POLYROTAXANE COMPOSITE FORMED BODY AND PRODUCTION METHOD THEREFOR
20210379877 · 2021-12-09
Inventors
- Shinji TAKANO (Kiyosu-shi, Aichi-ken, JP)
- Koya MATSUNO (Kiyosu-shi, Aichi-ken, JP)
- Yoshinori NAGAMORI (Kiyosu-shi, Aichi-ken, JP)
- Akira HARADA (Suita-shi, Osaka, JP)
- Yoshinori TAKASHIMA (Suita-shi, Osaka, JP)
- Motofumi OSAKI (Suita-shi, Osaka, JP)
- Katsunari INOUE (Kashiwashi, Chiba, JP)
Cpc classification
B32B37/10
PERFORMING OPERATIONS; TRANSPORTING
C08J5/12
CHEMISTRY; METALLURGY
C08L101/00
CHEMISTRY; METALLURGY
B32B2255/10
PERFORMING OPERATIONS; TRANSPORTING
B32B2250/244
PERFORMING OPERATIONS; TRANSPORTING
C09J5/02
CHEMISTRY; METALLURGY
B32B2037/0092
PERFORMING OPERATIONS; TRANSPORTING
C08J2387/00
CHEMISTRY; METALLURGY
C08J2400/00
CHEMISTRY; METALLURGY
B32B27/28
PERFORMING OPERATIONS; TRANSPORTING
B32B2310/14
PERFORMING OPERATIONS; TRANSPORTING
C08K5/15
CHEMISTRY; METALLURGY
B32B37/06
PERFORMING OPERATIONS; TRANSPORTING
International classification
B32B27/28
PERFORMING OPERATIONS; TRANSPORTING
B32B37/06
PERFORMING OPERATIONS; TRANSPORTING
B32B37/10
PERFORMING OPERATIONS; TRANSPORTING
Abstract
To provide a polyrotaxane composite formed body produced by strong bonding between a crosslinked polyrotaxane formed body and an elastomer formed body without intervention of an adhesive.
Provided is a method for producing a polyrotaxane composite formed body, the method including subjecting a surface of a crosslinked polyrotaxane formed body and a surface of an elastomer formed body to plasma treatment, and pressure joining the treated surfaces together, to thereby bond the formed bodies. Also provided is a polyrotaxane composite formed body including a crosslinked polyrotaxane formed body and an elastomer formed body, wherein these formed bodies are directly bonded together without being intermingled with each other in the absence of an adhesive layer between the formed bodies, an oxygen-rich layer is present between the bonding surfaces of the formed bodies, and the formed bodies exhibit a peel strength of 1 N/m or more.
Claims
1. A method for producing a polyrotaxane composite formed body, the method comprising subjecting a surface of a crosslinked polyrotaxane formed body and a surface of an elastomer formed body to plasma treatment, and pressure joining the treated surfaces together, to thereby bond the formed bodies.
2. The method for producing a polyrotaxane composite formed body according to claim 1, wherein plasma gas used for the plasma treatment contains substantially no oxygen.
3. The method for producing a polyrotaxane composite formed body according to claim 1, wherein the surface of the plasma-treated crosslinked polyrotaxane formed body exhibits a water contact angle of 90° or less.
4. The method for producing a polyrotaxane composite formed body according to claim 3, wherein the water contact angle is 75° or less.
5. The method for producing a polyrotaxane composite formed body according to claim 1, wherein the formed bodies are heated simultaneously with the pressure joining.
6. The method for producing a polyrotaxane composite formed body according to claim 5, wherein the heating temperature is 50° C. or higher.
7. The method for producing a polyrotaxane composite formed body according to claim 1, wherein the elastomer formed body has electrical conductivity.
8. The method for producing a polyrotaxane composite formed body according to claim 1, wherein the polyrotaxane composite formed body is an actuator or a sensor.
9. A polyrotaxane composite formed body comprising a crosslinked polyrotaxane formed body and an elastomer formed body, wherein these formed bodies are directly bonded together without being intermingled with each other in the absence of an adhesive layer between the formed bodies, an oxygen-rich layer is present between the bonding surfaces of the formed bodies, and the formed bodies exhibit a peel strength of 1 N/m or more.
10. A polyrotaxane composite formed body comprising a crosslinked polyrotaxane formed body and an elastomer formed body, wherein these formed bodies are directly bonded together without being intermingled with each other in the absence of an adhesive layer between the formed bodies, the crosslinked polyrotaxane formed body is modified with a high-affinity functional group, the elastomer formed body is modified with a high-affinity functional group, and the high-affinity functional groups are bonded to each other by covalent bonding or intermolecular interaction at the bonding surfaces of the formed bodies.
11. The polyrotaxane composite formed body according to claim 9, wherein the elastomer formed body has electrical conductivity.
12. The polyrotaxane composite formed body according to claim 9, wherein the polyrotaxane composite formed body is an actuator or a sensor.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0030]
[0031]
[0032]
[0033]
DETAILED DESCRIPTION
[0034] [1] Crosslinked Polyrotaxane Formed Body
[0035] A crosslinked polyrotaxane formed body is composed of a crosslinked polyrotaxane, and may contain a component other than a polyrotaxane. The crosslinked polyrotaxane is not limited to one containing a specific cyclic molecule, linear molecule, blocking group, and crosslinking agent.
[0036] Examples of the cyclic molecule include cyclodextrin, crown ether, cyclophane, calixarene, cucurbituril, and cyclic amide.
[0037] Examples of the linear molecule include polyethers such as polyethylene glycol, polypropylene glycol, and polytetrahydrofuran, polyesters such as polylactic acid, polyamides such as 6-nylon, diene polymers such as polyisoprene and polybutadiene, polyethylene, polypropylene, vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, and polyisobutylene, and polydimethylsiloxane.
[0038] Examples of the blocking group include dinitrophenyl group, cyclodextrin group, adamantane group, trityl group, fluorescein group, pyrene group, substituted benzene group (the substituent may be, for example, alkyl, alkyloxy, hydroxy, halogen, cyano, sulfonyl, carboxyl, amino, or phenyl), optionally substituted polynuclear aromatic group (the substituent may be, for example, the same as those described above), and steroid group.
[0039] Examples of the crosslinking agent include cyanuric chloride, trimesoyl chloride, terephthaloyl chloride, epichlorohydrin, dibromobenzene, glutaraldehyde, aliphatic polyfunctional isocyanate, aromatic polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, divinyl sulfone, 1,1′-carbonyldiimidazole, alkoxysilanes and derivatives thereof, and polysiloxane-containing block copolymers (e.g., polycaprolactone-polysiloxane block copolymers, polyadipate-polysiloxane block copolymers, and polyethylene glycol-polysiloxane block copolymers).
[0040] Currently, the commonest polyrotaxane contains cyclodextrin as a cyclic molecule and polyethylene glycol as a linear molecule.
[0041] Examples of the form of the polyrotaxane formed body include, but are not particularly limited to, film, wire, strip, ring, bar, and lump. A polyrotaxane formed body in the form of, for example, film may be applied onto another base material.
[0042] [2] Elastomer Formed Body
[0043] An elastomer formed body is composed of an elastomer, and may contain a component other than an elastomer.
[0044] Examples of the elastomer include, but are not particularly limited to, silicone elastomer, styrenic thermoplastic elastomer, natural rubber, nitrile rubber, acrylic rubber, urethane rubber, urea rubber, fluororubber, and crosslinked polyrotaxane. Examples of the crosslinked polyrotaxane include the same as those described above.
[0045] Examples of the form of the elastomer formed body include, but are not particularly limited to, film, wire, strip, ring, bar, and lump. An elastomer formed body in the form of, for example, film may be applied onto another base material.
[0046] The elastomer formed body may have electrical conductivity, and the polyrotaxane composite formed body may be, for example, an actuator or a sensor. Electrical conductivity can be imparted to the elastomer formed body by, for example, dispersing electrically conductive particles (e.g., carbon black, carbon nanotube, or platinum) into the elastomer formed body.
[0047] [3] Plasma Treatment
[0048] No particular limitation is imposed on the plasma treatment, and it may be, for example, atmospheric pressure plasma or low pressure plasma treatment. The low pressure plasma treatment requires the use of a hermetically sealed low pressure chamber. In contrast, the atmospheric pressure plasma treatment is preferred in view that it does not require the use of a low pressure chamber.
[0049] Examples of the plasma gas used for the plasma treatment include, but are not particularly limited to, air, nitrogen, a mixture of nitrogen and hydrogen, and argon. As shown in Tables 1 and 2 and Examples 1 to 15 below, plasma gas containing substantially no oxygen is preferably used in view of suppression of a decrease in the dielectric breakdown field strength of the crosslinked polyrotaxane formed body by the plasma treatment. Plasma gas containing oxygen in an amount of 0.1% by volume or less is obviously considered as plasma gas containing substantially no oxygen.
[0050] Water contact angle is an index for the degree of plasma treatment; i.e., the smaller the water contact angle, the higher the degree of plasma treatment. The degree of plasma treatment correlates with bonding strength.
[0051] On the basis of Tables 1 and 2 and Examples 1 to 15 shown below, the surface of the plasma-treated crosslinked polyrotaxane formed body exhibits a water contact angle of preferably 90° or less, more preferably 750 or less. Still more preferably, the water contact angle is 90° or less, and the aforementioned peel strength is 1 N/m or more. Much more preferably, the water contact angle is 75° or less, and the aforementioned peel strength is 4 N/m or more.
[0052] The surface of the plasma-treated elastomer formed body exhibits a water contact angle of preferably 92° or less, more preferably 70° or less.
[0053] [4] Heating During Pressure Joining
[0054] Heating is preferably performed simultaneously with pressure joining, since the heating promotes bonding between the high-affinity functional group provided on the plasma-treated crosslinked polyrotaxane formed body and the high-affinity functional group provided on the plasma-treated elastomer formed body.
[0055] The heating temperature is preferably 50° C. or higher, more preferably 80° C. or higher. However, the heating temperature is required to be lower than both of the melting point of the crosslinked polyrotaxane formed body and the melting point of the (thermoplastic) elastomer formed body. Preferably, the heating temperature is lower than either of the melting points. When the heating temperature is higher than both of the melting points, the crosslinked polyrotaxane formed body intermingles with the elastomer formed body; i.e., these formed bodies are fuse-bonded with each other, which differs from the bonding proposed by the present invention.
[0056] [5] Applications
[0057] No particular limitation is imposed on the application of the polyrotaxane composite formed body. One exemplary application is an electronic component wherein the crosslinked polyrotaxane formed body serves as a dielectric body and the electrically conductive elastomer formed body serves as an electrode. Examples of the electronic component include an actuator and a sensor.
Examples
[0058] Embodiments of the present invention; i.e., examples of the polyrotaxane composite formed body of the invention will be described in the following order. The present invention should not be construed as being limited to the examples.
<1> Preparation of Crosslinked Polyrotaxane Formed Body
<2> Preparation of Elastomer Formed Body
<3> Plasma Treatment of Crosslinked Polyrotaxane Formed Body and Elastomer Formed Body and Measurement of Contact Angle
[0059] <4> Measurement of Dielectric Breakdown Field Strength of Crosslinked Polyrotaxane Formed Body before and after Plasma Treatment
<5> Bonding by Pressure Joining of Crosslinked Polyrotaxane Formed Body and Elastomer Formed Body
<6> Measurement of Peel Strength of Crosslinked Polyrotaxane Formed Body and Elastomer Formed Body
<7> Plasma Treatment of Crosslinked Polyrotaxane Formed Body and Additional Crosslinked Polyrotaxane Formed Body and Measurement of Contact Angle
<8> Bonding by Pressure Joining of Crosslinked Polyrotaxane Formed Body and Additional Crosslinked Polyrotaxane Formed Body
<9> Measurement of Peel Strength of Crosslinked Polyrotaxane Formed Body and Additional Crosslinked Polyrotaxane Formed Body
<10> Preparation of Actuator
[0060] <1> Preparation of Crosslinked Polyrotaxane Formed Body
[0061] A polyrotaxane composition was prepared in the same manner as in Example 1 of Patent Document 5.
[0062] Firstly, there were prepared polyrotaxane A, block copolymer B containing polysiloxane, and polymer C not containing polysiloxane as disclosed in Patent Document 5.
[0063] Specifically, polyrotaxane A contains cyclodextrin as a cyclic molecule and polyethylene glycol as a linear molecule, wherein blocking groups are disposed at both ends of the linear molecule. Polyrotaxane A of the Examples further contains a caprolactone group for achieving solubility and compatibility.
[0064] Block copolymer B containing polysiloxane is incorporated for improving moisture resistance by polysiloxane (silicone component). Specifically, block copolymer B is a polycaprolactone-polydimethylsiloxane-polycaprolactone block copolymer having end-blocked isocyanate groups. Addition of block copolymer B is optional.
[0065] Polymer C not containing polysiloxane has high compatibility with polyrotaxane, and is incorporated for achieving high dielectric constant and low elasticity. Specifically, polymer C is polypropylene glycol having end-blocked isocyanate groups. Addition of polymer C is optional.
[0066] These components and other components were added in amounts described below (represented by “parts by mass”), and the resultant mixture was stirred and thoroughly defoamed, to thereby prepare a polyrotaxane composition solution.
TABLE-US-00001 Polyrotaxane A 10 Polysiloxane block copolymer B 4.9 Polymer C 10.5 Polypropylene glycol diol 4.7 Methyl cellosolve 25.9 Dibutyltin dilaurate 0.014 DBL-C31 (available from GELEST) 0.14 IRGANOX 1726 (available from BASF) 0.42
[0067] As shown in
[0068] Subsequently, the polyrotaxane formed body 1 having the PET sheet 11 was crosslinked and cured in an oven at 130° C. under reduced pressure for five hours, to thereby form a crosslinked polyrotaxane formed body 1.
[0069] <2> Preparation of Elastomer Formed Body
[0070] Silicone elastomer and other components were added in amounts described below (represented by “parts by mass”), and the resultant mixture was stirred and thoroughly defoamed, to thereby prepare an elastomer composition solution. Carbon particles are added for imparting electrical conductivity to an elastomer formed body.
TABLE-US-00002 Silicone elastomer 10 Organic solvent (heptane) 300 Carbon particles (ketjen black) 1
[0071] As shown in
[0072] Subsequently, the elastomer formed body 2 having the PET sheet 12 was crosslinked and cured in an oven at 100° C. under reduced pressure for 24 hours.
[0073] <3> Plasma Treatment of Crosslinked Polyrotaxane Formed Body and Elastomer Formed Body and Measurement of Contact Angle
[0074] Plasma treatment was performed on a surface of the crosslinked polyrotaxane formed body 1 having the PET sheet 11 prepared in <1> above and a surface of the elastomer formed body 2 having the PET sheet 12 prepared in <2> above. The plasma treatment was performed with atmospheric pressure plasma requiring no use of a low pressure chamber.
[0075] As shown in
[0076] As shown in
[0077] As shown in Table 1 below, Examples 1 to 13 wherein both of the formed bodies 1 and 2 were subjected to plasma treatment (the type of plasma gas and the degree of plasma treatment were varied) were compared with Comparative Examples 1 to 10 wherein either or both of the formed bodies 1 and 2 were not subjected to plasma treatment (in Comparative Examples 8 to 10, UV treatment was performed instead of plasma treatment).
[0078] The type of plasma gas was air, nitrogen (N.sub.2) (99.99%), a mixture of nitrogen (N.sub.2) (975) and hydrogen (H2) (3%), or argon (Ar).
[0079] The degree of plasma treatment was varied by changing the rate of plasma gas application and the scanning speed of the plasma jet nozzle (treatment time).
TABLE-US-00003 TABLE 1 Surface Modification Treatment Crosslinked Performance Polyrotaxane Elastomer Rate of Reduction in Formed Body Formed Body Dielectric Breakdown (Upper: Type of (Upper: Type of Water Contact Angle Field Strength of Treatment Treatment Crosslinked Crosslinked Lower: Type of Lower: Type of Polyrotaxane Elastomer Polyrotaxane Peel Gas, etc.) Gas, etc.) Formed Body Formed Body Formed Body Strength Comparative 1 Untreated Untreated 92.1° 96.3° 0% 0 N/m Example 2 Untreated Plasma treatment 92.1° 50.5° 0% 0 N/m Air 3 Untreated Plasma treatment 92.1° 44.3° 0% 0 N/m N.sub.2 4 Untreated Plasma treatment 92.1° 53.1° 0% 0 N/m N.sub.2 (97%) + H.sub.2 (3%) 5 Plasma treatment Untreated 49.5° 96.3° 16% 0 N/m Air 6 Plasma treatment Untreated 44.5° 96.3° 2% 0 N/m N.sub.2 7 Plasma treatment Untreated 55.8° 96.3° 1% 0 N/m N.sub.2 (97%) + H.sub.2 (3%) 8 Untreated UV treatment 92.1° 20.0° 0% 0 N/m Wavelength: 172 nm 9 UV treatment Untreated 39.3° 96.3° 27% 0 N/m Wavelength: 172 nm 10 UV treatment UV treatment 39.3° 20.0° 27% 6.2 N/m Wavelength: 172 nm Wavelength: 172 nm Example 1 Plasma treatment Plasma treatment 49.5° 50.5° 16% 6.3 N/m Air Air 2 Plasma treatment Plasma treatment 49.5° 44.3° 16% 8.1 N/m Air N.sub.2 3 Treatment: Plasma Plasma treatment 49.5° 53.1° 16% 8.5 N/m treatment Air N.sub.2 (97%) + H.sub.2 (3%) 4 Plasma treatment Plasma treatment 86.6° 50.5° 6% 2.5 N/m Air Air 5 Plasma treatment Plasma treatment 44.5° 50.5° 2% 8.8 N/m N.sub.2 Air 6 Plasma treatment Plasma treatment 44.5° 44.3° 2% 8.1 N/m N.sub.2 N.sub.2 7 Plasma treatment Plasma treatment 44.5° 53.1° 2% 7.0 N/m N.sub.2 N.sub.2 (97%) + H.sub.2 (3%) 8 Plasma treatment Plasma treatment 55.8° 50.5° 1% 6.8 N/m N.sub.2 (97%) + H.sub.2 (3%) Air 9 Plasma treatment Plasma treatment 55.8° 44.3° 1% 5.9 N/m N.sub.2 (97%) + H.sub.2 (3%) N.sub.2 10 Plasma treatment Plasma treatment 55.8° 53.1° 1% 5.0 N/m N.sub.2 (97%) + H.sub.2 (3%) N.sub.2 (97%) + H.sub.2 (3%) Example 11 Plasma treatment Plasma treatment 79.2° 89.4° 2% 3.1 N/m Ar Ar 12 Plasma treatment Plasma treatment 83.1° 23.9° 2% 3.6 N/m N.sub.2 N.sub.2 13 Plasma treatment Plasma treatment 83.1° 73.1° 2% 3.3 N/m N.sub.2 N.sub.2
[0080] As described above, water contact angle is an index for the degree of plasma treatment. Thus, the water contact angles of both the formed bodies 1 and 2 were measured after the plasma treatment (“Untreated” corresponds to the water contact angle of a untreated formed body, and “UV treatment” corresponds to the water contact angle of a UV-treated formed body). The water contact angle was measured with a contact angle meter. Specifically, a certain amount of a water droplet was applied onto the surface of a horizontally placed formed body using a dispenser, and the droplet was photographed laterally, followed by analysis of a contour shape based on the resultant image. The results of measurement are shown in Table 1.
[0081] <4> Measurement of Dielectric Breakdown Field Strength of Crosslinked Polyrotaxane Formed Body Before and after Plasma Treatment
[0082] The dielectric breakdown field strength of the crosslinked polyrotaxane formed body 1 was measured at ambient temperature and ambient humidity before and after the plasma treatment in <3> above (“UV treatment” corresponds to values before and after the UV treatment). As shown in
[0083] <5> Bonding by Pressure Joining of Crosslinked Polyrotaxane Formed Body and Elastomer Formed Body
[0084] The formed bodies 1 and 2 having the PET sheets after the plasma treatment in <3> above were bonded together by pressure joining, to thereby prepare a composite formed body.
[0085] As shown in
[0086] Subsequently, as shown in
[0087] <6> Measurement of Peel Strength of Crosslinked Polyrotaxane Formed Body and Elastomer Formed Body
[0088] The peel strength of the composite formed body having the PET sheets after the bonding in <5> above was measured with a tensile tester at ambient temperature and ambient humidity. As shown in
[0089] <7> Plasma Treatment of Crosslinked Polyrotaxane Formed Body and Additional Crosslinked Polyrotaxane Formed Body and Measurement of Contact Angle
[0090] Next will be described the bonding between crosslinked polyrotaxane formed bodies.
[0091] In the same manner as in <3> described above, plasma treatment was performed on two surfaces of crosslinked polyrotaxane formed bodies 1 having PET sheets 11 prepared in <1> above.
[0092] As shown in Table 2 below, Example 14 wherein plasma treatment was performed with nitrogen (N.sub.2) serving as plasma gas to the same degree as in Examples 5 and 6 shown in Table 1 was compared with Example 15 wherein plasma treatment was performed with nitrogen (N.sub.2) serving as plasma gas to a degree higher than that in Examples 5 and 6 shown in Table 1. Comparative Example 11 corresponds to the case of bonding between untreated crosslinked polyrotaxane formed bodies.
[0093] The water contact angle was measured in the same manner as in <3> described above. The results of measurement are shown in Table 2.
TABLE-US-00004 TABLE 2 Surface Modification Treatment Crosslinked Crosslinked Performance Polyrotaxane Polyrotaxane Rate of Reduction in Formed Body Formed Body Dielectric Breakdown (Upper: Type of (Upper: Type of Water Contact Angle Field Strength of Treatment Treatment Crosslinked Crosslinked Crosslinked Lower: Type of Lower: Type of Polyrotaxane Polyrotaxane Polyrotaxane Peel Gas, etc.) Gas, etc.) Formed Body Formed Body Formed Body Strength Comparative Untreated Untreated 92.1° 92.1° 0% 1.4 N/m Example 11 Example Plasma treatment Plasma treatment 44.5° 44.5° 2% 6.0 N/m 14 N.sub.2 N.sub.2 Example Plasma treatment Plasma treatment 72.5° 72.5° 2% 6.7 N/m 15 N.sub.2 N.sub.2
[0094] <8> Bonding by Pressure Joining of Crosslinked Polyrotaxane Formed Body and Additional Crosslinked Polyrotaxane Formed Body
[0095] The crosslinked polyrotaxane formed bodies 1 having the PET sheets 11 after the plasma treatment in <7> above were bonded together by pressure joining, to thereby prepare a composite formed body.
[0096] As shown by replacing the elastomer formed body 2 in
[0097] Subsequently, as shown in
[0098] <9> Measurement of Peel Strength of Crosslinked Polyrotaxane Formed Body and Additional Crosslinked Polyrotaxane Formed Body
[0099] In the same manner as in <6> described above, the peel strength of the composite formed body having the PET sheets after the bonding in <8> above was measured with a tensile tester at ambient temperature and ambient humidity. The results of measurement are shown in Table 2.
[0100] <10> Preparation of Actuator
[0101] A plurality of plasma-treated crosslinked polyrotaxane formed bodies 1 and plasma-treated elastomer formed bodies 2 of the aforementioned Examples were alternately stacked as shown in
[0102] Since the crosslinked polyrotaxane formed bodies 1 are strongly bonded to the elastomer formed bodies 2 in the actuator 10, the actuator can resist a tensile stress applied between the layers caused by contraction of the crosslinked polyrotaxane formed bodies, resulting in reduced layer peeling.
[0103] The absence of an adhesive layer between the crosslinked polyrotaxane formed body 1 and the elastomer formed body 2 is more advantageous than the case of the presence of an adhesive layer between these formed bodies in terms of (A) a decrease in the total height of the actuator 10; (B) no loss in the amount of displacement because of the absence of an adhesive layer that restricts the movement of the crosslinked polyrotaxane formed body 1; and (C) an increase in capacitance.
[0104] The present invention is not limited to the aforementioned examples, and may be appropriately modified and embodied without departing from the spirit of the invention.