JP2007261281A - Mold releasing agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a mold releasing agent composition which forms a film being excellent in mold releasing property, heat-resistance and durability, and having a high flexibility on a molding die, and maintains the mold releasing effect between various kinds of organic resins or rubber products and the molding die for a long period of time. <P>SOLUTION: The mold releasing agent composition contains a colloidal silica core-silicone shell body consisting of (a) 80 to 5 wt.% of a colloidal silica core, and (b) 20 to 95 wt.% of a polyorganosiloxane shell, as the major component. In this case, the polyorganosiloxane is represented by average composition formula R<SP>1</SP><SB>a</SB>SiO<SB>(4-a)/2</SB>(in the formula, R<SP>1</SP>represents a hydrogen atom or a substitutional or non-substitutional monatomic hydrocarbon group, and a is a number of 1.80 to 2.20). The mold releasing agent composition can further contain an organic acid metal salt and/or an organic functional group-containing silane compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a release agent composition containing a colloidal silica core-silicone shell body, and in particular, a release agent composition that is excellent in release properties and capable of forming a highly flexible film on a mold or the like. Related to things.

  In recent years, there has been a strong demand for pollution-free or safety-sanitation of various coating agents including organic solvents such as paints and adhesives, for the purpose of environmental protection and health and safety. For this reason, the application of the emulsion-type coating agent is being expanded, and has attracted attention in the field where solvent-type coating is used.

  Along with the above circumstances, a high degree of coating film performance is being demanded for emulsion type coating agents. For this purpose, it has been widely practiced to add colloidal silica to organic polymer emulsions to improve the performance of the coating film, but the interaction between the organic polymer and silica is weak, and as a result, long-term However, there is a drawback that deterioration in durability such as water resistance and alkali resistance of the coating film cannot be avoided. In particular, the mold release agent has the following problems.

  That is, in the process of molding various thermosetting or thermoplastic organic resins, or various rubbers into molded articles of rubber products such as plastic products, rubber hoses, and tires by methods such as pressure molding and injection molding, A mold release agent is used to prevent the molded product from sticking to the mold and to facilitate removal of the molded product from the mold.

  Such release agents include an external mold release agent that is applied to a mold and used, and an internal addition mold release agent that is added to the inside of a molded product and used. In general, an external mold release agent is a solution obtained by dissolving a non-reactive silicone oil in a volatile organic solvent, or emulsifying and dispersing it in water using a surfactant. Used by applying to.

  However, in such an external mold release agent (hereinafter simply referred to as a release agent), when the molded product is released from the mold, the release agent adheres to the molded product and the molded product is released from the mold. This needs to be compensated for in order to move to. For this reason, there is a disadvantage that the amount of the release agent used is increased and it becomes uneconomical.

  In addition, the mold is heavily soiled because the release agent is frequently applied, the process is complicated because the process of removing the dirt frequently occurs, and it adheres when the molded product is coated in a later process. Since a process for removing the mold release agent is required, there is a drawback in that the production cost of the molded product increases.

On the other hand, in order to solve such drawbacks, for example, a silicone film-forming mold release agent that forms a film fixed to the mold surface, such as a mold release composition using an organosilazane siloxane polymer, has been proposed. (For example, refer to Patent Document 1), however, there is a drawback that the durability of the coating is not sufficient and the releasability is insufficient. In addition, an attempt to improve the durability and releasability of the coating by combining a silicone resin and a phenyl group-containing polyorganosiloxane has been proposed (for example, see Patent Document 2), but it is dissolved in a volatile organic solvent. The solution type has a problem in terms of safety, and the coating film cannot be used for a flexible mold such as a vulcanization bladder used at the time of molding a tire because the film is not flexible.
Japanese Patent Publication No. 3-11248 Japanese Patent Laid-Open No. 5-24047

  The present invention has been made against the background of the problems of the prior art as described above. Various organic resins are formed on a mold by forming a highly flexible film having excellent releasability, heat resistance and durability. Another object of the present invention is to provide a release agent composition that maintains the release effect between a rubber product and a mold for a long period of time.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a release agent composition containing a silica core-silicone shell body obtained by bonding polyorganosiloxane to colloidal silica via a siloxane bond. The inventors have found that the above object can be achieved and have completed the present invention.

That is, the present invention comprises (a) 80-5% by weight of colloidal silica core, and (b) average composition formula R ¹ _a SiO _{(4-a) / 2} (I) (where R ¹ is A colloidal silica core-silicone comprising 20 to 95% by weight of a polyorganosiloxane shell represented by a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, a being a number of 1.80 to 2.20) A release agent composition comprising a shell body as a main component is provided.

  According to the present invention, by applying a colloidal silica core-silicone shell body obtained by bonding a polyorganosiloxane to a colloidal silica via a siloxane bond to a mold release agent composition, the mold has a release property and heat resistance. The film can be formed with a high flexibility and durability, and a highly flexible film, and the release effect between various organic resins and rubber products and the mold can be maintained for a long time. Therefore, the productivity of these molded products can be improved and the occurrence of quality defects can be suppressed as much as possible.

  Embodiments of the present invention will be described below.

Embodiments of the present invention include: (a) 80-5 wt% of colloidal silica core; and (b) average composition formula R ¹ _a SiO _{(4-a) / 2} (I) where R ¹ Is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and a is a number of 1.80 to 2.20). A silicone shell body is contained as a main component.

  The colloidal silica core-silicone shell used in the present invention is a component that forms an elastomeric cured product after water has been removed. One colloidal silica particle of component (a) is replaced with polyorgano of component (b). It is covered with siloxane.

  More simply, the core-shell body is: 1) one in which both ends of the polyorganosiloxane are bonded to the silica surface via a siloxane bond, 2) one end of the polyorganosiloxane is on the silica surface 3) A structure in which the other end is blocked with a hydroxyl group, and 3) Polyorganosiloxane is blocked with a hydroxyl group and has no siloxane bond with the silica surface. It has been done.

  Further, the combined use of 3, 4 functional alkoxysilanes and chain stoppers increases the types of these forms and makes them complicated. Here, the colloidal silica core-silicone shell body is mainly composed of colloidal silica as a core and at least partly coated with silicone, and may contain some separated silicone particles.

The component (a) colloidal silica used in the present invention refers to an underwater dispersion containing SiO ₂ as a basic unit. In the present invention, the average particle diameter is 4 to 300 nm, particularly preferably 30 to 30 nm. 150 nm is suitable. The colloidal silica has both acidic and alkaline properties from its characteristic classification, and these can be appropriately selected depending on the conditions during emulsion polymerization. For example, when conducting emulsion polymerization under acidic conditions using an anionic surfactant, it is preferable to use acidic colloidal silica.

  The content of the polyorganosiloxane shell of component (b) used in the present invention is selected in the range of 20 to 95% by weight. If it is less than 20% by weight, impact resilience, flexibility, etc. are greatly reduced, resulting in lack of elastomeric properties, and a protective film inferior in weather resistance, adhesion, water resistance, heat resistance, water repellency, and stain resistance. . On the other hand, if it exceeds 95% by weight, the reinforcing properties of colloidal silica cannot be sufficiently imparted to the polyorganosiloxane, and sufficient strength as a film cannot be obtained, and the film formability also deteriorates.

  The organosiloxane of component (b) used in the present invention has a structural unit represented by the above formula (I) and has 2 to 10 silicon atoms not containing a hydroxyl group. Although it does not specifically limit, such as linear form, branched form, or cyclic | annular form, what has a cyclic structure is preferable.

  Here, when the number of silicon atoms exceeds 10, when emulsion polymerization is carried out, it is difficult to incorporate colloidal silica into the siloxane micelles, so that some of them cannot participate in the formation of the core-shell body. The resulting emulsion is an emulsion in which colloidal silica and polyorganosiloxane are present together. In addition, a hydroxyl group-containing siloxane is not preferred because it causes a polycondensation reaction at the initial stage of emulsification, resulting in a siloxane having more than 10 silicon atoms, resulting in the above problems.

  Specific examples of the organosiloxane of the component (b) include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1,3,5,7-tetramethyl-1,3,5, Cyclic compounds such as 7-tetraphenylcyclotetrasiloxane and 1,3,5,7-tetrabenzyltetramethylcyclotetrasiloxane are exemplified, and these are used alone or as a mixture of two or more.

R ¹ bonded to the silicon atom of the polyorganosiloxane shell of component (b) is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group.

  Examples of the unsubstituted hydrocarbon group include a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a decyl group, a hexadecyl group, an octadecyl group and other linear or branched alkyl groups, a phenyl group, a naphthyl group, Examples include aryl groups such as xenyl group, aralkyl groups such as benzyl group, β-phenylethyl group, methylbenzyl group and naphthylmethyl group, and cycloalkyl groups such as cyclohexyl group and cyclopentyl group.

  On the other hand, examples of the substituted hydrocarbon group include groups in which the hydrogen atom of the unsubstituted organic group exemplified above is substituted with a halogen atom such as fluorine or chlorine, and as such, 3, 3, 3- Examples thereof include a trifluoropropyl group and a 3-fluoropropyl group.

  Further, as another monovalent organic group in the component (b), an organic functional group constituted by a carbon atom and a hydrogen atom, and at least one atom of nitrogen and oxygen, or an ethylenically unsaturated group, When the colloidal silica core-silicone shell body containing such an organic functional group or an ethylenically unsaturated group is used, the adhesiveness to the base material is excellent, so that the durability is better.

などが挙げられる。 Examples of such organic functional groups include

Etc.

で表されるものが挙げられる。その他、エチレン性不飽和基を含む基として、一般式ＣＨ₂ ＝ＣＨ−（ＣＨ₂ ）_ｎ ⁻………（Ｖ）で表されるものが挙げられる。ただし、上記（II）〜（Ｖ）の式中、ｎは０〜１０の整数を示す。 In addition, as a group containing an ethylenically unsaturated group, a general formula

The thing represented by is mentioned. In addition, examples of the group containing an ethylenically unsaturated group include those represented by the general formula CH ₂ ═CH— (CH ₂ ) _n ⁻ (V). However, n shows the integer of 0-10 in the formula of said (II)-(V).

  Examples of the group containing an ethylenically unsaturated group represented by the formula (II) include a vinyloxypropyl group and a vinyloxyethyl group, and a vinyloxypropyl group is preferable.

When the ethylenically unsaturated group is represented by the above formula (III), R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group. Examples of the group containing an ethylenically unsaturated group represented by the formula (III) include a vinylphenyl group, a 1- (vinylphenyl) ethyl group, a 2- (vinylphenyl) ethyl group, and a (vinylphenyl) methyl group. And isopropenylphenyl group, and the like, preferably vinylphenyl group, 1- (vinylphenyl) ethyl group, and 2- (vinylphenyl) ethyl group.

When the ethylenically unsaturated group is represented by the above formula (IV), R ⁴ is a hydrogen atom or a methyl group. R ⁵ is an alkylene group having 1 to 6 carbon atoms, —O—, —S—, or a group represented by —N (R ⁶ ) R ⁷ —, and R ⁶ is a hydrocarbon having 1 to ⁶ carbon atoms. Group or (meth) acryloyl group, R < ⁷ > is a C1-C6 alkylene group. Examples of the group containing an ethylenically unsaturated group represented by the formula (IV) include γ-acryloxypropyl group, γ-methacryloxypropyl group, N-methacryloyl-N-methyl-γ-aminopropyl group, N- Examples include acryloyl-N-methyl-γ-aminopropyl group, N, N-bis- (methacryloyl) -γ-aminopropyl group, and preferably N-methacryloyl-N-methyl-γ-aminopropyl group, N- An acryloyl-N-methyl-γ-aminopropyl group;

  Examples of the group containing an ethylenically unsaturated group represented by the above formula (V) include a vinyl group, an allyl group, a homoallyl group, a 5-hexenyl group, and a 7-octenyl group, preferably a vinyl group. , An allyl group.

Such an organic functional group and a group containing an ethylenically unsaturated group are usually in the range of 0.01 to 25 mol%, preferably 0.05 to 5 mol%, based on the total amount of R ^{1 in} the formula (I). Is within. If it is less than 0.01%, the effect of improving the durability of the composition is small. Conversely, if it exceeds 25 mol%, the film formed by the coating treatment becomes too hard and the adhesion to the substrate may be deteriorated.

  Furthermore, in order to introduce such organic functional groups or groups containing ethylenically unsaturated groups, silane compounds containing these organic functional groups, silane compounds containing ethylenically unsaturated groups, containing organic functional groups Organosiloxanes or organosiloxanes containing ethylenically unsaturated groups can be used.

Examples of the silane compound containing an organic functional group include 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, N- (aminoethyl) -3-aminopropyltriethoxysilane, and N-triethylenediaminepropylmethyldimethoxysilane. , 3-glycidoxypropylmethyldiethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, and the like, and mixtures thereof.
Examples of the silane compound (b-2) containing an ethylenically unsaturated group include 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, (vinyloxypropyl) methyldimethoxysilane, (vinyl Loxyethoxypropyl) methyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, 1- (m-vinylphenyl) methyldimethylisopropoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, 3- (p-vinylphenoxy) ) Propyltriethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane, 1- (p-vinylphenyl) ethylmethyldimethoxysilane, 1- (o-vinylphenyl) -1,1,2-trimethyl -2,2-Dimeth Sidisilane, m-vinylphenyl-[(3-triethoxysilyl) propyl] diphenylsilane, [3- (p-isopropenylbenzoylamino) propyl] phenyldipropoxysilane, N-methacryloyl-N-methyl-3-aminopropyl Methyldimethoxysilane, N-acryloyl-N-methyl-3-aminopropylmethyldimethoxysilane, N, N-bis (methacryloyl) -3-aminopropyltrimethoxysilane, N, N-bis (acryloyl) -3-aminopropyl Methyldimethoxysilane, N-methacryloyl-N-methyl-3-aminopropylphenyldiethoxysilane, 1-methacryloxypropyl-1,1,3-trimethyl-3,3-dimethoxydisiloxane, vinylmethyldimethoxysilane, vinylethyl Gii Propoxysilane, allyl methyl dimethoxy silane, hexenyl to 5 methyl diethoxy silane, and 3-octenyl ethyldiethoxysilane are exemplified, using these alone or in combination of two or more.

  On the other hand, as organosiloxane (b-3) containing an organic functional group, trimethyltriphenylcyclotrisiloxane, tris (3,3,3-trifluoropropyl) trimethylcyclotrisiloxane, 1,3,5,7-tetra (3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [N- (2-aminoethyl) -3-aminopropyl] tetramethylcyclotetrasiloxane, 1,3,5,7- Examples thereof include cyclic products such as tetra (3-mercaptopropyl) tetramethylcyclotetrasiloxane and 1,3,5,7-tetra (3-glycidoxypropyl) tetramethylcyclotetrasiloxane.

  Furthermore, as the organosiloxane (b-4) containing an ethylenically unsaturated group, 1,3,5,7-tetra (3-methacryloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7- Tetra (3-acryloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (vinyloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (vinyloxyethoxypropyl) tetra Methylcyclotetrasiloxane, 1,3,5,7-tetra (p-vinylphenyl) tetramethyl cyclotetrasiloxane, 1,3,5,7-tetra [1- (m-vinylphenyl) methyl] tetramethylcyclotetra Siloxane, 1,3,5,7-tetra [2- (p-vinylphenyl) ethyl] tetramethylcyclo Tetrasiloxane, 1,3,5,7-tetra [3- (p-vinylphenoxy) propyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [3- (p-vinylbenzoyloxy) propyl ] Tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [3- (p-isopropenylbenzoylamino) propyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N-methacryloyl-N) -Methyl-3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N-acryloyl-N-methyl-3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7 -Tetra [N, N-bis (methacryloyl) -3-aminopropyl] tetramethylcyclotetrasiloxane, 1 3,5,7-tetra [N, N-bis (acryloyl) -3-aminopropyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, octavinylcyclotetrasiloxane, 1,3,5-trivinyltrimethylcyclotrisiloxane, 1,3,5,7-tetraallyltetramethylcyclotetrasiloxane, 1,3,5,7-tetra (5-hexenyl) tetramethylcyclotetrasiloxane, 1 , 3,5,7-tetra (7-octenyl) tetramethylcyclotetrasiloxane and the like, and these may be used alone or as a mixture of two or more. In addition, an organosiloxane oligomer containing a linear or branched organic functional group or an ethylenically unsaturated group may be used. However, in the case of an organosiloxane oligomer containing a linear or branched organic functional group, the molecular chain terminal is not particularly limited, but it is easy to handle and introduces an organic functional group into the resulting polyorganosiloxane. From the viewpoint, the molecular chain terminal is an organic group other than a hydroxyl group, such as an alkoxy group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group, a methyldiphenylsilyl group, a 3,3,3-trifluoropropyldimethylsilyl group, etc. What is blocked is preferred.

  The organosiloxane of the component (b) as described above, or a silane compound containing an organic functional group to be used if necessary, a silane compound containing an ethylenically unsaturated group, an organosiloxane containing an organic functional group, or ethylene The organosiloxane containing a polymerizable unsaturated group is blended so that the silicone shell part in the colloidal silica core-silicone shell body according to the present invention is 20 to 95% by weight.

  Next, the manufacturing method of the composition concerning this invention is demonstrated. First, (a) component colloidal silica, (b) component organosiloxane organosiloxane, and, if necessary, an organic functional group or ethylenically unsaturated group-containing silane compound or organic functional group or ethylenically unsaturated group Colloidal silica core-silicone by shear mixing with an organosiloxane containing a group in an aqueous medium using a homogenizer in the presence of a surfactant and polycondensing in the presence of an effective amount of an emulsifier or emulsifier mixture. A shell body emulsion is prepared.

  Next, various conventional inorganic powders, adhesion improvers, curing catalysts, viscosity adjusters, pH adjusters, antioxidants, antiseptics, rust preventives, fragrances, colorants, and other optional components It can manufacture by mix | blending suitably.

  The above-mentioned emulsifier mainly serves as a surfactant for emulsifying the organosiloxane of component (b) and the resulting colloidal silica core-silicone shell, and at the same time, component (a) and component (b) And a catalyst for polycondensation reaction with a silane compound containing an organic functional group or an ethylenically unsaturated group or an organosiloxane containing an organic functional group or an ethylenically unsaturated group, if necessary, and an anion A system surfactant or a cationic surfactant can be appropriately selected and used.

As such an anionic surfactant, R ⁸ C ₆ H ₄ SO ₃ H (VII), R ⁸ OSO ₃ H (VIII), R ⁹ CH═CH (CH ₂ ) _n SO ₃ H ......... (IX) and _{^{R 9 CH 2 CH (OH)}} (CH 2) nSO 3 H ......... (X) ( provided that wherein R ⁸ is a monovalent 6 to 30 carbon atoms An aliphatic hydrocarbon group, R ⁹ is a monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, and n is a total of 6 to 6 carbon atoms in the surfactants of formulas (IX) and (X) And an aliphatic substituted benzenesulfonic acid, an aliphatic hydrogen sulfate, or a mixture of an unsaturated aliphatic sulfonic acid and a hydroxylated aliphatic sulfonic acid.

Here, R ⁸ in the formulas (VII) and (VIII) is a monovalent aliphatic hydrocarbon group having 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms, such as hexyl group, octyl group, decyl group. Group, dodecyl group, cetyl group, stearyl group, myristyl group, oleyl group, nonenyl group, octynyl group, phytyl group, pentadecadienyl group and the like.

R ⁹ in the formula (X) is a monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, preferably 6 to 18 carbon atoms. For example, the same monovalent aliphatic hydrocarbon group as R ⁸ is Can be mentioned.

  Examples of the anionic surfactant of the formula (VII) or (VIII) include hexylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, octyl sulfate, lauryl sulfate, oleyl sulfate. And cetyl sulfate.

  Examples of the anionic surfactant of the formula (IX) include tetradecenesulfonic acid, and examples of the anionic surfactant of the formula (X) include hydroxytetradecanesulfonic acid.

  Furthermore, an anionic surfactant having a weak catalytic action can also be used in combination with the polymerization catalyst. Examples of such anionic surfactants include aliphatic substituted benzenesulfonic acids of the above formula (VII), aliphatic hydrogen sulfates of the formula (VIII), or unsaturated aliphatic sulfones of the formulas (IX) and (X) Examples include sodium salt, potassium salt, ammonium salt of a mixture of acid and hydroxy aliphatic sulfonic acid, specifically sodium dodecylbenzenesulfonate, sodium octylbenzenesulfonate, ammonium dodecylbenzenesulfonate, sodium lauryl sulfate, Examples include ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium tetradecene sulfonate, and sodium hydroxytetradecane sulfonate.

  In addition to the anionic surfactants of the formula (VII) or (VIII) described above, for example, polyoxyethylene (4) lauryl ether sulfate, polyoxyethylene (13) cetyl ether sulfate, polyoxyethylene 6) stearyl. Ether sulfuric acid, polyoxyethylene (4) sodium lauryl sulfate, polyoxyethylene (4) octylphenyl ether ammonium sulfate or other polyoxyethylene alkyl ether sulfates or salts thereof, polyoxyethylene (3) lauryl ether carboxylic acid, polyoxyethylene (3) Polyoxyethylene alkyl ethers such as stearyl ether carboxylic acid, polyoxyethylene (6) sodium lauryl ether carboxylate, polyoxyethylene (6) sodium octyl ether carboxylate It may be used one or more such phosphate ester or a salt thereof, which by no means limited thereto.

  As the polymerization catalyst used in combination with the above anionic surfactant, aliphatic substituted benzene sulfonic acid, aliphatic hydrogen sulfate, unsaturated aliphatic sulfonic acid and hydroxylation which are usually used as a polymerization catalyst for low molecular weight organosiloxane are used. A mixture of aliphatic sulfonic acids, and an acidic catalyst such as chlorine, sulfuric acid, and phosphoric acid is preferably used, but is not limited to these, and it is possible to polymerize a low molecular weight organosiloxane in the presence of water. Any catalyst can be used.

  The amount of the anionic surfactant used includes the components (a) and (b) and, if necessary, a silane compound containing an organic functional group or ethylenically unsaturated group, or an organic functional group or ethylenically unsaturated group. 0.5 to 20 parts by weight, particularly 0.5 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total organosiloxane, and the emulsion stability is poor if less than 0.5 parts by weight. There is a possibility of separation, and when the amount exceeds 20 parts by weight, the emulsion may thicken and flowability may deteriorate.

  In addition, when the polymerization catalyst is used in combination, the amount of the polymerization catalyst used is not particularly limited, but the silane compound or the organic functional group or ethylenically unsaturated group-containing silane compound or organic component (a) and the component (b) and if necessary The amount is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the total amount of the organosiloxane containing functional groups or ethylenically unsaturated groups.

（但し、式中Ｒ¹⁰は炭素原子数６以上の脂肪族一価炭化水素基、Ｒ¹¹、Ｒ¹²、Ｒ¹³はそれぞれ一価の有機基、Ｘは水酸基、塩素原子または臭素原子である。）で示される第四アンモニウム塩系界面活性剤が好適である。 In addition, as a cationic surfactant that can be used as a surfactant, the following general formula

Wherein R ¹⁰ is an aliphatic monovalent hydrocarbon group having 6 or more carbon atoms, R ¹¹ , R ¹² and R ¹³ are each a monovalent organic group, and X is a hydroxyl group, a chlorine atom or a bromine atom. A quaternary ammonium salt-based surfactant represented by

In the formula (XI), R ¹⁰ is an aliphatic hydrocarbon group having 6 or more carbon atoms, preferably 8 to 18 carbon atoms, such as hexyl group, octyl group, decyl group, dodecyl group, cetyl group, stearyl group, myristyl group. Group, oleyl group, hexadecyl group, nonenyl group, octynyl group, phytyl group, pentadecadienyl group and the like. R ¹¹ , R ¹² and R ¹³ are the same or different monovalent organic groups, for example, alkyl groups such as methyl group, ethyl group and propyl group, alkenyl groups such as vinyl group and allyl group, and phenyl groups. Aryl groups such as xenyl group and naphthyl group, cycloalkyl groups such as cyclohexyl group, and the like.

  Examples of the quaternary ammonium salt surfactant of the formula (XI) include lauryl trimethyl ammonium hydroxide, stearyl trimethyl ammonium hydroxide, dioctyl dimethyl ammonium hydroxide, distearyl dimethyl ammonium hydroxide, lauryl trimethyl chloride. Examples thereof include ammonium, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, dicoroyldimethylammonium chloride, distearyldimethylammonium chloride, benzaluronium chloride, stearyldimethylbenzylammonium chloride, and one or more of these may be used. it can.

  The cationic surfactant is weak in catalysis, and is preferably used in combination with a polymerization catalyst. As the polymerization catalyst used in combination, lithium hydroxide usually used as a polymerization catalyst for low molecular weight organosiloxanes is used. And alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide.

  The amount of the cationic surfactant used includes the components (a) and (b) and, if necessary, a silane compound containing an organic functional group or ethylenically unsaturated group, or an organic functional group or ethylenically unsaturated group. 0.5 to 50 parts by weight, particularly 1 to 20 parts by weight, with respect to 100 parts by weight of the total amount of the organosiloxane, and if the amount is less than 0.5 parts by weight, the cationic nature of the emulsion itself is insufficient. In addition, the emulsion may have poor stability and may be separated, and if it exceeds 50 parts by weight, the emulsion may thicken and lose its fluidity.

  In addition, when the polymerization catalyst is used in combination, the amount of the polymerization catalyst used is not particularly limited, but the silane compound or the organic functional group or ethylenically unsaturated group-containing silane compound or organic component (a) and the component (b) and if necessary It is preferable to set it as 0.05-10 weight part with respect to 100 weight part of total amounts of the organosiloxane containing a functional group or an ethylenically unsaturated group.

  Furthermore, in order to improve the stability of the composition finally obtained, after adding arbitrary components as described above to the colloidal silica core-silicone shell emulsion obtained by emulsion polymerization, a nonionic surfactant is added. As long as the object of the present invention is not impaired, the surfactant may be used in combination with emulsion polymerization before or after emulsion polymerization.

  As such nonionic surfactants, those having an HLB (hydrophilic lipophilic balance) of 6 to 20 are preferable. Examples of such nonionic surfactants include polyoxyethylene (6) lauryl ether, polyoxyethylene (7 ) Cetyl ether, polyoxyethylene (20) stearyl ether, polyoxyethylene (3) octylphenyl ether, polyoxyethylene (18) nonylphenyl ether, polyethylene glycol monostearate (EO14), polyethylene glycol distearate (EO80), Polyoxyethylene (20) hydrogenated castor oil, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monovalmitate, polyoxyethylene (6) sorbitan triolein monostearate Polyoxyethylene (20) sorbitan, polyoxyethylene tetraoleate (40) sorbit, polyoxyethylene (15) glyceryl monooleate, posooxyethylene monostearate (15) glyceryl, sorbitan monovalmitate, polyoxyethylene ( 10) behenyl ether, polyoxyethylene (10) phytosterol, polyoxyethylene (10) polyoxypropylene (4) cetyl ether, polyoxyethylene (5) stearylamine, polyoxyethylene (8) stearylpropylenediamine polyoxyethylene ( 5) Although cetyl ether sodium phosphate etc. are mentioned, it is not limited to this.

  When the nonionic surfactant is used in combination prior to emulsion polymerization, if it exceeds 500 parts by weight relative to 100 parts by weight of the surfactant, the activity as a polymerization catalyst is impaired. It is preferable to set it to -500 weight part.

  In preparing the colloidal silica core-silicone shell emulsion, the combination of acidic colloidal silica-anionic surfactant and alkaline colloidal silica-cationic surfactant is used to keep the colloidal silica in a stable state. select.

  The amount of water used here is (a) component, (b) component and, if necessary, a silane compound containing an organic functional group or an ethylenically unsaturated group, or an organo containing an organic functional group or an ethylenically unsaturated group. The amount of siloxane is usually 50 to 500 parts by weight, preferably 100 to 300 parts by weight with respect to 100 parts by weight of the total amount of siloxane, and the condensation temperature is usually 5 to 100 ° C.

  In preparing the colloidal silica core-silicone shell emulsion in the composition according to the present invention, a crosslinking agent may be added to improve the strength of the silicone shell part.

  Examples of the crosslinking agent include trimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, ethyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane. And a tetrafunctional crosslinking agent such as tetraethoxysilane.

  The addition amount of this crosslinking agent is the component (a) and component (b) and, if necessary, a silane compound containing an organic functional group or an ethylenically unsaturated group, or an organosiloxane containing an organic functional group or an ethylenically unsaturated group. The amount is usually 10 parts by weight, preferably 5 parts by weight or less, based on 100 parts by weight of the total amount.

  Since the colloidal silica core-silicone shell emulsion in the composition according to the present invention obtained as described above is acidic or alkaline, it needs to be neutralized with alkali or acid in order to maintain long-term stability.

  As this alkaline substance, for example, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethanolamine and the like are used, and as the acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid and the like are used.

  The release agent composition of the present invention only needs to contain the above-described colloidal silica core-silicone shell emulsion, and any component can be added as it is or without compromising the purpose of the present invention. It is obtained by adding a quantity. Preferably, 0 to 99.9% by weight of optional ingredients are added.

  Such optional components include fumed silica, precipitated silica, diatomaceous earth, mica, talc, zinc oxide, titanium oxide, aluminum oxide, iron oxide, cerium oxide, zinc carbonate, calcium carbonate, manganese carbonate, water Inorganic powders such as cerium oxide, carbon black, graphite, glass beads, metal powder; emulsion stabilizers such as lecithin, methylcellulose, polyvinyl alcohol; trimethoxysilane, vinyltrimethoxysilane, triethoxysilane, vinyltriethoxysilane, Silane compounds such as tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, and one or more partial hydrolysates thereof; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) ) -3-Amino Propyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 4 -Organic functional group-containing silane compounds such as ethenylphenyltrimethoxysilane, and one or more partial hydrolysates or reaction mixtures thereof; 3-aminopropyl group, N- (2-aminoethyl) -3 Organic functions containing aminopropyl group, 3-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, 3-mercaptopropyl group, vinyl group, 3-methacryloxypropyl group, 4-ethenylphenyl group, etc. Group-containing polydimethylsiloxane A reaction mixture of the above-mentioned organic functional group-containing silane compound and an organic functional group-containing polydimethylsiloxane; a linear or branched chain having a SiH bond-containing molecular end sealed with a trimethylsilyl group, an alkoxy group or a hydroxyl group Polyorganohydrogensiloxane in the form of a straight chain or branched polyorganosiloxane in which the molecular terminal not containing the specific organic functional group is sealed with a trimethylsilyl group, an alkoxy group or a hydroxyl group; dibutyltin dilaurate; Organic acid metal salts such as dioctyltin laurate, dibutyltin diacetate, tin octylate, iron octylate and zinc octylate; transition metal compounds such as cobalt, rhodium, nickel, palladium and platinum; organic metals such as tetrabutoxytitanium Alcoholate; Amines such as n-butylamine and imidazole; water; various surfactants exemplified above; viscosity adjusting agents, pH adjusting agents, antioxidants, preservatives, rust preventives, fragrances, coloring agents, and other components as necessary Can be added.

  In order to add the above-mentioned optional components to the release agent composition of the present invention, the above-described modified polyorganosiloxane emulsion and other optional components are simply mixed uniformly, or other than the modified polyorganosiloxane emulsion The components may be preliminarily emulsified with an emulsifier such as a homogenizer, colloid mill, or line mixer, or mixed uniformly with a stirrer, and a modified polyorganosiloxane emulsion may be added thereto.

  The mold release agent composition of the present invention can be applied to the mold by any of a brushing method, a spray gun method, a method using an aerosol container, etc., and after application, heating, decompression, nitrogen or air can be used. Water may be volatilized by a method such as blowing in water. By such a method, good releasability can be imparted to various molds made of various materials such as metal, ceramic, synthetic resin, synthetic rubber, wood and paper.

  Examples of the application object of the release agent composition of the present invention include polystyrene, AS, ABS, polyvinyl chloride, vinylidene chloride-vinyl chloride copolymer resin, polyethylene, polypropylene, polyacetal, polyamide, polycarbonate, polyoxymethylene, Polyethylene terephthalate, polybutylene terephthalate, polyacrylate, epoxy resin, phenol resin, polyester resin, polyphenylene sulfide resin, urea resin, melamine resin, diallyl phthalate resin, formaldehyde resin, xylene resin, xylene formaldehyde resin, ketone formaldehyde resin, furan resin, Imide resin, melamine resin, alkyd resin, unsaturated polyester resin, aniline resin, sulfonamide resin, maleic anhydride modified polypropylene And organic resins such as copolymer resins thereof; natural rubber (NB), styrene-butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), acrylonitrile-butadiene rubber (NBR), nitrile Rubber, hydrogenated NBR, chloroprene rubber (CR), ethylene-propylene rubber (EPM), ethylene-propylene-diene terpolymer (EPDM), butyl rubber (IIR), acrylic rubber (ACM), ethylene-acrylic rubber, chlorosulfonated Organic rubbers such as polyethylene (CSM), fluoro rubber (FKM, etc.), epichlorohydrin rubber (CO, ECO), polysulfide rubber (T), urethane rubber (U) and the like can be mentioned.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, unless otherwise indicated, the part and% in an Example are a weight part and weight%. The colloidal silica core-silicone shell emulsion was evaluated as follows.

[Evaluation method of colloidal silica core-silicone shell emulsion]
(1) Average particle size The average particle size of the colloidal silica and colloidal silica core-silicone shell bodies used as raw materials is the laser particle size prayer system LPA-3000S / manufactured by Otsuka Electronics Co., Ltd., which employs the dynamic light scattering method. Measurement was performed using 3100.

(2) Graft ratio and graft efficiency When the colloidal silica core-silicone shell body is regarded as a graft polymer, that is, when the colloidal silica core is regarded as a trunk polymer and the silicone shell is regarded as a branch polymer, the graft ratio and graft efficiency are It calculated | required with the following method.

  That is, a constant weight (1) of the dried core-shell body obtained by drying the core-shell body-containing emulsion at 40 ° C./0.5 mmHg for 5 hours under reduced pressure was put into cyclohexane and shaken with a shaker for 2 hours. Free polyorganosiloxane was dissolved and subjected to concentric separation at a rotational speed of 23,000 rpm for 30 minutes using a centrifugal separator to obtain an insoluble matter. Next, it dried at 120 degreeC for 1 hour using the vacuum dryer, the insoluble content weight (m) was obtained, and the graft ratio and the grafting efficiency were computed by following Formula.

[Preparation of polyorganosiloxane emulsion]
[Emulsion A]
500 parts of Snowtex OL-40 (manufactured by Nissan Chemical Industries, Ltd., average particle size 84 nm, SiO ₂ 40.8%, Na ₂ O 0.0049%, pH 2.3; abbreviated as silica-1), which is acidic colloidal silica In a mixed solution of 500 parts of ion-exchanged water and n-dodecylbenzenesulfonic acid (Nissan Chemical Industry Co., Ltd., Soft Oarai 5S; abbreviated as emulsifier 1), octamethylcyclotetrasiloxane (b- 204 parts were abbreviated as 1), pre-stirred with a homomixer, and then emulsified and dispersed by passing twice with a homogenizer at a pressure of 300 kgf / cm ² .

  The mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, heated at 85 ° C. for 5 hours with stirring and mixed, and cooled at 5 ° C. for 48 hours to complete the polymerization. Next, this polyorganosiloxane emulsion was neutralized with an aqueous sodium carbonate solution to pH 7 to complete the polymerization. The non-volatile content of the obtained polyorganosiloxane emulsion at 105 ° C. × 3 hours was 34.2%, and the polymerization rate of octamethylcyclotetrasiloxane was 99.4%. Further, it was confirmed by particle size solution based on the dynamic light scattering method and observation with an electron microscope that the polyorganosiloxane was a colloidal silica core-silicone shell body. That is, when the particle size was reconciled using a laser particle size analysis system (LPA-3000S / 3100 manufactured by Otsuka Electronics Co., Ltd.), the single-dispersed particle size distribution having a peak near 84 nm of the raw material colloidal silica was completely obtained. It disappeared and a new monodisperse particle size distribution with a peak near 153 nm appeared. Furthermore, when observed with an electron microscope, only the silicone particle image was confirmed, and the raw silica particle image was not observed at all.

  On the other hand, a part of this core-shell emulsion was put into a large amount of acetone to pour out the core-shell, and after filtration, dried in a vacuum dryer at 50 ° C. for 12 hours to obtain a core-shell aggregate.

  When the core-shell aggregate was regarded as a graft polymer, the graft ratio and graft efficiency were 41.7%, respectively.

[Emulsions B to E, a, b]
In Emulsion A, a polyorganosiloxane emulsion was prepared in the same manner as Emulsion A except that each raw material composition was changed. The results of evaluating these emulsions in the same manner as in the case of Emulsion A are shown in Table 1.

[Emulsion F, G]
In emulsion A, 2.1 parts of 3-aminopropylmethyldimethoxysilane (abbreviated as b-2) (D) or 4-ethenylphenylmethyldimethoxysilane (abbreviated as b-3) (F) was added to b-1. A polyorganosiloxane emulsion was prepared in the same manner as in Emulsion A except that it was added and blended in advance. These obtained polyorganosiloxanes could be confirmed to be colloidal silica core-silicone shell bodies having a monodispersed particle size distribution by particle size praying based on dynamic light scattering and observation with an electron microscope. Table 1 shows the results of evaluating these core-shell bodies in the same manner as in the case of emulsion A.

[Emulsion H]
Alcohol colloidal silica Snowtex 20L (manufactured by Nissan Chemical Industries, Ltd., average particle size 72 nm, SiO ₂ 20.4%, Na ₂ O 0.0022%, pH 9.9; abbreviated as silica-2) 1000 parts, 30% Cetyltrimethylammonium chloride aqueous solution (Kao Co., Ltd., Cotamine 60W, active ingredient 30%; abbreviated as emulsifier 2) 54.7 parts, polyoxyethylene (18) nonylphenyl ether (Nikko Chemicals Co., Ltd., NIKKOL NP-) 18TX, HLB19; abbreviated as emulsifier 3) Into a mixed solution of 32.8 parts and 6.0 parts of potassium hydroxide, 204 parts of b-1 was added to prepare a polyorganosiloxane emulsion under the same conditions as in emulsion A. did. The obtained polyorganosiloxane was confirmed to be a colloidal silica core-silicone shell body having a monodispersed particle size distribution by particle size analysis based on dynamic light scattering and electron microscope observation. Table 1 shows the results of evaluating the core-shell body in the same manner as in the case of emulsion A.

[Emulsion c]
In a mixed solution of 4.1 parts of emulsifier 1 and 337 parts of ion-exchanged water, 204 parts of b-1 was added, pre-stirred with a homomixer, and then passed twice with a homogenizer at a pressure of 300 kgf / cm ² . Emulsified and dispersed.

  The mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, heated at 85 ° C. for 5 hours with stirring and mixed, and cooled at 5 ° C. for 48 hours to complete the polymerization. The dispersion was neutralized to pH 7 with a 10% aqueous sodium carbonate solution to stop the polymerization reaction, thereby obtaining a polyorganosiloxane emulsion.

  This emulsion had a non-volatile content of 34.4% at 10 ° C. for 3 hours and an average particle size of 260 nm. Further, this emulsion was broken with isopropyl alcohol, and the polyorganosiloxane polymer was taken out and subjected to GPC measurement. As a result, the weight average molecular weight was 520,000.

[Emulsion d]
3. 500 parts by weight of silica-1 and sodium n-dodecylbenzenesulfonate (Lypon LS-250; abbreviated as emulsifier 4) with respect to 545 parts by weight of the polyorganosiloxane emulsion produced with emulsion c. 1 part by weight and 163 parts by weight of ion-exchanged water were placed in a separable flask equipped with a stirrer and stirred at room temperature for 15 minutes to obtain a polyorganosiloxane emulsion.

  The non-volatile content of this emulsion at 105 ° C. × 3 hours is 32.6%. As a result of particle size analysis, the peak at 84 nm caused by the raw material colloidal silica and the vicinity of 260 nm caused by the polyorganosiloxane emulsion of Comparative Example 3 were obtained. Only a peak was confirmed (average particle diameter 139 nm).

以下、離型剤組成物としての実施形態について説明する。

Hereinafter, an embodiment as a release agent composition will be described.

[Tire molding using vulcanization bladder] (Examples 9 to 14 and Comparative Examples 5 to 8)
The surface of the vulcanization bladder mainly composed of butyl rubber was washed with acetone or the like and sufficiently dried.

  Emulsions A to C, F to H and a to d 100 parts, 50% dibutyltin dilaurate aqueous emulsion (dibutyltin dilaurate 50 parts, sodium dodecylbenzenesulfonate 5 parts and distilled water 45 parts) 0.25 parts, thickener HPC (Hydroxypropyl cellulose) A release agent composition having a composition comprising 5 parts of grade M (manufactured by Nippon Soda Co., Ltd.), 2 parts of 3-glycidoxypropyltrimethoxysilane and 2 parts of 3-aminopropyltrimethoxysilane is applied. The film was left for 72 hours under conditions of an air temperature of 25 ° C. and a relative humidity of 70% to form a cured film. Then, this vulcanization bladder was mounted on a tire vulcanizer, a passenger car radial tire was vulcanized, and the number of vulcanizations until the bladder failed was measured. The results are shown in Table 2.

[Molding of Various Organic Resins Using Iron Mold] (Examples 15-20, Comparative Examples 9-12)
In Examples 9 to 13 and Comparative Examples 5 to 8, a release agent composition having the same composition was prepared except that the thickener was removed, and spray-coated on an iron mold for injection molding held at 333K. A mold coating was formed.

  Next, this mold was set on an injection molding machine (manufactured by Toshiba Corporation, IS-80A), and injection molding of various resins shown in Table 3 was performed using this mold. The injection conditions were a cylinder temperature of 553 to 593K and a mold temperature of 333K.

  As an evaluation of releasability, the number of possible releasations was measured. The evaluation results are also shown in Table 3. In addition, ABS which is resin in the table is manufactured by Nippon Synthetic Rubber Co., Ltd., ABS85 and PPS are manufactured by Toprene Co., Ltd., Toprene T-4 (polyphenylene sulfide resin), Nylon 6 is manufactured by Toray Industries, Inc., and Amilan CM1017 , PBT is manufactured by Polyplastics Co., Ltd., Duranex XD499 (polybutylene terephthalate), PC is manufactured by Idemitsu Petrochemical Co., Ltd., A-2200 (polycarbonate), PVC is manufactured by Toagosei Chemical Co., Ltd., Aron TS700 (Polyethylene) (Vinyl chloride), MPP manufactured by Mitsubishi Oil Chemical Co., Ltd., MODIC P-10B (maleic anhydride modified polypropylene), POM manufactured by Polyplastics, Duracon M90 (polyoxymethylene), polyarylate manufactured by Unitika Co., Ltd. Made from U polymer U-8000.

[Vulcanization of various organic rubbers using iron mold] (Examples 21 to 26, Comparative Examples 13 to 16)
A release agent composition having the same composition as in Examples 9 to 13 and Comparative Examples 5 to 8 except for the thickener was prepared and spray-coated on an iron mold for pressing held at 443K, and a release coating was obtained. Formed.

Next, press vulcanization of various organic rubber compositions shown in Table 4 was performed using this mold. The press vulcanization was performed by heating and pressing under conditions of 100 to 150 kgf / cm ² , 443 K and 20 minutes.

  As an evaluation of releasability, the number of possible releasations was measured. The evaluation results are shown in Table 5. In addition, ethylene-propylene rubber which is an organic rubber composition in Table 5 is manufactured by Nippon Synthetic Rubber Co., Ltd., EP43, fluororubber is manufactured by Nippon Synthetic Rubber Co., Ltd., Aphras 150P, and ethylene-acrylic rubber is manufactured by DuPont Co., Ltd. ), VAMACB124, acrylic rubber manufactured by Nippon Synthetic Rubber Co., Ltd., AR101, nitrile rubber manufactured by Nippon Synthetic Rubber Co., Ltd., N230S, silica manufactured by Nippon Silica Co., Ltd., Mip Seal VN3, process oil manufactured by Idemitsu Kosan Co., Ltd. ), Process Oil PW-380, Peroxide is manufactured by Kayaku Nouri Co., Ltd., Parkadox 14/40, Cross-linking auxiliary is Kayaku Nouri Co., Ltd., triallyl isocyanurate, and vulcanizing agent is DuPont ( Co., Ltd., Diac No. 1. The vulcanization accelerator was Nouchira-D, manufactured by Ouchi Shinsei Chemical Co., Ltd.

  As is apparent from the results of Tables 2, 3 and 5, Examples 9 to 26 (emulsions A to C, F to H) are examples using colloidal silica core-silicone shell bodies within the scope of the present invention. The release agent composition which is the object of the invention is obtained. On the other hand, Comparative Examples 5, 9 and 13 (emulsion a) are examples in which the constituent weight percentage of the core of colloidal silica exceeds the range of the present invention, and is inferior in releasability. Comparative Examples 6, 10 and 14 (Emulsion b) are examples in which the constituent weight percentage of the polyorganosiloxane shell exceeds the scope of the present invention, and the constituent weight percentage of the colloidal silica core does not fall within the scope of the present invention. Comparative Examples 7, 11, and 15 (emulsion c) are examples of simple emulsion polymerization emulsions that do not contain a colloidal silica core, and are each inferior in releasability. Further, Comparative Examples 8, 12 and 16 (emulsion d) are simple emulsion polymerization emulsions and colloidal silica mixtures in which a core shell body is not formed, and are inferior in releasability.

Claims (2)

(A) 80 to 5% by weight of a colloidal silica core;
(B) Average composition formula R ¹ _a SiO _{(4-a) / 2} (I)
(Wherein R ¹ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, a is a number of 1.80 to 2.20) and a shell of 20 to 95% by weight of a polyorganosiloxane represented by The mold release agent composition characterized by containing the colloidal silica core-silicone shell body which consists of these as a main component.   The mold release agent composition according to claim 1, further comprising an organic acid metal salt and / or an organic functional group-containing silane compound.