JPWO2013115237A1 - Low friction base material manufacturing method - Google Patents

Abstract

A low friction group comprising a step of irradiating the resin layer of the substrate having at least a resin layer with an electron beam; and a step of irradiating the resin layer with an electron beam and then attaching a silicone component to the resin layer surface. A method of manufacturing the material is provided.

Description

  The present invention relates to a method for producing a low friction base material having a low surface friction coefficient and excellent slip property (slip property). More specifically, the present invention relates to a method for manufacturing a base material whose surface has been subjected to a low friction treatment. Such a low friction substrate is applied to, for example, an infrared reflective film having high transparency in the visible light region and high reflectivity in the infrared light region.

  An infrared reflective film is mainly used to suppress the thermal effect of emitted sunlight. For example, an infrared reflecting film is pasted on a window glass of a building or an automobile, so that infrared rays (particularly near infrared rays) that enter the room through the window glass are shielded and the temperature rise in the room is thereby suppressed. It is possible to save energy by suppressing power consumption.

  For infrared reflection, an infrared reflection layer having a laminated structure of metal or metal oxide is used. However, metals and metal oxides have low scratch resistance. Therefore, in an infrared reflective film, it is common to provide a protective layer on an infrared reflective layer. For example, Patent Document 1 discloses using polyacrylonitrile (PAN) as a material for the protective layer. Polymers such as polyacrylonitrile have a low infrared absorptivity and can shield far-infrared rays emitted from the room through the translucent member. Energy saving can also be achieved by the heat insulation effect.

  When a polymer such as polyacrylonitrile is used as the material for the protective layer, the protective layer is prepared by first dissolving the polymer in a solvent to prepare a solution, and then applying this solution on the infrared reflective layer. Is dried (the solvent is volatilized).

Japanese Patent Publication No. 61-51762

  By the way, it is known that the solvent in which polyacrylonitrile is soluble is only a high boiling point solvent such as dimethylformamide (DMF) (boiling point: 153 ° C.). When the boiling point of the solvent is high, it is possible to reduce the time of the drying process by increasing the temperature of the drying process, but when the base material is a polymer material, the base material can be damaged by high temperature There is sex. Therefore, it is necessary to perform the drying process at a temperature at which the substrate is not damaged. When polyacrylonitrile is used as the material for the protective layer, there is a problem that the drying process takes a long time. In order to solve this problem, the inventors have found that a protective layer is made of a copolymer of acrylonitrile and other monomer components soluble in a solvent having a low boiling point such as methyl ethyl ketone (MEK) (boiling point: 80 ° C.). It was.

  However, the inventors faced the problem that the copolymer of acrylonitrile and other monomer components does not have sufficient slip properties (slip properties) on the surface of the protective layer. Since the infrared reflective film using polyacrylonitrile as the protective layer has sufficient slip properties, it is speculated that the problem of slip properties is caused by other monomer components. If the slip property of the surface of the protective layer is poor, for example, when cleaning a building or an automobile window to which an infrared reflective film is adhered, an excessive force (stress) acts on the surface of the protective layer, and the protective layer is partially This causes a problem that the infrared reflecting layer having low scratch resistance is exposed due to destruction of the entire surface or the entire surface.

  Then, this invention is made | formed in view of this situation, and makes it a subject to provide the manufacturing method of the low friction base material with the low friction coefficient of the surface and excellent in slip property (sliding property).

The manufacturing method of the low friction substrate according to the present invention is as follows:
Irradiating the resin layer of the substrate having a resin layer on at least the surface with an electron beam;
And a step of attaching a silicone component to the surface of the resin layer after irradiating the resin layer with an electron beam.

  According to this method, radicals are generated on the surface of the resin layer by irradiating the resin layer with an electron beam. When the silicone component is attached to the resin layer surface in this state, the silicone component is easily transferred to the resin layer surface. Therefore, the friction coefficient on the surface of the resin layer is lowered, and slip properties (slip properties) are imparted. Thereby, a base material changes to a low friction base material.

Here, as one aspect of the method for producing a low friction substrate according to the present invention,
The step of attaching the silicone component may be a step of coating the resin layer on the surface side of the polymer film having the silicone component formed on the surface.

  According to this method, the silicone component on the polymer film adheres to the surface of the resin layer by coating the polymer film on the resin layer.

Moreover, as another aspect of the manufacturing method of the low friction base material which concerns on this invention,
Before the step of irradiating the electron beam, a step of forming on the resin layer a layer containing a compound that generates radicals when the resin layer is irradiated with the electron beam can be further included.

  According to such a method, even if the resin layer does not have a sufficiently high degree of radical generation, a layer containing a compound that generates radicals when the resin layer is irradiated with an electron beam is formed on the resin layer. The degree of radical generation can be increased, thereby increasing the amount of transfer of the silicone component to the resin layer surface.

Moreover, as another aspect of the manufacturing method of the low friction base material which concerns on this invention,
It is preferable that the dynamic friction coefficient on the surface of the resin layer after the step of attaching the silicone component is 0.001 to 0.45.

As still another aspect of the method for producing a low friction base material according to the present invention,
The resin layer may be a layer containing a polymer containing at least any two of repeating units A, B, and C of the following chemical formula I.

Moreover, as another aspect of the manufacturing method of the low friction base material which concerns on this invention,
The resin layer can be a protective layer of an infrared reflective film in which a reflective layer and a protective layer are sequentially laminated on one surface of the substrate.

  According to this method, an infrared reflective film having a low surface friction coefficient and excellent slip properties (slip properties) can be obtained.

in this case,
The vertical emissivity of the protective layer side surface is preferably 0.20 or less.

  According to such a method, far infrared rays are not easily absorbed by the protective layer even if they are incident on the protective layer, reach the reflective layer, and as a result, are easily reflected by the reflective layer. Therefore, by sticking an infrared reflective film on a translucent member such as a window glass from the indoor side, it is possible to shield far infrared rays emitted from the room through the translucent member to the outside.

The protective layer further includes a silicone component constituting the protective layer surface,
It is also preferable that the amount of the silicone component is 0.0001 to 1.0000 g / m ² .

  According to the present invention, a low-friction base material having a low surface friction coefficient and excellent slip properties (slip properties) can be obtained.

The schematic diagram for demonstrating the laminated structure of the infrared reflective film which concerns on one Embodiment of this invention is shown. The figure of the basic composition of the test part of the ball-on-disk type friction and abrasion tester for measuring the dynamic friction coefficient of the infrared reflective film concerning one embodiment of the present invention is shown.

  Hereinafter, as one embodiment of the low friction substrate according to the present invention, an infrared reflective film having a low surface friction coefficient and excellent slip property (slip property) will be described. In addition, the infrared reflective film which concerns on this embodiment is an infrared reflective film which has a heat insulation characteristic (reflective characteristic of far infrared rays) in addition to the thermal insulation characteristic (reflective characteristic of near infrared rays) which the conventional infrared reflective film has.

  In the infrared reflective film according to this embodiment, as shown in FIG. 1, a reflective layer 2 and a protective layer 3 are laminated in that order on one surface 1a of a substrate 1, and an adhesive layer 4 is provided on the other surface 1b. It has a layer structure. The protective layer 3 is a form of the resin layer according to the present invention.

  As the substrate 1, a polyester film is used. For example, a film made of polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexylene methylene terephthalate, or a mixed resin in which two or more of these are combined is used. . Among these, from the viewpoint of performance, a polyethylene terephthalate (PET) film is preferable, and a biaxially stretched polyethylene terephthalate (PET) film is particularly preferable.

  The reflective layer 2 is a vapor deposition layer formed on the surface (one surface) 1a of the substrate 1 by vapor deposition. Examples of the method for forming the vapor deposition layer include physical vapor deposition (PVD) such as sputtering, vacuum vapor deposition, and ion plating. Here, in vacuum vapor deposition, the reflective layer 2 is formed on the substrate 1 by heating and evaporating the vapor deposition material by a method such as resistance heating, electron beam heating, laser beam heating, or arc discharge in vacuum. In sputtering, in a vacuum containing an inert gas such as argon, cations such as Ar + accelerated by glow discharge are bombarded on the target (deposition material) to sputter evaporate the deposition material. Thus, the reflective layer 2 is formed on the substrate 1. Ion plating is a vapor deposition method that combines vacuum vapor deposition and sputtering. In this method, the evaporation layer released by heating is ionized and accelerated in an electric field in vacuum, and is deposited on the substrate 1 in a high energy state, whereby the reflective layer 2 is formed.

  The reflective layer 2 has a multi-layer structure in which a translucent metal layer 2a is sandwiched between a pair of metal oxide layers 2b and 2c. Surface) 1a, a metal oxide layer 2b is deposited, then a semitransparent metal layer 2a is deposited on the metal oxide layer 2b, and finally a metal oxide layer 2c is deposited on the semitransparent metal layer 2a. Formed. The translucent metal layer 2a includes, for example, aluminum (Al), silver (Ag), silver alloy (MgAg, Ag—Pd—Cu alloy (APC), AgCu, AgAuCu, AgPd, AgAu, etc.), aluminum alloy (AlLi, AlCa, etc.) , AlMg, etc.), or a metal material in which two or more of these are combined. The metal oxide layers 2b and 2c are for imparting transparency to the reflective layer 2 and preventing deterioration of the translucent metal layer 2a. For example, indium tin oxide (ITO), indium titanium oxide (IT) An oxide such as indium zinc oxide (IZO), gallium zinc oxide (GZO), aluminum zinc oxide (AZO), or indium gallium oxide (IGO) is used.

The protective layer 3 is a layer containing a polymer containing at least any two or more repeating units among the repeating units A, B and C of the following chemical formula I. As R1 in Chemical Formula I, H or a methyl group can be used. As R2 to R5 in Chemical Formula I, H, an alkyl group having 1 to 4 carbon atoms, or an alkenyl group can be used. By the way, those composed of repeating units A, B and C and using H as R1 to R5 are hydrogenated nitrile rubber (HNBR).

Examples of monomer components for obtaining these polymers include acrylonitrile (repeating unit D) and derivatives thereof as shown in Chemical Formula II, alkyl having 4 carbon atoms (repeating unit E) and derivatives thereof, and butadiene ( And a copolymer of the repeating unit F1 or F2) and derivatives thereof. Here, R6 represents H or a methyl group, and R7 to R18 represent H or an alkyl group having 1 to 4 carbon atoms. Each of F1 and F2 represents a repeating unit in which butadiene is polymerized, and F1 is a main repeating unit. These polymers are contained in nitrile rubber or nitrile rubber which is a copolymer of acrylonitrile of formula II (repeating unit D) and derivatives thereof, 1,3-butadiene (repeating unit F1) and derivatives thereof. Hydrogenated nitrile rubber in which part or all of the double bond is hydrogenated may be used.

The relationship between the copolymer obtained by polymerizing acrylonitrile, butadiene, and alkyl and each of the repeating units A, B, and C will be described using the chemical formula III obtained by partially cutting the copolymer. Formula III is obtained by cutting out a part of the polymer chain used in the protective layer 3, and 1,3-butadiene (repeating unit F1), acrylonitrile (repeating unit D), and 1,3-butadiene (repeating unit F1). Are combined in order. Chemical formula III shows an example in which R7, R11 to R14 are H. In Formula III, the butadiene on the left side is bonded to the side to which the cyano group (—CN) of acrylonitrile is bonded, and the butadiene on the right side is formed to the side to which the cyano group (—CN) of acrylonitrile is not bonded. . In such a coupling example, one repeating unit A, one repeating unit B, and two repeating units C are included. Among them, the repeating unit A contains a carbon atom in which the carbon atom on the right side of the left butadiene and the cyano group (—CN) of acrylonitrile are bonded, and the repeating unit B is bonded to the cyano group (—CN) of acrylonitrile. A combination of carbon atoms that are not present and the left carbon atom of the right butadiene. The leftmost carbon atom of the left butadiene and the rightmost carbon atom of the right butadiene become part of the repeating unit A or the repeating unit B depending on the type of molecule to be bonded.

  The protective layer 3 is prepared by dissolving the above-described polymer in a solvent (with a crosslinking agent if necessary), applying the solution on the reflective layer 2, and then drying the solution (solvent Is volatilized). The solvent is a solvent in which the above-described polymer is soluble. For example, a solvent such as methyl ethyl ketone (MEK) or methylene chloride (dichloromethane) is used. Methyl ethyl ketone and methylene chloride are low-boiling solvents (methyl ethyl ketone is 79.5 ° C. and methylene chloride is 40 ° C.). Therefore, when these solvents are used, the solvent can be volatilized at a low drying temperature, so that the substrate 1 (or the reflective layer 2) is not damaged by heat.

  The thickness of the protective layer 3 is 1 μm or more as a lower limit value. Preferably, it is 3 μm or more. Moreover, as an upper limit, it is 20 micrometers or less. Preferably, it is 15 μm or less. More preferably, it is 10 μm or less. When the thickness of the protective layer 3 is small, the infrared reflection characteristics are enhanced, but the scratch resistance is impaired, and the function as the protective layer 3 cannot be sufficiently exhibited. If the thickness of the protective layer 3 is large, the heat insulating property of the infrared reflective film is deteriorated. When the thickness of the protective layer 3 is within the above range, the protective layer 3 that can absorb the infrared rays and can appropriately protect the reflective layer 2 is obtained.

  The vertical emissivity is expressed by vertical emissivity (εn) = 1−spectral reflectance (ρn) as defined in JIS R3106. Spectral reflectance ρn is measured in a wavelength range of 5 to 50 μm of normal temperature thermal radiation. The wavelength region of 5 to 50 μm is the far infrared region, and the vertical emissivity decreases as the reflectance of the far infrared wavelength region increases.

  In the chemical formula I, the ratio of k, l and m is k: l: m = 5 to 50% by weight: 25 to 85% by weight: 0 to 60% by weight (however, the sum of k, l and m is 100 % By weight). More preferably, it is k: l: m = 15-40 weight%: 55-85 weight%: 0-20 weight% (however, the sum total of k, l, and m is 100 weight%). More preferably, it is k: l: m = 25-40 weight%: 55-75 weight%: 0-10 weight% (however, the sum of k, l, and m is 100 weight%).

  By the way, from the viewpoint of imparting good solvent resistance to the protective layer 3, the protective layer 3 preferably has a crosslinked structure of polymers. By cross-linking the polymers, the solvent resistance of the protective layer 3 is improved, so that the protective layer 3 is prevented from eluting even when a solvent soluble in the polymer contacts the protective layer 3. can do.

  As a means for imparting a cross-linked structure between polymers, it is possible to irradiate an electron beam after drying the solution. The cumulative irradiation dose of the electron beam is 50 kGy or more as a lower limit value. Preferably, it is 100 kGy or more. More preferably, it is 200 kGy or more. Moreover, as an upper limit, it is 1000 kGy or less. Preferably, it is 600 kGy or less. More preferably, it is 400 kGy or less. The cumulative irradiation dose refers to the irradiation dose when the electron beam is irradiated once, and the total irradiation dose when the electron beam is irradiated a plurality of times. The single irradiation dose of the electron beam is preferably 300 kGy or less. If the integrated irradiation dose of the electron beam is within the above range, sufficient crosslinking between the polymers can be obtained. Moreover, if the integrated irradiation dose of the electron beam is within the above range, yellowing of the polymer and the substrate 1 generated by the electron beam irradiation can be minimized, and an infrared reflective film with less coloring can be obtained. Can do. These electron beam irradiation conditions are irradiation conditions at an acceleration voltage of 150 kV.

  Moreover, it is preferable to add a crosslinking agent such as a polyfunctional monomer such as a radical polymerization monomer when the polymer is dissolved in the solvent or after the polymer is dissolved in the solvent. In particular, radical polymerization monomers of (meth) acrylate monomers are preferred. When a polyfunctional monomer is added, the functional group contained in the polyfunctional monomer reacts (bonds) with each polymer chain, so that the polymers are easily cross-linked (via the polyfunctional monomer). Therefore, sufficient cross-linking between the polymers can be obtained even when the integrated irradiation dose of the electron beam is lowered (to about 50 kGy). Therefore, the accumulated irradiation dose of the electron beam can be completed with a low irradiation dose. Moreover, yellowing of the polymer and the substrate 1 can be further suppressed by reducing the cumulative irradiation dose of the electron beam, and productivity can be improved.

  However, if the additive amount is increased, the vertical emissivity of the surface of the infrared reflective film on the protective layer 3 side (based on the reflective layer 2) deteriorates. When the vertical emissivity is deteriorated, the infrared reflection property of the infrared reflection film is lowered, and the heat insulation property of the infrared reflection film is deteriorated. Therefore, it is preferable that the addition amount of an additive is 1-35 weight% with respect to a polymer | macromolecule. More preferably, it is 2 to 25% by weight based on the polymer.

  The dynamic friction coefficient on the surface of the protective layer 3 is 0.001 to 0.45. The dynamic friction coefficient can be measured by, for example, a ball-on-disk type frictional wear tester 5. More specifically, as shown in FIG. 2, in the ball-on-disk type frictional wear testing machine 5, the fixed ball 7 is disposed on the sample disk 6, and a load from the weight 8 is applied from above the fixed ball 7. It is configured as follows. In this state, the frictional force generated by the rotation of the sample disk 6 is measured by the sensor 9, and the frictional coefficient is calculated by dividing the measured frictional force by the load applied from above the fixed ball 7. By setting the dynamic friction coefficient on the surface of the protective layer 3 within the above range, it is possible to impart a good slip property (slip property) to the surface of the protective layer 3.

  As a method for adjusting the dynamic friction coefficient of the surface of the protective layer 3 to the above range, a base material (release liner) in which a silicone component is formed on a protective layer (layer formed of the above-described polymer) irradiated with an electron beam is used. The method of bonding and transferring a silicone component to the surface of the protective layer 3 is mentioned.

  The silicone component in the present invention is a methyl group or a methoxy group in the silicon atom of a siloxane skeleton (the number of repeating units of silicon atom and oxygen atom is usually about 10 to 8000) in which silicon atoms and oxygen atoms are alternately bonded in the molecule. Is a bonded polymer. The methyl group may be a compound partially substituted with an organic functional group such as a phenyl group, a vinyl group, or an amino group. The terminal or side chain of the polymer may have a polymerizable functional group such as a silanol group (—Si—OH), an alkenyl group, an epoxy group, or a (meth) acryloyl group, and is included in the polymer. The number of the polymerizable functional groups to be formed is not particularly limited, and may have a polymerizable functional group at both ends, and in the case of a branched polymer, the polymerizable functional group at both ends and side chains. You may have. Moreover, the friction coefficient of a protective layer should just be reduced sufficiently, and the number of repetitions of a silicon atom and an oxygen atom is not limited to the said value.

  As another transfer method, the pressure-sensitive adhesive layer side of the base material in which the silicone component is formed on the surface opposite to the pressure-sensitive adhesive layer of the resin base material (release liner) having the pressure-sensitive adhesive layer is used as the silicone component. A method of transferring the silicone component to the surface of the protective layer 3 by coating (bonding) the resin base material (release liner) on the protective layer 3 or forming a silicone component on one surface There is a method of transferring the silicone component to the surface of the protective layer 3 by coating (bonding) the one surface side of the resin base material (release liner) on the protective layer 3.

  The base material (release liner) on which these silicone components are formed is classified into a heat curable type or an active energy ray curable type. The thermosetting type is further classified into a condensation reaction type and an addition reaction type. The active energy ray curable type is further classified into an ultraviolet ray curable type (radical polymerization type and cationic polymerization type) and an electron beam curable type.

  In the condensation reaction type, for example, a base polymer having silanol groups (—Si—OH) at both ends of a siloxane molecule and a part of methyl groups of polymethylhydrosiloxane or polymethylhydrosiloxane having hydrogen atoms are converted to methoxy groups. A crosslinked product obtained by subjecting the modified crosslinking agent to a dehydrogenation reaction or dealcoholization reaction under an organotin catalyst is used for the silicone treatment. A silicone polymer having a molecular weight lower than that of the base polymer may be separately added to the crosslinked product for the purpose of adjusting the peeling force from the base material. Among these, it is presumed that the base polymer, the component of the crosslinking agent, and the low molecular weight silicone polymer, which are unreacted components of the above reaction, contribute to the reduction of the dynamic friction coefficient.

  In the addition reaction type, for example, a base polymer having an alkenyl group such as a vinyl group at both ends or both ends and side chains of a siloxane molecule and polymethylhydrosiloxane having a hydrogen atom are hydrosilylated under a platinum catalyst (addition reaction). The cross-linked product obtained by is used. For the purpose of adjusting the peeling force from the release liner, a silicone polymer having a lower molecular weight than the base polymer may be added separately to the crosslinked product. Among these, it is presumed that the base polymer, the component of the crosslinking agent, and the low molecular weight silicone polymer, which are unreacted components of the above reaction, contribute to the reduction of the dynamic friction coefficient.

  In the active energy ray curable type as well, it is presumed that the unreacted components of the respective materials contribute to the reduction of the dynamic friction coefficient on the surface of the protective layer 3 in the same manner as above.

  Since there is a tendency for more unreacted components to contribute to the reduction of the dynamic friction coefficient compared to other reaction types, the resin base material is preferably a condensation reaction type.

  Since the low molecular weight silicone polymer added for the purpose of adjusting the peeling force contributes to the reduction of the dynamic friction coefficient, the release liner preferably contains a low molecular weight silicone polymer in the silicone component layer.

  The material used for the substrate is not particularly limited, but is typically polyethylene terephthalate. As a base material (release liner) having a silicone component formed on the surface, a release polyester film treated with a commercially available silicone such as “MRE” series and “MRN” series of trade name “Diafoil” manufactured by Mitsubishi Plastics, Inc. Can be used. In the examples, a thermosetting condensation reaction type silicone component and a thermosetting addition type silicone component are employed as the base material (release liner), but the base material is not limited to this. .

  By the way, the reason for irradiating the electron beam prior to bonding the base material (release liner) onto the protective layer 3 is not only to give a cross-linked structure to the polymers in the protective layer 3 as described above. This is because radicals are generated on the surface of the protective layer 3 by irradiating the electron beam, so that the transfer of the silicone component to the surface of the protective layer 3 after the base material is bonded onto the protective layer 3 is promoted. That is, the purpose of electron beam irradiation is to impart a crosslinked structure to the polymers in the protective layer 3 and to promote the transfer of the silicone component to the surface of the protective layer 3.

  So, when irradiating an electron beam several times, after irradiating an electron beam, a base material is bonded together on the protective layer 3, and after a while (after sufficient time for the silicone component to be transferred), It is preferable to repeat the procedure of peeling and irradiating the electron beam again, and then newly bonding the base material on the protective layer 3. Thereby, the transfer amount of a silicone component can be increased, and slip property (slip property) can further be improved.

  The bonding of the base material onto the protective layer 3 is preferably performed within 15 minutes after irradiation with an electron beam. More preferably, it is within 1 minute. More preferably, it is within 15 seconds. After irradiating the electron beam, the dynamic friction coefficient can be satisfactorily reduced by laminating the base material on the protective layer 3 within the above time.

  Moreover, after bonding a base material on the protective layer 3, it is preferable to maintain the bonded state (covering state) for 2 days or more. More preferably, it is 6 days or more. However, when the base material is pasted on the protective layer 3 after 15 minutes have elapsed after irradiation with the electron beam, the dynamic friction coefficient can be reduced by maintaining the pasted state for 7 days or longer. It becomes possible.

  The time sufficient to transfer a sufficient amount of silicone can be shortened by heating. For example, when the base material is bonded onto the protective layer 3 and then heated at 50 ° C., it is desirable to maintain the bonded state (covered state) for 12 hours. More preferably, it is one day or longer. By setting the covering state within the above range, the dynamic friction coefficient can be reduced more favorably.

After transfer, the range of the amount of the silicone component constituting the surface of the protective layer 3 (silicone transfer amount) is ^{0.0001g / m 2 ~1.0000g / m 2} . Preferably ^{0.0002g / m 2 ~0.5000g / m 2} , more preferably ^{0.0004g / m 2 ~0.3000g / m 2} , more preferably at 0.0005g ^{/ m 2} ~0.1000g ^/ m 2 is there. When the silicone transfer amount is 0.0001 g / m ² or less, the protective layer 3 is not imparted with good slip properties, and when it exceeds 1.0000 g / m ² , the surface may be whitened.
On the other hand, by setting the silicone transfer amount within the above range, it is possible to impart good slip properties (slip properties) to the infrared reflective film. The silicone transfer amount is the amount of the silicone component present on the surface of the protective layer 3 after the substrate used for transfer is peeled to expose the silicone component.

The amount of silicone transferred can be measured using, for example, a fluorescent X-ray diffractometer. More specifically, as shown in the examples described later, measurement is performed on the silicone component layer on the surface of the protective layer 3 using fluorescent X-ray diffraction (XRF) to obtain a Si-Ka curve. The strength of Si element is obtained from the obtained Si-Ka curve, the strength is converted into the amount of Si element, and the amount of Si element is further converted into the amount of transferred silicone (the amount of compound). Can be measured.

  In addition, when an electron beam is irradiated in a state where the base material is bonded to the protective layer 3, the polymer contained in the protective layer 3 activated by the electron beam and the component contained in the base material are combined, Since peeling of a base material becomes difficult, it is not preferable.

  According to the infrared reflective film according to the present embodiment having the above-described configuration, the thickness of the layer structure on the reflective layer 2, that is, the thickness of the protective layer 3 is reduced to protect (based on the reflective layer 2). The vertical emissivity of the surface on the layer 3 side is small. In particular, if the protective layer 3 is made of nitrile rubber, hydrogenated nitrile rubber, fully hydrogenated nitrile rubber, or the like, which hardly absorbs far-infrared rays and is easily transmitted, the vertical emissivity is also reduced. Accordingly, far infrared rays are not easily absorbed by the protective layer 3 even if they are incident on the protective layer 3, reach the reflective layer 2, and as a result, are easily reflected by the reflective layer 2. Therefore, by sticking the infrared reflective film according to the present embodiment to a light transmissive member such as a window glass from the indoor side, it is possible to shield far infrared rays emitted from the room through the light transmissive member to the outside. In this way, a heat insulation effect can be expected in winter and at night when the indoor temperature decreases. In the infrared reflective film according to the present embodiment, the vertical emissivity of the surface on the protective layer 3 side is set to 0.20 or less for the purpose. More preferably, the vertical emissivity is 0.15 or less.

  Moreover, according to the infrared reflective film which concerns on this embodiment, the translucency of a translucent member is not inhibited by making visible light transmittance (refer JISA5759) high. In the infrared reflective film according to this embodiment, the visible light transmittance is set to 50% or more for the purpose.

  Further, even if near-infrared rays are incident on the base material 1 (adhesive layer 4 and) and are hardly absorbed by the base material 1 and reach the reflective layer 2, and as a result, are reflected by the reflective layer 2. It becomes easy. Therefore, by sticking the infrared reflective film according to the present embodiment to a light transmissive member such as a window glass from the indoor side, the near infrared light incident on the room through the light transmissive member such as the window glass is shielded. Thus, as in the case of a conventional infrared reflective film, a heat shielding effect in summer can be expected. In the infrared reflective film according to this embodiment, for that purpose, the solar transmittance (see JIS A5759) when light is incident from the surface of the substrate 1 side (based on the reflective layer 2) is 60% or less. Set to

  And according to the infrared reflective film which concerns on this embodiment, the favorable solvent resistance is provided to the protective layer 3 as mentioned above. That is, the solvent resistance of the protective layer 3 is improved by crosslinking the polymers in the protective layer 3 together. Accordingly, even when a solvent capable of dissolving a polymer comes into contact with the protective layer 3, it is possible to prevent the protective layer 3 from being eluted. Can be prevented from decreasing.

  And according to the infrared reflective film which concerns on this embodiment of the above structure, since the dynamic friction coefficient of the protective layer 3 surface is 0.001-0.45 as mentioned above, the slip property (slippery) of the protective layer 3 surface is Property), an excessive force (stress) does not act on the surface of the protective layer 3, and the protective layer 3 is not easily or partially destroyed. Therefore, it is possible to prevent a situation in which the reflective layer 2 having low scratch resistance is exposed due to destruction of the protective layer 3 and the reflective layer 2 is damaged. Moreover, this can prevent the infrared reflection characteristics from being impaired and the infrared reflection film from sufficiently functioning.

  Here, the present inventors produced the infrared reflective film which concerns on this embodiment (Example), and also produced the infrared reflective film for a comparison (comparative example).

  In both the examples and the comparative examples, the manufacturing method is as follows. A polyethylene terephthalate film (trade name “Diafoil T602E50” manufactured by Mitsubishi Plastics, Inc.) having a thickness of 50 μm was used as the substrate 1. A reflective layer 2 was formed on one surface 1a of the substrate 1 by DC magnetron sputtering. Specifically, using a DC magnetron sputtering method, a metal oxide layer 2b made of indium tin oxide is formed on one surface 1a of the substrate 1 with a thickness of 35 nm, and a translucent made of an Ag—Pd—Cu alloy is formed thereon. The metal layer 2a was formed with a thickness of 18 nm, and the metal oxide layer 2c made of indium tin oxide was formed thereon with a thickness of 35 nm. A protective layer 3 was formed on the reflective layer 2 by a coating method. The detailed formation conditions of the protective layer 3 will be described in detail in the description of Examples and Comparative Examples.

<Example 1>
Hydrogenated nitrile rubber (trade name “Telvan 5065” [k: 33.3, l: 63, m: 3.7, R1 to R3: H]) 10% by weight and methyl ethyl ketone (Wako Pure Chemical Industries, Ltd.) 90% by weight was mixed and stirred and dissolved at a temperature of 80 ° C. for 5 hours to dissolve the hydrogenated nitrile rubber in a solvent of methyl ethyl ketone to prepare a solution. And the solution was apply | coated using the applicator on the reflection layer 2, and it put into the air circulation type drying oven, and dried for 10 minutes at 80 degreeC. Thereby, the protective layer 3 having a thickness of 5 μm was formed. Then, the electron beam was irradiated from the surface side of the protective layer 3 using the electron beam irradiation apparatus (Iwasaki Electric Co., Ltd. product name "EC250 / 30 / 20mA"). The electron beam irradiation conditions were a line speed of 3 m / min, an acceleration voltage of 150 kV, and an integrated irradiation dose of 600 kGy. In this example, an electron beam having a single irradiation dose of 200 kGy was irradiated three times. More specifically, first, an electron beam having an irradiation dose of 200 kGy is irradiated from the surface side of the protective layer 3 as described above (first time), and then a polyester-based release liner ( A product name “Diafoil MRN38” manufactured by Mitsubishi Plastics, Inc.) was attached. Then, after 1 minute, the polyester release liner was peeled off. Next, an electron beam having an irradiation dose of 200 kGy was irradiated from the surface side of the protective layer 3 (second time), and then a new polyester release liner was bonded to the surface of the protective layer 3. Then, after 1 minute, the polyester release liner was peeled off. Similarly, an electron beam having an irradiation dose of 200 kGy was irradiated from the surface side of the protective layer 3 (third time), and then a new polyester release liner was bonded to the surface of the protective layer 3. Then, after 1 minute, the polyester release liner was peeled off. By doing in this way, the infrared reflective film which concerns on Example 1 was obtained. In addition, after irradiating the electron beam for the 3rd time, the polyester-type release liner was bonded together on the surface of the protective layer 3 within 10 second.

<Example 2>
Hydrogenated nitrile rubber (HNBR: trade name “Terban 5005” [k: 33.3, l: 66.7, m: 0, R1 to R3: H]) manufactured by LANXESS was used as a material for the protective layer. Except for this point, the second embodiment is the same as the first embodiment.

<Example 3>
As a material used for the protective layer, acrylonitrile butadiene rubber (NBR: trade name “JSR N222L” manufactured by JSR Corporation [k: 27.4, l: 36.3, m: 36.3, R1, R4, R5: H] ) Is the same as Example 1.

<Example 4>
When preparing the solution, as a leveling agent, 0.5% of the product name “GRANDIC PC4100” manufactured by DIC was added to the solid content of the hydrogenated nitrile rubber, and the electron beam was irradiated once. An infrared reflective film was obtained in the same manner as in Example 2 except that the irradiation dose was 100 kGy and the release film was a polyester release liner (trade name “Diafoil MRE38” manufactured by Mitsubishi Plastics, Inc.). In addition, after irradiating an electron beam, the polyester-type release liner was bonded together on the surface of the protective layer 3 within 10 second.

<Example 5>
An infrared reflective film was obtained in the same manner as in Example 4 except that bonding of the polyester release liner to the surface of the protective layer 3 was performed about 10 minutes after irradiation with the electron beam.

<Example 6>
When irradiating an electron beam, the infrared reflective film was obtained by the method similar to Example 5 except the irradiation dose being 80 kGy.

<Comparative Example 1>
An infrared reflective film was obtained in the same manner as in Example 1 except that the polyester release liner was not laminated after each electron beam irradiation.

<Comparative example 2>
As the polyester release liner, the product name “Diafoil MRF38” manufactured by Mitsubishi Plastics, Inc. was used instead of the product name “Diafoil MRN38” manufactured by Mitsubishi Plastics, and the electron beam was irradiated from the surface side of the protective layer 3 After that, the polyester release liner was not bonded to the surface of the protective layer 3, but the electron beam was irradiated while the polyester release liner was bonded to the surface of the protective layer 3. Example 1 In the same manner, an infrared reflective film was obtained.

<Evaluation>
And about each of Examples 1-6 and Comparative Examples 1-2, the dynamic friction coefficient of the protective layer 3 surface of an infrared reflective film, the vertical emissivity of an infrared reflective film, and the silicone transfer amount were measured with the following method. These results are shown in Table 1. The measurement of the dynamic friction coefficient, the vertical emissivity, and the amount of silicone transfer were performed after the last release of the polyester-based release liner bonded after the last electron beam irradiation (or after the irradiation when the electron beam is irradiated only once). I went there.

  For the measurement of the dynamic friction coefficient of the surface of the protective layer 3 in each of Examples 1 to 6 and Comparative Examples 1 and 2, a friction and wear tester (FPR-2100 manufactured by Reska Co., Ltd.) was used. The measurement conditions of the dynamic friction coefficient in Examples 1 to 6 and Comparative Examples 1 to 2 were 50 g load, 5 rpm rotation speed, 5 mm rotation radius, 60 s measurement time, and 500 ms sampling time. Samples used in Examples 1 to 6 and Comparative Examples 1 and 2 were prepared by sticking to a glass (5 cm × 4.5 cm × 1.2 mm thickness) via an adhesive. The dynamic friction coefficient was calculated from the average value of the sampling data. In addition, when the dynamic friction coefficient on the surface of the protective layer 3 is 0.001 to 0.45, the slip property (slip property) is considered good.

  The method for measuring the vertical emissivity is as follows. Using a Fourier transform infrared spectroscopic (FT-IR) apparatus (manufactured by Varian) equipped with a variable angle reflection accessory, the regular reflectance of infrared light having a wavelength of 5 to 25 microns was measured, and JIS R 3106 It calculated | required according to 2008 (The test method of the transmittance | permeability, reflectance, emissivity, and solar heat acquisition rate of plate glass).

The silicone transfer amount was measured using a fluorescent X-ray diffraction (XRF) apparatus (ZSX100e, manufactured by Rigaku Corporation). The XRF measurement conditions were as follows: X-ray source: vertical Rh tube, analysis area: 30 mmφ, analysis element: Si, spectral crystal: RX4, output: 50 kV, 70 mA. The Si-Ka curve was obtained from the above measurement, the strength of the Si element was obtained from the obtained Si-Ka curve, and the amount of Si element was obtained from the obtained strength. Then, the amount of Si element obtained was converted to the mass of dimethylsiloxane, and the transfer amount of the silicone component was determined.

As shown in Table 1, in the result of Example 1, the dynamic friction coefficient of the surface of the protective layer 3 in the infrared reflective film is 0.015 (within a range of 0.001 to 0.45), and the vertical emissivity is 0. .11 (0.20 or less), and both the dynamic friction coefficient and the normal emissivity showed good values. The silicone transfer amount was 0.0040 g / m ² .

Moreover, in the result of Example 2, as a material used for the protective layer 3, hydrogenated nitrile rubber (trade name “Terban 5005” manufactured by HNBR: LANXESS Co., Ltd. [k: 33.3, l: 66.7, m: 0, R1-R3: H]), the dynamic friction coefficient of the surface of the protective layer 3 in the infrared reflective film is 0.026 (in the range of 0.001-0.45), and the vertical emissivity is 0.00. 10 (0.20 or less), and both the dynamic friction coefficient and the vertical emissivity showed good values. Moreover, the silicone transfer amount was 0.0026 g / m ² .

And in the result of Example 3, as a material used for the protective layer 3, acrylonitrile butadiene rubber (trade name "JSR N222L" manufactured by NBR: JSR Corporation [k: 27.4, l: 36.3, m: 36. 3, R1, R4, R5: H]), the dynamic friction coefficient of the surface of the protective layer 3 in the infrared reflective film is 0.030 (in the range of 0.001 to 0.45), and the vertical radiation The rate was 0.14 (0.20 or less), and both the dynamic friction coefficient and the vertical emissivity showed good values. The silicone transfer amount was 0.0021 g / m ² .

Moreover, in the result of Example 4, as a leveling agent, 0.5% of the product name “GRANDIC PC4100” manufactured by DIC was added to the solid content of the hydrogenated nitrile rubber, and the electron beam was irradiated once, and the polyester was used. Even when a system release liner (trade name “Diafoil MRE38” manufactured by Mitsubishi Plastics, Inc.) is used, the coefficient of dynamic friction on the surface of the protective layer 3 in the infrared reflective film is 0.066 (within a range of 0.001 to 0.45). In addition, the vertical emissivity was 0.12 (0.20 or less), and both the dynamic friction coefficient and the vertical emissivity showed good values. Moreover, the silicone transfer amount was 0.0014 g / m ² .

Further, in the result of Example 5, even when the time for bonding the polyester release liner to the surface of the protective layer 3 after irradiation with the electron beam was extended from within 10 seconds to about 10 minutes, the protective layer in the infrared reflective film 3 The dynamic friction coefficient of the surface is 0.088 (within the range of 0.001 to 0.45), the vertical emissivity is 0.13 (0.20 or less), and both the dynamic friction coefficient and the vertical emissivity are good. Showed a good value. The silicone transfer amount was 0.0006 g / m ² .

In the result of Example 6, even when the electron beam irradiation dose was 80 kGy and the number of irradiations was 1, the dynamic friction coefficient of the surface of the protective layer 3 in the infrared reflective film was 0.086 (in the range of 0.001 to 0.45). ), The vertical emissivity was 0.12 (0.20 or less), and both the dynamic friction coefficient and the vertical emissivity showed good values. The silicone transfer amount was 0.0006 g / m ² .

Further, in the result of Comparative Example 1, when the polyester release liner is not laminated after each electron beam irradiation, the vertical emissivity is 0.11 (0.20 or less), but the dynamic friction coefficient is 0.54 and 0.00. A value higher than 001 to 0.45 was shown, and good results were not obtained. In Comparative Example 1, the silicone component was not transferred to the protective layer 3 (the transfer amount of the silicone component was 0.0000 g / m ² ), and from this, the transfer of the silicone component contributed to imparting slipperiness. I found out.

  And in the result of the comparative example 2, when using Mitsubishi Plastics Co., Ltd. brand name "Diafoil MRF38" as a polyester-type release liner, as mentioned above, it is included in the protective layer 3 activated by the electron beam. Since the polymer to be bonded to the component contained in the base material (release liner) is difficult to release the base material (release liner) after the first electron beam irradiation, the dynamic friction on the surface of the protective layer 3 The coefficient, vertical emissivity, and silicone transfer amount were not measurable. For this reason, the electron beam was irradiated only once.

  In addition, the low friction base material and its manufacturing method which concern on this invention are not limited to the said embodiment, A various change is possible in the range which does not deviate from the summary of this invention.

  For example, in the said embodiment, the infrared reflective film was made into object and the improvement of the slip property (slidability) in the surface (protective layer 3) of the infrared reflective film was demonstrated. However, the present invention is not limited to the infrared reflective film. INDUSTRIAL APPLICABILITY The present invention can be applied to all fields and products that require a low friction base material having a low surface friction coefficient and excellent slip property (slip property).

  Therefore, in the said embodiment, although the base material 1 was resin, such as a polyester-type film, it is not limited to resin, For example, a metal sheet may be sufficient.

  Moreover, in the said embodiment, although the multilayer substrate of the base material 1 and the protective layer 3 became object, a single layer base material may be sufficient as the base material made into a low friction base material. Therefore, for example, a method for transferring a silicone component to the surface of a single-layer polyester film is also within the scope of the present invention.

  Moreover, in the said embodiment, the example which mainly irradiates an electron beam in multiple times was demonstrated. However, even when the electron beam is irradiated only once, the slipping property (sliding property) can be improved, which is the range intended by the present invention.

  Prior to the first irradiation when the electron beam is irradiated a plurality of times or prior to the irradiation when the electron beam is irradiated only once, the resin layer (in the above embodiment, the protective layer 3) is subjected to a resin. If a layer containing a compound that generates radicals when irradiated with an electron beam is formed on the layer, even if the resin layer is not sufficiently high in radical generation when irradiating the electron beam on the resin layer itself, The degree of radical generation can be increased, thereby increasing the amount of transfer of the silicone component to the resin layer surface. An example of a method for forming a layer containing a compound that generates radicals when irradiated with an electron beam is a method of applying a silicone leveling agent.

  Moreover, in the said embodiment, the polymer which consists of at least any two or more repeating units among repeating units A and C or repeating units A, B, and C was demonstrated. However, the present invention is not limited to this. Other repeating units other than these repeating units can also be included as long as the properties required for the protective layer are not impaired. Examples of other repeating units include styrene, α-methylstyrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, vinyl acetate, and (meth) acrylamide. Etc. The ratio of these to the whole polymer is preferably 10% by weight or less.

  Moreover, in the said embodiment, the reflection layer 2 was formed by vapor deposition. However, the present invention is not limited to this.

  Moreover, in the said embodiment, although the polyester-type release liner was used as a release liner, it is not limited to this.

  Moreover, the infrared reflective film which concerns on the said embodiment is an infrared reflective film which has a heat-insulating characteristic and a heat insulation characteristic. However, the present invention is not limited to this. Needless to say, the infrared reflective film according to the present invention can also be applied to an infrared reflective film having only a conventional heat shielding property.

  DESCRIPTION OF SYMBOLS 1 ... Base material, 1a ... One side, 1b ... The other side, 2 ... Reflective layer, 2a ... Semi-transparent metal layer, 2b, 2c ... Metal oxide layer, 3 ... Protective layer (resin layer), 4 ... Adhesion layer

Claims (8)

Irradiating the resin layer of the substrate having a resin layer on at least the surface with an electron beam;
A method for producing a low friction substrate, comprising: irradiating the resin layer with an electron beam, and then attaching a silicone component to the surface of the resin layer. The method for producing a low-friction substrate according to claim 1, wherein the step of attaching the silicone component is a step of coating the resin layer on the surface side of the polymer film having the silicone component formed on the surface. The low-friction base material according to claim 1, further comprising a step of forming, on the resin layer, a layer containing a compound that generates radicals when the resin layer is irradiated with the electron beam before the electron beam irradiation step. Production method. The manufacturing method of the low friction base material of Claim 1. The dynamic friction coefficients of the resin layer surface after the process of making a silicone component adhere are 0.001-0.45. The resin layer is a layer containing a polymer containing at least any two or more repeating units among the repeating units A, B and C of the following chemical formula I.

The manufacturing method of the low friction base material of Claim 1. The method for producing a low friction base material according to claim 1, wherein the resin layer is a protective layer of an infrared reflective film in which a reflective layer and a protective layer are sequentially laminated on one surface of the base material. The method for producing a low friction substrate according to claim 6, wherein the vertical emissivity of the protective layer side surface is 0.20 or less. The protective layer further includes a silicone component constituting the surface of the protective layer,
Method for producing a low-friction base according to claim 6 the amount of the silicone component is 0.0001~1.0000g / ^{m 2.}

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