JP2010024279A - Surface treatment agent, rubber surface treatment method and rubber product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface treatment agent imparting super water-repellency to the surface of various substrates including rubber surfaces. <P>SOLUTION: The surface treatment agent includes (A) a fluorine-containing compound represented by general formula (I) (wherein, R<SB>F</SB>represents a group with a fluoroalkyl group, R<SP>1</SP>represents an alkyl group or alkoxy group, and x is an integer of 1-100), (B1) a polyorganosiloxane having both terminals blocked by a Si-OH group or (B3) a polyorganosiloxane having in its one molecule two or more alkenyl groups linked to a silicon atom, (B2) a polyorganohydrogensiloxane having in its one molecule two or more Si-H groups, a curing catalyst, and an organic solvent. The surface treating agent also preferably includes (E) a silane coupling agent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a surface treatment agent, a rubber surface treatment method, and a rubber product. More specifically, the present invention relates to a surface treatment agent capable of imparting super water repellency to various products, and a rubber surface treatment method using the surface treatment agent. And a rubber product treated with the surface treatment agent.

  Various surface treatment agents (water repellents) have been proposed to impart water repellency to the surface of a substrate. For example, it has been proposed to use a liquid silicone resin or a liquid fluororesin as a water repellent to impregnate a breathable waterproof rubber molded body obtained by compression molding pulverized rubber vulcanized particles (Patent Literature). 1).

  In addition, it contains dimethyl silicone oil, fluorine oil, strong acid catalyst, and alcohol as a water repellent that is said to have excellent initial water repellency and long-term durability when spread on a surface to be treated such as a glass surface. The thing is proposed (refer patent document 2).

  Furthermore, as a surface treatment agent (hard coat liquid) that can form a film that can exhibit high water repellency and oil repellency even when the surface is worn due to long-term use, it is a silicone-based polymerization curing A product obtained by partially condensing a product and a silane coupling agent having a fluorine bonding group has been proposed (see Patent Document 3). This Patent Document 3 describes methyltrimethoxysilane as a specific example of a silicone-based polymerized cured product, and perfluoroalkylsilane (FAS) having an alkoxy group as a specific example of a silane coupling agent having a fluorine bonding group. Is described.

However, when the surface of the rubber is treated with a conventionally known surface treatment agent including those described in Patent Documents 1 to 3, the surface has a sufficient super-water repellency (for example, a contact angle with water of 120 ° or more). Could not get.
In addition, when an organic solvent is brought into contact with the surface of a rubber product imparted with water repellency by treatment with a conventionally known surface treatment agent, the imparted water repellency may be greatly reduced. A rubber product treated with such a surface treating agent cannot be used for applications requiring solvent resistance.
Japanese Patent Laid-Open No. 2002-361749 JP 2003-277735 A JP-A-9-324139

The present invention has been made based on the above situation.
An object of the present invention is to provide a surface treatment agent capable of imparting super water repellency to various substrate surfaces including the surface of rubber.
Another object of the present invention is to form a surface treatment layer excellent in durability (solvent resistance) capable of maintaining the imparted super water repellency even after contact with an organic solvent. The object is to provide a surface treatment agent that can be used.

  According to the surface treatment agent comprising a combination of a fluorine compound having a specific structure and a specific reactive silicone (reactive polyorganosiloxane) as a result of intensive studies to achieve the above object The present inventors have found that excellent water repellency that cannot be exhibited by treating each of them alone can be imparted to the substrate surface, and the present invention has been completed based on such knowledge.

  That is, the surface treating agent of the present invention (first invention) includes (A) a fluorine-containing compound represented by the following general formula (I) (hereinafter referred to as “specific fluorine-containing compound”), and (B1) Si. A polyorganosiloxane having both ends blocked with —OH groups; (B2) a polyorganohydrogensiloxane having two or more Si—H groups in one molecule; (C1) a curing catalyst; and (D) an organic solvent. It is characterized by containing.

  The surface treating agent of the present invention (second invention) includes (A) a specific fluorine-containing compound, and (B3) a polyorganosiloxane having two or more alkenyl groups bonded to a silicon atom in one molecule, (B2) A polyorganohydrogensiloxane having two or more Si—H groups in one molecule, (C1) a platinum-based curing catalyst, and (D) an organic solvent.

(In the formula, R _F represents a group containing a fluoroalkyl group, R ¹ represents an alkyl group or an alkoxy group, and x is an integer of 1 to 100.)

  The surface treatment agent of the present invention preferably contains (E) a silane coupling agent.

  In the surface treatment agent of the present invention (first invention), the content of the specific fluorine-containing compound is a, (B1) the content of the polyorganosiloxane blocked at both ends by Si—OH groups is b1, ( B2) When the content of polyorganohydrogensiloxane having two or more Si-H groups in one molecule is b2, and the content of (E) silane coupling agent is e, the value of a / (b1 + b2 + e) is 1. It is preferable that it is 0-4.5.

  In the surface treatment agent of the present invention (second invention), the content of the specific fluorine-containing compound is a, and (B3) a polyorganosiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule. When the content is b3, (B2) the content of polyorganohydrogensiloxane having two or more Si-H groups in one molecule is b2, and (E) the content of the silane coupling agent is e, a / (b3 + b2 + e ) Is preferably 1.0 to 4.5.

The surface treatment agent of the present invention preferably contains (F) an acid catalyst. The surface treatment agent of the present invention is suitable for treating the surface of rubber.

The surface treatment method of the present invention includes a step of applying the surface treatment agent of the present invention to a rubber surface, and a step of heating a coating film by the surface treatment agent.
The rubber product of the present invention is treated with the surface treatment agent of the present invention, and has a contact angle with water of 120 ° or more.

According to the surface treating agent of the present invention, super water repellency having a contact angle with water of 120 ° or more can be imparted to various surfaces including a rubber surface. The super water repellency imparted by the surface treatment agent of the present invention cannot be predicted from the water repellency expressed when the specific fluorine-containing compound or reactive silicone constituting the surface treatment agent is used alone. Is.
Furthermore, according to the surface treatment agent of the present invention containing a silane coupling agent, it is possible to form a surface treatment layer (super water repellency imparting layer) excellent in durability (solvent resistance), and the surface Even when the organic solvent is brought into contact with the surface treated with the treating agent, the imparted super water repellency is sufficiently maintained.

Hereinafter, the present invention will be described in detail.
<First invention>
The surface treating agent of the present invention (first invention) comprises (A) a specific fluorine-containing compound, (B1) a polyorganosiloxane blocked at both ends by Si—OH groups, and (B2) Si—H. A polyorganohydrogensiloxane having two or more groups in one molecule, (C1) a curing catalyst, and (D) an organic solvent are contained as essential components.

The “specific fluorine-containing compound” constituting the surface treating agent according to the first invention as the component (A) has a group (R _F ) containing a fluoroalkyl group at both molecular ends and —Si (OR ¹ ) A fluorine-based oligomer having an intermediate chain to which a group represented by ₃ (trialkoxysilyl group or trialkoxyalkoxysilyl group) is bonded.

By using a specific fluorine-containing compound in combination with reactive silicone, a surface treating agent capable of imparting super water repellency to the substrate surface can be obtained.
Even if another fluorine-containing compound (for example, FAS described in Citation 3) is contained instead of the specific fluorine-containing compound, depending on the surface treatment agent to be obtained, super water repellency is imparted to the surface of the substrate. Can not do it.

Specific examples of the group (R _F ) containing a fluoroalkyl group constituting the specific fluorine-containing compound include —CF ₃ , —C ₂ F ₅ , —C ₃ F ₇ , —C ₆ F ₁₃ and —C _7. fluoroalkyl group represented by -C like _{F 15 q F 2q + 1 (} q = 1~10); -CF (CF 3) OC 3 F 7, -CF (CF 3) [OCF 2 CF (CF 3) ] Exemplifying a group represented by OC ₃ F ₇ and —CF (CF ₃ ) [OCF ₂ CF (CF ₃ )] ₂ OC ₃ F ₇ (a group containing an oxyfluoroalkylene group and a fluoroalkyl group) Among these, a group represented by —CF (CF ₃ ) OC ₃ F ₇ is particularly preferable.

Specific examples of the group represented by —Si (OR ¹ ) ₃ in the intermediate chain constituting the specific fluorine-containing compound include trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group; tri (methoxymethoxy) Examples include trialkoxyalkoxysilyl groups such as silyl group, tri (methoxyethoxy) silyl group, tri (ethoxymethoxy) silyl group, and tri (ethoxyethoxy) silyl group. Of these, trialkoxysilyl groups are preferred, and trimethoxysilyl groups are particularly preferred.

  In the above general formula (I) showing a specific fluorine-containing compound, the number of intermediate chains (x) is 1 to 100, preferably 1 to 50, more preferably 1 to 10, particularly preferably 2 to 5. The

  The polyorganosiloxane constituting the surface treatment agent according to the first invention as the component (B1) is one in which both molecular ends are blocked with Si—OH groups (silanol groups). That is, this polyorganosiloxane is subjected to a curing reaction by the reactivity of OH groups bonded to silicon atoms at both ends of the molecule. An organic group is bonded to the silicon atom in the component (B1) molecule. Examples of such an organic group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, an alkenyl group such as a propenyl group, an aryl group such as a phenyl group, an aralkyl group such as a styrenyl group, and a hydrocarbon group thereof. An example in which a part of hydrogen atoms is substituted with a halogen atom, a nitrile group or the like can be exemplified. Of these, a methyl group is preferred because it is easy to synthesize and has a balance between the viscosity before curing and the physical properties of the cured film (surface treatment layer) formed by the surface treatment agent to be obtained.

  The viscosity (25 ° C.) of the component (B1) is preferably 50 cSt or more, more preferably 1,000 to 10,000,000 cSt. When the viscosity of the component (B1) is less than 50 cSt, the formed cured film becomes brittle. On the other hand, when it exceeds 10,000,000 cSt, the viscosity of the surface treatment agent to be obtained becomes excessive and the handleability is lowered. In such a case, it is preferable to dilute the component (B1) with an organic solvent.

The polyorganohydrogensiloxane constituting the surface treatment agent according to the first invention as the component (B2) has two or more Si—H groups (hydrosilyl groups) in one molecule.
An organic group is bonded to the silicon atom in the component (B2) molecule. Examples of such an organic group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, an alkenyl group such as a propenyl group, an aryl group such as a phenyl group, an aralkyl group such as a styrenyl group, and a hydrocarbon group thereof. Examples in which a part of hydrogen atoms are substituted with a halogen atom, a nitrile group or the like can be exemplified, and among these, a methyl group is preferable. The molecular structure of the component (B2) may be linear, branched or cyclic.

In the first invention, the polyorganohydrogensiloxane as the component (B2) undergoes a dehydrogenative condensation reaction with the specific fluorine-containing compound as the component (A) and the component (B1) to form a three-dimensional network structure (crosslinked structure). To form a cured film.
Furthermore, the polyorganohydrogensiloxane as the component (B2) reacts with the OH group present on the surface of the base material (for example, the OH group of the inorganic filler in the case of using rubber as the base material), thereby reacting to the base material. Adhesion can be improved.

  As usage-amount of (B2) component in 1st invention, it is preferable that it is 0.1-100 mass parts with respect to 100 mass parts of (B1) component, More preferably, it is 1-80 mass parts, More preferably, it is. 3 to 60 parts by mass. When the amount of the component (B2) used [ratio to the component (B1)] is too small, it may not be possible to form a film completely cured by the obtained surface treatment agent, and sufficient film characteristics may not be obtained. In addition, the curing reaction may take a long time. On the other hand, when the amount of component (B2) used is excessive, the film formed by the surface treatment agent obtained may be too soft or brittle.

  The curing catalyst constituting the surface treatment agent according to the first invention as the component (C1) is a dehydrogenation of the component (B1) having Si—OH groups at both ends and the component (B2) having Si—H groups. The catalyst promotes the condensation reaction and further promotes the dehydrogenative condensation reaction between the component (A) and the component (B2). Specific examples include metal fatty acid salts, amines and ammoniums.

  Metal fatty acid salts include dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin distearate, tributyltin acetate, tributyltin octoate, tributyltin laurate, dioctyltin diacetate, dioctyltin dilaurate, diethyltin Those having organic groups directly bonded to metal atoms such as dioleate and monomethyltin dioleate, and those having no organic groups directly bonded to metal atoms such as zinc octenoate, iron octenoate and tin octenoate Are illustrated. Examples of amines include organic amines such as monomethylamine, dimethylamine, monoethylamine, diethylamine, ethylenediamine, and hexamethyltetraamine and salts thereof; silane compounds having an amino group such as α-aminopropyltriethoxysilane and salts thereof. Illustrated. Examples of ammoniums include tetramethylammonium, dimethylbenzylammonium, and salts thereof.

  The amount of component (C1) used is preferably 0.5 to 15 parts by weight, more preferably 5 to 12 parts by weight, based on 100 parts by weight of the total amount of component (B1) and component (B2). Especially preferably, it is 8-10 mass parts. When the amount of the component (C1) used is less than 0.5 parts by mass, the resulting surface treating agent has a slow curing rate and may cause blocking after heat-treating the coating film. On the other hand, if the amount of the component (C1) used exceeds 10 parts by mass, the curing reaction may proceed before the resulting surface treatment is applied, which may make it impossible to apply.

The organic solvent constituting the surface treatment agent according to the first invention as the component (D) can be selected from those capable of dissolving both the specific fluorine-containing compound and the reactive silicone. N-hexane, n-heptane, petroleum hydrocarbon, methanol, ethanol, isopropyl alcohol, butyl alcohol, 1,1,1-trichloroethane, trichloroethylene, tetrahydrofuran, dichloromethane, chloroform, ethyl acetate, dimethyl sulfoxide ( DMSO), N, N-dimethylformamide (DMF), organic solvents such as benzene, toluene, xylene, cyclohexanone, and acetone can be exemplified, and these can be used alone or in admixture of two or more. it can.
The amount of component (D) used is preferably 1 to 10 times the total amount of components other than component (D).
When the amount of component (D) used is too small, the cured film formed by the surface treatment agent obtained is inferior in smoothness. On the other hand, when the amount of component (D) used is excessive, the workability of the coating operation is inferior.

<Second invention>
The surface treating agent of the present invention (second invention) includes (A) a specific fluorine-containing compound, (B3) a polyorganosiloxane having two or more alkenyl groups bonded to a silicon atom in one molecule, and (B2 It contains, as essential components, a polyorganohydrogensiloxane having two or more Si—H groups in one molecule, (C2) a platinum-based curing catalyst, and (D) an organic solvent.

  Examples of the “specific fluorine-containing compound” constituting the surface treatment agent according to the second invention as the component (A) include the same compounds as those constituting the surface treatment agent according to the first invention.

The polyorganosiloxane constituting the surface treatment agent according to the second invention as the component (B3) has two or more alkenyl groups bonded to silicon atoms in one molecule.
In the component (B3), examples of the alkenyl group bonded to the silicon atom include a vinyl group, an allyl group, a butynyl group, and a hexenyl group.
In addition, as silicon atom bonding groups other than alkenyl groups, alkyl groups such as methyl, ethyl and propyl groups, aryl groups such as phenyl groups, 3,3,3-trifluoropropyl groups, 2-phenylethyl groups, 2 -Substituted hydrocarbon groups such as a cyanoethyl group can be exemplified.
The alkenyl group-containing form in the component (B3) is not particularly limited. For example, in the case of a linear polyorganoalkyloxane, it is bonded to a terminal and / or a side chain, and in the case of a cyclic polyorganosiloxane, a side chain. In the branched polyorganosiloxane, there may be mentioned those bonded to the terminal and / or side chain.

  The viscosity (25 ° C.) of the component (B3) is preferably 1 cSt or more, more preferably 10 to 10,000,000 cSt, particularly preferably 50 to 2,000,000 cSt. When the viscosity of the component (B3) exceeds 10,000,000 cSt, or when the component (B3) is solid, it is preferable to dilute or dissolve the component (B3) with an organic solvent.

Examples of the polyorganohydrogensiloxane constituting the surface treatment agent according to the second invention as the component (B2) include the same compounds as those constituting the surface treatment agent according to the first invention.
In the second invention, the polyorganohydrogensiloxane as component (B2) undergoes a dehydrogenative condensation reaction with a specific fluorine-containing compound as component (A) and undergoes a hydrosilylation reaction with component (B3) to produce a three-dimensional A cured film having a network structure (crosslinked structure) is formed.
Furthermore, the polyorganohydrogensiloxane as the component (B2) reacts with the OH group present on the surface of the base material (for example, the OH group of the inorganic filler in the case of using rubber as the base material), thereby reacting to the base material. Adhesion can be improved.

  As usage-amount of (B2) component in 2nd invention, it is preferable that it is 0.1-100 mass parts with respect to 100 mass parts of (B3) component, More preferably, it is 1-50 mass parts, More preferably, 3 to 20 parts by mass. When the amount of the component (B2) used [ratio to the component (B3)] is too small, it may not be possible to form a film completely cured by the obtained surface treatment agent, and sufficient film characteristics may not be obtained. In addition, the curing reaction may take a long time. On the other hand, when the amount of component (B2) used is excessive, the film formed by the resulting surface treatment agent becomes soft and exhibits tackiness, which is not preferable.

The curing catalyst constituting the surface treatment agent according to the second invention as the component (C2) is a platinum-based catalyst that promotes the hydrosilylation reaction between the component (B3) and the component (B2). Specifically, chloroplatinic acid, an alcohol solution of chloroplatinic acid, Lamorro's catalyst (platinum-octanol complex, US Pat. No. 474337), Ashby's catalyst (platinum-vinyl group-containing cyclic siloxane complex, US Pat. No. 4,288,345) ), Karlstedt catalyst (platinum-vinyl group-containing disiloxane complex, US Pat. No. 3,814,730), and the like.
The amount of the component (C2) used is a so-called catalytic amount, and specifically, it is preferably 2 ppm to 1000 ppm as platinum with respect to the component (B3), more preferably 5 to 30 ppm.

(D) As an organic solvent which comprises the surface treating agent which concerns on 2nd invention as a component, the same compound as what comprises the surface treating agent which concerns on 1st invention can be mentioned.
Moreover, the usage-amount of (D) component is also comparable as the usage-amount in the surface treating agent which concerns on 1st invention.

As the silane coupling agent that can be contained in the surface treatment agent of the present invention (first invention / second invention) as the component (E), the formula: Si (OR ² ) _q R ³ _3-q- ( CH ₂ ) _r —R ⁴ (wherein R ² represents an alkyl group or an alkoxy group, R ³ represents an alkyl group, q is an integer of 1 to 3, preferably 3, and r is 0 to 5) It is an integer, and R ⁴ represents an organic functional group.)

The group represented by —Si (OR ² ) _q R ³ _3-q possessed by the silane coupling agent is the group represented by —Si (OR ¹ ) ₃ possessed by the specific fluorine-containing compound, or Si possessed by the component (B1). Reactive with -OH group and Si-H group of component (B2).
The organic functional group (R ⁴ ) of the silane coupling agent has reactivity with a base material made of an organic material (for example, a polymer main chain of the rubber when rubber is used as the base material).
As a result, according to the obtained surface treatment agent, it is possible to form a surface treatment layer (coating layer / modified layer) having excellent adhesion to a substrate made of an organic material.
Examples of the organic functional group (R ⁴ ) include an epoxy group, an amino group, a mercapto group, and a vinyl group.

  Specific examples of the silane coupling agent that can be used as the component (E) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylethoxysilane, 3,4-epoxycyclohexyltrimethoxysilane, 3,4-epoxycyclohexyltriethoxysilane, and γ-oxetanylpropyltrimethoxysilane Epoxy silane coupling agents, acrylic silane coupling agents such as γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. Lucapto silane coupling agent, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) -γ -Amino silane coupling agents such as aminopropyltriethoxysilane, chlorinated alkyl silane coupling agents such as γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane and γ-chloropropylmethyldiethoxysilane; Vinyl-based silane coupling agents such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane and vinyldimethylethoxysilane, methyltrimethoxy Run, and the like alkyl-based silane coupling agents such as methyl triethoxysilane, dimethyl dimethoxysilane and dimethyl diethoxy silane.

As the acid catalyst that can be contained in the surface treating agent of the present invention (first invention / second invention) as the component (F), inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid, propionic acid, Mention may be made of organic acids such as butanoic acid and pentanoic acid.
An acid catalyst is contained to make an acidic (pH of 6 or less, particularly 2 to 5) surface treatment agent, whereby (A) component having a group represented by -Si (OR ¹ ) ₃ , Si-OH group a component (B1), Si-H containing the group (B2) component and -Si (oR ²⁾ _q a R ³ _3-q silane coupling agent having a group represented by may be efficiently reacted.

<Content ratio>
In the surface treatment agent according to the first invention, when the content of the component (A) is a, the content of the component (B1) is b1, the content of the component (B2) is b2, and the content of the component (E) is e , A / (b1 + b2 + e) is preferably 1.0 to 4.5, more preferably 1.3 to 3.9, and particularly preferably 2.6 to 3.9.

  In the surface treatment agent according to the second invention, the content of the component (A) is a, the content of the component (B3) is b3, the content of the component (B2) is b2, and the content of the component (E) is e. In this case, the value of a / (b3 + b2 + e) is preferably 1.0 to 4.5, more preferably 1.4 to 3.9, and particularly preferably 2.5 to 3.9.

  When the value of a / (b1 + b2 + e) or a / (b3 + b2 + e) is 1.0 to 4.5, fluorine atoms and silicon atoms are introduced into the crosslinked structure in a balanced manner in the surface treatment layer to be formed. Further, super water repellency with a contact angle with water of 120 ° or more can be reliably imparted.

The surface treating agent of the present invention is suitable for treating the surface of rubber.
Moreover, according to the surface treatment agent of the present invention containing a silane coupling agent, a surface treatment layer (water repellency imparting layer) excellent in durability (solvent resistance) can be formed on the rubber surface. The desired super water repellency is sufficiently exhibited even after the organic solvent is brought into contact with the rubber product treated with the surface treating agent of the present invention.
Of course, the surface treating agent of the present invention can also be applied to the surface of a substrate other than rubber (eg, resin, fiber, glass, metal).

<Surface treatment method>
The surface treatment method of the present invention comprises a step of applying the surface treatment agent of the present invention to the rubber surface (hereinafter referred to as “coating step”) and a step of heating the coating film with the surface treatment agent (hereinafter referred to as “heating step”). Including).

  In the application step, the method for applying the surface treatment agent of the present invention to the rubber surface is not particularly limited, such as a spray method, a dipping method, or a method using an application means such as a brush or a roller.

In addition, after completion | finish of this application | coating process, in order to remove a solvent from the coating film formed on the surface of rubber | gum, it is preferable to perform a drying process.
In the heating step, the method for heating the coating film is not particularly limited, such as heating with an oven or heating with a hot press. The heating condition is, for example, 80 to 200 ° C. for 5 minutes to 2 hours, preferably 100 to 150 ° C. for 10 to 60 minutes.

  Dehydration condensation reaction of component (A) and component (B1) by heating the coating film by the surface treatment agent according to the first invention applied to the surface of the rubber to be processed, A dehydrogenation condensation reaction with the component (B2) and a dehydrogenation condensation reaction with the component (B1) and the component (B2) occur, and a crosslinked structure (cured film) in which fluorine atoms and silicon atoms are introduced is formed.

  Further, when the silane coupling agent as the component (E) is contained in the surface treatment agent, the dehydration condensation reaction between the component (E) and the component (A), the component (E) and the component (B1) The dehydration condensation reaction with the component, the dehydrogenation condensation reaction between the component (E) and the component (B2), the reaction between the component (E) (organic functional group) and the molecular chain of the rubber occurs, Excellent adhesion to rubber.

  Dehydrogenation condensation reaction between component (A) and component (B2) by heating the coating film of the surface treatment agent according to the second invention applied to the surface of the rubber that is the object to be treated, component (B3) And a (B2) component undergo a hydrosilylation reaction to form a crosslinked structure (cured film) in which fluorine atoms and silicon atoms are introduced.

  Further, when the silane coupling agent as the component (E) is contained in the surface treatment agent, the dehydration condensation reaction between the component (E) and the component (A), the component (E) and the component (B2) A dehydrogenative condensation reaction with the component, a reaction between the component (E) (organic functional group) and the molecular chain of the rubber occurs, and the formed cured film has excellent adhesion to the rubber.

  The rubber product surface-treated with the surface treating agent (treatment method) of the present invention is a rubber product surface-treated with a specific fluorine-containing compound (Comparative Example 2 described later), (B1) component, (B2) component, ( C1) Rubber products surface-treated with reactive silicone containing component (Comparative Example 3 and Comparative Example 4 to be described later), (B3) component, (B2) component, surface treated with reactive silicone containing component (C2) Super water-repellent properties (contact angle with water of 120 ° or more) that cannot be obtained with rubber products (Comparative Examples 5 and 6 described later) can be obtained.

  Moreover, the surface treatment layer formed by the surface treatment agent of the present invention containing the component (E) has various chemical solvents that are excellent in chemical stability and are good solvents for specific fluorine-containing compounds and silicone resins. [For example, it becomes insoluble or hardly soluble in methanol, ethanol, tetrahydrofuran, dichloromethane, chloroform, benzene, ethyl acetate, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), toluene, acetone). As a result, even when an organic solvent is brought into contact with the rubber product (surface treatment layer) surface-treated with the surface treatment agent of the present invention, a part of the surface treatment layer does not elute, and the super-water-repellent property imparted thereby Is not substantially impaired.

  Examples of the present invention will be described below, but the present invention is not limited thereto. In the following, “part” means “part by mass”.

<Example 1>
According to the formulation shown in Table 1 below, 200 parts of component (A) comprising a specific fluorine-containing compound represented by the following formula (1) and polyorganosiloxane having both ends blocked with Si-OH groups (B1 100 parts of component), 3.3 parts of component (B2) made of polyorganohydrogensiloxane, 10 parts of component (C1) made of curing catalyst, 50 parts of component (E) made of silane coupling agent, and 0.1 N 40 parts of the component (F) made of hydrochloric acid is added to 2000 parts of toluene as the component (D), and the system is stirred at room temperature for 1 hour, whereby the surface according to the present invention (first invention) is obtained. A treating agent (a / (b1 + b2 + e) = 1.3) was produced.

(In the formula, x ′ is 2 or 3, the proportion of x ′ = 2 is 6% by mass, and the proportion of x ′ = 3 is 94% by mass.)

  The surface treatment agent of the present invention produced as described above (immediately after completion of the stirring operation for 1 hour) was spray-coated on the surface of a rubber plate (80 mm × 80 mm) made of EPDM that had been subjected to alcohol cleaning and static electricity removal. (Application amount = 3 mL). Next, the rubber plate is allowed to stand at room temperature to dry the coating film, and then heat-treated in an oven at 150 ° C. for 10 minutes to form a surface treatment layer (cured film) by the surface treatment agent of the present invention. A rubber plate was obtained.

<Examples 2 to 5>
According to the formulation shown in Table 1 below, the surface treatment agent according to the present invention (first invention) was produced in the same manner as in Example 1 except that the addition amount of the component (A) was changed, and the surface treatment obtained A rubber plate having a surface treatment layer formed of the surface treatment agent of the present invention was obtained in the same manner as in Example 1 except that each of the agents was applied.

<Example 6>
According to the prescription shown in Table 1 below, the amount of component (A) added was changed to 250 parts, and component (E) was not added to the present invention (first invention) in the same manner as in Example 1. In the same manner as in Example 1 except that the surface treatment agent (a / (b1 + b2 + e) = 2.4) was produced and the obtained surface treatment agent was applied, the surface treatment layer by the surface treatment agent of the present invention was used. A formed rubber plate was obtained.

<Comparative Example 1>
A rubber plate (80 mm × 80 mm) made of EPDM subjected to alcohol washing and static electricity removal was prepared. This comparative example 1 is a comparative example in which the rubber plate is not treated with the surface treatment agent.

<Comparative example 2>
According to the formulation shown in Table 1 below, except that 400 parts of a specific fluorine-containing compound was added to 2000 parts of toluene, a surface treatment agent was produced in the same manner as in Example 1 and this surface treatment agent was applied. In the same manner as in Example 1, a rubber plate on which a surface treatment layer with a surface treatment agent for comparison was formed was obtained.
This comparative example 2 is a comparative example processed with the surface treating agent manufactured without including the component (B1), the component (B2), the component (C1), the component (E) and the component (F).

<Comparative Example 3>
According to the prescription shown in Table 1 below, 100 parts of (B1) component, 3.3 parts of (B2) component, 10 parts of (C1) component, and 50 parts of (E) component were added to 2000 parts of toluene. A rubber plate on which a surface treatment layer was formed with a comparative surface treatment agent in the same manner as in Example 1 except that the surface treatment agent was produced in the same manner as in Example 1 and this surface treatment agent was applied. Got.
This comparative example 3 is a comparative example which processed with the surface treating agent manufactured without containing (A) component and (F) component.

<Comparative example 4>
According to the prescription shown in Table 1 below, the same procedure as in Example 1 was conducted except that 100 parts of (B1), 3.3 parts of (B2), and 10 parts of (C1) were added to 2000 parts of toluene. A rubber plate on which a surface treatment layer with a surface treatment agent for comparison was formed was obtained in the same manner as in Example 1 except that the surface treatment agent was produced and the surface treatment agent was applied.
This comparative example 4 is a comparative example which processed with the surface treating agent manufactured without containing (A) component, (E) component, and (F) component.

<Example 7>
In accordance with the formulation shown in Table 2 below, 200 parts of component (A) composed of a specific fluorine-containing compound, 100 parts of component (B3) composed of polyorganosiloxane blocked at both ends with vinyl groups, and polyorganohydrogensiloxane (B2) component 9.4 parts, (C2) component 0.2 parts comprising a curing catalyst, (E) component 30 parts comprising a silane coupling agent, and (N) hydrochloric acid (F) 40 Is added to 2000 parts of toluene which is the component (D), and this system is stirred at room temperature for 1 hour, whereby the surface treatment agent (a / (b3 + b2 + e) = 1.4) was produced.
A rubber plate having a surface treatment layer (cured film) formed by the surface treatment agent of the present invention was obtained in the same manner as in Example 1 except that the obtained surface treatment agent was applied.

<Examples 8 to 11>
According to the formulation shown in Table 2 below, the surface treatment agent according to the present invention (second invention) was produced in the same manner as in Example 7 except that the addition amount of the component (A) was changed, and the surface treatment obtained. A rubber plate having a surface treatment layer formed of the surface treatment agent of the present invention was obtained in the same manner as in Example 1 except that each of the agents was applied.

<Example 12>
According to the prescription shown in Table 2 below, the amount of component (A) added was changed to 270 parts, and component (E) was not added to the present invention (second invention) in the same manner as in Example 7. The surface treatment layer by the surface treatment agent of the present invention was prepared in the same manner as in Example 1 except that the surface treatment agent (a / (b3 + b2 + e) = 2.5) was produced and the obtained surface treatment agent was applied. A formed rubber plate was obtained.

<Comparative Example 5>
In accordance with the formulation shown in Table 2 below, 100 parts of (B3) component, 9.4 parts of (B2) component, 0.2 part of (C2) component and 30 parts of (E) component are added to 2000 parts of toluene. A surface treatment agent was produced in the same manner as in Example 7 except that the surface treatment layer was formed with a comparative surface treatment agent in the same manner as in Example 1 except that this surface treatment agent was applied. A rubber plate was obtained.
This comparative example 5 is a comparative example processed with the surface treating agent manufactured without including the component (A) and the component (F).

<Comparative Example 6>
Example 7 except that 100 parts of (B3) component, 9.4 parts of (B2) component, and 0.2 part of (C2) component were added to 2000 parts of toluene according to the formulation shown in Table 2 below. Similarly, a surface treatment agent was produced, and a rubber plate on which a surface treatment layer with a surface treatment agent for comparison was formed was obtained in the same manner as in Example 1 except that this surface treatment agent was applied.
This comparative example 6 is a comparative example which processed with the surface treating agent manufactured without containing (A) component, (E) component, and (F) component.

<Evaluation>
(1) Water repellency (initial value):
About each of the rubber plate surface-treated by Examples 1-12 and Comparative Examples 1-6, about 0.05 cc of water droplets were put on the treated surface, and the contact angle after 5 minutes from dropping was made by ERMA. The contact angle to water was measured using a G-1-1000 type goniometer. The results are also shown in Table 1 below.

(2) Water repellency (after solvent cleaning):
About each of the rubber plate surface-treated by Examples 1-12 and Comparative Examples 1-6, after performing ultrasonic cleaning for 1 hour in methanol, the contact angle with respect to water is measured like said (1). did. The results are also shown in Table 1 below.

* 1 (Specific fluorine-containing compounds):
-Specific fluorine-containing compound represented by the above formula (1) * 2 (Si-OH group both end-blocked polyorganosiloxane):
A 1: 1 (mass) mixture of one with a viscosity (25 ° C.) of 5 million cSt and 3000 cSt.
* 3 (Polyorganohydrogensiloxane):
-Polymethylhydrogensiloxane having a polymerization degree of about 50 with both ends blocked with trimethylsiloxy groups. The hydrogen content (measured by the volume of hydrogen gas generated by adding alkali to polyorganosiloxane) was 57 mol% in terms of (CH ₃ ) ₂ HSiO _1/2 units.
* 4 (Curing catalyst):
・ Dibutyltin diacetate * 5 (Silane coupling agent):
・ Γ-Glycidoxypropyltrimethoxysilane

* 1 (Specific fluorine-containing compounds):
-Specific fluorine-containing compound represented by the above formula (1) * 3 (polyorganohydrogensiloxane):
-Polymethylhydrogensiloxane having a polymerization degree of about 50 with both ends blocked with trimethylsiloxy groups. The hydrogen content (measured by the volume of hydrogen gas generated by adding alkali to polyorganosiloxane) was 57 mol% in terms of (CH ₃ ) ₂ HSiO _1/2 units.
* 5 (Silane coupling agent):
・ Γ-Glycidoxypropyltrimethoxysilane * 6 (vinyl group-blocked polyorganosiloxane):
A polyorganosiloxane having a viscosity (25 ° C.) of 5200 cSt, represented by the formula: CH ₂ ═CH— [Si (CH ₃ ) ₂ O] _n —CH═CH ₂ .
* 7 (Curing catalyst):
-Ashby's catalyst (Pt 1.8%)

  The surface treating agent of the present invention can impart super water repellency to the surface of various substrates including the surface of rubber. The rubber product obtained by the surface treatment method of the present invention is suitably used as a power connection component (power cable connection component).

Claims (9)

(A) a fluorine-containing compound represented by the following general formula (I);
(B1) a polyorganosiloxane having both ends blocked with Si-OH groups;
(B2) a polyorganohydrogensiloxane having two or more Si-H groups in one molecule;
(C1) a curing catalyst;
(D) A surface treatment agent comprising an organic solvent.

(Wherein, R _F represents a group having a fluoroalkyl group, R ¹ represents an alkyl group or an alkoxy group, x is an integer of 1 to 100.) (A) a fluorine-containing compound represented by the following general formula (I);
(B3) a polyorganosiloxane having two or more alkenyl groups bonded to a silicon atom in one molecule;
(B2) a polyorganohydrogensiloxane having two or more Si-H groups in one molecule;
(C2) a platinum-based curing catalyst;
(D) A surface treatment agent comprising an organic solvent.

(Wherein, R _F represents a group having a fluoroalkyl group, R ¹ represents an alkyl group or an alkoxy group, x is an integer of 1 to 100.)   Furthermore, (E) Silane coupling agent is contained, The surface treating agent of Claim 1 or Claim 2 characterized by the above-mentioned. (A) The content of the fluorine-containing compound represented by the general formula (I) is a,
(B1) The content of polyorganosiloxane having both ends blocked with Si-OH groups is b1,
(B2) The content of polyorganohydrogensiloxane having two or more Si—H groups in one molecule is b2,
(E) When the content of the silane coupling agent is e,
The surface treatment agent according to claim 1 or 3, wherein a / (b1 + b2 + e) has a value of 1.0 to 4.5. (A) The content of the fluorine-containing compound represented by the general formula (I) is a,
(B3) The content of polyorganosiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule is b3,
(B2) The content of polyorganohydrogensiloxane having two or more Si—H groups in one molecule is b2,
(E) When the content of the silane coupling agent is e,
The surface treatment agent according to claim 2 or 3, wherein a / (b3 + b2 + e) has a value of 1.0 to 4.5.   The surface treatment agent according to any one of claims 1 to 5, further comprising (F) an acid catalyst.   The surface treating agent according to any one of claims 1 to 6 for treating the surface of rubber.   A rubber surface treatment method comprising a step of applying the surface treatment agent according to claim 7 to a rubber surface, and a step of heating a coating film by the surface treatment agent.   A rubber product treated with the surface treating agent according to claim 7 and having a contact angle with water of 120 ° or more.