JP2010139336A - Adhesion test method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To evaluate exfoliation difficulty of a rubber member from a metal member when a rubber-metal complex product is released from a mold. <P>SOLUTION: An adhesion test method includes: a test piece preparation step of setting a metal piece 11 onto which a vulcanizing adhesive is applied and an unvulcanized rubber composition on a test piece forming mold, and heating it, to thereby prepare an adhesion test piece 10 wherein a rubber composition 12 adheres in the vulcanized state partially to the metal piece 11 through the vulcanizing adhesive; and a rubber exfoliation step of releasing the adhesion test piece 10 prepared in the test piece preparation step from the test piece forming mold, and exfoliating the rubber composition 12 from the metal piece 11 before the temperature is lowered to room temperature. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an adhesion test method.

  For various products, in addition to the standards such as JIS, various adhesion test methods in accordance with the use modes have been proposed.

  In Patent Document 1, a measurement evaluation substrate in which a measurement sample substrate and a counter substrate are bonded together with a thermosetting adhesive is prepared, and a load is applied to the adhesion portion of the measurement evaluation substrate to remove the film. And a coating adhesion evaluation method for measuring peel strength.

  In Patent Document 2, a second film is formed on a first film formed on a substrate, a peeling auxiliary film is adhered on the second film, and the first film, the second film, After partially peeling the interface, the substrate is fixed and pulled at a predetermined pulling angle with respect to the substrate surface while holding the peeled end of the laminated film composed of the second film and the peeling auxiliary film. An adhesive force measuring method for measuring the adhesive strength at the interface between the first film and the second film by measuring the tensile strength necessary for peeling the interface between the first film and the second film Is disclosed.

  Patent Document 3 discloses that a transfer foil sheet in which at least a release layer and a heat-sensitive adhesive layer are formed as a transfer layer on a substrate film is laminated on a transfer target body, and the transfer foil sheet is attached to a heat-sensitive adhesive. By measuring the change in peel strength using the method of JIS 6854 for the obtained transfer laminate, the breaking strength at the boundary of the thermocompression bonding portion, A method for evaluating the peelability and breakability of a transfer foil sheet for easily obtaining peel strength between a material film and a transfer layer is disclosed.

  In Patent Document 4, the base material of the adhesive tape or sheet of the test specimen is fixed to a fixing part having a smooth surface without being easily deformed, such as a steel plate, and several types with different thicknesses are provided on the adhesive layer of the adhesive tape or sheet. A method for evaluating the anchor strength of an adhesive tape or sheet is disclosed in which the peeled bodies are attached separately, each peeled body is peeled off, and the presence or absence of adhesive residue on the adhesive layer is observed.

Patent Document 5 discloses a means for energizing a rubber composition-metal composite with an alternating current, a means for measuring the complex impedance of the rubber composition-metal composite, and an actual resistance of low frequency side dispersion from the measured complex impedance value. An adhesion interface evaluation apparatus including a means for calculating a value is disclosed.
JP 2007-285795 A JP 2002-122533 A JP 2002-90276 A JP-A-6-34520 JP 2008-51521 A

  By the way, in general, when manufacturing a rubber metal composite product in which a rubber member is vulcanized and bonded to a metal member, a metal member coated with a vulcanized adhesive and an unvulcanized rubber composition are set in a mold, and then heated and heated. By applying pressure, the rubber member is molded and vulcanized and vulcanized and bonded to the metal member.

  However, there are cases where it is difficult to remove the rubber-metal composite product due to various causes. In that case, if an attempt is made to remove the rubber metal composite product by applying force, an excessive force acts on the bonded portion and the rubber member is removed from the metal member. Peeling can occur.

  This invention is evaluating the difficulty of peeling of the rubber member from a metal member in the case of mold release of a rubber metal composite product.

The adhesion test method of the present invention comprises:
Set a metal piece coated with a vulcanized adhesive and an unvulcanized rubber composition on a test piece mold, heat it, and partially vulcanize the rubber composition to the metal piece via the vulcanized adhesive. A test piece preparation step for preparing a bonded test piece,
The rubber stripping step of stripping the rubber composition from the metal strip before the adhesive test strip fabricated in the above-mentioned test strip fabrication step is removed from the test strip mold and the temperature is lowered to room temperature,
It is provided with.

  According to the present invention, the adhesive test piece is removed from the test piece mold, and the rubber composition is peeled off from the metal piece before the temperature drops to room temperature. In addition, the difficulty of peeling the rubber member from the metal member at the time of demolding the rubber-metal composite product can be evaluated based on the peeled state and the like.

  Hereinafter, embodiments will be described in detail based on the drawings.

  The adhesion test method according to the present embodiment evaluates the difficulty of peeling the rubber member from the metal member when the rubber-metal composite product is removed. Here, examples of the rubber metal composite product include automobile parts such as bushes and vibration-proof rubber devices.

(Preparation step)
First, a test piece mold, a metal piece, a vulcanized adhesive, and an unvulcanized rubber composition for preparing an adhesive test piece are prepared. 1 and 2 show an example of the adhesion test piece 10 having the same shape as the 90-degree peel test piece of the metal piece 11 and rubber in JIS K6256.

  Here, the test piece mold is not particularly limited, but from the viewpoint that a general-purpose mold can be diverted and used, the metal piece of the metal piece and rubber 90-degree peel test piece in JIS K6256. A mold is preferred.

  As the metal piece 11, for example, a plate-like material made of the same material or a similar material as the metal member of the rubber metal composite product can be used. When the adhesion test piece 10 having the same shape as the 90 ° peel test piece for metal pieces and rubber in JIS K6256 is manufactured, the thickness is 1.5 ± 0.1 mm, the width is 25.0 ± 0.1 mm, and It is a metal plate having a length of 60 ± 1 mm.

  The metal piece 11 is applied with a vulcanized adhesive on a predetermined portion and dried.

  As the vulcanized adhesive, for example, a single-layer adhesive composed of a single agent, a two-layer adhesive composed of a primer applied on the metal side and an overcoat applied on the rubber side. Agents. In the latter case, the metal piece 11 is coated with a primer and dried, and then a top coat is coated thereon and dried. Specific examples of the vulcanized adhesive include, for example, a chemlock series manufactured by Lord Far East and a metal lock series manufactured by Toyo Chemical Laboratory. The film thickness of the vulcanized adhesive is, for example, 2 to 50 μm. In the case of a two-layer adhesive, the thickness of the primer is, for example, 1 to 30 μm.

  Examples of the unvulcanized rubber composition include those made of the same material or similar materials as those forming the rubber member of the rubber metal composite product. The unvulcanized rubber composition is prepared by putting raw rubber into a rubber kneader such as a Banbury mixer and kneading, and then putting a rubber compounding agent and kneading them. Examples of the raw rubber include natural rubber (NR), ethylene-α-olefin elastomer (EPR, EPDM), styrene butadiene copolymer (SBR), acrylonitrile butadiene copolymer (NBR), chloroprene rubber (CR), chloro Examples thereof include sulfonated polyethylene rubber (CSM). Examples of rubber compounding agents include rubber softeners, reinforcing materials such as carbon black, vulcanization acceleration aids, processing aids, anti-aging agents, vulcanization accelerators, and vulcanization agents.

(Test piece preparation step)
A metal piece 11 coated with a vulcanized adhesive and a predetermined amount of an unvulcanized rubber composition are set on a test piece mold. At this time, the unvulcanized rubber composition is brought into contact with the surface of the metal piece 11 to which the vulcanized adhesive is applied, but the rubber composition 12 is partially vulcanized and bonded to the metal piece 11 at the bonding portion 13. Cellophane, release paper or the like is interposed in the non-bonded portion 14 between the metal piece 11 and the unvulcanized rubber composition, and the vulcanized adhesive is interposed only in the bonded portion 13. When the vulcanized adhesive is applied only to the bonding portion 13 of the metal piece 11, the unvulcanized rubber composition may be brought into contact with the surface of the metal piece 11 on which the vulcanized adhesive is applied.

  Here, the bonding portion 13 is preferably elongated so that the peeling direction is the length direction, and the length is, for example, 10 to 30 mm. The width of the bonding portion 13 is preferably 5 mm or less so that the peeling width of the rubber composition 12 from the metal piece 11 in the subsequent rubber peeling step is 5 mm or less. If the peeling width is larger than 5 mm, when the rubber composition 12 is to be peeled from the metal piece 11, the rubber composition 12 itself may be broken and the adhesion performance may not be evaluated.

  Next, a test piece molding die in which the metal piece 11 and a predetermined amount of the unvulcanized rubber composition are set is sandwiched by a hot plate press and heated and pressed for a predetermined time. At this time, the rubber composition 12 obtained by vulcanizing the unvulcanized rubber composition is molded and vulcanized and bonded to the metal piece 11 to obtain the adhesion test piece 10. In the case of the adhesion test piece 10 having the same shape as the test piece for 90 ° peel test of metal pieces and rubber in JIS K6256, the thickness is 6.0 ± 0.1 mm, the width is 25.0 ± 0.1 mm, and the length. 125 mm.

  Here, although the molding process conditions differ depending on the rubber composition and the like, generally, for example, the temperature is 120 to 200 ° C., the pressure is 3 to 50 MPa, and the time is 3 to 30 minutes.

(Rubber peeling step)
Before the adhesive test piece 10 is removed from the test piece mold and the temperature is lowered to room temperature (for example, 25 ° C.), the rubber composition 12 is moved from the metal piece 11 to the 90 ° direction or 180 ° as shown in FIG. Peel in the direction.

  Here, the time from demolding to peeling is preferably within 60 seconds, more preferably within 10 seconds, but the peeling of the rubber composition 12 from the metal piece 11 is performed on the adhesion test piece 10. Most preferably, it is performed immediately after demolding from the test piece mold.

  The temperature of the adhesion test piece 10 at the time of peeling is preferably within −10 ° C., more preferably within −5 ° C. from the molding temperature.

  The peeling operation may be performed manually, using a jig, or using a peeling device.

  After the rubber composition 12 is peeled from the metal piece 11, for example, by visually observing the destruction state, the rubber part is damaged by R, the rubber part and the adhesive are damaged by RC, the adhesive between the adhesives is CP, and Breakage between metal and adhesive can be classified as M and their proportion can be evaluated.

  According to the above method, the adhesive test piece 10 is removed from the test piece mold, and the rubber composition 12 is peeled off from the metal piece 11 before the temperature drops to room temperature. Production of a composite product is imitated, and the difficulty of peeling off the rubber member from the metal member at the time of demolding the rubber-metal composite product can be evaluated based on the peeled state and the like.

  According to JIS K6256, the adhesion test piece is left in the test room for 16 hours or more, and then the peel test is performed. When peeling, the same result as when peeling before the temperature drops to room temperature is not obtained. Therefore, it is necessary to evaluate the difficulty of peeling the rubber member from the metal member when removing the rubber metal composite product. I can't.

[Test Evaluation 1]
(Adhesive specimen material)
<Metal piece>
As a metal piece, a steel plate (SPH) having a thickness of 1.5 mm, a width of 25.0 mm, and a length of 60 mm was prepared.

<Vulcanized adhesive>
The following adhesives A and B were prepared.

-Adhesive A-
Adhesive A was a vulcanized adhesive having Chemprim 205 as a primer from Lord Far East and Chemlock 6108 from Lord Far East as a top coat.

-Adhesive B-
Adhesive B was a vulcanized adhesive in which the primer was Rohm and Haas Megam 3351 and the top coat was Rohm and Haas Megam 531.

<Rubber composition>
The following rubbers A and B were prepared. Each formulation is also shown in Table 1.

-Rubber A-
Natural rubber is used as raw rubber, and 3 parts by weight of oil, 50 parts by weight of carbon black, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 4 parts by weight of anti-aging agent, 3 parts of vulcanizing agent, and 100 parts by weight of raw rubber. An unvulcanized rubber composition obtained by kneading and mixing 1 part by mass of a mass part and 1 part by mass of a vulcanization accelerator was designated as rubber A.

-Rubber B-
A blend rubber obtained by blending natural rubber and styrene-butadiene rubber at a ratio of the former / the latter = 70/30 (mass ratio) is used as a raw rubber, and 18 parts by mass of oil and 75 parts by mass of carbon black with respect to 100 parts by mass of the raw rubber. An unvulcanized rubber composition obtained by kneading and blending 10 parts by mass of zinc oxide, 1 part by mass of stearic acid, 6 parts by mass of anti-aging agent, 0.8 part by mass of vulcanizing agent, and 2 parts by mass of vulcanization accelerator. Rubber B was designated.

(Adhesion test)
<Example 1>
A combination of adhesive A and rubber A is used so that the width of the bonded portion is 5 mm and the length is 25 mm, and an adhesive test piece having the same shape as a 90 ° peel test piece of metal and rubber in JIS K6256 is used. The temperature conditions for the molding process were 165 ° C., 170 ° C., 175 ° C., 180 ° C., and 185 ° C., respectively. In addition, the film thickness of the primer was 1 to 3 μm, and the total film thickness of the adhesive was 3 to 5 μm. The pressure condition of the molding process was 8 MPa and the time was 10 minutes.

Immediately after removing the adhesive test piece produced at each temperature from the test piece mold, the rubber composition was peeled off from the metal piece in the 90 ° direction, and the broken state was visually observed to show R and rubber damage. The failure between the part and the adhesive was classified as RC, the failure between the adhesives was classified as CP, and the failure between the metal and the adhesive was classified as M, and their ratios were evaluated. In addition, the trial was performed twice <Example 2>
A combination of adhesive A and rubber B, except that the temperature conditions for molding the adhesive test piece were 165 ° C, 170 ° C, 175 ° C, 180 ° C, 185 ° C, 190 ° C, 195 ° C, and 200 ° C. The same adhesion test as in Example 1 was performed.

<Example 3>
The same adhesion test as in Example 1 except that the combination of adhesive B and rubber A was used, and the temperature conditions for molding the adhesive test piece were 165 ° C, 170 ° C, 175 ° C, 180 ° C, and 185 ° C. Went.

<Example 4>
Same as Example 1 except that the combination of adhesive B and rubber B was used, and the temperature conditions for molding the adhesive test piece were 150 ° C., 155 ° C., 160 ° C., 165 ° C., 170 ° C., and 175 ° C. The adhesion test was conducted.

(Test results)
The test results are shown in Table 2.

  In Example 1, it was R100% for both trials at 165 ° C. At 170 ° C., R2 was 100% for both trials. At 175 ° C., R2 was 100% for both trials. At 180 ° C., the first trial was R100%, and the second trial was R98% / M2%. At 185 ° C., the first trial was R85% / M15%, and the second trial was R60% / M40%.

  In Example 2, when the temperature was 165 ° C., R2 was 100% for both trials. At 170 ° C., R2 was 100% for both trials. At 175 ° C., R2 was 100% for both trials. At 180 ° C., R2 was 100% for both trials. At 185 ° C, R2 was 100% for both trials. At 190 ° C., R2 was 100% for both trials. At 195 ° C., R95% / M5% was obtained in both trials. At 200 ° C., the first trial was R50% / M50%, and the second trial was M100%.

  In Example 3, when the temperature was 165 ° C., R2 was 100% for both trials. At 170 ° C., R2 was 100% for both trials. At 175 ° C., R2 was 100% for both trials. At 180 ° C., the first trial was R100%, and the second trial was R98% / M2%. At 185 ° C., the first trial was R100%, and the second trial was R95% / M5%.

  In Example 4, when the temperature was 150 ° C., the first trial was R10% / RC90%, and the second trial was RC100%. At 155 ° C., the first trial was R20% / RC80%, and the second trial was RC100%. At 160 ° C., the first trial was R90% / RC10%, and the second trial was R95% / RC5%. At 165 ° C., R90% / RC10% in both trials. At 170 ° C., the first trial was R70% / RC30%, and the second trial was R85% / RC15%. At 160 ° C., the first trial was R5% / RC95%, and the second trial was RC100%.

  From the above results, regarding the difficulty of peeling off the rubber member from the metal member at the time of demolding of the rubber metal composite product, the molding temperature condition is 165 to 175 ° C. in the combination of the adhesive A and the rubber A. Preferably, the combination of the adhesive A and the rubber B is preferably 165 to 190 ° C., the combination of the adhesive B and the rubber A is preferably 165 to 175 ° C., and the adhesive B and the rubber B It can be seen that it is preferably 160 to 165 ° C. in combination with

[Test evaluation 2]
An adhesion test piece was produced under the same conditions as when the temperature condition of the molding process in Example 1 was 185 ° C. Then, the rubber composition was left in the test room for one day, cooled to room temperature, and then placed in a gear oven set at 185 ° C. and heated for 30 minutes. It peeled and evaluated similarly to the above. In addition, as a result of performing the trial twice, both trials were R100%. In the case of peeling immediately after demolding (185 ° C. in Example 1), the first trial is R85% / M15%, the second trial is R60% / M40%, and both results are different. . This is considered to be because the reaction of the vulcanized adhesive progresses during the period when it is left in the test room for one day and once cooled to room temperature. Therefore, even if the adhesive test piece once cooled is heated and peeled, it is impossible to evaluate the difficulty of peeling the rubber member from the metal member when the rubber-metal composite product is removed.

[Test Evaluation 3]
Except that the width of the bonded portion was 7 mm and 9 mm, an adhesive test piece was produced under the same conditions as in the case where the molding processing temperature condition of Example 1 was 165 ° C., and an adhesion test was performed.

  However, when the width of the bonded portion was 7 mm and 9 mm, the rubber composition itself was destroyed and the bonding performance could not be evaluated. In the case of the rubber A, it is considered that the strength of the rubber A is lower than the adhesive strength when the width of the bonded portion, that is, the peeling width is wider than 5 mm.

  INDUSTRIAL APPLICABILITY The present invention is useful for an adhesion test method for evaluating the difficulty of peeling off a rubber member from a metal member at the time of demolding a rubber metal composite product.

It is a perspective view of an adhesion test piece. It is (a) top view and (b) side view of an adhesion specimen. It is explanatory drawing which shows a rubber peeling step.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Adhesion test piece 11 Metal piece 12 Rubber composition 13 Adhesion part 14 Non-adhesion part

Claims (4)

Set a metal piece coated with a vulcanized adhesive and an unvulcanized rubber composition on a test piece mold, heat it, and partially vulcanize the rubber composition to the metal piece via the vulcanized adhesive. A test piece preparation step for preparing a bonded test piece,
The rubber stripping step of stripping the rubber composition from the metal strip before the adhesive test strip fabricated in the above-mentioned test strip fabrication step is removed from the test strip mold and the temperature is lowered to room temperature,
An adhesion test method comprising: In the adhesion test method according to claim 1,
In the rubber peeling step, the rubber composition is peeled off from the metal piece immediately after the adhesion test piece is removed from the test piece molding die. In the adhesion test method according to claim 1 or 2,
In the test piece preparation step, the adhesion test method is characterized in that an adhesion test piece is prepared so that a peeling width of the rubber composition from the metal piece in the rubber peeling step is 5 mm or less. In the adhesion test method according to any one of claims 1 to 3,
An adhesion test method, wherein the test piece mold used in the test piece preparation step is a metal mold of 90 degree peel test piece of metal piece and rubber according to JIS K6256.

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