JPH043431B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a self-crosslinking material which is useful as a phosphoric acid ester group-containing organopolysiloxane latex, particularly as a fiber treatment agent, a lubricant, a mold release agent, a glass fiber treatment agent, a polishing agent, etc. This invention relates to an organopolysiloxane latex with excellent properties and film-forming properties. (Prior art) Methods for producing organopolysiloxane latex include a method in which organopolysiloxane is emulsion polymerized in the presence of a strong acid or a strong alkali (see Japanese Patent Publication No. 34-2041), a cyclic organopolysiloxane with amino groups, A method of obtaining an organic functional organopolysiloxane latex by emulsion polymerization in the presence of a trialkoxysilane containing an epoxy group or the like is known (see Japanese Patent Publication No. 38609/1983). However, the latex compositions obtained by these methods have insufficient reactivity, and although self-crosslinking compositions can be obtained by increasing the amount of trialkoxysilane, the reactivity for self-crosslinking is insufficient. Alternatively, there was the fatal disadvantage that an undesirable gel was formed due to the reaction of epoxy groups as organic functional groups or the hydrolytic polymerization of alkoxy groups. (Structure of the Invention) The present invention relates to an organopolysiloxane latex which solves these disadvantages, and which has the general formula

[Formula] [Here, R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, R ² is the same as R ¹ or an OX group (where X is a hydrogen atom or (same monovalent hydrocarbon group as R ¹ ), a and b are positive numbers from 0 to 3, and 1≦a+b≦
4] Organosilicon compound represented by (2) general formula

[Formula] [Here, R ³ is the same monovalent hydrocarbon group as R ¹ above, and R ⁴ is the same as R ³ or
OY group (here, Y is a hydrogen atom or 1 similar to R ³
valence hydrocarbon group), Z is the formula

[Formula] (where R ⁵ is a lower alkyl group, R ⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms), c, d, and e are positive numbers from 0 to 2, and 1≦c+d+
e≦3] and an organopolysiloxane containing at least one phosphoric acid ester group in one molecule in the presence of (3) a sulfonic acid surfactant and/or a sulfuric acid ester surfactant. It is characterized by being formed by emulsion polymerization in water. That is, the present inventors have conducted various studies on organopolysiloxane latexes that do not have the above-mentioned disadvantages, and have found that organopolysiloxanes containing at least one phosphate group in one molecule and organopolysiloxane latexes with low molecular weight. Silane and/or
or organosiloxane in water in the presence of a specific surfactant, it has been found that an organopolysiloxane latex with excellent self-crosslinking properties and film-forming properties can be obtained in a stable emulsified state, The present invention was completed by conducting research on this phosphate group-containing organopolysiloxane, the organosilicon compound to be reacted with it, the type of surfactant to be used, the amount of these, etc. In the present invention, the organosilicon compound as component (a), which is used as an initiator, has the general formula

[Formula], where R is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an alkenyl group such as a vinyl group or an allyl group, an aryl group such as a phenyl group or a naphthyl group,
Monovalent hydrocarbon groups having 1 to 20 carbon atoms, such as aralyl groups such as tolyl and xylyl groups, or some or all of the hydrogen atoms bonded to the carbon atoms of these groups are replaced with halogen atoms, cyano groups, etc. a group substituted with, R ² is the same as this R ¹ or an OX group (herein, X is a hydrogen atom or the same group as R ¹ ), a,
b is a positive number from 0 to 3 and satisfies 1≦a+b≦4; however, it may be organosilane, organosiloxane, or a mixture thereof; It may be either branched or cyclic. In addition, these may have molecular chain terminals blocked with trialkylsilyl groups or may contain hydroxyl groups at the terminals. This organopolysiloxane has the formula

[Formula] (m is an integer) liquid dimethylpolysiloxane, formula

[Formula] (n is an integer) Liquid dimethylpolysiloxane with both ends blocked with hydroxyl groups, Formula

【formula】

[Formula] (p, q are integers) Liquid dimethylpolysiloxane with both ends blocked with alkoxy groups, Formula

Cyclic dimethylpolysiloxane represented by [Formula] (r is an integer) and the following _CH3Si ( _OCH3 ) ₃ , ( _CH3 ) _2Si ( _OCH3 ) ₂ ,
( _{CH3 ) 3SiOCH3 , C6H5Si ( OCH3} ) ₃ , _C6H5Si
(OC ₂ H ₅ ) ₃ , (C ₆ H ₅ ) ₂ Si (OC ₂ H ₅ ) ₂ , CH ₂ =CHSi
( _OCH3 ) ₃ , _CH2 =CH( _CH3 )Si( _OCH3 ) ₂ ,
C ₃ H ₇ Si (OCH ₃ ) ₃ , C ₁₂ H ₂₅ Si (OCH ₃ ) ₃ (s, t,
(u, v are integers) Organopolysiloxane and organosilane may be used, but among these, the formula Since the cyclic siloxane represented by (r=3 to 10) is widely used in the art as an intermediate raw material for polymer synthesis, it is considered to be the most preferred for obtaining the composition of the present invention. The phosphate group-containing organopolysiloxane as the component (b) that is reacted with the organosilicon compound as the component (a) has the general formula

[Formula], R ³ is the same monovalent hydrocarbon group as R ¹ , R ⁴ is the same as R ³ or OY group (Y
is a hydrogen atom or a monovalent hydrocarbon group similar to R ³ ),
Z is the formula

[Formula] (where R ⁵ is a lower alkyl group, R ⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms), c, d, and e are positive numbers from 0 to 2, and 1≦c+d+
It is said to be an organosiloxane containing at least one phosphoric acid ester group in one molecule, where e≦3.

[Formula] (wherein R ⁵ , R ⁷ , and R ⁸ are alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, and dodecyl groups, vinyl groups, and allyl groups) alkenyl groups such as phenyl groups, aryl groups such as naphthyl groups, aralyl groups such as tolyl groups and xylyl groups, cycloalkyl groups such as cyclohexyl groups, or some or all of the hydrogen atoms bonded to the carbon atoms of these groups. is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom, cyano group, etc., R ⁶ is a carbon number such as a methylene group, ethylene group, propylene group, butylene group, etc. 1 to 8 divalent hydrocarbon groups,
f is a positive number of 0 to 2) obtained as a hydrolysis product of a phosphate ester group-containing organoalkoxysilane or a cohydrolyzate of this phosphate ester group-containing organoalkoxysilane and another organoalkoxysilane. However, this is an organopolysiloxane containing one or more halogenated alkyl groups such as -(CH ₃ ) ₃ Cl as a substituent in one molecule.

It can also be produced by dehydrochlorination reaction with a phosphoric acid ester such as [Formula]. In addition,
The above-mentioned organoalkoxysilane containing a phosphate ester group is, for example, an alkoxysilane represented by the formula (CH ₃ O) ₃ Si(CH ₂ ) ₃ Cl and the above formula.

It can be easily produced by a dehydrochlorination reaction with a phosphoric acid ester represented by the formula. The following organopolysiloxanes containing phosphate ester groups are used. (Here, n, p, q, and r are all positive numbers) are exemplified, but branched versions thereof can be used as well. The amount of this organopolysiloxane compound containing a phosphoric acid ester group is determined based on 100 parts by weight of the organosilicon compound as component (a). If the amount is too large, the stability of the emulsion will be impaired due to the reactivity, so the amount is preferably in the range of 0.1 to 30 parts by weight. Note that this organopolysiloxane is preferably dissolved in component (a) in advance before use, so that its emulsion polymerization in water can be easily carried out. Next, the surfactant as component (c) is as described above in (a).
This is for emulsifying and dispersing component (b) in water, but since it also acts as a catalyst to copolymerize both components in an emulsified state, it is a sulfonic acid surfactant. and/or sulfate ester surfactants. This sulfonic acid surfactant has the general formula R ⁹ C ₆ H ₄ SO ₃ H, R ¹⁰ (OC ₂ H ₄ ) _o OSO ₃ H (where R ⁹ is an aliphatic monovalent hydrocarbon having 6 or more carbon atoms). group, R ¹⁰ is a monovalent aliphatic hydrocarbon group having 6 or more carbon atoms or an aryl group substituted with an aliphatic monovalent hydrocarbon group,
n=1 to 15), and the following are exemplified.

[Formula] C ₈ H ₁₇ (OC ₂ H ₄ ) ₂ OSO ₃ H, C ₁₀ H ₂₁ (OC ₂ H ₄ ) ₂ OSO ₃ H In addition, this sulfate ester surfactant has the general formula
It is a sulfate ester salt type represented by R ¹¹ OSO ₂ M (where R ¹¹ is the same hydrocarbon group as R ¹⁰ above, M is an alkali metal such as Na or K), and this includes sodium lauryl sulfate, sodium lauryl sulfate, Examples include polyoxyethylene dodecyl phenyl sodium sulfate. This sulfate ester surfactant can be used as it is as a surfactant for emulsification, and a good emulsification state can be obtained, but if it is brought into contact with a cation exchange resin after emulsification, the sulfate ester salt will be released. It can be used in this manner because it has the effect of quickly converting into the corresponding acid type, thereby promoting the copolymerization of organosiloxane in the system. Note that the sulfonic acid surfactant and the sulfuric acid ester surfactant may be used in combination, whereby a more stable emulsified state can be obtained and emulsion polymerization can proceed. If the amount of this surfactant used is too small, a sufficient emulsified state will not be obtained and the time required for polymerization will become longer; if it is too large, the stability of the emulsion will be improved, but an unnecessary amount of emulsifier will be present. Since the film obtained by drying may become non-uniform and the heat resistance may decrease, it is necessary to set the amount in the range of 0.5 to 30 parts by weight per 100 parts by weight of component (a). Preferably it is 1 to 10 parts by weight. In addition, increasing the amount used improves the stability of the emulsion and enables fine emulsification, giving an emulsion with a strong bluish appearance, but this is due to the hydrophilicity and heat resistance of the composition obtained after emulsion polymerization. It is preferable to set the criteria based on the requirements such as: The organopolysiloxane latex of the present invention is produced by emulsifying and dispersing components (a) and (b) in the presence of component (c) in water, which serves as a medium for emulsion polymerization of components (a) and (b). , this amount of water is component (a)
The amount may be in the range of 100 to 500 parts by weight per 100 parts by weight. This method can usually be carried out using various emulsifying devices known in the industry, and a typical method is to dissolve and stir the surfactant (component (c)) in water. A mixed solution of component (a) organopolysiloxane and component (b) containing organopolysiloxane is added to form an emulsion, and then made into an emulsion using a colloid mill etc. An example is a method of mixing at a suitable temperature of .degree. C. for several hours to about one week. However, in this method, component (c) and component (a)
If the contact effect on the copolymerization reaction with component (b) is insufficient, add an arbitrary amount of a strong acidic substance such as sulfuric acid, hydrochloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, etc. to the system. Good too,
According to this, the copolymerization reaction can be carried out more easily and quickly. The organopolysiloxane latex obtained by this method can be used as is for various purposes, but if necessary, the acid components remaining in the system can be removed by adding sodium carbonate, sodium hydroxide, or triethanolamine. It may be neutralized with an alkali such as. In addition, in this method, a nonionic surfactant may be added to the above-mentioned surfactant as component (c) to the reaction system to stabilize the emulsion, and furthermore, a known preservative may be added. It is optional to add agents, dyes, etc. to the extent that the emulsified state is not destroyed. The phosphate ester group-containing organopolysiloxane latex of the present invention can be used as a softener for various organic natural fibers, synthetic fibers, knitted fabrics or non-woven fabrics thereof, as well as inorganic glass fibers, rock wool, asbestos, and knitted fabrics thereof. It is said to be useful as a texture improver or as a binder between fibers, but because it contains a phosphate ester group, it has the characteristic of making flame-retardant treated organic fibers flexible without impairing their flame retardancy. Furthermore, it is said to be useful as a mold release agent, peeling agent, polishing agent, antifoaming agent, and paint component for various molded products. Next, examples of the present invention will be given, in which viscosity values are measured at 25°C. Example 1 Put 680 g of water into the glass beaker of 2 and uniformly dissolve 10 g of dodecylbenzenesulfonic acid.
Add 300g of octamethylcyclotetrasiloxane to this while stirring with a high-speed mixer. A mixture of 10 g of organopolysiloxane containing a phosphoric acid ester group was added to emulsify the mixture, and this was further uniformly dispersed using a colloid mill to prepare an emulsion. Next, this emulsion was heated to 70°C for 16 hours, and the reaction solution was neutralized with sodium carbonate water, resulting in a dimethyl silicone latex containing phosphate ester groups (hereinafter referred to as latex A).
was obtained, but the nonvolatile content was 28% at 100° C. for 3 hours, and the dried film was rubber-like. Example 2 300 g of octamethylcyclotetrasiloxane and the formula

Formula obtained by hydrolyzing a phosphoric ester acid-containing organoalkoxysilane shown by [Formula] in water.

Add 25 g of liquid organopolysiloxane represented by the formula (n = 3 to 10) and dissolve it uniformly, then add a mixed solution of 670 g of water and 10 g of sodium lauryl sulfate, and use a colloid mill to dissolve it uniformly. It was emulsified and dispersed. Next, add H-type cation exchange resin Amberlite 200 (trade name manufactured by Organo) to this emulsion.
50 g was added, stirred at room temperature for 1 hour, filtered to remove amberlite, and the emulsion, which had become strongly acidic through this treatment, was heated at 70°C for 10 hours and then neutralized to pH 7 using an aqueous solution of sodium carbonate. However,
Latex with a high degree of polymerization (hereinafter referred to as latex B)
) was obtained. This latex B is 100℃,
The nonvolatile content after 3 hours was 29.5%, and when dried, a rather soft rubbery film was formed. Example 3 Dimethylpolysiloxane with a viscosity of 200 cS and end-capped with hydroxyl groups was placed in the glass beaker of 2.
Add 300g and 20g of the same phosphate group-containing organopolysiloxane used in Example 2 and dissolve them uniformly, and add 640g of water and 20g of an aqueous solution of sodium lauryl sulfate while stirring with a high-speed mixer. This was further dispersed using a colloid mill to form a uniform emulsion. Next, 50 g of Amberlite 200 used in Example 2 was added to this emulsion, stirred for 1 hour to make the emulsion acidic, and then Amberlite was removed. After heating at 40°C for 20 hours, a 10% aqueous sodium carbonate solution was added to the emulsion. Upon neutralization, a stable emulsion (hereinafter referred to as latex C) was obtained.
The nonvolatile content of this latex C after 3 hours at 100°C was 29.5%. Comparative Example 1 An emulsion was made in the same manner as in Example 2 from 300 g of octamethylcyclotetrasiloxane, 670 g of water, and 10 g of sodium lauryl sulfate without adding the phosphate group-containing organopolysiloxane. By the way, this emulsion (hereinafter referred to as latex D) was heated at 100℃, 3
The non-volatile content after hours was 28.5%, which showed raw rubber-like properties. Experimental Example A treatment solution was prepared by mixing 1 g of latex A, B, C, and D obtained in Examples 1, 2, and 3, and Comparative Example 1 with 99 g of water.
After soaking a 35/65 mixed broadcloth, the adhesion rate of the treatment solution was reduced to 100%, dried at 100℃ for 2 minutes, and then cured at 150℃ for 2 minutes. When evaluated using a hand feel meter and by touch, the results shown in Table 1 were obtained.

【table】

【table】

Claims (1)

[Claims] 1 (a) General formula [Formula] [wherein R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ² is the same as R ¹ or Or an organosilicon compound represented by OX group (where X is a hydrogen atom or a monovalent hydrocarbon group similar to R ¹ ), a and b are positive numbers from 0 to 3, and 1≦a+b≦4] and ( b) General formula [Formula] [where R ³ is the same monovalent hydrocarbon group as R ¹ above, R ⁴ is the same as R ³ or an OY group (here, Y is a hydrogen atom or the same as R ³ ) (monovalent hydrocarbon group), Z is the formula [formula] (where R ⁵ is a lower alkyl group, R ⁶ is a divalent hydrocarbon group having 1 to 8 carbon atoms)
The group represented by c, d, and e are positive numbers of 0 to 2 and 1
≦c+d+e≦3] in the presence of (c) a sulfonic acid surfactant and/or a sulfuric acid ester surfactant. An organopolysiloxane latex containing a phosphate group, which is obtained by emulsion polymerization in water. 2. The phosphate group-containing organopolysiloxane latte according to claim 1, wherein the organosilicon compound as component (a) is a cyclic dimethylpolysiloxane represented by the formula (n=3 to 10) Tsukusu. 3. The phosphoric acid ester group-containing organopolysiloxane latex according to claim 1 or 2, wherein the emulsion polymerization is carried out in the presence of a strongly acidic substance. 4 (b) component is the formula (R ⁵ , R ⁶ are the same as above, m=3 to 10); Siloxane latex. 5 Claim 1, which is obtained by neutralizing the acid remaining in the system using an alkali after the completion of emulsion polymerization,
The phosphoric acid ester group-containing organopolysiloxane latex according to item 2, 3, or 4. 6 Claims 1, 2, and 3 in which 0.1 to 30 parts by weight of component (b) and 0.5 to 30 parts by weight of component (c) are added to 100 parts by weight of component (a). , the phosphoric acid ester group-containing organopolysiloxane latex according to item 4 or 5.