JP5343408B2 - Metal / olefin resin adhesive composition with excellent salt water adhesion - Google Patents

Description

  The present invention relates to an adhesive composition.

  Conventionally, a window edge that seals a window opening edge of a door of a vehicle body of a vehicle such as an automobile by extruding a vinyl chloride resin on a metal plate such as stainless steel, iron (or alloy), galvanized steel plate, or aluminum (or alloy). The mall is manufactured.

Vinyl chloride resin can be mass-produced at low cost, has many varieties ranging from hard to soft, and can be freely colored, so it has been used in large quantities as a thermoplastic general-purpose plastic. However, since there is a concern that dioxins are generated when vinyl chloride resin is burned, olefin-based resins have been studied as an alternative material. Accordingly, there is a demand for an adhesive that can be bonded to an olefin resin elastomer.
In particular, when adhering between stainless steel and an olefin resin elastomer, not only water resistance but also high adhesion durability in salt water immersion is required.

  The adhesive composition described in Patent Document 1 adheres glass, and does not describe adhesion with metal or adhesion durability in salt water immersion.

JP 2006-307104 A

  However, the conventionally known adhesive compositions for window edge moldings have insufficient points for adhesion between olefin resin elastomers and metals. There was a problem that the adhesion durability in the immersion in salt water was insufficient.

  Accordingly, an object of the present invention is to provide an adhesive composition having excellent water resistance and high salt water adhesion.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor used maleic acid-modified chlorinated polypropylene as a base material, and an adhesive composition containing this and a chelate epoxy resin has excellent water resistance and salt resistance. It was found that the adhesiveness was high.

That is, the present invention provides the following (1) to (3).
(1) An adhesive composition containing maleic acid-modified chlorinated polypropylene, a chelate epoxy resin, and a solvent.
(2) The adhesive composition according to (1), wherein the solvent is a non-toluene / xylene solvent composition containing a high-boiling aromatic hydrocarbon, methylcyclohexane, and methyl ethyl ketone.
(3) The adhesive according to (1) or (2), wherein the maleic acid-modified chlorinated polypropylene is 5 to 20 parts by mass, the chelate epoxy resin is 0.1 to 5 parts by mass, and the solvent is 60 to 200 parts by mass. Composition.
(4) An adhesive structure in which the adhesive composition according to any one of (1) to (3) is applied to a metal substrate, and an olefin-based resin molded product is adhered.
(5) The adhesive composition according to any one of (1) to (3) is applied to a metal substrate, the adhesive composition is dried, the olefin resin molded product is joined, and high-frequency heating is performed. A method for manufacturing an adhesive structure to be bonded.
(6) An adhesive composition for adhering a metal substrate and an olefinic resin or an olefinic elastomer containing maleic acid-modified chlorinated polypropylene, a chelate epoxy resin, and a solvent.

  The adhesive composition of the present invention is easy to apply and excellent in workability. When used for bonding an olefin resin containing an elastomer and a metal, the adhesive composition has excellent water resistance and high salt water adhesion.

The present invention is described in detail below.
The adhesive composition of the present invention is an adhesive composition containing maleic acid-modified chlorinated polypropylene, a chelate epoxy resin, and a solvent.

The maleic acid-modified chlorinated polypropylene will be described below.
Maleic acid-modified chlorinated polypropylene is a polypropylene that has been modified with maleic acid and chlorinated. In the present invention, the maleic acid-modified chlorinated polypropylene includes maleic anhydride-modified chlorinated polypropylene.

  Examples of the polypropylene used as the base of the maleic acid-modified chlorinated polypropylene include one or more selected from propylene homopolymer, propylene and other olefins (for example, ethylene, pentene, hexene, octene, decene). The copolymer of these is mentioned. The content of propylene in the copolymer is preferably 40% by mass or more, and more preferably 60% by mass or more, from the viewpoint of adhesiveness with the olefin elastomer.

Maleic acid-modified chlorinated polypropylene is not particularly limited with respect to its production method. For example, a method of graft-modifying maleic acid (including maleic anhydride, the same shall apply hereinafter) on a base polypropylene and then chlorinating the same, a method in which the order of graft modification and chlorination is reversed, graft modification and chlorine A method of simultaneously performing the conversion is mentioned.
The modification with maleic acid is not particularly limited, and can be performed, for example, by reacting maleic acid in a mixed solution of polypropylene and an organic solvent in the presence of a radical generator.

Chlorination of the maleic acid-modified polypropylene is not particularly limited, and can be performed, for example, by introducing chlorine gas into a mixed liquid of maleic acid-modified polypropylene and an organic solvent.
The chlorine content of the maleic acid-modified chlorinated polypropylene is preferably 5 to 30% by mass, and more preferably 10 to 25% by mass. In such a range, it is easy to melt | dissolve with respect to an organic solvent, and it is excellent in the storage stability of an adhesive composition, coating property, and adhesiveness with an olefin type elastomer.

The weight average molecular weight of the maleic acid-modified chlorinated polypropylene is preferably 50,000 to 300,000, more preferably 100,000 to 150,000, from the viewpoints of adhesion and solubility in organic solvents. .
Maleic acid-modified chlorinated polypropylene has excellent adhesion to olefin elastomers.

The chelate epoxy resin will be described below.
Also called chelate-modified epoxy resin, it refers to an epoxy resin containing a functional group having a chelate-forming ability at the basic skeleton, side chain, or terminal of the epoxy resin.

Examples of the epoxy resin include glycidyl ether type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and novolak type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, cyclic aliphatic epoxy resins, Examples thereof include brominated epoxy resins and the like, or those modified with polyester resins, phenol resins, melamine resins, and the like.
Specific examples of the epoxy resin include bifunctional epoxy resins and trifunctional or higher functional epoxy resins.

  Examples of the functional group having chelate forming ability include functional groups having coordination ability such as carboxyl group, sulfonic acid group, phosphoric acid group, hydroxyl group, amino group, and carbonyl group. Particularly preferred are a hydroxyl group, a phosphate group, a carboxyl group, a carbonyl group, and the like.

The chelate epoxy resin contains such a chelate-forming functional group in the basic skeleton or side chain / terminal of the epoxy resin described above. For example, a ketone-modified epoxy resin, a phosphate-modified epoxy resin, etc. Preferably used.
The molecular weight of the chelate epoxy resin is usually 1000 to 10000, preferably 1500 to 6000.
Specific examples include Adeka Resins EP-49-10, EP-49-20, EP-49-72, EP-9003, and EPU-78-11 commercially available from ADEKA Corporation.

The organic solvent will be described below.
Examples of the organic solvent include alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; chain aliphatic hydrocarbons such as n-hexane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetic acid Esters such as methyl, ethyl acetate and butyl acetate; ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene and xylene, especially high boiling aromatics such as Solvesso 150 and Solvesso 200 A hydrocarbon is mentioned.
Among these, from the viewpoint of environmental hygiene, the organic solvent is preferably a non-toluene / xylene solvent composition other than toluene and xylene. In addition, from the viewpoint of solubility, volatility, environmental hygiene, and ease of application (applicability), a solvent containing a high-boiling aromatic hydrocarbon, methylcyclohexane, and methyl ethyl ketone is excellent in solubility and applicability. Therefore, it is preferable.

The ratio of each component in the composition is preferably 5 to 20 parts by mass for maleic acid-modified chlorinated polypropylene, 0.1 to 5 parts by mass for the chelate epoxy resin, and 60 to 200 parts by mass for the solvent.
It is preferable that the maleic acid-modified chlorinated polypropylene is 5 to 20 parts by mass because the adhesiveness with the olefin elastomer is good. More preferably, the maleic acid-modified chlorinated polypropylene is 5 to 15 parts by mass, and more preferably 5 to 10 parts by mass.
It is preferable that the chelating epoxy resin is 0.1 to 5 parts by mass because the salt water adhesion is good. More preferably, chelate epoxy resin is 0.5-3 mass parts, More preferably, it is 0.5-2 mass parts.
The solvent is preferably 60 to 200 parts by mass. More preferably, a solvent is 100-200 mass parts, More preferably, it is 120-200 mass parts. The adhesive composition of the present invention has a low mass of maleic acid-modified chlorinated polypropylene and chelate epoxy, and has high adhesiveness even with a large amount of solvent.

  The adhesive composition of this invention can contain a compounding agent in the range which does not impair the objective of this invention other than a maleic acid modified chlorinated polypropylene, a chelate epoxy resin, and an organic solvent. Examples of the compounding agent include a curing catalyst, a filler, a plasticizer, an antioxidant, an antiaging agent, an inorganic pigment, an organic pigment, an adhesion imparting agent, a flame retardant, a dehydrating agent, a stabilizer, a thixotropy imparting agent, and an antistatic agent. Is mentioned. The amount of the compounding agent is not particularly limited, and an amount that can be generally used in a maleic acid-modified chlorinated polypropylene composition can be blended.

  The adhesive composition of the present invention is not particularly limited for its production. For example, a one-component adhesive composition can be prepared by mixing maleic acid-modified chlorinated polypropylene, a chelate epoxy resin, and an organic solvent. Separately, a main component containing an epoxy resin and an epoxy resin curing agent (maleic acid-modified chlorinated polypropylene) and a curing agent may be separately mixed and adjusted to form a two-component adhesive composition. The compounding agent used as needed can be added.

Examples of the use of the adhesive composition of the present invention include a sealing material, an adhesive, a coating material, a primer, and a paint.
Examples of adherends that can be used for the adhesive composition of the present invention include olefin elastomers, olefin resins, iron, galvanized steel sheets, aluminum, resin coatings of these metal plates, and metals such as stainless steel. And the like. The olefin elastomer and olefin resin are not particularly limited. A conventionally well-known thing can be used. For example, the hard segment is made of isotactic polypropylene and the soft segment is made of olefin rubber mainly composed of EPDM and EPM. This is because the adherend of the present invention does not contain glass and is substantially free of chelate formation.

  As a specific application of the adhesive composition of the present invention, for example, an olefin-based elastomer or olefin resin is extruded on a metal plate such as stainless steel (for example, SUS430), iron, galvanized steel plate, etc. When manufacturing the window edge molding which seals the window opening edge of the door of a vehicle body, the adhesive agent which adhere | attaches a metal plate and an olefin type elastomer or olefin resin is mentioned. Moreover, it is applicable not only to resin extrusion bonding but also to injection molding. This is because the softening temperature of chlorinated polypropylene is low and the adhesive layer softens and adheres with the heat of fusion of the olefin elastomer, and this effect is exhibited after the adhesive applied to the metal surface is dried and baked. In addition, it can be widely used for bonding between metals and non-polar resins (for example, olefinic elastomers or olefin resins), and consists of a multi-layered laminate of a hose and a metal, an elastomer and a metal plate. It can be widely used for bonding seismic isolation bearings.

Next, the adhesion structure which apply | coated the adhesive composition of this invention to the metal base material, and adhere | attached the olefin resin molded product on the metal base material is demonstrated. The bonded structure will be specifically described using the window edge molding shown in FIGS.
As shown in FIG. 1, a window frame 6 and a window glass 5 are attached to the vehicle body panel 7, and a window edge molding 3 having a seal member 10 is provided between the vehicle body panel and the window glass along the vertical movement of the window glass. It is sealed. As shown in FIG. 2, the window edge molding 3 includes a molding mounting portion 1 and a vehicle outer edge portion 2 to which a seal member 10 is mounted. In the sealing member 10, a lip portion 12 which is a molded body of an olefin resin or an elastomer is bonded to a plate portion 14 which is a metal substrate with the adhesive composition of the present invention. The seal member 10 is attached to the molding attachment portion 1 through the attachment hole 16. As shown in FIG. 3, the elastic member 8 elastically tightly fixes between the vehicle outer edge portion 2 and the vehicle body panel 7 when the window edge molding 3 is attached to the vehicle body panel 7. When the seal member 10 is attached to the molding attachment portion 1 via the attachment hole 16, the lip portion 12 seals between the vehicle body panel and the window glass along the vertical movement of the window glass. The adhesive composition of the present invention can be used for a long time because it can strongly bond between the lip portion that moves in pressure contact with the vertically moving window glass and the metal substrate that is the plate portion, and has high salt water adhesion. It can also be used when the vehicle body is exposed to harsh environments.

  Adhesion to the metal substrate using the adhesive composition of the present invention is performed, for example, in the following steps. First, in the coating step, the adhesive composition of the present invention is applied to a metal substrate and air-dried. In the next heating step, the metal substrate is placed in an oven heated to 80 to 250 ° C. The entire metal substrate is heated in order to further dry the organic solvent therein and dry it, and at the same time, to cure the adhesive to the metal plate. As soon as the heated metal substrate is removed from the oven, it is loaded into the mold. Next, in the extrusion or injection process, the olefin-based elastomer that has been thermally melted at a temperature of 190 to 220 ° C. is extruded or injected into the mold. The heating method is not limited to an oven, and induction heating (high frequency) may be used. The hot-melted olefin-based elastomer is extruded or injection-molded in a mold, and at the same time, it is bonded to a metal substrate with sufficient adhesive force through an adhesive composition. Thereafter, the bonded structure of the metal substrate and the olefin resin or elastomer is taken out from the mold.

The adhesive composition of the present invention is easy to apply and excellent in workability. This is because the maleic acid-modified chlorinated polypropylene can be dissolved in the organic solvent and become a solution by containing the organic solvent in the adhesive composition of the present invention.
In addition, since the maleic acid-modified chlorinated polypropylene is dissolved in an organic solvent, the adhesive composition of the present invention can be formed into a film of the adhesive composition by simply applying it to an adherend and drying it. Moreover, the chelate epoxy resin used in the adhesive composition of the present invention suppresses the corrosion reaction, and the resulting bonded structure is excellent in salt water adhesion.
The adhesive composition of the present invention has high adhesiveness in a normal state. Moreover, the adhesive composition of this invention is excellent in salt water adhesiveness, and has high adhesiveness after being immersed in warm salt water. This is because the maleic acid-modified chlorinated polypropylene cures the chelate epoxy resin contained in the adhesive composition of the present invention, and an adhesive film having high strength and high corrosion resistance is obtained by the synergistic action of these two components. The inventor speculates.

EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
1. Preparation of Adhesive Composition Each component shown in Table 1 was mixed in the amount shown in Table 1 (unit: parts by mass) at 20 ° C. and 65% RH to prepare each composition.

2. Evaluation of Adhesive Composition Each composition obtained was evaluated for normal adhesion and salt water adhesion by the following methods. The results are shown in Table 1.
(1) Production of Adhesion Test Piece One SUS430 stainless steel plate having a length of 25 mm, a width of 120 mm, and a thickness of 5 mm was used as an adherend. The adhesive composition prepared above is applied to the entire surface of a SUS430 plate so that the coating thickness after drying is 5 μm, air-dried, placed in an oven at 200 ° C., heated for 1 minute, and the adhesive baked. And allowed to cool at room temperature. Place the olefin-based elastomer (Mirastomer 65 degree product, Mitsui Chemicals Co., Ltd.) on a hot press at 200 ° C and melt the SUS430 plate onto which the adhesive composition was first baked, and press-bond for about 30 seconds. Then, an olefin-based elastomer film having a thickness of about 2 mm was bonded onto the SUS430 plate. After cooling to room temperature and cooling, an adhesive test piece was obtained.
(2) Adhesiveness 2-1. Normal adhesion After leaving the adhesion test piece obtained as described above at room temperature (20 ° C.) and 65% RH for 24 hours, the adhesion test piece is knife-cut and the olefin elastomer film is peeled off from the SUS430 plate by hand. And normal adhesion was evaluated.
2-2. The adhesion test piece obtained was cured and cured at room temperature (20 ° C.) and 65% RH for 24 hours, then immersed in 5 wt% salt water at 50 ° C. for 10 days, and then taken out from the salt water. Was cut with a knife, and the olefin-based elastomer film was peeled off from the SUS430 plate by hand to evaluate water-resistant adhesion.
In the evaluation of adhesiveness, the case where the material failure of the olefinic elastomer was evaluated as ◯, and the case where the olefinic elastomer was separated from the SUS430 surface was evaluated as ×. It can be said that the adhesive strength of the adhesive is strong when the material of the olefin-based elastomer is broken, and the adhesive strength of the adhesive is weak when the olefin-based elastomer is peeled off the SUS430 surface.

The details of each component in Table 1 are as follows.
(1) Solvesso 150: ExxonMobil Chemical (organic solvent)
MEK: Methyl ethyl ketone (organic solvent)
(2) Supercron 892LS: Maleic acid-modified chlorinated polypropylene, manufactured by Nippon Paper Chemicals Co., Ltd.
(3) Super Clone 803MWS: Chlorinated polypropylene, manufactured by Nippon Paper Chemicals Co., Ltd.
(4) Adeka Resin EP-49-10: Chelate epoxy resin, manufactured by ADEKA
(5) Adeka Resin EP-4100E: Bisphenol A type epoxy resin, manufactured by ADEKA Corporation

The compositions of Examples 1 to 3 were in a liquid state after mixing. The obtained adhesive composition was easy to apply and could be uniformly applied to the adherend.
Moreover, the uniform film | membrane of the adhesive composition was able to be obtained on the to-be-adhered body only by apply | coating the adhesive composition of Examples 1-3 to an to-be-adhered body, and making it dry.

It is a schematic diagram which shows a part of vehicle body. It is a disassembled perspective view which shows a window edge molding. It is sectional drawing explaining a mode that a sealing member is attached to a molding attachment part and a glass which moves up and down as a window edge molding, and is sealed in a molding attachment part.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Mall mounting part 2 Car outer edge part 3 Window edge molding 5 Window glass 6 Window frame 7 Car body panel 8 Elastic member 10 Seal member 12 Lip part 14 Plate part 16 Mounting hole

Claims (6)

  An adhesive composition containing maleic acid-modified chlorinated polypropylene, a chelate epoxy resin, and a solvent.   The adhesive composition according to claim 1, wherein the solvent is a non-toluene / xylene solvent composition containing a high-boiling aromatic hydrocarbon, methylcyclohexane, and methyl ethyl ketone.   The adhesive composition according to claim 1 or 2, wherein the maleic acid-modified chlorinated polypropylene is 5 to 20 parts by mass, the chelate epoxy resin is 0.1 to 5 parts by mass, and the solvent is 60 to 200 parts by mass.   The adhesion structure which apply | coated the adhesive composition in any one of Claims 1-3 to the metal base material, and adhere | attached the olefin resin molding.   An adhesive structure in which the adhesive composition according to any one of claims 1 to 3 is applied to a metal substrate, the adhesive composition is dried, an olefin-based resin molded article is bonded, and high-frequency heating is used for bonding. Manufacturing method.   An adhesive composition for adhering a metal substrate and an olefin resin or an olefin elastomer, which contains maleic acid-modified chlorinated polypropylene, a chelate epoxy resin, and a solvent.

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