JP2022191186A - Substrate coated with pyrolytic fluorine compound and method for producing the same - Google Patents
Substrate coated with pyrolytic fluorine compound and method for producing the same Download PDFInfo
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Abstract
Description
本発明は、フッ素系化合物の技術分野に属する。本発明は、分子中に「ＣＦ２Ｏ」のみを繰り返し単位とするパーフルオロポリエーテル鎖を含む界面活性剤ないし添加剤でコーティングされた基材とその製造方法に関するものである。 The present invention belongs to the technical field of fluorine compounds. TECHNICAL FIELD The present invention relates to a base material coated with a surfactant or additive containing a perfluoropolyether chain having only "CF 2 O" as a repeating unit in the molecule, and a method for producing the same.
フッ素系界面活性剤ないしフッ素系添加剤は、これまでその高機能、特に表面張力の低下能や表面偏析性・レベリング性を活かして、半導体や電子分野をはじめとする製造業で必要欠くべからざるものとされてきた。 Fluorine-based surfactants and fluorine-based additives have been indispensable in the manufacturing industry, including the semiconductor and electronic fields, by taking advantage of their high functionality, especially the ability to reduce surface tension, surface segregation, and leveling. has been taken for granted.
しかしながら、近年の含フッ素化合物の化学的安定性に起因する体内蓄積性や環境中での難分解性から、各国での規制が始まり、既にＰＦＯＡ（パーフルオロオクタン酸）関連化合物はその対象となっており、その代替化合物として使用されているパーフルオロへキシル基含有化合物も、規制論議の対象となりつつあり、さらなる代替化合物が望まれている。 However, in recent years, PFOA (perfluorooctanoic acid)-related compounds have already been subject to regulations in various countries due to the accumulation in the body and persistence in the environment due to the chemical stability of fluorine-containing compounds. However, perfluorohexyl group-containing compounds used as alternative compounds are also becoming the subject of regulatory debate, and further alternative compounds are desired.
また、これらフッ素系界面活性剤や添加剤を各種コーティング剤に添加して使用した場合に、フッ素化合物の持つ撥液性が災いとなって、さらに最外層へコーティングしようとしても濡れ性を阻害しリコート性に不具合を生じる場合が多い。 In addition, when these fluorine-based surfactants and additives are added to various coating agents and used, the liquid repellency of the fluorine compound becomes a disaster, and even if an attempt is made to coat the outermost layer, the wettability is hindered. Defects in recoating property often occur.
特許文献１には、「ＣＦ２Ｏ」のみを繰り返し単位とするパーフルオロポリエーテル鎖を含む表面処理剤について開示されているものの、そのほかの含フッ素構造のものと並列に例示されているに過ぎない。その構造の違いによる、特に分解性に関しては開示されていない。 Although Patent Document 1 discloses a surface treatment agent containing a perfluoropolyether chain having only "CF 2 O" as a repeating unit, it is merely exemplified in parallel with other fluorine-containing structures. No. There is no disclosure regarding the degradability due to the difference in structure.
特許文献２には、熱処理によって分解する含フッ素熱分解性ポリマーが開示されている。しかし、分解箇所はフッ素鎖の連結部分であって、フッ素鎖そのものを分解するものではないため、フッ素化合物の環境懸念への対応が十分とは言い難い。 Patent Document 2 discloses a fluorine-containing thermally decomposable 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 concern of the fluorine compound is adequately addressed.
非特許文献１には、環境懸念物質とされるパーフルオロアルキル基の熱分解開始温度が少なくとも２００℃以上であると記載されている。 Non-Patent Document 1 describes that the thermal decomposition initiation temperature of perfluoroalkyl groups, which are regarded as substances of environmental concern, is at least 200° C. or higher.
パーフルオロポリエーテル基含有化合物は、ハードディスクの潤滑剤等に使用される高耐熱性物質であり、非特許文献２には、金属フッ化物や金属酸化物の存在下においてのみ１６０℃程度から熱分解が始まることが記載されている。
Perfluoropolyether group-containing compounds are highly heat-resistant substances used as hard disk lubricants and the like. is stated to begin.
本発明の課題は、従来のフッ素系界面活性剤ないしフッ素系添加剤の不具合であるリコート性を改善し、かつ環境負荷が少ない新たな基材やその製造方法を提供することにある。
SUMMARY OF THE INVENTION An object of the present invention is to improve the recoating property, which is a problem of conventional fluorine-based surfactants and fluorine-based additives, and to provide a new substrate with less environmental load and a method for producing the same.
本発明者は、鋭意検討した結果、一定のパーフルオロポリエーテル鎖を含む化合物で基材をコーティングした後、加熱処理することにより上記課題を解決しうることを見出し、本発明を完成するに到った。
本発明として、例えば、以下の態様を挙げることができる。
［１］次の工程１および２を含む、フッ素系化合物でコーティングされた基材の製造方法：
工程１．繰り返し単位が「ＣＦ２Ｏ」のみからなるパーフルオロポリエーテル鎖を含む化合物を含有する組成物を添加したコーティング剤で基材をコーティング処理する工程、
工程２．上記コーティング処理された基材を加熱する工程。
［２］加熱温度が１２０℃以上である、上記［１］に記載の製造方法。
［３］コーティング剤が、レジスト、ハードコート層形成用溶液、ブラックマトリックス形成用組成物、カラーフィルター保護膜形成用組成物、またはインクである、上記［１］または［２］に記載の製造方法。
［４］上記［１］または［２］に記載の製造方法で製造されたコーティング基材に、さらに別のコーティング剤でコーティング処理する工程を含む、フッ素系化合物でコーティングされた基材の製造方法。
［５］コーティング剤が、レジスト、ハードコート層形成用溶液、ブラックマトリックス形成用組成物、カラーフィルター保護膜形成用組成物、またはインクである、上記［４］に記載の製造方法。
［６］上記［１］または［２］に記載の製造方法により製造された、基材。
［７］上記［４］に記載の製造方法により製造された、基材。
As a result of intensive studies, the present inventors found that the above problems can be solved by coating a substrate with a compound containing a certain perfluoropolyether chain and then subjecting it to heat treatment, and have completed the present invention. was
The present invention includes, for example, the following aspects.
[1] A method for producing a substrate coated with a fluorine compound, comprising the following steps 1 and 2:
Step 1. a step of coating a substrate with a coating agent to which a composition containing a compound containing a perfluoropolyether chain consisting of only "CF 2 O" repeating units is added;
Step 2. a step of heating the coated substrate;
[2] The production method according to [1] above, wherein the heating temperature is 120° C. or higher.
[3] The manufacturing method according to [1] or [2] above, 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 producing a substrate coated with a fluorine-based compound, comprising the step of coating the coated substrate produced by the production method according to [1] or [2] above with another coating agent. .
[5] The production method according to [4] above, 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.
[6] A substrate produced by the production method described in [1] or [2] above.
[7] A substrate produced by the production method described in [4] above.
本発明によれば、フッ素系化合物でコーティング処理された基材表面の接触角を低下させることができ、かつ、当該基材を環境負荷の少ないものとすることができる。
ADVANTAGE OF THE INVENTION According to this invention, the contact angle of the base material surface coated with the fluorine-type compound can be reduced, and the said base material can be made into a thing with little environmental load.
以下、本発明について詳述する。
本発明に係る製造方法（以下、「本発明製法」という。）は、フッ素系化合物でコーティングされた基材の製造方法であって、次の工程１および２を含むことを特徴とする。
工程１．繰り返し単位が「ＣＦ２Ｏ」のみからなるパーフルオロポリエーテル鎖を含む化合物を含有する組成物（以下、「本発明組成物」という。）を添加したコーティング剤で基材をコーティング処理する工程
工程２．上記コーティング処理された基材を加熱する工程
The present invention will be described in detail below.
A 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 including the following steps 1 and 2.
Step 1. A process of coating a substrate with a coating agent to which a composition containing a compound containing a perfluoropolyether chain whose repeating unit consists of only "CF 2 O" (hereinafter referred to as "the composition of the present invention") is added. 2. The step of heating the coated base material
本発明においては、分子中に「ＣＦ２Ｏ」のみを繰り返し単位とするパーフルオロポリエーテル鎖を含む本発明組成物に係る界面活性剤や添加剤をコーティング剤に添加して、基材に塗布したのち加熱することにより、当該パーフルオロポリエーテル鎖が分解し、かかる分解により、フッ素化合物の撥液性を失い、表面の濡れ性が向上することによりリコート性が改善される。 In the present invention, the surfactant and additive according to the composition of the present invention containing a perfluoropolyether chain having only "CF 2 O" as a repeating unit in the molecule are added to the coating agent and applied to the substrate. By heating thereafter, the perfluoropolyether chain is decomposed, and the decomposition causes the fluorine compound to lose its liquid repellency, thereby improving the wettability of the surface and improving the recoatability.
本発明においては、コーティング処理された基材表面を加熱処理することを特徴とするが、本発明組成物に係る、分子中に「ＣＦ２Ｏ」のみを繰り返し単位とするパーフルオロポリエーテル鎖は、熱分解されやすい構造である。１２０℃以上の環境下に保持することにより、当該パーフルオロポリエーテル鎖は分解される。従って、工程２における加熱温度としては、例えば、１２０℃以上が適当であり、１２０℃～１６０℃の範囲内の温度が好ましい。加熱時間としては、加熱温度や当該パーフルオロポリエーテル鎖を含む界面活性剤等の種類などにより異なるが、例えば、１分以上を挙げることができる。好ましくは２分～１０分の範囲内である。 The present invention is characterized in that the coated substrate surface is heat-treated, and the perfluoropolyether chain having only "CF 2 O" as a repeating unit in the molecule according to the composition of the present invention is , is a structure that is easily decomposed by heat. The perfluoropolyether chain is decomposed by keeping in an environment of 120° C. or higher. Therefore, the heating temperature in step 2 is, for example, 120°C or higher, preferably in the range of 120°C to 160°C. The heating time varies depending on the heating temperature, the type of the surfactant containing the perfluoropolyether chain, and the like, but can be, for example, 1 minute or longer. It is preferably within the range of 2 minutes to 10 minutes.
本発明組成物に係る界面活性剤や添加剤としては、分子中に「ＣＦ２Ｏ」のみを繰り返し単位とするパーフルオロポリエーテル鎖を含んでいれば特に制限されることはなく、また当該パーフルオロポリエーテル鎖を１つ以上含む分子であれば、その結合様式は問わない。
また、当該パーフルオロポリエーテル鎖を含む単量体を単独または他の単量体と共重合したポリマーについても使用することができる。
Surfactants and additives for the composition of the present invention are not particularly limited as long as they contain a perfluoropolyether chain having only "CF 2 O" as a repeating unit in the molecule. As long as the molecule contains one or more fluoropolyether chains, the binding mode is not limited.
Also, a polymer obtained by copolymerizing a monomer containing the perfluoropolyether chain alone or with another monomer can be used.
分子中に「ＣＦ２Ｏ」のみを繰り返し単位とするパーフルオロポリエーテル鎖の好ましい例としては、次の一般式（１）で表される構造のものが挙げられる。 A preferred example of a perfluoropolyether chain having only "CF 2 O" as a repeating unit in the molecule includes a structure represented by the following general formula (1).
本発明組成物に係る界面活性剤や添加剤は、コーティング剤中０．００１～１００重量％の範囲内で含有することができる。コーティング剤には溶媒を使用することも可能であり、かかる溶媒の種類についても、水や各種有機溶剤を適宜使用することができる。 The surfactant and additive used in the composition of the present invention can be contained within the range of 0.001 to 100% by weight in the coating agent. A solvent can also be used for the coating agent, and water and various organic solvents can be used as appropriate for the type of such solvent.
コーティング剤で基材をコーティング処理する方法としては、常法で可能であり特に制限されず、例えば、スプレーコーティング法、バーコーティング法、スピンコーティング法、ロールコーティング法、グラビアコーティング法、インクジェット法、ダイコーティング法、ディップコーティング法等、公知の方法を挙げることができる。 The method for coating the substrate with the coating agent is not particularly limited and can be a conventional method. For example, spray coating, bar coating, spin coating, roll coating, gravure coating, ink jet method, die Known methods such as a coating method and a dip coating method can be used.
コーティング対象となる基材としては、例えば、金属、樹脂、ゴム、ガラス、木材等が挙げられるがこれらに制限されるものではない。 Substrates to be coated include, but are not limited to, metals, resins, rubbers, glass, and wood.
本発明製法ないし本発明製法で製造された基材の使用用途も制限されるものではないが、例えば、レジスト等を用いた半導体製造、ハードコート層形成用途、ブラックマトリックス形成用途、カラーフィルター保護膜形成用途等での使用を挙げることができ、それらの用途において有効である。
The production method of the present invention or the use of the base material produced by the production method of the present invention is not limited, but for example, semiconductor production using resist, hard coat layer formation, black matrix formation, color filter protective film It can be used in forming applications and the like, and is effective in those applications.
以下に実施例等を掲げて、本発明をさらに具体的に説明するが、本発明は下記の実施例に何ら限定されるものではない。 EXAMPLES The present invention will be described in more detail with reference to examples, etc., but the present invention is not limited to the following examples.
［合成例］「ＣＦ２Ｏ」を繰り返し単位とするパーフルオロポリエーテル鎖を含むモノマーの合成
原料として、ＣＦ３Ｏ（ＣＦ２Ｏ）４ＣＦ２ＣＯ２ＣＨ３（Ａｎｌｅｓ社製）を用いて、特許文献１に記載の方法に準じて、ＣＦ３Ｏ（ＣＦ２Ｏ）４ＣＦ２ＣＯＮＨＣＨ２ＣＨ２ＯＨ（化合物１）を調製した。
[Synthesis example] Synthesis of a monomer containing a perfluoropolyether chain having a repeating unit of “CF 2 O” Using CF 3 O(CF 2 O) 4 CF 2 CO 2 CH 3 (manufactured by Anles) as a starting material , CF 3 O(CF 2 O) 4 CF 2 CONHCH 2 CH 2 OH (compound 1) was prepared according to the method described in Patent Document 1.
次に、冷却管・温度計・滴下ロートを付属した５００ｍＬ容４ツ口フラスコに、１００ｇの化合物１と２１ｇのトリエチルアミンとを入れ、撹拌下、室温で１８ｇのアクリル酸クロリドを滴下した。滴下後、室温で１時間撹拌後、トリエチルアミン塩酸塩をろ別し、テトラヒドロフランを留去することにより、９７ｇのＣＦ３Ｏ（ＣＦ２Ｏ）４ＣＦ２ＣＯＮＨＣＨ２ＣＨ２ＯＣ（Ｏ）ＣＨ＝ＣＨ２（化合物２）を得た。 Next, 100 g of compound 1 and 21 g of triethylamine were placed in a 500 mL four-necked flask equipped with a condenser, thermometer and dropping funnel, and 18 g of acrylic acid chloride was added dropwise at room temperature while stirring. After dropping and stirring for 1 hour at room temperature, triethylamine hydrochloride was filtered off and tetrahydrofuran was distilled off to give 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.
［実施例１］
冷却管・温度計・滴下ロートを付属した５００ｍＬ容４ツ口フラスコに、合成例で得た化合物２を３０ｇ、および７０ｇのブレンマーＡＭＥ４００（日油株式会社製）、４ｇのαチオグリセロール、１００ｇの酢酸エチルを入れ、４５℃に加熱撹拌下、４ｇのアゾイソブチロニトリルを加えた。７０℃で４時間撹拌後、酢酸エチルを留去し、ポリマー１を得た。
なお、ブレンマーＡＭＥ４００の構造は、以下の通りである。
[Example 1]
Into a 500 mL four-necked flask equipped with a condenser, a thermometer, and a dropping funnel, 30 g of Compound 2 obtained in Synthesis Example, 70 g of Blenmer AME400 (manufactured by NOF Corporation), 4 g of α-thioglycerol, 100 g of Ethyl acetate was added, and 4 g of azoisobutyronitrile was added while heating to 45° C. with stirring. After stirring at 70° C. for 4 hours, ethyl acetate was distilled off to obtain Polymer 1.
The structure of the Blenmer AME400 is as follows.
［実施例２］
化合物２を２０ｇ、ブレンマーＡＭＥ４００を８０ｇとした以外は、実施例１と同様に行い、ポリマー２を得た。
[Example 2]
Polymer 2 was obtained in the same manner as in Example 1, except that 20 g of Compound 2 and 80 g of Blenmer AME400 were used.
［実施例３］
２００ｍＬ容ナスフラスコにＣＦ３Ｏ（ＣＦ２Ｏ）ｍＣＦ２ＣＯ２ＣＨ３（式中、ｍは３～１０の整数、Ａｎｌｅｓ社製）１８．５ｇを入れ、撹拌下、室温で３０ｇのジェファーミンＭ－１０００（ハンツマン社製）を滴下した。滴下後、内温６０℃にて５時間撹拌後、発生したメタノールを留去し、ポリマー３を得た。
なお、ジェファーミンＭ－１０００およびポリマー３の構造は以下の通りである。
[Example 3]
18.5 g of CF 3 O(CF 2 O) m CF 2 CO 2 CH 3 (where m is an integer of 3 to 10, manufactured by Anles) was placed in a 200 mL eggplant flask, and 30 g of Jefferson was stirred at room temperature. Min M-1000 (manufactured by Huntsman) was added dropwise. After the dropwise addition, the mixture was stirred at an internal temperature of 60° C. for 5 hours, and the generated methanol was distilled off to obtain Polymer 3.
The structures of Jeffamine M-1000 and Polymer 3 are as follows.
・ジェファーミンＭ－１０００の構造式
・ポリマー３の構造式
［参考例１］Ｐｏｌｙｍｅｒ１の調製
ＷＯ２０２０／１６９４９３公報のＥｘａｍｐｌｅｓに従い、Ｐｏｌｙｍｅｒ１を重合した。
[Reference Example 1] Preparation of Polymer 1 Polymer 1 was polymerized according to Examples in WO2020/169493.
・Ｐｏｌｙｍｅｒ１の構造式
ＷＯ２０２０／１６９４９３公報の段落００７３に記載されている。
レジスト塗膜での評価
［調製例１］組成物１の調製
２ｇのＰｏｌｙｍｅｒ１、０．０４ｇの（＋）－１０－カンファースルホン酸（東京化成工業社製）、０．０１８ｇのトリエチルアミン（東京化成工業社製）、６８．４ｇのプロピレングリコール１－モノメチルエーテル２－アセタート（東京化成工業社製）および２９．４ｇのプロピレングリコール１－モノメチルエーテル（東京化成工業社製）の混合溶液に、２．４ｍｇのポリマー１を添加し、組成物１とした。
Evaluation with resist coating film [Preparation Example 1] Preparation of composition 1 2 g of Polymer 1, 0.04 g of (+) -10-camphorsulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.018 g of triethylamine (Tokyo Chemical Industry Co., Ltd. 2.4 mg in a mixed solution of 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.). of Polymer 1 was added to obtain Composition 1.
［調製例２］組成物２の調製
ポリマー１をポリマー２に変更した以外は調製例１と同様に行い、組成物２を得た。
[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.
［調製例３］組成物３の調製
ポリマー１をポリマー３に変更した以外は調製例１と同様に行い、組成物３を得た。
[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.
［比較調製例１］比較組成物１の調製
ポリマー１をメガファックＲ－４０（ＤＩＣ製含フッ素基・親水性基・親油性基含有オリゴマー）に変更した以外は調製例１と同様に行い、比較組成物１を得た。
[Comparative Preparation Example 1] Preparation of Comparative Composition 1 In the same manner as in Preparation Example 1 except that Polymer 1 was changed to MEGAFACE R-40 (fluorine-containing group/hydrophilic group/lipophilic group-containing oligomer manufactured by DIC), A comparative composition 1 was obtained.
［実施例４］
組成物１をシリコンウェハ上にスピンコートし、加熱炉内で１００℃に４時間保持して塗膜を形成し、室温まで放冷後塗膜の表面状態を観察した。その後、加熱炉で１４０℃に２時間保持した後、室温まで放冷後、再度、組成物１をスピンコートし、加熱炉内で１００℃に４時間保持して塗膜を形成し、室温まで放冷後塗膜の表面状態を観察した。
[Example 4]
The composition 1 was spin-coated on a silicon wafer, held at 100° C. for 4 hours in a heating furnace to form a coating film, allowed to cool to room temperature, and then the surface condition of the coating film was observed. Then, after being held at 140 ° C. for 2 hours in a heating furnace, after cooling to room temperature, composition 1 was again spin-coated, held at 100 ° C. for 4 hours in a heating furnace to form a coating film, and cooled to room temperature. After standing to cool, the surface condition of the coating film was observed.
［実施例５］
組成物１を組成物２に変更して、実施例４と同様の操作を行った。
[Example 5]
The same operation as in Example 4 was performed except that composition 1 was changed to composition 2.
［実施例６］
組成物１を組成物３に変更して、実施例４と同様の操作を行った。
[Example 6]
The same operation as in Example 4 was performed except that composition 1 was changed to composition 3.
［比較例１］
組成物１を比較組成物１に変更して、実施例４と同様の操作を行った。
[Comparative Example 1]
The same operation as in Example 4 was performed except that the composition 1 was changed to the comparative composition 1.
実施例４、実施例５、実施例６および比較例１での塗膜状態の変化を表１に示す。 Table 1 shows changes in coating film conditions in Examples 4, 5, 6 and Comparative Example 1.
以上の結果より、本発明によれば、最初の塗膜形成後のみならず、２回目の塗膜形成後であっても、表面の塗膜状態を均一で良好なものとすることができることが分かる。 From the above results, according to the present invention, not only after forming the first coating film, but also after forming the second coating film, it is possible to make the coating film state of the surface uniform and good. I understand.
ハードコート表面での評価
［調製例４］組成物４の調製
３０ｇのトリプロピレングリコールジアクリレート（東京化成工業社製）、１０ｇのライトアクリレートＰＥ－３Ａ（共栄社化学社製）、１６０ｇの酢酸エチル（東京化成工業社製）を混合し、さらに２５０ｍｇのポリマー１を添加し、撹拌混合し組成物４を得た。
Evaluation on hard coat surface [Preparation Example 4] Preparation of composition 4 30 g of tripropylene glycol diacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 10 g of light acrylate PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.), 160 g of ethyl acetate ( (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 250 mg of polymer 1 was further added, and mixed with stirring to obtain composition 4.
［調製例５］組成物５の調製
ポリマー１をポリマー２に変更した以外は調製例４と同様に行い、組成物５を得た。
[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.
［調製例６］組成物６の調製
ポリマー１をポリマー３に変更した以外は調製例５と同様に行い、組成物６を得た。
[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.
［比較調製例２］比較組成物２の調製
ポリマー１をメガファックＲ－４０（ＤＩＣ製含フッ素基・親水性基・親油性基含有オリゴマー）に変更した以外は調製例４と同様に行い、比較組成物２を得た。
[Comparative Preparation Example 2] Preparation of Comparative Composition 2 The procedure of Preparation Example 4 was repeated except that Polymer 1 was changed to MEGAFACE R-40 (fluorine-containing group-hydrophilic-lipophilic group-containing oligomer manufactured by DIC). Comparative composition 2 was obtained.
［実施例７］
組成物４をスライドガラスにディップコートし、３０分間室温で乾燥後、サンエナジー社製紫外線照射装置を用いて、波長３６５ｎｍ、紫外線照度９０ｍＷ／ｃｍ２で塗膜を硬化させ、塗膜の表面状態を観察した。また、２μＬの水滴を用いて塗膜表面の接触角を測定した。その後、加熱炉で１４０℃に２時間保持した後、室温まで放冷後、再度、組成物４をディップコートし、３０分間室温で乾燥後、先と同様に紫外線照射により塗膜を硬化させ、塗膜の表面状態の観察と接触角測定を実施した。
[Example 7]
The composition 4 was dip-coated on a slide glass and dried at room temperature for 30 minutes. Then, the coating film was cured at a wavelength of 365 nm and an ultraviolet illuminance of 90 mW/cm 2 using an ultraviolet irradiation device manufactured by Sun Energy Co., Ltd., and the surface condition of the coating film was measured. observed. Moreover, the contact angle of the coating film surface was measured using a water droplet of 2 μL. After that, after holding at 140 ° C. for 2 hours in a heating furnace, after cooling to room temperature, composition 4 was again dip-coated, dried at room temperature for 30 minutes, and the coating film was cured by ultraviolet irradiation in the same manner as before. The surface condition of the coating film was observed and the contact angle was measured.
［実施例８］
組成物４を組成物５に変更して、実施例７と同様の操作を行った。
[Example 8]
The same operation as in Example 7 was performed except that composition 4 was changed to composition 5.
［実施例９］
組成物４を組成物６に変更して、実施例７と同様の操作を行った。
[Example 9]
The same operation as in Example 7 was performed except that composition 4 was changed to composition 6.
［比較例２］
組成物４を比較組成物２に変更して、実施例７と同様の操作を行った。
[Comparative Example 2]
The same operation as in Example 7 was performed except that the composition 4 was changed to the comparative composition 2.
実施例７、実施例８、実施例９および比較例２での塗膜の表面状態と接触角を表２に示す。 Table 2 shows the surface conditions and contact angles of the coating films in Examples 7, 8, 9 and Comparative Example 2.
以上の結果より、本発明によれば、最初の塗膜形成後のみならず、２回目の塗膜形成後であっても、表面の塗膜状態を均一で良好なものとすることができることが分かる。また、本発明によれば、フッ素系化合物でコーティング処理された基材表面の接触角を低下させることができることも明らかとなった。 From the above results, according to the present invention, not only after forming the first coating film, but also after forming the second coating film, it is possible to make the coating film state of the surface uniform and good. I understand. It was also found that the present invention can reduce the contact angle of the substrate surface coated with a fluorine-based compound.
［試験例１］
ＣＦ３Ｏ（ＣＦ２Ｏ）ｍＣＦ２ＣＯ２ＣＨ３（式中、ｍは３～１０の整数。）の熱分解温度を調べるため、熱重量および示差熱分析（ＴＧ－ＤＴＡ分析）を行った。測定は、セイコーインスツル株式会社製熱重量分析装置ＴＧ/ＤＴＡ７２００を用い、２５℃～２５０℃まで、４℃／分の昇温条件で行った。ｍの平均値（数平均）が５．５の混合試料を用いた場合の結果を図１に示す。
[Test Example 1]
Thermogravimetry and differential thermal analysis (TG-DTA analysis) were performed to investigate the thermal decomposition temperature of CF 3 O(CF 2 O) m CF 2 CO 2 CH 3 (where m is an integer of 3 to 10). rice field. The measurement was performed using a thermogravimetric analyzer TG/DTA7200 manufactured by Seiko Instruments Inc. from 25° C. to 250° C. under conditions of temperature increase of 4° C./min. FIG. 1 shows the results when a mixed sample having an average value (number average) of m of 5.5 was used.
図１のＤＴＧ曲線より、ピーク（Ｔｐ）の９４℃にて分解反応が最大加速を示し、１１５℃付近（Ｔｆ）にて概ね分解が完了していることが分かる。これは、「ＣＦ２Ｏ」のみからなるパーフルオロポリエーテル鎖が、従来のパーフルオロアルキル基やパーフルオロポリエーテル鎖よりはるかに低温で分解することを示している。 From the DTG curve in FIG. 1, it can be seen that the decomposition reaction shows maximum acceleration at the peak (T p ) of 94° C., and the decomposition is almost complete at around 115° C. (T f ). This indicates that a perfluoropolyether chain consisting only of "CF 2 O" decomposes at a much lower temperature than conventional perfluoroalkyl groups and perfluoropolyether chains.
以上の結果より、「ＣＦ２Ｏ」のみを繰り返し単位とするパーフルオロポリエーテル鎖は、従来のフッ素鎖より熱分解しやすいことが明らかである。そして、本発明製法により製造されたコーティング基剤に係るフッ素系化合物は、当該パーフルオロポリエーテル鎖を含んだものであるから、本発明製法に係る基材は環境負荷が少ないということも明らかである。
From the above results, it is clear that the perfluoropolyether chain having only "CF 2 O" as the repeating unit is more likely to be thermally decomposed than the conventional fluorine chain. Further, since the fluorine-based compound related to the coating substrate produced by the production method of the present invention contains the perfluoropolyether chain, it is also clear that the substrate produced by the production method of the present invention has less environmental load. be.
本発明製法や、本発明製法により製造されたコーティング基材は、レジスト等を用いた半導体製造、ハードコート層形成、ブラックマトリックス形成、カラーフィルター保護膜形成などにおいて有用である。 The manufacturing method of the present invention and the coating substrate manufactured by the manufacturing method of the present invention are useful in the manufacture of semiconductors using a resist or the like, the formation of a hard coat layer, the formation of a black matrix, the formation of a color filter protective film, and the like.
Claims (7)
工程１．繰り返し単位が「ＣＦ２Ｏ」のみからなるパーフルオロポリエーテル鎖を含む化合物を含有する組成物を添加したコーティング剤で基材をコー ティング処理する工程、
工程２．上記コーティング処理された基材を加熱する工程。 A method for producing a substrate coated with a fluorine compound, comprising the following steps 1 and 2:
Step 1. a step of coating a base material with a coating agent to which a composition containing a compound containing a perfluoropolyether chain whose repeating unit consists only of "CF 2 O" is added;
Step 2. a step of heating the coated substrate;
A substrate manufactured by the manufacturing method according to claim 4.
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