Substrate coated with pyrolytic fluorine-based compound and method for producing same

Abstract

To provide a new substrate that achieves improvement in recoatability, which has been a problem in the conventional fluorine-based surfactants and additives, and has little environmental load, and a method for producing the same.SOLUTION: The present invention provides, for example, a method for producing a substrate coated with a fluorine compound, including the following steps 1 and 2: the step 1 of coating a substrate with a coating agent, which comprises a composition containing a compound having a perfluoropolyether chain with a repeat unit consisting of only 'CF2O'; and the step 2 of heating the coated substrate.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention belongs to the technical field of fluorine-based compounds. 2 The present invention relates to a substrate coated with a surfactant or additive containing a perfluoropolyether chain having only a repeating unit of "O", and a method for producing the same. [Background technology]

[0002] Fluorosurfactants and fluorine additives have been considered indispensable in the manufacturing industry, including the semiconductor and electronics fields, due to their high functionality, particularly their ability to reduce surface tension and their surface segregation and leveling properties.

[0003] However, in recent years, restrictions on fluorine-containing compounds have been introduced in various countries due to their tendency to accumulate in the body and their persistence in the environment, which are due to their chemical stability. PFOA (perfluorooctanoic acid)-related compounds are already subject to restrictions, and perfluorohexyl-containing compounds, which are used as alternative compounds, are also becoming the subject of regulatory discussions, and further alternative compounds are desired.

[0004] Furthermore, when these fluorine-based surfactants and additives are added to various coating agents, the liquid repellency of the fluorine compounds can become a problem, and even when attempting to coat the outermost layer, they often inhibit wettability and cause problems with recoating.

[0005] In Patent Document 1, "CF 2 Although a surface treatment agent containing a perfluoropolyether chain with only "O" as a repeating unit is disclosed, it is merely exemplified alongside other fluorine-containing structures. There is no disclosure of the differences in structure, particularly in terms of decomposability.

[0006] Patent Document 2 discloses a fluorine-containing pyrolyzable polymer that is decomposed by heat treatment. However, since the decomposition site is the linking portion of the fluorine chain, and the fluorine chain itself is not decomposed, it is difficult to say that the environmental concerns of fluorine compounds are sufficiently addressed.

[0007] Non-Patent Document 1 describes that the thermal decomposition starting temperature of perfluoroalkyl groups, which are considered to be substances of environmental concern, is at least 200° C. or higher.

[0008] Perfluoropolyether group-containing compounds are highly heat-resistant substances used as lubricants for hard disks, etc., and Non-Patent Document 2 describes that thermal decomposition begins at about 160°C only in the presence of metal fluorides or metal oxides. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Special Publication No. 2012-509937 [Patent Document 2] JP 2016-017172 A [Non-patent literature]

[0010] [Non-Patent Document 1] Environ. Sci. Technol. Lett. 7 343-350 (2020) [Non-Patent Document 2] Macromolecules 25 6791-6799 (1992) Summary of the Invention [Problem to be solved by the invention]

[0011] An object of the present invention is to provide a new substrate and a method for producing the same which improves the recoatability, which is a drawback of conventional fluorine-based surfactants or fluorine-based additives, and which imposes a low environmental load. [Means for solving the problem]

[0012] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by coating a substrate with a compound containing a certain perfluoropolyether chain and then subjecting the substrate to a heat treatment, thereby completing the present invention. The present invention can include, for example, the following aspects. [1] A method for producing a substrate coated with a fluorine-based compound, comprising the following steps 1 and 2: Step 1. The repeating unit is "CF 2 A step of coating a substrate with a coating agent to which a composition containing a compound having a perfluoropolyether chain consisting only of "O" has been added; Step 2: Heating the coated substrate. [2] The manufacturing method described in [1] above, wherein the heating temperature is 120°C or higher. [3] The method according to the above [1] or [2], wherein the coating agent is a resist, a solution for forming a hard coat layer, a composition for forming a black matrix, a composition for forming a protective film for a color filter, or an ink. [4] A method for producing a substrate coated with a fluorine-based compound, comprising the step of further coating the substrate produced by the method described in [1] or [2] above with another coating agent. [5] The method according to the above [4], wherein the coating agent is a resist, a solution for forming a hard coat layer, a composition for forming a black matrix, a composition for forming a protective film for a color filter, or an ink. [6] A substrate manufactured by the manufacturing method described in [1] or [2] above. [7] A substrate produced by the method described in [4] above. Effect of the Invention

[0013] According to the present invention, the contact angle of the surface of a substrate coated with a fluorine-based compound can be reduced, and the substrate can be made to have a low environmental impact. [Brief description of the drawings]

[0014] [Figure 1] This shows the results of TG-DTA analysis. Each curve is a TG curve, a DTG curve, or a DTA curve, respectively. The vertical axis shows the weight change (mg), differential weight change (decrease) (mg / min), and temperature difference (μV) for each line type, and the horizontal axis shows the temperature (℃). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present invention will be described in detail below. The production method according to the present invention (hereinafter referred to as the "production method of the present invention") is a method for producing a substrate coated with a fluorine-based compound, and is characterized by comprising the following steps 1 and 2: Step 1. The repeating unit is "CF 2 A step of coating a substrate with a coating agent to which a composition containing a compound having a perfluoropolyether chain consisting only of "O" (hereinafter referred to as "the composition of the present invention") has been added. Step 2: Heating the coated substrate

[0016] In the present invention, the molecule contains "CF 2 When a surfactant or additive according to the composition of the present invention, which contains a perfluoropolyether chain having only "O" as a repeating unit, is added to a coating agent, which is applied to a substrate and then heated, the perfluoropolyether chain is decomposed, and due to this decomposition, the liquid repellency of the fluorine compound is lost, and the wettability of the surface is improved, thereby improving the recoatability.

[0017] The present invention is characterized in that the surface of the substrate that has been subjected to the coating treatment is heat-treated. 2A perfluoropolyether chain having only "O" as a repeating unit has a structure that is easily thermally decomposed. The perfluoropolyether chain is decomposed by holding in an environment of 120°C or higher. Therefore, the heating temperature in step 2 is, for example, appropriately 120°C or higher, and preferably within a range of 120°C to 160°C. The heating time varies depending on the heating temperature and the type of surfactant containing the perfluoropolyether chain, and can be, for example, 1 minute or more. It is preferably within a range of 2 minutes to 10 minutes.

[0018] The surfactants and additives in the composition of the present invention contain "CF 2 There are no particular limitations as long as the molecule contains a perfluoropolyether chain whose only repeating unit is "O", and the bonding mode is not important so long as the molecule contains one or more perfluoropolyether chains. Furthermore, a polymer in which the monomer containing the perfluoropolyether chain is polymerized alone or copolymerized with other monomers can also be used.

[0019] "CF" in the molecule 2 A preferred example of the perfluoropolyether chain having only "O" as a repeating unit is one having a structure represented by the following general formula (1).

[0020] [ka]

[0021] The surfactant and additives of the composition of the present invention can be contained in the coating agent in the range of 0.001 to 100% by weight. A solvent can be used in the coating agent, and water or various organic solvents can be appropriately used as the type of the solvent.

[0022] The method for coating the substrate with the coating agent can be a conventional method without any particular limitation, and examples of the method include known methods such as spray coating, bar coating, spin coating, roll coating, gravure coating, inkjet, die coating, and dip coating.

[0023] Examples of substrates to be coated include, but are not limited to, metals, resins, rubber, glass, and wood.

[0024] The applications of the production method of the present invention or the substrate produced by the production method of the present invention are not limited, and examples thereof include use in semiconductor production using resists, hard coat layer formation, black matrix formation, and color filter protective film formation, and the like, and the method is effective in these applications. EXAMPLES

[0025] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples in any way.

[0026] [Synthesis example] “CF 2 Synthesis of Monomers Containing Perfluoropolyether Chains with the Repeating Unit "O" As a raw material, CF 3 O(CF 2 O) 4 CF 2 CO 2 CH 3 (manufactured by Anles) in accordance with the method described in Patent Document 1. 3 O(CF 2 O) 4 CF 2 CONHCH 2 CH 2 OH (Compound 1) was prepared.

[0027] Next, 100 g of compound 1 and 21 g of triethylamine were placed in a 500 mL 4-neck flask equipped with a condenser, a thermometer, and a dropping funnel, and 18 g of acrylic acid chloride was added dropwise at room temperature with stirring. After the dropwise addition, the mixture was stirred at room temperature for 1 hour, and then triethylamine hydrochloride was filtered off and tetrahydrofuran was distilled off to obtain 97 g of CF 3 O(CF 2 O) 4 CF 2 CONHCH 2 CH 2 OC(O)CH=CH 2 (Compound 2) was obtained.

[0028] [Example 1] In a 500mL 4-neck flask equipped with a condenser, thermometer, and dropping funnel, 30g of compound 2 obtained in the synthesis example, 70g of Blenmar AME400 (NOF Corporation), 4g of α-thioglycerol, and 100g of ethyl acetate were placed, and 4g of azoisobutyronitrile was added while heating and stirring at 45°C. After stirring at 70°C for 4 hours, the ethyl acetate was distilled off to obtain polymer 1. The structure of the Blenmar AME400 is as follows:

[0029] [ka]

[0030] [Example 2] Polymer 2 was obtained in the same manner as in Example 1, except that the amount of Compound 2 was 20 g and the amount of Blenmer AME400 was 80 g.

[0031] [Example 3] CF in a 200mL eggplant flask 3 O(CF 2 O) m CF 2 CO 2 CH 3(wherein m is an integer of 3 to 10, manufactured by Anles) 18.5 g was added, and 30 g of Jeffamine M-1000 (manufactured by Huntsman) was added dropwise at room temperature with stirring. After the dropwise addition, the mixture was stirred at an internal temperature of 60° C. for 5 hours, and then the generated methanol was distilled off to obtain Polymer 3. The structures of Jeffamine M-1000 and Polymer 3 are as follows:

[0032] Structural formula of Jeffamine M-1000 [ka]

[0033] Structural formula of polymer 3 [ka]

[0034] [Reference Example 1] Preparation of Polymer 1 Polymer 1 was polymerized according to the Examples in WO2020 / 169493.

[0035] Structural formula of Polymer 1 This is described in paragraph 0073 of WO2020 / 169493. [ka]

[0036] Evaluation of resist coating [Preparation Example 1] Preparation of Composition 1 To a mixed solution of 2 g of Polymer 1, 0.04 g of (+)-10-camphorsulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.018 g of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 68.4 g of propylene glycol 1-monomethyl ether 2-acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 29.4 g of propylene glycol 1-monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.4 mg of Polymer 1 was added to prepare Composition 1.

[0037] [Preparation Example 2] Preparation of Composition 2 Composition 2 was obtained in the same manner as in Preparation Example 1, except that Polymer 1 was changed to Polymer 2.

[0038] [Preparation Example 3] Preparation of Composition 3 Composition 3 was obtained in the same manner as in Preparation Example 1, except that Polymer 1 was changed to Polymer 3.

[0039] [Comparative Preparation Example 1] Preparation of Comparative Composition 1 Comparative composition 1 was obtained in the same manner as in Preparation Example 1, except that Polymer 1 was changed to Megafac R-40 (a fluorine-containing, hydrophilic and lipophilic group-containing oligomer manufactured by DIC).

[0040] [Example 4] Composition 1 was spin-coated onto a silicon wafer, and held in a heating furnace at 100°C for 4 hours to form a coating film, which was then allowed to cool to room temperature and the surface condition of the coating film was observed.Then, the wafer was held in a heating furnace at 140°C for 2 hours and then allowed to cool to room temperature, after which Composition 1 was again spin-coated, held in a heating furnace at 100°C for 4 hours to form a coating film, which was then allowed to cool to room temperature and the surface condition of the coating film was observed.

[0041] [Example 5] The same procedure as in Example 4 was carried out except that composition 1 was changed to composition 2.

[0042] [Example 6] The same procedure as in Example 4 was carried out except that composition 1 was changed to composition 3.

[0043] [Comparative Example 1] The same procedure as in Example 4 was carried out except that composition 1 was replaced with comparative composition 1.

[0044] The changes in the coating state in Examples 4, 5, and 6 and Comparative Example 1 are shown in Table 1.

[0045] [Table 1]

[0046] From the above results, it can be seen that according to the present invention, the surface coating condition can be made uniform and good not only after the first coating film is formed, but also after the second coating film is formed.

[0047] Evaluation on hard coat surface [Preparation Example 4] Preparation of Composition 4 30 g of tripropylene glycol diacrylate (Tokyo Chemical Industry Co., Ltd.), 10 g of Light Acrylate PE-3A (Kyoeisha Chemical Co., Ltd.), and 160 g of ethyl acetate (Tokyo Chemical Industry Co., Ltd.) were mixed, and 250 mg of Polymer 1 was added thereto and stirred to obtain Composition 4.

[0048] [Preparation Example 5] Preparation of Composition 5 Composition 5 was obtained in the same manner as in Preparation Example 4, except that Polymer 1 was changed to Polymer 2.

[0049] [Preparation Example 6] Preparation of Composition 6 Composition 6 was obtained in the same manner as in Preparation Example 5, except that Polymer 1 was changed to Polymer 3.

[0050] [Comparative Preparation Example 2] Preparation of Comparative Composition 2 Comparative composition 2 was obtained in the same manner as in Preparation Example 4, except that Polymer 1 was changed to Megafac R-40 (a fluorine-containing, hydrophilic and lipophilic group-containing oligomer manufactured by DIC).

[0051] [Example 7] Composition 4 was dip-coated onto a slide glass, dried at room temperature for 30 minutes, and then exposed to ultraviolet light at a wavelength of 365 nm and an ultraviolet irradiance of 90 mW / cm using a SunEnergy Corporation ultraviolet irradiator. 2 The coating film was cured by 20°C, and the surface state of the coating film was observed. In addition, the contact angle of the coating film surface was measured using a 2μL water drop. After that, the coating film was kept at 140°C for 2 hours in a heating furnace, cooled to room temperature, and then dip-coated with composition 4 again, dried at room temperature for 30 minutes, and then cured by UV irradiation in the same manner as above, and the surface state of the coating film was observed and the contact angle was measured.

[0052] [Example 8] The same procedure as in Example 7 was carried out, except that composition 4 was changed to composition 5.

[0053] [Example 9] The same procedure as in Example 7 was carried out, except that composition 4 was changed to composition 6.

[0054] [Comparative Example 2] The same procedure as in Example 7 was carried out except that composition 4 was replaced with comparative composition 2.

[0055] The surface state and contact angle of the coating film in Examples 7, 8, 9 and Comparative Example 2 are shown in Table 2.

[0056] [Table 2]

[0057] From the above results, it is clear that the present invention can make the surface coating film condition uniform and good not only after the first coating film formation but also after the second coating film formation. It is also clear that the present invention can reduce the contact angle of the substrate surface coated with a fluorine-based compound.

[0058] [Test Example 1] CF 3 O(CF 2 O) m CF 2 CO 2 CH 3 (where m is an integer between 3 and 10) was subjected to thermogravimetry and differential thermal analysis (TG-DTA analysis) to investigate the thermal decomposition temperature. The measurement was performed using a thermogravimetry analyzer TG / DTA7200 manufactured by Seiko Instruments Inc., with the temperature rising from 25°C to 250°C at a rate of 4°C / min. The results for the case where a mixed sample with an average value (number average) of m of 5.5 was used are shown in Figure 1.

[0059] From the DTG curve in Figure 1, the peak (T p The decomposition reaction accelerates to the maximum at 94°C, and at around 115°C (T f ) decomposition is almost complete.2 This shows that perfluoropolyether chains consisting only of "O" decompose at much lower temperatures than conventional perfluoroalkyl groups or perfluoropolyether chains.

[0060] From the above results, 2 It is clear that the perfluoropolyether chain having only "O" as a repeating unit is more susceptible to thermal decomposition than conventional fluorine chains. And since the fluorine-based compound related to the coating base material produced by the process of the present invention contains the perfluoropolyether chain, it is also clear that the substrate produced by the process of the present invention has a low environmental impact. [Industrial Applicability]

[0061] The process of the present invention and the coating substrate produced by the process of the present invention are useful in the production of semiconductors using resists, the formation of hard coat layers, the formation of black matrices, the formation of protective films for color filters, and the like.

Claims

1. A method for manufacturing a substrate coated with a fluorine-based compound, comprising the following steps 1 and 2: Step 1. Coating a substrate with a coating agent containing a compound comprising a perfluoropolyether chain having a repeating unit consisting only of "CF ２ O"; Step 2. A step of heating the coated substrate to decompose the compound containing the perfluoropolyether chain.

2. The manufacturing method according to Claim 1, wherein the heating temperature is 120°C or higher.

3. The manufacturing method according to Claim 1 or 2, wherein the coating agent is a resist, a solution for forming a hard coat layer, a composition for forming a black matrix, a composition for forming a color filter protective film, or an ink.

4. A method for manufacturing a substrate coated with a fluorine-based compound, comprising a step of further coating the coated substrate manufactured by the manufacturing method according to Claim 1 or 2 with another coating agent.

5. The manufacturing method according to Claim 4, wherein the another coating agent is a resist, a solution for forming a hard coat layer, a composition for forming a black matrix, a composition for forming a color filter protective film, or an ink.

6. A substrate manufactured by the manufacturing method according to Claim 1 or 2.

7. A substrate manufactured by the manufacturing method according to Claim 4.

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