JP6035953B2 - Urethane adhesive composition - Google Patents

Description

  The present invention relates to a urethane adhesive composition.

  Steel plates are generally used for the interior and exterior parts of automobiles such as automobile bodies, front doors, rear doors, back doors, front bumpers, rear bumpers, and locker moldings. In parts, materials made of olefin resins such as plastics and polypropylene resins are increasingly used.

  In automobile assembly work, when olefin-based resins such as plastic and polypropylene resin are used as interior and exterior parts for automobiles, sufficient adhesion may not be obtained even if the interior and exterior parts are bonded with an adhesive alone. Many.

  Therefore, for the purpose of improving the adhesive strength between the interior and exterior parts of an automobile, the primer surface is usually subjected to a dry treatment such as frame treatment or corona treatment on the adhesive surface of the interior or exterior part of an automobile in advance. Application is performed, and an adhesive or the like is applied thereon to ensure sufficient adhesion.

  As a primer composition used before applying an adhesive to the adhesion surface of an interior / exterior part of an automobile, for example, a primer composition as disclosed in Patent Documents 1 and 2 has been proposed.

  Patent Document 1 describes that a thermosetting epoxy primer layer containing aluminum trihydrogenphosphate and zinc oxide is provided between an adhesive surface and adhesive polyethylene. Patent Document 2 describes a primer composition containing an isocyanate component and a phosphate containing aluminum dihydrogen triphosphate, and having sufficient adhesive force even with difficult-to-adhere materials such as polyolefins and high solid paints. Yes.

JP-A-8-184034 JP-A-5-320536

  However, sufficient adhesion may not be ensured even when a primer composition is used for bonding between interior and exterior parts of an automobile formed using a material comprising an olefin resin such as plastic or polypropylene resin.

  In particular, in the adhesion with olefin resin, in order to improve adhesion, surface treatment such as flame treatment, corona treatment, plasma treatment, and intro treatment is generally applied to the adhesion surface, and then the primer is applied and adhered. The agent is applied. That is, it was necessary to perform the treatment twice before applying the adhesive. For this reason, there is a demand for an adhesion method that can save as much work as possible.

  In view of the above problems, an object of the present invention is to provide a urethane adhesive composition that has stable and excellent adhesion to an adherend without applying a primer composition.

（２） フレーム処理、コロナ処理、プラズマ処理、イトロ処理の何れかで表面処理を施したオレフィン樹脂の接着面に塗布されることを特徴とする上記（１）に記載のウレタン接着剤組成物。 The present invention includes the following (1) to (2).
(1) a main agent containing a silane-modified isocyanate and a urethane prepolymer represented by the following general formula (3) ;
A curing agent containing rosin polyol;
Have
The content of the silane-modified isocyanate is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the main agent,
Content of the said rosin polyol is 1 to 40 mass parts with respect to 100 mass parts of said hardening | curing agents, The urethane adhesive composition characterized by the above-mentioned.

(2) The urethane adhesive composition as described in (1) above, which is applied to an adhesive surface of an olefin resin which has been subjected to surface treatment by any one of flame treatment, corona treatment, plasma treatment and itro treatment.

  According to the present invention, it is possible to stably and excellently adhere to an adherend without applying a primer composition.

FIG. 1 is a view showing a pair of test bodies used in the present example and the comparative example.

  The present invention will be described in detail below. The present invention is not limited by the following modes for carrying out the invention (hereinafter referred to as embodiments). In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those in a so-called equivalent range. Furthermore, the constituent elements disclosed in the following embodiments can be appropriately combined.

  The urethane adhesive composition according to the present embodiment (hereinafter referred to as “the composition of the present embodiment”) has a main component containing a silane-modified isocyanate and a curing agent containing a rosin polyol. It is.

  The urethane adhesive composition of this embodiment is a two-component mixed type containing a main agent and a curing agent. Compared to a one-component system, the two-component mixed adhesive composition is capable of rapid curing and is excellent in strength development because of rapid internal curing.

<Main agent>
The main agent contained in the composition of this embodiment contains a silane-modified isocyanate.

(Silane-modified isocyanate)
The silane-modified isocyanate (hereinafter also referred to as “adhesion imparting agent”) contained in the main component of the composition of the present embodiment is not particularly limited as long as it is a silane-modified isocyanate obtained by modifying an isocyanate compound with a silane compound. Examples of the silane-modified isocyanate include hexamethylene diisocyanate burette (HDI burette) having the structure represented by the following formula (1) and 3- (N-phenyl) having the structure represented by the following formula (2). Preferable is an isocyanate silane compound represented by the following formula (3) which is a reaction product with aminopropyltrimethoxysilane. The silane-modified isocyanate is modified with one 3- (N-phenyl) aminopropyltrimethoxysilane of the following formula (2), one of the three NCOs in the molecule of the HDI burette body of the following formula (1). Thus, it is modified with isocyanate silane.

  The silane-modified isocyanate comprises an HDI burette and 3- (N-phenyl) aminopropyltrimethoxysilane, and an isocyanate group / amino group (NCO group / NH group) of 1.5 / 1.0 to 9.0 / It is obtained by adding within the range of 1.0 or less. NCO group / NH group refers to the ratio of isocyanate groups in HDI per amino group in 3- (N-phenyl) aminopropyltrimethoxysilane.

  The NCO group / NH group reacts with HDI burette and 3- (N-phenyl) aminopropyltrimethoxysilane in a range of 1.5 / 1.0 to 9.0 / 1.0. However, it is preferably 1.5 / 1.0 to 6.0 / 1.0, and more preferably 3.0 / 1.0 to 6.0 / 1.0. If the NCO group / NH group is within the above range, the adhesion of the adhesion-imparting agent is sufficiently exhibited. At this time, an unreacted HDI burette body may remain.

  The content of the silane-modified isocyanate is 1 part by mass or more and 10 parts by mass or less, preferably 1.5 parts by mass or more and 8 parts by mass or less, more preferably 1.5 parts by mass or more with respect to 100 parts by mass of the main agent. 5 parts by mass or less. When the content of the silane-modified isocyanate is less than 1 part by mass, the effect of improving the adhesion performance cannot be obtained, and when it exceeds 10 parts by mass, the cured product of the composition of the present embodiment becomes hard and easily foamed, Cost increases. When the content of the silane-modified isocyanate is within the above range, the composition of the present embodiment is stable without using a primer composition for an adherend made of a material such as an olefin resin such as a polypropylene resin. And has excellent adhesion.

  The production of silane-modified isocyanate can be carried out in the same manner as in the production of ordinary polyurethane. For example, a reaction between HDI burette of the above-mentioned equivalent ratio and 3- (N-phenyl) aminopropyltrimethoxysilane is performed. It can carry out by stirring at the temperature of 50 to 60 degreeC. Moreover, urethanation catalysts, such as an organic tin compound, organic bismuth, and an amine, etc. can also be used as needed.

  The silane-modified isocyanate contained in the main component of the composition of the present embodiment has an action as an adhesion promoter.

  The composition of this embodiment contains a silane-modified isocyanate as a main component, and thus has stable and excellent adhesiveness without using a primer composition for an adherend. In particular, the composition of the present embodiment has excellent adhesion to an adherend made of a material such as an olefin resin such as a polypropylene resin. That is, it is considered that the adhesiveness is excellent because the compatibility is changed by containing the silane-modified isocyanate and the silane-modified isocyanate easily moves to the interface. When the surface of an adherend made of a non-polar polymer material such as an olefin resin such as polypropylene resin is dry-treated, any one of a carbonyl group, a hydroxyl group, and a carboxyl group is formed on the surface and has polarity. It is considered that the isocyanate group imparts high adhesiveness to these polar groups. Moreover, since a phenyl group couple | bonds a nitrogen atom with a silane modification isocyanate directly, it is thought that high adhesiveness is provided by the steric hindrance and the electron withdrawing effect.

(Urethane prepolymer)
The composition of this embodiment can contain the urethane prepolymer containing an isocyanate compound in the main ingredient. The urethane prepolymer contained in the main component of the composition of the present embodiment is a prepolymer containing a plurality of isocyanate groups in the molecule at the molecular ends. The urethane prepolymer is preferably liquid at room temperature from the viewpoint of handling. The method for producing the urethane prepolymer is not particularly limited, and conventionally known methods can be mentioned. The urethane prepolymer is, for example, a reaction product obtained by reacting a polyisocyanate compound and a polyol compound so that isocyanate groups (NCO groups) are excessive with respect to hydroxy groups (OH groups). The urethane prepolymer generally contains 0.5% by mass or more and 10% by mass or less of NCO groups at the molecular ends. This isocyanate group may be bonded to either an aromatic hydrocarbon or an aliphatic hydrocarbon.

The polyisocyanate compound used when producing the urethane prepolymer is not particularly limited as long as it has two or more isocyanate groups in the molecule. Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (4,4 ' -MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, tolidine Aromatic polyisocyanates such as diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), triphenylmethane triisocyanate; Aliphatic polyisocyanates such as xamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate (NBDI); transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), bis (isocyanate methyl) ) Cycloaliphatic polyisocyanates such as cyclohexane (H ₆ XDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI); polyisocyanate compounds such as polymethylene polyphenylene polyisocyanate; carbodiimide-modified polyisocyanates of these isocyanate compounds; these isocyanate compounds Isocyanurate-modified polyisocyanates; these isocyanates Urethane prepolymer obtained a polyol compound to be described later compound is reacted; and the like. These polyisocyanate compounds can be used alone or in combination of two or more.

  The polyol compound used when producing the urethane prepolymer is not particularly limited, and may be, for example, any of polyether polyol, polyester polyol, acrylic polyol, polycarbonate polyol, and other polyols. These polyols can be used alone or in combination of two or more. Specific examples of the polyol compound include polypropylene ether diol, polyethylene ether diol, polypropylene ether triol, polytetramethylene glycol, polyethylene glycol (PEG), polypropylene glycol (PPG), polyoxyethylene glycol, polyoxypropylene glycol, polyoxy Propylene triol, polyoxybutylene glycol, polytetramethylene ether glycol (PTMG), polymer polyol, poly (ethylene adipate), poly (diethylene adipate), poly (propylene adipate), poly (tetramethylene adipate), poly (hexamethylene adipate) ), Poly (neopentylene adipate), poly-ε-caprolactone, poly (hexamethylene carbonate) Sulfonate), silicone polyol, and the like. A natural polyol compound such as castor oil may be used.

  The amount ratio of the polyol and the polyisocyanate in producing the urethane prepolymer is, for example, such that the equivalent ratio of the isocyanate group in the polyisocyanate to the hydroxy group in the polyol (NCO group / OH group) is 1.2 to 2. 2 is preferable, and 1.5 to 1.8 is more preferable.

  The number average molecular weight of the urethane prepolymer is 2000 or more, preferably 2000 or more and 15000 or less, and more preferably 2000 or more and 10,000 or less.

  As a 1-component moisture hardening type urethane adhesive containing the isocyanate compound contained in the main ingredient of the composition of the present embodiment, for example, WS-292 manufactured by Yokohama Rubber Co., Ltd. can be used. WS-292 adds carbon black as a reinforcing agent to the urethane prepolymer, calcium carbonate and a catalyst as fillers, and adheres to the interior and exterior parts of automobiles for the purpose of adhering the interior and exterior parts of automobiles. Is a one-component moisture-curing urethane adhesive. However, in order to use WS-292, it is necessary to apply a dedicated primer to the adhesive surface in advance.

<Curing agent>
The curing agent contained in the composition of this embodiment contains rosin polyol.

(Rosin polyol)
The rosin polyol contained in the curing agent of the composition of the present embodiment is not particularly limited as long as it is a rosin-modified polyol having a rosin skeleton in the molecule. Polyols having a rosin component in the molecule are referred to as rosin polyols. For this, a skeleton excluding the rosin component is a polyether type such as PPG, a condensed polyester polyol, a lactone polyester polyol, and a polycarbonate diol. There are some polyester types. Examples of the rosin polyol include a rosin ester obtained by reacting rosin and a polyhydric alcohol; an epoxy-modified rosin ester obtained by reacting rosin and an epoxy compound; a modified compound having a hydroxyl group such as a polyether having a rosin skeleton. Examples include rosin.

  Examples of the rosin component include abietic acid and its derivatives, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, dibietic acid, neoabietic acid, levopimaric acid and other pimaric acid resin acids, and hydrogenated water. Examples thereof include adjunct rosin and disproportionated rosin obtained by disproportionating these.

  Examples of commercially available rosin polyols include D-6011, KE-601, KE-615-3, KE-622, KE-623, and KE-624 manufactured by Arakawa Chemical Industries, Ltd.

  Among these, for example, the above-mentioned D-6011 is obtained by reacting a rosin component and a bisphenol A type epoxy resin, and is a rosin diol having approximately two rosin skeletons and two hydroxyl groups in the molecule. . Further, the above KE-615-3 and the like are ester type polyols having an aliphatic polyester structure having a rosin component in the molecule and a part of the skeleton being an aromatic polyester. These rosin polyols can be suitably used for the composition of this embodiment.

  The content of the rosin polyol is 1 part by mass or more and 40 parts by mass or less, and preferably 10 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the curing agent. When the content of the rosin polyol is within the above range, the composition of the present embodiment improves the initial adhesion to an adherend made of a material such as an olefin resin such as a polypropylene resin. Even if it does not perform, it can adhere | attach stably and can promote bridge | crosslinking of a urethane resin. For this reason, the composition of the present embodiment also applies a dedicated primer to an adherend made of a material such as an olefin resin such as a polypropylene resin whose surface is subjected to surface treatment such as frame treatment or corona treatment. Adheses well without.

(Polyol compound)
The composition of this embodiment may contain a polyol compound in the curing agent. Although the polyol compound contained in a hardening | curing agent is not specifically limited, For example, polybutadiene diol is mentioned suitably from water resistance, adhesiveness, a physical property, etc.

  Since the composition of this embodiment can improve the initial adhesiveness by including rosin polyol in the curing agent, the adhesive composition can stably and excellently adhere to an adherend without using a primer composition. Have. In particular, the composition of the present embodiment has excellent adhesion because it can improve initial adhesion to an adherend made of a material such as olefin resin such as polypropylene resin. That is, in order to improve the adhesiveness of the adhesive composition to the adherend, it is necessary that the main agent and the curing agent molecules, that is, the polar groups of the main agent and the curing agent molecules be close to each other. In order to allow the main agent and the curing agent to approach each other and advance the urethane bond, it is preferable to add a molecule having polarity to the curing agent. Thereby, the reaction of the urethane bond can be promoted by bringing the main agent and the curing agent close to each other. When the surface of an adherend made of a non-polar polymer material such as an olefin resin such as polypropylene resin is dry-treated, any one of a carbonyl group, a hydroxyl group, and a carboxyl group is formed on the surface and has polarity. Since the rosin polyol has a rosin skeleton in the molecule, a terminal is a hydroxyl group, and has polarity, the surface of the adherend that has been subjected to the dry treatment can easily approach the molecules of the main agent and the curing agent. As a result, since the surface of the adherend composed of a non-polar polymer material such as an olefin resin such as polypropylene resin is dry-treated, the main agent and the curing agent molecules easily approach the surface. The object can stably have excellent adhesiveness even if the primer composition is not previously applied to the adherend.

(filler)
The composition of this embodiment may contain a filler in the main agent and the curing agent. The filler contained in the main agent and the curing agent is not particularly limited. For example, calcium carbonate, aluminum hydroxide, carbon black, white carbon, silica, glass, kaolin, talc (magnesium silicate), fumed silica, precipitated Silica, anhydrous silicic acid, hydrous silicic acid, clay, calcined clay, bentonite, glass fiber, asbestos, glass filament, ground quartz, diatomaceous earth, aluminum silicate, zinc oxide, magnesium oxide, titanium oxide, or surface treatment thereof Inorganic fillers such as carbonates; carbonates, organic bentonite, high styrene resin, coumarone-indene resin, phenol resin, formaldehyde resin, modified melamine resin, cyclized rubber, lignin, ebonite powder, shellac, cork powder, bone powder, wood powder , Cellulose powder, co Organic fillers such as nut palm, wood pulp, etc .; inorganic pigments such as lamp black, titanium white, bengara, titanium yellow, zinc white, red lead, cobalt blue, iron black, aluminum powder and neozabon black RE, neoblack RE And organic pigments such as Orazole Black CN, Orazole Black Ba (all manufactured by Ciba-Geigy) and Spiron Blue 2BH (manufactured by Hodogaya Chemical Co., Ltd.). Of these, carbon black and calcium carbonate are preferably used in order to impart desired characteristics. These carbon black and calcium carbonate are not particularly limited, and commercially available products can be used. For example, carbon black includes N110, N220, N330, N550, N770, etc., or a mixture thereof according to the American Society for Testing Materials standard, and calcium carbonate includes heavy calcium carbonate, precipitated calcium carbonate, and the like. These fillers can be used singly or in combination of two or more.

(catalyst)
The composition of this embodiment may contain a catalyst in the main agent and the curing agent. The catalyst is not particularly limited as long as it can react with the polymer contained in the main agent and the curing agent.

  The catalyst is not particularly limited, for example, stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin dimaleate, dibutyltin bisacetylacetonate, dibutyltin silylate, Metal catalysts such as bismuth octylate; divalent organic tin compounds such as tin octoate, tin octylate, tin butanoate, tin naphthenate, tin caprylate, tin oleate; dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin Diacetate, Dibutyltin dimaleate, Dibutyltin distearate, Dibutyltin dioleate, Dioctyltin dilaurate, Dioctyltin diversate, Diphenyltin diacetate, Dibutyltin dimethoxide, Dibutyltin oxide, Dib Tetravalent organic tin compounds such as rutin bis (triethoxysilicate), a reaction product of dibutyltin oxide and phthalate; dibutyltin bis (acetylacetonate), tin-based chelate compound; butylamine, hexylamine, octylamine , Dodecylamine, oleylamine, cyclohexylamine, benzylamine and other primary amines; dibutylamine and other secondary amines; diethylenetriamine, triethylenetetramine, guanidine, diphenylguanidine, xylylenediamine and other polyamines; triethylenediamine and its derivatives Cyclic amines such as 2-methyltriethylenediamine, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo [5.4.0] -7-undecene; monoethano Amino alcohol compounds such as ruamine, diethanolamine and triethanolamine; amine compounds such as aminophenol compounds such as 2,4,6-tris (dimethylaminomethyl) phenol and carboxylates thereof; fourth compounds such as benzyltriethylammonium acetate; Secondary ammonium salt; low molecular weight amide resin obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound. Among these, a tin-based catalyst and an amine-based catalyst are preferable from the viewpoint of having a small amount and a large catalytic ability. These catalysts can be used singly or in combination of two or more.

  The composition according to this embodiment can be obtained by mixing the above-described essential components. The composition of this embodiment can contain an additive as needed, in addition to the above-mentioned essential components, as long as a suitable pot life can be secured during mixing. Examples of additives include amine-based curing agents having active hydrogen, amino alcohols, water, plasticizers, reactive diluents, thixotropic agents, silane coupling agents, pigments, dyes, anti-aging agents, and antioxidants. , Antistatic agents, flame retardants, drying oils, adhesion-imparting agents, dispersants, dehydrating agents, ultraviolet absorbers, solvents and the like. Two or more of these may be contained. The additives and the like can be kneaded by a general method to obtain a composition, which can be used for vulcanization or crosslinking. The blending amounts of these additives can be conventional conventional blending amounts as long as the object of the present embodiment is not violated.

  The method for producing the composition of the present embodiment is not particularly limited. For example, a method of sufficiently mixing the main agent, the curing agent, and an optional component using a rotary mixer, a static mixer, or the like can be used.

  Thus, the composition of the present embodiment is a urethane adhesive composition having a main agent containing a silane-modified isocyanate and a curing agent containing a rosin polyol. The main agent contains a predetermined amount of silane-modified isocyanate and the curing agent contains a predetermined amount of rosin polyol, so that it has stable and excellent adhesiveness even when the primer composition is not applied to the surface of the adherend. Can do. In addition, the composition of the present embodiment has a primer composition on the surface of the adherend even when the olefin resin adherend is subjected to surface treatment such as flame treatment, corona treatment, plasma treatment, and itro treatment. Even when it is not applied, it can have stable and excellent adhesiveness as well. In addition, the composition of the present embodiment is particularly applied by applying the composition of the present embodiment after performing surface treatment on the adhesion surface of the olefin resin by any one of flame treatment, corona treatment, plasma treatment, and itro treatment. Therefore, even when the primer composition is not applied to the surface of the adherend, excellent adhesiveness can be stably obtained.

  The usage method of the composition of this embodiment is not specifically limited. For example, after sufficiently mixing the above main agent and curing agent using a rotary mixer, static mixer, etc., after applying to the adherend, it is bonded to the non-adherent, and both adherends are pressure-bonded and bonded. Form a structure.

  The composition of this embodiment is mainly used as an adhesive composition to be applied to objects to be bonded such as automobile interior and exterior parts such as automobile bodies, front doors, rear doors, back doors, front bumpers, rear bumpers, and rocker moldings. be able to. The composition of the present embodiment is an object to be bonded formed by using a material such as an olefin resin such as plastic or polypropylene resin subjected to surface treatment such as flame treatment, corona treatment, plasma treatment, and intro treatment. Since it can improve adhesiveness to an object, it can be suitably used. In addition, the composition of the present embodiment can be suitably used as an adhesive composition for automobile structures (adhesion of resin-resin, metal-resin, etc.) and window sealant. The method for applying the adhesive composition to the object to be bonded is not particularly limited. For example, a method of applying the adhesive composition to the object to be bonded with a brush or the like, or a method of applying with a gun can be appropriately selected.

  The composition of the present embodiment exhibits good adhesion to various substrates such as glass, plastic, metal, and has high adhesion after curing. Since the composition of this embodiment has such characteristics, it can be used as an adhesive for automobiles, vehicles (bullet trains, trains), ships, aircraft, architecture / civil engineering, electronics, space industry, and other industrial products. In particular, it can be suitably used as an adhesive for interior and exterior parts such as automobiles and vehicles (bullet trains, trains).

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

<Production of urethane prepolymer>
600 g of polypropylene ether triol having a number average molecular weight of 5000 (G-5000, trade name “EXCENOL5030”, manufactured by Asahi Glass Co., Ltd.), and 300 g of polypropylene ether diol having a number average molecular weight of 2000 (D-2000, trade name “EXCENOL2020”, Asahi Glass Co., Ltd.) Made into a flask, heated to 100 ° C. to 130 ° C., stirred while degassing, and dehydrated until the water content became 0.01% or less. Then, after cooling to 90 ° C. and adding diphenylmethane diisocyanate (MDI, trade name “Sumijoule 44S”, manufactured by Sumitomo Bayer Japan Co., Ltd.) so that NCOmol / OHmol = 1.70, nitrogen atmosphere was obtained for about 24 hours. The reaction was advanced below to produce urethane prepolymers shown in Table 1.

<Preparation of main agent>
Each component shown in Table 1 was blended in the blending amount (parts by mass) shown in the same table, and these were uniformly mixed for about 1 hour while degassing with a mixer. -1 to S-4) were produced. Table 1 shows the blending amount (parts by mass) of each component in each main ingredient.

Each component shown in Table 1 is as follows.
-Urethane prepolymer: Urethane prepolymer obtained above, manufactured by Yokohama Rubber Co., Ltd.-Isocyanate (HDI burette): Trade name "D-165N", manufactured by Mitsubishi Chemical Corporation-Silane modified isocyanate: Trade name "D- 165N ", a product of Mitsubishi Chemical Corporation, and a product name" Y9669 ", manufactured by Momentive Performance Materials Japan GK ・ Plasticizer: Diisononyl adipate (DINA), manufactured by J Plus Corporation ・ Carbon black : Product name “MA600”, manufactured by Mitsubishi Chemical Corporation ・ Calcium carbonate: Product name “Super S”, manufactured by Maruo Calcium Co., Ltd. ・ Amine catalyst: 2-methyltriethylenediamine, product name “ME-DABCO”, Air Products Japan Co., Ltd. -Tin catalyst: Dibutyltin diacetate, trade name " U-200 ", manufactured by Nitto Kasei Corporation

<Production of curing agent>
The polyol compound and rosin polyol shown in Table 2 were blended in the blending amounts (parts by mass) shown in the same table, and these were uniformly mixed for about 3 hours while heating to 90 ° C. with a mixer. And after melt | dissolving solid rosin resin, it cools, and each other component shown in Table 2 is thrown in, these are uniformly mixed for about 1 hour, degassing, and each hardening | curing agent shown in Table 2 ( B-1 to B-7) were produced. Table 2 shows the amount (parts by mass) of each component in each curing agent.

Each component shown in Table 2 is as follows.
Polyol compound 1 (trifunctional PPG): trade name “EXCENOL835”, number average molecular weight 6000, manufactured by Asahi Glass Co., Ltd. • Polyol compound 2 (bifunctional PPG): polybutadiene diol, trade name “R-45HT”, number average molecular weight 2600 , Idemitsu Kosan Co., Ltd. ・ Rosin polyol 1: Trade name “Pine Crystal D-6011”, rosin content 60%, Arakawa Chemical Industries, Ltd. ・ Rosin polyol 2: Trade name “KE-615-3”, containing rosin 40%, manufactured by Arakawa Chemical Industries, Ltd. ・ Carbon black: trade name “A2899”, manufactured by Asahi Carbon Co., Ltd. ・ Amine catalyst: 2-methyltriethylenediamine, trade name “ME-DABCO”, manufactured by Air Products Japan Co., Ltd. Tin catalyst: Dibutyltin diacetate, trade name “U-200”, Nitto Manufactured by forming Co., Ltd.

<Preparation of adhesive composition>
The main agent and curing agent obtained above were uniformly mixed at a blending ratio (main agent: curing agent) of 100: 10 to prepare the compositions of Examples and Comparative Examples shown in Tables 3 to 5. The blending amounts (parts by mass) of the components of the main agent and the curing agent shown in Tables 3 to 5 are those shown in Tables 1 and 2. Tables 3 to 5 show combinations of the main agent and the curing agent in Examples 1 to 36 and Comparative Examples 1 to 20.

<Evaluation>
About each composition of each Example and comparative example obtained above, the initial stage adhesiveness after hardening and evaluation of a fracture | rupture form were performed by the method shown below.

[Preparation of specimen]
FIG. 1 is a view showing a pair of test bodies used in the present example and the comparative example. As shown in FIG. 1, olefin resin plates 11 and 12 (25 mm × 150 mm × 3 mm) that have been subjected to frame treatment, ittro treatment, plasma treatment, or corona treatment in advance are prepared as adherends, and frame treatment, ittro treatment, Spacers (25 × 10 × 3 mm) 13 were provided between the plasma-treated or corona-treated olefin resin plates 11 and 12 in order to adjust the thickness of the adhesive composition to about 3 mm. Next, Examples 1 to 3 shown in Tables 3 to 5 are formed on the joint portion (25 × 10 mm) 14 on the opposite surface side between the olefin resin plates 11 and 12 that have been subjected to frame treatment, ittro treatment, plasma treatment, or corona treatment in advance. 36 and each of the adhesive compositions 15 of Comparative Examples 1 to 20 were respectively applied, and the olefin resin plates 11 and 12 that had been previously subjected to frame treatment, ittro treatment, plasma treatment, or corona treatment were pressure-bonded to form an adhesive structure, After curing at 60 ° C. for 30 minutes, curing was performed at 20 ° C. and 60% RH for 72 hours to cure the adhesive composition 15, thereby preparing a test body 16.

[Initial adhesion]
Evaluation of initial adhesiveness measured the shear strength using the test body 16. FIG. Moreover, the fracture | rupture form in a shear test was observed visually. The evaluation results are shown in Tables 3 to 5 below.

(Shear strength)
The shear strength was measured according to JIS K6850-1999 under the conditions of 20 ° C. and 60% RH at a tensile speed of 50 mm / min. Tables 3 to 5 show the measurement results.

(Destruction mode)
The evaluation of the fracture mode was performed by visually observing the fracture mode of each adhesive composition 15 after shearing the above-mentioned surface-treated olefin resin plates 11 and 12 in the shear strength test. For the evaluation of the fracture mode, the fracture of the adhesive itself with respect to the bonded area was represented by “CF”, and the ratio (%) of the area was represented by a number. The higher the proportion of CF, the better the adhesion. For example, the case where the ratio of the area of cohesive failure of the adhesive composition to the area of the adhesive surface was 100% (complete destruction of the adhesive) was described as “CF100”. Also, the one where the adhesive composition and the olefin resin as the adherend were peeled from each other was denoted as “AF”. It was evaluated that the higher the AF ratio, the poorer the adhesiveness. For example, the case where the ratio of the interface peeling (AF) area to the bonding area of the adhesive composition-olefin resin adherend was 100% (complete peeling) was expressed as “AF100”. Further, when the above two destruction states coexist, the ratio of the area is described as, for example, “CF50AF50”. The evaluation results of the fracture mode are shown in Tables 3 to 5 below.

(Adhesion evaluation criteria)
The case where the shear strength was 3.0 MPa or more and the fracture state was CF100 (complete adhesive fracture mode) was evaluated as good adhesion.

  From the results shown in Tables 3 to 5, all the adhesives of the test bodies 16 obtained using the adhesive compositions of Examples 1 to 36 were sheared after being cured at 20 ° C. and 60% RH for 72 hours. The strength was 3.1 MPa or more. Further, the fracture mode of the adhesive was all cohesive fracture CF100. Therefore, it was confirmed that the adhesives obtained using the adhesive compositions of Examples 1 to 36 are all excellent in initial adhesiveness. Moreover, from the results shown in Tables 3 and 4, for each surface treatment (frame treatment, itro treatment, plasma treatment, corona treatment) of the olefin resin, main agents S-1 to S-3 and curing agents B-1 to B-6. It was confirmed that the adhesives obtained by using the adhesive compositions of Examples 1 to 36 in which each of these were combined had good adhesiveness for any surface treatment.

  On the other hand, all of the adhesives of the test bodies 16 obtained using the adhesive compositions of Comparative Examples 1 to 20 have a shear strength of 2 after curing at 20 ° C. and 60% RH for 72 hours. It was 5 MPa or less, and the fracture mode of the adhesive was CF50AF50 to AF100. Moreover, the fracture | rupture form of the adhesive agent was interface peeling (AF) between the olefin resin plates 11 and 12 and the adhesive composition which were surface-treated in advance. Therefore, it was confirmed that all the adhesives obtained using the adhesive compositions of Comparative Examples 1 to 20 were inferior in initial adhesiveness.

  Therefore, each adhesive composition of Examples 1 to 36 is bonded to each of Comparative Examples 1 to 20 with respect to the olefin resin surface-treated by any of the frame treatment, corona treatment, plasma treatment, and itro treatment. Compared with the agent composition, it was found that the cured product had high strength and excellent adhesiveness.

  The composition of this embodiment is a urethane adhesive composition having a main agent containing a silane-modified isocyanate and a curing agent containing a rosin polyol, as in Examples 1 to 36. Thereby, the obtained adhesive composition can improve the initial adhesiveness, and even when the adhesive surface is subjected to a surface treatment, the adhesive surface is stably applied without applying the primer composition. It can be said that it has excellent adhesiveness. Therefore, it has been found that the composition of this embodiment can provide a highly reliable adhesive composition as an adhesive for interior and exterior parts of automobiles such as automobile bodies and back doors.

  As described above, since the adhesive composition according to the present invention has excellent adhesiveness, it can be used for automobiles, ships, aircraft, construction / civil engineering, and other industrial products. Suitable for use as an adhesive composition for bonding.

11, 12 Flame treatment, corona treatment, plasma treatment, or itro treatment olefin resin plate 13 Spacer 14 Joint 15 Adhesive composition 16 Specimen

Claims (2)

A main agent containing a silane-modified isocyanate and a urethane prepolymer represented by the following general formula (3) ;
A curing agent containing rosin polyol;
Have
The content of the silane-modified isocyanate is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the main agent,
Content of the said rosin polyol is 1 to 40 mass parts with respect to 100 mass parts of said hardening | curing agents, The urethane adhesive composition characterized by the above-mentioned.

  2. The urethane adhesive composition according to claim 1, wherein the urethane adhesive composition is applied to an adhesive surface of an olefin resin that has been subjected to surface treatment by any one of flame treatment, corona treatment, plasma treatment, and itro treatment.

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