, the content of the monomer unit having no UV crosslinking property is more preferably 99% by mass or less.
  • the polymer block A is bonded to both ends of the polymer block B described later, and 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 may be different. 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 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 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, and further preferably 20,000 or less.
  • the crosslinkable block copolymer has excellent peel resistance after crosslinking.
  • 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 preferably 2.0 or less, more preferably 1.8 or less, and particularly preferably 1.6 or less.
  • the ratio of the molecular weights is a value obtained by dividing the larger molecular weight of the two polymer blocks A and A by the smaller molecular weight.
  • 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 UV crosslinking property (UV noncrosslinking property). That is, it is preferable that the monomer constituting the polymer block B of the polymer block B is a monomer not containing an ultraviolet crosslinking group (an ultraviolet noncrosslinking 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 crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability.
  • Alkyl (meth)acrylates having an alkyl group with 1 to 12 carbon atoms are preferred because they have excellent adhesive properties such as peel resistance after crosslinking, and alkyl (meth) with an alkyl group with 2 to 10 carbon atoms Acrylate is more preferred, and alkyl(meth)acrylate in which the alkyl group has 4 to 8 carbon atoms is particularly preferred.
  • the (meth)acrylic monomers may be used alone or in combination of two or more.
  • Examples of the (meth)acrylamide-based monomer include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, 2-hydroxyethyl(meth)acrylamide, N- Phenyl(meth)acrylamide, N-benzyl(meth)acrylamide, N-isobornyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-3,5,5-trimethylcyclohexyl(meth)acrylamide, N-dicyclopenta Examples thereof include nyl(meth)acrylamide, N-dicyclopentenyl(meth)acrylamide, N-adamantyl(meth)acrylamide, N,N-diphenyl(meth)acrylamide and the like.
  • the (meth)acrylamide-based monomers may be used alone or in combination of two or more kinds.
  • the monomer constituting the polymer block B of the crosslinkable block copolymer preferably contains a carboxy group-containing monomer unit.
  • the carboxy group-containing monomer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, ⁇ -carboxyethyl acrylate, ⁇ -carboxyethyl methacrylate, maleic acid, fumaric acid, and the like, with methacrylic acid and acrylic acid being preferred.
  • the content of the carboxy group-containing monomer unit is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. 2 mass% or more is more preferable, and 2.5 mass% or more is more preferable.
  • the content of the carboxy group-containing monomer unit is preferably 25% by mass or less, more preferably 23% by mass or less, more preferably 20% by mass or less, and 10% by mass. The following is more preferable, and 5% by mass or less is more preferable.
  • the content of the carboxy group-containing monomer is 0.1% by mass or more, the peeling resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the content of the carboxy group-containing monomer is 25 mass% or less, the coatability of the crosslinkable block copolymer is improved.
  • the monomer that constitutes the polymer block B and the monomer that does not have ultraviolet crosslinking property among the monomers that constitute the polymer block A may be the same or different.
  • the glass transition temperature of the polymer constituting the polymer block B is preferably 0° C. (273.15K (Kelvin)) or lower, more preferably ⁇ 20° C. (253.15K) or lower, and ⁇ 30° C. (243. 15 K) or less is more preferable, and ⁇ 40° C. (233.15 K) or less is particularly preferable.
  • the glass transition temperature of the polymer constituting the polymer block B is preferably ⁇ 80° C. (193.15K) or higher, more preferably ⁇ 70° C. (203.15K) or higher, and ⁇ 60° C. (213.15K). The above is particularly preferable.
  • peeling resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the glass transition temperature (Kelvin) of the polymer constituting the polymer block B is calculated, for example, based on the following formula (Fox's formula).
  • Tg is the glass transition temperature (K, Kelvin) of the polymer constituting the polymer block B.
  • m is the number of kinds of monomers constituting the polymer in the polymer constituting the polymer block B and is a natural number.
  • Tgn is a glass transition temperature (K, Kelvin) of a polymer constituting the polymer block B, which a homopolymer of the n-th monomer constituting the polymer has.
  • Wn is the content (mass %) of the n-th monomer constituting the polymer of the polymer constituting the polymer block B.
  • Tgn was measured by DSC in accordance with JIS K7121, and after heating and cooling at a rate of 10°C/min, the DSC curve measured in the second run under a rate condition of 10°C/min. The temperature is at the midpoint of the step.
  • the total content of the polymer block A is preferably 5% by mass or more, more preferably 10% by mass or more, and further 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 It 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 particularly preferably 25% by mass or less.
  • the crosslinkable block copolymer When the total content of the polymer block A is within the above range, the crosslinkable block copolymer has appropriate melt viscosity and excellent coatability, and at the same time, the crosslinkable block copolymer is It 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 an appropriate melt viscosity and excellent coatability, and at the same time, the crosslinkable block copolymer is It 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 When the total content of the polymer block B is within the above range, the crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability, and at the same time, the crosslinkable block copolymer is It 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 30,000 or more, particularly 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 crosslinkable block copolymer has excellent peel resistance after crosslinking.
  • the molecular weight of the polymer constituting the polymer block A is 400000 or less, the crosslinkable block copolymer has an appropriate melt viscosity and excellent coatability.
  • the ratio of the molecular weight of the polymer constituting the polymer block A to the molecular weight of the polymer constituting the polymer block B is preferably 0.03 or more, more preferably 0.05 or more, and particularly preferably 0.08 or more.
  • the ratio of the molecular weight of the polymer constituting the polymer block A to the molecular weight of the polymer constituting the polymer block B is preferably 0.32 or less, more preferably 0.22 or less, and particularly preferably 0.17 or less.
  • the ratio of the molecular weight of the polymer forming the polymer block A to the molecular weight of the polymer forming the polymer block B is 0.03 or more, the crosslinkable block copolymer is excellent after crosslinking. Has peeling resistance.
  • the crosslinkable block copolymer has an appropriate melt viscosity. And has excellent coatability.
  • the molecular weight of the polymer constituting the polymer block A means the arithmetic average value of the molecular weights of the polymers constituting the polymer block A bonded to both ends of the polymer block B.
  • 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 The molecular weight of is a value obtained by subtracting the peak top molecular weight of the polymer block A partial polymer from the peak top molecular weight of the polymer block A-polymer block B partial polymer.
  • 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 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, and more 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 more preferably 200,000 or less.
  • the weight average molecular weight (Mw) is 10,000 or more, the peeling resistance of the crosslinkable block copolymer 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 crosslinkable block copolymer has excellent peel resistance after crosslinking.
  • 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 of the crosslinkable block copolymer are measured by GPC (gel permeation chromatography) method. It is a value converted into polystyrene. 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 crosslinkable block copolymer is an ABA type triblock copolymer, and the hard component is mainly composed of one of the polymer blocks A and B having a high glass transition temperature.
  • the soft component is mainly composed of one of the polymer blocks A and B having a low glass transition temperature.
  • 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.
  • a block copolymer obtained by crosslinking a crosslinkable block copolymer by incorporating a carboxy group-containing monomer as a monomer that does not have ultraviolet crosslinkability constituting the polymer block B has more excellent peeling resistance. ..
  • 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.
  • 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.
  • 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 content of the benzyl (meth)acrylate-based monomer in the raw material monomer for producing the polymer block A is preferably 60% by mass or more, more preferably 90% by mass or more, and particularly preferably 98% by mass or more. ..
  • the content of the benzyl (meth)acrylate-based monomer is preferably 99% by mass or less.
  • the content of the UV-crosslinkable monomer is preferably 40% by mass or less, more preferably 10% by mass or less, and particularly preferably 2% by mass or less.
  • the content of the UV-crosslinkable monomer in the monomer, which is a raw material for producing the polymer block A is preferably 1% by mass or more.
  • the content of the monomer having no ultraviolet crosslinking property is preferably 60% by mass or more, more preferably 90% by mass or more, and particularly preferably 98% by mass or more. ..
  • the content of the monomer having no ultraviolet crosslinking property in the raw material monomer for producing the polymer block A is preferably 99% by mass or less.
  • the content of the carboxy group-containing monomer in the raw material monomer for producing the polymer block B is preferably 1 to 20% by mass, more preferably 2 to 10% by mass, and 2.5 to 5% by mass. Particularly preferred.
  • the content of the carboxy group-containing monomer is 1% by mass or more, the peeling resistance of the crosslinkable block copolymer after crosslinking is improved.
  • the content of the carboxy group-containing monomer is 20% by mass or less, the coatability of the crosslinkable block copolymer is improved.
  • 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.
  • Hot-melt pressure-sensitive adhesives are tackifiers, photo-acid generators (UV cation generators), UV polymerization initiators, plasticizers, antioxidants, colorants, flame retardants and antistatic agents, as long as their physical properties are not impaired. Additives such as agents may be included.
  • the crosslinkable block copolymer of the present invention has a low viscosity, excellent coatability, and excellent thermal stability.
  • the block copolymer obtained by cross-linking the cross-linkable block copolymer of the present invention is excellent in adhesive property, particularly peeling resistance.
  • Examples 1 to 3 and 5 to 17 and Comparative Examples 1 to 4 In a separable flask equipped with a stirrer, a cooling tube, a thermometer and a nitrogen gas inlet, benzyl acrylate, benzyl methacrylate, n-butyl acrylate, isobornyl acrylate, phenoxyethyl acrylate and t-butyl acrylate as UV non-crosslinking monomers.
  • Propanoic acid (one exchange chain reaction site) and 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid (one exchange chain reaction site) and ethyl acetate as the solvent are shown in Tables 1 and 2, respectively. Each of the compounding amounts shown in 1 was supplied and stirred to prepare a reaction liquid.
  • 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 4 and 5.
  • a reaction liquid containing the polymer block A partial polymer n-butyl acrylate, 2-ethylhexyl acrylate, acrylic acid and ⁇ -carboxyethyl acrylate as a UV non-crosslinking monomer, and ethyl acetate as a solvent are shown in Tables 1 and 2, respectively. The respective compounding amounts shown in 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.
  • Tables 4 and 5 show the peak top molecular weights of the polymers constituting the polymer block A-polymer block B partial polymer and the weight average molecular weights of the polymer block A-polymer block B partial polymer. ..
  • a reaction solution containing a polymer block A-polymer block B partial polymer benzyl acrylate, benzyl methacrylate, n-butyl acrylate, isobornyl acrylate, phenoxyethyl acrylate and t-butyl acrylate as UV non-crosslinkable monomers, 4-Acryloyloxybenzophenone, 4-hydroxybutyl acrylate glycidyl ether and 4-[2-(acryloyloxy)ethoxy]benzophenone were used as crosslinking monomers, and ethyl acetate was used as a solvent 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, weight average molecular weight and dispersity of the crosslinkable block copolymer are shown in Tables 1 and 2.
  • the total content of polymer block A and the content of polymer block B in the crosslinkable block copolymer are shown in Tables 4 and 5.
  • Example 4 In a separable flask equipped with a stirrer, a cooling tube, a thermometer and a nitrogen gas inlet, benzyl acrylate as a UV non-crosslinking monomer, 4-acryloyloxybenzophenone as a crosslinkable monomer, and S,S- as a trithiocarbonate compound. Dibenzyl trithiocarbonate (two exchange chain reaction sites) and ethyl acetate as a solvent were supplied in the respective compounding amounts shown in Table 1 and stirred to prepare a reaction solution.
  • 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. Next, 2,2'-azobis(isobutyronitrile) as a polymerization initiator was supplied to the reaction solution in the separable flask in the compounding amounts shown in Table 1 to initiate reversible chain transfer polymerization (RAFT). 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 Table 4.
  • RAFT reversible chain transfer polymerization
  • RAFT reversible chain transfer polymerization
  • 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.
  • Table 4 shows the peak top molecular weight, weight average molecular weight, and dispersity of the crosslinkable block copolymer.
  • Table 4 shows the total content of the polymer block A and the content of the polymer block B in the crosslinkable block copolymer.
  • RAFT reversible chain transfer polymerization
  • Table 3 shows the peak top molecular weight, weight average molecular weight and dispersity of the crosslinkable random copolymer.
  • the glass transition temperatures of the polymers constituting the polymer block B are shown in Tables 4 and 5.
  • 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.
  • melt viscosity initial melt viscosity
  • melt viscosity change rate Melt viscosity after 1 week/initial melt viscosity A... The melt viscosity change rate was less than 2.
  • B The rate of change in melt viscosity was 2 or more.
  • UV curable The hot melt adhesive was applied onto a polyethylene terephthalate (PET) film that had been subjected to a mold release treatment so that the thickness would be 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
  • the cured hot melt adhesive was peeled off from the polyethylene terephthalate film, and 0.2 g of the hot melt adhesive was supplied to the glass bottle. 30 g of tetrahydrofuran was supplied to a glass bottle and left at 25° C. for 24 hours to swell the hot melt adhesive.
  • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne un copolymère séquencé réticulable, lequel est excellent en termes de faible viscosité à l'état fondu, de caractéristiques de revêtement et de thermostabilité, et lequel fait preuve de propriétés adhésives (et plus particulièrement de résistance au décollement) supérieures après réticulation et lequel présente de très bonnes caractéristiques de durcissement sous l'effet des ultra-violets. Ce copolymère séquencé réticulable se caractérise en ce qu'il contient: un bloc polymère B; et un bloc polymère A, lequel est lié à chacune des deux extrémités du polymère B, et lequel contient une unité monomère de type benzyl (meth)acrylate ainsi qu'une unité monomère réticulable sous l'action des utlra-violets.
PCT/JP2020/001387 2019-01-16 2020-01-16 Copolymere sequence reticulable, son procede de fabrication ainsi qu'adhesif thermofusible WO2020149386A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008088368A (ja) * 2006-10-04 2008-04-17 Canon Inc 高分子化合物を含有する組成物の製造方法、組成物、及び液体付与方法
JP2011201973A (ja) * 2010-03-24 2011-10-13 Seiko Epson Corp 光重合性ポリマーミセル及びその製造方法、並びに光重合性ポリマーミセルを含むインク組成物
JP2012533652A (ja) * 2009-07-15 2012-12-27 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ジブロックポリマー分散剤をベースとした架橋顔料分散体を含む水性インクジェットインク
WO2015163321A1 (fr) * 2014-04-21 2015-10-29 日立化成株式会社 Polymère séquencé
JP2017206700A (ja) * 2011-03-24 2017-11-24 スリーエム イノベイティブ プロパティズ カンパニー 難燃接着剤
JP2018535283A (ja) * 2015-12-10 2018-11-29 エルジー・ケム・リミテッド 粘着剤組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008088368A (ja) * 2006-10-04 2008-04-17 Canon Inc 高分子化合物を含有する組成物の製造方法、組成物、及び液体付与方法
JP2012533652A (ja) * 2009-07-15 2012-12-27 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ジブロックポリマー分散剤をベースとした架橋顔料分散体を含む水性インクジェットインク
JP2011201973A (ja) * 2010-03-24 2011-10-13 Seiko Epson Corp 光重合性ポリマーミセル及びその製造方法、並びに光重合性ポリマーミセルを含むインク組成物
JP2017206700A (ja) * 2011-03-24 2017-11-24 スリーエム イノベイティブ プロパティズ カンパニー 難燃接着剤
WO2015163321A1 (fr) * 2014-04-21 2015-10-29 日立化成株式会社 Polymère séquencé
JP2018535283A (ja) * 2015-12-10 2018-11-29 エルジー・ケム・リミテッド 粘着剤組成物

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