JP2023094406A - Mold release agent for vulcanized rubber and method of manufacturing vulcanized rubber molded products using agent - Google Patents

Abstract

To provide a mold release agent for vulcanized rubber that has excellent mold release and cleaning properties and can prevent whitening of the surface of vulcanized rubber products.SOLUTION: A mold release agent for vulcanized rubber contains a low molar adduct of alkylene oxide represented by following general formula (1): [In Formula (1), R1 is an alkyl or alkenyl group having 4 to 32 carbons, X is -O-, -N(R11)- or -CON(R12)-, A1O is an alkyleneoxy group having 2 to 3 carbons], and a high molar adduct of aliphatic alcohol alkylene oxide represented by following general formula (2): [In Formula (2), R2 is an alkyl or alkenyl group having 14 to 22 carbons, PO is a propyleneoxy group, A2O is an alkyleneoxy group having 2 to 4 carbons, and the sum of n and m is 35 to 200, except when all of plural A2O are propyleneoxy groups].SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a release agent for vulcanized rubber and a method for producing a vulcanized rubber molded product using the same, and more particularly, a release agent for vulcanized rubber containing an aliphatic alcohol alkylene oxide high-molar adduct as a main agent. The present invention relates to an agent and a method for producing vulcanized rubber moldings using the same.

Rubber products such as rubber hoses are widely used as parts of various machines including automobiles. Most rubber products are 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, fluorine rubber, etc. Vulcanization is performed by adding sulfur or a cross-linking agent to the raw rubber of , and vulcanization is performed to cross-link the rubber molecules, and the vulcanized rubber that has given stretchability and elasticity to the raw rubber is molded by extrusion molding, mold molding, etc. is. For example, rubber hoses are mainly manufactured by inserting a vulcanized rubber into a mold such as a mandrel molded into a predetermined shape and pulling it out after molding, or by inserting an unvulcanized raw rubber composition into the mold. It is manufactured by a method of drawing after vulcanizing and molding.

In the molding of such rubber products, a release agent is used to facilitate the release of the molded vulcanized rubber product from the mold, or to facilitate the insertion of the raw rubber composition into the mold before molding. Known release agents for vulcanized rubber include, for example, polyalkylene glycols such as polypropylene glycol and polyethylene glycol, polyoxyalkylene glycols, fatty acid soaps, dimethyl silicones, and modified silicone oils.

Further, for example, Japanese Patent Application Laid-Open No. 7-292236 (Patent Document 1) describes a vulcanized rubber composed of an alkylene oxide adduct of a diamine, in which each alkylene oxide adduct is an alternate combination of ethylene oxide and propylene oxide. Japanese Patent Application Laid-Open No. 2004-114472 (Patent Document 2) discloses that an aliphatic hydrocarbon group having 3 to 10 carbon atoms and an ethyleneoxy group and a propyleneoxy group are randomly mixed together. A release agent for vulcanized rubber containing a polymerized compound is described. A type agent is described, and in JP-A-2012-250495 (Patent Document 4), a polyoxyalkylene skeleton is obtained by block addition polymerization or random addition polymerization of an ethylene oxide ring-opening product and a propylene oxide ring-opening product. Vulcanized rubber release agents containing certain polyoxyalkylene fatty acid esters are described. However, in these release agents for vulcanized rubber, there is a characteristic (mold release property) that makes it easy to pull out the vulcanized rubber product after molding, and the release that adheres to the surface of the vulcanized rubber product after molding. The properties of easy removal of the mold agent (washability) are still insufficient, and there is also the problem that white stains adhere to the surface of the vulcanized rubber product after molding (whitening). This white stain is caused by the ingredients mixed in the raw rubber oozing out to the surface of the rubber (bleed out) due to heating during vulcanization, and the surface of the rubber product to prevent adhesion between rubber products before vulcanization. It is thought that this is caused by the remaining anti-adhesion agent applied, which causes defects during assembly (for example, problems such as rubber products falling off metal parts when attached to metal parts). Therefore, it had to be removed from the surface of the vulcanized rubber product. However, it was difficult to completely remove the white stains even after repeated cleaning, and it was necessary to manually wipe off the stains, which caused a decrease in work efficiency. In addition, there is also the problem that the repeated washing causes the white dirt accumulated in the washing tank to re-adhere to the vulcanized rubber product.

Further, in JP-A-2019-111724 (Patent Document 5), an alkylene oxide adduct is a propyleneoxy group having an average addition mole number of 1 to 12 and an average addition mole number of 23 to 199 and an alkyleneoxy group having 2 to 4 carbon atoms. A release agent for vulcanizate containing a fatty alcohol alkylene oxide high molar adduct having a group is described. Although this release agent for vulcanized rubber has excellent releasability and washability, it is still insufficient in terms of preventing whitening of vulcanized rubber products after molding.

JP-A-7-292236 Japanese Patent Application Laid-Open No. 2004-114472 Japanese Patent Application Laid-Open No. 2008-201010 JP 2012-250495 A JP 2019-111724 A

The present invention has been made in view of the above problems of the prior art, and has excellent releasability and washability, and prevents the surface of vulcanized rubber products from whitening (excellent whitening To provide a mold release agent for vulcanized rubber capable of preventing redeposition (in particular, preventing redeposition due to white dirt (excellent anti-recontamination property)) and a method for producing a vulcanized rubber molded product using the same. for the purpose.

The present inventors have made intensive studies to achieve the above object, and found that an alkylene oxide chain having a specific structure in which a propyleneoxy group is singly added and an alkyleneoxy group having 2 to 4 carbon atoms is added thereto. By blending an alkylene oxide low molar adduct of an aliphatic alcohol, an aliphatic amine or a fatty acid amide with a release agent for vulcanized rubber containing an aliphatic alcohol alkylene oxide high molar adduct with and a release agent for vulcanized rubber that has washability and is capable of preventing whitening of the surface of vulcanized rubber products (especially, preventing redeposition due to white stains). I have completed my invention.

That is, the release agent for vulcanized rubber of the present invention has the following general formula (1):

[In formula (1), R ¹ represents an alkyl group or alkenyl group having 4 to 32 carbon atoms, X represents -O-, -N(R ¹¹ )- or -CON(R ¹² )-, and R ¹¹ represents a hydrogen atom or -(A ¹ O) _q H, R ¹² represents a hydrogen atom, -(A ¹ O) _q H or an alkyl group having 1 to 3 carbon atoms, and each A ¹ O independently represents a carbon number 2 to 3 alkyleneoxy groups, p and q are the average number of added moles of the alkyleneoxy groups and each independently represent a number of 1 to 20, and the total of p and q is 1 to 20 . ]
and an alkylene oxide low molar adduct represented by
The following general formula (2):

[In formula (2), R ² represents an alkyl or alkenyl group having 14 to 22 carbon atoms, PO represents a propyleneoxy group, and A ² O each independently represents an alkyleneoxy group having 2 to 4 carbon atoms. , m is the average addition mole number of the propyleneoxy group and represents a number of 1 to 12, n is the average addition mole number of the alkyleneoxy group and represents a number of 23 to 199, and n and m is 35-200. However, this excludes the case where all of the multiple A ² O are propyleneoxy groups. ]
It is characterized by containing an aliphatic alcohol alkylene oxide high molar adduct represented by.

In the release agent for vulcanized rubber of the present invention, the alkylene oxide low molar adduct represented by the general formula (1) and the aliphatic alcohol alkylene oxide high molar adduct represented by the general formula (2) is preferably (1):(2)=0.5:99.5 to 20:80.

Further, in the method for producing a vulcanized rubber molded article of the present invention, the unvulcanized rubber mold release agent according to claim 1 or 2 is adhered to the contact surface between the mold and the unvulcanized rubber. The method is characterized by including the step of vulcanizing vulcanized rubber.

According to the present invention, it has excellent releasability and washability, and prevents whitening of the surface of vulcanized rubber products (excellent whitening prevention property) (in particular, prevents redeposition due to white stains (excellent anti-soil redeposition property)). In addition, by using such a release agent for vulcanized rubber of the present invention, it becomes possible to efficiently produce a vulcanized rubber product in which whitening of the surface is suppressed.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments.

[Release agent for vulcanized rubber]
First, the release agent for vulcanized rubber of the present invention will be described. The release agent for vulcanized rubber of the present invention has the following general formula (1):

[In formula (1), R ¹ represents an alkyl group or alkenyl group having 4 to 32 carbon atoms, X represents -O-, -N(R ¹¹ )- or -CON(R ¹² )-, and R ¹¹ represents a hydrogen atom or -(A ¹ O) _q H, R ¹² represents a hydrogen atom, -(A ¹ O) _q H or an alkyl group having 1 to 3 carbon atoms, and each A ¹ O independently represents a carbon number 2 to 3 alkyleneoxy groups, p and q are the average number of added moles of the alkyleneoxy groups and each independently represent a number of 1 to 20, and the total of p and q is 1 to 20 . ]
and an alkylene oxide low molar adduct represented by
The following general formula (2):

[In formula (2), R ² represents an alkyl or alkenyl group having 14 to 22 carbon atoms, PO represents a propyleneoxy group, and A ² O each independently represents an alkyleneoxy group having 2 to 4 carbon atoms. , m is the average addition mole number of the propyleneoxy group and represents a number of 1 to 12, n is the average addition mole number of the alkyleneoxy group and represents a number of 23 to 199, and n and m is 35-200. However, this excludes the case where all of the multiple A ² O are propyleneoxy groups. ]
and an aliphatic alcohol alkylene oxide high molar adduct represented by By using together the alkylene oxide low molar adduct represented by the general formula (1) and the aliphatic alcohol alkylene oxide high molar adduct represented by the general formula (2), excellent releasability and washing are obtained. It is possible to obtain a release agent for vulcanized rubber that has properties and is capable of preventing whitening of the surface of vulcanized rubber products (in particular, preventing redeposition due to white stains).

(Alkylene oxide low molar adduct)
The alkylene oxide low-molar adduct according to the present invention is represented by the general formula (1). In general formula (1), R ¹ represents an alkyl or alkenyl group having 4 to 32 carbon atoms. The number of carbon atoms in the alkyl group and alkenyl group is preferably 4 to 22, more preferably 6 to 16, even more preferably 8 to 14. If the number of carbon atoms is less than the lower limit, the anti-whitening property tends to deteriorate, and if it exceeds the upper limit, the detergency and the anti-whitening property tend to deteriorate. R ¹ may be linear or branched, preferably linear, more preferably linear alkyl.

Further, in the general formula (1), X represents -O-, -N(R ¹¹ )- or -CON(R ¹² )-, and R ¹¹ represents a hydrogen atom or -(A ¹ O) _q H , R ¹² represents a hydrogen atom, —(A ¹ O) _q H, or an alkyl group having 1 to 3 carbon atoms. In addition, in the alkylene oxide low molar adduct according to the present invention, in the general formula (1), when X is —O—, the “aliphatic alcohol alkylene oxide low molar adduct”, X is —N (R ¹¹ )— is also referred to as “aliphatic amine alkylene oxide low molar adduct”, and X is —CON(R ¹² )— is also referred to as “fatty amide alkylene oxide low molar adduct”. A ¹ O and q will be described later.

In the alkylene oxide low-molar adduct according to the present invention, the alkylene oxide chain is a chain formed by adding an alkyleneoxy group and having a terminal hydrogen atom, and in the general formula (1), -(A ¹ O) _pH and -(A ¹ O) _q H. The alkyleneoxy group is represented by A ¹ O in the general formula (1), and multiple A ¹ O may be the same or different. A ¹ O (including A ¹ O in R ¹¹ and R ¹² ) in the general formula (1) is each independently an alkyleneoxy group having 2 to 3 carbon atoms, that is, an ethyleneoxy group having 2 carbon atoms. (hereinafter sometimes referred to as "EO"), or a propyleneoxy group having 3 carbon atoms (hereinafter sometimes referred to as "PO").

In the present invention, the addition form of A ¹ O in the general formula (1) may be single addition of one group among the alkyleneoxy groups or co-addition of two or more groups. In the case of co-addition, it may be block addition or random addition. Among these, the addition form of A ¹ O is preferably single addition of EO, co-addition of EO and PO (random addition or block addition), single addition of EO, and addition of EO, from the viewpoint of excellent cleaning properties. Random addition of and PO is more preferred, and single addition of EO is even more preferred.

When the addition form of A ¹ O in the general formula (1) is a co-addition of EO and PO, the proportion of PO in A ¹ O is preferably 50 mol% or less, more preferably 40 mol% or less. Preferably, 30 mol % or less is more preferable. When the proportion of PO exceeds the above upper limit, there is a tendency for detergency and anti-whitening properties to deteriorate.

In the alkylene oxide low-molar adduct of the aliphatic alcohol, the average addition mole number per alkylene oxide chain of A ¹ O as the whole adduct is represented by p in the general formula (1), and the aliphatic alcohol In the alkylene oxide low-molar adduct of amine and the alkylene oxide low-molar adduct of fatty acid amide, the average number of added moles per alkylene oxide chain of A ¹ O as the whole adduct is represented by the general formula (1) Denoted by p and q. The average added mole numbers (p and q) of A ¹ O each independently need to be a number of 1 to 20, preferably a number of 1 to 15, and a number of 1 to 10. is more preferable. If p or q is less than the above lower limit, the washability and anti-whitening properties tend to deteriorate, whereas if it exceeds the above upper limit, the washability, handleability and anti-whitening properties tend to deteriorate.

In addition, in the alkylene oxide low-molar adduct according to the present invention, the average addition mole number per molecule of the A ¹ O adduct (average for the entire adduct) is It is represented by the total (p+q) and must be a number from 1 to 20, preferably a number from 1 to 15, more preferably a number from 1 to 10. If p or q is less than the above lower limit, the washability and anti-whitening properties tend to deteriorate, whereas if it exceeds the above upper limit, the washability, handleability and anti-whitening properties tend to deteriorate.

Such alkylene oxide low-molar adducts, for example, when X in the general formula (1) is —O—, have 4 to 32 carbon atoms (preferably 4 to 22, more preferably 6 to 16 , more preferably 8 to 14) can be obtained by addition polymerization of an alkylene oxide having 2 to 3 carbon atoms in accordance with a conventional method, and X in the general formula (1) is —N (R ¹¹ )-, an aliphatic amine having 4 to 32 carbon atoms (preferably 4 to 22, more preferably 6 to 16, more preferably 8 to 14) and an alkylene oxide having 2 to 3 carbon atoms are added in a conventional manner. It can be obtained by addition polymerization. Further, when X in the general formula (1) is —CON(R ¹² )—, the number of carbon atoms is 4 to 32 (preferably 4 to 22, more preferably 6 to 16, still more preferably 8 to 14). The aliphatic carboxylic acid ester of is reacted with an alkanolamine having 2 to 3 carbon atoms in a conventional manner, and if necessary, an alkylene oxide having 2 to 3 carbon atoms is added in a conventional manner. It can also be obtained by addition polymerization of an alkylene oxide having 2 to 3 carbon atoms to a fatty acid amide having 4 to 32 carbon atoms (preferably 4 to 22, more preferably 6 to 16, still more preferably 8 to 14). can.

The aliphatic alcohol is a monohydric alcohol, which may be saturated or unsaturated, linear or branched, preferably linear. , preferably saturated.

Examples of such aliphatic alcohols include butanol, pentanol, hexanol, heptanol, capryl alcohol, nonanol, decanol, undecanol, lauryl alcohol, tridecanol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecanol, stearyl alcohol. , nonadecyl alcohol, arachidyl alcohol, heneicosanol, behenyl alcohol, etc. Linear saturated aliphatic alcohols having a hydroxyl group at the end of the hydrocarbon group; C 12-24 linear secondary alcohols such as Linear saturated aliphatic alcohols having hydroxyl groups other than both ends of the hydrocarbon group; crotyl alcohol, penten-1-ol, hexen-1-ol, heptene-1-ol, octen-1-ol, nonen Linear unsaturated fatty alcohols such as 1-ol, palmitoleyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, elaidolinoleyl alcohol, linolenyl alcohol, elaidolinolenyl alcohol, and erucyl alcohol isobutyl alcohol, isopentyl alcohol, 2-ethylhexanol, isooctanol, 2-butyloctanol, 2-butyldecanol, isocetyl alcohol, 2-hexyloctanol, 2-hexyldecanol, isostearyl alcohol, 2-octyldecanol, Branched aliphatic alcohols such as 2-hexyldodecanol, 2-octyldodecanol, 2-decyltetradecanol, 2-dodecylhexadecanol, 2-tetradecyloctadecanol, among others, It is preferably linear with 6 to 16 carbon atoms, and more specifically, hexanol, heptanol, capryl alcohol, nonanol, decanol, undecanol, lauryl alcohol, tridecanol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, hexene. -1-ol, heptene-1-ol, octen-1-ol, nonen-1-ol, preferably at least one selected from the group consisting of palmitoleol alcohol, straight chain having 8 to 14 carbon atoms more preferably in the form of at least One type is more preferable.

The aliphatic amine is a compound having one amino group in one molecule, may be saturated or unsaturated, and may be linear or branched, It is preferably linear and preferably saturated.

Examples of such aliphatic amines include butylamine, pentylamine, hexylamine, heptylamine, caprylamine, nonylamine, decylamine, undecylamine, laurylamine, tridecylamine, myristylamine, pentadecylamine, cetylamine, heptylamine, linear saturated aliphatic amines such as decylamine, stearylamine, nonadecylamine, arachidylamine, heneicosylamine, behenylamine; Linear unsaturated aliphatic amines such as nonene-1-amine, oleylamine, linoleylamine, linolenylamine and erucylamine; branched aliphatic amines such as isobutylamine, isopentylamine, isooctylamine and isostearylamine Among these, linear amines having 6 to 16 carbon atoms are preferred, and more specifically, hexylamine, heptylamine, caprylamine, nonylamine, decylamine, undecylamine, laurylamine, It is preferably at least one selected from the group consisting of tridecylamine, myristylamine, pentadecylamine, cetylamine, hexen-1-amine, octen-1-amine, nonene-1-amine, and has 8 to 8 carbon atoms. 14 linear is more preferred, more specifically caprylamine, nonylamine, decylamine, undecylamine, laurylamine, tridecylamine, myristylamine, octen-1-amine, nonene-1-amine At least one selected from the group consisting of is more preferable.

The aliphatic carboxylic acid ester is a compound having one carboxylic acid ester group in one molecule, and may be saturated or unsaturated, linear or branched. However, it is preferably linear and preferably saturated.

Examples of such aliphatic carboxylic acid esters include butyrate, valerate, caproate, enanthate, caprylate, pelargonate, caprate, laurate, myristate, and palmitate. Linear saturated aliphatic esters such as acid esters, margaric acid esters, stearic acid esters, nonadecanic acid esters, arachidic acid esters, heneicosylic acid esters, and behenic acid esters; Linear unsaturated aliphatic carboxylic acid esters such as octenoic acid ester, nonenoic acid ester, oleic acid ester, linoleic acid ester, linolenic acid ester, and erucic acid ester; Branched aliphatic carboxylic acid esters such as isoenanthate, isocaprylate, isopelargonate, isocaprate, isolaurate, isopalmitate, isomargarate, and isostearate, and these Among them, it is preferably a straight chain having 6 to 16 carbon atoms, and more specifically, caproate, enanthate, caprylate, pelargonate, caprate, laurate, myristic It is preferably at least one selected from the group consisting of an acid ester, palmitate, hexenoate, octenoate, and nonenoate, more preferably a straight chain having 8 to 14 carbon atoms, More specifically, it is more preferably at least one selected from the group consisting of caprylate, pelargonate, caprate, laurate, myristate, octenoate, and nonenoate. . Examples of the ester include methyl ester, ethyl ester, propyl ester and the like, with methyl ester being preferred.

The alkanolamine is a compound having 2 to 3 carbon atoms and having one or more hydroxyl groups and one primary or secondary amino group in one molecule. amine), diethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, di-2-propanolamine and the like.

In the release agent for vulcanized rubber of the present invention, as the alkylene oxide low-molar adduct, even if one of the compounds represented by the general formula (1) is contained alone, two or more of them may be used. It may be contained in combination.

(Aliphatic alcohol alkylene oxide high molar adduct)
The fatty alcohol alkylene oxide high molar adduct according to the present invention is represented by the general formula (2). In the present invention, the fatty alcohol alkylene oxide high molar adduct is a compound having a structure in which an alkylene oxide chain (total of one per compound) is added in high molarity in place of the hydrogen atom of one hydroxyl group of the aliphatic alcohol. Say things.

The fatty alcohol in such fatty alcohol alkylene oxide high molar adducts is a monohydric alcohol, which may be saturated or unsaturated, linear or branched. However, it is preferably linear and saturated or unsaturated, more preferably linear and saturated. The aliphatic alcohol must have 14 to 22 carbon atoms, preferably 16 to 20 carbon atoms, and more preferably 18 carbon atoms. Examples of such aliphatic alcohols include linear alcohols such as myristyl alcohol, pentadecyl alcohol, cetyl alcohol, 1-heptadecanol, stearyl alcohol, nonadecyl alcohol, arachidyl alcohol, heneicosanol, and behenyl alcohol. straight chain unsaturated fatty alcohols such as palmitoleyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, elaidolinoleyl alcohol, linolenyl alcohol, elaidolinolenyl alcohol, erucyl alcohol, etc. Aliphatic alcohols; branched chain fatty alcohols such as isostearyl alcohol, etc. Among them, straight chain alcohols having 16 to 20 carbon atoms are preferred, and more specifically, myristyl alcohol, pentadecyl Alcohol, cetyl alcohol, 1-heptadecanol, stearyl alcohol, nonadecyl alcohol, arachidyl alcohol, heneicosanol, palmitoleyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, elaide linoleyl alcohol, linoleate It is preferably at least one selected from the group consisting of nyl alcohol and elalide linolenyl alcohol.

Therefore, in the general formula (2), R ² represents an alkyl or alkenyl group having 14 to 22 carbon atoms. The number of carbon atoms in R ² is preferably 16-20, more preferably 18. When the number of carbon atoms is less than the lower limit, the adhesiveness tends to decrease and the releasability tends to decrease. If the amount is too large, the compounds tend to coagulate with each other, making it difficult to absorb water and detergency.

Examples of such R ² include residues obtained by removing hydroxyl groups from the above-mentioned aliphatic alcohols.

In the fatty alcohol alkylene oxide high-molar 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 its terminal. Such an alkylene oxide adduct can be obtained, for example, by subjecting the above-mentioned aliphatic alcohol to addition polymerization of alkylene oxide according to a conventional method. In such a method, the order of reactions, the order of addition of raw materials, and the like can be changed as appropriate.

In the present invention, the alkyleneoxy group is represented by PO and A ² O in the general formula (2), and multiple A ² O may be the same or different. PO in the general formula (2) represents a propyleneoxy group, and A ² O each independently represents an alkyleneoxy group having 2 to 4 carbon atoms, that is, an ethyleneoxy group having 2 carbon atoms (hereinafter, optionally "EO"), a propyleneoxy group with 3 carbon atoms (hereinafter sometimes referred to as "PO"), or a butyleneoxy group with 4 carbon atoms (hereinafter sometimes referred to as "BO"). . The number of carbon atoms in the alkyleneoxy group represented by A ² O in the general formula (2) is more preferably 2-3. When the number of carbon atoms is within the above range, detergency tends to be good.

As the alkylene oxide chain formed by addition of these alkyleneoxy groups (PO and A ² O in the general formula (2)), in the present invention, as shown in the general formula (2), first the fatty PO is added to the residue obtained by removing the hydrogen atom from the group alcohol (hereinafter sometimes this PO is referred to as the “initial PO”), and then at least one group (A ² It is necessary to have a structure to which O) is added. However, the case where the alkylene oxide chain consists entirely of PO is excluded. That is, at least one of the plurality of A ² O in general formula (2) must be EO or BO. In the present invention, the high-molecular-weight aliphatic alcohol alkylene oxide adduct has an alkylene oxide chain with such a structure, thereby exhibiting particularly excellent releasability and washability.

In the present invention, the addition form of A ² O in the general formula (2) may be single addition of one group among the alkyleneoxy groups or co-addition of two or more groups. In the case of co-addition, it may be block addition or random addition. However, in the case of block addition, this excludes the case where a block consisting of PO is directly added after the first PO is added to the residue obtained by removing the hydrogen atom from the aliphatic alcohol. Among these, the addition form of A ² O is co-addition (random addition or block addition, more preferably co-addition of EO and PO) from the viewpoint of achieving both excellent releasability and cleanability. is preferred, random addition is more preferred, and random addition of EO and PO is particularly preferred.

When the addition form of A ² O in the general formula (2) is a co-addition of EO and PO, the average addition mole number ratio of EO and PO (including the first PO) in the formula (EO (average added mole number of PO: average added mole number of PO) is preferably from 80:20 to 20:80, more preferably from 60:40 to 40:60. If the average number of added moles of EO relative to the average number of added moles of PO is less than the lower limit, the hydrophobicity of the high-molecular addition product of the aliphatic alcohol alkylene oxide tends to be high, resulting in a decrease in cleanability. If it exceeds , the hydrophilicity of the high-molecular-weight aliphatic alcohol alkylene oxide adduct tends to be too high, resulting in a decrease in releasability, or aggregation between compounds tends to occur, resulting in a decrease in cleanability.

In the present invention, the average number of added moles of PO (initial PO) first added to the residue obtained by removing the hydrogen atom from the aliphatic alcohol is represented by m in the general formula (2). The average added mole number (m) is required to be 1 to 12, preferably 3 to 12. If the initial average addition mole number of PO is less than the lower limit, the cleaning property tends to be deteriorated. As a result, the compounds tend to coagulate with each other, making it difficult for the release agent to blend in with water, resulting in a decrease in washability.

Further, in the present invention, the average added mole number of A ² O added after the first addition of PO is represented by n in the general formula (2). The average added mole number (n) of A ² O is required to be 23-199, preferably 23-179, and more preferably 23-147. When the average number of added moles of A ² O is less than the lower limit, the viscosity tends to be low and the releasability tends to decrease. tends to decline.

Furthermore, in the present invention, the average number of added moles of all alkyleneoxy groups per alkylene oxide chain is represented by the sum of m and n (m+n) in the general formula (2), and is 35 to 200. is required, preferably 35-180, more preferably 35-150. When the average added mole number of all the alkyleneoxy groups is less than the lower limit, the viscosity tends to decrease and the releasability tends to decrease. tend to decline.

In the release agent for vulcanized rubber of the present invention, as the aliphatic alcohol alkylene oxide high molar adduct, even if one of the compounds represented by the general formula (2) is contained alone, 2 A combination of more than one species may be contained.

In the release agent for vulcanized rubber of the present invention, the content of the fatty alcohol alkylene oxide high-molar adduct (the total content thereof when there are two or more, the same applies hereinafter) is for vulcanized rubber It is preferably 10 to 99.5% by mass, more preferably 15 to 85% by mass, even more preferably 20 to 70% by mass, based on the total mass of the release agent. When the content of the fatty alcohol alkylene oxide high-molar adduct is less than the lower limit, the releasability tends to be deteriorated.

(Mold release agent for vulcanized rubber)
The release agent for vulcanized rubber of the present invention comprises an alkylene oxide low molar adduct represented by the general formula (1) and an aliphatic alcohol alkylene oxide high molar adduct represented by the general formula (2). It contains

In the release agent for vulcanized rubber of the present invention, the alkylene oxide low molar adduct represented by the general formula (1) and the aliphatic alcohol alkylene oxide high molar adduct represented by the general formula (2) The total amount is preferably 5% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, relative to the total amount of the release agent for vulcanized rubber. When the total amount of the alkylene oxide low-molar adduct and the aliphatic alcohol alkylene oxide high-molar adduct is less than the lower limit, the releasability, washability, and anti-whitening properties (in particular, anti-soil redeposition properties) are poor. tend to decline. The upper limit of the total amount of the alkylene oxide low molar adduct represented by the general formula (1) and the aliphatic alcohol alkylene oxide high molar adduct represented by the general formula (2) is 100% by mass. be.

Further, in the release agent for vulcanized rubber of the present invention, the alkylene oxide low molar adduct represented by the general formula (1) and the aliphatic alcohol alkylene oxide high molar adduct represented by the general formula (2) Although there is no particular limitation on the mass ratio of (1):(2) = 0.5:99.5 to 20:80. If the mass ratio of the alkylene oxide low-molar adduct to the fatty alcohol alkylene oxide high-molar adduct is less than the lower limit, the anti-whitening property (particularly, anti-soil redeposition property) tends to decrease. If the above upper limit is exceeded, the releasability tends to decrease.

The release agent for vulcanized rubber of the present invention may further contain water. As described below, the release agent for vulcanized rubber of the present invention can be used by appropriately diluting it with water as necessary at the time of use. The water is not particularly limited, and includes purified water, sterilized water, natural water, mixtures thereof, and the like.

Furthermore, as the release agent for vulcanized rubber of the present invention, in addition to the alkylene oxide low molar adduct and the aliphatic alcohol alkylene oxide high molar adduct, within a range that does not impair the effects of the present invention, It may further contain 1 to 8 alcohols or glycol ethers.

Further, as the release agent for vulcanized rubber of the present invention, within a range that does not impair the effects of the present invention, foam inhibitors, preservatives, rust preventives, surfactants (however, the alkylene oxide low molar adduct and the fatty alcohol alkylene oxide high molar adducts), antioxidants, colorants, deodorants, fragrances, solvents, conventionally known release agent components (for example, JP 2012-250495 and patent It may further contain other components such as the release agent component contained in the release agent for vulcanized rubber described in JP-A-2017-177717. These other components may be used alone or in combination of two or more.

Examples of foam inhibitors include silicone-based, polyglycol-based, higher alcohol-based and mineral oil-based foam inhibitors. These foam inhibitors may be used alone or in combination of two or more. Examples of antiseptics include benzoic acid, p-toluic acid, p-ethylbenzoic acid, p-isopropylbenzoic acid, p-tert-butylbenzoic acid, xylyl acid, isophthalic acid, terephthalic acid, salicylic acid, cinnamic acid, Aromatic carboxylic acids such as hemimellitic acid, trimellitic acid, trimesic acid, hydroxybenzoic acid, dihydroxybenzoic acid, trihydroxybenzoic acid, and the like are included. These preservatives may be used alone or in combination of two or more.

Examples of rust inhibitors include aliphatic dicarboxylic acids, alkylphosphonic acids, benzotriazoles, benzothiazoles, (2-benzothiazylthio)acetic acid and 3-(2-benzothiazylthio)propionic acid. be done. 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 alkylene oxide low molar adducts and the above fatty alcohol alkylene oxide high molar adducts).

Examples of solvents include water, alcohols, glycol ethers, alkylene glycol alkyl ethers, and the like. Examples of alcohols include monohydric alcohols having 1 to 4 carbon atoms, alkylene glycols having 2 to 6 carbon atoms, glycerin, and polyhydric alcohols such as benzyl alcohol. Numbers 2 to 4) glycols, and examples of alkylene glycol alkyl ethers include alkyl (C 1 to 4) ethers of the above alkylene glycols or di- or trialkylene glycols.

In the present invention, when the release agent for vulcanized rubber further contains the above-mentioned other components, the content thereof (the total content thereof in the case of two or more kinds, the same shall apply hereinafter) is It is preferably 0.5 parts by mass or less per 1 part by mass of the total content of the adduct and the high-molecular-weight fatty alcohol alkylene oxide adduct.

In the present invention, a mixture of the alkylene oxide low-molar adduct and the fatty alcohol alkylene oxide high-molar adduct may be used as the release agent for vulcanized rubber of the present invention. Other components may be further mixed to form the release agent for vulcanized rubber of the present invention. Such a mixing method is not particularly limited.

The release agent for vulcanized rubber of the present invention can also be used as a release agent solution by diluting with water so that the concentration becomes low at the time of use, if necessary. Since the release agent for vulcanized rubber of the present invention is easily dissolved in water and has excellent adhesion to molds, it exhibits both excellent releasability and washability even at low concentrations. can be done.

In the release agent solution, the total content of the alkylene oxide low-molar adduct and the fatty alcohol alkylene oxide high-molar adduct is appropriately adjusted according to the method of use and is not particularly limited. It is preferably at least 5% by mass, more preferably at least 5% by mass, even more preferably from 15 to 80% by mass, and particularly preferably from 20 to 50% by mass. A release agent solution in which the total content of the alkylene oxide low molar adduct and the fatty alcohol alkylene oxide high molar adduct is in the above range exhibits excellent releasability, detergency and anti-whitening properties. can do.

[Manufacturing method of vulcanized rubber molding]
The method for producing a vulcanized rubber molded product of the present invention is a method for producing a vulcanized rubber molded product using the release agent for vulcanized rubber of the present invention. The method includes the step of vulcanizing the unvulcanized rubber in a state in which the release agent for vulcanized rubber of the present invention is adhered to the contact surface with the rubber.

As a method of adhering the release agent for vulcanized rubber to the contact surface between the mold and the unvulcanized rubber, for example, the release agent is attached to the part of the mold that contacts the vulcanized rubber or unvulcanized rubber. A method of applying a solution; a method of applying the release agent solution to the end of an unvulcanized rubber hose; a method combining these methods, and the like.

In the method for producing the vulcanized rubber molded article of the present invention, the method for molding the vulcanized rubber is not particularly limited, and conventionally known vulcanized rubber molding methods can be employed. Even if the release agent is mixed with the components exuding from the rubber during vulcanization, it can exhibit excellent releasability, washability, and anti-whitening properties. A method of inserting an unvulcanized raw rubber composition into a mold, vulcanizing and molding the composition, and then withdrawing the composition can also be suitably employed.

Examples of the mold include molds made of iron, stainless steel, duralumin, etc., and the shape is not particularly limited. It can be suitably used as a mold release agent. The coating method is not particularly limited, and conventionally known methods can be employed, including a method of spraying using a spray gun (spray coating), a method of coating with a brush, and the like. The coating amount can be appropriately adjusted depending on the concentration of the release agent solution, the type and insertion speed of the vulcanized rubber or unvulcanized rubber, the temperature of the mold, and the like.

The vulcanized rubber is not particularly limited, and includes 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, Vulcanized silicone rubber, fluororubber and the like can be mentioned. The release agent for vulcanized rubber of the present invention can be suitably used for vulcanized rubber obtained by vulcanizing ethylene-propylene-diene rubber, for example.

EXAMPLES The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples. The properties of the release agents for vulcanized rubber obtained in Examples and Comparative Examples were evaluated by the following methods.

(Releasability)
First, each release agent for vulcanized rubber obtained in Examples and Comparative Examples was diluted twice with water to prepare a release agent solution. An unvulcanized rubber hose (diameter: 7.5 mm x length: 80 mm) of EPDM (ethylene-propylene-diene copolymer rubber) was immersed in this release agent solution up to a portion of 40 mm from the tip and taken out. . Next, a cylindrical stainless steel rod (made of SUS304, diameter: 8.0 mm × length: 300 mm) heated to 60 ° C. ) was inserted as a sample. This was placed in a drier and heated at 180° C. for 14 minutes for vulcanization treatment, after which the temperature of the drier was lowered to 100° C. and cooled at 100° C. for 5 minutes. After removing the sample after cooling from the dryer, confirm that the surface temperature of the stainless steel rod is 100 ° C. or less with a surface thermometer, fix the stainless steel rod and pull out the rubber hose. of the resistance, according to the following criteria:
4: Pulls out smoothly 3: Pulls out 2: Pulls out with strong resistance 1: Does not come out. Ten samples were evaluated, and the average value was used as the evaluation result of releasability.

(washability)
First, each release agent for vulcanized rubber obtained in Examples and Comparative Examples was diluted twice with water to prepare a release agent solution. This release agent solution was applied to an unvulcanized EPDM (ethylene-propylene-diene copolymer rubber) rubber plate (length: 12 cm x width: 6 cm) so that the coating amount of the release agent was 0.3 g. It was applied to the surface and heated at 180° C. for 10 minutes to simulate vulcanization to prepare a test piece. Next, the test piece was immersed for 1 minute in a cleaning bath maintained at 40° C. while circulating tap water in a 10 L constant temperature bath. After that, 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 release agent and white stains. When no release agent residue and white stain are observed, the cleaning is completed. When release agent residue and white stain are observed, the test piece is again immersed in the cleaning bath for 1 minute, air-dried, and then tested. The single surface was visually observed to confirm the presence or absence of residual release agent and white stains. This operation was repeated until the washing was completed, and the washability was evaluated by the number of times of washing.

(Anti-recontamination property)
Various compounding ingredients and anti-adhesion agents are considered to be causative substances for the whitening of the surface of vulcanized rubber products. In this example, zinc stearate was used as a whitening substance to evaluate the redeposition prevention property of a vulcanized rubber product. Specifically, 0.1 g of each release agent for vulcanized rubber obtained in Examples and Comparative Examples and 0.03 g of zinc stearate were added to 100 g of water at room temperature and washed in a washing bath (washing was repeated several times). was assumed) was prepared. A vulcanized rubber plate (length: 12 cm x width: 6 cm) of EPDM (ethylene-propylene-diene copolymer rubber) was immersed in this washing bath for 10 seconds, and the liquid was gently drained off. After that, the immersed portion was dried with a drier, and the surface of the vulcanized rubber plate was visually observed and evaluated according to the following criteria:
5: Whitening is not observed 4: Light whitening is observed in part of the surface 3: Light whitening is observed throughout 2: Whitening is observed uniformly over the entire surface 1: The entire surface is whitened , evaluated according to the presence of aggregates.

(Synthesis example 1)
A 5 L autoclave was charged with 200 g of stearyl alcohol (manufactured by Shin Nippon Rika Co., Ltd., "Conol 30SS") as raw material alcohol and 4.64 g of 48% by mass potassium hydroxide aqueous solution as a catalyst, and the inside of the reactor was sufficiently replaced with nitrogen. After that, the temperature was raised and dehydration was performed under reduced pressure. After reaching 120°C, dropwise addition of 346 g of propylene oxide as the first PO was started, and the reaction was carried out at a pressure within the range of 0-0.5 MPa while maintaining the temperature at 120-150°C. After dropping the entire amount of propylene oxide, the mixture was aged for 1 hour until the pressure did not decrease. Then, a mixture of 1508 g of ethylene oxide (EO in A ² O) and 1126 g of propylene oxide (PO in A ² O) was added dropwise thereto at the same temperature, and the pressure was within the range of 0 to 0.5 MPa. and aged for 1 hour until the pressure no longer drops. After cooling, 2.41 g of 99% by mass acetic acid was added at 50° C. to neutralize the catalyst to obtain 3185 g of the desired compound, ethylene oxide (46) propylene oxide (34) adduct of stearyl alcohol. The resulting ethylene oxide (46) propylene oxide (34) adduct of stearyl alcohol has R ² in the above general formula (2) being an alkyl group having 18 carbon atoms, a propyleneoxy group (PO) added alone, and a compound (chemical formula: C ₁₈ H ₃₇ O(8PO)(46EO/26PO)H) having an alkyleneoxy group (A ² O) in which an ethyleneoxy group (EO) and a propyleneoxy group (PO) are randomly co-added The average added mole number of the singly added propyleneoxy group (PO) is 8 mol/chain as an average of the entire compound obtained, and the average added mole number of the alkyleneoxy group (A ² O) is The average of all the compounds obtained is 46 mol/chain of ethyleneoxy groups (EO) and 26 mol/chain of propyleneoxy groups (PO).

(Example A1)
First, a 1 L autoclave was charged with 270 g of lauryl alcohol (“Conol 20P” manufactured by Shin Nippon Rika Co., Ltd.) as a raw material alcohol and 0.58 g of a 48% by mass potassium hydroxide aqueous solution as a catalyst, and the reactor was sufficiently filled with nitrogen. After substituting with , the temperature was raised and dehydration was performed under reduced pressure. After reaching 120°C, dropwise addition of 127 g of ethylene oxide (EO as A ¹ O) was started, and the reaction was carried out at a pressure within the range of 0-0.5 MPa while maintaining the temperature at 120-150°C. After dropping the entire amount of ethylene oxide, the mixture was aged for 1 hour until the pressure did not decrease. After cooling, 0.30 g of 99% by mass acetic acid was added at 50° C. to neutralize the catalyst, thereby obtaining 397 g of the target compound, ethylene oxide (2) adduct of lauryl alcohol. The resulting ethylene oxide (2) adduct of lauryl alcohol is such that R ¹ in the general formula (1) is an alkyl group having 12 carbon atoms, X is —O—, and A ¹ O is an ethyleneoxy group (EO). It is a compound (chemical formula: C ₁₂ H ₂₅ O(2EO)H), and the average number of added moles of the ethyleneoxy group (EO) is 2 mol/chain on average for the entire compound obtained.

Next, 3 parts by mass of the ethylene oxide (2) adduct of lauryl alcohol obtained above as the alkylene oxide low-molar adduct and the stearyl alcohol obtained in Synthesis Example 1 as the fatty alcohol alkylene oxide high-molar adduct. 70 parts by mass of ethylene oxide (46) and propylene oxide (34) adducts were added to water and stirred and mixed to obtain a total of 100 parts by mass of a release agent for vulcanized rubber. The releasability, washability and anti-soil redeposition properties of the resulting vulcanized rubber release agent were evaluated according to the methods described above.

(Examples A2 to A4 and Comparative Example A1)
First, in the same manner as in Example A1, except that the amounts of raw material alcohol, 48% by mass potassium hydroxide aqueous solution, EO as A ¹ O, and 99% by mass acetic acid were set to the amounts shown in Table 1 below. Each alkylene oxide low molar adduct described in 2 was synthesized. In Table 2, the number in parentheses ("()") in the name of each alkylene oxide adduct indicates the average number of added moles per molecule of the entire compound of the added alkyleneoxy group, and , The unit delimited by parentheses ("()") in the chemical formula indicates the addition unit of the alkyleneoxy group, and the number in the parentheses is the average addition per molecule of the added alkyleneoxy group as a whole compound The average number of moles added per alkylene oxide chain is shown, and the slashes ("/") between alkyleneoxy groups indicate random addition of these alkyleneoxy groups (the same applies hereinafter).

Next, each release agent for vulcanized rubber was obtained in the same manner as in Example A1, except that the obtained alkylene oxide low-molar adducts were used and the compositions shown in Table 2 below were used. The releasability, washability and anti-soil redeposition properties of each of the obtained release agents for vulcanized rubber were evaluated according to the methods described above.

(Example A5)
First, a 1 L autoclave was charged with 213 g of lauryl alcohol (“Conol 20P” manufactured by Shin Nippon Rika Co., Ltd.) as a raw material alcohol and 0.89 g of a 48% by mass potassium hydroxide aqueous solution as a catalyst, and the inside of the reactor was sufficiently filled with nitrogen. After substituting with , the temperature was raised and dehydration was performed under reduced pressure. After reaching 120° C., dropwise addition of a mixture of 200 g of ethylene oxide (EO as A ¹ O) and 198 g of propylene oxide (PO as A ¹ O) was started at the same temperature, and the pressure was 0 to 0.5 MPa. React within range. After dropping the entire amount of ethylene oxide, the mixture was aged for 1 hour until the pressure did not decrease. After cooling, 0.30 g of 99% by weight acetic acid was added at 50° C. to neutralize the catalyst, thereby obtaining 612 g of the desired compound, ethylene oxide (4) propylene oxide (3) adduct of lauryl alcohol. The resulting ethylene oxide (4) propylene oxide (3) adduct of lauryl alcohol has a structure in which R ¹ in the general formula (1) is an alkyl group having 12 carbon atoms, X is —O—, and A ¹ O is ethyleneoxy. A compound (chemical formula: C ₁₂ H ₂₅ O(4EO/3PO)H) which is an alkyleneoxy group in which a group (EO) and a propyleneoxy group (PO) are randomly co-added, and the alkyleneoxy group (A ¹ O) is 4 mol/chain of ethyleneoxy group (EO) and 3 mol/chain of propyleneoxy group (PO) as an average of the entire compound obtained.

Next, 3 parts by mass of the ethylene oxide (4) propylene oxide (3) adduct of lauryl alcohol obtained above as the alkylene oxide low molar adduct and the aliphatic alcohol alkylene oxide high molar adduct obtained in Synthesis Example 1 70 parts by mass of the stearyl alcohol ethylene oxide (46) propylene oxide (34) adduct was added to water and stirred and mixed to obtain a total of 100 parts by mass of a release agent for vulcanized rubber. rice field. The releasability, washability and anti-soil redeposition properties of the resulting vulcanized rubber release agent were evaluated according to the methods described above.

(Examples A6 to A7)
First, the same procedure as in Example A5 was performed except that the raw material alcohol, 48% by mass aqueous potassium hydroxide solution, EO and PO as A ¹ O, and 99% by mass acetic acid were charged in amounts shown in Table 1 below. Each of the alkylene oxide low molar adducts listed in Table 2 was synthesized.

Next, each release agent for vulcanized rubber was obtained in the same manner as in Example A5, except that the obtained alkylene oxide low-molar adduct was used and the composition shown in Table 2 below was used. The releasability, washability and anti-soil redeposition properties of each of the obtained release agents for vulcanized rubber were evaluated according to the methods described above.

(Example A8 and Comparative Example A2)
First, as the raw material alcohol, in Example A8, oleyl alcohol (“Rikacol 60B” manufactured by Shin Nippon Rika Co., Ltd.) was used, and in Comparative Example A2, tristyrenated phenol (Sanko Co., Ltd. “TSP”) was used. Table 1 was carried out in the same manner as in Example A1, except that the amounts of raw material alcohol, 48% by mass aqueous potassium hydroxide solution, EO as A ¹ O, and 99% by mass acetic acid were set to the amounts shown in Table 1 below. Each alkylene oxide low molar adduct described in 2 was synthesized.

Next, each release agent for vulcanized rubber was obtained in the same manner as in Example A1, except that the obtained alkylene oxide low-molar adducts were used and the compositions shown in Table 2 below were used. The releasability, washability and anti-soil redeposition properties of each of the obtained release agents for vulcanized rubber were evaluated according to the methods described above.

(Example A9)
A release agent for vulcanized rubber was obtained in the same manner as in Example A1 except that the composition shown in Table 2 below was used. The releasability, washability and anti-soil redeposition properties of the resulting vulcanized rubber release agent were evaluated according to the methods described above.

(Example B1)
First, coconut amine ("Furmin CS" manufactured by Kao Corporation) as a raw material amine in a 1 L autoclave, main alkyl composition: C8 (7%), C10 (7%), C12 (51%), C14 (19%) . After reaching 120°C, dropwise addition of 156 g of ethylene oxide (EO as A ¹ O) was started, and the reaction was carried out at a pressure within the range of 0-0.5 MPa while maintaining the temperature at 120-150°C. After dropping the entire amount of ethylene oxide, the mixture was aged for 1 hour until the pressure did not decrease. After cooling, 506 g of an ethylene oxide (2) adduct of coconut amine, which is the target compound, was obtained. The obtained ethylene oxide (2) adduct of coconut amine is such that R ¹ in the general formula (1) is an alkyl group derived from coconut amine, X is -N(R ¹¹ )-[R ¹¹ is - (A ¹ O) _q H], a compound (chemical formula: R ¹ N[(1EO)H] ₂ ) in which A ¹ O is an ethyleneoxy group (EO), and the average addition mole of the ethyleneoxy group (EO) The number is 2 mol per molecule as an average for the entire compound obtained, or 1 mol/chain when converted to one alkylene oxide chain.

Next, 3 parts by mass of the ethylene oxide (2) adduct of coconut amine obtained above as the alkylene oxide low molar adduct, and the stearyl alcohol obtained in Synthesis Example 1 as the fatty alcohol alkylene oxide high molar adduct and 70 parts by mass of the ethylene oxide (46) propylene oxide (34) adduct of No. 1 were added to water and stirred and mixed to obtain a total of 100 parts by mass of a release agent for vulcanized rubber. The releasability, washability and anti-soil redeposition properties of the resulting vulcanized rubber release agent were evaluated according to the methods described above.

(Example B2)
First, coconut amine ("Furmin CS" manufactured by Kao Corporation) as a raw material amine in a 1 L autoclave, main alkyl composition: C8 (7%), C10 (7%), C12 (51%), C14 (19%) . After reaching 120°C, dropwise addition of 89 g of ethylene oxide (EO as A ¹ O) was started, and the reaction was carried out at a pressure of 0 to 0.5 MPa while maintaining the temperature at 120 to 150°C. After dropping the entire amount of ethylene oxide, the mixture was aged for 1 hour until the pressure did not decrease. After cooling, 0.62 g of a 48% by mass potassium hydroxide aqueous solution as a catalyst was charged at 50° C., the inside of the reactor was sufficiently replaced with nitrogen, the temperature was raised, and dehydration was performed under reduced pressure. After reaching 120° C., dropwise addition of 134 g of ethylene oxide (EO as A ¹ O) was started, and the reaction was carried out at a pressure within the range of 0 to 0.5 MPa. After dropping the entire amount of ethylene oxide, the mixture was aged for 1 hour until the pressure did not decrease. After cooling, 0.32 g of 99% by mass acetic acid was added at 50° C. to neutralize the catalyst, and 424 g of an ethylene oxide (5) adduct of coconut amine, which was the desired compound, was obtained. The obtained ethylene oxide (5) adduct of coconut amine is such that R ¹ in the general formula (1) is an alkyl group derived from coconut amine, X is -N(R ¹¹ )-[R ¹¹ is - (A ¹ O) _q H], a compound in which A ¹ O is an ethyleneoxy group (EO) (chemical formula: R ¹ N[(2.5EO)H] ₂ ); The number of added moles is 5 mol per molecule on average for the entire compound obtained, which is 2.5 mol/chain when converted to one alkylene oxide chain.

Next, 3 parts by mass of the ethylene oxide (5) adduct of coconut amine obtained above as the alkylene oxide low molar adduct, and the stearyl alcohol obtained in Synthesis Example 1 as the aliphatic alcohol alkylene oxide high molar adduct and 70 parts by mass of the ethylene oxide (46) propylene oxide (34) adduct of No. 1 were added to water and stirred and mixed to obtain a total of 100 parts by mass of a release agent for vulcanized rubber. The releasability, washability and anti-soil redeposition properties of the resulting vulcanized rubber release agent were evaluated according to the methods described above.

(Examples B3 to B4 and Comparative Example B1)
First, the amounts of the raw material amine, 48% by mass potassium hydroxide aqueous solution, EO as A ¹ O, and 99% by mass acetic acid were set to the amounts shown in Table 3 below, respectively, in the same manner as in Example B2. Each alkylene oxide low molar adduct described in 4 was synthesized.

Next, each release agent for vulcanized rubber was obtained in the same manner as in Example B2, except that the obtained alkylene oxide low-molar adduct was used and the composition shown in Table 4 below was used. The releasability, washability and anti-soil redeposition properties of each of the obtained release agents for vulcanized rubber were evaluated according to the methods described above.

(Example B5)
First, coconut amine ("Furmin CS" manufactured by Kao Corporation) as a raw material amine in a 1 L autoclave, main alkyl composition: C8 (7%), C10 (7%), C12 (51%), C14 (19%) . After reaching 120°C, dropwise addition of 89 g of ethylene oxide (EO as A ¹ O) was started, and the reaction was carried out at a pressure of 0 to 0.5 MPa while maintaining the temperature at 120 to 150°C. After dropping the entire amount of ethylene oxide, the mixture was aged for 1 hour until the pressure did not decrease. After cooling, 0.81 g of a 48% by mass potassium hydroxide aqueous solution as a catalyst was charged at 50° C., the inside of the reactor was sufficiently replaced with nitrogen, the temperature was raised, and dehydration was performed under reduced pressure. After reaching 120°C, dropwise addition of a mixture of 89 g of ethylene oxide (EO as A ¹ O) and 177 g of propylene oxide (PO as A ¹ O) was started, and the reaction was performed at a pressure within the range of 0 to 0.5 MPa. let me After dropping the entire amount of ethylene oxide and propylene oxide, the mixture was aged for 1 hour until the pressure did not decrease. After cooling, 0.42 g of 99% by mass acetic acid was added at 50° C. to neutralize the catalyst, thereby obtaining 557 g of the target compound, ethylene oxide (4) propylene oxide (3) adduct of coconut amine. . The obtained ethylene oxide (4) propylene oxide (3) adduct of coconut amine is such that R ¹ in the general formula (1) is an alkyl group derived from coconut amine and X is -N(R ¹¹ )- [R ¹¹ is -(A ¹ O) _q H], A ¹ O is a single addition of an ethyleneoxy group (EO), and a random co-addition of an ethyleneoxy group (EO) and a propyleneoxy group (PO) A compound that is an alkyleneoxy group (chemical formula: R ¹ N[(1EO)(1EO/1.5PO)H] ₂ ), and the average added mole number of the singly added ethyleneoxy group (EO) was The average of the entire compound is 2 mol per molecule, which is 1 mol/chain when converted to one alkylene oxide chain, and the average number of moles of the co-added ethyleneoxy group (EO) is On average, it is 2 mol per molecule, which is 1 mol/chain when converted to one alkylene oxide chain, and the average number of moles of the co-added propyleneoxy group (PO) is, as an average of the entire compound obtained, It is 3 mol per molecule, which is 1.5 mol/chain when converted to one alkylene oxide chain.

Next, 3 parts by mass of the ethylene oxide (4) propylene oxide (3) adduct of coconut amine obtained above as the alkylene oxide low molar adduct and the aliphatic alcohol alkylene oxide high molar adduct in Synthesis Example 1 Using 70 parts by mass of the obtained ethylene oxide (46) propylene oxide (34) adduct of stearyl alcohol, these are added to water and stirred and mixed to obtain a total of 100 parts by mass of a release agent for vulcanized rubber. Obtained. The releasability, washability and anti-soil redeposition properties of the resulting vulcanized rubber release agent were evaluated according to the methods described above.

(Examples B6-B7)
First, the same procedure as in Example B5 was performed except that the amounts of the raw material amine, 48% by mass aqueous potassium hydroxide solution, EO and PO as A ¹ O, and 99% by mass acetic acid were set to the amounts shown in Table 3 below. Each of the alkylene oxide low molar adducts listed in Table 4 was synthesized.

Next, each release agent for vulcanized rubber was obtained in the same manner as in Example B5, except that the obtained alkylene oxide low-molar adduct was used and the composition shown in Table 4 below was used. The releasability, washability and anti-soil redeposition properties of each of the obtained release agents for vulcanized rubber were evaluated according to the methods described above.

(Examples B8 to B9 and Comparative Example B2)
First, as raw material amines, octylamine (“Farmin 08D” manufactured by Kao Corporation) was used in Example B8, and oleylamine (“Farmin OV” manufactured by Kao Corporation) was used in Example B9. , in Comparative Example B2, cyclohexylamine (reagent) was used, and the amounts of the raw material amine, 48% by mass potassium hydroxide aqueous solution, EO as A ¹ O, and 99% by mass acetic acid are shown in Table 3 below. Each alkylene oxide low molar adduct shown in Table 4 was synthesized in the same manner as in Example B2 except that the amount was changed.

Next, each release agent for vulcanized rubber was obtained in the same manner as in Example B2, except that the obtained alkylene oxide low-molar adduct was used and the composition shown in Table 4 below was used. The releasability, washability and anti-soil redeposition properties of each of the obtained release agents for vulcanized rubber were evaluated according to the methods described above.

(Example B10)
A release agent for vulcanized rubber was obtained in the same manner as in Example B1 except that the composition shown in Table 4 below was used. The releasability, washability and anti-soil redeposition properties of the resulting vulcanized rubber release agent were evaluated according to the methods described above.

(Example C1)
First, a 1 L autoclave was charged with 214 g of methyl laurate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a raw material carboxylic acid ester, 106 g of diethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a raw material alkanolamine, and sodium methylate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a catalyst. 28% methanol solution) (3.92 g) was charged, and the inside of the reactor was sufficiently replaced with nitrogen. After raising the temperature to 90° C. in a nitrogen atmosphere, the pressure was reduced to −0.09 MPaG in 1 hour, and aging was performed in this state for 2 hours. After cooling, 1.23 g of 99% by mass acetic acid was added at 50° C. to neutralize the catalyst, and 323 g of the desired compound, ethylene oxide (2) adduct of lauric acid amide was obtained. The resulting ethylene oxide (2) adduct of lauric acid amide is such that R ¹ in the general formula (1) is an alkyl group having 11 carbon atoms, X is —CON(R ¹² )—[R ¹² is —(A ¹ O) _q H], a compound in which A ¹ O is an ethyleneoxy group (EO) (chemical formula: C ₁₁ H ₂₃ CON[(1EO)H] ₂ ), wherein the average addition mole of the ethyleneoxy group (EO) The number is 2 mol per molecule as an average for the entire compound obtained, or 1 mol/chain when converted to one alkylene oxide chain.

Next, 3 parts by mass of the ethylene oxide (2) adduct of lauric acid amide obtained above as the alkylene oxide low molar adduct, and the stearyl alcohol obtained in Synthesis Example 1 as the fatty alcohol alkylene oxide high molar adduct and 70 parts by mass of the ethylene oxide (46) propylene oxide (34) adduct of No. 1 were added to water and stirred and mixed to obtain a total of 100 parts by mass of a release agent for vulcanized rubber. The releasability, washability and anti-soil redeposition properties of the resulting vulcanized rubber release agent were evaluated according to the methods described above.

(Example C2)
First, a 1 L autoclave was charged with 214 g of methyl laurate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a raw material carboxylic acid ester, 106 g of diethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a raw material alkanolamine, and sodium methylate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a catalyst. A 28% methanol solution) (5.71 g) was charged, and the inside of the reactor was sufficiently replaced with nitrogen. After raising the temperature to 90° C. in a nitrogen atmosphere, the pressure was reduced to −0.09 MPaG in 1 hour, and aging was performed in this state for 2 hours. After introducing nitrogen into the reactor and returning the pressure to normal pressure, the temperature was raised to 130° C., 132 g of ethylene oxide (EO as A ¹ O) was added dropwise, and the pressure was within the range of 0 to 0.5 MPa. reacted. After dropping the entire amount of ethylene oxide, the mixture was aged for 1 hour until the pressure did not decrease. After cooling, 1.80 g of 99% by mass acetic acid was added at 50° C. to neutralize the catalyst, thereby obtaining 424 g of the target compound, ethylene oxide (5) adduct of lauric acid amide. The resulting ethylene oxide (5) adduct of lauric acid amide is such that R ¹ in the general formula (1) is an alkyl group having 11 carbon atoms, X is —CON(R ¹² )—[R ¹² is —(A ¹ O) _q H], a compound in which A ¹ O is an ethyleneoxy group (EO) (chemical formula: C ₁₁ H ₂₃ CON[(2.5EO)H] ₂ ), and the average of the ethyleneoxy groups (EO) The number of added moles is 5 mol per molecule on average for the entire compound obtained, which is 2.5 mol/chain when converted to one alkylene oxide chain.

Next, 3 parts by mass of the ethylene oxide (5) adduct of lauric acid amide obtained above as the alkylene oxide low molar adduct, and the stearyl alcohol obtained in Synthesis Example 1 as the fatty alcohol alkylene oxide high molar adduct and 70 parts by mass of the ethylene oxide (46) propylene oxide (34) adduct of No. 1 were added to water and stirred and mixed to obtain a total of 100 parts by mass of a release agent for vulcanized rubber. The releasability, washability and anti-soil redeposition properties of the resulting vulcanized rubber release agent were evaluated according to the methods described above.

(Examples C3 to C4 and Comparative Example C1)
First, the amounts of the raw material carboxylic acid ester, raw material alkanolamine, sodium methylate (28% methanol solution), EO as A ¹ O, and 99% by mass acetic acid were set to the amounts shown in Table 5 below. Each alkylene oxide low molar adduct listed in Table 6 was synthesized in the same manner as in Example C2.

Next, each release agent for vulcanized rubber was obtained in the same manner as in Example C2, except that the obtained alkylene oxide low-molar adduct was used and the composition shown in Table 6 below was used. The releasability, washability and anti-soil redeposition properties of each of the obtained release agents for vulcanized rubber were evaluated according to the methods described above.

(Example C5)
First, a 1 L autoclave was charged with 214 g of methyl laurate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a raw material carboxylic acid ester, 106 g of diethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a raw material alkanolamine, and sodium methylate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a catalyst. 28% methanol solution) was charged, and the inside of the reactor was sufficiently replaced with nitrogen. After raising the temperature to 90° C. in a nitrogen atmosphere, the pressure was reduced to −0.09 MPaG in 1 hour, and aging was performed in this state for 2 hours. After introducing nitrogen into the reactor and returning the pressure to normal, the temperature was raised to 130° C., and a mixture of 44 g of ethylene oxide (EO as A ¹ O) and 117 g of propylene oxide (PO as A ¹ O) was added. It was added dropwise and reacted within a pressure range of 0 to 0.5 MPa. After dropping the entire amount of ethylene oxide and propylene oxide, the mixture was aged for 1 hour until the pressure did not decrease. After cooling, 1.92 g of 99% by mass acetic acid was added at 50° C. to neutralize the catalyst, and 453 g of the desired compound ethylene oxide (3) propylene oxide (2) adduct of lauric acid amide was obtained. . The resulting ethylene oxide (3) propylene oxide (2) adduct of lauric acid amide is such that R ¹ in the general formula (1) is an alkyl group having 11 carbon atoms, X is —CON(R ¹² )—[R ¹² is -(A ¹ O) _q H], A ¹ O is an alkyleneoxy group obtained by the single addition of an ethyleneoxy group (EO) and the random co-addition of an ethyleneoxy group (EO) and a propyleneoxy group (PO). group (chemical formula: C ₁₁ H ₂₃ CON[(1EO)(0.5EO/1PO)H] ₂ ), and the average added mole number of the singly added ethyleneoxy groups (EO) was obtained The average of the entire compound is 2 mol per molecule, which is 1 mol/chain when converted to one alkylene oxide chain, and the average number of moles of the co-added ethyleneoxy group (EO) is On average, it is 1 mol per molecule, which is 0.5 mol/chain when converted to one alkylene oxide chain. 2 mol per molecule, which is 1 mol/chain when converted to one alkylene oxide chain.

Next, 3 parts by mass of the ethylene oxide (3) propylene oxide (2) adduct of lauric acid amide obtained above as the alkylene oxide low molar adduct and the aliphatic alcohol alkylene oxide high molar adduct in Synthesis Example 1 Using 70 parts by mass of the obtained ethylene oxide (46) propylene oxide (34) adduct of stearyl alcohol, these are added to water and stirred and mixed to obtain a total of 100 parts by mass of a release agent for vulcanized rubber. Obtained. The releasability, washability and anti-soil redeposition properties of the resulting vulcanized rubber release agent were evaluated according to the methods described above.

(Examples C6-C7)
First, the amounts of the raw material carboxylic acid ester, raw material alkanolamine, sodium methylate (28% methanol solution), EO and PO as A ¹ O, and 99% by mass acetic acid were set to the amounts shown in Table 5 below. Each alkylene oxide low molar adduct shown in Table 6 was synthesized in the same manner as in Example C5 except for the above.

Next, each release agent for vulcanized rubber was obtained in the same manner as in Example C5, except that the obtained alkylene oxide low-molar adduct was used and the composition shown in Table 6 below was used. The releasability, washability and anti-soil redeposition properties of each of the obtained release agents for vulcanized rubber were evaluated according to the methods described above.

(Examples C8-C9)
First, as the raw material carboxylic acid ester, in Example C8, methyl octanoate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used, and in Example C9, methyl oleate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used. was used, and the amounts of the raw material carboxylic acid ester, raw material alkanolamine, sodium methylate (28% methanol solution), and 99% by mass acetic acid were set to the amounts shown in Table 5 below, respectively. Each of the alkylene oxide low molar adducts listed in Table 6 was synthesized as follows.

Next, each release agent for vulcanized rubber was obtained in the same manner as in Example C1, except that the obtained alkylene oxide low-molar adduct was used and the composition shown in Table 6 below was used. The releasability, washability and anti-soil redeposition properties of each of the obtained release agents for vulcanized rubber were evaluated according to the methods described above.

(Example C10)
A release agent for vulcanized rubber was obtained in the same manner as in Example C1 except that the composition shown in Table 6 below was used. The releasability, washability and anti-soil redeposition properties of the resulting vulcanized rubber release agent were evaluated according to the methods described above.

(Comparative Example C2)
First, a 1 L autoclave was charged with 121 g of benzamide (manufactured by Tokyo Chemical Industry Co., Ltd.) as a starting amide and 0.30 g of a 48% by mass aqueous solution of potassium hydroxide as a catalyst. It was warmed and dehydrated under reduced pressure. After the temperature reached 130° C., 88 g of ethylene oxide (EO as A ¹ O) was started to drop, and the reaction was carried out at a pressure of 0 to 0.5 MPa. After dropping the entire amount of ethylene oxide, the mixture was aged for 1 hour until the pressure did not decrease. After cooling, 0.16 g of 99% by mass acetic acid was added at 50° C. to neutralize the catalyst, thereby obtaining 209 g of an ethylene oxide (2) adduct of benzamide, which is the desired compound. In the obtained ethylene oxide (2) adduct of benzamide, the alkyl group or the like represented by R ¹ in the general formula (1) is replaced with a phenyl group, and X is -CON(R ¹² )-[R ¹² is - (A ¹ O) _q H], a compound in which A ¹ O is an ethyleneoxy group (EO) (chemical formula: C ₆ H ₅ CON[(1EO)H] ₂ ), and the average of the ethyleneoxy groups (EO) The number of added moles is 2 mol per molecule as an average of the whole compound obtained, which is 1 mol/chain when converted to one alkylene oxide chain.

Next, 3 parts by mass of the ethylene oxide (3) propylene oxide (2) adduct of lauric acid amide obtained above as the alkylene oxide low molar adduct and the aliphatic alcohol alkylene oxide high molar adduct in Synthesis Example 1 Using 70 parts by mass of the obtained ethylene oxide (46) propylene oxide (34) adduct of stearyl alcohol, these are added to water and stirred and mixed to obtain a total of 100 parts by mass of a release agent for vulcanized rubber. Obtained. The releasability, washability and anti-soil redeposition properties of the resulting vulcanized rubber release agent were evaluated according to the methods described above.

(Comparative Example C3)
First, 200 g of diethylene glycol (manufactured by Mitsubishi Chemical Corporation) as a raw material alcohol and 0.31 g of potassium hydroxide (flakes) as a catalyst were charged in a 1 L autoclave, and the inside of the reactor was sufficiently replaced with nitrogen, and then the temperature was raised. , dehydrated under reduced pressure. After the temperature reached 120, dropwise addition of ethylene oxide (EO as A ¹ O) was started, and the reaction was carried out at a pressure of 0 to 0.5 MPa while maintaining the temperature at 120 to 150°C. After dropping the entire amount of ethylene oxide, the mixture was aged for 1 hour until the pressure did not decrease. After cooling, 0.34 g of 99% by mass acetic acid was added at 50° C. to neutralize the catalyst, and 449 g of polyethylene glycol (PEG240) was obtained.

Next, in a 1 L autoclave, 400 g of the polyethylene glycol (PEG240) obtained above as a raw material alcohol, 167.92 g of lauric acid (“lauric acid P” manufactured by Shin Nippon Rika Co., Ltd.) as a raw material carboxylic acid, and paratoluene sulfone as a catalyst 2.84 g of acid monohydrate was charged, and the reaction solution was stirred while nitrogen was passed through it at 10 ml/min, heated to 110° C., and dehydrated for 30 minutes. After that, the temperature was raised to 210°C while nitrogen flow was continued, and a dehydration reaction was performed for 6 hours until the acid value became 4.0 mgKOH/g or less. 550 g was obtained. In the obtained ethylene oxide (5) adduct of lauric acid, R ¹ in the general formula (1) is an alkyl group having 11 carbon atoms, and -CON(R ¹² )- as X is -COO- A ¹ O is an ethyleneoxy group (EO) (chemical formula: C ₁₁ H ₂₃ COO(5EO)H), and the average number of added moles of the ethyleneoxy group (EO) is The overall average is 5 mol/chain.

Next, 3 parts by mass of the ethylene oxide (5) adduct of lauric acid obtained above as the alkylene oxide low-molar adduct and the stearyl alcohol obtained in Synthesis Example 1 as the fatty alcohol alkylene oxide high-molar adduct. 70 parts by mass of ethylene oxide (46) and propylene oxide (34) adducts were added to water and stirred and mixed to obtain a total of 100 parts by mass of a release agent for vulcanized rubber. The releasability, washability and anti-soil redeposition properties of the resulting vulcanized rubber release agent were evaluated according to the methods described above.

(Synthesis Examples 2-9 and Comparative Synthesis Examples 1-4)
Synthesis Example 1 was the same as in Synthesis Example 1, except that the starting alcohol, 48% by mass aqueous potassium hydroxide solution, initial PO, EO and PO as A ² O, and 99% by mass acetic acid were charged in amounts shown in Table 7 below. In the same manner, each alkylene oxide high molar adduct represented by the chemical formula shown in Table 7 was synthesized. As the raw material alcohol, in Synthesis Example 8, behenyl alcohol (“Conol 2280” manufactured by Shin Nippon Rika Co., Ltd.) is used, and in Synthesis Example 9, oleyl alcohol (“Licacol 60B” manufactured by Shin Nippon Rika Co., Ltd.) is used. However, in Comparative Synthesis Examples 3 and 4, 1-butanol (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used.

(Comparative Synthesis Example 5)
A 5 L autoclave was charged with 90 g of ethylenediamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a raw material amine and 37.48 g of a 48% by mass aqueous solution of potassium hydroxide as a catalyst, and the inside of the reactor was sufficiently purged with nitrogen and then heated. It was warmed and dehydrated under reduced pressure. After the temperature reached 120°C, dropwise addition of 3480 g of propylene oxide was started as the first PO, and the temperature was kept at 120°C and the reaction was carried out under a pressure within the range of 0 to 0.2 MPa. After dropping the entire amount of propylene oxide, the mixture was aged for 1 hour until the pressure did not decrease. Then, 427 g of ethylene oxide (EO in A ² O) was added dropwise thereto at the same temperature, and the mixture was reacted at a pressure of 0 to 0.2 MPa, and aged for 1 hour until the pressure no longer decreased. After cooling, 19.45 g of 99% by weight acetic acid was added at 50° C. to neutralize the catalyst to obtain 4035 g of the desired compound, ethylene oxide (8) propylene oxide (40) adduct of ethylene diamine. The resulting ethylene oxide (8) propylene oxide (40) adduct of ethylene diamine has the following formula:
[ _H (2EO)(10PO)] _2NC2H4N [(10PO)(2EO)H _{] 2}
is a compound having an alkyleneoxy group in which a propyleneoxy group (PO) is singly added and an ethyleneoxy group (EO) is singly added, and the average number of added moles of the ethyleneoxy group (EO) is The average of the entire compound obtained is 8 mol per molecule, which is 2 mol/chain when converted to one alkylene oxide chain. 40 mol per molecule, or 10 mol/chain when converted to one alkylene oxide chain.

(Comparative Synthesis Example 6)
The same as Comparative Synthesis Example 5 except that the amounts of the raw material amine, 48% by mass potassium hydroxide aqueous solution, initial PO, EO as A ² O, and 99% by mass acetic acid were set to the amounts shown in Table 7 below. Then, alkylene oxide high molar adducts represented by the chemical formulas shown in Table 7 were synthesized.

(Comparative Synthesis Example 7)
Using glycerin monostearate as a raw material glycerin fatty acid ester instead of a raw material amine, charging raw material glycerin fatty acid ester, 48% by mass potassium hydroxide aqueous solution, initial PO, EO as A ² O, and 99% by mass acetic acid An alkylene oxide high-molar adduct represented by the following formula (3) was synthesized in the same manner as in Comparative Synthesis Example 5 except that the amounts were set to the amounts shown in Table 7 below.

(Examples D1 to D11)
The procedure was the same as in Example A2 except that each of the fatty alcohol alkylene oxide high molar adducts obtained in Synthesis Examples 1 to 9 was used as the fatty alcohol alkylene oxide high molar adduct and the composition shown in Table 8 below was used. to obtain each release agent for vulcanized rubber. The releasability, washability and anti-soil redeposition properties of each of the obtained release agents for vulcanized rubber were evaluated according to the methods described above.

(Comparative Examples D1 to D7)
The procedure was the same as in Example A2 except that each alkylene oxide high molar adduct obtained in Comparative Synthesis Examples 1 to 7 was used instead of the fatty alcohol alkylene oxide high molar adduct and the composition shown in Table 9 below was used. to obtain each release agent for vulcanized rubber. The releasability, washability and anti-soil redeposition properties of each of the obtained release agents for vulcanized rubber were evaluated according to the methods described above.

(Comparative Example D8)
A release agent for vulcanized rubber was obtained in the same manner as in Example A2, except that the composition shown in Table 9 below was used without using an aliphatic alcohol alkylene oxide high-molar adduct. The releasability, washability and anti-soil redeposition properties of the resulting vulcanized rubber release agent were evaluated according to the methods described above.

As described above, according to the present invention, it has excellent releasability and washability, and prevents whitening of the surface of vulcanized rubber products (excellent whitening prevention property) (especially white It is possible to obtain a release agent for vulcanized rubber that can prevent redeposition due to dirt (excellent redeposition prevention property). Therefore, since the method for producing a vulcanized rubber molded product of the present invention uses such a release agent for vulcanized rubber, it is a method for efficiently producing a vulcanized rubber product in which whitening of the surface is suppressed. Useful.

Claims (3)

The following general formula (1):

[In formula (1), R ¹ represents an alkyl group or alkenyl group having 4 to 32 carbon atoms, X represents -O-, -N(R ¹¹ )- or -CON(R ¹² )-, and R ¹¹ represents a hydrogen atom or -(A ¹ O) _q H, R ¹² represents a hydrogen atom, -(A ¹ O) _q H or an alkyl group having 1 to 3 carbon atoms, and each A ¹ O independently represents a carbon number 2 to 3 alkyleneoxy groups, p and q are the average number of added moles of the alkyleneoxy groups and each independently represent a number of 1 to 20, and the total of p and q is 1 to 20 . ]
and an alkylene oxide low molar adduct represented by
The following general formula (2):

[In formula (2), R ² represents an alkyl or alkenyl group having 14 to 22 carbon atoms, PO represents a propyleneoxy group, and A ² O each independently represents an alkyleneoxy group having 2 to 4 carbon atoms. , m is the average addition mole number of the propyleneoxy group and represents a number of 1 to 12, n is the average addition mole number of the alkyleneoxy group and represents a number of 23 to 199, and n and m is 35-200. However, this excludes the case where all of the multiple A ² O are propyleneoxy groups. ]
A release agent for vulcanized rubber characterized by containing an aliphatic alcohol alkylene oxide high molar adduct represented by. The mass ratio of the alkylene oxide low molar adduct represented by the general formula (1) and the aliphatic alcohol alkylene oxide high molar adduct represented by the general formula (2) is (1):(2)=0 The release agent for vulcanized rubber according to claim 1, wherein the ratio is 0.5:99.5 to 20:80. A step of vulcanizing the unvulcanized rubber in a state where the releasing agent for vulcanized rubber according to claim 1 or 2 adheres to the contact surface between the mold and the unvulcanized rubber. A method for producing a vulcanized rubber molded product.