JPH0112866B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention provides a fiber treatment agent, particularly a polyester fiber or a fiber structure containing polyester fiber, which imparts a wash-resistant and flexible texture, has excellent antistatic properties, and is capable of dissolving disperse dye migration and sublimation. This invention relates to a fiber treatment agent that can impart moisture-permeable and waterproof properties without any moisture. (Prior technology) For the production of moisture-permeable waterproof fabric, there are two methods: using a porous film made by coagulating a urethane polymer dissolved in a water-soluble organic solvent in water, or copolymerization with a water-soluble substance mixed therein. A method is known in which acrylate is applied to a fiber structure and water-soluble substances are removed in water. However, because the polymer resins used in these methods are highly compatible with the disperse dyes used to dye polyester fibers, the products suffer from the migration of disperse dyes during storage and wear. Many problems occur due to color transfer due to sublimation. On the other hand, fiber treatment agents based on polysiloxane do not cause the migration and sublimation phenomenon of disperse dyes. A method in which a compound containing a sublimation agent, a sublimation agent, and an adhesion agent is dissolved or dispersed in an organic solvent such as trichlorethylene or toluene and then applied to a synthetic fiber structure (see Japanese Patent Application Laid-open No. 120880/1983). A solution-type composition prepared by adding methylhydrodiene polysiloxane, aminoalkylalkoxysilane, an organometallic compound, and an organic solvent to a linear organopolysiloxane having a hydroxyl group bonded to a silicon atom at the chain end is applied to the fabric,
Method of heat treatment after volatilizing the solvent (Tokukosho)
42-1795) are known, but
Since the organopolysiloxane used here is highly insulating, it is easily charged with static electricity.Therefore, when synthetic fiber components such as polyester, which are naturally easily charged, are treated with such a treatment agent, their chargeability may be reduced. The disadvantage is that this is further encouraged. Therefore, it has been proposed to mix conductive substances such as metal powder or carbon black into this type of composition to reduce the chargeability.
This has the disadvantage that the film strength decreases and becomes discolored, and the method of mixing a water-soluble substance has the disadvantage that the film strength decreases and the waterproof performance also suffers from significant defects. (Structure of the Invention) The present invention relates to a silicone-based fiber treatment agent that solves the above-mentioned disadvantages.
100 parts by weight of an essentially linear liquid organopolysiloxane containing at least two silicon-bonded hydroxyl groups in one molecule; 2) at least three silicon-bonded hydrogen atoms in one molecule; Contains 1 to 50 parts by weight of liquid organohydrodiene polysiloxane, 3) (a) General formula (Here, R ¹ is a divalent organic group, R ² and R ³ are the same or different unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and X is an OH group, -SH group, -NH ₂ units, -
NR ⁴ H group (R ⁴ is a monovalent hydrocarbon group having 1 to 6 carbon atoms), an active hydrogen-containing functional group selected from COOH group, n is a positive number], (b) hydrophilic 1 to 50 parts by weight of a block copolymer with a polyol compound containing a polyoxyalkylene group, (c) a diisocyanate compound, 4) General formula (Here, R ⁵ is a divalent hydrocarbon group having 1 to 4 carbon atoms,
R ⁶ and R ⁷ are the same or different unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, a and m are 0 or 1) aminoalkylalkoxysilane
0.1 to 20 parts by weight, formula 5) [Here, R ⁸ is −CH ₂ CH=CH ₂ or −
CH ₂ CH ₂ CH ₂ SiR ⁹ _b (OR ¹⁰ ) _3-b (R ⁹ and R ¹⁰ are the same or different unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms), b is 0, 1 or 2],
1 to 50 parts by weight of an isocyanurate compound in which at least one valence of R ⁸ is a silylated propylene group, (b)
A catalytic amount of a condensation reaction catalyst. That is, as a result of various studies by the present inventors on processing agents that do not cause migration and sublimation of disperse dyes and provide fibers with excellent antistatic properties and wash resistance, we found that ≡Si
An organopolysiloxane having at least two (OH) groups and an organohydrodiene polysiloxane having at least three ≡SiH bonds, to which a block copolymer as described above, an aminoalkylalkoxysilane, and an isocyanurate compound are added. There is no migration sublimation of disperse dyes,
The presence of this block copolymer provides strong antistatic properties, and the aminoalkyl alkoxysilane and isocyanurate compounds improve adhesion, making fiber structures treated with this highly effective. They discovered that this imparts washing resistance, and completed the present invention by conducting research on the types and amounts of each of these constituent components. The organopolysiloxane as the first component constituting the composition of the present invention must have at least two hydroxyl groups (≡SiOH) bonded to a silicon atom in one molecule. The following formula is well known in (wherein R is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms);
It is an ω-dihydroxydiorganopolysiloxane, and the R group includes an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group,
Alkenyl groups such as allyl groups, aryl groups such as phenyl groups and tolyl groups, cycloalkyl groups such as cyclohexyl groups, or some or all of the hydrogen atoms bonded to carbon atoms of these groups are replaced with halogen atoms, cyano groups, etc. The group is selected from a substituted chloromethyl group, trifluoropropyl group, cyanomethyl group, etc., and it is preferable that 50 mol% of the group is a methyl group. This organopolysiloxane has the following formula:

【formula】 【formula】

[(CH ₃ ) ₃ SiO _0.5 ] _x [SiO ₂ ] _y (OH) _z , [(CH ₃ ) ₃ SiO _0.5 ] _x [CH ₃ SiO _1.5 ] _y (OH) _z (here x, y, z) is a positive number), but these may also contain an organic group containing a small amount of epoxy group, alkylamino group, carboxyl group, acryloxy group, or mercapto group. In addition, these organopolysiloxanes have the formula A polymerization reaction of a cyclic organopolysiloxane represented by (R is the same as above, n=3 to 10) using a strong alkaline substance such as caustic potash or caustic soda or a strong acidic substance such as sulfuric acid or trifluoromethanesulfonic acid as a catalyst. It can be obtained by Furthermore, the organohydrodiene polysiloxane as the second component constituting this composition must contain at least three hydrogen atoms bonded to silicon atoms (≡SiH bonds) in one molecule. Things are general formulas

[Formula] (where R is the same as above, a and b are 0<a<3
It may be expressed as a positive number such that 0<b<1 and 1.5<a+b<2.5). This organohydrodiene polysiloxane has the following formula: The following is an example, but these are the formulas

[expression] or

A cyclic organosiloxane represented by the formula is polymerized in the presence of a strong acidic substance such as sulfuric acid or trifluoromethanesulfonic acid, or CH ₃ HSiCl ₂ ,
It can be obtained by cohydrolyzing organochlorosilanes such as (CH ₃ ) ₂ SiCl ₂ , (CH ₃ ) ₃ SiCl, and SiCl ₄ . If the amount of organohydrodiene polysiloxane is less than 1 part by weight, the resulting film will not be sufficiently cured and the required waterproofness will not be obtained, and if it exceeds 50 parts by weight, the resulting film will be hard and brittle. The texture of the treated fabric may also become hard and the product value may be lost.
The amount may range from 50 parts by weight to 50 parts by weight, with the preferred range being 5 to 10 parts by weight. Next, the block copolymer as the third component in this composition is used to impart antistatic properties to the object treated with this composition; It must be made by copolymerizing an organopolysiloxane having an active hydrogen-containing organic group with b) a polyol compound and c) a diisocyanate compound. The organopolysiloxane as component a) that constitutes this block copolymer has the general formula

[Formula], R ¹ is a divalent organic group, R ² and R ³ are alkyl groups such as methyl group, ethyl group, propyl group, butyl group, vinyl group,
Alkenyl groups such as allyl groups, aryl groups such as phenyl groups and tolyl groups, cycloalkyl groups such as cyclohexyl groups, or some or all of the hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. the same or different unsubstituted or substituted monovalent hydrocarbon groups, preferably 50% or more of which are methyl groups;
X is an organic group selected from OH group, -SH group, _-NH2 group, ^-NR4H group ( ^R4 is a monovalent hydrocarbon having 1 to 6 carbon atoms), COOH group, etc., and n is 10 or more. is considered to be a positive number. Therefore, this XR ¹ − group is HO−(CH ₂ ) ₂ −, HO−(CH ₂ ) ₃ , CH ₂ =CH
(OH)CH ₂ CH ₂ −, HO− (C ₂ H ₄ O) _a − (CH ₂ ) ₂ −
(a is 1 or more), HS-( _CH2 ) _3- , HOOC-
(CH ₂ ) ₂ −, H ₂ N− (CH ₂ ) ₃ −, H ₂ NCH ₂ CH ₂ NH
−(CH ₂ ) ₃ −, ClCH ₂ CH ₂ (OH)CH ₂ O−(CH ₂ ) ₃
-,

[Formula] etc. are exemplified, and this organopolysiloxane is expressed by the following formula: The following are examples. Next, the polyol compound containing a polyoxyalkylene group as component b) has the formula HO-(R ¹¹ O).
_b is represented by H, R ¹¹ is a divalent hydrocarbon group having 2 to 4 carbon atoms such as C ₂ H ₄ group, C ₃ H ₆ group, C ₄ H ₈ group, or a mixture thereof, b is the molecular weight of this compound 100~5000
It is said that this is _a positive number necessary to maintain _the HO-( _{C 2} ^H ₄ O)
Examples include H, HO-( _C2H4O )-( _C3H6O ) _{dH ,} and _the like. In addition, this b) component may contain a nitrogen atom, which has the formula

[Formula], R ¹² has 2 to 4 carbon atoms as in R ¹¹ above.
R ¹³ is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms as R ² described above, and e and f are each 1
An example is a polyoxyalkylene-adducted diol of an alkylamine, which is a positive number of ~100, but this diol has stronger hydrophilicity and flexibility than the above-mentioned polyoxyalkylene diol. Since it is an amine compound, the copolymer containing it tends to yellow, and there is a risk of imparting a yellow tint to textile products treated with it, so care must be taken. The diisocyanate compound as component c) acts as a coupling agent for making a copolymer of the organopolysiloxane as component a) and the polyol compound as component b). Tolylene diisocyanate (TDI), methyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), diphenylmethane diisocyanate (DMDI), trimethylhexamethylene diisocyanate (TMDI), which are commercially available as raw materials.
It may be selected from dimer acid diisocyanate and the like. However, this diisocyanate compound has extremely high reactivity, and if it is liberated or remains at the end of the reaction, the composition of the present invention may be dissolved in an aqueous dispersion system.
The amount used is such that the NCO/active hydrogen molar ratio is 1 or less, since in any case an organic solvent system may cause unnecessary or undesirable reactions, resulting in gelation of the reaction product. range is required. The block copolymer used in the composition of the present invention can be obtained by copolymerizing the three components a), b), and c) described above. In this copolymerization reaction, the reaction between the reactive OH group and the organic diisocyanate proceeds sufficiently by their coexisting contact alone, but it is necessary to carry out the reaction in an organic solvent in order to prevent unnecessary gelation or thickening of the reaction product. According to this method, it is possible to react in a homogeneous system the organopolysiloxane (a) component, which is inherently incompatible, the Poleol compound (b) component, and the diisocyanate compound (c) component. It is preferable to add a catalyst to quickly complete the reaction. This solvent is benzene,
Examples include aromatic solvents such as toluene and xylene, chlorine solvents such as trichlorethylene, perchloroethylene, and trichloroethane, and petroleum solvents such as kerosene and mineral spirits. Examples of catalysts include dioctyltin, dibutyltin, Diacetate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin octate, dioctylzinc, dilauryl lead,
Known metal organic acid salts and organometallic organic acid salts such as titanium tetrabutanate and aluminum triacetate may be used. This reaction may be carried out by charging the above-described components a), b), and c), as well as the above-mentioned catalyst added as necessary, into an organic solvent and heating and stirring the mixture. may be added to the reactor one after another to cause the reaction, but in any case, in order to maintain the stability of the reaction product, the amount of diisocyanate added should be within the range such that NCO/H≦1, and the isocyanate group should be adjusted as described above. It is necessary to ensure that no residue remains. If the amount of this block copolymer is less than 1 part by weight per 100 parts by weight of the organopolysiloxane as the first component, the effect will not be sufficient;
If the amount exceeds 1 to 50 parts by weight, the hydrophilicity of the resulting film will become excessive and the waterproof property, which is the objective of the present invention, will be lost. The preferred range is 5 to 10 parts by weight. The aminoalkylalkoxysilane as the fourth component and the isocyanurate compound as the fifth component of the composition of the present invention improve the adhesion of the composition, thereby imparting wash resistance to the treated fibrous structures. The purpose of this is to grant the following. The aminoalkylalkoxysilane as the fourth component is known in the art and has the general formula R ⁵ is a divalent hydrocarbon group such as a methylene group, ethylene group, or propylene group, and R ⁶ and R ⁷ are unsubstituted or substituted monovalent hydrocarbons having 1 to 20 carbon atoms, the same as R ² described above. The group, a, and m are 0 or 1, and this has the following formula: NH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ , _{NH2CH2CH2CH2Si ( OC2H5 ) 3 , _} The following are examples. The blending amount of this aminoalkylalkoxysilane is based on 100 parts by weight of the organopolysiloxane as the first component.
If it is less than 0.1 part by weight, it will not be effective, and if it is less than 20 parts by weight, the obtained film will become hard and the texture of the treated fabric will become hard, and furthermore, the obtained treated fabric may yellow, so use 0.1 to 20 parts by weight. The preferred range is 1 to 5 parts by weight. Moreover, the isocyanurate compound as this fifth component has the formula , R ⁸ has the same number of carbon atoms as R ² described above, 1 to 20
is considered to be an unsubstituted or substituted monovalent hydrocarbon group, but at least one of the R ⁸ groups must be a silylated propylene group,
This includes the following The following are exemplified. If the amount of this compound is less than 1 part by weight per 100 parts by weight of the organopolysiloxane as the first component, it will not be effective, and if it exceeds 50 parts by weight, the resulting film will be hard and brittle, and the texture of the treated fabric will deteriorate. Since it becomes hard, the amount may be in the range of 1 to 50 parts by weight, but the preferred range is 5 to 10 parts by weight. Further, the condensation reaction catalyst as the sixth component in this composition is added to promote the crosslinking and curing reaction of this composition, and this is a metal organic acid known for this type of reaction. Salts, organometallic compounds, metal alkoxides, amino compounds, etc. may be used. These metals include zinc, tin,
Examples include aluminum, titanium, lead, zirconium, platinum, palladium, etc., specifically zinc formate, zinc acetate, zinc octylate, zinc laurate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dimaleate. , dioctyltin diacetate, dioctyltin dioctoate, dioctyltin dilaurate, dioctyltin maleate, aluminum alkoxide, aluminum acetylacetonate, lead octylate, lead laurate, isopropyl titanate, propyl titanate, butyl titanate, octyl titanate,
Examples include zirconium acetate, chloroplatinic acid, alcohol-modified chloroplatinic acid, siloxane-modified chloroplatinic acid, and various palladium compounds.
The amount of this condensation catalyst to be blended may be a catalytic amount, specifically in the range of 0.1 to 20 parts by weight per 100 parts by weight of the organopolysiloxane as the first component,
Preferably, the amount may be in the range of 1 to 5 parts by weight. The fiber treatment agent of the present invention can be obtained by uniformly mixing predetermined amounts of the above-mentioned first to sixth components, but fibers can be treated with this composition by using a solution of the composition in an organic solvent or a suitable solution thereof. It may also be carried out as an aqueous treatment agent which is emulsified and dispersed in water in the presence of an emulsifier. In fibers or fiber structures treated with this fiber treatment agent, since this treatment agent is mainly composed of organopolysiloxane, migration and sublimation of disperse dyes does not occur, and this treatment agent is used as a third component. Since it contains the above-mentioned block copolymer, it provides antistatic properties, and furthermore, the 4th and 5th components mentioned above provide excellent washing resistance, so it has especially antistatic properties and waterproof properties. It is said to be useful as a coating agent for applying disperse dyes and at the same time preventing migration of disperse dyes. Next, examples of the present invention will be given. In the examples, parts are parts by weight, and viscosity is the measured value at 25°C. The test results for this treated product are shown below. be. 1) Moisture permeability... JIS-Z-0208, unit g/m ² /24 hours, 2) Water pressure resistance... JIS-L-1092A, unit mm water column, 3) Electrostatic half-life... JIS-L-1094A, unit seconds ( 20℃, 40%RH), 4) Friction withstand voltage... JIS-L-1094B, unit volt (20℃, 40%
RH), 5) Water repellency...JIS-L-1032 spray method, unit point, 6) Washability...JIS-L-217-103 Example 1, Comparative Example 1 (Production of block copolymer) Stirrer, Water-cooled condenser with thermometer attached 1
In a glass reactor, the following formula with both ends of the molecular chain blocked with hydroxyl groups 34 g of dimethylpolysiloxane with a viscosity of 45 cS, polyethylene glycol with a molecular weight of 400, shown as
78g, diphenylmethane diisocyanate 10.5g
Add 500g of toluene and add 100g of toluene while stirring.
After reacting at ℃ for 3 hours, 1 g of dibutyltin dilaurate was added and the reaction was further carried out at 80℃ for 3 hours. At this point, infrared spectroscopy showed that the absorption at 2260 cm ^-1 disappeared, indicating that no isocyanate remained. Confirm that the reaction is complete, then heat to 80℃/10
When the solvent was distilled off by heating under reduced pressure at mmHg for 2 hours, a pale yellow, cloudy product with a viscosity of 15,000 cp was obtained. (Manufacture of fiber treatment agent) Add 100 parts of dimethylpolysiloxane, which has a relative viscosity of 2.3 and whose molecular chain ends are blocked with hydroxyl groups, to
10 parts of methylhydrodiene polysiloxane containing 1.7 mol/100 g of ≡SiH bonds at 35 cS, 10 parts of the block copolymer obtained above, having the formula H ₂ N (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ 1 part of aminoalkylalkoxysilane and average formula Silylated triallylisocyanurate represented by
This was uniformly dissolved in 500 parts of perchlorethylene to make a translucent composition with a viscosity of 15,000 cp, and then 0.5 part of dioctyltin diacetate was added to 100 parts of this composition to form a fiber. I made a processing agent. Next, for comparison, 100 parts of the organopolysiloxane used above and 10 parts of methylhydrodiene polysiloxane were uniformly dispersed in 500 parts of perchlorethylene to make a composition with a viscosity of 15,000 cp, and then this 100 parts A fiber treatment agent was prepared by adding 0.5 part of dioctyltin diacetate. (Fiber processing) Warp: 80 denier, 48 filaments, inch-to-inch density: 85, weft: 80 denier, 48 filaments,
Plain woven polyester fibers with an inch-to-inch density of 82 fibers are scoured, heat-set, and dyed in advance using a known method, and then coated with fluorine-based water repellent agent Asahi Guard AG730.
After padding with a 5% solution of [trade name manufactured by Asahi Glass Co., Ltd.] to a pick-up rate of 30% and dry heat treatment at 150°C for 1 minute, the solid content of the fiber treatment agent obtained above was added to this material. Coat with a knife coater to give an equivalent concentration of 6.3g/ ^m2 , heat treat at 170℃ for 30 seconds,
When the physical properties of this fabric were examined, the results shown in Table 1 were obtained.

[Table] Example 2, Comparative Example 2 (Production of block copolymer) 77.4 g of dimethylpolysiloxane with a viscosity of 45 cS, the formula 110.2g of amine polyoxyethylene adduct diol, diphenylmethane diisocyanate
Prepare 21.0g and 500g of toluene and heat at 100℃.
After heating and stirring for an hour, 0.1 g of tin octylate was added and further heating and stirring for 3 hours. At this point, it was confirmed by infrared spectroscopy that no diisocyanate remained, and the reaction was terminated. The reaction product obtained was When the solvent was distilled off by heating under reduced pressure, a viscous block copolymer was obtained. (Manufacture of fiber treatment agent) Add 100 parts of dimethylpolysiloxane with a relative viscosity of 2.3, in which both ends of the molecular chain are blocked with hydroxyl groups, and a viscosity of 35 cp and a content of ≡SiH bonds of 1.7 mol/100 g.
Methylhydrodiene polysiloxane 10
parts, 10 parts of the block copolymer obtained above, 1 part of aminoalkylalkoxysilane having the formula H ₂ N(CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ and the average formula Silylated triallylisocyanurate represented by
When these were uniformly dissolved in 500 parts of perchlorethylene, a translucent composition with a viscosity of 20,000 cps was obtained.
A fiber treatment agent was prepared by adding 0.5 part of dioctyltin diacetate to 100 parts. For comparison, 10 parts of methylhydrodiene polysiloxane, 1 part of aminoalkylalkoxysilane, and 10 parts of silylated allyl isocyanurate were added to 100 parts of the organopolysiloxane used above.
These were dissolved in 500 parts of perchlorethylene to make a composition with a viscosity of 15,000 cps, and then 0.5 parts of dioctyltin diacetate was added to 100 parts of this composition.
A fiber treatment agent was prepared by adding 50% of (Fiber treatment) The fiber treatment agent obtained above was applied to the same polyester fiber plain weave as that used in Example 1 using a knife coater to give a solid content of 6.3 g/m ² and heated at 170°C. When the physical properties of this fabric were examined after heat treatment for 30 seconds, the results shown in Table 2 were obtained.

【table】

Claims (1)

[Scope of Claims] 1 (1) 100 parts by weight of an essentially linear liquid organopolysiloxane containing at least two hydroxyl groups bonded to silicon atoms in one molecule (2) Silicon in one molecule Liquid organohydrodiene polysiloxane containing at least 3 hydrogen atoms bonded to atoms 1 to 50 parts by weight (3) (a) General formula [Here, R ¹ is a divalent organic group, R ² and R ³ are the same or different unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, X is -OH group, -SH group,
An organosiloxane represented by an active hydrogen-containing functional group selected from _-NH2 group, ^-NR4H group ( ^R4 is a monovalent hydrocarbon group having 1 to 6 carbon atoms), and -COOH group, where n is a positive number. (b) Polyol compound containing a hydrophilic polyoxyalkylene group (c) Block copolymer with diisocyanate compound 1 to 50 parts by weight (4) General formula (Here, R ⁵ is a divalent hydrocarbon group having 1 to 4 carbon atoms,
R ⁶ and R ⁷ are the same or different unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, a and m are 0 or 1) 0.1 to 20 parts by weight of aminoalkylalkoxysilane (5) Formula [Here, R ⁸ is −CH ₂ CH=CH ₂ or −
CH ₂ CH ₂ CH ₂ SiR ⁹ _b (OR ¹⁰ ) _3-b (R ⁹ and R ¹⁰ are the same or different unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms), b is 0, 1 or 2], and at least one of R ⁸ is a silylated propylene group
A fiber treatment agent comprising 1 to 50 parts by weight (6) of a catalytic amount of a condensation reaction catalyst.