WO2021130640A1 - Two-component solvent-free adhesive and main agent for two-component solvent-free adhesive - Google Patents

Two-component solvent-free adhesive and main agent for two-component solvent-free adhesive Download PDF

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Publication number
WO2021130640A1
WO2021130640A1 PCT/IB2020/062235 IB2020062235W WO2021130640A1 WO 2021130640 A1 WO2021130640 A1 WO 2021130640A1 IB 2020062235 W IB2020062235 W IB 2020062235W WO 2021130640 A1 WO2021130640 A1 WO 2021130640A1
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Prior art keywords
epoxy
component
curing agent
agent
mass
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PCT/IB2020/062235
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French (fr)
Inventor
Norihisa Watanabe
Jun Fujita
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3M Innovative Properties Company
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Publication of WO2021130640A1 publication Critical patent/WO2021130640A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/223—Di-epoxy compounds together with monoepoxy compounds

Definitions

  • Patent Document 1 JP HI 1-293216 A
  • An organic solvent is used in the adhesive of Patent Document 1, but in recent years, the use of volatile organic compounds (VOCs) has become a problem from the perspective of environmental pollution, effects on the human body, and the like. In terms of VOC reduction, it is desirable for the adhesive to have substantially no organic solvent, i.e., to be solvent-free.
  • a two-component solvent-free adhesive is easy to handle, such as when mixing various materials, or when producing a two-component solvent-free adhesive set having a main agent and a curing agent, and has substantially no solvent so that no VOC remains after curing, thereby being useful in applications where improvement of work efficiency is required and applications where heating is limited.
  • a known two-component solvent-free adhesive it is difficult to obtain sufficient adhesiveness to a member with low surface energy, and particularly, it is difficult to obtain adhesiveness to polypropylene.
  • One object of the present invention is to provide a two-component solvent-free adhesive having adhesiveness even to polypropylene.
  • One aspect of the present invention relates to a two-component solvent-free adhesive including a main agent and a curing agent, in which the main agent contains an epoxy component containing a liquid epoxy compound as a main component and a terpene phenol resin, the curing agent contains a liquid amine curing agent, a content of the terpene phenol resin is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component, and a content of the liquid amine curing agent is 20 to 65 parts by mass with respect to 100 parts by mass of the epoxy component.
  • the adhesive has adhesiveness to polypropylene.
  • the epoxy component may include an epoxy oligomer.
  • the epoxy oligomer may be liquid.
  • the epoxy component may include a monofunctional epoxy compound.
  • the monofunctional epoxy compound may be liquid.
  • the liquid amine curing agent may include a diamine having viscosity of 100 Pa s or less.
  • At least one of the main agent and the curing agent may include a reaction rate adjusting agent.
  • Another aspect of the present invention relates to a main agent for a two- component solvent-free adhesive containing an epoxy component containing a liquid epoxy compound as a main component and a terpene phenol resin, in which a content of the terpene phenol resin is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component.
  • the main agent is, for example, combined with a curing agent containing a liquid amine curing agent to provide a two-component solvent-free adhesive having adhesiveness to polypropylene.
  • a two-component solvent-free adhesive of one embodiment includes a main agent (Part B) and a curing agent (Part A).
  • the main agent and the curing agent are present separately, and the adhesive can be cured by mixing the main agent and the curing agent.
  • solvent-free means that the total content (total amount) of solvents in the main agent and the curing agent is 0 to 1 mass%.
  • the solvent is a compound normally used as a solvent for adhesives, and examples thereof include acetone, methanol, isopropyl alcohol, ethyl acetate, toluene, hexane, methyl ethyl ketone, and the like.
  • the main agent contains an epoxy component containing an epoxy compound in a liquid form (liquid epoxy compound) as a main component and a terpene phenol resin, and the curing agent contains an amine curing agent in a liquid form (liquid amine curing agent).
  • the content of the terpene phenol resin is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component, and the content of the liquid amine curing agent is 20 to 65 parts by mass with respect to 100 parts by mass of the epoxy component.
  • the adhesive of the present embodiment uses an epoxy component and a liquid amine curing agent, and thus can be cured at room temperature (for example, 5 to 40°C). Specifically, when the main agent and the curing agent are mixed at room temperature, the reaction between the epoxy component in the main agent and the liquid amine curing agent begins, and curing proceeds. This results in a cured product of the adhesive of the present embodiment.
  • the timing of mixing the main agent and the curing agent is not particularly limited and may be, for example, a timing before the adhesive is applied to an adherend such as a substrate (a member to which an adhesive is applied).
  • the adhesive of the present embodiment is room-temperature curable and solvent-free, and thus is useful in applications where heating is limited. Furthermore, curing can be promoted by heating, and heating and curing can be performed for shortening the working time to improve work efficiency. Specifically, it can be widely used as an adhesive for, for example, building components such as a sash that uses resin and aluminum in combination, a mobile portable terminal, a screen display member, electronic devices such as an electronic module, and the like.
  • the epoxy component, terpene phenol resin, and the liquid amine curing agent which are essential components of the adhesive of the present embodiment, and optional components will be described in detail.
  • the epoxy component includes a compound having at least one epoxy group (epoxy compound).
  • the epoxy compound needs to have at least two epoxy groups for sufficient curing by reacting with the liquid amine curing agent (liquid amine compound).
  • the epoxy component usually includes a multifunctional epoxy compound having two or more epoxy groups.
  • the epoxy component may include a monofunctional epoxy compound having one epoxy group.
  • the epoxy compound may be a monomer or an oligomer.
  • An “epoxy oligomer” refers to an epoxy compound that is a compound having an epoxy group at one or both terminal(s) of a main chain including repeating units of a specific molecular structure, in which the number of repeating units of the specific molecular structure is 100 or less.
  • flexibility of the epoxy compound after curing tends to improve.
  • a compound commonly referred to as an “epoxy resin” is included in the epoxy compound of the present embodiment.
  • an acrylic adhesive and a urethane-based adhesive are known.
  • the acrylic adhesive and the urethane-based adhesive have a faster curing rate compared to the epoxy -based adhesive, so that the adhesive may cure before being wet- spread to an application target, and the operation of applying the adhesive may be complicated in order to avoid such curing.
  • the epoxy component contains a bisphenol epoxy compound in the adhesive of the present embodiment
  • the time until curing of the adhesive can be secured relatively long after mixing the two liquids (the main agent and the curing agent).
  • the epoxy component includes the bisphenol epoxy compound in the adhesive of the present embodiment, failure such as curing of the adhesive before wet-spreading the adhesive to the application target is unlikely to occur, and the operation of applying the adhesive is facilitated.
  • a bisphenol-based epoxy compound is a compound having a bisphenol skeleton or a hydrogenated bisphenol skeleton (a skeleton where a hydrogen atom is added to some or all carbon atoms on an aromatic ring of bisphenol) and an epoxy group, and is typically a condensate of bisphenol and epichlorohydrin (bisphenol glycidyl ether).
  • the viscosity of the liquid epoxy is 100 Pa s or less. Note that the viscosity is viscosity measured by a B-type viscometer at 25°C and 1 atm.
  • the liquid epoxy compound may be a multifunctional epoxy compound or a monofunctional epoxy compound.
  • the liquid epoxy compound include liquid bisphenol-based epoxy compounds (compounds in a liquid form among the bisphenol- based epoxy compounds described above), liquid aliphatic epoxides, and the like.
  • the liquid epoxy compound may be modified with alkyl or the like from the perspective of adjusting the hardness of the cured product.
  • the liquid epoxy compound is preferably an oligomer. That is, the epoxy component preferably includes a liquid epoxy oligomer. When the epoxy component includes a liquid epoxy oligomer, it tends to be uniformly dispersible and less prone to layer separation.
  • a liquid epoxy compound capable of dissolving the terpene phenol resin contained in the main agent is preferably used from the perspective of allowing the terpene phenol resin to be more uniformly present in the adhesive and further improve the adhesiveness to polypropylene.
  • a hydrogenated bisphenol A-type glycidyl ether is preferable. It can be visually confirmed that the terpene phenol resin can be dissolved.
  • the liquid epoxy compound has the property that the terpene phenol resin can be dissolved therein, when the terpene phenol resin is dissolved in the liquid epoxy compound, no insoluble component is generated, and the transparency of the liquid epoxy compound can be visually confirmed.
  • liquid epoxy compound does not have the property that the terpene phenol resin can be dissolved therein, turbidity is generated in the liquid epoxy compound because an insoluble component remains or the terpene phenol resin cannot be sufficiently dissolved.
  • a liquid epoxy compound in which the terpene phenol resin can be dissolved and an epoxy compound in which the terpene phenol resin cannot be dissolved may be used in combination.
  • the epoxy compound in which the terpene phenol resin cannot be dissolved bisphenol A-type (or AD-, S-, or F-type) glycidyl ether or the like is preferably used.
  • the structure of the monofunctional epoxy compound is not particularly limited, but from the perspective of further improving the flexibility of the cured product, the monofunctional epoxy compound preferably has an aliphatic group having 8 or more carbon atoms (long chain aliphatic group).
  • the long chain aliphatic group may be linear or branched, and may be either saturated or unsaturated.
  • Examples of the monofunctional epoxy compound having a long chain aliphatic group include glycidyl ethers of long chain fatty alcohols, glycidyl esters of long chain fatty acids, and the like. These monofunctional epoxy compounds tend to have the excellent property that the terpene phenol resin is dissolved.
  • a silane coupling agent having an epoxy group may be used.
  • the use of the silane coupling agent tends to improve adhesiveness to polypropylene.
  • a silane coupling agent represented by Formula (1) below is preferably used.
  • R 2 represents a hydrogen atom or an alkyl group (e.g., a methyl group or an ethyl group), and n is an integer of 1 to 10.
  • the plurality of R 2 may be the same as or different from each other.
  • the molecular weight of the monofunctional epoxy compound may be, for example, 100 or more and 500 or less. That is, the molecular weight of the monofunctional epoxy compound is, for example, 100 to 500.
  • the content of the monofunctional epoxy compound may be 80 mass% or less, 70 mass% or less, or 65 mass% or less with respect to the total amount of the epoxy component from the perspective of improving the flexibility of the cured product. In the present embodiment, the content of the liquid monofunctional epoxy compound is preferably within the range described above.
  • the epoxy equivalent (g/eq) of the epoxy compound may be 150 or more and 500 or less from the perspective of achieving both flexibility and toughness of the cured product. That is, the epoxy equivalent (g/eq) of the epoxy compound is, for example, 150 to 500. In the present embodiment, the epoxy equivalent of the entire epoxy component is more preferably within the aforementioned range.
  • YD 128 available from NIPPON STEEL Chemical & Materials Co., Ltd.
  • HBE100 available from New Japan Chemical Co.
  • the terpene phenol resin is a polymer obtained by, for example, copolymerization of a terpene monomer with phenol and includes a terpene residue and a phenolic residue.
  • the terpene phenol resin is preferably uniformly present in the main agent (for example, dispersed or dissolved), and is more preferably dissolved in the main agent. The fact that the terpene phenol resin is dissolved in the main agent can be confirmed similarly to the aforementioned method of confirming that the terpene phenol resin can be dissolved in the liquid epoxy compound.
  • the OH value of the terpene phenol resin may be 1 mgKOH/g or more, and may be 5 mgKOH/g or more or 10 mgKOH/g or more.
  • the OH value of the terpene phenol resin may be 200 mgKOH/g or less, and may be 180 mgKOH/g or less or 150 mgKOH/g or less.
  • the softening point of the terpene phenol resin may be 80°C or higher, and may be 90°C or higher or 100°C or higher.
  • the softening point of the terpene phenol resin may be 160°C or lower, and may be 150°C or lower or 140°C or lower.
  • Examples of the commercially available products include U115 (available from Yasuhara Chemical Co., Ltd.), T115 (available from Yasuhara Chemical Co., Ltd.), and the like.
  • the content of the terpene phenol resin may be 40 parts by mass or less or 30 parts by mass or less with respect to 100 parts by mass of the epoxy component.
  • Liquid amine curing agent Liquid amine curing agent
  • the liquid amine curing agent is an amine compound in a liquid form that reacts with an epoxy compound to form a crosslinked structure.
  • the liquid amine curing agent has, for example, a primary amino group (-NFL) and/or a secondary amino group (-NHR 1 ; R 1 is an organic group).
  • the number of amino groups (primary amino groups and secondary amino groups) in the liquid amine curing agent is not particularly limited.
  • the liquid amine curing agent may be, for example, a monoamine having one amino group, a diamine having two amino groups, or a polyamine having three or more amino groups.
  • the liquid amine curing agent may also be a compound (oligomer or polymer) having a plurality of repeating units of a specific molecular structure.
  • the liquid amine curing agent may be a compound having an amino group at one or both terminal(s) of a main chain including a plurality of repeating units (e.g., a polymer of a compound having an amino group and a compound having a functional group capable of reacting with an amino group), or a compound having a plurality of repeating units of a molecular structure having an amino group (e.g., a polymer of a compound having an amino group).
  • the liquid amine curing agent is an oligomer or a polymer
  • the molecular weight of the molecular structure constituting the repeating unit is preferably 50 or more and 2000 or less.
  • the liquid amine curing agent may be a dimer diamine (diamine dimer) in which two terminal carboxyl groups in a dimer of an aliphatic unsaturated carboxylic acid are substituted by a primary amino group or a secondary amino group.
  • the aliphatic unsaturated carboxylic acid is, for example, an unsaturated carboxylic acid having an aliphatic group having 12 to 24 carbon atoms, and specific examples thereof include oleic acid, linoleic acid, and the like.
  • the dimer diamine is preferably a diamine derived from a dimer acid having 28 to 44 carbon atoms (having a dimer acid skeleton of 28 to 44 carbon atoms).
  • the amine equivalent (g/eq) of the liquid amine curing agent may be 100 or more and 600 or less from the perspective of achieving both flexibility and toughness of the cured product. That is, the amine equivalent (g/eq) of the amine curing agent is, for example, 100 to 600.
  • Commercially available products may be used as the liquid amine curing agent.
  • Examples of the commercially available products include Sunmide 506 (available from Evonik Japan Co., Ltd.), Sunmide 70 (available from Evonik Japan Co., Ltd.), Sunmide 75 (available from Evonik Japan Co., Ltd.), Sunmide 76T (available from Evonik Japan Co., Ltd.), Sunmide 76TK (available from Evonik Japan Co., Ltd.), Ancamide 2137 (available from Evonik Japan Co., Ltd.), Ancamide 2396A (available from Evonik Japan Co., Ltd.), Ancamide 501 (available from Evonik Japan Co., Ltd.), Ancamide 502 (available from Evonik Japan Co., Ltd.), Ancamide 506 (available from Evonik Japan Co., Ltd.), Ancamide 2050 (available from Evonik Japan Co., Ltd.), Ancamide 221 (available from Evonik Japan Co., Ltd.), Ancamide 2353 (available from Evonik
  • the content of the liquid amine curing agent is 20 to 65 parts by mass with respect to 100 parts by mass of the epoxy component. From the perspective of the curing speed, the content of the liquid amine curing agent may be 25 parts by mass or more with respect to 100 parts by mass of the epoxy component. From the perspective of the hardness of the final cured product, the content of the liquid amine curing agent may be 60 parts by mass or less with respect to 100 parts by mass of the epoxy component.
  • the curing agent may include an amine curing agent other than the liquid amine curing agent.
  • the content of the liquid amine curing agent in the amine curing agent is not particularly limited, and the content may be, for example, more than 50 mass%, 70 mass% or more, 90 mass% or more, or 95 mass% or more, with respect to the total amount of the amine curing agent, and the amine curing agent may include only the liquid amine curing agent.
  • At least one of the main agent and the curing agent in the adhesive may contain, as optional components, a toughening agent, a reaction rate adjusting agent, and the like.
  • at least one of the main agent and the curing agent preferably contains at least one optional component selected from the group consisting of a toughening agent and a reaction rate adjusting agent.
  • the toughening agent is a material that can impart flexibility and toughness to an epoxy cured product that is hard and brittle.
  • a compound having rubber elasticity such as a copolymer rubber or a compound in which these materials are formed into a core-shell structure is preferably used.
  • the toughening agent may be contained in either the main agent or the curing agent.
  • These toughening agents may have a reactive group (e.g., a functional group capable of reacting with an amino group (such as an epoxy group)) as long as separation or thickening of the main agent is unlikely to occur and can be stably blended.
  • These toughening agents may have a reactive group (e.g., a functional group (such as an amine group) capable of reacting with an epoxy group) as long as separation or thickening of the curing agent is unlikely to occur and can be stably blended.
  • the toughening agent may have fluidity (viscosity of greater than 100 Pa s) from the perspective of handleability when mixing various materials or when producing a two- component solvent-free adhesive set of the main agent and the curing agent.
  • Such toughening agents can be incorporated into the cured product during curing to impart flexibility. Therefore, it is desirable to have a functional group that reacts with the epoxy compound or the amine curing agent to cure.
  • a functional group that reacts with the epoxy compound or the amine curing agent to cure.
  • examples thereof include an elastomer such as carboxyl-terminated butadiene acrylonitrile rubber (CTBN), an epoxy-terminated butadiene acrylonitrile rubber (ETBN), an amine-terminated butadiene acrylonitrile rubber (ATBN), and a mixture thereof.
  • commercially available products may be used as the toughening agent having fluidity (viscosity of greater than 100 Pa s).
  • Examples of the commercially available products include Hypro 1300x8 CTBN (available from CVC Thermoset Specialties), Hypro 1300x9 CTBN (available from CVC Thermoset Specialties), Hypro 1300x13 CTBN (available from CVC Thermoset Specialties), Hypro 1300x63 ETBN (available from CVC Thermoset Specialties), Hypro 1300x68 ETBN (available from CVC Thermoset Specialties), Hypro 1300x16 ATBN (available from CVC Thermoset Specialties), Hypro 1300x21 ATBN (available from CVC Thermoset Specialties), and the like.
  • the molecular weight of the toughening agent is preferably greater than 2000.
  • the content of the toughening agent may be, for example, 0 mass% or more, and may be 20 mass% or more, and may be 35 mass% or less. In other words, the content of the toughening agent may be 0 to 35 mass%, and may be 20 to 35 mass%, when the total amount of all the adhesive components is 100 mass%.
  • the reaction-rate adjusting agent is a compound having a function of adjusting a rate of a curing reaction, and is, for example, a compound having a function of promoting the curing reaction (curing accelerator).
  • the reaction-rate adjusting agent include tertiary amine-based reaction rate adjusting agents having one or more tertiary amino groups, thiol-based reaction rate adjusting agents having one or more thiol groups, and the like.
  • tertiary amine-based reaction-rate adjusting agent examples include 2,4,6- tris(dimethylaminomethyl)phenol, and the like.
  • tertiary amine-based reaction rate adjusting agent examples include TAP (available from Kayaku Akzo Co., Ltd.), and the like.
  • thiol-based reaction rate adjusting agent examples include polyfunctional thiol compounds having an aliphatic ether structure, polyfunctional thiol compounds having an aliphatic ester structure, and the like.
  • thiol-based reaction rate adjusting agent examples include Thiokol LP-3 (available from Toray Fine Chemicals Co., Ltd.), Thiokol LP-23 (available from Toray Fine Chemicals Co., Ltd.), Thiokol LP-33 (available from Toray Fine Chemicals Co.,
  • MTTP available from Sakai Chemical Industries, Co., Ltd.
  • QX11 available from Mitsubishi Chemical Corporation
  • QX40 available from Mitsubishi Chemical Corporation
  • Karenz MT-PE1 available from Showa Denko KK
  • Karenz MT-BD1 available from Showa Denko KK
  • Karenz MT-NR1 available from Showa Denko KK
  • Karenz MT-TPMB available from Showa Denko KK
  • the content of the reaction-rate adjusting agent is, for example, 0 parts by mass or more with respect to 100 parts by mass of the epoxy component, and may be 10 parts by mass or more and 60 parts by mass or less. That is, the content of the reaction-rate adjusting agent may be 0 to 60 parts by mass and may be 10 to 60 parts by mass, with respect to 100 parts by mass of the epoxy component.
  • the main agent and the curing agent of the adhesive according to the embodiment described above can be produced by mixing the components described above.
  • the adhesive of the embodiment described above may be sold as a two-component solvent-free adhesive set.
  • the two-component solvent-free adhesive set includes a main agent container including the main agent and a curing agent container including the curing agent, and the main agent contains the epoxy component including the liquid epoxy compound as a main component and the terpene phenol resin, the curing agent contains the liquid amine curing agent, and the content of the terpene phenol resin is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component.
  • the main agent and the curing agent are used so that the amount of the liquid amine curing agent used (content when used as an adhesive) is 20 to 65 parts by mass with respect to 100 parts by mass of an amount of the epoxy component used.
  • the distribution form of the two-component solvent-free adhesive set is not particularly limited.
  • it may be a distribution form in which the amount of the main agent (amount of the main agent contained in the main agent container) and the amount of the curing agent (amount of the curing agent contained in the curing agent container) are the same and it is recommended to use the main agent and the curing agent at the mass ratio or volume ratio of 1 : 1, or a distribution form in which it is recommended to use the main agent and the curing agent at the mass ratio or volume ratio of 1 : 1 but the amount of the main agent (amount of the main agent contained in the main agent container) and the amount of the curing agent (amount of the curing agent contained in the curing agent container) are different.
  • one embodiment of the present invention relates to a main agent for a two-component solvent-free adhesive containing an epoxy component including a liquid epoxy compound as a main component and a terpene phenol resin, in which a content of the terpene phenol resin is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component.
  • the details of the components included in the main agent are the same as those of the main agent in the two-component solvent-free adhesive of the embodiment described above.
  • the main agent of the present embodiment provides a two-component solvent-free adhesive having adhesiveness to polypropylene, for example, by combining with a curing agent containing a liquid amine curing agent.
  • one embodiment of the present invention relates to a mixture (adhesive composition) of the main agent and the curing agent of the two-component solvent-free adhesive of the embodiment described above.
  • the mixture contains at least the epoxy component including the liquid epoxy compound as the main component, the terpene phenol resin, and the liquid amine curing agent, and may contain the optional components described above.
  • the content of the terpene phenol resin in the mixture is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component
  • the content of the liquid amine curing agent is 20 to 65 parts by mass with respect to 100 parts by mass of the epoxy component
  • the content of the solvent is 0 to 1 mass% based on the total mass of the mixture.
  • one embodiment of the present invention relates to a cured product of the two-component solvent-free adhesive of the embodiment described above (a cured product of the mixture of the main agent and the curing agent).
  • the cured product contains at least a reaction product (crosslinked body) of the epoxy component containing the liquid epoxy compound as the main component and the liquid amine curing agent, and the terpene phenol resin, and may contain the optional components described above.
  • the optional components may be present in a state where they have reacted with the epoxy compound and/or the amine curing agent.
  • one embodiment of the present invention relates to a method for producing the cured product of the embodiment described above.
  • the production method includes, for example, obtaining a mixture by mixing a main agent and a curing agent, and applying the obtained mixture to a surface of an adherend.
  • the main agent and the curing agent are mixed so that the blended amount of the liquid amine curing agent is 20 to 65 parts by mass with respect to 100 parts by mass of the epoxy component.
  • the mixture can be cured at room temperature, but the production method of the present embodiment may further carry out a curing step such as heating.
  • another adherend different from the adherend to which the mixture has been applied may be placed (e.g. laminated) onto the mixture.
  • the two adherends can be joined with the cured product of the embodiment described above interposed therebetween.
  • the mixture of the main agent and the curing agent may be poured and cured between the two oppositely-disposed adherends, thereby joining the two adherends.
  • the method of mixing the main agent and the curing agent is not particularly limited and may be a manual method or a method using a stirring device such as a mixer.
  • the method of applying the mixture to an adherend is not particularly limited and may be a variety of methods such as a gravure method, a roll coating method, a die coating method, a bar coating method, a dipping method, a spray coating method, a curtain coating method, a spin coating method, a flexographic coating method, a screen coating method, or a method of coating with a brush.
  • the adherend is, for example, a base material having a surface including polypropylene, the surface being to which at least the adhesive is applied, and preferably a substrate (for example, a polypropylene film) having at least a surface composed of polypropylene, the surface being to which the adhesive is applied.
  • Epoxy component liquid epoxy compound
  • YD128 Bisphenol A-type epoxy compound (polycondensate of 4,4'- isopropylidene diphenol and epichlorohydrin, available from Nippon Steel Chemical & Material Co., Ltd., trade name, dissolubility of terpene phenol resin: impossible, viscosity: 13 Pa s)
  • HBE100 Hydrogenated bisphenol A-type epoxy compound (poly condensate of 4,4'-isopropylidene dicyclohexanol and epichlorohydrin, available from New Japan Chemical Co., Ltd., trade name, dissolubility of terpene phenol resin: possible, viscosity: 2.2 Pa s)
  • YX7400 Modified bisphenol A-type epoxy compound (available from Mitsubishi Chemical Corporation, trade name, dissolubility of terpene phenol resin: impossible, viscosity: 0.2 Pa ⁇ s)
  • N2513HP Monofunctional epoxy compound (epoxidized cashew nut oil, available from Cardolite Corporation, trade name, dissolubility of terpene phenol resin: possible, viscosity: 0.032 Pa s)
  • OFS-6040 Epoxy group-containing silane coupling agent (3-glycidyloxypropyl trimethoxysilane, available from Dow Coming Toray Co., Ltd., dissolubility of terpene phenol resin: impossible, viscosity: 0.032 Pa s)
  • T115 Terpene phenol resin (available from Yasuhara Chemical Co., Ltd., trade name) Liquid amine curing agent
  • Ancamide 910 Polyamidoamine (Evonik Japan Co., Ltd., trade name, amine equivalent: 230, viscosity: 6 Pa s)
  • Priamine 1073 Dimer diamine (available from Croda Japan KK, trade name, amine equivalent: 163, viscosity: 0.21 Pa s)
  • ATBN 1300X16 Amino group-containing toughening agent (amino-terminated acrylonitrile butadiene rubber, available from CVC THERMOSET SPECIALITIES, trade name, viscosity: 210 Pa ⁇ s)
  • TAP Tertiary amine-based reaction-rate adjusting agent (2,4,6- tris(dimethylaminomethyl)phenol, available from Kayaku Akzo Co., Ltd., trade name) Examples 1 to 4 and Comparative Examples 1 to 3 Preparation of adhesive
  • Two-component solvent-free adhesives (main agents and curing agents) of Examples 1 to 4 and Comparative Examples 1 to 3 were obtained by mixing materials shown in Table 1 at blended amounts (parts by mass) shown in Table 1 using a planetary centrifugal mixer. For each of the adhesives of Examples 1 to 4, it was confirmed that when the main agent and the curing agent were mixed, the mixture was cured at room temperature (25°C) to obtain a final cured product.
  • the mixture was applied to a polypropylene substrate (100 mm x 25 mm x 2.0 mm) with a thickness of 0.35 mm, and heated at 65°C for 4 hours to obtain an evaluation sample.
  • the cured state of the cured product and the adhesive strength (PP shear strength) of the cured product to the polypropylene substrate were confirmed using a tensile tester. Specifically, the adhesive strength was measured using a tensile tester at a measurement speed of 500 mm/min.

Abstract

A two-component solvent-free adhesive having adhesiveness to polypropylene is provided. A two-component solvent-free adhesive including a main agent and a curing agent, in which the main agent contains an epoxy component including a liquid epoxy compound as a main component and a terpene phenol resin, the curing agent contains a liquid amine curing agent, a content of the terpene phenol resin is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component, and a content of the liquid amine curing agent is 20 to 65 parts by mass with respect to 100 parts by mass of the epoxy component.

Description

TWO-COMPONENT SOLVENT-FREE ADHESIVE AND MAIN AGENT FOR TWO-COMPONENT SOLVENT-FREE ADHESIVE
Technical Field
The present invention relates to a two-component solvent-free adhesive and a main agent for a two-component solvent-free adhesive.
Background
There is a demand for adhesives that have sufficient adhesiveness to members with low surface energy such as polypropylene. For example, Patent Document 1 discloses an adhesive composition for a polyolefin resin formed by blending a curing agent (II) into a resin solution (I) obtained by graft polymerization of a monomer containing an ethylenically unsaturated double bond in the presence of a polyolefin resin (A), epoxy, or a phenoxy resin (B).
Citation List Patent Literature
[Patent Document 1] JP HI 1-293216 A
Summary Technical Problem
An organic solvent is used in the adhesive of Patent Document 1, but in recent years, the use of volatile organic compounds (VOCs) has become a problem from the perspective of environmental pollution, effects on the human body, and the like. In terms of VOC reduction, it is desirable for the adhesive to have substantially no organic solvent, i.e., to be solvent-free.
In contrast, a two-component solvent-free adhesive is easy to handle, such as when mixing various materials, or when producing a two-component solvent-free adhesive set having a main agent and a curing agent, and has substantially no solvent so that no VOC remains after curing, thereby being useful in applications where improvement of work efficiency is required and applications where heating is limited. On the other hand, in a known two-component solvent-free adhesive, it is difficult to obtain sufficient adhesiveness to a member with low surface energy, and particularly, it is difficult to obtain adhesiveness to polypropylene. One object of the present invention is to provide a two-component solvent-free adhesive having adhesiveness even to polypropylene.
Solution to Problem
One aspect of the present invention relates to a two-component solvent-free adhesive including a main agent and a curing agent, in which the main agent contains an epoxy component containing a liquid epoxy compound as a main component and a terpene phenol resin, the curing agent contains a liquid amine curing agent, a content of the terpene phenol resin is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component, and a content of the liquid amine curing agent is 20 to 65 parts by mass with respect to 100 parts by mass of the epoxy component. The adhesive has adhesiveness to polypropylene.
The epoxy component may include an epoxy oligomer. The epoxy oligomer may be liquid.
The epoxy component may include a monofunctional epoxy compound. The monofunctional epoxy compound may be liquid.
The liquid amine curing agent may include a diamine having viscosity of 100 Pa s or less.
At least one of the main agent and the curing agent may include a toughening agent.
At least one of the main agent and the curing agent may include a reaction rate adjusting agent.
Another aspect of the present invention relates to a main agent for a two- component solvent-free adhesive containing an epoxy component containing a liquid epoxy compound as a main component and a terpene phenol resin, in which a content of the terpene phenol resin is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component. The main agent is, for example, combined with a curing agent containing a liquid amine curing agent to provide a two-component solvent-free adhesive having adhesiveness to polypropylene.
Advantageous Effects of Invention
According to the present invention, it is possible to provide a two-component solvent-free adhesive having adhesiveness to polypropylene. Detailed Description
Hereinafter, one embodiment of the present invention will be described. However, the present invention is not limited to the following embodiment. Note that, in the present specification, numerical ranges indicated using “to” indicate ranges that include numerical values described before and after “to” as a minimum value and a maximum value, respectively. Materials exemplified herein can be used alone or in combinations of two or more, unless otherwise specified.
A two-component solvent-free adhesive of one embodiment (hereinafter, also simply referred to as “adhesive”) includes a main agent (Part B) and a curing agent (Part A). The main agent and the curing agent are present separately, and the adhesive can be cured by mixing the main agent and the curing agent. Here, “solvent-free” means that the total content (total amount) of solvents in the main agent and the curing agent is 0 to 1 mass%. The solvent is a compound normally used as a solvent for adhesives, and examples thereof include acetone, methanol, isopropyl alcohol, ethyl acetate, toluene, hexane, methyl ethyl ketone, and the like.
The main agent contains an epoxy component containing an epoxy compound in a liquid form (liquid epoxy compound) as a main component and a terpene phenol resin, and the curing agent contains an amine curing agent in a liquid form (liquid amine curing agent).
The content of the terpene phenol resin is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component, and the content of the liquid amine curing agent is 20 to 65 parts by mass with respect to 100 parts by mass of the epoxy component.
The adhesive of the present embodiment uses an epoxy component and a liquid amine curing agent, and thus can be cured at room temperature (for example, 5 to 40°C). Specifically, when the main agent and the curing agent are mixed at room temperature, the reaction between the epoxy component in the main agent and the liquid amine curing agent begins, and curing proceeds. This results in a cured product of the adhesive of the present embodiment. The timing of mixing the main agent and the curing agent is not particularly limited and may be, for example, a timing before the adhesive is applied to an adherend such as a substrate (a member to which an adhesive is applied).
As described above, the adhesive of the present embodiment is room-temperature curable and solvent-free, and thus is useful in applications where heating is limited. Furthermore, curing can be promoted by heating, and heating and curing can be performed for shortening the working time to improve work efficiency. Specifically, it can be widely used as an adhesive for, for example, building components such as a sash that uses resin and aluminum in combination, a mobile portable terminal, a screen display member, electronic devices such as an electronic module, and the like.
The adhesive of the present embodiment has adhesiveness to polypropylene while being a two-component solvent-free adhesive. That is, according to the adhesive of the present embodiment, a cured product of the adhesive having adhesiveness even to polypropylene is obtained.
Hereinafter, the epoxy component, terpene phenol resin, and the liquid amine curing agent, which are essential components of the adhesive of the present embodiment, and optional components will be described in detail.
Epoxy component
The epoxy component includes a compound having at least one epoxy group (epoxy compound). The epoxy compound needs to have at least two epoxy groups for sufficient curing by reacting with the liquid amine curing agent (liquid amine compound). As such, the epoxy component usually includes a multifunctional epoxy compound having two or more epoxy groups. However, in the present embodiment, the epoxy component may include a monofunctional epoxy compound having one epoxy group.
The epoxy compound may be a monomer or an oligomer. An “epoxy oligomer” refers to an epoxy compound that is a compound having an epoxy group at one or both terminal(s) of a main chain including repeating units of a specific molecular structure, in which the number of repeating units of the specific molecular structure is 100 or less. When the epoxy compound is an oligomer, flexibility of the epoxy compound after curing tends to improve. Note that a compound commonly referred to as an “epoxy resin” is included in the epoxy compound of the present embodiment.
The epoxy compound may be an aliphatic epoxy compound having an aliphatic skeleton, an alicyclic epoxy compound having an alicyclic skeleton, or an aromatic epoxy compound having an aromatic skeleton. When the epoxy compound is an epoxy oligomer, the epoxy compound may be an aliphatic epoxy oligomer in which the repeating unit has an aliphatic skeleton, an alicyclic epoxy oligomer in which the repeating unit has an alicyclic skeleton, or an aromatic epoxy compound in which the repeating unit has an aromatic skeleton. From the perspective of improving hardness of the cured product, the epoxy component preferably includes an alicyclic epoxy compound or an aromatic epoxy compound, and more preferably includes a bisphenol epoxy compound. The bisphenol epoxy compound is also preferable from the perspective of cost reduction.
As a two-component adhesive, in addition to an epoxy -based adhesive using an epoxy component, an acrylic adhesive and a urethane-based adhesive are known.
However, the acrylic adhesive and the urethane-based adhesive have a faster curing rate compared to the epoxy -based adhesive, so that the adhesive may cure before being wet- spread to an application target, and the operation of applying the adhesive may be complicated in order to avoid such curing. On the other hand, when the epoxy component contains a bisphenol epoxy compound in the adhesive of the present embodiment, the time until curing of the adhesive can be secured relatively long after mixing the two liquids (the main agent and the curing agent). Thus, when the epoxy component includes the bisphenol epoxy compound in the adhesive of the present embodiment, failure such as curing of the adhesive before wet-spreading the adhesive to the application target is unlikely to occur, and the operation of applying the adhesive is facilitated.
A bisphenol-based epoxy compound is a compound having a bisphenol skeleton or a hydrogenated bisphenol skeleton (a skeleton where a hydrogen atom is added to some or all carbon atoms on an aromatic ring of bisphenol) and an epoxy group, and is typically a condensate of bisphenol and epichlorohydrin (bisphenol glycidyl ether). Examples of a bisphenol-based epoxy compound include bisphenol A diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol AP diglycidyl ether, bisphenol AF diglycidyl ether, bisphenol B diglycidyl ether, bisphenol BP diglycidyl ether, bisphenol C diglycidyl ether, bisphenol E diglycidyl ether, bisphenol F diglycidyl ether, bisphenol G diglycidyl ether, bisphenol M diglycidyl ether, bisphenol S diglycidyl ether, bisphenol P diglycidyl ether, bisphenol PH diglycidyl ether, bisphenol TMC diglycidyl ether, bisphenol Z diglycidyl ether, hydrogenated compounds thereof, any mixture of the above compounds, and the like.
The epoxy component contains a liquid epoxy compound as a main component. That is, the content of the liquid epoxy compound in the epoxy component is greater than 50 mass% with respect to the total amount of the epoxy component. From the perspective of allowing the terpene phenol resin to be more uniformly present in the adhesive and further improve the adhesiveness to polypropylene, the content of the liquid epoxy compound is preferably 70 mass% or more, more preferably 90 mass% or more, and still more preferably 95 mass% or more, with respect to the total amount of the epoxy component. The epoxy component may include only the liquid epoxy compound.
The viscosity of the liquid epoxy is 100 Pa s or less. Note that the viscosity is viscosity measured by a B-type viscometer at 25°C and 1 atm.
The liquid epoxy compound may be a multifunctional epoxy compound or a monofunctional epoxy compound. Examples of the liquid epoxy compound include liquid bisphenol-based epoxy compounds (compounds in a liquid form among the bisphenol- based epoxy compounds described above), liquid aliphatic epoxides, and the like. The liquid epoxy compound may be modified with alkyl or the like from the perspective of adjusting the hardness of the cured product.
The liquid epoxy compound is preferably an oligomer. That is, the epoxy component preferably includes a liquid epoxy oligomer. When the epoxy component includes a liquid epoxy oligomer, it tends to be uniformly dispersible and less prone to layer separation.
As the liquid epoxy compound, a liquid epoxy compound capable of dissolving the terpene phenol resin contained in the main agent is preferably used from the perspective of allowing the terpene phenol resin to be more uniformly present in the adhesive and further improve the adhesiveness to polypropylene. From the perspective of easily dissolving the terpene phenol resin, a hydrogenated bisphenol A-type glycidyl ether is preferable. It can be visually confirmed that the terpene phenol resin can be dissolved. In a case where the liquid epoxy compound has the property that the terpene phenol resin can be dissolved therein, when the terpene phenol resin is dissolved in the liquid epoxy compound, no insoluble component is generated, and the transparency of the liquid epoxy compound can be visually confirmed. On the other hand, in a case where the liquid epoxy compound does not have the property that the terpene phenol resin can be dissolved therein, turbidity is generated in the liquid epoxy compound because an insoluble component remains or the terpene phenol resin cannot be sufficiently dissolved.
In the present embodiment, a liquid epoxy compound in which the terpene phenol resin can be dissolved and an epoxy compound in which the terpene phenol resin cannot be dissolved may be used in combination. As the epoxy compound in which the terpene phenol resin cannot be dissolved, bisphenol A-type (or AD-, S-, or F-type) glycidyl ether or the like is preferably used. By using these epoxy compounds in combination, the hardness of the cured product tends to be improved, and adhesiveness to polypropylene tends to be improved.
The epoxy component preferably includes a monofunctional epoxy compound from the perspective of improving the flexibility of the cured product. The monofunctional epoxy compound may be included in the epoxy component as a flexibilizer. From the perspective of further improving the flexibility of the cured product and the perspective of further improving the adhesiveness to polypropylene, the monofunctional epoxy compound is preferably liquid, and it is further preferable that the terpene phenol resin can be dissolved therein.
The structure of the monofunctional epoxy compound is not particularly limited, but from the perspective of further improving the flexibility of the cured product, the monofunctional epoxy compound preferably has an aliphatic group having 8 or more carbon atoms (long chain aliphatic group). The long chain aliphatic group may be linear or branched, and may be either saturated or unsaturated. Examples of the monofunctional epoxy compound having a long chain aliphatic group include glycidyl ethers of long chain fatty alcohols, glycidyl esters of long chain fatty acids, and the like. These monofunctional epoxy compounds tend to have the excellent property that the terpene phenol resin is dissolved.
As the monofunctional epoxy compound, a silane coupling agent having an epoxy group may be used. The use of the silane coupling agent tends to improve adhesiveness to polypropylene. As the silane coupling agent having an epoxy group, a silane coupling agent represented by Formula (1) below is preferably used.
[Chemical Formula 1]
Figure imgf000008_0001
In Formula (1), R2 represents a hydrogen atom or an alkyl group (e.g., a methyl group or an ethyl group), and n is an integer of 1 to 10. The plurality of R2 may be the same as or different from each other.
The molecular weight of the monofunctional epoxy compound may be, for example, 100 or more and 500 or less. That is, the molecular weight of the monofunctional epoxy compound is, for example, 100 to 500. The content of the monofunctional epoxy compound may be 80 mass% or less, 70 mass% or less, or 65 mass% or less with respect to the total amount of the epoxy component from the perspective of improving the flexibility of the cured product. In the present embodiment, the content of the liquid monofunctional epoxy compound is preferably within the range described above.
The epoxy equivalent (g/eq) of the epoxy compound may be 150 or more and 500 or less from the perspective of achieving both flexibility and toughness of the cured product. That is, the epoxy equivalent (g/eq) of the epoxy compound is, for example, 150 to 500. In the present embodiment, the epoxy equivalent of the entire epoxy component is more preferably within the aforementioned range.
Commercially available products may be used as the epoxy compound. Examples of the commercially available products include YD 128 (available from NIPPON STEEL Chemical & Materials Co., Ltd.), HBE100 (available from New Japan Chemical Co.,
Ltd.), YX7400 (available from Mitsubishi Chemical Corporation), EPICOAT 825 (available from JER Corporation), EPICOAT 827 (available from JER Corporation), EPICOAT 828 (available from JER Corporation), GAN (available from Nippon Kayaku Co., Ltd.), GOT (available from Nippon Kayaku Co., Ltd.), RE-3035-L (available from Nippon Kayaku Co., Ltd.), and the like.
Terpene phenol resin
The terpene phenol resin is a polymer obtained by, for example, copolymerization of a terpene monomer with phenol and includes a terpene residue and a phenolic residue. The terpene phenol resin is preferably uniformly present in the main agent (for example, dispersed or dissolved), and is more preferably dissolved in the main agent. The fact that the terpene phenol resin is dissolved in the main agent can be confirmed similarly to the aforementioned method of confirming that the terpene phenol resin can be dissolved in the liquid epoxy compound.
The terpene monomer is not particularly limited, but monoterpenes such as a- pinene, b-pinene, limonene, and the like are preferably used.
The OH value of the terpene phenol resin may be 1 mgKOH/g or more, and may be 5 mgKOH/g or more or 10 mgKOH/g or more. The OH value of the terpene phenol resin may be 200 mgKOH/g or less, and may be 180 mgKOH/g or less or 150 mgKOH/g or less. The softening point of the terpene phenol resin may be 80°C or higher, and may be 90°C or higher or 100°C or higher. The softening point of the terpene phenol resin may be 160°C or lower, and may be 150°C or lower or 140°C or lower.
Commercially available products can be used as the terpene phenol resin.
Examples of the commercially available products include U115 (available from Yasuhara Chemical Co., Ltd.), T115 (available from Yasuhara Chemical Co., Ltd.), and the like.
The content of the terpene phenol resin is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component. From the perspective of improving adhesiveness to polypropylene, the content of the terpene phenol resin may be 7 parts by mass or more or 10 parts by mass or more, with respect to 100 parts by mass of the epoxy component.
From the perspective of facilitating the progress of cuing of the adhesive, the content of the terpene phenol resin may be 40 parts by mass or less or 30 parts by mass or less with respect to 100 parts by mass of the epoxy component.
Liquid amine curing agent
The liquid amine curing agent is an amine compound in a liquid form that reacts with an epoxy compound to form a crosslinked structure. The liquid amine curing agent has, for example, a primary amino group (-NFL) and/or a secondary amino group (-NHR1; R1 is an organic group).
The number of amino groups (primary amino groups and secondary amino groups) in the liquid amine curing agent is not particularly limited. The liquid amine curing agent may be, for example, a monoamine having one amino group, a diamine having two amino groups, or a polyamine having three or more amino groups. The liquid amine curing agent may also be a compound (oligomer or polymer) having a plurality of repeating units of a specific molecular structure. For example, the liquid amine curing agent may be a compound having an amino group at one or both terminal(s) of a main chain including a plurality of repeating units (e.g., a polymer of a compound having an amino group and a compound having a functional group capable of reacting with an amino group), or a compound having a plurality of repeating units of a molecular structure having an amino group (e.g., a polymer of a compound having an amino group). When the liquid amine curing agent is an oligomer or a polymer, the molecular weight of the molecular structure constituting the repeating unit is preferably 50 or more and 2000 or less. The liquid amine curing agent may be an aliphatic amine having an aliphatic skeleton, an alicyclic amine having an alicyclic skeleton, or an aromatic amine having an aromatic skeleton. When the liquid amine curing agent is an oligomer or a polymer, the liquid amine curing agent may be an aliphatic amine in which the repeating unit has an aliphatic skeleton, an alicyclic amine in which the repeating unit has an alicyclic skeleton, or an aromatic amine in which the repeating unit has an aromatic skeleton. When the liquid amine curing agent is an aliphatic amine, the aliphatic structure may be linear or branched, or may be either saturated or unsaturated.
The liquid amine curing agent may be a dimer diamine (diamine dimer) in which two terminal carboxyl groups in a dimer of an aliphatic unsaturated carboxylic acid are substituted by a primary amino group or a secondary amino group. The aliphatic unsaturated carboxylic acid is, for example, an unsaturated carboxylic acid having an aliphatic group having 12 to 24 carbon atoms, and specific examples thereof include oleic acid, linoleic acid, and the like. The dimer diamine is preferably a diamine derived from a dimer acid having 28 to 44 carbon atoms (having a dimer acid skeleton of 28 to 44 carbon atoms).
The viscosity of the liquid amine curing agent is 100 Pa s or less. Because the viscosity of the liquid amine curing agent is 100 Pa s or less, handleability and dispersibility are excellent. Note that the viscosity is viscosity measured by a B type viscometer at 25°C and 1 atm.
The amine equivalent (g/eq) of the liquid amine curing agent may be 100 or more and 600 or less from the perspective of achieving both flexibility and toughness of the cured product. That is, the amine equivalent (g/eq) of the amine curing agent is, for example, 100 to 600.
Commercially available products may be used as the liquid amine curing agent. Examples of the commercially available products include Sunmide 506 (available from Evonik Japan Co., Ltd.), Sunmide 70 (available from Evonik Japan Co., Ltd.), Sunmide 75 (available from Evonik Japan Co., Ltd.), Sunmide 76T (available from Evonik Japan Co., Ltd.), Sunmide 76TK (available from Evonik Japan Co., Ltd.), Ancamide 2137 (available from Evonik Japan Co., Ltd.), Ancamide 2396A (available from Evonik Japan Co., Ltd.), Ancamide 501 (available from Evonik Japan Co., Ltd.), Ancamide 502 (available from Evonik Japan Co., Ltd.), Ancamide 506 (available from Evonik Japan Co., Ltd.), Ancamide 2050 (available from Evonik Japan Co., Ltd.), Ancamide 221 (available from Evonik Japan Co., Ltd.), Ancamide 2353 (available from Evonik Japan Co., Ltd.), Ancamide 2589 (available from Evonik Japan Co., Ltd.), Ancamide 260A (available from Evonik Japan Co., Ltd.), Ancamide 350A (available from Evonik Japan Co., Ltd.), Ancamide 351 A (available from Evonik Japan Co., Ltd.), Ancamide 375A (available from Evonik Japan Co., Ltd.), Ancamide 910 (available from Evonik Japan Co., Ltd.), and the like. As the commercially available products of the dimer diamine, for example, Priamine 1071 (available from Croda Japan KK), Priamine 1073 (available from Croda Japan KK), Priamine 1074 (available from Croda Japan KK), Priamine 1075 (available from Croda Japan KK), Versamid 115 (available from BASF Japan Ltd.), Versamid 125 (available from BASF Japan Ltd.), Versamid 140 (available from BASF Japan Ltd.), Versamid 150 (available from BASF Japan), and the like can also be used.
The content of the liquid amine curing agent is 20 to 65 parts by mass with respect to 100 parts by mass of the epoxy component. From the perspective of the curing speed, the content of the liquid amine curing agent may be 25 parts by mass or more with respect to 100 parts by mass of the epoxy component. From the perspective of the hardness of the final cured product, the content of the liquid amine curing agent may be 60 parts by mass or less with respect to 100 parts by mass of the epoxy component.
The curing agent may include an amine curing agent other than the liquid amine curing agent. The content of the liquid amine curing agent in the amine curing agent is not particularly limited, and the content may be, for example, more than 50 mass%, 70 mass% or more, 90 mass% or more, or 95 mass% or more, with respect to the total amount of the amine curing agent, and the amine curing agent may include only the liquid amine curing agent.
Optional component
At least one of the main agent and the curing agent in the adhesive may contain, as optional components, a toughening agent, a reaction rate adjusting agent, and the like. Among these, at least one of the main agent and the curing agent preferably contains at least one optional component selected from the group consisting of a toughening agent and a reaction rate adjusting agent.
Toughening agent The toughening agent is a material that can impart flexibility and toughness to an epoxy cured product that is hard and brittle. As the toughening agent, for example, a compound having rubber elasticity such as a copolymer rubber or a compound in which these materials are formed into a core-shell structure is preferably used.
The toughening agent may be contained in either the main agent or the curing agent.
Examples of the toughening agent that can be blended into the main agent include conjugated diene-based copolymer rubbers such as polyisoprene synthetic rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (HR), and a copolymer (MBS) composed of three components of methylmethacrylate, butadiene, and styrene; acrylic rubbers such as polybutyl acrylate; copolymer rubbers including elastomers such as urethane rubber and silicone rubber; and compounds in which these are formed in a core shell structure. These toughening agents may have a reactive group (e.g., a functional group capable of reacting with an amino group (such as an epoxy group)) as long as separation or thickening of the main agent is unlikely to occur and can be stably blended.
Examples of the toughening agent that can be blended into the curing agent include conjugated diene-based copolymer rubbers such as polyisoprene synthetic rubber (IR), polybutadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (HR), and a copolymer (MBS) composed of three components of methylmethacrylate, butadiene, and styrene; acrylic rubbers such as polybutyl acrylate; elastomers such as urethane rubber and silicone rubber; and compounds in which these are formed in a core-shell structure. These toughening agents may have a reactive group (e.g., a functional group (such as an amine group) capable of reacting with an epoxy group) as long as separation or thickening of the curing agent is unlikely to occur and can be stably blended.
The toughening agent may have fluidity (viscosity of greater than 100 Pa s) from the perspective of handleability when mixing various materials or when producing a two- component solvent-free adhesive set of the main agent and the curing agent. Such toughening agents can be incorporated into the cured product during curing to impart flexibility. Therefore, it is desirable to have a functional group that reacts with the epoxy compound or the amine curing agent to cure. Examples thereof include an elastomer such as carboxyl-terminated butadiene acrylonitrile rubber (CTBN), an epoxy-terminated butadiene acrylonitrile rubber (ETBN), an amine-terminated butadiene acrylonitrile rubber (ATBN), and a mixture thereof.
Commercially available products may be used as the toughening agent having fluidity (viscosity of greater than 100 Pa s). Examples of the commercially available products include Hypro 1300x8 CTBN (available from CVC Thermoset Specialties), Hypro 1300x9 CTBN (available from CVC Thermoset Specialties), Hypro 1300x13 CTBN (available from CVC Thermoset Specialties), Hypro 1300x63 ETBN (available from CVC Thermoset Specialties), Hypro 1300x68 ETBN (available from CVC Thermoset Specialties), Hypro 1300x16 ATBN (available from CVC Thermoset Specialties), Hypro 1300x21 ATBN (available from CVC Thermoset Specialties), and the like.
From the perspective of expressing the flexibility and toughness of the final cured product, the molecular weight of the toughening agent is preferably greater than 2000.
When the total amount of all the adhesive components is 100 mass%, the content of the toughening agent may be, for example, 0 mass% or more, and may be 20 mass% or more, and may be 35 mass% or less. In other words, the content of the toughening agent may be 0 to 35 mass%, and may be 20 to 35 mass%, when the total amount of all the adhesive components is 100 mass%.
Reaction rate adjusting agent
The reaction-rate adjusting agent is a compound having a function of adjusting a rate of a curing reaction, and is, for example, a compound having a function of promoting the curing reaction (curing accelerator). Examples of the reaction-rate adjusting agent include tertiary amine-based reaction rate adjusting agents having one or more tertiary amino groups, thiol-based reaction rate adjusting agents having one or more thiol groups, and the like.
Examples of the tertiary amine-based reaction-rate adjusting agent include 2,4,6- tris(dimethylaminomethyl)phenol, and the like.
Commercially available products may be used as the tertiary amine-based reaction rate adjusting agent. Examples of the commercially available products include TAP (available from Kayaku Akzo Co., Ltd.), and the like. Examples of the thiol-based reaction rate adjusting agent include polyfunctional thiol compounds having an aliphatic ether structure, polyfunctional thiol compounds having an aliphatic ester structure, and the like.
Commercially available products may be used as the thiol-based reaction rate adjusting agent. Examples of the commercially available products include Thiokol LP-3 (available from Toray Fine Chemicals Co., Ltd.), Thiokol LP-23 (available from Toray Fine Chemicals Co., Ltd.), Thiokol LP-33 (available from Toray Fine Chemicals Co.,
Ltd.), MTTP (available from Sakai Chemical Industries, Co., Ltd.), QX11 (available from Mitsubishi Chemical Corporation), QX40 (available from Mitsubishi Chemical Corporation), Karenz MT-PE1 (available from Showa Denko KK), Karenz MT-BD1 (available from Showa Denko KK), Karenz MT-NR1 (available from Showa Denko KK), Karenz MT-TPMB (available from Showa Denko KK), and the like.
The content of the reaction-rate adjusting agent is, for example, 0 parts by mass or more with respect to 100 parts by mass of the epoxy component, and may be 10 parts by mass or more and 60 parts by mass or less. That is, the content of the reaction-rate adjusting agent may be 0 to 60 parts by mass and may be 10 to 60 parts by mass, with respect to 100 parts by mass of the epoxy component.
The main agent and the curing agent of the adhesive according to the embodiment described above can be produced by mixing the components described above.
The adhesive of the embodiment described above may be sold as a two-component solvent-free adhesive set. The two-component solvent-free adhesive set includes a main agent container including the main agent and a curing agent container including the curing agent, and the main agent contains the epoxy component including the liquid epoxy compound as a main component and the terpene phenol resin, the curing agent contains the liquid amine curing agent, and the content of the terpene phenol resin is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component. In this two-component solvent-free adhesive set, the main agent and the curing agent are used so that the amount of the liquid amine curing agent used (content when used as an adhesive) is 20 to 65 parts by mass with respect to 100 parts by mass of an amount of the epoxy component used.
The distribution form of the two-component solvent-free adhesive set is not particularly limited. For example, it may be a distribution form in which the amount of the main agent (amount of the main agent contained in the main agent container) and the amount of the curing agent (amount of the curing agent contained in the curing agent container) are the same and it is recommended to use the main agent and the curing agent at the mass ratio or volume ratio of 1 : 1, or a distribution form in which it is recommended to use the main agent and the curing agent at the mass ratio or volume ratio of 1 : 1 but the amount of the main agent (amount of the main agent contained in the main agent container) and the amount of the curing agent (amount of the curing agent contained in the curing agent container) are different. Alternatively, it may be a distribution form in which the amount of the main agent (amount of the main agent contained in the main agent container) and the amount of the curing agent (amount of the curing agent contained in the curing agent container) are the same but the recommended ratio of used amounts of the main agent and the curing agent is a mass ratio or a volume ratio other than 1:1.
The two-component solvent-free adhesive and the two-component solvent-free adhesive set of one embodiment have been described above, but the present invention is not limited to the embodiment described above.
For example, one embodiment of the present invention relates to a main agent for a two-component solvent-free adhesive containing an epoxy component including a liquid epoxy compound as a main component and a terpene phenol resin, in which a content of the terpene phenol resin is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component. The details of the components included in the main agent are the same as those of the main agent in the two-component solvent-free adhesive of the embodiment described above. The main agent of the present embodiment provides a two-component solvent-free adhesive having adhesiveness to polypropylene, for example, by combining with a curing agent containing a liquid amine curing agent.
In addition, one embodiment of the present invention relates to a mixture (adhesive composition) of the main agent and the curing agent of the two-component solvent-free adhesive of the embodiment described above. The mixture contains at least the epoxy component including the liquid epoxy compound as the main component, the terpene phenol resin, and the liquid amine curing agent, and may contain the optional components described above. The content of the terpene phenol resin in the mixture is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component, the content of the liquid amine curing agent is 20 to 65 parts by mass with respect to 100 parts by mass of the epoxy component, and the content of the solvent is 0 to 1 mass% based on the total mass of the mixture.
Furthermore, one embodiment of the present invention relates to a cured product of the two-component solvent-free adhesive of the embodiment described above (a cured product of the mixture of the main agent and the curing agent). The cured product contains at least a reaction product (crosslinked body) of the epoxy component containing the liquid epoxy compound as the main component and the liquid amine curing agent, and the terpene phenol resin, and may contain the optional components described above. The optional components may be present in a state where they have reacted with the epoxy compound and/or the amine curing agent.
Furthermore, one embodiment of the present invention relates to a method for producing the cured product of the embodiment described above. The production method includes, for example, obtaining a mixture by mixing a main agent and a curing agent, and applying the obtained mixture to a surface of an adherend. In the production method, the main agent and the curing agent are mixed so that the blended amount of the liquid amine curing agent is 20 to 65 parts by mass with respect to 100 parts by mass of the epoxy component. The mixture can be cured at room temperature, but the production method of the present embodiment may further carry out a curing step such as heating. In addition, before the curing of the mixture is completed, another adherend different from the adherend to which the mixture has been applied may be placed (e.g. laminated) onto the mixture. As a result, the two adherends can be joined with the cured product of the embodiment described above interposed therebetween. The mixture of the main agent and the curing agent may be poured and cured between the two oppositely-disposed adherends, thereby joining the two adherends.
The method of mixing the main agent and the curing agent is not particularly limited and may be a manual method or a method using a stirring device such as a mixer.
The method of applying the mixture to an adherend is not particularly limited and may be a variety of methods such as a gravure method, a roll coating method, a die coating method, a bar coating method, a dipping method, a spray coating method, a curtain coating method, a spin coating method, a flexographic coating method, a screen coating method, or a method of coating with a brush. The adherend is, for example, a base material having a surface including polypropylene, the surface being to which at least the adhesive is applied, and preferably a substrate (for example, a polypropylene film) having at least a surface composed of polypropylene, the surface being to which the adhesive is applied.
Examples
Hereinafter, the contents of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not intended to be limited to the Examples described below.
The following materials were prepared.
Epoxy component (liquid epoxy compound)
YD128: Bisphenol A-type epoxy compound (polycondensate of 4,4'- isopropylidene diphenol and epichlorohydrin, available from Nippon Steel Chemical & Material Co., Ltd., trade name, dissolubility of terpene phenol resin: impossible, viscosity: 13 Pa s)
HBE100: Hydrogenated bisphenol A-type epoxy compound (poly condensate of 4,4'-isopropylidene dicyclohexanol and epichlorohydrin, available from New Japan Chemical Co., Ltd., trade name, dissolubility of terpene phenol resin: possible, viscosity: 2.2 Pa s)
YX7400: Modified bisphenol A-type epoxy compound (available from Mitsubishi Chemical Corporation, trade name, dissolubility of terpene phenol resin: impossible, viscosity: 0.2 Pa· s)
N2513HP: Monofunctional epoxy compound (epoxidized cashew nut oil, available from Cardolite Corporation, trade name, dissolubility of terpene phenol resin: possible, viscosity: 0.032 Pa s)
OFS-6040: Epoxy group-containing silane coupling agent (3-glycidyloxypropyl trimethoxysilane, available from Dow Coming Toray Co., Ltd., dissolubility of terpene phenol resin: impossible, viscosity: 0.032 Pa s)
Terpene phenol resin
U115: Terpene phenol resin (available from Yasuhara Chemical Co., Ltd., trade name)
T115: Terpene phenol resin (available from Yasuhara Chemical Co., Ltd., trade name) Liquid amine curing agent
Ancamide 910: Polyamidoamine (Evonik Japan Co., Ltd., trade name, amine equivalent: 230, viscosity: 6 Pa s)
Priamine 1073: Dimer diamine (available from Croda Japan KK, trade name, amine equivalent: 163, viscosity: 0.21 Pa s)
Toughening agent
ATBN 1300X16: Amino group-containing toughening agent (amino-terminated acrylonitrile butadiene rubber, available from CVC THERMOSET SPECIALITIES, trade name, viscosity: 210 Pa· s)
Reaction-rate adjusting agent
QX1 1 : Thiol-based reaction-rate adjusting agent (polyether polythiol, available from Mitsubishi Chemical Corporation, trade name)
TAP: Tertiary amine-based reaction-rate adjusting agent (2,4,6- tris(dimethylaminomethyl)phenol, available from Kayaku Akzo Co., Ltd., trade name) Examples 1 to 4 and Comparative Examples 1 to 3 Preparation of adhesive
Two-component solvent-free adhesives (main agents and curing agents) of Examples 1 to 4 and Comparative Examples 1 to 3 were obtained by mixing materials shown in Table 1 at blended amounts (parts by mass) shown in Table 1 using a planetary centrifugal mixer. For each of the adhesives of Examples 1 to 4, it was confirmed that when the main agent and the curing agent were mixed, the mixture was cured at room temperature (25°C) to obtain a final cured product.
Evaluation
[0001] After mixing the main agent and the curing agent of the obtained adhesive, the mixture was applied to a polypropylene substrate (100 mm x 25 mm x 2.0 mm) with a thickness of 0.35 mm, and heated at 65°C for 4 hours to obtain an evaluation sample. In the obtained evaluation sample, the cured state of the cured product and the adhesive strength (PP shear strength) of the cured product to the polypropylene substrate were confirmed using a tensile tester. Specifically, the adhesive strength was measured using a tensile tester at a measurement speed of 500 mm/min. When the obtained adhesive strength was less than 0.05 MPa and the failure mode was cohesive failure, it was determined that curing of the adhesive was insufficient (evaluation B), and in the other cases, it was determined that curing of the adhesive was sufficient (evaluation A). In addition, when the strength as a cured product was 0.3 MPa or greater, it was determined to be acceptable.
Figure imgf000021_0001

Claims

What is claimed is:
1. A two-component solvent-free adhesive, comprising: a main agent; and a curing agent, wherein the main agent contains an epoxy component including a liquid epoxy compound as a main component and a terpene phenol resin, the curing agent contains a liquid amine curing agent, a content of the terpene phenol resin is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component, and a content of the liquid amine curing agent is 20 to 65 parts by mass with respect to 100 parts by mass of the epoxy component.
2. The two-component solvent-free adhesive according to claim 1, wherein the epoxy component comprises an epoxy oligomer.
3. The two-component solvent-free adhesive according to claim 2, wherein the epoxy oligomer is liquid.
4. The two-component solvent-free adhesive according to any one of claims 1 to 3, wherein the epoxy component comprises a monofunctional epoxy compound.
5. The two-component solvent-free adhesive according to claim 4, wherein the monofunctional epoxy compound is liquid.
6. The two-component solvent-free adhesive according to any one of claims 1 to 5, wherein the liquid amine curing agent comprises a diamine having viscosity of 100 Pa s or less.
7. The two-component solvent-free adhesive according to any one of claims 1 to 6, wherein at least one of the main agent and the curing agent comprises a toughening agent.
8. The two-component solvent-free adhesive according to any one of claims 1 to 7, wherein at least one of the main agent and the curing agent comprises a reaction rate adjusting agent.
9. A main agent for a two-component solvent-free adhesive, the main agent comprising: an epoxy component containing a liquid epoxy compound as a main component; and a terpene phenol resin, wherein a content of the terpene phenol resin is 5 to 50 parts by mass with respect to 100 parts by mass of the epoxy component.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4133789A (en) * 1977-11-03 1979-01-09 Gulf Oil Corporation Adhesive composition for bonding a low-energy plastic surface to metal
US5753727A (en) * 1995-03-20 1998-05-19 Konishi Co., Ltd. Chloroprene rubber adhesive with chlorinated polyolefin and epoxy resin
JPH11293216A (en) 1998-04-06 1999-10-26 Toyo Ink Mfg Co Ltd Adhesive composition
US6280557B1 (en) * 1996-02-26 2001-08-28 3M Innovative Properties Company Pressure sensitive adhesives for use on low energy surfaces
CN102367354A (en) * 2011-08-26 2012-03-07 江苏达胜热缩材料有限公司 Solvent-free epoxy primer for corrosion protection of 3 polypropylene (PP) at craters of steel pipelines

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4133789A (en) * 1977-11-03 1979-01-09 Gulf Oil Corporation Adhesive composition for bonding a low-energy plastic surface to metal
US5753727A (en) * 1995-03-20 1998-05-19 Konishi Co., Ltd. Chloroprene rubber adhesive with chlorinated polyolefin and epoxy resin
US6280557B1 (en) * 1996-02-26 2001-08-28 3M Innovative Properties Company Pressure sensitive adhesives for use on low energy surfaces
JPH11293216A (en) 1998-04-06 1999-10-26 Toyo Ink Mfg Co Ltd Adhesive composition
CN102367354A (en) * 2011-08-26 2012-03-07 江苏达胜热缩材料有限公司 Solvent-free epoxy primer for corrosion protection of 3 polypropylene (PP) at craters of steel pipelines

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