WO2020225919A1 - Adhesive set, and structure manufacturing method - Google Patents

Adhesive set, and structure manufacturing method Download PDF

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Publication number
WO2020225919A1
WO2020225919A1 PCT/JP2019/018620 JP2019018620W WO2020225919A1 WO 2020225919 A1 WO2020225919 A1 WO 2020225919A1 JP 2019018620 W JP2019018620 W JP 2019018620W WO 2020225919 A1 WO2020225919 A1 WO 2020225919A1
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WIPO (PCT)
Prior art keywords
component
adhesive
group
base material
agent
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PCT/JP2019/018620
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French (fr)
Japanese (ja)
Inventor
周哉 山崎
和彦 森
菜々子 有馬
峻 佐藤
Original Assignee
昭和電工マテリアルズ株式会社
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Application filed by 昭和電工マテリアルズ株式会社 filed Critical 昭和電工マテリアルズ株式会社
Priority to JP2021518290A priority Critical patent/JP7380683B2/en
Priority to PCT/JP2019/018620 priority patent/WO2020225919A1/en
Publication of WO2020225919A1 publication Critical patent/WO2020225919A1/en

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Classifications

    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

Definitions

  • the present invention relates to an adhesive set and a method for manufacturing a structure.
  • Steel plates are generally used for interior and exterior parts of automobile bodies, front doors, rear doors, back doors, front bumpers, rear bumpers, rocker moldings, etc., but weight reduction is required to meet recent demands for improved fuel efficiency. Has been done. For this reason, plastic materials such as polypropylene are increasingly used as interior / exterior parts of automobiles instead of steel plates. Since plastic materials such as polypropylene have lower strength than steel sheets, it is common to add talc, glass filler, or the like to improve the strength.
  • Urethane-based compositions have been proposed as an adhesive between plastic automobile parts such as polypropylene.
  • a one-component composition called a moisture-curing type, which is cured by moisture in the air
  • an adhesive set composed of a main agent and a curing agent are used to prepare a main agent and a curing agent.
  • two-component compositions that mix. Among these, from the viewpoint of workability in the bonding process, sufficient pot life (time until the paint starts to cure due to a chemical reaction in a pot life or a multi-component paint) can be sufficiently secured, and quick curing becomes possible. Two-component compositions tend to be preferred.
  • polypropylene base material has a small surface polarity and is difficult to adhere. Therefore, in order to facilitate adhesion, a surface treatment for introducing a polar group into the surface of the base material is performed. Examples of the surface treatment include frame treatment and the like. Furthermore, since it is difficult to directly apply the urethane-based composition to the adhesion between the surface-treated polypropylene base materials, the urethane-based composition is applied after the primer treatment is performed on each polypropylene base material as a pretreatment. It is common to do. However, in recent years, from the viewpoint of simplifying the process, improving the working environment, etc., improvement of adhesiveness (that is, non-primer adhesiveness) when primer treatment is not performed has been required.
  • Patent Document 1 discloses a two-component curable composition in which a main agent containing an isocyanate compound (first liquid) and a curing agent containing ketimine (second liquid) are mixed during work. ..
  • the two-component curable composition used is an excellent non-primer even for a base material that has been frame-treated under a wide range of treatment conditions (that is, a base material having a different surface tension (wetting property)). It is required to have adhesiveness.
  • the conventional two-component curable composition does not have sufficient non-primer adhesiveness to a substrate that has been frame-treated under a wide range of treatment conditions, and there is room for further improvement.
  • the main invention of the present invention is to provide an adhesive set capable of preparing an adhesive having excellent non-primer adhesiveness even on a substrate that has been frame-treated under a wide range of treatment conditions. The purpose.
  • the adhesive set can be applied to a substrate which has been frame-treated under a wide range of treatment conditions by using a specific component in the curing agent. They have found that it is possible to prepare an adhesive having excellent non-primer adhesiveness, and have completed the present invention.
  • One aspect of the present invention is an adhesive set composed of a main agent and a curing agent, wherein the main agent contains a urethane prepolymer having an isocyanate group as an end group, and the curing agent is a polyol containing an acrylic polyol.
  • the adhesive set to be contained.
  • the present invention attaches a first substrate and a second substrate to a structure via a mixture obtained by mixing a main agent and a curing agent in the above-mentioned adhesive set.
  • a method for manufacturing a structure which comprises a step of obtaining.
  • At least one of the first base material and the second base material may be a polypropylene base material.
  • an adhesive set capable of preparing an adhesive having excellent non-primer adhesiveness even on a substrate that has been frame-treated under a wide range of processing conditions. Further, according to the present invention, there is provided a method for manufacturing a structure using an adhesive set.
  • the numerical range indicated by using “-" indicates the range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value of the numerical range of one step may be replaced with the upper limit value or the lower limit value of the numerical range of another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • the adhesive set according to one embodiment is composed of a main agent and a curing agent.
  • a mixture two-component curing urethane-based composition
  • the mixture cures over time and can act as an adhesive that adheres the substrates.
  • the main agent contains (a) urethane prepolymer having an isocyanate group as a terminal group.
  • the main agent (A) may further contain the interfacial adhesive component (b).
  • the curing agent contains (c) polyol containing an acrylic polyol.
  • At least one of (A) main agent and (B) curing agent may contain any one of (d) curing catalyst, (e) carbon black, (f) filler, and (g) plasticizer.
  • the component (a) is a reaction product of a compound having two or more active hydrogen groups and a polyisocyanate compound having two or more isocyanate groups.
  • a component having an isocyanate group as a terminal group can be obtained by reacting so that the number of isocyanate groups becomes excessive.
  • the active hydrogen group include a hydroxy group (OH group), a carboxyl group (COOH group), an amino group (NH 2 group), a mercapto group (SH group) and the like.
  • the compound having two or more active hydrogen groups may be a polyol which is a compound having two or more hydroxy groups (OH groups), or may be a (a-1) polyether polyol.
  • polyisocyanate compound examples include aromatic polyisocyanates in which an isocyanate group is bonded to an aromatic hydrocarbon, and alicyclic polyisocyanates in which an isocyanate group is bonded to an alicyclic hydrocarbon.
  • the polyisocyanate compound may be (a-2) aromatic polyisocyanate or diphenylmethane diisocyanate.
  • the compound having two or more active hydrogen groups and the polyisocyanate compound having two or more isocyanate groups one kind may be used alone or two or more kinds may be used in combination.
  • the component (a-1) is not particularly limited as long as it is a polyether polyol having two or more OH groups. Specific examples thereof include polyethylene glycol (PEG), polypropylene glycol (PPG), ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), and sorbitol-based polyol. Among these, the component (a-1) may be polypropylene glycol (PPG). Further, as the component (a-1), one type may be used alone, or two or more types may be used in combination.
  • the number average molecular weight of the component (a-1) may be 10,000 or less, and may be 9000 or less, 8000 or less, 7000 or less, or 6000 or less. When the number average molecular weight of the component (a-1) is 10,000 or less, the number of cross-linking points tends to increase and the mechanical properties at the time of curing tend to improve.
  • the number average molecular weight of the component (a-1) is not particularly limited, but may be, for example, 500 or more.
  • the "number average molecular weight" is calculated by using gel permeation chromatography (GPC) and using a standard polystyrene calibration curve.
  • GPC gel permeation chromatography
  • the GPC measurement conditions are as follows. Measuring instrument: ACQUITY UPLC APC system (manufactured by Waters) Columns: APC XT-900, APC XT-200, APC XT-125, APC XT-45 (manufactured by Waters) Carrier: tetrahydrofuran (THF) Detector: Differential refractometer Sample: 0.5 mass% THF solution Calibration curve: Polystyrene
  • ((A-2) Aromatic polyisocyanate
  • Examples of the component (a-2) include 4,4'-diphenylmethane diisocyanate (4,4'-MDI (monomeric MDI)), 2,4'-diphenylmethane diisocyanate) (2,4'-MDI) and the like. Can be mentioned.
  • the content of the component (a) may be 20 to 55% by mass, 25 to 50% by mass, or 30 to 45% by mass based on the total amount of the main agent (A).
  • the content of the component (a) is 20% by mass or more based on the total amount of the main agent (A)
  • the amount is 55% by mass or less based on the total amount of (A) main agent, deterioration of the adhesive properties after curing tends to be prevented.
  • (b-1) a multimer of hexamethylene diisocyanate having an unmodified isocyanurate group (hereinafter, may be referred to as “unmodified hexamethylene diisocyanate multimer”), (b-. 2) A silane coupling agent having a mercapto group or an amino group, a multimer of hexamethylene diisocyanate having an isocyanate group modified with the components (b-3) and (b-2) and at least two unmodified isocyanate groups ( Hereinafter, it may be referred to as “modified hexamethylene diisocyanate multimer”) and the like.
  • the component (b-1) is not particularly limited as long as it is a multimer of hexamethylene diisocyanate having an unmodified isocyanate group, but for example, isocyanurate, biuret, trimethylolpropane (TMP) adduct, and the like. It may be a trimer. Examples of such trimeric commercial products include Sumijour N3300 (trade name, manufactured by Sumika Bayer Urethane Co., Ltd.), Duranate 24A-100 (trade name, manufactured by Asahi Kasei Corporation), and Duranate E402-100 (product name). Name, manufactured by Asahi Kasei Corporation), etc. As the component (b-1), one type may be used alone, or two or more types may be used in combination.
  • the silane coupling agent having a mercapto group is a silane compound having a mercapto group (SH group) which is an active hydrogen group capable of reacting with an isocyanurate group and a hydrolyzable group.
  • Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.
  • the silane coupling agent having a mercapto group one type may be used alone, or two or more types may be used in combination. Further, it may be used in combination with a silane coupling agent having an amino group described later.
  • Silane coupling agents having an amino group, an amino group (NH 2 group or NHR group (R: hydrocarbon group)) is an active hydrogen group capable of reacting with isocyanurate groups is a silane compound having a and hydrolyzable groups .
  • the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2.
  • silane coupling agent having an amino group one type may be used alone, or two or more types may be used in combination. Further, it may be used in combination with the above-mentioned silane coupling agent having a mercapto group.
  • the component (b-3) is a reaction product of the component (b-1) and the component (b-2).
  • the reaction product includes an isocyanate group modified with the component (b-1), the component (b-2), and one component in addition to the component (b-3). It may contain a multimer of hexamethylene diisocyanate having an unmodified isocyanate group.
  • an unmodified hexamethylene diisocyanate trimer is used as the component (b-1)
  • the component (b-3) contains an isocyanate group modified with the component (b-2) and two unmodified isocyanate groups.
  • the isocyanate group modified with the component (b-2) in the component (b-3) contributes to the improvement of the interfacial adhesive force with the polypropylene base material, and at least two unmodified isocyanate groups are contained in the curing agent.
  • (C) Can contribute to the formation of crosslinks with polyols.
  • the component (b-3) is the equivalent ratio of the component (b-1) and the component (b-2) to the SH group or NH group of the component (b-2) and the NCO group of the component (b-1). It can be obtained by adjusting the NCO group / SH group or NH group). For example, when an unmodified hexamethylene diisocyanate trimeric is used as the component (b-1), it usually has three NCO groups, and therefore (NCO group / SH group or NH group) is 2.5 to 3. By adjusting to the range of 5, a component (b-3) having an isocyanate group modified with the component (b-2) and two unmodified isocyanate groups can be obtained.
  • the reaction between the component (b-1) and the component (b-2) may be carried out in the presence of a catalyst.
  • the catalyst may be, for example, the same as the curing catalyst (d) described later.
  • the content of the catalyst can be appropriately set according to the types of the component (b-1) and the component (b-2).
  • the temperature and time for reacting the component (b-1) and the component (b-2) may be, for example, 35 to 50 ° C. and 2 to 5 hours.
  • the content of the component (b) may be 2 to 10% by mass, 2 to 7% by mass, or 3 to 6% by mass based on the total amount of the (A) main agent.
  • the content of the component (b) is 2% by mass or more based on the total amount of the main agent (A)
  • the primerless adhesiveness is improved and the adhesive durability between the substrate surface and the adhesive is prevented from being lowered.
  • the content of the component (b) is 10% by mass or less based on the total amount of the main agent (A) it tends to be possible to prevent deterioration of the adhesive property at the time of curing.
  • the component (c) contains (c-1) acrylic polyol.
  • the component (c) may contain a polyol (c-2) component other than the component (c-1).
  • the component (c-1) is an acrylic polymer of acrylic acid, methacrylic acid, and an ester thereof, and means an acrylic polymer having two or more OH groups (hydroxyl group-containing acrylic polymer). Since the component (c) contains the component (c-1), it is possible to prepare an adhesive having excellent non-primer adhesiveness even on a substrate that has been frame-treated under a wide range of treatment conditions. Become. The reason for this is not always clear, but for example, polyether polyols such as polyethylene glycol (PEG), polypropylene glycol (PPG), ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), and sorbitol-based polyols.
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • PTMEG polytetramethylene ether glycol
  • sorbitol-based polyols sorbitol-based polyols.
  • Polyester polyol having an ester bond main skeleton obtained by dehydration condensation of a carboxylic acid and a polyhydric alcohol, and the like all have a polar bond in the main chain.
  • the acrylic polyol does not have a polar bond in the main chain and is expected to have a lower polarity than the above-mentioned polyol.
  • the present inventors consider that the presence of such a low-polarity acrylic polyol having different properties from the above-mentioned polyol in the curing agent (B) improves the non-primer adhesiveness to the substrate having different treatment conditions. There is.
  • Examples of the copolymer component having an OH group constituting an acrylic polymer having two or more OH groups include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 3-acrylate. Examples thereof include chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, and allyl alcohol.
  • Examples of copolymerization components other than acrylic acid, methacrylic acid, and esters thereof include styrene, ⁇ -methylstyrene, vinyltoluene, acrylamide, methacrylamide and derivatives thereof, vinyl acetate, maleic anhydride, and the like.
  • the component (c-1) Commercially available products of the component (c-1) include, for example, UH-2000 (trade name, manufactured by Toa Synthetic Co., Ltd.), UT-1001 (trade name, manufactured by Soken Chemical Co., Ltd.), UH-2190 (product name, manufactured by Toa). Examples include (manufactured by Synthetic Co., Ltd.) and UH-2041 (product name, manufactured by Toa Synthetic Co., Ltd.).
  • the component (c-1) one type may be used alone, or two or more types may be used in combination.
  • the number average molecular weight of the component (c-1) may be 15,000 or less, 13000 or less, or 12000 or less, and may be 2000 or more and 4000 or more, or 6000 or more.
  • the content of the component (c-1) may be 30 to 90% by mass, 40 to 80% by mass, or 50 to 80% by mass based on the total amount of the component (c).
  • the content of the component (c-1) is 30% by mass or more based on the total amount of the component (c)
  • the adaptability to a wide range of frame-processed surfaces is improved, and when the component is peeled off, interface destruction occurs.
  • the content of the component (c-1) is 90% by mass or less based on the total amount of the component (c), it is possible to prevent the adhesive strength from being lowered during curing. Tend to be able to.
  • the component (c-2) is not particularly limited as long as it is a polyol having two or more OH groups other than the component (c-1), and is, for example, the polyether exemplified in the above-mentioned component (a-1). Polyxyl can be used.
  • the number average molecular weight of the component (c-2) may be the same as the number average molecular weight of the component (a-1).
  • the content of the component (c) may be 35 to 65% by mass, 40 to 60% by mass, or 45 to 55% by mass based on the total amount of the (B) curing agent.
  • the content of the component (c) is 35% by mass or more based on the total amount of the curing agent (B), it tends to be possible to prevent a decrease in the flexibility of the adhesive during curing, and the component (b)
  • the content of (B) is 65% by mass or less based on the total amount of the curing agent (B)
  • a known catalyst that promotes the urethanization reaction or the urea conversion reaction can be used.
  • the component (d) include a tin catalyst, an amine catalyst, and the like, which can be appropriately selected according to a desired curing rate.
  • the tin catalyst include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin didecanete, dioctyltin didecanate, tin 2-ethylhexanoate and the like.
  • the amine catalyst include triethylenediamine, bis (dimethylaminoethyl) ether, di (N, N-dimethylaminoethyl) amine and the like.
  • the total content of the component (d) is 0.1 to 10.0% by mass, 0.1 to 5.0% by mass, or 0.1 to 0.1 to 1,0.0% by mass, based on the total amount of (A) main agent and (B) curing agent. It may be 3.0% by mass.
  • the component (e) may have an average particle size (D50: particle size of 50% of the volume particle size distribution curve) of 20 to 40 nm or 25 to 35 nm.
  • D50 average particle size of 50% of the volume particle size distribution curve
  • the average particle size (D50) of carbon black can be measured by a laser diffracted light scattering method using, for example, "Model LS-230" manufactured by Beckman Coulter.
  • the component (e) Commercially available products of the component (e) include, for example, Monarch 460 (manufactured by Cabot Corporation), Asahi Carbon 70 (manufactured by Asahi Carbon Co., Ltd.), Seest 3 (manufactured by Tokai Carbon Co., Ltd.), and Mitsubishi Carbon 32 (manufactured by Mitsubishi Chemical Corporation). (Manufactured by), Niteron 200 (manufactured by Shin Nikka Carbon Co., Ltd.) and the like.
  • the total content of the component (e) may be 5 to 40% by mass based on the total amount of the (A) main agent and (B) curing agent.
  • the strength of the adhesive tends to improve, and when it is 40% by mass or less. If there is, there is a tendency that the strength of the adhesive can be maintained because the dispersibility is improved.
  • the total content of the component (e) may be 10 to 30% by mass because the workability and weather resistance of the adhesive can be further improved.
  • the component (f) includes kaolin, talc, silica, titanium oxide, calcium carbonate, bentonite, mica, sericite, glass flakes, glass fibers, graphite, magnesium hydroxide, and hydroxide.
  • examples thereof include aluminum, antimony trioxide, barium sulfate, zinc borate, alumina, magnesia, wollastonite, zonotrite, whisker and the like.
  • the total content of the component (f) may be 5 to 40% by mass or 10 to 30% by mass based on the total amount of the (A) main agent and (B) curing agent.
  • phthalate ester compounds examples include dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), butyl benzyl phthalate (BBP) and the like. ..
  • DOP dioctyl phthalate
  • DBP dibutyl phthalate
  • DINP diisononyl phthalate
  • DIDP diisodecyl phthalate
  • BBP butyl benzyl phthalate
  • the total content of the component (g) may be 5 to 40% by mass or 10 to 30% by mass based on the total amount of the (A) main agent and (B) curing agent.
  • At least one of (A) main agent and (B) curing agent is an ultraviolet absorber, a dehydrating agent, a pigment, a dye, an antioxidant, an antioxidant, an antistatic agent, a flame retardant, and an adhesive. It may further contain an imparting agent, a dispersant, a solvent and the like.
  • the viscosity of the main agent at 20 ° C. may be, for example, 500 to 2000 Pa ⁇ s, 750 to 1750 Pa ⁇ s, or 1000 to 1500 Pa ⁇ s.
  • the viscosity of the main agent at 20 ° C. is 500 Pa ⁇ s or more, the bead shape when the adhesive is applied tends to be easily maintained.
  • the viscosity of the main agent at 20 ° C. is 2000 Pa ⁇ s or less, it is not necessary to increase the pressure when discharging the adhesive, and the adhesive tends to be easily discharged.
  • the viscosity at 20 ° C. is the viscosity at 20 ° C. measured using a B-type rotational viscometer (trade name: VISCOMETER-TV25H, manufactured by Toki Sangyo Co., Ltd., applicable rotor: No. 7). Means.
  • the viscosity of the curing agent (B) at 20 ° C. may be, for example, 500 to 2000 Pa ⁇ s, 750 to 1750 Pa ⁇ s, or 1000 to 1500 Pa ⁇ s.
  • the viscosity of the curing agent at 20 ° C. is 500 Pa ⁇ s or more, the bead shape when the adhesive is applied tends to be easily maintained.
  • the viscosity at 20 ° C. is 2000 Pa ⁇ s or less, it is not necessary to increase the pressure when discharging the adhesive, and the adhesive tends to be easily discharged.
  • the equivalent ratio (NCO group / OH group) of (A) the isocyanate group (NCO) in the main agent to the hydroxyl group (OH) in the (B) curing agent is determined, for example. , 1.0 to 5.0 is preferable.
  • the equivalent ratio (NCO group / OH group) is 1.0 or more, the abundance ratio of the unreacted polyol decreases when the main agent and the curing agent are mixed, so that sufficient adhesive properties tend to be obtained. is there.
  • the equivalent ratio (NCO group / OH group) is 5.0 or less, the abundance ratio of isocyanate and prepolymer becomes an appropriate range when the main agent and the curing agent are mixed, and the ratio with the water in the air becomes The reaction ratio can be suppressed, and sufficient curability tends to be obtained.
  • the isocyanate group in (A) the main agent is mainly derived from (a) urethane prepolymer, and the hydroxyl group in (B) the curing agent is mainly derived from (c) polyol.
  • a mixture (two-component curing type urethane-based composition) can be prepared by mixing (A) a main agent and (B) a curing agent.
  • the temperature and time when the main agent (A) and the curing agent (B) are mixed may be, for example, 10 to 35 ° C. for 1 to 5 minutes.
  • the method of mixing the main agent (A) and the curing agent (B) is not particularly limited, and for example, a method of mixing by hand coating using a normal caulking gun may be used, and a fixed amount is used for sending the raw material.
  • a method may be used in which a flexible pump (for example, a gear pump, a plunger pump, etc.) and a throttle valve are used in combination and mixed using a mechanical rotary mixer, a static mixer, or the like.
  • the prepared mixture (two-component curable urethane-based composition) can be an adhesive that adheres the base materials to each other by curing.
  • the conditions for curing the mixture may be, for example, 10 to 35 ° C., 30 to 60% RH (relative humidity), and 3 to 7 days.
  • the method for producing a structure of one embodiment is a structure in which a first base material and a second base material are bonded together via a mixture obtained by mixing a main agent and a curing agent in the above-mentioned adhesive set. It has a process to obtain a body.
  • the structure include a vehicle back door, a trunk lid, a windshield, a spoiler, and the like.
  • At least one of the first base material and the second base material may be a polypropylene base material.
  • the base material other than the polypropylene base material in the first base material and the second base material include polyvinyl chloride, acryliconitrile / butadiene / styrene copolymer (ABS), polycarbonate (PC), polyamide (PA), and poly ().
  • Plastic groups such as methyl methacrylate (PMMA), polyester, epoxy resin, polyurethane (PUR), polyoxymethylene (POM), polyethylene (PE), ethylene / propylene copolymer (EPM), ethylene / propylene / diene polymer (EPDM)
  • PMMA methyl methacrylate
  • PUR polyurethane
  • POM polyoxymethylene
  • PE polyethylene
  • EPM ethylene / propylene copolymer
  • EPDM ethylene / propylene / diene polymer
  • fiber reinforced plastic base materials such as materials, carbon fiber reinforced plastics (CFRP) and glass fiber reinforced plastics (GFRP), and resin compound base materials such as sheet molding compounds (SMC).
  • the structure is a vehicle back door.
  • the first substrate may be an inner panel made of a polypropylene substrate and the second substrate may be an outer panel.
  • the equivalent ratio (NCO group / OH group) of the isocyanate group (NCO) in the (A) main agent to the hydroxyl group (OH) in the (B) curing agent may be, for example, 1.0 to 5.0.
  • the temperature and time when the (A) main agent and (B) curing agent in the adhesive set are mixed may be, for example, 10 to 35 ° C. for 1 to 5 minutes.
  • the conditions for curing the mixture may be, for example, 10-35 ° C., 30-60% RH (relative humidity), 3-7 days.
  • Exenol 2020 polypropylene glycol, manufactured by Asahi Glass Co., Ltd., number average molecular weight: 2000, number of functional groups: 2) 20.0 g, UH-2000 (acrylic) in a kneading container with a stirrer, nitrogen introduction pipe, vacuum pump, and heating / cooling device.
  • Polypropylene (hydroxyl-containing acrylic polymer), manufactured by Toa Synthetic Co., Ltd., number average molecular weight: 11000, number of functional groups: 2 or more) 80.0 g, EDP-1100 (polypropylene glycol, manufactured by ADEKA Co., Ltd., number average molecular weight: 260, functional Number of groups: 4) 2.4 g, Monarch 460 (carbon black, manufactured by Cabot Corporation) 35.1 g, Iceberg (baked kaolin, manufactured by Shiraishi Calcium Co., Ltd.) 22.6 g, DINP (diisononyl phthalate) 29.3 g, BHT Add 0.4 g of (dibutylhydroxytoluene), 1.2 g of polymer sieve 4A (dehydrating agent), and 1.4 g of KS-1260 (dibutyltin dilaurate, manufactured by Sakai Chemical Industry Co., Ltd.) until the carbon black lumps disappear.
  • EDP-1100 polypropylene glyco
  • ⁇ Comparative example 1> (Main agent) The main agent of Example 1 was used as it was as the main agent of Comparative Example 1. (Hardener) The same as the curing agent of Example 1 except that 80.0 g of UH-2000 was changed to 80.0 g of Excelol 837 (polypropylene glycol, manufactured by Asahi Glass Co., Ltd., number average molecular weight: 6000, number of functional groups: 3). The curing agent of Comparative Example 1 was obtained.
  • the non-primer adhesiveness was evaluated by the method shown below using the above-mentioned main agent and curing agent.
  • the mixed mass ratio of the main agent and the curing agent was 1: 1.
  • Non-primer adhesiveness (Preparation of base material)
  • a base material an olefin-based thermoplastic elastomer base material (inner base material of the back door) and a glass long fiber reinforced polypropylene base material (outer base material of the back door) are prepared, and only for the glass long fiber reinforced polypropylene base material.
  • Frame processing was performed. First, as a pretreatment, the surface of the base material was degreased with isopropanol. Next, the surface of the degreased base material was frame-treated. The frame processing was performed by a Bunsen burner (trade name, manufactured by Wazef Co., Ltd.) using propane gas, and the processing speed was set to 80 mm / s.
  • the base material was frame-treated 1 to 5 times to prepare base materials having different surface states.
  • the surface tension of the glass long fiber reinforced polypropylene base material was 300 ⁇ N / cm (30 dyn / cm) and 350 ⁇ N / cm (35 dyn / cm), respectively, in the untreated, 1, 2, 3, 4, and 5 times.
  • 420 ⁇ N / cm (42 dyn / cm) 540 ⁇ N / cm (54 dyn / cm), 650 ⁇ N / cm (65 dyn / cm), and 720 ⁇ N / cm (72 dyn / cm).
  • the surface tension was measured by Wako Pure Chemical Industries, Ltd.'s Wetting Tension Test Mixing Solution No. 30, No. 35, No. 42, No. 54, No. 65, using water (720 ⁇ N / cm (72 dyn / cm)), the procedure was carried out according to JIS K6768: 1999.
  • Table 1 shows the compounding composition of the materials, and Table 2 shows the evaluation results.
  • the adhesive set of Example 1 using the curing agent containing the polyol containing the component (c-1) is compared with the adhesive set of Comparative Example 1 not using such a curing agent.
  • the non-primer adhesiveness of the adhesive to the substrates with different number of frame treatments was excellent. From these results, it can be seen that the adhesive set of the present invention can prepare an adhesive having excellent non-primer adhesiveness even on a substrate that has been frame-treated under a wide range of treatment conditions. confirmed.

Abstract

An adhesive set that is structured from a main agent and a curing agent, wherein the main agent includes a urethane prepolymer that has as isocyanate group as a terminal group thereof, and the curing agent includes a polyol that includes an acrylic polyol.

Description

接着剤セット及び構造体の製造方法Manufacturing method of adhesive set and structure
　本発明は、接着剤セット及び構造体の製造方法に関する。 The present invention relates to an adhesive set and a method for manufacturing a structure.
　自動車のボディ、フロントドア、リアドア、バックドア、フロントバンパー、リアバンパー、ロッカーモール等の内外装部品には一般的に鋼板が使用されているが、近年の燃費改善要求に応えるため、軽量化が求められている。このため、鋼板に代えてポリプロピレン等のプラスチック材料を自動車の内外装部品として使用する場合が増えている。なお、ポリプロピレン等のプラスチック材料は鋼板と比較して強度が低いため、タルク、ガラスフィラー等を添加して強度を向上させることが一般的である。 Steel plates are generally used for interior and exterior parts of automobile bodies, front doors, rear doors, back doors, front bumpers, rear bumpers, rocker moldings, etc., but weight reduction is required to meet recent demands for improved fuel efficiency. Has been done. For this reason, plastic materials such as polypropylene are increasingly used as interior / exterior parts of automobiles instead of steel plates. Since plastic materials such as polypropylene have lower strength than steel sheets, it is common to add talc, glass filler, or the like to improve the strength.
　ポリプロピレン等のプラスチック製自動車部品同士の接着剤としてはウレタン系組成物が提案されている。ウレタン系組成物としては、空気中の湿気等によって硬化する、湿気硬化型と呼ばれる一液型の組成物と、主剤と硬化剤とで構成される接着剤セットを用いて、主剤と硬化剤とを混合する二液型の組成物が知られている。これらの中でも、接着工程における作業性の観点から、可使時間（ポットライフ、多液塗料において化学反応等で塗料が硬化し始めるまでの時間）を充分に確保でき、かつ速硬化が可能となる二液型の組成物が好まれる傾向にある。 Urethane-based compositions have been proposed as an adhesive between plastic automobile parts such as polypropylene. As the urethane-based composition, a one-component composition called a moisture-curing type, which is cured by moisture in the air, and an adhesive set composed of a main agent and a curing agent are used to prepare a main agent and a curing agent. There are known two-component compositions that mix. Among these, from the viewpoint of workability in the bonding process, sufficient pot life (time until the paint starts to cure due to a chemical reaction in a pot life or a multi-component paint) can be sufficiently secured, and quick curing becomes possible. Two-component compositions tend to be preferred.
　一般に、ポリプロピレン基材は、表面の極性が小さく、難接着であることから、接着を容易にするために、基材表面に極性基を導入する表面処理が行われる。表面処理としては、例えば、フレーム処理等が挙げられる。さらに、表面処理を施したポリプロピレン基材同士の接着にウレタン系組成物を直接適用することは困難であるため、各々のポリプロピレン基材に前処理としてプライマー処理を行ってからウレタン系組成物を適用することが一般的である。しかし、近年、工程の簡略化、作業環境改善等の観点からプライマー処理を行わない場合の接着性（すなわち、ノンプライマー接着性）の向上が求められている。 In general, polypropylene base material has a small surface polarity and is difficult to adhere. Therefore, in order to facilitate adhesion, a surface treatment for introducing a polar group into the surface of the base material is performed. Examples of the surface treatment include frame treatment and the like. Furthermore, since it is difficult to directly apply the urethane-based composition to the adhesion between the surface-treated polypropylene base materials, the urethane-based composition is applied after the primer treatment is performed on each polypropylene base material as a pretreatment. It is common to do. However, in recent years, from the viewpoint of simplifying the process, improving the working environment, etc., improvement of adhesiveness (that is, non-primer adhesiveness) when primer treatment is not performed has been required.
　例えば、特許文献１には、イソシアネート化合物を含有する主剤（第１液）と、ケチミンを含有する硬化剤（第２液）とを作業時に混合する二液型硬化性組成物が開示されている。 For example, Patent Document 1 discloses a two-component curable composition in which a main agent containing an isocyanate compound (first liquid) and a curing agent containing ketimine (second liquid) are mixed during work. ..
特開２００４－１３１６２５号公報Japanese Unexamined Patent Publication No. 2004-131625
　ところで、基材のフレーム処理は、処理条件（例えば、回数）によって、基材表面への極性基の導入割合（すなわち、表面張力（濡れ性））を変化させることができる。そのため、使用される二液型硬化性組成物には、幅広い処理条件でフレーム処理が施された基材（すなわち、表面張力（濡れ性）の異なる基材）に対しても、優れたノンプライマー接着性を有することが求められる。しかしながら、従来の二液型硬化性組成物では、幅広い処理条件でフレーム処理が施された基材に対するノンプライマー接着性が充分でなく、さらなる改善の余地がある。 By the way, in the frame treatment of the base material, the introduction ratio of polar groups (that is, surface tension (wetting property)) to the surface of the base material can be changed depending on the treatment conditions (for example, the number of times). Therefore, the two-component curable composition used is an excellent non-primer even for a base material that has been frame-treated under a wide range of treatment conditions (that is, a base material having a different surface tension (wetting property)). It is required to have adhesiveness. However, the conventional two-component curable composition does not have sufficient non-primer adhesiveness to a substrate that has been frame-treated under a wide range of treatment conditions, and there is room for further improvement.
　そこで、本発明は、幅広い処理条件でフレーム処理が施された基材に対しても、優れたノンプライマー接着性を有する接着剤を調製することが可能な接着剤セットを提供することを主な目的とする。 Therefore, the main invention of the present invention is to provide an adhesive set capable of preparing an adhesive having excellent non-primer adhesiveness even on a substrate that has been frame-treated under a wide range of treatment conditions. The purpose.
　上記目的を達成するため、本発明者らが鋭意検討した結果、硬化剤において特定の成分を用いることによって、接着剤セットが、幅広い処理条件でフレーム処理が施された基材に対しても、優れたノンプライマー接着性を有する接着剤を調製することが可能であることを見出し、本発明を完成するに至った。 As a result of diligent studies by the present inventors in order to achieve the above object, the adhesive set can be applied to a substrate which has been frame-treated under a wide range of treatment conditions by using a specific component in the curing agent. They have found that it is possible to prepare an adhesive having excellent non-primer adhesiveness, and have completed the present invention.
　本発明の一側面は、主剤と硬化剤とで構成される接着剤セットであって、主剤が、末端基としてイソシアネート基を有するウレタンプレポリマーを含有し、硬化剤が、アクリルポリオールを含むポリオールを含有する、接着剤セットを提供する。 One aspect of the present invention is an adhesive set composed of a main agent and a curing agent, wherein the main agent contains a urethane prepolymer having an isocyanate group as an end group, and the curing agent is a polyol containing an acrylic polyol. Provided is an adhesive set to be contained.
　別の側面において、本発明は、上述の接着剤セットにおける主剤と硬化剤とを混合して得られる混合物を介して、第１の基材と第２の基材とを貼り合わせて構造体を得る工程を備える、構造体の製造方法を提供する。 In another aspect, the present invention attaches a first substrate and a second substrate to a structure via a mixture obtained by mixing a main agent and a curing agent in the above-mentioned adhesive set. Provided is a method for manufacturing a structure, which comprises a step of obtaining.
　第１の基材及び第２の基材の少なくとも一方は、ポリプロピレン基材であってよい。 At least one of the first base material and the second base material may be a polypropylene base material.
　本発明によれば、幅広い処理条件でフレーム処理が施された基材に対しても、優れたノンプライマー接着性を有する接着剤を調製することが可能な接着剤セットが提供される。また、本発明によれば、接着剤セットを用いた構造体の製造方法が提供される。 According to the present invention, there is provided an adhesive set capable of preparing an adhesive having excellent non-primer adhesiveness even on a substrate that has been frame-treated under a wide range of processing conditions. Further, according to the present invention, there is provided a method for manufacturing a structure using an adhesive set.
　以下、本発明の実施形態について説明する。ただし、本発明は以下の実施形態に限定されるものではない。なお、本明細書において、「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。また、本明細書中に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。 Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. In addition, in this specification, the numerical range indicated by using "-" indicates the range including the numerical values before and after "-" as the minimum value and the maximum value, respectively. Further, in the numerical range described stepwise in the present specification, the upper limit value or the lower limit value of the numerical range of one step may be replaced with the upper limit value or the lower limit value of the numerical range of another step. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
［接着剤セット］
　一実施形態に係る接着剤セットは、主剤と硬化剤とで構成される。本実施形態に係る接着剤セットは、主剤と硬化剤とを混合することによって、混合物（二液硬化型ウレタン系組成物）を調製することができる。混合物（二液硬化型ウレタン系組成物）は時間経過とともに硬化し、基材同士を接着する接着剤として作用し得る。 [Adhesive set]
The adhesive set according to one embodiment is composed of a main agent and a curing agent. In the adhesive set according to the present embodiment, a mixture (two-component curing urethane-based composition) can be prepared by mixing the main agent and the curing agent. The mixture (two-component curable urethane-based composition) cures over time and can act as an adhesive that adheres the substrates.
　（Ａ）主剤は、末端基としてイソシアネート基を有する（ａ）ウレタンプレポリマーを含有する。（Ａ）主剤は、（ｂ）界面接着成分をさらに含有していてもよい。（Ｂ）硬化剤は、アクリルポリオールを含む（ｃ）ポリオールを含有する。（Ａ）主剤及び（Ｂ）硬化剤の少なくとも一方は、（ｄ）硬化触媒、（ｅ）カーボンブラック、（ｆ）充填剤、及び（ｇ）可塑剤のいずれかを含有していてもよい。以下、各成分について説明する。 (A) The main agent contains (a) urethane prepolymer having an isocyanate group as a terminal group. The main agent (A) may further contain the interfacial adhesive component (b). (B) The curing agent contains (c) polyol containing an acrylic polyol. At least one of (A) main agent and (B) curing agent may contain any one of (d) curing catalyst, (e) carbon black, (f) filler, and (g) plasticizer. Hereinafter, each component will be described.
＜（ａ）ウレタンプレポリマー＞
　（ａ）成分は、活性水素基を２個以上有する化合物とイソシアネート基を２個以上有するポリイソシアネート化合物との反応生成物である。（ａ）成分は、イソシアネート基の数が過剰となるように反応させることによって、末端基としてイソシアネート基を有するものを得ることができる。活性水素基としては、例えば、ヒドロキシ基（ＯＨ基）、カルボキシル基（ＣＯＯＨ基）、アミノ基（ＮＨ２基）、メルカプト基（ＳＨ基）等が挙げられる。活性水素基を２個以上有する化合物は、ヒドロキシ基（ＯＨ基）を２個以上有する化合物であるポリオールであってよく、（ａ－１）ポリエーテルポリオールであってもよい。 <(A) Urethane prepolymer>
The component (a) is a reaction product of a compound having two or more active hydrogen groups and a polyisocyanate compound having two or more isocyanate groups. As the component (a), a component having an isocyanate group as a terminal group can be obtained by reacting so that the number of isocyanate groups becomes excessive. Examples of the active hydrogen group include a hydroxy group (OH group), a carboxyl group (COOH group), an amino group (NH 2 group), a mercapto group (SH group) and the like. The compound having two or more active hydrogen groups may be a polyol which is a compound having two or more hydroxy groups (OH groups), or may be a (a-1) polyether polyol.
　ポリイソシアネート化合物としては、例えば、イソシアネート基が芳香族炭化水素と結合している芳香族ポリイソシアネート、イソシアネート基が脂環式炭化水素と結合している脂環族ポリイソシアネート等が挙げられる。これらの中でも、ポリイソシアネート化合物は、（ａ－２）芳香族ポリイソシアネートであってよく、ジフェニルメタンジイソシアネートであってもよい。活性水素基を２個以上有する化合物及びイソシアネート基を２個以上有するポリイソシアネート化合物は、それぞれ１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the polyisocyanate compound include aromatic polyisocyanates in which an isocyanate group is bonded to an aromatic hydrocarbon, and alicyclic polyisocyanates in which an isocyanate group is bonded to an alicyclic hydrocarbon. Among these, the polyisocyanate compound may be (a-2) aromatic polyisocyanate or diphenylmethane diisocyanate. As the compound having two or more active hydrogen groups and the polyisocyanate compound having two or more isocyanate groups, one kind may be used alone or two or more kinds may be used in combination.
（（ａ－１）ポリエーテルポリオール）
　（ａ－１）成分は、ＯＨ基を２個以上有するポリエーテルポリオールであれば特に制限されない。具体的には、ポリエチレングリコール（ＰＥＧ）、ポリプロピレングリコール（ＰＰＧ）、エチレンオキサイド／プロピレンオキサイド共重合体、ポリテトラメチレンエーテルグリコール（ＰＴＭＥＧ）、ソルビトール系ポリオール等が挙げられる。これらの中でも、（ａ－１）成分は、ポリプロピレングリコール（ＰＰＧ）であってよい。また、（ａ－１）成分は、１種を単独で用いてもよく、２種以上を併用してもよい。 ((A-1) Polyether polyol)
The component (a-1) is not particularly limited as long as it is a polyether polyol having two or more OH groups. Specific examples thereof include polyethylene glycol (PEG), polypropylene glycol (PPG), ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), and sorbitol-based polyol. Among these, the component (a-1) may be polypropylene glycol (PPG). Further, as the component (a-1), one type may be used alone, or two or more types may be used in combination.
　（ａ－１）成分の数平均分子量は、１００００以下であってよく、９０００以下、８０００以下、７０００以下、又は６０００以下であってもよい。（ａ－１）成分の数平均分子量が１００００以下であると、架橋点が増加し、硬化時の機械物性が向上する傾向にある。（ａ－１）成分の数平均分子量は、特に制限されないが、例えば、５００以上であってもよい。 The number average molecular weight of the component (a-1) may be 10,000 or less, and may be 9000 or less, 8000 or less, 7000 or less, or 6000 or less. When the number average molecular weight of the component (a-1) is 10,000 or less, the number of cross-linking points tends to increase and the mechanical properties at the time of curing tend to improve. The number average molecular weight of the component (a-1) is not particularly limited, but may be, for example, 500 or more.
　なお、本明細書中、「数平均分子量」とは、ゲル浸透クロマトグラフィー（ＧＰＣ）を利用し、標準ポリスチレンの検量線を使用して算出したものである。
　ＧＰＣ測定条件は、下記のとおりである。
　測定器：ＡＣＱＵＩＴＹ　ＵＰＬＣ　ＡＰＣシステム（Ｗａｔｅｒｓ社製）
　カラム：ＡＰＣ　ＸＴ－９００、ＡＰＣ　ＸＴ－２００、ＡＰＣ　ＸＴ－１２５、ＡＰＣ　ＸＴ－４５　（Ｗａｔｅｒｓ社製）
　キャリア：テトラヒドロフラン（ＴＨＦ）
　検出器：示差屈折
　サンプル：０．５質量％ＴＨＦ溶液
　検量線：ポリスチレン In the present specification, the "number average molecular weight" is calculated by using gel permeation chromatography (GPC) and using a standard polystyrene calibration curve.
The GPC measurement conditions are as follows.
Measuring instrument: ACQUITY UPLC APC system (manufactured by Waters)
Columns: APC XT-900, APC XT-200, APC XT-125, APC XT-45 (manufactured by Waters)
Carrier: tetrahydrofuran (THF)
Detector: Differential refractometer Sample: 0.5 mass% THF solution Calibration curve: Polystyrene
（（ａ－２）芳香族ポリイソシアネート）
　（ａ－２）成分としては、例えば、４，４’－ジフェニルメタンジイソシアネート（４，４’－ＭＤＩ（モノメリックＭＤＩ））、２，４’－ジフェニルメタンジイソシアネート）（２，４’－ＭＤＩ）等が挙げられる。 ((A-2) Aromatic polyisocyanate)
Examples of the component (a-2) include 4,4'-diphenylmethane diisocyanate (4,4'-MDI (monomeric MDI)), 2,4'-diphenylmethane diisocyanate) (2,4'-MDI) and the like. Can be mentioned.
　（ａ）成分の含有量は、（Ａ）主剤全量を基準として、２０～５５質量％、２５～５０質量％、又は３０～４５質量％であってよい。（ａ）成分の含有量が、（Ａ）主剤全量を基準として、２０質量％以上であると、硬化時の接着剤伸び率の低下を防ぐことができる傾向にあり、（ａ）成分の含有量が、（Ａ）主剤全量を基準として、５５質量％以下であると、養生後の接着特性の低下を防ぐことができる傾向にある。 The content of the component (a) may be 20 to 55% by mass, 25 to 50% by mass, or 30 to 45% by mass based on the total amount of the main agent (A). When the content of the component (a) is 20% by mass or more based on the total amount of the main agent (A), it tends to be possible to prevent a decrease in the adhesive elongation rate during curing, and the content of the component (a) is contained. When the amount is 55% by mass or less based on the total amount of (A) main agent, deterioration of the adhesive properties after curing tends to be prevented.
＜（ｂ）界面接着成分＞
　（ｂ）成分としては、例えば、（ｂ－１）未変性のイソシアヌレート基を有するヘキサメチレンジイソシアネートの多量体（以下、「未変性ヘキサメチレンジイソシアネート多量体」という場合がある。）、（ｂ－２）メルカプト基又はアミノ基を有するシランカップリング剤、（ｂ－３）（ｂ－２）成分で変性されているイソシアネート基及び少なくとも２つの未変性のイソシアネート基を有するヘキサメチレンジイソシアネートの多量体（以下、「変性ヘキサメチレンジイソシアネート多量体」という場合がある。）等が挙げられる。 <(B) Interface adhesive component>
As the component (b), for example, (b-1) a multimer of hexamethylene diisocyanate having an unmodified isocyanurate group (hereinafter, may be referred to as “unmodified hexamethylene diisocyanate multimer”), (b-. 2) A silane coupling agent having a mercapto group or an amino group, a multimer of hexamethylene diisocyanate having an isocyanate group modified with the components (b-3) and (b-2) and at least two unmodified isocyanate groups ( Hereinafter, it may be referred to as “modified hexamethylene diisocyanate multimer”) and the like.
（（ｂ－１）未変性ヘキサメチレンジイソシアネート多量体）
　（ｂ－１）成分は、未変性のイソシアネート基を有するヘキサメチレンジイソシアネートの多量体であれば特に制限されないが、例えば、イソシアヌレート体、ビウレット体、トリメチロールプロパン（ＴＭＰ）のアダクト体等の３量体であってよい。このような３量体の市販品としては、例えば、スミジュールＮ３３００（商品名、住化バイエルウレタン株式会社製）、デュラネート２４Ａ－１００（商品名、旭化成株式会社製）、デュラネートＥ４０２－１００（商品名、旭化成株式会社製）等が挙げられる。（ｂ－１）成分は、１種を単独で用いてもよく、２種以上を併用してもよい。 ((B-1) Unmodified hexamethylene diisocyanate multimer)
The component (b-1) is not particularly limited as long as it is a multimer of hexamethylene diisocyanate having an unmodified isocyanate group, but for example, isocyanurate, biuret, trimethylolpropane (TMP) adduct, and the like. It may be a trimer. Examples of such trimeric commercial products include Sumijour N3300 (trade name, manufactured by Sumika Bayer Urethane Co., Ltd.), Duranate 24A-100 (trade name, manufactured by Asahi Kasei Corporation), and Duranate E402-100 (product name). Name, manufactured by Asahi Kasei Corporation), etc. As the component (b-1), one type may be used alone, or two or more types may be used in combination.
（（ｂ－２）メルカプト基又はアミノ基を有するシランカップリング剤）
　メルカプト基を有するシランカップリング剤は、イソシアヌレート基と反応し得る活性水素基であるメルカプト基（ＳＨ基）及び加水分解性基を有するシラン化合物である。メルカプト基を有するシランカップリング剤としては、例えば、３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン等が挙げられる。メルカプト基を有するシランカップリング剤は、１種を単独で用いてもよく、２種以上を併用してもよい。また、後述のアミノ基を有するシランカップリング剤と組み合わせて用いてもよい。 ((B-2) Silane coupling agent having a mercapto group or an amino group)
The silane coupling agent having a mercapto group is a silane compound having a mercapto group (SH group) which is an active hydrogen group capable of reacting with an isocyanurate group and a hydrolyzable group. Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane. As the silane coupling agent having a mercapto group, one type may be used alone, or two or more types may be used in combination. Further, it may be used in combination with a silane coupling agent having an amino group described later.
　アミノ基を有するシランカップリング剤は、イソシアヌレート基と反応し得る活性水素基であるアミノ基（ＮＨ２基又はＮＨＲ基（Ｒ：炭化水素基））及び加水分解性基を有するシラン化合物である。アミノ基を有するシランカップリング剤としては、例えば、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、Ｎ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピルトリメトキシシラン等が挙げられる。アミノ基を有するシランカップリング剤は、１種を単独で用いてもよく、２種以上を併用してもよい。また、上述のメルカプト基を有するシランカップリング剤と組み合わせて用いてもよい。 Silane coupling agents having an amino group, an amino group (NH 2 group or NHR group (R: hydrocarbon group)) is an active hydrogen group capable of reacting with isocyanurate groups is a silane compound having a and hydrolyzable groups .. Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2. -(Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, Examples thereof include N-phenyl-3-aminopropyltrimethoxysilane and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane. As the silane coupling agent having an amino group, one type may be used alone, or two or more types may be used in combination. Further, it may be used in combination with the above-mentioned silane coupling agent having a mercapto group.
（（ｂ－３）変性ヘキサメチレンジイソシアネート多量体）
　（ｂ－３）成分は、（ｂ－１）成分と（ｂ－２）成分との反応生成物である。当該反応生成物を（ｂ）成分として用いる場合、反応生成物は、（ｂ－３）成分以外に、（ｂ－１）成分、（ｂ－２）成分で変性されているイソシアネート基及び１つの未変性のイソシアネート基を有するヘキサメチレンジイソシアネートの多量体等を含むものであってよい。（ｂ－１）成分として、未変性ヘキサメチレンジイソシアネート３量体を用いる場合、（ｂ－３）成分は、（ｂ－２）成分で変性されているイソシアネート基及び２つの未変性のイソシアネート基を有するヘキサメチレンジイソシアネートの３量体であってよい。（ｂ－３）成分における（ｂ－２）成分で変性されているイソシアネート基は、ポリプロピレン基材との界面接着力の向上に寄与し、少なくとも２つの未変性のイソシアネート基は、硬化剤に含まれる（ｃ）ポリオールとの架橋形成に寄与し得る。 ((B-3) Modified Hexamethylene Diisocyanate Multimer)
The component (b-3) is a reaction product of the component (b-1) and the component (b-2). When the reaction product is used as the component (b), the reaction product includes an isocyanate group modified with the component (b-1), the component (b-2), and one component in addition to the component (b-3). It may contain a multimer of hexamethylene diisocyanate having an unmodified isocyanate group. When an unmodified hexamethylene diisocyanate trimer is used as the component (b-1), the component (b-3) contains an isocyanate group modified with the component (b-2) and two unmodified isocyanate groups. It may be a trimer of hexamethylene diisocyanate having. The isocyanate group modified with the component (b-2) in the component (b-3) contributes to the improvement of the interfacial adhesive force with the polypropylene base material, and at least two unmodified isocyanate groups are contained in the curing agent. (C) Can contribute to the formation of crosslinks with polyols.
　（ｂ－３）成分は、（ｂ－１）成分と（ｂ－２）成分とを、（ｂ－２）成分のＳＨ基又はＮＨ基に対する（ｂ－１）成分のＮＣＯ基の当量比（ＮＣＯ基／ＳＨ基又はＮＨ基）を調整することによって得ることができる。例えば、（ｂ－１）成分として、未変性ヘキサメチレンジイソシアネート３量体を用いる場合、通常、ＮＣＯ基を３個有することから、（ＮＣＯ基／ＳＨ基又はＮＨ基）を２．５～３．５の範囲に調整することによって、（ｂ－２）成分で変性されているイソシアネート基及び２つの未変性のイソシアネート基を有する（ｂ－３）成分を得ることができる。（ｂ－１）成分と（ｂ－２）成分との反応は、触媒存在下で行ってもよい。触媒としては、例えば、後述の（ｄ）硬化触媒と同様であってよい。触媒の含有量は、（ｂ－１）成分及び（ｂ－２）成分の種類等に合わせて、適宜設定することができる。（ｂ－１）成分と（ｂ－２）成分とを反応させるときの温度及び時間は、例えば、３５～５０℃で、２～５時間であってよい。 The component (b-3) is the equivalent ratio of the component (b-1) and the component (b-2) to the SH group or NH group of the component (b-2) and the NCO group of the component (b-1). It can be obtained by adjusting the NCO group / SH group or NH group). For example, when an unmodified hexamethylene diisocyanate trimeric is used as the component (b-1), it usually has three NCO groups, and therefore (NCO group / SH group or NH group) is 2.5 to 3. By adjusting to the range of 5, a component (b-3) having an isocyanate group modified with the component (b-2) and two unmodified isocyanate groups can be obtained. The reaction between the component (b-1) and the component (b-2) may be carried out in the presence of a catalyst. The catalyst may be, for example, the same as the curing catalyst (d) described later. The content of the catalyst can be appropriately set according to the types of the component (b-1) and the component (b-2). The temperature and time for reacting the component (b-1) and the component (b-2) may be, for example, 35 to 50 ° C. and 2 to 5 hours.
　（ｂ）成分の含有量は、（Ａ）主剤全量を基準として、２～１０質量％、２～７質量％、又は３～６質量％であってよい。（ｂ）成分の含有量が、（Ａ）主剤全量を基準として、２質量％以上であると、プライマレス接着性が向上し、基材表面と接着剤との接着耐久性の低下を防ぐことができる傾向にあり、（ｂ）成分の含有量が、（Ａ）主剤全量を基準として、１０質量％以下であると、硬化時の接着特性の低下を防ぐことができる傾向にある。 The content of the component (b) may be 2 to 10% by mass, 2 to 7% by mass, or 3 to 6% by mass based on the total amount of the (A) main agent. When the content of the component (b) is 2% by mass or more based on the total amount of the main agent (A), the primerless adhesiveness is improved and the adhesive durability between the substrate surface and the adhesive is prevented from being lowered. When the content of the component (b) is 10% by mass or less based on the total amount of the main agent (A), it tends to be possible to prevent deterioration of the adhesive property at the time of curing.
＜（ｃ）ポリオール＞
　（ｃ）成分は、（ｃ－１）アクリルポリオールを含む。（ｃ）成分は、（ｃ－１）成分以外のポリオール（ｃ－２）成分を含んでいてもよい。 <(C) polyol>
The component (c) contains (c-1) acrylic polyol. The component (c) may contain a polyol (c-2) component other than the component (c-1).
（（ｃ－１）アクリルポリオール）
　（ｃ－１）成分は、アクリル酸、メタクリル酸、及びそれらのエステルのアクリル系ポリマーであって、ＯＨ基を２個以上有するアクリル系ポリマー（水酸基含有アクリル系ポリマー）を意味する。（ｃ）成分が（ｃ－１）成分を含むことによって、幅広い処理条件でフレーム処理が施された基材に対しても、優れたノンプライマー接着性を有する接着剤を調製することが可能となる。この理由は、必ずしも明らかではないが、例えば、ポリエチレングリコール（ＰＥＧ）、ポリプロピレングリコール（ＰＰＧ）、エチレンオキサイド／プロピレンオキサイド共重合体、ポリテトラメチレンエーテルグリコール（ＰＴＭＥＧ）、ソルビトール系ポリオール等のポリエーテルポリオール、カルボン酸と多価アルコールを脱水縮合することにより得られる、エステル結合主骨格とするポリエステルポリオール等は、いずれも主鎖に極性結合を有している。これに対して、アクリルポリオールは主鎖に極性結合を有しておらず、上記ポリオールと比較して低極性であることが予想される。このような上記ポリオールと性質の異なる低極性のアクリルポリオールが（Ｂ）硬化剤に存在することによって、処理条件の異なる基材に対するノンプライマー接着性が向上していると本発明者らは考えている。 ((C-1) Acrylic polyol)
The component (c-1) is an acrylic polymer of acrylic acid, methacrylic acid, and an ester thereof, and means an acrylic polymer having two or more OH groups (hydroxyl group-containing acrylic polymer). Since the component (c) contains the component (c-1), it is possible to prepare an adhesive having excellent non-primer adhesiveness even on a substrate that has been frame-treated under a wide range of treatment conditions. Become. The reason for this is not always clear, but for example, polyether polyols such as polyethylene glycol (PEG), polypropylene glycol (PPG), ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol (PTMEG), and sorbitol-based polyols. , Polyester polyol having an ester bond main skeleton obtained by dehydration condensation of a carboxylic acid and a polyhydric alcohol, and the like all have a polar bond in the main chain. On the other hand, the acrylic polyol does not have a polar bond in the main chain and is expected to have a lower polarity than the above-mentioned polyol. The present inventors consider that the presence of such a low-polarity acrylic polyol having different properties from the above-mentioned polyol in the curing agent (B) improves the non-primer adhesiveness to the substrate having different treatment conditions. There is.
　ＯＨ基を２個以上有するアクリル系ポリマーを構成するＯＨ基を有する共重合体成分としては、例えば、アクリル酸ヒドロキシエチル、メタクリル酸ヒドロキシエチル、アクリル酸ヒドロキシプロピル、メタクリル酸ヒドロキシプロピル、アクリル酸３－クロロ－２－ヒドロキシプロピル、メタクリル酸３－クロロ－２－ヒドロキシプロピル、アリルアルコール等が挙げられる。アクリル酸、メタクリル酸、及びそれらのエステル以外の共重合成分としては、例えば、スチレン、α－メチルスチレン、ビニルトルエン、アクリルアミド、メタアクリルアミド及びその誘導体、酢酸ビニル、無水マレイン酸等が挙げられる。（ｃ－１）成分の市販品としては、例えば、ＵＨ－２０００（商品名、東亜合成株式会社製）、ＵＴ－１００１（商品名、綜研化学株式会社製）、ＵＨ－２１９０（製品名、東亜合成株式会社製）、ＵＨ－２０４１（製品名、東亜合成株式会社製）等が挙げられる。（ｃ－１）成分は、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the copolymer component having an OH group constituting an acrylic polymer having two or more OH groups include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 3-acrylate. Examples thereof include chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, and allyl alcohol. Examples of copolymerization components other than acrylic acid, methacrylic acid, and esters thereof include styrene, α-methylstyrene, vinyltoluene, acrylamide, methacrylamide and derivatives thereof, vinyl acetate, maleic anhydride, and the like. Commercially available products of the component (c-1) include, for example, UH-2000 (trade name, manufactured by Toa Synthetic Co., Ltd.), UT-1001 (trade name, manufactured by Soken Chemical Co., Ltd.), UH-2190 (product name, manufactured by Toa). Examples include (manufactured by Synthetic Co., Ltd.) and UH-2041 (product name, manufactured by Toa Synthetic Co., Ltd.). As the component (c-1), one type may be used alone, or two or more types may be used in combination.
　（ｃ－１）成分の数平均分子量は、１５０００以下、１３０００以下、又は１２０００以下であってよく、２０００以上、４０００以上、又は６０００以上であってよい。 The number average molecular weight of the component (c-1) may be 15,000 or less, 13000 or less, or 12000 or less, and may be 2000 or more and 4000 or more, or 6000 or more.
　（ｃ－１）成分の含有量は、（ｃ）成分全量を基準として、３０～９０質量％、４０～８０質量％、又は５０～８０質量％であってよい。（ｃ－１）成分の含有量が、（ｃ）成分全量を基準として、３０質量％以上であると、幅広いフレーム処理面への適応性が向上し、引き剥がしたときに界面破壊となってしまうことを防ぐことができる傾向にあり、（ｃ－１）成分の含有量が、（ｃ）成分全量を基準として、９０質量％以下であると、硬化時の接着剤強度の低下を防ぐことができる傾向にある。 The content of the component (c-1) may be 30 to 90% by mass, 40 to 80% by mass, or 50 to 80% by mass based on the total amount of the component (c). When the content of the component (c-1) is 30% by mass or more based on the total amount of the component (c), the adaptability to a wide range of frame-processed surfaces is improved, and when the component is peeled off, interface destruction occurs. When the content of the component (c-1) is 90% by mass or less based on the total amount of the component (c), it is possible to prevent the adhesive strength from being lowered during curing. Tend to be able to.
（（ｃ－１）アクリルポリオール以外のポリオール（ｃ－２））
　（ｃ－２）成分は、（ｃ－１）成分以外であって、ＯＨ基を２個以上有するポリオールであれば特に制限されないが、例えば、上述の（ａ－１）成分で例示したポリエーテルポリオールを使用することができる。（ｃ－２）成分の数平均分子量は、（ａ－１）成分の数平均分子量と同様であってよい。 (Polycarbonate other than (c-1) acrylic polyol (c-2))
The component (c-2) is not particularly limited as long as it is a polyol having two or more OH groups other than the component (c-1), and is, for example, the polyether exemplified in the above-mentioned component (a-1). Polyxyl can be used. The number average molecular weight of the component (c-2) may be the same as the number average molecular weight of the component (a-1).
　（ｃ）成分の含有量は、（Ｂ）硬化剤全量を基準として、３５～６５質量％、４０～６０質量％、又は４５～５５質量％であってよい。（ｃ）成分の含有量が、（Ｂ）硬化剤全量を基準として、３５質量％以上であると、硬化時の接着剤の柔軟性の低下を防ぐことができる傾向にあり、（ｂ）成分の含有量が、（Ｂ）硬化剤全量を基準として、６５質量％以下であると、硬化時の強度の低下を防ぐことができる傾向にある。 The content of the component (c) may be 35 to 65% by mass, 40 to 60% by mass, or 45 to 55% by mass based on the total amount of the (B) curing agent. When the content of the component (c) is 35% by mass or more based on the total amount of the curing agent (B), it tends to be possible to prevent a decrease in the flexibility of the adhesive during curing, and the component (b) When the content of (B) is 65% by mass or less based on the total amount of the curing agent (B), it tends to be possible to prevent a decrease in strength during curing.
＜（ｄ）硬化触媒＞
　（ｄ）成分は、ウレタン化反応又は尿素化反応を促進する公知の触媒が使用できる。（ｄ）成分としては、例えば、スズ触媒、アミン触媒等が挙げられ、所望の硬化速度に合わせて適宜選択することができる。スズ触媒としては、例えば、ジブチルスズジラウレート、ジオクチルスズジラウレート、ジブチルスズジデカネート、ジオクチルスズジデカネート、２－エチルヘキサン酸スズ等が挙げられる。アミン触媒としては、例えば、トリエチレンジアミン、ビス（ジメチルアミノエチル）エーテル、ジ（Ｎ，Ｎ－ジメチルアミノエチル）アミン等が挙げられる。 <(D) Curing catalyst>
As the component (d), a known catalyst that promotes the urethanization reaction or the urea conversion reaction can be used. Examples of the component (d) include a tin catalyst, an amine catalyst, and the like, which can be appropriately selected according to a desired curing rate. Examples of the tin catalyst include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin didecanete, dioctyltin didecanate, tin 2-ethylhexanoate and the like. Examples of the amine catalyst include triethylenediamine, bis (dimethylaminoethyl) ether, di (N, N-dimethylaminoethyl) amine and the like.
　（ｄ）成分の総含有量は、（Ａ）主剤及び（Ｂ）硬化剤全量を基準として、０．１～１０．０質量％、０．１～５．０質量％、又は０．１～３．０質量％であってよい。 The total content of the component (d) is 0.1 to 10.0% by mass, 0.1 to 5.0% by mass, or 0.1 to 0.1 to 1,0.0% by mass, based on the total amount of (A) main agent and (B) curing agent. It may be 3.0% by mass.
＜（ｅ）カーボンブラック＞
　（ｅ）成分は、その平均粒子径（Ｄ５０：体積粒度分布曲線の５０％値の粒径）が２０～４０ｎｍ又は２５～３５ｎｍであるものであってよい。カーボンブラックの平均粒子径が上記範囲であることによって、接着剤の粘性及びカーボンブラックの分散性がより適切な範囲に調整され、接着剤の作業性及び強度がより向上する傾向にある。なお、カーボンブラックの平均粒子径（Ｄ５０）は、例えば、ベックマン・コールター社製「モデルＬＳ－２３０」を用いて、レーザー回折光散乱法によって測定することができる。 <(E) Carbon black>
The component (e) may have an average particle size (D50: particle size of 50% of the volume particle size distribution curve) of 20 to 40 nm or 25 to 35 nm. When the average particle size of the carbon black is in the above range, the viscosity of the adhesive and the dispersibility of the carbon black are adjusted in a more appropriate range, and the workability and strength of the adhesive tend to be further improved. The average particle size (D50) of carbon black can be measured by a laser diffracted light scattering method using, for example, "Model LS-230" manufactured by Beckman Coulter.
　（ｅ）成分の市販品としては、例えば、モナーク４６０（キャボットコーポレーション社製）、旭カーボン７０（旭カーボン株式会社製）、シースト３（東海カーボン株式会社製）、三菱カーボン３２（三菱化学株式会社製）、ニテロン２００（新日化カーボン株式会社製）等が挙げられる。 Commercially available products of the component (e) include, for example, Monarch 460 (manufactured by Cabot Corporation), Asahi Carbon 70 (manufactured by Asahi Carbon Co., Ltd.), Seest 3 (manufactured by Tokai Carbon Co., Ltd.), and Mitsubishi Carbon 32 (manufactured by Mitsubishi Chemical Corporation). (Manufactured by), Niteron 200 (manufactured by Shin Nikka Carbon Co., Ltd.) and the like.
　（ｅ）成分の総含有量は、（Ａ）主剤及び（Ｂ）硬化剤の全量を基準として、５～４０質量％であってよい。（ｅ）成分の総含有量が、（Ａ）主剤及び（Ｂ）硬化剤の全量を基準として、５質量％以上であると、接着剤の強度が向上する傾向にあり、４０質量％以下であると、分散性が向上するため接着剤の強度を維持できる傾向にある。（ｅ）成分の総含有量は、接着剤の作業性及び耐候性をより向上させることができることから、１０～３０質量％であってもよい。 The total content of the component (e) may be 5 to 40% by mass based on the total amount of the (A) main agent and (B) curing agent. When the total content of the component (e) is 5% by mass or more based on the total amount of the main agent (A) and the curing agent (B), the strength of the adhesive tends to improve, and when it is 40% by mass or less. If there is, there is a tendency that the strength of the adhesive can be maintained because the dispersibility is improved. The total content of the component (e) may be 10 to 30% by mass because the workability and weather resistance of the adhesive can be further improved.
＜（ｆ）充填剤＞
　（ｆ）成分としては、上述の（ｅ）成分の他に、カオリン、タルク、シリカ、酸化チタン、炭酸カルシウム、ベントナイト、マイカ、セリサイト、ガラスフレーク、ガラス繊維、黒鉛、水酸化マグネシウム、水酸化アルミニウム、三酸化アンチモン、硫酸バリウム、ホウ酸亜鉛、アルミナ、マグネシア、ウォラストナイト、ゾノトライト、ウィスカー等が挙げられる。 <(F) Filler>
In addition to the above-mentioned component (e), the component (f) includes kaolin, talc, silica, titanium oxide, calcium carbonate, bentonite, mica, sericite, glass flakes, glass fibers, graphite, magnesium hydroxide, and hydroxide. Examples thereof include aluminum, antimony trioxide, barium sulfate, zinc borate, alumina, magnesia, wollastonite, zonotrite, whisker and the like.
　（ｆ）成分の総含有量は、（Ａ）主剤及び（Ｂ）硬化剤の全量を基準として、５～４０質量％又は１０～３０質量％であってよい。 The total content of the component (f) may be 5 to 40% by mass or 10 to 30% by mass based on the total amount of the (A) main agent and (B) curing agent.
＜（ｇ）可塑剤＞
　（ｇ）成分としては、例えば、フタル酸エステル系化合物、アルキルスルホン酸エステル系化合物、アジピン酸エステル系化合物等が挙げられる。フタル酸エステル系化合物の具体例としては、フタル酸ジオクチル（ＤＯＰ）、フタル酸ジブチル（ＤＢＰ）、フタル酸ジイソノニル（ＤＩＮＰ）、フタル酸ジイソデシル（ＤＩＤＰ）、フタル酸ブチルベンジル（ＢＢＰ）等が挙げられる。 <(G) Plasticizer>
Examples of the component (g) include phthalate ester compounds, alkyl sulfonic acid ester compounds, adipate ester compounds and the like. Specific examples of the phthalate ester compound include dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), butyl benzyl phthalate (BBP) and the like. ..
　（ｇ）成分の総含有量は、（Ａ）主剤及び（Ｂ）硬化剤の全量を基準として、５～４０質量％又は１０～３０質量％であってよい。 The total content of the component (g) may be 5 to 40% by mass or 10 to 30% by mass based on the total amount of the (A) main agent and (B) curing agent.
　（Ａ）主剤及び（Ｂ）硬化剤の少なくとも一方は、上述の成分に加えて、紫外線吸収剤、脱水剤、顔料、染料、老化防止剤、酸化防止剤、帯電防止剤、難燃剤、接着性付与剤、分散剤、溶剤等をさらに含有してもよい。 At least one of (A) main agent and (B) curing agent, in addition to the above-mentioned components, is an ultraviolet absorber, a dehydrating agent, a pigment, a dye, an antioxidant, an antioxidant, an antistatic agent, a flame retardant, and an adhesive. It may further contain an imparting agent, a dispersant, a solvent and the like.
　（Ａ）主剤の２０℃における粘度は、例えば、５００～２０００Ｐａ・ｓ、７５０～１７５０Ｐａ・ｓ、又は１０００～１５００Ｐａ・ｓであってよい。（Ａ）主剤の２０℃における粘度が５００Ｐａ・ｓ以上であると、接着剤を塗布したときのビード形状を保持し易い傾向にある。（Ａ）主剤の２０℃における粘度が２０００Ｐａ・ｓ以下であると、接着剤を吐出するときに高圧力とする必要がなく、吐出がし易い傾向にある。なお、本明細書において、２０℃における粘度は、Ｂ型回転粘度計（商品名：ＶＩＳＣＯＭＥＴＥＲ－ＴＶ２５Ｈ、東機産業株式会社製、適用ロータ：Ｎｏ．７）を用いて測定される２０℃における粘度を意味する。 (A) The viscosity of the main agent at 20 ° C. may be, for example, 500 to 2000 Pa · s, 750 to 1750 Pa · s, or 1000 to 1500 Pa · s. (A) When the viscosity of the main agent at 20 ° C. is 500 Pa · s or more, the bead shape when the adhesive is applied tends to be easily maintained. (A) When the viscosity of the main agent at 20 ° C. is 2000 Pa · s or less, it is not necessary to increase the pressure when discharging the adhesive, and the adhesive tends to be easily discharged. In the present specification, the viscosity at 20 ° C. is the viscosity at 20 ° C. measured using a B-type rotational viscometer (trade name: VISCOMETER-TV25H, manufactured by Toki Sangyo Co., Ltd., applicable rotor: No. 7). Means.
　（Ｂ）硬化剤の２０℃における粘度は、例えば、５００～２０００Ｐａ・ｓ、７５０～１７５０Ｐａ・ｓ、又は１０００～１５００Ｐａ・ｓであってよい。（Ｂ）硬化剤の２０℃における粘度が５００Ｐａ・ｓ以上であると、接着剤を塗布したときのビード形状を保持し易い傾向にある。２０℃における粘度が２０００Ｐａ・ｓ以下であると、接着剤を吐出するときに高圧力とする必要がなく、吐出がし易い傾向にある。 The viscosity of the curing agent (B) at 20 ° C. may be, for example, 500 to 2000 Pa · s, 750 to 1750 Pa · s, or 1000 to 1500 Pa · s. (B) When the viscosity of the curing agent at 20 ° C. is 500 Pa · s or more, the bead shape when the adhesive is applied tends to be easily maintained. When the viscosity at 20 ° C. is 2000 Pa · s or less, it is not necessary to increase the pressure when discharging the adhesive, and the adhesive tends to be easily discharged.
　（Ａ）主剤と（Ｂ）硬化剤とを混合する場合、（Ｂ）硬化剤における水酸基（ＯＨ）に対する（Ａ）主剤におけるイソシアネート基（ＮＣＯ）の当量比（ＮＣＯ基／ＯＨ基）を、例えば、１．０～５．０となるように調整することが好ましい。当量比（ＮＣＯ基／ＯＨ基）が１．０以上であると、主剤と硬化剤とを混合させた際に未反応ポリオールの存在割合が少なくなることから、充分な接着特性が得られる傾向にある。当量比（ＮＣＯ基／ＯＨ基）が５．０以下であると、主剤と硬化剤とを混合させた際にイソシアネート及びプレポリマーの存在比率が適切な範囲となって、空気中の水分との反応割合を抑えることができ、充分な硬化性が得られる傾向にある。なお、（Ａ）主剤におけるイソシアネート基は主に（ａ）ウレタンプレポリマーに由来するものであり、（Ｂ）硬化剤における水酸基は主に（ｃ）ポリオールに由来するものである。 When (A) the main agent and (B) the curing agent are mixed, the equivalent ratio (NCO group / OH group) of (A) the isocyanate group (NCO) in the main agent to the hydroxyl group (OH) in the (B) curing agent is determined, for example. , 1.0 to 5.0 is preferable. When the equivalent ratio (NCO group / OH group) is 1.0 or more, the abundance ratio of the unreacted polyol decreases when the main agent and the curing agent are mixed, so that sufficient adhesive properties tend to be obtained. is there. When the equivalent ratio (NCO group / OH group) is 5.0 or less, the abundance ratio of isocyanate and prepolymer becomes an appropriate range when the main agent and the curing agent are mixed, and the ratio with the water in the air becomes The reaction ratio can be suppressed, and sufficient curability tends to be obtained. The isocyanate group in (A) the main agent is mainly derived from (a) urethane prepolymer, and the hydroxyl group in (B) the curing agent is mainly derived from (c) polyol.
　本実施形態に係る接着剤セットは、（Ａ）主剤と（Ｂ）硬化剤とを混合することによって、混合物（二液硬化型ウレタン系組成物）を調製することができる。（Ａ）主剤と（Ｂ）硬化剤とを混合するときの温度及び時間は、例えば、１０～３５℃で、１～５分間であってよい。 In the adhesive set according to the present embodiment, a mixture (two-component curing type urethane-based composition) can be prepared by mixing (A) a main agent and (B) a curing agent. The temperature and time when the main agent (A) and the curing agent (B) are mixed may be, for example, 10 to 35 ° C. for 1 to 5 minutes.
　（Ａ）主剤と（Ｂ）硬化剤とを混合する方法は、特に制限されず、例えば、通常のコーキングガンを用いて手塗りによって混合する方法であってもよく、原料の送液用に定量性のあるポンプ（例えば、ギヤポンプ、プランジャーポンプ等）と絞り弁とを併用し、機械式回転ミキサー、スタティックミキサー等を用いて混合する方法であってもよい。 The method of mixing the main agent (A) and the curing agent (B) is not particularly limited, and for example, a method of mixing by hand coating using a normal caulking gun may be used, and a fixed amount is used for sending the raw material. A method may be used in which a flexible pump (for example, a gear pump, a plunger pump, etc.) and a throttle valve are used in combination and mixed using a mechanical rotary mixer, a static mixer, or the like.
　調製された混合物（二液硬化型ウレタン系組成物）は、硬化させることによって、基材同士を接着する接着剤となり得る。混合物を硬化させる条件（養生条件）は、例えば、１０～３５℃、３０～６０％ＲＨ（相対湿度）、３～７日間であってよい。 The prepared mixture (two-component curable urethane-based composition) can be an adhesive that adheres the base materials to each other by curing. The conditions for curing the mixture (curing conditions) may be, for example, 10 to 35 ° C., 30 to 60% RH (relative humidity), and 3 to 7 days.
　一実施形態の構造体の製造方法は、上述の接着剤セットにおける主剤と硬化剤とを混合して得られる混合物を介して、第１の基材と第２の基材とを貼り合わせて構造体を得る工程を備える。構造体としては、例えば、車両用バックドア、トランクリッド、ウィンドシールド、スポイラー等が挙げられる。 The method for producing a structure of one embodiment is a structure in which a first base material and a second base material are bonded together via a mixture obtained by mixing a main agent and a curing agent in the above-mentioned adhesive set. It has a process to obtain a body. Examples of the structure include a vehicle back door, a trunk lid, a windshield, a spoiler, and the like.
　第１の基材及び第２の基材の少なくとも一方は、ポリプロピレン基材であってよい。第１の基材及び第２の基材におけるポリプロピレン基材以外の基材としては、例えば、ポリ塩化ビニル、アクリロニトリル／ブタジエン／スチレンコポリマー（ＡＢＳ）、ポリカーボネート（ＰＣ）、ポリアミド（ＰＡ）、ポリ（メタクリル酸メチル（ＰＭＭＡ）、ポリエステル、エポキシ樹脂、ポリウレタン（ＰＵＲ）、ポリオキシメチレン（ＰＯＭ）、ポリエチレン（ＰＥ）、エチレン／プロピレンコポリマー（ＥＰＭ）、エチレン／プロピレン／ジエンポリマー（ＥＰＤＭ）等のプラスチック基材、炭素繊維強化プラスチック（ＣＦＲＰ）、ガラス繊維強化プラスチック（ＧＦＲＰ）等の繊維強化プラスチック基材、シート成形コンパウンド（ＳＭＣ）等の樹脂コンパウンド基材などが挙げられる。構造体が車両用バックドアである場合、第１の基材はポリプロピレン基材からなるインナパネルであってよく、第２の基材はアウタパネルであってよい。 At least one of the first base material and the second base material may be a polypropylene base material. Examples of the base material other than the polypropylene base material in the first base material and the second base material include polyvinyl chloride, acryliconitrile / butadiene / styrene copolymer (ABS), polycarbonate (PC), polyamide (PA), and poly (). Plastic groups such as methyl methacrylate (PMMA), polyester, epoxy resin, polyurethane (PUR), polyoxymethylene (POM), polyethylene (PE), ethylene / propylene copolymer (EPM), ethylene / propylene / diene polymer (EPDM) Examples include fiber reinforced plastic base materials such as materials, carbon fiber reinforced plastics (CFRP) and glass fiber reinforced plastics (GFRP), and resin compound base materials such as sheet molding compounds (SMC). The structure is a vehicle back door. In some cases, the first substrate may be an inner panel made of a polypropylene substrate and the second substrate may be an outer panel.
　（Ｂ）硬化剤における水酸基（ＯＨ）に対する（Ａ）主剤におけるイソシアネート基（ＮＣＯ）の当量比（ＮＣＯ基／ＯＨ基）は、例えば、１．０～５．０であってよい。接着剤セットにおける（Ａ）主剤と（Ｂ）硬化剤とを混合するときの温度及び時間は、例えば、１０～３５℃で、１～５分間であってよい。混合物を硬化させる条件は、例えば、１０～３５℃、３０～６０％ＲＨ（相対湿度）、３～７日間であってよい。 The equivalent ratio (NCO group / OH group) of the isocyanate group (NCO) in the (A) main agent to the hydroxyl group (OH) in the (B) curing agent may be, for example, 1.0 to 5.0. The temperature and time when the (A) main agent and (B) curing agent in the adhesive set are mixed may be, for example, 10 to 35 ° C. for 1 to 5 minutes. The conditions for curing the mixture may be, for example, 10-35 ° C., 30-60% RH (relative humidity), 3-7 days.
　以下、本発明について実施例を挙げてより具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
［主剤中間品の調製］
　撹拌機、窒素導入管、真空ポンプ、及び加熱冷却装置付き混練容器に、エクセノール８３７（ポリプロピレングリコール、旭硝子株式会社製、数平均分子量：６０００、官能基数：３）８０．０ｇ、エクセノール２０２０（ポリプロピレングリコール、旭硝子株式会社製、数平均分子量：２０００、官能基数：２）２０．０ｇ、モナーク４６０（カーボンブラック、キャボットコーポレーション社製）４５．５ｇ、アイスバーグ（焼成カオリン、白石カルシウム株式会社製）９１．０ｇ、ＤＩＮＰ（フタル酸ジイソノニル）４９．７ｇ、及びＫＯＳＭＯＳ２９（２－エチルヘキサン酸スズ、エボニックジャパン株式会社）０．０２ｇを仕込み、カーボンブラックの塊がなくなるまで、室温（２５℃）で３０分間撹拌した。次いで、内容物が１００℃となるまで混練容器を加熱し、真空ポンプにより混練容器内部が２．７ｋＰａ（２０ｍｍＨｇ）になるまで減圧して、内容物を１時間撹拌した。次いで、内容物の温度が７０℃になるまで冷却し、混練容器にミリオネートＭＴ（４，４’－ジフェニルメタンジイソシアネート、東ソー株式会社製、ＮＣＯ含有量：３３．６％）２４．０ｇを添加し、窒素導入後、内容物を１時間撹拌した。内容物の温度を４０℃になるまで冷却し、これを主剤中間品とした。 [Preparation of main agent intermediate product]
In a kneading container with a stirrer, nitrogen introduction pipe, vacuum pump, and heating / cooling device, Exenol 837 (polypropylene glycol, manufactured by Asahi Glass Co., Ltd., number average molecular weight: 6000, number of functional groups: 3) 80.0 g, Excelol 2020 (polypropylene glycol) , Asahi Glass Co., Ltd., Number average molecular weight: 2000, Number of functional groups: 2) 20.0 g, Monarch 460 (carbon black, manufactured by Cabot Corporation) 45.5 g, Iceberg (baked kaolin, manufactured by Shiraishi Calcium Co., Ltd.) 91. Add 0 g, DINP (diisononyl phthalate) 49.7 g, and KOSMOS29 (tin 2-ethylhexanoate, Ebonic Japan Co., Ltd.) 0.02 g, and stir at room temperature (25 ° C) for 30 minutes until the carbon black lumps disappear. did. Next, the kneading container was heated until the content reached 100 ° C., the pressure was reduced to 2.7 kPa (20 mmHg) inside the kneading container by a vacuum pump, and the content was stirred for 1 hour. Next, the contents were cooled to 70 ° C., and 24.0 g of millionate MT (4,5'-diphenylmethane diisocyanate, manufactured by Tosoh Corporation, NCO content: 33.6%) was added to the kneading vessel. After the introduction of nitrogen, the contents were stirred for 1 hour. The temperature of the contents was cooled to 40 ° C., and this was used as the main agent intermediate product.
［接着剤セットの作製］
＜実施例１＞
（主剤）
　上記主剤中間品に、ヘキサメチレンジイソシアネートのイソシアヌレート３量体（商品名：スミジュールＮ３３００、住化バイエルウレタン株式会社製）１０．２ｇ、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン（商品名：ＫＢＭ－５７３、信越化学株式会社製）３．５ｇ、及びＤＩＮＰ（フタル酸ジイソノニル）６．８ｇを添加し、１０分間撹拌することによって、実施例１の主剤を得た。
（硬化剤）
　撹拌機、窒素導入管、真空ポンプ、及び加熱冷却装置付き混練容器に、エクセノール２０２０（ポリプロピレングリコール、旭硝子株式会社製、数平均分子量：２０００、官能基数：２）２０．０ｇ、ＵＨ－２０００（アクリルポリオール（水酸基含有アクリル系ポリマー）、東亜合成株式会社製、数平均分子量：１１０００、官能基数：２以上）８０．０ｇ、ＥＤＰ－１１００（ポリプロピレングリコール、株式会社ＡＤＥＫＡ製、数平均分子量：２６０、官能基数：４）２．４ｇ、モナーク４６０（カーボンブラック、キャボットコーポレーション社製）３５．１ｇ、アイスバーグ（焼成カオリン、白石カルシウム株式会社製）２２．６ｇ、ＤＩＮＰ（フタル酸ジイソノニル）２９．３ｇ、ＢＨＴ（ジブチルヒドロキシトルエン）０．４ｇ、脱水剤モレキュラーシーブ４Ａ（脱水剤）１．２ｇ、及びＫＳ－１２６０（ジブチルスズジラウレート、堺化学工業株式会社製）１．４ｇを仕込み、カーボンブラックの塊がなくなるまで、室温（２５℃）で３０分間撹拌した。次いで、内容物が１００℃となるまで混練容器を加熱し、真空ポンプにより混練容器内部が２．７ｋＰａ（２０ｍｍＨｇ）になるまで減圧して、内容物を１時間撹拌した。内容物の温度を４０℃になるまで冷却し、これを硬化剤とした。 [Preparation of adhesive set]
<Example 1>
(Main agent)
Hexamethylene diisocyanate isocyanurate trimerate (trade name: Sumijuru N3300, manufactured by Sumika Bayer Urethane Co., Ltd.) 10.2 g, N-phenyl-3-aminopropyltrimethoxysilane (trade name:) KBM-573 (manufactured by Shin-Etsu Chemical Co., Ltd.) (3.5 g) and DINP (diisononyl phthalate) (6.8 g) were added and stirred for 10 minutes to obtain the main agent of Example 1.
(Hardener)
Exenol 2020 (polypropylene glycol, manufactured by Asahi Glass Co., Ltd., number average molecular weight: 2000, number of functional groups: 2) 20.0 g, UH-2000 (acrylic) in a kneading container with a stirrer, nitrogen introduction pipe, vacuum pump, and heating / cooling device. Polypropylene (hydroxyl-containing acrylic polymer), manufactured by Toa Synthetic Co., Ltd., number average molecular weight: 11000, number of functional groups: 2 or more) 80.0 g, EDP-1100 (polypropylene glycol, manufactured by ADEKA Co., Ltd., number average molecular weight: 260, functional Number of groups: 4) 2.4 g, Monarch 460 (carbon black, manufactured by Cabot Corporation) 35.1 g, Iceberg (baked kaolin, manufactured by Shiraishi Calcium Co., Ltd.) 22.6 g, DINP (diisononyl phthalate) 29.3 g, BHT Add 0.4 g of (dibutylhydroxytoluene), 1.2 g of polymer sieve 4A (dehydrating agent), and 1.4 g of KS-1260 (dibutyltin dilaurate, manufactured by Sakai Chemical Industry Co., Ltd.) until the carbon black lumps disappear. , Stirred at room temperature (25 ° C.) for 30 minutes. Next, the kneading container was heated until the content reached 100 ° C., the pressure was reduced to 2.7 kPa (20 mmHg) inside the kneading container by a vacuum pump, and the content was stirred for 1 hour. The temperature of the contents was cooled to 40 ° C., which was used as a curing agent.
＜比較例１＞
（主剤）
　実施例１の主剤をそのまま比較例１の主剤として用いた。
（硬化剤）
　８０．０ｇのＵＨ－２０００を、８０．０ｇのエクセノール８３７（ポリプロピレングリコール、旭硝子株式会社製、数平均分子量：６０００、官能基数：３）に変更した以外は、実施例１の硬化剤と同様にして、比較例１の硬化剤を得た。 <Comparative example 1>
(Main agent)
The main agent of Example 1 was used as it was as the main agent of Comparative Example 1.
(Hardener)
The same as the curing agent of Example 1 except that 80.0 g of UH-2000 was changed to 80.0 g of Excelol 837 (polypropylene glycol, manufactured by Asahi Glass Co., Ltd., number average molecular weight: 6000, number of functional groups: 3). The curing agent of Comparative Example 1 was obtained.
　上述の主剤及び硬化剤を用いて、ノンプライマー接着性を以下に示す方法によって評価した。なお、主剤及び硬化剤の混合質量比は１：１とした。 The non-primer adhesiveness was evaluated by the method shown below using the above-mentioned main agent and curing agent. The mixed mass ratio of the main agent and the curing agent was 1: 1.
［ノンプライマー接着性］
（基材の作製）
　基材として、オレフィン系熱可塑性エラストマー基材（バックドアのインナー基材）及びガラス長繊維強化ポリプロピレン基材（バックドアのアウター基材）を準備し、ガラス長繊維強化ポリプロピレン基材のみに対してフレーム処理を行った。まず、前処理として、当該基材の表面を、イソプロパノールを用いて脱脂した。次いで、脱脂した基材の表面に対して、フレーム処理を行った。フレーム処理は、ブンゼンバーナー（商品名、ワーゼフ株式会社製）によって、プロパンガスを用いて行い、処理速度を８０ｍｍ／ｓとした。基材に対して、１～５回の範囲でフレーム処理を行い、基材の表面状態が異なる基材を作製した。ガラス長繊維強化ポリプロピレン基材の表面張力は、未処理、１回、２回、３回、４回、及び５回において、それぞれ３００μＮ／ｃｍ（３０ｄｙｎ／ｃｍ）、３５０μＮ／ｃｍ（３５ｄｙｎ／ｃｍ）、４２０μＮ／ｃｍ（４２ｄｙｎ／ｃｍ）、５４０μＮ／ｃｍ（５４ｄｙｎ／ｃｍ）、６５０μＮ／ｃｍ（６５ｄｙｎ／ｃｍ）、及び７２０μＮ／ｃｍ（７２ｄｙｎ／ｃｍ）であった。なお、表面張力の測定は、和光純薬株式会社製ぬれ張力試験用混合液Ｎｏ．３０、Ｎｏ．３５、Ｎｏ．４２、Ｎｏ．５４、Ｎｏ．６５、水（７２０μＮ／ｃｍ（７２ｄｙｎ／ｃｍ））を用い、ＪＩＳ　Ｋ６７６８：１９９９に準じて行った。 [Non-primer adhesiveness]
(Preparation of base material)
As a base material, an olefin-based thermoplastic elastomer base material (inner base material of the back door) and a glass long fiber reinforced polypropylene base material (outer base material of the back door) are prepared, and only for the glass long fiber reinforced polypropylene base material. Frame processing was performed. First, as a pretreatment, the surface of the base material was degreased with isopropanol. Next, the surface of the degreased base material was frame-treated. The frame processing was performed by a Bunsen burner (trade name, manufactured by Wazef Co., Ltd.) using propane gas, and the processing speed was set to 80 mm / s. The base material was frame-treated 1 to 5 times to prepare base materials having different surface states. The surface tension of the glass long fiber reinforced polypropylene base material was 300 μN / cm (30 dyn / cm) and 350 μN / cm (35 dyn / cm), respectively, in the untreated, 1, 2, 3, 4, and 5 times. , 420 μN / cm (42 dyn / cm), 540 μN / cm (54 dyn / cm), 650 μN / cm (65 dyn / cm), and 720 μN / cm (72 dyn / cm). The surface tension was measured by Wako Pure Chemical Industries, Ltd.'s Wetting Tension Test Mixing Solution No. 30, No. 35, No. 42, No. 54, No. 65, using water (720 μN / cm (72 dyn / cm)), the procedure was carried out according to JIS K6768: 1999.
（ナイフカット試験）
　上述の実施例１及び比較例１の主剤及び硬化剤を混合して得られた混合物を、作製した基材に厚みが５ｍｍとなるように塗布し、塗布した基材を２３℃、５０％ＲＨ（相対湿度）で７２時間養生することによって試験体を作製した。各試験体を、養生後の混合物（接着剤）をナイフでカットし、カット部分を手で摘まんで引っ張ることによって剥離させ、その剥離状態を観察した（ナイフカットによる手剥離試験）。なお、表１中、「ＣＦ１００」は、養生後の混合物（接着剤）が、接着面の全域（１００％）において凝集破壊が発生したことを示し、「ＡＦ１００」は、養生後の混合物（接着剤）が、接着面の全域（１００％）において界面破壊が発生したことを示す。表１中、「ＣＦ」及び「ＡＦ」の両方が記載されているものは、それぞれ接着面に対して記載されている数値の割合で凝集破壊及び界面破壊が発生したことを示す。なお、本試験においては、接着面に対する凝集破壊の割合が大きいほど、ノンプライマー接着性に優れることを意味する。 (Knife cut test)
The mixture obtained by mixing the main agent and the curing agent of Example 1 and Comparative Example 1 described above was applied to the prepared base material so as to have a thickness of 5 mm, and the applied base material was applied at 23 ° C. and 50% RH. Specimens were prepared by curing at (relative humidity) for 72 hours. Each test piece was peeled off by cutting the cured mixture (adhesive) with a knife, picking the cut portion by hand and pulling it, and observing the peeling state (hand peeling test by knife cutting). In Table 1, "CF100" indicates that the mixture (adhesive) after curing caused cohesive failure in the entire area (100%) of the adhesive surface, and "AF100" indicates the mixture (adhesive) after curing. The agent) indicates that interfacial fracture occurred over the entire adhesive surface (100%). In Table 1, when both "CF" and "AF" are described, it indicates that cohesive fracture and interfacial fracture occurred at the ratio of the numerical values described with respect to the adhesive surface, respectively. In this test, the larger the ratio of cohesive failure to the adhesive surface, the better the non-primer adhesiveness.
　材料の配合組成を表１に示し、評価結果を表２に示す。 Table 1 shows the compounding composition of the materials, and Table 2 shows the evaluation results.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２に示すとおり、（ｃ－１）成分を含むポリオールを含有する硬化剤を用いた実施例１の接着剤セットは、このような硬化剤を用いなかった比較例１の接着剤セットに比べて、フレーム処理回数の異なる基材に対する接着剤のノンプライマー接着性に優れていた。これらの結果から、本発明の接着剤セットは、幅広い処理条件でフレーム処理が施された基材に対しても、優れたノンプライマー接着性を有する接着剤を調製することが可能であることが確認された。 As shown in Table 2, the adhesive set of Example 1 using the curing agent containing the polyol containing the component (c-1) is compared with the adhesive set of Comparative Example 1 not using such a curing agent. As a result, the non-primer adhesiveness of the adhesive to the substrates with different number of frame treatments was excellent. From these results, it can be seen that the adhesive set of the present invention can prepare an adhesive having excellent non-primer adhesiveness even on a substrate that has been frame-treated under a wide range of treatment conditions. confirmed.

Claims (3)

  1. 　主剤と硬化剤とで構成される接着剤セットであって、
    　前記主剤が、末端基としてイソシアネート基を有するウレタンプレポリマーを含有し、
    　前記硬化剤が、アクリルポリオールを含むポリオールを含有する、接着剤セット。     An adhesive set consisting of a main agent and a curing agent.
    The main agent contains a urethane prepolymer having an isocyanate group as a terminal group,
    An adhesive set in which the curing agent contains a polyol containing an acrylic polyol.
  2. 　請求項１に記載の接着剤セットにおける前記主剤と前記硬化剤とを混合して得られる混合物を介して、第１の基材と第２の基材とを貼り合わせて構造体を得る工程を備える、構造体の製造方法。 A step of laminating a first base material and a second base material to obtain a structure via a mixture obtained by mixing the main agent and the curing agent in the adhesive set according to claim 1. A method for manufacturing a structure.
  3. 　前記第１の基材及び前記第２の基材の少なくとも一方が、ポリプロピレン基材である、請求項２に記載の構造体の製造方法。 The method for producing a structure according to claim 2, wherein at least one of the first base material and the second base material is a polypropylene base material.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000248238A (en) * 1999-03-03 2000-09-12 Sekisui Chem Co Ltd Adhesive sheet
JP2004131625A (en) * 2002-10-11 2004-04-30 Yokohama Rubber Co Ltd:The Two-pack curable composition
JP2008248152A (en) * 2007-03-30 2008-10-16 Dic Corp Moisture-hardening polyurethane hot-melt adhesive and fixture material using it
JP2010501649A (en) * 2006-08-18 2010-01-21 ピーピージー インダストリーズ オハイオ， インコーポレイテッド Multi-layer composite formed from a composition having improved adhesion
JP2010168549A (en) * 2008-12-25 2010-08-05 Cemedine Co Ltd Urethane-based resin, method for producing the same and urethane-based resin composition
JP2012011677A (en) * 2010-06-30 2012-01-19 Dainippon Printing Co Ltd Thermal-transfer film and hard coat body using the same
JP2018021104A (en) * 2016-08-02 2018-02-08 横浜ゴム株式会社 Two-pack curable urethane adhesive composition

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011026418A (en) 2009-07-24 2011-02-10 Toyo Ink Mfg Co Ltd Adhesive composition and pressure-sensitive adhesive laminate obtained by using the same
CN102858898B (en) 2010-03-31 2014-10-08 琳得科株式会社 Adhesive sheet
JP5718515B1 (en) 2014-01-23 2015-05-13 古河電気工業株式会社 Adhesive tape for protecting semiconductor wafer surface and method for processing semiconductor wafer
US10793758B2 (en) 2014-06-03 2020-10-06 The Yokohama Rubber Co., Ltd. Two-pack type urethane-based adhesive composition
JP2020083901A (en) 2018-11-15 2020-06-04 ライオン・スペシャリティ・ケミカルズ株式会社 Adhesive and adhesive sheet

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000248238A (en) * 1999-03-03 2000-09-12 Sekisui Chem Co Ltd Adhesive sheet
JP2004131625A (en) * 2002-10-11 2004-04-30 Yokohama Rubber Co Ltd:The Two-pack curable composition
JP2010501649A (en) * 2006-08-18 2010-01-21 ピーピージー インダストリーズ オハイオ， インコーポレイテッド Multi-layer composite formed from a composition having improved adhesion
JP2008248152A (en) * 2007-03-30 2008-10-16 Dic Corp Moisture-hardening polyurethane hot-melt adhesive and fixture material using it
JP2010168549A (en) * 2008-12-25 2010-08-05 Cemedine Co Ltd Urethane-based resin, method for producing the same and urethane-based resin composition
JP2012011677A (en) * 2010-06-30 2012-01-19 Dainippon Printing Co Ltd Thermal-transfer film and hard coat body using the same
JP2018021104A (en) * 2016-08-02 2018-02-08 横浜ゴム株式会社 Two-pack curable urethane adhesive composition

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