JP2005041999A - Polyolefin-based resin composition, polyolefin-based resin product, and product for automobile using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin-based resin composition to which a cyanoacrylate-based adhesive can be attached without carrying out pretreatment such as coating of a primer; and to provide a polyolefin-based resin product and a product for an automobile using the resin product. <P>SOLUTION: The resin composition contains (A) a polyolefin-based resin and (B) an amine derivative regulated so that the formulated proportion of the component (B) based on the component (A) may be 1-20 mass%. In another aspect, the resin composition contains components (A) and (B), and (C) a rubber component, regulated so that the boiling point of the component (B) may be higher than that of the component (A), the component (C) may be an ethylene-α-olefin copolymer rubber or an ethylene-α-olefin-nonconjugated diene terpolymer rubber, and the compounded proportion of the components (A), (B) and (C) may be 1-95 mass%, 0.01-10 mass% and 1-95 mass% respectively. The polyolefin-based resin product is obtained by molding the composition to a desired shape. The product for the automobile comprises the product. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polyolefin-based resin composition, a polyolefin-based resin product, and an automotive product using the same, and more specifically, a cyanoacrylate-based adhesive can be bonded without performing a pretreatment such as primer application. The present invention relates to a polyolefin resin composition, a polyolefin resin product, and an automobile product using the same.

Since the cyanoacrylate adhesive, so-called instant adhesive, does not adhere to the surface of the molded product of the polyolefin resin composition, it is necessary to pre-treat the surface of the part to be joined, such as primer application. .
FIG. 2 is a diagram for explaining a primer treatment step and an adhesion step of a conventional molded product of a polyolefin resin composition. In FIG. 2A, first, the primer 22 is applied to the molded product 21 of the polyolefin resin composition with the brush 23, and then the applied primer 22 is dried as shown in FIG. 2B. After that, as shown in FIG. 2 (c), a cyanoacrylate adhesive 25 is applied from the adhesive application device 24 to the primer-treated portion, and is adhered to an object to be joined (not shown).

  Conventionally, vulcanized molded products (molded parts) of EPDM rubber have been used for automotive products such as glass runs, drip weather strips, door weather strips, and opening trim weather strips. Since the cyanoacrylate adhesive adheres to the surface of the vulcanized molded article of EPDM rubber, the above primer treatment is not necessary. However, recently, there is a movement in which a part of a vulcanized molded product of EPDM rubber is switched to an injection molded product of a polyolefin resin composition, and the primer is used when there is a secondary processing using a cyanoacrylate adhesive. Since it is necessary to perform processing, the manufacturing cost is increased. Moreover, since many types of primers are used, it is desirable not to use them as much as possible from an environmental viewpoint.

  Accordingly, an object of the present invention is to provide a polyolefin resin composition, a polyolefin resin product, and an automotive product using the same, to which a cyanoacrylate adhesive can be bonded without performing a pretreatment such as primer application. It is in.

  In order to achieve the above object, the present inventors have a composition in which an amine compound is blended in a specific ratio with a polyolefin resin, and a composition in which an amine compound and a rubber component are blended in a specific ratio with a polyolefin resin. The present inventors have found that it is possible to adhere to a cyanoacrylate adhesive without performing a pretreatment such as primer application, and have reached the present invention based on this finding.

That is, the present invention is as follows.
(1) A polyolefin resin composition comprising a polyolefin resin (A) and an amine derivative (B), wherein the blending ratio of the component (B) is 1 to 20 masses relative to the component (A). % Polyolefin resin composition, characterized by being in the range of%.
(2) A polyolefin resin composition comprising a polyolefin resin (A), an amine derivative (B) and a rubber component (C), wherein the boiling point of the component (B) is that of the component (A). Higher than the melting point, and the component (C) is an ethylene-α-olefin copolymer rubber or an ethylene-α-olefin-nonconjugated diene terpolymer rubber, and the components (A), (B) and The blending ratio of the component (C) is (A) 1 to 95% by mass, (B) 0.01 to 10% by mass, and (C) 1 to 95% by mass (provided that (A) + (B) + ( C) component = 100% by mass), a polyolefin-based resin composition.

(3) The polyolefin resin composition as described in (1) or (2), wherein the component (B) is a tertiary amine derivative.
(4) The polyolefin system according to any one of (1) to (3), wherein the component (B) is a hindered amine derivative having a 2,2,6,6-tetramethylpiperidinyl structure. Resin composition.
(5) A polyolefin resin product obtained by bonding molded products of the polyolefin resin composition according to any one of (1) to (4) with a cyanoacrylate adhesive.
(6) A molded product of the polyolefin resin composition according to any one of (1) to (4) and a molded product of a different material are bonded with a cyanoacrylate adhesive. Polyolefin resin products characterized by
(7) An automotive product comprising the polyolefin resin product according to (5) or (6).

  The composition of the present invention is formulated with a specific proportion of an amine compound in a polyolefin resin, or by blending an amine compound and a rubber component in a specific proportion with a polyolefin resin, without performing pretreatment such as primer application, Adhesion with cyanoacrylate adhesives became possible.

  According to the present invention, there are provided a polyolefin resin composition, a polyolefin resin product, and an automobile product using the same, to which a cyanoacrylate adhesive can be bonded without performing pretreatment such as primer application.

Hereinafter, the present invention will be described in more detail.
The present invention is mainly characterized by the following two compositions.
(I) a polyolefin resin composition comprising the polyolefin resin (A) and an amine derivative (B) and comprising the two components as main constituents; and (ii) a polyolefin resin (A), an amine derivative ( A polyolefin-based resin composition comprising B) and a rubber component (C), the main component being the three components.

First, the polyolefin resin composition having the former two components as main components will be described.
The polyolefin-based resin (A) is not particularly limited and can be appropriately selected according to the use. Among them, polyethylene, polypropylene, filler-containing polypropylene (as the filler, talc (magnesium silicate hydrate), Calcium carbonate, glass fiber, etc. are preferable), and those having a MFR of 0.5 to ³⁰ g / 10 min (230 ° C., 21.2 N) and a density of 1.0 to 1.3 g / cm ³ are more preferable.

  The amine derivative (B) is preferably a tertiary amine derivative. Examples include aliphatic amines such as tetraalkylethylenediamine and dimethyl-n-octadecylamine, and aromatic amines such as N, N-dialkylbenzylamine and N, N-dialkylaminopyridine.

  The amine derivative (B) is preferably a hindered amine derivative, particularly a hindered amine derivative having a 2,2,6,6-tetramethylpiperidinyl structure. As such a hindered amine derivative, a commercially available product can be used. For example, trade name LA-52 (molecular weight 847), trade name LA-57 (molecular weight 791), trade name LA-62 (molecular weight about 900), trade name, manufactured by Asahi Denka Kogyo Co., Ltd., having a molecular weight of 200 to 2000 LA-67 (molecular weight about 900), trade name LA-63P (molecular weight about 2000), trade name LA-77 (molecular weight 481) trade name LA-82 (molecular weight 239), trade name LA-87 (molecular weight 225), etc. It is mentioned as a suitable thing.

  Other components (B) that can be used in the present invention include aliphatic amines such as stearylamine, oleylamine, erucamine, dicyclohexylamine; diphenylamine or a derivative thereof, dibenzylamine or a derivative thereof, naphthylamine or a derivative thereof, etc. An aromatic amine etc. are mentioned.

  In the polyolefin-based resin composition having two components (A) and (B) as main components, the component (B) is in the range of 1 to 20% by mass with respect to the component (A). is necessary. Preferably it is 3-10 mass%. When the blending ratio of the component (B) is less than 1% by mass, the adhesive effect of the obtained composition with the cyanoacrylate adhesive is not exhibited. Conversely, if it exceeds 20% by mass, the adhesive effect of the obtained composition with the cyanoacrylate adhesive and the physical properties of the polyolefin resin composition are adversely affected. In addition, the adhesive effect with the cyanoacrylate adhesive of the obtained composition is further enhanced by setting the blending ratio of the component (B) to 3 to 10% by mass with respect to the component (A).

  In order to uniformly mix the component (B) in the component (A), the component (A) can be easily melted by heating it to a melting point or higher and kneading the component (B) therein. At this time, in order to surely mix the total amount of the component (B) with the component (A), the boiling point of the component (B) needs to be higher than the melting point of the component (A).

Next, the polyolefin resin composition having three components (A), (B) and (C) as main components will be described.
In this embodiment, the types of the component (A) and the component (B) are as described above.
The rubber component (C) is an ethylene-α-olefin copolymer rubber or an ethylene-α-olefin-nonconjugated diene terpolymer rubber.
Examples of the α-olefin include an α-olefin having 3 to 12 carbon atoms, specifically, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3 -Methyl-1-pentene, 4-methyl-1-pentene, 3-ethyl-1-pentene, 1-octene, 1-decene, 1-undecene and the like can be mentioned. Examples of the non-conjugated diene include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 3,6-dimethyl-1,7- Octadiene, 4,5-dimethyl-1,7-octadiene, 5-methyl-1,8-nonadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 2,5-norbornadiene, etc. Can be mentioned.
An ethylene unit should just be 50 mol% or more, for example.

In the polyolefin-based resin composition containing the three components (A), (B) and (C) as main constituent components, the blending ratio of each component (A), (B) and (C) is as follows. It is necessary to satisfy the relationship.
(A) Component 1 to 95% by mass, (B) Component 0.01 to 10% by mass, and (C) Component 1 to 95% by mass. However, the component (A) + (B) + (C) = 100% by mass.

  In order to uniformly mix the component (C) in the composition, it can be easily achieved by simultaneously melt-kneading the component (A), the component (B) and the component (C). Alternatively, the component (B) and the component (C) may be first melt-kneaded, and then the component (A) may be melt-kneaded into the obtained kneaded product. When the latter mode is adopted, the amount of the component (B) can be reduced to achieve the same effect, which is preferable in terms of cost. When the latter mode is adopted, first, appropriate amounts of the component (B) and the component (C) are melted and kneaded at the same time, and then the appropriate amount of the component (A) is added thereto and melt-kneaded. Can also be added at the end. It should be noted that the boiling point of the component (B) needs to be higher than the melting point of the component (A) in order to ensure that the total amount of the component (B) is mixed with the component (A). It is as follows.

Each composition of the present invention described above can be molded into a desired shape by various desired known molding methods such as an injection molding method. The obtained molded product can be bonded to a cyanoacrylate adhesive.
According to the present invention, a molded product of a polyolefin resin composition can be bonded to each other with a cyanoacrylate adhesive to obtain a polyolefin resin product having a desired shape.
The cyanoacrylate adhesive used is not particularly limited, and for example, a commercially available adhesive mainly composed of alkyl 2-cyanoacrylate can be selected and used.
Further, according to the present invention, a polyolefin-based resin product can be obtained by bonding a molded product of a polyolefin-based resin composition and a molded product of a different material with a cyanoacrylate adhesive. Examples of the molded product of the different material include various molded products that can be bonded without treatment with a cyanoacrylate adhesive. More specifically, EPDM rubber, nitrile rubber, chloroprene rubber, ABS resin, In addition to various rubbers or resin products such as PVC and polycarbonate resin, metal products such as iron, aluminum, and stainless steel are also included.

The polyolefin resin product can be used particularly as an automotive product. Examples of such automotive products include door outer weather strip, glass run, sunroof weather strip, roof side weather strip, drip weather strip, trunk lid weather strip, side molding, flush mount molding, fabric opening Examples include trim weather strips and various packings for electrical components.
In particular, the present invention is effective at the time of secondary processing (connection processing) of polyolefin-based resin products and repair. Specifically, in the terminal treatment such as belt line seal, if the polyolefin resin product of the present invention is used, a cyanoacrylate adhesive can be used without performing primer treatment, and a desired terminal processed product can be obtained. Can be glued directly.

EXAMPLES Hereinafter, although an Example and a comparative example further demonstrate this invention, this invention is not restrict | limited to these examples.
(Example 1)
Polypropylene resin (trade name MA3, melting point 150 to 160 ° C.) manufactured by Nippon Polychem Co., Ltd. is used as the polyolefin resin (A), and 2,2,6,6- manufactured by Asahi Denka Kogyo Co., Ltd. is used as the amine derivative (B). A hindered amine derivative (trade name LA-52, molecular weight 847, boiling point 300 ° C. or higher, hereinafter referred to as HA) having a tetramethylpiperidinyl structure was used. According to the blending ratio shown in Table 1 below, these components were uniformly mixed by a 180 ° C. kneading process using a lab plast mill apparatus to obtain the composition of the present invention.
This composition was molded into a sheet having a thickness of 2 mm at 180 ° C. using a hydraulic press molding machine to obtain a test piece (length 50 mm, width 10 mm). Next, a cyanoacrylate adhesive (manufactured by Taoka Chemical Industry Co., Ltd., trade name: cyanobond RP-X) was dropped on the surface of the test piece in an untreated state, and an adhesion test was performed.

FIG. 1 is a diagram for explaining an adhesion test performed in this example. In the adhesion test, similar test pieces 11 and 12 were prepared, one drop of adhesive was dropped on the surface of the test piece 12, and the two test pieces were overlapped in the range of 2 cm ² (reference numeral 13), and a weight of 9 Crimped for 1 minute at 8 N, and after 1 minute under standard conditions, pulled by autograph at a speed of 50 mm / min until the specimen breaks in the direction of the arrow, and evaluated by visual confirmation of the breakage of the specimen. went.
The results are shown in Table 1 below.

(Example 2)
The same components (A) and (B) as in Example 1 were used, and as the rubber component (C), an ethylene-α-olefin-nonconjugated diene terpolymer rubber (trade name 3072E manufactured by Mitsui Chemicals, Inc.) was used. , Α-olefin component = 94 mass%, non-conjugated diene component = 6 mass%, hereinafter referred to as EPT). According to the blending ratio shown in Table 1 below, these components were uniformly mixed by a 180 ° C. kneading process using a lab plast mill apparatus to obtain the composition of the present invention, and the same evaluation as in Example 1 was performed. The results are shown in Table 1. In this example, first, all the components (B) and (C) were melt-kneaded, and then the total amount of component (A) was melt-kneaded into the obtained kneaded material to prepare a composition. In Table 1, EPT / HA means that EPT is 9% by mass and HA is 1% by mass.

(Example 3)
Using the same components (A), (B) and (C) as in Example 2, according to the blending ratio shown in Table 1 below, these components were uniformly mixed by 180 ° C. kneading using a lab plast mill apparatus. Mixing was performed to obtain the composition of the present invention, and the same evaluation as in Example 1 was performed. The results are shown in Table 1. In this example, component (A), component (B) and component (C) were melt kneaded at the same time.

(Comparative Example 1)
Example 1 was repeated except that the component (B) was not used. The results are shown in Table 1.
(Comparative Example 2)
Example 2 was repeated except that only the EPT component (C) was used and the components (A) and (B) were not used. The results are shown in Table 1.
(Comparative Example 3)
Example 3 was repeated except that the component (B) was not used. The results are shown in Table 1.
(Comparative Example 4)
Example 3 was repeated except that the components (A), (B), and (C) were mixed in the proportions shown in Table 1 below. The results are shown in Table 1.

  From the results of Table 1, it can be seen that the product of the present invention has good adhesion to cyanoacrylate adhesives.

It is a figure for demonstrating the adhesive test done in the Example. It is a figure for demonstrating the primer processing process and the adhesion process of the shaping | molding processed product of the conventional polyolefin resin composition.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11, 12 Test piece 13 Overlapping part 21 Molded product of polyolefin resin composition 22 Primer 23 Brush 24 Adhesive coating device 25 Cyanoacrylate adhesive

Claims (7)

  A polyolefin resin composition comprising a polyolefin resin (A) and an amine derivative (B), wherein the blending ratio of the component (B) is in the range of 1 to 20% by mass with respect to the component (A). A polyolefin-based resin composition characterized by being:   A polyolefin resin composition comprising a polyolefin resin (A), an amine derivative (B) and a rubber component (C), wherein the boiling point of the component (B) is higher than the melting point of the component (A). The component (C) is ethylene-α-olefin copolymer rubber or ethylene-α-olefin-nonconjugated diene terpolymer rubber, and the components (A), (B) and (C) The blending ratio of the components is (A) 1 to 95% by mass, (B) 0.01 to 10% by mass and (C) 1 to 95% by mass (provided that the component (A) + (B) + (C) = 100% by mass). A polyolefin-based resin composition.   The polyolefin resin composition according to claim 1 or 2, wherein the component (B) is a tertiary amine derivative.   The polyolefin resin composition according to any one of claims 1 to 3, wherein the component (B) is a hindered amine derivative having a 2,2,6,6-tetramethylpiperidinyl structure. .   A polyolefin resin product obtained by bonding molded products of the polyolefin resin composition according to any one of claims 1 to 4 with a cyanoacrylate adhesive.   The molded product of the polyolefin resin composition according to any one of claims 1 to 4 and a molded product of a material different from the molded product are bonded with a cyanoacrylate adhesive. Polyolefin resin products.   An automotive product comprising the polyolefin resin product according to claim 5 or 6.

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