JPH0339549B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention provides a phosphoric acid ester group-containing organosiloxane composition, in particular a self-crosslinking property useful for fiber treatment agents, lubricants, mold release agents, glass fiber treatment agents, polishing agents, etc. This invention relates to an organosiloxane composition with excellent film-forming properties. (Prior Art) Compositions comprising liquid organopolysiloxanes and polyfunctional organoalkoxysilanes and having reactivity and self-crosslinking properties are well known.
Publication No. 56-41479 discloses a compound containing an alkoxy group and an aminoalkyl group at the molecular chain end, which is derived from a dialkylorganopolysiloxane having a functional group at the molecular chain end and an aminoalkyltrialkoxysilane. This material has good reactivity and film-forming properties due to self-crosslinking properties. However, the compounds obtained in this way have an undesirable tendency to yellowing of the film due to the aminoalkyl group, and therefore, although they give excellent texture to textile products, especially when they have been previously treated, It has the fatal drawback of losing its commercial value due to yellowing or changes in color tone. Therefore, in order to avoid this yellowing, it is possible to create a composition using an alkoxysilane containing a group other than an amino group, such as an epoxy group, but in this case, the reactivity of the alkoxy group must be low. In addition to this, there is a disadvantage that the film-forming property becomes poor as a result, and there is also a disadvantage that means such as adding a catalyst or heating are required to promote the reaction. (Structure of the Invention) The present invention relates to an organosiloxane composition that solves the above disadvantages, which includes (a)
General formula R ¹ _a R ² _b SiO _4-ab/2 [Here, R ¹ is carbon number 1~
20 same or different unsubstituted or substituted monovalent hydrocarbon groups, R ² is the same as R ¹ or an OX group (where X
is a hydrogen atom or a monovalent hydrocarbon group identical to R ¹ ),
100 parts by weight of an organosilicon compound represented by 1≦a+b≦4, where a and b are positive numbers from 0 to 3, and (b) general formula
R ³ _c R ⁴ _d Z _e SiO _4-cde/2 [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 a monovalent hydrocarbon group similar to ^R3 ), 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 0<c+d+
an organosilicon compound containing at least one phosphate ester group in one molecule represented by e≦4]
It is characterized in that it consists essentially of 0.1 to 30 parts. That is, the present inventors have conducted various studies on organosiloxane compositions that do not have the disadvantages mentioned above, and have found that a composition containing an alkoxysilane containing a phosphate group and an organosiloxane in a specific ratio is superior. The present invention was completed by conducting research on the types of alkoxysilanes and organosiloxanes to be used, and their blending amounts. The organosilicon compound as component (a) constituting the composition of the present invention is represented by the general formula R ¹ _a R ² _b SiO _4-ab/2 , where R ¹ is a methyl group,
Alkyl groups such as ethyl, propyl, and butyl groups, alkenyl groups such as vinyl and allyl groups, aryl groups such as phenyl and naphthyl groups, and aralaryl groups such as tolyl and xylyl groups with a carbon number of 1. ~20 monovalent hydrocarbon groups, or a group in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, etc., R ² is the same as this R ¹ or an OX group (Here is X
is a hydrogen atom or the same group as ^R1 ), a and b are 0 to 3
It is an organosilicon compound with a positive number of 1≦a+b≦4, and it may be linear, branched, or cyclic. In addition, these may have molecular chain terminals blocked with trialkylsilyl groups or may contain hydroxyl groups at the terminals. This organosilicon compound has, for example, the formula (m is an integer) Liquid dimethylpolysiloxane, represented by the formula

[Formula] (n is an integer) Liquid dimethylpolysiloxane with both ends blocked with hydroxyl groups, Formula (p, q are integers) Liquid dimethylpolysiloxane with both ends blocked with alkoxy groups, formula: (s, t, u, v are integers) are exemplified. Next, the phosphoric acid ester group-containing organosilicon compound as component (b) constituting this composition has the general formula
R ³ _c R ⁴ _d Z _e SiO _4-cde/2 , and this R ³ is
R is the same monovalent hydrocarbon group as R ¹ , R ⁴ is the same monovalent hydrocarbon group as R ³ or OY group (here, Y is a hydrogen atom or the same monovalent hydrocarbon group as R ³ ), and Z is the same monovalent hydrocarbon group as R 3. formula

[Formula], R ⁵ is a lower alkyl group such as a methyl group, ethyl group, propyl group, butyl group, and R ⁶ is a carbon number of 1 to 8 such as a methylene group, ethylene group, propylene group, butylene group, etc. A phosphoric acid ester group that is considered to be a divalent hydrocarbon, c, d,
e is a positive number from 0 to 2 and satisfies 0<c+d+e≦4, and examples thereof include the following. (n, p, q, r are all positive numbers) is exemplified. This phosphoric acid ester group-containing organosilicon compound can be combined with an alkoxysilane represented by the formula (CH ₃ O ₃ )Si(CH ₂ ) ₃ Cl, etc.

[Formula] It can be easily produced by a dehydrochlorination reaction with _{a phosphoric} acid ester represented by organopolysiloxane containing more than

It can be produced by a dehydrochloric acid reaction with a phosphoric acid ester represented by the formula, but it is a hydrolysis product of a phosphoric acid ester group-containing organoalkoxysilane or a combination of this phosphoric acid ester group-containing organoalkoxysilane and other It may be obtained as a cohydrolyzate with organoalkoxysilane. The amount of this phosphoric acid ester group-containing silicon compound added is the same as the organosilicon compound as component (a) mentioned above.
With respect to 100 parts by weight, if it is too small, the film-forming properties of the resulting organosiloxane composition and the bonding properties with the fibers treated with it will be weakened, so it is necessary to set the amount to 0.1 parts by weight or more, but this preferred range is
The amount is 0.1 to 30 parts by weight. The composition of the present invention can be obtained by uniformly mixing predetermined amounts of the organosilicon compound as component (a) and the organosilicon compound containing a phosphate group as component (b). However, it can be used in various forms. This composition may be used after being diluted with an organic solvent to an appropriate concentration, but
This may be used by reacting the above-mentioned components (a) and (b) in advance, and in that case, the composition may be diluted with various organic solvents and then used as necessary. Components (a) and (b) may be reacted by adding an organometallic compound or an amine compound as a catalyst, and then the solvent may be removed and the reaction product may be taken out for use. In addition, various catalyst substances for condensation reactions may be added to this composition for the purpose of promoting the film-forming reaction, and such catalyst substances include organic acid salts such as zinc, lead, tin, and aluminum, titanium, etc. Examples include acid esters, which may be added in an amount of 0.1 to 30 parts by weight per 100 parts by weight of the composition. However, to promote crosslinking, a small amount of methylhydrodiene polysiloxane or methylhydrodiene polysiloxane and dimethyl If necessary, a copolymer with polysiloxane or a polyfunctional alkoxysilane may be added together with the above-mentioned condensation reaction catalyst substance. The phosphoric acid ester group-containing organosiloxane composition of the present invention can be used as a softener for various organic natural fibers, synthetic fibers, knitted fabrics or non-woven fabrics thereof, and 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, and because it contains phosphate ester groups, it is said to make flame-retardant 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, and the viscosity in the examples is a value measured at 25°C. Example 1 Both ends of the molecular chain are blocked with hydroxyl groups, and the viscosity is
1000cS dimethylpolysiloxane and formula A treatment liquid composition is prepared by dissolving phosphoric acid ester group-containing alkoxysilane shown in Table 1 in the ratio shown in Table 1, and a polyester/cotton = 35/65 blended broad cloth is immersed in this liquid. Liquid adhesion rate
After adjusting to 100%, the treated fabric was dried at 100°C for 2 minutes and further cured at 150°C for 2 minutes. Next, the texture of the treated fabric obtained in this way was evaluated using a Ueno style texture meter and the texture was placed in an aluminum dish.
When the state of the film obtained by heating at 100°C for 30 minutes was observed and evaluated, the results shown in Table 1 were obtained, indicating that dimethylsiloxane and phosphorus, in which the molecular chain terminals are blocked with hydroxyl groups, were evaluated. Mixing ratio with acid ester group-containing alkoxysilane is 0.5~
Those with a molar ratio of 10.0 (sample No. 2 to No. 5) give treated fabrics that are flexible, slippery, and have a good feel with a sense of repulsion; No. 1) had no such effect, and when the blending ratio exceeded 20 (molar ratio) (sample No. 6), the film was hard and the resulting treated fabric had an extremely poor texture. Ivy.

[Table] Example 2 1 equipped with a stirring device, cooling pipe and thermometer
Formula in a round bottom flask of 6.5 g of ethoxysilane containing a phosphoric acid ester group and 300 g of toluene were charged and heated to 80°C, and 300 g of dimethylpolysiloxane with a viscosity of 1000 cS, in which both ends of the molecular chain were blocked with hydroxyl groups, was heated for about 1 hour. After the dropwise addition was completed, the solution was further heated at 100°C for 2 hours, and then treated at 80°C/5 mmHg for 3 hours to distill off the solvent.
A transparent oil of 4800 cS was obtained (hereinafter referred to as Polymer A). This product forms a rubbery film when heated at 100℃ for 1 hour, and when 100g of this material is mixed with 0.5g of dibutyltin dilaurate as a condensation catalyst, it becomes a rubbery cured product after 1 day when left at room temperature. Ta. Next, we made a 0.5% toluene solution of Polymer A, dipped a 35/65 blended broadcloth of polyester/cotton in it, reduced the adhesion rate to 100%, dried it at 100°C for 2 minutes, and then heated it to 150°C. Curing is performed for 2 minutes to make a treated cloth.
Viscosity 1000cS with both ends of the molecular chain blocked by hydroxyl groups
dimethylpolysiloxane (referred to as Polymer B)
and dimethylpolysiloxane (referred to as Polymer C) having a viscosity of 1000 cS, in which both ends of the molecular chain are blocked with trimethyl serial groups, were treated in the same manner as above to produce treated fabrics. When the texture was evaluated using a Ueno type texture meter and touch, the results shown in Table 2 were obtained, confirming that the composition of the present invention can produce treated fabrics with good texture. .

【table】

Claims (1)

[Claims] 1 (a) General formula R ¹ _a R ² _b SiO _4-ab/2 [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 OX
Group (where X is a hydrogen atom or 1 similar to R ¹
valence hydrocarbon group), a and b are positive numbers from 0 to 3, 1≦
an organosilicon compound represented by a+b≦4]
100 parts by weight (b) General formula R ³ _c R ⁴ _d Z _e SiO _4-cde/2 [Here, R ³ is the same substituted monovalent hydrocarbon group as R 1 above, and R ⁴ is the same as R ^{3 .} or an OY group (where Y is a hydrogen atom or a monovalent hydrocarbon group similar to R ³ ), Z is a formula [formula] (where R ⁵ is a lower alkyl group, and R ⁶ is a C 1-8 divalent hydrocarbon group), c, d, and e are positive numbers from 0 to 2, and 0<
0.1 to 30 parts by weight of an organosilicon compound containing at least one phosphoric ester group in one molecule, represented by c+d+e≦4]; Containing organosiloxane composition. 2 (a) component is the formula (R ¹ is the same as above, m is a positive number) is a liquid organopolysiloxane in which both ends of the molecular chain are blocked with hydrogen groups, and the amount of component (b) per mole of component (a) is
Claim 1 in which 0.1 to 10 mol is blended
The phosphoric acid ester group-containing organosiloxane composition described in 1.