Release agent composition

Abstract

The present invention provides a mold release agent composition that exhibits good continuous release properties and is easy to remove from the mold after use. [Solution] (A) A compound comprising a perfluoropolyether group and a functional group having hydrogen bonding ability, (B) A water-soluble thickener having hydrogen bonding ability, (C) Emulsifier and, (D)Water A mold release agent composition containing the following:

Description

[Technical Field]

[0001] This invention relates to a mold release agent composition. [Background technology]

[0002] Fluorine-containing compounds are widely used as mold release agents and the like. For example, Patent Document 1 discloses a mold release agent that contains a fluorine-based surfactant as an essential component. Although the mold release agent described in Patent Document 1 exhibits good mold release properties, the mold release agent components migrate to the molded product during the release process, making it difficult to perform multiple moldings with a single application of the mold release agent.

[0003] One technique for improving the continuous release properties of mold release agents is to form a covalent bond between the mold and the mold release agent component. Patent document 2 discloses an invention using a silane coupling agent having a perfluoro group. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication No. 63-6330 [Patent Document 2] International Publication No. 2008-108438 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, while forming a covalent bond between the mold and the release agent component improves continuous release properties, it has the drawback of making it difficult to remove the release agent component from the mold after demolding, thus increasing the cost of mold cleaning.

[0006] In view of the above problems, the present invention aims to provide a mold release agent composition that exhibits good continuous release properties and is easy to remove from the mold after use. [Means for solving the problem]

[0007] In order to solve the above problems, the present inventors conducted extensive research and found that a release agent composition with good continuous release properties can be prepared by using a compound containing a perfluoropolyether group and a functional group having hydrogen bonding ability, a water-soluble thickener having hydrogen bonding ability, an emulsifier, and water.

[0008] This invention was completed based on these findings and includes the following broad embodiments of the invention. [Section 1] (A) A compound comprising a perfluoropolyether group and a functional group having hydrogen bonding ability, (B) A water-soluble thickener having hydrogen bonding ability, (C) Emulsifier and, (D)Water A mold release agent composition containing the following: [Section 2] The mold release agent composition according to item 1, wherein the compound (A) is a compound represented by the following formula (I). [ka] [In the formula, Rf is a perfluoroalkyl group having 1 to 4 carbon atoms. X is a fluoro group or a trifluoromethyl group. Y is a divalent group having 1 to 10 carbon atoms. m is 5 to 60. n is 1 or 2.] [Section 3] The release agent composition according to item 1 or 2, wherein the content of compound (A) is 0.3% by mass or more relative to the total amount of the release agent. [Section 4] The mold release agent composition according to any one of claims 1 to 3, wherein the water-soluble thickener (B) has at least one functional group selected from the group consisting of a hydroxyl group, an amide group, an ester group, an ether group, an amino group, a carboxyl group, a phosphate ester group, and a phosphate group. [Section 5] The release agent composition according to any one of items 1 to 4, wherein the content of the water-soluble thickener (B) is 0.05% by mass or more relative to the total amount of the release agent. [Section 6] The mold release agent composition according to any one of items 1 to 5, wherein the emulsifier (C) is a fluorine-based anionic surfactant having a counter cation. [Item 7] (E) The mold release agent composition according to any one of items 1 to 6, further comprising an emulsification aid. [Item 8] The mold release agent composition according to any one of items 1 to 7, wherein the content ratio (B / A) of the water-soluble thickener (B) to the compound (A) is 0.05 to 1.5. [Item 9] A method for producing a molded article, using the mold release agent composition according to any one of items 1 to 8. [Advantages of the Invention]

[0009] According to the present invention, it is possible to provide a mold release agent composition having good continuous mold release properties and easy removal of the mold release agent from the mold after use. [Modes for Carrying Out the Invention]

[0010] [Mold Release Agent Composition] The mold release agent composition according to the present invention contains the following (A) to (D). (A) A compound containing a perfluoropolyether group and a functional group having a hydrogen bonding ability. (B) A water-soluble thickener having a hydrogen bonding ability. (C) An emulsifier. (D) Water. Hereinafter, each component will be described in detail.

[0011] (A) A compound containing a perfluoropolyether group and a functional group having a hydrogen bonding ability The mold release agent composition of the present invention contains a compound (A) containing a perfluoropolyether group and a functional group having a hydrogen bonding ability. The compound containing a perfluoropolyether group and a functional group having a hydrogen bonding ability is a compound having one or more perfluoropolyether groups in one molecule and one or more functional groups having a hydrogen bonding ability in one molecule.

[0012] Examples of functional groups having hydrogen bonding ability include phosphate ester groups, phosphate groups, carboxyl groups, amide groups, hydroxyl groups, amino groups, ester groups, carbamoyl groups, pyridyl groups, and carbonyl groups. Among these, phosphate ester groups, phosphate groups, carboxyl groups, amide groups, hydroxyl groups, amino groups, and ester groups are preferred.

[0013] In the release agent composition of the present invention, one compound (A) containing a perfluoropolyether group and a functional group having hydrogen bonding ability may be used alone, or two or more compounds may be used in combination.

[0014] The weight-average molecular weight of compound (A), which contains a perfluoropolyether group and a functional group having hydrogen bonding ability, is preferably 2,000 or more, more preferably 2,500 or more, and particularly preferably 3,000 or more. Furthermore, the weight-average molecular weight is preferably 20,000 or less, more preferably 15,000 or less, even more preferably 12,000 or less, even more preferably 10,000 or less, particularly preferably 8,000 or less, and most preferably 5,000 or less. The weight-average molecular weight can be measured by conventionally known methods such as gel filtration chromatography.

[0015] The content of compound (A) containing a perfluoropolyether group and a functional group having hydrogen bonding ability in the release agent composition of the present invention is preferably 0.3% by mass or more, more preferably 0.3 to 10% by mass, even more preferably 0.5 to 7% by mass, particularly preferably 0.7 to 5% by mass, and most preferably 0.7 to 3% by mass, based on 100% by mass of the total amount of the release agent composition, from the viewpoint of continuous release properties.

[0016] In one embodiment, the compound containing a perfluoropolyether group and a functional group having hydrogen bonding ability is preferably a perfluoropolyether phosphate ester compound represented by the following formula (I). [ka]

[0017] Rf is a perfluoroalkyl group having 1 to 4 carbon atoms. Examples of perfluoroalkyl groups having 1 to 4 carbon atoms include trifluoromethyl, perfluoroethyl, perfluoropropyl, and perfluorobutyl groups.

[0018] X is a fluoro group or a trifluoromethyl group, with a trifluoromethyl group being preferred.

[0019] The divalent group represented by Y, having 1 to 10 carbon atoms, may contain heteroatoms and may be an aromatic group, a heteroaromatic group, a heterocyclic group, an aliphatic group, or an alicyclic group. Specifically, the following groups are examples. -(CH2) N1 - (N1=1~10) -A-(CH2) N2 - (N2=1~5) -B-(CH2) N3 - (N3=1~5) -CH2CH2(OCH2CH2) N4 - (N4=1~4) -BCO(OCH2CH2) N5 - (N5=1~4) (In the formula, A represents -O-CO-, -CO-O-, -CONH-, or -NHCO-. B represents phenylene which may have 1 to 3 substituents selected from the group consisting of C1-C3 alkyl groups (methyl, ethyl, propyl), C1-C4 alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), and halogen atoms (F, Cl, Br, I).)

[0020] Preferred divalent groups represented by Y, having 1 to 10 carbon atoms, include the following divalent groups with the following structures. -(CH2) N1 - (N1=1~10) -CONH-(CH2) N2 - (N2=1~5) -CO-O-(CH2) N2- (N2=1~5)

[0021] m is 5 to 60, preferably 10 to 50, and more preferably 15 to 35.

[0022] n is either 1 or 2.

[0023] In the release agent composition of the present invention, as the perfluoropolyether phosphate ester compound represented by formula (I), a mixture of a compound where n=1 and a compound where n=2 in formula (I) can also be used.

[0024] The perfluoropolyether phosphate compound represented by formula (I) above preferably has a weight-average molecular weight of 2,000 or more, more preferably 2,500 or more, and particularly preferably 3,000 or more. Furthermore, it is preferable that the weight-average molecular weight be 20,000 or less, more preferably 15,000 or less, even more preferably 12,000 or less, even more preferably 10,000 or less, particularly preferably 8,000 or less, and most preferably 5,000 or less. The weight-average molecular weight can be measured by conventionally known methods such as gel filtration chromatography.

[0025] Furthermore, the perfluoropolyether phosphate ester compound represented by formula (I) above can be reacted with basic metal compounds, amine compounds, ammonia, etc. to form metal salts, amine salts, ammonium salts, etc., and these salts also have similar usefulness. Examples of metal salts include alkali metal salts, alkaline earth metal salts, transition metal salts, etc. Specific examples of metal atoms that form metal salts include Li, Na, K, Ca, Mg, Cu, Co, Ni, Zn, Mn, Fe, Pb, Hg, Zr, etc. Examples of amine compounds or ammonia that form amine salts or ammonium salts include ammonia, trimethylamine, triethylamine, benzylamine, methylbenzylamine, dimethylbenzylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, pyridine, etc.

[0026] Specific examples of perfluoropolyether phosphate compounds represented by the above formula (I) include, but are not limited to, the following. [ka] [In the formula, m is between 5 and 60.] [ka] [In the formula, m is between 5 and 60.] [ka] [In the formula, m is between 5 and 60.] [ka] [In the formula, m is between 5 and 60.] [ka] [In the formula, m is between 5 and 60.] [ka] [In the formula, m is between 5 and 60.]

[0027] Perfluoropolyether phosphate compounds represented by formula (I) can be obtained commercially or produced by known methods. For example, they can be obtained by phosphate esterification of the hydroxyl group of a perfluoropolyether monool represented by the following formula (II). [ka] [In the formula, Rf is a perfluoroalkyl group having 1 to 4 carbon atoms. X is a fluoro group or a trifluoromethyl group. Y is a divalent group having 1 to 10 carbon atoms. m is 5 to 60.]

[0028] In equation (II) above, Rf, X, Y, and m are the same as those used in equation (I) above.

[0029] The perfluoropolyether monool represented by formula (II) above preferably has a weight-average molecular weight of 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, particularly preferably 2,500 or more, and most preferably 3,000 or more. Furthermore, it is preferable that the weight-average molecular weight be 20,000 or less, more preferably 15,000 or less, even more preferably 12,000 or less, even more preferably 10,000 or less, particularly preferably 8,000 or less, and most preferably 5,000 or less. The weight-average molecular weight can be measured by conventionally known methods such as gel filtration chromatography.

[0030] The perfluoropolyether monool represented by formula (II) above can be obtained commercially or produced by known methods. The perfluoropolyether monool represented by formula (II) can be synthesized according to the method disclosed, for example, in U.S. Patent Publication No. 3293306.

[0031] Furthermore, known methods can be used to phosphate esterify the hydroxyl group of the perfluoropolyether monool represented by formula (II). For example, it can be obtained using phosphorus pentoxide (P2O5), etc.

[0032] The content of the perfluoropolyether phosphate compound represented by formula (I) in the release agent composition of the present invention is preferably 0.3% by mass or more, more preferably 0.3 to 10% by mass, even more preferably 0.5 to 7% by mass, particularly preferably 0.7 to 5% by mass, and most preferably 0.7 to 3% by mass, based on 100% by mass of the total amount of the release agent composition, from the viewpoint of continuous release properties.

[0033] (B) Water-soluble thickener having hydrogen bonding ability The mold release agent composition of the present invention contains a water-soluble thickener (B) having hydrogen bonding ability. A water-soluble thickener having hydrogen bonding ability is a thickener that has multiple functional groups having hydrogen bonding ability in a single molecule and is water-soluble.

[0034] The mold release agent composition of the present invention can be improved by including a water-soluble thickener (B) having hydrogen bonding ability. The reason for this effect is presumed to be that the water-soluble thickener (B) exhibits the effect of bonding the compound (A) (mold release component) and the mold by hydrogen bonding, making it easier to leave the mold release component on the mold, but is not limited to this. Furthermore, since the mold release component and the mold are bonded by hydrogen bonding rather than covalent bonding, it is presumed that the removal of the mold release component from the mold after use becomes easier.

[0035] Examples of functional groups having hydrogen bonding ability include carboxyl groups, amide groups, hydroxyl groups, amino groups, ester groups, carbamoyl groups, pyridyl groups, carbonyl groups, phosphate ester groups, and phosphate groups. Among these, hydroxyl groups, amide groups, ester groups, amino groups, carboxyl groups, phosphate ester groups, and phosphate groups are preferred. These functional groups may be included individually in the hydrogen-bonding water-soluble thickener (B), or in combination of two or more.

[0036] Examples of water-soluble thickeners (B) with hydrogen bonding ability include: chitin-based polymers such as chitin, carboxymethyl chitin, chitosan, and hydroxypropyl chitosan; plant-based polymers such as starch, gum arabic, tragacanth gum, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), and algae colloid (brown algae extract); microbial polymers such as dextran, succinoglucan, pullulan, and xanthan gum; animal-based polymers such as collagen, casein, albumin, and gelatin; and methylcellulose, nitrocellulose, ethylcellulose, and methylhydroxypropyl Examples include cellulosic polymers such as cellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, sodium carboxymethylcellulose, crystalline cellulose, and cellulose powder; alginic acid polymers such as sodium alginate and propylene glycol alginate; vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, and carboxyvinyl polymer; polyoxyethylene polymers such as hydrophobic modified polyether urethane; and acrylic polymers such as sodium polyacrylate, polyethyl acrylate, and polyacrylamide.

[0037] The content of the water-soluble thickener (B) having hydrogen bonding ability in the release agent composition of the present invention is preferably 0.05% by mass or more, more preferably 0.05 to 10% by mass, even more preferably 0.1 to 7% by mass, particularly preferably 0.2 to 5% by mass, and most preferably 0.5 to 3% by mass, based on 100% by mass of the total amount of the release agent composition, from the viewpoint of continuous release properties.

[0038] Furthermore, from the viewpoint of continuous release properties, the content of the water-soluble thickener (B) having hydrogen bonding ability in the release agent composition of the present invention is preferably such that the mass content ratio (B / A) of the water-soluble thickener (B) to the compound (A) is 0.05 to 1.5, more preferably 0.07 to 1.0, and particularly preferably 0.1 to 0.5.

[0039] (C) Emulsifier The release agent composition of the present invention contains an emulsifier (C). By including the emulsifier (C), the above compound (A) can be stably dispersed in water.

[0040] As for the emulsifier (C), a fluorine-based emulsifier is preferable from the viewpoint of emulsification stability. A fluorine-based emulsifier refers to a compound that contains a fluorine atom in its structure and has surface activity. Among fluorine-based surfactants, a fluorine-based anionic surfactant having a countercation is preferable, and a surfactant having a perfluoroalkyl group or a perfluoroalkenyl group is more preferable.

[0041] In one embodiment, the emulsifier (C) may be, for example, a fluorine-based anionic surfactant having a countercation represented by (i) to (iv) below. Among these, a carboxylate salt (i) or a sulfonate salt (ii) is preferred. These may be used individually or in combination of two or more. (i) Carboxylate salt represented by the following formula Rf1COOM1 (In the formula, Rf1 represents a fluoroorganic group. M1 represents an alkali metal, amine base, or ammonium base.) (ii) Sulfonates represented by the following formula Rf2SO3M2 (In the formula, Rf2 represents a fluoroorganic group. M2 represents an alkali metal, amine base, or ammonium base.) (iii) Phosphonates represented by the following formula Rf3PO(OM3)(OM4) (In the formula, Rf3 represents a fluoroorganic group. M3 represents a hydrogen atom, alkali metal, amine base, or ammonium base. M4 represents an alkali metal, amine base, or ammonium base.) (iv) Phosphates represented by the following formula Rf4OPO(OM5)(OM6) (In the formula, Rf4 represents a fluoroorganic group. M5 represents a hydrogen atom, alkali metal, amine base, or ammonium base. M6 represents an alkali metal, amine base, or ammonium base.)

[0042] The fluoroorganic groups represented by Rf1 to Rf4 are preferably substituted or unsubstituted fluorohydrocarbon groups having 3 to 20 carbon atoms (preferably 5 to 20 carbon atoms, more preferably 10 to 20 carbon atoms).

[0043] Examples of substituted or unsubstituted fluorohydrocarbon groups having 3 to 20 carbon atoms include substituted or unsubstituted fluoroalkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted fluoroalkenyl groups having 3 to 20 carbon atoms, substituted or unsubstituted fluorocycloalkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted fluoroaryl groups having 6 to 20 carbon atoms, and substituted or unsubstituted fluoroaralkyl groups having 7 to 20 carbon atoms. Among these, substituted or unsubstituted fluoroalkyl groups having 3 to 20 carbon atoms or substituted or unsubstituted fluoroalkenyl groups having 3 to 20 carbon atoms are preferred, and substituted or unsubstituted perfluoroalkyl groups having 3 to 20 carbon atoms or substituted or unsubstituted perfluoroalkenyl groups having 3 to 20 carbon atoms are more preferred.

[0044] Examples of substituents include halogen atoms, C1-C4 alkoxys, aryloxys, aralkyloxys, C1-C4 alkyls, C2-C4 alkenyls, NO, NO2, NH2, CN, OH, SH, COOH, CONH2, NHCOCH3, monoalkylaminos, dialkylaminos, monoalkylaminocarbonyls, dialkylaminocarbonyls, alkoxycarbonyls, and aryloxycarbonyls.

[0045] Furthermore, in Rf1 to Rf4, the fluorohydrocarbon group may be substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. The number of heteroatoms can preferably be 1 to 10, more preferably 1 to 6. When the fluorohydrocarbon group is substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the fluorohydrocarbon group has at least one of the following groups: -O-, -N<, -S-, -SO2-, -(C=O)-, -(C=O)O-, -O(C=O)-, -NH(C=O)-, -(C=O)NH-, -NH(C=O)O-, -O(C=O)NH-, and the fluorohydrocarbon chain is interrupted by these groups. In Rf1 to Rf4, the substitution of the fluorohydrocarbon group with heteroatoms may result in a structure in which Rf1 to Rf4 have a heterocycle.

[0046] When the fluoroorganic groups represented by Rf1 to Rf4 are substituted fluorohydrocarbon groups having 3 to 20 carbon atoms, it is preferable that they have one or more ether bonds (-O-).

[0047] Examples of alkali metals in M1-M6 include lithium, sodium, and potassium. Examples of amine bases include trimethylamine, triethylamine, benzylamine, methylbenzylamine, dimethylbenzylamine, monoethanolamine, diethanolamine, triethanolamine, morpholine, and pyridine. Countercations consisting of alkali metals, amine bases, or ammonium bases may be introduced (salt formation) by a neutralization reaction with an acid compound (free acid) in which all of the above M1-M6 are hydrogen atoms.

[0048] Examples of commercially available emulsifiers (C) include Futegent 100, Futegent 110, Futegent 150 (all manufactured by Neos Co., Ltd.), Surflon S-211 (manufactured by AGC Seikamika Co., Ltd.), Zonyl TBS (manufactured by DuPont), Megafac F-410, Megafac F-510 (both manufactured by DIC Corporation), PF-136A, PF-156A (both manufactured by OMNOVA Corporation), and others.

[0049] The content of the emulsifier (C) in the release agent composition of the present invention is preferably 0.005 to 5.0% by mass, more preferably 0.01 to 2.0% by mass, even more preferably 0.05 to 1.0% by mass, and particularly preferably 0.1 to 0.5% by mass, based on 100% by mass of the total amount of the release agent composition, from the viewpoint of emulsification stability and continuous release properties.

[0050] Furthermore, from the viewpoint of emulsification stability and continuous release properties, the content of the emulsifier (C) in the release agent composition of the present invention is preferably 10 to 40 parts by mass, more preferably 12 to 35 parts by mass, particularly preferably 15 to 30 parts by mass, and most preferably 15 to 25 parts by mass, per 100 parts by mass of compound (A).

[0051] (D)Water From the viewpoint of continuous release properties, the water (D) content in the release agent composition of the present invention is preferably 70 to 99.9% by mass, more preferably 80 to 99.5% by mass, and particularly preferably 90 to 99% by mass, based on 100% by mass of the total amount of the release agent composition.

[0052] (E) Emulsifying agent In one embodiment, the release agent composition of the present invention may further contain an emulsifying agent. The emulsifying agent is preferably a water-soluble alcohol, more preferably a water-soluble alcohol having 1 to 10 carbon atoms, even more preferably a water-soluble alcohol having 1 to 8 carbon atoms, and particularly preferably a water-soluble alcohol having 1 to 6 carbon atoms.

[0053] Examples of such alcohols include lower alcohols and polyhydric alcohols, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, and other lower alcohols; ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanol. Examples include dihydric alcohols such as benzoyl diol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,2-pentanediol, and 2-methyl-2,4-pentanediol; trihydric alcohols such as glycerin, trimethylolpropane, 1,2,4-butanetriol, 1,2,5-pentanetriol, and 1,2,6-hexanetriol; tetrahydric alcohols such as pentaerythritol; pentahydric alcohols such as xylitol; and hexahydric alcohols such as sorbitol and mannitol. Among these, methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, glycerin, and 2-methyl-2,4-pentanediol (hexylene glycol) are preferred. These may be used individually or in combination of two or more.

[0054] From the viewpoint of emulsification stability, the content of the emulsifying aid (E) in the release agent composition of the present invention is preferably 0 to 10% by mass, more preferably 0.01 to 5.0% by mass, even more preferably 0.05 to 2.0% by mass, and particularly preferably 0.1 to 1.0% by mass, based on 100% by mass of the total amount of the release agent composition.

[0055] Furthermore, from the viewpoint of emulsification stability, the content of the emulsifying aid (E) in the release agent composition of the present invention is preferably 0 to 100 parts by mass, more preferably 5 to 90 parts by mass, particularly preferably 10 to 80 parts by mass, and most preferably 15 to 70 parts by mass, per 100 parts by mass of compound (A).

[0056] (Other additives) The mold release agent composition of the present invention may appropriately contain organic solvents, rust inhibitors, catalysts, antibacterial agents, flame retardants, defoaming agents, thickeners, viscosity modifiers, leveling agents, ultraviolet absorbers, preservatives, antifreeze agents, wetting agents, pH adjusters, stabilizers, antifungal agents, light-resistant stabilizers, weather-resistant stabilizers, neutralizing agents, matting agents, drying accelerators, foaming agents, non-stick agents, degradation inhibitors, etc., within a range that does not impede the objectives of the present invention. These may be used individually or in combination of two or more. Each of these additives can be used in an amount ranging from 0.01 to 10 parts by mass per 100 parts by mass of the total of compound (A), water-soluble thickener (B), and emulsifier (C).

[0057] <Method for producing a mold release agent composition> The mold release agent composition of the present invention can be manufactured, for example, by methods such as manufacturing method 1 or 2 described below. Manufacturing Method 1 (Step 1) A step of preparing a dispersion containing compound (A), a water-soluble thickener (B), an emulsifier (C), and, if necessary, an emulsifying aid (E). (Step 2) A step in which the dispersion and water (D) are mixed. Manufacturing Method 2 (Step 1') A step of preparing a mixture containing compound (A), emulsifier (C), water (D), and, if necessary, emulsifying aid (E). (Step 2') A step of mixing the mixed liquid with the water-soluble thickener (B).

[0058] In step 1 of manufacturing method 1, the mixing order in the dispersion is not particularly limited. Compound (A) may be mixed with a water-soluble thickener (B), an emulsifier (C), and, if necessary, an emulsifying aid (E), or other mixing orders may be used. Furthermore, various additives may be mixed as needed. In addition, the water-soluble thickener (B) may be mixed as an aqueous solution. When using an aqueous solution of the water-soluble thickener, it is preferable to prepare the aqueous solution so that the viscosity is in the range of 50 to 1000 mPa·s. It is preferable to mix these components and stir them thoroughly to ensure that each component is uniformly dispersed.

[0059] The amount of water-soluble thickener (B) mixed in the dispersion is preferably 5 to 150 parts by mass, more preferably 7 to 100 parts by mass, and particularly preferably 10 to 50 parts by mass, per 100 parts by mass of compound (A).

[0060] The amount of emulsifier (C) mixed in the dispersion is preferably 10 to 40 parts by mass, more preferably 12 to 35 parts by mass, particularly preferably 15 to 30 parts by mass, and most preferably 15 to 25 parts by mass, per 100 parts by mass of compound (A).

[0061] The amount of emulsifying agent (E) mixed in the dispersion is preferably 0 to 100 parts by mass, more preferably 5 to 90 parts by mass, particularly preferably 10 to 80 parts by mass, and most preferably 15 to 70 parts by mass, per 100 parts by mass of compound (A).

[0062] For example, in step 2 of manufacturing method 1, it is preferable to gradually add water (D) to the dispersion obtained in step 1 while stirring. Gradually adding water (D) to the dispersion and mixing makes it easier to uniformly disperse each component.

[0063] For example, the amount of water (D) mixed in step 2 of manufacturing method 1 is preferably 100 to 10,000 parts by mass, more preferably 150 to 3,500 parts by mass, even more preferably 200 to 2,000 parts by mass, particularly preferably 250 to 1,500 parts by mass, and most preferably 300 to 900 parts by mass, per 100 parts by mass of dispersion.

[0064] Various additives can be mixed into the mold release agent composition obtained in this manner, as needed.

[0065] Furthermore, even when producing the mold release agent composition of the present invention using the method shown in Production Method 2, it can be produced using the respective component amounts shown in Production Method 1.

[0066] <Uses of mold release agent compositions> Since the coating film obtained from the release agent composition of the present invention exhibits excellent continuous release properties, the release agent composition of the present invention can be suitably used as a release agent.

[0067] The material to which the mold release agent composition of the present invention is applied is not particularly limited, but examples include metals such as aluminum, SUS, and iron; resins such as PP, PE, and epoxy; rubber; FRP (fiber-reinforced plastic); gypsum substrates; wooden substrates; fibers; glass; and composite materials.

[0068] Furthermore, the molding material released using the release agent composition of the present invention is not particularly limited, but examples include rubbers such as urethane rubber, H-NBR, NBR, silicone rubber, EPDM, CR, NR, fluororubber, SBR, BR, IIR and IR, as well as thermosetting resins such as urethane foam, epoxy resin, polyimide resin, polyamide resin, melamine resin, urea resin, polyurethane, silicone resin, alkyd resin, phenolic resin, unsaturated polyester resin, vinyl ester resin and FRP (glass fiber reinforced plastic (GFRP), carbon fiber reinforced plastic (CFRP), aramid fiber reinforced plastic (AFRP)), as well as PP (polypropylene), PE (polyethylene), PVC (polyvinyl chloride), PS (polystyrene), PA (polyamide), polyester, polycarbonate, ABS resin, poly(meth)acrylic acid, polyacetal, polyvinylidene fluoride, polyphenylene sulfide, polyetherimide, polyetheretherketone, Examples include thermoplastic resins such as FRTP (glass fiber reinforced thermoplastic (GFRTP), carbon fiber reinforced thermoplastic (CFRTP), and aramid fiber reinforced thermoplastic (AFRTP)). In particular, they are useful as mold release agents for resins such as polyurethane and epoxy resins.

[0069] The mold release agent composition of the present invention can be used by applying it to the part to be treated with the mold release agent composition and drying it. The application method is not particularly limited and includes, for example, spray application, brush application, roll coater application, dipping application, etc. The drying method includes air drying or heating to evaporate the solvent and form a film. The dry thickness of the film containing the mold release agent composition of the present invention is usually 0.01 to 15 μm, preferably 0.1 to 5.0 μm.

[0070] Using the mold release agent composition of the present invention, molded products such as the above-mentioned molding material can be manufactured by conventional methods. For example, the mold release agent composition is applied to the inner surface of a mold, and after the solvent and dispersant have dried and been removed, a mold release agent film (a film of fluorine-containing polymer) is formed on the mold, the molding material composition is filled into the mold to mold the molding material, and the molding material is removed from the mold.

[0071] Furthermore, the removal of the mold release agent coating of the present invention (for example, the removal of the mold release agent coating from a mold after use) can be achieved by, for example, immersing the substrate (e.g., a mold) to which the mold release agent coating has adhered in an organic solvent (ketones, alcohols, ethers, etc.) or by immersing it in an alkaline solution (e.g., an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, etc.). The liquid temperature can be room temperature (e.g., 10°C to 35°C), and the immersion should be for a sufficient amount of time to remove the mold release agent coating. When using an organic solvent, the mold release agent coating of the present invention can also be removed by wiping with a nonwoven fabric soaked in the organic solvent.

[0072] In one embodiment, the mold release agent composition of the present invention can also be used as a water-repellent and oil-repellent agent because it has excellent liquid-repellent properties. When the mold release agent composition of the present invention is used as a water-repellent and oil-repellent agent, the material to which the mold release agent composition of the present invention is applied is not particularly limited, but examples include metals such as aluminum, SUS, and iron; resins such as PP, PE, and epoxy; rubber; FRP (fiber-reinforced plastic); gypsum substrates; wooden substrates; fibers; glass; and composite materials.

[0073] In one embodiment, since the release agent composition of the present invention has excellent liquid repellency, it can also be used as a fiber treatment agent. The fibers treated using the release agent composition of the present invention may be in any form such as short fibers (fibers), lint, roving, sliver, yarn, woven fabric, knitted fabric, non-woven fabric, etc. Examples of the fiber material include cellulose fibers such as cotton, linen, jute, hemp, ramie, regenerated fiber cellulose, rayon, and polyvinyl alcohol-based synthetic fibers.

Examples

[0074] Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited thereto.

[0075] (Materials used) · PFPE phosphate ester 1: Perfluoropolyether phosphate ester CF3CF2CF2O-[CF(CF3)CF2O] n -CF(CF3)CH2OPO(OH)2 (weight average molecular weight 4000, n is about 22.) · PFPE phosphate ester 1: Perfluoropolyether phosphate ester CF3CF2CF2O-[CF(CF3)CF2O] n -CF(CF3)CH2OPO(OH)2 (weight average molecular weight 3500, n is about 19.) · PVP: Polyvinylpyrrolidone, manufactured by Nippon Shokubai Co., Ltd., PVPK85. · corn starch: Corn starch. · chitin: Chitin nanofibers, manufactured by Sugino Machine, Ltd., SFo-20002. · Metolose: Methyl cellulose, manufactured by Shin-Etsu Chemical Co., Ltd., Methocel (registered trademark) SM25. · Emulsifier: Ftergent 150, fluorine-based anionic surfactant, sodium sulfonate salt, manufactured by Neos Co., Ltd. · Emulsification aid: Isopropanol

[0076] <Example 1> PFPE phosphate ester 1 (1.0g), emulsifier (0.2g), and emulsifying aid (0.2g) were placed in a 200ml beaker containing a stirring bar, and the mixture was stirred with a magnetic stirrer for 10 minutes. Next, PVP (0.1g) was added, and the mixture was stirred with a magnetic stirrer for 10 minutes to prepare a dispersion. While stirring the dispersion, distilled water (98.5g) was gradually added dropwise to prepare the release agent composition.

[0077] Subsequently, the mold release agent composition was applied to the mold, and a continuous mold release test was conducted. The results are shown in Table 1.

[0078] (Continuous release properties test) A stainless steel mold (molded product shape: cylindrical with a diameter of 30 mm and a height of 12 mm) was degreased with acetone, then heated to 170°C, and a release agent composition was sprayed using a spray gun at a rate of 100 g / m². 2 The material was applied (coating pressure 0.1 MPa). After application, it was heated at 170°C for 1 minute. Then, 13-15 g of peroxide vulcanized silicone rubber was placed in the mold and press-molded at 170-180°C for 10 minutes (15 MPa). After removing the molded product, the same amount of rubber was placed in the mold and press-molded in the same manner, and the load during the 10th consecutive extrusion of the molded product was measured using a push-pull scale. ◎: The release force on the 10th attempt is 30N or less. ○: The release force on the 10th attempt is between 30N and 40N. △: The release force on the 10th attempt is between 40N and 80N. ×: The release force on the 10th attempt exceeded 80N.

[0079] <Examples 2-7, Comparative Examples 1-4> A mold release agent composition was prepared in the same manner as in Example 1, except that the composition was changed as shown in Tables 1 and 2. Subsequently, the continuous mold release properties were evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

[0080] [Table 1]

[0081] [Table 2]

[0082] The mold release agent compositions of Examples 1 to 7 all exhibited excellent continuous mold release properties. This is presumed to be because the water-soluble thickener with hydrogen bonding ability exerts an effect of bonding the mold release component, PFPE phosphate ester, to the mold via hydrogen bonds, making it easier for the mold release component to remain on the mold. Furthermore, the mold release agent coating could be easily removed from the mold by immersion in an organic solvent (ketones, alcohols, ethers, etc.) at room temperature (approximately 20°C) or by immersion in an alkaline solution (such as an aqueous sodium hydroxide solution) at room temperature (approximately 20°C).

[0083] In contrast, Comparative Examples 1 and 2, which did not contain a thickening agent, showed poor continuous release properties. Similarly, Comparative Example 3, which used metolose (a thickening agent lacking hydrogen bonding ability), also showed poor continuous release properties. Furthermore, Comparative Example 4, which did not contain a release agent, also showed poor continuous release properties.

Claims

1. (A) A compound containing a perfluoropolyether group and a functional group having hydrogen bonding ability, (B) A water-soluble thickener having hydrogen bonding ability, (C) Emulsifier and (D) Water A mold release agent composition containing the following:

2. The mold release agent composition according to claim 1, wherein the compound (A) is a compound represented by the following formula (I). 【Chemistry 1】 [In the formula, Rf is a perfluoroalkyl group having 1 to 4 carbon atoms. X is a fluoro group or a trifluoromethyl group. Y is a divalent group having 1 to 10 carbon atoms. m is 5 to 60. n is 1 or 2.]

3. The release agent composition according to claim 1, wherein the content of compound (A) is 0.3% by mass or more relative to the total amount of the release agent.

4. The mold release agent composition according to claim 1, wherein the water-soluble thickener (B) has at least one functional group selected from the group consisting of a hydroxyl group, an amide group, an ester group, an amino group, a carboxyl group, a phosphate ester group, and a phosphate group.

5. The release agent composition according to claim 1, wherein the content of the water-soluble thickener (B) is 0.05% by mass or more relative to the total amount of the release agent.

6. The mold release agent composition according to claim 1, wherein the emulsifier (C) is a fluorine-based anionic surfactant having a countercation.

7. (E) The release agent composition according to claim 1, further comprising an emulsifying agent.

8. The release agent composition according to claim 1, wherein the content ratio (B / A) of the water-soluble thickener (B) to the compound (A) is 0.05 to 1.

5.

9. A method for producing a molded article using the mold release agent composition described in any one of claims 1 to 8.

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