JPS61278562A - Phosphate ester group-containing organosiloxane composition - Google Patents

Abstract

PURPOSE:To provide an organosiloxane compsn. having excellent self- crosslinkability and film-forming properties and useful as a fiber treating agent, a lubricant, a glass fiber treating agent, etc., by blending an organosilicon compd. with an organosilicon compd. contg. a phosphate ester group. CONSTITUTION:The title compsn.is composed of 100pts.wt. organosilicon compd. (a) of formula I [wherein Rs<1> are the same or different groups and each is a 1-20C (substd.) monovalent hydrocarbon group; R<2> is R<1> or OX (wherein X is H or R<1>); a and bv are each 0-3 and 1<=a+b<=4] and 0.1-30pts.wt. organosilicon compd. (b) contg. at least one phosphate ester group, represented by formula II [wherein R<3> is R<1>; R<4> is R<1> or OY (wherein Y is H or R<3>); Z is a group of formula III (wherein R<5> is lower alkyl; R<6> is a 1-8C bivalent hydrocarbon group); c, d and e are 0-2 and 0<c+d+e<=4].

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a phosphate ester group-containing organosilochitin composition, particularly a fiber treatment agent, a lubricant, a mold release agent, a glass fiber treatment agent, and a polishing agent. The present invention relates to an organosylochitin composition with excellent self-crosslinking and film-forming properties, which is useful in pharmaceuticals and the like.

(Prior art) Mi compounds are known which have high reactivity 3 and self-crosslinking properties and are composed of liquid organopolysilochitin and polyfunctional organoalkoxy VV run.
Publication C: discloses a compound containing an alkoxy group and an aminoalkyl group at the molecular chain end, which is derived from a dialkylorganopolysilochitin carrying a difunctional group at the molecular chain end and an aminoalkyltrialkoxysilane. This material has good reactivity and film-forming properties due to self-crosslinking.

However, the compounds that have been improved in this way have an undesirable tendency to cause yellowing of the film due to the aminoalkyl group. 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, groups other than amino groups 1
For example, it is possible to create a composition using an alkoxysilane containing an epoxy group, but in this case, the reactivity of the alkoxy group becomes low, resulting in poor film-forming properties. There is also the 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, and is composed of a) the same or different unsubstituted or substituted monovalent hydrocarbon radicals R having a prime number of 1 to 20;
1 is the same as R1 or oxi (where X is a hydrogen atom or the same monovalent hydrocarbon group as R), a and b are positive numbers from O to 3, and 1≦a + b≦4] Organosilicon compounds lo.

[KR is the same monovalent hydrocarbon group as R above.

R is the same as R or an OY group (wherein Y is a hydrogen atom or a monovalent hydrocarbon group similar to R), z is the formula 0 (R○), PR- (wherein R is a lower alkyl group, R is a divalent hydrocarbon group having a carbon number of 1 to 8], c and de are positive numbers of 0 to 2, and 0<c+d+e≦
4] is characterized in that it is substantially composed of ~30 parts of a silicon compound O,

In other words, as a result of various studies on organosiloxane compositions that do not have the above-mentioned disadvantages, the inventors and their colleagues found a composition containing an alkoxysilane containing a phosphate group and an organosiloxane in a specific ratio. discovered that it has excellent self-crosslinking properties and film-forming properties.

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 has the general formula: an alkyl group such as a thyl group, an ethyl group-probyl group, a butyl group, an alkyl group such as a vinyl group or an allyl group, or a phenyl group. group, and an aryol group such as a naphthyl group.

Monovalent hydrocarbon groups having 1 to 20 carbon atoms such as aralaryl groups such as tolyl group and xylyl group, or some or all of the water bulk atoms bonded to the carbon atoms of these groups are replaced by halogen atoms, cyano groups, etc. , R is the same as R or an OX group (where X is a water bulk atom or the same group as R).

a and b are positive numbers from O to 3, and are organosilicon compounds in which 1≦a + b≦4, and this is a linear monobranched compound.

It may be any ring shape. In addition, these may have molecular chain terminals blocked with trialkylsilyl groups, or may contain hydroxyl groups at the terminals. This organosilicon compound is, for example, a liquid dimethylpolysiloxane represented by (m is an integer).

A liquid dimethylpolysiloxane with both ends capped with hydroxyl groups.

(p, q are integers) A liquid dimethylpolysiloxane whose both ends are blocked with an alkoxy group.

(s, t, u, v are tatami mats) are exemplified.

Next, the phosphoric acid ester group-containing organosilicon compound as component b) constituting this composition has the general formula R
R is the same monovalent hydrocarbon group as R, or OY group (where Y is a water bulk atom or the same monovalent hydrocarbon group as R3) is a methyl group, ethyl group, propyl group, butyl group. R is a lower alkyl group such as a methylene group, a diterene group, a propylene group, a butylene group, etc. with a carbon number of 1.
~8 divalent hydrocarbon phosphoric acid ester group -a,
d and e are positive numbers between 0 and 2, and O<c+d+e≦4; an example of this is that of a queen.

(OH30), 810H2P (OCH3),.

I C0H30), B1OH20H2PCOCjH,)2
.

(OH8O), 81(OH2), P(OCR,),.

(0!H,03,8i(0472PCOOH3)2.

(0!H,O), 81(OEI, )s P(OOH
s ) g −(C2H,O)s S i (OH2)
S P (001□H3λ.

straight Oh.

(n, p, q, r are all positive numbers) is exemplified.

This phosphoric acid ester group-containing organosilicon compound is produced by decomposition of an alkoxysilane represented by the formula (OH,O), 31(OH2), OL, etc. with a phosphoric acid ester represented by the formula OHP(002H,)2, etc. It can be easily produced by a hydrochloric acid reaction, and it contains −(OH
It can be produced by a dehydrochlorination reaction between an organopolysiloxane containing one or more halogenated alkyl groups as a substituent such as However, this is a water decomposition product of a phosphate ester group-containing organoalkoxysilane, and it was obtained by co-hydrolysis of this phosphate ester group-containing organoalkoxysilane and Ike's organoalkoxysilane. There may be.

The amount of this phosphoric acid ester group-containing C silicon compound added is 100 parts and 2 parts of the organosilicon compound as component a). Since the bonding properties with the fibers to be treated with are weakened, it is necessary to make it 0.1 electric area or more, but the preferable range is 0.1 to 30 electric area.

The composition of the present invention can be obtained by uniformly mixing predetermined amounts of the above-mentioned organic (silicon compound as component a) and a phosphoric acid ester group-containing organosilicon compound as component b). , which can be used in various forms. This composition may be used after being diluted with an organic solvent to an appropriate concentration of C or X, but it may also be used after reacting the above-mentioned components a) and b) in advance. ,
In that case, the second step is to dilute this composition with, for example, various organic solvents, and then add an organometallic compound or an amine compound as a catalyst as necessary to react components a) and b). Then, the solvent can be removed and the reaction product can be taken out and used. S, various catalyst substances for condensation reaction may be added to this composition in order to promote the film-forming reaction, and such catalyst substances include zinc,
Examples include amate salts of lead, tin, aluminum, etc., titanate esters, etc., and these are composition 100! 0 in quantity
．． The addition amount may be within the range of 1 to 301111 parts, but a small amount of methylhydrodiembo ν may be used to promote crosslinking.
If necessary, a copolymer of chitin or methylhydrodiene polyv chitin and dimethylpolysilochitin, a polyfunctional alkoxysilane, or the like may be added as a co-addition agent with the above-mentioned catalyst material for the condensation reaction.

The phosphoric acid ester group-containing organosylochitin composition of the present invention can be applied to various organic natural fibers, synthetic fibers, their woven fabrics or non-woven fabrics, as well as inorganic glass fibers, Rock Coeur, asbestos, and soft fabrics thereof. It is said to be useful as an agent, texture improver, or as a binder between fibers, but since it contains a phosphate ester group, it does not inhibit the flame retardancy of organic fibers when subjected to flame retardant treatment.C: Flexibility Furthermore, C is also useful as a mold release agent, stripping agent, polishing agent, antifoaming agent, and paint component for various molded products C2.

Next C: Examples of the present invention are given, and the viscosity in the examples is 25
Measured values are shown in °C.

Example 1 Both ends of the molecule are blocked with hydroxyl groups and the viscosity is 1.0.
A treatment liquid composition is prepared by dissolving dimethylpolysilochitin of 00o8 and a phosphoric acid ester group-containing alkoxysilane represented by the formula (%) in toluene in the ratio shown in Table 1. A cotton-35/65 blended broad cloth was dipped, and the adhesion rate was adjusted to 100%, dried at 100°C for 2 minutes, and further cured at 62150°C for 2 minutes to prepare a treated cloth.

Next, the texture of the treated fabric obtained in this way was evaluated using a Ueno-type texture meter and a hand test, and the treatment solution was placed in an aluminum dish and heated at 100°C for 30 minutes.
When the state of the obtained film was observed and evaluated, the results shown in Table 1 C were obtained, and from this, it was determined that dimethylsilochitin whose molecular chain terminal was blocked with a hydroxyl group was obtained. Those with a blending ratio of 0.5 to 10.0 (mole ratio) (sample rot 2 to scrap 5) with alkoxysilane containing phosphate ester groups are flexible and have good pickpability, and are anti-II? ! +i
%, but if this blending ratio is less than 0.1 (sample/l 61), this effect is not achieved, and if this blending ratio is 20 (molar ratio 2 or more (sample 4)
It was found that in case 6), the film was hard and the resulting treated fabric had an extremely poor feel.

Example 2 Ethoxysilane 6,5 Ij containing a phosphoric acid ester group represented by the formula %) and 300 g of toluene were charged into a 1 liter round bottom flask equipped with a stirrer, a condenser and a thermometer. C(
After heating, this SA
00g was dripped over about 1 hour, and after the dripping was finished, another 10g was added.
After heating at 0°C for 2 hours, the solvent was distilled off at 80°C for 3 hours at 151111 Hg, and the viscosity was 4.
, 800oS was obtained (hereinafter referred to as Polymer A).

This product forms a rubbery film when heated at 100°C for 1 hour, and this 100°C. ! 9 (dibutyl silaclay as a catalyst for condensation) 0.5, !i+ was added to room temperature C: When left to stand, it became a rubber-like cured product after 1 day. After making a .5% to/l/ene solution and soaking a 35/65 mixed fabric of ζ-nipolyester/cotton in this solution, the liquid adhesion rate was reduced to 100%, and after drying at 100°C for 2 minutes, it was washed with g. When a treated cloth is prepared by curing at 150°C for 2 minutes, dimethylpolysilochitin (referred to as polymer B) with a viscosity of 1.000o8, in which both ends of the molecular chain are blocked with hydroxyl groups, and both ends of the molecular chain are Viscosity 1,00 blocked with trimethylsilyl group
0o8 dimethylpolysiloxane (referred to as Polymer C)
Treated fabrics were prepared in the same manner as above, and the texture of the three types of treated fabrics C obtained was evaluated using a Ueno style texture meter and hand feel. The same results were obtained, and it was confirmed that the composition of the present invention (2) produced treated fabrics with good texture.

! ! c2 table

Claims (1)

[Claims] 1, a) General formula R^1_aR^2_bSiO_(_4_
-_a_-_b_)_/_2 [Here, R^1 is the number of carbons 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 similar to R^1), a
, b is a positive number from 0 to 3 and 1≦a+b≦4] 100 parts by weight b) General formula R^3_cR^4_dZ_eSiO_(_4
＿−＿c＿−＿d＿−＿e＿）＿／＿２〔Here is R^3
is a monovalent hydrocarbon group similar to R^1 above, R^4 is R^3
or OY group (where Y is a hydrogen atom or R_
3), Z is a formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R^5 is a lower alkyl group, and R^6 is a divalent hydrocarbon having 1 to 8 carbon atoms. The group represented by (representative group), o, d, and e are positive numbers from 0 to 2, and 0<c+
d+e≦4], an organosilicon compound containing at least one phosphate ester group in one molecule from 0.1 to
30 parts by weight of a phosphoric acid ester group-containing organosiloxane composition. 2.a) The component is a liquid organopolysiloxane whose molecular chain ends are blocked with hydroxyl groups and is represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^1 is the same as above, m is a positive number) 2. The phosphate group-containing organosiloxane composition according to claim 1, wherein component b) is blended in an amount of 0.1 to 10 moles per mole of component a).