Laminated structure

Abstract

To provide a curable perfluoropolyether adhesive composition which gives a rubber-like or gel-like cured product adhering to a substrate.SOLUTION: The curable perfluoropolyether adhesive composition contains: (A) 100 pts.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; (B) an organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule; (C) a hydrosilylation reaction catalyst; and (D) 0.05-5 pts.mass of an organosilicon compound other than the component (B), which has two or more selected from a hydrogen atom bonded to a silicon atom, an epoxy group bonded to a silicon atom via a carbon atom or both a carbon atom and an oxygen atom, and a trialkoxysilyl group bonded to a silicon atom via a carbon atom or both a carbon atom and an oxygen atom in one molecule.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable perfluoropolyether pressure-sensitive adhesive composition (hereinafter referred to as "perfluoropolyether pressure-sensitive adhesive composition") that forms a pressure-sensitive adhesive (cured perfluoropolyether rubber or cured perfluoropolyether gel) that has excellent heat resistance, oil resistance, chemical resistance, solvent resistance, low-temperature properties, moisture resistance, low gas permeability, etc., and that has particularly good adhesion to resins and metal substrates, and to a pressure-sensitive adhesive using the cured product thereof. [Background technology]

[0002] It has been proposed that a cured product having excellent and well-balanced properties such as heat resistance, chemical resistance, solvent resistance, water repellency, oil repellency, and weather resistance can be obtained from a composition comprising a linear perfluoropolyether compound having at least two alkenyl groups in one molecule and a perfluoropolyether structure in the main chain, an organosilicon compound having two or more H-SiOSiO structures in one molecule, and a hydrosilylation reaction catalyst (Patent Document 1, Patent Document 2).

[0003] Meanwhile, adhesives are used in a variety of applications, primarily in labels and adhesive tapes attached to products. Recently, advances in electronic device-related technology have led to a wide range of applications, including adhesive films for display protection and protective films used during the manufacturing process. Furthermore, in addition to surface protection, adhesives are also used in optical components, taking advantage of the transparency of the material, and are being used in applications within products, such as Optical Clear Adhesive Tape (OCA tape).

[0004] The main classifications of adhesives are acrylic, rubber, and silicone, each with its own advantages and disadvantages. Silicone adhesives are less costly than acrylic or rubber adhesives, but are superior to the other two types in terms of heat resistance, cold resistance, weather resistance, chemical resistance, and electrical insulation.

[0005] Recently, mobile phones and other devices have become widely used, and most of the adhesive films used to protect their displays use silicone adhesives. Silicone has good wettability to adherends, so it does not trap air bubbles when applied, and it does not shift or peel off on its own. It also has good reworkability, so it can be reapplied (Patent Document 3). The same is true for protective films used during product manufacturing processes, which also require heat resistance, so adhesive films using silicone adhesives are used in large quantities.

[0006] Furthermore, among mobile phones, smartphones, which have more advanced functions than conventional devices, are rapidly becoming popular, and many of them can be operated by touching a display called a touch panel instead of the traditional buttons. A similar device is a tablet device, which is a portable computer equipped with a touch panel. As these devices become more popular, the display area is becoming larger, and the demand for adhesive film for screen protection is on the rise.

[0007] However, although such silicone pressure-sensitive adhesives have sufficient performance for most applications, there has been a strong demand for pressure-sensitive adhesive compositions with excellent chemical and solvent resistance, such as for applications requiring even greater chemical and solvent resistance, such as those used around automobile engines and barcode labels used in clinical and pathological testing processes.

[0008] Among these, a curable perfluoropolyether pressure-sensitive adhesive composition has been proposed (Patent Document 4). This composition has been shown to have excellent heat resistance, weather resistance, water repellency, oil repellency, etc., and to give a cured product with excellent chemical resistance and solvent resistance. However, in order to apply and adhere the pressure-sensitive adhesive to rigid substrates such as resins and metals, rather than to tapes, a primer must be applied, and there has been a demand for simplification of the primer application process. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Patent No. 2990646 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-248166 [Patent Document 3] Japanese Patent Application Publication No. 07-197008 [Patent Document 4] Japanese Patent Application Publication No. 2019-38904 Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention has been made in view of the above circumstances, and aims to provide a curable perfluoropolyether pressure-sensitive adhesive composition and a cured product thereof which give a cured product that has excellent heat resistance, weather resistance, water repellency, oil repellency, and other properties, as well as excellent chemical resistance and solvent resistance, and which is characterized by not peeling off from resin or metal substrates and adhering tightly to them, particularly during heating steps. [Means for solving the problem]

[0011] In order to solve the above problems, the present invention provides a curable perfluoropolyether pressure-sensitive adhesive composition comprising the following components (A) to (D): (A) A compound having at least two alkenyl groups in one molecule and having -C in the main chain a F 2a 100 parts by mass of a linear perfluoropolyether compound having a perfluoropolyether structure containing a repeating unit represented by O- (a is an integer of 1 to 6) (B) An organosilicon compound having at least two hydrogen atoms bonded to a silicon atom in one molecule: a curing effective amount (C) Hydrosilylation reaction catalyst: catalytic amount (D) 0.05 to 5 parts by mass of an organosilicon compound other than component (B), which has per molecule two or more selected from a hydrogen atom bonded to a silicon atom, 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, The present invention provides a curable perfluoropolyether pressure-sensitive adhesive composition comprising:

[0012] The curable perfluoropolyether pressure-sensitive adhesive composition of the present invention containing components (A) to (D) is a curable perfluoropolyether pressure-sensitive adhesive composition that not only has excellent heat resistance, weather resistance, oil resistance, low-temperature properties, moisture resistance, low gas permeability, water repellency, oil repellency, etc., but also has excellent chemical resistance and solvent resistance, and provides a cured product (adhesive) that has good adhesion to substrates, such as resins and metal substrates. Furthermore, the curable perfluoropolyether pressure-sensitive adhesive composition of the present invention containing components (A) to (D) as described above can provide a rubbery cured product (perfluoropolyether rubber cured product).

[0013] The present invention also provides a curable perfluoropolyether pressure-sensitive adhesive composition, comprising the following components (A) to (E): (A) A compound having at least two alkenyl groups in one molecule and having -C in the main chain a F 2a Linear perfluoropolyether compound having a perfluoropolyether structure containing an O- repeating unit (a is an integer of 1 to 6): 40 to 80 parts by mass (E) Polyfluoromonoalkenyl compound having one alkenyl group per molecule and a perfluoropolyether structure in the main chain: 20 to 60 parts by mass (where the total amount of components (A) and (E) is 100 parts by mass). (B) An organosilicon compound having at least two hydrogen atoms bonded to a silicon atom in one molecule: a curing effective amount (C) Hydrosilylation reaction catalyst: catalytic amount (D) 0.05 to 5 parts by mass of an organosilicon compound other than component (B), which has per molecule two or more selected from a hydrogen atom bonded to a silicon atom, 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, The present invention also provides a curable perfluoropolyether pressure-sensitive adhesive composition comprising:

[0014] The curable perfluoropolyether pressure-sensitive adhesive composition of the present invention containing components (A) to (E) is a curable perfluoropolyether pressure-sensitive adhesive composition that not only has excellent heat resistance, weather resistance, oil resistance, low-temperature properties, moisture resistance, low gas permeability, water repellency, oil repellency, etc., but also has particularly excellent chemical resistance and solvent resistance, and provides a cured product (pressure-sensitive adhesive) that has good adhesion to substrates, such as resins and metal substrates. Furthermore, the curable perfluoropolyether pressure-sensitive adhesive composition of the present invention containing components (A) to (E) as described above can provide a cured gel product (cured perfluoropolyether gel product).

[0015] The component (E) is represented by the following general formula (2): Rf 1 -(X') p -CH=CH2(2) [wherein X' is -CH2-, -OCH2-, -CH2OCH2-, or -CO-NR2-Y'- (wherein Y' is -CH2- or a group represented by the following structural formula (Z'), [ka] (Dimethylphenylsilylene group shown in the ortho, meta, or para position) R 2 is a hydrogen atom, a methyl group, a phenyl group, or an allyl group.) and p is 0 or 1. Rf 1 has the general formula F-[CF(CF3)CF2O] w It is a perfluoropolyether structure represented by -CF(CF3)- (wherein w is an integer of 1 to 500).) is preferred.

[0016] A composition containing such component (E) is a curable perfluoropolyether pressure-sensitive adhesive composition that gives a cured product (pressure-sensitive adhesive) with better chemical resistance and solvent resistance.

[0017] The composition is preferably a curable perfluoropolyether adhesive composition that cures to form an adhesive having an adhesive strength of 0.001 N / 25 mm to 10.0 N / 25 mm.

[0018] A composition having such adhesive strength will be a curable perfluoropolyether adhesive composition having good adhesive strength to an adherend.

[0019] The component (A) is a compound represented by the following general formula (1): [ka] wherein X is —CH—, —CHO—, —CHOCH—, or —Y—NR 1 -CO- (wherein Y is -CH2- or a group represented by the following structural formula (Z) and R 1 is a hydrogen atom, a methyl group, a phenyl group, or an allyl group. X' is -CH2-, -OCH2-, -CH2OCH2-, or -CO-NR 2 -Y'- (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. p is independently 0 or 1, r is an integer of 2 to 6, m and n are each an integer of 0 to 600, and the sum of m and n is 50 to 600. [ka] (Dimethylphenylsilylene group shown in the ortho, meta, or para position) [ka] (dimethylphenylsilylene group shown in the ortho, meta, or para position)] It is preferable that the compound is a linear perfluoropolyether compound represented by the following formula:

[0020] A composition containing such component (A) can provide a cured product (adhesive) that has superior chemical resistance and solvent resistance, and also provides a curable perfluoropolyether adhesive composition with high adhesive strength.

[0021] In addition, the cured product of the curable perfluoropolyether pressure-sensitive adhesive composition has a volume resistivity of 1×10 9 It is preferable to use a non-conductive adhesive with a resistance of Ω·cm or more.

[0022] The curable perfluoropolyether pressure-sensitive adhesive composition of the present invention can be suitably used as a material for such non-conductive pressure-sensitive adhesives.

[0023] The present invention also provides a pressure-sensitive adhesive comprising a cured product of the curable perfluoropolyether pressure-sensitive adhesive composition.

[0024] Thus, the curable perfluoropolyether pressure-sensitive adhesive composition of the present invention can be used as a pressure-sensitive adhesive that provides a cured perfluoropolyether rubber or perfluoropolyether gel that has excellent adhesion to various substrates. [Effects of the Invention]

[0025] As described above, the perfluoropolyether pressure-sensitive adhesive composition of the present invention can provide a rubbery or gel-like cured product (pressure-sensitive adhesive) that has excellent heat resistance, weather resistance, oil resistance, low-temperature characteristics, moisture resistance, low gas permeability, water repellency, oil repellency, etc., and is particularly excellent in chemical resistance and solvent resistance, as well as good adhesive strength with resins and metal substrates. DETAILED DESCRIPTION OF THE INVENTION

[0026] As described above, there has been a need for the development of a curable perfluoropolyether pressure-sensitive adhesive composition that provides a cured pressure-sensitive adhesive (adhesive) that has excellent heat resistance, weather resistance, water repellency, oil repellency, etc., in particular excellent chemical resistance and solvent resistance, and further has good adhesion to resins and metal substrates, and a pressure-sensitive adhesive containing the cured pressure-sensitive adhesive composition.

[0027] As a result of extensive research to achieve the above object, the inventors of the present invention have found that the specific perfluoropolyether pressure-sensitive adhesive composition of the present invention can provide a pressure-sensitive adhesive composition that gives a rubber-like or gel-like cured product (perfluoropolyether rubber cured product or perfluoropolyether gel cured product) that has superior chemical resistance and solvent resistance compared to conventional silicone pressure-sensitive adhesives, and have thus completed the present invention.

[0028] That is, a first aspect of the present invention is a curable perfluoropolyether pressure-sensitive adhesive composition that gives a rubber-like cured product (cured perfluoropolyether rubber product), comprising the following components (A) to (D): (A) A compound having at least two alkenyl groups in one molecule and having -C in the main chain a F 2a 100 parts by mass of a linear perfluoropolyether compound having a perfluoropolyether structure containing a repeating unit represented by O- (a is an integer of 1 to 6) (B) An organosilicon compound having at least two hydrogen atoms bonded to a silicon atom in one molecule: a curing effective amount (C) Hydrosilylation reaction catalyst: catalytic amount (D) 0.05 to 5 parts by mass of an organosilicon compound other than component (B), which has per molecule two or more selected from a hydrogen atom bonded to a silicon atom, 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, The curable perfluoropolyether pressure-sensitive adhesive composition comprises:

[0029] The first embodiment of the present invention will be described in detail below, but the present invention is not limited thereto.

[0030] [Component (A)] Component (A) contained in the curable perfluoropolyether pressure-sensitive adhesive composition of the present invention acts as the main component (base polymer) of the curable perfluoropolyether pressure-sensitive 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) in the main chain, preferably a divalent perfluorooxyalkylene structure.

[0031] Here, the perfluorooxyalkylene structure is -C a F 2a It contains a large number of repeating oxyalkylene units represented by the formula: O- (wherein a in each unit is independently an integer of 1 to 6), and examples thereof include those represented by the following general formula (5). (C a F 2a O) q (5) (In the formula, q is an integer of 50 to 600, preferably an integer of 50 to 400, and more preferably an integer of 50 to 200.)

[0032] Each repeating unit -C constituting the perfluorooxyalkylene structure represented by the above formula (5) a F 2a Examples of O- (that is, oxyalkylene unit) include the following structures: The perfluoroalkyl ether structure may be composed of one type of these repeating structures alone, or may be a combination of two or more types.

[0033] -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O- -CF2CF2CF2CF2O- -CF2CF2CF2CF2CF2CF2O- -C(CF3)2O-

[0034] Among these, the following structure is particularly preferred: -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O-

[0035] In the present invention, the term "linear" refers to the individual repeating units -C constituting the perfluoropolyether structure (perfluorooxyalkylene structure) of the main chain. a F 2a This means that O- (oxyalkylene units) are bonded together in a linear chain, and each repeating unit (oxyalkylene unit) itself may be a linear oxyalkylene unit or a branched oxyalkylene unit (for example, -CF(CF3)CF2O-, -C(CF3)2O-, etc.).

[0036] The alkenyl group in the linear perfluoropolyether compound of component (A) preferably has 2 to 8 carbon atoms, particularly 2 to 6 carbon atoms, and has a CH2=CH- structure at its terminal, such as a vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, or hexenyl group, and is particularly preferably a vinyl group or allyl group. The alkenyl group may be directly bonded to both ends of the perfluoropolyether structure, particularly a divalent perfluorooxyalkylene structure, that constitutes the main chain of the linear perfluoropolyether compound, or may be bonded to a divalent linking group, such as -CH2-, -CHO-, -CHOCH2-, or -Y-NR-CO- (wherein Y is -CH2- or a group represented by the following structural formula (Z) [ka] (Dimethylphenylsilylene group shown in the ortho, meta, or para position) and R is a hydrogen atom, a methyl group, a phenyl group, or an allyl group.] In addition, component (A) has at least two alkenyl groups per molecule.

[0037] Examples of the component (A) include polyfluorodialkenyl compounds represented by the following general formula (6) or (7). CH2=CH-(X) p -Rf 2 -(X') p -CH=CH2(6) CH2=CH-(X) p -Q-Rf 2 -Q-(X') p -CH=CH2(7) wherein X is independently —CH—, —CHO—, —CHOCH—, or —Y—NR 1 -CO- (wherein Y is -CH2- or a group represented by the following structural formula (Z) and R 1 is a hydrogen atom, a methyl group, a phenyl group, or an allyl group; and X' is -CH2-, -OCH2-, -CH2OCH2-, or -CO-NR 2 -Y'- (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.

[0038] [ka] (Dimethylphenylsilylene group shown in the ortho, meta, or para position)

[0039] [ka] (Dimethylsilylphenylene group shown in the ortho, meta, or para position)

[0040] Rf 2 is a divalent perfluoropolyether structure (perfluorooxyalkylene structure), and is represented by the above formula (5), that is, (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.]

[0041] As such a linear perfluoropolyether compound of component (A), one represented by the following general formula (1) is particularly suitable. [ka] [In the formula, X, X', and p are the same as above, r is an integer of 2 to 6, m and n are each an integer of 0 to 600, and the sum of m and n is 50 to 600.]

[0042] The linear perfluoropolyether compound of the general formula (1) preferably has a polyethylene-equivalent weight-average molecular weight of 3,000 to 100,000, particularly 4,000 to 50,000, as measured by gel permeation chromatography (GPC) analysis using a fluorinated solvent as the developing solvent to determine molecular weight distribution. A weight-average molecular weight of 4,000 or more results in reduced swelling in gasoline and various solvents. In particular, swelling in gasoline is 6% or less, satisfying the properties required for components requiring gasoline resistance. Furthermore, a weight-average molecular weight of 100,000 or less provides practical application because the viscosity is not too high and workability is excellent. The degree of polymerization (m+n) of the linear perfluoropolyether compound of the general formula (1) can also be determined as a polyethylene-equivalent number-average polymerization degree or weight-average polymerization degree, as measured by gel permeation chromatography (GPC) analysis using a fluorinated solvent as the developing solvent to determine molecular weight distribution. These number-average polymerization degrees and number-average molecular weights are 19 It can also be calculated from the ratio of the terminal structure to the repeating unit structure obtained from the F-NMR spectrum.

[0043] Specific examples of the linear perfluoropolyether compound represented by general formula (1) include those represented by the following formulas.

[0044] [ka]

[0045] [ka]

[0046] [ka] (In the formula, m and n each represent an integer of 0 to 600, preferably an integer of 0 to 200, and an integer that satisfies m+n=50 to 600, preferably m+n=50 to 200.)

[0047] 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 depending on the purpose, it is also possible to use the chain-extended product as component (A) by subjecting the linear perfluoropolyether compound described above to a hydrosilylation reaction with an organosilicon compound containing two SiH groups in the molecule in a conventional manner and under conventional conditions. The linear perfluoropolyether compound of component (A) may be used alone or in combination of two or more.

[0048] [(B) Component] Component (B) acts as a crosslinking agent and / or chain extender for component (A). Component (B) is an organosilicon compound such as an organohydrogenpolysiloxane having at least two, and preferably three or more, silicon-bonded hydrogen atoms (hydrosilyl groups represented by SiH) per molecule. Examples of component (B) include, but are not limited to, the known organosilicon compounds described in Patent Documents 1, 2, and 4.

[0049] The organosilicon compound of component (B) is clearly distinguishable from the organosilicon compound of component (D), which will be described later, in that it does not contain functional groups such as epoxy groups and trialkoxysilyl groups in the molecule.

[0050] From the viewpoints of compatibility with component (A) or, in the second embodiment of the present invention described below, component (A) and component (E) described below, dispersibility, uniformity of the cured rubber or gel (adhesive), etc., the organosilicon compound of component (B) can preferably be a fluorine-containing organohydrogenpolysiloxane having one or more monovalent perfluoroalkyl groups, monovalent perfluorooxyalkyl groups, divalent perfluoroalkylene groups, and / or divalent perfluorooxyalkylene groups per molecule.

[0051] Examples of the monovalent or divalent fluorine-containing organic group include perfluoroalkyl groups, perfluorooxyalkyl groups, perfluoroalkylene groups and perfluorooxyalkylene groups represented by the following formulae. C g F 2g+1 - -C g F 2g - (In the formula, g is an integer of 1 to 20, preferably an integer of 2 to 10.)

[0052] [ka] (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.)

[0053] [ka] (In the formula, i and j are each an integer of 1 or more, preferably an integer of 1 to 100, and the average of i+j is 2 to 200, preferably 2 to 100.)

[0054] -(CF2O) d -(CF2CF2O) e -CF2- (In the formula, d and e are each an integer of 1 to 50, preferably an integer of 1 to 40.)

[0055] Furthermore, it is preferable that these perfluoroalkyl groups, perfluorooxyalkyl groups, perfluoroalkylene groups, or perfluorooxyalkylene groups are linked to the silicon atom by a divalent linking group, and the divalent linking group may be an alkylene group, an arylene group, or a combination thereof, or one in which an ether-bonded oxygen atom, an amide bond, a carbonyl bond, an ester bond, a diorganosilylene group, or the like is interposed in these groups, and examples thereof include, but are not limited to, the following divalent linking groups having 2 to 12 carbon atoms: -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2OCH2-, -CH2CH2CH2-NH-CO-, -CH2CH2CH2-N(Ph)-CO-, -CH2CH2CH2-N(CH3)-CO-, -CH2CH2CH2-N(CH2CH3)-CO-, -CH2CH2-Si(CH3)2-Ph'-N(CH3)-CO-, -CH2CH2CH2-Si(CH3)2-Ph'-N(CH3)-CO-, -CH2CH2CH2-O-CO- (In the formula, Ph is a phenyl group, and Ph' is a phenylene group.)

[0056] Furthermore, in the fluorine-containing organohydrogenpolysiloxane of component (B), examples of the monovalent or divalent fluorine-containing organic group and the monovalent substituent bonded to the silicon atom other than a hydrogen atom bonded to the silicon atom include 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, in which some or all of the hydrogen atoms of these groups have been substituted with chlorine atoms, cyano groups, or the like, such as chloromethyl, chloropropyl, and cyanoethyl.

[0057] The fluorine-containing organohydrogenpolysiloxane of component (B) may be cyclic, linear, branched, three-dimensional network, or a combination thereof. The number of silicon atoms in this fluorine-containing organohydrogenpolysiloxane is not particularly limited, but is usually about 2 to 60, preferably about 3 to 30. Particularly preferred fluorine-containing organohydrogenpolysiloxane of component (B) is a cyclic fluorine-containing organohydrogenpolysiloxane containing a monovalent perfluoroalkyl group or a monovalent perfluorooxyalkyl group, or a fluorine-containing organohydrogenpolysiloxane having a branched or cyclic organohydrogenpolysiloxane structure at both ends of a divalent perfluoroalkylene group or a divalent perfluorooxyalkylene group.

[0058] Examples of component (B) having such a monovalent or divalent fluorine-containing organic group and a silicon-bonded hydrogen atom include the following compounds. These compounds may be used alone or in combination of two or more. In the following formulae, Me represents a methyl group, and Ph represents a phenyl group.

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064]

change

[0065]

change

[0066]

change

[0067]

change

[0068]

change

[0069]

change

[0070]

change

[0071]

change

[0072] The amount of component (B) is an effective amount for curing component (A) and component (E), described below, i.e., a curing-effective amount. In particular, the amount is such that the hydrosilyl groups (Si-H) in component (B) are preferably 0.2 to 4 moles, more preferably 0.5 to 3 moles, per mole of alkenyl groups in component (A) in the present composition, or, in the second embodiment of the present invention described below, per mole of the total alkenyl groups in components (A) and (E). An amount of 0.2 moles or more of hydrosilyl groups (Si-H) ensures a sufficient degree of crosslinking, and there is no risk of a cured product not being obtained. Furthermore, an amount of 4 moles or less of hydrosilyl groups (Si-H) ensures there is no risk of foaming during curing.

[0073] The component (B) can be used alone or in combination of two or more.

[0074] [(C) component] The hydrosilylation catalyst (addition reaction catalyst) of component (C) of the present invention is a catalyst that promotes the addition reaction of the alkenyl groups in component (A) or, in the second embodiment of the present invention described below, the alkenyl groups in component (A) and component (E) described below with the hydrosilyl groups in component (B). This hydrosilylation catalyst is generally a compound of a noble metal (platinum group metal) and is expensive, so relatively readily available platinum or platinum compounds are often used.

[0075] Examples of platinum compounds include chloroplatinic acid or complexes of chloroplatinic acid with olefins such as ethylene, complexes with alcohols or vinylsiloxanes, and metallic platinum supported on silica, alumina, carbon, etc. As platinum group metal catalysts other than platinum compounds, rhodium, ruthenium, iridium, and palladium compounds are also known, such as RhCl(PPh3)3, RhCl(CO)(PPh3)2, and Ru3(CO). 12 , IrCl(CO)(PPh3)2, Pd(PPh3)4, etc. can be mentioned as examples.

[0076] The hydrosilylation catalyst may be used in a catalytic amount, but is generally used in an amount of 0.1 to 500 ppm (calculated as the mass of platinum group metal) based on the total mass of components (A), (B), and (E), and more preferably in an amount of 0.1 to 100 ppm.The hydrosilylation catalyst of component (C) may be used singly or in combination of two or more different types.

[0077] [(D) component] The organosilicon compounds (D), such as organosilanes and organopolysiloxanes, having adhesive functional groups act as aids (adhesion aids or adhesion improvers) for improving substrate adhesion. These organosilicon compounds are organosilicon compounds (organo(hydrogen)silanes, organo(hydrogen)polysiloxanes) that contain at least two or more adhesive functional groups in one molecule selected from the group consisting of hydrogen atoms bonded to silicon atoms (SiH groups), epoxy groups bonded to silicon atoms via carbon atoms or carbon atoms and oxygen atoms, and trialkoxysilyl groups bonded to silicon atoms via carbon atoms or carbon atoms and oxygen atoms. Preferably, the organopolysiloxanes further contain one or more monovalent perfluoroalkyl groups or monovalent perfluorooxyalkyl groups bonded to silicon atoms via a divalent linking group containing a silicon atom, a carbon atom, or a carbon atom and an oxygen atom (i.e., fluorine-containing organo(hydrogen)polysiloxanes containing adhesive functional groups). From the viewpoint of improving substrate adhesion, the organosilicon compound of component (D) is preferably a (fluorine-containing) organohydrogenpolysiloxane that essentially contains, among the two or more adhesive functional groups described above, a hydrogen atom bonded to a silicon atom (SiH group) 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 essentially contains a hydrogen atom bonded to a silicon atom (SiH group) 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; or a (fluorine-containing) organohydrogenpolysiloxane that essentially contains a hydrogen atom bonded to a silicon atom (SiH group) 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. Component (D) differs from component (B) in that it contains an epoxy group and / or a trialkoxysilyl group in the molecule.

[0078] The siloxane skeleton of such organopolysiloxane may be cyclic, linear, branched, or a mixture of these.

[0079] Specific examples of component (D) that can be used include adhesive functional group-containing hydrolyzable organosilane compounds (so-called epoxy group-containing silane coupling agents) that have epoxy groups and trialkoxysilyl groups in the molecule, such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(2,3-epoxycyclohexyl)ethyltrimethoxysilane, and β-(2,3-epoxycyclohexyl)ethyltriethoxysilane, as well as organopolysiloxanes represented by the following formula:

[0080] [ka] (In the formula, R 1 ' are independently unsubstituted or halogen-substituted monovalent hydrocarbon groups, and A and B are as shown below. w is an integer of 0≦w≦100, x is an integer of 1≦x≦100, y is an integer of 1≦y≦100, and z is an integer of 0≦z≦100.

[0081] R 1 The halogen-substituted or unsubstituted monovalent hydrocarbon group represented by ' preferably has 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, and octyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and phenylethyl; and substituted monovalent hydrocarbon groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as fluorine, and of these, methyl is particularly preferred.

[0082] w is preferably an integer of 0≦w≦20, x is preferably an integer of 1≦x≦20, y is preferably an integer of 1≦y≦20, z is preferably an integer of 1≦z≦20, and 3≦w+x+y+z≦50 is preferred.

[0083] A represents an epoxy group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom and / or a trialkoxysilyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom, and specific examples include the following groups:

[0084] [ka] [In the formula, R 2 ' represents a divalent hydrocarbon group (such as an alkylene group or cycloalkylene group) having 1 to 10 carbon atoms, particularly 1 to 5 carbon atoms, optionally containing an oxygen atom.

[0085] -R 3 -Si(OR 4 )3 [In the formula, R 3 represents a divalent hydrocarbon group (such as an alkylene group) having 1 to 10 carbon atoms, especially 1 to 4 carbon atoms, and R 4represents a monovalent hydrocarbon group (such as an alkyl group) having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms.

[0086] [ka] [In the formula, R 5 represents a monovalent hydrocarbon group (such as an alkyl group) having 1 to 8 carbon atoms, especially 1 to 4 carbon atoms, and R 6 represents a hydrogen atom or a methyl group, and k represents an integer of 2 to 10.

[0087] B represents a monovalent perfluoroalkyl or perfluorooxyalkyl group bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom. Examples of the monovalent perfluoroalkyl or perfluorooxyalkyl group include those represented by the following general formula:

[0088] C g’ F 2g’+1 - (In the formula, g' is an integer of 1 to 20, preferably an integer of 2 to 10.) F-[CF(CF3)CF2O] f’ -C h’ F 2h’ - (In the formula, f' is an integer of 2 to 200, preferably an integer of 2 to 100, and h' is an integer of 1 to 3.)

[0089] The divalent linking group containing a carbon atom or a carbon atom and an oxygen atom may be an alkylene group, an arylene group, or a combination thereof, or these groups may be linked via an ether bond oxygen atom, an amide bond, a carbonyl bond, or the like, and examples thereof include: -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2OCH2-, -CH2CH2CH2-NH-CO-, -CH2CH2CH2-N(CH3)-CO-, -CH2CH2CH2-N(Ph)-CO- (wherein Ph is a phenyl group.) Examples of divalent linking groups having 2 to 12 carbon atoms include the following.

[0090] These organopolysiloxanes can be obtained by subjecting an organohydrogenpolysiloxane having three or more silicon-bonded hydrogen atoms (Si-H groups) per molecule to a partial addition reaction, according to a conventional method, with a compound containing an aliphatic unsaturated group such as a vinyl group or an allyl group, an epoxy group and / or a trialkoxysilyl group, and optionally a compound containing an aliphatic unsaturated group and a perfluoroalkyl group or a perfluorooxyalkyl group. Note that the number of the aliphatic unsaturated groups must be less than the number of Si-H groups.

[0091] In producing this organopolysiloxane, the target substance may be isolated after the reaction is complete, but it is also possible to use the mixture from which the unreacted materials and addition reaction catalyst have simply been removed.

[0092] Specific examples of organopolysiloxanes of component (D) include those represented by the following structural formula: In the following formula, Me is a methyl group, and Ph is a phenyl group.

[0093] [ka]

[0094] [ka]

[0095] [ka] (o, q, r are positive integers, and p is an integer greater than or equal to 0.)

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [ka] (o, q, r are positive integers, and p is an integer greater than or equal to 0.)

[0100] [ka]

[0101] [ka]

[0102] The component (D) may be used alone or in combination of two or more types.

[0103] The amount of component (D) used is 0.05 to 5.0 parts by mass, preferably 0.1 to 3.0 parts by mass, and more preferably 0.2 to 1.0 parts by mass, per 100 parts by mass of component (A), or per 100 parts by mass of the combined total of component (A) and component (E) in the second embodiment of the present invention described below. If the amount is less than 0.05 parts by mass, the effect of adding it will not be obtained, while if it exceeds 5.0 parts by mass, the fluidity of the composition will be poor and curability may be impaired.

[0104] [Other ingredients] In addition to the above components (A) to (D), various additives may be optionally added to the composition. Examples of inhibitors for the hydrosilylation reaction catalyst include acetylene alcohols such as 1-ethynyl-1-hydroxycyclohexane, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-ol, and phenylbutynol, as well as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne, polymethylvinylsiloxane cyclic compounds, and organic phosphorus compounds. The addition of these inhibitors allows the curing reactivity and storage stability to be maintained at an appropriate level.

[0105] A second aspect of the present invention is a curable perfluoropolyether pressure-sensitive adhesive composition that gives a gel-like cured product (cured perfluoropolyether gel product), comprising the following components (A) to (E): (A) A compound having at least two alkenyl groups in one molecule and having -C in the main chain a F 2a Linear perfluoropolyether compound having a perfluoropolyether structure containing an O- repeating unit (a is an integer of 1 to 6): 40 to 80 parts by mass (E) Polyfluoromonoalkenyl compound having one alkenyl group per molecule and a perfluoropolyether structure in the main chain: 20 to 60 parts by mass (where the total amount of components (A) and (E) is 100 parts by mass). (B) An organosilicon compound having at least two hydrogen atoms bonded to a silicon atom in one molecule: a curing effective amount (C) Hydrosilylation reaction catalyst: catalytic amount (D) 0.05 to 5 parts by mass of an organosilicon compound other than component (B), which has per molecule two or more selected from a hydrogen atom bonded to a silicon atom, 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, The present invention provides a curable perfluoropolyether pressure-sensitive adhesive composition comprising:

[0106] In this case, the components (A) to (D) that can be used are the same as those explained above.

[0107] [(E) component] Component (E) is a component used in a specific second embodiment (i.e., a composition that produces a cured gel product) of the curable perfluoropolyether pressure-sensitive adhesive composition of the present invention, as opposed to the first embodiment (i.e., a composition that produces a cured rubber product) of the present invention described above, and is a polyfluoromonoalkenyl compound having one alkenyl group per molecule and a perfluoropolyether structure in the main chain. In particular, polyfluoromonoalkenyl compounds of the following formula (2) are preferred: Rf 1 -(X') p -CH=CH2(2) [wherein X′ and p are the same as above, and Rf 1 is represented by the following general formula: F-[CF(CF3)CF2O] w -CF(CF3)- (wherein w represents an integer of 1 to 500, preferably an integer of 2 to 200).

[0108] Specific examples of the polyfluoromonoalkenyl compound represented by the above general formula (2) include the following.

[0109] [ka]

[0110] [ka] (In the above formula, m is an integer of 1 to 200, particularly an integer of 2 to 100.)

[0111] When the polyfluoromonoalkenyl compound of formula (2) is blended, the blending amount is selected so that in the curable perfluoropolyether pressure-sensitive adhesive composition, the linear perfluoropolyether dialkenyl compound of component (A) and this component (E) are in the proportions of 40 to 80 parts by mass of component (A) and 20 to 60 parts by mass of component (E), with the total amount of component (A) and component (E) being 100 parts by mass.

[0112] [Other ingredients] In addition to the components (A) to (E), various additives may be optionally added to the composition, as in the first embodiment. Examples of inhibitors for the hydrosilylation reaction catalyst include those described above.

[0113] [Cured product] The perfluoropolyether pressure-sensitive adhesive composition of the present invention is obtained by curing the above-described composition to form a pressure-sensitive adhesive comprising a cured product of perfluoropolyether rubber or gel having a surface adhesion of, for example, 0.001 to 10.0 N / 25 mm, preferably 0.002 to 8.0 N / 25 mm, and more preferably 0.003 to 6.0 N / 25 mm. This pressure-sensitive adhesive composition is excellent in heat resistance, water repellency, oil repellency, weather resistance, chemical resistance, solvent resistance, etc., and can form a cured product (pressure-sensitive adhesive) that has good adhesion to resins and metal substrates, and can be used for a variety of applications.

[0114] For example, in a first embodiment of the present invention, the perfluoropolyether pressure-sensitive adhesive composition can be formed by curing 100 parts by mass of component (A), component (B) in an amount such that the hydrosilyl groups of component (B) are 0.2 to 3.0 moles per mole of the total number of alkenyl groups in component (A) is 1, component (D) in an amount such that the hydrosilyl groups of component (B) are 0.05 to 5.0 parts by mass per 100 parts by mass of component (A), and component (C) in an amount of 0.1 to 100 ppm, calculated as platinum, relative to the total amount of components (A), (B), and (D).

[0115] Furthermore, for example, in a second embodiment of the present invention, the perfluoropolyether pressure-sensitive adhesive composition can be formed by curing 40 to 80 parts by mass of the (A) component, 20 to 60 parts by mass of the (E) component, so that the total of the (A) and (E) components is 100 parts by mass, the (B) component is present in an amount such that the hydrosilyl groups of the (B) component are 0.2 to 3.0 moles per 1 mole of the total alkenyl groups in the (A) and (E) components, the (D) component is present in an amount such that the (A) and (E) components have 0.05 to 5.0 parts by mass per 100 parts by mass of the (A) and (E) components, and the (C) component is present in an amount of 0.1 to 100 ppm, calculated as platinum, relative to the total amount of the (A), (B), (D), and (E) components.

[0116] The above-mentioned perfluoropolyether pressure-sensitive adhesive compositions are formed by coating each composition of the present invention onto a suitable substrate and then curing it, or by laminating them together, using a conventionally known method. Curing can usually be easily carried out by heat treatment at a temperature of 60 to 150°C for about 1 to 30 minutes.

[0117] The pressure-sensitive adhesive using the perfluoropolyether pressure-sensitive adhesive composition of the present invention can be used as a component for automobiles, chemical plants, semiconductor production lines, analytical and physical / chemical equipment, medical equipment, aircraft, optics, etc.

[0118] The substrate used in the present invention is not particularly limited, but examples thereof include metals such as iron, aluminum, and stainless steel, glass, ceramics, and synthetic resins such as PPS, PBT, PET, and nylon.

[0119] In order to enhance the effect of surface modification, the surface of the substrate may be subjected to a degreasing treatment using an organic solvent or a pre-baking treatment before the plasma irradiation.

[0120] Furthermore, the cured product of the curable perfluoropolyether pressure-sensitive adhesive composition of the present invention (cured perfluoropolyether rubber or cured perfluoropolyether gel) has a volume resistivity of 1×10 9Preferably, the pressure-sensitive adhesive has a non-conductive resistance of Ω·cm or more. Such a curable perfluoropolyether pressure-sensitive adhesive composition of the present invention is suitable as a material for a non-conductive pressure-sensitive adhesive. The upper limit of the volume resistivity of the cured product of the curable perfluoropolyether pressure-sensitive adhesive composition of the present invention is not particularly limited, but may be, for example, 1×10 13 It can be expressed as Ω·cm.

[0121] Such a perfluoropolyether pressure-sensitive adhesive composition of the present invention can give an excellent cured product (pressure-sensitive adhesive) that has excellent heat resistance, weather resistance, oil resistance, chemical resistance, solvent resistance (solvent resistance), low-temperature characteristics, moisture resistance, low gas permeability, water repellency, oil repellency, etc., and particularly has good adhesion to resins and metal substrates.

[0122] A third aspect of the present invention is a pressure-sensitive adhesive comprising the cured product (cured perfluoropolyether rubber or cured perfluoropolyether gel) of the curable perfluoropolyether pressure-sensitive adhesive composition of the present invention as explained above.

[0123] As explained above, the perfluoropolyether pressure-sensitive adhesive composition of the present invention can give an excellent cured product (pressure-sensitive adhesive) that is excellent in heat resistance, weather resistance, oil resistance, chemical resistance, solvent resistance (solvent resistance), low-temperature properties, moisture resistance, low gas permeability, water repellency, oil repellency, etc., and particularly has good adhesion to resins and metal substrates. Therefore, the pressure-sensitive adhesive of the present invention is excellent in heat resistance, weather resistance, oil resistance, chemical resistance, solvent resistance (solvent resistance), low-temperature properties, moisture resistance, low gas permeability, water repellency, oil repellency, etc., and particularly has good adhesion to resins and metal substrates. [Example]

[0124] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, % indicates % by mass.

[0125] [Examples 1 to 5, Comparative Examples 1 to 4] The curable perfluoropolyether pressure-sensitive adhesive compositions shown in Table 1 were prepared using the following raw materials. These pressure-sensitive adhesive compositions were cured at 130°C for 5 minutes, and the surface adhesive strength of each cured product was measured. Solvent resistance tests and adhesion tests were also conducted using the methods described below. The results are also shown in Table 1.

[0126] raw material (A) Linear perfluoropolyether compound (A-1) Bifunctional perfluoropolyether (perfluoropolyether 1) [ka]

[0127] (A-2) Bifunctional perfluoropolyether (perfluoropolyether 2) CH2=CH―CH2―O―CH2―Rf―CH2―O-CH2―CH=CH2 (Rf:-CF2O(CF2CF2O) 20.8 (CF2O) 22.1 CF2-, However, the repeating units CF2CF2O and CF2O are arranged randomly.

[0128] (E) Monofunctional perfluoropolyether compound (perfluoropolyether 3) [ka]

[0129] (B) Organohydrogenpolysiloxane (b-1) Organohydrogensiloxane 1 [ka]

[0130] (b-2) Organohydrogensiloxane 2 [ka]

[0131] (C) Platinum-divinyltetramethyldisiloxane complex / ethanol solution (platinum content 3.0%)

[0132] (D) Organosilicon compounds containing adhesive functional groups (adhesion aids) (d-1) Adhesion-imparting siloxane compound (siloxane compound 1) [ka]

[0133] (d-2) Adhesion-imparting silane compound (silane compound 1) [ka]

[0134] (f) Hardening inhibitor: ethynylcyclohexanol / 50% toluene solution

[0135] Adhesion measurement Each composition in the Examples and Comparative Examples was applied to a 50 μm-thick, 25 mm-wide PET (polyethylene terephthalate) film using an applicator to a thickness of 30 μm, and then heated at 130°C for 5 minutes to harden into a rubber or gel form. This produced an adhesive tape consisting of a 30 μm-thick adhesive layer (rubber or cured gel layer) laminated on a 50 μm-thick PET film. This adhesive tape was attached to a metal plate (polished stainless steel plate), and a 2 kg rubber-coated roller was rolled back and forth across the tape substrate to press the adhesive tape into place. After leaving the tape at room temperature for 20 hours, the adhesive strength of each adhesive layer (rubber or cured gel layer) was measured at 25°C using a tensile tester, measuring the force (N / 25 mm) required to peel the adhesive tape from the stainless steel plate at a pulling rate of 300 mm / min at an angle of 180°.

[0136] Solvent resistance test (weight change) 3 g of the compositions of the examples and comparative examples were filled into a 32 mm diameter x 15 mm glass container, and then cured at 130°C for 5 minutes to create samples. These samples were then immersed in xylene and Fuel C (a 50 / 50 (wt%) mixed solution of toluene and isooctane) at 25°C for 7 days, and the weight change rate before and after immersion was measured.

[0137] Adhesion Test Each composition of the Examples and Comparative Examples was applied to an epoxy glass substrate to a thickness of 100 μm, and then heated at 130° C. for 5 minutes to harden into a rubber or gel state, producing a substrate with a laminated adhesive layer. The adhesive layer on the substrate was rubbed with a finger 10 times, and samples that did not peel from the substrate were marked with an O, and samples that peeled and exposed the substrate surface were marked with an X.

[0138] [Table 1]

[0139] As shown in Table 1, adhesives using the curable perfluoropolyether adhesive composition of the present invention, such as those in Examples 1 to 5, showed good adhesion to the substrate. In contrast, Comparative Examples 1 and 2, which did not contain component (B) or component (C), which are essential components of the present invention, did not cure, and Comparative Examples 3 and 4, which did not contain component (D), showed poor adhesion to the substrate and peeled off.

[0140] From the above, it was found that the present invention provides a curable perfluoropolyether adhesive composition that not only has excellent heat resistance, weather resistance, water repellency, oil repellency, chemical resistance and solvent resistance, but also gives a cured product (adhesive) that has particularly good adhesion to the substrate.

[0141] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention.

Claims

1. A laminated structure having, on a rigid substrate, a cured layer of a curable perfluoropolyether pressure-sensitive adhesive composition containing the following components (A) to (D): (A) A polymer having at least two alkenyl groups in one molecule and a -C group in the main chain ａ F ２ａ A linear perfluoropolyether compound having a perfluoropolyether structure containing a repeating unit represented by O- (where a is an integer of 1 to 6). (B) An organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule. (C) Hydrosilylation reaction catalyst (D) An organosilicon compound other than component (B), which contains in one molecule two or more groups selected from the group consisting of a hydrogen atom bonded to a silicon atom, 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.

2. A laminate structure having, on a rigid substrate, a cured layer of a curable perfluoropolyether pressure-sensitive adhesive composition containing the following components (A) to (E): (A) A polymer having at least two alkenyl groups in one molecule and a -C group in the main chain ａ F ２ａ A linear perfluoropolyether compound having a perfluoropolyether structure containing a repeating unit of O- (where a is an integer of 1 to 6) (E) Polyfluoromonoalkenyl compound having one alkenyl group in one molecule and having a perfluoropolyether structure in the main chain (B) An organosilicon compound having at least two hydrogen atoms bonded to silicon atoms in one molecule. (C) Hydrosilylation reaction catalyst (D) An organosilicon compound other than component (B), which contains in one molecule two or more groups selected from the group consisting of a hydrogen atom bonded to a silicon atom, 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.

3. 3. The laminated structure according to claim 1, wherein the substrate is made of a synthetic resin or a metal.

4. The laminate structure according to claim 1 or 2, wherein the cured layer of the curable perfluoropolyether pressure-sensitive adhesive composition is in direct contact with the substrate.

5. 3. The laminate structure according to claim 1, wherein the cured layer of the curable perfluoropolyether pressure-sensitive adhesive composition has an adhesive strength of 0.001 N / 25 mm to 10.0 N / 25 mm.

6. 3. The laminate structure according to claim 1 or 2, wherein the organosilicon compound in component (D) is an organosilicon compound that has no hydrogen atoms bonded to silicon atoms, but has one or more epoxy groups bonded to silicon atoms via carbon atoms or carbon atoms and oxygen atoms, and one or more trialkoxysilyl groups bonded to silicon atoms via carbon atoms or carbon atoms and oxygen atoms.

7. 3. The laminate structure according to claim 1, wherein the organosilicon compound in component (D) is an organosilicon compound having two or more epoxy groups bonded to silicon atoms via carbon atoms or carbon atoms and oxygen atoms, and represented by the following formula (2): 【Chemical 1】

8. 3. The laminate structure according to claim 1, wherein the organosilicon compound in component (D) is an organosilicon compound containing no fluorine atoms.

9. 3. The laminate structure according to claim 1, wherein the organosilicon compound in component (D) is an organosilicon compound having two or more trialkoxysilyl groups bonded to a silicon atom via a carbon atom or a carbon atom and an oxygen atom.

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