Curable perfluoropolyether adhesive composition, adhesive using cured product thereof, and adhesive tape

Abstract

The present invention provides a curable perfluoropolyether adhesive composition containing the following components (A)-(C) and forming an adhesive having an adhesive force of less than 0.5 N / 25 mm by curing; (A) 100 parts by mass of a linear perfluoropolyether compound having at least two alkenyl groups in one molecule and having a perfluoropolyether structure containing a repeating unit represented by-CaF2aO-in the main chain, a being an integer of 1-6; (B) a curing effective amount of an organosilicon compound, one molecule of which has at least two hydrogen atoms bonded to a silicon atom; and (C) a hydrosilylation reaction catalyst in a catalytic amount. As a result, it is possible to provide a curable perfluoropolyether adhesive composition which is capable of providing a cured product having excellent heat resistance, weather resistance, hydrophobicity, oleophobicity, and the like, as well as excellent reagent resistance and solvent resistance, and in particular, the cured product is characterized by having micro-adhesiveness.

Description

[0001] The present invention is a divisional application of the Chinese patent application with application number 202080086829.1, application date November 26, 2020, and invention name “Curable perfluoropolyether adhesive composition, adhesive using its cured product, and adhesive tape”. This application claims the priority of Japanese Patent Application No. 2019-227304 filed in Japan on December 17, 2019. Technical Field

[0002] The present invention relates to a curable perfluoropolyether adhesive composition (hereinafter referred to as a perfluoropolyether adhesive composition), an adhesive and an adhesive tape using the cured product thereof, wherein the curable perfluoropolyether adhesive composition can form an adhesive (cured perfluoropolyether rubber or cured perfluoropolyether gel) having excellent properties such as heat resistance, oil resistance, chemical resistance, solvent resistance, low temperature characteristics, moisture resistance, low air permeability, etc., and particularly having a slight adhesive property. Background Art

[0003] In the past, a technology has been proposed that can obtain a cured product with good and excellent properties such as heat resistance, reagent resistance, solvent resistance, hydrophobicity, oleophobicity, and weather resistance by using a composition consisting of a straight-chain perfluoropolyether compound having at least two alkenyl groups in one molecule and a perfluoropolyether structure in the main chain, an organic silicon compound having two or more H-SiOSiO structures in one molecule, and a hydrosilylation reaction catalyst (Patent Documents 1 and 2).

[0004] On the other hand, adhesives are used in various situations, mainly as labels or adhesive tapes attached to products. Recently, with the advancement of electronic terminal related technologies such as adhesive films for display protection and protective films in product manufacturing processes, their uses have also expanded. In addition, they are not only used for surface protection, but also for optical components by utilizing the transparency of the material, and optical clear adhesive tape (OCA tape) has been developed for product applications.

[0005] The main types of adhesives include acrylic, rubber, and silicone, each with its own advantages and disadvantages. Silicone adhesives are more disadvantageous in terms of cost than acrylic and rubber adhesives, but they are superior to the other two adhesives in terms of heat resistance, cold resistance, weather resistance, chemical resistance, and electrical insulation.

[0006] Recently, terminals such as mobile phones have become widely popular, but most of the adhesive films that protect these displays use silicone adhesives. In terms of properties, silicone has good wettability to the adherend, so it will not be involved in bubbles during lamination, will not fall off or peel off by itself, and because of its good reprocessability, it can be reattached (Patent Document 3). In addition, since the protective film used in the product manufacturing process is the same as this and further requires heat resistance, etc., a large number of adhesive films are used, and the adhesive films use silicone adhesives.

[0007] In addition, among mobile phones, terminals with higher functions than before, called smart phones, are rapidly becoming popular. So far, most of them can be operated by touching a display called a touch panel instead of the previous buttons. Similar products include tablet terminals, which are easy-to-carry computers equipped with touch panels. Due to their popularity, there is a tendency for the demand for adhesive films for screen protection to increase as the display area increases.

[0008] However, although such silicone adhesives have sufficient performance in most applications, there is still a strong demand for an adhesive composition with excellent chemical resistance and solvent resistance, such as in applications around automobile engines or in barcode labels used in clinical examinations and pathological examinations, where chemical resistance and solvent resistance are further required.

[0009] Among them, a curable perfluoropolyether adhesive composition is proposed (Patent Document 4). The composition can provide a cured product having excellent heat resistance, weather resistance, hydrophobicity, oleophobicity, and excellent reagent resistance and solvent resistance, but since its adhesive force is 0.5N / 25mm or more, it is not suitable for micro-adhesion applications that can avoid the situation where the adherend is easily damaged due to weak strength.

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: Japanese Patent No. 2990646

[0013] Patent Document 2: Japanese Patent Application Publication No. 2000-248166

[0014] Patent Document 3: Japanese Patent Application Laid-Open No. 07-197008

[0015] Patent Document 4: Japanese Patent Application Publication No. 2019-38904 Summary of the invention

[0016] 1. Technical issues to be resolved

[0017] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a curable perfluoropolyether adhesive composition, and an adhesive and an adhesive tape comprising a cured product thereof, wherein the curable perfluoropolyether adhesive composition can provide a cured product having excellent heat resistance, weather resistance, hydrophobicity, oleophobicity, etc., as well as chemical resistance and solvent resistance, and in particular, the cured product is characterized in that it is slightly adhesive.

[0018] (II) Technical solution

[0019] In order to solve the above technical problems, the present invention provides a curable perfluoropolyether adhesive composition, which contains the following (A) to (C) components and forms an adhesive having an adhesive force (micro-adhesion force) of less than 0.5N / 25mm by curing,

[0020] 100 parts by mass of (A) a linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a main chain containing -C a F 2a O-repeating unit perfluoropolyether structure, a is an integer of 1 to 6;

[0021] a curing effective amount of (B) an organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule;

[0022] A catalytic amount of (C) a hydrosilylation reaction catalyst.

[0023] If it is a curable perfluoropolyether adhesive composition containing components (A) to (C) as described in the present invention, a curable perfluoropolyether adhesive composition is formed, which can provide excellent heat resistance, weather resistance, hydrophobicity, oleophobicity, oil resistance, low temperature characteristics, moisture resistance, low air permeability, etc., especially excellent reagent resistance and solvent resistance and a cured product (adhesive) with an adhesion of less than 0.5N / 25mm. An adhesive tape containing a cured product with an adhesion of less than 0.5N / 25mm can be peeled off from the substrate without damaging the substrate even when attached to a fragile substrate. In addition, if it is a curable perfluoropolyether adhesive composition containing components (A) to (C) described above, a rubber cured product (perfluoropolyether rubber cured product) can be provided.

[0024] In addition, the present invention provides a curable perfluoropolyether adhesive composition, which contains the following components (A) to (D) and forms an adhesive having an adhesive force of less than 0.5 N / 25 mm by curing.

[0025] 100 to 40 parts by mass of (A) a linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a main chain containing -C a F 2aO-repeating unit perfluoropolyether structure, a is an integer of 1 to 6;

[0026] 0 to 60 parts by weight of (D) a polyfluoromonoalkenyl compound having one alkenyl group in one molecule and a perfluoropolyether structure in the main chain, wherein the total amount of components (A) and (D) is 100 parts by weight;

[0027] a curing effective amount of (B) an organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule;

[0028] A catalytic amount of (C) a hydrosilylation reaction catalyst.

[0029] If it is a curable perfluoropolyether adhesive composition containing (A) to (D) components as in the present invention, a curable perfluoropolyether adhesive composition is formed, which can provide excellent heat resistance, weather resistance, hydrophobicity, oleophobicity, oil resistance, low temperature characteristics, moisture resistance, low air permeability, etc., especially excellent reagent resistance and solvent resistance and a cured product (adhesive) with an adhesion of less than 0.5N / 25mm. An adhesive tape containing a cured product with an adhesion of less than 0.5N / 25mm can be peeled off from the substrate without damaging the substrate even when attached to a fragile substrate. In addition, if it is a curable perfluoropolyether adhesive composition containing (A) to (D) components of the present invention as described above, a rubber or gel cured product (perfluoropolyether rubber cured product or gel cured product) can be provided.

[0030] In this case, the component (D) is preferably a polyfluoromonoolefin compound represented by the following general formula (2):

[0031] R 1 -(X') p -CH=CH2(2)

[0032] In formula (2), X' is -CH2-, -OCH2-, -CH2OCH2- or -CO-NR 2 -Y'-, p is 0 or 1; wherein Y' is -CH2- or a group represented by the following structural formula (Z'), R 2 It is a hydrogen atom, a methyl group, a phenyl group or an allyl group.

[0033] [Chemical formula 1]

[0034]

[0035] The group represented by the structural formula (Z') is a dimethylphenylsilylene group represented in the ortho, meta or para position.

[0036] R 1 The general formula is F-[CF(CF3)CF2O] wThe perfluoropolyether structure is represented by -CF(CF3)-, wherein w represents an integer of 1 to 500.

[0037] Such a composition containing the component (D) can provide a curable perfluoropolyether adhesive composition capable of providing a cured product (adhesive) having better chemical resistance and solvent resistance.

[0038] Furthermore, the component (A) is preferably a linear perfluoropolyether compound represented by the following general formula (1):

[0039] [Chemical formula 2]

[0040]

[0041] In formula (1), X is -CH2-, -CH2O-, -CH2OCH2- or -Y-NR 1 -CO-, X' is -CH2-, -OCH2-, -CH2OCH2- or -CO-NR 2 -Y'-, p is independently 0 or 1, r is an integer of 2 to 6, m and n are integers of 0 to 600, and the sum of m and n is 50 to 600; wherein Y is -CH2- or a group represented by the following structural formula (Z), R 1 is a hydrogen atom, a methyl group, a phenyl group or an allyl group; Y' is -CH2- or a group represented by the following structural formula (Z'); R 2 is a hydrogen atom, a methyl group, a phenyl group or an allyl group,

[0042] [Chemical formula 3]

[0043]

[0044] The group represented by the structural formula (Z) is a dimethylphenylsilylene group represented in the ortho, meta or para position.

[0045] [Chemical formula 4]

[0046]

[0047] The group represented by the structural formula (Z') is a dimethylphenylsilylene group represented in the ortho, meta or para position.

[0048] Such a composition containing the component (A) can provide a curable perfluoropolyether adhesive composition that can provide a cured product (adhesive) having better chemical resistance and solvent resistance and has sufficient adhesive strength to provide the adhesiveness required for an adhesive tape.

[0049] For example, it is preferred that: the component (A) is a linear perfluoropolyether compound represented by the general formula (1), 0 to 20 parts by mass of the component (D) is contained relative to 100 to 80 parts by mass of the component (A), wherein the total of the components (A) and (D) is 100 parts by mass, and the component (B) is a fluorinated organohydrogenpolysiloxane having a cyclic siloxane structure.

[0050] In addition, it is preferred that: the component (A) is a linear perfluoropolyether compound represented by the above general formula (1), the component (D) is contained in an amount of 21 to 45 parts by mass relative to 79 to 55 parts by mass of the component (A), wherein the total of the components (A) and (D) is 100 parts by mass, and the component (B) is a fluorinated polyorganohydrogensiloxane having a linear and / or branched siloxane structure.

[0051] In addition, it is preferred that: the component (A) is a linear perfluoropolyether compound having a divalent perfluoropolyether structure composed of a (CF2O) unit and a repeating (CF2CF2O) unit in the main chain, and contains 0 to 50 parts by mass of the component (D) relative to 100 to 50 parts by mass of the component (A), wherein the total of the components (A) and (D) is 100 parts by mass, and the component (B) is a fluorinated organohydrogenpolysiloxane having a linear and / or branched siloxane structure.

[0052] In addition, it is preferred that: the component (A) is a linear perfluoropolyether compound represented by the above general formula (1) and having a divalent perfluoropolyether structure composed of a repeating (CF2O) unit and a (CF2CF2O) unit in the main chain, and 0 to 50 parts by mass of the component (D) is contained relative to 100 to 50 parts by mass of the component (A), wherein the total of the components (A) and (D) is 100 parts by mass, and the component (B) is a fluorinated organohydrogenpolysiloxane having a linear and / or branched siloxane structure.

[0053] The compositions of these examples can provide a cured product (adhesive) having better chemical resistance and solvent resistance, and an adhesive tape including the obtained cured product can be peeled from a fragile substrate without damaging the substrate even when attached to the substrate.

[0054] In addition, it is preferred that the cured product of the curable perfluoropolyether adhesive composition has a volume resistivity of 1×10 9 Non-conductive adhesive with Ω·cm or more.

[0055] The curable perfluoropolyether adhesive composition of the present invention can be suitably used as a material for such a non-conductive adhesive.

[0056] In addition, an adhesive is provided, comprising a cured product of the curable perfluoropolyether adhesive composition.

[0057] Thus, the curable perfluoropolyether adhesive composition of the present invention can be used as an adhesive.

[0058] The present invention also provides an adhesive tape comprising a substrate and a cured layer of the curable perfluoropolyether adhesive composition laminated thereon.

[0059] Thus, by laminating a cured product layer (adhesive layer composed of cured perfluoropolyether rubber or cured perfluoropolyether gel) of the curable perfluoropolyether adhesive composition of the present invention on a substrate, it can be used as an adhesive tape having a non-conductive adhesive layer.

[0060] (III) Beneficial effects

[0061] As described above, the perfluoropolyether adhesive composition of the present invention can provide a cured product (adhesive) having excellent heat resistance, weather resistance, hydrophobicity, oleophobicity, oil resistance, low temperature characteristics, moisture resistance, low air permeability, etc., especially excellent chemical resistance and solvent resistance, and having an adhesive force (micro-adhesive force) of less than 0.5N / 25mm. An adhesive tape (micro-adhesive tape) containing a cured product having an adhesive force of less than 0.5N / 25mm can be peeled off from a fragile substrate without damaging the substrate even when attached to the substrate. DETAILED DESCRIPTION

[0062] As described above, a curable perfluoropolyether adhesive composition capable of providing a slightly adhesive cured product (adhesive) and an adhesive comprising the cured product thereof are sought to be developed, wherein the slightly adhesive cured product has excellent heat resistance, weather resistance, hydrophobicity, oleophobicity, etc., especially excellent chemical resistance and solvent resistance, and further can avoid damage to the adherend when the strength of the adherend is weak.

[0063] The present inventors have conducted intensive studies to achieve the above-mentioned purpose, and as a result, have found that according to the specific perfluoropolyether adhesive composition of the present invention, a slightly adhesive adhesive composition can be obtained, which can provide a rubber-like or gel-like cured product (perfluoropolyether rubber cured product or perfluoropolyether gel cured product) having better reagent resistance and solvent resistance than conventional silicone adhesives.

[0064] Therefore, the present invention can provide the following curable perfluoropolyether adhesive composition, and an adhesive and an adhesive tape using a cured product thereof.

[0065] [1] A curable perfluoropolyether adhesive composition comprising the following components (A) to (C) and forming an adhesive having an adhesive force of less than 0.5 N / 25 mm upon curing,

[0066] 100 parts by mass of (A) a linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a main chain containing -C a F 2a O-repeating unit perfluoropolyether structure, a is an integer of 1 to 6;

[0067] a curing effective amount of (B) an organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule;

[0068] A catalytic amount of (C) a hydrosilylation reaction catalyst.

[0069] [2] A curable perfluoropolyether adhesive composition comprising the following components (A) to (D) and forming an adhesive having an adhesive force of less than 0.5 N / 25 mm upon curing,

[0070] 100 to 40 parts by mass of (A) a linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a main chain containing -C a F 2a O-repeating unit perfluoropolyether structure, a is an integer of 1 to 6;

[0071] 0 to 60 parts by weight of (D) a polyfluoromonoalkenyl compound having one alkenyl group in one molecule and a perfluoropolyether structure in the main chain, wherein the total amount of components (A) and (D) is 100 parts by weight;

[0072] a curing effective amount of (B) an organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule;

[0073] A catalytic amount of (C) a hydrosilylation reaction catalyst.

[0074] [3] The curable perfluoropolyether adhesive composition according to [2], wherein the component (D) is a polyfluoromonoolefin compound represented by the following general formula (2):

[0075] R 1 -(X') p -CH=CH2(2)

[0076] In formula (2), X' is -CH2-, -OCH2-, -CH2OCH2- or -CO-NR 2 -Y'-, p is 0 or 1, wherein Y' is -CH2- or a group represented by the following structural formula (Z'), R 2 is a hydrogen atom, a methyl group, a phenyl group or an allyl group;

[0077] [Chemical formula 5]

[0078]

[0079] The group represented by the structural formula (Z') is a dimethylphenylsilylene group represented in the ortho, meta or para position.

[0080] R 1 The general formula is F-[CF(CF3)CF2O] w The perfluoropolyether structure is represented by -CF(CF3)-, wherein w represents an integer of 1 to 500.

[0081] [4] The curable perfluoropolyether adhesive composition according to any one of [1] to [3], wherein the component (A) is a linear perfluoropolyether compound represented by the following general formula (1):

[0082] [Chemical formula 6]

[0083]

[0084] In formula (1), X is -CH2-, -CH2O-, -CH2OCH2- or -Y-NR 1 -CO-, X' is -CH2-, -OCH2-, -CH2OCH2- or -CO-NR 2 -Y'-, p is independently 0 or 1, r is an integer of 2 to 6, m and n are integers of 0 to 600, and the sum of m and n is 50 to 600; wherein Y is -CH2- or a group represented by the following structural formula (Z), R 1 is a hydrogen atom, a methyl group, a phenyl group or an allyl group; Y' is -CH2- or a group represented by the following structural formula (Z'); R 2 is a hydrogen atom, a methyl group, a phenyl group or an allyl group,

[0085] [Chemical formula 7]

[0086]

[0087] The group represented by the structural formula (Z) is a dimethylphenylsilylene group represented in the ortho, meta or para position.

[0088] [Chemical formula 8]

[0089]

[0090] The group represented by the structural formula (Z') is a dimethylphenylsilylene group represented in the ortho, meta or para position.

[0091] [5] The curable perfluoropolyether adhesive composition according to [2] or [3], wherein the component (A) is a linear perfluoropolyether compound represented by the general formula (1), and the component (D) is contained in an amount of 0 to 20 parts by mass based on 100 to 80 parts by mass of the component (A), wherein the total of the components (A) and (D) is 100 parts by mass, and the component (B) is a fluorinated organohydrogenpolysiloxane having a cyclic siloxane structure.

[0092] [6] The curable perfluoropolyether adhesive composition according to [2] or [3], wherein the component (A) is a linear perfluoropolyether compound represented by the general formula (1), and the component (D) is contained in an amount of 21 to 45 parts by mass based on 79 to 55 parts by mass of the component (A), wherein the total of the components (A) and (D) is 100 parts by mass, and the component (B) is a fluorinated organohydrogenpolysiloxane having a linear and / or branched siloxane structure.

[0093] [7] The curable perfluoropolyether adhesive composition according to [2] or [3], wherein the component (A) is a linear perfluoropolyether compound having a divalent perfluoropolyether structure composed of a repeating (CF2O) unit and a (CF2CF2O) unit in the main chain, and the component (D) is contained in an amount of 0 to 50 parts by mass based on 100 to 50 parts by mass of the component (A), wherein the total of the components (A) and (D) is 100 parts by mass, and the component (B) is a fluorinated organohydrogenpolysiloxane having a linear and / or branched siloxane structure.

[0094] [8] The curable perfluoropolyether adhesive composition according to [2] or [3], wherein the component (A) is a linear perfluoropolyether compound represented by the general formula (1) having a divalent perfluoropolyether structure composed of a repeating (CF2O) unit and a (CF2CF2O) unit in the main chain, and the component (D) is contained in an amount of 0 to 50 parts by mass based on 100 to 50 parts by mass of the component (A), wherein the total of the components (A) and (D) is 100 parts by mass, and the component (B) is a fluorinated organohydrogenpolysiloxane having a linear and / or branched siloxane structure.

[0095] [9] The curable perfluoropolyether adhesive composition according to any one of [1] to [8], wherein the cured product of the curable perfluoropolyether adhesive composition has a volume resistivity of 1×10 9 Non-conductive adhesive with Ω·cm or more.

[0096]

[10] An adhesive comprising a cured product of the curable perfluoropolyether adhesive composition according to any one of [1] to [9].

[0097]

[11] An adhesive tape comprising a substrate and a cured layer of the curable perfluoropolyether adhesive composition according to any one of [1] to [9] laminated on the substrate.

[0098] That is, the first embodiment of the present invention is a curable perfluoropolyether adhesive composition, which can provide a rubber-like cured product (cured perfluoropolyether rubber), the curable perfluoropolyether adhesive composition containing the following (A) to (C) components and forming an adhesive (cured perfluoropolyether rubber) having an adhesive force of less than 0.5N / 25mm by curing;

[0099] 100 parts by mass of (A) a linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a main chain containing -C a F 2a O-repeating unit perfluoropolyether structure, a is an integer of 1 to 6;

[0100] a curing effective amount of (B) an organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule;

[0101] A catalytic amount of (C) a hydrosilylation reaction catalyst.

[0102] Hereinafter, a first aspect of the present invention will be described, but the present invention is not limited thereto.

[0103] [(A) ingredient]

[0104] The component (A) contained in the curable perfluoropolyether adhesive composition of the present invention functions as a main agent (base polymer) of the curable perfluoropolyether adhesive composition of the present invention, and is a linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a perfluoropolyether structure (perfluorooxyalkylene structure), preferably a divalent perfluorooxyalkylene structure, in the main chain.

[0105] Among them, as a perfluorooxyalkylene structure, it contains -C a F 2a Examples of the multiple repeating structures of the oxyalkylene unit represented by O— (wherein a in each unit is independently an integer of 1 to 6) include the structure represented by the following general formula (5).

[0106] (C a F 2a O) q (5)

[0107] In formula (5), q is an integer of 50 to 600, preferably an integer of 50 to 400, and more preferably an integer of 50 to 200.

[0108] As each repeating structure constituting the perfluorooxyalkylene structure represented by the above formula (5),a F 2a O- (ie, oxyalkylene unit) includes the following structures. The perfluoroalkyl ether structure may be composed of one of these repeating structures alone or a combination of two or more of these repeating structures.

[0109] -CF2O-

[0110] -CF2CF2O-

[0111] -CF2CF2CF2O-

[0112] -CF(CF3)CF2O-

[0113] -CF2CF2CF2CF2O-

[0114] -CF2CF2CF2CF2CF2CF2O-

[0115] -C(CF3)2O-

[0116] Among them, the following structures are particularly suitable.

[0117] -CF2O-

[0118] -CF2CF2O-

[0119] -CF2CF2CF2O-

[0120] -CF(CF3)CF2O-

[0121] In the present invention, "linear" means that each repeating unit of the perfluoropolyether structure (perfluorooxyalkylene structure) constituting the main chain is -C a F 2a O-(oxyalkylene units) are bonded to each other in a straight chain, and each repeating unit (oxyalkylene unit) itself can be a straight chain oxyalkylene unit or a branched chain oxyalkylene unit (for example: -CF(CF3)CF2O-, -C(CF3)2O-, etc.).

[0122] The component (A) is particularly preferably a linear perfluoropolyether compound having a main chain containing a divalent perfluoropolyether structure composed of a repeating (CF2O) unit and a (CF2CF2O) unit.

[0123] As the alkenyl group in the linear perfluoropolyether compound of the component (A), it is preferred that the number of carbon atoms is 2 to 8, especially the number of carbon atoms is 2 to 6 and the group having a CH2=CH- structure at the end, for example, vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl and other groups having a CH2=CH- structure at the end, especially vinyl, allyl, etc. are preferred. The alkenyl group can be directly bonded to the two ends of the perfluoropolyether structure, especially the divalent perfluorooxyalkylene structure, which constitutes the main chain of the linear perfluoropolyether compound, or can be bonded via a divalent connecting group such as -CH2-, -CH2O-, -CH2OCH2- or -Y-NR-CO-, wherein Y is -CH2- or a group shown in the following structural formula (Z), and R is a hydrogen atom, a methyl group, a phenyl group or an allyl group. In addition, one molecule of the component (A) has at least two alkenyl groups.

[0124] [Chemical formula 9]

[0125]

[0126] The group represented by the structural formula (Z) is a dimethylphenylsilylene group represented in the ortho, meta or para position.

[0127] Furthermore, the component (A) has at least two alkenyl groups in one molecule.

[0128] As the component (A), there can be mentioned a polyfluorodiene compound represented by the following general formula (6) or (7):

[0129] CH2=CH-(X) p -Rf 2 -(X') p -CH=CH2(6)

[0130] CH2=CH-(X) p -Q-Rf 2 -Q-(X') p -CH=CH2(7)

[0131] In formula (6) and (7), X is independently -CH2-, -CH2O-, -CH2OCH2- or -Y-NR 1 -CO-, X' is -CH2-, -OCH2-, -CH2OCH2- or -CO-NR 2 -Y'-, wherein Y is -CH2- or a radical represented by the following structural formula (Z), R 1 is a hydrogen atom, a methyl group, a phenyl group or an allyl group, Y' is -CH2- or a group represented by the following structural formula (Z'), R 2 It is a hydrogen atom, a methyl group, a phenyl group or an allyl group.

[0132] [Chemical formula 10]

[0133]

[0134] The group represented by the structural formula (Z) is a dimethylphenylsilylene group represented in the ortho, meta or para position.

[0135] [Chemical formula 11]

[0136]

[0137] The group represented by the structural formula (Z') is a dimethylphenylsilylene group represented in the ortho, meta or para position.

[0138] R 2 is a divalent perfluoropolyether structure (perfluorooxyalkylene structure), preferably the above formula (5) (C a F 2a O) q Q is a divalent hydrocarbon group having 1 to 15 carbon atoms, which may contain an ether bond, and specifically, an alkylene group or an alkylene group which may contain an ether bond. p is independently 0 or 1.

[0139] The component (A) is particularly preferably a linear perfluoropolyether compound having a main chain containing a divalent perfluoropolyether structure composed of a repeating (CF2O) unit and a (CF2CF2O) unit.

[0140] As such a linear perfluoropolyether compound of the component (A), a linear perfluoropolyether compound represented by the following general formula (1) is particularly suitable.

[0141] [Chemical formula 12]

[0142]

[0143] In formula (1), X, X' and p are the same as those described above, r is an integer of 2 to 6, m and n are integers of 0 to 600 respectively, and the sum of m and n is 50 to 600.

[0144] For the linear perfluoropolyether compound of the general formula (1), it is expected that the weight average molecular weight in terms of polystyrene in the molecular weight distribution measurement determined by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing agent is 3,000 to 100,000, particularly 4,000 to 50,000. If the weight average molecular weight is 4,000 or more, the swelling to gasoline and various solvents is reduced. In particular, the swelling to gasoline is 6% or less, which can satisfy the characteristics of a component that requires gasoline resistance. In addition, if the weight average molecular weight is 100,000 or less, the viscosity will not be too high, and the operability is excellent, so it has practicality. In addition, the value of the degree of polymerization (m+n) of the linear perfluoropolyether compound of the general formula (1) can also be obtained by the number average degree of polymerization or weight average degree of polymerization in terms of polystyrene in the molecular weight distribution measurement determined by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing agent. In addition, these number average polymerization degrees or number average molecular weights can also be obtained from 19 The ratio of the terminal structure to the repeating unit structure obtained by F-NMR spectrum was calculated.

[0145] Specific examples of the linear perfluoropolyether compound represented by the general formula (1) include compounds represented by the following formulas.

[0146] [Chemical formula 13]

[0147]

[0148] [Chemical formula 14]

[0149]

[0150] [Chemical formula 15]

[0151]

[0152] In the formula, m and n each represent an integer of 0 to 600, preferably an integer of 0 to 200, and are integers satisfying m+n=50 to 600, preferably m+n=50 to 200.

[0153] Furthermore, in the present invention, in order to adjust the linear perfluoropolyether compound of the above formula (1) to a desired weight average molecular weight according to the purpose, the above linear perfluoropolyether compound can be subjected to a hydrosilylation reaction with an organosilicon compound containing two SiH groups in the molecule in advance under a conventional method and conditions, and the product with a longer chain length can be used as the component (A). In addition, the linear perfluoropolyether compound of the component (A) can be used alone or in combination of two or more.

[0154] [(B) ingredient]

[0155] The component (B) acts as a crosslinking agent and / or chain extender for the component (A). The component (B) is an organosilicon compound such as an organohydrogenpolysiloxane having at least two, preferably three or more hydrogen atoms (hydrosilyl groups represented by SiH) bonded to silicon atoms in one molecule. In addition, from the perspective of compatibility with the component (A), or the component (A) in the second embodiment of the present invention described later and the component (D) described later, dispersibility, uniformity of the cured rubber or gel cured product (adhesive), etc., the organosilicon compound of the component (B) is preferably a fluorinated organohydrogenpolysiloxane having one or more monovalent perfluoroalkyl groups, monovalent perfluorooxyalkyl groups, divalent perfluoroalkylene groups and / or divalent perfluorooxyalkylene groups in one molecule.

[0156] Examples of such component (B) include known organosilicon compounds described in Patent Document 1, Patent Document 2, and Patent Document 4, but the present invention is not particularly limited thereto.

[0157] Examples of the monovalent or divalent fluorine-containing organic group include a perfluoroalkyl group, a perfluorooxyalkyl group, a perfluoroalkylene group, and a perfluorooxyalkylene group represented by the following formula.

[0158] C g F 2g+1 -

[0159] -C g F 2g -

[0160] In the formula, g is an integer of 1 to 20, preferably an integer of 2 to 10.

[0161] [Chemical formula 16]

[0162]

[0163] In the formula, f is an integer of 1 to 200, preferably an integer of 1 to 100, and h is an integer of 1 to 3.

[0164] [Chemical formula 17]

[0165]

[0166] In the formula, i and j are each an integer greater than 1, preferably an integer from 1 to 100, and the average of i+j is 2 to 200, preferably 2 to 100.

[0167] -(CF2O) d -(CF2CF2O) e -CF2-

[0168] In the formula, d and e are respectively integers of 1 to 50, preferably integers of 1 to 40.

[0169] In addition, it is preferred that these perfluoroalkyl groups, perfluorooxyalkyl groups, perfluoroalkylene groups or perfluorooxyalkylene groups are connected to the silicon atom via a divalent linking group, and examples of the divalent linking group include alkylene groups, arylene groups and combinations thereof; or groups in which ether bond oxygen atoms, amide bonds, carbonyl bonds, ester bonds, diorganosilyl groups and the like are mixed, such as the following divalent linking groups having 2 to 12 carbon atoms, but are not limited thereto.

[0170] -CH2CH2-

[0171] -CH2CH2CH2-

[0172] -CH2CH2CH2OCH2-

[0173] -CH2CH2CH2-NH-CO-

[0174] -CH2CH2CH2-N(Ph)-CO-

[0175] -CH2CH2CH2-N(CH3)-CO-

[0176] -CH2CH2CH2-N(CH2CH3)-CO-

[0177] -CH2CH2-Si(CH3)2-Ph'-N(CH3)-CO-

[0178] -CH2CH2CH2-Si(CH3)2-Ph'-N(CH3)-CO-

[0179] -CH2CH2CH2-O-CO-

[0180] In the formula, Ph is a phenyl group, and Ph' is a phenylene group.

[0181] In addition, in the fluorinated organohydrogenpolysiloxane as the component (B), the monovalent substituents bonded to silicon atoms other than the above-mentioned monovalent or divalent fluorinated organic groups and hydrogen atoms bonded to silicon atoms include, for example, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, and decyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl, tolyl, and naphthyl; aralkyl groups such as benzyl and phenylethyl; and unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, such as chloromethyl, chloropropyl, and cyanoethyl, in which a part or all of the hydrogen atoms of these groups are substituted with chlorine atoms, cyano groups, etc.

[0182] The siloxane structure in the fluorinated organohydrogenpolysiloxane as component (B) may be any one of cyclic, linear, branched, three-dimensional network and combinations thereof. The number of silicon atoms in the fluorinated organohydrogenpolysiloxane is not particularly limited, but is generally 2 to 60, preferably about 3 to 30. The fluorinated organohydrogenpolysiloxane as component (B) is particularly preferably a fluorinated organohydrogenpolysiloxane having a cyclic structure of a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group; or a fluorinated organohydrogenpolysiloxane having a branched or cyclic organohydrogenpolysiloxane structure at both ends of a divalent perfluoroalkylene group or a divalent perfluorooxyalkylene group.

[0183] As such a component (B) having a monovalent or divalent fluorine-containing organic group and a hydrogen atom bonded to a silicon atom, for example, the following compounds can be cited. These compounds can be used alone or in combination of two or more. In addition, in the following formula, Me represents a methyl group, and Ph represents a phenyl group.

[0184] [Chemical formula 18]

[0185]

[0186] [Chemical formula 19]

[0187]

[0188] [Chemical formula 20]

[0189]

[0190] [Chemical formula 21]

[0191]

[0192] [Chemical formula 22]

[0193]

[0194] [Chemical formula 23]

[0195]

[0196] [Chemical formula 24]

[0197]

[0198] [Chemical formula 25]

[0199]

[0200] [Chemical formula 26]

[0201]

[0202] [Chemical formula 27]

[0203]

[0204] [Chemical formula 28]

[0205]

[0206] [Chemical formula 29]

[0207]

[0208] [Chemical formula 30]

[0209]

[0210] The amount of the above-mentioned (B) component is an effective amount for curing the (A) component and the (D) component described later, i.e., a curing effective amount, and is particularly the following amount: relative to 1 mole of the alkenyl group possessed by the above-mentioned (A) component in the present composition, or 1 mole of the total of the alkenyl groups possessed by the (A) component and the (D) component in the second embodiment of the present invention described later, the hydrosilyl group (Si-H) in the (B) component is preferably 0.2 to 4 moles, and more preferably 0.5 to 3 moles. If the amount of the hydrosilyl group (Si-H) is 0.2 moles or more, the degree of crosslinking is sufficient, and there is no possibility of not being able to obtain a cured product. In addition, if the amount of the hydrosilyl group (Si-H) is 4 moles or less, there is no possibility of foaming during curing.

[0211] The component (B) may be used alone or in combination of two or more.

[0212] [(C) ingredient]

[0213] The hydrosilylation reaction catalyst (addition reaction catalyst) of the component (C) of the present invention is a catalyst that promotes the addition reaction of the alkenyl group in the component (A), or the alkenyl group in the component (A) in the second embodiment of the present invention described later and the component (E) described later, with the hydrosilyl group in the component (B). The hydrosilylation reaction catalyst is usually a compound of a noble metal (platinum group metal), and since it is expensive, platinum or a platinum compound that is relatively easy to obtain is often used.

[0214] Examples of platinum compounds include chloroplatinic acid or complexes of chloroplatinic acid and olefins such as ethylene, complexes with alcohols or vinylsiloxanes, and metal platinum supported on silicon oxide, aluminum oxide, carbon, and the like. Rhodium, ruthenium, iridium, and palladium compounds are also known as platinum group metal catalysts other than platinum compounds, and examples thereof include RhCl(PPh3)3, RhCl(CO)(PPh3)2, Ru3(CO) 12 , IrCl(CO)(PPh3)2, Pd(PPh3)4, etc.

[0215] The amount of the hydrosilylation reaction catalyst added can be a catalytic amount, and is usually preferably added at a ratio of 0.1 to 500 ppm (calculated as the mass of the platinum group metal) relative to the total mass of the components (A), (B) and (D), and preferably at a ratio of 0.1 to 100 ppm. The hydrosilylation reaction catalyst of the component (C) can be used alone or in combination of two or more.

[0216] [Other ingredients]

[0217] In this composition, in addition to the above-mentioned (A) to (C) components, various additives can be added arbitrarily. As a control agent for the hydrosilylation reaction catalyst, for example, 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentene-3-ol, phenylbutynol and other acetylene alcohols; and 3-methyl-3-pentene-1-yne, 3,5-dimethyl-3-hexene-1-yne, etc.; or polymethylvinylsiloxane cyclic compounds, organic phosphorus compounds, etc. can be cited, and curing reactivity and storage stability can be appropriately maintained by adding them.

[0218] In addition, in order to impart adhesion, a known adhesion imparting agent containing an epoxy group, an alkoxy group, etc. may be added (for example, a hydrolyzable organosilane compound containing an adhesive functional group having an epoxy group and a trialkoxysilyl group in the molecule (so-called epoxy-containing silane coupling agent); a (fluorine-containing) organohydrogenpolysiloxane that necessarily contains a hydrogen atom (SiH group) bonded to a silicon atom and further contains an epoxy group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom in the molecule; a (fluorine-containing) organohydrogenpolysiloxane that necessarily contains a hydrogen atom (SiH group) bonded to a silicon atom and further contains a trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom in the molecule; a (fluorine-containing) organohydrogenpolysiloxane that necessarily contains a hydrogen atom (SiH group) bonded to a silicon atom and further contains an epoxy group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom in the molecule and a trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, etc.).

[0219] In addition, the second embodiment of the present invention also provides a curable perfluoropolyether adhesive composition, which can provide a rubber-like cured product (perfluoropolyether rubber cured product) or a gel-like cured product (perfluoropolyether gel cured product), which contains the following (A) to (D) components and forms an adhesive (perfluoropolyether rubber or gel cured product) having an adhesive force of less than 0.5N / 25mm by curing.

[0220] 100 to 40 parts by mass of (A) a linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a main chain containing -C a F 2a O-repeating unit perfluoropolyether structure, a is an integer of 1 to 6;

[0221] 0 to 60 parts by weight of (D) a polyfluoromonoalkenyl compound having one alkenyl group in one molecule and a perfluoropolyether structure in the main chain, wherein the total amount of components (A) and (D) is 100 parts by weight;

[0222] a curing effective amount of (B) an organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule;

[0223] A catalytic amount of (C) a hydrosilylation reaction catalyst.

[0224] As the components (A) to (C) in this case, the same components as those described above can be used.

[0225] In addition, the blending amount of the (D) component of the curable perfluoropolyether adhesive composition of the second embodiment of the present invention is 0 to 60 parts by mass. Therefore, the composition of the second embodiment of the present invention may include the (D) component or may not include the (D) component. That is, in the composition of the second embodiment of the present invention, the (D) component is an arbitrary component. When the composition of the second embodiment of the present invention contains a specified amount of the (D) component, the composition is a composition that can provide a gel-like solidified product (perfluoropolyether gel solidified product) by curing. In addition, since the (A)~(C) components of the composition of the second embodiment of the present invention are the (A)~(C) components of the composition of the first embodiment described above, the composition of the second embodiment of the present invention does not contain the (D) component, and can form the curable perfluoropolyether adhesive composition of the first embodiment described above that can provide a rubber-like solidified product by curing. That is, the curable perfluoropolyether adhesive composition of the second embodiment of the present invention includes the curable perfluoropolyether adhesive composition of the first embodiment of the present invention. The curable perfluoropolyether adhesive composition of the second aspect of the present invention preferably contains 100 to 55 parts by mass of the component (A) and 0 to 45 parts by mass of the component (D) (wherein the total amount of the components (A) and (D) is 100 parts by mass).

[0226] [(D) ingredient]

[0227] The curable perfluoropolyether adhesive composition of the present invention is different from the first embodiment of the present invention (i.e., the composition that can provide a rubber cured product), and the component (D) is a component used in a specific second embodiment (i.e., the composition that can provide a rubber cured product or a gel cured product), which is a polyfluoromonoolefin compound having one alkenyl group in one molecule and a perfluoropolyether structure in the main chain. The polyfluoromonoolefin compound of the following formula (2) is particularly preferred.

[0228] R 1 -(X') p -CH=CH2(2)

[0229] In formula (2), X' and p are the same as those described above, and Rf 1 It is shown in the following general formula.

[0230] F-[CF(CF3)CF2O] w -CF(CF3)-

[0231] In the formula, w is an integer of 1 to 500, preferably an integer of 2 to 200.

[0232] Specific examples of the polyfluoromonoalkenyl compound represented by the general formula (2) include the following compounds.

[0233] [Chemical formula 31]

[0234]

[0235] [Chemical formula 32]

[0236]

[0237] In the above formula, m is an integer of 1-200, particularly an integer of 2-100.

[0238] When the polyfluoromonoolefin compound of the above formula (2) is blended, its blending amount is selected as follows: in the curable perfluoropolyether adhesive composition, the ratio between the linear perfluoropolyether diene compound of the above component (A) and the component (D) in the composition is such that the component (A) is 100 to 40 parts by mass, the component (D) is 0 to 60 parts by mass, and the total amount of the components (A) and (D) is 100 parts by mass.

[0239] For example, the perfluoropolyether adhesive composition of the second embodiment of the present invention can include component (D) in a ratio of 20 to 60 parts by mass relative to 80 to 40 parts by mass of component (A) and in a total amount of component (A) and component (D) of 100 parts by mass. In addition, the polyfluoromonoolefin compound of component (D) can be used alone or in combination of two or more.

[0240] [Other ingredients]

[0241] In addition to the above-mentioned components (A) to (D), various additives such as various adhesive agents and the like as the additives described above can be added to the present composition as in the first embodiment. As the control agent for the hydrosilylation reaction catalyst, the same control agents as those described above can be exemplified.

[0242] [cured material]

[0243] The perfluoropolyether adhesive composition of the present invention is formed by curing the above-mentioned composition to form an adhesive composed of a cured product of a perfluoropolyether rubber or gel having an adhesive force (surface micro-adhesion force) of less than 0.5N / 25mm, preferably 0.001~0.45N / 25mm, and more preferably 0.002~0.4N / 25mm. The perfluoropolyether adhesive composition can form a cured product (adhesive) excellent in heat resistance, hydrophobicity, oleophobicity, weather resistance, etc., especially excellent in chemical resistance and solvent resistance, and can be used in various applications.

[0244] In addition, in order to obtain a rubber or gel-like cured product having a surface adhesive force of less than 0.5 N / 25 mm in the cured product obtained by curing the perfluoropolyether adhesive composition of the present invention, it is preferred to use a perfluoropolyether adhesive composition that satisfies the following conditions:

[0245] When the linear perfluoropolyether compound represented by the above general formula (1) is used as the component (A),

[0246] (i) in a composition containing 0 to 20 parts by mass of the component (D) with respect to 100 to 80 parts by mass of the component (A) (the total of the components (A) and (D) being 100 parts by mass), using a fluorinated organohydrogenpolysiloxane having a cyclic siloxane structure as a crosslinking agent for the component (B),

[0247] (ii) in a composition containing 21 to 45 parts by mass of the component (D) relative to 79 to 55 parts by mass of the component (A) (the total of the components (A) and (D) being 100 parts by mass), a fluorinated polyorganohydrogensiloxane having a linear and / or branched siloxane structure is used as a crosslinking agent for the component (B);

[0248] Alternatively, when a polyfluorodiene compound represented by the general formula (6) or (7) is used, the repeating structure of (CF2O) units and (CF2CF2O) units is used as the main chain Rf 2 When a linear perfluoropolyether compound of a divalent perfluoropolyether of

[0249] (iii) In a composition comprising 0 to 50 parts by mass of the component (D) relative to 100 to 50 parts by mass of the component (A) (the total of the components (A) and (D) being 100 parts by mass), a fluorinated organohydrogenpolysiloxane having a linear and / or branched siloxane structure is used as a crosslinking agent for the component (B).

[0250] For example, the perfluoropolyether adhesive composition in the first embodiment of the present invention can be formed by curing the following components: relative to 100 parts by mass of the component (A), the amount of the component (B) is 0.2 to 3.0 mol of the hydrosilyl group of the component (B) relative to the total molar number of alkenyl groups possessed by the component (A), and the amount of the component (C) is 0.1 to 100 ppm in terms of platinum relative to the total amount of the components (A) and (B).

[0251] Furthermore, for example, the perfluoropolyether adhesive composition of the second embodiment of the present invention can be formed by curing the following components: relative to 100 to 40 parts by mass of the component (A), 0 to 60 parts by mass of the component (D), and the total of the components (A) and (D) is 100 parts by mass, the amount of the component (B) is 0.2 to 3.0 mol of the hydrosilyl group of the component (B) relative to the total molar number of alkenyl groups possessed by the component (A), and the component (C) is 0.1 to 100 ppm in terms of platinum relative to the total amount of the components (A), (B), and (D).

[0252] The perfluoropolyether adhesive composition can be formed by coating each composition of the present invention on a suitable substrate and then curing it, or by conventionally known methods such as lamination. Curing can be performed by heating at a temperature of 60 to 150° C. for about 1 to 30 minutes.

[0253] The adhesive using the perfluoropolyether adhesive composition of the present invention can be used as components for automobiles, chemical plants, semiconductor production lines, analytical / physical and chemical equipment, medical equipment, aircraft, optics, and the like.

[0254] In addition, for example, an adhesive tape in which a cured product (cured perfluoropolyether rubber or cured perfluoropolyether gel) of the curable perfluoropolyether adhesive composition of the present invention is laminated on a substrate composed of an organic resin film such as a polyethylene terephthalate (PET) film can be used as an adhesive tape having a non-conductive adhesive layer having excellent heat resistance, oil resistance, low temperature characteristics, moisture resistance, low air permeability, etc., and particularly excellent chemical resistance and solvent resistance.

[0255] In addition, when applying the adhesive composition of the present invention, in order to improve the closeness or adhesion between the substrate, a known primer can be used simultaneously. Primer can be utilized to prevent reagents and solvents from penetrating from the substrate interface, thereby improving the acid resistance, reagent resistance, and solvent resistance of the entire component.

[0256] As the primer, a silane-based primer mainly composed of a silane coupling agent, a primer mainly composed of an organohydrogenpolysiloxane, a primer mainly composed of a synthetic rubber, a primer mainly composed of an acrylic resin, a primer mainly composed of a urethane resin, or a primer mainly composed of an epoxy resin can be used. In addition, a composition obtained by adding an adhesion-imparting agent to the perfluoropolyether rubber composition of the present invention can also be used as a primer.

[0257] Furthermore, it is preferred that the cured product (cured perfluoropolyether rubber or cured perfluoropolyether gel) of the curable perfluoropolyether adhesive composition of the present invention has a volume resistivity of 1×10 9 The curable perfluoropolyether adhesive composition of the present invention is suitable for use as a material for a non-conductive adhesive. The upper limit of the volume resistivity of the cured product of the curable perfluoropolyether adhesive composition of the present invention is not particularly limited, and can be, for example, 1×10 13 Ω·cm.

[0258] The perfluoropolyether adhesive composition of the present invention can provide a slightly adhesive cured product (adhesive) having excellent heat resistance, weather resistance, oil resistance, low temperature characteristics, moisture resistance, low air permeability, hydrophobicity, oleophobicity, etc., and particularly excellent chemical resistance and solvent resistance (solvent resistance). An adhesive tape containing a slightly adhesive cured product can be peeled off without damaging the substrate even when attached to a fragile substrate.

[0259] Furthermore, a third aspect of the present invention is a cured product (cured perfluoropolyether rubber or cured perfluoropolyether gel) of the curable perfluoropolyether adhesive composition of the present invention described above.

[0260] As described above, the perfluoropolyether adhesive composition of the present invention can provide a cured product (adhesive) having excellent heat resistance, weather resistance, oil resistance, reagent resistance, solvent resistance (solvent resistance), low temperature characteristics, moisture resistance, low air permeability, hydrophobicity, oleophobicity, etc. Therefore, the heat resistance, weather resistance, oil resistance, reagent resistance, solvent resistance (solvent resistance), low temperature characteristics, moisture resistance, low air permeability, hydrophobicity, oleophobicity, etc. of the adhesive of the present invention are excellent. Further, the cured product included in the adhesive of the present invention has slight adhesion. Therefore, the adhesive tape using the adhesive of the present invention can be peeled off from the substrate without damaging the substrate even when attached to a fragile substrate.

[0261] Furthermore, a fourth aspect of the present invention is an adhesive tape having a cured product layer of the curable perfluoropolyether adhesive composition of the present invention described above laminated thereon.

[0262] As described above, the perfluoropolyether adhesive composition of the present invention can provide a cured product (adhesive) having excellent heat resistance, weather resistance, oil resistance, reagent resistance, solvent resistance (solvent resistance), low temperature characteristics, moisture resistance, low air permeability, hydrophobicity, oleophobicity, etc. Therefore, the adhesive tape of the present invention has excellent heat resistance, weather resistance, oil resistance, reagent resistance, solvent resistance (solvent resistance), low temperature characteristics, moisture resistance, low air permeability, hydrophobicity, oleophobicity, etc. Further, the cured product contained in the adhesive tape of the present invention has slight adhesion. Therefore, the adhesive tape of the present invention can be peeled off from the substrate without damaging the substrate even when attached to a fragile substrate.

[0263] Example

[0264] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, % represents mass %.

[0265] [Examples 1 to 9, Comparative Examples 1 to 3]

[0266] The following raw materials were used to prepare the curable perfluoropolyether adhesive compositions shown in Table 1. These adhesive compositions were cured under the curing conditions of 130° C. and 5 minutes, and the surface adhesive strength of each cured product was measured, and the solvent resistance test was performed by the following method. The results are collectively recorded in Table 1.

[0267] [raw material]

[0268] (A) Linear perfluoropolyether compounds

[0269] (A-1) Difunctional perfluoropolyether (perfluoropolyether 1)

[0270] [Chemical formula 33]

[0271]

[0272] (A-2) Difunctional perfluoropolyether (perfluoropolyether 2)

[0273] CH2=CH-CH2-O-CH2-Rf-CH2-O-CH2-CH=CH2

[0274] (Rf: -CF2O(CF2CF2O) 20.8 (CF2O) 22.1 CF2-),

[0275] Among them, the repeating units CF2CF2O and CF2O are arranged randomly.

[0276] (D) Monofunctional perfluoropolyether compound (perfluoropolyether 3)

[0277] [Chemical formula 34]

[0278]

[0279] (B) Organohydrogenpolysiloxane

[0280] (b-1) Organohydrogensiloxane 1

[0281] [Chemical formula 35]

[0282]

[0283] (b-2) Organohydrogensiloxane 2

[0284] [Chemical formula 36]

[0285]

[0286] (C) Platinum-divinyltetramethyldisiloxane complex / ethanol solution (platinum content 3.0%)

[0287] (e) Curing control agent: ethynyl cyclohexanol / 50% toluene solution

[0288] (f) KR-3700 (trade name of Shin-Etsu Chemical Co., Ltd.) is an addition-curing silicone adhesive based on dimethyl silicone.

[0289] [Adhesion strength measurement]

[0290] After applying each composition of the embodiment and the comparative example to a PET (polyethylene terephthalate) film having a thickness of 50 μm and a width of 25 mm using an applicator in a manner of 30 μm, the composition was cured into a rubber or gel state by heating at 130°C for 5 minutes, thereby preparing an adhesive tape having an adhesive layer (rubber or gel cured layer) having a thickness of 30 μm laminated on a PET film having a thickness of 50 μm. The adhesive tape was attached to a metal plate (polished stainless steel plate), and a roller coated with a rubber layer having a weight of 2 kg was moved back and forth once on the tape substrate to crimp the adhesive tape. After being placed at room temperature for 20 hours, a tensile tester was used to measure the force (N / 25 mm) required to peel the adhesive tape from the stainless steel plate at an angle of 180° at a tensile speed of 300 mm / min at 25°C, and it was used as the adhesion of each adhesive layer (rubber or gel cured layer).

[0291] [Solvent resistance test (weight change)]

[0292] After filling 3 g of the composition of the embodiment and the comparative example into a 32φ×15 mm glass container, it was cured at 130°C for 5 minutes to prepare a sample, and then immersed in xylene and fuel C (Fuel C) (a 50 / 50 (weight %) mixed solution of toluene / isooctane) at 25°C for 7 days, and then the weight change rate before and after the immersion was measured.

[0293] [Table 1]

[0294]

[0295] As shown in Table 1, adhesives such as Examples 1 to 9 using the curable perfluoropolyether adhesive composition of the present invention have high solvent resistance. On the contrary, Comparative Example 1, which is a silicone adhesive, has too high adhesive force and low solvent resistance. In addition, Comparative Examples 2 and 3, which do not contain the essential components (B) or (C) of the present invention, cannot be cured.

[0296] As can be seen from the above, the present invention can provide a slightly adhesive curable perfluoropolyether adhesive composition which can be cured (adhesive) with excellent heat resistance, weather resistance, hydrophobicity, oleophobicity, etc., and particularly excellent chemical resistance and solvent resistance.

[0297] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any embodiments having substantially the same configuration and exhibiting the same functions and effects as the technical concept described in the claims of the present invention are all within the technical scope of the present invention.

Claims

1. A curable perfluoropolyether adhesive composition, comprising the following components (A) to (C) and forming an adhesive having an adhesive force of less than 0.5 N / 25 mm by curing, 100 parts by mass of (A) a linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a main chain containing -C a F 2a O-repeating unit perfluoropolyether structure, a is an integer of 1 to 6; a curing effective amount of (B) an organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule; a catalytic amount of (C) a hydrosilylation reaction catalyst, in, The curable perfluoropolyether adhesive composition does not include: a hydrolyzable organosilane compound containing an adhesive functional group having an epoxy group and a trialkoxysilyl group in the molecule; a (fluorine-containing) organohydrogenpolysiloxane that must contain a hydrogen atom (SiH group) bonded to a silicon atom in the molecule and further contains an epoxy group bonded to the silicon atom via a carbon atom or a carbon atom and an oxygen atom; a (fluorine-containing) organohydrogenpolysiloxane that must contain a hydrogen atom (SiH group) bonded to a silicon atom in the molecule and further contains a trialkoxysilyl group bonded to the silicon atom via a carbon atom or a carbon atom and an oxygen atom; a (fluorine-containing) organohydrogenpolysiloxane that must contain a hydrogen atom (SiH group) bonded to a silicon atom in the molecule and further contains an epoxy group bonded to the silicon atom via a carbon atom or a carbon atom and an oxygen atom, and a trialkoxysilyl group bonded to the silicon atom via a carbon atom or a carbon atom and an oxygen atom.

2. A curable perfluoropolyether adhesive composition, which contains the following components (A) to (D) and forms an adhesive having an adhesive force of less than 0.5N / 25mm by curing; 100 to 40 parts by mass of (A) a linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a main chain containing -C a F 2a O-repeating unit perfluoropolyether structure, a is an integer of 1 to 6; 0 to 60 parts by weight of (D) a polyfluoromonoolefinic compound having one olefinic group in one molecule and a perfluoropolyether structure in the main chain, wherein: The total amount of components (A) and (D) is 100 parts by mass; a curing effective amount of (B) an organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule; a catalytic amount of (C) a hydrosilylation reaction catalyst, The curable perfluoropolyether adhesive composition does not include: a hydrolyzable organosilane compound containing an adhesive functional group having an epoxy group and a trialkoxysilyl group in the molecule; a (fluorine-containing) organohydrogenpolysiloxane that must contain a hydrogen atom (SiH group) bonded to a silicon atom and further contains an epoxy group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom in the molecule; a (fluorine-containing) organohydrogenpolysiloxane that must contain a hydrogen atom (SiH group) bonded to a silicon atom and further contains a trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom in the molecule; a (fluorine-containing) organohydrogenpolysiloxane that must contain a hydrogen atom (SiH group) bonded to a silicon atom and further contains an epoxy group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, and a trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom in the molecule.

3. The curable perfluoropolyether adhesive composition according to claim 2, wherein The component (D) is a polyfluoromonoolefin compound represented by the following general formula (2): Rf 1 -(X’) p -CH=CH2 (2) In formula (2), X' is -CH2-, -OCH2-, -CH2OCH2- or -CO-NR 2 -Y'-, p is 0 or 1, Rf 1 The general formula is F-[CF(CF3)CF2O] w -CF(CF3)-, wherein w represents an integer from 1 to 500. Wherein, Y' is -CH2- or a group represented by the following structural formula (Z'), R 2 is a hydrogen atom, a methyl group, a phenyl group or an allyl group, The group represented by the structural formula (Z') is a dimethylphenylsilylene group represented in the ortho, meta or para position.

4. The curable perfluoropolyether adhesive composition according to any one of claims 1 to 3, wherein The component (A) is a linear perfluoropolyether compound represented by the following general formula (1): In formula (1), X is -CH2-, -CH2O-, -CH2OCH2- or -Y-NR 1 -CO-, X' is -CH2-, -OCH2-, -CH2OCH2- or -CO-NR 2 -Y'-, p is independently 0 or 1, r is an integer of 2 to 6, m and n are integers of 0 to 600, and the sum of m and n is 50 to 600; wherein Y is -CH2- or a group represented by the following structural formula (Z), R 1 is a hydrogen atom, a methyl group, a phenyl group or an allyl group, Y' is -CH2- or a group represented by the following structural formula (Z'), R 2 is a hydrogen atom, a methyl group, a phenyl group or an allyl group, The group represented by the structural formula (Z) is a dimethylphenylsilylene group represented in the ortho, meta or para position, The group represented by the structural formula (Z') is a dimethylphenylsilylene group represented in the ortho, meta or para position.

5. The curable perfluoropolyether adhesive composition according to claim 2 or 3, wherein The component (A) is a linear perfluoropolyether compound represented by the following general formula (1): In formula (1), X is -CH2-, -CH2O-, -CH2OCH2- or -Y-NR 1 -CO-, X' is -CH2-, -OCH2-, -CH2OCH2- or -CO-NR 2 -Y'-, p is independently 0 or 1, r is an integer of 2 to 6, m and n are integers of 0 to 600, and the sum of m and n is 50 to 600; wherein Y is -CH2- or a group represented by the following structural formula (Z), R 1 is a hydrogen atom, a methyl group, a phenyl group or an allyl group, Y' is -CH2- or a group represented by the following structural formula (Z'), R 2 is a hydrogen atom, a methyl group, a phenyl group or an allyl group, The group represented by the structural formula (Z) is a dimethylphenylsilylene group represented in the ortho, meta or para position, The group represented by the structural formula (Z') is a dimethylphenylsilylene group represented in the ortho, meta or para position, The component (B) contains 0 to 20 parts by mass of the component (D) relative to 100 to 80 parts by mass of the component (A), wherein the total of the components (A) and (D) is 100 parts by mass, and the component (B) is a fluorinated organohydrogenpolysiloxane having a cyclic siloxane structure.

6. The curable perfluoropolyether adhesive composition according to claim 2 or 3, wherein The component (A) is a linear perfluoropolyether compound represented by the following general formula (1): In formula (1), X is -CH2-, -CH2O-, -CH2OCH2- or -Y-NR 1 -CO-, X' is -CH2-, -OCH2-, -CH2OCH2- or -CO-NR 2 -Y'-, p is independently 0 or 1, r is an integer of 2 to 6, m and n are integers of 0 to 600, and the sum of m and n is 50 to 600; wherein Y is -CH2- or a group represented by the following structural formula (Z), R 1 is a hydrogen atom, a methyl group, a phenyl group or an allyl group, Y' is -CH2- or a group represented by the following structural formula (Z'), R 2 is a hydrogen atom, a methyl group, a phenyl group or an allyl group, The group represented by the structural formula (Z) is a dimethylphenylsilylene group represented in the ortho, meta or para position, The group represented by the structural formula (Z') is a dimethylphenylsilylene group represented in the ortho, meta or para position, The composition comprises 21 to 45 parts by mass of the component (D) relative to 79 to 55 parts by mass of the component (A), wherein the total of the components (A) and (D) is 100 parts by mass, and the component (B) is a fluorinated polyorganohydrogensiloxane having a linear and / or branched siloxane structure.

7. The curable perfluoropolyether adhesive composition according to claim 2 or 3, wherein The component (A) is a linear perfluoropolyether compound having a divalent perfluoropolyether structure composed of a repeating (CF2O) unit and a (CF2CF2O) unit in the main chain, and contains 0 to 50 parts by mass of the component (D) relative to 100 to 50 parts by mass of the component (A), wherein the total of the components (A) and (D) is 100 parts by mass, and the component (B) is a fluorinated organohydrogenpolysiloxane having a linear and / or branched siloxane structure.

8. The curable perfluoropolyether adhesive composition according to claim 2 or 3, wherein The component (A) is a linear perfluoropolyether compound represented by the following general formula (1), having a divalent perfluoropolyether structure consisting of a repeating (CF2O) unit and a (CF2CF2O) unit in the main chain, In formula (1), X is -CH2-, -CH2O-, -CH2OCH2- or -Y-NR 1 -CO-, X' is -CH2-, -OCH2-, -CH2OCH2- or -CO-NR 2 -Y'-, p is independently 0 or 1, r is an integer of 2 to 6, m and n are integers of 0 to 600, and the sum of m and n is 50 to 600; wherein Y is -CH2- or a group represented by the following structural formula (Z), R 1 is a hydrogen atom, a methyl group, a phenyl group or an allyl group, Y' is -CH2- or a group represented by the following structural formula (Z'), R 2 is a hydrogen atom, a methyl group, a phenyl group or an allyl group, The group represented by the structural formula (Z) is a dimethylphenylsilylene group represented in the ortho, meta or para position, The group represented by the structural formula (Z') is a dimethylphenylsilylene group represented in the ortho, meta or para position, The composition comprises 0 to 50 parts by mass of the component (D) relative to 100 to 50 parts by mass of the component (A), wherein the total of the components (A) and (D) is 100 parts by mass, and the component (B) is a fluorinated organohydrogenpolysiloxane having a linear and / or branched siloxane structure.

9. The curable perfluoropolyether adhesive composition according to any one of claims 1 to 3, wherein the cured product of the curable perfluoropolyether adhesive composition has a volume resistivity of 1×10 9 Non-conductive adhesive with Ω·cm or more.

10. The curable perfluoropolyether adhesive composition according to claim 4, wherein the cured product of the curable perfluoropolyether adhesive composition has a volume resistivity of 1×10 9 Non-conductive adhesive with Ω·cm or more.

11. The curable perfluoropolyether adhesive composition according to claim 5, wherein the cured product of the curable perfluoropolyether adhesive composition has a volume resistivity of 1×10 9 Non-conductive adhesive with Ω·cm or more.

12. The curable perfluoropolyether adhesive composition according to claim 6, wherein the cured product of the curable perfluoropolyether adhesive composition has a volume resistivity of 1×10 9 Non-conductive adhesive with Ω·cm or more.

13. The curable perfluoropolyether adhesive composition according to claim 7, wherein the cured product of the curable perfluoropolyether adhesive composition has a volume resistivity of 1×10 9 Non-conductive adhesive with Ω·cm or more.

14. The curable perfluoropolyether adhesive composition according to claim 8, wherein the cured product of the curable perfluoropolyether adhesive composition has a volume resistivity of 1×10 9 Non-conductive adhesive with Ω·cm or more. 15 . An adhesive comprising a cured product of the curable perfluoropolyether adhesive composition according to claim 1 . 16 . An adhesive tape comprising a substrate and a cured layer of the curable perfluoropolyether adhesive composition according to claim 1 laminated thereon.

17. The adhesive tape according to claim 16, wherein: The substrate is a resin film.

18. The adhesive tape according to claim 16, wherein The substrate is a polyethylene terephthalate film.

Images