Release agent composition and its use

Abstract

The present invention aims to provide a mold release agent composition that exhibits excellent release properties, sustained release effect, minimal transfer to the molded body, and good finish quality when forming a molded body using a mold. [Solution] A mold release agent composition comprising the following organosilicon compound (A) and the following silicone (B). Organosilicon compound (A): Contains R in the molecule 1 SiO 3 / 2 The T units and SiO shown are indicated by 4 / 2 It has at least one selected from the Q units shown, R 1 An organosilicon compound in which the is a monovalent organic group. Silicone (B): Silicone excluding organosilicon compounds (A).

Description

Technical Field

[0001] The present invention relates to a release agent composition and its use.

Background Art

[0002] Conventionally, when molding products made of rubber, resin, composite materials thereof, etc. by heat and pressure molding or vulcanization molding, in order to facilitate the removal of the molded product from the mold or resin mold, a release agent is applied in advance to the inner surface of the mold or resin mold or the surface of the molded product before vulcanization. <00,00098> As release agents, emulsion-based release agents are known, such as silicone emulsions and those obtained by adding powders of inorganic compounds with high lubricity, such as mica and talc, to silicone emulsions. Since they have high workability and safety, they are widely used. These release agents are usually applied and used every one molding or every two or three moldings. However, from the perspective of workability, the development of a release agent with a sustained release effect is desired.

[0004] In Patent Document 1, a silicone emulsion composition containing a silicone oil and a nonionic surfactant having a polyoxyalkylene unit is proposed as a release agent. However, during the molding of the molded body, the consumption of the silicone oil is severe, the release effect does not persist, the silicone oil adheres to the molded body, the molded product becomes sticky, and problems such as defects occur during subsequent painting or adhesion, resulting in a decrease in finish quality. In addition, in Patent Document 2, a release agent composition containing a liquefied silicone resin and a urethane resin-based aqueous dispersion is proposed.But for the formation of the film, high-temperature treatment is required, and additional treatment when the release effect is lost is difficult. In addition, the smoothness of the formed film is not sufficient, and there is a problem that the release effect does not persist in rubber materials that are difficult to peel off.

Prior Art Documents

Patent Documents

[0005] [Patent Document 1] Japanese Patent Publication No. 2002-129016 [Patent Document 2] Japanese Patent Publication No. 2009-137050 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a mold release agent composition that exhibits excellent release properties, sustained release effect, minimal transfer to the molded body, and good finish quality when forming a molded body using a mold. [Means for solving the problem]

[0007] As a result of diligent research, the inventors discovered that the above problems can be solved by a mold release agent composition containing specific components, and thus arrived at the present invention. In other words, the mold release agent composition of the present invention includes the following embodiments.

[0008] <1> A mold release agent composition comprising the following organosilicon compound (A) and the following silicone (B). Organosilicon compound (A): Contains R in the molecule 1 SiO 3 / 2 The T units and SiO shown are indicated by 4 / 2 It has at least one selected from the Q units shown, R 1 An organosilicon compound in which the is a monovalent organic group. Silicone (B): Silicone excluding organosilicon compounds (A). <2> The silanol group concentration of the organosilicon compound (A) is 15 mmol / g or less. <1> The mold release agent composition described above. <3> The organosilicon compound (A) is solid at 20°C. <1> or <2> The mold release agent composition described above. <4> The viscosity of the aforementioned silicone (B) at 25°C is 1 to 2 million mPa·s. <1> ~ <3> A mold release agent composition as described in any of the following. <5> Claim that the content of the silicone (B) is 10 to 10,000 parts by weight per 100 parts by weight of the organosilicon compound (A). <1> ~ <4> A mold release agent composition as described in any of the following. <6> The following polymer (C) is further included: <1> ~ <5> A mold release agent composition as described in any of the following. Polymer (C): A polymer having a structural unit (c1) having at least one selected from an acidic group and a group that is a salt of that acidic group. <7> The acidic group is at least one selected from a carboxyl group, a sulfate group, and a sulfonic acid group. <6> The mold release agent composition described above. <8> The structural unit (c1) is at least one selected from acrylic acid units, acrylic acid salt units, maleic anhydride units, maleic acid units, maleic acid salt units, sulfonic acid units, and sulfonate salt units. <6> or <7> The mold release agent composition described above. <9> Further containing surfactant (D), <1> ~ <8> A mold release agent composition as described in any of the following. <10> A method for manufacturing a molded article comprising steps (1) and (2), wherein step (1) is <1> ~ <8> A method for manufacturing a molded article, comprising the step of applying a mold release agent composition described in any of the above to the surface of a mold, wherein step (2) is a step of placing a raw material composition containing at least one selected from unvulcanized rubber and resin inside the mold after step (1), and heating and pressurizing the raw material composition. [Effects of the Invention]

[0009] The mold release agent composition of the present invention exhibits excellent mold release properties when forming a molded body using a mold, provides sustained mold release, minimizes transfer to the molded body, and results in a good finish for the molded body. The method for manufacturing a molded article of the present invention uses the above-mentioned mold release agent composition, making it possible to obtain a molded article with good finish quality. [Modes for carrying out the invention]

[0010] The details of the mold release agent composition according to the present invention will be described below. First, each component constituting the mold release agent composition will be described in detail.

[0011] [Organosilicon compound (A)] The organosilicon compound (A) that the release agent composition of the present invention essentially contains has R in the molecule 1 SiO 3 / 2 It has at least one selected from the T unit which is a siloxane unit represented by and the Q unit which is a siloxane unit represented by SiO 4 / 2 and is an organosilicon compound in which R 1 is a monovalent organic group. Hereinafter, the "T unit represented by R 1 SiO 3 / 2 " may be referred to as "T unit", and the "Q unit represented by SiO 4 / 2 " may be referred to as "Q unit". Compound (A) is a component that contributes to the coating property of the release agent composition.

[0012] R 1 possessed by the T unit is monovalent, and its carbon number is not particularly limited, but in terms of achieving the effects of the present application, it is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8. R 1 possessed by the T unit is not particularly limited, but in terms of achieving the effects of the present application, it is preferably an unsubstituted monovalent hydrocarbon group or a substituted monovalent hydrocarbon group, and more preferably an unsubstituted monovalent hydrocarbon group. Examples of the unsubstituted monovalent hydrocarbon group include, but are not particularly limited to, alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, cetyl group, stearyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group; alkenyl groups such as vinyl group, allyl group, isopronyl group, 1-butenyl group, 2-butenyl group; aryl groups such as phenyl group, vinylphenyl group, tolyl group, xylyl group, naphthyl group; aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, etc. There are no particular limitations on the substituted monovalent hydrocarbon group, but for example, a group having a substituent in which some or all of the hydrogen atoms bonded to the carbon atom of the above monovalent hydrocarbon group are substituted with other atoms or groups can be cited as a substituted monovalent hydrocarbon group. There are no particular limitations on the substituents in the substituted monovalent hydrocarbon group, but for example, halogen atoms such as chlorine atoms, fluorine atoms, and bromine atoms, hydroxyl groups, amino groups, vinyl groups, epoxy groups, glycidyloxy groups, mercapto groups, acryloyloxy groups, methacryloyloxy groups, carboxyl groups, cyano groups, isocyanate groups, etc. The R that the T unit possesses 1 It is preferable that it is an alkyl group having 1 to 18 carbon atoms.

[0013] The ratio of the number of at least one type of T unit and Q unit to the total number of siloxane units constituting compound (A) is not particularly limited, but is preferably 0.3 to 1, more preferably 0.4 to 0.9. When this ratio is 0.3 or higher, it tends to exhibit good coating properties and improved mold release persistence.

[0014] Compound (A) has T units, Q units, and a monovalent organic group R 2 and a monovalent organic group R 3 tr R 2 R 3 SiO 2 / 2 The D unit is a siloxane unit represented by and the R is a monovalent organic group. 4 and a monovalent organic group R 5 and a monovalent organic group R 6 trR 4 R 5 R 6 SiO 1 / 2 It may have at least one selected from the M units, which are siloxane units represented by . In the following, "R 2 R 3 The D unit represented by SiO2 / 2 is called the "D unit," and "R 4 R 5 R 6 SiO 1 / 2 The unit "M" shown is sometimes referred to simply as "M unit".

[0015] The R that the D unit possesses 2 and R 3 The number of carbon atoms is not particularly limited, but is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8, in that it improves the flexibility of the resulting coating. The R that the D unit possesses 2 and R 3 While there are no particular limitations, it is preferable that each be an unsubstituted monovalent hydrocarbon group or a substituted monovalent hydrocarbon group independently, in order to achieve the effects of the present invention. 2 and R 3 They may be the same or they may be different. There are no particular limitations on the unsubstituted and substituted monovalent hydrocarbon groups, but for example, the above-mentioned R in units of T. 1 Examples include: If compound (A) has T units and D units, R 1 ~R 3 They may be the same, some of them may be the same, or they may all be different.

[0016] The R that M units possess 4 and R 5 and R 6 The number of carbon atoms is not particularly limited, but is preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8, in that it improves the flexibility of the resulting coating. The R that M units possess 4 and R 5 and R 6 While there are no particular limitations, it is preferable that each be an unsubstituted monovalent hydrocarbon group or a substituted monovalent hydrocarbon group independently, in order to achieve the effects of the present invention. 4 and R 5 and R 6 They may be the same, one of them may be the same, or they may be different. There are no particular limitations on the unsubstituted and substituted monovalent hydrocarbon groups, but for example, the above-mentioned R in units of T. 1 Examples include: In compound (A), R 1 ~R 6They may be the same, some of them may be the same, or they may all be different.

[0017] When compound (A) contains at least one selected from D units and M units, there are no particular limitations, but the ratio of the number of at least one selected from D units and M units to the total number of siloxane units constituting compound (A) is preferably 0.1 to 0.7, more preferably 0.1 to 0.5. When this ratio is within the above range, embrittlement of the coating is suppressed and the release persistence tends to improve.

[0018] Compound (A) is not particularly limited, but it is preferable that its form be at least one selected from those consisting only of Q units and M units, those containing Q units and D units as essential, those containing T units and D units as essential, those containing T units and M units as essential, and those consisting only of T units, in order to obtain good coating properties.

[0019] Compound (A) may have a silanol group. The silanol group concentration of compound (A) is not particularly limited, but is preferably 15 mmol / g or less, more preferably 0.01 to 12 mmol / g, even more preferably 0.02 to 10 mmol / g, particularly preferably 0.03 to 8 mmol / g, and most preferably 0.05 to 5 mmol / g. When the silanol group concentration is 15 mmol / g or less, the adhesion to the mold tends to improve. The silanol group concentration of compound (A) is measured by IR (infrared spectrophotometer) within the characteristic absorption band of silanol groups, 4200-4800 cm⁻¹. -1 Or 6800~7400cm -1 The absorbance was measured, and the silanol group concentration (mmol / g) was determined by comparing the obtained absorbance with that of a standard substance with a known silanol group concentration.

[0020] The molecular weight of compound (A) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, even more preferably 3,000 to 30,000, particularly preferably 4,000 to 25,000, and most preferably 5,000 to 20,000. When the molecular weight is within the above range, the coating tends to be formed efficiently. Note that the molecular weight of compound (A) is the weight-average molecular weight, meaning the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography. Examples of compound (A) include silicone resins and silicone oligomers.

[0021] Compound (A) is not particularly limited, but it is preferable if it is a solid at 20°C, as this makes it less likely to transfer to the molded article and provides good coverage.

[0022] The organosilicon compound (A) can be obtained, for example, by hydrolyzing a silane compound A in which a hydrolyzable group is bonded to 3 to 4 silicon atoms in water. Commonly known methods can be used to hydrolyze silane compound A in water. For example, one method involves adding silane compound A dropwise to water while carrying out the hydrolysis reaction, or one involves mixing water and the silane compound together and then carrying out the hydrolysis reaction. Silane compound A, which is the raw material for organosilicon compound (A), undergoes a hydrolysis reaction in which most of its hydrolyzable groups are hydrolyzed, followed by a polymerization reaction. As a result, organosilicon compound (A) is substantially free of hydrolyzable groups.

[0023] The silane compound A, which is the raw material for organosilicon compound (A), is not particularly limited as long as it is a silane compound in which 3 to 4 hydrolyzable groups, such as chloro groups or alkoxy groups, are bonded to silicon atoms. Examples of silane compound A include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxylan, methyltriisopropoxysilane, methyltributoxylan, ethyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, cyclohexyltrichlorosilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and their partial hydrolysates. One or more of the above silane compound A may be used in combination.

[0024] The organosilicon compound (A) may also be prepared using silane compound B, which has one to two hydrolyzable groups bonded to silicon atoms, in addition to silane compound A. Silane compound B is not particularly limited as long as it is a silane compound in which one or two hydrolyzable groups, such as chloro or alkoxy groups, are bonded to silicon atoms. Examples of silane compound B include trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxylan, trimethylisopropoxysilane, dimethylphenylchlorosilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, dimethyldimethoxylane, dimethyldiethoxylan, dimethyldiisopropoxysilane, propylmethyldichlorosilane, propylmethyldimethoxysilane, propylmethyldiethoxysilane, hexylmethyldichlorosilane, hexylmethyldimethoxysilane, hexylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and their partial hydrolysates. One or more of the above silane compound B may be used in combination. For silane compounds A and B, methoxysilane and ethoxysilane are good choices due to their availability.

[0025] A hydrolysis catalyst may be used when carrying out the hydrolysis reaction. Conventional known catalysts can be used as the hydrolysis catalyst, and it is preferable to use an acidic catalyst or an alkaline catalyst. Examples of acidic catalysts include solid acids such as hydrogen halides, carboxylic acids, sulfonic acids, acidic or weakly acidic inorganic salts, and ion exchange resins. Examples of alkaline catalysts include alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate; alkali metal silanolates such as sodium silanolate and potassium silanolate; amines such as triethylamine, diethylamine, and aniline; and aqueous ammonia. There are no particular limitations on the amount of catalyst used, but it is preferable to adjust the pH of the aqueous solution to 2-7 or 7-12. After the reaction is complete, a neutralizing agent may be added to neutralize the acidic or alkaline catalyst as needed. Examples of neutralizing agents when using an acidic catalyst include ammonia, sodium carbonate, sodium bicarbonate, sodium hydroxide, and triethanolamine. Examples of neutralizing agents when using an alkaline catalyst include acetic acid, formic acid, phosphoric acid, and hydrochloric acid.

[0026] An aqueous solution containing a surfactant may be used to disperse the silane compound and the hydrolysis reaction product in water. There are no particular restrictions on the surfactants used, but examples include anionic surfactants such as alkyl sulfates, alkylbenzene sulfons, and alkyl phosphates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene oxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene fatty acid esters; cationic surfactants such as quaternary ammonium salts and alkylamine acetates; and amphoteric surfactants such as alkyl betaines and alkylimidazolines. One or more of these may be used in combination. Furthermore, surfactants that exhibit acidity or alkalinity can also be used as hydrolysis catalysts.

[0027] When hydrolyzing silane compounds in water, there are no particular limitations, but one method involves adding a hydrolysis catalyst or surfactant as needed to a mixture of water and the silane compound, and carrying out the hydrolysis reaction at 0-90°C for 10 minutes to 24 hours. Subsequently, an organosilicon compound (A) can be obtained by carrying out a neutralization reaction as needed. In addition, alcohols and neutralization salts produced as by-products of the hydrolysis reaction can be removed by vacuum distillation or filtration. Organic solvents may be used when hydrolyzing silane compounds. Examples of organic solvents include methanol, ethanol, propanol, acetone, methyl ethyl ketone, toluene, and xylene.

[0028] [Silicone (B)] The mold release agent composition of the present invention contains silicone (B). Silicone (B) is a silicone (organopolysiloxane) other than the organosilicon compound (A) described above. Silicone (B) does not have the T and Q units described above, and its main chain is usually composed mainly of D units. Silicone (B) is a component that contributes to the release properties of the release agent composition.

[0029] Examples of silicone (B) include silicone oil. Furthermore, there are no particular limitations on silicone (B), but examples include dialkylpolysiloxanes such as dimethylpolysiloxane, diethylpolysiloxane, methylisopropylpolysiloxane, and methyldodecylpolysiloxane; alkylphenylpolysiloxanes such as methylphenylpolysiloxane, dimethylsiloxane-methylphenylsiloxane copolymer, and dimethylsiloxane-diphenylsiloxane copolymer; alkylaralkylpolysiloxanes such as methyl(phenylethyl)polysiloxane and methyl(phenylpropyl)polysiloxane; and 3,3,3-trifluoropropylmethylpolysiloxane, and one or more of these may be used in combination.

[0030] While there are no particular limitations on silicone (B), it is preferable in terms of release properties if it has a linear molecular structure and is fluid at room temperature. The viscosity of silicone (B) at 25°C is not particularly limited, but is preferably 1 million to 2 million mPa·s, more preferably 1,000 to 1 million mPa·s, and even more preferably 5,000 to 500,000 mPa·s. When the viscosity is 100 mPa·s or higher, the stability of the release agent composition tends to improve. When the viscosity is 2 million mPa·s or lower, the release properties tend to improve. The viscosity of silicone (B) at 25°C is measured using a B-type viscometer (BL type, manufactured by Tokyo Keiki).

[0031] [Polymer (C)] The mold release agent composition of the present invention may contain, in addition to the organosilicon compound (A) and silicone (B), the following polymer (C). Polymer (C): A polymer having a structural unit (c1) having at least one selected from an acidic group and a group that is a salt of that acidic group. The release agent composition is preferable in that it contains polymer (C) because it improves the persistence of the release.

[0032] The acidic groups that the structural unit (c1) may have are not particularly limited, but examples include carboxyl groups, phosphate groups, sulfate groups, sulfonic acid groups, phenol groups, thiol groups, etc., and may consist of one or more of these groups. The acidic groups that the structural unit (c1) may have are not particularly limited, but it is preferable that it has at least one selected from a carboxyl group, a sulfate group, and a sulfonic acid group, as this improves the release persistence. The salts with acidic groups that the structural unit (c1) may have are not particularly limited, but examples include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; and ammonium salts, and may consist of one or more of these.

[0033] There are no particular limitations on the structural unit (c1), but examples include monocarboxylic acid units such as acrylic acid units, methacrylic acid units, ethacrylic acid units, crotonic acid units, and cinnamic acid units, and monocarboxylic acid salt units which are salts of these units; dicarboxylic acid units such as maleic acid units, itaconic acid units, fumaric acid units, citraconic acid units, and chloromaleic acid units, and dicarboxylic acid salt units which are salts of these units; dicarboxylic acid anhydride units such as maleic anhydride units; dicarboxylic acid monoester units such as monomethyl maleic acid units, monoethyl maleic acid units, monobutyl maleic acid units, monomethyl fumarate units, monoethyl fumarate units, monomethyl itaconic acid units, and monoethyl itaconic acid units, and dicarboxylic acid monoester salt units which are salts of these units; sulfonic acid units such as vinyl sulfonic acid, styrene sulfonic acid, naphthalene sulfonic acid, and Nt-butylacrylamide sulfonic acid, and sulfonate salt units which are salts of these units; and phosphate units such as vinylphosphonic acid, and phosphate salt units which are salts of these units. The unit may consist of one or more of these types. The structural unit (c1) is not particularly limited, but it is preferable that it be at least one selected from acrylic acid units, acrylic acid salt units, maleic anhydride units, maleic acid units, maleic acid salt units, sulfonic acid units, and sulfonate salt units, as this further improves mold release persistence.

[0034] The ratio of the number of structural units (c1) to the total number of all structural units constituting polymer (C) is not particularly limited, but is preferably 0.3 or more, more preferably 0.4 to 1, and even more preferably 0.5 to 0.9. When this ratio is 0.3 or more, the finish quality of the coating tends to improve.

[0035] The polymer (C) may have structural units other than structural unit (c1), such as (c2). The structural unit (c2) is not particularly limited, but examples include vinyl halide units such as vinyl chloride units and vinylidene chloride units; (meth)acrylic acid ester units such as methyl (meth)acrylate units, ethyl (meth)acrylate units, 2-hydroxyethyl (meth)acrylate units, hydroxypropyl (meth)acrylate units, and butyl (meth)acrylate units; vinyl ester units such as vinyl formate units and vinyl acetate units; styrene units that do not have acidic groups or groups that are salts thereof, such as styrene units, α-methylstyrene units, vinyltoluene units, t-butylstyrene units, and chloromethylstyrene units; and olefin units such as ethylene units, propylene units, n-butylene units, and isobutylene units. It may be composed of one or more of these. In this invention, the notation (meth)acrylic means acrylic or methacrylic. The structural unit (c2) is not particularly limited, but it is preferable that it be at least one selected from olefin units, styrene units that do not have acidic groups or salts thereof, and vinyl halogen units, as this improves the ability to form coatings.

[0036] If the polymer (C) further contains structural units (c2), the ratio of the number of structural units (c2) to the total number of structural units constituting the polymer (C) is not particularly limited, but is preferably 0.1 to 0.7, more preferably 0.2 to 0.6, and even more preferably 0.3 to 0.5. When this ratio is within the above range, the hardness of the coating tends to be appropriate.

[0037] The weight-average molecular weight of polymer (C) is not particularly limited, but is preferably 1,000 or more, more preferably 2,000 to 500,000, even more preferably 4,000 to 300,000, particularly preferably 5,000 to 100,000, and most preferably 5,000 to 50,000. When the weight-average molecular weight is 1,000 or more, it tends to impart sufficient hardness to the coating. Note that the weight-average molecular weight of polymer (C) refers to the weight-average molecular weight in terms of polystyrene, measured by gel permeation chromatography.

[0038] [Surfactants (D)] The mold release agent composition of the present invention may contain a surfactant (D). The inclusion of a surfactant (D) in the mold release agent composition is preferable because it can suppress liquid repellency when the mold release agent composition is applied. Examples of surfactant (D) include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, and one or more may be used in combination. There are no particular limitations on surfactant (D), but it is preferable that it be at least one selected from nonionic surfactants and anionic surfactants.

[0039] There are no particular limitations on nonionic surfactants, but examples include polyoxyalkylene alkyl ethers such as polyoxyethylene cetyl ether and polyoxyethylene lauryl ether; polyoxyalkylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether; polyoxyalkylene fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monooleate; polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate; polyoxyalkylene hydrogenated castor oil; polyoxyalkylene sorbitol fatty acid ester; polyglycerin fatty acid ester; alkylglycerin ether; polyoxyalkylene cholesteryl ether; alkyl polyglucoside; sucrose fatty acid ester; polyoxyalkylene alkylamine; oxyethylene-oxypropylene block polymer, etc., and one or more of these may be used in combination.

[0040] There are no particular limitations on the anionic surfactants, but examples include fatty acid salts such as sodium oleate, potassium palmitate, and triethanolamine oleate; alkyl sulfate esters such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium stearyl sulfate, and sodium cetyl sulfate; polyoxyalkylene alkyl ether acetates such as sodium polyoxyethylene tridecyl ether acetate; alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate; polyoxyalkylene alkyl ether sulfates; sodium stearoyl methyl taurate, sodium lauroyl methyl taurate, sodium myristoyl methyl taurate, and palmitoyl methyl taurate. Examples include higher fatty acid amide sulfonates such as sodium lauroyl sarcosinate; N-acyl sarcosinate salts such as sodium lauroyl sarcosinate; alkyl phosphates such as sodium monostearyl phosphate; polyoxyalkylene alkyl ether phosphate salts such as sodium polyoxyethylene oleyl ether phosphate and sodium polyoxyethylene stearyl ether phosphate; long-chain sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate and sodium dioctyl sulfosuccinate; long-chain N-acyl glutamate salts such as sodium N-lauroyl glutamate monosodium and disodium N-stearoyl-L-glutamate; and one or more of these may be used in combination.

[0041] There are no particular limitations on the cationic surfactant, but examples include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, and cetyltrimethylammonium bromide; dialkyldimethylammonium salts; trialkylmethylammonium salts; and alkylamine salts. One or more of these may be used in combination. There are no particular limitations on the amphoteric surfactants, but examples include imidazoline-based amphoteric surfactants such as 2-undecyl-N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium and 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt; betaine-based amphoteric surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amide betaine, and sulfobetaine; and amino acid-type amphoteric surfactants such as N-laurylglycine, N-lauryl-β-alanine, and N-stearyl-β-alanine. One or more of these may be used in combination.

[0042] The HLB value of surfactant (D) is not particularly limited, but a value of 6 to 16 is preferred in that it can suppress liquid repellency of the mold release agent composition and allow for more uniform coating. The HLB value is a numerical value from 1 to 20 that represents the degree of affinity of surfactant (D) to water and oil, with a smaller value indicating higher lipophilicity and a larger value indicating higher hydrophilicity. The HLB value of surfactant (D) can be calculated using the Griffin method (HLB value = 20 × sum of molecular weights of hydrophilic groups / molecular weight).

[0043] In addition to the above-mentioned organosilicon compounds (A), silicones (B), polymers (C), and surfactants (D), the mold release agent composition of the present invention may further contain other components such as defoaming agents, preservatives, curing catalysts, and water.

[0044] [Antifoaming agent] There are no particular limitations on the defoaming agent, but examples include: silicone-based defoaming agents such as polyether-modified silicone; oil-based defoaming agents such as castor oil, sesame oil, linseed oil, and animal and vegetable oils; fatty acid-based defoaming agents such as oleic acid; fatty acid ester-based defoaming agents such as isoamyl stearate, distearyl succinate, ethylene glycol distearate, and butyl stearate; and polyoxyalkylene monohydrate alcohols such as di-t-amylphenoxyethanol, 3-heptanol, and 2-ethylhexanol. Examples of antifoaming agents include: ethanol-based antifoaming agents; ether-based antifoaming agents such as di-t-amylphenoxyethanol, 3-heptylcellosolve, nonylcellosolve, and 3-heptylcarbitol; phosphate ester-based antifoaming agents such as tributylphosphate and tris(butoxyethyl)phosphate; amine-based antifoaming agents such as diamylamine; amide-based antifoaming agents such as polyalkyleneamide and acylate polyamine; sulfate-based antifoaming agents such as sodium lauryl sulfate; polyoxyalkylene-based antifoaming agents; and mineral oil.

[0045] [Preservatives] There are no particular limitations on preservatives, but examples include: thiazoles such as thiazole and 2-mercaptothiazole; thiocyanates such as methylene bisthiocyanate and ammonium thiocyanate; sulfimides such as o-benzoix sulfimide and phenylmercuric-o-benzoix sulfimide; alkyldialkylthiocarbamates such as methyldimethylthiocarbamate and ethyldiethyldithiocarbamate; thiraum sulfides such as tetramethylthiraum sulfide and tetraethylthiraum sulfide; thiraum disulfides such as tetramethylthiraum disulfide and tetraethylthiraum disulfide; dithiocarbamates such as ferric diethyldithiocarbamate and reed dimethyldithiocarbamate; sulfamides such as o-toluenesulfonamide and benzenesulfonanilide; and 1-aminonaphthyl- Examples include aminosulfonic acids such as 4-sulfonic acid and 1-amino-2-naphthol-4-sulfonic acid; phenols such as pentachlorophenol and o-phenylphenol and their alkali metal salts; chloride quinones such as tetrachloro-p-benzoquinone and 2,3-dichloro-1,4-naphthoquinone; nitro group-containing compounds such as dinitrocaprylphenylcrotonate and dinitro-o-cresol; triazines such as 1,3,5-trihydroxyethylhexahydro-1,3,5-triazine and 1,3,5-triethylhexahydro-1,3,5-triazine; organic mercury compounds such as phenylmercuric phthalate and o-hydroxyphenylmercuric chloride; amines such as p-aminoazobenzene and diphenylamine; amides such as cinnamanilide; and iodine-containing compounds such as 1,3-diiodo-2-propanol.

[0046] [Curing catalyst] There are no particular limitations on the curing catalyst, but examples include organotin compounds such as dibutyltin diacetate, dibutyltin dioctylate, and dibutyltin dilaurate; organoaluminum compounds such as aluminum tris(acetylacetone), aluminum tris(acetacetate ethyl), and aluminum diisopropoxy(acetacetate ethyl); zirconium (acetylacetone), zirconium tris(acetylacetone), zirconium tetrakis(ethylene glycol monomethyl ether), zirconium tetrakis(ethylene glycol monoethyl ether), zirconium tetrakis(ethylene glycol monobutyl ether), zirconium chloride, and zirconium lactate ammonium Examples include organozirconium compounds such as nium; organotitanium compounds such as titanium tetrakis (ethylene glycol monomethyl ether), titanium tetrakis (ethylene glycol monoethyl ether), titanium tetrakis (ethylene glycol monobutyl ether), titanium lactate, titanium lactate ammonium, and titanium diethanolamine; mineral acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid, and trifluoroacetic acid; inorganic bases such as ammonia, sodium hydroxide, and potassium hydroxide; organic bases such as ethylenediamine and alkanolamine; and amino compounds such as aminosilane, silazane, and amines. One or more of these may be used in combination. Among these, it is preferable that at least one is selected from organotin compounds, organoaluminum compounds, organotitanium compounds, mineral acids, and amino compounds.

[0047] [Release agent composition and method for producing the same] The mold release agent composition of the present invention essentially contains the organosilicon compound (A) and silicone (B) described above, and exhibits excellent mold release properties, sustained release effect, minimal transfer to the molded body, and good finish quality when forming a molded body using a mold. The above effects can be further exhibited when the mold release agent composition of the present invention is used for molds that are applied to the mold for treatment.

[0048] The weight percentage of organosilicon compound (A) in the nonvolatile content of the release agent composition of the present invention is not particularly limited, but is preferably 1 to 90% by weight, more preferably 5 to 85% by weight, even more preferably 10 to 80% by weight, and most preferably 15 to 75% by weight. When the weight percentage is 1% by weight or more, the coating properties tend to improve. When the weight percentage is 90% by weight or less, the release properties tend to improve. The non-volatile components of the release agent composition are the residue remaining after the release agent composition is heated to 110°C and its weight becomes constant.

[0049] The amount of silicone (B) contained in the mold release agent composition of the present invention is not particularly limited, but is preferably 10 to 10,000 parts by weight, more preferably 20 to 5,000 parts by weight, even more preferably 30 to 3,000 parts by weight, particularly preferably 50 to 2,000 parts by weight, and most preferably 100 to 1,500 parts by weight, per 100 parts by weight of the organosilicon compound (A). When the content is 10 parts by weight or more, the mold release properties tend to improve. When the content is 10,000 parts by weight or less, the transfer to the molded article tends to be further suppressed.

[0050] The weight percentage of silicone (B) in the nonvolatile content of the mold release agent composition of the present invention is not particularly limited, but is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, even more preferably 15 to 85% by weight, and particularly preferably 20 to 80% by weight. When the weight percentage is 5% by weight or more, the mold release properties tend to improve. When the weight percentage is 95% by weight or less, the transfer to the molded article tends to be further suppressed.

[0051] When the release agent composition of the present invention contains polymer (C), the amount of polymer (C) contained in the release agent composition is not particularly limited, but is preferably 5 to 500 parts by weight, more preferably 10 to 350 parts by weight, and particularly preferably 15 to 200 parts by weight, per 100 parts by weight of the organosilicon compound (A). When the content is 5 parts by weight or more, the release properties tend to improve. When the content is 500 parts by weight or less, the release persistence tends to improve.

[0052] When the mold release agent composition of the present invention contains polymer (C), the weight percentage of polymer (C) in the nonvolatile content of the mold release agent composition is not particularly limited, but is preferably 1 to 65% by weight, more preferably 5 to 60% by weight, even more preferably 10 to 50% by weight, and particularly preferably 15 to 40% by weight. When the weight percentage is 1% by weight or more, the mold release properties tend to improve. When the weight percentage is 65% by weight or less, the mold release persistence tends to improve.

[0053] When the mold release agent composition of the present invention contains a surfactant (D), the content of surfactant (D) is not particularly limited, but is preferably 5 to 300 parts by weight, more preferably 10 to 200 parts by weight, even more preferably 20 to 150 parts by weight, and particularly preferably 30 to 100 parts by weight, per 100 parts by weight of the content of organosilicon compound (A). When the content is 5 parts by weight or more, the coating properties tend to improve. When the content is 300 parts by weight or less, foaming tends to be suppressed.

[0054] When the mold release agent composition of the present invention contains a surfactant (D), the weight percentage of the mold release surfactant (D) in the nonvolatile content of the mold release agent composition is not particularly limited, but is preferably 1 to 40% by weight, more preferably 3 to 30% by weight, even more preferably 5 to 25% by weight, and particularly preferably 7 to 20% by weight. When the weight percentage is 1% by weight or more, the coating properties tend to improve. When the weight percentage is 40% by weight or less, foaming tends to be suppressed.

[0055] The pH of a 1% by weight aqueous dispersion of the mold release agent composition of the present invention at 25°C is not particularly limited, but is preferably 6 to 11, more preferably 7 to 10. When the pH is 7.0 or higher, the adhesion of the mold release agent composition tends to improve. When the pH is 11 or lower, the workability tends to improve.

[0056] The Knoop hardness (KH) of the thin film made from the non-volatile components of the mold release agent composition of the present invention is not particularly limited, but is preferably 2 or higher, more preferably 5 or higher. When the Knoop hardness is 2 or higher, the mold release persistence tends to improve. Here, a thin film consisting of the non-volatile components of the mold release agent composition was used with a thickness of 5 μm (please specify the thickness). The Knoop hardness (KH) of the thin film was determined by contacting a diamond indenter with the surface of the thin film consisting of the non-volatile components of the mold release agent composition, applying a load (HK 0.01), and then measuring the size of the rhomboid indentation formed on the surface of the thin film. The Knoop hardness (KH) was measured using a microhardness tester (HMV-1, manufactured by Shimadzu Corporation).

[0057] The release agent composition of the present invention may be a dispersion in water or an emulsified dispersion in water. A release agent composition that is an emulsified dispersion in water is preferable because it improves the coating properties on the target object. When the release agent composition of the present invention is in the form of an aqueous dispersion, the weight percentage of water in the release agent composition is not particularly limited, but is preferably 80 to 99.5% by weight, more preferably 85 to 99% by weight, and even more preferably 90 to 99% by weight. When the weight percentage is 80% by weight or more, the drying properties tend to improve, and when it is 99.5% by weight or less, the handling properties tend to improve. When the release agent composition is in the form of an aqueous dispersion, the water used can be tap water, deionized water, distilled water, etc., and is not particularly limited, but deionized water or distilled water is preferred. Furthermore, from the viewpoint of quality control, soft water is preferred because its hardness can be adjusted.

[0058] There are no particular limitations on the method for producing the mold release agent composition of the present invention, but examples include mixing an organosilicon compound (A), silicone (B), and, if necessary, a polymer (C), a surfactant (D), water, and other components. In the method for producing the mold release agent composition, there are no particular limitations on the mixing order, and all components may be mixed simultaneously, or components may be mixed sequentially, or some components may be mixed in advance, and the remaining components or the mixture may be added, mixed, or dispersed in the resulting mixture. When manufacturing a mold release agent composition, an aqueous dispersion in which an organosilicon compound (A) or silicone (B) is emulsified and dispersed in water may be used. This aqueous dispersion may contain a surfactant (D) as an emulsifier for emulsifying and dispersing the organosilicon compound (A) or silicone (B). There are no particular limitations on the mixing process; it can be carried out using a device with a very simple mechanism, such as a container and a stirring blade. Examples of mixing devices include homomixers, homogenizers, colloid mills, and line mixers.

[0059] [Method for manufacturing molded products] The present invention provides a method for manufacturing a molded article, comprising steps (1) and (2). Step (1) is the step of applying the above-mentioned release agent composition to the surface of the mold. Step (2) is a step performed after step (1), in which a mold on which a mold release agent composition has been applied to the surface contains a raw material composition containing at least one selected from unvulcanized rubber or resin, and the raw material composition is heated and pressurized. In step (1), the surface of the mold to which the release agent composition is applied is the part that comes into contact with the raw material composition. Furthermore, when manufacturing a molded body, the above-mentioned release agent composition is suitable for use in the mold.

[0060] In step (1), there are no particular limitations on the method for attaching the mold release agent composition to the mold surface, but examples include applying the mold release agent composition, its aqueous dispersion, or a diluted version thereof by brush application, roll coating, spray coating, knife coating, or dip coating. The mold release agent composition may be applied to the surface of the mold and then dried at room temperature or by heating. By drying after the mold release agent composition has been applied, it is possible to suppress the dripping or detachment of the mold release agent composition that has adhered to the object, and a film of the mold release agent composition can be formed. There are no particular limitations on the drying temperature after coating, but it is preferably 20 to 160°C.

[0061] In step (1), curing may be performed between step (1) and step (2) in order to form a coating with sufficient performance on the surface of the mold. If curing is performed, there are no particular limitations on the duration, but it is preferably 0.01 to 168 hours, more preferably 0.01 to 120 hours, particularly preferably 0.01 to 72 hours, and most preferably 0.01 to 24 hours. There are no particular limitations on the ambient temperature for curing, but it is preferably 0 to 200°C, more preferably 5 to 190°C, particularly preferably 10 to 180°C, and most preferably 15 to 170°C. When the ambient temperature is within the above range, a film of the mold release agent composition can be efficiently formed. Furthermore, if drying is performed in step 1, the curing may be performed immediately after drying, or the curing may be performed simultaneously with drying.

[0062] The amount of release agent composition adhering to the mold is adjusted as appropriate depending on the size and shape of the mold, but after drying it is 10-50 g / m². 2 Preferably, the amount of adhesion is 10 g / m². 2 When the amount exceeds 50 g / m², sufficient release properties tend to be obtained. 2 The following conditions tend to reduce pollution of the work environment:

[0063] Examples of molds used in the manufacturing method of the molded article of the present invention include molds having a fixed mold and a movable mold, and molds consisting only of a fixed mold. Step (2) involves placing the raw material composition into the mold as described above. In step (2), the raw material composition is heated and pressurized, thereby enabling the production of a molded body having the desired shape and size.

[0064] Examples of molding methods in step (2) include compression molding, press-fitting, injection molding, and extrusion molding. The heating temperature in step (2) is not particularly limited, but is preferably 100 to 200°C, and more preferably 110 to 190°C. There are no particular limitations on the molding pressure in step (2), but it is preferably 5 to 50 kgf / cm².2 , more preferably 10-40 kgf / cm² 2 More preferably 12-30 kgf / cm² 2 That is the case.

[0065] The raw material composition used in the manufacturing method of the present invention comprises at least one selected from unvulcanized rubber and resin. There are no particular limitations on the unvulcanized rubber, but examples include natural rubber, butadiene rubber, silicone rubber, styrene-butadiene rubber (SBR), ethylene-propylene-diene rubber (EPDM), etc., and one or more types may be used in combination. The resins are not particularly limited, but examples include thermosetting resins such as unsaturated polyesters, epoxy resins, and phenolic resins; thermoplastic resins such as ethylene-vinyl acetate copolymer (EVA), ionomers, polyethylene, polypropylene, polyvinyl chloride (PVC), acrylic resins, thermoplastic polyurethanes, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polystyrene (PS), polyamide resins (such as nylon 6 and nylon 66), polycarbonate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyacetal (POM), and polyphenylene sulfide (PPS); and thermoplastic elastomers such as olefin-based elastomers and styrene-based elastomers. One or more types may be used in combination.

[0066] The raw material composition may contain other raw materials besides unvulcanized rubber and resin. Examples of other raw materials include stabilizers, modifiers, fillers, and foaming agents. There are no particular limitations on the stabilizers, but examples include phenolic stabilizers such as pentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] and triethylene glycol-bis-[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], phosphorus-based stabilizers such as tris(mononylphenyl)phosphite and tris(2,4-di-t-butylphenyl)phosphite, and sulfur-based stabilizers such as dilauroyl dipropionate. One or more types may be used in combination. There are no particular limitations on the modifiers, but examples include sodium, calcium, magnesium, etc. salts of fatty acids such as lauric acid, palmitic acid, oleic acid, and stearic acid, and one or more of these may be used in combination.

[0067] Examples of fillers include inorganic fillers and organic fillers. While there are no particular limitations on inorganic fillers, examples include glass fibers (including those coated with metal), carbon fibers (including those coated with metal), potassium titanate, silicon carbide, silicon nitride, ceramic fibers, metal fibers, aramid fibers, barium sulfate, calcium sulfate, calcium silicate, calcium carbonate, magnesium carbonate, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, magnesium hydroxide, aluminum hydroxide, mica, talc, kaolin, pyrophyllite, bentonite, sericite, zeolite, wollastonite, alumina, clay, ferrite, graphite, gypsum, glass beads, glass balloons, quartz, and the like. There are no particular limitations on organic fillers, but examples include plant fibers such as cellulose, kenaf, and wheat bran; animal fibers such as wool and silk; synthetic fibers such as aramid fibers, phenolic fibers, polyester fibers, acrylic fibers, polyolefin fibers such as polyethylene and polypropylene, polyvinyl alcohol fibers, polyvinyl chloride fibers, and fluororesin fibers; regenerated fibers such as rayon; semi-synthetic fibers such as cellulose acetate; wood flour; okara (soy pulp); rice husks; monosaccharides; and polysaccharides such as starch. These fillers may be used individually or in combination of two or more types.

[0068] Foaming agents are thermal decomposition type foaming agents that decompose and gasify (foam) when heated. Examples of foaming agents include organic and inorganic thermal decomposition type foaming agents. There are no particular limitations on organic pyrolysis-type blowing agents, but examples include azodicarbonamide (ADCA), N,N'-dinitrosopentamethylenetetramine (DPT), and 4,4'-oxybisbenzenesulfonyl hydrazide (OBSH). Inorganic thermal decomposition type blowing agents are not particularly limited, but examples include bicarbonates, carbonates, and bicarbonates combined with organic acid salts. These blowing agents may be used individually or in combination of two or more types.

[0069] The weight percentage of at least one selected from unvulcanized rubber and resin in the raw material composition is not particularly limited, but is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more. When the weight percentage is within the above range, it becomes easier to obtain the desired molded article.

[0070] In the method for producing a molded article of the present invention, if the raw material composition used includes unvulcanized rubber, the unvulcanized rubber is vulcanized in step (2) to obtain a molded article. The molded articles obtained by the method for manufacturing molded articles of the present invention are not particularly limited, but examples include rubber products such as tires, vibration-damping rubber, automobile belts, seals, fenders, conveyor belts, rubber pads, rubber mats, seismic isolation rubber, sealing materials, waterproofing agents, rubber wires, rubber cables, rubber gloves, rubber balloons, gaskets, and packings; and resin products such as soft sheets, hard sheets, and foamed sheets. [Examples]

[0071] The present invention will be described in detail below with reference to examples and comparative examples. The present invention is not limited to these examples. In the following examples and comparative examples, unless otherwise specified, "parts" means "parts by weight". Furthermore, the evaluation of each physical property in the following examples and comparative examples was carried out as follows.

[0072] <Coating properties> On the surface of a steel plate (40mm wide x 70mm long x 1mm thick, made of SUS steel) that corresponds to the mold used for forming, the weight after drying is 10g / m². 2 To that end, the adhesion of the release agent composition when applied by a sprayer was visually judged according to the following evaluation criteria, with ○ being considered a pass. ○: It adhered evenly without any repelling. ×: It repels and adheres unevenly.

[0073] <Finish quality of the coating> After applying the release agent composition as described above and allowing it to dry, the finish of the film formed on the steel plate was visually inspected according to the following evaluation criteria, with ○ indicating a pass. ○: A smooth, even coating is uniformly formed on the steel plate. △: The coating is formed uniformly on the steel plate, but the coating has large irregularities. ×: The coating is unevenly distributed on the steel plate.

[0074] <Release retention> A release agent composition is applied to the surface of a steel plate (40mm wide x 70mm long x 1mm thick, made of SUS steel) that corresponds to the mold used for forming, with a dry weight of 10g / m². 2 The coating was applied using a sprayer and then dried. This steel plate was then placed on top of an unvulcanized rubber sheet (40mm x 70mm x 0.5mm) and heated at 160°C and 20kgf / cm². 2 The steel plate was press-vulcanized for 20 minutes under these conditions. The vulcanized rubber sheet was peeled off, and the required peel load was measured to evaluate the release properties. Using the treated steel sheets whose release properties were evaluated as described above, vulcanization molding of unvulcanized rubber sheets was repeatedly performed using the same method as in the evaluation above, and the number of times the release properties lasted was measured. The more times vulcanization molding can be repeated, the better the release durability. Release durability was judged according to the following evaluation criteria, with ◎ and ○ being considered passing grades. ◎: Even after 10 or more consecutive vulcanization cycles, it releases with a peel load of less than 1.0 N, demonstrating excellent release durability. ○: During continuous vulcanization cycles of 5 to 10 times, demolding occurs with a peel load of less than 1.0 N, and the demolding persistence is slightly superior. △: During continuous vulcanization cycles of 3 to 5 times, demolding occurs with a peel load of less than 1.0 N, and the demolding persistence is somewhat inferior. ×: During fewer than three consecutive vulcanization cycles, demolding occurs with a peel load of less than 1.0 N, resulting in poor demolding persistence.

[0075] <Knoop hardness of thin films> A release agent composition was applied to a hole slide glass to form a thin film with a thickness of 5 μm, and then dried at 110°C. The Knoop hardness (KH) was measured by contacting a diamond indenter with the obtained thin film, applying a load (HK 0.01), and then measuring the size of the rhomboid indentations formed in the thin film.

[0076] <Finish quality of molded products> A release agent composition is applied to the surface of a steel plate (40mm wide x 70mm long x 1mm thick, material: SUS steel) that corresponds to the mold used for forming, with a dry weight of 10g / m². 2 The coating was applied using a sprayer and then dried. This steel plate was then placed on top of an unvulcanized rubber sheet (40mm x 70mm x 0.5mm) and heated at 160°C and 20kgf / cm². 2 The material was press-vulcanized for 20 minutes under the specified conditions. The vulcanized rubber sheet, which was the molded body, was peeled off, and the amount of mold release agent component transferred to the rubber sheet was measured to evaluate the finish of the molded body. A lower amount of transfer indicates a better finish. The finish of the molded body was judged according to the following evaluation criteria, with ○ indicating a pass. ○: The amount of release agent component transferred to the rubber sheet is less than 30% by weight, resulting in excellent finish. △: The amount of release agent component transferred to the rubber sheet is more than 30% by weight and less than 70% by weight, resulting in slightly inferior finish. ×: The amount of release agent component transferred to the rubber sheet is 70% by weight or more, resulting in poor finish quality.

[0077] (Manufacturing Example 1: Synthesis of Organosilicon Compound 1) Five parts of dodecylbenzenesulfonic acid and 750 parts of water are mixed and heated to 50-60°C. Then, a mixture of 100 parts of hexamethyldisiloxane and 145 parts of a partially hydrolyzed condensate (tetramer) of tetramethoxysilane is added dropwise over 2 hours. Polymerization is then carried out at 60°C for 6 hours, and finally, the mixture is neutralized with 5 parts of a 5% by weight aqueous ammonia solution to obtain (CH3)3SiO 1 / 2 Units: 50 mol%, SiO 4 / 2 An aqueous dispersion of organosilicon compound 1 consisting of 50 mol% units (effective concentration 13.5% by weight, pH 6.5) was obtained. The physical properties of the obtained organosilicon compound 1 are shown in Table 1.

[0078] (Production Example 2: Synthesis of Organosilicon Compound 2) Five parts of dodecylbenzenesulfonic acid and 750 parts of water are mixed and heated to 50-60°C. Then, a mixture of 19 parts of hexamethyldisiloxane and 226 parts of methyltrimethoxysilane is added dropwise over 2 hours. Polymerization is then carried out at 60°C for 6 hours, and finally, the mixture is neutralized with 5 parts of 5% by weight aqueous ammonia solution to obtain (CH3)3SiO 1 / 2 Unit: 12 mol%, (CH3)SiO 3 / 2 An aqueous dispersion of organosilicon compound 2 (effective concentration 14.0 wt%, pH 6.8) consisting of 88 mol% units was obtained. The physical properties of the obtained organosilicon compound 2 are shown in Table 1.

[0079] (Manufacturing Example 3: Synthesis of Organosilicon Compound 3) Mix 5 parts dodecylbenzenesulfonic acid and 750 parts water, heat to 50-60°C, then add dropwise a mixture of 25 parts hexamethyldisiloxane and 220 parts methyltrimethoxysilane over 2 hours. Polymerize at 60°C for 6 hours, then neutralize with 15 parts of 10% by weight sodium bicarbonate aqueous solution to obtain (CH3)3SiO 1 / 2 Units: 16 mol%, (CH3)SiO 3 / 2 An aqueous dispersion of organosilicon compound 3 (effective concentration 14.2% by weight, pH 7.2) consisting of 84 mol% units was obtained. The physical properties of the obtained organosilicon compound 3 are shown in Table 1.

[0080] (Manufacturing Example 4: Synthesis of Organosilicon Compound 4) Mix 5 parts dodecylbenzenesulfonic acid with 750 g of water, heat to 50-60°C, then add dropwise a mixture of 41 parts hexamethyldisiloxane and 204 parts methyltrimethoxysilane over 2 hours. Polymerize at 60°C for 6 hours, then neutralize with 15 parts of 10% by weight sodium bicarbonate aqueous solution to obtain (CH3)3SiO 1 / 2 Units: 25 mol%, (CH3)SiO 3 / 2 An aqueous dispersion of organosilicon compound 4, consisting of 75 mol% units, with an effective concentration of 14.3% by weight and pH 7.0, was obtained. The physical properties of the obtained organosilicon compound 4 are shown in Table 1.

[0081] (Manufacturing Example 5: Synthesis of Organosilicon Compound 5) Mix 5 parts dodecylbenzenesulfonic acid and 750 parts water, heat to 50-60°C, then add dropwise a mixture of 25 parts hexamethyldisiloxane, 38 parts dimethyltrimethoxysilane, and 182 parts methyltrimethoxysilane over 2 hours. Polymerize at 60°C for 6 hours, then neutralize with 5 parts of 5% by weight aqueous ammonia solution to obtain (CH3)3SiO 1 / 2 Units: 16 mol%, (CH3)2SiO 2 / 2 Units: 16 mol%, (CH3)SiO 3 / 2 An aqueous dispersion of organosilicon compound 5 consisting of 68 mol% units (effective concentration 12.5 wt%, pH 6.8) was obtained. The physical properties of the obtained organosilicon compound 5 are shown in Table 1.

[0082] (Production Example 6: Synthesis of Organosilicon Compound 6) Mix 5 parts dodecylbenzenesulfonic acid and 750 parts water, heat to 50-60°C, then add dropwise a mixture of 75 parts dimethyldimethoxysilane and 170 parts methyltrimethoxysilane over 2 hours. Polymerize at 60°C for 6 hours, then neutralize with 20 parts of 10% by weight sodium carbonate aqueous solution to obtain (CH3)2SiO 2 / 2 Units: 33 mol%, (CH3)SiO 3 / 2 An aqueous dispersion of organosilicon compound 6 consisting of 67 mol% units (effective concentration 12.0 wt%, pH 7.8) was obtained. The physical properties of the obtained organosilicon compound 6 are shown in Table 1.

[0083] (Production Example 7: Synthesis of Organosilicon Compound 7) Mix 5 parts dodecylbenzenesulfonic acid and 750 parts water, heat to 50-60°C, then add dropwise a mixture of 41 parts dimethyldimethoxysilane, 66 parts phenyltrimethoxysilane, and 138 parts methyltrimethoxysilane over 2 hours. Polymerize at 60°C for 6 hours, then neutralize with 5 parts of 5% by weight aqueous ammonia solution to obtain (CH3)2SiO 2 / 2 Units: 20 mol%, (C6H5)SiO 3 / 2 Units: 20 mol%, (CH3)SiO 3 / 2 An aqueous dispersion of organosilicon compound 7 consisting of 60 mol% units (effective concentration 12.8 wt%, pH 6.8) was obtained. The physical properties of the obtained organosilicon compound 7 are shown in Table 1.

[0084] (Manufacturing Example 8: Synthesis of Organosilicon Compound 8) Mix 5 parts dodecylbenzenesulfonic acid and 750 parts water, heat to 50-60°C, then dropwise add a mixture of 34 parts dimethyldimethoxysilane, 47 parts n-propyltrimethoxysilane, and 164 parts methyltrimethoxysilane over 2 hours. Polymerize at 60°C for 6 hours, then neutralize with 5 parts of 5% by weight aqueous ammonia solution to obtain (CH3)2SiO 2 / 2 Units: 16 mol%, (CH3CH2CH2)SiO 3 / 2 Units: 16 mol%, (CH3)SiO 3 / 2 An aqueous dispersion of organosilicon compound 8 consisting of 68 mol% units (effective concentration 13.0 wt%, pH 6.8) was obtained. The physical properties of the obtained organosilicon compound 8 are shown in Table 1. Trimethylsilanol was used as the standard substance when measuring the silanol group concentration of each organosilicon compound.

[0085] [Table 1]

[0086] [Example 1] A mold release agent composition was obtained by mixing 0.5 parts of organosilicon compound 1, 1 part of silicone 1, 0.5 parts of styrene / maleic anhydride copolymer 1, 0.1 parts of POE alkyl ether, and 97.9 parts of water. The amounts of organosilicon compound (A) listed in Table 2 represent the amounts of the active ingredient in the aqueous dispersion of organosilicon compound (A) used. On the surface of the steel plate, the dry weight is 10g / m². 2 The material was applied and dried to form a film on the steel plate. Next, the resulting steel plate and the unvulcanized rubber sheet were placed on top of each other and heated at 160°C and 20 kgf / cm². 2 The rubber sheet was press-vulcanized for 20 minutes under these conditions. After vulcanization, the molded product peeled off, demonstrating excellent release properties. Subsequently, continuous vulcanization molding was performed, and the release properties were maintained for 13 cycles, indicating excellent release durability.

[0087] [Examples 2-26] In Examples 2-26, release agent compositions were obtained and evaluated in the same manner as in Example 1, except that the raw materials and their proportions were changed as shown in Tables 2-3. The evaluation results are shown in Tables 2-3. Details of the raw materials used are shown in Table 4. In Tables 2-3, "POE" indicates that the structure has a polyoxyethylene group attached.

[0088] [Comparative Examples 1-2] In Comparative Examples 1 and 2, release agent compositions were obtained and evaluated in the same manner as in Example 1, except that the raw materials and their proportions were changed as shown in Table 3. The evaluation results are shown in Table 3.

[0089] [Table 2]

[0090] [Table 3]

[0091] [Table 4]

[0092] As can be seen from Tables 2 and 3, the mold release agent compositions of the examples contain an organosilicon compound (A) and silicone (B), and thus the problem of the present invention is solved. On the other hand, the cases in Comparative Example 1 (without silicone (B)) and Comparative Example 2 (without organosilicon compound (A)) fail to solve the problem of the present invention.

Claims

1. A mold release agent composition comprising the following organosilicon compound (A) and the following silicone (B). Organosilicon compound (A): Contains R in the molecule １ SiO ３／２ The T units and SiO shown are indicated by ４／２ It has at least one selected from the Q units shown, R １ An organosilicon compound in which the is a monovalent organic group. Silicone (B): Silicone excluding organosilicon compounds (A).

2. The release agent composition according to claim 1, wherein the silanol group concentration of the organosilicon compound (A) is 15 mmol / g or less.

3. The mold release agent composition according to claim 1 or 2, wherein the organosilicon compound (A) is solid at 20°C.

4. The mold release agent composition according to claim 1 or 2, wherein the viscosity of the silicone (B) at 25°C is 1 million to 2 million mPa·s.

5. The mold release agent composition according to claim 1 or 2, wherein the content of the silicone (B) is 10 to 10,000 parts by weight per 100 parts by weight of the organosilicon compound (A).

6. The mold release agent composition according to claim 1 or 2, further comprising the polymer (C) below. Polymer (C): A polymer having a structural unit (c1) having at least one selected from an acidic group and a group that is a salt thereof.

7. The release agent composition according to claim 6, wherein the acidic group is at least one selected from a carboxyl group, a sulfate group, and a sulfonic acid group.

8. The release agent composition according to claim 6, wherein the structural unit (c1) is at least one selected from acrylic acid units, acrylic acid salt units, maleic anhydride units, maleic acid units, maleic acid salt units, sulfonic acid units, and sulfonate salt units.

9. The mold release agent composition according to claim 1 or 2, further comprising a surfactant (D).

10. A method for manufacturing a molded article, comprising steps (1) and (2), The above step (1) is a step of applying the release agent composition according to claim 1 or 2 to the surface of the mold, Step (2) is a step, after step (1), in which a raw material composition containing at least one selected from unvulcanized rubber and resin is placed in the mold, and the raw material composition is heated and pressurized. A method for manufacturing a molded product.

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