JP2010083964A - Film forming organopolysiloxane, emulsion composition, and preparation of organopolysiloxane emulsion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film forming organopolysiloxane capable of obtaining a silicone film only by drying without the need of using a crosslinking agent such as an alkoxy silane, and furthermore, capable of obtaining a silicone film having the rubber strength and elasticity in the case of use in combination with a film reinforcing agent such as a colloidal silica and a curing catalyst. <P>SOLUTION: The film forming organopolysiloxane is obtained by reaction of an organopolysiloxane represented by formula (I): HO-[R<SP>1</SP><SB>2</SB>SiO]<SB>n</SB>-H and/or an organopolysiloxane represented by formula (II): [R<SP>1</SP><SB>2</SB>SiO]<SB>m</SB>with a compound represented by formula (III) in the presence of an acid catalyst, wherein R<SP>1</SP>is a monovalent hydrocarbon group, n is 2-5,000, m is 3-10, X is either R<SP>1</SP><SB>a</SB>(R<SP>2</SP>O)<SB>b</SB>Si-R<SP>3</SP>-, a monovalent hydrocarbon group, or a hydrogen atom, with at least one of them being R<SP>1</SP><SB>a</SB>(R<SP>2</SP>O)<SB>b</SB>Si-R<SP>3</SP>-, R<SP>2</SP>is a monovalent hydrocarbon group, R<SP>3</SP>is a divalent hydrocarbon group, a is 0 or 1, b is 2 or 3, and a+b=3. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel film-forming organopolysiloxane capable of obtaining an organopolysiloxane film by simply removing water, an emulsion composition, and a method for producing an organopolysiloxane emulsion.

  Organopolysiloxanes that are crosslinked and cured to form rubber films and resin films are used as surface coating agents for various substrates such as fibers, wood, and rubber, as binders for functional inorganic fillers such as photocatalysts, and paint additives. When such a curable organopolysiloxane is used, it is common to use a composition having a complicated composition containing a crosslinking agent such as a reactive organic group-containing alkoxysilane (Japanese Patent Laid-Open No. Hei 5-98579). JP, 2005-325253, A, JP, 2007-51236, A: patent documents 1-3. Moreover, as what mix | blended an isocyanuric acid ester type compound and silicone, Unexamined-Japanese-Patent No. 10-87993, Unexamined-Japanese-Patent No. 2007-9072, Unexamined-Japanese-Patent No. 2007-126596, Unexamined-Japanese-Patent No. 2007-186596 (patent document 4) -7), etc., these relate to an addition reaction with a platinum catalyst and a condensation reaction with a titanium catalyst. Furthermore, as isocyanuric acid derivative group-containing siloxanes, disclosed in JP-A No. 2004-99751 and JP-A No. 2008-143554 (Patent Documents 8 and 9), these are also produced by addition reaction, A substituted isocyanuric acid and a dihalogen compound are reacted with an alkali metal catalyst, and there is no exemplification regarding a product generated by a reaction with an acid catalyst. Furthermore, there is no example of performing these reactions in an emulsion.

Japanese Patent Laid-Open No. 5-98579 JP 2005-325253 A JP 2007-51236 A Japanese Patent Laid-Open No. 10-87993 JP 2007-9072 A JP 2007-126696 A JP 2007-186596 A JP 2004-99751 A JP 2008-143594 A

  The present invention has been made in view of the above circumstances, and provides a novel film-forming organopolysiloxane capable of obtaining an organopolysiloxane film only by drying, an emulsion composition thereof, and a method for producing an organopolysiloxane emulsion. For the purpose.

  As a result of intensive studies to achieve the above object, the present inventors have found that both terminal hydroxyorganopolysiloxanes represented by the following general formula (I) and / or cyclic organopolysiloxanes represented by the following general formula (II): By reacting an alkoxysilyl group-containing isocyanuric acid ester represented by the following chemical formula (III) in the presence of an acid catalyst, a film-forming organopolysiloxane can be obtained, which can form an organopolysiloxane film only by drying. This has been found and the present invention has been made.

（ここで、Ｘは同一又は異種の、Ｒ¹ _a（Ｒ²Ｏ）_bＳｉ−Ｒ³−で示される１価有機基、炭素数１〜１０の１価炭化水素基、水素原子のいずれかであり、少なくとも１つはＲ¹ _a（Ｒ²Ｏ）_bＳｉ−Ｒ³−で示される１価有機基である。なお、Ｒ¹は上記の通り、Ｒ²は炭素数１〜１０の１価炭化水素基、Ｒ³は炭素数１〜１０の２価炭化水素基、ａは０又は１、ｂは２又は３、ａ＋ｂ＝３である。）
請求項２：
（Ａ）下記一般式（Ｉ）で示される両末端ヒドロキシオルガノポリシロキサン及び／又は下記一般式（ＩＩ）で示される環状オルガノポリシロキサンと、下記化学式（ＩＩＩ）で示されるアルコキシシリル基含有イソシアヌル酸エステルを酸触媒存在下で反応させて得られるオルガノポリシロキサン １００質量部
ＨＯ−［Ｒ¹ ₂ＳｉＯ］_n−Ｈ （Ｉ）
（ここで、Ｒ¹は炭素数１〜２０の置換又は非置換の１価炭化水素基、ｎは２〜５，０００の正数である。）
［Ｒ¹ ₂ＳｉＯ］_m （ＩＩ）
（ここで、Ｒ¹は上記の通り、ｍは３〜１０の正数である。）

（ここで、Ｘは同一又は異種の、Ｒ¹ _a（Ｒ²Ｏ）_bＳｉ−Ｒ³−で示される１価有機基、炭素数１〜１０の１価炭化水素基、水素原子のいずれかであり、少なくとも１つはＲ¹ _a（Ｒ²Ｏ）_bＳｉ−Ｒ³−で示される１価有機基である。なお、Ｒ¹は上記の通り、Ｒ²は炭素数１〜１０の１価炭化水素基、Ｒ³は炭素数１〜１０の２価炭化水素基、ａは０又は１、ｂは２又は３、ａ＋ｂ＝３である。）
（Ｂ）界面活性剤 ０．１〜５０質量部
（Ｃ）水 ２５〜１０，０００質量部
を含むことを特徴とする皮膜形成性オルガノポリシロキサンエマルジョン組成物。
請求項３：
更に、（Ａ）成分１００質量部に対し、
（Ｄ）コロイダルシリカ １〜５０質量部
（Ｅ）縮合触媒 ０．１〜２０質量部
を含むことを特徴とする請求項２記載の皮膜形成性オルガノポリシロキサンエマルジョン組成物。
請求項４：
下記一般式（Ｉ）で示される両末端ヒドロキシオルガノポリシロキサン及び／又は下記一般式（ＩＩ）で示される環状オルガノポリシロキサンと、下記化学式（ＩＩＩ）で示されるアルコキシシリル基含有イソシアヌル酸エステルからなるエマルジョンに酸触媒を添加し、０〜９０℃の温度で６〜２００時間反応させた後、アルカリ化合物で中和することを特徴とする皮膜形成性オルガノポリシロキサンのエマルジョンの製造方法。
ＨＯ−［Ｒ¹ ₂ＳｉＯ］_n−Ｈ （Ｉ）
（ここで、Ｒ¹は炭素数１〜２０の置換又は非置換の１価炭化水素基、ｎは２〜５，０００の正数である。）
［Ｒ¹ ₂ＳｉＯ］_m （ＩＩ）
（ここで、Ｒ¹は上記の通り、ｍは３〜１０の正数である。）

（ここで、Ｘは同一又は異種の、Ｒ¹ _a（Ｒ²Ｏ）_bＳｉ−Ｒ³−で示される１価有機基、炭素数１〜１０の１価炭化水素基、水素原子のいずれかであり、少なくとも１つはＲ¹ _a（Ｒ²Ｏ）_bＳｉ−Ｒ³−で示される１価有機基である。なお、Ｒ¹は上記の通り、Ｒ²は炭素数１〜１０の１価炭化水素基、Ｒ³は炭素数１〜１０の２価炭化水素基、ａは０又は１、ｂは２又は３、ａ＋ｂ＝３である。） Accordingly, the present invention provides the following matters.
Claim 1:
Hydroxyl organopolysiloxane represented by the following general formula (I) and / or cyclic organopolysiloxane represented by the following general formula (II) and an alkoxysilyl group-containing isocyanuric acid ester represented by the following chemical formula (III) are acidified. A film-forming organopolysiloxane obtained by reacting in the presence of a catalyst.
HO— [R ¹ ₂ SiO] _n —H (I)
(Here, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and n is a positive number of 2 to 5,000.)
[R ¹ ₂ SiO] _m (II)
(Here, R ¹ is a positive number of 3 to 10 as described above.)

(Where X is the same or different, R ¹ _a (R ² O) _b Si—R ³ —, a monovalent organic group represented by R 1 —, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. And at least one is _a monovalent organic group represented by R ¹ _a (R ² O) _b Si—R ³ —, where R ¹ is as described above, and R ² is 1 having 1 to 10 carbon atoms. A valent hydrocarbon group, R ³ is a C 1-10 divalent hydrocarbon group, a is 0 or 1, b is 2 or 3, and a + b = 3.)
Claim 2:
(A) Both-end hydroxyorganopolysiloxane represented by the following general formula (I) and / or cyclic organopolysiloxane represented by the following general formula (II), and an alkoxysilyl group-containing isocyanuric acid represented by the following chemical formula (III) Organopolysiloxane obtained by reacting an ester in the presence of an acid catalyst 100 parts by mass HO— [R ¹ ₂ SiO] _n —H (I)
(Here, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and n is a positive number of 2 to 5,000.)
[R ¹ ₂ SiO] _m (II)
(Here, R ¹ is a positive number of 3 to 10 as described above.)

(Where X is the same or different, R ¹ _a (R ² O) _b Si—R ³ —, a monovalent organic group represented by R 1 —, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. And at least one is _a monovalent organic group represented by R ¹ _a (R ² O) _b Si—R ³ —, where R ¹ is as described above, and R ² is 1 having 1 to 10 carbon atoms. A valent hydrocarbon group, R ³ is a C 1-10 divalent hydrocarbon group, a is 0 or 1, b is 2 or 3, and a + b = 3.)
(B) Surfactant 0.1-50 mass parts (C) The film-forming organopolysiloxane emulsion composition characterized by including 25-10,000 mass parts of water.
Claim 3:
Furthermore, for 100 parts by mass of component (A),
(D) Colloidal silica 1-50 mass parts (E) Condensation catalyst 0.1-20 mass parts is included, The film-forming organopolysiloxane emulsion composition of Claim 2 characterized by the above-mentioned.
Claim 4:
It consists of both ends hydroxyorganopolysiloxane represented by the following general formula (I) and / or cyclic organopolysiloxane represented by the following general formula (II) and an alkoxysilyl group-containing isocyanuric acid ester represented by the following chemical formula (III) A method for producing an emulsion of a film-forming organopolysiloxane, comprising adding an acid catalyst to an emulsion, reacting at a temperature of 0 to 90 ° C for 6 to 200 hours, and then neutralizing with an alkali compound.
HO— [R ¹ ₂ SiO] _n —H (I)
(Here, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and n is a positive number of 2 to 5,000.)
[R ¹ ₂ SiO] _m (II)
(Here, R ¹ is a positive number of 3 to 10 as described above.)

(Where X is the same or different, R ¹ _a (R ² O) _b Si—R ³ —, a monovalent organic group represented by R 1 —, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. And at least one is _a monovalent organic group represented by R ¹ _a (R ² O) _b Si—R ³ —, where R ¹ is as described above, and R ² is 1 having 1 to 10 carbon atoms. A valent hydrocarbon group, R ³ is a C 1-10 divalent hydrocarbon group, a is 0 or 1, b is 2 or 3, and a + b = 3.)

  According to the present invention, a silicone film can be obtained simply by drying without using a cross-linking agent such as alkoxysilane. Further, when a film reinforcing agent such as colloidal silica and a curing catalyst are used in combination, rubber strength, elasticity A silicone film can be obtained. Further, by changing the crosslinking source from conventional alkoxysilane to alkoxysilyl group-containing isocyanuric acid ester, a rubber film having excellent elasticity can be obtained.

The present invention is described in detail below.
First, both terminal hydroxyorganopolysiloxane which is one of the raw materials is represented by the following general formula (I).
HO— [R ¹ ₂ SiO] _n —H (I)
(Here, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and n is a positive number of 2 to 5,000.)

Here, R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl Alkyl groups such as cyclopentyl, cyclohexyl and cycloheptyl; aryl groups such as phenyl, tolyl and naphthyl; and alkenyl groups such as vinyl and allyl. In addition, those obtained by substituting a part of hydrogen atoms with an organic group such as an amino group, an epoxy group, or a mercapto group can also be used. In the present invention, as R ¹ , 90 mol% or more is preferably a methyl group. n is a positive number of 2 to 5,000, and when it is larger than 5,000, the reactivity with the alkoxysilyl group-containing isocyanuric acid ester is lowered. Preferably it is 10-3,000, More preferably, it is 10-1,000.

The cyclic organopolysiloxane is represented by the following general formula (II).
[R ¹ ₂ SiO] _m (II)
(Here, R ¹ is a positive number of 3 to 10 as described above.)

Here, R ¹ is the above-mentioned monovalent hydrocarbon group having 1 to 20 carbon atoms, and as R ¹ in the present invention, 90 mol% or more is preferably a methyl group. m is a positive number of 3 to 10, and a single compound such as a cyclic trimer, a cyclic tetramer, or a cyclic pentamer may be used, or a mixture of these cyclic bodies may be used. Under the present circumstances, it is preferable that 50 mass% or more of cyclic tetramers are included.

（ここで、Ｘは同一又は異種の、Ｒ¹ _a（Ｒ²Ｏ）_bＳｉ−Ｒ³−で示される１価有機基、炭素数１〜１０の１価炭化水素基、水素原子のいずれかであり、少なくとも１つはＲ¹ _a（Ｒ²Ｏ）_bＳｉ−Ｒ³−で示される１価有機基である。なお、Ｒ¹は上記の通り、Ｒ²は炭素数１〜１０の１価炭化水素基、Ｒ³は炭素数１〜１０の２価炭化水素基、ａは０又は１、ｂは２又は３、ａ＋ｂ＝３である。） Next, another raw material alkoxysilyl group-containing isocyanuric acid ester is represented by the following chemical formula (III).

(Where X is the same or different, R ¹ _a (R ² O) _b Si—R ³ —, a monovalent organic group represented by R 1 —, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. And at least one is _a monovalent organic group represented by R ¹ _a (R ² O) _b Si—R ³ —, where R ¹ is as described above, and R ² is 1 having 1 to 10 carbon atoms. A valent hydrocarbon group, R ³ is a C 1-10 divalent hydrocarbon group, a is 0 or 1, b is 2 or 3, and a + b = 3.)

Here, X is either the same or different, a monovalent organic group represented by R ¹ _a (R ² O) _b Si—R ³ —, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. is there. R ¹ is the above-mentioned monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably a methyl group. R ² is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like. From the viewpoint of reactivity, R ² is preferably a methyl group, an ethyl group, or a propyl group, and more preferably a methyl group. R ³ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and specific examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene. Of these, methylene, propylene, and hexylene are preferable, and propylene is more preferable. a is 0 or 1, b is 2 or 3, and a + b = 3. From the viewpoint of crosslinkability, a = 0 and b = 3 are preferable. In order to achieve film formation, at least one of X needs to be a monovalent organic group represented by R ¹ _a (R ² O) _b Si—R ³ —. Preferably two and more preferably three are monovalent organic groups represented by R ¹ _a (R ² O) _b Si—R ³ —.

  In this case, both terminal hydroxyorganopolysiloxane and / or cyclic organopolysiloxane and alkoxysilyl group-containing isocyanuric acid ester are alkoxysilyl group-containing with respect to 100 parts by mass of both terminal hydroxyorganopolysiloxane and / or cyclic organopolysiloxane. Isocyanuric acid ester is preferably used in a proportion of 0.01 to 5 parts by mass. If the alkoxysilyl group-containing isocyanuric acid ester is too much, the stability of the emulsion may be lowered, and if it is too little, a film-forming organopolysiloxane may not be obtained.

  The reaction product of the above-mentioned both-end hydroxyorganopolysiloxane and / or cyclic organopolysiloxane and an alkoxysilyl group-containing isocyanuric acid ester can be obtained by a reaction using an acid catalyst. Examples of the acid catalyst include sulfuric acid, hydrochloric acid, trifluoromethanesulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and lauryl sulfuric acid.

  The amount of the acid catalyst is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the reaction product of both ends hydroxyorganopolysiloxane and / or cyclic organopolysiloxane and alkoxysilyl group-containing isocyanuric acid ester. If the amount is less than 0.01 parts by weight, the reaction may not proceed. If the amount is more than 10 parts by weight, the stability of the emulsion may be lowered. Therefore, the amount is preferably 0.01 to 10 parts by weight, more preferably. It is 0.02-5 mass parts, More preferably, it is 0.05-3 mass parts.

  Since the reaction product of both ends hydroxyorganopolysiloxane and / or cyclic organopolysiloxane and alkoxysilyl group-containing isocyanuric acid ester changes from a gel to a film, each raw material is emulsified and dispersed in water using a surfactant. It is preferable to react. The reaction temperature is 0 to 90 ° C, preferably 10 to 80 ° C. The reaction time is 6 to 200 hours, preferably 8 to 150 hours. Then, the target film-forming organopolysiloxane emulsion can be obtained by neutralizing with an alkali compound.

  There is no restriction | limiting in particular as surfactant (B) component, For example, nonionic surfactants, such as polyoxyethylene alkyl ether, polyoxyethylene propylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, etc. Anionic surfactants such as alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, quaternary alkyl ammonium salts, Examples include cationic surfactants such as alkylamine acetates, and amphoteric surfactants such as alkylbetaines and alkylimidazolines. Of these, alkyl sulfates and alkyl benzene sulfonates are preferred from the standpoints of emulsification and stability.

  The amount of the surfactant used is 0.1 to 50 parts by mass with respect to 100 parts by mass of the reaction product of both ends hydroxyorganopolysiloxane and / or cyclic organopolysiloxane and alkoxysilyl group-containing isocyanuric acid ester. If the amount is less than 0.1 parts by mass, the stability of the emulsion is lowered. If the amount is more than 50 parts by mass, the strength of the dry rubber film is lowered. Preferably it is 0.5-30 mass parts, More preferably, it is 1-20 mass parts.

  In addition, the content of water as component (C) when emulsifying is 25 with respect to 100 parts by mass of a reaction product of both-end hydroxyorganopolysiloxane and / or cyclic organopolysiloxane and alkoxysilyl group-containing isocyanurate. -10,000 parts by mass. When the amount is less than 25 parts by mass, the viscosity of the emulsion is increased and the workability is lowered. When the amount is more than 10,000 parts by mass, the stability of the emulsion is lowered. Preferably it is 50-5,000 mass parts.

  The organopolysiloxane emulsion composition comprising the above components (A), (B), and (C) becomes a film only by drying, but the colloidal that is component (D) for the purpose of improving the rubber strength of the film. It is preferable to use silica and a condensation catalyst which is component (E) in combination.

  Colloidal silica as component (D) is added as a film reinforcing agent, and a commercially available one can be used, and there is no limitation on the kind thereof, but for example, the average particle diameter is 5 to 50 nm, sodium , Ammonium, aluminum, and the like may be used. Specifically, Snowtex (manufactured by Nissan Chemical Industries), Ludox (manufactured by Grace), silica doll (manufactured by Nippon Kagaku Kogyo), Adelite AT (ADEKA) And commercial products such as Cataloid S (manufactured by Catalyst Kasei Kogyo Co., Ltd.).

  (D) It is preferable that the compounding quantity of a component is 1-50 mass parts with respect to 100 mass parts of reaction materials of both terminal hydroxyorganopolysiloxane and / or cyclic organopolysiloxane, and an alkoxy silyl group containing isocyanuric acid ester. When the amount is less than 1 part by mass, the effect of reinforcing the rubber film is weak. When the amount is more than 50 parts by mass, the film may be hard and brittle, and the amount is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass. It is 5 mass parts, More preferably, it is 5-30 mass parts.

  The (E) component condensation catalyst is a catalyst for condensation crosslinking of the (A) component alkoxy group and the (D) component hydroxyl group, and is not particularly limited as long as the condensation reaction proceeds. And organic metal compounds such as organic zinc compounds, organic iron compounds, organic titanium compounds, organic bismuth compounds, organic zirconium compounds, organic aluminum compounds, organic cerium compounds, organic indium compounds, and organic yttrium compounds. Specifically, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin dilaurate, dioctyltin diversate, dibutyltin bisoleyl malate, tin octylate, zinc stearate, zinc octylate, zinc acetate, iron octylate, octylate Examples thereof include organic acid metal salts such as titanium, bismuth octylate, zirconium octylate, cerium octylate, indium octylate, and yttrium octylate. These condensation catalysts are preferably used in the form of an emulsion that has been previously emulsified and dispersed in water using a surfactant, except when water-soluble.

  (E) The compounding quantity of a component should be 0.1-20 mass parts with respect to 100 mass parts of reaction materials of both-ends hydroxyorganopolysiloxane and / or cyclic organopolysiloxane, and an alkoxy silyl group containing isocyanuric acid ester. preferable. If the amount is less than 0.1 parts by mass, the condensation reaction may not proceed, and if it is more than 20 parts by mass, it is uneconomical. More preferably, it is 0.2-15 mass parts, More preferably, it is 0.3-10 mass parts.

  Further, the organopolysiloxane emulsion composition of the present invention includes various thickeners, pigments, dyes, penetrants, antistatic agents, antifoaming agents, flame retardants, antibacterial agents, antiseptics, water repellents, crosslinking agents, Adhesion improvers and other silicone oils, silicone resins, acrylic resins, urethane resins and the like are arbitrarily blended. The organopolysiloxane emulsion composition of the present invention is used by treating the surface of various substrates such as fibers, paper, metal, wood, rubber, plastic, glass, etc. Various conventionally known coating methods such as spraying, roll coating, bar coating, and brush coating are possible.

The coating weight of the organopolysiloxane emulsion composition is not particularly limited, but is generally an amount that the coating amount is 0.1 to 200 g / m ^2, especially 1 to 100 g / m ^2. After coating, the organopolysiloxane film can be obtained only by drying, and the drying may be performed under the condition that water is volatilized. It is 1 to 3 days at room temperature, and 100 to 180 ° C. when heated. It may be dried for about 1 to 30 minutes.

  The organopolysiloxane emulsion composition of the present invention is a surface coating agent for various substrates, a release agent or slipperiness imparting agent to the surface of a rubber article, a binder agent for a functional inorganic filler such as a photocatalyst, a texture improver for fibers, Although it can be used for water repellents for paper and wood, it is not limited to these.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples,% indicates mass%.

[Example 1]
500 g of dimethylcyclosiloxane (trimer / tetramer / pentamer / 6mer = 5/65/25/5%), 2,4,6-tris [3- (trimethoxysilyl) propyl] isocyanuric acid 3.1 g of ester, 50 g of 10% aqueous sodium lauryl sulfate solution and 50 g of 10% aqueous dodecylbenzenesulfonic acid solution were charged into a 2-liter polyethylene beaker and uniformly emulsified with a homomixer, and then 352.6 g of ion-exchanged water was gradually added. Diluted and passed twice through a high pressure homogenizer at a pressure of 30 MPa to obtain a uniform white emulsion. This emulsion was transferred to a 2 liter glass flask equipped with a stirrer, thermometer and reflux condenser, subjected to a polymerization reaction at 50 ° C. for 48 hours, aged at 15 ° C. for 24 hours, and then pH 7 with 11 g of 3% aqueous ammonia. And 33.3 g of a 15% aqueous sodium lauryl sulfate solution was added to obtain a milky white emulsion A. This emulsion had a non-volatile content of 45.9% after drying at 105 ° C. for 3 hours, and the non-volatile residue was a film.

[Example 2]
500 g of dimethylcyclosiloxane (trimer / tetramer / pentamer / 6mer = 5/65/25/5%), 2,4,6-tris [3- (trimethoxysilyl) propyl] isocyanuric acid 1.5 g of ester, 50 g of 10% aqueous sodium lauryl sulfate solution, 50 g of 10% aqueous dodecylbenzenesulfonic acid solution were charged into a 2 liter polyethylene beaker and uniformly emulsified with a homomixer, and then 354.2 g of ion-exchanged water was gradually added. Diluted and passed twice through a high pressure homogenizer at a pressure of 30 MPa to obtain a uniform white emulsion. This emulsion was transferred to a 2 liter glass flask equipped with a stirrer, thermometer and reflux condenser, subjected to a polymerization reaction at 50 ° C. for 48 hours, aged at 15 ° C. for 24 hours, and then pH 7 with 11 g of 3% aqueous ammonia. And 33.3 g of a 15% sodium lauryl sulfate aqueous solution was added to obtain a milky white emulsion B. This emulsion had a non-volatile content of 45.6% after drying at 105 ° C. for 3 hours, and the non-volatile residue was in the form of a soft film.

[Example 3]
631.9 g of emulsion B obtained in Example 2, 355.5 g of Snowtex C (20% aqueous solution of solids manufactured by Nissan Chemical Industries) as colloidal silica, and 12.6 g of a curing catalyst emulsion containing 30% of dioctyltin dilaurate are mixed. As a result, milky white emulsion C was obtained. This emulsion had a non-volatile content of 36.1% after drying at 105 ° C. for 3 hours, and the non-volatile residue was a film. The emulsion C was air-dried at room temperature for 2 days and then dried at 105 ° C. for 1 hour to prepare a sheet having a thickness of about 0.7 mm. The tensile strength and elongation at break were measured according to JIS K-6249. . The results are shown in Table 1.

[Example 4]
General formula: 500 g of both end hydroxydimethylpolysiloxane represented by HO — [(CH ₃ ) ₂ SiO] ₄₀ —H, 3.1 g of 2,4,6-tris [3- (trimethoxysilyl) propyl] isocyanuric acid ester 50 g of 10% aqueous sodium lauryl sulfate solution and 50 g of 10% aqueous 10% dodecylbenzenesulfonic acid solution were charged into a 2 liter polyethylene beaker and uniformly emulsified with a homomixer. Then, 352.6 g of ion-exchanged water was gradually added and diluted. A uniform white emulsion was obtained by passing twice through a high-pressure homogenizer at 50 MPa. This emulsion was transferred to a 2 liter glass flask equipped with a stirrer, thermometer and reflux condenser, subjected to a polymerization reaction at 50 ° C. for 48 hours, aged at 15 ° C. for 24 hours, and then pH 7 with 11 g of 3% aqueous ammonia. And 33.3 g of a 15% aqueous sodium lauryl sulfate solution were added to obtain a milky white emulsion D. This emulsion had a non-volatile content of 45.7% after drying at 105 ° C. for 3 hours, and the non-volatile residue was a film.

[Comparative Example 1]
500 g of dimethylcyclosiloxane (trimer / tetramer / pentamer / 6mer = 5/65/25/5%), 2,4,6-tris [3- (trimethoxysilyl) propyl] isocyanuric acid 3.1 g of ester, 50 g of 10% aqueous sodium lauryl sulfate solution, 50 g of 10% aqueous sodium dodecylbenzenesulfonate solution were charged into a 2 liter polyethylene beaker and uniformly emulsified with a homomixer, and 363.6 g of ion-exchanged water was gradually added. Then, the mixture was passed through a high-pressure homogenizer twice at a pressure of 30 MPa, and 33.3 g of a 15% aqueous sodium lauryl sulfate solution was added to obtain a uniform white emulsion E. This emulsion had a non-volatile content of 1.5% after drying at 105 ° C. for 3 hours, and the non-volatile residue was in the form of a paste.

[Comparative Example 2]
Dimethylcyclosiloxane (trimer / 4mer / 5mer / 6mer = 5/65/25/5%) 500 g, 10% sodium lauryl sulfate aqueous solution 50 g, 10% dodecylbenzenesulfonic acid aqueous solution 50 g 2 liters After charging in a polyethylene beaker and uniformly emulsifying with a homomixer, 355.7 g of ion exchange water was gradually added to dilute, and the mixture was passed twice through a high pressure homogenizer at a pressure of 30 MPa to obtain a uniform white emulsion. This emulsion was transferred to a 2 liter glass flask equipped with a stirrer, thermometer and reflux condenser, subjected to a polymerization reaction at 50 ° C. for 48 hours, aged at 15 ° C. for 24 hours, and then pH 7 with 11 g of 3% aqueous ammonia. And 33.3 g of a 15% aqueous sodium lauryl sulfate solution was added to obtain a milky white emulsion F. This emulsion had a non-volatile content of 45.4% after drying at 105 ° C. for 3 hours, and the non-volatile residue was in the form of a viscous oil.

[Comparative Example 3]
500 g of dimethylcyclosiloxane (trimer / 4-mer / 5-mer / 6-mer = 5/65/25/5%), 1.5 g of triethoxyphenylsilane, 50 g of 10% aqueous sodium lauryl sulfate solution, 10% dodecyl 50 g of benzenesulfonic acid aqueous solution was charged into a 2 liter polyethylene beaker and uniformly emulsified with a homomixer, then 354.2 g of ion exchange water was gradually added to dilute, and passed through a high pressure homogenizer at a pressure of 30 MPa twice. An emulsion was obtained. This emulsion was transferred to a 2 liter glass flask equipped with a stirrer, thermometer and reflux condenser, subjected to a polymerization reaction at 50 ° C. for 48 hours, aged at 15 ° C. for 24 hours, and then pH 7 with 11 g of 3% aqueous ammonia. And 33.3 g of a 15% aqueous sodium lauryl sulfate solution was added to obtain a milky white emulsion G. This emulsion had a non-volatile content of 45.5% after drying at 105 ° C. for 3 hours, and the non-volatile residue was in the form of a gel.

[Comparative Example 4]
Emulsion G631.9 g obtained in Comparative Example 3, Snowtex C (Nissan Chemical Industries 20% solid content aqueous solution) 355.5 g as colloidal silica, and curing catalyst emulsion 12.6 g containing 30% dioctyltin dilaurate were mixed. As a result, a milky white emulsion H was obtained. This emulsion had a non-volatile content of 36.0% after drying at 105 ° C. for 3 hours, and the non-volatile residue was a film. The emulsion H was air-dried at room temperature for 2 days and then dried at 105 ° C. for 1 hour to prepare a sheet having a thickness of about 0.7 mm. The tensile strength and elongation at break were measured according to JIS K-6249. . The results are shown in Table 1.

Claims (4)

Hydroxyl organopolysiloxane represented by the following general formula (I) and / or cyclic organopolysiloxane represented by the following general formula (II) and an alkoxysilyl group-containing isocyanuric acid ester represented by the following chemical formula (III) are acidified. A film-forming organopolysiloxane obtained by reacting in the presence of a catalyst.
HO— [R ¹ ₂ SiO] _n —H (I)
(Here, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and n is a positive number of 2 to 5,000.)
[R ¹ ₂ SiO] _m (II)
(Here, R ¹ is a positive number of 3 to 10 as described above.)

(Where X is the same or different, R ¹ _a (R ² O) _b Si—R ³ —, a monovalent organic group represented by R 1 —, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. And at least one is _a monovalent organic group represented by R ¹ _a (R ² O) _b Si—R ³ —, where R ¹ is as described above, and R ² is 1 having 1 to 10 carbon atoms. A valent hydrocarbon group, R ³ is a C 1-10 divalent hydrocarbon group, a is 0 or 1, b is 2 or 3, and a + b = 3.) (A) Both-end hydroxyorganopolysiloxane represented by the following general formula (I) and / or cyclic organopolysiloxane represented by the following general formula (II), and an alkoxysilyl group-containing isocyanuric acid represented by the following chemical formula (III) Organopolysiloxane obtained by reacting an ester in the presence of an acid catalyst 100 parts by mass HO— [R ¹ ₂ SiO] _n —H (I)
(Here, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and n is a positive number of 2 to 5,000.)
[R ¹ ₂ SiO] _m (II)
(Here, R ¹ is a positive number of 3 to 10 as described above.)

(Where X is the same or different, R ¹ _a (R ² O) _b Si—R ³ —, a monovalent organic group represented by R 1 —, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. And at least one is _a monovalent organic group represented by R ¹ _a (R ² O) _b Si—R ³ —, where R ¹ is as described above, and R ² is 1 having 1 to 10 carbon atoms. A valent hydrocarbon group, R ³ is a C 1-10 divalent hydrocarbon group, a is 0 or 1, b is 2 or 3, and a + b = 3.)
(B) Surfactant 0.1-50 mass parts (C) The film-forming organopolysiloxane emulsion composition characterized by including 25-10,000 mass parts of water. Furthermore, for 100 parts by mass of component (A),
(D) Colloidal silica 1-50 mass parts (E) Condensation catalyst 0.1-20 mass parts is included, The film-forming organopolysiloxane emulsion composition of Claim 2 characterized by the above-mentioned. It consists of both ends hydroxyorganopolysiloxane represented by the following general formula (I) and / or cyclic organopolysiloxane represented by the following general formula (II) and an alkoxysilyl group-containing isocyanuric acid ester represented by the following chemical formula (III) A method for producing an emulsion of a film-forming organopolysiloxane, comprising adding an acid catalyst to an emulsion, reacting at a temperature of 0 to 90 ° C for 6 to 200 hours, and then neutralizing with an alkali compound.
HO— [R ¹ ₂ SiO] _n —H (I)
(Here, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and n is a positive number of 2 to 5,000.)
[R ¹ ₂ SiO] _m (II)
(Here, R ¹ is a positive number of 3 to 10 as described above.)

(Where X is the same or different, R ¹ _a (R ² O) _b Si—R ³ —, a monovalent organic group represented by R 1 —, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a hydrogen atom. And at least one is _a monovalent organic group represented by R ¹ _a (R ² O) _b Si—R ³ —, where R ¹ is as described above, and R ² is 1 having 1 to 10 carbon atoms. A valent hydrocarbon group, R ³ is a C 1-10 divalent hydrocarbon group, a is 0 or 1, b is 2 or 3, and a + b = 3.)