JP2017074778A - Crosslinked fluorine-containing polystyrene derivative coating film, crosslinking group-containing fluorine-containing polystyrene derivative, composite material and crosslinking resin composition solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crosslinking resin composition, a crosslinked coating film and the like, which exhibit excellent biosafety, stability and adhesiveness to a base material and can impart excellent surface characteristics (water and oil repellency and optical characteristics) equal to or more than those of a (meth)acrylate polymer material containing a perfluoroalkyl group having 6 to 8 carbon atoms to the base material.SOLUTION: A crosslinked fluorine-containing polystyrene derivative coating film produced by coating a base material with the following crosslinking resin composition and then crosslinking the composition has excellent surface characteristics (water and oil repellency and optical characteristics), adhesiveness, stability and the like. The crosslinking resin composition comprises a crosslinking group-containing fluorine-containing derivative containing a repeating unit represented by formula [1] by 1 mass% or more and a crosslinking group-containing repeating unit by 1 mass% or more.SELECTED DRAWING: None

Description

  The present invention relates to a crosslinked fluorine-containing polystyrene derivative coating film, a crosslinking group-containing fluorine-containing polystyrene derivative, a composite material, and a crosslinkable resin composition solution.

  Fluorine-based materials are widely used in the coating field and the like because they have water and oil repellency and high heat resistance. In such a field, from the viewpoint of excellent water and oil repellency, a fluorine-based polymer having a fluoroalkyl group having 8 or more carbon atoms is often used as an active ingredient (see, for example, Patent Document 1).

  In particular, (meth) acrylic acid ester-based polymers having a perfluoroalkyl group having 8 or more carbon atoms have been used as industrial water and oil repellents. However, when a (meth) acrylic acid ester polymer having a perfluoroalkyl group having 8 or more carbon atoms is decomposed, perfluorooctanoic acid (hereinafter referred to as PFOA) may be generated. In recent years, PFOA has been studied for products, materials, processes, and the like to replace fluoropolymers having a perfluoroalkyl group having 8 or more carbon atoms because there is a concern about accumulation in a living body.

  In recent years, as a water / oil repellent agent that replaces a (meth) acrylic acid ester polymer having a perfluoroalkyl group having 8 or more carbon atoms, a (meth) acrylic acid ester system having a perfluoroalkyl group having 6 carbon atoms or less. Polymers have been proposed. However, when a known fluorine-based material having a perfluoroalkyl group having 6 or less carbon atoms is used in the coating field, compared with the case of using a fluorine-based polymer having a perfluoroalkyl group having 8 or more carbon atoms. The water and oil repellency imparted to the substrate is poor. In addition, the (meth) acrylic acid ester polymer having a long-chain perfluoroalkyl group having 6 or 8 or more carbon atoms as described above has insufficient stability such as heat resistance, moisture resistance or weather resistance. It also has the problem of being. Therefore, it has been desired to develop a new material that drastically solves the above-mentioned problems of conventional long-chain perfluoroalkyl group-containing (meth) acrylic acid ester-based polymers having 6 or 8 carbon atoms.

  The following polymers as water / oil repellents that have a structure different from that of (meth) acrylic acid ester-based polymers having a long-chain perfluoroalkyl group and do not generate PFOA even when decomposed: Has been reported.

  Patent Document 2 discloses a water / oil repellent comprising a polymer in which a perfluoropolyether group-containing alcohol chain is linked to a (meth) acrylic acid polymer skeleton via an ester bond. However, since the polymer has an ester bond, there is a problem that stability such as heat resistance, moisture resistance or weather resistance is insufficient.

  Patent Document 3 discloses a modified polystyrene resin in which a perfluoropolyether chain is directly bonded to an aromatic nucleus of polystyrene. However, since the perfluoropolyether group-containing peroxide having the same number of moles as the perfluoropolyether chain to be introduced is used for the synthesis of the polymer, industrial mass production is difficult due to safety and economic concerns. It is.

Patent Document 4 discloses a fluorine-containing polystyrene resin in which a polyfluoro (poly) ether chain (that is, a polyfluoropolyether chain and a polyfluoroether chain) is bonded to an aromatic nucleus of polystyrene via an ether bond. Yes. However, since the fluorine-containing polystyrene resin is a soft material having a glass transition temperature of room temperature or lower and its surface is sticky, it is difficult to use it as a molding material or a coating film material. Patent Document 4 discloses various properties required for the coating film of fluorine-containing polystyrene (that is,
No specific data regarding surface characteristics (water / oil repellency, surface hardness), stability (heat resistance, moisture resistance, weather resistance, etc.) or adhesion to various substrates is shown.

JP 2006-299016 A JP-A-63-42954 JP-A-5-78419 JP-A-2-103210

  A (meth) acrylic acid ester-based polymer having a perfluoroalkyl group having 8 or more carbon atoms may generate perfluorooctanoic acid (PFOA) that is harmful to the human body. (Meth) acrylic acid ester polymers having a perfluoroalkyl group of 6 or less have been proposed. However, this alternative material is not sufficient in water and oil repellency, and in the same way as a (meth) acrylic acid ester-based polymer having a long-chain perfluoroalkyl group having 8 or more carbon atoms, heat resistance and moisture resistance. There is also an essential problem that stability such as stability or weather resistance is insufficient. Furthermore, when a base material (particularly an organic material base material) is coated with a (meth) acrylic acid ester polymer having a perfluoroalkyl group having 6 or 8 carbon atoms, the adhesion to the base material is extremely high. It also has an essential problem as a coating material that is low.

  Therefore, in the coating field, etc., development of a new material that drastically solves the above problems of long chain perfluoroalkyl group-containing (meth) acrylic acid ester-based polymers having 6 or 8 carbon atoms. Was desired.

  The present invention has been completed based on the above circumstances, and is a cross-linked coating film (cross-linked fluorine-containing polystyrene derivative coating) that can stably provide sufficient water and oil repellency to a substrate for a long period of time. Film), and a composite material formed by coating a substrate with the crosslinked coating film.

The present inventor has studied the properties of various polystyrene resins to which polyfluoro (poly) ether chains are bonded, and solved the problems, thereby providing a conventional long-chain perfluoroalkyl group-containing (meth) acrylic acid ester. Intensive study continued to develop a practical water- and oil-repellent agent to replace the polymer. As a result, the present inventors have synthesized various cross-linkable group-containing fluorine-containing polystyrene derivatives by introducing a cross-linking group into a polystyrene resin to which a specific polyfluoro (poly) ether chain is bound, and examining its utilization methods. A useful material having characteristics was developed to complete the present invention.
That is, this invention relates to the following invention which solves the subject of the water / oil repellent which consists of a conventional long-chain perfluoroalkyl group containing (meth) acrylic acid ester polymer.

  <1> A crosslinkable group-containing fluorine-containing polystyrene derivative containing a repeating unit represented by the following formula [1] in an amount of 1 to 99 mass% and a crosslinking group-containing repeating unit in the range of 1 to 95 mass%. A cross-linked fluorine-containing polystyrene derivative coating film prepared by coating a base material with a cross-linkable resin composition solution containing the following requirements (A), (B) and (C): A cross-linked fluorine-containing polystyrene derivative coating film characterized by satisfying.

(In the formula [1], Y represents a hydrogen atom or an alkyl group having 6 or less carbon atoms, and Q represents a divalent group containing at least one ether bond and having a total number of carbon atoms of 5 or less. , .z Rf _o is at least one of the total number of carbon atoms containing an ether group is a monovalent which may contain 25 or less of one hydrogen atom perfluoroether group is selected from 1 to 3 The bond position of Q to the aromatic nucleus may be any of the ortho, meta, or para positions relative to the bond position of the aromatic nucleus and the polymer main chain, bonded to the aromatic nucleus in formula [1]. Some or all of the hydrogen atoms may be substituted with fluorine atoms.)
(A) The contact angle of water on the surface of the crosslinked fluorine-containing polystyrene derivative coating film is 100 ° or more, the contact angle of hexadecane is 60 ° or more, or the contact angle of water is 100 ° or more and the contact angle of hexadecane is 60 ° or more. Be.
(B) The number of residual wrinkles in the adhesion evaluation test for at least one kind of base material selected from organic base materials and inorganic material base materials of the crosslinked fluorine-containing polystyrene derivative coating film is 24% or more in 25% There is.
(C) The crosslinked fluorine-containing polystyrene derivative coating film satisfies at least one of the following conditions (1) to (3).
(1) The surface hardness of the crosslinked fluorine-containing polystyrene derivative coating film is a pencil (scratch) hardness of 3B or more.
(2) The contact angle of water on the surface after the crosslinked fluorine-containing polystyrene derivative coating film is heated in the atmosphere at 250 ° C. for 3 hours is 90% or more of the contact angle before heating.
(3) The contact angle of water on the surface after subjecting the crosslinked fluorine-containing polystyrene derivative coating film to a weather resistance test for 500 hours is 93% or more of the contact angle before the test.

<2> The crosslinked fluorine-containing polystyrene derivative coating film according to <1>, wherein the repeating unit represented by the formula [1] is a repeating unit represented by the following formula [1-1]: .

(In Formula [1-1], Y1 is a hydrogen atom or a methyl group, and Q1 is a divalent group containing an ether bond having 3 or less carbon atoms. Rfo ₁ is Rfa ₁ -O- [CF _{(CF 3) CF 2 O]} n1 - [CF 2 CF 2 CF 2 O] n2 - [CF 2 CF 2 O] n3 - [CF 2 O] n4 -Rfc 1 - a a, Rfa ₁ 1 carbon atoms To 6 perfluoroalkyl groups, n1, n2, n3 and n4 are each an integer selected from 0 or 1 to 6, n1 + n2 + n3 + n4 is 0 to 6, and Rfc ₁ is _one having 3 or less carbon atoms. A perfluoroalkylene group which may contain a hydrogen atom of

  <3> The <1> or <1>, wherein the repeating unit represented by the formula [1] or the formula [1-1] is a repeating unit represented by the following formula [1-2]: The cross-linked fluorine-containing polystyrene derivative coating film according to 2>.

(Wherein [1-2], Y2 is a hydrogen atom or a methyl group, an integer _{L 1} is selected from 0 or 1 to 6, Rfa ₂ is a perfluoroalkyl group having 1 to 6 carbon atoms).

  <4> The crosslinked fluorine-containing polystyrene derivative coating film according to any one of <1> to <3>, wherein two or more items of the conditions (1) to (3) are satisfied. Cross-linked fluorine-containing polystyrene derivative coating film.

  <5> The crosslinked fluorine-containing polystyrene derivative coating according to any one of <1> to <4>, wherein the base material in the adhesion evaluation test of (B) is an organic material base material film.

  <6> The organic material substrate is at least one organic material substrate selected from an acrylic resin substrate, a polycarbonate resin substrate, an ester resin substrate, and a polystyrene resin substrate. <5> characterized in that the cross-linked fluorine-containing polystyrene derivative coating film.

  <7> The repeating unit represented by the formula [1], the formula [1-1] or the formula [1-2] is 1% by mass or more and 99% by mass or less and the crosslinking group-containing repeating unit is 1% by mass or more and 95%. A crosslinkable group-containing fluorine-containing polystyrene derivative contained in a mass% or less range.

  <8> 1% by mass or more and 99% by mass or less of the repeating unit represented by the formula [1], [1-1] or [1-2] and 1% by mass or more of the repeating unit containing a crosslinking group. A crosslinkable group-containing fluorine-containing polystyrene derivative contained in a mass% or less range, wherein the crosslinked coating film satisfies the requirements (A), (B), and (C) described in <1> above. Cross-linked group-containing fluorine-containing polystyrene derivative.

  <9> A substrate selected from an organic material substrate and an inorganic material substrate is coated with the crosslinked fluorine-containing polystyrene derivative coating film according to any one of the above items <1> to <6>. Composite material.

  <10> The composite material according to <9>, wherein the substrate is an organic material substrate.

  <11> The above-mentioned <10>, wherein the organic material substrate is a substrate selected from an acrylic resin substrate, a polycarbonate resin substrate, an ester resin substrate, and a polystyrene resin substrate. The composite material described in 1.

  <12> The composite material according to <10>, wherein the organic material substrate is a transparent resin substrate.

  <13> The repeating unit represented by the formula [1], the formula [1-1], or the formula [1-2] is 1% by mass to 99% by mass and the crosslinking group-containing repeating unit is 1% by mass to 95%. A crosslinkable resin composition solution containing a crosslinkable group-containing fluorine-containing polystyrene derivative contained in a mass% or less range.

  <14> A crosslinkable resin composition solution containing a crosslinkable group-containing fluorine-containing polystyrene derivative used for producing the crosslinked fluorine-containing polystyrene derivative coating film according to any one of <1> to <6>.

  The present inventor has studied in detail the properties of various polystyrene resins to which polyfluoro (poly) ether chains are bonded, and has intensively studied methods for improving the properties. As a result, polyfluoro (poly) ether chains having a specific structure are obtained. By synthesizing a cross-linked group-containing fluorine-containing polystyrene derivative in which a cross-linking group is introduced into a bonded polystyrene-based resin and examining its utilization, useful materials having various excellent practical properties as described below were realized.

(Water / oil repellency and mechanical properties)
Polystyrene resins having a polyfluoro (poly) ether chain bonded thereto are disclosed in Patent Document 4 and are well known, but Patent Document 4 describes how much water and oil repellency the polymer exhibits. Nothing is shown. Therefore, when the present inventors evaluated in detail the water and oil repellency of various fluorine-containing polystyrene resins to which a polyfluoro (poly) ether chain is bonded, the content of the polyfluoro (poly) ether chain having a specific structure is bonded. It was confirmed that the fluoropolystyrene resin exhibits water repellency and oil repellency equivalent to or higher than those of a (meth) acrylic acid ester polymer having a perfluoroalkyl group having 6 or 8 carbon atoms. Conventionally, the excellent water and oil repellency of (meth) acrylic acid ester-based polymers having a long-chain perfluoroalkyl group is that the surface of low surface energy is obtained by the orientation and aggregation of rigid long-chain perfluoroalkyl chains. It was interpreted to be formed. Therefore, the fluorine-containing polystyrene resin to which a flexible polyfluoro (poly) ether chain is bonded as described above is a (meth) acrylic acid ester polymer having a rigid perfluoroalkyl chain having 6 or 8 carbon atoms. It was a completely unexpected finding based on the conventional knowledge that water repellency and oil repellency equivalent or higher were exhibited.

  However, since the fluorine-containing polystyrene resin contains a flexible polyfluoro (poly) ether chain, it has a low glass transition temperature and is a soft material inferior in self-holding property, or its surface is sticky or used. Since the mechanical strength at temperature is insufficient, it has been difficult to use it as a molding material or a coating film material.

  Accordingly, as a result of intensive studies by the present inventors on a method for solving the problem, a crosslinkable group-containing fluorinated polystyrene in which a crosslinkable group is introduced into a fluorinated polystyrene resin to which a polyfluoro (poly) ether chain having a specific structure is bonded. A cross-linked coating film formed from a derivative (hereinafter sometimes abbreviated as “cross-linking group-containing fluorine-containing polystyrene derivative of the present invention”) has no tackiness and sufficient hardness, and has excellent water and water repellency. It was confirmed to have both oiliness and excellent mechanical properties. For example, even when an uncrosslinked coating film containing a crosslinkable group-containing fluorine-containing polystyrene derivative used in the present invention has a pencil hardness of 6B or less, the pencil hardness can easily be 3B or more or HB or more by crosslinking treatment. Surface hardness is achieved.

  Furthermore, it was also confirmed that the crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention is a useful material having various unexpected and excellent characteristics as described below.

(Various uniform solution composition forming ability)
The crosslinking group-containing fluorine-containing polystyrene derivative of the present invention has been found to be soluble in a wide variety of solvents. That is, it has been found that the crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention exhibits good solubility in a very wide variety of solvents from fluorine-containing organic solvents to non-fluorinated organic solvents depending on the structure. Therefore, it was possible to form various types of uniform crosslinkable resin composition solutions containing the crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention.

  The “crosslinkable resin composition solution” containing a crosslinkable group-containing fluorine-containing polystyrene derivative in the present invention means a homogeneous solution in which a composition capable of a crosslinking reaction containing the crosslinkable group-containing fluorine-containing polystyrene derivative is dissolved. Examples thereof include, for example, a) a homogeneous solution in which the crosslinkable group-containing fluorine-containing polystyrene derivative capable of undergoing a crosslinking reaction alone is dissolved, and b) a multi-layer that reacts with the crosslinkable group-containing fluorine-containing polystyrene derivative and the crosslinkable group. A homogeneous solution in which a mixture of functional compounds is dissolved; c) a uniform solution in which a mixture of the crosslinkable group-containing fluorine-containing polystyrene derivative and the polymerization initiator of the crosslinkable group is dissolved; d) in the solutions a) to c) above. Further, a homogeneous solution in which at least one other polymer selected from a fluorine-based polymer and a non-fluorine-based polymer is added, or e) the above a) to d Homogeneous solution or the like was added a solution further various additives (resin properties modifiers and colorants, etc.) and the like.

  That is, the crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention can form a uniform crosslinkable resin composition solution with various substances having various molecular structures with various molecular weights from low molecular weight to high molecular weight. Is possible. Therefore, by using these various crosslinkable resin composition solutions, it is possible to produce cross-linked coating films having various compositions, and the way to produce materials having a wide range of functions according to purposes has been opened. For example, the crosslinkable group-containing fluorine-containing polystyrene derivative to which the polyfluoro (poly) ether chain of the present invention is bonded is not limited to various non-fluorinated polymers and various polyfunctional non-fluorinated oligomers (not only fluorine-based materials). By using a common solvent, a uniform crosslinkable resin composition solution can be formed. Examples of the use of the crosslinkable resin composition solution include, for example, optimizing the composition of the crosslinkable resin composition solution and applying the solution to the crosslinkable group-containing fluorine-containing polystyrene derivative by coating, drying, and crosslinking. It has become possible to produce a crosslinked coating film that combines the excellent water and oil repellency derived from it with the mechanical properties of non-fluorine materials.

  On the other hand, in the case of a conventional (meth) acrylic acid ester polymer having a long chain having 6 or 8 carbon atoms and a rigid perfluoroalkyl chain, a high fluorine content polymer exhibiting high water and oil repellency. Shows good solubility only in fluorine-based organic solvents. In addition, various non-fluorine polymers, non-fluorine additives, or non-fluorine polyfunctional substances hardly dissolve in fluorine-based organic solvents. Therefore, since the (meth) acrylic acid ester polymer having a high fluorine content does not form a uniform solution with various non-fluorine materials as described above, the (meth) acrylic acid ester polymer having a high fluorine content is not included. There is little room for property modification (for example, improvement in mechanical strength) with non-fluorine materials.

  Uniform crosslinkable resin composition solution comprising the above-mentioned crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention and various types of additives as described above, and excellent produced from the crosslinkable resin composition solution The coating film of cross-linked fluorinated polystyrene derivative that has both water and oil repellency and excellent mechanical properties is difficult to predict from the knowledge of conventional (meth) acrylate polymers with high fluorine content, which are water and oil repellent polymers. Thus, this has been realized for the first time by studying the present invention.

  Regarding the cross-linked coating film formed from the cross-linkable resin composition solution, as a particularly noteworthy feature, a cross-linkable resin composition solution containing a non-fluorine resin which is a kind of the solution described in d) above In the crosslinked fluorine-containing polystyrene derivative coating film formed by coating the various substrates with a crosslinking treatment, even when the content of the crosslinking group-containing fluorine-containing polystyrene derivative of the present invention is extremely low, excellent water and water repellency is achieved. It is mentioned that oiliness is expressed. The reason for this is not clear, but one possibility is that the crosslinked fluorine-containing polystyrene derivative coating film has a high cross-linking group-containing fluorine-containing polystyrene derivative due to the effect of the polyfluoro (poly) ether chain during coating of the crosslinkable resin composition. It is assumed that the surface is concentrated with efficiency.

(Heat resistance and weather resistance)
The crosslinked fluorine-containing polystyrene derivative coating film formed from the crosslinkable resin composition containing the crosslinkable group-containing fluorine-containing polystyrene derivative to which the polyfluoro (poly) ether chain is bonded according to the present invention has the above excellent water and oil repellency. In addition to the above, it was confirmed that extremely excellent heat resistance and weather resistance were exhibited, and it became possible to provide a highly durable water- and oil-repellent material having excellent practicality.

  In the polystyrene structure which is a skeleton of a crosslinkable group-containing fluorine-containing polystyrene derivative to which the polyfluoro (poly) ether chain of the present invention is bonded, benzyl hydrogen active in photoreaction, oxygen oxidation reaction, or oxygen oxidation reaction under light irradiation is added. Have. Accordingly, polystyrene is a resin that is susceptible to an oxidation reaction, and is particularly susceptible to a photo-oxidation reaction, so that it is avoided to be used outdoors. On the other hand, the cross-linked coating film formed from the cross-linkable group-containing fluorine-containing polystyrene derivative to which the polyfluoro (poly) ether chain of the present invention having benzyl hydrogen bonded as in the case of polystyrene has excellent heat resistance and weather resistance (light irradiation) (Oxidation resistance below) is an extremely important characteristic practically discovered for the first time by the inventors of the present invention, which is completely unexpected from the knowledge of conventional polystyrene-based materials.

  Conventional (meth) acrylic acid ester-based polymers having a long, rigid perfluoroalkyl chain with 6 or 8 carbon atoms are inferior in heat resistance and weather resistance, and are therefore difficult to use as outdoor coating materials. It is. On the other hand, the cross-linked fluorine-containing polystyrene derivative coating film of the present invention is not only water and oil repellency, but also excellent heat resistance and weather resistance. Is to provide.

(Adhesion to various substrates)
The water / oil repellent coating film made of a long chain perfluoroalkyl group-containing (meth) acrylate polymer that has been used conventionally has no adhesion to both inorganic and organic material substrates. It is sufficient, and particularly has a problem that the adhesion is extremely poor with respect to a substrate made of an organic material. On the other hand, the cross-linked fluorine-containing polystyrene derivative coating film formed from the cross-linkable group-containing fluorine-containing polystyrene derivative to which the polyfluoro (poly) ether chain of the present invention is bonded is not limited to various inorganic material substrates. It was confirmed that extremely excellent adhesion was exhibited even with respect to the organic material base material.

  Therefore, the crosslinked fluorine-containing polystyrene derivative coating film of the present invention has excellent surface properties (high water and oil repellency, high corrosion resistance, high low refractive index, etc.) and high durability (high weather resistance, High-performance coating film with high heat resistance and high adhesion) can be formed. Among them, in particular, the “crosslinked fluorine-containing polystyrene derivative coating film of the present invention formed on various organic material base materials” is a highly adhesive highly functional coating film that could not be realized by a conventional coating film. This is particularly important because it can be applied to a wide range of new uses.

  In addition, composite materials formed by coating various substrates with the crosslinked fluorine-containing polystyrene derivative coating film of the present invention have excellent surface properties (high water and oil repellency, high corrosion resistance, high and low) for various substrates. Refractive index, etc.) and high durability (high weather resistance, high heat resistance, high adhesion) are imparted, and are extremely practically important. Among them, in particular, “a composite material formed by coating a substrate made of an organic material with the crosslinked fluorine-containing polystyrene derivative coating film of the present invention” has various new functions that cannot be realized with a conventional coating film. It is particularly important because it can be applied to a wide range of new uses.

  Conventional fluorine-containing methacrylate polymer-based highly water- and oil-repellent polymers have inferior heat resistance and weather resistance, as well as problems of biosafety (PFOA accumulation), or various base materials (especially organic material bases). Since there were various problems such as poor adhesion to the material, its use (particularly in the field of highly durable coating films) was greatly restricted.

On the other hand, the crosslinked coating film produced from the crosslinkable group-containing fluorine-containing polystyrene derivative to which the polyfluoro (poly) ether chain of the present invention is bonded not only exhibits excellent water and oil repellency, but also has a PFOA accumulation property. No heat resistance, weather resistance, and excellent adhesion to various substrates (particularly organic material substrates) were confirmed.
A cross-linked coating film produced from such a crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention, and a composite material produced by coating the coating film on various base materials (particularly organic material base materials) have been conventionally used. The present invention provides a high-performance material having new functions that could not be realized with the fluorine-containing methacrylate polymer. In particular, the material of the present invention is extremely useful as a highly durable coating film material.

  Conventional fluorine-containing methacrylic ester polymer-based highly water- and oil-repellent polymers have low physical properties (adhesiveness / pencil hardness) and are difficult to use in applications where there is physical contact. In addition, copolymerization of non-fluorinated (meth) acrylic acid monomers to improve physical properties has the problem of lowering the contact angle and solvent resistance. was there. Especially practically used in places where cleaning is routinely performed or where wiping and cleaning is performed using detergents or alcohol preparations, because the effects are lost in a very short time due to insufficient chemical resistance and physical properties. It was difficult.

In contrast, the cross-linked coating film produced from the cross-linking group-containing fluorine-containing polystyrene derivative to which the polyfluoro (poly) ether chain of the present invention is bonded not only exhibits excellent water and oil repellency, but also has excellent adhesion and pencil hardness. It was confirmed that it had excellent chemical resistance.
A cross-linked coating film produced from such a crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention, and a composite material produced by coating the coating film on various base materials (particularly organic material base materials) have been conventionally used. The present invention provides a high-performance material having new functions that could not be realized with the fluorine-containing methacrylate polymer. In particular, the material of the present invention is extremely useful as a coating film material that requires high durability, such as home appliance housings, IT (IoT) device housings, various device housings, bathrooms, bathroom tools, car interiors, and car exteriors. is there.

  According to the present invention, it contains a cross-linking group containing a polyfluoro (poly) ether chain bonded to a (meth) acrylic acid ester polymer containing a perfluoroalkyl group having 6 or 8 carbon atoms. A fluorine polystyrene derivative, a crosslinkable resin composition solution containing the crosslinkable group-containing fluorine-containing polystyrene derivative, a cross-linked fluorine-containing polystyrene derivative coating film, a composite material coated with the cross-linked fluorine-containing polystyrene derivative, and the like can be provided.

  That is, according to the present invention, excellent environmental compatibility (no risk of PFOA generation), excellent water / oil repellency, excellent stability (heat resistance, moisture resistance / hydrolysis resistance, weather resistance, etc.), It is possible to provide a practical high-performance crosslinked coating film having excellent adhesion to various substrates and excellent mechanical properties and related materials.

  The present invention relates to a crosslinkable group-containing fluorine-containing polystyrene derivative to which a polyfluoro (poly) ether chain having a specific structure is bonded, and a related material thereof. The present invention is described in detail below.

<Fluorine-containing polystyrene derivative containing crosslinking groups>
As a crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention, the repeating unit represented by the formula [1] is 1% by mass or more and 99% by mass or less and the crosslinking group-containing repeating unit is 1% by mass or more and 95% by mass or less. The fluorine-containing polystyrene derivative containing a crosslinking group is used.

(In the formula [1], Y represents a hydrogen atom or an alkyl group having 6 or less carbon atoms, and Q represents a divalent group containing at least one ether bond and having a total number of carbon atoms of 5 or less. , Rf ₀ is a monovalent perfluoroether group which may contain one hydrogen atom with a total number of carbon atoms containing at least one ether group of 25 or less, and z is selected from 1 to 3. The bond position of Q to the aromatic nucleus may be any of the ortho, meta, or para positions relative to the bond position of the aromatic nucleus and the polymer main chain, bonded to the aromatic nucleus in formula [1]. Some or all of the hydrogen atoms may be substituted with fluorine atoms.)

  Y in the formula [1] is a hydrogen atom or an alkyl group having 6 or less carbon atoms. The alkyl group having 6 or less carbon atoms may be any of a linear alkyl group and a branched alkyl group, and specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Tert-butyl group, isobutyl group, sec-butyl group, n-amyl group, n-hexyl group and the like. Y is preferably a hydrogen atom and an alkyl group having 4 or less carbon atoms, particularly preferably a hydrogen atom and a methyl group.

  Q in the formula [1] is a divalent group containing at least one ether bond and having a total number of carbon atoms of 5 or less, for example, a divalent group represented by the following formula [2] The group of is mentioned.

(In Formula [2], a is 0 or 1, and b is an integer selected from 0 or 1 to 3. The right hand of the bond in Formula [2] is a hand that bonds to Rf _0. )

As Q, for example, —O—, —OCH ₂ —, —OCH ₂ CH ₂ —, —OCH ₂ CH ₂ CH ₂ —, —OCH ₂ CH ₂ CH ₂ CH ₂ —, —OCH (CH ₃ ) CH _{2 -, - OCH 2 CH (CH} 3) -, - OCH 2 CH (OH) CH 2 -, - OCH 2 CH (OH) CH 2 OCH 2 -, - CH 2 O -, - CH 2 OCH 2 -, - _{CH 2 OCH 2 CH 2 -,} - CH 2 OCH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH 2 CH 2 CH 2 -, - CH 2 OCH 2 CH (CH 3) OCH 2 -, - OCH 2 CH ₂ OCH ₂ —, —OCH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ OCH ₂ CH ₂ OCH ₂ —, —CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ — and the like (the bond on the right side of each group) Hand is R ₀ to be a hand to bond).

Among these, —O—, —OCH ₂ —, —OCH ₂ CH ₂ —, —CH ₂ OCH ₂ — and —CH ₂ OCH ₂ CH ₂ — are preferable because the polymer can be easily synthesized. OCH ₂ — and —CH ₂ OCH ₂ — are more preferable, and —O— is particularly preferable in terms of particularly excellent chemical stability.

Rf ₀ in the formula [1] is a monovalent perfluoroether group that contains at least one ether bond and may contain one hydrogen atom, and the number of carbon atoms in Rf ₀ is 25 or less. is there. The ratio of [number of carbon atoms / number of ether bonds] in Rf ₀ is usually 2.0 or more and 9.0 or less, preferably 2.2 or more and 8.0 or less, and more preferably 3.3. It is 6.0 or less and particularly preferably 3.5 or more and 5.0 or less.

Examples of Rf ₀ include a group represented by the following formula [3].

In the formula [3], Rf ₁ is a perfluoroalkyl group having 7 or less carbon atoms, and Rf ₂ is one or more kinds of perfluoroalkyl groups selected from linear or branched perfluoroalkylene groups having 4 or less carbon atoms. Rf ₃ is a perfluoroalkylene group having 3 or less carbon atoms, or a polyfluoroalkylene group having a structure in which one fluorine atom of the perfluoroalkylene group is substituted with a hydrogen atom, and L is 0 Or it is an integer chosen from 1-10.

Examples of Rf ₁ include linear or branched perfluoroalkyl groups having 7 or less carbon atoms, preferably perfluoroalkyl groups having 6 or less carbon atoms, and more preferably perfluoroalkyl groups having 3 or less carbon atoms. A fluoroalkyl group;

Specific examples of Rf ₁ include CF ₃ −, CF ₃ CF ₂ —, CF ₃ CF ₂ CF ₂ —, (CF ₃ ) ₂ CF—, CF ₃ CF ₂ CF ₂ CF ₂ —, CF ₃ CF ₂ CF _2. CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- , and CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF _2- . Of these, CF ₃ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF _2- , and CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ -are preferred, and they are easy to synthesize and have good water and oil repellency. From the viewpoint of showing, CF ₃ CF ₂ CF ₂ — is particularly preferable.

Rf ₂ is one or more perfluoroalkylene groups selected from linear or branched perfluoroalkylene groups having 4 or less carbon atoms. The number of carbon atoms in Rf ₂ is usually 1 to 4, preferably 1 to 3, and particularly preferably 3.

Specific examples of _{Rf 2, -CF (CF 3)} CF 2 -, - CF (CF 3) -, - CF 2 -, - CF 2 CF 2 -, - CF 2 CF 2 CF 2 -, - CF 2 _{CF 2 CF 2 CF 2 -,} - CF 2 CF (CF 3) CF 2 - and the like. Of these _{-CF (CF 3) CF 2 -} , - CF 2 -, - CF 2 CF 2 -, - CF 2 CF 2 CF 2 - is preferred, showing a easy and good water and oil repellency synthesis particularly -CF _(CF 3) CF ₂ from the viewpoint of - or _-CF 2 _CF 2 CF ₂ - is preferred. (Right side of the join hand of each group of specific examples of Rf ₂ is a hand that binds to the oxygen atom in (Rf 2 _O) units of the formula [3].)

  L in the formula [3] is an integer selected from 0 or 1 to 10, preferably an integer selected from 0 or 1 to 6, more preferably an integer selected from 0 or 1 to 3, More preferably, it is 0 or an integer selected from 1 or 2, particularly preferably 0 or 1.

In the (Rf ₂ O) _L segment in the formula [3], when Rf ₂ is composed of a plurality of perfluoroalkylene groups, —CF (CF ₃ ) CF ₂ O—CF ₂ CF ₂ CF ₂ O As in —CF (CF ₃ ) CF ₂ O—, different types of Rf ₂ may be randomly mixed and arranged, or a plurality of the same type of Rf ₂ may be arranged. .

Specific examples of (Rf ₂ O) L in the case where Rf ₂ is composed of a plurality of perfluoroalkylene groups include a group represented by the following formula [4].

_{- [CF (CF 3) CF2O} ] n1 - [CF 2 CF 2 CF 2 O] n2 - [CF 2 CF 2 O] n3 - [CF 2 O] n4 - [4]

  (In Formula [4], n1, n2, n3, and n4 are each an integer selected from 0 or 1 to 6. The sum of n1 + n2 + n3 + n4 is the same as L in Formula [3].)

Examples of Rf ₃ include a perfluoroalkylene group having 3 or less carbon atoms, or a polyfluoroalkylene group having a structure in which one fluorine atom of the perfluoroalkylene group is substituted with a hydrogen atom.

Examples of _{Rf 3, -CF 2 -, -} CF 2 CF 2 -, - CF (CF 3) -, - CF 2 CF 2 CF 2 -, - CF (CF 3) CF 2 -, - CF 2 CF (CF ₃ ) —, —CHFCF ₂ —, —CF ₂ CHFCF ₂ — and the like can be mentioned. Of _{these, -CF 2 CF 2 -, -} CF (CF 3) -, - CHFCF 2 - are preferable, -CHFCF ₂ from the viewpoint of synthesis shows the easy and good water and oil repellency - preferably (The bond on the right side of each group in the specific example of Rf ₃ is a bond to Q).

Specific examples of Rf ₀ include groups represented by the following formula [R-1], formula [R-2], formula [R-3], and formula [R-4].

Specific examples of the group represented by the formula [R-1] include CF ₃ CF ₂ CF ₂ OCHFCF ₂ —, CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCHFCF ₂ —, CF ₃ CF ₂ CF _2. OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CF ₂ OCHFCF ₂ —, CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CF ₂ OCHFCF ₂ — It is done.

Specific examples of the group represented by the formula [R-2], the formula [R-3] or the formula [R-4] include the specific examples of the group represented by the above formula [R-1]. Examples include groups having a structure in which the terminal CHFCF ₂ group of each of the listed structures is replaced with a CF (CF ₃ ) group, a CF ₂ CF ₂ group, or CF ₂ CHFCF ₂ , respectively.

In addition, as Rf ₀ , the terminal group CF ₃ CF ₂ CF ₂ group in each group of the formula [R-1], the formula [R-2], the formula [R-3], and the formula [R-4] The structure may be substituted with 1 to 7, preferably 1 to 6 linear or branched perfluoroalkyl groups. Examples of the perfluoroalkyl group include CF _3- , CF ₃ CF _2- , (CF ₃ ) ₂ CF-, CF ₃ CF ₂ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ —.

  Z in formula [1] is an integer selected from 1 to 3, but z is more preferably 1 from the viewpoint of easy synthesis.

  The bonding position of Q in the formula [1] to the aromatic nucleus may be any of the ortho position, the meta position, and the para position with respect to the bonding position of the aromatic nucleus and the polymer main chain. Is more preferable from the viewpoint of easy availability.

  Some or all of the hydrogen atoms bonded to the aromatic nucleus in the formula [1] may be substituted with fluorine atoms, but from the viewpoint of easy synthesis, those not substituted with fluorine atoms are more preferred. preferable.

  As the repeating unit represented by the formula [1], a repeating unit represented by the following formula [1-1] is more preferable, and a repeating unit represented by the following formula [1-2] is particularly preferable.

(In Formula [1-1], Y ₁ is a hydrogen atom or a methyl group, Q ₁ is a divalent group containing an ether bond having 3 or less carbon atoms. Rf ₀₁ is Rfa ₁ —O—. _{[CF (CF 3) CF 2} O] m1 - [CF 2 CF 2 CF 2 O] m2 - [CF 2 CF 2 O] m3 - [CF 2 O] m4 -Rfc 1 - a a, Rfa ₁ carbon The perfluoroalkyl groups of formulas _{1 to} 6, m1, m2, m3, and m4 are each an integer selected from 0 or 1 to 6, and the sum of m1 + m2 + m3 + m4 is 0 to 6, and Rfc ₁ has 3 carbon atoms. (It is a perfluoroalkylene group which may contain one hydrogen atom below.)

Q ₁ is a divalent group containing an ether bond having 3 or less carbon atoms. Examples thereof include —O—, —OCH ₂ —, —CH ₂ O—, —OCH ₂ CH ₂ —. , —CH ₂ OCH ₂ —, —CH ₂ OCH ₂ CH ₂ — and the like. Q ₁ is more preferably —O—, —CH ₂ OCH ₂ — or —OCH ₂ —, and particularly preferably —O—. (The bond on the right side of each group in the specific example of Q ₁ is a bond that binds to Rfo ₁ in formula [1-1].)

The sum of m1 + m2 + m3 + m4 is an integer selected from 0 or 1 to 6, preferably 0 to 3, more preferably 0 to 2, and particularly preferably 0 to 1. Rfo ₁ is a perfluoroalkylene group that may contain one hydrogen atom having 3 or less carbon atoms. Specific examples thereof include —CF ₂ CF ₂ —, —CF (CF ₃ ) —, — CF ₂ —, —CF ₂ CHFCF ₂ — or —CHFCF ₂ — may be mentioned. Rfo ₁ is more preferably —CF (CF ₃ ) — or —CHFCF ₂ —, and particularly preferably —CHFCF ₂ —. (The bond on the right side of each group in the specific example of Rfo ₁ is the hand that binds to Q ₁ in formula [1-1].)

The bonding position of Q _{1 to} the aromatic nucleus in the formula [1-1] may be any of the ortho position, the meta position, and the para position with respect to the bonding position of the aromatic nucleus and the polymer main chain, but is easily synthesized. The para position is more preferable in terms of the point and the availability of raw materials.

(Wherein [1-2], _{Y 2} is a hydrogen atom or a methyl group, an integer _{L 1} is selected from 0 or 1 to 6, Rfa ₂ is a perfluoroalkyl group having 1 to 6 carbon atoms).

L ₁ is an integer selected from 0 or 1 to 6, preferably 0 to 4, more preferably 0 to 2, and particularly preferably 0 to 1. Rfa ₂ is usually a C 1-6 perfluoroalkyl group, preferably a C 2-4 perfluoroalkyl group, and particularly preferably CF ₃ CF ₂ CF ₂ —.

The fluorine-containing polystyrene derivative containing a repeating unit represented by formula [1], formula [1-1] or formula [1-2] used in the present invention is a polymer containing a p-hydroxystyrene type repeating unit. And a reactive group-containing polystyrene derivative such as a polymer containing a repeating unit derived from p-chloromethylstyrene and a perfluoro (poly) ether compound or a polyfluoro (poly) ether compound containing an active terminal group. be able to. For example, a polymer containing a repeating unit of p-hydroxystyrene type and CF ₂ = CF— [OCF ₂ CF (CF ₃ )] _{L 1} —ORfa ₂ type monomer (L ₁ and Rfa ₂ are the same as those in the formula [1-2]. ), A polystyrene derivative containing a repeating unit of the formula [1-2] can be produced. The repeating unit represented by the formula [1] is also obtained by copolymerization of a monomer having a CH ₂ ═CY—Ph— [Q—Rfo] _Z structure (Y, Q, Rfo and z are the same as those in the formula [1]). The fluorine-containing polystyrene derivative containing can be manufactured.

  The content of the repeating unit represented by formula [1], formula [1-1] or formula [1-2] in the crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention is 1% by mass or more and 99% by mass or less. However, fluorine-containing polystyrene derivatives having various repeating unit contents represented by the formula [1] can be used depending on the application and expected effects. That is, the content of the repeating unit represented by the formula [1] in the fluorine-containing polystyrene derivative of the present invention is appropriately selected from the range of 1% by mass to 99% by mass. For example, the lower limit of the content of the repeating unit represented by the formula [1] in the fluorine-containing polystyrene derivative of the present invention is usually 1% by mass or more, but depending on the use, 5% by mass or more and 10% by mass. % Or more, 30 mass% or more, or 50 mass% or more is adopted. Moreover, although the upper limit of the content of the repeating unit is usually 99% by mass or less, a range of 90% by mass or less, 80% by mass or less, or 90% by mass or less is adopted depending on the application.

The crosslinking group-containing fluorine-containing polystyrene derivative of the present invention contains a repeating unit containing a crosslinking group in the range of 1% by mass to 95% by mass in addition to the repeating unit represented by the formula [1]. The crosslinkable group-containing repeating unit in the crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention includes, for example, an active hydrogen-containing group, a carbon-carbon multiple bond, an epoxy group, an isocyanate group, and an alkoxysilane group. A repeating unit containing at least one kind is preferred. Examples of the active hydrogen-containing group include a hydroxyl group (phenolic hydroxyl group, alcoholic hydroxyl group), amino group, thiol group, carboxyl group and the like. Examples of carbon-carbon multiple bond-containing groups include, for example, carbons such as acrylate groups, methacrylate groups, styryl groups, allyl groups, vinyloxy groups, trifluorovinyloxy groups (CF ₂ = CFO- groups), maleimide groups, etc. Examples thereof include a carbon double bond-containing group or a carbon-carbon triple bond-containing group such as a propargyl group or an ethynyl group. Examples of the epoxy group include glycidyl groups linked to various groups. Examples of the isocyanate group include aliphatic isocyanate groups and aromatic isocyanate groups. Examples of the alkoxysilane group include trialkoxysilane groups, dialkoxymonoalkylsilane groups, and monoalkoxydialkylsilane groups.

  The crosslinking group in the repeating unit containing the crosslinking group can undergo a crosslinking reaction in various ways. Examples thereof include the following crosslinking reactions.

(I) A type that crosslinks by a reaction between an active hydrogen type crosslinkable group and a polyfunctional substance (eg, active hydrogen (alcohol, phenol, amine, thiol, carboxylic acid, etc.) type crosslinkable group and a polyfunctional compound (polyvalent isocyanate) , Crosslinking by reaction with polyhydric epoxy, etc.)

(Ii) A type that crosslinks by a reaction between a highly active crosslinking group and a polyfunctional substance (eg, an isocyanate type crosslinking group or an epoxy group type crosslinking group and a polyvalent active hydrogen compound (polyhydric alcohol, polyhydric phenol, polyvalent amine) , Polythiols, polycarboxylic acid type compounds))

(Iii) A type in which a single type of crosslinking group is polymerized to crosslink (eg, (meth) acrylate type crosslinking group, styryl type crosslinking group, epoxy type crosslinking group, oxetane type crosslinking group, episulfide type crosslinking group, etc.) Examples: radical polymerization, cationic polymerization, anionic polymerization, thermal polymerization, UV irradiation)

(IV) A type in which several types of crosslinkable groups are linked to form a crosslink (eg, ethynyl or propargyl type crosslinkable group, alkoxysilane type crosslinkable group, trifluorovinyloxy type crosslinkable group, etc.)

  Although the specific example of the repeating unit containing the crosslinking group in the crosslinking group containing fluorine-containing polystyrene derivative of this invention is illustrated below, it is not limited to this.

  The crosslinkable group-containing repeating unit in the crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention as described above can be introduced by various methods.

  For example, a polymer containing a p-hydroxystyrene unit as a repeating unit can be produced by a hydrolysis reaction of a polymer containing a repeating unit derived from p-acetoxystyrene. The p-hydroxystyrene unit can be used as a phenolic active hydrogen type crosslinking group. Furthermore, the p-hydroxystyrene unit can be easily converted into various repeating units containing a crosslinking group using its high reactivity. Examples thereof include an example in which the —OH group of the p-hydroxystyrene unit is converted into various types of crosslinking groups as described below. Moreover, the aliphatic alcohol group of the copolymer containing repeating units, such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, can be similarly converted into various types of crosslinking groups as described below.

  The crosslinkable group-containing repeating unit in the crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention is represented by the vinyl polymerizable monomer containing various crosslinkable groups and the formula [1], formula [1-1] or formula [1-2]. It can also introduce | transduce by copolymerization with the polystyrene derivative monomer which forms the repeating unit represented. Examples of vinyl polymerizable (radical polymerizable, cationic polymerizable, anionic polymerizable) monomers containing a crosslinking group that can be used in this way are shown below, but are not limited thereto. Further, it is also effective to stabilize the active group such as an active hydrogen group or isocyanate group in the vinyl polymerizable monomer with a protective group, copolymerize it, and then remove the protective group for activation.

  The content of the crosslinkable group-containing repeating unit in the crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention is 1% by mass or more and 50% by mass or less. An amount of fluorine-containing polystyrene derivative can be used. That is, the content of the crosslinking group-containing repeating unit in the crosslinking group-containing fluorine-containing polystyrene derivative of the present invention is usually selected from the range of 1% by mass to 95% by mass, preferably 1% by mass to 80% by mass. % Or less, 1 mass% or more and 60 mass% or less, or 1 mass% or more and 50 mass% or less. In addition, when the content of the crosslinking group-containing repeating unit is less than 1% by mass, the effect of improving properties by crosslinking is insufficient, such being undesirable. In addition, the crosslinking group containing repeating unit in the crosslinking group containing fluorine polystyrene derivative of this invention may be one type, and may be multiple types.

  In addition to the repeating unit represented by the formula [1], the formula [1-1] or the formula [1-2] and the crosslinking group-containing repeating unit, the crosslinked group-containing fluorine-containing polystyrene derivative of the present invention includes: In order to adjust the characteristics, one type or a plurality of types of repeating units having various structures may be included.

  For example, as a repeating unit other than the repeating unit represented by the formula [1], the formula [1-1] or the formula [1-2] and the repeating unit containing a crosslinking group, radical polymerizable, cationic polymerizable or anionic polymerizable These monomer units may contain one kind or a plurality of kinds. Specific examples of the polymerizable monomer include, for example, α-methyl styrene, p-methyl styrene, p-alkoxy styrene, p-acetoxy styrene, p-hydroxy styrene (synthesized using a deprotection group reaction), and the like. Various substituted styrene, unsubstituted styrene, vinyl naphthalene, acenaphthylene, maleic anhydride or its derivatives, maleimide derivatives, (meth) acrylonitrile, (meth) acrylamide and its derivatives, various (meth) acrylic acid esters, fluorine-containing (meth) acrylic Examples include various polymerizable monomers such as acid esters, various fluorine-containing olefins, various vinyl carboxylates, and various vinyl ethers.

  In the crosslinkable group-containing fluoropolystyrene derivative of the present invention, a recurring unit other than the recurring unit represented by the formula [1], the formula [1-1] or the formula [1-2] and the recurring group-containing recurring unit, The crosslinking group-containing fluoropolystyrene derivative may be contained in an amount in the range of 0 to 90% by mass, 0 to 60% by mass, or 0 to 40% by mass.

Examples of a method for producing a crosslinking group-containing polystyrene derivative containing a repeating unit other than the repeating unit represented by the above formula [1] and a crosslinking group-containing repeating unit include 1) p-hydroxystyrene unit and crosslinking group-containing repeating unit. and _CF to the phenolic hydroxyl group of the copolymer composed of various monomeric units _{2 = CF- [OCF 2 CF (} CF 3)] L1 active end group-containing perfluoro like -ORfa ₂ (poly) ether compound (L ₁ , Rfa ₂ is the same as the production method by the addition reaction of the formula [1-2], or 2) a monomer having a CH ₂ ═CY—Ph— [Q—Rf _o ] _Z structure (Y, Q, Rf _o And z are the same as those in the formula [1]), and a production method by copolymerization of a crosslinking group-containing monomer and various comonomers can be mentioned, but is not limited thereto.

  As the crosslinkable group-containing fluorine-containing polystyrene derivative used in the present invention, polymers having various structures and sequences produced by various production methods can be used. For example, the crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention can be produced by various copolymerization methods such as radical copolymerization, cation copolymerization or anion copolymerization. Furthermore, a polymer having a desired crosslinking reactivity can be produced by converting a reactive group contained in the copolymer produced by such copolymerization into another type of reactive group. Further, the crosslinking group-containing fluorine-containing polystyrene derivative of the present invention can use polymers having various structures such as a random copolymer, a block copolymer, a graft copolymer or a star polymer.

  “The repeating unit represented by the formula [1], the formula [1-1] or the formula [1-2] is 1% by mass to 99% by mass and the crosslinking group-containing repeating unit is 1% by mass to 95% by mass. Crosslinking group-containing fluorine-containing polystyrene derivative contained in the following range ”or“ crosslinking group-containing fluorine-containing polystyrene used for producing a crosslinked fluorine-containing polystyrene derivative coating film according to <1> to <4> above ” “Derivatives” are essential for forming the novel coating film and novel composite material of the present invention having various excellent properties (water / oil repellency, heat resistance, weather resistance, adhesion, surface hardness, etc.) as described below. New material.

<Crosslinkable resin composition solution>
The “crosslinkable resin composition solution” containing a crosslinkable group-containing fluorine-containing polystyrene derivative in the present invention means a uniform solution in which a composition capable of a crosslinking reaction containing the crosslinkable group-containing fluorine-containing polystyrene derivative is dissolved.

  Examples of the crosslinkable resin composition solution include, for example, a) a uniform solution in which the crosslinkable group-containing fluorine-containing polystyrene derivative capable of undergoing a crosslinking reaction alone is dissolved; b) the crosslinkable group-containing fluorine-containing polystyrene derivative and the crosslinkable A homogeneous solution in which a mixture of polyfunctional compounds that react with groups is dissolved, c) a homogeneous solution in which a mixture of the crosslinkable group-containing fluorine-containing polystyrene derivative and the polymerization initiator of the crosslinkable group is dissolved, d) a) to a) above a uniform solution in which at least one other polymer selected from a fluororesin and a non-fluorine resin is further added to the solution of c), or e) the solutions a) to d) above, and various additives (resin properties) And uniform solutions to which modifiers and coloring agents are added.

  Examples of a) include, for example, a thermally crosslinkable substituent (eg, ethynyl group, episulfide group, trifluorovinyloxy group, etc.) or a UV crosslinkable substituent (methacryl group, acrylic group, styryl). And a homogeneous solution in which a fluorine-containing polystyrene derivative containing a group or the like is dissolved.

  Examples of b) include, for example, a homogeneous solution in which a mixture of the fluorine-containing polystyrene derivative of the present invention containing an epoxy group or an isocyanate group as a crosslinking group and a polyhydric alcohol or polyamine is dissolved, a phenolic hydroxyl group or an aliphatic group. A homogeneous solution in which a mixture of the fluorine-containing polystyrene derivative of the present invention containing an alcohol group as a crosslinking group and a polyvalent epoxy compound or a polyvalent isocyanate group is dissolved, or a mixture of an ester group-containing fluorine-containing polystyrene derivative and a polyvalent amine, etc. A dissolved homogeneous solution is exemplified. Specifically, for example, instead of the polyol of the existing polyol-containing curable coating, a homogeneous solution to which the fluorine-containing polystyrene derivative of the present invention containing various hydroxyl groups as crosslinking groups is added, or a polyvalent epoxy compound or a polyvalent isocyanate Examples include a uniform solution in which the fluorine-containing polystyrene derivative of the present invention containing an epoxy group or an isocyanate group as a crosslinking group is added in place of the polyol of the existing curable paint containing a group.

  Examples of c) include, for example, fluorine-containing polystyrene derivatives containing various vinyl polymerizable substituents (methacrylate groups, acrylate groups, styryl groups, vinyl ether groups) and polymerization initiators thereof (radical polymerization initiators, anionic polymerizations). Mixtures containing initiators, cationic polymerization initiators, various photopolymerization initiators, etc.) or various ring-opening polymerizable substituents (epoxy groups, oxetane groups, cyclic ester structure-containing groups, cyclic amide structure-containing groups, etc.) And a homogeneous solution in which a mixture containing a fluorine-containing polystyrene derivative containing a polymerization initiator and its polymerization initiator is dissolved. In the case of this type of crosslinkable resin composition, it may further contain a monofunctional or polyfunctional vinyl polymerizable monomer or ring-opening polymerizable monomer copolymerizable with the crosslinkable group.

  Examples of the additive resin described in d) include various resins that are soluble in a solvent. Examples of non-fluorine resins include, for example, various styrene resins such as polystyrene and poly-α-methylstyrene, various acrylic resins such as polymethyl methacrylate, and modified cellulose polymers such as triacetyl cellulose. And polycondensation polymers such as various polyester resins represented by polyethylene terephthalate and various polycarbonate resins, and various polyaddition polymers. In addition, examples of the fluorine-based resin include various fluorine-containing polymers such as fluorine-containing acrylate polymers and fluorine-containing olefins. In the crosslinkable resin composition solution, the characteristics of the crosslinkable group-containing fluorine-containing polystyrene derivative coating film can be greatly modified according to the characteristics of the added polymer, so that the characteristics of the coating film can be adjusted according to the purpose. Among the various additive resins described above, the non-fluorine resin is particularly useful because it can realize excellent surface characteristics at a low cost.

  As an example of e), for example, various additives such as various resin property modifiers, antioxidants, ultraviolet absorbers, fillers, and colorants are further added to the solutions described in the above a) to d). The added uniform solution is mentioned. The crosslinkable resin composition solution is basically a homogeneous solution, but depending on the purpose, a suspension solution in which an insoluble substance such as a filler is further added to the homogeneous solution may be used.

After coating these “crosslinkable resin composition solutions” on various substrates, drying is carried out as necessary, and then crosslinking treatment is carried out to obtain “crosslinked fluorine-containing polystyrene derivative coating film” or “crosslinked fluorine-containing polystyrene derivative”. Can be produced.
The crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention has good solubility not only in fluorine-containing organic solvents but also in various non-fluorine organic solvents, despite being a fluorine-containing polymer exhibiting excellent water and oil repellency. I found out that By utilizing the solubility characteristics, the crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention can form a uniform solution with not only fluorine-based materials but also various non-fluorine-based materials. A functional resin composition solution could be realized.

On the other hand, in the case of a conventional (meth) acrylic acid ester polymer having a long chain having a carbon number of 8 or more and a rigid perfluoroalkyl chain, a high fluorine content polymer exhibiting high water and oil repellency is fluorine. Good solubility only in organic solvents. Therefore, it is difficult for the long-chain perfluoroalkyl group-containing (meth) acrylic acid ester-based polymer to form a uniform solution with various non-fluorinated polymers that are not soluble in the fluorine-based solvent. In addition, even if a crosslinking group similar to the present invention is introduced into a long-chain perfluoroalkyl group-containing (meth) acrylic acid ester polymer, a non-fluorinated polyfunctional compound (such as a polyhydric alcohol or a polyamine) It is difficult to form a uniform solution with), so that there is a great limitation in forming a uniform crosslinkable composition.
Accordingly, the “crosslinked fluorine-containing polystyrene derivative coating film” and the “crosslinked fluorine-containing film” formed by coating the substrate with the uniform crosslinkable resin composition solution containing the crosslinkable group-containing fluorine-containing polystyrene derivative of the present invention and then crosslinking. “Composite material coated with polystyrene derivatives” is difficult to predict from the knowledge of conventional water- and oil-repellent agents comprising a long-chain perfluoroalkyl group-containing (meth) acrylic acid ester polymer. It was realized for the first time.

  The content of the crosslinkable group-containing fluorine-containing polystyrene derivative in the non-volatile component obtained by removing the volatile solvent from the crosslinkable resin composition solution of the present invention is usually in the range of 0.1% by mass to 100% by mass. The content of the crosslinkable group-containing fluorine-containing polystyrene derivative in the nonvolatile content is appropriately selected according to the composition of the crosslinkable group-containing fluorine-containing polystyrene derivative, the types of various additive components, the properties expected of the crosslinked product, and the like. . That is, the lower limit of the content of the crosslinkable group-containing fluorine-containing polystyrene derivative in the nonvolatile composition is usually 0.1% by mass, but in order to express particularly excellent water and oil repellency, 1.0% by mass Is preferable, 10.0% by mass is more preferable, and 20.0% by mass or 40.0% by mass is particularly preferable. Moreover, although the upper limit of the content of the crosslinkable group-containing fluorine-containing polystyrene derivative is usually 100% by mass, it is 99.0% by mass, 95.0% by mass, 90.0% by mass depending on the intended properties. , 70.0% by mass or 50.0% by mass or the like is selected.

  The solvent used in the crosslinkable resin composition solution of the present invention is selected from various solvents such as a non-halogen solvent and a halogen solvent depending on the type and use of the dissolved substance. Non-halogen solvents include, for example, ketone solvents such as acetone and methyl ethyl ketone (MEK), ester solvents such as ethyl acetate and butyl acetate, and aliphatic hydrocarbons such as n-hexane, cyclohexane, isohexane and n-heptane. Solvents, aromatic hydrocarbon solvents such as toluene and xylene, heteroatom-containing aromatic solvents such as anisole, dimethylaniline and pyridine, nitrogen atom-containing solvents such as triethylamine and diethylamine, dimethylformamide and dimethylacetamide Such as amide solvents, sulfur atom-containing solvents such as dimethyl sulfoxide, cyclic ether solvents such as dioxane and tetrahydrofuran (THF), ether solvents such as di-n-butyl ether and methyl-t-butyl ether, monoglyme and diglyme Yo A glyme-based solvent, ethyl cellosolve, cellosolve solvents such as butyl cellosolve and cellosolve acetate, ethyl alcohol, alcohol-based solvents such as isopropyl alcohol or n- butyl alcohol and the like.

Examples of halogen solvents include perfluorocarbon (PFC) solvents such as perfluorohexane and perfluorocyclohexane, hydrofluorocarbon (HFC) solvents such as CF ₃ CF ₃ CHFCHFCF ₃ and c-C ₅ F ₇ H ₃ , Hydrochlorofluorocarbon (HCFC) solvents such as CClF ₂ CF ₂ CHClF and CF ₃ CF ₂ CHCl ₂ , hydrofluoroether (HFE) solvents such as C ₄ F ₉ OCH ₃ and C ₄ F ₉ OC ₂ H ₅ Various fluorine-based solvents such as perfluoropolyether (PFPE) solvents, hydrofluoropolyether (HFPE) solvents, fluorine-containing aromatic solvents such as 1,3-bistrifluoromethylbenzene and hexafluorobenzene, or Dichloromethane, trichloro Chlorinated solvents such as roethylene and chlorobenzene can be used. The above solvents may be used alone or as a mixed solvent of two or more.

  The amount of the solvent in the crosslinkable resin composition solution of the present invention is appropriately selected according to the properties and applications of the crosslinkable resin composition other than the solvent, but is usually 50% by mass with respect to the total mass of the solution. It is selected from the range of 99.99% by mass, preferably from 70% by mass to 99.99% by mass, more preferably from 80% by mass to 99.9% by mass, particularly preferably. It is selected from the range of 90% by mass or more and 99.9% by mass. When the additive component other than the crosslinkable group-containing fluorine-containing polystyrene derivative in the crosslinkable resin composition solution is liquid, the amount of the solvent used may be small, and in some cases the liquid additive may be regarded as the solvent. is there.

<Crosslinked fluorine-containing polystyrene derivative coating film>
A cross-linked fluorine-containing polystyrene derivative coating film can be formed by coating the base material with the cross-linkable resin composition solution of the present invention and then performing cross-linking treatment. The coating method to a base material is not specifically limited, Well-known coating methods, such as a dip (Dip), brush coating, a spray, dispensing, a roll coater, a gravure coater, a curtain coater, a die coater, can be used. After coating the crosslinkable resin composition solution of the present invention on the substrate, (after drying as necessary), the resultant is crosslinked by various crosslinking methods to thereby form “crosslinked fluorine-containing polystyrene derivative coating film” and “crosslinked fluorine-containing film”. A composite material in which a substrate is coated with a polystyrene derivative coating film is produced. As the crosslinking method, various crosslinking methods can be employed. Examples thereof include a thermal crosslinking method (use of polyaddition reaction or polycondensation reaction), photocrosslinking method, UV crosslinking method, EB curing method, moisture, and the like. Examples include a crosslinking method and a wet heat crosslinking method.

<Type of base material and its shape>
As the target substrate to which the crosslinkable resin composition solution of the present invention is applied, various substrates of various shapes made of various materials can be used. After coating the crosslinkable resin composition solution of the present invention on various substrates, the substrate is coated with “crosslinked fluorine-containing polystyrene derivative coating film” and “crosslinked fluorine-containing polystyrene derivative coating film” formed by drying and crosslinking treatment. The "composite material" is a new type of high-performance material that has various excellent properties and is used for various applications depending on the properties.

As a base material used for this invention, the base material which consists of the following materials is mentioned, for example.
(I) Organic material substrate: Acrylic resin substrate (Polymethyl methacrylate (PMMA) and polymethyl methacrylate (PMA) and other (meth) acrylate polymers and copolymers thereof Etc.), polycarbonate (PC) resin base materials (bisphenol-A type PC, full orange all type PC, etc.), ester resin base materials (polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), etc.) Cellulose ester resins such as acetyl cellulose (TAC)) and polystyrene resin substrates (polymers of styrene and various substituted styrenes (α-methylstyrene, p-methylstyrene, etc.) and copolymers thereof) Made of various organic resin base materials such as epoxy resins and urethane resins Charge and coatings of various substrates coated organic material coated substrate or the like formed by.

  Among various organic material base materials, acrylic resin base materials, polycarbonate resin base materials, ester resin base materials, and polystyrene resin base materials are important because they have a wide range of uses. A transparent resin substrate is important as a high-performance optical material.

(Ii) Substrate made of inorganic material (ii-1) Metal substrate: Stainless steel substrate such as SUS304, SUS430, iron substrate or copper substrate.
(Ii-2) Ceramic base materials: Various base materials such as silica, silica / alumina, alumina, zirconia, quartz glass, borosilicate glass, ferrite, zinc oxide, silicon, silicon carbide, or barium titanate.

  Among various inorganic material substrates, metal substrates are particularly useful because they have a wide range of uses.

  As the shape of the substrate suitable for the formation of the composite material coated with the crosslinked fluorine-containing polystyrene derivative coating film of the present invention, or the shape of the substrate whose surface characteristics are improved by the crosslinkable resin composition solution of the present invention, Examples of the base material include various shapes such as a molded body shape, a flat plate shape, a curved surface shape, a film shape, a pipe shape, a fiber-like material, a fabric shape, and a porous shape. Among these, a molded body, flat plate, curved surface, film, fiber, or pipe material is particularly useful.

  Specific examples of use include, for example, surface protection coating materials for various molded products, surface coating agents for various planar materials and films, surface coating materials for optical fibers (low refractive index sheath materials), and various fiber materials (natural Examples thereof include fiber treatment materials that impart water and oil repellency to fibers and synthetic fibers) and fabrics, and water repellent and antifouling coating materials for porous building materials.

  Hereinafter, the surface characteristics of the “crosslinked fluorine-containing polystyrene derivative coating film” and “composite material in which the substrate is coated with the crosslinked fluorine-containing polystyrene derivative coating film” of the present invention and the evaluation method thereof will be described in detail.

(Water / oil repellency (contact angle))
Since the crosslinked fluorine-containing polystyrene derivative coating film of the present invention is excellent in water and oil repellency, it has the following characteristics. For example, in the present invention, water on the surface of a crosslinked fluorine-containing polystyrene derivative coating film obtained by applying a crosslinking resin composition solution containing a crosslinking group-containing fluorine-containing polystyrene derivative to a substrate and drying (crosslinking) after drying. The contact angle is 100 ° or more, the contact angle of hexadecane is 60 ° or more, or the contact angle of water is 100 ° or more and the contact angle of hexadecane is 60 ° or more. More preferably, the contact angle of water on the surface of the crosslinked fluorine-containing polystyrene derivative coating film is 110 ° or more, or the contact angle of hexadecane is 65 ° or more, or the contact angle of water is 110 ° or more and the contact angle of hexadecane is It is 65 ° or more.

  The contact angle of water on the surface of the crosslinked fluorine-containing polystyrene derivative coating film of the present invention is 100 ° or more, preferably 105 ° or more, more preferably 110 ° or more, and particularly preferably 120 ° or more. Furthermore, the cross-linked fluorine-containing polystyrene derivative coating film of the present invention can realize a higher water contact angle if conditions are selected, for example, a contact angle of about 130 ° can be realized. . The contact angle of hexadecane on the surface of the crosslinked fluorine-containing polystyrene derivative coating film of the present invention is 60 ° or more, more preferably 65 ° or more, and particularly preferably 70 ° or more. A contact angle of about 80 ° can be realized if the conditions for film production are selected. Moreover, the surface of the composite material in which various base materials are coated with the crosslinked fluorine-containing polystyrene derivative coating film of the present invention also exhibits the same water and oil repellency (contact angle).

  The measuring method of “contact angle with respect to water and hexadecane” in the present invention is shown below. Regarding the contact angle of the cross-linked fluorine-containing polystyrene derivative coating film of the present invention, the contact angle measuring device DM-300 (manufactured by Kyowa Interface Science) is used to measure the static contact angle of pure water and the static contact of hexadecane by the droplet method. Measure the corner.

  The sample for contact angle measurement is, for example, a substrate made of various materials (length: 75 mm × X) in a crosslinkable resin composition solution (solid content concentration: 0.1% by mass or more) containing the crosslinked fluorine-containing polystyrene derivative of the present invention. (Width 25 mm, thickness 1 mm) is dipped once to apply the solution, followed by drying and crosslinking treatment.

(Adhesion)
The water / oil repellent coating film made of a long chain perfluoroalkyl group-containing (meth) acrylate polymer that has been used conventionally has no adhesion to both inorganic and organic material substrates. It is sufficient, and particularly has a problem that the adhesion is extremely poor with respect to a substrate made of an organic material.

  On the other hand, the crosslinked fluorine-containing polystyrene derivative coating film of the present invention is applicable not only to inorganic material substrates (metal substrates and ceramic substrates) but also to various organic material substrates. It was confirmed that extremely excellent adhesion was exhibited. As a result, by using the crosslinked fluorine-containing polystyrene derivative coating film of the present invention, the surface of various base materials (particularly organic material base materials) has excellent water and oil repellency, antifouling properties, low refractive index properties, etc. This makes it possible to form a highly practical coating film that has not only the characteristics peculiar to fluorine-based materials but also excellent stability and adhesion.

  An example of a method for measuring the adhesion of the coating film of the present invention to various types of materials is shown below. In the case of a base material made of an inorganic material, a plate-like various material base material having a length of 75 mm × width of 25 mm and a thickness of 1 mm is applied once to the target crosslinkable resin composition solution, and the solution is applied. It dried at 100 degreeC for 1 hour, and in the case of the base material made from an organic material, it dried at 70 degreeC for 3 hours, and produced the uncrosslinked test piece. Next, each uncrosslinked test piece was subjected to a crosslinking treatment operation according to the characteristics of the crosslinkable resin composition to obtain a test piece.

  A 25-mm jig for JIS K 5600 was used for the test piece, and a craft knife cut into a grid pattern, and cellophane tape (manufactured by Nichiban, 24 mm width) was attached. Next, after pressing the cellophane tape against the substrate with an eraser, the cellophane tape is peeled off at a right angle with respect to the substrate, and then the crosslinked coating film is observed, and the crosslinked coating film is peeled off, floated or cracked. There were no wrinkles, and the adhesion was evaluated by the number.

  The crosslinked fluorine-containing polystyrene derivative coating film of the present invention is extremely excellent for both organic material base materials and inorganic material base materials (metal base materials, ceramic base materials) by the above-mentioned adhesion evaluation method. Tight adhesion (over 24 mm out of 25 mm).

  For example, the cross-linked fluorine-containing polystyrene derivative coating film of the present invention is made of a ceramic substrate such as a glass substrate, a metal substrate such as a stainless steel (for example, SUS304) substrate, an iron substrate, or a copper substrate, or Excellent adhesion of at least 24 mm in 25 mm to various organic material substrates such as acrylic resin substrate, polycarbonate resin substrate, ester resin substrate and polystyrene resin substrate In most cases, it exhibits an adhesion of 25 cm out of 25 cm.

  On the other hand, the adhesion of the conventional perfluorooctyl group- or perfluorohexyl group-containing methacrylate polymer coating film to the inorganic material substrate is insufficient, and particularly the adhesion to the organic material substrate is 10 mm or less in 25 mm. It was a (polycarbonate resin substrate) and was extremely insufficient.

  Therefore, the above-mentioned crosslinked fluorine-containing polystyrene derivative coating film of the present invention is at least one organic material substrate (industrially useful) selected from an acrylic resin substrate, a polycarbonate resin substrate and a polystyrene resin substrate. It is an extremely important feature for practical use that the number of residual wrinkles in an adhesion evaluation test on a base material made of an organic material is at least 24 mm in 25 mm, and further 25 mm in 25 mm.

  As described above, it can be said that the coating film having both excellent water / oil repellency and excellent adhesion to various substrates is realized for the first time by the crosslinked fluorine-containing polystyrene derivative coating film of the present invention. In particular, excellent adhesion to various organic material substrates is an extremely important characteristic that enables high performance of various organic materials.

<Pencil (scratch) hardness>
The measuring method of the pencil hardness of the surface of various materials in the present invention is shown below.
Based on JIS K 5600-5-4, evaluation was carried out using a pencil scratch tester (manufactured by Coating Tester Kogyo).

  The results of the pencil hardness test for various coating films often depend on the type of substrate. Therefore, the pencil hardness of the coating film coated on the surface of a planar acrylic substrate or planar polycarbonate (PC) substrate is adopted as the pencil hardness on the surface of the organic material in the present invention unless otherwise specified. It should be noted that since the acrylic substrate and the PC substrate may be deformed at a high crosslinking temperature of 100 ° C. or higher or 140 ° C. or higher, in such a case, a stainless steel flat substrate such as SUS304 stainless steel is used. The pencil hardness of the coating film coated on the surface may be adopted.

  Even when the pencil hardness measured by the above method of the uncrosslinked coating film containing the crosslinkable group-containing fluorine-containing polystyrene derivative used in the present invention is 6B or less, the pencil hardness is easily 3B or more by crosslinking. A practical crosslinked coating film of hardness is formed. Furthermore, a pencil hardness of HB or higher, F or higher, or H or higher can be realized.

(Heat-resistant)
The crosslinked fluorine-containing polystyrene derivative coating film of the present invention exhibits the following excellent heat resistance characteristics. That is, the surface water contact angle after the crosslinked fluorine-containing polystyrene derivative coating film of the present invention is heated in the atmosphere at 250 ° C. for 3 hours usually has a contact angle of 90% or more of the surface contact angle before heating. Furthermore, a contact angle retention of 95% or more or 97% or more can be easily realized.

(Weatherability)
The crosslinked fluorine-containing polystyrene derivative coating film of the present invention exhibits extremely excellent weather resistance. That is, after the crosslinked fluorine-containing polystyrene derivative coating film of the present invention is subjected to the following 500 hour weather resistance test, the water contact angle retention is 93% or more with respect to the surface contact angle before the test. Furthermore, a retention rate of 95% or more or 97% or more can be easily realized. On the other hand, the retention rate of the water contact angle after the weather resistance test of the coating film of the conventional perfluorooctylethyl methacrylate-based water / oil repellent was around 70% and was insufficient. Thus, it was confirmed that the cured coating film of the present invention exhibits extremely excellent weather resistance as compared with conventional perfluorooctylethyl methacrylate water / oil repellents.

  The method for evaluating the weather resistance of the crosslinked fluorine-containing polystyrene derivative coating film of the present invention is shown below. JIS B 7754 “Xenon arc lamp type light and weather resistance tester” is used, and JIS K 7350-2: 2008 “Plastic-Laboratory light source exposure test method part 2“ Xenon arc ” The weather resistance test under the test conditions described in “Lamp” (cycle No. 8 exposure cycle: continuous irradiation, exposure time: 500 hours, irradiance: 50 W / m 2, black standard temperature: 65 ° C., relative humidity: 50%) was performed. The contact angle of water on the sample surface after the weather resistance test was measured, compared with the contact angle of water on the sample surface before the weather resistance test, and the weather resistance was evaluated by the retention rate.

<Method for evaluating surface properties of various coating films and composite materials>
1) Characteristic evaluation of coating film on non-planar substrate When the shape of the composite material provided with the coating film on the surface is not planar, contact angle measurement, adhesion test and pencil hardness test by the above evaluation methods are performed. Can not. Therefore, in that case, in the present invention, the characteristic evaluation of the coating film on the non-planar substrate is replaced with the evaluation result by the following method.
-Contact angle measurement: The contact angle of water or hexadecane on the surface of the coating film to the planar substrate formed of the same material as the target non-planar composite substrate is the contact angle of the present invention. It shall be sufficient if the requirements are met.
In addition, the evaluation of the water contact angle retention in the heat resistance evaluation of the coating film on the substrate of the non-planar composite material is carried out by the coating film on the flat substrate made of SUS304 stainless steel as described in 2) below. The water contact angle retention rate evaluation results will be substituted.
In addition, the evaluation of the retention rate of water contact angle in the weather resistance evaluation of the coating film on the substrate of the non-planar composite material is as follows. The coating film on the flat substrate made of SUS304 stainless steel as described in 3) below The water contact angle retention rate evaluation results will be substituted.
-Adhesion test: The result of the adhesion test of the coating film on the substrate of the non-planar composite material is the coating on the planar substrate made of the same material as the target non-planar composite material substrate The film adhesion test result will be used instead.
Pencil hardness test: The pencil hardness test result of the coating film on the substrate of the non-planar composite material is replaced with the pencil hardness test result of the coating film coated on the surface of the planar acrylic substrate or PC substrate. To do.

2) Evaluation of heat resistance of various coating films of the present invention The heat resistance evaluation of various coating films of the present invention and various coating films forming the composite material of the present invention is an accelerated evaluation of the heat resistance (stability of properties at high temperatures). Therefore, an evaluation method under extremely severe temperature conditions of “250 ° C. in the atmosphere” is employed. Under these temperature conditions, when the base material is an organic material base material, many organic material base materials are altered or deformed, and unless otherwise specified, the heat resistance of various coating films on various base materials. The evaluation is made based on the heat resistance evaluation result (water contact angle retention rate) of the coating film made of the same material as the coating film on the SUS304 stainless steel flat substrate.

3) Weather resistance evaluation of various coating films of the present invention The weather resistance evaluation of various coating films of the present invention and various coating films forming the composite material of the present invention also employs an evaluation method under severe acceleration conditions. The determination is made based on the weather resistance evaluation result (water contact angle retention rate) of the coating film made of the same material as the coating film on the SUS304 stainless steel flat substrate.

<Use of crosslinked fluorine-containing polystyrene derivative coating film and its composite material>
The cross-linked fluorine-containing polystyrene derivative coating film formed by coating the cross-linkable resin composition of the present invention on the base material is excellent in water and oil repellency, antifouling property and low on the surface of various base materials. Not only properties unique to fluorine materials such as refractive index, but also excellent stability (heat resistance, weather resistance, moisture resistance, hydrolysis resistance, solvent resistance, etc.) not found in conventional fluorine-containing polyacrylate resins In addition, it provides a highly practical coating film that also has excellent adhesion and is extremely useful. In addition, a composite material coated with a cross-linked fluorine-containing polystyrene derivative coating film formed by coating a cross-linkable resin composition solution of the present invention on a base material and also having the above-described coating film characteristics on its surface is also provided. It is extremely useful.
Although the example of the specific use which utilized the characteristic of the bridge | crosslinking fluorine-containing polystyrene derivative coating film of this invention below is given, it is not limited to this.

1) Paints for outdoor use Paints for outdoor use (cross-linked coating film) utilizing the excellent weather resistance and stability (heat resistance, hydrolysis resistance) of the crosslinked fluorine-containing polystyrene derivative coating film of the present invention.

  Example) Anti-salt and anti-corrosion paints, anti-fouling and anti-corrosion (anti-rust) paints for outdoor structures, paints for home exteriors, anti-corrosion paints for automobiles, automotive repair paints, anti-stain and anti-corrosion paints for trains and aircraft Paints, harbor-related building paints, hot springs-related building paints, agricultural-related building paints, bridge paints, various infrastructure paints, various outdoor and civil engineering structure paints, etc.

2) Coating film for transparent resin substrate The crosslinked fluorine-containing polystyrene derivative coating film of the present invention is not only applied to a metal material substrate and a ceramic material substrate as described above, but also to various organic material substrates. A major feature is that it exhibits excellent adhesion. Among the organic material base materials, in particular, in the case of transparent resin base materials such as transparent acrylic resin base materials, transparent polycarbonate resin base materials, and transparent ester resin base materials, there are the following merits. It is useful.

  i) Extremely excellent adhesion to an organic material base material that could not be realized with conventional fluorine-containing polyacrylate resins.

  ii) It exhibits excellent stability (heat resistance, weather resistance, moisture resistance, hydrolysis resistance, solvent resistance, etc.) that could not be realized with conventional fluorine-containing polyacrylate resins.

  iii) Since the cross-linked fluorine-containing polystyrene derivative coating film is excellent in transparency, it improves surface properties of transparent optical resin products composed of various transparent resin substrates (providing water / oil repellency, antifouling properties, low refractive index, etc.). Is suitable.

  The “crosslinked fluorine-containing polystyrene derivative coating film formed on the surface of a transparent resin substrate” and “composite material in which a transparent resin substrate is coated with a crosslinked fluorine-containing polystyrene derivative coating film” having the above-mentioned various merits are Especially useful for improving the surface properties of organic optical resin products and their components (water / oil repellency imparting materials, antifouling treatment materials, solvent resistance imparting materials, antireflection materials, low refractive index sheath materials for plastic optical fibers, etc.) is there.

3) Other uses Cross-linked fluorine-containing polystyrene derivative coating film formed by coating the cross-linkable resin composition solution of the present invention on various base materials and then cross-linking treatment has excellent surface characteristics, durability and chemical stability. It can be applied to a wide range of uses as described below.

  Example) Moisture-proof coating agent for electronic substrates, chemical protection coating agent that protects the substrate from salt water, electrolyte, corrosive gas, etc., oil barrier agent that prevents the diffusion of lubricating oil used in micro motor bearings, HDD motor Oil barrier agent that prevents the diffusion of lubricating oil used for fluid bearings, leakage preventive agent that prevents leakage of ink such as sign pens and ballpoint pens, antifouling agent for connectors and electronic parts, anti-scooping agent for insulating resin, MF capacitor Anti-adhesion agent for lead sealing resin, anti-rust agent for metal parts, dry lubricant for guide rails such as DVD / CD, anti-reflection coating agent, waterproof spray undiluted solution, anti-corrosion paint, electronic equipment casing paint, Toy paint, etc.

<Example>
Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1
-Preparation of copolymer-
A copolymer A represented by the following formula [S-1] was produced by the method shown below.

A 1 L separable flask, a three-necked lid, a stirrer, a stirring blade, a dropping funnel, and a water bath with temperature control were prepared. 120 g (1.00 mol as p-hydroxystyrene unit) of poly (p-hydroxystyrene) (trade name “Marcalinker M”, manufactured by Maruzen Petrochemical Co., Ltd., Mw = 4,000), dimethyl sulfoxide (DMSO) In addition to 300 g, it melt | dissolved by heating and stirring at 60 degreeC, 20.0 ml of 50-% KOH aqueous solution was added and it stirred for 5 hours, keeping 60 degreeC. Next, the mixture was cooled to 15 ° C., 240 g (0.90 mol) of perfluoro (propyl vinyl ether) (FVE) was added, and the mixture was stirred for 24 hours. The reaction solution was poured into a large amount of water, and the precipitated resin was transferred to a vat and vacuum dried at 60 ° C. for 24 hours to obtain a polystyrene derivative with an approximate yield of 100%. As a result of this reaction, the molar ratio of the styrene unit having a CF ₃ CF ₂ CF ₂ OCHFCF ₂ O— group at the p- (para) position and the styrene unit having an OH group at the p- (para) position was 90:10 (mass). Copolymer A having a ratio of 97: 3) was obtained.

-Production of curable resin composition X1-
10 parts by mass of the copolymer A and Duranate TPA-100 (registered trademark) manufactured by Asahi Kasei Co., Ltd., which is a curable resin (isocyanurate type trifunctional isocyanate. Hereinafter, may be referred to as Duranate TPA-100). 1.4 parts by mass was dissolved in 10 parts by mass of methyl ethyl ketone (MEK) to obtain a uniform solution (curable resin composition solution X1). In addition, the ratio of the copolymer A in curable resin composition X1 (Copolymer A and curable resin) was 88 mass%. Moreover, the molar ratio of the amount of the hydroxyl group in the copolymer A and the amount of the isocyanate group in the duranate TPA-100 in the curable resin composition X1 is 1: 1.

(Example 2)
-Production of curable resin composition X2-
Except that the addition amount of Duranate TPA-100 (isocyanurate type trifunctional isocyanate) was changed to 2.1 parts by mass, a homogeneous solution was obtained (curable resin composition solution) in the same manner as in Example 1 above. X2). In addition, the ratio of the copolymer A in curable resin composition X2 (Copolymer A and curable resin) was 83 mass%. Moreover, the molar ratio of the amount of the hydroxyl group in the copolymer A and the amount of the isocyanate group in Duranate TPA-100 in the curable resin composition X2 is 1: 1.5.

(Example 3)
-Production of curable resin composition X3-
Except that the addition amount of Duranate TPA-100 (isocyanurate type trifunctional isocyanate) was changed to 2.8 parts by mass, a homogeneous solution was obtained (curable resin composition solution) in the same manner as in Example 1 above. X3). In addition, the ratio of the copolymer A in curable resin composition X3 (Copolymer A and curable resin) was 78 mass%. Moreover, the molar ratio of the amount of the hydroxyl group in the copolymer A and the amount of the isocyanate group in Duranate TPA-100 in the curable resin composition X3 is 1: 2.

(Preparation of test sample)
For each evaluation test described later, a test sample (test piece) was prepared by the method shown below. Each of the curable resin composition solutions X1, X2, and X3 of Examples 1 to 3 was applied to a polycarbonate (PC) plate (100 mm × 120 mm, thickness 1.5 mm) with a # 20 bar coater, respectively. A test sample (test piece) in which a cured coating film was formed on a polycarbonate (PC) plate by heating at 60 ° C. for 60 minutes was obtained.

  In addition, the same size acrylic plate and polyethylene terephthalate (PET) plate were applied in the same manner, and heated at 60 ° C. for 48 hours to prepare test samples (test pieces).

(Comparative Example 1)
10 parts by mass of the copolymer A was dissolved in 10 parts by mass of methyl ethyl ketone (MEK) to obtain a uniform solution (solution K). In addition, the ratio of the copolymer A in the comparative example 1 was 100 mass%.

(Comparative Example 2)
A 1 L separable flask, a three-necked lid, a stirrer, a stirring blade, and a water bath with temperature control were prepared. In a flask, 70 parts by mass of perfluorooctylethyl methacrylate (PFOEMA), 30 parts by mass of methyl methacrylate, 200 parts by mass of hexafluorometaxylene, 2 parts by mass of azobisisobutyronitrile were dissolved by heating and stirring at 60 ° C. The mixture was stirred for 8 hours while maintaining at 75 ° C. Next, the mixture was cooled to 15 ° C., 350 parts by mass of normal hexane was added, and the mixture was stirred well and allowed to stand overnight. The precipitate was collected by filtration and vacuum-dried at 60 ° C. for 24 hours to obtain a fluorinated acrylic resin (copolymer C) with an approximate yield of 100%.

  This polymer C did not dissolve in MEK. Copolymer C was dissolved in 2 parts by mass and 98 parts by mass of HCFC (Asahi Clin (registered trademark) AK-225 manufactured by Asahi Glass) to obtain a uniform solution (Solution L).

(Comparative Example 3)
The same procedure as in Comparative Example 2 was carried out except that 70 parts by mass of perfluorooctylethyl methacrylate (PFOEMA) was changed to 70 parts by mass of perfluorohexylethyl methacrylate (PFHEMA), and a copolymer D was obtained in an approximate yield of 100%.

  This copolymer D did not dissolve in MEK. Copolymer D was dissolved in 2 parts by mass and 98 parts by mass of HCFC (Asahi Clin (registered trademark) AK-225 manufactured by Asahi Glass) to obtain a uniform solution (Solution M).

  For Comparative Examples 1 to 3, a test sample was prepared in which a coating film composed of the solutions K, L, and M of each Comparative Example was formed on a support substrate, as in the above Examples.

[Evaluation 1: Water and oil repellency (contact angle)]
About the coating film of each Example and each comparative example, the contact angle with respect to water and hexadecane (HD) was measured by the method shown below. Specifically, the contact angle of the coating film of each Example and each Comparative Example was determined by using a contact angle measuring device (DM-300, manufactured by Kyowa Interface Science Co., Ltd.) and a pure static contact angle by a droplet method. And the static contact angle of hexadecane (HD) was measured. The evaluation results of each example and each comparative example are shown in Table 1.

[Evaluation 2: Heat resistance test]
About the coating film of each Example and each comparative example, heat resistance was evaluated by the method shown below. Specifically, after heating the coating film of each Example and each Comparative Example in the atmosphere at a temperature condition of 250 ° C. for 24 hours, the contact angle of water on the surface of the coating film was measured, and before the heat resistance test Compared with the contact angle of water on the sample surface (coating film surface), the heat resistance was evaluated by the retention rate. For the contact angle of water, the above contact angle measuring device was used. The results are shown in Table 1.

[Evaluation 3: Adhesion]
About the coating film of each Example and each comparative example, the adhesiveness with respect to various support substrates (PC board, an acrylic board, PET board) was evaluated by the method shown below. Specifically, while using a 25 mm jig for JIS K 5600, the coating film of the measurement sample was cut so that it was divided into 25 in a grid pattern with a craft knife. Next, a cellophane tape (24 mm width, manufactured by Nichiban Co., Ltd.) was applied to the cut-out coating film, and the cellophane tape was adhered to the support substrate by pressing with an eraser. Subsequently, the cellophane tape is peeled upward at a right angle with respect to the support substrate (coating film), and then the coating film on the support substrate is visually observed to eliminate defects such as peeling, floating, and cracking of the coating film. And the adhesion was evaluated by the number of the ridges. The evaluation results are shown in Table 1. In addition, the blank part of Table 1 means that adhesive evaluation is not performed.

[Evaluation 4: Pencil hardness]
About the coating film of each Example and each comparative example, pencil (scratch) hardness was measured by the method shown below. Specifically, the pencil hardness of each coating film was measured using a pencil scratch tester (manufactured by Coating Tester Kogyo Co., Ltd.) in accordance with JIS K 5600-5-4. In the measurement of pencil hardness, a PC plate, an acrylic plate, and a PET plate were used as a support substrate for the measurement sample. The measurement results are shown in Table 1. In addition, the blank part of Table 1 means that the pencil hardness is not measured.

It was confirmed that the coating film of each example was excellent in heat resistance as compared with the coating film of each comparative example, could be used for automobiles and industrial equipment, and was practically useful.
Moreover, the coating film of each Example was excellent in adhesiveness compared with the coating film of Comparative Examples 2 and 3, and it was confirmed that it was practically useful.
Moreover, the coating film of each Example was excellent in pencil hardness compared with the coating film of each comparative example, and it was confirmed that it was useful for the exterior use etc.

Example 4
-Preparation of copolymer-
Copolymer B represented by the following formula [S-2] was produced by the method shown below.

  A 1 L separable flask, a three-necked lid, a stirrer, a stirring blade, and a water bath with temperature control were prepared. Add 4- [1,1,2-trifluoro-2- [1,1,2,3,3,3-hexafluoro-2- (1,1,2,2,3,3,3-hepta] to the flask. In addition to 100 parts by mass of propoxy]-ethoxy] styrene, 2.6 parts by mass of 2-hydroxyethyl methacrylate, 200 parts by mass of hexafluorometaxylene, 2.4 parts by mass of azobisisobutyronitrile at 60 ° C. It melt | dissolved by heating and stirring, and stirred for 8 hours, keeping at 75 degreeC. Next, after cooling to 15 ° C., adding 300 parts by mass of normal hexane and stirring well, the mixture was allowed to stand overnight. The precipitate was collected by filtration and vacuum-dried at 60 ° C. for 24 hours to obtain a polystyrene derivative with an approximate yield of 100%. As a result of this reaction, a copolymer B having a styrene unit: methacrylate unit molar ratio of 90:10 was obtained.

-Production of curable resin composition Y1-
6 parts by mass of the copolymer B and 0.2 parts by mass of Duranate TPA-100 (isocyanurate type trifunctional isocyanate) manufactured by Asahi Kasei Co., Ltd., which is a curable resin, are dissolved in 14 parts by mass of methyl ethyl ketone (MEK). As a result, a homogeneous solution was obtained (curable resin composition solution Y1). In addition, the ratio of the copolymer B in curable resin composition Y1 (Copolymer B and curable resin) was 97 mass%. Moreover, the molar ratio of the amount of the hydroxyl group in the copolymer B and the amount of the isocyanate group in Duranate TPA-100 in the curable resin composition Y1 is 1: 1.

(Example 5)
-Production of curable resin composition Y2-
Except that the addition amount of Duranate TPA-100 (isocyanurate-type trifunctional isocyanate) was changed to 0.3 parts by mass, a homogeneous solution was obtained (curable resin composition solution) in the same manner as in Example 4 above. Y2). In addition, the ratio of the copolymer B in curable resin composition Y2 (Copolymer B and curable resin) was 95.2 mass%. Moreover, the molar ratio of the amount of the hydroxyl group in the copolymer B and the amount of the isocyanate group in Duranate TPA-100 in the curable resin composition Y2 is 1: 1.5.

(Example 6)
-Production of curable resin composition Y3-
Except having changed the addition amount of Duranate TPA-100 (isocyanurate type trifunctional isocyanate) into 0.4 mass part, it carried out similarly to the said Example 4, and obtained the uniform melt | dissolution solution (curable resin composition solution) Y3). In addition, the ratio of the copolymer B in curable resin composition Y3 (Copolymer B and curable resin) was 93.8 mass%. In the curable resin composition Y3, the molar ratio of the amount of hydroxyl groups in the copolymer B to the amount of isocyanate groups in the duranate TPA-100 is 1: 2.

(Comparative Example 4)
6 parts by mass of the copolymer B was dissolved in 14 parts by mass of methyl ethyl ketone (MEK) to obtain a uniform solution (solution N). In addition, the ratio of the copolymer B in a resin composition (Copolymer B and curable resin) was 100 mass%.

(Preparation of test sample)
For each evaluation test described later, a test sample (test piece) was prepared by the method shown below. Each of the curable resin composition solutions Y1, Y2, and Y3 of Examples 4 to 6 was applied to a polycarbonate (PC) plate (100 mm × 120 mm, thickness 1.5 mm) with a # 20 bar coater, respectively. A test sample (test piece) in which a cured coating film was formed on a polycarbonate (PC) plate by heating at 60 ° C. for 60 minutes was obtained.

  Moreover, also about the comparative example 4, the test sample which formed the coating film which consists of the solution N of a comparative example on the support substrate (PC board) similarly to each said Example was produced.

[Evaluation 5: Water and oil repellency (contact angle)]
About the coating film of Examples 4-6, it carried out similarly to the measuring method of the evaluation 1 mentioned above, and measured the contact angle with respect to water and hexadecane (HD). The results are shown in Table 2.

[Evaluation 6: Adhesion]
About the coating film of Examples 4-6, it carried out similarly to the method of the evaluation 3 mentioned above, and evaluated the adhesiveness with respect to a PC board. The results are shown in Table 2.

  Table 2 also shows the results of Comparative Examples 2 to 4 described above. In addition, all the cured coating films on the PC substrates of Examples 4 to 6 exhibited a pencil hardness of HB or higher.

  As shown in Table 2, the evaluation of the adhesion of Comparative Example 4 resulted in the measurement being impossible because the coating film was highly tacky and the coating film was sticky.

  The coating films of Examples 4 to 6 showed a high contact angle even when compared with Comparative Example 2, and it was confirmed that the coating films were extremely useful as materials having environmental friendliness and high water and oil repellency. Furthermore, it was confirmed that the coating films of Examples 4 to 6 were excellent in adhesion, applicable to various coating materials such as exterior coating materials, and practically useful.

(Example 7)
-Production of copolymer C11-
A 1 L separable flask, a three-necked lid, a stirrer, a stirring blade, and a water bath with temperature control were prepared. 4- [1,1,2-trifluoro-2- (1,1,2,2,3,3,3-heptafluoropropoxy) ethoxy] styrene (hereinafter sometimes referred to as monomer A) in a flask In addition to 96.4 parts by mass, 3.6 parts by mass of hydroxypropyl acrylate (hereinafter sometimes referred to as HPA), 200 parts by mass of hexafluorometaxylene, 2.4 parts by mass of azobisisobutyronitrile, 60 ° C. Then, the mixture was dissolved by heating and stirring, and the mixture was stirred for 8 hours while maintaining at 75 ° C. Next, after cooling to 15 ° C., adding 300 parts by mass of normal hexane and stirring well, the mixture was allowed to stand overnight. The precipitate was collected by filtration and vacuum-dried at 60 ° C. for 24 hours to obtain a polystyrene derivative with an approximate yield of 100%. As a result of this reaction, a copolymer C11 having a molar ratio of fluorine-containing styrene unit to HPA unit of 90:10 was obtained.

—Preparation of Curable Resin Composition K11— 9 parts by mass of the copolymer C11 and 0.62 parts by mass of Duranate TPA-100, which is a curable resin, are expressed as propylene glycol monomethyl ether (hereinafter referred to as PGM-Ac). It was dissolved in 20 parts by mass to obtain a uniform solution (curable resin composition solution K11). In addition, in the curable resin composition K11, the molar ratio of the amount of hydroxyl groups in the copolymer C11 and the amount of isocyanate groups in the duranate TPA-100 is 1: 1.5.

(Example 8)
-Production of copolymer C12-
The molar ratio of the fluorinated styrene unit and the HPA unit was 70: as in Example 7 except that the addition amount of monomer A was changed to 87.4 parts by mass and the addition amount of HPA was changed to 12.6 parts by mass. A copolymer C12 of 30 was obtained.

-Production of curable resin composition K12-
In the same manner as in Example 7 except that 9 parts by mass of the copolymer C12 was used instead of the copolymer C11, and the addition amount of duranate TPA-100 was changed to 2.15 parts by mass. A solution was obtained (curable resin composition K12). In addition, in the curable resin composition K12, the molar ratio of the amount of hydroxyl groups in the copolymer C12 and the amount of isocyanate groups in the duranate TPA-100 is 1: 1.5.

Example 9
-Production of copolymer C13-
The molar ratio of the fluorinated styrene unit to the HPA unit was 50: as in Example 7 except that the addition amount of monomer A was changed to 74.8 parts by mass and the addition amount of HPA to 25.2 parts by mass. A copolymer C13 of 50 was obtained.

-Production of curable resin composition K13-
Uniform dissolution was carried out in the same manner as in Example 7 except that 9 parts by mass of the copolymer C13 was used instead of the copolymer C11 and the addition amount of Duranate TPA-100 was changed to 4.39 parts by mass. A solution was obtained (curable resin composition K13). In addition, in the curable resin composition K3, the molar ratio of the amount of hydroxyl groups in the copolymer C13 and the amount of isocyanate groups in the duranate TPA-100 is 1: 1.5.

(Example 10)
-Production of copolymer C14-
The molar ratio of the fluorine-containing styrene unit to the HPA unit was 40: in the same manner as in Example 7 except that the amount of monomer A added was changed to 66.4 parts by mass and the amount of HPA added was changed to 33.6 parts by mass. A copolymer C14 of 60 was obtained.

-Production of curable resin composition K14-
In the same manner as in Example 7 except that 9 parts by mass of the copolymer C14 was used instead of the copolymer C11 and the addition amount of Duranate TPA-100 was changed to 5.85 parts by mass. A solution was obtained (curable resin composition K14). In addition, in the curable resin composition K14, the molar ratio of the amount of hydroxyl groups in the copolymer C15 and the amount of isocyanate groups in the duranate TPA-100 is 1: 1.5.

(Example 11)
-Production of copolymer C15-
The molar ratio of the fluorine-containing styrene unit to the HPA unit was 30 as in Example 7 except that the addition amount of monomer A was changed to 56.0 parts by mass and the addition amount of HPA was changed to 44.0 parts by mass. A copolymer C15 of 70 was obtained.

-Production of curable resin composition K15-
Uniform dissolution was carried out in the same manner as in Example 7 except that 9 parts by mass of the copolymer C15 was used instead of the copolymer C11 and the addition amount of duranate TPA-100 was changed to 7.67 parts by mass. A solution was obtained (curable resin composition K15). In addition, in the curable resin composition K15, the molar ratio of the amount of hydroxyl groups in the copolymer C15 and the amount of isocyanate groups in the duranate TPA-100 is 1: 1.5.

(Example 12)
-Production of copolymer C21-
The above implementation was performed except that the amount of monomer A added was 94.6 parts by mass, and 5.4 parts by mass of 1,4-cyclohexanedimethanol monoacrylate (hereinafter sometimes referred to as CHDMMA) was added instead of HPA. In the same manner as in Example 7, a copolymer C21 having a molar ratio of fluorine-containing styrene unit to CHDMMA unit of 90:10 was obtained.

-Production of curable resin composition K21-
In the same manner as in Example 7 except that 9 parts by mass of the copolymer C21 was used instead of the copolymer C11, and the addition amount of duranate TPA-100 was changed to 0.60 parts by mass. A solution was obtained (curable resin composition K21). In addition, in the curable resin composition K21, the molar ratio of the amount of hydroxyl groups in the copolymer C21 and the amount of isocyanate groups in the duranate TPA-100 is 1: 1.5.

(Example 13)
-Production of copolymer C22-
The molar ratio of the fluorine-containing styrene unit to the CHDMMA unit was 70: as in Example 12 except that the amount of monomer A added was 82.0 parts by mass and the amount of CHDMMA added was 18.0 parts by mass. 30 copolymer C22 was obtained.

-Production of curable resin composition K22-
In the same manner as in Example 12, except that 9 parts by mass of the copolymer C22 was used instead of the copolymer C21 and the addition amount of Duranate TPA-100 was changed to 2.06 parts by mass. A solution was obtained (curable resin composition K22). In the curable resin composition K22, the molar ratio of the amount of hydroxyl groups in the copolymer C22 to the amount of isocyanate groups in the duranate TPA-100 is 1: 1.5.

(Example 14)
-Production of copolymer C23-
The molar ratio of the fluorinated styrene unit to the CHDMMA unit was 50: as in Example 12 except that the amount of monomer A added was 66.1 parts by mass and the amount of CHDMMA added was 33.9 parts by mass. A copolymer C23 of 50 was obtained.

-Production of curable resin composition K23-
In the same manner as in Example 12 except that 9 parts by mass of the copolymer C23 was used instead of the copolymer C21 and the addition amount of Duranate TPA-100 was changed to 3.88 parts by mass. A solution was obtained (curable resin composition K23). In addition, in the curable resin composition K23, the molar ratio of the amount of hydroxyl groups in the copolymer C23 and the amount of isocyanate groups in the duranate TPA-100 is 1: 1.5.

(Example 15)
-Production of copolymer C31-
The same as Example 7 except that the amount of monomer A added was 86.2 parts by mass, and 13.8 parts by mass of 4-hydroxybutyl acrylate (hereinafter sometimes referred to as 4HBA) was added instead of HPA. Thus, a copolymer C31 having a molar ratio of the fluorine-containing styrene unit to the 4HBA unit of 70:30 was obtained.

-Production of curable resin composition K31-
Uniform dissolution was carried out in the same manner as in Example 7 except that 9 parts by mass of the copolymer C31 was used instead of the copolymer C11 and the addition amount of duranate TPA-100 was changed to 2.06 parts by mass. A solution was obtained (curable resin composition K31). In the curable resin composition K31, the molar ratio of the amount of hydroxyl groups in the copolymer C31 to the amount of isocyanate groups in the duranate TPA-100 is 1: 1.5.

(Preparation of test sample)
For each evaluation test described later, a test sample (test piece) was prepared by the method shown below. Each of the curable resin composition solutions K11 to K15, K21 to K23, and K31 of Examples 7 to 15 was placed on a polycarbonate (PC) plate (100 mm × 120 mm, thickness 1.5 mm) with a # 20 bar coater. The sample was applied and heated at 120 ° C. for 60 minutes to obtain a test sample (test piece) in which a cured coating film was formed on a polycarbonate (PC) plate.

(Comparative Examples 7-15)
Each of the curable resin composition solutions K11 to K15, K21 to K23, and K31 of Examples 7 to 15 was placed on a polycarbonate (PC) plate (100 mm × 120 mm, thickness 1.5 mm) with a # 20 bar coater. The test sample which consists of an uncured coating film which apply | coated and has not performed hardening reaction was produced, and it was set as Comparative Examples 7-15, respectively.

[Evaluation 6: Water and oil repellency (contact angle)]
About the test sample of Examples 7-15 and Comparative Examples 7-15, it carried out similarly to the measuring method of the evaluation 1 mentioned above, and measured the contact angle with respect to water and hexadecane (HD). The results are shown in Table 3.

[Evaluation 7: Adhesion]
About the test sample of Examples 7-15 and Comparative Examples 7-15, it carried out similarly to the method of the evaluation 3 mentioned above, and evaluated the adhesiveness with respect to a PC board. The results are shown in Table 3.

[Evaluation 8: Pencil hardness]
About the test sample of Examples 7-15 and Comparative Examples 7-15, it carried out similarly to the method of the evaluation 4 mentioned above, and evaluated pencil (scratch) hardness. The results are shown in Table 3.

  The coating film of each example was particularly excellent in pencil hardness as compared with the coating film of each comparative example, and it was confirmed that the coating film was useful for exterior use and the like.

[Evaluation 9: Heat resistance test]
About the test sample of Examples 7-8, it carried out similarly to the method of the evaluation 2 mentioned above, and evaluated heat resistance. The results are shown in Table 4.

[Evaluation 10: Weather resistance test]
About the test sample of Examples 7-8, the weather resistance was evaluated by the method shown below. The results are shown in Table 4. Specifically, with respect to the coating films of each Example and each Comparative Example, JIS K 7350-2: 2008 was used by using a tester defined by “Xenon arc lamp light resistance and weather resistance tester” of JIS B 7754. Test conditions described in “Plastics—Exposure test method using laboratory light source” Part 2 “Xenon arc lamp” (cycle No8 exposure cycle: continuous irradiation, exposure time: 500 hours, irradiance: 50 W / m 2, black standard temperature: 65 ° C., relative humidity: 50%). The contact angle of water on the sample surface before and after the weather resistance test was measured, compared with the contact angle of water on the sample surface before the weather resistance test, and the weather resistance was evaluated by the retention rate. The contact angle was measured by the method described in Evaluation 1, and the results are shown in Table 4.

  It was confirmed that the coating film of each example is excellent in heat resistance and weather resistance, can be used for automobiles and industrial equipment, and is practically useful.

[Evaluation 11: Solvent rubbing test]
About the test sample of Examples 7-8 and Example 13, and Comparative Examples 7-8 and Comparative Example 13, solvent resistance was evaluated by the solvent rubbing test. The solvent rubbing test was performed by applying a load of 500 g to a waste impregnated with various solvents, rubbing the surface of each test sample 100 times, and measuring the change in contact angle before and after that. The results are shown in Table 5.

  The coating film of each Example was excellent in solvent resistance, and it was confirmed that it was practically useful. The coating film of each comparative example was inferior in solvent resistance as compared with the coating film of each corresponding example. It was confirmed that the contact angle decrease due to water rubbing and solvent rubbing was largely suppressed by the crosslinking, and that the solvent resistance was improved by using a crosslinked body.

(Example 16)
-Production of copolymer D11-
The amount of monomer A added is 96.1 parts by mass, and Karenz AOI (registered trademark) (2-acryloyloxyethyl isocyanate, hereinafter referred to as Karenz AOI) manufactured by Showa Denko KK is used instead of HPA. A copolymer D11 having a molar ratio of the fluorinated styrene unit to the Karenz AOI unit of 90:10 was obtained in the same manner as in Example 7 except that 9 parts by mass was added.

-Production of curable resin composition L11-
9 parts by mass of the above copolymer D11 was used instead of copolymer C11, and “Marcalinker” CST-50 (styrene-hydroxystyrene copolymer produced by Maruzen Petrochemical Co., Ltd.) was used instead of duranate TPA-100. A homogeneous solution was obtained (curable resin composition L11) in the same manner as in Example 7 except that 0.40 part by mass of CST-50 was sometimes added). In addition, in the curable resin composition L11, the molar ratio of the amount of isocyanate groups in the copolymer D11 and the amount of hydroxyl groups in CST-50 is 1.5: 1.

(Example 17)
-Production of copolymer D12-
The molar ratio of the fluorinated styrene unit to the Karenz AOI unit was the same as in Example 16 except that the addition amount of the monomer A was changed to 86.5 parts by mass and the addition amount of the Karenz AOI was changed to 13.5 parts by mass. A copolymer D12 of 70:30 was obtained.

-Production of curable resin composition L12-
Uniformly dissolved solution in the same manner as in Example 16 except that 9 parts by mass of the copolymer D12 was used instead of the copolymer D11, and the addition amount of CST-50 was changed to 1.40 parts by mass. (Curable resin composition L12) was obtained. In addition, in the curable resin composition L12, the molar ratio of the amount of isocyanate group in the copolymer D12 and the amount of hydroxyl group in CST-50 is 1: 1.5.

(Example 18)
-Production of copolymer D13-
The molar ratio of the fluorinated styrene unit to the Karenz AOI unit was the same as in Example 16 except that the addition amount of the monomer A was changed to 73.2 parts by mass and the addition amount of the Karenz AOI was changed to 26.8 parts by mass. Copolymer D13 having a ratio of 50:50 was obtained.

-Production of curable resin composition L13-
A homogeneous solution as in Example 16 except that 9 parts by weight of the copolymer D13 was used instead of the copolymer D11 and the amount of CST-50 added was changed to 2.80 parts by weight. (Curable resin composition L13) was obtained. In addition, in the curable resin composition L13, the molar ratio of the amount of isocyanate groups in the copolymer D13 and the amount of hydroxyl groups in CST-50 is 1: 1.5.

(Preparation of test sample)
For each evaluation test described later, a test sample (test piece) was prepared by the method shown below. Each of the curable resin composition solutions L11 to L13 of Examples 16 to 21 was applied to a polycarbonate (PC) plate (100 mm × 120 mm, thickness 1.5 mm) with a # 20 bar coater. The test sample (test piece) by which the cured coating film was formed in the polycarbonate (PC) board by heating for a minute was obtained.

(Comparative Examples 16-18)
Each of the curable resin composition solutions L11 to L13 of Examples 16 to 18 was applied to a polycarbonate (PC) plate (100 mm × 120 mm, thickness 1.5 mm) with a # 20 bar coater, and a curing reaction was performed. Test samples comprising uncured uncured coatings were prepared and used as Comparative Examples 16 to 18, respectively.

[Evaluation 12: Water and oil repellency (contact angle)]
About the test sample of Examples 16-18 and Comparative Examples 16-18, it carried out similarly to the measuring method of the evaluation 1 mentioned above, and measured the contact angle with respect to water and hexadecane (HD). The results are shown in Table 6.

[Evaluation 13: Adhesion]
About the test sample of Examples 16-18 and Comparative Examples 16-18, it carried out similarly to the method of the evaluation 3 mentioned above, and evaluated the adhesiveness with respect to a PC board. The results are shown in Table 6.

[Evaluation 14: Pencil hardness]
About the test sample of Examples 16-18 and Comparative Examples 16-18, it carried out similarly to the method of the evaluation 4 mentioned above, and pencil (scratch) hardness was evaluated. The results are shown in Table 6.

  The coating film of each example was particularly excellent in pencil hardness as compared with the coating film of each comparative example, and it was confirmed that the coating film was useful for exterior use and the like.

(Example 19)
-Production of copolymer E11-
The amount of the monomer A was 96.1 parts by mass, and fluoridated styrene unit and glycidyl methacrylate unit were added in the same manner as in Example 7 except that glycidyl methacrylate was added instead of HPA. A copolymer E11 having a molar ratio of 90:10 was obtained.

-Production of curable resin composition M11-
Instead of the copolymer C11, 10 parts by mass of the copolymer E11 is used, and instead of Duranate TPA-100, “ADEKA Hardener” EH-479A (polyamine. Except that 0.40 parts by mass of (A) was added, a homogeneous solution was obtained in the same manner as in Example 7 (curable resin composition L11).

(Example 20)
-Production of copolymer E12-
The moles of the fluorine-containing styrene unit and the glycidyl methacrylate unit were the same as in Example 19 except that the addition amount of monomer A was changed to 86.4 parts by mass and the addition amount of glycidyl methacrylate to 13.6 parts by mass. A copolymer E12 having a ratio of 70:30 was obtained.

-Production of curable resin composition M12-
10 parts by mass of the copolymer E12 and 0.40 parts by mass of EH-479 were used instead of the copolymer E11, and a homogeneous solution was obtained in the same manner as in Example 19 (curable resin composition). M12).

(Example 21)
-Production of copolymer E21-
The above implementation was performed except that the amount of monomer A added was 81.8 parts by mass, and 18.2 parts by mass of 4-hydroxybutyl acrylate glycidyl ether (hereinafter sometimes referred to as 4HBAGE) was used instead of glycidyl methacrylate. In the same manner as in Example 19, a copolymer E21 having a molar ratio of the fluorine-containing styrene unit to the glycidyl methacrylate unit of 70:30 was obtained.

-Production of curable resin composition M21-
10 parts by mass of the copolymer E21 and 0.40 parts by mass of EH-479 were used instead of the copolymer E11, and a homogeneous solution was obtained in the same manner as in Example 19 (curable resin composition). M21).

(Preparation of test sample)
For each evaluation test described later, a test sample (test piece) was prepared by the method shown below. Each of the curable resin composition solutions M11, M12, and M21 of Examples 19 to 21 was applied to a SUS304 stainless steel plate (100 mm × 120 mm, thickness 1.5 mm) with a # 20 bar coater, and 150 ° C. The test sample (test piece) in which a cured coating film was formed on the stainless steel plate by heating for 60 minutes was obtained.

(Comparative Examples 19-21)
The curable resin composition solutions M11, M12, and M21 of Examples 19 to 21 were applied to a SUS304 stainless steel plate (100 mm × 120 mm, thickness 1.5 mm) with a # 20 bar coater, and cured. Test samples composed of uncured coatings that had not been reacted were prepared and used as Comparative Examples 19 to 21, respectively.

[Evaluation 15: Water and oil repellency (contact angle)]
About the test sample of Examples 19-21 and Comparative Examples 19-21, it carried out similarly to the measuring method of the evaluation 1 mentioned above, and measured the contact angle with respect to water and hexadecane (HD). The results are shown in Table 7.

[Evaluation 16: Adhesion]
About the test sample of Examples 19-21 and Comparative Examples 19-21, it carried out similarly to the method of the evaluation 3 mentioned above, and evaluated the adhesiveness with respect to a PC board. The results are shown in Table 7.

[Evaluation 17: Pencil hardness]
About the test sample of Examples 19-21 and Comparative Examples 19-21, it carried out similarly to the method of the evaluation 4 mentioned above, and evaluated pencil (scratch) hardness. The results are shown in Table 7.

  The coating film of each example was particularly excellent in pencil hardness as compared with the coating film of each comparative example, and it was confirmed that the coating film was useful for exterior use and the like.

(Example 22)
-Production of copolymer C41-
The amount of monomer A added was 71.1 parts by mass, the amount of HPA added was 12.0 parts by mass, and 4- [1,1,2-trifluoro-2- [1,1,2,3,3, 16.9 parts by mass of 3-hexafluoro-2- (1,1,2,2,3,3,3-heptafluoropropoxy) propoxy] -ethoxy] styrene (hereinafter sometimes referred to as monomer B) In the same manner as in Example 7 except that the copolymer C41 in which the molar ratio of the fluorine-containing styrene unit of monomer A, the fluorine-containing styrene unit of monomer B, and the HPA unit is 60:10:30 is obtained. Obtained.

-Production of curable resin composition K41-
A homogeneous solution was obtained in the same manner as in Example 7 except that 9 parts by mass of the copolymer C41 was used instead of the copolymer C11 and 2.00 parts by mass of Duranate TPA-100 was added. (Curable resin composition K41).

(Example 23)
-Production of copolymer C42-
Except for using 66.9 parts by mass of monomer A, 15.9 parts by mass of monomer B, and 18.2 parts by mass of CHDMMA instead of HPA, the same as in Example 22 above, A copolymer C42 in which the molar ratio of the fluorine-containing styrene unit of monomer A, the fluorine-containing styrene unit of monomer B, and the CHDMMA unit was 60:10:30 was obtained.

-Production of curable resin composition K42-
A homogeneous solution as in Example 22 except that 9 parts by mass of the copolymer C42 was used instead of the copolymer C41, and the addition amount of Duranate TPA-100 was 1.97 parts by mass. (Curable resin composition K42) was obtained.

(Preparation of test sample)
For each evaluation test described later, a test sample (test piece) was prepared by the method shown below. Each of the curable resin composition solutions K41 and 42 of Examples 22 and 23 was applied to a polycarbonate (PC) plate (100 mm × 120 mm, thickness 1.5 mm) with a # 20 bar coater, respectively, at 120 ° C., 60 ° C. The test sample (test piece) by which the cured coating film was formed in the polycarbonate (PC) board by heating for a minute was obtained.

(Comparative Examples 19-21)
Each of the curable resin composition solutions K41 and 42 of Examples 22 and 23 was applied to a polycarbonate (PC) plate (100 mm × 120 mm, thickness 1.5 mm) with a # 20 bar coater to cause a curing reaction. Test samples made of uncured coatings that were not performed were prepared as Comparative Examples 22 and 23, respectively.

[Evaluation 18: Water and oil repellency (contact angle)]
For the test samples of Examples 22 and 23 and Comparative Examples 22 and 23, the contact angles for water and hexadecane (HD) were measured in the same manner as in the measurement method of Evaluation 1 described above. The results are shown in Table 8.

[Evaluation 19: Adhesion]
About the test sample of Examples 22 and 23 and Comparative Examples 22 and 23, it carried out similarly to the method of the evaluation 3 mentioned above, and evaluated the adhesiveness with respect to a PC board. The results are shown in Table 8.

[Evaluation 20: Pencil hardness]
For the test samples of Examples 22 and 23 and Comparative Examples 22 and 23, the pencil (scratch) hardness was evaluated in the same manner as in the method of Evaluation 4 described above. The results are shown in Table 8.

  The coating film of each example was particularly excellent in pencil hardness as compared with the coating film of each comparative example, and it was confirmed that the coating film was useful for exterior use and the like.

Claims (14)

1 to 99% by mass of a repeating unit represented by the following formula [1] and a crosslinking group-containing fluorine-containing polystyrene derivative containing a crosslinking group-containing repeating unit in a range of 1 to 95% by mass. A cross-linked fluorine-containing polystyrene derivative coating film prepared by coating a cross-linkable resin composition solution on a substrate and then performing cross-linking treatment, and satisfying the following requirements (A), (B) and (C) A characteristic cross-linked fluorine-containing polystyrene derivative coating film.

(In the formula [1], Y represents a hydrogen atom or an alkyl group having 6 or less carbon atoms, and Q represents a divalent group containing at least one ether bond and having a total number of carbon atoms of 5 or less. , .z Rf _o is at least one of the total number of carbon atoms containing an ether group is a monovalent which may contain 25 or less of one hydrogen atom perfluoroether group is selected from 1 to 3 The bond position of Q to the aromatic nucleus may be any of the ortho, meta, or para positions relative to the bond position of the aromatic nucleus and the polymer main chain, bonded to the aromatic nucleus in formula [1]. Some or all of the hydrogen atoms may be substituted with fluorine atoms.)
(A) The contact angle of water on the surface of the crosslinked fluorine-containing polystyrene derivative coating film is 100 ° or more, the contact angle of hexadecane is 60 ° or more, or the contact angle of water is 100 ° or more and the contact angle of hexadecane is 60 ° or more. Be.
(B) The number of residual wrinkles in the adhesion evaluation test for at least one kind of base material selected from organic base materials and inorganic material base materials of the crosslinked fluorine-containing polystyrene derivative coating film is 24% or more in 25% There is.
(C) The crosslinked fluorine-containing polystyrene derivative coating film satisfies at least one of the following conditions (1) to (3).
(1) The surface hardness of the crosslinked fluorine-containing polystyrene derivative coating film is a pencil (scratch) hardness of 3B or more.
(2) The contact angle of water on the surface after the crosslinked fluorine-containing polystyrene derivative coating film is heated in the atmosphere at 250 ° C. for 3 hours is 90% or more of the contact angle before heating.
(3) The contact angle of water on the surface after subjecting the crosslinked fluorine-containing polystyrene derivative coating film to a weather resistance test for 500 hours is 93% or more of the contact angle before the test. 2. The crosslinked fluorine-containing polystyrene derivative coating film according to claim 1, wherein the repeating unit represented by the formula [1] is a repeating unit represented by the following formula [1-1].

(In Formula [1-1], Y1 is a hydrogen atom or a methyl group, and Q1 is a divalent group containing an ether bond having 3 or less carbon atoms. Rfo ₁ is Rfa ₁ -O- [CF _{(CF 3) CF 2 O]} n1 - [CF 2 CF 2 CF 2 O] n2 - [CF 2 CF 2 O] n3 - [CF 2 O] n4 -Rfc 1 - a a, Rfa ₁ 1 carbon atoms To 6 perfluoroalkyl groups, n1, n2, n3 and n4 are each an integer selected from 0 or 1 to 6, n1 + n2 + n3 + n4 is 0 to 6, and Rfc ₁ is _one having 3 or less carbon atoms. A perfluoroalkylene group which may contain a hydrogen atom of The repeating unit represented by the formula [1] or the formula [1-1] is a repeating unit represented by the following formula [1-2]. Cross-linked fluorine-containing polystyrene derivative coating film.

(Wherein [1-2], Y2 is a hydrogen atom or a methyl group, an integer L1 is selected from 0 or 1 to 6, Rfa ₂ is a perfluoroalkyl group having 1 to 6 carbon atoms).   The crosslinked fluorine-containing polystyrene derivative coating film according to any one of claims 1 to 3, wherein the crosslinked fluorine-containing film satisfies two or more of the conditions (1) to (3). Polystyrene derivative coating film.   The crosslinked fluorine-containing polystyrene derivative coating film according to any one of claims 1 to 4, wherein the substrate in the adhesion evaluation test (B) is a substrate made of an organic material.   The organic material substrate is at least one organic material substrate selected from an acrylic resin substrate, a polycarbonate resin substrate, an ester resin substrate, and a polystyrene resin substrate. The crosslinked fluorine-containing polystyrene derivative coating film according to claim 5.   1 to 99% by mass of the repeating unit represented by the formula [1], [1-1] or [1-2] and 1 to 95% by mass of the repeating unit containing a crosslinking group. Crosslinkable group-containing fluorine-containing polystyrene derivative contained in the range of   1 to 99% by mass of the repeating unit represented by the formula [1], [1-1] or [1-2] and 1 to 95% by mass of the repeating unit containing a crosslinking group. A crosslinkable group-containing fluorine-containing polystyrene derivative contained in the range of the above, wherein the crosslinkable coating film satisfies the requirements (A), (B) and (C) according to claim 1 Fluorine-containing polystyrene derivative.   A composite material formed by coating a substrate selected from an organic material substrate and an inorganic material substrate with the crosslinked fluorine-containing polystyrene derivative coating film according to any one of claims 1 to 6.   The composite material according to claim 9, wherein the base material is an organic material base material.   11. The composite according to claim 10, wherein the organic material substrate is a substrate selected from an acrylic resin substrate, a polycarbonate resin substrate, an ester resin substrate, and a polystyrene resin substrate. material.   11. The composite material according to claim 10, wherein the organic material substrate is a transparent resin substrate.   1 to 99% by mass of the repeating unit represented by the formula [1], [1-1] or [1-2] and 1 to 95% by mass of the repeating unit containing a crosslinking group. A crosslinkable resin composition solution containing a crosslinkable group-containing fluorine-containing polystyrene derivative contained in the range of.   A crosslinkable resin composition solution containing a crosslinkable group-containing fluorine-containing polystyrene derivative used for producing the crosslinked fluorine-containing polystyrene derivative coating film according to any one of claims 1 to 6.