Release agent for vulcanized rubber and method for producing vulcanized rubber molded product using the same

Abstract

To provide a release agent for vulcanized rubber which has excellent releasability and cleanability and can prevent whitening of a surface of a vulcanized rubber product.SOLUTION: A release agent for vulcanized rubber contains: an aliphatic alcohol alkylene oxide high molar adduct represented by the following general formula (1); and an aromatic anionic surfactant. [In the formula (1), R1 represents a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms, PO represents a propyleneoxy group, A1O represents an alkyleneoxy group having 2 to 4 carbon atoms, a1 is 0 or more, a2 is 1 or more, and the sum of a1 and a2 is 35 to 200, except for a case where all of the A1O are propyleneoxy groups.]SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a mold release agent for vulcanized rubber and a method for manufacturing a vulcanized rubber molded article using the same. More specifically, the present invention relates to a mold release agent for vulcanized rubber containing an aliphatic alcohol alkylene oxide high molar adduct as a main component and a method for manufacturing a vulcanized rubber molded article using the same.

Background Art

[0002] Rubber products such as rubber hoses are widely used as parts of various machines including automobiles. Many rubber products are obtained by vulcanizing raw rubber such as natural rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, styrene-butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber, butyl rubber, nitrile-butadiene rubber, urethane rubber, silicone rubber, and fluororubber by adding sulfur or a crosslinking agent to crosslink rubber molecules, and then molding the vulcanized rubber imparted with elasticity and stretchability to the raw rubber by extrusion molding or mold molding. For example, a rubber hose is mainly manufactured by a method of inserting vulcanized rubber into a mold such as a mandrel molded into a predetermined shape, molding it, and then pulling it out, or a method of inserting an unvulcanized raw rubber composition into the mold, vulcanizing and molding it, and then pulling it out.

[0003] In the molding of such rubber products, a mold release agent is used to easily separate the vulcanized rubber product after molding from the mold or to easily insert the raw rubber composition before molding into the mold. Examples of such mold release agents for vulcanized rubber include polyalkylene glycols such as polypropylene glycol and polyethylene glycol, polyoxyalkylene glycols, fatty acid soaps, dimethyl silicone, and modified silicone oils.

[0004] Also, for example, Japanese Patent Application Laid-Open No. 7-292236 (Patent Document 1) describes a mold release agent for vulcanized rubber composed of an alkylene oxide adduct of a diamine in which each alkylene oxide adduct is a copolymer of ethylene oxide and propylene oxide bonded alternately. Japanese Patent Application Laid-Open No. 2004-114472 (Patent Document 2) describes a mold release agent for vulcanized rubber containing a compound in which an ethylene oxy group and a propylene oxy group are randomly copolymerized with an aliphatic hydrocarbon group having 3 to 10 carbon atoms. Japanese Patent Application Laid-Open No. 2008-201010 (Patent Document 3) describes a mold release agent for vulcanized rubber containing an alkylene oxide adduct of glycerin fatty acid ester. Japanese Patent Application Laid-Open No. 2012-250495 (Patent Document 4) describes a mold release agent for vulcanized rubber containing a polyoxyalkylene fatty acid ester in which a polyoxyalkylene skeleton is a block copolymerization or random copolymerization of an ethylene oxide ring-opened body and a propylene oxide ring-opened body. However, in these mold release agents for vulcanized rubber, the property of facilitating the extraction operation of the vulcanized rubber product after molding (release property) and the property of easily removing the mold release agent adhering to the surface of the vulcanized rubber product after molding (cleanability) are not yet sufficient. Also, there was a problem that white stains adhered to the surface of the vulcanized rubber product after molding (whitening). This white stain is considered to be caused by components such as lubricants and vulcanization accelerators compounded in the raw rubber oozing out to the rubber surface due to heating during vulcanization (bleed out), or the anti-adhesive agent applied to the surface of the rubber product remaining in order to prevent adhesion between rubber products before vulcanization. Since it causes poor product appearance and defects during assembly (for example, problems such as the rubber product falling off from the metal part when attaching to the metal part), it was necessary to remove it from the surface of the vulcanized rubber product. However, it was difficult to completely remove the white stain even after repeated cleaning, and it was necessary to wipe it off manually, which caused a decrease in work efficiency. Also, there was a problem that the white stain components accumulated in the cleaning tank after repeated cleaning re-adhered to the vulcanized rubber product. Furthermore, in recent years, due to the soaring raw material prices, not only rubber materials but also compounding agents are required to be reduced in cost without exception, and it is necessary to achieve the same quality with limited materials, and difficult product designs are required.Under such circumstances, whitening of the rubber surface, particularly caused by the bleeding of compounding agents onto the rubber surface, has become an even more significant issue than before.

[0005] In addition, Japanese Patent Application Laid-Open No. 2023-94406 (Patent Document 5) describes a mold release agent for vulcanized rubber containing an aliphatic alcohol alkylene oxide high-mole addition product in which the alkylene oxide adduct has a propyleneoxy group with an average addition mole number of 1 to 12 and an alkyleneoxy group having 2 to 4 carbon atoms with an average addition mole number of 23 to 199. This mold release agent for vulcanized rubber has excellent mold release properties and detergency, and prevents whitening of the surface of vulcanized rubber products (particularly, re-staining due to white stains). However, it is not yet sufficient in preventing whitening of vulcanized rubber products after molding due to the bleeding of compounding agents (whitening due to the sticking of the bled compounding agents).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0007] The present invention has been made in view of the problems of the above prior art, and has excellent mold release properties and detergency, and can prevent whitening of the surface of vulcanized rubber products (that is, has excellent anti-whitening properties) (in particular, can prevent the adhesion of white stains that have bled out onto the rubber surface due to the bleeding of compounding agents) (that is, has excellent anti-adhesion properties for white bleeding stains). The object is to provide a mold release agent for vulcanized rubber and a method for manufacturing a vulcanized rubber molded product using the same.

Means for Solving the Problems

[0008] As a result of intensive research to achieve the above object, the present inventors have found that by blending an aromatic anionic surfactant with a mold release agent for vulcanized rubber containing an aliphatic alcohol alkylene oxide high-molar adduct having an alkylene oxide chain with a specific structure to which an alkyleneoxy group having 2 to 4 carbon atoms is added, a mold release agent for vulcanized rubber having excellent mold release properties and detergency and capable of preventing whitening of the surface of vulcanized rubber products (in particular, preventing the adhesion of white stains that have bled out onto the rubber surface due to the bleeding of compounding agents) can be obtained, and the present invention has been completed.

[0009] That is, the present invention provides the following aspects. [1] The following general formula (1):

[0010]

Chemical Formula

[0011] [In formula (1), R 1 represents a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms, PO represents a propyleneoxy group, A 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms, a1 is 0 or more, a2 is 1 or more, and the sum of a1 and a2 is 35 to 200. However, the case where all of A 1 O are propyleneoxy groups is excluded.] an aliphatic alcohol alkylene oxide high-molar adduct represented by, and An aromatic anionic surfactant and, A mold release agent for vulcanized rubber containing [2] The aromatic anionic surfactant is The following general formula (2):

[0012] [Chemical formula]

[0013] [In formula (2), R 2 represents a phenyl group which may have an alkyl group having 1 to 18 carbon atoms or a naphthyl group which may have an alkyl group having 1 to 4 carbon atoms, and M 1 represents a hydrogen atom or a monovalent cationic group.] A sulfonic acid type anionic surfactant represented by An alkyl diphenyl ether disulfonate in which the alkyl group has 4 to 14 carbon atoms, An aromatic sulfonic acid formaldehyde condensate, A sulfuric acid ester of styrenated phenol, and A sulfuric acid ester of an alkylene oxide adduct of styrenated phenol The mold release agent for vulcanized rubber according to [1], which is at least one selected from the group consisting of [3] The mass ratio of the aliphatic alcohol alkylene oxide high mole adduct represented by the general formula (1) to the aromatic anionic surfactant is 80:20 to 99.5:0.5, and the mold release agent for vulcanized rubber according to [1] or [2]. [4] A method for producing a vulcanized rubber molded article, which includes a step of vulcanizing the unvulcanized rubber in a state where the mold release agent for vulcanized rubber according to any one of [1] to [3] is adhered to the contact surface between the mold and the unvulcanized rubber. [Advantages of the Invention]

[0014] According to the present invention, it is possible to obtain a mold release agent for vulcanized rubber that has excellent mold release properties and detergency and can prevent whitening of the surface of vulcanized rubber products (that is, has excellent whitening prevention properties) (in particular, can prevent the adhesion of white stains that have bled out onto the rubber surface due to the bleeding of compounding agents) (that is, has excellent white stain adhesion prevention properties). Further, by using such a mold release agent for vulcanized rubber of the present invention, it is possible to efficiently produce vulcanized rubber products in which surface whitening is suppressed (in particular, adhesion of white stains that have bled out onto the surface due to the bleeding of compounding agents is suppressed).

Mode for Carrying Out the Invention

[0015] Hereinafter, the present invention will be described in detail based on its preferred embodiments.

[0016] 〔Mold Release Agent for Vulcanized Rubber〕 First, the mold release agent for vulcanized rubber of the present invention will be described. The mold release agent for vulcanized rubber of the present invention is represented by the following general formula (1):

[0017]

Chemical formula

[0018] [In formula (1), R 1 represents a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms, PO represents a propyleneoxy group, A 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms, a1 is 0 or more, a2 is 1 or more, and the sum of a1 and a2 is 35 to 200. However, the case where all of A 1 O are propyleneoxy groups is excluded.] an aliphatic alcohol alkylene oxide high molar adduct represented by, an aromatic anionic surfactant, It contains the following. By using the aliphatic alcohol alkylene oxide high-mole adduct represented by the general formula (1) and an aromatic anionic surfactant in combination, a mold release agent for vulcanized rubber can be obtained which has excellent mold release properties and detergency and suppresses whitening of the surface of the vulcanized rubber product (particularly, suppresses the adhesion of white stains that have bled out onto the rubber surface due to the bleeding of compounding agents).

[0019] <Aliphatic alcohol alkylene oxide high-mole adduct> The aliphatic alcohol alkylene oxide high-mole adduct according to the present invention is represented by the general formula (1). In the present invention, the aliphatic alcohol alkylene oxide high-mole adduct refers to a compound having a structure in which an alkylene oxide chain (one per compound) is highly added in place of the hydrogen atom of one hydroxyl group of the aliphatic alcohol.

[0020] In such an aliphatic alcohol alkylene oxide high mole addition product, the aliphatic alcohol is a monohydric alcohol, which may be saturated or unsaturated, and may be linear or branched, but is preferably linear and saturated or unsaturated, and more preferably linear and saturated. The aliphatic alcohol needs to have 1 to 22 carbon atoms, preferably 4 to 20 carbon atoms, and more preferably 8 to 18 carbon atoms. Examples of such aliphatic alcohols include linear saturated aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, lauryl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, 1-heptadecanol, stearyl alcohol, nonadecyl alcohol, arachidyl alcohol, heneicosanol, and behenyl alcohol; linear unsaturated aliphatic alcohols such as allyl alcohol, butenol, pentenol, hexenol, heptenol, octenol, nonenol, decenol, undecenol, dodecenol, tridecenol, palmitoleyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, elaidolinoleyl alcohol, linolenyl alcohol, elaidolinolenyl alcohol, and erucyl alcohol; and branched aliphatic alcohols such as isopropanol, isobutanol, 2-ethylhexanol, isodecanol, 2-butyl-1-octanol, isotridecanol, isostearyl alcohol, and 2-octyl-1-dodecanol. Among these, it is preferably linear and has 8 to 18 carbon atoms. More specifically, it is preferably at least one selected from the group consisting of octanol, nonanol, decanol, undecanol, lauryl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, 1-heptadecanol, stearyl alcohol, nonadecyl alcohol, arachidyl alcohol, heneicosanol, palmitoleyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, elaidolinoleyl alcohol, linolenyl alcohol, and elaidolinolenyl alcohol.

[0021] Therefore, in the general formula (1), R 1 represents a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms. The aliphatic hydrocarbon group may be linear or branched, and may be saturated (alkyl group) or unsaturated (alkenyl group). As for the number of carbon atoms of R 1 , it is preferably 4 to 20, more preferably 8 to 18. When the number of carbon atoms is less than the lower limit, the adhesiveness tends to decrease and the mold release property tends to decrease. On the other hand, when it exceeds the upper limit, the hydrophobicity of the aliphatic alcohol alkylene oxide high mole adduct becomes too high, and aggregation of the compounds easily occurs, and it becomes difficult to be compatible with water and the detergency tends to decrease.

[0022] Such R 1 includes, for example, the residue obtained by removing the hydroxyl group from the aliphatic alcohol.

[0023] In the aliphatic alcohol alkylene oxide high mole adduct according to the present invention, the alkylene oxide chain is a chain formed by adding an alkyleneoxy group and having a hydrogen atom at the terminal. Such an alkylene oxide adduct can be obtained, for example, by addition polymerization of an alkylene oxide to the aliphatic alcohol according to a conventional method. In such a method, the reaction order, the addition order of raw materials, etc. can be appropriately changed.

[0024] In the present invention, the alkyleneoxy group is represented by PO and A 1 O in the general formula (1). When there are a plurality of A 1 O, they may be the same or different from each other. PO in the general formula (1) represents a propyleneoxy group, and A 1 O represents an alkyleneoxy group having 2 to 4 carbon atoms, that is, an ethyleneoxy group having 2 carbon atoms (hereinafter, sometimes referred to as "EO"), a propyleneoxy group having 3 carbon atoms (hereinafter, sometimes referred to as "PO"), or a butyleneoxy group having 4 carbon atoms (hereinafter, sometimes referred to as "BO"). A 2The number of carbon atoms in the alkyleneoxy group represented by O is more preferably from 2 to 3. When the number of carbon atoms is within the above range, the cleaning properties tend to be good.

[0025] These alkyleneoxy groups (PO and A in the above general formula (1) 1 In the present invention, the alkylene oxide chain to which at least one group (A O) selected from EO, PO, and BO is added is, as shown in the general formula (1), directly (preferably after PO is first added (hereinafter, this PO is sometimes referred to as the "initial PO")) to the residue obtained by removing a hydrogen atom from the aliphatic alcohol. 1 O) must be added. 1 Except when all O are propyleneoxy groups. 1 If there is one O, then that A 1 When O is PO and A 1 If there are multiple Os, 1 The case where all of O are PO is excluded. That is, in the general formula (1), 1 If there is one O, then that A 1 O must be EO or BO, and A 1 If there are multiple Os, 1 At least one of O must be EO or BO. In the present invention, the aliphatic alcohol alkylene oxide high molar adduct has an alkylene oxide chain with such a structure, and thus exhibits particularly excellent releasability and cleanability.

[0026] In the present invention, A in the general formula (1) 1 The addition form of O may be a single addition of one of the alkyleneoxy groups or a co-addition of two or more groups. In the case of co-addition, it may be a block addition or a random addition. However, in the case of block addition, the case where an initial PO is added to the residue obtained by removing hydrogen atoms from the aliphatic alcohol and then a block consisting of PO is directly added is excluded. Among these, the above-mentioned A 1As an addition form of O, from the viewpoint of achieving both excellent mold release properties and detergency, co-addition (random addition or block addition, more preferably co-addition of EO and PO) is preferred, random addition is more preferred, and random addition of EO and PO is particularly preferred.

[0027] A in the general formula (1) 1 When the addition form of O is co-addition of EO and PO, the ratio of the average number of moles of addition of EO to PO (including the first PO) in the formula (average number of moles of addition of EO: average number of moles of addition of PO) is preferably 20:80 to 80:20, and more preferably 40:60 to 60:40. When the average number of moles of addition of EO relative to the average number of moles of addition of PO is less than the lower limit, the hydrophobicity of the higher mole addition product of aliphatic alcohol alkylene oxide tends to increase and the detergency tends to decrease. On the other hand, when it exceeds the upper limit, the hydrophilicity of the higher mole addition product of aliphatic alcohol alkylene oxide becomes too high, the mold release property tends to decrease, or aggregation of the compounds tends to occur and the detergency tends to decrease.

[0028] In the present invention, the average number of moles of addition of PO (the first PO) added to the residue obtained by removing a hydrogen atom from the aliphatic alcohol is represented by a1 in the general formula (1). The average number of moles of addition (a1) is a number of 0 or more, preferably 1 to 12, and more preferably 3 to 8. When it exceeds the upper limit, the hydrophobicity of the higher mole addition product of aliphatic alcohol alkylene oxide becomes too high, aggregation of the compounds tends to occur, and the mold release agent becomes less compatible with water and the detergency tends to decrease.

[0029] Also, in the present invention, A to be added directly (preferably after the addition of the first PO) 1 The average number of moles of addition of O is represented by a2 in the general formula (1). The A 1The average number of moles of addition (a2) of O is a number of 1 or more, and the total of (a1 + a2) needs to be a number between 35 and 200, and a2 is preferably 23 to 200, more preferably 23 to 179, and even more preferably 23 to 147. The above A 1 When the average number of moles of addition of O is less than the above lower limit, the viscosity tends to decrease and the mold release property tends to deteriorate. On the other hand, when it exceeds the above upper limit, the viscosity tends to increase and the detergency and handleability tend to deteriorate.

[0030] Furthermore, in the present invention, the average number of moles of addition of all alkyleneoxy groups per alkylene oxide chain is represented by the total (a1 + a2) of a1 and a2 in the general formula (1), and it is necessary to be 35 to 200, preferably 35 to 180, and more preferably 35 to 150. When the average number of moles of addition of all alkyleneoxy groups is less than the above lower limit, the viscosity tends to decrease and the mold release property tends to deteriorate. On the other hand, when it exceeds the above upper limit, the viscosity tends to increase and the detergency and handleability tend to deteriorate.

[0031] In the mold release agent for vulcanized rubber of the present invention, as the aliphatic alcohol alkylene oxide high mole addition product, one kind of the compounds represented by the general formula (1) may be contained alone or two or more kinds may be combined and contained.

[0032] In the mold release agent for vulcanized rubber of the present invention, the content of the aliphatic alcohol alkylene oxide high mole addition product (when there are two or more kinds, their total content, the same hereinafter) is preferably 2.5 to 99.5% by mass, more preferably 5 to 95% by mass, and even more preferably 10 to 90% by mass based on the total mass of the mold release agent for vulcanized rubber. When the content of the aliphatic alcohol alkylene oxide high mole addition product is less than the above lower limit, the mold release property tends to deteriorate. On the other hand, when it exceeds the above upper limit, the detergency tends to deteriorate.

[0033] <Aromatic anionic surfactant> Examples of the aromatic anionic surfactant according to the present invention include a sulfonic acid type anionic surfactant or a sulfate type anionic surfactant having a phenyl group or a naphthyl group. These aromatic anionic surfactants may be used alone or in combination of two or more.

[0034] (Sulfonic acid type anionic surfactant) Examples of the sulfonic acid type anionic surfactant according to the present invention include the following general formula (2):

[0035] [Chemical formula]

[0036] [In formula (2), R 2 represents a phenyl group which may have an alkyl group having 1 to 18 carbon atoms or a naphthyl group which may have an alkyl group having 1 to 4 carbon atoms, and M 1 represents a hydrogen atom or a monovalent cationic group.] Examples of the sulfonic acid type anionic surfactant represented by the formula include a sulfonic acid type anionic surfactant, an alkyl diphenyl ether disulfonate having 4 to 14 carbon atoms in the alkyl group, and an aromatic sulfonic acid formaldehyde condensate. These sulfonic acid type anionic surfactants may be used alone or in combination of two or more.

[0037] (The sulfonic acid type anionic surfactant represented by the general formula (2)) In the general formula (2), R 2 represents a phenyl group which may have an alkyl group having 1 to 18 carbon atoms or a naphthyl group which may have an alkyl group having 1 to 4 carbon atoms, and M 1 represents a hydrogen atom or a monovalent cationic group.

[0038] In the general formula (2), from the viewpoint that the detergency and the whitening prevention property of the mold release agent for vulcanized rubber tend to be further improved, R 2It is preferably a phenyl group having an alkyl group with 1 to 18 carbon atoms, or a naphthyl group which may have an alkyl group with 1 to 4 carbon atoms, and more preferably a phenyl group having an alkyl group with 6 to 16 carbon atoms.

[0039] The alkyl group with 1 to 18 carbon atoms which is a substituent of the phenyl group and the alkyl group with 1 to 4 carbon atoms which is a substituent of the naphthyl group may be linear or may have a branched chain, but from the viewpoint of more improving the detergency and anti-whitening property of the mold release agent for vulcanized rubber, it is preferably linear.

[0040] In the general formula (2), M 1 represents a hydrogen atom or a monovalent cationic group, and the monovalent cationic group is not particularly limited as long as it can form a counter salt with an anion and neutralize it. For example, alkali metals (Li, Na, K, Rb, Cs), ammonium (NH4), alkanolamines (monoalkanolamine, dialkanolamine, trialkanolamine, etc.; preferably alkanolamines with 1 to 4 carbon atoms) can be mentioned. In the general formula (2), M 1 is preferably an alkali metal (Li, Na, K, Rb, Cs), or ammonium, or an alkanolamine with 1 to 4 carbon atoms, and more preferably Na, K, ammonium, or triethanolamine, from the viewpoint of more improving the detergency and anti-whitening property of the mold release agent for vulcanized rubber.

[0041] As the sulfonic acid type anionic surfactant represented by the general formula (2), p-toluenesulfonate, dodecylbenzenesulfonate, decylbenzenesulfonate, undecylbenzenesulfonate, tridecylbenzenesulfonate, and tetradecylbenzenesulfonate are particularly preferable.

[0042] In addition, as the sulfonic acid type anionic surfactant represented by the general formula (2), commercially available products can be used. For example, "Takeka Power B121", "Takeka Power BN2060", "Takeka Power L121", "Takeka Power LN2050D" manufactured by Takeka Corporation, "Neoperex GS", "Neoperex G-15", "Neoperex G-25" manufactured by Kao Corporation, "Takesurf A-40-S", "Takesurf A-41-S" (manufactured by Takemoto Yushi Co., Ltd.) and the like.

[0043] These sulfonic acid type anionic surfactants represented by the general formula (2) may be used alone or in combination of two or more.

[0044] (Alkyldiphenyl ether disulfonate) The alkyldiphenyl ether disulfonate according to the present invention has an alkyl group having 4 to 14 carbon atoms, and the alkyl group may be linear or branched, but is more preferably linear.

[0045] The salt of sulfonic acid is not particularly limited as long as it is a hydrogen atom and a monovalent cation, and examples thereof include the same as M in the general formula (2). For example, alkali metals (Li, Na, K, Rb, Cs), ammonium (NH4), alkanolamines (monoalkanolamine, dialkanolamine, trialkanolamine, etc.; preferably alkanolamines having 1 to 4 carbon atoms). From the viewpoint that the detergency and anti-whitening property of the mold release agent for vulcanized rubber tend to be further improved, the salt is preferably an alkali metal (Li, Na, K, Rb, Cs), or ammonium, or an alkanolamine having 1 to 4 carbon atoms, and more preferably Na, K, ammonium, or triethanolamine. 1 The same ones as those described above can be mentioned. For example, alkali metals (Li, Na, K, Rb, Cs), ammonium (NH4), alkanolamines (monoalkanolamine, dialkanolamine, trialkanolamine, etc.; preferably alkanolamines having 1 to 4 carbon atoms). From the viewpoint that the detergency and anti-whitening property of the mold release agent for vulcanized rubber tend to be further improved, the salt is preferably an alkali metal (Li, Na, K, Rb, Cs), or ammonium, or an alkanolamine having 1 to 4 carbon atoms, and more preferably Na, K, ammonium, or triethanolamine.

[0046] As these alkyl diphenyl ether disulfonates, commercially available products can be used. For example, Eleminol MON-7 (manufactured by Sanyo Chemical Industries, Ltd.), Pelelex SS-H (manufactured by Kao Corporation), Take Surf A-43-S (manufactured by Takemoto Yushi Co., Ltd.), Take Surf A-43-NQ (manufactured by Takemoto Yushi Co., Ltd.), etc. can be mentioned.

[0047] These alkyl diphenyl ether disulfonates may be used alone or in combination of two or more.

[0048] (Aromatic sulfonic acid formaldehyde condensate) The aromatic sulfonic acid formaldehyde condensate according to the present invention is a condensate of an aromatic sulfonic acid and formaldehyde. Examples of the aromatic sulfonic acid include monocyclic aromatic sulfonic acids such as cresol sulfonic acid and phenol sulfonic acid; alkylnaphthalene sulfonic acids such as α-naphthalene sulfonic acid, β-naphthalene sulfonic acid, α-naphthol sulfonic acid, β-naphthol sulfonic acid, methylnaphthalene sulfonic acid, and butylnaphthalene sulfonic acid; polycyclic aromatic sulfonic acids such as creosote oil sulfonic acid; lignin sulfonic acid, etc. Among these, α-naphthalene sulfonic acid or β-naphthalene sulfonic acid is preferred.

[0049] Regarding the molecular weight of the aromatic sulfonic acid formaldehyde condensate, the weight average molecular weight (polystyrene conversion) by gel permeation chromatography (GPC) is preferably 20,000 or less, more preferably 10,000 or less, and even more preferably 1,000 to 10,000.

[0050] In the present invention, examples of the salt of the aromatic sulfonic acid formaldehyde condensate include monovalent salts of the aromatic sulfonic acid formaldehyde condensate, more specifically, alkali metal (Li, Na, K, Rb, Cs) salts; ammonium (NH4), alkanolamine (monoalkanolamine, dialkanolamine, trialkanolamine, etc.; preferably alkanolamine having 1 to 4 carbon atoms) salts. Among these, in the present invention, from the viewpoint of easy availability, etc., the salt of the aromatic sulfonic acid formaldehyde condensate is preferably at least one selected from the group consisting of sodium salts and ammonium salts.

[0051] More preferably, examples of such an aromatic sulfonic acid formaldehyde condensate and its salt include sodium naphthalene sulfonate formaldehyde condensate (weight average molecular weight: 5,000), and one of these may be used alone or in combination of two or more.

[0052] The aromatic sulfonic acid formaldehyde condensate according to the present invention can be obtained by a conventional method, for example, by obtaining a condensate through a condensation reaction of the aromatic sulfonic acid and formaldehyde and neutralizing it with a basic substance as necessary. Note that water-insoluble substances present in the system after neutralization may be removed.

[0053] Commercially available products can be used as the aromatic sulfonic acid formaldehyde condensate. For example, Demol N (manufactured by Kao Corporation), Take Surf A-45-K (manufactured by Takemoto Yushi Co., Ltd.), Lavelin FN-40 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), etc. can be mentioned.

[0054] These aromatic sulfonic acid formaldehyde condensates may be used alone or in combination of two or more.

[0055] As such a sulfonic acid type anionic surfactant, from the viewpoint that the detergency and whitening prevention property of the mold release agent for vulcanized rubber tend to be further improved, the sulfonic acid type anionic surfactant represented by the general formula (2) and the alkyldiphenyl ether disulfonate are more preferable, and the sulfonic acid type anionic surfactant represented by the general formula (2) is more preferable.

[0056] (Sulfuric acid ester type anionic surfactant) As the sulfuric acid ester type anionic surfactant according to the present invention, the sulfuric acid ester of styrenated phenol and the sulfuric acid ester of an alkylene oxide adduct of styrenated phenol are preferable.

[0057] (Sulfuric acid ester of styrenated phenol and sulfuric acid ester of alkylene oxide adduct of styrenated phenol) In the present invention, the styrenated phenol may be monostyrenated phenol, polystyrenated phenol, or a mixture thereof. As the polystyrenated phenol, di-, tri-, tetra-, and pentastyrenated phenols are preferable, and di- and tristyrenated phenols are more preferable.

[0058] In the present invention, the sulfuric acid ester of styrenated phenol is a compound in which the hydroxyl group of styrenated phenol is substituted with a group represented by -SO3M 2 where M 2 is the same as those exemplified for M 1 in the general formula (2).

[0059] In the present invention, the sulfuric acid ester of an alkylene oxide adduct of styrenated phenol is a compound in which an alkylene oxide chain is added to the hydroxyl group of styrenated phenol, and the hydroxyl group at the end of the alkylene oxide chain is -SO3M 2It is a compound substituted with the group represented by. As the alkylene oxide chain, those formed by adding an alkyleneoxy group having 2 to 4 carbon atoms are preferable, and the average number of moles of addition of the alkyleneoxy group per one alkylene oxide chain is preferably more than 0 and 30 or less.

[0060] Examples of such sulfuric acid esters of styrenated phenols and sulfuric acid esters of alkylene oxide adducts of styrenated phenols include, for example, the following general formula (3):

[0061] [Chemical formula]

[0062] [In formula (3), R 3 , R 4 , and R 5 each independently represents a hydrogen atom or a methyl group, A 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms, M 2 represents a hydrogen atom or a monovalent cation group, b represents an integer of 1 to 3, c represents 0 or 1 or 2, d represents 0 or an integer of 1 to 5, (b + 1) × c + d is an integer of 1 to 5, and a3 is the average number of moles of addition of the alkyleneoxy group A 2 O and represents a number from 0 to 30.] Compounds represented by are exemplified.

[0063] In the general formula (3), when there are a plurality of alkyleneoxy groups A 2 O (when a3 is 2 or more), they may be the same or different from each other. As the alkyleneoxy group, the number of carbon atoms is 2 to 4 (EO, PO, BO), and it is preferably 2 to 3 (EO, PO). When the number of carbon atoms is within the above range, the mold release property and cleanability of the mold release agent for vulcanized rubber are good.

[0064] The alkylene oxide chain formed by adding these alkyleneoxy groups (-(A 2 O) a3The group represented by -H) may be a chain consisting of a single addition of one of the alkyleneoxy groups or a chain consisting of a co-addition of two or more groups. In the case of co-addition, it may be block addition or random addition.

[0065] In the general formula (3), the average number of moles of alkyleneoxy groups added per alkyleneoxide chain represented by a3 is from 0 to 30, preferably from 4 to 20. When the average number of moles of alkyleneoxy groups added is less than the lower limit, the mold release property of the mold release agent for vulcanized rubber tends not to be sufficiently improved. On the other hand, when it exceeds the upper limit, the detergency and the property of preventing whitening tend not to be sufficiently improved.

[0066] In the general formula (3), b represents an integer of 1 to 3, c represents 0 or 1 or 2, d represents 0 or an integer of 1 to 5, and (b + 1) × c + d is an integer of 1 to 5. From the viewpoint that the detergency of the mold release agent for vulcanized rubber tends to be better, it is preferable that b represents an integer of 1 to 3, c represents 0 or 1, d represents 0 or an integer of 1 to 3, and (b + 1) × c + d is an integer of 1 to 3.

[0067] As such a compound represented by the general formula (3), more preferably, for example, sulfuric acid esters of mono- or di- or tristyrenated phenols, sulfuric acid esters of alkyleneoxide adducts of mono- or di- or tristyrenated phenols (average number of moles of alkyleneoxy groups added: 4 to 20), more specifically, ammonium salts of polyoxyethylene styrylphenyl ether sulfuric acid esters (average number of moles of ethyleneoxy groups added: 5), ammonium salts of polyoxyethylene distyrylphenyl ether sulfuric acid esters (average number of moles of ethyleneoxy groups added: 5), ammonium salts of polyoxyethylene tristyrylphenyl ether sulfuric acid esters (average number of moles of ethyleneoxy groups added: 5) may be mentioned, and one of these may be used alone or a combination of two or more may be used.

[0068] The compound represented by the general formula (3) can be obtained by, for example, subjecting mono- or polystyrenated phenol to addition polymerization of an alkyleneoxy group having 2 to 4 carbon atoms, if necessary, and then converting it into a sulfate ester according to a conventional method. As the method for addition polymerization of the alkyleneoxy group, the same methods as those described for the aliphatic alcohol alkylene oxide high molar addition product can be appropriately employed.

[0069] These sulfate ester type anionic surfactants may be used alone or in combination of two or more.

[0070] In the present invention, as the aromatic anionic surfactant, the above-mentioned ones can be used alone or in combination of two or more. Further, from the viewpoint that the detergency and whitening prevention property of the mold release agent for vulcanized rubber tend to be more improved, it is particularly preferable to use the sulfonic acid type anionic surfactant represented by the general formula (2).

[0071] (Mold release agent for vulcanized rubber) The mold release agent for vulcanized rubber of the present invention contains the aliphatic alcohol alkylene oxide high molar addition product represented by the general formula (1) and the aromatic anionic surfactant.

[0072] In the mold release agent for vulcanized rubber of the present invention, the total amount of the aliphatic alcohol alkylene oxide high molar addition product represented by the general formula (1) and the aromatic anionic surfactant is preferably 3% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more based on the total amount of the mold release agent for vulcanized rubber. When the total amount of the aliphatic alcohol alkylene oxide high molar addition product and the aromatic anionic surfactant is less than the above lower limit, the mold release property, detergency, and whitening prevention property of the surface of the vulcanized rubber product (particularly, the prevention property of adhesion of white stains bleeding out onto the rubber surface due to the bleeding of the compounding agent) tend to decrease. The upper limit of the total amount of the aliphatic alcohol alkylene oxide high molar addition product represented by the general formula (1) and the aromatic anionic surfactant is 100% by mass.

[0073] Further, in the mold release agent for vulcanized rubber of the present invention, the mass ratio of the aliphatic alcohol alkylene oxide high mole adduct represented by the general formula (1) to the aromatic anionic surfactant is not particularly limited, but the aliphatic alcohol alkylene oxide high mole adduct: aromatic anionic surfactant = 80:20 to 99.5:0.5 is preferable. When the mass ratio of the aliphatic alcohol alkylene oxide high mole adduct to the aromatic anionic surfactant is less than the lower limit, the mold release property tends to decrease. On the other hand, when it exceeds the upper limit, the whitening prevention property of the surface of the vulcanized rubber product (particularly, the adhesion prevention property of the white stain that has bled out onto the rubber surface due to the bleeding of the compounding agent) tends to decrease.

[0074] Further, the mold release agent for vulcanized rubber of the present invention may further contain water. The mold release agent for vulcanized rubber of the present invention can be appropriately diluted with water as needed during use as follows. The water is not particularly limited, and examples include river water, industrial water, purified water, sterilized water, natural water, and mixtures thereof.

[0075] Furthermore, as the mold release agent for vulcanized rubber of the present invention, in addition to the aliphatic alcohol alkylene oxide high mole adduct represented by the general formula (1) and the aromatic anionic surfactant, within a range that does not inhibit the effects of the present invention, it may further contain an alcohol or glycol ether having 1 to 8 carbon atoms.

[0076] Also, as the mold release agent for vulcanized rubber of the present invention, within a range that does not inhibit the effects of the present invention, antifoaming agents, preservatives, rust preventives, surfactants (excluding the aliphatic alcohol alkylene oxide high mole adduct and the aromatic anionic surfactant), antioxidants, colorants, deodorants, fragrances, solvents, conventionally known mold release agent components (for example, mold release agent components contained in the mold release agents for vulcanized rubber described in JP-A-2012-250495 and JP-A-2017-177717), and other components may be further contained. These other components may be used alone or in combination of two or more.

[0077] Examples of defoaming agents include defoaming agents such as silicone-based, polyglycol-based, higher alcohol-based, and mineral oil-based agents. These defoaming agents may be used alone or in combination of two or more. Examples of preservatives include aromatic carboxylic acids such as benzoic acid, p-toluic acid, p-ethylbenzoic acid, p-isopropylbenzoic acid, p-tert-butylbenzoic acid, xylylic acid, isophthalic acid, terephthalic acid, salicylic acid, cinnamic acid, hemimellitic acid, trimellitic acid, trimesic acid, hydroxybenzoic acid, dihydroxybenzoic acid, and trihydroxybenzoic acid. These preservatives may be used alone or in combination of two or more.

[0078] Examples of rust inhibitors include aliphatic dicarboxylic acids, alkylphosphonic acids, benzotriazoles, benzothiazoles, (2-benzothiazylthio)acetic acid, or 3-(2-benzothiazylthio)propionic acid. These rust inhibitors may be used alone or in combination of two or more. Examples of surfactants include nonionic surfactants such as soaps, fatty acid alkylene oxide adducts, and polyhydric alcohol fatty acid ester alkylene oxide adducts; and amphoteric surfactants such as alkylamino fatty acid salts, alkylbetaines, and alkylamine oxides (excluding the above-mentioned aliphatic alcohol alkylene oxide high-molar adducts and aromatic anionic surfactants).

[0079] Examples of solvents include water, alcohols, glycol ethers, and alkylene glycol alkyl ethers. Examples of alcohols include monohydric alcohols having 1 to 4 carbon atoms, alkylene glycols having 2 to 6 carbon atoms, polyhydric alcohols such as glycerin and benzyl alcohol. Examples of glycol ethers include di-, tri-, or tetra-alkylene (having 2 to 4 carbon atoms) glycols. Examples of alkylene glycol alkyl ethers include alkyl (having 1 to 4 carbon atoms) ethers of the above-mentioned alkylene glycol or di- or tri-alkylene glycol.

[0080] In the present invention, when the mold release agent for vulcanized rubber further contains the other components, the content thereof (in the case of two or more kinds, the total content thereof; the same shall apply hereinafter) is preferably 0.5 part by mass or less with respect to 1 part by mass of the total content of the aliphatic alcohol alkylene oxide high mole adduct represented by the general formula (1) and the aromatic anionic surfactant.

[0081] In the present invention, a mixture of the aliphatic alcohol alkylene oxide high mole adduct represented by the general formula (1) and the aromatic anionic surfactant may be directly used as the mold release agent for vulcanized rubber of the present invention, or the water and, if necessary, the other components may be further mixed to be used as the mold release agent for vulcanized rubber of the present invention. Such a mixing method is not particularly limited.

[0082] The mold release agent for vulcanized rubber of the present invention can also be diluted with water so as to have a low concentration during use, if necessary, and used as a mold release agent solution. Since the mold release agent for vulcanized rubber of the present invention is easily soluble in water and has excellent adhesion to the mold, it can exhibit excellent mold release properties and detergency even at a low concentration.

[0083] In the mold release agent solution, the total content of the aliphatic alcohol alkylene oxide high mole adduct represented by the general formula (1) and the aromatic anionic surfactant is appropriately adjusted according to the usage method and is not particularly limited, but is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 10 to 95% by mass. A mold release agent solution having a total content of the aliphatic alcohol alkylene oxide high mole adduct represented by the general formula (1) and the aromatic anionic surfactant within such a range can exhibit excellent mold release properties, detergency, and whitening prevention properties.

[0084] [Method for producing vulcanized rubber molded article] The method for manufacturing a vulcanized rubber molded product of the present invention is a method for manufacturing a vulcanized rubber molded product using the mold release agent for vulcanized rubber of the present invention. Specifically, it is a method including a step of vulcanizing the unvulcanized rubber in a state where the mold release agent for vulcanized rubber of the present invention adheres to the contact surface between the mold and the unvulcanized rubber.

[0085] As a method for adhering the mold release agent for vulcanized rubber to the contact surface between the mold and the unvulcanized rubber, for example, a method of previously applying the mold release agent solution to a portion of the mold that contacts the vulcanized rubber or the unvulcanized rubber; a method of applying the mold release agent solution to the end of the unvulcanized rubber hose; a method combining these methods, etc. can be mentioned.

[0086] In the method for manufacturing a vulcanized rubber molded product of the present invention, the method for molding the vulcanized rubber is not particularly limited, and a conventionally known method for molding vulcanized rubber can be adopted. However, since the mold release agent for vulcanized rubber of the present invention can exhibit excellent mold release properties, detergency, and whitening prevention properties even when mixed with components that seep out from the rubber during vulcanization, a method of inserting vulcanized rubber into the mold, molding it, and then pulling it out, or a method of inserting an unvulcanized raw rubber composition into the mold, vulcanizing and molding it, and then pulling it out can also be preferably adopted.

[0087] Examples of the mold include molds made of iron, stainless steel, gelamine, etc., and the shape is not particularly limited. However, the mold release agent for vulcanized rubber of the present invention can be preferably used as a mold release agent applied to a mandrel used for molding a vulcanized rubber hose. The method of application is not particularly limited, and a conventionally known method can be adopted, and examples include a method of spraying using a spray gun (spray coating) and a method of applying with a brush. The application amount can be appropriately adjusted according to the concentration of the mold release agent solution, the type and insertion speed of the vulcanized rubber or the unvulcanized rubber, the temperature of the mold, etc.

[0088] The vulcanized rubber is not particularly limited, and examples thereof include those obtained by vulcanizing natural rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, styrene-butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber, butyl rubber, nitrile-butadiene rubber, urethane rubber, silicone rubber, fluororubber, and the like. The mold release agent for vulcanized rubber of the present invention can be suitably used, for example, for vulcanized rubber obtained by vulcanizing ethylene-propylene-diene rubber.

Examples

[0089] Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples. The characteristics of the mold release agent for vulcanized rubber obtained in the examples and comparative examples were evaluated by the following methods.

[0090] (Release property) First, each mold release agent for vulcanized rubber obtained in the examples and comparative examples was diluted 3-fold with water to prepare a mold release agent solution. An unvulcanized rubber hose (diameter: 7.5 mm × length: 80 mm) of EPDM (ethylene-propylene-diene copolymer rubber) was immersed in this mold release agent solution from its tip to a portion 40 mm in length and then taken out. Next, a cylindrical stainless steel rod (made of SUS304, diameter: 8.0 mm × length: 300 mm) heated to 60°C was inserted into the inner side of the rubber hose from the tip to a portion 40 mm in length on the side immersed in the mold release agent for vulcanized rubber to prepare a sample. This was placed in a dryer and heated at 180°C for 14 minutes for vulcanization treatment, and then the temperature of the dryer was lowered to 100°C and cooled at 100°C for 5 minutes. After the cooled sample was taken out of the dryer, it was confirmed with a surface thermometer that the surface temperature of the stainless steel rod was 100°C or lower, the stainless steel rod was fixed, and the rubber hose was pulled out. The resistance between the rubber hose and the stainless steel rod at that time was evaluated according to the following criteria: 4: Smooth release 3: Release 2: Strong resistance but can be released 1: Cannot be released The evaluation was performed on 10 samples, and the average value was taken as the evaluation result of the release property.

[0091] (Washability) Regarding the whitening of the hose due to the bleed-out of rubber compounding agents, various compounding components can be considered. In this example, zinc dibutyldithiocarbamate, which is a vulcanization accelerator, and zinc stearate, which is a processing aid, were used. First, the mold release agents for each vulcanized rubber obtained in the examples and comparative examples were diluted three times with water to prepare a mold release agent solution. This mold release agent solution, zinc dibutyldithiocarbamate, which is a vulcanization accelerator, and zinc stearate, which is a processing aid, were taken into a magnetic mortar so that the compounding amounts were 87% by weight, 5% by weight, and 8% by weight, respectively, and thoroughly mixed with a pestle to prepare a test solution. The test solution was applied to the surface of a vulcanized rubber plate (length: 12 cm × width: 6 cm) of EPDM (ethylene-propylene-diene copolymer rubber) so that the application amount was 0.3 g, and a vulcanization simulation treatment was performed by heating at 150°C for 30 minutes to prepare a test piece. Next, the test piece was immersed in a washing bath maintained at 60°C while circulating tap water in a 10 L constant temperature bath for 1 minute. Then, the test piece was taken out and air-dried, and the surface of the test piece was visually observed to confirm the presence or absence of residual mold release agent. When no residual mold release agent was observed, the washing was considered complete. When residual mold release agent was observed, the test piece was immersed in the washing bath again for 1 minute, and the surface of the air-dried test piece was visually observed to confirm the presence or absence of residual mold release agent. This operation was repeated until no residual mold release agent was observed, and the washability was evaluated based on the number of washes.

[0092] (Anti-whitening property) Regarding the test plate after washing was completed, the presence or absence of white stains (white stains due to scorching of rubber compounding agents) in the test solution application part was visually observed according to the following criteria: 5: No whitening is observed. 4: Slight whitening is observed on a part of the surface. 3: Slight whitening is observed overall. 2: Uniform whitening is observed over the entire surface. 1: The entire surface is whitened and aggregates are observed. The evaluation was made according to the following.

[0093] (Synthesis Example 1) 200.0 g of lauryl alcohol (Konoal 20P manufactured by Shin Nippon Rika Co., Ltd.) as a raw material alcohol and 14.0 g of a 48% by mass potassium hydroxide aqueous solution as a catalyst were charged into a 5 L autoclave. After thoroughly replacing the inside of the reaction apparatus with nitrogen, the temperature was raised and dehydration was carried out under reduced pressure. After reaching 120 °C, the dropping of 498.9 g of propylene oxide as the first PO was started, and the reaction was carried out within a pressure range of 0 to 0.5 MPa while maintaining the temperature at 120 to 150 °C. After dropping all of the propylene oxide, aging was carried out for 1 hour until the pressure drop ceased. Next, a mixture of 2172.5 g of ethylene oxide (EO in A 1 O) and 1621.4 g of propylene oxide (PO in A 1 O) was dropped at the same temperature, the reaction was carried out within a pressure range of 0 to 0.5 MPa, and aging was carried out for 1 hour until the pressure drop ceased while maintaining the temperature at 120 to 150 °C. Then, it was cooled, and 7.3 g of 99% by mass acetic acid was added at 50 °C to neutralize the catalyst, and 4492.8 g of an adduct of ethylene oxide (46) propylene oxide (34) of lauryl alcohol, which is the target compound, was obtained. The obtained adduct of ethylene oxide (46) propylene oxide (34) of lauryl alcohol has an alkyl group having 12 carbon atoms in the general formula (1), a propyleneoxy group (PO) added alone, and an alkyleneoxy group (A 1 O) in which an ethyleneoxy group (EO) and a propyleneoxy group (PO) are randomly added (chemical formula: C 1 H 12 (8PO)(46EO / 26PO)H). The average number of moles of the propyleneoxy group (PO) added alone is 8 moles / chain as the average of the entire obtained compound, and the average number of moles added in the alkyleneoxy group (A 25 O) is 46 moles / chain for the ethyleneoxy group (EO) and 26 moles / chain for the propyleneoxy group (PO) as the average of the entire obtained compound. 1 O) has an average addition molar number of 46 moles / chain for the ethyleneoxy group (EO) and 26 moles / chain for the propyleneoxy group (PO) as the average of the entire obtained compound.

[0094] (Synthesis Examples 2 to 5, 7 to 11, and Comparative Synthesis Example 1) The type of raw material alcohol, the amount of raw material alcohol, 48 mass% potassium hydroxide aqueous solution, propylene oxide (PO) as the initial PO, A 1 The target compounds shown in Table 2 were synthesized in the same manner as in Synthesis Example 1, except that the amounts of ethylene oxide (EO) and propylene oxide (PO) as O and 99% by mass acetic acid charged were changed to the types and amounts shown in Table 1. In Table 1, the numbers in parentheses ("()") in the name of each alkylene oxide adduct indicate the average number of moles added per molecule of the added alkyleneoxy groups as a whole compound, and the units separated by parentheses ("()") in the chemical formula indicate the added units of alkyleneoxy groups, and the numbers in the same parentheses indicate the average number of moles added per molecule of the added alkyleneoxy groups as a whole compound converted into the average number of moles added per alkylene oxide chain, and the diagonal line (" / ") between alkyleneoxy groups indicates that these alkyleneoxy groups are randomly added (the same applies below).

[0095] (Synthesis Example 6) A 5-liter autoclave was charged with 220.0 g of lauryl alcohol ("Conol 20P" manufactured by New Japan Chemical Co., Ltd.) as the raw material alcohol and 13.7 g of 48% by mass potassium hydroxide aqueous solution as the catalyst, and the inside of the reactor was thoroughly replaced with nitrogen, after which the temperature was raised and dehydrated under reduced pressure. After the temperature reached 120°C, ethylene oxide (A 1 1783.6g of propylene oxide (EO) and 1783.6g of propylene oxide (A 1 A mixture of 389.7 g of PO) and 2389.7 g of PO (out of O) was added dropwise while maintaining the temperature at 120 to 150°C, and the reaction was carried out within a pressure range of 0 to 0.5 MPa, and the mixture was aged at the same temperature for 1 hour until the pressure drop ceased. After that, the mixture was cooled, and 7.1 g of 99% by mass acetic acid was added at 50°C to neutralize the catalyst, thereby obtaining 4393.3 g of an ethylene oxide (46) propylene oxide (26) adduct of lauryl alcohol, which was the target compound. The obtained ethylene oxide (46) propylene oxide (26) adduct of lauryl alcohol is represented by the formula (1) R 1 is an alkyl group having 12 carbon atoms, and an alkyleneoxy group (A1 A compound having an O) (chemical formula: C 12 H 25 (46EO / 26PO)H), wherein the average number of moles added in the alkyleneoxy group (A 1 O) is, as the average of the entire obtained compound, 46 moles / chain of ethyleneoxy group (EO) and 26 moles / chain of propyleneoxy group (PO).

[0096] (Comparative Synthesis Example 2) 250.0 g of tetrahydroxypropyl ethylenediamine (N,N,N’,N’-tetrakis(2-hydroxyalkyl)alkylenediamine) as a raw material and 27.7 g of a 48% by mass aqueous potassium hydroxide solution as a catalyst were charged into a 5 L autoclave. After thoroughly replacing the inside of the reaction apparatus with nitrogen, the temperature was raised and dehydration was carried out under reduced pressure. After reaching 120°C, the dropping of 2384.2 g of propylene oxide was started, and the reaction was carried out within a pressure range of 0 to 0.5 MPa while maintaining the temperature at 120 to 150°C. After dropping the entire amount of propylene oxide, aging was carried out until the pressure drop ceased. Next, while maintaining the temperature at 120 to 150°C, 1805.6 g of ethylene oxide was introduced and reacted at a pressure of less than 0.5 MPa. After introducing the entire amount of ethylene oxide, aging was carried out until the pressure drop ceased. Then, it was cooled, and 14.4 g of 99% acetic acid was added at 50°C to neutralize the catalyst, and 4439.9 g of an adduct of propylene oxide (52) ethylene oxide (48) of ethylenediamine, which is the target compound, was obtained. The obtained adduct of propylene oxide (52) ethylene oxide (48) of ethylenediamine is a compound in which two alkyleneoxy groups (A 1 O) in which an ethyleneoxy group (EO) and a propyleneoxy group (PO) are block-added are bonded to each of the two N atoms of ethylenediamine, and the average number of moles added in the alkyleneoxy group (A 1 O) is, as the average of the entire obtained compound, 13 moles / chain of propyleneoxy group (PO) and 12 moles / chain of ethyleneoxy group (EO).

[0097]

Table 1

[0098] (Preparation Example 1) 100 parts by mass of p-toluenesulfonic acid monohydrate (manufactured by Meiyo Sangyo Co., Ltd.) and 43.8 parts by mass of a 48% by mass aqueous sodium hydroxide solution were mixed to prepare an aqueous sodium p-toluenesulfonate solution (concentration: 84.2% by mass).

[0099] (Preparation Example 2) 100 parts by mass of dodecylbenzenesulfonic acid (manufactured by Teika Co., Ltd.) and 25.6 parts by mass of a 48% by mass aqueous sodium hydroxide solution were mixed to prepare an aqueous sodium dodecylbenzenesulfonate solution (concentration: 89.4% by mass).

[0100] (Preparation Example 3) 100 parts by mass of dodecylbenzenesulfonic acid (manufactured by Teika Co., Ltd.) and 20.9 parts by mass of a 25% by mass aqueous ammonia solution were mixed to prepare an aqueous ammonium dodecylbenzenesulfonate solution (concentration: 87% by mass).

[0101] (Preparation Example 4) 100 parts by mass of dodecylbenzenesulfonic acid (manufactured by Teika Co., Ltd.) and 45.8 parts by mass of triethanolamine were mixed to prepare dodecylbenzenesulfonic acid triethanolamine (concentration: 100% by mass).

[0102] (Preparation Example 5) In a 1 L heat-resistant reaction vessel, 100 parts by mass of tristyrenated phenol (trade name: TSP, manufactured by Mitsuho Corporation) and 1.0 part by mass of a 48% by mass aqueous potassium hydroxide solution as a catalyst were charged. After thoroughly replacing the inside of the reaction apparatus with nitrogen, the temperature was raised to 100 °C and dehydration was carried out under reduced pressure. After heating this to reach 120 °C, the dropping of 53.8 parts by mass of ethylene oxide was started, and the reaction was carried out within a pressure range of 0 to 0.5 MPa while maintaining the temperature at 120 to 140 °C, and aging was carried out at the same temperature for 3 hours. After cooling to 80 °C, 0.5 part by mass of 99% acetic acid was added and mixed uniformly to obtain 153.8 parts by mass of an ethylene oxide (5) adduct of tristyrenated phenol. 100 parts by mass of the obtained adduct was charged into a 300 ml separable flask, dehydrated at 110 °C while passing nitrogen, and then heated to 120 to 130 °C. Here, 60.8 parts by mass of sulfamic acid was introduced and the reaction was carried out for 3 hours to obtain 160.8 parts by mass of ammonium sulfate ester of ethylene oxide (5) adduct of tristyrenated phenol (concentration 100% by mass), which is the target compound. The obtained ammonium sulfate ester of ethylene oxide (5) adduct of tristyrenated phenol is a compound in which the alkyleneoxy group (A 2 O) in the general formula (3) is an ethyleneoxy group (EO), and the average number of moles of addition of the ethyleneoxy group (EO) is 5 moles / chain as the average of the entire obtained compound.

[0103] (Example A1) 80 parts by mass of an ethylene oxide (46) propylene oxide (34) adduct of lauryl alcohol obtained in Synthesis Example 1 as an aliphatic alcohol alkylene oxide high-mole adduct was used, and 10 parts by mass in terms of the active ingredient amount of an aqueous sodium p-toluenesulfonate solution (active ingredient concentration 84.2% by mass) obtained in Preparation Example 1 as an aromatic anionic surfactant was used. These were added to water and stirred and mixed to obtain a mold release agent for vulcanized rubber with a total amount of 100 parts by mass. The mold release property, detergency, and whitening prevention property of the obtained mold release agent for vulcanized rubber were evaluated according to the above method. The results are shown in Table 2.

[0104] (Examples A2 to A13 and Comparative Examples A1 to A2) A mold release agent for vulcanized rubber was obtained in the same manner as in Example A1, except that the type and amount of the aromatic anionic surfactant were changed to those shown in Table 2. The mold release property, detergency, and whitening prevention property of the obtained mold release agent for vulcanized rubber were evaluated according to the above method. The results are shown in Table 2.

[0105] [Table 2]

[0106] (Example B1) 80 parts by mass of the ethylene oxide (46) - propylene oxide (34) adduct of lauryl alcohol obtained in Synthesis Example 1 as an aliphatic alcohol alkylene oxide high - mole adduct was used, and 10 parts by mass in terms of the active ingredient amount of triethanolamine dodecylbenzenesulfonate (active ingredient concentration 100% by mass) obtained in Preparation Example 4 as an aromatic anionic surfactant was used. These were added to water and stirred and mixed to obtain a mold release agent for vulcanized rubber with a total amount of 100 parts by mass. The mold release property, detergency, and whitening prevention property of the obtained mold release agent for vulcanized rubber were evaluated according to the above method. The results are shown in Table 3.

[0107] (Examples B2 - B12 and Comparative Examples B1 - B4) A mold release agent for vulcanized rubber was obtained in the same manner as in Example B1, except that the type and amount of the aliphatic alcohol alkylene oxide high - mole adduct were changed to those shown in Table 3. The mold release property, detergency, and whitening prevention property of the obtained mold release agent for vulcanized rubber were evaluated according to the above method. The results are shown in Table 3.

[0108] [Table 3] [Industrial Applicability]

[0109] As described above, according to the present invention, it is possible to obtain a mold release agent for vulcanized rubber that has excellent mold release properties and detergency and can prevent whitening of the surface of vulcanized rubber products (i.e., has excellent whitening prevention properties), and in particular, can prevent the adhesion of white stains that have bled out onto the rubber surface due to the bleeding of compounding agents (i.e., has excellent white stain adhesion prevention properties). Therefore, since the method for manufacturing a vulcanized rubber molded product of the present invention uses such a mold release agent for vulcanized rubber, it is useful as a method for efficiently manufacturing a vulcanized rubber product in which surface whitening is suppressed (in particular, adhesion of white stains that have bled out onto the surface due to the bleeding of compounding agents is suppressed).

Claims

1. The aliphatic alcohol alkylene oxide high-molar addition product represented by the following general formula (1): 【Chemical 1】 [In formula (1), R １ represents a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms, PO represents a propyleneoxy group, and A １ O represents an alkyleneoxy group having 2 to 4 carbon atoms, a1 is 0 or more, a2 is 1 or more, and the sum of a1 and a2 is 35 to 200. However, the case where all of A １ O are propyleneoxy groups is excluded.] and an aromatic anionic surfactant, characterized in that it contains a mold release agent for vulcanized rubber.

2. The aromatic anionic surfactant is the sulfonic acid type anionic surfactant represented by the following general formula (2): [Chemical 2] [In formula (2), R ２ represents a phenyl group which may have an alkyl group having 1 to 18 carbon atoms or a naphthyl group which may have an alkyl group having 1 to 4 carbon atoms, and M １ represents a hydrogen atom or a monovalent cationic group.] an alkyl diphenyl ether disulfonate having 4 to 14 carbon atoms in the alkyl group, an aromatic sulfonic acid formaldehyde condensate, a sulfate ester of styrenated phenol, and a sulfate ester of an alkylene oxide adduct of styrenated phenol The mold release agent for vulcanized rubber according to claim 1, characterized in that it is at least one selected from the group consisting of

3. The mold release agent for vulcanized rubber according to claim 1, characterized in that the mass ratio of the aliphatic alcohol alkylene oxide high-molar addition product represented by the general formula (1) to the aromatic anionic surfactant is 80:20 to 99.5:0.

5.

4. A method for producing a vulcanized rubber molded article, characterized by including a step of vulcanizing the unvulcanized rubber in a state where the mold release agent for vulcanized rubber according to any one of claims 1 to 3 is adhered to the contact surface between the mold and the unvulcanized rubber. ​

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