JP7333278B2

JP7333278B2 - Release liquid composition

Info

Publication number: JP7333278B2
Application number: JP2020002495A
Authority: JP
Inventors: 真也白石
Original assignee: Jemco Inc
Current assignee: Mitsubishi Materials Electronic Chemicals Co Ltd
Priority date: 2020-01-10
Filing date: 2020-01-10
Publication date: 2023-08-24
Anticipated expiration: 2040-01-10
Also published as: JP2021109917A

Description

本発明は、金型に代表される型（以下、金型等という。）に離型性を付与する離型用液組成物に関する。更に詳しくは樹脂成形体の金型等からの離型を容易にする離型用液組成物に関するものである。 TECHNICAL FIELD The present invention relates to a mold release liquid composition that imparts mold releasability to molds represented by molds (hereinafter referred to as molds and the like). More particularly, it relates to a release liquid composition that facilitates release of a resin molded product from a mold or the like.

従来、この種の離型用液組成物として、シリコーン系の離型用組成物、フッ素系の離型用組成物、水溶性の離型用組成物が知られている。このシリコーン系の離型用組成物としては、シクロシロキサン置換ポリシロキサン化合物を含む組成物が開示されている（例えば、特許文献１（要約）参照。）。またフッ素系の離型用組成物としては、パーフルオロアルキル又はアルケニル基を有する化合物と、ポリテトラフルオロエチレンと、シリコーンオイル、シリコーン樹脂及び沸点が１００℃以上の高度にフッ素化された化合物とを少なくとも１つ有する化合物を含んでなる非粘着性組成物が開示されている（例えば、特許文献２（請求項１）参照。）。更に水溶性の離型用組成物としては、ポリビニルアルコール、タルク、水酸化アルミニウム等を含む組成物が開示されている（例えば、特許文献３（特許請求の範囲第１項）参照。）。 Conventionally, as this type of release liquid composition, a silicone-based release composition, a fluorine-based release composition, and a water-soluble release composition are known. As this silicone-based release composition, a composition containing a cyclosiloxane-substituted polysiloxane compound has been disclosed (see, for example, Patent Document 1 (abstract)). The fluorine-based release composition includes a compound having a perfluoroalkyl or alkenyl group, polytetrafluoroethylene, silicone oil, silicone resin, and a highly fluorinated compound having a boiling point of 100° C. or higher. A non-stick composition comprising at least one compound has been disclosed (see, for example, Patent Document 2 (claim 1)). Furthermore, as a water-soluble release composition, a composition containing polyvinyl alcohol, talc, aluminum hydroxide, etc. is disclosed (see, for example, Patent Document 3 (claim 1)).

特表２０１３－５３９４８４号公報Japanese Patent Publication No. 2013-539484 ＷＯ１９９５／００３０７号公報WO1995/00307 特開昭５８－８７１９６号公報JP-A-58-87196

特許文献１に示されるシリコーン系の離型用組成物及び特許文献２に示されるフッ素系の離型用組成物は、ともに離型性に優れるけれども、金型等により作られる成形体に離型用組成物が転写した場合に成形体に転写された離型用組成物を除去するために別途専用の剥離溶剤が必要となる不具合があった。また特許文献３に示される水溶性の離型用組成物は、上記不具合がない反面、離型性に劣る問題があった。 The silicone-based mold release composition disclosed in Patent Document 1 and the fluorine-based mold release composition described in Patent Document 2 are both excellent in mold release properties. When the release composition is transferred, there is a problem that a separate dedicated release solvent is required in order to remove the release composition transferred to the molded article. Although the water-soluble mold release composition disclosed in Patent Document 3 does not have the above problems, it has a problem of inferior mold release properties.

本発明の目的は、樹脂成形体の金型等からの離型が容易であって、金型等で作られた成形体に離型膜が転写した場合に成形体に転写された離型膜を水で除去することができる離型用液組成物を提供することにある。本発明の別の目的は、成形体に転写された離型膜を目視で容易に確認できる離型用液組成物を提供することにある。 An object of the present invention is to provide a release film that is easy to release from a mold or the like of a resin molded product and that is transferred to the molded product when the release film is transferred to the molded product made by the mold or the like. is to provide a release liquid composition which can be removed with water. Another object of the present invention is to provide a release liquid composition that allows easy visual confirmation of the release film transferred to the molded article.

本発明の第１の観点は、ポリビニルアルコール（以下、ＰＶＡという。）、フッ素化合物、炭素数が１～３の範囲にある１種又は２種以上のアルコール及び水を含有する離型用液組成物であって、前記液組成物１００質量％に対して前記ＰＶＡと前記フッ素化合物とを合計して０．５質量％～１０質量％含み、前記ＰＶＡと前記フッ素化合物の質量比がＰＶＡ：フッ素化合物＝９９．９：０．１～９０：１０であり、前記液組成物１００質量％に対して前記アルコールを５質量％～５０質量％含み、前記フッ素化合物が下記式（１）又は式（２）で表される両性型フッ素系化合物であることを特徴とする。 A first aspect of the present invention is a release liquid composition containing polyvinyl alcohol (hereinafter referred to as PVA), a fluorine compound, one or more alcohols having 1 to 3 carbon atoms, and water. wherein the total amount of the PVA and the fluorine compound is 0.5% by mass to 10% by mass with respect to 100% by mass of the liquid composition, and the mass ratio of the PVA and the fluorine compound is PVA:fluorine Compound = 99.9:0.1 to 90:10, containing 5% by mass to 50% by mass of the alcohol with respect to 100% by mass of the liquid composition, and the fluorine compound represented by the following formula (1) or ( 2) is characterized by being an amphoteric fluorine-based compound represented by 2).

（１）

(1)

上記式（１）中、ｐ、ｑ及びｒは、それぞれ同一又は互いに異なる１～６の整数である。また上記式（１）中、Ｘは、炭素数２～１０の炭化水素基であって、エーテル結合、ＣＯ－ＮＨ結合、Ｏ－ＣＯ－ＮＨ結合及びスルホンアミド結合から選択される１種以上の結合を含んでいてもよい。また上記式（１）中、Ｙは、ベタイン構造である親水基である。 In the above formula (1), p, q and r are the same or different integers of 1 to 6. Further, in the above formula (1), X is a hydrocarbon group having 2 to 10 carbon atoms, and is selected from an ether bond, a CO—NH bond, an O—CO—NH bond and a sulfonamide bond. It may contain a bond. In the above formula (1), Y is a hydrophilic group having a betaine structure.

（２）

(2)

上記式（２）中、ｐ及びｑは、それぞれ同一又は互いに異なる１～６の整数である。また上記式（２）中、Ｘは、炭素数２～１０の炭化水素基であって、エーテル結合、ＣＯ－ＮＨ結合、Ｏ－ＣＯ－ＮＨ結合及びスルホンアミド結合から選択される１種以上の結合を含んでいてもよい。また上記式（２）中、Ｙは、ベタイン構造である親水基である。 In formula (2) above, p and q are the same or different integers of 1 to 6, respectively. Further, in the above formula (2), X is a hydrocarbon group having 2 to 10 carbon atoms, and is selected from an ether bond, a CO—NH bond, an O—CO—NH bond and a sulfonamide bond. It may contain a bond. In the above formula (2), Y is a hydrophilic group having a betaine structure.

本発明の第２の観点は、第１の観点に基づく発明であって、前記離型用液組成物は、液組成物１００質量％に対して、着色剤が０．０１質量％～１質量％含まれることを特徴とする。 A second aspect of the present invention is an invention based on the first aspect, wherein the release liquid composition contains 0.01% by mass to 1% by mass of a colorant with respect to 100% by mass of the liquid composition. % is included.

本発明の第１の観点の離型用液組成物は、ＰＶＡとフッ素化合物とを合計した質量割合、ＰＶＡとフッ素化合物の質量比及びアルコールの質量割合をそれぞれ所定の範囲に制御して構成され、フッ素化合物が両性型フッ素系化合物である。この液組成物はアルコールを所定の質量割合含むため、液組成物の溶液安定性に優れる。ＰＶＡは、成膜性に優れ、アルコールに対する溶解性がなく水に溶けやすい。離型用液組成物を金型等の表面に塗工してＰＶＡの離型膜を形成した後、金型等の表面に樹脂を塗工し硬化させて樹脂成形体を作る際に、この離型膜はアルコールに対する溶解性がないため、樹脂との結合が生じにくい。また液組成物は両性型フッ素系化合物を所定の質量割合含むため、金型等に塗工し易くかつ樹脂成形体が金型等から容易に離脱して離型性に優れる。また炭素数が１～３の範囲にあるアルコールを用いるため、両性型フッ素系化合物のアルコールへの溶解性が良好である。更に金型等から離脱した樹脂成形体表面に離型膜が転写していても、ＰＶＡが水溶性であることからこの離型膜を水で容易に除去することができる。特に本発明のフッ素化合物は、フッ素を含む官能基のフッ素含有率が高いことから離型性に優れ、更に両性基を含有することから水へのなじみが良く、他のフッ素化合物と異なり、水で容易に除去できる。 The release liquid composition according to the first aspect of the present invention is configured by controlling the total mass ratio of PVA and fluorine compound, the mass ratio of PVA and fluorine compound, and the mass ratio of alcohol to predetermined ranges. , the fluorine compound is an amphoteric fluorine compound. Since this liquid composition contains alcohol in a predetermined mass ratio, the solution stability of the liquid composition is excellent. PVA has excellent film-forming properties, is insoluble in alcohol, and easily dissolves in water. After the release liquid composition is applied to the surface of a mold or the like to form a release film of PVA, a resin is applied to the surface of the mold or the like and cured to form a resin molding. Since the release film is not soluble in alcohol, it is less likely to bond with the resin. In addition, since the liquid composition contains the amphoteric fluorine-based compound in a predetermined mass ratio, it is easy to apply to a mold or the like, and the resin molded product is easily released from the mold or the like, resulting in excellent releasability. Further, since an alcohol having a carbon number in the range of 1 to 3 is used, the solubility of the amphoteric fluorine-based compound in alcohol is good. Furthermore, even if the release film is transferred to the surface of the resin molded article released from the mold or the like, the release film can be easily removed with water because PVA is water-soluble. In particular, the fluorine compound of the present invention is excellent in releasability due to the high fluorine content of the functional group containing fluorine. can be easily removed with

本発明の第２の観点の離型用液組成物は、着色剤を所定の割合で含むため、成形体に転写された離型膜を目視で容易に確認することができる。 Since the release liquid composition of the second aspect of the present invention contains a coloring agent in a predetermined ratio, the release film transferred to the molded article can be easily visually confirmed.

次に本発明を実施するための形態を説明する。 Next, a mode for carrying out the present invention will be described.

〔離型用液組成物〕
本実施の形態の離型用液組成物は、ＰＶＡ、フッ素化合物、炭素数が１～３のアルコール及び水を混合して調製される。更に上記液組成物は、着色剤を含むことが好ましい。着色剤は成形体に転写された離型膜を目視で容易に確認するために用いられる。本実施の形態のＰＶＡは、ビニルエステルの重合体を完全又は部分ケン化したものである。ケン化方法としては、公知のアルカリケン化法や酸ケン化法を用いることができる。中でも、メタノール中で水酸化アルカリを使用して加アルコール分解する方法が好ましい。このＰＶＡは、水と混合して用いるため、水溶性であることが必要である。ＰＶＡとしては、一般に離型用液組成物で使用されているものであれば特に限定されず、各種ケン化度や重合度を有する未変性のポリビニルアルコールや、カルボキシル基、スルホ基等のアニオンで変性されたアニオン変性ポリビニルアルコール、アミノ基、アンモニウム基等のカチオンで変性されたカチオン変性ポリビニルアルコール、シラノール変性ポリビニルアルコール、アルコキシル変性ポリビニルアルコール、エポキシ変性ポリビニルアルコール、チオール変性ポリビニルアルコール等のランダム共重合体；アニオン変性、カチオン変性、チオール変性、シラノール変性、アルコキシル変性及びエポキシ変性等変性が末端基のみに行われているポリビニルアルコール、アクリルアミド、アクリル酸等の水溶性モノマーを導入したブロック共重合ポリビニルアルコール、シラノール基等をグラフトさせたグラフト共重合ポリビニルアルコール等を使用することができる。例えば、完全ケン化型のＰＶＡとしては、クラレ社製ＰＶＡ１０３、ＰＶＡ１１７，ＰＶＡ１２４、日本合成化学社製ＮＨ－２０、ＮＨ－１８等が挙げられる。カルボキシ変性ＰＶＡとしては、日本合成化学社製Ｔ－３３０Ｈ、スルホ基変性ＰＶＡとしては、日本合成化学社製Ｌ－８２３等が挙げられる。 [Release liquid composition]
The release liquid composition of the present embodiment is prepared by mixing PVA, a fluorine compound, an alcohol having 1 to 3 carbon atoms, and water. Further, the liquid composition preferably contains a coloring agent. The coloring agent is used for easy visual confirmation of the release film transferred to the molded article. The PVA of the present embodiment is obtained by completely or partially saponifying a vinyl ester polymer. As the saponification method, a known alkali saponification method or acid saponification method can be used. Among them, a method of alcoholysis using an alkali hydroxide in methanol is preferred. Since this PVA is used by mixing with water, it must be water-soluble. The PVA is not particularly limited as long as it is generally used in a release liquid composition, and may be unmodified polyvinyl alcohol having various degrees of saponification or polymerization, or an anion such as a carboxyl group or a sulfo group. Random copolymers such as anion-modified polyvinyl alcohol, cation-modified polyvinyl alcohol modified with cations such as amino groups and ammonium groups, silanol-modified polyvinyl alcohol, alkoxyl-modified polyvinyl alcohol, epoxy-modified polyvinyl alcohol, thiol-modified polyvinyl alcohol, etc. block copolymerized polyvinyl alcohol into which water-soluble monomers such as polyvinyl alcohol, acrylamide, and acrylic acid are introduced, in which modifications such as anion modification, cation modification, thiol modification, silanol modification, alkoxy modification, and epoxy modification are performed only on terminal groups; Graft copolymerized polyvinyl alcohol or the like grafted with a silanol group or the like can be used. For example, fully saponified PVA includes PVA103, PVA117 and PVA124 manufactured by Kuraray Co., Ltd., NH-20 and NH-18 manufactured by Nippon Synthetic Chemical Co., Ltd., and the like. Examples of carboxy-modified PVA include T-330H manufactured by Nippon Synthetic Chemical Co., Ltd., and examples of sulfo group-modified PVA include L-823 manufactured by Nippon Synthetic Chemical Co., Ltd. and the like.

上記着色剤は、上記液組成物１００質量％に対して、０．０１質量％～１質量％、好ましくは０．０２質量％～０．８質量％含まれる。０．０１質量％未満では、塗膜が着色しにくい。１質量％を超えると、塗膜の撥油性が劣り易くなり、液組成物の保存安定性が低下し易くなる。着色剤を例示すれば、β－アポ－８’－カロテナール、β-カロテン、カンタキサンチン、三二酸化鉄、食用赤色2号（別名アマランス）及びそのアルミニウムレーキ、食用赤色3号（別名エリスロシン）及びそのアルミニウムレーキ、食用赤色40号（別名アルラレッドAC）及びそのアルミニウムレーキ、食用赤色102号（別名ニューコクシン）、食用赤色104号（別名フロキシン）、食用赤色105号（別名ローズベンガル）、食用赤色106号（別名アシッドレッド）、食用黄色4号（別名タートラジン）及びそのアルミニウムレーキ、食用黄色5号（別名サンセットイエローFCF）及びそのアルミニウムレーキ、食用緑色3号（別名フアストグリーンFCF）及びそのアルミニウムレーキ、食用青色1号（別名ブリリアントプルーFCF）及びそのアルミニウムレーキ、食用青色2号（別名インジゴカルミン）及びそのアルミニウムレーキ、水溶性アナトー、アナトー色素、アルミニウム、ウコン色素、オレンジ色素、カカオ色素、カキ色素、カラメルI、カラメルII、カラメルIII、カラメルIV、カロブ色素、魚鱗箔、金、銀、クチナシ青色素、クチナシ赤色素、クチナシ黄色素、クーロー色素、クロロフィリン、クロロフィル、酵素処理ルチン（抽出物）、コウリャン色素、コチニール色素、骨炭色素、シアナット色素、シタン色素、植物炭末色素、スピルリナ色素、タマネギ色素、タマリンド色素、デュナリエラカロテン、トウガラシ色素、トマト色素、ニンジンカロテン、パーム油カロテン、ビートレッド、ファフィア色素、ブドウ果皮色素、ペカンナッツ色素、ベニコウジ黄色素、ベニコウジ色素、ベニバナ赤色素、ベニバナ黄色素、ヘマトコッカス藻色素、マリーゴールド色素、ムラサキイモ色素、ムラサキトウモロコシ色素、ムラサキヤマイモ色素、ラック色素、ルチン（抽出物）、ログウッド色素等が挙げられる。 The coloring agent is contained in an amount of 0.01% by mass to 1% by mass, preferably 0.02% by mass to 0.8% by mass, based on 100% by mass of the liquid composition. If it is less than 0.01% by mass, the coating film is difficult to color. If it exceeds 1% by mass, the oil repellency of the coating film tends to deteriorate, and the storage stability of the liquid composition tends to deteriorate. Examples of coloring agents include β-apo-8′-carotenal, β-carotene, canthaxanthin, iron sesquioxide, Food Red No. 2 (also known as amaranth) and its aluminum lake, Food Red No. 3 (also known as erythrosine) and its Food Red No. 40 (also known as Allura Red AC) and its aluminum lake Food Red No. 102 (also known as New Coxin), Food Red No. 104 (also known as Phloxine), Food Red No. 105 (also known as Rose Bengal), Food Red No. 106 Food Yellow No. 4 (aka Tartrazine) and its aluminum lake Food Yellow No. 5 (aka Sunset Yellow FCF) and its aluminum lake Food Green No. 3 (aka Fast Green FCF) and its aluminum lake , Food Blue No. 1 (also known as brilliant blue FCF) and its aluminum lake, Food Blue No. 2 (also known as indigo carmine) and its aluminum lake, water-soluble annatto, annatto pigment, aluminum, turmeric pigment, orange pigment, cocoa pigment, oyster pigment , caramel I, caramel II, caramel III, caramel IV, carob pigment, fish scale foil, gold, silver, gardenia blue pigment, gardenia red pigment, gardenia yellow pigment, coulo pigment, chlorophyllin, chlorophyll, enzyme-treated rutin (extract), sorghum pigment, cochineal pigment, bone carbon pigment, sheanut pigment, rosewood pigment, vegetable charcoal pigment, spirulina pigment, onion pigment, tamarind pigment, dunaliella carotene, red pepper pigment, tomato pigment, carrot carotene, palm oil carotene, beet red, faffia Pigment, grape skin pigment, pecan nut pigment, safflower yellow pigment, safflower pigment, safflower red pigment, safflower yellow pigment, haematococcus algae pigment, marigold pigment, purple sweet potato pigment, purple corn pigment, purple yam pigment, lac pigment, rutin ( extracts), logwood pigments, and the like.

本実施の形態のフッ素化合物は、上記式（１）又は式（２）で示される両性型フッ素系化合物、である。 The fluorine compound of the present embodiment is an amphoteric fluorine compound represented by the above formula (1) or (2).

本実施の形態の防汚性膜形成用液組成物におけるフッ素系化合物の上記式（１）又は式（２）中のペルフルオロエーテル基としては、より具体的には、下記式（３）～（７）で示されるペルフルオロエーテル基を挙げることができる。 More specifically, the perfluoroether group in the above formula (1) or (2) of the fluorine-based compound in the antifouling film-forming liquid composition of the present embodiment includes the following formulas (3) to ( A perfluoroether group represented by 7) can be mentioned.

（３）

(3)

（４）

(4)

（５）

(5)

（６）

(6)

（７）

(7)

本実施の形態の防汚性膜形成用液組成物におけるフッ素系化合物の上記式（２）中のペルフルオロエーテル基としては、より具体的には、下記式（８）～（１１）で示されるペルフルオロエーテル基を挙げることができる。 More specifically, the perfluoroether group in the above formula (2) of the fluorine-based compound in the antifouling film-forming liquid composition of the present embodiment is represented by the following formulas (8) to (11). Mention may be made of perfluoroether groups.

（８）

(8)

（９）

(9)

（１０）

(10)

（１１）

(11)

また、上記式（１）又は式（２）中のＸとしては、下記式（１２）～（１６）で示される構造を挙げることができる。なお、下記式（１２）はエーテル結合、下記式（１３）はエステル結合、下記式（１４）はアミド結合、下記式（１５）はウレタン結合、下記式（１６）はスルホンアミド結合を含む例を示している。 Further, examples of X in the above formula (1) or (2) include structures represented by the following formulas (12) to (16). In addition, the following formula (12) is an ether bond, the following formula (13) is an ester bond, the following formula (14) is an amide bond, the following formula (15) is an urethane bond, and the following formula (16) is an example containing a sulfonamide bond. is shown.

（１２）

(12)

（１３）

(13)

（１４）

(14)

（１５）

(15)

（１６）

(16)

ここで、上記式（１２）～（１６）中、Ｒ²及びＲ³は炭素数が０から１０の炭化水素基、Ｒ⁴は水素原子または炭素数１から６の炭化水素基である。Ｒ²及びＲ³の炭化水素基の例とは、メチレン基、エチレン基等のアルキレン基が挙げられ、Ｒ⁴の炭化水素基の例とは、メチル基、エチル基等のアルキル基の他、フェニル基、ビニル基等も挙げられる。 In formulas (12) to (16) above, R ² and R ³ are hydrocarbon groups having 0 to 10 carbon atoms, and R ⁴ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Examples of hydrocarbon groups for R ² and R ³ include alkylene groups such as methylene group and ethylene group, and examples of hydrocarbon groups for R ⁴ include alkyl groups such as methyl group and ethyl group, A phenyl group, a vinyl group, and the like are also included.

また、上記式（１）又は式（２）中のＹとしては、Ｙとしては、カルボキシベタイン型、スルホベタイン型、アミンオキシド型、フォスフォベタイン型等が挙げられる。 Y in the above formula (1) or (2) includes carboxybetaine type, sulfobetaine type, amine oxide type, phosphobetaine type and the like.

ここで、上記式（１）及び式（２）で表されるペルフルオロエーテル構造を有するフッ素系化合物の具体例としては、例えば、下記式（１７）～（２２）で表される構造が挙げられる。 Here, specific examples of the fluorine-based compound having a perfluoroether structure represented by the above formulas (1) and (2) include structures represented by the following formulas (17) to (22). .

（１７）

(17)

（１８）

(18)

（１９）

(19)

（２０）

(20)

（２１）

(21)

（２２）

(22)

本実施の形態の炭素数が１～３の範囲にあるアルコールとしては、例えば、メタノール、エタノール、プロパノール（ｎ－プロパノール、イソプロパノール）が挙げられる。炭素数が４以上のアルコールを用いると、上記両性型フッ素系化合物のアルコールへの溶解性が良好でなくなる。本実施の形態の水としては、イオン交換水、蒸留水などの純水、又は超純水が挙げられる。 Examples of alcohols having 1 to 3 carbon atoms in the present embodiment include methanol, ethanol, and propanol (n-propanol, isopropanol). When an alcohol having 4 or more carbon atoms is used, the solubility of the amphoteric fluorine-based compound in the alcohol becomes poor. Water used in the present embodiment includes pure water such as ion-exchanged water and distilled water, or ultrapure water.

本実施の形態の離型用液組成物におけるＰＶＡとフッ素化合物とを合計した質量割合は液組成物１００質量％に対して０．５質量％～１０質量％、好ましくは１．５質量％～５質量％である。合計した質量割合が下限値未満では、成膜時に上記液組成物を塗布した膜が弾いてしまい、成膜性に劣る。また上限値を超えると、液組成物の粘度が高過ぎて、成膜時に、表面に凹凸が生じ離型性に劣る。また本実施の形態の離型用液組成物におけるＰＶＡとフッ素化合物の質量比はＰＶＡ：フッ素化合物＝９９．９：０．１～９０：１０、好ましくは９９．８：０．２～９５：５である。ＰＶＡが９９．９を超えかつフッ素化合物が０．１未満である場合、金型等への離型性付与が不十分になる。またＰＶＡが９０未満でかつフッ素化合物が１０を超えると、フッ素化合物の表面張力が強く出現し、塗布膜の弾きが生じて、塗工性が悪化し成膜できずかつ液組成物の溶液安定性が悪化する。更に本実施の形態の離型用液組成物におけるアルコールの質量割合は液組成物１００質量％に対して５質量％～５０質量％、好ましくは２０質量％～４０質量％である。アルコールの質量割合が下限値未満では、液組成物中でフッ素化合物が析出し、溶液安定性が悪化し、上限値を超えると、水の割合が減少し、これによりＰＶＡが析出し、液組成物の溶液安定性が悪化する。またＰＶＡと水のみの系であれば、成膜性に優れているが、アルコールを添加すると、成膜時に塗布膜に弾きが生じてしまう。この弾きを減少させるために、フッ素化合物を添加することで、界面活性性能が発現され、成膜性を大きく改善することができる。そのため本実施の形態では、ＰＶＡ、水、アルコール、フッ素化合物の４つの組合せをすることで初めて機能を発現できる液組成物になる。本実施の形態の離型用液組成物は、ＰＶＡを含むため、金型等表面との濡れ性、密着性に優れる。上記液組成物が着色剤を含む場合には、塗布膜を目視で容易に確認することができる。 The total mass ratio of the PVA and the fluorine compound in the release liquid composition of the present embodiment is 0.5% by mass to 10% by mass, preferably 1.5% by mass to 100% by mass, relative to 100% by mass of the liquid composition. 5% by mass. If the total mass ratio is less than the lower limit, the film coated with the liquid composition will be repelled during film formation, resulting in poor film formability. On the other hand, when the upper limit is exceeded, the viscosity of the liquid composition is too high, and unevenness occurs on the surface during film formation, resulting in poor releasability. The mass ratio of PVA to fluorine compound in the release liquid composition of the present embodiment is PVA: fluorine compound = 99.9:0.1 to 90:10, preferably 99.8:0.2 to 95: 5. If the PVA exceeds 99.9 and the fluorine compound content is less than 0.1, releasability to a mold or the like will be insufficient. Further, when the PVA is less than 90 and the fluorine compound exceeds 10, the surface tension of the fluorine compound appears strong, the coating film is repelled, the coatability is deteriorated, and the film cannot be formed, and the solution stability of the liquid composition. sexuality worsens. Furthermore, the mass ratio of alcohol in the liquid composition for release of the present embodiment is 5% by mass to 50% by mass, preferably 20% by mass to 40% by mass with respect to 100% by mass of the liquid composition. If the mass ratio of alcohol is less than the lower limit, the fluorine compound will precipitate in the liquid composition and the solution stability will deteriorate. The solution stability of the product deteriorates. A system consisting of only PVA and water is excellent in film-forming properties, but if alcohol is added, the coating film is repelled during film-forming. By adding a fluorine compound to reduce this repulsion, the surfactant performance can be expressed and the film formability can be greatly improved. Therefore, in the present embodiment, a liquid composition capable of exhibiting its function is obtained only by combining PVA, water, alcohol, and a fluorine compound. Since the release liquid composition of the present embodiment contains PVA, it is excellent in wettability and adhesion to the surface of a mold or the like. When the liquid composition contains a coloring agent, the coating film can be easily visually confirmed.

〔離型膜の形成方法〕
本実施の形態の離型膜は、後述する樹脂成形体の接触面となる金型等の表面に上記液組成物を塗工して乾燥することにより形成される。離型膜の厚さは、金型等の表面形状に依存するが、０．５μｍ～５μｍが好ましい。０．５μｍ未満では離型効果に乏しく、５μｍを超えると塗布膜が不均一になることで膜表面に凹凸が発生し、離型効果に劣る。金型等の基材としては、アルミニウム（Ａｌ）、ステンレス鋼（ＳＵＳ）等の金属製基材の他、ポリ塩化ビニル（ＰＶＣ）、繊維強化プラスチック（ＦＲＰ）等の樹脂製基材、木材からなる木製基材等が挙げられる。金型等の表面への塗工法としては、特に制限されず、例えば上記離型用液組成物をディッピング法、刷毛塗り法、スプレーコーティング法等の公知の方法が挙げられる。塗工後の乾燥は、大気雰囲気下、常温で１０分～６０分間放置して行われる。特に加熱を必要としない。乾燥した離型膜は表面平滑性に優れる。 [Method for forming release film]
The release film of the present embodiment is formed by applying the above liquid composition to the surface of a mold or the like, which will be the contact surface of the resin molding described later, and drying the composition. The thickness of the release film depends on the surface shape of the mold and the like, but is preferably 0.5 μm to 5 μm. If the thickness is less than 0.5 μm, the release effect is poor, and if the thickness exceeds 5 μm, the coating film becomes non-uniform and irregularities are generated on the film surface, resulting in a poor release effect. Base materials for molds include metal base materials such as aluminum (Al) and stainless steel (SUS), as well as resin base materials such as polyvinyl chloride (PVC) and fiber reinforced plastic (FRP). wooden substrates and the like. There are no particular restrictions on the method of coating the surface of a mold or the like, and examples thereof include known methods such as dipping, brush coating, and spray coating. Drying after coating is carried out by allowing the coating to stand at room temperature for 10 to 60 minutes in an air atmosphere. No special heating required. The dried release film has excellent surface smoothness.

〔金型等による樹脂成形体の作製方法〕
本実施の形態の金型等で成形される樹脂としては、アクリル樹脂、エポキシ樹脂、ポリエステル樹脂などが挙げられる。上記樹脂に硬化剤を添加し、溶液状態で離型膜を介して金型等の外面又は内面に積層又は注入した後、上記樹脂を硬化させて樹脂成形体を作製する。この硬化した樹脂成形体は、金型等の表面に上述した離型膜が形成されているため、金型等の表面に成形体の一部が付着せずに、所望の形状で円滑かつ容易に金型等から離型することができる。また樹脂成形体を金型等から離型した後で、樹脂成形体の表面に離型膜が残存しても、ＰＶＡが水に溶解しやすいために、水で残存した離型膜を除去することができる。 [Method for producing a resin molded body using a mold or the like]
Acrylic resin, epoxy resin, polyester resin, and the like can be given as resins molded by the mold or the like of the present embodiment. A curing agent is added to the above resin, and the solution is laminated or injected onto the outer surface or the inner surface of a mold or the like via a release film, and then the resin is cured to produce a resin molding. Since the above-described release film is formed on the surface of the mold, the cured resin molded product can be smoothly and easily molded into a desired shape without part of the molded product adhering to the surface of the mold. It can be released from the mold or the like immediately. Even if a release film remains on the surface of the resin molded product after the resin molded product is released from the mold, etc., the remaining release film is removed with water because PVA is easily dissolved in water. be able to.

次に本発明の実施例を比較例とともに詳しく説明する。 Next, examples of the present invention will be described in detail together with comparative examples.

＜実施例１＞
ＰＶＡ濃度が４質量％のクラレ社製ＰＶＡ１１７を溶解した水溶液３０．６３ｇと、蒸留水３５．１３ｇと、エタノール８５質量％、イソプロパノール５質量％及びｎ－プロパノール１０質量％からなるアルコール３４．２３ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（１７）で表される化合物を０．０２５ｇ添加混合して離型用液組成物を調製した。 <Example 1>
30.63 g of an aqueous solution in which PVA117 manufactured by Kuraray Co., Ltd. with a PVA concentration of 4% by mass is dissolved, 35.13 g of distilled water, and 34.23 g of an alcohol composed of 85% by mass of ethanol, 5% by mass of isopropanol and 10% by mass of n-propanol were weighed and thoroughly mixed, and then 0.025 g of the compound represented by the above formula (17) was added and mixed to prepare a release liquid composition.

＜実施例２＞
ＰＶＡ濃度が４質量％のクラレ社製ＰＶＡ１２４を溶解した水溶液１２．２５ｇと、蒸留水６２．７４ｇと、エタノール８５質量％、イソプロパノール５質量％及びｎ－プロパノール１０質量％からなるアルコール２５．００ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（１８）で表される化合物を０．０１０ｇ添加混合して離型用液組成物を調製した。 <Example 2>
12.25 g of an aqueous solution in which PVA124 manufactured by Kuraray Co., Ltd. with a PVA concentration of 4% by mass is dissolved, 62.74 g of distilled water, and 25.00 g of alcohol consisting of 85% by mass of ethanol, 5% by mass of isopropanol and 10% by mass of n-propanol were weighed and thoroughly mixed, and then 0.010 g of the compound represented by the above formula (18) was added and mixed to prepare a release liquid composition.

＜実施例３＞
ＰＶＡ濃度が１５質量％のクラレ社製ＰＶＡ１０３を溶解した水溶液６２．７０ｇと、蒸留水２．２１ｇと、エタノール８５質量％、イソプロパノール５質量％及びｎ－プロパノール１０質量％からなるアルコール３５．００ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（１９）で表される化合物を０．０９５ｇ添加混合して離型用液組成物を調製した。 <Example 3>
62.70 g of an aqueous solution in which PVA103 manufactured by Kuraray Co., Ltd. with a PVA concentration of 15% by mass is dissolved, 2.21 g of distilled water, and 35.00 g of an alcohol composed of 85% by mass of ethanol, 5% by mass of isopropanol and 10% by mass of n-propanol were weighed and thoroughly mixed, and then 0.095 g of the compound represented by the above formula (19) was added and mixed to prepare a release liquid composition.

＜実施例４＞
ＰＶＡ濃度が１５質量％のクラレ社製ＰＶＡ１０３を溶解した水溶液５３．２８ｇと、蒸留水１１．７１ｇと、エタノール３５．００ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（２０）で表される化合物を０．００８ｇ添加混合して離型用液組成物を調製した。 <Example 4>
53.28 g of an aqueous solution in which PVA103 manufactured by Kuraray Co., Ltd. with a PVA concentration of 15% by mass was dissolved, 11.71 g of distilled water, and 35.00 g of ethanol were weighed and thoroughly mixed. 0.008 g of the compound represented by (20) was added and mixed to prepare a release liquid composition.

＜実施例５＞
ＰＶＡ濃度が４質量％の日本合成化学社製ゴーセネックスＴ－３３０Ｈを溶解した水溶液３８．８０ｇと、蒸留水３６．１５ｇと、エタノール８５質量％、イソプロパノール５質量％及びｎ－プロパノール１０質量％からなるアルコール２５．００ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（２１）で表される化合物を０．０４８ｇ添加混合して離型用液組成物を調製した。 <Example 5>
Consists of 38.80 g of an aqueous solution of Gohsenex T-330H manufactured by Nippon Synthetic Chemical Co., Ltd. with a PVA concentration of 4% by mass, 36.15 g of distilled water, 85% by mass of ethanol, 5% by mass of isopropanol and 10% by mass of n-propanol. 25.00 g of alcohol was weighed and thoroughly mixed, and then 0.048 g of the compound represented by the above formula (21) was added and mixed to prepare a release liquid composition.

＜実施例６＞
ＰＶＡ濃度が４質量％の日本合成化学社製ゴーセネックスＴ－３３０Ｈを溶解した水溶液１６．８８ｇと、蒸留水４８．０５ｇと、エタノール８５質量％、イソプロパノール５質量％及びｎ－プロパノール１０質量％からなるアルコール３５．００ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（２２）で表される化合物を０．０７５ｇ添加混合して離型用液組成物を調製した。 <Example 6>
Consists of 16.88 g of an aqueous solution of Gohsenex T-330H manufactured by Nippon Synthetic Chemical Co., Ltd. with a PVA concentration of 4% by mass, 48.05 g of distilled water, 85% by mass of ethanol, 5% by mass of isopropanol, and 10% by mass of n-propanol. 35.00 g of alcohol was weighed and thoroughly mixed, and then 0.075 g of the compound represented by the above formula (22) was added and mixed to prepare a release liquid composition.

＜実施例７＞
ＰＶＡ濃度が４質量％のクラレ社製ＰＶＡ１１７を溶解した水溶液２４．７５ｇと、蒸留水７０．２４ｇと、エタノール８５質量％、イソプロパノール５質量％及びｎ－プロパノール１０質量％からなるアルコール５．００ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（２２）で表される化合物を０．０１０ｇ添加混合して離型用液組成物を調製した。 <Example 7>
24.75 g of an aqueous solution in which PVA117 manufactured by Kuraray Co., Ltd. with a PVA concentration of 4% by mass is dissolved, 70.24 g of distilled water, and 5.00 g of alcohol consisting of 85% by mass of ethanol, 5% by mass of isopropanol and 10% by mass of n-propanol were weighed and thoroughly mixed, and then 0.010 g of the compound represented by the above formula (22) was added and mixed to prepare a release liquid composition.

＜実施例８＞
ＰＶＡ濃度が４質量％のクラレ社製ＰＶＡ１０３を溶解した水溶液２４．５０ｇと、蒸留水２５．４８ｇと、エタノール８５質量％、イソプロパノール５質量％及びｎ－プロパノール１０質量％からなるアルコール５０．００ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（２２）で表される化合物を０．０２０ｇ添加混合して離型用液組成物を調製した。 <Example 8>
24.50 g of an aqueous solution in which PVA103 manufactured by Kuraray Co., Ltd. with a PVA concentration of 4% by mass is dissolved, 25.48 g of distilled water, and 50.00 g of an alcohol composed of 85% by mass of ethanol, 5% by mass of isopropanol and 10% by mass of n-propanol were weighed and thoroughly mixed, and then 0.020 g of the compound represented by the above formula (22) was added and mixed to prepare a release liquid composition.

＜実施例９＞
実施例１で調製した離型用液組成物１００ｇ（１００質量％）に着色剤として食用青色１号を０．５ｇ（０．５質量％）添加し、十分に混合して、最終的な液組成物を得た。 <Example 9>
To 100 g (100% by mass) of the release liquid composition prepared in Example 1, 0.5 g (0.5% by mass) of Food Blue No. 1 was added as a coloring agent and mixed thoroughly to obtain the final liquid. A composition was obtained.

＜比較例１＞
ＰＶＡ濃度が４質量％のクラレ社製ＰＶＡ１１７を溶解した水溶液９．７０ｇと、蒸留水５５．２９ｇと、エタノール８５質量％、イソプロパノール５質量％及びｎ－プロパノール１０質量％からなるアルコール３５．００ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（２１）で表される化合物を０．０１２ｇ添加混合して離型用液組成物を調製した。 <Comparative Example 1>
9.70 g of an aqueous solution in which PVA117 manufactured by Kuraray Co., Ltd. with a PVA concentration of 4% by mass is dissolved, 55.29 g of distilled water, and 35.00 g of an alcohol composed of 85% by mass of ethanol, 5% by mass of isopropanol and 10% by mass of n-propanol. were weighed and thoroughly mixed, and then 0.012 g of the compound represented by the above formula (21) was added and mixed to prepare a release liquid composition.

＜比較例２＞
ＰＶＡ濃度が１５質量％のクラレ社製ＰＶＡ１０３を溶解した水溶液６９．３０ｇと、蒸留水５．６０ｇと、エタノール８５質量％、イソプロパノール５質量％及びｎ－プロパノール１０質量％からなるアルコール２５．００ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（２１）で表される化合物を０．１０５ｇ添加混合して離型用液組成物を調製した。 <Comparative Example 2>
69.30 g of an aqueous solution in which PVA103 manufactured by Kuraray Co., Ltd. with a PVA concentration of 15% by mass is dissolved, 5.60 g of distilled water, and 25.00 g of an alcohol composed of 85% by mass of ethanol, 5% by mass of isopropanol and 10% by mass of n-propanol were weighed and thoroughly mixed, and then 0.105 g of the compound represented by the above formula (21) was added and mixed to prepare a release liquid composition.

＜比較例３＞
ＰＶＡ濃度が４質量％のクラレ社製ＰＶＡ１１７を溶解した水溶液２４．９９ｇと、蒸留水４０．０１ｇと、エタノール８５質量％、イソプロパノール５質量％及びｎ－プロパノール１０質量％からなるアルコール３５．００ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（２１）で表される化合物を０．０００５ｇ添加混合して離型用液組成物を調製した。 <Comparative Example 3>
24.99 g of an aqueous solution in which PVA117 manufactured by Kuraray Co., Ltd. with a PVA concentration of 4% by mass is dissolved, 40.01 g of distilled water, and 35.00 g of an alcohol composed of 85% by mass of ethanol, 5% by mass of isopropanol and 10% by mass of n-propanol were weighed and thoroughly mixed, and then 0.0005 g of the compound represented by the above formula (21) was added and mixed to prepare a release liquid composition.

＜比較例４＞
ＰＶＡ濃度が４質量％のクラレ社製ＰＶＡ１１７を溶解した水溶液２２．２５ｇと、蒸留水４２．６４ｇと、エタノール８５質量％、イソプロパノール５質量％及びｎ－プロパノール１０質量％からなるアルコール３５．００ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（２２）で表される化合物を０．１１０ｇ添加混合して離型用液組成物を調製した。 <Comparative Example 4>
22.25 g of an aqueous solution in which PVA117 manufactured by Kuraray Co., Ltd. with a PVA concentration of 4% by mass is dissolved, 42.64 g of distilled water, and 35.00 g of an alcohol composed of 85% by mass of ethanol, 5% by mass of isopropanol and 10% by mass of n-propanol were weighed and thoroughly mixed, and then 0.110 g of the compound represented by the above formula (22) was added and mixed to prepare a release liquid composition.

＜比較例５＞
ＰＶＡ濃度が４質量％のクラレ社製ＰＶＡ１１７を溶解した水溶液６７．５０ｇと、蒸留水２９．２０ｇと、エタノール３．００ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（２２）で表される化合物を０．３００ｇ添加混合して離型用液組成物を調製した。 <Comparative Example 5>
67.50 g of an aqueous solution in which PVA117 manufactured by Kuraray Co., Ltd. with a PVA concentration of 4% by mass is dissolved, 29.20 g of distilled water, and 3.00 g of ethanol are weighed and thoroughly mixed. 0.300 g of the compound represented by (22) was added and mixed to prepare a release liquid composition.

＜比較例６＞
ＰＶＡ濃度が４質量％のクラレ社製ＰＶＡ１２４を溶解した水溶液４７．５０ｇと、蒸留水０．４０ｇと、エタノール８５質量％、イソプロパノール５質量％及びｎ－プロパノール１０質量％からなるアルコール５２．００ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（２２）で表される化合物を０．１００ｇ添加混合して離型用液組成物を調製した。 <Comparative Example 6>
47.50 g of an aqueous solution in which PVA124 manufactured by Kuraray Co., Ltd. with a PVA concentration of 4% by mass is dissolved, 0.40 g of distilled water, and 52.00 g of alcohol composed of 85% by mass of ethanol, 5% by mass of isopropanol and 10% by mass of n-propanol were weighed and thoroughly mixed, and then 0.100 g of the compound represented by the above formula (22) was added and mixed to prepare a release liquid composition.

＜比較例７＞
ＰＶＡ濃度が４質量％のクラレ社製ＰＶＡ１１７を溶解した水溶液３０．６３ｇと、蒸留水３４．１７ｇとエタノール８５質量％、イソプロパノール５質量％及びｎ－プロパノール１０質量％からなるアルコール３５．００ｇとを秤量し、これらを十分に混合した後、この混合液にシリコーン系剥離剤（信越化学工業社製ＫＭ－２４４Ｆ）を０．２０ｇ添加混合して離型用液組成物を調製した。 <Comparative Example 7>
30.63 g of an aqueous solution in which PVA117 manufactured by Kuraray Co., Ltd. with a PVA concentration of 4% by mass is dissolved, 34.17 g of distilled water, and 35.00 g of alcohol composed of 85% by mass of ethanol, 5% by mass of isopropanol and 10% by mass of n-propanol. After weighing and sufficiently mixing these, 0.20 g of a silicone-based release agent (KM-244F manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed to prepare a release liquid composition.

＜比較例８＞
ＰＶＡ濃度が４質量％のクラレ社製ＰＶＡ１１７を溶解した水溶液３０．６３ｇと、蒸留水３５．１３ｇと、ｎ－ブタノール３４．２３ｇとを秤量し、これらを十分に混合した後、この混合液に上記式（２２）で表される化合物を０．０２５ｇ添加混合して離型用液組成物を調製した。 <Comparative Example 8>
30.63 g of an aqueous solution in which PVA 117 manufactured by Kuraray Co., Ltd. with a PVA concentration of 4% by mass is dissolved, 35.13 g of distilled water, and 34.23 g of n-butanol are weighed and thoroughly mixed. 0.025 g of the compound represented by the above formula (22) was added and mixed to prepare a release liquid composition.

＜比較例９＞
比較例９では、実施例１で調製した液組成物１００ｇ（１００質量％）に着色剤として食用青色１号を２．０ｇ（２質量％）添加し、十分に混合して、最終的な液組成物を得た。 <Comparative Example 9>
In Comparative Example 9, 2.0 g (2% by mass) of Food Blue No. 1 was added as a coloring agent to 100 g (100% by mass) of the liquid composition prepared in Example 1, and the mixture was thoroughly mixed to obtain the final liquid composition. A composition was obtained.

実施例１～９及び比較例１～９の離型用液組成物における、ＰＶＡ水溶液の濃度と秤量値、両性型フッ素系化合物の種類と秤量値、アルコール及び水の各秤量値を表１に示す。表１中、両性型フッ素系化合物は、単に「フッ素化合物」と記載し、その種類として、例えば「式（１７）」と記載したものは、「式（１７）に示される化合物」を意味する。またＰＶＡとフッ素化合物とを合計した質量割合、ＰＶＡとフッ素化合物の質量比及びアルコールの質量割合をそれぞれ表２に示す。 Table 1 shows the concentration and weighed value of the PVA aqueous solution, the type and weighed value of the amphoteric fluorine-based compound, and the weighed values of alcohol and water in the release liquid compositions of Examples 1 to 9 and Comparative Examples 1 to 9. show. In Table 1, the amphoteric fluorine-based compound is simply described as "fluorine compound", and as its type, for example, what is described as "formula (17)" means "compound represented by formula (17)". . In addition, Table 2 shows the total mass ratio of PVA and the fluorine compound, the mass ratio of PVA and the fluorine compound, and the mass ratio of alcohol.

＜比較試験及び評価＞
次に述べる方法で、(1) 金型からの樹脂層の剥離性（離型性）と、(2) 離型膜の易洗浄性を調べた。 <Comparative test and evaluation>
The following methods were used to examine (1) the releasability (mold releasability) of the resin layer from the mold and (2) the ease of cleaning of the release film.

(1) 金型からの樹脂層の剥離性（離型性）
実施例１～９及び比較例１～９で得られた離型用液組成物を厚さ３ｍｍ、たて１５０ｍｍ、よこ７５ｍｍの板状のＳＵＳ基材（金型）表面に刷毛で塗布し、大気雰囲気下、常温で１時間放置し乾燥することにより離型膜を形成した。この離型膜の平均厚さはマイクロメーターにより測定したところ１μｍであった。このＳＵＳ基材表面に形成された離型膜上に、アクリル樹脂（日本合成化学製コーボニールN-7520）とポリイソシアネート（東ソー社製コロネートL-55E）と希釈用溶媒である酢酸ブチルを質量比で１００：０．２：１００の割合で混合した樹脂液を刷毛を用いて積層塗布した。樹脂液により形成された樹脂層上にポリエチレンテレフタレート（ＰＥＴ）のフィルムを置き、ＰＥＴ表面をウレタン製ローラを転がして荷重を加えた。この状態で大気雰囲気下、常温で１８時間放置することにより樹脂層を乾燥し、アクリル樹脂を硬化させて厚さ１ｍｍの樹脂層（樹脂成形体）を得た。ＰＥＴフィルムを樹脂層から静かに剥がした後、ＳＵＳ基材（金型）からの樹脂層の剥離性（離型性）を目視により調べた。ＳＵＳ基材（金型）から樹脂層が完全に剥離した場合を「良好」とし、樹脂層が一部でもＳＵＳ基材（金型）の表面に付着残存した場合を「不良」と評価した。 (1) Peelability of the resin layer from the mold (releasability)
The release liquid compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 9 were applied with a brush to the surface of a plate-like SUS substrate (mold) having a thickness of 3 mm, a length of 150 mm, and a width of 75 mm, The mold release film was formed by leaving it to stand at normal temperature for 1 hour and drying in an air atmosphere. The average thickness of this release film was 1 μm when measured with a micrometer. On the release film formed on the surface of this SUS substrate, acrylic resin (Corbonyl N-7520 manufactured by Nippon Synthetic Chemical Industry), polyisocyanate (Coronate L-55E manufactured by Tosoh Corporation) and butyl acetate as a diluent solvent are mixed in a mass ratio of A resin liquid mixed at a ratio of 100:0.2:100 was applied in layers using a brush. A polyethylene terephthalate (PET) film was placed on the resin layer formed by the resin liquid, and a urethane roller was rolled on the PET surface to apply a load. In this state, the resin layer was dried by allowing it to stand at room temperature for 18 hours in an air atmosphere, and the acrylic resin was cured to obtain a resin layer (resin molding) having a thickness of 1 mm. After gently peeling the PET film from the resin layer, the releasability (mold releasability) of the resin layer from the SUS substrate (mold) was visually examined. A case where the resin layer was completely peeled off from the SUS base material (mold) was evaluated as "good", and a case where even a part of the resin layer remained attached to the surface of the SUS base material (mold) was evaluated as "bad".

(2) 離型膜の易洗浄性
ＳＵＳ基材（金型）から剥離した樹脂層を１４℃の水道水で洗浄した。水洗乾燥後、走査型電子顕微鏡－エネルギー分散型Ｘ線分析装置（ＳＥＭ－ＥＤＳ）（ＳＥＭ：株式会社日立ハイテクノロジーズ社製S-3500N、ＥＤＳ：堀場製作所製EMAX モデル7021-H）を用いて、樹脂層の表面に離型膜成分のフッ素が存在しているか調べた。フッ素が全く存在しなかった場合を離型膜の易洗浄性が「良好」であると評価し、フッ素が少しでも存在した場合を離型膜の易洗浄性が「不良」であると評価した。これらの結果を次の表２に示す。 (2) Easy Washability of Release Film The resin layer separated from the SUS substrate (mold) was washed with 14° C. tap water. After washing and drying, using a scanning electron microscope-energy dispersive X-ray spectrometer (SEM-EDS) (SEM: S-3500N manufactured by Hitachi High-Technologies Corporation, EDS: EMAX model 7021-H manufactured by Horiba, Ltd.), It was examined whether or not fluorine, which is a release film component, is present on the surface of the resin layer. The ease of cleaning of the release film was evaluated as "good" when no fluorine was present, and the ease of cleaning of the release film was evaluated as "poor" when even a small amount of fluorine was present. . These results are shown in Table 2 below.

表２から明らかなように、比較例１では、ＰＶＡとフッ素化合物を合計した固形分濃度が０．４０質量％と低いため、成膜時に、膜の弾きが発生し、均一に成膜できなかった。この結果、金型からの離型性が不良であった。金型からの離型が不良であったため、洗浄テストはできなかった。 As is clear from Table 2, in Comparative Example 1, since the total solid concentration of PVA and the fluorine compound was as low as 0.40% by mass, the film was repelled during film formation, and a uniform film could not be formed. Ta. As a result, the releasability from the mold was poor. A cleaning test was not possible due to poor release from the mold.

比較例２では、固形分濃度が１０．５０質量％と高すぎたため、液組成物の粘度が高く、成膜時に膜に凹凸が発生し、均一に成膜できなかった。この結果、金型からの離型性が不良であった。金型からの離型が不良であったため、洗浄テストはできなかった。 In Comparative Example 2, since the solid content concentration was too high at 10.50% by mass, the viscosity of the liquid composition was high, and unevenness was generated in the film during film formation, and uniform film formation was not possible. As a result, the releasability from the mold was poor. A cleaning test was not possible due to poor release from the mold.

比較例３では、フッ素化合物の質量比が０．０５と低すぎたため、金型からの離型性が不良であった。金型からの離型が不良であったため、洗浄テストはできなかった。 In Comparative Example 3, since the mass ratio of the fluorine compound was too low at 0.05, the releasability from the mold was poor. A cleaning test was not possible due to poor release from the mold.

比較例４では、フッ素化合物の質量比が１１．０と高すぎたため、成膜時に膜の弾きが発生し、凹凸が発生し、均一に成膜できなかった。この結果、金型からの離型性が不良であった。金型からの離型が不良であったため、洗浄テストはできなかった。 In Comparative Example 4, the mass ratio of the fluorine compound was as high as 11.0, so that the film was repelled during film formation, causing irregularities, and the film could not be formed uniformly. As a result, the releasability from the mold was poor. A cleaning test was not possible due to poor release from the mold.

比較例５では、アルコール濃度が３．０質量％と低過ぎたため、液組成物中にフッ素化合物が析出しており、成膜時に膜に凹凸が発生し、均一に成膜できなかった。この結果、金型からの離型性が不良であった。金型からの離型が不良であったため、洗浄テストはできなかった。 In Comparative Example 5, since the alcohol concentration was as low as 3.0% by mass, the fluorine compound was precipitated in the liquid composition, and unevenness was generated in the film during film formation, making it impossible to form a uniform film. As a result, the releasability from the mold was poor. A cleaning test was not possible due to poor release from the mold.

比較例６では、アルコール濃度が５２．０質量％と高過ぎたため、液組成物中にＰＶＡが析出しており、成膜時に膜に凹凸が発生し、均一に成膜できなかった。この結果、金型からの離型性が不良であった。金型からの離型が不良であったため、洗浄テストはできなかった。 In Comparative Example 6, since the alcohol concentration was too high at 52.0% by mass, PVA precipitated in the liquid composition, causing irregularities in the film during film formation, and uniform film formation was not possible. As a result, the releasability from the mold was poor. A cleaning test was not possible due to poor release from the mold.

比較例７では、フッ素化合物の代わりに、シリコーンを用いたが、シリコーンの添加量が少なかったため、金型からの離型性が不良であった。金型からの離型が不良であったため、洗浄テストはできなかった。 In Comparative Example 7, silicone was used instead of the fluorine compound, but since the amount of silicone added was small, the releasability from the mold was poor. A cleaning test was not possible due to poor release from the mold.

比較例８では、アルコールが炭素数が４であるｎ－ブタノールであるため、液組成物中にＰＶＡが析出しており、成膜時に膜に凹凸が発生し、均一に成膜できなかった。この結果、金型からの離型性が不良であった。金型からの離型が不良であったため、洗浄テストはできなかった。 In Comparative Example 8, since the alcohol was n-butanol having 4 carbon atoms, PVA was deposited in the liquid composition, and unevenness was generated in the film during film formation, and uniform film formation was not possible. As a result, the releasability from the mold was poor. A cleaning test was not possible due to poor release from the mold.

比較例９では、更に比較例９の液組成物では、着色剤の含有割合が１質量％を超えたため、金型からの離型性が不良であった。金型からの離型が不良であったため、洗浄テストはできなかった。 In Comparative Example 9, the liquid composition of Comparative Example 9 contained more than 1% by mass of the colorant, so that the releasability from the mold was poor. A cleaning test was not possible due to poor release from the mold.

これに対して、表２から明らかなように、実施例１～９では、ＰＶＡとフッ素化合物とを合計した質量割合が０．５質量％～１０質量％の範囲にあり、ＰＶＡとフッ素化合物の質量比が９９．９：０．１～９０：１０の範囲にあり、アルコールの質量割合が５質量％～５０質量％の範囲にあり、かつフッ素化合物が式（１７）～式（２２）で表される両性型フッ素系化合物であったため、金型からの樹脂層の剥離性（離型性）はすべて「良好」であり、また離型膜の易洗浄性もすべて「良好」であった。更に実施例９で形成された膜は着色されていたため、目視で膜を容易に確認することができた。 On the other hand, as is clear from Table 2, in Examples 1 to 9, the total mass ratio of PVA and the fluorine compound was in the range of 0.5% by mass to 10% by mass, and the ratio of PVA and the fluorine compound was The mass ratio is in the range of 99.9:0.1 to 90:10, the alcohol mass ratio is in the range of 5% by mass to 50% by mass, and the fluorine compound is represented by formulas (17) to (22) Since it was an amphoteric fluorine-based compound represented by the above, the releasability (mold releasability) of the resin layer from the mold was all "good", and the ease of cleaning of the release film was all "good". . Furthermore, since the film formed in Example 9 was colored, the film could be easily confirmed visually.

本発明の離型用液組成物は、プレス成形法、ＦＲＰ成形法等により樹脂成形体を作る場合に、樹脂成形体を金型等から容易に離型させる分野に用いられる。 The release liquid composition of the present invention is used in the field of easily releasing a resin molded article from a mold or the like when a resin molded article is produced by a press molding method, an FRP molding method, or the like.

Claims

A release liquid composition containing polyvinyl alcohol, a fluorine compound, one or more alcohols having 1 to 3 carbon atoms, and water,
The total amount of the polyvinyl alcohol and the fluorine compound is 0.5% by mass to 10% by mass with respect to 100% by mass of the liquid composition,
The mass ratio of the polyvinyl alcohol and the fluorine compound is polyvinyl alcohol: fluorine compound = 99.9:0.1 to 90:10,
5% by mass to 50% by mass of the alcohol with respect to 100% by mass of the liquid composition,
A release liquid composition, wherein the fluorine compound is an amphoteric fluorine compound represented by the following formula (1) or (2).

(1)
In the above formula (1), p, q and r are the same or different integers of 1 to 6. Further, in the above formula (1), X is a hydrocarbon group having 2 to 10 carbon atoms, and is selected from an ether bond, a CO—NH bond, an O—CO—NH bond and a sulfonamide bond. It may contain a bond. In the above formula (1), Y is a hydrophilic group having a betaine structure.

(2)
In formula (2) above, p and q are the same or different integers of 1 to 6, respectively. Further, in the above formula (2), X is a hydrocarbon group having 2 to 10 carbon atoms, and is selected from an ether bond, a CO—NH bond, an O—CO—NH bond and a sulfonamide bond. It may contain a bond. In the above formula (2), Y is a hydrophilic group having a betaine structure.

The release liquid composition according to claim 1, wherein the colorant is contained in an amount of 0.01% by mass to 1% by mass with respect to 100% by mass of the release liquid composition.