JP2014080511A - Adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition stably having excellent adhesiveness to an adherend.SOLUTION: An adhesive composition contains a basis containing an urethane prepolymer and an isocyanate silane compound, and a curing agent containing a polyfunctional polyol compound obtained by denaturing a glycidyl amine type epoxy resin with a diol compound having a molecular weight of 200 or more and 3000 or less through a tin catalyst.

Description

  The present invention relates to an 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 rocker moldings. Parts such as plastics and polypropylene resins such as olefin resins are increasingly used for parts.

  In automobile assembly work, when plastic or polypropylene resin is used as an interior / exterior part of an automobile, sufficient adhesiveness is often not obtained even if the interior / exterior part is adhered by an adhesive alone. Moreover, since the adhesive agent used has many adhesion | attachment with the surroundings of glass, it is also necessary to adhere | attach both resin and glass.

  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.

Japanese Patent Laid-Open No. 1996-184034 Japanese Patent Laid-Open No. 1993-320536

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

  Moreover, carbon black etc. are generally mix | blended with the primer composition in order to improve adhesiveness. However, when carbon black or the like is blended, the adhesion surface is colored by the primer composition, so even if the interior and exterior parts of an automobile are directly adhered to each other without using the primer composition, stable and sufficient adhesion is achieved. There is a demand for an adhesive composition capable of ensuring the above.

  In view of the above problems, an object of the present invention is to provide an adhesive composition having stable and excellent adhesion to an adherend.

The present invention includes the following (1) to (4).
(1) a main agent containing a urethane prepolymer and an isocyanate silane compound;
A curing agent containing a polyfunctional polyol compound obtained by modifying a glycidylamine type epoxy resin with a diol compound having a molecular weight of 200 or more and 3000 or less by a tin catalyst;
An adhesive composition comprising:
(2) Content of the said tin catalyst is 0.5 mass part or more and 10 mass parts or less with respect to 100 mass parts of said diol compounds, The adhesive composition as described in said (1) characterized by the above-mentioned.
(3) The above (1), wherein the glycidyl group of the glycidylamine type epoxy resin and the hydroxyl group of the diol compound have a molar ratio of glycidyl group / hydroxyl group of ½ or more and 1/50 or less. The adhesive composition according to (2).
(4) The adhesive composition according to any one of (1) to (3), wherein the content of the isocyanate silane compound 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. .

  According to the present invention, it is possible to stably have excellent adhesion to an adherend.

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 adhesive composition according to the present embodiment (hereinafter referred to as “the composition of the present embodiment”) includes a main agent containing a urethane prepolymer and an isocyanate silane compound, and a glycidylamine type epoxy resin having a molecular weight of 200 or more. And a curing agent containing a polyfunctional polyol compound obtained by modification with a diol compound of 3000 or less with a tin catalyst.

<Main agent>
The main agent contained in the composition of this embodiment contains a urethane prepolymer and an isocyanate compound.

(Urethane prepolymer)
The urethane prepolymer contained in the main component of the composition of the present embodiment is a polymer 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 polyisocyanates; 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, polytetramethylene glycol, polyethylene glycol (PEG), polypropylene glycol (PPG), polyoxyethylene glycol, polyoxypropylene glycol, polyoxypropylene triol, poly Oxybutylene 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), silicone polyol, etc. 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.

(Isocyanate silane compound)
The isocyanate silane compound (hereinafter also referred to as “adhesion imparting agent”) contained in the main component of the composition of the present embodiment is a compound having an isocyanate group and a hydrolyzable silicon-containing group. The isocyanate silane compound can be obtained, for example, by reacting an isocyanate group-containing compound with a compound having a functional group capable of reacting with an isocyanate group and a hydrolyzable silicon-containing group. Specifically, as the isocyanate silane compound, for example, a diisocyanate such as hexamethylene diisocyanate (MDI) or tolylene diisocyanate (TDI) is reacted with a silane coupling agent such as aminoalkoxysilane or mercaptoalkoxysilane. The compound obtained etc. are mentioned suitably. The isocyanate silane compound is not particularly limited, but in the present embodiment, for example, an isocyanate silane compound having a structure represented by the following structural formula (1) (hereinafter simply referred to as the following structural formula (1)). Is referred to as an isocyanate silane compound). The isocyanate silane compound of the following structural formula (1) includes a hexamethylene diisocyanate burette body (hereinafter simply referred to as “HDI burette body”) having a structure represented by the following structural formula (2), and the following structural formula ( 3) Trimethoxy [3- (phenylamino) propyl] silane (hereinafter, simply referred to as “trimethoxy [3- (phenylamino) propyl] silane of the following structural formula (3)”) having the structure represented by 3). It is a reactant. The isocyanate silane compound of the following structural formula (1) is obtained by converting one of the three NCO groups in the molecule of the following HDI burette body to trimethoxy [3- (phenylamino) propyl] silane 1 of the following structural formula (3). It is modified by an individual to form an isocyanate silane.

  The isocyanate silane compound represented by the chemical formula (1) is obtained by combining the HDI burette body and the H trimethoxy [3- (phenylamino) propyl] silane represented by the chemical formula (3) with an isocyanate group / amino group (NCO group / NH group). Is added in the range of 1.5 / 1.0 to 9.0 / 1.0. NCO group / NH group refers to the ratio of NCO groups in HDI per NH group in trimethoxy [3- (phenylamino) propyl] silane.

  NCO group / NH group includes the above-mentioned HDI burette and the trimethoxy [3- (phenylamino) propyl] silane represented by the chemical formula (3) in the range of 1.5 / 1.0 to 9.0 / 1.0. Although it is made to react, it becomes like this. Preferably it is 1.5 / 1.0-6.0 / 1.0, More preferably, it is 3.0 / 1.0-6.0 / 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 isocyanate silane compound 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. If the content of the isocyanate silane compound is less than 1 part by mass, the effect of improving the adhesion performance cannot be obtained. When content of an isocyanate silane compound exceeds 10 mass parts, the hardened | cured material of the composition of this embodiment will become hard and it will become easy to foam. Moreover, the cost for producing the adhesive increases. When the content of the isocyanate silane compound is within the above range, the composition of the present embodiment is stable without using a primer composition on an adherend made of a material such as an olefin resin such as a polypropylene resin. And has excellent adhesion.

<Curing agent>
The curing agent contained in the composition of the present embodiment contains a polyfunctional polyol compound. The polyfunctional polyol compound is obtained by modifying a polyfunctional epoxy resin with a diol compound. The polyfunctional epoxy resin contains a glycidylamine type epoxy resin. The polyfunctional polyol compound can be represented as the following structural formula (4).

(Glycidylamine type epoxy resin)
The glycidylamine type epoxy resin is a kind of polyfunctional epoxy resin, and is a glycidylamine type epoxy resin. The glycidylamine type epoxy resin plays a role of improving the heat resistance of the epoxy resin composition. Since the glycidylamine type epoxy resin is highly reactive in the epoxy group in the skeleton, it can react with the primary alcoholic OH group of the polymer under a tin catalyst. Examples of the glycidylamine type epoxy resin include 1,3-bis (N, N-dimethylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-1,3-benzenedi (methanamine), 4, 4'-methylenebis [N, N-bis (oxiranylmethyl) aniline], triglycidylaminophenol, triglycidylaminocresol and the like can be mentioned. Among these, from the viewpoint of reactivity with diol compounds such as polybutadiene diol, adhesion, and physical properties, in this embodiment, glycidylamine type epoxy resin is 1,3-bis (N, N-dimethylaminomethyl) cyclohexane. And N, N, N ′, N′-tetraglycidyl-1,3-benzenedi (methanamine) or both.

  1,3-bis (N, N-dimethylaminomethyl) cyclohexane is represented by the following structural formula (5), and N, N, N ′, N′-tetraglycidyl-1,3-benzenedi (methanamine) is: It is represented by the following structural formula (6).

(Diol compound)
Examples of the diol compound may include polyether diol, polyester diol, acrylic diol, polycarbonate diol, and other diols. These diols may be used alone or in combination. Specific examples of the diol compound include polyether diol, polyester diol, polybutadiene diol, polyethylene ether diol, polymer polyol, poly (ethylene adipate), poly (diethylene adipate), poly (propylene adipate), and poly (tetramethylene adipate). , Poly (hexamethylene adipate), poly-ε-caprolactone, poly (hexamethylene carbonate), silicone diol and the like. Moreover, a diol compound obtained by using natural castor oil as a raw material, a rosin diol (tackfire) using pine resin as a raw material, and the like can be exemplified. A diol compound can be used individually or in combination of 2 types or more, respectively.

  In the present embodiment, polybutadiene diol is preferable from the viewpoints that it is easy to obtain and can improve adhesion between different types of glass and resin.

  Moreover, it is preferable to use a diol having a rosin skeleton from the viewpoint of further improving the adhesiveness of the obtained composition of the present embodiment, particularly the adhesion with a resin. The rosin diol is preferably used in combination with polybutadiene diol. At this time, the ratio of the polybutadiene diol to the diol of the rosin skeleton is preferably in the range of 99: 1 to 50:50, more preferably in the range of 95: 5 to 60:40, 10 to 70:30 is more preferable. The more the rosin diol is added, the better the adhesion of the resulting composition of this embodiment is. However, the ratio of the polybutadiene diol to the rosin skeleton exceeds 50:50, and the content of the rosin skeleton diol is higher. This is because if the amount is too large, the diol having the rosin skeleton is not dissolved in the polybutadiene diol.

  Since the diol compound of this embodiment can improve the peel strength while maintaining good reactivity with the epoxy resin, storage stability of the composition, and viscosity of the cured product, the number average molecular weight (Mn) is: It is preferably 200 or more and 3000 or less, and more preferably 200 or more and 1500 or less. In the present embodiment, the number average molecular weight (Mn) is measured by gel permeation chromatography (GPC).

  The blending amount of the diol compound is the molar ratio (hydroxyl group / glycidyl group (epoxy group)) of the hydroxyl group (OH group) of the diol compound to the glycidyl group (epoxy group (EP group)) of the polyfunctional epoxy resin. 2/1 to 50/1 are preferable, 2/1 to 20/1 are more preferable, and 2/1 to 5/1 are further preferable.

[Tin catalyst]
The tin catalyst (hereinafter referred to as “organotin compound”) of the composition of the present embodiment is used to modify the modified epoxy resin. The organic tin compound is not particularly limited. The organotin compound is preferably an organotin catalyst. Examples of the organic tin compound include divalent tin carboxylates such as tin octylate, tin naphthenate, and tin laurate, dibutyltin diurarate, dibutyltin maleate, dibutyltin diacetate, dibutyltin dioctoate, and dibutyltin oxide. And tetravalent tin carboxylates such as dioctyltin oxide and dibutyltin benzoate; reaction products of dibutyltin oxide and phthalate; and chelates such as dibutyltin diacetylacetonate. Others include dimethyltin dilaurate, dioctyltin laurate (DOTL), stannous octate, dioctyltin maleate, dibutyltin dioleate, diphenyltin diacetate, dioctyltin dilaurate, dibutyltin distearate, dioctyltin diversate, dibutyltin bis (tri Ethoxysilicate), dialkylstannoxane dicarboxylate, dialkyltin alcoholate such as dibutyltin dimethoxide, dibutyltin silicate, (dialkylstannoxane) disilicate compound and the like. Among them, divalent tin octylate represented by the following structural formula (7), tetravalent dibutyltin dilaurate represented by the following structural formula (8), and hexavalent represented by the following structural formula (9). Dibutyltin diacetyl acetate is preferably used. These organotin compounds may be used alone or in combination of two or more.

  The organotin compound is preferably at least one organotin selected from divalent, tetravalent or hexavalent, since it can improve the peel strength while maintaining good storage stability of the composition. Moreover, the said tin catalyst and an amine catalyst can also be used together as needed. As the amine catalyst, tris (dimethylaminomethyl) phenol (common name: DMP-30), benzyldimethylamine (common name: BDMA), 1.8-dizabicyclo [5,4,0] undecene-7 (common name: DBMA), 1.8-diazabicyclo [5.4.0] undecene-7 (common name: DBU), and the like. Among these, 1.8-diazabicyclo [5.4.0] undecene-7 is the most preferable considering that it is an epoxy ring-opening catalyst and is used as a urethane adhesive.

  The compounding amount of the organic tin compound largely depends on the molecular weight of the reacting diol compound and the reactivity of the hydroxyl group, but is preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the diol compound. More preferred is 7 parts by mass or less. When the amount of the organic tin compound is within the above range, the storage stability of the resulting composition is excellent and the physical properties of the cured product of the composition are excellent.

  An organotin compound is a catalyst used as a ring-opening catalyst for opening an epoxy ring of a polyfunctional epoxy resin and reacting with a hydroxyl group of a diol compound, for example, as represented by the following reaction formula (A). Moreover, as represented by the following reaction formula (B), the polyfunctional polyol compound obtained by the reaction is introduced with a soft segment having four diol compound skeletons, and selectively reacts in the main chain direction (linear direction). Therefore, the toughness of the polyfunctional polyol compound obtained can be increased. Moreover, the polyfunctional polyol compound excellent in storage stability can be obtained with an organotin compound.

[Production method of polyfunctional polyol compound]
The polyfunctional polyol compound contained in the composition of the present embodiment includes 1,3-bis (N, N-dimethylaminomethyl) cyclohexane and N, N, N ′, N′-tetraglycidyl in the presence of a tin catalyst. It is obtained by modifying a polyfunctional epoxy resin containing either or both of m-xylenediamine and a diol compound. Specifically, a predetermined amount of the above-mentioned polyfunctional epoxy resin and diol compound is added and mixed uniformly and heated. Thereby, a polyfunctional polyol compound is obtained by making the epoxy group of a polyfunctional epoxy resin react with the hydroxyl group of a diol compound.

  Moreover, when mixing a polyfunctional epoxy resin and a diol compound, it is preferable to include a tin catalyst. As a result, the epoxy ring of the polyfunctional epoxy resin can be opened and reacted with the hydroxyl group of the diol compound to obtain a polyfunctional polyol compound.

  The temperature at which the polyfunctional epoxy resin reacts with the diol compound is preferably 60 ° C. or higher and 100 ° C. or lower, more preferably 70 ° C. or higher and 90 ° C. or lower. By setting the reaction temperature within the above range, the reaction between the polyfunctional epoxy resin and the diol compound can be promoted.

  The time for reacting the polyfunctional epoxy resin with the diol compound is generally preferably 6 hours to 48 hours, more preferably 12 hours to 24 hours. In addition, when the tin catalyst is included, it depends on the reaction temperature with the tin catalyst to be used. In this case, the time for reacting the polyfunctional epoxy resin with the diol compound is preferably 6 hours or more and 48 hours or less, More preferably, it is 12 hours or more and 24 hours or less.

  In general, a tertiary amine such as DBU (1,8-diazabicyclo [5,4,0] undecene-7) is used as a reaction catalyst between an alcoholic hydroxyl group and an epoxy group, but only these tertiary amines are used. When used, the polyfunctional epoxy resin and the polyol (diol) compound may crosslink three-dimensionally, so that the polyfunctional polyol compound obtained is hard. Also, depending on the polyol compound that reacts, the viscosity may increase or may be cured during storage. On the other hand, when the polyfunctional epoxy resin is modified with a diol compound as in the present embodiment, if combined use with a tin catalyst or an amine catalyst is used, the polyfunctional epoxy resin is represented by the above structural formula (B). Since the diol compound skeleton (soft segment) is introduced into the epoxy resin in the main chain direction (lateral direction), the resulting polyfunctional polyol compound has low viscosity and high adhesion, and is excellent in storage stability. Further toughness can be increased.

  In the composition of the present embodiment, the curing agent is either 1,3-bis (N, N-dimethylaminomethyl) cyclohexane and N, N, N ′, N′-tetraglycidyl m-xylenediamine or Since it contains a polyfunctional polyol compound obtained by modifying a polyfunctional epoxy resin containing both with a diol compound, it has a stable and excellent adhesion to the adherend. In particular, the composition of the present embodiment can stably have excellent adhesion to adherends and glass made of polypropylene resins such as olefin resins.

  Generally, when an adherend made of polypropylene resin such as olefin resin is dry-treated, both the polar part such as carbonyl group, hydroxyl group and carboxyl group and the non-polar part of olefin resin skeleton are present on the surface. It becomes localized on the resin surface. In order to improve the adhesiveness of the adhesive, an adhesive having both of these polar parts and nonpolar parts is preferable. When a polyfunctional polyol skeleton obtained by modifying a glycidylamine-type epoxy resin with polybutadiene is used as a curing agent component, as shown in the structural formula (B), a hydrophobic portion that is a polybutadiene skeleton, an epoxy group, and a polybutadiene diol are included in the skeleton. There are secondary hydroxyl groups having polarity derived from the reaction of the hydroxyl groups and primary hydroxyl groups of the polybutadiene diol remaining unreacted. There is a difference in reaction rate between the primary hydroxyl group and the secondary hydroxyl group with isocyanate. That is, since the secondary hydroxyl group in the curing agent reacts very slowly, immediately after mixing with the main agent, the primary hydroxyl group reacts in advance and the secondary hydroxyl group remains partially unreacted. This remaining hydroxyl group improves the polar part and adhesion to the surface-treated resin. For the above reasons, it is considered that the adhesiveness with the resin is improved. Moreover, since the polyol of structural formula (B) has four primary hydroxyl groups in the skeleton, the curability of the adhesive is very fast. Further, since the glycidylamine type epoxy resin is more reactive than other epoxy resins, it can react with a relatively high-molecular primary alcoholic OH group under a tin catalyst.

  The composition according to this embodiment can be obtained by mixing the above-described essential components. In addition to the above-mentioned essential components, the composition of the present embodiment can contain additives as long as necessary so long as the pot life suitable for mixing can be secured. Can be included. Examples of the additive include a curing agent, a plasticizer, a filler, a reactive diluent, a curing accelerator (catalyst), a thixotropic agent, a silane coupling agent, a pigment, a dye, an antiaging agent, an antioxidant, Examples thereof include an antistatic agent, a flame retardant, a drying oil, an adhesiveness imparting agent, a dispersant, a dehydrating agent, an ultraviolet absorber, and a solvent. 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 adhesive composition of this embodiment is a two-component urethane composed of a main agent and a curing agent. Therefore, it is necessary to mix a main ingredient and a hardening | curing agent at the time of use. The mixing of the main agent and the curing agent when used is not particularly limited, but the predetermined mixing ratio of the main agent and the curing agent should be homogeneously mixed at room temperature using a rotary mixer, static mixer or the like. Can be obtained at

  Thus, the composition of this embodiment contains a main agent and a curing agent, a urethane prepolymer containing isocyanate silane as the main agent, and a glycidylamine type epoxy resin as the curing agent, particularly 1,3-bis ( N, N-dimethylaminomethyl) cyclohexane and N, N, N ′, N ′,-tetraglycidyl m-xylenediamine, or a polyfunctional epoxy resin obtained by modifying a polyfunctional epoxy resin with a diol compound. It is an adhesive composition containing a functional polyol compound. By containing a polyfunctional polyol compound obtained by modifying a polyfunctional epoxy resin with a diol compound in a curing agent, it is possible to form a cured adhesive having both polarity and nonpolarity in the cured adhesive. This makes it possible to improve the adhesiveness with the resin or glass.

  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 the present embodiment is an adhesive composition mainly applied to an object to be bonded such as an interior / exterior part of an automobile such as an automobile body, a front door, a rear door, a back door, a front bumper, a rear bumper, and a rocker molding. . The method of applying the adhesive composition to the object to be bonded is not particularly limited, but for example, a method of applying the adhesive composition to the object to be bonded with a dedicated gun is common.

  The composition of the present embodiment expresses good adhesion to various substrates such as glass, plastic, metal, etc., has high adhesion after being exposed to warm water for a long time after curing, and has water-resistant adhesion Excellent in properties. 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).

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

<Production of urethane prepolymer>
600 g of polypropylene ether triol having a number average molecular weight of 5000 (trade name “EXCENOL 5030”, manufactured by Asahi Glass Co., Ltd.) and 300 g of polypropylene ether diol having a number average molecular weight of 2000 (trade name “EXCENOL 2020”, manufactured by Asahi Glass Co., Ltd.) are charged into the flask. Then, the mixture was 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 “Sumijour 44S”, manufactured by Sumitomo Bayer Japan Co., Ltd.) so that NCOmol / OHmol = 1.80, about 24 hours in a nitrogen atmosphere Then, the reaction was advanced to produce a urethane prepolymer.

<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 to produce the main agent shown in Table 1. .

Each component shown in Table 1 is as follows.
Isocyanate silane compound: Isocyanate silane compound having the structure represented by the above formula (1) (reaction product of HDI burette and trimethoxy [3- (phenylamino) propyl] silane)
HDI burette: Trade name “D-165N”, Mitsubishi Chemical Corporation trimethoxy [3- (phenylamino) propyl] silane: Trade name “y9669”, manufactured by Momentive Performance Materials
・ Plasticizer: Diisononyl adipate (DINA), manufactured by J Plus Co. ・ Carbon black: Trade name “MA600”, manufactured by Mitsubishi Chemical Corporation ・ Calcium carbonate: Trade name “Super S”, manufactured by Maruo Calcium 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”, manufactured by Nitto Kasei Co., Ltd.

<Synthesis of polyfunctional polyol compound>
The diol compounds 1 to 6, the polyfunctional epoxy resins 1 and 2, the tin catalyst and the amine catalyst shown in Table 2 were blended in the addition amounts (parts by mass) shown in the same table, and these were uniformly mixed, and then 24 ° C at 80 ° C. By reacting for a period of time, polyfunctional polyol compounds 1 to 6 were synthesized. Table 2 shows the blending amount (parts by mass) of each component used for the synthesis of each polyfunctional polyol compound.

Each component shown in Table 2 is as follows.
-Diol compound 1: Polybutadiene diol (polybutadiene skeleton terminal OH), trade name "Poly-15HT", number average molecular weight 1200, manufactured by Idemitsu Petrochemical Co., Ltd.-Diol compound 2: Polybutadiene diol (polybutadiene skeleton terminal OH), trade name " Poly-45HT ”, number average molecular weight 2800, manufactured by Idemitsu Petrochemical Co., Ltd. ・ Diol compound 3: hydroxyl-terminated liquid polyisoprene, trade name“ Poly-ip ”, number average molecular weight 2500, manufactured by Idemitsu Petrochemical Co., Ltd. ・ Diol compound 4 : Polyoxypropylene diol, trade name “Mitsui Polyol D200”, number average molecular weight 200, manufactured by Mitsui Chemicals, Inc.)
-Diol compound 5: Polyoxypropylene diol, trade name "Mitsui polyol D3000", number average molecular weight 3000, manufactured by Mitsui Chemicals-Diol compound 6: rosin skeleton diol (rosin tackifier), trade name "Pine Crystal D- 6011 ”, number average molecular weight 950, manufactured by Arakawa Chemical Industries, Ltd. ・ Multifunctional epoxy resin 1: 1,3-bis (N, N-dimethylaminomethyl) cyclohexane, trade name“ TEDRAD-C ”, number average molecular weight 385, Mitsubishi Made by Gas Chemical Co., Ltd. ・ Polyfunctional epoxy resin 2: N, N, N ′, N′-tetraglycidyl m-xylenediamine, trade name “TEDRAD-X”, number average molecular weight 380, manufactured by Mitsubishi Gas Chemical Co., Inc. Tin octylate (divalent organotin compound), trade name “Neostan U-28”, manufactured by Nitto Kasei Co., Ltd. ・ Amine catalyst : Tertiary amine catalyst (DBU (1.8-diazabicyclo (5.4.0) -undecene-7), manufactured by San Apro Co., Ltd.)

<Preparation of adhesive composition>
Each polyfunctional polyol compound 1-6 shown in Table 2 was allowed to stand at 20 ° C. for 24 hours, and then mixed with the main agent and curing agent shown in Table 3 in the blending amounts shown in the same table to produce an adhesive. . The evaluation results are shown in Table 3.

<Test content>
A shear test body shown in FIG. 1 was prepared for each composition of each example and comparative example, and the shear strength and adhesion after being placed at 50 ° C. for 30 minutes and the shear test body placed at 50 ° C. for 30 minutes were Further, it was cured for 7 days in an atmosphere of 20 ° C. and 60% RH, and the shear strength and adhesiveness when the curing was completed were confirmed.

[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, an olefin resin plate (25 × 100 × 0.8 mm) 11 and a plate glass (25 × 100) subjected to a set of dry treatment (corona treatment, flame treatment, plasma test, etc.) as an adherend. In order to adjust the thickness of the adhesive composition to about 5 mm, spacers (25 × 100 × 5 mm) 13 were provided. Subsequently, each adhesive composition 15 of Examples 1 to 6 and Comparative Examples 1 to 6 shown in Table 1 is applied to the joint portion (25 × 10 mm) 14 on the opposite surface side of the pair of the resin plate 11 and the mild steel plate 12. Each was applied, and a pair of resin plate 11 and mild steel plate 12 were pressure-bonded to produce the shear test body of FIG. In Examples 4 and 5 and Comparative Examples 4 and 5, before applying the adhesive composition to the resin plate 11, a resin primer composition (trade name “M (RC-50E)”) was previously applied to the resin plate 11. , Manufactured by Yokohama Rubber Co., Ltd.).

[Adhesive curing conditions]
(Curing condition 1)
In order to confirm the speed of curing of the adhesive and the adhesiveness at that time, the shear test specimen of FIG. 1 was heat-cured in a 50 ° C. oven for 30 minutes, and immediately measured for shear strength in an atmosphere of 20 ° C. and 60% RH. .
(Curing condition 2)
In order to confirm the final strength of the adhesive and the adhesiveness at that time, the shear test specimen prepared in Evaluation 1 was further cured for 7 days in an atmosphere of 20 ° C. and 60% RH, and sheared in an atmosphere of 20 ° C. and 60% RH. The strength was measured.

[Shear strength]
1 was cured under each curing condition, and was then pulled at 20 ° C. in a 60% RH atmosphere at a tensile speed of 50 mm / min in accordance with JIS K6850-1999, and the shear strength was measured. The measurement results are shown in Table 3 below.

[Destruction state]
The cohesive failure rate of the adhesive of the shear test specimen for which the shear strength was measured was represented by CF, and the peel rate was represented by AF. “CF50AF50” in Table 2 means that the cohesive failure is 50% and the peeling is 50% in the fracture state of the shear test body after the adhesion test. “CF100” indicates complete cohesive failure of the adhesive. “AF100” indicates complete release of the adhesive. The evaluation results are shown in Table 3 below.

(Evaluation)
The shear strength when cured under curing condition 1 is 2.0 MPa or more and the fracture state is CF100, and the shear strength when cured under curing condition 2 is 4.0 MPa or more, and the fracture state is CF100. Evaluation with the case of was made into ○.

  From the results shown in Table 3, it was confirmed that Comparative Examples 1 to 6 were slow in curability, and in particular, Comparative Example 3 was not good in adhesiveness. On the other hand, Examples 1-6 were able to confirm that both sclerosis | hardenability and adhesiveness were favorable. As described above, the composition of the present embodiment can improve the curability and adhesiveness, and stably adheres well to a resin plate and glass made of polypropylene resin, such as an olefin resin. Have good adhesion. 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 and water-resistant adhesiveness, it can be used for automobiles, ships, aircraft, construction / civil engineering, and other industrial products, and particularly for automobiles. It is suitable for use as an adhesive composition for bonding interior and exterior parts.

DESCRIPTION OF SYMBOLS 11 Resin plate 12 Glass plate 13 Spacer 14 Joining part 15 Adhesive composition 16 Test piece

Claims (4)

A main agent containing a urethane prepolymer and an isocyanate silane compound;
A curing agent containing a polyfunctional polyol compound obtained by modifying a glycidylamine type epoxy resin with a diol compound having a molecular weight of 200 or more and 3000 or less by a tin catalyst;
An adhesive composition comprising:   2. The adhesive composition according to claim 1, wherein the content of the tin catalyst is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the diol compound.   The glycidyl group of the glycidylamine-type epoxy resin and the hydroxyl group of the diol compound are 1/2 or more and 1/50 or less in a molar ratio of glycidyl group / hydroxyl group. Adhesive composition.   The adhesive composition according to any one of claims 1 to 3, wherein a content of the isocyanate silane compound 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.

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