JP2019107783A - Liquid composition for mold release and wet sheet impregnated with the liquid composition - Google Patents

Abstract

To provide a liquid composition for mold release that has an excellent film forming property to a resin molding die or the like made of a metal including SUS, that has an excellent releasability with respect to the mold release of a resin molded article from the die or the like, and that can remove a mold release film transferred to a molded article with water when the mold release film is transferred to the molded article made of the die or the like.SOLUTION: The liquid composition for the mold release of the present invention comprises: polyvinyl alcohol (PVA), a fluorine compound (F compound), water, one or more alcohols having a carbon number in a range of 1 to 3 and having a weight of 40 mass% or less based on the liquid composition, and polyalkylene glycol (PAG). The liquid composition has the weight of 0.5 to 10 mass% of a total of PVA, the F compound and PAG, and a ratio between a first mass of the total of PVA and PAG and a second mass of the F compound is 80-99.9: 0.1-20 (first mass: second mas), and the ratio of PAG to (PAG+PVA) is 0.5 to 20 mass%, and the F compound is represented by a following chemical formula (1).SELECTED DRAWING: None

Description

  The present invention relates to a liquid composition for mold release that imparts mold releasability to a mold represented by a mold (hereinafter referred to as a mold or the like), and a wet sheet impregnated with the liquid composition. More particularly, the present invention relates to a liquid composition for mold release that facilitates mold release of a resin molded product from a mold or the like, and a wet sheet impregnated with the liquid composition.

  As this type of mold release liquid composition, the present applicants have found that the mold contains a polyvinyl alcohol (PVA), a fluorine compound, one or more types of alcohol having 1 to 3 carbon atoms, and water. A liquid composition has been proposed (see Patent Document 1). The liquid composition for mold release contains 0.5 to 10% by mass in total of PVA and a fluorine compound, and the mass ratio of PVA and the fluorine compound is PVA: fluorine compound = 99.9: 0.1 to 90: 10, containing 5 to 50% by mass of an alcohol, and the fluorine compound being an amphoteric nitrogen-containing fluorine-based compound represented by the following formula (44). This liquid composition for mold release is easy to release the resin molded body from the mold or the like, and a coating film having releasability on the molded body made of the mold or the like (hereinafter referred to as a mold release film) ) Has a feature that the release film transferred to the molded body can be removed with water.

However, in the formula (44), Rf ⁸ and Rf ⁹ are each the same or different, and each a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms and having 1 to 6 carbon atoms. Rf ¹⁰ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms. R is a linking group which is a divalent organic group, and Y is a amphiphilic hydrophilic group.

  On the other hand, the applicant has proposed a nonionic fluorinated surfactant represented by the following general formula (1) (see Patent Document 2). This nonionic fluorine-containing surfactant has excellent ability to reduce surface tension, has low bioaccumulation ability, and is excellent in environmental adaptability.

However, in the formula (1), Rf ¹ and Rf ² are each a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, which is the same as or different from each other. The Rf ¹ and Rf ² may be directly bonded to form a ring, or may be bonded via an oxygen atom or a nitrogen atom to form a heterocycle. Furthermore, Rf ³ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms.
Further, in the above formula (1), R ¹ is a hydrogen atom or a methyl group. Further, R ² is a linear or branched alkyl group having 1 to 8 carbon atoms. Furthermore, n is an integer of 3 to 50.

JP, 2017-177401, A (abstract) JP-A-2015-163662 (abstract, paragraph [0028])

  Among the nonionic fluorine-containing surfactants shown in Patent Document 2 among many uses, Patent Application 2 has a use as a coating additive for imparting releasability and a surface treatment agent. The main components to which this nonionic fluorinated surfactant is added are not disclosed.

  In the liquid composition for release shown in Patent Document 1 which contains PVA and a fluorine compound in addition to the solvent, when the substrate such as a mold is stainless steel (hereinafter referred to as SUS), the liquid composition is a SUS substrate When applied to the surface, the liquid composition is easily repelled on the surface of the SUS base material, and there is still a problem to be solved that the formed coating film can not be sufficiently provided with releasability. This problem is still unsolved even if the fluorine compound shown in Patent Document 1 is replaced with the nonionic fluorine-containing surfactant shown in Patent Document 2.

  The object of the present invention is to form a film formed on a metal mold for resin molding containing SUS, etc., to be excellent in the releasability of the resin molded body from the mold etc. It is an object of the present invention to provide a releasing liquid composition capable of removing the release film transferred to the molded body with water when the mold film is transferred. Another object of the present invention is to move the wet sheet impregnated with the above-mentioned liquid composition for mold release along the surface of the substrate to form a coating film having releasability on the substrate surface, An object of the present invention is to provide a wet sheet which is made to be releasable.

  A first aspect of the present invention is a mold release liquid composition containing polyvinyl alcohol (hereinafter sometimes referred to as PVA), a fluorine compound (hereinafter also referred to as F compound) and water, The liquid composition further contains 0% by mass to 40% by mass, relative to 100% by mass of the liquid composition, of one or more alcohols having a carbon number in the range of 1 to 3 and a polyalkylene glycol (PAG) And containing 0.5% by mass to 10% by mass of the polyvinyl alcohol, the fluorine compound and the polyalkylene glycol which are solid components in the liquid composition, relative to 100% by mass of the liquid composition. The ratio of the first mass of the total of the polyvinyl alcohol and the polyalkylene glycol to the second mass of the fluorine compound is: first mass: second mass = 80 to 99.9: 0.1 20, the ratio (PAG / (PAG + PVA)) of the first mass (mass of PAG + PVA) to the mass of the polyalkylene glycol (PAG) is 0.5 mass% to 20 mass%, and the F compound is It is characterized by being a nonionic fluorine compound represented by Formula (1).

However, in the formula (1), Rf ¹ and Rf ² are each a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, which is the same as or different from each other. The Rf ¹ and Rf ² may be directly bonded to form a ring, or may be bonded via an oxygen atom or a nitrogen atom to form a heterocycle. Furthermore, Rf ³ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms.
Further, in the above formula (1), R ¹ is a hydrogen atom or a methyl group. Further, R ² is a linear or branched alkyl group having 1 to 8 carbon atoms. Furthermore, n is an integer of 3 to 50.

  A second aspect of the present invention is the invention based on the first aspect, wherein the nonionic fluorine compound represented by the formula (1) is a nonionic fluorine compound represented by the following formula (2) It is a liquid composition for molds.

However, in the formula (2), Rf ⁴ and Rf ⁵ are each a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, which is the same as or different from each other. Rf ⁶ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms. In addition, X is an oxygen atom, a nitrogen atom or a CF ₂ group. Further, in the above formula (2), R ³ is a hydrogen atom or a methyl group. R ⁴ is a linear or branched alkyl group having 1 to 8 carbon atoms. Furthermore, n is an integer of 3 to 50.

  A third aspect of the present invention is the invention based on the first aspect, wherein the nonionic fluorine compound represented by the formula (1) is a nonionic fluorine compound represented by the following formula (3) It is a liquid composition for molds.

However, in Formula (3), m and l are respectively the same or mutually different integers of 1 to 6. Rf ⁷ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms. Further, in the above formula (3), R ⁵ is a hydrogen atom or a methyl group. R ⁶ is a linear or branched alkyl group having 1 to 8 carbon atoms. Furthermore, n is an integer of 3 to 50.

A fourth aspect of the present invention is a wet sheet impregnated with one aspect of the liquid composition of the first to third aspect, the sheet base material of 30g / m ² ~100g / m ² basis weight and consists ^{1cm 3 / cm 2 / sec~250cm 3} / cm 2 / sec nonwoven having a permeability of, to include the liquid composition per unit area of the nonwoven fabric at a rate of 10g / m ² ~200g / m ² It features.

  A fifth aspect of the present invention is the invention based on the fourth aspect, wherein the non-woven fabric is a group consisting of polypropylene (PP) fibers, polyethylene terephthalate (PET) fibers, nylon fibers, rayon fibers, pulp fibers and glass fibers. It is a wet sheet which consists of a fiber which mixed 1 type, or 2 or more types chosen from a plurality, and a plurality of the above-mentioned nonwoven fabrics are laminated.

  According to a sixth aspect of the present invention, a wet sheet impregnated with a liquid composition according to any one of the first to third aspects or a wet sheet of the fourth or fifth aspect is moved along the surface of a substrate. The liquid composition is applied to the surface of the substrate, and the applied liquid composition is dried to form a coating film having releasability on the surface of the substrate.

  The liquid composition for mold release according to any one of the first to third aspects of the present invention has a mass ratio of the total of PVA, F compound and PAG, a mass ratio of the total mass of PVA and PAG to the F compound, and a content ratio of F compound Are each controlled to a predetermined range, and the fluorine compound is a nonionic fluorine compound represented by the above formulas (1) to (3). PVA is excellent in film forming property and easily soluble in water. After the liquid composition for mold release is coated on the surface of a mold or the like to form a mold release film of PVA, the resin is coated on the surface of the mold or the like and cured to form a resin molded product. Since the release film has no solubility in alcohol, bonding with the resin hardly occurs. PAG also increases the viscosity of the liquid composition to prevent repelling during application of the liquid composition. Further, since the liquid composition contains the nonionic fluorine compound represented by the above formulas (1) to (3) in a predetermined mass ratio, it is easy to apply to a mold etc. and the resin molded product is easily detached from the mold etc Excellent releasability. Furthermore, even if the mold release film is transferred to the surface of the resin molded body separated from the mold or the like, since the PVA is water-soluble, the mold release film can be easily removed with water. In particular, the fluorine compound of the present invention is excellent in releasability because of the high fluorine content of the fluorine-containing functional group, and further has surfactant properties due to being nonionic, while it has less foaming of the liquid composition, Unlike other fluorine compounds, it has the effect of improving the film forming property. Furthermore, when the alcohol having a carbon number in the range of 1 to 3 is contained in a predetermined mass ratio, the solution stability of the liquid composition is excellent, and the fluorine compound is more easily dissolved.

  In the wet sheet according to the fourth aspect of the present invention, the non-woven fabric of the sheet base material has a predetermined basis weight, so that the non-woven fabric does not become too thick and facilitates its handling. In addition, when the wet sheet is moved along the surface of the substrate, the wet sheet does not tear or the like, and has a certain strength. Further, since the nonwoven fabric of the sheet base material has a predetermined air permeability, when the liquid composition is brought into contact with the nonwoven fabric, the liquid composition reliably penetrates into the nonwoven fabric. By allowing the nonwoven fabric to contain a predetermined amount of water or a combination of water and alcohol, the liquid composition does not drip from the nonwoven fabric by gravity or when the wet sheet is held, and the wet sheet extends along the substrate surface. The liquid composition can be coated with a uniform thickness on the surface of the substrate when it is moved. In addition, since each raw material component is contained in a predetermined ratio in the liquid composition held in the non-woven fabric, the liquid composition spreads on the surface of the substrate with good wettability, and the formed coating film has releasability. Demonstrate.

  In the wet sheet according to the fifth aspect of the present invention, the nonwoven fabric is one or two selected from the group consisting of polypropylene (PP) fiber, polyethylene terephthalate (PET) fiber, nylon fiber, rayon fiber, pulp fiber and glass fiber. Since it is comprised from the fiber which mixed the above, liquid retention property is good and a liquid composition can be apply | coated smoothly to the base-material surface. In addition, when the non-woven fabric is a laminate, the liquid retention property of the liquid composition is further enhanced, and even when a wide area is applied, the non-woven fabric is less damaged and the durability is excellent.

  In the method for forming a releasable coating film according to the sixth aspect of the present invention, the wet sheet is moved along the surface of the substrate to apply the liquid composition to the surface of the substrate, and the applied liquid composition By drying the product, this coating film has the effect of exhibiting releasability.

  Next, an embodiment of the present invention will be described.

[Liquid composition for mold release]
The releasing liquid composition of the present embodiment is prepared by mixing PVA, PAG, F compound and water. Although it is preferable that the liquid composition for mold release contains an alcohol having 1 to 3 carbon atoms, it may not be contained. Hereinafter, each raw material component will be described in detail.

(Polyvinyl alcohol (PVA))
The PVA of the present embodiment is excellent in film formability, has no solubility in organic solvents, and is characterized by being easily soluble in water. When a mold-releasing film containing PVA is formed on the surface of a mold or the like and a resin is molded on the mold-releasing film, PVA does not have solubility in an organic solvent, so bonding with the resin is small. Excellent in moldability. In addition, there is an advantage that even if the mold release film containing PVA is transferred to the resin molded body after the resin molded body is demolded, it can be easily washed out with water.

  The PVA is a completely or partially saponified vinyl ester polymer. As a saponification method, a known alkali saponification method or acid saponification method can be used. Among them, the method of alcoholysis using alkali hydroxide in methanol is preferable. The PVA is not particularly limited as long as it is generally used in a liquid composition for mold release, and is an unmodified polyvinyl alcohol having various saponification degrees and polymerization degrees, and anions such as a carboxyl group and a sulfo group. Of anionically modified polyvinyl alcohol, cationically modified polyvinyl alcohol modified with a cation such as amino group and ammonium group, silanol modified polyvinyl alcohol, alkoxyl modified polyvinyl alcohol, epoxy modified polyvinyl alcohol, thiol modified polyvinyl alcohol etc. Incorporation of a water-soluble monomer such as polyvinyl alcohol, acrylamide, acrylic acid or the like in which modification such as anion modification, cation modification, thiol modification, silanol modification, alkoxyl modification and epoxy modification is performed only on the terminal group Block copolymers of polyvinyl alcohol, a graft copolymer of polyvinyl alcohol obtained by grafting a silanol group, and the like can be used. For example, as complete saponification type PVA, Kuraray PVA103, PVA117, PVA124, Nippon Synthetic Chemical Co., Ltd. NH-20, NH-18 etc. are mentioned. Examples of carboxy-modified PVA include T-330H manufactured by Japan Synthetic Chemical Co., Ltd., and examples of sulfo-group-modified PVA include L-823 manufactured by Japan Synthetic Chemical Co., Ltd.

(Polyalkylene glycol (PAG))
The PAG of this embodiment is characterized by being easily soluble in water and being thermoplastic. When the liquid composition is applied to the surface of the SUS base material, the PAG is applied to the surface of the SUS base material only when the component of the liquid composition is a combination of PVA and the F compound and the base material such as a mold is SUS. Since the liquid composition is easily repelled and the liquid composition can not be uniformly applied to the SUS substrate, it has a function to prevent this. Examples of this PAG include polymers of ethylene oxide, polymers of propylene oxide, and copolymers of ethylene oxide and propylene oxide (for example, Alcox series manufactured by Meisei Chemical Co., Ltd.).

(Fluorine compound (F compound))
The fluorine compound (F compound) of the present embodiment is characterized by being easily soluble in water. The liquid composition for mold release according to the present embodiment is applied to the surface of a substrate such as a mold to form a mold release film, and a resin is molded on the mold release film, and then the resin compact is removed. Even when the release film is transferred to the resin molded product, the release film can be easily removed with water. The fluorine compound (F compound) is a nonionic fluorine compound represented by the following formula (1), which is different from other silicone compounds and fluorine compounds.

In the above formula (1), Rf ¹ and Rf ² are each a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, which is the same as or different from each other. The Rf ¹ and Rf ² may be directly bonded to form a ring, or may be bonded via an oxygen atom or a nitrogen atom to form a heterocycle. Furthermore, Rf ³ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms.

Further, in the above formula (1), R ¹ is a hydrogen atom or a methyl group. Further, R ² is a linear or branched alkyl group having 1 to 8 carbon atoms. Furthermore, n is an integer of 3 to 50, and preferably in the range of 4 to 30. Here, by setting n to a large value, more polyether structures can be added in one molecule of the nonionic fluorine compound represented by the above formula (1) (ie, hydrophilic ethylene oxide Because more groups can be added), the solubility of the aqueous system in solvents can be increased. On the other hand, when n is a large value, the molecular weight of the nonionic fluorine compound represented by the above formula (1) increases, and the fluorine content per unit amount decreases, so the surface tension reducing ability decreases. Therefore, it is preferable to appropriately select the value of n according to the purpose of use.

  As an example of the nonionic fluorine compound represented by the above formula (1), one having a perfluoroheterocycle represented by the following general formula (2) and one having a perfluoroamine structure represented by the following formula (3) And.

However, in the formula (2), Rf ⁴ and Rf ⁵ are each a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, which is the same as or different from each other. Rf ⁶ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms. In addition, X is an oxygen atom, a nitrogen atom or a CF ₂ group. Further, in the above formula (2), R ³ is a hydrogen atom or a methyl group. R ⁴ is a linear or branched alkyl group having 1 to 8 carbon atoms. Furthermore, n is an integer of 3 to 50.

However, in Formula (3), m and l are respectively the same or mutually different integers of 1 to 6. Rf ⁷ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms. Further, in the above formula (3), R ⁵ is a hydrogen atom or a methyl group. R ⁶ is a linear or branched alkyl group having 1 to 8 carbon atoms. Furthermore, n is an integer of 3 to 50.

  As a specific example of the nonionic fluorine compound represented by the said Formula (2), what has a perfluoro piperidine, perfluoro pyrrolidine, perfluoro piperazine, perfluoro morpholine, and perfluoro hexamethylene imine can be illustrated as a perfluoro heterocyclic ring. More specifically, for example, structures represented by the following formulas (4) to (11) (however, structures including up to a “-CO-” portion) can be mentioned.

  In addition, as a specific example of the nonionic fluorine compound represented by the above formula (3), for example, a structure represented by the following formulas (12) to (21) (however, a structure including up to "-CO-" part) Can be mentioned.

  Moreover, as a structure after the "-CO-" part of the nonionic fluorine compound represented by said Formula (1)-(3), specifically, following formula (22)-(36), for example The structure represented is mentioned.

(Alcohol and water with carbon number in the range of 1 to 3)
Examples of the alcohol having a carbon number in the range of 1 to 3 used as a preferable raw material in the present embodiment include methanol, ethanol and propanol (1-propanol, 2-propanol). When an alcohol having 4 or more carbon atoms, for example, 1-butanol (BuOH) is used as a raw material, the fluorine compound tends to precipitate in the liquid composition, and the solution stability tends to deteriorate. In addition, BuOH has a strong odor and has a problem of giving discomfort to the user of the wet sheet described later. As water of this embodiment, pure water such as ion exchange water, distilled water, or ultrapure water may be mentioned.

(Composition of liquid composition for mold release)
The mass ratio of the solid content of PVA and F compound and PAG in the liquid composition for mold release of the present embodiment is 0.5% by mass to 10% by mass, preferably 1% with respect to 100% by mass of the liquid composition. .5 mass% to 5 mass%. If the total mass ratio is less than the lower limit value, the film becomes too thin, so that the expression of mold release performance is insufficient. If the upper limit is exceeded, the viscosity of the liquid composition is too high, and as a result, irregularities are formed on the film surface during film formation, resulting in poor releasability.

  Moreover, the ratio of the 1st mass which totaled PVA and PAG in the liquid composition for mold release of this embodiment, and the 2nd mass of a fluorine compound (F compound) is 1st mass: 2nd mass = 80-99: 0 1 to 20, preferably 90 to 99.5: 0.5 to 10. If the first mass, which is the total mass of PVA and PAG, exceeds 99.9 and the second mass of the fluorine compound is less than 0.1, the above effect is not obtained, and the provision of releasability becomes insufficient. When the first mass is less than 80 and the second mass exceeds 20, the surface tension of the fluorine compound is strongly expressed, the coating film is repelled, the coatability is deteriorated, and the film can not be formed, and the liquid composition Solution stability of the On the other hand, by adding the fluorine compound in the above range, the surface active performance can be expressed, and the mold release performance can be expressed without deteriorating the film forming property.

  In addition, the ratio (PAG / (PAG + PVA)) of the first mass (mass of PAG + PVA) to the mass of PAG in the liquid composition for mold release of the present embodiment is 0.5 mass% to 20 mass%, and 1 mass It is preferable that it is%-15 mass%. If this ratio is less than the above lower limit, the coating film may be repelled during film formation in many cases, and the releasability is difficult to be expressed. If the above upper limit is exceeded, the PAG dissolves in a specific organic solvent, Problems occur.

  Furthermore, when the liquid composition for mold release of this embodiment contains an alcohol having 1 to 3 carbon atoms, the mass ratio of the alcohol is 0.1 mass% to 40 mass% with respect to 100 mass% of the liquid composition. Is preferred. 1% by mass to 20% by mass is more preferable. If the mass ratio of the alcohol is less than the lower limit value, the fluorine compound tends to precipitate in the liquid composition, and the solution stability may be deteriorated. If the upper limit is exceeded, the proportion of water decreases, whereby PVA is deposited and the solution stability of the liquid composition is degraded.

  As described above, in the present embodiment, when the predetermined proportions of PVA, F compound, PAG, and water are included, the liquid composition for mold release that exhibits the objects and effects of the present invention can be obtained. The liquid composition for mold release according to the present embodiment is mainly composed of PVA and PAG, so it is excellent in film forming property and can easily remove a coating film by washing with water, and contains the fluorine compound of the present invention. The liquid composition does not bounce on the surface of the material, and the substrate surface is excellent in wettability and adhesion, and exhibits mold release performance.

[Method of producing liquid composition for mold release]
The method for producing a releasing liquid composition of the present embodiment is prepared by mixing PVA, PAG, F compound and water, and, if necessary, an alcohol having a carbon number in the range of 1 to 3. First, PVA is dissolved in water to prepare a PVA aqueous solution. Meanwhile, PAG is dissolved in water to prepare a PAG aqueous solution. The PVA aqueous solution and the PAG aqueous solution are mixed so that the first mass ratio (PAG / (PAG + PVA)) of the total of PVA and PAG with respect to the mass of PAG becomes 0.5 mass% to 20 mass%. 1 Prepare a mixture. Next, water and, if necessary, an alcohol having a carbon number in the range of 1 to 3 are mixed with the first mixed solution to prepare a second mixed solution. Furthermore, the total amount of the above-mentioned fluorine compound (F compound) in the second liquid mixture is 0.5% by mass to 100% by mass of the liquid composition, the total amount of PVA, PAG, and F compound being solid content of the liquid composition. The ratio of the first mass of the total of PVA and PAG to the second mass of the F compound so as to be 0.1 mass% to 20 mass% of the F compound in the above solid content so as to be mass% It mixes so that it may become 1st mass: 2nd mass = 80-99.9: 0.1-20, and the liquid composition for mold release of this embodiment is manufactured.

[Composition of wet sheet]
The wet sheet impregnated with the above-mentioned liquid composition for mold release of this embodiment is constituted by impregnating the above-mentioned liquid composition in nonwoven fabric which is a sheet base material. The seat member has a basis weight of ^{30g / m 2 ~100g / m 2} , made of ^{1cm 3 / cm 2 / sec~250cm 3} / cm 2 / sec nonwoven having a air permeability of. Preferred mass per unit area is a ^{40g / m 2 ~80g / m 2} , preferably the air permeability is ^{10cm 3 / cm 2 / sec~180cm 3} / cm 2 / sec. If the basis weight of this nonwoven fabric is less than 30 g / m ² , the strength is insufficient, and when the wet sheet is moved along the surface of the substrate, the nonwoven fabric is easily torn. If the fabric weight exceeds 100 g / m ² , the nonwoven fabric is too thick and difficult to handle. Basis weight of the nonwoven fabric, the nonwoven fabric was cut to a size of 100 mm × 100 mm, moisture equilibrium at a temperature 25 ° C. and a humidity of 50% cut nonwoven (hereinafter, simply referred to as. Water equilibrium) measuring the mass of, 1 m ² per Converted to the basis weight of to determine.

When the air permeability of the non-woven fabric is less than 1 cm ³ / cm ² / sec, the liquid composition is less likely to permeate into the non-woven fabric when it is brought into contact with the non-woven fabric, and it is difficult to impregnate the liquid composition in a predetermined amount. When the air permeability exceeds 250 cm ³ / cm ² / sec, after the liquid composition is contained in a predetermined amount in the nonwoven fabric, the liquid composition tends to drip from the nonwoven fabric by gravity or when the wet sheet is held. Permeability of non-woven fabric is cut into non-woven fabric 100 mm × 100 mm size, and the cut non-woven fabric is in moisture equilibrium, and conforms to “Air Permeability A method (Frazil type method)” of JIS L 1096 “General Textile Testing Method”. And measure with a Frazier type tester.

In addition, water or a combination of water and alcohol contained in the wet sheet prevents dripping and prevents coating unevenness, 10 g / m ^{2 to} 200 g per 100 mass% of the non-woven fabric in a water equilibrium state. m ^2, preferably a rate of ^{30g / m 2 ~160g / m 2} . The nonwoven fabric has a basis weight and air permeability in the above range, and contains a liquid or a combination of water and alcohol in the above range, so that the liquid composition does not drip from the non-woven fabric in the wet sheet. By moving along the surface of the material, the liquid composition can be applied to the surface of the substrate with a uniform thickness. Moreover, each raw material component of PVA, PAG, and F compound mentioned above is contained in a predetermined ratio in the nonwoven fabric. As a result, the liquid composition spreads on the surface of the substrate with good wettability, and the formed coating film exhibits releasability.

  In addition, the non-woven fabric is composed of fibers mixed with one or more selected from the group consisting of polypropylene (PP) fibers, polyethylene terephthalate (PET) fibers, nylon fibers, rayon fibers, pulp fibers and glass fibers. Is preferred. By forming a non-woven fabric from the above-mentioned fibers, the liquid retention property is good, and the liquid composition can be smoothly applied to the surface of the substrate. When a plurality of non-woven fabrics are stacked and stitched to form a laminate, the liquid retention of the liquid composition is further enhanced, and even if a wide area is applied, the non-woven fabric is less damaged and the durability is excellent.

[Method of producing wet sheet]
The non-woven fabric as the sheet base material is cut into a predetermined size. The liquid composition is then contacted with the nonwoven. The first method is to immerse a non-woven fabric sheet or a non-woven fabric laminate (hereinafter referred to as non-woven fabric etc.) obtained by overlapping a plurality of sheets in a liquid composition above stored in a pad or wide-mouthed container for a predetermined time Pull up from the composition and drain. In the second method, the liquid composition is sprayed onto a non-woven fabric or the like by a predetermined amount from a spray nozzle.

The liquid portion of the non-woven fabric or a liquid composition such as a nonwoven fabric after spray after draining is impregnated into the nonwoven fabric at a rate of 10g / m ² ~200g / m ² with respect to non-woven fabric 100 mass% moisture equilibrium. As another method, the liquid component of the liquid composition to include a nonwoven respect nonwoven fabric moisture equilibrium at a rate of ^{10g / m 2 ~200g / m 2} , after nonwoven fabric or sprayed after draining Pressurize the non-woven fabric or the like while holding it between the upper press and the lower press to adjust the liquid content. When the non-woven fabric is a non-woven fabric laminate, by applying pressure, the liquid can be uniformly impregnated from the lower-layer non-woven fabric to the upper-layer non-woven fabric. When a wet sheet obtained by impregnating a liquid composition with a non-woven fabric etc. is not immediately used, a moisturizing container or an aluminum-deposited one or a plurality of wet sheets may be used to prevent evaporation of water and volatilization of alcohol. It is preferable to store it in a moisturizing case.

[Method of forming release film]
The release film of this embodiment is applied to the surface of a substrate by moving a wet sheet impregnated with the liquid composition on the surface of a mold or the like to be a contact surface of a resin molded body described later. And formed by drying at room temperature. The thickness of the release film depends on the surface shape of the mold or the like, but is preferably 0.5 μm to 5 μm. If the thickness is less than 0.5 μm, the mold release effect is poor, and if it exceeds 5 μm, the coating film becomes nonuniform to cause unevenness on the film surface, resulting in a poor mold release effect. As substrates for molds and the like, metal substrates such as aluminum (Al) and stainless steel (SUS), resin substrates such as polyvinyl chloride (PVC) and fiber reinforced plastic (FRP), wood And the like. Drying after coating is performed by leaving it to stand at room temperature for 10 to 60 minutes in an air atmosphere. In particular, no heating is required. The dried coating film is excellent in releasability.

[Production Method of Resin Molded Product by Mold etc.]
Examples of the resin molded by the mold of the present embodiment include acrylic resin, epoxy resin, polyester resin and the like. A curing agent is added to the above-mentioned resin, and after laminating or injecting in a solution state on the outer surface or the inner surface of a mold or the like via a release film, the above-mentioned resin is cured to produce a resin molded body. The cured resin molded product has the above-described release film formed on the surface of a mold or the like, so that a part of the molded product does not adhere to the surface of the mold or the like, and is smooth and easy in a desired shape. Can be released from a mold or the like. In addition, even if the mold release film remains on the surface of the resin molded body after the resin molded body is released from the mold or the like, the PVA, PAG, and F compound are easily dissolved in water, so the release from the water remains. The mold membrane can be removed.

  Next, an example of the present invention will be described in detail along with a comparative example.

Example 1
A PVA aqueous solution was prepared by dissolving Kuraray PVA 117 at a concentration of 12% by mass in distilled water. On the other hand, a PAG aqueous solution was prepared by dissolving Alcox manufactured by Meisei Chemical Industry Co., Ltd. in distilled water at a concentration of 4% by mass. 1.96 g of this PVA aqueous solution, 0.31 g of PAG aqueous solution, and 45.68 g of distilled water are mixed, and to this solution, an F compound aqueous solution having a concentration of F compound represented by the following formula (37) is 5 mass%. 05g was added and mixed further. Finally, 2.0 g of ethanol (EtOH) was added and sufficiently mixed by stirring to obtain a liquid composition for release.

  In the liquid composition for mold release of Example 1, 0.47% by mass of PVA, 0.005% by mass of F compound, 0.025% by mass of PAG, and EtOH are based on 100% by mass of the liquid composition. 4 mass% and 95.50 mass% of distilled water were contained, respectively. The solid content of this liquid composition was 0.5% by mass, and the total content of PAG and PVA and the mass ratio of the F compound in the solid content were 99: 1. Furthermore, the ratio (PAG / (PAG + PVA)) of the first mass (mass of PAG + PVA) to the mass of PAG was 5.0 mass%. The blend ratio of each raw material component in the liquid composition obtained in Example 1, the type of the compound F, the type of alcohol and the ratio of the solid content are shown in Table 1. Further, the mass ratio of the total amount of PAG and PVA in the solid content to the amount of the F compound, the mass% of PAG / (PAG + PVA) and the weighed values of the respective raw material components are shown in Table 2.

<Examples 2 to 9 and Comparative Examples 1 to 8>
In Examples 2 to 9 and Comparative Examples 1 to 8, as shown in Table 2, each raw material component was weighed, and as shown in Table 1, the alcohol and the F compound were selected. A release composition was obtained in the same manner as in Example 1 except the above. The blending proportions of the respective raw material components in the liquid compositions obtained in Examples 2 to 9 and Comparative Examples 1 to 8, the kind of the compound F, the kind of alcohol and the proportion of the solid content are shown in Table 1. Further, the mass ratio of the total amount of PAG and PVA in the solid content to the amount of the F compound, the mass% of PAG / (PAG + PVA) and the weighed values of the respective raw material components are shown in Table 2. In Table 1, “MeOH” is methanol, “BuOH” is 1-butanol, “mixed alcohol” is industrial alcohol mixed with 85% by mass of ethanol, 10% by mass of 1-propanol and 5% by mass of 2-propanol Each means. Furthermore, in Table 1, the F compound of Example 2 is the following formula (38), the F compound of Example 3 is the following formula (39), and the F compound of Example 4 is the following formula (40); The F compound of is represented by the following formula (41), and the F compound of Example 6 is represented by the following formula (42). Moreover, F compound of Examples 7-9 and Comparative Examples 1-8 is shown by following formula (43). The liquid composition of Example 9 did not contain alcohol.

<Comparison test and evaluation part 1>
About the 17 types of releasing liquid compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 8, (1) presence or absence of abnormality of the liquid composition, and (2) liquid composition Film-forming properties of (3) releasability of mold release film from mold (removal property), (4) releasability of resin layer from mold (removal property), (5) mold release The ease of washing of the membrane was investigated. The results are shown in Table 3.

(1) Presence or absence of abnormality of liquid composition The presence or absence of abnormality was examined depending on whether or not precipitates were generated when the liquid composition was prepared for the above 17 types of liquid compositions for release. When the liquid composition was prepared, the case where there was no precipitate was judged as "abnormal", and when the liquid composition was prepared, the case where there was a precipitate was judged as "abnormal".

(2) Film-Forming Properties of Liquid Composition In order to investigate the film-forming properties of the above liquid composition, the above 17 types of liquid composition for mold release have a plate-like SUS group with a thickness of 3 mm, 150 mm, and 75 mm flat. The surface of the material (mold) was coated with a brush and left in an air atmosphere at room temperature for 1 hour for drying to form a release film. The average thickness of the release film was 1 μm when measured by a micrometer. When the mold release film formed on the surface of the SUS substrate is visually observed to have cracks or irregularities in the mold release film or to exhibit a mottled pattern without uniformly forming the mold release film, it is determined as "defective". The case where the mold release film was uniformly formed without cracks or irregularities in the mold release film was judged as “good”.

(3) Peelability of mold release film from mold (mold release property 1)
In order to investigate the releasability of the release film from the mold of the above liquid composition, that is, the releasability, JIS Z 0237 “Adhesive tape test method” “Test method for peeling tape at 180 ° to stainless steel test plate” Based on the above, a pressure sensitive adhesive tape (No. 31B made by Nitto Denko Corporation) is pasted on the mold release film formed on the surface of the above SUS substrate, and this pressure sensitive adhesive tape is released from the SUS substrate. The tensile strength (N) when peeling off the adhesive tape with a film at 180 degrees was measured. The tensile strength of less than 2 N is a standard for good releasability of the release film.

(4) Peelability of resin layer from mold (mold releasability 2)
In order to investigate the releasability of the resin layer from the mold of the liquid composition, that is, the releasability, an acrylic resin (Corbonyl N-7520 made by Nippon Gohsei Co., Ltd.) is formed on the release film formed on the SUS substrate surface. Then, a resin solution prepared by mixing a polyisocyanate (Coronate L-55E manufactured by Tosoh Corp.) and butyl acetate as a dilution solvent in a mass ratio of 100: 0.2: 100 was laminated and applied using a brush. A film of polyethylene terephthalate (PET) was placed on the resin layer formed of the resin solution, and a urethane roller was rolled on the PET surface to apply a load. In this state, the resin layer was dried by leaving it to stand at room temperature for 18 hours in the air atmosphere, and the acrylic resin was cured to obtain a resin layer (resin molded body) having a thickness of 1 mm. After the PET film was gently peeled off from the resin layer, the releasability (removal property) of the resin layer from the SUS base material (mold) was examined visually. The case where the resin layer was completely peeled off from the SUS base material (mold) was regarded as “good”, and the case where even a part of the resin layer adhered and remained on the surface of the SUS base material (mold) was evaluated as “defect”.

(5) Easy-to-clean property of release film The resin layer peeled off from the above-mentioned SUS base material (mold) was washed with tap water at 14 ° C. After washing with water, using a scanning electron microscope-energy dispersive X-ray analyzer (SEM-EDS) (SEM: S-3500N manufactured by Hitachi High-Technologies Corporation, EDS: EMAX model 7021-H manufactured by Horiba, Ltd.), It was examined whether fluorine of the release film component was present on the surface of the resin layer. When the fluorine was not present at all, the ease of cleaning of the release film was evaluated as "good", and when any of the fluorine was present, the ease of cleaning of the release film was evaluated as "poor". .

  As is clear from Table 1, in Comparative Example 1, the proportion of the solid content in the liquid composition was too low at 0.4% by mass, and therefore, as shown in Table 3, there was no abnormality in the liquid composition, and film formation Although the property was good, the tensile strength of the adhesive tape was as high as 5.0 N, and the releasability of the release film was not good. In addition, the resin layer was defective without peeling from the release film.

  In Comparative Example 2, the ratio of the solid content in the liquid composition was too high at 10.3% by mass, so there was no abnormality in the liquid composition, but the film forming property was poor and the tensile strength of the adhesive tape was The releasability of the release film was as high as 2.0 N and not good. In addition, the resin layer was defective without peeling from the release film.

  In Comparative Example 3, since the proportion of the F compound in the liquid composition was too low at 0.001% by mass, the mass ratio of the total amount of PAG and PVA to the amount of the F compound was 99.95: 0.05. Therefore, there was no abnormality in the liquid composition, and the film forming property was good, but the tensile strength of the pressure-sensitive adhesive tape was as high as 5.5 N, and the peeling property of the release film was not good. In addition, the resin layer was defective without peeling from the release film.

  In Comparative Example 4, the ratio of the F compound in the liquid composition was too high at 0.525 mass%, so the mass ratio of the total amount of PAG and PVA to the amount of the F compound was 79:21. Therefore, although there was no abnormality in the liquid composition, the film forming property was poor, and the tensile strength of the adhesive tape was as high as 3.2 N, and the releasability of the release film was not good. In addition, the resin layer was defective without peeling from the release film.

  In Comparative Example 5, since the liquid composition did not contain PAG, the ratio of the total mass of PAG and PVA to the mass of PAG (PAG / (PAG + PVA)) was 0 mass%. Therefore, although there was no abnormality in the liquid composition, the film forming property was poor, and the tensile strength of the adhesive tape was as high as 2.4 N, and the releasability of the release film was not good. In addition, the resin layer was defective without peeling from the release film.

  In Comparative Example 6, since the liquid composition contained a large amount of PAG relative to PVA, the ratio of the total mass of PAG and PVA to the mass of PAG (PAG / (PAG + PVA)) was 21% by mass. Therefore, there is no abnormality in the liquid composition, the film forming property is good, the tensile strength of the pressure-sensitive adhesive tape is as low as 0.8 N, and the peelability of the pressure-sensitive adhesive tape is good. It was defective without peeling from the It is considered that when the amount of PAG is too large, the PAG dissolves in the organic solvent in which the resin layer is dissolved, and thus the adhesion of the release film to the resin layer is increased. In Comparative Examples 1 to 6, since the resin layer could not be peeled off, the evaluation of the ease of cleaning of the release film was not performed.

  In Comparative Example 7, the proportion of alcohol (EtOH) in the liquid composition was too high, 42.0% by mass, and therefore, the F compound was precipitated in the liquid composition. Further, in Comparative Example 8, since BuOH having 4 carbon atoms was used as the alcohol, the F compound was precipitated in the liquid composition. Therefore, in Comparative Examples 7 and 8, the film formation using the liquid composition was not performed, and the evaluation of the release film was not performed.

  On the other hand, as is clear from Tables 1 to 3, in Examples 1 to 9, the content of the alcohol having 1 to 3 carbon atoms, the content ratio of the solid content in the liquid composition, and PAG and PVA And the mass ratio of the amount of F compound to the mass ratio of PAG / (PAG + PVA) satisfy the requirements of the first aspect of the present invention, and the fluorine compound is a table of formulas (37) to (43) Since the nonionic fluorine compound to be made was based on Formula (1) in the 1st viewpoint of the present invention, there was no abnormality of all the liquid compositions, and the film-forming property was favorable. Moreover, the tensile strength of all the adhesive tapes was 1.5 N or less, and the peelability of the release film was favorable. Furthermore, all the resin layers peeled from the release film and were good.

[17 types of wet sheets of Test Examples 1 to 9 and Comparative Test Examples 1 to 8]
<Test Example 1>
A nonwoven fabric was prepared by mixing PET fibers and pulp fibers, each having a basis weight of 60 g / m ² , a thickness of 0.3 mm, and an air permeability of 150 cm ³ / cm ² / sec, which was cut into A4 size (297 mm, 210 mm). The non-woven fabric is placed horizontally on a balance, the liquid composition of Example 3 is uniformly sprayed onto the non-woven fabric by spraying, and the non-woven fabric is impregnated by absorption into the non-woven fabric until reaching a predetermined mass. A wet sheet was produced. The impregnated amount of the liquid composition was 160 g / m ² .

Comparative Test Example 1
A nonwoven fabric was prepared by mixing PET fibers and pulp fibers, each having a basis weight of 60 g / m ² , a thickness of 0.3 mm, and an air permeability of 150 cm ³ / cm ² / sec, which was cut into A4 size (297 mm, 210 mm). The non-woven fabric is placed horizontally on a balance, the liquid composition of Example 4 is uniformly sprayed onto the non-woven fabric by spraying, and the non-woven fabric is impregnated by absorption into a non-woven fabric until reaching a predetermined mass. The wet sheet of was produced. The impregnation amount of the liquid composition was 8 g / m ² .

  Type of liquid composition constituting wet sheets of Test Example 1 and Comparative Test Example 1, weight of nonwoven fabric as base material sheet, air permeability, material and liquid composition for release after absorption of liquid composition by nonwoven fabric The content of the substance is shown in Table 4.

<Test Examples 2 to 9, Comparative Test Examples 2 to 8>
As shown in Table 4, the type of liquid composition is changed, the basis weight, air permeability, and material of the non-woven fabric sheet are changed, and the liquid composition is absorbed by the non-woven fabric in the same manner as in Test Example 1 and Comparative Test Example 1. As shown in Table 4, the content and liquid content of the liquid composition for mold release were changed. Wet sheets of Test Examples 2 to 9 and Comparative Test Examples 2 to 8 were produced in the same manner as Test Example 1 or Comparative Test Example 1 except for the above.

<Comparative test and evaluation part 2>
Each of the wet sheets impregnated with the 17 types of liquid compositions of Test Examples 1 to 9 and Comparative Test Examples 1 to 8 is hand-held, and is degreased with acetone in advance, and a SUS substrate of 1 mm in thickness, 150 mm in height and 70 mm in width was degreased in advance. After being placed horizontally, the wet sheet was moved along the entire surface of the SUS substrate and dried at 25 ° C. for 18 hours to form a release film on the substrate surface. In the method described next, (6) presence or absence of abnormality of the wet sheet immediately after the above 17 types of preparation, (7) film formability of the liquid composition by the above 17 types of wet sheets, and (8) after film formation The releasability (mold releasability) of the resin layer was examined. These results are shown in Table 5.

(6) Existence of Abnormality of Wet Sheet The wet sheets immediately after preparation of 17 types of Test Examples 1 to 9 and Comparative Test Examples 1 to 8 were vertically made for 10 seconds to check whether the liquid drips from the wet sheet or not. . The case where the liquid did not drip from the wet sheet immediately after preparation was judged as "abnormal", and the case where the liquid dripped from the wet sheet immediately after preparation was judged as "abnormal".

(7) Film Formability of Liquid Composition by Wet Sheet The film formability was determined in the same manner as “(2) Film formability of liquid composition” in the above <Comparison Test and Evaluation 1>.

(8) Peelability (releasability) of resin layer after film formation by wet sheet
The releasability was determined in the same manner as "(4) Releasability of the resin layer from the mold" in the above <Comparison Test and Evaluation 1>.

As apparent from Table 5, in Comparative Test Example 1, the basis weight of the non-woven fabric is too small at 20 g / m ² , the air permeability is too high at 300 cm ³ / cm ² / sec, and the liquid content of the liquid composition is Since the amount was as small as 5 g / cm ² , when the wet sheet was moved along the surface of the SUS substrate, the sheet was torn and the coating film was too thin. For this reason, although the film formability was favorable, the peelability of the resin layer was inferior.

In Comparative Test Example 2, the basis weight of the non-woven fabric is too large at 150 g / m ² , the air permeability is too low at 0.5 cm ³ / cm ² / sec, and the liquid content of the liquid composition is as large as 300 g / cm ^2. Since it passed, in the state which held the wet sheet immediately after preparation, the liquid composition dripped from the wet sheet, and the wet sheet was abnormal. Moreover, the peelability of the resin layer was unsatisfactory. Furthermore, the wet sheet was also hard and could not form a coating film of uniform thickness on the curved substrate surface.

  In Comparative Test Example 3, since the liquid composition of Comparative Example 1 in which the ratio of solid content in the liquid composition was 0.4% by mass was used, there was no abnormality in the wet sheet immediately after preparation, and the film forming property was also good. Hmm. The removability of the resin layer was poor.

  In Comparative Test Example 4, since the liquid composition of Comparative Example 2 in which the ratio of solid content in the liquid composition was 10.3% by mass was used, there was no abnormality in the wet sheet immediately after preparation, but the viscosity of the liquid composition Is too high, the wet sheet can not form a hard and uniform coating film, and the film forming property is poor. In addition, the removability of the resin layer was also poor.

  In Comparative Test Example 5, since the liquid composition of Comparative Example 3 in which the proportion of the F compound in the liquid composition is 0.001% by mass was used, there was no abnormality in the wet sheet immediately after preparation, and the film forming property was good. However, the removability of the resin layer was poor.

  In Comparative Test Example 6, since the liquid composition of Comparative Example 4 in which the ratio of the F compound in the liquid composition was 0.525 mass% was used, there was no abnormality in the wet sheet immediately after preparation, but in the liquid composition The ratio of the F compound was too high to form a uniform coating film, and the film forming property was poor. In addition, the removability of the resin layer was also poor.

  In Comparative Test Example 7, since the liquid composition of Comparative Example 5 not containing PAG was used as the liquid composition, there was no abnormality in the wet sheet immediately after the preparation, but the liquid composition bounces on the SUS substrate and becomes uniform. Film could not be formed, and the film forming property was poor. In addition, the removability of the resin layer was also poor.

  In Comparative Test Example 8, since the liquid composition of Comparative Example 6 containing a large amount of PAG relative to PVA was used as the liquid composition, there was no abnormality in the wet sheet immediately after preparation, and the film forming property was good. Since the PAG was dissolved in the solvent, the removability of the resin layer was poor.

  On the other hand, in Test Examples 1 to 9, the contents of the respective raw material components in the liquid composition satisfy the requirements of the liquid composition according to the first aspect of the present invention, and the basis weight of the non-woven fabric, the air permeability, the non-woven fabric On the other hand, since the content ratio of the liquid component of the liquid composition satisfies the requirements of the wet sheet according to the fourth aspect of the present invention, there is no abnormality in all wet sheets immediately after preparation, and the formation of the liquid composition in the SUS substrate The film properties and the removability of the resin layer were all good.

  The liquid composition for mold release according to the present invention and the wet sheet impregnated with the liquid composition can be easily molded from the resin molded product from a mold or the like when the resin molded product is produced by a press molding method, FRP molding method or the like. Used in the field of

Claims (6)

It is a liquid composition for mold release containing polyvinyl alcohol (PVA), a fluorine compound (F compound) and water,
The liquid composition further contains 0% by mass to 40% by mass, relative to 100% by mass of the liquid composition, of one or more alcohols having a carbon number in the range of 1 to 3 and a polyalkylene glycol (PAG) Including
The total content of the polyvinyl alcohol, the fluorine compound, and the polyalkylene glycol, which are solid components in the liquid composition, is 0.5% by mass to 10% by mass with respect to 100% by mass of the liquid composition.
The ratio of the first mass of the total of the polyvinyl alcohol and the polyalkylene glycol to the second mass of the fluorine compound is first mass: second mass = 80 to 99.9: 0.1 to 20,
The ratio (PAG / (PAG + PVA)) of the first mass (mass of PAG + PVA) to the mass of the polyalkylene glycol (PAG) is 0.5 mass% to 20 mass%.
The liquid composition for mold release, wherein the fluorine compound is a nonionic fluorine compound represented by the following formula (1).

However, in the formula (1), Rf ¹ and Rf ² are each a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, which is the same as or different from each other. The Rf ¹ and Rf ² may be directly bonded to form a ring, or may be bonded via an oxygen atom or a nitrogen atom to form a heterocycle. Furthermore, Rf ³ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms.
Further, in the above formula (1), R ¹ is a hydrogen atom or a methyl group. Further, R ² is a linear or branched alkyl group having 1 to 8 carbon atoms. Furthermore, n is an integer of 3 to 50. The liquid composition for mold release according to claim 1, wherein the nonionic fluorine compound represented by the formula (1) is a nonionic fluorine compound represented by the following formula (2).

However, in the formula (2), Rf ⁴ and Rf ⁵ are each a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, which is the same as or different from each other. Rf ⁶ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms. In addition, X is an oxygen atom, a nitrogen atom or a CF ₂ group. Further, in the above formula (2), R ³ is a hydrogen atom or a methyl group. R ⁴ is a linear or branched alkyl group having 1 to 8 carbon atoms. Furthermore, n is an integer of 3 to 50. The liquid composition for mold release according to claim 1, wherein the nonionic fluorine compound represented by the formula (1) is a nonionic fluorine compound represented by the following formula (3).

However, in Formula (3), m and l are respectively the same or mutually different integers of 1 to 6. Rf ⁷ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms. Further, in the above formula (3), R ⁵ is a hydrogen atom or a methyl group. R ⁶ is a linear or branched alkyl group having 1 to 8 carbon atoms. Furthermore, n is an integer of 3 to 50. A wet sheet impregnated with the liquid composition according to any one of claims 1 to 3;
Seat member is made of a nonwoven fabric having air permeability of 30g / m ² ~100g / m ² of basis weight and ^{1cm 3 / cm 2 / sec~250cm 3} / cm 2 / sec, the liquid composition per unit area of the nonwoven fabric wet sheet characterized by comprising at a rate of ^{10g / m 2 ~200g / m 2} .   The non-woven fabric is composed of fibers obtained by mixing one or more selected from the group consisting of polypropylene (PP) fibers, polyethylene terephthalate (PET) fibers, nylon fibers, rayon fibers, pulp fibers and glass fibers, and the non-woven fabric is The wet sheet according to claim 4, wherein a plurality of sheets are laminated.   A wet sheet impregnated with the liquid composition according to any one of claims 1 to 3 or a wet sheet according to claim 4 or 5 is moved along the surface of a substrate to bring the liquid composition onto the surface of the substrate A method of forming a coating film having releasability on the surface of the substrate by applying and drying the applied liquid composition.