JP2010215763A - Addition curing type silicone adhesive for fixing roll, and fixing roll - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone adhesive that becomes hard after elapse of several hours and becomes adhesive when it is coated on a silicone rubber layer, that has a remaining unreacted vinyl group and has low hardness, therefore processibility of producing the fixing roll is markedly improved. <P>SOLUTION: The addition curing type silicone adhesive for the fixing roll includes (A) an organopolysiloxane comprised of a 5-95 mass% organopolysiloxane (A-1) whose dynamic viscosity at 25°C is 100-50,000 mm<SP>2</SP>/s and having at least two alkenyl group in one molecule and a 95-5 mass% organopolysiloxane (A-2) whose dynamic viscosity at 25°C is more than 50,000 mm<SP>2</SP>/s but not more than 500,000 mm<SP>2</SP>/s and having at least two alkenyl group in one molecule, (B) an organohydrogenpolysiloxane represented by formula (1) and having at least two SiH group in one molecule (wherein A is CH<SB>3</SB>or H, m≥2, n≥0, and m+n is an integer of at least 50), (C) a hydrosilylation catalyst, and (D) an adhesiveness imparting component. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an addition-curable silicone adhesive for a fixing roll and a fixing roll using the same.

  Fixing rolls used in fixing devices such as copiers, laser beam printers, and facsimile machines are usually made by coating a fluorine-based resin layer with an adhesive on a silicone rubber elastic layer provided on a metal core. ing. In recent years, with the increase in speed of copying machines and the like, in order to increase the time required for fixing in the fixing device, the hardness of the silicone rubber elastic layer has been lowered for the purpose of widening the fixing width (nip width).

On the other hand, the fixing roll is required to have a high thermal conductivity, and in order to improve the thermal conductivity, many inorganic fillers may be added to the silicone rubber elastic layer. However, when a large amount of inorganic filler is added, there is a problem that the silicone rubber elastic layer becomes hard. In order to widen the fixing width (nip width), the silicone rubber elastic layer is preferably soft, so the amount of the curing agent used may be reduced. In that case, many unreacted vinyl groups remain in the cured silicone rubber elastic layer. In order to bond such a silicone rubber elastic layer and a fluororesin layer, when a conventional addition curable silicone adhesive (Japanese Patent No. 2656194; Patent Document 1) is used, it is included in the addition curable silicone adhesive. Since the organohydrogenpolysiloxane migrates to the silicone rubber elastic layer, the number of cross-linking points that react in the addition-curable silicone adhesive is reduced, and a phenomenon may occur in which it does not cure when left for several hours after coating. In addition to the above Patent Document 1, the following Patent Documents 2 to 4 are listed as technical documents preceding the present invention.
Moreover, although the following patent documents 5, 6 etc. are proposed as an adhesive agent for adhere | attaching a silicone rubber elastic layer and a fluorine resin layer, it was not fully satisfied about the said subject.

Japanese Patent No. 2656194 JP-A-6-332334 Japanese Patent Laid-Open No. 9-212028 JP 2004-86163 A JP-A-4-173328 JP 2007-310212 A

  The present invention has been made in view of the above circumstances, and in a fixing roll formed by adhering a silicone rubber elastic layer and a fluorine resin layer, several hours after being applied to the silicone rubber elastic layer in which unreacted vinyl groups remain. Provided are an addition-curable silicone adhesive for a fixing roll that can be cured and bonded even if left standing, and a fixing roll formed by bonding a silicone rubber elastic layer and a fluororesin layer with the addition-curable silicone adhesive. The purpose is to do.

  As a result of earnest research to achieve the above object, the present inventor has found that in the fixing roll formed by adhering the silicone rubber elastic layer and the fluororesin layer, the silicone rubber elastic layer in which unreacted vinyl groups remain. The main component of the addition-curable silicone adhesive to be applied is a mixture of low-viscosity and high-viscosity organopolysiloxanes, and the cross-linking agent organohydrogenpolysiloxane has a specific high polymerization degree. It has been found that even if it is allowed to stand for several hours, the addition-curable silicone adhesive can be cured to adhere the silicone rubber elastic layer and the fluororesin layer, and the present invention has been completed.

（Ａはメチル基又は水素原子であり、互いに同一であっても異なっていてもよい。ｍは２以上の整数、ｎは０以上の整数、ｍ＋ｎは５０以上の整数である。）
で表されるケイ素原子に結合する水素原子を一分子中に少なくとも２個含有するオルガノハイドロジェンポリシロキサン：一分子中に含まれるケイ素原子に結合した水素原子の数が、（Ａ）成分のオルガノポリシロキサンが有するアルケニル基１個当たり、０．５〜１０．０個となる量、
（Ｃ）ヒドロシリル化反応触媒：触媒量、
（Ｄ）接着付与成分：０．０１〜２０質量部
を含有することを特徴とする定着ロール用付加硬化型シリコーン接着剤。
［請求項２］
（Ａ−１）成分と（Ａ−２）成分とを混合してなる（Ａ）成分の動粘度が、５００〜１００，０００ｍｍ²／ｓであることを特徴とする請求項１記載のシリコーン接着剤。
［請求項３］
上記式（１）におけるｍ＋ｎが、５０〜１５０の整数であることを特徴とする請求項１又は２記載のシリコーン接着剤。
［請求項４］
更に、（Ｈ）シリコーンレジンを含有する請求項１〜３のいずれか１項記載のシリコーン接着剤。
［請求項５］
芯金上に形成されるシリコーンゴム層が、付加硬化型シリコーンゴム組成物の硬化物であることを特徴とする請求項１〜４のいずれか１項記載のシリコーン接着剤。
［請求項６］
芯金上に形成されるシリコーンゴム層が、ベースポリマーである少なくとも２個のアルケニル基含有オルガノポリシロキサンのアルケニル基１個当たり、ケイ素原子に結合した水素原子の数として１個未満となる量のオルガノハイドロジェンポリシロキサンを含む、付加硬化型シリコーンゴム組成物の硬化物であることを特徴とする請求項５記載のシリコーン接着剤。
［請求項７］
芯金上にシリコーンゴム層が形成され、その上に最外層としてフッ素系樹脂層が被覆されている定着ロールであって、請求項１〜６のいずれか１項記載のシリコーン接着剤でシリコーンゴム層とフッ素系樹脂層が接着されてなることを特徴とする定着ロール。 Accordingly, the present invention provides the following addition-curable silicone adhesive for fixing rolls and fixing rolls.
[Claim 1]
An adhesive for adhering a silicone rubber layer and a fluororesin layer of a fixing roll in which a silicone rubber layer is formed on a core metal and a fluororesin layer is coated thereon as an outermost layer,
The following components (A) to (D),
(A) (A-1) Organopolysiloxane having a kinematic viscosity at 25 ° C. of 100 to 50,000 mm ² / s and containing at least two alkenyl groups in one molecule: 5 to 95% by mass, and ( kinematic viscosity of greater than 50,000 mm ² / s at a-2) 25 ℃, or less 500,000 ² / s, an organopolysiloxane containing at least 2 alkenyl groups in one molecule: 95-5 weight %
Organopolysiloxane comprising: 100 parts by mass,
(B) The following formula (1)

(A is a methyl group or a hydrogen atom, and may be the same or different. M is an integer of 2 or more, n is an integer of 0 or more, and m + n is an integer of 50 or more.)
An organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to a silicon atom represented by the formula: The number of hydrogen atoms bonded to a silicon atom included in one molecule is the organo of component (A) An amount of 0.5 to 10.0 per alkenyl group of the polysiloxane,
(C) Hydrosilylation reaction catalyst: catalyst amount,
(D) Adhesion-imparting component: Addition-curable silicone adhesive for fixing rolls, containing 0.01 to 20 parts by mass.
[Claim 2]
The kinematic viscosity of the component (A) obtained by mixing the component (A-1) and the component (A-2) is 500 to 100,000 mm ² / s. Agent.
[Claim 3]
3. The silicone adhesive according to claim 1 or 2, wherein m + n in the formula (1) is an integer of 50 to 150.
[Claim 4]
The silicone adhesive according to any one of claims 1 to 3, further comprising (H) a silicone resin.
[Claim 5]
The silicone adhesive according to any one of claims 1 to 4, wherein the silicone rubber layer formed on the metal core is a cured product of an addition-curable silicone rubber composition.
[Claim 6]
The amount of the silicone rubber layer formed on the metal core is less than 1 as the number of hydrogen atoms bonded to silicon atoms per alkenyl group of at least two alkenyl group-containing organopolysiloxanes as the base polymer. 6. The silicone adhesive according to claim 5, which is a cured product of an addition-curable silicone rubber composition containing an organohydrogenpolysiloxane.
[Claim 7]
A fixing roll in which a silicone rubber layer is formed on a core metal and a fluororesin layer is coated thereon as an outermost layer, wherein the silicone rubber is coated with the silicone adhesive according to any one of claims 1 to 6. A fixing roll comprising a layer and a fluororesin layer bonded together.

  The addition curable silicone adhesive for fixing rolls of the present invention can be cured and adhered even after several hours after being applied to a low hardness silicone rubber layer in which unreacted vinyl groups remain. The workability when manufacturing the fixing roll is remarkably improved.

The present invention will be described in detail below.
(A) Alkenyl group-containing organopolysiloxane The (A) component alkenyl group-containing organopolysiloxane is the main agent of the adhesive of the present invention, and the (A-1) component and the (A-2) component organopolysiloxane. It is prepared by mixing. In this case, the organopolysiloxanes of the component (A-1) and the component (A-2) are preferably diorganopolysiloxanes. Here, the component (A-1) is an organopolysiloxane containing at least two alkenyl groups in one molecule having a kinematic viscosity at 25 ° C. of 100 to 50,000 mm ² / s, and (A-2 ) component is an organopolysiloxane having a kinematic viscosity at 25 ° C. exceed 50,000 mm ² / s, containing at least 2 alkenyl groups in one molecule or less 500,000 ² / s. The viscosity is a value measured with a rotational viscometer.

  Examples of the alkenyl group contained in the organopolysiloxane containing at least two alkenyl groups in one molecule of the component (A-1) and the component (A-2) include a vinyl group, an allyl group, a butenyl group, Examples include groups having about 2 to 8 carbon atoms such as a pentenyl group, a hexenyl group, and a heptenyl group, and a vinyl group is particularly preferable. The bonding position of the alkenyl group may be either the molecular chain terminal or the molecular chain side chain of the organopolysiloxane, or may be both in the molecular chain terminal and in the molecular chain side chain.

  Examples of the organic group bonded to the silicon atom other than the alkenyl group of the component (A-1) and the component (A-2) include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Alkyl groups such as phenyl groups, tolyl groups, xylyl groups, naphthyl groups and the like; aralkyl groups such as benzyl groups and phenethyl groups; chloromethyl groups, 3-chloropropyl groups, 3,3,3-trifluoropropyl Examples include groups having about 1 to 10 carbon atoms such as hydrocarbon groups in which some or all of hydrogen atoms such as groups are substituted with halogen atoms, and in particular, methyl groups, phenyl groups, 3,3,3-tri A fluoropropyl group is preferred, and a methyl group is particularly preferred. The molecular structures of the component (A-1) and the component (A-2) are basically linear, but the cured product of the composition may be branched within a range having elasticity.

Examples of the organopolysiloxane of the component (A-1) and the component (A-2) include, for example, a molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer, and a molecular chain both ends trimethylsiloxy group-capped methylvinyl. Polysiloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends dimethylvinylsiloxy group-blocked dimethylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked methylvinylpoly Siloxane, dimethylvinylsiloxy group-capped dimethylvinylsiloxy copolymer, both ends of molecular chain, dimethylvinylsiloxy group-capped dimethylsiloxane, methylvinylsiloxane, methylphenylsilo San copolymer both molecular chain terminals by trimethylsiloxy blocked with dimethylvinylsiloxy groups, wherein: the siloxane units of the formula R ¹ ₃ SiO _0.5: siloxane units represented by the formula _{^{R 1 2 R 2 SiO 0.5:}} R 1 ₂ Organopolysiloxane copolymer comprising units represented by SiO and a small amount of formula: siloxane units represented by SiO ₂ , siloxane units represented by formula: R ¹ ₃ SiO _0.5 and formula: R ¹ ₂ R ² SiO _0.5 An organopolysiloxane copolymer comprising a siloxane unit represented by the formula: SiO ₂ and a siloxane unit represented by the formula: R ¹ ₂ R ² SiO _0.5 and a siloxane unit represented by the formula: R ¹ ₂ SiO a small amount of the formula: organopolysiloxane copolymers composed of siloxane units represented by SiO _2, wherein: R ¹ R ² siloxane units and a minor amount represented by SiO Wherein: the siloxane units or of the formula represented by R ¹ SiO _1.5: organopolysiloxane copolymers composed of siloxane units represented by R ² SiO _1.5, and mixtures of two or more of these organopolysiloxanes. In the above formula, R ¹ is a monovalent hydrocarbon group other than an alkenyl group, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group; a phenyl group, a tolyl group Aryl groups such as a group, xylyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; and halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group A methyl group is preferred. In the above formula, R ² is an alkenyl group, and examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group, and a vinyl group is preferable.
The component (A-1) and the component (A-2) may be used alone or in combination of two or more.

The viscosities of the component (A-1) and the component (A-2) are as described above, but the difference in viscosity between the component (A-1) and the component (A-2) effectively achieves the object of the present invention. from the viewpoint for, 100~490,000mm ² / s, particularly preferably is in 500~200,000mm ² / s.

  The blending ratio of the component (A-1) and the component (A-2) is as follows: (A-1) component: (A-2) component = 5 to 95% by mass: 95 to 5% by mass, preferably 10 It is necessary from the point which achieves the objective of this invention that it is -90 mass%: 90-10 mass%, More preferably, it is 20-80 mass%: 80-20 mass%. In addition, the sum total of (A-1) component and (A-2) component is 100 mass%.

The kinematic viscosity at 25 ° C. of the component (A) in which the component (A-1) is mixed at a ratio of 5 to 95 mass% and the component (A-2) is mixed at a ratio of 95 to 5 mass% is a physical property of the obtained silicone rubber. Is good and the workability of the composition is good, it is preferably in the range of 500 to 100,000 mm ² / s, especially 1,000 to 80,000 mm ² / s. It is preferable to be within the range. If the kinematic viscosity is less than 500 mm ² / s, the liquid may easily drip and workability may be reduced. If the kinematic viscosity exceeds 100,000 mm ² / s, it may be difficult to uniformly apply the adhesive.

(B) Organohydrogenpolysiloxane The organohydrogenpolysiloxane which is the component (B) of the present invention is a hydrogen atom (that is, SiH group) bonded to at least 2, preferably 3 or more silicon atoms in one molecule. ). Its molecular structure is linear, and is represented by the following formula (1).

（Ａはメチル基又は水素原子であり、互いに同一であっても異なっていてもよい。ｍは２以上の整数、ｎは０以上の整数である。ｍ＋ｎは５０以上の整数、好ましくは５０〜３００、特に５０〜１５０の整数であることが好ましい。）

(A is a methyl group or a hydrogen atom and may be the same or different. M is an integer of 2 or more, n is an integer of 0 or more. M + n is an integer of 50 or more, preferably 50 to 300, particularly preferably an integer of 50 to 150)

The organohydrogenpolysiloxane used in the adhesive of the present invention can be obtained by a known method. For example, the general formula: R ¹ SiHCl ₂ and R ¹ ₂ SiHCl (wherein R ¹ is the same as above) Or at least one selected from the above chlorosilanes and the general formulas: R ¹ ₃ SiCl and R ¹ ₂ SiCl ₂ (wherein R ¹ is the same as above). These chlorosilanes can be combined and obtained by cohydrolysis. In addition, the organohydrogenpolysiloxane may be one obtained by equilibrating the polysiloxane obtained by cohydrolysis.

  The amount of component (B) used is that of component (B) per alkenyl group in the alkenyl group-containing organopolysiloxane of component (A) (the sum of components (A-1) and (A-2)). The amount of hydrogen atoms (that is, SiH groups) bonded to silicon atoms in the organohydrogenpolysiloxane is usually 0.5 to 10.0, preferably 1.0 to 8.0. It is an amount. If it is less than 0.5, curing is insufficient and the adhesiveness is insufficient, and if it is more than 10.0, the cured product becomes too hard and adhesion followability becomes insufficient.

(C) Hydrosilylation Reaction Catalyst The hydrosilylation reaction catalyst which is the component (C) of the present invention is a catalyst for promoting the addition reaction between the component (A) and the component (B), and is a known platinum group. A metal-based catalyst may be used. Specific examples include platinum group metals such as platinum (including platinum black), rhodium and palladium; H ₂ PtCl ₄ · nH ₂ O, H ₂ PtCl ₆ · nH ₂ O, NaHPtCl ₆ · nH ₂ O, KHPtCl ₆ NH ₂ O, Na ₂ PtCl ₆ · nH ₂ O, K ₂ PtCl ₄ · nH ₂ O, PtCl ₄ · nH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ · nH ₂ O (where n is 0 Chloroplatinic acid, chloroplatinic acid and chloroplatinic acid salt, such as ˜6, preferably 0 or 6, alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972); Platinum acid and olefin complex (see US Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum black, palladium, etc. Platinum group metal Supported on a carrier such as Rica and carbon; rhodium-olefin complex; chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst); platinum chloride, chloroplatinic acid or chloroplatinate and vinyl group-containing siloxane, especially vinyl group And a complex with the containing cyclic siloxane.

  The amount of the component (C) used may be a so-called catalytic amount, and is usually 0.1 to 500 ppm, particularly 0.5 to 0.5 ppm in terms of mass of the platinum group metal relative to the total amount of the components (A) and (B). About 200 ppm is sufficient.

(D) Adhesion imparting component (D) The component is an adhesion imparting agent that imparts self-adhesion to the composition of the present invention. The self-adhesiveness is particularly favorable for metals and organic resins. The component (D) is, for example, selected from the group consisting of alkenyl groups such as vinyl groups, (meth) acryloxy groups, hydrosilyl groups (SiH groups), epoxy groups, alkoxysilyl groups, carbonyl groups, and phenyl groups. Silane having at least one, preferably two or more functional groups, silane coupling agent, organosilicon such as cyclic or linear siloxane having 2 to 30 silicon atoms, preferably about 4 to 20 silicon atoms Contains 1 to 4 and preferably 1 to 2, preferably 1 to 2 aromatic rings such as a compound and 1 to 4 valent, preferably 2 to 4 valent phenylene structures, and can contribute to the hydrosilylation addition reaction Contains at least one, preferably 2 to 4, functional groups (for example, alkenyl group, (meth) acryloxy group) in one molecule, and may contain oxygen atoms in the molecule. Lee-containing system (i.e., containing no silicon atoms in the molecule) can be exemplified organic compound. Specific examples of the component (D) include the following compounds.

  Component (D) can be used alone or in combination of two or more. The blending amount of the component (D) is an amount by which the composition of the present invention can obtain good self-adhesiveness to an adherend, particularly a metal and an organic resin. It is 0.01-20 mass parts, Preferably it is 0.1-5 mass parts.

In the present invention, it is preferable to add (H) silicone resin in order to improve adhesiveness and reinforcement. As such a silicone resin, a silicone resin composed of a siloxane unit represented by R ¹ ₃ SiO _0.5 and a siloxane unit represented by SiO ₂ , a siloxane unit represented by R ¹ ₃ SiO _0.5 and a siloxane represented by R ¹ SiO _1.5 Examples include a silicone resin comprising a unit and a siloxane unit represented by SiO ₂ (R ¹ is as described above), specifically, a resin comprising (CH ₃ ) ₃ SiO _0.5 unit and SiO ₂ unit, (CH ₃ ) ₃ SiO _0.5 unit, (CH ₂ ═CH) Resin composed of SiO _1.5 unit and SiO ₂ unit, (CH ₂ ═CH) (CH ₃ ) ₂ Resin composed of SiO _0.5 unit and SiO ₂ unit, (CH ₂ ═CH ) Resins composed of (CH ₃ ) ₂ SiO _0.5 units, (CH ₂ ═CH) SiO _1.5 units and SiO ₂ units are shown. Among these, a silicone resin having an alkenyl group, particularly a vinyl group, is preferable because it is excellent in the effect of improving adhesiveness and reinforcement. In particular, methyl vinyl silicone resin is preferable.

As other components, reinforcing fine powdery silica can be blended. The compounding quantity is 1-200 mass parts with respect to 100 mass parts of (A) component, Especially 3-50 mass parts is preferable. This fine powder silica is for reinforcing the mechanical strength of the cured product, and may be a known one conventionally used in silicone rubber compositions, such as fumed silica, precipitated silica, calcined silica, quartz powder, There is diatomaceous earth. These may be used alone or in combination of two or more. These silica particles specific surface area of 50 m ² / g or more usually by the BET method, in particular 50~500m general of about ² / g. Such finely divided silica may be used as it is, but it is treated with an organosilicon compound such as methylchlorosilanes, dimethylpolysiloxane, hexamethyldisilazane, etc. in order to impart good fluidity to the composition of the present invention. Is preferably used.

  Furthermore, in the composition of the present invention, in addition to the components (A), (B), (C), and (D), various additives such as fumed titanium dioxide can be reinforced as necessary. Non-reinforcing inorganic fillers such as calcium silicate, titanium dioxide, ferric oxide, and carbon black; curing control agents; heat resistance imparting agents and the like can be added. The amount of these used is a range which does not impair adhesiveness, and is the range currently used with the usual silicone adhesive.

  Moreover, the addition-curable silicone adhesive of the present invention can be obtained by mixing the above-mentioned components, and can be not only a one-component type but also a two-component type used after mixing immediately before use.

  The fixing roll of the present invention is a fixing roll in which a silicone rubber layer is formed on a cored bar and a fluorine-based resin layer is coated thereon as an outermost layer. The resin layer is bonded.

  The silicone rubber layer formed on the metal core is preferably a cured product of an addition reaction curable silicone rubber composition, and the silicone rubber composition contains at least two alkenyl group-containing organopolysiloxane (base polymer). , An organohydrogenpolysiloxane (crosslinking agent), and a hydrosilylation reaction catalyst as essential components. Moreover, in order to improve thermal conductivity, it is preferable to add a high thermal conductive inorganic filler, for example, alumina, crystalline silica, metal silicon powder, zinc oxide and the like. The blending amount of the high thermal conductive inorganic filler is preferably 50 to 500 parts by mass with respect to 100 parts by mass of the alkenyl group-containing organopolysiloxane (base polymer).

  In the case of adding a highly heat conductive inorganic filler, it is preferable to reduce the amount of the crosslinking agent in order to reduce the rubber hardness. In this case, the amount of the organohydrogenpolysiloxane that is the crosslinking agent is such that the number of hydrogen atoms bonded to the silicon atom of the organohydrogenpolysiloxane is one alkenyl group of the alkenyl group-containing origanopolysiloxane that is the base polymer. The number is preferably less than 1, more preferably 0.1 to 0.8, and particularly preferably 0.2 to 0.6. If the amount is too small, the curability may be lowered. If the amount is too large, the resulting rubber will be hard, and the properties required for the roll may be insufficient.

  The silicone rubber layer can be formed on the core metal according to a conventional method. For example, a primer is applied to the surface of an aluminum shaft (core metal), air-dried, heated if necessary, baked, and a silicone rubber layer is heat-cured (usually about 80 to 170 ° C.) to form it. If necessary, the surface of the rubber roll may be polished.

  Next, the fixing roll of the present invention can be produced by applying the adhesive of the present invention on the silicone rubber layer and sticking the fluororesin layer to the silicone rubber layer. The curing (adhesion) conditions of the adhesive of the present invention are not particularly limited, but are preferably heat-cured (adhered), and particularly preferably heat-cured (adhered) at 80 to 170 ° C.

  In addition, the fluororesin forming the fluororesin layer is not particularly limited, and examples thereof include tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin (PFA resin), tetrafluoroethylene resin (PTFE resin), and the like. Is preferred.

  In addition, the thickness of the said silicone rubber layer is 0.1-10 mm normally, Preferably it is 0.5-5 mm, and the thickness of a fluorine-type resin layer is 10-200 micrometers normally, Preferably it is 20-100 micrometers. The thickness of the adhesive layer made of the adhesive of the present invention for adhering the silicone rubber layer and the fluororesin layer is preferably 1 to 100 μm, more preferably 5 to 50 μm.

  The present invention will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, the viscosity was measured with a rotational viscometer.

（Ｅ）硬化制御剤：
（Ｅ−１）エチニルシクロヘキサノール
（Ｅ−２）トリアリルイソシアヌレート
（Ｆ）補強性フィラー：
結晶性シリカ（ＵＳ ＳＩＬＩＣＡ ＣＯＭＰＡＮＹ社製ミニシル１５ミクロン）
（Ｇ）耐熱性付与剤：
戸田工業（株）製ベンガラ１３０ＥＤ
（Ｈ）補強性レジン：
信越化学工業（株）製ビニル基含有シリコーンレジン（製品名１３００ＱＴ−Ｓ）
（Ｉ）補強製シリカ：
信越化学工業（株）製表面疎水化処理ヒュームドシリカ（製品名Ｍｕｓｉｌ１２０Ａ） The raw materials for the addition-curable silicone adhesive are as follows.
(A) Organopolysiloxane containing at least two alkenyl groups in one molecule:
(A-1) The viscosity at 25 ° C. is 30,000 mm ² / s, and the vinyl group-containing linear organopolysiloxane (A-2) represented by the following formula (2) has a viscosity at 25 ° C. of 100, 000mm was ² / s, a straight-chain organopolysiloxane Vi vinyl group-containing represented by the following formula _{(2) (Me) 2 Si-} (OSiMe 2) n -OSi (Me) 2 Vi (2)
(In the formula, Me is a methyl group, Vi is a vinyl group, and n is a number such that the viscosity of the siloxane at 25 ° C. is 30,000 mm ² / s or 100,000 mm ² / s)
(B) Organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to silicon atoms in one molecule:
(B-1)
_{(CH 3) 3 SiO- (Si} (CH 3) (H) O) 8 -Si (CH 3) 3
(B-2)
_{(CH 3) 3 SiO- (Si} (CH 3) 2 O) 18 - (Si (CH 3) (H) O) 20 -Si (CH 3) 3
(B-3)
_{(CH 3) 3 SiO- (Si} (CH 3) 2 O) 75 - (Si (CH 3) (H) O) 25 -Si (CH 3) 3
(B-4)
_{(CH 3) 3 SiO- (Si} (CH 3) 2 O) 17 - (Si (CH 3) (H) O) 45 -Si (CH 3) 3
(B-5)
_{(CH 3) 3 SiO- (Si} (CH 3) 2 O) 28 - (Si (CH 3) (H) O) 70 -Si (CH 3) 3
(C) Hydrosilylation reaction catalyst:
Platinum-divinyltetramethyldisiloxane complex / toluene solution (platinum element content 0.5 mass%)
(D) Adhesion imparting component represented by the following formula

(E) Curing control agent:
(E-1) Ethynylcyclohexanol (E-2) Triallyl isocyanurate (F) Reinforcing filler:
Crystalline silica (Minisil 15 micron made by US SILICA COMPANY)
(G) Heat resistance imparting agent:
Bengala 130ED manufactured by Toda Industry Co., Ltd.
(H) Reinforcing resin:
Vinyl group-containing silicone resin (product name: 1300QT-S) manufactured by Shin-Etsu Chemical Co., Ltd.
(I) Reinforced silica:
Surface-hydrophobized fumed silica manufactured by Shin-Etsu Chemical Co., Ltd. (product name Musil120A)

[Examples 1-9, Comparative Examples 1-5]
An addition-curable silicone adhesive was produced using the above raw materials. (A) component, (F) component, (G) component, (H) component, and (I) component are mixed by the compounding amount described in the following Table 1, and in order of (C) component and (D) component. Addition and mixing were performed. Next, the remaining raw materials (B) and (E) were added all at once or appropriately. After mixing well, the pressure was reduced and defoaming was performed to obtain an addition-curable silicone adhesive.

  The following adhesion test was performed using the addition curing type silicone adhesive finished by this method. Silicone rubber elastic layer [manufactured by Shin-Etsu Chemical Co., Ltd. (the hardness is 14 points as measured by Asuka C, the hydrogen atom (SiH group) bonded to the silicon atom of the organohydrogenpolysiloxane as a crosslinking agent) on the surface of the core metal The number is 0.42 per alkenyl group of the alkenyl group-containing origanopolysiloxane, which is the base polymer)], and an addition-curable silicone adhesive was applied so that the thickness was 30 μm. On top of that, a fluororesin composed of tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (manufactured by Nippon Valqua Kogyo Co., Ltd.) is applied, and the evaluation is made at two levels: when cured immediately and when allowed to stand at room temperature for 6 hours. It was. The curing conditions were 120 ° C. × 60 minutes. After the heating, the fluororesin composed of tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer was peeled off from the silicone cured product, and it was confirmed whether the silicone adhesive was cured and adhered. The results are shown in Table 1.

  As shown in the above results, depending on the composition of the main component of the adhesive and the type of the crosslinking agent, it was not cured when left for 6 hours after coating. It was confirmed that the adhesive of the present invention has good adhesion to the fluororesin and silicone rubber even after being left for 6 hours after application.

Claims (7)

An adhesive for adhering a silicone rubber layer and a fluororesin layer of a fixing roll in which a silicone rubber layer is formed on a core metal and a fluororesin layer is coated thereon as an outermost layer,
The following components (A) to (D),
(A) (A-1) Organopolysiloxane having a kinematic viscosity at 25 ° C. of 100 to 50,000 mm ² / s and containing at least two alkenyl groups in one molecule: 5 to 95% by mass, and ( kinematic viscosity of greater than 50,000 mm ² / s at a-2) 25 ℃, or less 500,000 ² / s, an organopolysiloxane containing at least 2 alkenyl groups in one molecule: 95-5 weight %
Organopolysiloxane comprising: 100 parts by mass,
(B) The following formula (1)

(A is a methyl group or a hydrogen atom, and may be the same or different. M is an integer of 2 or more, n is an integer of 0 or more, and m + n is an integer of 50 or more.)
An organohydrogenpolysiloxane containing at least two hydrogen atoms bonded to a silicon atom represented by the formula: The number of hydrogen atoms bonded to a silicon atom included in one molecule is the organo of component (A) An amount of 0.5 to 10.0 per alkenyl group of the polysiloxane,
(C) Hydrosilylation reaction catalyst: catalyst amount,
(D) Adhesion-imparting component: Addition-curable silicone adhesive for fixing rolls, containing 0.01 to 20 parts by mass. The kinematic viscosity of the component (A) obtained by mixing the component (A-1) and the component (A-2) is 500 to 100,000 mm ² / s. Agent.   3. The silicone adhesive according to claim 1 or 2, wherein m + n in the formula (1) is an integer of 50 to 150.   The silicone adhesive according to any one of claims 1 to 3, further comprising (H) a silicone resin.   The silicone adhesive according to any one of claims 1 to 4, wherein the silicone rubber layer formed on the metal core is a cured product of an addition-curable silicone rubber composition.   The amount of the silicone rubber layer formed on the metal core is less than 1 as the number of hydrogen atoms bonded to silicon atoms per alkenyl group of at least two alkenyl group-containing organopolysiloxanes as the base polymer. 6. The silicone adhesive according to claim 5, which is a cured product of an addition-curable silicone rubber composition containing an organohydrogenpolysiloxane.   A fixing roll in which a silicone rubber layer is formed on a core metal and a fluororesin layer is coated thereon as an outermost layer, wherein the silicone rubber is coated with the silicone adhesive according to any one of claims 1 to 6. A fixing roll comprising a layer and a fluororesin layer bonded together.