Patent Application
20250018525
This application claims priority to Japanese Patent Application No. 2023-112229 filed on Jul. 7, 2023, the disclosure of which is incorporated herein by reference in its entirety.
The present disclosure relates to a chemical mechanical polishing apparatus.
Chemical mechanical polishing is widely used as a method for polishing wafers, typified by semiconductor wafers. In the chemical mechanical polishing method, a surface is flattened by using a combination of physical and chemical polishing.
As such CMP apparatus, JP 2003-179021 A describes a chemical mechanical polishing apparatus to polish an object to be polished attached to a polishing head with a polishing pad, and further describes that each component of the chemical mechanical polishing apparatus positioned higher than the top surface of the polishing pad is hydrophobically treated. As such hydrophobic treatment, it describes the application of a fluorocarbon-based water-repellent coating material to form a fluorocarbon polymer.
JP 2018-531804 A describes an external clamp ring for a chemical mechanical polishing carrier head, and describes that the external clamp ring comprises a cylindrical body having a cylindrical outer wall and a cylindrical inner wall, and a hydrophobic layer disposed on the cylindrical outer wall of the body. It further describes that the hydrophobic layer can be formed from a silicone-based coating material, a PTFE-based coating material, or a carbon-containing material.
JP 2020-2183 A describes a silicone rubber formed article having a surface to be in contact with an article, wherein the surface to be in contact with the article is fluorinated to lower the rolling resistance coefficient. It further describes that the silicone rubber formed article can be an elastic film for holding wafers in a chemical mechanical polishing apparatus.
The present disclosure provides the following embodiments:
A chemical mechanical polishing apparatus, comprising one or more components,
The present disclosure can provide a novel chemical mechanical polishing apparatus and a novel method for treating a chemical mechanical polishing apparatus.
The FIGURE is a schematic diagram showing an example of the chemical mechanical polishing apparatus.
The chemical mechanical polishing apparatus of the present disclosure is provided with one or more components having a surface-treating layer formed using a fluoropolyether group-containing compound.
The present disclosure provides a novel chemical mechanical polishing apparatus.
A chemical mechanical polishing method typically uses a polishing slurry containing abrasive grains of silicon dioxide or the like and a basic compound. When such polishing slurry adheres to the surface of the chemical mechanical polishing apparatus, it may solidify and affect the polishing performance. In the chemical mechanical polishing apparatus of the present disclosure, in a preferred embodiment, the workability of the polishing slurry (such as repellency and/or removability of the polishing slurry) is good, and in a more preferred embodiment, the workability is good even after a period of time has passed since the adhesion of the polishing slurry. Although the present disclosure should not be construed as being limited to any particular theory, the reasons why such effects are exhibited in the chemical mechanical polishing apparatus of the present disclosure are thought to be as follows.
Namely, in the chemical mechanical polishing apparatus of the present disclosure, one or more of the components have a surface-treating layer formed using a fluoropolyether group-containing compound. Therefore, the adhesion of the polishing slurry can be suppressed and the interaction with solidified polishing slurry can be suppressed, which is thought to improve workability, particularly the workability after a period of time has passed. On the other hand, fluorocarbon polymers or fluorinated silicone rubber are used in conventional surface-treating layers, which may limit the surface-treatable components, and may make it difficult to sufficiently suppress the adhesion of the polishing slurry.
The chemical mechanical polishing apparatus of the present disclosure is typically provided with a rotatable surface plate, a polishing pad disposed on the surface plate, a polishing head disposed on the polishing pad, an arm part of the polishing head to fix the polishing head, a polishing slurry supply part, a polishing part cover, and a discharge groove.
The surface plate is typically formed in the shape of a disc and connected to a rotating shaft disposed below the surface plate. The rotation of the rotating shaft causes the surface plate to rotate. A polishing pad is fixed to the top of the surface plate, and polishing slurry is supplied on the polishing pad from the polishing slurry supply part.
The polishing head can be formed in the shape of a disc with a smaller diameter than the surface plate, and can be connected to the arm part of the polishing head disposed above the polishing head. The arm part may be provided with a rotating shaft, which is not shown in the FIGURE, and the direction of rotation of the rotating shaft of the arm part can be opposite to the direction of rotation of the rotating shaft of the surface plate.
An object to be polished can be mounted on the polishing head. The polishing head may be provided with a head body, a pressing member that presses the object to be polished downward (to the polishing pad), and a cushioning member disposed between the object to be polished and the pressing member.
The polishing part cover is disposed around the periphery of the surface plate, and a discharge groove can be disposed between the polishing part cover and the surface plate.
In one embodiment, in such chemical mechanical polishing apparatus, the object to be polished can be mounted on the polishing head. The object to be polished rotates together with the polishing head, and the polishing head presses one surface of the object to be polished onto the rotating surface plate at a predetermined pressure while rotating. In addition, polishing slurry is supplied from the polishing slurry supply part onto the surface plate (polishing pad), and the polishing slurry enters the gap between the surface plate (polishing pad) and the object to be polished, which allows one surface of the object to be polished and flattened.
The polishing slurry supplied on the rotating surface plate can be discharged from the discharge groove disposed between the polishing part cover and the surface plate as it is delivered to the polishing head.
The chemical mechanical polishing apparatus may be further provided with a conditioner disc disposed on the polishing pad and an arm part of the conditioner disc to fix the conditioner disc.
The conditioner disc can be formed in the shape of a disc with a smaller diameter than the surface plate, and can be connected to the arm part of the conditioner disc disposed above the conditioner disc. The arm part of the conditioner disc may be provided with a rotating shaft, which is not shown in the FIGURE, and the direction of rotation of the rotating shaft of the arm part can be opposite to the direction of rotation of the rotating shaft of the surface plate.
In one embodiment, when provided with such a conditioner disc, the conditioner disc can grind (dress) the surface of the polishing pad. This allows to suppress clogging of the polishing pad, which can be caused by the abrasive grains of the polishing slurry entering the pores of the polishing pad, thereby maintaining the polishing performance.
One or more of the components have a surface-treating layer formed using a fluoropolyether group-containing compound.
Examples of such component preferably include one or more selected from the surface plate, the polishing head, and the polishing slurry supply part, and more preferably include one or more selected from the surface plate, the rotating shaft of the surface plate, the polishing head, the arm part of the polishing head, the polishing slurry supply part, the arm part of the polishing slurry supply part, the polishing part cover, the discharge groove, and the arm part of the conditioner disc, but are not limited thereto. In one embodiment, such component preferably does not include the polishing pad and the conditioner disc.
Hereinafter, the present embodiment will be described more specifically based on the chemical mechanical polishing apparatus schematically shown in the FIGURE. The surface-treating layer is not shown in the FIGURE.
In the chemical mechanical polishing apparatus shown in the FIGURE, a surface plate 6a is connected to a rotating shaft 6b. A polishing pad 5 is fixed to the top of the surface plate 6a, and polishing slurry is supplied on the polishing pad 5 from a polishing slurry supply part 9. The polishing slurry supply part 9 is connected to an arm part 10 disposed above it.
On the polishing pad 5 are disposed a polishing head 3 and a conditioner disc 7. The polishing head 3 is formed with a smaller diameter than the surface plate 6a, and is connected to an arm part 4 disposed above the polishing head 3. On the polishing head 3 is mounted an object to be polished 2. The conditioner disc 7 is formed with a smaller diameter than the surface plate 6a, and is preferably formed with a smaller diameter than the polishing head 3. The conditioner disc is connected to an arm part 8 disposed above the conditioner disc.
Around the periphery of the surface plate 6a is disposed a polishing part cover 12, and between the surface plate 6a and the polishing part cover 12 is disposed a discharge groove 11.
In the chemical mechanical polishing apparatus shown in the FIGURE, as the surface plate 6a fixed to the polishing pad 5 begins to rotate, polishing slurry is added dropwise from the polishing slurry supply part 9. Here, the polishing slurry supply part 9 adds polishing slurry dropwise onto the polishing pad 5 and starts swinging. This swinging consists of swinging in a semicircular arc between the approximate center and the outer periphery of the surface plate 6a. When the polishing slurry has been uniformly added dropwise onto the polishing pad 5 of the surface plate 6a and is covering the entire surface of the polishing pad 5, the polishing head 3 on which the object to be polished 2 is fixed then presses the surface of the object to be polished 2 onto the polishing pad 5 while rotating. Here, the surface of the object to be polished 2, which is adsorbed on the polishing head 3, can swing in a direction horizontal to the top surface of the polishing pad 5, and can thereby be polished and flattened.
The polishing slurry can contain microparticles (abrasive grains) of silica (SiO2) and the like, a basic compound such as potassium hydroxide (KOH) and ammonium hydroxide (NH4OH), and an aqueous medium (typically water), and can be a suspension of the abrasive grains, basic compound, and aqueous medium. The particle size of the abrasive grains can be 0.1 μm or less.
In the chemical mechanical polishing apparatus 1 shown in the FIGURE, it is preferable that one or more selected from the surface plate 6a, the polishing head 3, and the polishing slurry supply part 9 have the surface-treating layer, and more preferable that one or more selected from the group consisting of the surface plate 6a, the rotating shaft 6b of the surface plate 6a, the polishing head 3, the arm part 4 of the polishing head, the polishing slurry supply part 9, the arm part 10 of the polishing slurry supply part, the polishing part cover 12, the discharge groove 11, the conditioner disc 7, and the arm part 8 of the conditioner disc have the surface-treating layer.
The thickness of the surface-treating layer is preferably 1 nm or more and 20 nm or less, more preferably 1 nm or more and 10 nm or less, and still more preferably 5 nm or more and 10 nm or less.
The surface-treating layer may be formed by applying a surface-treating agent containing a fluoropolyether group-containing compound according to the structure and material of the component to be treated. In one embodiment, such surface-treating agent may contain a compound having an acrylic group or an epoxy group, or a polyimide-based compound, in addition to the fluoropolyether group-containing compound. In such embodiment, the fluoropolyether group-containing compound is preferably a compound into which a functional group capable of reacting with a compound having an acrylic group or an epoxy group, or a polyimide-based compound, has been introduced.
In a preferred embodiment, the surface-treating layer can be formed using a fluoropolyether group-containing compound. Typically, the fluoropolyether group-containing compound can be a compound having a group in which one or more hydrogen atoms of a polyether group are substituted with a fluorine atom (fluoropolyether group).
Preferably, the fluoropolyether group-containing compound includes a fluoropolyether group-containing silane compound. Including a fluoropolyether group-containing silane compound allows to suppress particle generation even when polishing slurry adheres to the surface-treating layer.
The fluoropolyether group-containing silane compound preferably includes at least one fluoropolyether group-containing silane compound represented by the following formula
RF1α—XA—RSiβ (1)
RSiγ—XA—RF2—XA—RSiγ (2)
In the formula (1), RF1 is each independently at each occurrence Rf1—RF—Oq— or a fluoroalkyl group. In one embodiment, RF1 is preferably Rf1—RF—Oq—, and in another embodiment, RF1 is preferably a fluoroalkyl group. When RF1 is Rf1—RF—Oq—, the compound represented by formula (1) contains a fluoropolyether group and corresponds to a fluoropolyether group-containing silane compound.
In the formula (2), RF2 is —Rf2p—RF—Oq— or a fluoroalkylene group. In one embodiment, RF2 is preferably Rf2p—RF—Oq—, and in another embodiment, RF2 is preferably a fluoroalkylene group. When RF2 is Rf2p—RF—Oq—, the compound represented by formula (2) contains a fluoropolyether group and corresponds to a fluoropolyether group-containing silane compound.
In the formula, Rf1 is each independently at each occurrence a C1-16 alkyl group optionally substituted with one or more fluorine atoms.
In the C1-16 alkyl group optionally substituted with one or more fluorine atoms, the “C1-16 alkyl group” may be linear or branched, and is preferably a linear or branched C1-6 alkyl group, in particular C1-3 alkyl group, and more preferably a linear C1-6 alkyl group, in particular C1-3 alkyl group.
Rf1 is preferably a C1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF2H—C1-15 perfluoroalkyl group, still more preferably a C1-16 perfluoroalkyl group.
The C1-16 perfluoroalkyl group may be linear or branched, and is preferably a linear or branched C1-6 perfluoroalkyl group, in particular C1-3 perfluoroalkyl group, more preferably a linear C1-6 perfluoroalkyl group, in particular C1-3 perfluoroalkyl group, and specifically —CF3, —CF2CF3, or —CF2CF2CF3.
In the formula, Rf2 is a C1-6 alkylene group optionally substituted with one or more fluorine atoms.
In the C1-6 alkylene group optionally substituted with one or more fluorine atoms, the “C1-6 alkylene group” may be linear or branched, and is preferably a linear or branched C1-3 alkylene group, and more preferably a linear C1-3 alkylene group.
Rf2 is preferably a C1-6 alkylene group that is substituted with one or more fluorine atoms, more preferably a C1-6 perfluoroalkylene group, and still more preferably a C1-3 perfluoroalkylene group.
The C1-6 perfluoroalkylene group may be linear or branched, and is preferably a linear or branched C1-3 perfluoroalkylene group, more preferably a linear C1-3 perfluoroalkylene group, and specifically —CF2—, —CF2CF2—, or —CF2CF2CF2—.
In the formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.
In the formulae, q is each independently at each occurrence 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.
In the formulae (1) and (2), RF is each independently at each occurrence a divalent fluoropolyether group.
RF may preferably include a group represented by the following:
—(OCh1RFa2h1)h3—(OCh2RFa2h2-2)h4—
wherein
In one embodiment, RF may be linear or branched. RF is preferably a group represented by the formula:
—(OC6F12)a—(OC5F10)b—(OC4F8)c—(OC3RFa6)d—(OC2F4)e—(OCF2)f—
wherein
RFa is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom. However, when all RFa are a hydrogen atom or a chlorine atom, at least one of a, b, c, e, and f is 1 or more.
Preferably, a, b, c, d, e, and f are each independently an integer of 0 to 100.
The sum of a, b, c, d, e, and f is preferably 5 or more, and more preferably 10 or more, and may be, for example, 15 or more or 20 or more. The sum of a, b, c, d, e, and f is preferably 200 or less, more preferably 100 or less, and still more preferably 60 or less, and may be, for example, 50 or less or 30 or less.
These repeating units may be linear or branched, and may contain a ring structure. For example, —(OC6F12)— may be —(OCF2CF2CF2CF2CF2CF2)—, —(OCF(CF3)CF2CF2CF2CF2)—, —(OCF2CF(CF3)CF2CF2CF2)—, —(OCF2CF2CF(CF3)CF2CF2)—, —(OCF2CF2CF2CF(CF3) CF2)—, —(OCF2CF2CF2CF2CF(CF3))—, or the like. —(OC5F10)— may be —(OCF2CF2CF2CF2CF2)—, —(OCF(CF3)CF2CF2CF2)—, —(OCF2CF(CF3)CF2CF2)—, —(OCF2CF2CF(CF3)CF2)—, —(OCF2CF2CF2CF(CF3))—, or the like. —(OC4F8)— may be any of —(OCF2CF2CF2CF2)—, —(OCF(CF3)CF2CF2)—, —(OCF2CF(CF3)CF2)—, —(OCF2CF2CF(CF3))—, —(OC(CF3)2CF2)—, —(OCF2C(CF3)2)—, —(OCF(CF3)CF(CF3))—, —(OCF(C2F5)CF2)—, and —(OCF2CF(C2F5))—, —(OC3F6)— (that is, in the formula, RFa is a fluorine atom) may be any of —(OCF2CF2CF2)—, —(OCF(CF3)CF2)—, and —(OCF2CF(CF3))—, —(OC2F4)— may be any of —(OCF2CF2)— and —(OCF(CF3))—.
In one embodiment, the repeating units are linear. When the repeating units are linear, the surface lubricity, abrasion durability, and the like of the surface-treating layer can be improved.
In one embodiment, the repeating units are branched. When the repeating units are branched, the dynamic friction coefficient of the surface-treating layer can be increased.
In one embodiment, RF may contain a ring structure.
The ring structure may be the following three-membered ring, four-membered ring, five-membered ring, or six-membered ring:
wherein, * represents a binding position.
The ring structure may be preferably a four-membered ring, a five-membered ring, or a six-membered ring, and more preferably a four-membered ring or a six-membered ring.
The repeating units having a ring structure may be preferably the following units:
wherein, * represents a binding position.
In one embodiment, the repeating units are linear. When the repeating units are linear, the surface lubricity, abrasion durability, and the like of the surface-treating layer can be improved.
In one embodiment, the repeating units are branched. When the repeating units are branched, the dynamic friction coefficient of the surface-treating layer can be increased.
In one embodiment, RF is each independently at each occurrence a group represented by any of the following formulae (f1) to (f6):
—(OC3F6)d—(OC2F4)e— (f1)
wherein d is an integer of 1 to 200, and e is 0 or 1;
—(OC4F8)c—(OC3F6)d—(OC2F4)e—(OCF2)f— (f2)
wherein c and d are each independently an integer of 0 or more and 30 or less, and e and f are each independently an integer of 1 or more and 200 or less;
—(R6—R7)g- (f3)
wherein R6 is OCF2 or OC2F4;
—(R6—R7)g—Rr—(R7′—R6′)g′- (f4)
wherein R6 is OCF2 or OC2F4;
wherein, * represents a binding position;
—(OC6F12)a—(OC5F10)b—(OC4F8)c—(OC3F6)d—(OC2F4)e—(OCF2)f- (f5)
wherein e is an integer of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, and the occurrence order of the respective repeating units enclosed in parentheses provided with a, b, c, d, e or f is not limited in the formula; and
—(OC6F12)a—(OC5F10)b—(OC4F8)c—(OC3F6)d—(OC2F4)e—(OCF2)f- (f6)
wherein f is an integer of 1 or more and 200 or less, a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, and the occurrence order of the respective repeating units enclosed in parentheses provided with a, b, c, d, e or f is not limited in the formula.
In the formula (f1), d is preferably 5 to 200, more preferably 10 to 100, and still more preferably 15 to 50, and is, for example, an integer of 25 to 35. OC3F6 in the formula (f1) is preferably (OCF2CF2CF2), (OCF(CF3)CF2), or (OCF2CF(CF3)), and more preferably (OCF2CF2CF2). (OC2F4) in the formula (f1) is preferably (OCF2CF2) or (OCF(CF3)), and more preferably (OCF2CF2). In one embodiment, e is 0. In another embodiment, e is 1.
In the formula (f2), e and f are each independently an integer of preferably 5 to 200, and more preferably 10 to 200. In addition, the sum of c, d, e, and f is preferably 5 or more, and more preferably 10 or more, and it may be, for example, 15 or more or 20 or more. In one embodiment, the formula (f2) is preferably a group represented by —(OCF2CF2CF2CF2)c—(OCF2CF2CF2)d—(OCF2CF2)e—(OCF2)f—. In another embodiment, the formula (f2) may be a group represented by —(OC2F4)e—(OCF2)f—.
In the formula (f3), R6 is preferably OC2F4. In the formula (f3), R7 is preferably a group selected from OC2F4, OC3F6, and OC4F8, or a combination of two or three groups independently selected from these groups, and is more preferably a group selected from OC3F6 and OC4F8. Examples of the combination of two or three groups independently selected from OC2F4, OC3F6, and OC4F8 are not limited, but include —OC2F4OC3F6—, —OC2F4OC4F8—, —OC3F6OC2F4—, —OC3F6OC3F6—, —OC3F6OC4F8—, —OC4F8OC4F8—, —OC4F8OC3F6—, —OC4F8OC2F4—, —OC2F40C2F4OC3F6—, —OC2F4OC2F4OC4F8—, —OC2F40C3F6OC2F4—, —OC2F40C3F6OC3F6—, —OC2F40C4F8OC2F4—, —OC3F6OC2F4OC2F4—, —OC3F6OC2F40C3F6—, —OC3F6OC3F6OC2F4—, and —OC4F8OC2F4OC2F4—. In the formula (f3), g is an integer of preferably 3 or more, and more preferably 5 or more. g is preferably an integer of 50 or less. In the formula (f3), OC2F4, OC3F6, OC4F8, OC5F10, and OC6F12 may be either linear or branched, and they are preferably linear. In this embodiment, the formula (f3) is preferably —(OC2F4—OC3F6)g— or —(OC2F4—OC4F8)g—.
In the formula (f4), R6, R7, and g have the same definition as described for the formula (f3), and have the same embodiments. R6, R7, and g′ have the same definition as R6, R7, and g described in the formula (f3), respectively, and have the same embodiments. Rr is preferably
In the formula (f5), e is an integer of preferably 1 or more and 100 or less, and more preferably 5 or more and 100 or less. The sum of a, b, c, d, e, and f is preferably 5 or more, and more preferably 10 or more, and is, for example, 10 or more and 100 or less.
In the formula (f6), f is an integer of preferably 1 or more and 100 or less, and more preferably 5 or more and 100 or less. The sum of a, b, c, d, e, and f is preferably 5 or more, and more preferably 10 or more, and is, for example, 10 or more and 100 or less.
In one embodiment, RF is a group represented by the formula (f1).
In one embodiment, RF is a group represented by the formula (f2).
In one embodiment, RF is a group represented by the formula (f3).
In one embodiment, RF is a group represented by the formula (f4).
In one embodiment, RF is a group represented by the formula (f5).
In one embodiment, RF is a group represented by the formula (f6).
In one embodiment, the fluoropolyether group-containing silane compound contained in the surface-treating layer preferably contains a structure represented by the formula (f1), (f2), (f3), (f5), or (f6), more preferably contains a structure represented by the formula (f1) or (f2), and still more preferably contains a structure represented by the formula (f1), from the viewpoint of the lubricity of the surface-treating layer.
In another embodiment, the fluorine-containing silane compound which can be contained in the surface-treating layer preferably contains a structure represented by the formula (f1), (f2), (f3), (f4), (f5), or (f6), more preferably contains a structure represented by the formula (f1) or (f2), and still more preferably contains a structure represented by the formula (f2).
In RF, the ratio of e to f (hereinafter, referred to as an “e/f ratio”) is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and further preferably 0.2 to 0.85. With an e/f ratio of 10 or less, the lubricity, abrasion durability, and chemical resistance (such as durability against artificial sweat) of a surface-treating layer obtained from the compound are further improved. The lower the e/f ratio is, the more improved the lubricity and the abrasion durability of the surface-treating layer are. On the other hand, with an e/f ratio of 0.1 or more, the stability of the compound can be further enhanced. The larger the e/f ratio is, the more improved the stability of the compound is.
The fluoroalkyl group represented by RF1 is a group in which a hydrogen atom of the alkyl group has been replaced by a fluorine atom, and may be linear or branched. The fluoroalkyl group represented by RF1 is preferably a C1-50 fluoroalkyl group, more preferably a C1-20 fluoroalkyl group, and still more preferably a C1-16 fluoroalkyl group, and may be, for example, a C1-10 fluoroalkyl group, furthermore, a C1-6 fluoroalkyl group, and particularly, a C1-3 fluoroalkyl group. In one embodiment, the fluoroalkyl group represented by RF1 is a perfluoroalkyl group in which all of the hydrogen atoms have been substituted with fluorine atoms. In such embodiment, the perfluoroalkyl group is preferably a linear or branched C1-50 perfluoroalkyl group, more preferably a linear or branched C1-20 perfluoroalkyl group, and still more preferably a linear or branched C1-16 perfluoroalkyl group, and may be, for example, a linear or branched C1-10 perfluoroalkyl group, furthermore, a linear or branched C1-6 perfluoroalkyl group, and particularly, a linear or branched C1-3 perfluoroalkyl group.
The fluoroalkylene group represented by RF2 is a group in which a hydrogen atom of the alkylene group has been replaced by a fluorine atom, and may be linear or branched. The fluoroalkyl group represented by RF2 is preferably a C1-50 fluoroalkylene group, more preferably a C1-20 fluoroalkylene group, and still more preferably a C1-16 fluoroalkylene group, and may be, for example, a C1-10 fluoroalkylene group, furthermore, a C1-6 fluoroalkylene group, and particularly, a C1-3 fluoroalkylene group. In one embodiment, the fluoroalkylene group represented by RF2 is a perfluoroalkylene group in which all of the hydrogen atoms have been substituted with fluorine atoms. In such embodiment, the perfluoroalkylene group is preferably a linear or branched C1-50 perfluoroalkylene group, more preferably a linear or branched C1-20 perfluoroalkylene group, and still more preferably a linear or branched C1-16 perfluoroalkylene group, and may be, for example, a linear or branched C1-10 perfluoroalkylene group, furthermore, a linear or branched C1-6 perfluoroalkylene group, and particularly, a linear or branched C1-3 perfluoroalkylene group.
In the fluoropolyether group-containing silane compound, the number average molecular weight of RF1 and RF2 moieties is not limited, and is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. Herein, the number average molecular weight of RF1 and RF2 is defined as a value obtained by 19F-NMR measurement.
In another embodiment, the number average molecular weight of RF1 and RF2 moieties is 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, and still more preferably 2,000 to 10,000, and may be, for example, 3,000 to 6,000.
In another embodiment, the number average molecular weight of RF1 and RF2 moieties may be 4,000 to 30,000, preferably 5,000 to 10,000, and more preferably 6,000 to 10,000.
In the formulae (1) and (2), RSi is each independently at each occurrence a monovalent group containing a Si atom to which a hydroxy group, a hydrolyzable group, a hydrogen atom, or a monovalent organic group is bonded, and at least one RSi is a monovalent group containing a Si atom to which a hydroxy group or a hydrolyzable group is bonded.
Here, the term “hydrolyzable group” means a group which can undergo a hydrolysis reaction, namely, means a group which can be removed from a main backbone of the compound by a hydrolysis reaction. Examples of the hydrolyzable group include —ORj, —OCORj, —O—N═CRj2, —NRj2, —NHRj, —NCO, and halogen (in these formulae, Rj represents a substituted or unsubstituted C1-4 alkyl group).
In a preferred embodiment, RSi is a monovalent group containing a Si atom to which a hydroxy group or a hydrolyzable group is bonded.
In a preferred embodiment, RSi is a group represented by the following formula
—SiR11n1R123-n1 (S2)
—SiRa1k1Rb1l1Rc1m1 (S3)
—CRd1k2Re1l2Rf1m2 (S4)
—NRg1Rh1 (S5)
In the formula, R11 is each independently at each occurrence a hydroxy group or a hydrolyzable group.
Preferably, R11 is each independently at each occurrence a hydrolyzable group.
R11 is each independently at each occurrence preferably —ORj, —OCORj, —O—N═CRj2, —NRj2, —NHRj, —NCO, or a halogen (wherein Rj represents a substituted or unsubstituted C1-4 alkyl group), more preferably —ORj (alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Of them, an alkyl group, particularly an unsubstituted alkyl group, is preferable, and a methyl group or an ethyl group is more preferable. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
In the formula, R12 is each independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
In R12, the monovalent organic group is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, and still more preferably a methyl group.
In the formula, n1 is each independently an integer of 0 to 3 for each (SiR11n1R123-n1) unit. However, in a case where RSi is a group represented by the formula (S1) or (S2), at least one (SiR11n1R123-n1) unit in which n1 is 1 to 3 is present in the end RSi moieties of the formula (1) and the formula (2) (hereinafter, also simply referred to as “ends” of the formula (1) and the formula (2)). That is, in such ends, not all n1 are 0 at the same time. In other words, in the ends of the formula (1) and the formula (2), at least one Si atom to which the hydroxy group or the hydrolyzable group is bonded is present.
n1 is each independently an integer of preferably 1 to 3, more preferably 2 to 3, still more preferably 3 for each (SiR11n1R123-n1) unit.
In the formula, X11 is each independently at each occurrence a single bond or a divalent organic group. Such a divalent organic group is preferably —R28—Ox—R29—, wherein R28 and R29 are each independently at each occurrence a single bond or a C1-20 alkylene group, and x is 0 or 1. Such a C1-20 alkylene group may be linear or branched, but is preferably linear. Such a C1-20 alkylene group is preferably a C1-10 alkylene group, more preferably a C1-6 alkylene group, and still more preferably a C1-3 alkylene group.
In one embodiment, X11 is each independently at each occurrence —C1-6 alkylene-O—C1-6 alkylene- or —O—C1-6 alkylene-.
In a preferable embodiment, X11 is each independently at each occurrence a single bond or a linear C1-6 alkylene group, preferably a single bond or a linear C1-3 alkylene group, more preferably a single bond or a linear C1-2 alkylene group, and still more preferably a linear C1-2 alkylene group.
In the formula, R13 is each independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is preferably a C1-20 alkyl group. Such a C1-20 alkyl group may be linear or branched, but is preferably linear.
In a preferred embodiment, R13 is each independently at each occurrence a hydrogen atom or a linear C1-6 alkyl group, preferably a hydrogen atom or a linear C1-3 alkyl group, preferably a hydrogen atom or a methyl group.
In the formula, t is each independently at each occurrence an integer of 2 or more.
In a preferable embodiment, t is each independently at each occurrence an integer of 2 to 10, preferably an integer of 2 to 6.
In the formula, R14 is each independently at each occurrence a hydrogen atom, a halogen atom, or —X11—SiR11n1R123-n1. Such a halogen atom is preferably an iodine atom, a chlorine atom, or a fluorine atom, and more preferably a fluorine atom. In a preferred embodiment, R14 is a hydrogen atom.
In the formula, R15 is each independently at each occurrence a single bond, an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.
In one embodiment, R15 is each independently at each occurrence an oxygen atom, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group having 1 to 6 carbon atoms.
In a preferred embodiment, R15 is a single bond.
In one embodiment, the formula (S1) is the following formula (S1-a):
wherein
In a preferred embodiment, the formula (S1) is the following formula (S1-b):
wherein R11, R12, R13, X11, n1, and t have the same definition as described for the formula (S1).
In the formula, Ra1 is each independently at each occurrence —Z1—SiR21p1R22q1R23r1.
Z1 is each independently at each occurrence an oxygen atom or a divalent organic group. The structure denoted as Z1 hereinafter is bonded to (SiR21p1R22q1R23r1) on the right side.
In a preferred embodiment, Z1 is a divalent organic group.
In a preferred embodiment, Z1 does not include a group that forms a siloxane bond with a Si atom to which Z1 is bonded. Preferably, in the formula (S3), (Si-Z1—Si) does not contain a siloxane bond.
Z1 is preferably a C1-6 alkylene group, —(CH2)z1—O—(CH2)z2— (wherein z1 is an integer of 0 to 6; for example, an integer of 1 to 6, and z2 is an integer of 0 to 6; for example, an integer of 1 to 6) or, —(CH2)z3-phenylene-(CH2)z4— (wherein z3 is an integer of 0 to 6; for example, an integer of 1 to 6, and z4 is an integer of 0 to 6; for example, an integer of 1 to 6). Such a C1-6 alkylene group may be linear or branched, and is preferably linear. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, but are preferably unsubstituted.
In a preferred embodiment, Z1 is a C1-6 alkylene group or —(CH2)z3-phenylene-(CH2)z4—, and preferably -phenylene-(CH2)z4—. When Z1 is such a group, light resistance, in particular ultraviolet resistance, can be further enhanced.
In another preferred embodiment, Z1 is a C1-3 alkylene group. In one embodiment, Z1 may be —CH2CH2CH2—. In another embodiment, Z1 may be —CH2CH2—.
R21 is each independently at each occurrence —Z1′—SiR21′p1′R22′q1′R23′r1′.
Z1′ is each independently at each occurrence an oxygen atom or a divalent organic group. The structure denoted as Z1′ hereinafter is bonded to (SiR21′p1′R22′q1′R23′r1′) on the right side.
In a preferred embodiment, Z1′ is a divalent organic group.
In a preferred embodiment, Z1′ does not include a group that would form a siloxane bond with a Si atom to which Z1′ is bonded. Preferably, in the formula (S3), (Si-Z1′—Si) does not contain a siloxane bond.
Z1′ is preferably a C1-6 alkylene group, —(CH2)z1′—O—(CH2)z2′— (wherein z1′ is an integer of 0 to 6; for example, an integer of 1 to 6, and z2′ is an integer of 0 to 6; for example, an integer of 1 to 6), or —(CH2)z3′-phenylene-(CH2)z4′— (wherein z3′ is an integer of 0 to 6; for example, an integer of 1 to 6, z4′ is an integer of 0 to 6; for example, an integer of 1 to 6). Such a C1-6 alkylene group may be linear or branched, and is preferably linear. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, but are preferably unsubstituted.
In a preferred embodiment, Z1′ is a C1-6 alkylene group or —(CH2)z3′-phenylene-(CH2)z4′—, preferably -phenylene-(CH2)z4′—. When Z1′ is such a group, light resistance, in particular ultraviolet resistance, can be further enhanced.
In another preferred embodiment, Z1′ is a C1-3 alkylene group. In one embodiment, Z1′ may be —CH2CH2CH2—. In another embodiment, Z1′ may be —CH2CH2—.
R21′ is each independently at each occurrence —Z1″—SiR22″q1″R23″r1″.
Z1″ is each independently at each occurrence an oxygen atom or a divalent organic group. The structure denoted as Z1″ hereinafter is bonded to (SiR22″q1″R23″r1″) on the right side.
In a preferred embodiment, Z1″ is a divalent organic group.
In a preferred embodiment, Z1″ does not include a group that forms a siloxane bond with a Si atom to which Z1″ is bonded. Preferably, in the formula (S3), (Si-Z1″—Si) does not contain a siloxane bond.
Z1″ is preferably a C1-6 alkylene group, —(CH2)z1″—O—(CH2)z2″— (wherein z1″ is an integer of 0 to 6; for example, an integer of 1 to 6, and z2″ is an integer of 0 to 6; for example, an integer of 1 to 6), or —(CH2)z3″-phenylene-(CH2)z4″— (wherein z3″ is an integer of 0 to 6; for example, 1 to 6, z4″ is an integer of 0 to 6; for example, an integer of 1 to 6). Such a C1-6 alkylene group may be linear or branched, and is preferably linear. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, but are preferably unsubstituted.
In a preferred embodiment, Z1″ is a C1-6 alkylene group or —(CH2)z3″-phenylene-(CH2)z4″—, preferably -phenylene-(CH2)z4″—. When Z1″ is such a group, light resistance, in particular ultraviolet resistance, can be further enhanced.
In another preferred embodiment, Z1″ is a C1-3 alkylene group. In one embodiment, Z1″ may be —CH2CH2CH2—. In another embodiment, Z1″ may be —CH2CH2—.
R22″ is each independently at each occurrence a hydroxy group or a hydrolyzable group.
Preferably, R22″ is each independently at each occurrence a hydrolyzable group.
R22″ is each independently at each occurrence preferably —ORj, —OCORj, —O—N=CRj2, —NRj2, —NHRj, —NCO, or a halogen (wherein Rj represents a substituted or unsubstituted C1-4 alkyl group), more preferably —ORj (alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Of them, an alkyl group, particularly an unsubstituted alkyl group, is preferable, and a methyl group or an ethyl group is more preferable. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
R23″ is each independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
In R23″, the monovalent organic group is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, still more preferably a methyl group.
q1″ is each independently at each occurrence an integer of 0 to 3, and r1″ is each independently at each occurrence an integer of 0 to 3. The sum of q1″ and r1″ is 3 in the (SiR22″q1″R23″r1″) unit.
q1″ is each independently an integer of preferably 1 to 3, more preferably 2 to 3, still more preferably 3 for each (SiR22″q1″R23″r1″) unit.
R22′ is each independently at each occurrence a hydroxy group or a hydrolyzable group.
Preferably, R22′ is each independently at each occurrence a hydrolyzable group.
R22′ is each independently at each occurrence preferably —ORj, —OCORj, —O—N=CRj2, —NRj2, —NHRj, —NCO, or a halogen (wherein Rj represents a substituted or unsubstituted C1-4 alkyl group), more preferably —ORj (alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Of them, an alkyl group, particularly an unsubstituted alkyl group, is preferable, and a methyl group or an ethyl group is more preferable. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
R23′ is each independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
In R23′, the monovalent organic group is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, still more preferably a methyl group.
p1′ is each independently at each occurrence an integer 0 to 3, q1′ is each independently at each occurrence an integer of 0 to 3, and r1′ is each independently at each occurrence an integer of 0 to 3. The sum of p′, q1′, and r1′ is 3 in the (SiR21′p1′R22′q1′R23′r1′) unit.
In one embodiment, p1′ is 0.
In one embodiment, p1′ may be each independently an integer of 1 to 3, an integer of 2 to 3, or 3 for each (SiR21′p1′R22′q1′R23′r1′) unit. In a preferred embodiment, p1′ is 3.
In one embodiment, q1′ is each independently an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3 for each (SiR21′p1′R22′q1′R23′r1′) unit.
In one embodiment, p1′ is 0, and q1′ is each independently an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3 for each (SiR21′p1′R22′q1′R23′r1′) unit.
R22 is each independently at each occurrence a hydroxy group or a hydrolyzable group.
Preferably, R22 is each independently at each occurrence a hydrolyzable group.
R22 is each independently at each occurrence preferably —ORj, —OCORj, —O—N═CRj2, —NRj2, —NHRj, —NCO, or a halogen (wherein Rj represents a substituted or unsubstituted C1-4 alkyl group), more preferably —ORj (alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Of them, an alkyl group, particularly an unsubstituted alkyl group, is preferable, and a methyl group or an ethyl group is more preferable. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
R23 is each independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
In R23, the monovalent organic group is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, and still more preferably a methyl group.
p1 is each independently at each occurrence an integer of 0 to 3, q1 is each independently at each occurrence an integer of 0 to 3, and r1 is each independently at each occurrence 0 to 3. The sum of p1, q1, and r1 is 3 in the (SiR21p1R22q1R23r1) unit.
In one embodiment, p1 is 0.
In one embodiment, p1 may be each independently an integer of 1 to 3, an integer of 2 to 3, or 3 for each (SiR21p1R22q1R23r1) unit. In a preferred embodiment, p1 is 3.
In one embodiment, q1 is each independently an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3 for each (SiR21p1R22q1R23r1) unit.
In one embodiment, p1 is 0, and q1 is each independently an integer of 1 to 3, preferably an integer of 2 to 3, still more preferably 3 for each (SiR21p1R22q1R23r1) unit.
In the formula, Rb1 is each independently at each occurrence a hydroxy group or a hydrolyzable group.
Preferably, Rb1 is each independently at each occurrence a hydrolyzable group.
Rb1 is each independently at each occurrence preferably —ORj, —OCORj, —O—N—CRj2, —NRj2, —NHRj, —NCO, or a halogen (wherein Rj represents a substituted or unsubstituted C1-4 alkyl group), more preferably —ORj (alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Of them, an alkyl group, particularly an unsubstituted alkyl group, is preferable, and a methyl group or an ethyl group is more preferable. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
In the formula, Rc1 is each independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
In Rc1, the monovalent organic group is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, still more preferably a methyl group.
k1 is each independently at each occurrence an integer of 0 to 3, 11 is each independently at each occurrence an integer of 0 to 3, and m1 is each independently at each occurrence an integer of 0 to 3. The sum of k1, l1, and m1 is 3 in the (SiRa1k1Rb1l1Rc1m1) unit.
In one embodiment, k1 is each independently an integer of 1 to 3, preferably an integer of 2 or 3, more preferably 3 for each (SiRa1k1Rb1l1Rc1m1) unit. In a preferred embodiment, k1 is 3.
In the formulae (1) and (2), when RSi is a group represented by the formula (S3), preferably, at least two Si atoms to which a hydroxy group or a hydrolyzable group is bonded are present in the ends of the formulae (1) and (2).
In a preferred embodiment, the group represented by the formula (S3) has one of —Z1—SiR22q1R23r1 (wherein q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1 is an integer of 0 to 2), —Z1′—SiR22′q1R23′r1′ (wherein q1′ is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1′ is an integer of 0 to 2), and —Z1″—SiR22″q1″R23″r1″ (wherein q1″ is an integer of 1 to 3, preferably 2 or 3, more preferably 3, and r1″ is an integer of 0 to 2). Z1, Z1′, Z1″, R22, R23, R22′, R23′, R22″, and R23″ have the same definition as above.
In a preferred embodiment, when R21′ is present in the formula (S3), q1″ is an integer of 1 to 3, preferably 2 or 3, more preferably 3 in at least one, preferably all of R21′ groups.
In a preferred embodiment, when R21 is present in the formula (S3), p1′ is 0, and q1′ is an integer of 1 to 3, preferably 2 or 3, more preferably 3 in at least one, preferably all of R21 groups.
In a preferred embodiment, when Ra1 is present in the formula (S3), p1 is 0, and q1 is an integer of 1 to 3, preferably 2 or 3, more preferably 3 in at least one, preferably all of Ra1 groups.
In a preferred embodiment, in the formula (S3), k1 is 2 or 3, preferably 3, p1 is 0, q1 is 2 or 3, preferably 3.
Rd1 is each independently at each occurrence —Z2—CR31p2R32q2R33r2.
Z2 is each independently at each occurrence a single bond, an oxygen atom, or a divalent organic group. The structure denoted as Z2 hereinafter is bonded to (CR31p2R32q2R33r2) on the right side.
In a preferred embodiment, Z2 is a divalent organic group.
Z2 is preferably a C1-6 alkylene group, —(CH2)z5—O—(CH2)z6— (wherein z5 is an integer of 0 to 6; for example, an integer of 1 to 6, and z6 is an integer of 0 to 6; for example, an integer of 1 to 6), or —(CH2)z7-phenylene-(CH2)z8— (wherein z7 is an integer of 0 to 6; for example, an integer of 1 to 6, and z8 is an integer of 0 to 6; for example, an integer of 1 to 6). Such a C1-6 alkylene group may be linear or branched, and is preferably linear. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, but are preferably unsubstituted.
In a preferred embodiment, Z2 is a C1-6 alkylene group or —(CH2)z7-phenylene-(CH2)z8—, preferably -phenylene-(CH2)z8—. When Z2 is such a group, light resistance, in particular ultraviolet resistance, can be further enhanced.
In another preferred embodiment, Z2 is a C1-3 alkylene group. In one embodiment, Z2 may be —CH2CH2CH2—. In another embodiment, Z2 may be —CH2CH2—.
R31 is each independently at each occurrence —Z2′—CR32′q2′R33′r2′.
Z2′ is each independently at each occurrence a single bond, an oxygen atom, or a divalent organic group. The structure denoted as Z2′ hereinafter is bonded to (CR32′q2′R33′r2) on the right side.
Z2′ is preferably a C1-6 alkylene group, —(CH2)z5′—O—(CH2)z6′— (wherein z5′ is an integer of 0 to 6; for example, an integer of 1 to 6, and z6′ is an integer of 0 to 6; for example, an integer of 1 to 6), or —(CH2)z7-phenylene-(CH2)z8— (wherein z7′ is an integer of 0 to 6; for example, an integer of 1 to 6, and z8′ is an integer of 0 to 6; for example, an integer of 1 to 6). Such a C1-6 alkylene group may be linear or branched, and is preferably linear. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, but are preferably unsubstituted.
In a preferred embodiment, Z2′ is a C1-6 alkylene group or —(CH2)z7′-phenylene-(CH2)z8′—, preferably -phenylene-(CH2)z8′—. When Z2′ is such a group, light resistance, in particular ultraviolet resistance, can be further enhanced.
In another preferred embodiment, Z2′ is a C1-3 alkylene group. In one embodiment, Z2′ may be —CH2CH2CH2—. In another embodiment, Z2′ may be —CH2CH2—.
R32′ is each independently at each occurrence —Z3—SiR34n2R353-n2.
Z3 is each independently at each occurrence a single bond, an oxygen atom or a divalent organic group. The structure denoted as Z3 hereinafter is bonded to (SiR34n2R353-n2) on the right side.
In one embodiment, Z3 is an oxygen atom.
In one embodiment, Z3 is a divalent organic group.
Z3 is preferably a C1-6 alkylene group, —(CH2)z5″—O—(CH2)z6″— (wherein z5″ is an integer of 0 to 6; for example, an integer of 1 to 6, and z6″ is an integer of 0 to 6; for example, an integer of 1 to 6), or —(CH2)z7″-phenylene-(CH2)z8″— (wherein z7″ is an integer of 0 to 6; for example, an integer of 1 to 6, and z8″ is an integer of 0 to 6; for example, an integer of 1 to 6). Such a C1-6 alkylene group may be linear or branched, and is preferably linear. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, but are preferably unsubstituted.
In a preferred embodiment, Z3 is a C1-6 alkylene group or —(CH2)z7″-phenylene-(CH2)z8″—, preferably -phenylene-(CH2)z8″—. When Z3 is such a group, light resistance, in particular ultraviolet resistance, can be further enhanced.
In another preferred embodiment, Z3 is a C1-3 alkylene group. In one embodiment, Z3 may be —CH2CH2CH2—. In another embodiment, Z3 may be —CH2CH2—.
R34 is each independently at each occurrence a hydroxy group or a hydrolyzable group.
Preferably, R34 is each independently at each occurrence a hydrolyzable group.
R34 is each independently at each occurrence preferably —ORj, —OCORj, —O—N═CRj2, —NRj2, —NHRj, —NCO, or a halogen (wherein Rj represents a substituted or unsubstituted C1-4 alkyl group), more preferably —ORj (alkoxy group). Examples of Rj include unsubstituted alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and substituted alkyl groups such as a chloromethyl group. Of them, an alkyl group, particularly an unsubstituted alkyl group, is preferable, and a methyl group or an ethyl group is more preferable. In one embodiment, Rj is a methyl group, and in another embodiment, Rj is an ethyl group.
R35 is each independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
In R35, the monovalent organic group is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, still more preferably a methyl group.
In the formula, n2 is each independently an integer of 0 to 3 for each (SiR34n2R353-n2) unit. However, in a case where RSi is a group represented by the formula (S4), at least one (SiR34n2R353-n2) unit with n2 of 1 to 3 is present in the ends of the formula (1) and the formula (2). That is, in such ends, not all n2 are 0 at the same time. In other words, in the ends of the formula (1) and the formula (2), at least one Si atom to which the hydroxy group or the hydrolyzable group is bonded is present.
n2 is each independently an integer of preferably 1 to 3, more preferably 2 to 3, still more preferably 3 for each (SiR34n2R353-n2) unit.
R33′ is each independently at each occurrence a hydrogen atom, a hydroxy group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
In R33′, the monovalent organic group is preferably a C1-20 alkyl group or —(CsH2s)t1—(O—CsH2s)t2 (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, particularly preferably a methyl group.
In one embodiment, R33′ is a hydroxy group.
In another embodiment, the monovalent organic group as R33′ is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group.
q2′ is each independently at each occurrence an integer of 0 to 3, and r2′ is each independently at each occurrence an integer of 0 to 3. The sum of q2′ and r2′ is 3 in the (CR32′q2′R33′r2′) unit.
q2′ is each independently an integer of preferably 1 to 3, more preferably 2 to 3, still more preferably 3 for each (CR32′q2′R33′r2′) unit.
R32 is each independently at each occurrence —Z3—SiR34n2R353-n2. Such —Z3—SiR34n2R353-n2 has the same definition as described in R32′.
R33 is each independently at each occurrence a hydrogen atom, a hydroxy group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
In R33, the monovalent organic group is preferably a C1-20 alkyl group or —(CsH2s)t1—(O—CsH2s)t2 (wherein s is each independently at each occurrence an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, particularly preferably a methyl group.
In one embodiment, R33 is a hydroxy group.
In another embodiment, the monovalent organic group as R33 is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group.
p2 is each independently at each occurrence an integer of 0 to 3, q2 is each independently at each occurrence an integer of 0 to 3, and r2 is each independently at each occurrence an integer of 0 to 3. The sum of p2, q2, and r2 is 3 in the (CR31p2R32q2R33r2) unit.
In one embodiment, p2 is 0.
In one embodiment, p2 may be each independently an integer of 1 to 3, an integer of 2 to 3, or 3 for each (CR31p2R32q2R33r2) unit. In a preferred embodiment, p2 is 3.
In one embodiment, q2 is each independently an integer of 1 to 3, preferably an integer of 2 to 3, more preferably 3 for each (CR31p2R32q2R33r2) unit.
In one embodiment, p2 is 0, and q2 is each independently an integer of 1 to 3, preferably an integer of 2 to 3, still more preferably 3 for each (CR31p2R32q2R33r2) unit.
Re1 is each independently at each occurrence —Z3—SiR34a2R353-n2. Such —Z3—SiR34n2R353-n2 has the same definition as described in R32′.
Rf1 is each independently at each occurrence a hydrogen atom, a hydroxy group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the hydrolyzable group.
In Rf1, the monovalent organic group is preferably a C1-20 alkyl group or —(CsH2s)t1—(O—CsH2s)t2 (wherein s is an integer of 1 to 6, preferably an integer of 2 to 4, t1 is 1 or 0, preferably 0, and t2 is an integer of 1 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6), more preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group, particularly preferably a methyl group.
In one embodiment, Rf1 is a hydroxy group.
In another embodiment, the monovalent organic group as Rf1 is preferably a C1-20 alkyl group, more preferably a C1-6 alkyl group.
k2 is each independently at each occurrence an integer of 0 to 3, 12 is each independently at each occurrence an integer of 0 to 3, and m2 is each independently at each occurrence 0 to 3. The sum of k2, l2, and m2 is 3 in the (CRd1k2Re1t2Rf1m2) unit.
In the formulae (1) and (2), when RSi is a group represented by the formula (S4), preferably, at least two Si atoms to which a hydroxy group or a hydrolyzable group is bonded are present in the ends of the formulae (1) and (2).
In one embodiment, when RSi is a group represented by the formula (S4), two or more, for example, 2 to 27, preferably 2 to 9, more preferably 2 to 6, further preferably 2 to 3, particularly preferably 3 (SiR34n2R353-n2) units in which n2 is 1 to 3, preferably 2 or 3, more preferably 3 are present in each end of the formula (1) and the formula (2).
In a preferred embodiment, when R32′ is present in the formula (S4), n2 is an integer of 1 to 3, preferably 2 or 3, more preferably 3 in at least one, preferably all of R32′ groups.
In a preferred embodiment, when R32 is present in the formula (S4), n2 is an integer of 1 to 3, preferably 2 or 3, more preferably 3 in at least one, preferably all of R32 groups.
In a preferred embodiment, when Re1 is present in the formula (S4), n2 is an integer of 1 to 3, preferably 2 or 3, more preferably 3 in at least one, preferably all of Ra1 groups.
In a preferred embodiment, in the formula (S4), k2 is 0, 12 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.
Rg1 and Rh1 are each independently at each occurrence —Z4—SiR11n1R123-n1, —Z4—SiRa1k1Rb1l1Rc1m1, or —Z4—CRd1k2Re1l2Rf1m2. Here, R11, R12, Ra1, Rb2, Rc1, Rd1, Re1, Rf1, n1, k1, l1, m1, k2, l2, and m2 have the same definition as above.
Rg1 and Rh1 are each independently at each occurrence —Z4—SiR11n1R123-n1.
Z4 is each independently at each occurrence a single bond, an oxygen atom or a divalent organic group. The structure denoted as Z4 hereinafter is bonded to (SiR11n1R123-n1) on the right side.
In one embodiment, Z4 is an oxygen atom.
In one embodiment, Z4 is a divalent organic group.
Z4 is preferably a C1-6 alkylene group, —(CH2)z5″—O—(CH2)z6″— (wherein z5″ is an integer of 0 to 6; for example, an integer of 1 to 6, and z6″ is an integer of 0 to 6; for example, an integer of 1 to 6), or —(CH2)z7″-phenylene-(CH2)z8″— (wherein z7″ is an integer of 0 to 6; for example, an integer of 1 to 6, and z8″ is an integer of 0 to 6; for example, an integer of 1 to 6). Such a C1-6 alkylene group may be linear or branched, and is preferably linear. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C1-6 alkyl group, a C2-6 alkenyl group, and a C2-6 alkynyl group, but are preferably unsubstituted.
In a preferred embodiment, Z4 is a C1-6 alkylene group or —(CH2)z7″-phenylene-(CH2)z8″—, preferably -phenylene-(CH2)z8″—. When Z3 is such a group, light resistance, in particular ultraviolet resistance, can be further enhanced.
In another preferred embodiment, Z4 is a C1-3 alkylene group. In one embodiment, Z4 may be —CH2CH2CH2—. In another embodiment, Z4 may be —CH2CH2—.
In one embodiment, RSi is a group represented by the formula (S2), (S3), (S4), or (S5). These compounds are capable of forming a surface-treating layer having high surface lubricity.
In one embodiment, RSi is a group represented by the formula (S3), (S4), or (S5).
These compounds have a plurality of hydrolyzable groups at one end, and are therefore capable of forming a surface-treating layer which firmly adheres to a substrate and has high abrasion durability.
In one embodiment, RSi is a group represented by the formula (S3) or (S4). These compounds can have a plurality of hydrolyzable groups branched from one Si atom or C atom at one end, and are therefore capable of forming a surface-treating layer having higher abrasion durability.
In one embodiment, RSi is a group represented by the formula (S1).
In one embodiment, RSi is a group represented by the formula (S2).
In one embodiment, RSi is a group represented by the formula (S3).
In one embodiment, RSi is a group represented by the formula (S4).
In one embodiment, RSi is a group represented by the formula (S5).
In the formulae (1) and (2), XA is interpreted as a linker connecting fluoropolyether moieties (RF1 and RF2), which mainly provide water-repellency, surface lubricity and the like, to a moiety (RSi) providing a binding ability to a substrate. Accordingly, XA may be a single bond or any group as long as the compound represented by the formula (1) or (2) can stably exist.
In the formula (1), a is an integer of 1 to 9, and B is an integer of 1 to 9. These a and B may vary depending on the valence of XA. The sum of a and B is the same as the valence of XA. For example, when XA is a decavalent organic group, the sum of a and B is 10; for example, a case where a is 9 and B is 1, and a is 5 and B is 5, or a is 1 and Bis 9, can be considered. When XA is a divalent organic group, α and β each are 1.
In the formula (2), y is an integer of 1 to 9. γ may vary according to the valence of XA. That is, y is a value obtained by subtracting 1 from the valence of XA.
XA is each independently a single bond or a di- to decavalent organic group.
The di- to decavalent organic group in XA is preferably a di- to octavalent organic group. In one embodiment, the di- to decavalent organic group is preferably a di- to tetravalent organic group, and more preferably a divalent organic group. In another embodiment, the di- to decavalent organic group is preferably a tri- to octavalent organic group, and more preferably a tri- to hexavalent organic group.
In one embodiment, XA is a single bond or a divalent organic group, α is 1, and β is 1.
In one embodiment, XA is a single bond or a divalent organic group, γ is 1.
In one embodiment, XA is a tri- to hexavalent organic group, α is 1, and β is 2 to 5.
In one embodiment, XA is a tri- to hexavalent organic group, and γ is 2 to 5.
In one embodiment, XA is a trivalent organic group, α is 1, and β is 2.
In one embodiment, XA is a trivalent organic group, and γ is 2.
When XA is a single bond or a divalent organic group, the formulae (1) and (2) are represented by the following formulae (1′) and (2′).
RF1—XA—RSi (1′)
RSi—XA—RF2—XA—RSi (2′)
In one embodiment, XA is a single bond.
In another embodiment, XA is a divalent organic group.
In one embodiment, examples of XA include a single bond or a divalent organic group represented by the following formula:
—(R51)p5—(X51)q5—
wherein
In a preferred embodiment, XA is each independently —(R51)p5—(X51)q5—R52—. R52 represents a single bond, —(CH2)t5— or o-, m- or a p-phenylene group, and is preferably —(CH2)t5—. t5 is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. Here, R52 (typically a hydrogen atom of R52) may be substituted with one or more substituents selected from a fluorine atom, a C1-3 alkyl group and a C1-3 fluoroalkyl group. In a preferred embodiment, R56 is not substituted with these groups.
Preferably, XA may each independently be
More preferably, XA is each independently
More preferably, XA may be each independently
In a preferred embodiment, XA may each independently be
In a preferred embodiment, XA may each independently be
In one embodiment, XA may each independently be
In the formula, —(CvH2v)— may be linear or branched and may be, for example, —CH2CH2—, —CH2CH2CH2—, —CH(CH3)—, or —CH(CH3)CH2—.
XA may be each independently substituted with one or more substituents selected from a fluorine atom, a C1-3 alkyl group and a C1-3 fluoroalkyl group (preferably a C1-3 perfluoroalkyl group). In one embodiment, XA is unsubstituted.
XA is bonded to RF1 or RF2 on the left side, and bonded to RSi on the right side.
In one embodiment, XA may each independently be a group other than an —O—C1-6 alkylene group.
In another embodiment, examples of the XA group include the following groups:
Specific examples of XA include
In still another embodiment, XA is each independently a group represented by formula: —(R16)x1—(CFR17)y1—(CH2)z1—. In the formula, x1, y1 and z1 are each independently an integer of 0 to 10, and the sum of x1, y1 and z1 is 1 or more, the occurrence order of the respective repeating units enclosed in parentheses is not limited in the formula.
In the formula, R16 is each independently at each occurrence an oxygen atom, phenylene, carbazolylene, —NR18— (in the formula, R18 represents a hydrogen atom or an organic group), or a divalent organic group. Preferably, R18 is an oxygen atom or a divalent polar group.
Examples of the “divalent polar group” include, but are not limited to, —C(O)—, —C(═NR19)— and —C(O)NR19— (wherein R19 represents a hydrogen atom or a lower alkyl group). The “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, and n-propyl that is optionally substituted with one or more fluorine atoms.
In the formulae, R17 is each independently at each occurrence a hydrogen atom, a fluorine atom, or a lower fluoroalkyl group, and is preferably a fluorine atom. The “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms and preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or pentafluoroethyl group, and still more preferably a trifluoromethyl group.
In still another embodiment, examples of XA include the following group:
The radical scavenging group is not limited as long as it can scavenge a radical generated by light irradiation, and examples thereof include residues of benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonates, organoacrylates, hindered amines, hindered phenols, and triazines.
The UV absorbing group is not limited as long as it can absorb ultraviolet rays, and examples thereof include residues of benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxy cinnamates, oxamides, oxanilides, benzoxazinones, and benzoxazoles.
In a preferred embodiment, examples of the preferred radical scavenging group or UV absorbing group include:
In this embodiment, XA may each independently be a tri- to decavalent organic group.
In still another embodiment, examples of XA include the following group:
wherein R25, R26, and R27 are each independently a di- to hexavalent organic group; and
In one embodiment, R25 is a single bond, a C1-20 alkylene group, a C3-20 cycloalkylene group, a C5-20 arylene group, —R57—X58—R59—, —X58—R59—, or —R57—X58—. R57 and R59 are each independently a single bond, a C1-20 alkylene group, a C3-20 cycloalkylene group, or a C5-20 arylene group. X58 is —O—, —S—, —CO—, —O—CO—, or —COO—.
In one embodiment, R26 and R27 are each independently a hydrocarbon, or a group having at least one atom selected from N, O and S at the end or in the main chain of a hydrocarbon, and preferred examples thereof include C1-6 alkyl groups, —R36—R37—R36 and —R36—CHR382—. Here, R36 is each independently a single bond or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. R37 is N, O or S, preferably N or O. R38 is —R45—R46—R45—, —R46—R45— or —R45—R46—, where R45 is each independently an alkyl group having 1 to 6 carbon atoms. R46 is N, O or S, preferably O.
In this embodiment, XA may each independently be a tri- to decavalent organic group.
In still another embodiment, examples of XA include a group represented by the following:
wherein Xa is a single bond or a divalent organic group.
Xa is a single bond or a divalent linking group directly bonded to an isocyanuric ring. Xa is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond, and more preferably a single bond, an alkylene group having 1 to 10 carbon atoms, or a divalent organic group having 1 to 10 carbon atoms and containing at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a sulfide bond.
Xa is still more preferably a group represented by the following formula:
—(CX121X122)x1—(Xa1)y1—(CX123X124)z1—
wherein X121 to X124 are each independently H, F, OH, or —OSi(OR121)3 (wherein the three R121 are each independently an alkyl group having 1 to 4 carbon atoms),
Xa1 is preferably —O— or —C(═O)O—.
Xa is particularly preferably a group represented by the following formula:
—(CF2)m11—(CH2)m12—O—(CH2)m13—
—(CF2)m14—(CH2)m15—O—CH2CH(OH)-(CH2)m16—
—(CF2)m17—(CH2)m18—
—(CF2)m19—(CH2)m20—O—CH2CH(OSi(OCH3)3)-(CH2)m21—
—(CH2)m22—
Xa is not limited, but specific examples include:
In this embodiment, XA may each independently be a di- or trivalent organic group.
The fluoropolyether group-containing silane compound represented by the formula (1) or the formula (2) is not limited, but may have an average molecular weight of 5×102 to 1×105. In particular, the average molecular weight is preferably 2,000 to 32,000, more preferably 2,500 to 12,000, from the viewpoint of abrasion durability. The “average molecular weight” refers to a number average molecular weight, and the “average molecular weight” is a value obtained by 19F-NMR measurement.
The surface-treating layer may be preferably formed using a surface-treating agent containing the fluoropolyether group-containing compound.
The content of the fluoropolyether group-containing silane compound represented by the formula (1) or (2) may be preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, in the total 100% by mas of the fluoropolyether group-containing silane compound.
The content of the fluoropolyether group-containing silane compound may be preferably 0.02 to 40.0% by mass, more preferably 0.02 to 30.0% by mass, still more preferably 0.04 to 25.0% by mass, particularly preferably 0.05 to 20.0% by mass, in 100% by mass of the surface-treating agent. When the content of the fluoropolyether group-containing silane compound falls within the range, higher water- and oil-repellency can be obtained.
In the composition of the present disclosure, the non-volatile substances may be the total amount of the composition minus the solvent.
The content of the fluoropolyether group-containing compound may be preferably 0.02 to 40.0% by mass, more preferably 0.02 to 30.0% by mass, still more preferably 0.04 to 25.0% by mass, particularly preferably 0.05 to 20.0% by mass, in 100% by mass of the surface-treating agent. When the content of the fluoropolyether group-containing compound falls within the range, higher water- and oil-repellency can be obtained.
The surface-treating agent may further contain a solvent. By containing a solvent, the handleability of the composition is improved. When using such a composition to form a layer, the layer formed may be a continuous thin film. Such composition may also contribute to the formation of thin films of any thickness.
The solvent is not limited, and examples thereof include perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (such as perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (such as bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons (such as C6F13CH2CH3 (such as Asahiklin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), and 1,1,2,2,3,3,4-heptafluorocyclopentane (such as Zeorora (registered trademark) H manufactured by Zeon Corporation)); alkyl perfluoroalkyl ethers (the perfluoroalkyl group and the alkyl group may be linear or branched) such as hydrofluoroether (HFE) (such as perfluoropropyl methyl ether (C3F7OCH3) (such as Novec (trademark) 7000 manufactured by Sumitomo 3M Limited), perfluorobutyl methyl ether (C4F9OCH3) (such as Novec (trademark) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C4F9OC2H5) (such as Novec (trademark) 7200 manufactured by Sumitomo 3M Limited), and perfluorohexyl methyl ether (C2F5CF(OCH3)C3F7) (such as Novec (trademark) 7300 manufactured by Sumitomo 3M Limited), or CF3CH2OCF2CHF2 (such as Asahiklin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.)). One of these solvents may be used singly, or two or more may be used as a mixture. In particular, hydrofluoroether is preferable, and perfluorobutyl methyl ether (C4F9OCH3) and/or perfluorobutyl ethyl ether (C4F9OC2H5) is particularly preferable.
The boiling point of the solvent (under atmospheric pressure) may be preferably less than 105° C., more preferably 90° C. or less, still more preferably 80° C. or less. When the solvent has a boiling point within the above range, it allows the surface-treating agent of the present disclosure to be vaporized relatively easily without heating or the like, when applied to a substrate, which reduces the time and energy required for the surface-treating step. The lower limit of such boiling point is not limited, but may be, for example, 30° C. or more, preferably 50° C. or more.
The content of the solvent may be preferably 50 to 99.7% by mass, more preferably 60 to 99.7% by mass, still more preferably 70 to 99.7% by mass, particularly preferably 80 to 99.7% by mass, in the total 100% by mass of the surface-treating agent.
The surface-treating agent of the present disclosure can further contain a (unreactive) fluoropolyether compound which can be understood as a fluorine-containing oil, preferably a perfluoro (poly) ether compound (hereinafter, referred to collectively as “fluorine-containing oil”), a (unreactive) silicone compound which can be understood as a silicone oil (hereinafter, referred to as “silicone oil”), an alcohol, a catalyst, a surfactant, a polymerization inhibitor, a sensitizer and the like. The other components are different from the fluorine-containing silane compound and the solvent described above.
The fluorine-containing oil is not limited, and examples thereof include a compound (perfluoro (poly) ether compound) represented by the following general formula (4).
Rf5—(OC4F8)a″—(OC3F6)b″—(OC2F4)c″—(OCF2)d″—Rf6 (4)
In the formula, Rf5 represents a C1-16 alkyl group optionally substituted with one or more fluorine atoms (preferably, a C1-16 perfluoroalkyl group), Rf6 represents a C1-16 alkyl group optionally substituted with one or more fluorine atoms (preferably, a C1-16 perfluoroalkyl group), a fluorine atom, or a hydrogen atom, and Rf5 and Rf6 are each independently, more preferably, a C1-3 perfluoroalkyl group.
a″, b″, c″, and d″ represent the respective four numbers of repeating units in perfluoro (poly) ether constituting the main backbone of the polymer and are mutually independently an integer of 0 or more and 300 or less, and the sum of a″, b″, c″, and d″ is greater than 30, preferably 40 to 300, more preferably 50 to 300. The occurrence order of the respective repeating units enclosed in parentheses provided with the subscript a″, b″, c″, or d″ is not limited in the formula. Among such repeating units, —(OC4F8)— may be any of —(OCF2CF2CF2CF2)—, —(OCF(CF3)CF2CF2)—, —(OCF2CF(CF3)CF2)—, —(OCF2CF2CF(CF3))—, —(OC(CF3)2CF2)—, —(OCF2C(CF3)2)—, —(OCF(CF3)CF(CF3))—, —(OCF(C2F5)CF2)—, and (OCF2CF(C2F5))—, but it is preferably —(OCF2CF2CF2CF2)—. —(OC3F6)— may be any of —(OCF2CF2CF2)—, —(OCF(CF3)CF2)—, and (OCF2CF(CF3))—, and it is preferably —(OCF2CF2CF2)—. —(OC2F4)— may be any of —(OCF2CF2)— and (OCF(CF3))—, but it is preferably —(OCF2CF2)—.
Examples of the perfluoro (poly) ether compound represented by general formula (4) include a compound represented by any of the following general formulae (4a) and (4b) (which may be used singly or as a mixture of two or more kinds thereof).
Rf5—(OCF2CF2CF2)b″—Rf6 (4a)
Rf5—(OCF2CF2CF2CF2)a″—(OCF2CF2CF2)b″—(OCF2CF2)c″—(OCF2)d″—Rf6 (4b)
In these formulae, Rf5 and Rf6 are as described above; in formula (4a), b″ is an integer of 1 or more and 100 or less; and in formula (4b), a″ and b″ are each independently an integer of 0 or more and 30 or less, and c″ and d″ are each independently an integer of 1 or more and 300 or less. The occurrence order of the respective repeating units enclosed in parentheses provided with the subscript a″, b″, c″, or d″ is not limited in the formula.
Alternatively, from another viewpoint, the fluorine-containing oil may be a compound represented by general formula Rf3-F, wherein Rf3 is a C5-16 perfluoroalkyl group. The fluorine-containing oil may be a chlorotrifluoroethylene oligomer.
The fluorine-containing oil may have a number average molecular weight of preferably 1,000 or more, more preferably 1,500 or more, still more preferably 2,000 or more. In addition, the fluorine-containing oil may have a number average molecular weight of preferably 30,000 or less, more preferably 20,000 or less, still more preferably 10,000 or less. The molecular weight of the fluorine-containing oil can be measured using GPC.
The fluorine-containing oil may be contained in an amount of, for example, 0 to 50 mass %, preferably 0 to 30 mass %, and more preferably 0 to 5 mass % based on the surface-treating agent. In one embodiment, the surface-treating agent of the present disclosure is substantially free from the fluorine-containing oil. Being substantially free from the fluorine-containing oil means that the fluorine-containing oil is not contained at all, or an extremely small amount of the fluorine-containing oil may be contained.
In one embodiment, the number average molecular weight of the fluorine-containing oil may be smaller than the number average molecular weight of the fluorine-containing silane compound. With such average molecular weights, it is possible to form a cured product having high abrasion durability and high surface lubricity while suppressing reduction in the transparency of a surface-treating layer obtained from the compound.
The fluorine-containing oil contributes to improving surface lubricity of the layer formed by the surface-treating agent of the present disclosure.
For example, a linear or cyclic silicone oil having 2,000 or less siloxane bonds can be used as the silicone oil. The linear silicone oil may be a so-called straight silicone oil or modified silicone oil. Examples of the straight silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying a straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, or the like. Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.
In the surface-treating agent of the present disclosure, such a silicone oil may be contained in an amount of, for example, 0 to 300 parts by mass, and preferably 50 to 200 parts by mass, based on the total 100 parts by mass of the fluoropolyether group-containing compound (in the case of two or more kinds, the total thereof, and the same applies below).
The silicone oil contributes to improving the surface lubricity of the surface-treating layer.
Examples of the alcohols include alcohols having 1 to 6 carbon atoms optionally substituted with one or more fluorine atoms, such as methanol, ethanol, iso-propanol, tert-butanol, CF3CH2OH, CF3CF2CH2OH, and (CF3)2CHOH. By adding these alcohols to the surface-treating agent, the stability of the surface-treating agent is improved, and the miscibility between the fluoropolyether group-containing compound and the solvent is improved.
The alcohol is contained in an amount of preferably 0.1 to 5 times, more preferably 0.5 to 3 times, and still more preferably 0.8 to 1.2 times that of the metal compound in the surface-treating agent, in molar ratio. When the content of the alcohol falls within the range, the stability of the surface-treating layer can be further improved.
Examples of the catalyst include an acid (such as acetic acid and trifluoroacetic acid), a base (such as ammonia, triethylamine, and diethylamine), and a transition metal (such as Ti, Ni, and Sn).
The catalyst promotes hydrolysis and dehydrative condensation of the fluoropolyether group-containing silane compound of the present disclosure, and promotes formation of a layer formed of the surface-treating agent of the present disclosure.
Examples of the other components include, in addition to those described above, tetraethoxysilane, methyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and methyltriacetoxysilane.
A method for treating a chemical mechanical polishing apparatus is also included in the technical scope of the present disclosure.
The method for treating a chemical mechanical polishing apparatus of the present disclosure includes:
According to the treatment method, it is possible to provide a novel chemical mechanical polishing apparatus having a surface-treating layer. According to the treatment method, it is possible to provide a chemical mechanical polishing apparatus in which, in a preferred embodiment, the workability of the polishing slurry is good, and in a more preferred embodiment, the workability is good even after a period of time has passed since the adhesion of the polishing slurry.
The chemical mechanical polishing apparatus, surface-treating agent, surface-treating layer, and fluoropolyether group-containing compound each have the same definition as the chemical mechanical polishing apparatus, surface-treating agent, surface-treating layer, and fluoropolyether group-containing compound described in the first embodiment, and all of the configurations described in the first embodiment can be applied to the present embodiment.
The surface-treating layer is formed by applying a surface-treating agent to the surface of one or more components of the chemical mechanical polishing apparatus. This allows to impart, preferably, workability of the polishing slurry, and more preferably, workability of the polishing slurry after a long period of time. In addition, in a preferred embodiment, the formation of such surface-treating layer can further impart one or more selected from water-repellency, oil-repellency, lubricity, fingerprint adherability, antifouling properties, antireflection properties, antifogging properties, and the like.
The surface-treating agent can be applied by applying the surface-treating agent on the surface of one or more components of the chemical mechanical polishing apparatus such that the surface-treating agent coats the surface. The coating method is not limited. For example, a wet coating method and a dry coating method can be used, and a wet coating method is preferably used.
Examples of the wet coating method include dip coating, spin coating, brush coating, flow coating, spray coating, roll coating, gravure coating, and similar methods, with spray coating being preferred.
In one embodiment, a layer of the surface-treating agent is preferably formed such that the surface-treating agent of the present disclosure coexists in the layer with a catalyst for hydrolysis and dehydrative condensation. Conveniently, in the case of a wet coating method, the surface-treating agent of the present disclosure is diluted with a solvent, and then, immediately before application to the substrate surface, a catalyst may be added to the diluted solution of the surface-treating agent of the present disclosure.
Any suitable acid or base can be used as a catalyst. For example, acetic acid, formic acid, and trifluoroacetic acid can be used as the acid catalyst. For example, ammonia and organic amines can be used as the base catalyst.
After application, the surface-treating agent may be dried as necessary. Such drying promotes hydrolysis and dehydrative condensation of the fluoropolyether group-containing silane compound described below, which allows to remove the solvent and the like.
The drying of the precursor layer can be performed at a temperature of preferably 0° C. or more and 60° C. or less, more preferably 5° C. or more and 50° C. or less, still more preferably 10° C. or more and 30° C. or less, and can be performed for a period of time of preferably 1 hour or more and 48 hours or less, more preferably 3 hours or more and 24 hours or less, still more preferably 6 hours or more and 12 hours or less.
The thickness of the surface-treating layer is not limited. It is preferable that the thickness of the surface-treating layer be preferably 1 nm or more and 20 nm or less, more preferably 1 nm or more and 10 nm or less, and preferably in the range of 5 nm or more and 10 nm or less from the viewpoint of the workability of the polishing slurry, preferably, the workability of the polishing slurry after a long period of time, and furthermore, optical performance, abrasion durability, and antifouling properties.
The present disclosure can provide a novel chemical mechanical polishing apparatus and a novel method for treating a chemical mechanical polishing apparatus, and can provide a chemical mechanical polishing apparatus in which, preferably, the workability of the polishing slurry is good, and more preferably, the workability is good even after a period of time has passed since the adhesion of the polishing slurry.
Hereinafter, the present embodiments will be described further specifically with the following Examples, but the present embodiments are not limited thereto.
A fluoropolyether group-containing compound represented by the following formula:
CF3—(CF2O)22—(CF2CF2O)24—CF2CH2OCH2CH2CH2Si{CH2CH2CH2Si(OCH3)3}3
was dissolved in Novec HFE7200 (manufactured by 3M) to a concentration of 0.1% by mass to prepare a surface-treating agent 1.
A fluoropolyether group-containing compound represented by the following formula:
CF3CF2CF2O—(CF2CF2CF2O)25—(CH2CH2Si(OCH3)3)3—H
was dissolved in Novec HFE7200 (manufactured by 3M) to a concentration of 0.1% by mass to prepare a surface-treating agent 2.
A compound represented by the following formula:
CF3CF2CF2CF2CF2CF2—CH2CH2—Si-(OCH3)3
was dissolved in Novec HFE7200 (manufactured by 3M) to a concentration of 0.1% by mass to prepare a surface-treating agent 1.
The composition obtained in Production Example 1 was used and coated on a stainless steel baseboard (SUS304) to obtain a coating thickness of 10 nm. This was left at room temperature for 3 minutes and then heated at 150° C. for 30 minutes to form a film (surface-treating layer) and obtain a substrate.
The film (surface-treating layer) was formed and the substrate was obtained in the same manner as Example 1, except that the surface-treating agent shown in Table 1 was used.
The stainless steel baseboard (SUS304) was used as it is as a substrate.
The film (surface-treating layer) was formed and the substrate was obtained in the same manner as Example 1, except that the surface-treating agent shown in Table 1 was used and the heating conditions were 60° C. for 3 hours.
The treating layer was formed and the substrate was obtained in the same manner as Example 1, except that the surface-treating agent or treatment agent shown in Table 1 was used. A PTFE dispersion coating material was used as the treatment agent 4. The PTFE dispersion coating material used was a polyamide-imide dispersion of PTFE resin with a particle size of 25 μm. Specifically, the PTFE dispersion coating material used was an NMP dispersion with 20 parts by mass of PTFE resin per 100 parts by mass of polyamide-imide resin. The dispersion was coated on the SUS to obtain a film thickness of 100 μm, and heated at 180° C. for 40 minutes and 230° C. for 40 minutes to obtain an evaluation sample.
The polishing slurry was coated on the substrates of the Examples and Comparative Examples in a tilted position. The repellency was evaluated as ∘ if the polishing slurry flowed down, and evaluated as X if the polishing slurry did not flow down. The polishing slurry used was GLANZOX 3900.
1 g of polishing slurry was added dropwise to the surface of the substrates of the Examples and Comparative Examples in a horizontal position. After leaving it overnight, the substrate was washed with water to check its appearance and measure the water contact angle. The removability was evaluated as ∘ if the polishing slurry and its solidified matter could be removed with water, and evaluated as X if it could not be removed. The polishing slurry used was GLANZOX 3900.
The results are shown in Table 1.
Examples 1 and 2 are Examples of the present disclosure, where both repellency and removability of the slurry were good, and particle generation where polishing slurry adhered was also suppressed.
Comparative Example 1 is an example in which no surface-treating layer was formed, where the repellency and removability of the slurry were not satisfactory.
Comparative Example 2 is an example using a surface-treating agent containing a fluorocarbon compound but no fluoropolyether group-containing compound, where slurry removability was poor, and particle generation was observed.
Comparative Example 3 is an example using a mixture of fluorocarbon particles and resin, containing no fluoropolyether group-containing compound, where particle generation was observed.
The present disclosure can provide a novel chemical mechanical polishing apparatus and a novel method for treating a chemical mechanical polishing apparatus, and can provide a chemical mechanical polishing apparatus in which, preferably, the workability of the polishing slurry is good, and more preferably, the workability is good even after a period of time has passed since the adhesion of the polishing slurry.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2023-112229 | Jul 2023 | JP | national |
