WO2008004376A1 - Adhésif thermofusible durcissable de type caoutchouc - Google Patents

Adhésif thermofusible durcissable de type caoutchouc Download PDF

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Publication number
WO2008004376A1
WO2008004376A1 PCT/JP2007/059635 JP2007059635W WO2008004376A1 WO 2008004376 A1 WO2008004376 A1 WO 2008004376A1 JP 2007059635 W JP2007059635 W JP 2007059635W WO 2008004376 A1 WO2008004376 A1 WO 2008004376A1
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WIPO (PCT)
Prior art keywords
block copolymer
rubber
styrene
melt adhesive
polymer
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PCT/JP2007/059635
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English (en)
Japanese (ja)
Inventor
Hideo Goto
Ryohei Sakakibara
Eiso Tochigi
Masanori Kawaguchi
Takeshi Chiba
Original Assignee
Yasuhara Chemical Co., Ltd.
Kaneka Corporation
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Application filed by Yasuhara Chemical Co., Ltd., Kaneka Corporation filed Critical Yasuhara Chemical Co., Ltd.
Priority to JP2008523619A priority Critical patent/JPWO2008004376A1/ja
Publication of WO2008004376A1 publication Critical patent/WO2008004376A1/fr

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    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof

Definitions

  • the present invention relates to a rubber-based curable hot melt adhesive having heat resistance.
  • hot melt adhesives that require heat resistance include, for example, product assembly, solvent-based two-component curable adhesives, and solvent-free two-component curable types that have room temperature fluidity.
  • Adhesives, moisture-curing urethane hot melt adhesives, and the like are used.
  • Solvent-based two-component curable adhesives have a problem that they cannot be used due to recent environmentally conscious solvent regulations.
  • it is difficult to achieve both a short handling time and a moisture-curable urethane-based hot-melt adhesive and the stability of the adhesive between the melting tank and the coating head is difficult. Inconvenience is large, and humidity varies depending on the season, so the problem is that the curing characteristics are not constant.
  • Solvent-free adhesive that cures pressure-sensitive hot-melt adhesives based on maleic anhydride modified SEBS as a base polymer with aluminum chelate, taking into account the ease of handling of pressure-sensitive hot-melt adhesives and heat resistance
  • Examples of the agent are introduced in Patent Document 1.
  • the curing reaction between maleic anhydride and the curing agent by the aluminum chelate is extremely fast, the viscosity is increased and the fluidity is lost at the moment when the hot melt adhesive and the aluminum chelating agent are mixed. Therefore, in practice, it is impossible to apply with the hot melt applicator adjusting the coating amount.
  • the epoxidized diene polymer is converted into a polymer / aromatic anhydride molar ratio of 0.5 / 1.0 to 2.0 / 1.0 by using an aromatic anhydride curing agent, and a temperature of 100 to 200 ° C.
  • Non-Patent Document 1 which causes a curing reaction by bringing it into contact for 10 minutes to 6 hours, has been published, but there is a special device that maintains it at a high temperature even when the final cross-linking point is reached in 10 minutes at 100 ° C. It is necessary and the curing time is too long to be used in a practical production line, and the production speed is significantly reduced.
  • Patent Document 1 Japanese Translation of Special Publication 2000-506186
  • Non-Patent Document 1 Shingo Sugiyama, “Latest Technology of Rubber Solvent-Free Solvent Adhesives” Compatech, 40, (March 2002)
  • the present invention relates to the inconvenience of handling of moisture-curable polyurethane hot melt adhesives and conventional two-component curable hot melt adhesives, which are free from environmental problems of solvent-based curable adhesives, and before and after processing. It is an object of the present invention to provide a one-part curable rubber-based hot-melt adhesive that does not have economic unreasonableness and must be discarded.
  • the present invention provides a rubber-based curing in which a reactive composition having the following components (A) to (E) as a main component is reacted with the following component (F) from the surface to cause a gradient in the curing reaction.
  • Type hot melt adhesive That is, the adhesive of the present invention has superior performance such as heat resistance by adding (F) a curing accelerator to the surface of a hot melt reactive composition containing an epoxy resin, bringing it into contact with the surface, and reacting from the surface. It is a rubber-based curable hot melt adhesive.
  • the component (B) is preferably an epoxy resin containing 2 to 10 epoxy groups in the molecule.
  • non-reactive block copolymer of component (C) is a styrene block copolymer and And / or an acrylic block copolymer.
  • the component (C) is a styrene block copolymer
  • a polymer block ( ⁇ - ⁇ ) made of a styrene polymer, a butadiene polymer block, an isoprene polymer block, an ethylene butylene heavy polymer
  • a styrene block copolymer having a polymer block (Y-1) force composed of at least one of a polymer block and an ethylene propylene polymer block is preferred.
  • component (C) is an acrylic block copolymer
  • a polymer block (X-2) comprising at least one of a styrene polymer and a methacrylic polymer, and an acrylic An acrylic block copolymer having a polymer block (Y-2) strength is preferred.
  • the structure of the (C) component styrene block copolymer and Z or acrylic block copolymer is X—Y—X type block copolymer, X—Y type block copolymer, X—Y—X—Y—X. — Y-type multi-block copolymer and (XY) R-type radial block copolymer (where X is X—1 or X—2, Y is Y—1 or Y—2, R is a polyvalent compound, and n is at least It is preferably at least one of 3).
  • the ratio of the acrylic polymer block (Y-2) in the acrylic block copolymer of the component (C) is preferably 60% by weight to 99% by weight.
  • the number average molecular weight of the acrylic block copolymer of the component (C) is from 30,000 to 000
  • the acrylic block copolymer of the above component (C) is a metal having an organic halide or a sulfonyl halide compound as an initiator and at least one selected from Fe, Ru, Ni, and Cu as a central metal. It is preferably produced by an atom transfer radical polymerization method using a complex as a catalyst.
  • the reactive composition comprises (A) an acid anhydride-modified copolymer.
  • the component (F) is at least one kind selected from tertiary amines and salts thereof, imidazoles and salts thereof, organic phosphine compounds and salts thereof, and organic acid metal salts.
  • An accelerator is preferred.
  • the component (F) has a content of 0.05 with respect to 100 parts by mass of the reactive composition mainly comprising the components (A) to (E). ⁇ 5 parts by mass is further applied, or the component (F) is applied to the substrate in advance, so that curing is accelerated from the surface of the applied reactive composition, and the curing reaction causes a gradient from the surface.
  • a rubber-based hot-melt adhesive that can be seen. That is, the rubber-based curable hot melt adhesive of the present invention is (B) a (F) curing accelerator is added to and brought into contact with the surface of a hot melt reactive composition containing an epoxy resin, and the reaction is started from the surface. It is preferable that the rubber-based curable hot-melt adhesive has better performance such as heat resistance.
  • the rubber-based curable hot melt adhesive of the present invention is preferably used for applications of pressure-sensitive adhesive tapes that require stickiness and heat resistance.
  • the present invention can provide an adhesive with high heat resistance and convenient handling. Furthermore, in the present invention, by using the (F) curing accelerator, a hot melt adhesive (the above-mentioned reactive composition) is applied onto the adhesive after coating, and cured, thereby further improving handling convenience. A certain rubber type curable hot melt adhesive having high heat resistance can be provided.
  • the present invention is a rubber curable hot melt adhesive that is not moisture curable. Further, the adhesive of the present invention has a gradient in the curing reaction from the surface. Here, the gradient of the curing reaction is
  • the cross section in the depth direction of the hot melt adhesive is measured by microscopic ATR measurement.
  • the present invention provides (B) a coated surface of a hot-melt reactive composition containing an epoxy resin.
  • (F) A rubber-based curable hot melt adhesive that has heat resistance by adding a curing accelerator and reacting from the surface.
  • the rubber-based curable hot melt adhesive of the present invention comprises (A) an acid anhydride-modified copolymer as a reactive base polymer, (B) cross-linked with an epoxy resin, and (F) a curing accelerator is an acid. Those that promote the anhydride / epoxy resin reaction are preferred.
  • the acid anhydride-modified copolymer of component (A) is a styrene block copolymer containing 0.5 to 5% by mass of an acid anhydride, such as styrene 'butadiene' styrene block copolymer (SBS), styrene.isoprene.styrene.
  • Block copolymer SIS
  • SEBS Styrene block copolymer
  • SEPS Styrene block copolymer
  • a maleic anhydride-modified styrene-ethylene butylene-styrene block copolymer hereinafter referred to as “maleic anhydride-modified SEBS” is preferably used. If the amount of acid anhydride added is less than 0.5% by mass, the reactivity tends to be low and sufficient heat resistance tends not to be obtained. On the other hand, an acid anhydride exceeding 5% by mass is added to the styrene block copolymer. Is difficult.
  • maleic anhydride-modified SEBS examples include Kraton Polymer Japan Co., Ltd., trade name Clayton FG1901X, Asahi Kasei Co., Ltd., trade name Tuftec M1943.
  • the amount of the above-mentioned (A) acid anhydride-modified copolymer is preferably used in the components (A) to (E).
  • the epoxy resin as the component (B) of the present invention is preferably a monomer, oligomer or polymer having 2 to 10 epoxy groups in one molecule.
  • the epoxy resin having an epoxy equivalent of 100 to 5, OOOg / equivalent, more preferably 150 to: 1, OOOg / equivalent is more preferably used.
  • preferable (B) epoxy resin includes Japan Epoxy Resin Co., Ltd., trade name Meiko Picoat 828, Epoi Coat 1001, and Epoi Coat 1004.
  • the number of epoxy groups in one molecule is less than 2, the reactivity is low and sufficient heat resistance tends not to be obtained.
  • the number of epoxy groups in one molecule exceeds 10, the pot life and storage stability tend to be adversely affected.
  • (B) as an epoxy resin the presence of a functional group capable of promoting the ring opening of an acid anhydride in the molecule, for example, a hydroxyl group, nitrogen, etc.
  • a functional group capable of promoting the ring opening of an acid anhydride in the molecule for example, a hydroxyl group, nitrogen, etc.
  • An epoxy resin having a functional group content capable of accelerating the ring opening of the acid anhydride of 1.0% by mass or less is preferable because it adversely affects the properties.
  • Examples of such an epoxy resin include Japan Epoxy Resin Co., Ltd., trade name Meiko Picoat 825, Daicel Chemical Industries, Ltd., trade name Celoxide 2021, and the like.
  • the amount of the (B) epoxy resin used is preferably 0.5 :! to 20% by mass, more preferably 0.5 to 10% by mass in the components (A) to (E). .
  • the content is less than 1% by mass, the reactivity is poor.
  • the content exceeds 20% by mass, the stability decreases.
  • the component (C) of the present invention is preferably a styrene block copolymer and a Z or acrylic block copolymer.
  • the component (C) is a styrene block copolymer
  • the component (C) is a polymer block (X_l) made of a styrene polymer, as well as a butadiene polymer block, an isoprene polymer block, an ethylene butylene heavy polymer. It is a styrene block copolymer having a polymer block (Y-1) force composed of at least one polymer out of a polymer block and an ethylene propylene polymer block.
  • the component (C) of the present invention is an acrylic block copolymer
  • the component (C) is a polymer comprising at least one of a styrene polymer and a methacrylic polymer which are hard segments. It consists of block (X-2) and acrylic polymer block (Y-2), which is a soft segment, where the hard segment develops shape retention and the soft segment develops tackiness. .
  • the structure of the (C) component styrene block copolymer and / or acrylic block copolymer is X—Y—X type block copolymer and X—Y type block copolymer and X_Y_X_Y_X_Y type multiblock copolymer and (XY ) R type radial block copolymer (where X is X—1 or X — 2, Y is Y — 1 or Y — 2, R is a polyvalent compound, and ⁇ is an integer of at least 3)
  • X is X—1 or X — 2
  • Y is Y — 1 or Y — 2
  • R is a polyvalent compound
  • ⁇ is an integer of at least 3
  • the styrene polymer and the methacrylic polymer has a polymer block (X-2) ratio of 40 to :! %,
  • the proportion of acrylic polymer block ( ⁇ _2) should be 60-99 wt% I like it. If the proportion of the acrylic polymer block (Y-2) is greater than 99% by weight, the temperature dependence of the adhesive property is worse than the decrease in shape retention, while the proportion of the acrylic polymer block ( ⁇ -2) is low. If it is less than 60% by weight, the adhesive properties may not be exhibited.
  • the acrylic block copolymer is preferably adjusted so that the number average molecular weight measured by gel permeation chromatography is 30,000 to 300,000. If the molecular weight is less than 30,000, sufficient adhesive properties may not be exhibited. Conversely, if the molecular weight force is greater than 3 ⁇ 400, 000, the processing properties may deteriorate.
  • (C) The ratio (MwZMn) of the weight average molecular weight (Mw) to the number average molecular weight () ⁇ ) measured by gel permeation chromatography of the acrylic block copolymer is 1.8 or less. It is more preferable that it is 1.5 or less. When Mw / Mn exceeds 1.8, the uniformity of the acrylic block copolymer may deteriorate.
  • the acrylic block copolymer may be a linear block copolymer or a branched (star) block copolymer, or a mixture thereof.
  • the structure of such a block copolymer is preferably a linear block copolymer from the viewpoint of cost, cost and ease of polymerization, which are appropriately selected according to the required physical properties of the (C) acrylic block copolymer.
  • the linear block copolymer may have any structure (arrangement), but from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the styrenic polymer and the methacrylic polymer.
  • At least one polymer block (X—2) and acrylic polymer block (Y—2) are ((X—2) — (Y—2)) type, (Y—2) — ((X— 2) — (Y— 2)) type and ((X— 2) — (Y— 2)) — (X— 2) type (n is an integer greater than or equal to 1, for example, an integer from 1 to 3
  • a polymer block (X-2) consisting of at least one of a styrene polymer and a methacrylic polymer constituting an acrylic block copolymer and an acrylic polymer block ( ⁇ _2)
  • the glass transition temperature (Tg) of the polymer block (X-2) and the acrylic polymer block (Y-2), which are at least one of styrene polymer and methacrylic polymer, is: It can be measured by DSC (differential scanning calorimetry) or tan ⁇ peak of dynamic viscoelasticity.
  • the polymer block ( ⁇ -2) composed of at least one of a styrene polymer and a methacrylic polymer is a single monomer mainly composed of at least one of styrene and a methacrylic acid ester. It is a block formed by polymerizing a body, and is preferably composed of 50% by weight of styrene and methacrylic acid ester 50% by weight and 50% by weight of a butyl monomer copolymerizable therewith. If the proportion of styrene and methacrylic acid ester is less than 50% by weight, the weather resistance characteristic of styrene and methacrylic acid ester may be impaired.
  • Examples of the styrene-based polymer and meth methacrylic acid esters which constitute the ing from at least one polymer polymer block (X 2) of the acrylic polymer for example, Meta acrylic acid methyl, methacrylic acid Ethyl, methacrylic acid ⁇ propyl, methacrylic acid ⁇ -butyl, methacrylic acid isobutyl, methacrylic acid ⁇ pentyl, methacrylic acid ⁇ xyl, methacrylic acid ⁇ heptyl, methacrylic acid ⁇ -octyl, methacrylic acid 2 — Ethylhexyl, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, stearyl methacrylate, and other acrylate aliphatic hydrocarbons (eg, alkyl having 118 carbon atoms). At least one of these is used. Among these, methyl methacrylate is preferable
  • a polymer block ( ⁇ -2) comprising at least one of a styrene polymer and a methacrylic polymer
  • acrylate ester examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, Acrylic aliphatic hydrocarbons such as n-heptyl acrylate, n_octyl acrylate, 2-ethylhexyl acrylate, noel acrylate, decyl acrylate, dodecinole acrylate, stearyl acrylate, etc. ⁇ : 18 alkyl) esters and the like.
  • aromatic alkenyl compound examples include monomethylstyrene, p-methylstyrene, p-methoxystyrene, and the like.
  • Examples of the cyanide bur compound include acrylonitrile, methacrylonitrile, and the like.
  • conjugation compound examples include butadiene and isoprene.
  • halogen-containing unsaturated compound examples include vinyl chloride, vinyl chloride vinyl chloride, perfluoroethylene, perfluoropropylene, and vinylidene fluoride.
  • These compounds listed as bulur monomers can be used alone or in combination of two or more. These Biel monomers are used for the glass transition temperature of the polymer block (X-2) consisting of at least one of the styrene polymer and methacrylic polymer described later, and the phase with various compounding agents. It is selected as appropriate in consideration of solubility.
  • the glass transition temperature of the polymer block (X-2) comprising at least one of the styrene polymer and the methacrylic polymer is adjusted to be 50 to 130 ° C. This is because if the temperature is lower than 50 ° C, the physical properties change drastically and the characteristics become unstable in the temperature range where the adhesive is normally used. If it exceeds 130 ° C, a special monomer is used. This is necessary.
  • a methacrylic polymer is more preferable from the viewpoint of compatibility and thermal stability. .
  • acrylic polymer block (Y- 2) is desired to easily obtain a composition of properties point, in terms of cost and easy availability, acrylic acid ester monomer 50: 100 Mass 0/0 And 50 to 0% by mass of a vinyl monomer copolymerizable therewith.
  • acrylic acid ester monomer 50 100 Mass 0/0 And 50 to 0% by mass of a vinyl monomer copolymerizable therewith.
  • acrylate monomers ethyl acrylate, _n-butyl acrylate, 2-methoxyethyl acrylate, and -2-ethylhexyl acrylate are preferred because of their availability. More specifically, n-butyl acrylate and 2_ethylhexyl acrylate are preferred from the viewpoint of exhibiting the adhesive properties of the composition.
  • acrylic acid esters different from ethyl acrylate, acrylic acid _ ⁇ -butyl and acrylic acid _2-methoxyethyl constituting the acrylic polymer block (Y_ 2) include, for example, styrene polymers.
  • methacrylic polymers the same monomers as the acrylic ester exemplified as the monomer constituting the polymer block (X-2) can be given. These can be used alone or in combination of two or more thereof.
  • Examples of the vinyl monomer copolymerizable with the acrylic ester constituting the acrylic polymer block ( ⁇ -2) include, for example, methacrylic ester, aromatic alkenyl compound, cyanide bur compound Conjugated conjugation compounds, halogen-containing unsaturated compounds, cage-containing unsaturated compounds, unsaturated carboxylic acid compounds, unsaturated dicarboxylic acid compounds, and maleimide compounds.
  • Specific examples of these include: As for metaatanolates, aromatic alkenyl compounds, vinyl cyanide compounds, conjugation compounds, and halogen-containing unsaturated compounds, a polymer composed of at least one of a styrene polymer and a metaaryl polymer.
  • examples of the kale-containing unsaturated compound include trialkyl butyl silane and trialkoxy butyl silane.
  • examples of the unsaturated carboxylic acid compound include methacrylic acid and acrylic acid.
  • examples of the unsaturated dicarboxylic acid compound include maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid, fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid, and the like.
  • maleimide compounds examples thereof include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, fuelmaleimide, cyclohexylmaleimide and the like.
  • These vinyl monomers can be used alone or in combination of two or more. These bull monomers take into account the balance of glass transition temperature and adhesiveness required for the acrylic polymer block (Y_ 2), compatibility with the polymer block (X-2), etc. What is necessary is just to select a preferable thing suitably.
  • the glass transition temperature of the acrylic polymer block ( ⁇ ⁇ ⁇ -2) is preferably 25 ° C or less, more preferably 0 ° C or less, from the viewpoint of rubber elasticity of the composition. More preferably, the temperature is not more than 20 ° C. Glass transition temperature power of the acrylic polymer block (Y) When the temperature is higher than the environment in which the elastomer composition is used, flexibility and adhesive properties are hardly exhibited.
  • the method for producing the (C) acrylic block copolymer is not particularly limited, but it is preferable to use controlled polymerization using an initiator from the viewpoint of ease of structure control.
  • Examples of the control polymerization include living anion polymerization, radical polymerization using a chain transfer agent, and recently developed living radical polymerization. Of these, it is preferable to produce the polymer by living radical polymerization from the viewpoint of controlling the molecular weight and structure of the acrylic block copolymer.
  • Living radical polymerization is radical polymerization in which the activity at the polymerization terminal is maintained without loss.
  • living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the terminal is in equilibrium. It is. The definition here is also the latter.
  • Living radical polymerization has been actively researched by various groups in recent years. Examples include polysulfide and other chain transfer agents, cobalt borphyrin complex (Journal 'Ob' American 'Chemicanor' Society i. Am. Chem. So), 1994, 1 16 7943) and those using radical scavengers such as nitroxide compounds (Macromolecules (
  • Atom transfer radical polymerization uses an organic halide or a sulfonyl halide compound as an initiator, and a metal complex having a group 8 element, a group 9, group 10, or group 11 element as a central metal in the periodic table as a catalyst.
  • Polymerized eg, Matyjaszewski et al., Journal of American Chemical Society, 1995, 117, 5614, Macromolecules, 1995, 28, 7901, Science, 1996, 272, 866, or Sawamoto et al., Macromolecules, 1995, 2 8, 1721) .
  • a monofunctional, difunctional, or polyfunctional compound can be used as the organic halide or halogenated sulfonyl compound used as an initiator in the atom transfer radical polymerization. These can be used properly according to the purpose.
  • a diblock copolymer a monofunctional compound is preferred.
  • (X-2) One (Y-2) One (X-2) type triblock copolymer, ( ⁇ -2)-(X-2)-(Y-2) type triblock copolymer In the case of production, it is preferable to use a bifunctional compound.
  • a polyfunctional compound When producing a branched block copolymer, it is preferable to use a polyfunctional compound.
  • Examples of the monofunctional compound include compounds represented by the following chemical formulas.
  • CH represents a phenylene group. Phenylene groups are ortho-substituted, meta-substituted and
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryleno group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
  • X represents chlorine, fluorine or iodine.
  • R 2 represents a monovalent organic group having 1 to 20 carbon atoms.
  • bifunctional compound examples include a compound represented by the following chemical formula.
  • R 3 represents an alkyl group, the number 6 to 20 Ariru group or number 7-20 Ararukiru group carbon atoms of 1 to 20 carbon atoms.
  • CH represents a phenylene group. The phenyl group is ortho
  • C H represents a phenyl group.
  • X represents chlorine, bromine or iodine.
  • polyfunctional compound examples include compounds represented by the following chemical formulas.
  • C H represents a tri-substituted phenyl group.
  • the trisubstituted phenyl group is
  • X represents chlorine, bromine or iodine.
  • the carbon to which the halogen is bonded is bonded to a carbonyl group, a phenyl group, or the like, and the carbon-halogen bond is activated to perform polymerization.
  • the amount of initiator to be used can be determined from the ratio with the monomer, depending on the molecular weight of the block copolymer required. That is, the molecular weight of the block copolymer can be controlled by the number of monomers used per molecule of the initiator.
  • the transition metal complex used as a catalyst for atom transfer radical polymerization is not particularly limited, but preferred are monovalent and zero-valent copper, divalent ruthenium, divalent iron or divalent nickel. Complexes can be listed. Among these, the copper complex is preferable because of cost and reaction control.
  • Examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, shear Examples thereof include cuprous chloride, cuprous oxide and cuprous perchlorate.
  • copper compounds 2, 2 '-bibilidyl and its derivatives, 1, 10-phenantorin and its derivatives, tetramethylethylenediamine (TMEDA), pentamethylgerm Polyamines such as tylenetriamine and hexamethyl (2-aminoethyl) amine can also be added as ligands.
  • TMEDA tetramethylethylenediamine
  • Polyamines such as tylenetriamine and hexamethyl (2-aminoethyl) amine can also be added as ligands.
  • a tristophenyl phosphine complex of divalent salt ruthenium (RuCl (PPh)) can be used as a catalyst.
  • an aluminum alkoxide can be added as an activator.
  • divalent iron bistriphenylphosphine complex FeCl (PPh)
  • NiCl (PPh) Bivalent nickel bistriphenylphosphine complex (NiCl (PPh)), and divalent nickel
  • Nickel bistributylphosphine complex (NiBr (PBu)) can also be used as a catalyst.
  • the amount of the catalyst, ligand and activator used can be appropriately determined from the relationship between the amount of initiator, monomer and solvent used and the required reaction rate.
  • examples of the styrene block copolymer include those manufactured by Kraton Polymer Japan Co., Ltd., trade name: Kraton G-1726, and acryl-based block copolymer.
  • trade name “NYY-001” manufactured by Kane force Co., Ltd. may be mentioned.
  • the (D) tackifying resin used in the present invention includes, for example, terpene resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, coumarone 'indene resins, rosin resins, and the like. There are derivatives thereof. These may be used alone or in combination of two or more.
  • the (D) tackifier of the present invention includes, for example, trade names “Clearon M115” and “YS Resin TO-105” manufactured by Yasuhara Chemical Co., Ltd.
  • the amount of the above (D) tackifying resin used is preferably 30 to 70% by mass, more preferably 40 to 60% by mass in the components (A) to (E). If it is less than 30% by mass, the tackiness is poor, whereas if it exceeds 70% by mass, it becomes hard.
  • (E) As the plasticizer process oil, polyolefin fluid and wax are used. These may be used alone or in combination of two or more.
  • the (E) plasticizer of the present invention includes, for example, trade name process oil PW-32 manufactured by Idemitsu Kosan Co., Ltd.
  • the amount of the above-mentioned (E) tackifying resin used is preferably 5 to 30% by mass, preferably 10 to 25% by mass in the components (8) to). If it is less than 5% by mass, the viscosity is high and the coating property is poor, whereas if it exceeds 30% by mass, the heat resistance is deteriorated.
  • the rubber-based curable hot melt adhesive if necessary, the rubber-based curable hot melt adhesive.
  • an antioxidant 1J such as hindered phenol, a filler such as calcium carbonate, etc. may be appropriately added.
  • the (F) curing accelerator used in the present invention is a curing accelerator for the above-mentioned (A) acid anhydride-modified copolymer or (B) epoxy resin.
  • 1,8_Diazabicyclo (5,4,0) undecene 7,1,5_Diazabicyclo (4,3,0) can be used as a curing accelerator in an acid anhydride / epoxy resin reaction system.
  • Cycloamidine compounds such as nonene, 5, 6_dibutylamino-1,8_diazabibicyclo (5,4,0) undecene_7 and these compounds include maleic anhydride, 1,4_benzoquinone, 2, 5_Toluquinone, 1,4 Naphthoquinone, 2,3 Dimethylbenzoquinone, 2,6 Dimethylbenzoquinone, 2,3 Dimethoxy-5-Methyl-1,4 Monobenzoquinone, 2,3 Dimethoxy-1,4 Benzoquinone, Phoenix Quinone compounds such as 1,4-benzoquinone, dipolar compounds such as diazophenylmethane, phenolic resins and other compounds with intramolecular polarization, such as benzyldimethylamine, tri
  • Organophosphorus compounds such as compounds having an intramolecular polarization formed by adding a compound having a ⁇ bond such as maleic anhydride, the above quinone compound, diazophenylmethane, phenol resin, etc., tetraphenylphosphonium tetra
  • tetraboronyl boron salts such as phenyl borate, triphenylphosphine tetraphenyl borate, 2_ethyl _4-methylimidazole tetraphenyl borate, ⁇ -methylmorpholine tetraphenyl borate, and their derivatives. Use 2 You can use more than one species in combination.
  • tertiary amines and salts thereof imidazoles and salts thereof, organic phosphine compounds and salts thereof, and organic acid metal salts are preferred, and polyoxyethylene coconut alkylamine is preferred in terms of toxicity.
  • polyoxyethylene coconut alkylamine is preferred in terms of toxicity.
  • Air Products Japan Co., Ltd. brand name: Ancamine K-54 is mentioned.
  • the (F) curing accelerator used in the present invention is preferably added to the surface of a hot melt composition coating material after being diluted with water or a good solvent to an appropriate concentration in order to apply a necessary amount in a small amount. That's right. If there is another adherend, a curing accelerator may be applied to the surface of the adherend and then bonded to the hot melt composition coating. Alternatively, a curing accelerator may be applied in advance to a film or the like to which the hot melt composition is applied, and then the hot melt adhesive may be applied.
  • the solvent for diluting the (F) curing accelerator is not particularly defined as long as it can dissolve the (F) curing accelerator, but water, 2-propanol and the like are preferable from the environmental viewpoint.
  • the ratio of the (F) curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, but the reactive composition containing (A) to (E) as a main component is not limited. From the viewpoint of heat resistance, 0.05 to 5 parts by mass is preferable with respect to parts by mass. If it is less than 0.05 parts by mass, the heat resistance decreases. On the other hand, if it exceeds 5 parts by mass, it becomes sticky. Furthermore, it is preferably 0.1 to 3 parts by mass.
  • the (F) curing accelerator applied to the surface diffuses into the adhesive and the curing reaction proceeds to the bottom.
  • the rubber-based curable hot-melt adhesive in the present invention can be used for pressure-sensitive adhesive tapes and the like that require heat resistance because it has adhesiveness even after curing.
  • the above components (A) to (E) are first added to a melting / dissolving tank such as a heating type melting and stirring tank, preferably in a vacuum, under a nitrogen stream. At a temperature of 150 ° C or higher and 250 ° C or lower, each component is melted and mixed in turn by rotating the stirring blades.
  • the components (A) to (E) are mainly produced by a method such as melt mixing with heating using a twin rotary blade of a kneader, or by melt mixing with a screw of a single or twin screw extruder.
  • a reaction composition as a component is prepared.
  • the above reactive composition is laminated on a release paper or a release sheet or a non-coating material as a base material by a coating means such as a slot coater or a roll coater, and (F ) Apply a curing accelerator.
  • a curing accelerator is first applied to the surface of the base material, and then a reactive composition mainly composed of the components (A) to (E) is laminated to form the adhesive of the present invention.
  • a rubber-based curable hot melt adhesive is obtained in which curing is accelerated from the surface of the applied reactive composition and a gradient is observed from the surface in the curing reaction.
  • the synthesis method of the acrylic block copolymer used in the present invention will be described in more detail based on production examples, the synthesis method is not limited to these production examples.
  • BA, 2EHA, and MMA represent _n-butyl acrylate, -2-ethylhexyl acrylate, and methyl methacrylate, respectively.
  • the molecular weight described in the production examples was carried out according to the following method.
  • the molecular weight shown in this example was measured by the GPC analyzer shown below, and the molecular weight in terms of polystyrene was determined using the black mouth form as the mobile phase.
  • a GPC system manufactured by Waters was used.
  • Shodex (registered trademark) K-804 (polystyrene gel) manufactured by Showa Denko Co., Ltd. was used.
  • Toluene was added to the obtained reaction solution to adjust the polymer concentration to 25% by weight.
  • 16 g of p-toluenesulfonic acid was added, the inside of the reactor was purged with nitrogen, and the mixture was stirred at 30 ° C for 3 hours.
  • the reaction solution was sampled to confirm that the solution was colorless and transparent, and 23 g of Radiolite # 3000 manufactured by Showa Chemical Industry Co., Ltd. was added. Thereafter, the solid was separated by filtering the reaction solution.
  • the heat resistance of the cured hot melt adhesive was evaluated by SAFT (shear bond failure temperature) test.
  • a test piece was prepared by applying a curing accelerator to the surface of a hot melt adhesive applied to PET film to a thickness of 30 ⁇ m and curing it.
  • the test conditions were the same as the practical conditions in which the test piece was 25mm wide and 25mm long was melted on a SUS plate and then allowed to cool, and the temperature was raised at a rate of 2 ° CZ for 5 minutes with a 10 Og load. And measure the drop temperature. Measurements were performed up to 180 ° C at room temperature.
  • the tackiness of the hot melt adhesive was evaluated by measuring the 180 ° peel force.
  • a test piece was prepared by applying (F) a curing accelerator to the surface of a hot-melt adhesive applied to a PET film at a thickness of 30 ⁇ m and curing it.
  • the test condition is that the above test piece is cut to a width of 25 mm and attached to a SUS plate, and a 2 kg roll is reciprocated once on the shell-occupied part and crimped.
  • the test piece was measured for 180 ° peel force in an atmosphere of 23 ° C and 80 ° C to evaluate the tackiness.
  • Tris (dimethylaminomethyl) phenol (trade name: Ancamine K-54, manufactured by Air Products Japan Co., Ltd.) was used.
  • the hot melt adhesive was applied to PET film at 30 xm, and (F—1) curing accelerator DMP-30 was applied at 0.5 g / m 2. The test piece was cured and cured at 50 ° C for 1 day.
  • hot melt adhesive was applied to the release PET film at 30 / im, cured in the same way, and cured hot melt adhesive. Was peeled off from the release film to prepare a test piece, and infrared absorption measurement was performed by transmission. The results are shown in Table 1.
  • the hot melt adhesive was molded to have a surface of 10mm x 10111111 and a thickness of 300 to 350 111, and (F-1) curing accelerator 0.5g / m 2 was applied to the surface as before. Incubated for 3 days, cut from the surface to the depth direction using a microtome, and measured infrared absorption at 20 ⁇ from the surface to the depth direction to examine the gradient of the degree of hardening. The results are shown in Table 2.
  • Example 1 In order to verify the tack after curing, only the ratio of (A-1) maleic anhydride modified SEBS and (C) non-reactive block copolymer of Example 1 was changed.
  • Clayton FG—1901XZ Clayton G—1726 30/5.
  • the test piece was a hot melt adhesive applied to a PET film with a thickness of 30 ⁇ m, and 0.5 gZm 2 of curing accelerator DMP_ 30 (F_ 1) was applied to the surface and cured at 50 ° C for 1 day. A thing was used.
  • the test conditions were as follows. The above test piece was cut to a width of 25 mm and pasted on a SUS plate, and a 2 kg-load roll was reciprocated once on the shell-occupied portion and pasted onto the shell.
  • test piece was measured for 180 ° peel force at a pulling speed of 300 mm / min in an atmosphere of 23 ° C and 80 ° C to evaluate the tackiness.
  • results are shown in Table 4.
  • SAFT test was performed in the same manner as in Example 1, and the results are shown in Table 4.
  • Examples 1 to 15 of the present invention as shown in Tables 1 to 3, in comparison with Comparative Example 1, Tables 1 to 15 show an inclination in the degree of curing caused by the degree of progress of the crosslinking reaction with a curing accelerator other than moisture. It had excellent heat resistance. In addition, it was stored after manufacturing, and a pasting process was possible when needed, and the operation was simple. It was also excellent in terms of environment without the use of harmful solvents.
  • Examples 1, 12, 13, and 14 were compared with Example 15, and as shown in Table 4, a part of maleic anhydride-modified SEBS was converted to (C) a non-reactive block copolymer (Clayton G-1726, By replacing it with an acrylic block copolymer), it was possible to improve the adhesiveness particularly at high temperature (80 ° C) while giving heat resistance.
  • C a non-reactive block copolymer
  • the present invention is a rubber-based curable hot-melt adhesive having high cohesive strength and adhesiveness, and can be used without a solvent during coating. It is useful for applications such as adhesive tapes and adhesive sheets.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'objectif est de proposer un adhésif thermofusible durcissable à un seul composant, qui est exempt de toute préoccupation concernant les problèmes écologiques qui sont inévitables pour un adhésif durcissable de type à solvant, d'inconvénient dans la manipulation qui est inévitable pour un adhésif thermofusible de type polyuréthane durcissable par l'humidité ou pour un adhésif thermofusible durcissable à deux composants classique, et d'une telle absurdité économique qu'un agent adhésif devrait être mis au rebut avant et après le traitement. L'invention concerne un adhésif thermofusible durcissable de type caoutchouc. Dans l'adhésif, une composition réactive, composée principalement de (A) un copolymère modifié par un anhydride d'acide, (B) une résine époxy, (C) un copolymère à blocs non réactif, (D) un agent conférant le caractère adhésif et (E) un plastifiant, est mise à réagir avec (F) un agent favorisant le durcissement sur la surface de la composition, permettant ainsi de créer un gradient de réaction de durcissement à partir de la surface de la composition vers son intérieur.
PCT/JP2007/059635 2006-07-04 2007-05-10 Adhésif thermofusible durcissable de type caoutchouc WO2008004376A1 (fr)

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JP2010506999A (ja) * 2006-10-19 2010-03-04 ダウ グローバル テクノロジーズ インコーポレイティド 金属下地に対する改善された接着を有する硬化性エポキシ樹脂組成物ならびにその作製方法及び使用方法
JP2010100704A (ja) * 2008-10-22 2010-05-06 Kyoritsu Kagaku Sangyo Kk 主剤−プライマー型熱硬化性エポキシ樹脂及びその硬化方法
WO2012159867A1 (fr) * 2011-05-23 2012-11-29 Bostik S.A. Adhésifs thermofusibles contenant de la cire et articles absorbants jetables
US8404172B2 (en) 2010-11-24 2013-03-26 Tyco Electronics Corporation Methods of processing high service temperature hydrocarbon gels
US8691884B2 (en) 2010-11-24 2014-04-08 Tyco Electronics Corporation Crosslinked flame retardant thermoplastic elastomer gels
WO2023153196A1 (fr) * 2022-02-09 2023-08-17 サンスター技研株式会社 Agent de durcissement pour résine époxy, et adhésif

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Publication number Priority date Publication date Assignee Title
JP2010506999A (ja) * 2006-10-19 2010-03-04 ダウ グローバル テクノロジーズ インコーポレイティド 金属下地に対する改善された接着を有する硬化性エポキシ樹脂組成物ならびにその作製方法及び使用方法
JP2010100704A (ja) * 2008-10-22 2010-05-06 Kyoritsu Kagaku Sangyo Kk 主剤−プライマー型熱硬化性エポキシ樹脂及びその硬化方法
US8404172B2 (en) 2010-11-24 2013-03-26 Tyco Electronics Corporation Methods of processing high service temperature hydrocarbon gels
US8691884B2 (en) 2010-11-24 2014-04-08 Tyco Electronics Corporation Crosslinked flame retardant thermoplastic elastomer gels
WO2012159867A1 (fr) * 2011-05-23 2012-11-29 Bostik S.A. Adhésifs thermofusibles contenant de la cire et articles absorbants jetables
AU2012261164B2 (en) * 2011-05-23 2015-12-03 Bostik S.A. Wax-containing hot melt adhesives and disposable absorbent articles
WO2023153196A1 (fr) * 2022-02-09 2023-08-17 サンスター技研株式会社 Agent de durcissement pour résine époxy, et adhésif

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