Surface treatment agent, elastomer article, and surface treatment method

Abstract

To provide a surface treatment agent which enables formation of a surface treatment layer that has non-stickiness on an elastomer surface such as a rubber, and can follow expansion and contraction of the rubber or the like.SOLUTION: A surface treatment agent is composed of two liquids of a first surface treatment liquid containing a modified polyolefin-based resin, and a second surface treatment liquid containing a fluorine-containing compound represented by formula (1), two kinds of different silane coupling agents, an acid catalyst and an alcohol-based solvent, wherein one kind of the silane coupling agents is tetraethoxysilane. In formula (1), R1 represents a group containing a fluoroalkyl group, R2 represents an alkyl group or an alkoxyalkyl group, R3 and R4 each independently represents a hydrogen atom or a monovalent organic group, x is an integer of 1 to 100, and y is an integer of 0-100.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a surface treatment agent, an elastomer article, and a surface treatment method. [Background technology]

[0002] Certain fluorine-based compounds are known to impart excellent surface properties such as water repellency, oil repellency, non-stick properties, and antifouling properties when used in surface treatment of substrates. Surface treatment layers formed by surface treatment agents containing such fluorine-based compounds are provided as functional thin films, such as antifouling layers, on a wide variety of substrates, including glass, plastics, fibers, and building materials (see Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2014-196432 [Overview of the project] [Problems that the invention aims to solve]

[0004] There is a need to apply the above-mentioned fluorine-based compounds to elastomers such as rubber to provide surface properties such as water repellency to the elastomer surface, as well as to improve the non-stick properties of the elastomer surface. On the other hand, there is a problem that cracks may occur in the surface treatment layer using the above-mentioned fluorine-based compounds as the elastomer expands and contracts. Therefore, there is a need for a surface treatment agent that can improve the non-stick properties of the elastomer surface and form a surface treatment layer that also has conformability.

[0005] In view of the above problems, the present invention aims to provide a surface treatment agent and a surface treatment method that can form a non-adhesive surface treatment layer on the surface of an elastomer such as rubber that can follow the expansion and contraction of rubber, and an elastomer article having such a surface treatment layer. [Means for solving the problem]

[0006] To solve the above problems, the present invention comprises two liquids: a first surface treatment liquid containing a modified polyolefin resin, and a second surface treatment liquid containing a fluorine-containing compound represented by the following formula (1), two different silane coupling agents, an acid catalyst, and an alcohol-based solvent, wherein one of the silane coupling agents is tetraethoxysilane. It is used for surface treatment of elastomer surfaces. The present invention provides a surface treatment agent characterized by the following:

[0007] [ka] In the above equation (1), R 1 R represents a group containing a fluoroalkyl group. 2 R represents an alkyl group or alkoxyalkyl group, 3 and R 4 Each of these independently represents a hydrogen atom or a monovalent organic group, x is an integer from 1 to 100, and y is an integer from 0 to 100.

[0008] As the alcohol-based solvent, methanol or ethanol may be used; the silane coupling agent comprises a first silane coupling agent which is tetraethoxysilane and a second silane coupling agent, the second silane coupling agent may be 3-aminopropyltrimethoxysilane or 3-mercaptopropyltrimethoxysilane; as the acid catalyst, 6 to 12 mol / L hydrochloric acid may be used; and the modified polyolefin resin may be a hydroxyl-modified polyolefin resin or an acid-modified polyolefin resin. If, when an elastomer sheet having been surface-treated with the first surface treatment liquid to form a first surface treatment layer, and then surface-treated with the second surface treatment liquid to form a second surface treatment layer on the first surface treatment layer, is stretched in one direction to 50% of its area, no cracks appear in the second surface treatment layer, then good.

[0009] In equation (1) above, y may be 0, and R 1 The group containing the fluoroalkyl group represented by may also be the group represented by the following formula (2), R 2 x may be a methyl group, and in formula (1) above, x may be an integer from 1 to 10.

[0010] [Chemical formula] In the above formula (2), p is an integer from 0 to 2.

[0011] The present invention provides an elastomeric article comprising a base having an elastomeric surface and a surface treatment layer covering at least a part of the elastomeric surface of the base, wherein the surface treatment layer consists of a first surface treatment layer containing a modified polyolefin resin and a second surface treatment layer containing at least a fluorine-containing compound represented by the following formula (1), and the first surface treatment layer and the second surface treatment layer are laminated in this order from the elastomeric surface.

[0012] [Chemical formula] In the above formula (1), R 1 represents a group containing a fluoroalkyl group, R 2 represents an alkyl group or an alkoxyalkyl group, R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic group, x is an integer from 1 to 100, and y is an integer from 0 to 100.

[0013] The present invention provides a surface treatment method for performing surface treatment of a substrate to be treated using the above surface treatment agent, the method including a step of forming a first surface treatment layer by applying the first surface treatment liquid to the surface of the substrate to be treated, and a step of forming a second surface treatment layer by spray-applying the second surface treatment liquid to the first surface treatment layer, wherein the first surface treatment layer is formed by immersing the substrate to be treated in the first surface treatment liquid or by spray-applying the first surface treatment liquid to the surface of the substrate to be treated. Having an elastomer surface The elastomer

[0014] ​​The volume ratio of the amount of the first surface treatment liquid applied by spray coating to the amount of the second surface treatment liquid applied should be within the range of 3:1 to 1:3. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a surface treatment agent and a surface treatment method that can form a non-adhesive surface treatment layer on the surface of an elastomer such as rubber, which is capable of following the expansion and contraction of rubber, and an elastomer article having such a surface treatment layer. [Modes for carrying out the invention]

[0016] Let me describe one embodiment of the present invention. [Surface treatment agent] The surface treatment agent according to this embodiment is a two-component surface treatment agent comprising a first surface treatment liquid and a second surface treatment liquid, and is particularly suitable for surface treatment of elastomers such as rubber. The first surface treatment liquid is used to form a first surface treatment layer that functions as a primer layer on the surface of an elastomer such as rubber, and the second surface treatment liquid is used to form a second surface treatment layer that functions as a functional layer (e.g., a water-repellent layer, a non-stick layer, etc.) on the primer layer.

[0017] The first surface treatment solution contains a modified polyolefin resin and a solvent. Modified polyolefin resins are obtained by subjecting a polyolefin resin, used as a precursor, to a modification treatment using a modifying agent having functional groups, and are polyolefin resins having functional groups. Examples of modified polyolefin resins include hydroxyl group-modified polyolefin resins and acid-modified polyolefin resins. Examples of these hydroxyl group-modified polyolefin resins and acid-modified polyolefin resins that are commercially available include Unistoll® P-801, Unistoll® XP03F, and Unistoll® XP04A (all manufactured by Mitsui Chemicals, Inc.), and these can be used.

[0018] The polyolefin resin used as a precursor may be a polymer composed solely of repeating units derived from olefin monomers, or it may be a copolymer having repeating units derived from olefin monomers along with repeating units derived from monomers other than olefin monomers.

[0019] Examples of the polyolefin resins mentioned above include homopolymers and copolymers of olefins having 2 to 8 carbon atoms, and copolymers of olefins having 2 to 8 carbon atoms with other monomers. Specifically, examples include polyethylene such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene resin, polypropylene, polyisobutylene, poly(1-butene), poly-4-methylpentene, polyvinylcyclohexane, polystyrene, poly(p-methylstyrene), poly(α-methylstyrene), α-olefin copolymers such as ethylene-propylene block copolymer, ethylene-propylene random copolymer, ethylene-butene-1 copolymer, ethylene-4-methyl-1-pentene copolymer, and ethylene-hexene copolymer, as well as ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate-methyl methacrylate copolymer, and ionomer resins.

[0020] Modifiers used to obtain hydroxyl-modified polyolefin resins include, for example, hydroxyl-containing (meth)acrylic acid esters such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycerol (meth)acrylate, lactone-modified hydroxyethyl (meth)acrylate, polyethylene glycol (meth)acrylate, and polypropylene glycol (meth)acrylate; and hydroxyl-containing vinyl ethers such as 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinyl ether.

[0021] The modifier used to obtain the acid-modified polyolefin resin may be any compound having a functional group in its molecule that can contribute to the crosslinking reaction described later. Examples of functional groups that can contribute to the crosslinking reaction include carboxyl groups, groups derived from carboxylic acid anhydrides, carboxylic acid ester groups, hydroxyl groups, epoxy groups, amide groups, ammonium groups, nitrile groups, amino groups, imide groups, isocyanate groups, acetyl groups, thiol groups, ether groups, thioether groups, sulfone groups, phosphone groups, nitro groups, urethane groups, halogen atoms, and the like. Of these functional groups, carboxyl groups, groups derived from carboxylic acid anhydrides, carboxylic acid ester groups, hydroxyl groups, ammonium groups, amino groups, imide groups, and isocyanate groups are preferred. The modifier used to obtain the acid-modified polyolefin resin may also be a compound having two or more of the above functional groups in its molecule.

[0022] Acid-modified polyolefin resins are obtained, for example, by reacting a polyolefin resin with unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, and aconitic acid, and / or unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornenedicarboxylic acid anhydride, and tetrahydrophthalic anhydride, thereby introducing carboxyl groups and / or groups derived from carboxylic acid anhydrides (graft modification).

[0023] The weight-average molecular weight (Mw) of the modified polyolefin resin should be approximately 10,000 to 2,000,000, preferably 20,000 to 1,500,000, more preferably 25,000 to 250,000, and particularly preferably 30,000 to 150,000. The weight-average molecular weight (Mw) can be, for example, the value obtained by gel permeation chromatography (GPC) using tetrahydrofuran as the solvent, on a standard polystyrene basis.

[0024] The solvent included in the first surface treatment liquid can be any solvent capable of dissolving the modified polyolefin resin and that does not damage the elastomer, which is the target of surface treatment by the surface treatment agent according to this embodiment. For example, toluene, n-hexane, cyclohexane, methylcyclohexane, xylene, methyl ethyl ketone, methyl isobutyl ketone, etc., can be used.

[0025] In the first surface treatment solution, the content ratio (by mass) of the modified polyolefin resin to the solvent may be, for example, about 1:10 to 1:60, and preferably about 1:10 to 1:30.

[0026] The first surface treatment solution can be prepared by dissolving the modified polyolefin resin in the above-mentioned solvent, such as toluene or n-hexane.

[0027] Since the first surface treatment liquid described above is composed of a modified polyolefin resin dissolved in a solvent, it can form a first surface treatment layer that adheres to the elastomer surface and also adheres to the second surface treatment layer formed by the second surface treatment liquid described later. If the adhesion of this first surface treatment layer to the second surface treatment layer is too strong, it may adversely affect the non-stick properties exhibited by the second surface treatment layer. However, the adhesion of the first surface treatment layer to the second surface treatment layer is such that it does not adversely affect the non-stick properties exhibited by the second surface treatment layer. Furthermore, the first surface treatment liquid can form a first surface treatment layer that has good conformability to the expansion and contraction of the elastomer surface.

[0028] Primers used on elastomer surfaces are known to contain modified terpene phenol resin and mercapto-silane coupling agents. However, if the mercapto-silane coupling agent in these primers absorbs moisture (water), it will crosslink and gel. The above-mentioned first surface treatment liquid does not contain a silane coupling agent that crosslinks and gels due to moisture (water absorption), making it easy to store and allowing for stable long-term storage.

[0029] The second surface treatment solution contains a fluorine-containing compound represented by the following formula (1), two different silane coupling agents, an acid catalyst, and an alcohol-based solvent.

[0030] [ka] In formula (1), R 1 R represents a group containing a fluoroalkyl group. 2 R represents an alkyl group or alkoxyalkyl group, 3 and R 4 Each of these independently represents a hydrogen atom or a monovalent organic group, x is an integer from 1 to 100, and y is an integer from 0 to 100.

[0031] In equation (1), R 1 Examples of fluoroalkyl groups represented by include -CF3, -C2F5, -C3F7, and -C6F 13 , -C7F 15 -C etc. q F 2q+1 Examples include fluoroalkyl groups represented by (q=1~10) and oxyfluoroalkylene groups, of which the oxyfluoroalkylene group represented by the following formula (2) is preferred.

[0032] [ka] In equation (2), p is an integer between 0 and 2.

[0033] In equation (1), R 2 Examples of alkyl groups represented by R include alkyl groups having 1 to 2 carbon atoms, such as methyl groups and ethyl groups. 2 Examples of alkoxyalkyl groups represented by include alkoxyalkyl groups having 2 to 4 carbon atoms, such as methoxymethyl group, methoxyethyl group, ethoxymethyl group, and ethoxyethyl group. Among these, R 2 The group represented is preferably an alkyl group, and particularly preferably a methyl group.

[0034] In equation (1), R 3 and R 4 Examples of organic groups represented by the formulas (i) to (v) below include the groups shown in the following formulas.

[0035] [ka]

[0036] In formula (1), trialkoxysilyl group or trialkoxykoxysilyl group (-Si(OR 2 The number x of intermediate chains (-CH2-CH-) to which )3) is attached is 1 to 100, preferably 1 to 50, more preferably 1 to 10, and particularly preferably 2 to 3. Also, the intermediate chain (-CH2-CR 3 R 4 The number y (-) is between 0 and 100, preferably between 0 and 50, more preferably between 0 and 10, and most preferably 0.

[0037] Suitable compounds for the fluorine-containing compound mentioned above include those represented by formulas (3) to (7) below. In particular, if the fluorine-containing compound is a compound represented by formula (3) or formula (6) (a compound where y=0 in formula (1)), the proportion of fluorine atoms in one molecule becomes large.

[0038] [ka] In equation (3), x' is either 2 or 3.

[0039] [ka]

[0040] [ka] In equations (4) and (5), R 1’This is a base represented by -CF(CF3)OCF2CF(CF3)OC3F7. In equation (4), xa is an integer from 1 to 100. In equation (5), xb is an integer from 1 to 100, and yb is an integer from 1 to 500.

[0041] [ka] In equation (6), xc is an integer between 1 and 10, and yc is an integer between 0 and 100.

[0042] [ka] In equation (7), xd is an integer between 1 and 10, and yd is an integer between 0 and 100.

[0043] The fluorine-containing compound represented by formula (1) above is obtained by polymerizing the monomer represented by formula (Ib) below and the monomer represented by formula (Ic) below in the presence of the fluorine-containing peroxide represented by formula (Ia) below. Note that this reaction product (fluorine-containing compound) contains a group (R) containing a fluoroalkyl group. 1 The oligomer may contain oligomers in which the compound is introduced at only one end, in any proportion.

[0044] [ka] In formulas (Ia) to (Ic), R 1 R represents a group containing a fluoroalkyl group. 2 R represents an alkyl group or alkoxyalkyl group, 3 and R 4 Each of these independently represents a hydrogen atom or a monovalent organic group.

[0045] The second surface treatment solution in this embodiment includes two different silane coupling agents: a first silane coupling agent and a second silane coupling agent. For example, tetraethoxysilane (TEOS,Si(OC2H5)4) can be used as the first silane coupling agent. For example, 3-aminopropyltrimethoxysilane, (3-mercaptopropyl)trimethoxysilane, etc., can be used as the second silane coupling agent. Since the second surface treatment solution contains two different silane coupling agents (a first silane coupling agent and a second silane coupling agent), and the second silane coupling agent is particularly more reactive than the first silane coupling agent, the reactivity when forming the second surface treatment layer can be improved, so that a second surface treatment layer with good non-stick properties and conformability can be formed in a short time.

[0046] As the acid catalyst, for example, hydrochloric acid, nitric acid, etc., can be used, and hydrochloric acid is preferably used. The concentration of the acid catalyst can be, for example, 6 to 12 mol / L, and preferably around 10 to 12 mol / L. By including the acid catalyst in the second surface treatment solution, the reactivity when forming the second surface treatment layer can be improved, so that a second surface treatment layer with good non-stick properties and conformability can be formed in a short time.

[0047] As the alcohol-based solvent, for example, methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, etc. can be used, and methanol is preferably used. By including an alcohol-based solvent in the second surface treatment solution, the reactivity when forming the second surface treatment layer can be improved, so that a second surface treatment layer with good non-stick properties and conformability can be formed in a short time.

[0048] The second surface treatment solution in this embodiment can be prepared by mixing the above-mentioned fluorine-containing compound, the first silane coupling agent (TEOS), the second silane coupling agent, and an alcohol-based solvent, then adding an acid catalyst and stirring for about 10 minutes to 1 hour.

[0049] According to the second surface treatment liquid described above, a second surface treatment layer with excellent non-stick properties and conformability can be formed on the first surface treatment layer formed on the elastomer surface by the first surface treatment liquid.

[0050] [Surface treatment method] The surface treatment method in this embodiment is a surface treatment method that performs surface treatment on the surface of an elastomer substrate to be treated using a surface treatment agent according to this embodiment. The surface treatment method includes the steps of forming a first surface treatment layer by applying a first surface treatment liquid to the surface of the substrate to be treated, and forming a second surface treatment layer by spraying a second surface treatment liquid onto the first surface treatment layer.

[0051] The substrate to be treated can be any substrate whose surface to be treated with the surface treatment agent is composed of an elastomer. This may include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), chloroprene rubber (CR), butyl rubber (IIR), styrene-butadiene rubber (SBR), acrylic rubber (ACM, ANM), epichlorohydrin rubber (CO, ECO), urethane rubber (AU, EU), silicone rubber (VMQ, FVMQ), acrylonitrile butadiene rubber (NBR), ethylene propylene rubber (EPM, EPDM), fluororubber (FKM, FEPM), and rubber products (e.g., O-rings, X-rings, umbrellas, valves, etc.) composed of these elastomers (rubbers), or composites of elastomers (rubbers) with metals or resins, etc., that have an elastomer surface.

[0052] In the process of forming the first surface treatment layer, the first surface treatment liquid may be applied to the surface of the substrate to be treated by immersing the substrate in the first surface treatment liquid, or the first surface treatment liquid may be spray-applied to the surface of the substrate to be treated.

[0053] When spray-applying the first surface treatment solution to the surface of the substrate to be treated, the volume ratio of the spray-applied amount of the first surface treatment solution to the spray-applied amount of the second surface treatment solution should be approximately 3:1 to 1:3, and preferably 3:2 to 1:1. By having the volume ratio of the spray-applied amounts within the above range, a surface treatment layer with both non-stick properties and conformability can be formed.

[0054] The region in which the surface treatment layer is formed may be a part of the elastomer surface of the substrate to be treated, or it may be the entire surface.

[0055] In this embodiment, the coating film formed by applying the first surface treatment liquid and the second surface treatment liquid to the surface of the substrate to be treated may be heated. Examples of heating methods include heating in an oven and heating by a hot press, but are not particularly limited. As for heating conditions, for example, it is about 100 to 180°C for about 10 to 60 minutes, preferably about 120 to 160°C for about 10 to 30 minutes. By forming a surface treatment layer on the elastomer surface of the substrate to be treated in this way, an elastomer article can be manufactured comprising a base having an elastomer surface and a surface treatment layer (a laminate of the first surface treatment layer and the second surface treatment layer) that covers at least a part of the elastomer surface of the base.

[0056] The embodiments described above are provided to facilitate understanding of the present invention and are not intended to limit it. Accordingly, each element disclosed in the above embodiments is intended to include all design modifications and equivalents that fall within the technical scope of the present invention. [Examples]

[0057] The present invention will be described in more detail below with reference to manufacturing examples, test examples, etc., but the present invention is not limited in any way to the manufacturing examples, test examples, etc. described below.

[0058] [Manufacturing Example 1] Manufacturing Example of the First Surface Treatment Solution First surface treatment solutions (L1-1 to L1-10) were prepared by dissolving modified polyolefin resins (UNISTOL® XP03F, UNISTOL® XP04A, UNISTOL® P-801, all manufactured by Mitsui Chemicals, Inc.) in solvents (toluene (Tol), hexane (Hex)). Table 1 shows the amounts of modified polyolefin resin and solvent used in each first surface treatment solution. [Table 1]

[0059] [Manufacturing Example 2] Manufacturing Example of the Second Surface Treatment Solution The fluorine-containing compound shown in formula (5) above, a silane coupling agent (tetraethoxysilane (TEOS) as the first silane coupling agent and / or 3-aminopropyltrimethoxysilane (APTMS) or 3-mercaptopropyltrimethoxysilane (MPTMS) as the second silane coupling agent), and a solvent (methanol (MeOH), ethanol (EtOH), or acetone (Acetone)) were mixed, an acid catalyst (0.1M hydrochloric acid or 12M hydrochloric acid) was added, and the mixture was stirred for a further 10 minutes to prepare the second surface treatment solutions (L2-1 to L2-37). The amounts of the fluorine-containing compound, silane coupling agent (first silane coupling agent and / or second silane coupling agent), solvent, and acid catalyst used in each second surface treatment solution are shown in Table 2.

[0060] [Table 2]

[0061] [Manufacturing Example 3] Manufacturing Example 1 of Surface-treated Rubber Sheets Within an 8cm x 8cm square area, 2cm square rubber sheets (silicone rubber sheet (Q), acrylonitrile butadiene rubber sheet (NBR), ethylene propylene diene rubber sheet (EPDM), and fluororubber sheet (FKM)) were prepared. The first surface treatment solution (L1-1 to L1-3) prepared in Production Example 1 was spray-coated onto one side of each rubber sheet to form a first surface treatment layer. Next, the second surface treatment solution (L2-1 to L2-37) prepared in Production Example 2 was spray-coated onto the first surface treatment layer to form a second surface treatment layer. The rubber sheets with the first and second surface treatment layers (samples 1 to 47) were then baked at 150°C for 10 minutes. The types of the first and second surface treatment solutions and the amounts spray-coated are shown in Tables 3 to 7.

[0062] [Table 3]

[0063] [Table 4]

[0064] [Table 5]

[0065] [Table 6]

[0066] [Table 7]

[0067] [Manufacturing Example 4] Manufacturing Example 2 of Surface-treated Rubber Sheets Square-shaped rubber sheets measuring 2 cm on each side (silicone rubber sheet (Q), acrylonitrile butadiene rubber sheet (NBR), ethylene propylene diene rubber sheet (EPDM), and fluororubber sheet (FKM)) were prepared, and each rubber sheet was immersed in the first surface treatment solution (L1-4 to L1-10) for 1 minute to form the first surface treatment layer. Next, the second surface treatment solution (L2-22) prepared in Production Example 2 was spray-applied onto the first surface treatment layer to form the second surface treatment layer, and the rubber sheets with the first and second surface treatment layers (samples 48 to 56) were baked at 150°C for 10 minutes. The types of first surface treatment solutions and the amount of second surface treatment solution spray-applied are shown in Table 8.

[0068] [Table 8]

[0069] [Example Exam 1] TAC Exam Rubber sheets of samples 1 to 56 were mounted on a probe tack test apparatus (product name: Tacking Tester TAC-II, manufactured by Resca Co., Ltd.). A load of 100 gf was applied to the second surface treatment layer of the rubber sheet, and the probe (a cylindrical probe made of stainless steel (diameter: 5.1 mm)) was brought into contact with it for 3 seconds. Then, the probe was peeled off at a speed of 600 mm / min perpendicular to the surface of the test piece, and the force required for peeling (adhesion force, gf) was measured. The results are shown in Tables 9 to 11. Similarly, when the adhesive strength (gf) was measured for silicone rubber sheets (Q), acrylonitrile butadiene rubber sheets (NBR), ethylene propylene diene rubber sheets (EPDM), and fluororubber sheets (FKM) that did not have surface treatment layers (first surface treatment layer and second surface treatment layer), the adhesive strength of the silicone rubber sheet (Q) was 194.7 gf, the adhesive strength of the acrylonitrile butadiene rubber sheet (NBR) was 285.7 gf, the adhesive strength of the ethylene propylene diene rubber sheet (EPDM) was 486.5 gf, and the adhesive strength of the fluororubber sheet (FKM) was 387.5 gf.

[0070] [Test Example 2] Followability Test A conformability test was conducted on rubber sheets 1 to 56. This test involved stretching the rubber sheets in one direction to 25% and 50% of their area, and observing whether cracks formed in the surface treatment layer of the rubber sheets visually or using a scanning electron microscope (SEM). The results are shown in Tables 9 and 10. In the "conformability" column in Tables 9 to 11, "○" indicates that no cracks formed in the surface treatment layer by 50% stretching, "△" indicates that cracks formed in the surface treatment layer by 50% stretching, and "×" indicates that cracks formed in the surface treatment layer by 25% stretching.

[0071] [Table 9]

[0072] [Table 10]

[0073] The results shown in Tables 9 and 10 confirm that treating the surface of an elastomer (rubber) with a two-solution surface treatment agent consisting of a first surface treatment solution containing a modified polyolefin resin and a second surface treatment solution containing the fluorine-containing compound, TEOS and a different type of silane coupling agent, an acid catalyst and an alcohol-based solvent, can form a surface treatment layer with excellent non-stick properties and conformability that can follow the expansion and contraction of rubber and other materials. On the other hand, in samples 1 to 30, where the second surface treatment solution contained TEOS, APTMS, or MPTMS, i.e., contained only one type of silane coupling agent, the results were inferior in either non-stick properties or conformability.

Claims

1. A first surface treatment liquid containing a modified polyolefin resin, A second surface treatment solution containing a fluorine-containing compound represented by the following formula (1), two different silane coupling agents, an acid catalyst, and an alcohol-based solvent. It consists of two liquids, One of the silane coupling agents is tetraethoxysilane. A surface treatment agent characterized by its use in surface treatment of elastomer surfaces. 【Chemistry 1】 In the above formula (1), R １ R represents a group containing an fluoroalkyl group. ２ R represents an alkyl group or alkoxyalkyl group, ３ and R ４ Each of these independently represents a hydrogen atom or a monovalent organic group, x is an integer from 1 to 100, and y is an integer from 0 to 100.

2. The surface treatment agent according to claim 1, characterized in that the alcohol-based solvent is methanol or ethanol.

3. The silane coupling agent comprises a first silane coupling agent which is tetraethoxysilane and a second silane coupling agent. The surface treatment agent according to claim 1 or 2, characterized in that the second silane coupling agent is 3-aminopropyltrimethoxysilane or 3-mercaptopropyltrimethoxysilane.

4. The surface treatment agent according to any one of claims 1 to 3, characterized in that the acid catalyst is hydrochloric acid in a concentration of 6 to 12 mol / L.

5. The surface treatment agent according to any one of claims 1 to 4, characterized in that the modified polyolefin resin is a hydroxyl group modified polyolefin resin or an acid modified polyolefin resin.

6. The surface treatment agent according to any one of claims 1 to 5, characterized in that y is 0 in formula (1).

7. In the above formula (1), R １ The surface treatment agent according to any one of claims 1 to 6, characterized in that the group containing the fluoroalkyl group represented by is the group represented by the following formula (2). 【Chemistry 2】 In equation (2) above, p is an integer between 0 and 2.

8. In the above formula (1), R ２ The surface treatment agent according to any one of claims 1 to 7, characterized in that the group is a methyl group.

9. The surface treatment agent according to any one of claims 1 to 8, characterized in that x is an integer from 1 to 10 in formula (1).

10. The surface treatment agent according to any one of claims 1 to 9, characterized in that when an elastomer sheet, which has been surface-treated with the first surface treatment liquid to form a first surface treatment layer and has been surface-treated with the second surface treatment liquid to form a second surface treatment layer on the first surface treatment layer, is stretched in one direction to 50% of its area, no cracks occur in the second surface treatment layer.

11. A base having an elastomer surface, A surface treatment layer covering at least a portion of the elastomer surface of the base and Equipped with, The surface treatment layer comprises a first surface treatment layer containing a modified polyolefin resin and a second surface treatment layer containing at least a fluorine-containing compound represented by the following formula (1). An elastomer article characterized in that the first surface treatment layer and the second surface treatment layer are laminated in order from the elastomer surface. 【Transformation 3】 In the above formula (1), R １ represents a group containing a fluoroalkyl group, R ２ represents an alkyl group or an alkoxyalkyl group, R ３ and R ４ each independently represent a hydrogen atom or a monovalent organic group, x is an integer from 1 to 100, and y is an integer from 0 to 100.

12. A surface treatment method for performing surface treatment on a substrate having an elastomer surface using a surface treatment agent according to any one of claims 1 to 10, The process involves applying the first surface treatment liquid to the elastomer surface of the substrate to be treated to form a first surface treatment layer, The process involves spraying the second surface treatment liquid onto the first surface treatment layer to form a second surface treatment layer. Includes, A surface treatment method characterized by forming the first surface treatment layer by immersing the substrate to be treated in the first surface treatment liquid, or by spraying the first surface treatment liquid onto the surface of the substrate to be treated.

13. The surface treatment method according to claim 12, characterized in that the volume ratio of the amount of the first surface treatment liquid applied by spray application to the amount of the second surface treatment liquid applied is within the range of 3:1 to 1:3.

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