JPS6216454A - Blocked polyisocyanate compound, water and oil-repellent agent and treatment therewith - Google Patents

Abstract

PURPOSE:To provide the titled compound composed of a specific OH-containing compound, an oxime compound and an aromatic polyisocyanate compound, and effective to improve the recoverability of the water and oil repellency after washing or dry-cleaning by using in combination with a fluorine-based water and oil-repellent. CONSTITUTION:A blocked polyisocyanate is produced by the addition reaction of (A) a 2-50C compound having >=2 OH groups in one molecule (e.g. triethylene glycol), (B) an oxime compound, preferably a <=7C oxime (e.g. methyl ethyl ketoxime) and (C) an aromatic polyisocyanate (e.g. diphenylmethane diisocyanate) under anhydrous condition in an organic solvent at 50-100 deg.C in one or two steps. The amount of the component A and B is 0.9-1.1 equivalent each based on 2 equivalent of the component C. When the above compound is added to a fluorine-based water and oil-repellent composition in an amount of >=10wt%, preferably 50-200wt% based on the whole solid components in the composition, a water and oil-repellent agent having excellent air-drying recoverability and storage stability can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a water and oil repellent treatment agent improved with a blocked polyisocyanate compound, and a treatment method. More specifically, water and oil repellent for textile fabric materials such as textile fabrics, carpets, and raw cotton yarns, which have improved recovery of water and oil repellency after washing and dry cleaning, using a specific blocked polyisocyanate compound. The present invention relates to a processing agent and a processing method.

<Prior Art> It has been well known that fluorine thread compounds exhibit excellent potential as water- and oil-repellent treatment agents for textiles and the like.

However, even though this excellent performance is washed and dry cleaned, the water and oil repellency apparently deteriorates significantly, and in order to regain this performance, conventional heat treatments such as ironing and heat pressing have been used. It was essential. .

This is thought to be due to a structural problem with fluorine-based water and oil repellents, and rearrangement of fluoroalkyl groups or fluoroalkenyl groups is required to fully develop water and oil repellency. However, for consumers who actually use water- and oil-repellent textiles, even if the dry cleaning itself can be outsourced to a professional, ironing after washing is a tedious and complicated process. Ironing is not an easy task when it comes to shapes, and there are some items that are not normally ironed, such as diaper covers, so we are looking forward to the emergence of a water and oil repellent treatment that does not require ironing. The present inventors disclosed in Japanese Unexamined Patent Publication No. 56-165072 that a compound containing a fluoroalkyl group and a polyfunctional We are proposing a water and oil repellent finishing method that involves blending only incyanate or its blocks. However, this water and oil repellent cannot be used as a solvent type water and oil repellent because the polyfunctional incyanate block used in combination has poor solvent solubility, and it is highly crystalline, so even if it is used as an emulsion and dispersed, it cannot be stored. It lacks stability and commercially available trimethylolglopane tolylene diisocyanate adduct or 1
, 6-hexanediol, ano(-tolylene diisocyanate adduct, etc.) and methyl ethyl ketoxime have the problem of lacking storage stability as an emulsified dispersion because they contain high molecular weight components. was there.

<Problems to be Solved by the Invention> In view of the above-mentioned circumstances, the present inventors have found that the water and oil repellency performance after washing and dry cleaning is well recovered, and that no heat treatment such as ironing or heat pressing is required. Excellent storage stability (emulsion stability) with no need for air-dry recovery
As a result of intensive research to develop a water- and oil-repellent treatment agent for furisone yarn with excellent solvent solubility, we found a specific! It was discovered that a fluorine-based water and oil repellent using a locked 4-lisocyanate compound has excellent air-drying recovery properties and storage stability (emulsion stability), leading to the completion of the present invention.

That is, the present invention provides a blocked incyanate compound produced from a compound having at least two OH groups in one molecule having 2 to 50 carbon atoms and an oxime compound aromatic-liisocyanate compound. , The present invention also provides a fluorine-based water and oil repellent (n) and a carbon atom having 2 to 50 carbon atoms.
A blocked polyisocyanate compound produced from a compound having at least two or more OH groups in one molecule, an oxime compound, and an aromatic polyisocyanate compound (
The present invention provides a water- and oil-repellent treatment agent for textile fabric materials, which comprises I) as an essential component.

Furthermore, the present invention provides a fluorine-based water and oil repellent (U) and a carbon atom having 2 to 2 carbon atoms.
Water and oil repellent treatment for textile fabric material comprising a compound having at least two or more OH groups and a blocked polyisocyanate compound (I) produced from an oxime compound aromatic polyisocyanate compound The present invention provides a water and oil repellent treatment method characterized by immersing a fiber fabric material in a treatment solution containing an agent, then pulling it out of the bath, squeezing it, drying it, and then heat-treating it at 200°C or less. .

According to the present invention, almost the original water and oil repellency can be restored after many washings or dry cleanings simply by air drying without heat treatment.

The above-mentioned fluorine-based water and oil repellent, which is an essential component of the treatment agent of the present invention, is C5 to C2o, preferably C6 to C4.
It has two fluoroalkyl groups or fluoroalkenyl groups, is water-insoluble (solubility is 1 weight range or less at 25°C), and has a main transition temperature, melting point, glass transition point, or softening point of 20°C or higher, preferably is 50-160℃,
Preferably, a non-adhesive organic fluorine thread compound having a molecular weight of about 700 to about 200,000 is suitable. contains 10 to 50 heavy fluorine atoms, and
Must be water and oil repellent.

Representative examples of such organic fluorine thread compounds are as follows.

(I) First, there is a homopolymer of a vinyl monomer having a C5 to C2o fluoroalkyl group or a fluoroalkenyl group, or a copolymer of it and a vinyl monomer that does not contain fluorine. However, representative examples of the vinyl monomer having the above-mentioned fluoroalkyl group or fluoroalkenyl group include the following.

C, F, 5CH20COCH-CH2, C1゜Fl
, OCH2CH20COCH-CH2, C8F'1. C
H2CH20COCH-CH2,08F, , So□N
(C,f(,)CH2CH20COCH-CH2,08
F4,5o2N(CH,)CH2CH20COCCCH
3) -CH2, On the other hand, typical examples of the above-mentioned fluorine-free vinyl monomers include ethylene, propylene, butylene, butadiene, isoprene, chlorozolene, vinyl chloride, vinylidene chloride, styrene, (meth)acrylic acid and alcohol. or alkylamine (all below C2o)
ester or amide of, diacetone acrylamide, N-methylolacrylamide, acrylonitrile,
Examples include acrylamide, vinyl acetate, and vinyl compounds with siloxane bonds. Two or more of these monomers can also be used in combination.

These homopolymers or copolymers can be obtained by known methods for vinyl polymerization. for example,
Solution or emulsion polymerization using radical initiators is common. The molecular weight of the polymer can be adjusted to a preferred range by adjusting the concentration of the initiator and the type and concentration of the chain transfer agent, but generally a VC of 3,000 or more is preferred.

(2) A C5-C3゜-hydric or polyhydric alcohol having a C3-C2G fluoroalkyl group or a fluoroalkenyl group, and a 04-C20 mono- or polycardic acid which may be fluorinated. , preferably 1. (Poly)ester having a molecular weight of OO0 or more, and optionally fluorinated -C2-C
2o monohydric or polyhydric alcohol, and C5 to C2o
There are (poly)esters, preferably having a molecular weight of 1,000 or more, with a 03-C50 mono- or polycardic acid having a fluoroalkyl group or a fluoroalkenyl group, but in order to obtain these (poly)esters, Typical examples of component compounds used are as follows: 06F, , CH2CH20H, C, F', 5CH, 20
H, C, F, 5CH2CH20H.

08F,,CH2CH20H,C6F,,So□N(C
H,)CH2C120H.

08F, ,So□N(C5H,)CH2CH20H,
C8F,,5o2N(CH2CH20H)2.08F1
．． So□N(C2H5)CH2CH2(Of()CH2
0H.

;I C, F, 5CNCC2H6) CH2CH20H.

C1°Fl, N(C2I(5)CH2CH20f(,C
,F,5COOH.

Benzoic acid, adipic acid, heptapacic acid, phthalic acid.

Examples include maleic acid, trimellitic acid, ethylene glycol monomethyl ether, ethylene glycol, clopylene glycol, diethylene glycol, glycerin, I-lipropylene glycol, 2-ethylhexanol, and stearyl alcohol.

(3) C5-C5゜hydric or polyhydric alcohol having a C3-C2G fluoroalkyl group or fluoroalkenyl group (in some cases, containing fluorine and mixed with a monohydric or polyhydric alcohol) Polyisocyanates, e.g.
There are urethane compounds preferably having a molecular weight of 700 or more, such as urethane compounds containing diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and polymethylene polyphenylisocyanate. /S) Typical urethane compounds include the following:

H2O (4) Epoxide monomers having C, to C20 fluoroalkyl or fluoroalkenyl groups, such as homopolymers preferably having a molecular weight of 3,000 or more, and these epoxide monomers. A copolymer, preferably with a fluorine-free epoxy compound such as propylene oxide or epichlorohydrin, preferably having a molecular weight of 3,000 or more.

The fluorine-based water and oil repellent, which is an essential component of the treatment agent of the present invention, includes the above-mentioned fluorine-containing thread compounds, including various fluorine-containing urethane compounds (3) as listed above in %. The fluorine-containing vinyl compound of I) is preferably used. In this case, the fluorine-containing urethane compound may be used alone or as a mixture, or the fluorine-containing urethane compound may be further combined with (I) as described above.
, (2) and (4) may be blended with other fluorine-based water and oil repellents (fluorine thread compounds). In that case, they are mixed at a weight ratio of 1/9 to 9/1.

On the other hand, the other essential component of the treatment agent of the present invention,
Compounds containing at least two or more OH groups in one molecule and having 2 to 50 carbon atoms include, for example, triethylene glycol, glycerin, trimethylolethane, trimethylolethane, and trimethylol. Ethylene oxide (preferably 5 mol or less adduct) or propylene oxide (preferably 5 mol or less adduct) adduct, bisphenol A, bisphenol A ethylene oxide (preferably 5 mol or less adduct) adduct) or propylene oxide (preferably 5 moles or less of adduct),
(Taerythritol, neopentyl glycol, 2e
2t4-) IJ Methyl-1,3-bentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-bentanediol, 3-methyl-1,3,5
Examples include --e entanetriol, 3-methyl-1,5-bentanediol, N , N , N', N'-tetra(2-hydroxypropyl)ethylenediamine, sucrose, fructose, and the like.

The oxime compound is an oxime compound having 7 or less carbon atoms, such as acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, methyl isobutyl ketoxime, and the like.

Examples of aromatic polyisocyanate compounds include those to which -diol is not added, such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, triphenylmethane triisocyanate, tris(4-phenylisocyanate) thiophos For example, Fate etc.

The blocked polyisocyanate compound is usually prepared by adding 2 equivalents of an aromatic polyisocyanate compound in an organic solvent under anhydrous conditions to 0.0. It is produced by adding 9 to 1.1 equivalents of the oxime compound and 0.9 to 1.1 equivalents of the oxime compound simultaneously or in a two-step reaction at 50 to 100°C. In order to suppress the production of high molecular weight components, the production method is preferably performed by adding the oxime compound to the aromatic I-reincyanate compound and then adding the OH group-containing compound. Although it is unclear why such blocked polyisocyanate compound (I) has excellent solvent solubility and emulsion stability, the present inventors speculate as follows.

That is, by introducing an appropriate amount of hydrophilic or hydrophobic units or both into the molecule, the affinity with the emulsifier is improved, making it possible to obtain a stable emulsified dispersion. In addition, by introducing a compound containing at least two or more OH groups in one molecule with 2 to 5 carbon atoms, the symmetry of the molecule is lost, and the internal plasticizing effect reduces crystallization, thereby reducing organic solvents. It is thought that the solubility in the molecule is improved and the emulsion stability is also improved.

The use of the OH group-containing compound having a carbon number of more than 50,
Oil repellency decreases due to increased hydrophobicity. In addition, the OH group-containing compound having a carbon number of more than 50 has hydrophilic properties.
The use of compounds with ethylene oxide units)
Since hydrophilicity increases, water repellency decreases, which is undesirable. In addition, the use of the OH group-containing compound having a carbon number greater than 50 increases the molecular weight of the blocked polyisocyanate compound, which reduces the content of blocked NCO groups in one molecule and reduces durability. Undesirable.

Furthermore, if the number of OH groups in the OH group-containing compound increases, three-dimensionalization progresses during the reaction, resulting in an increase in molecular weight, which leads to a decrease in solubility and emulsion stability, which is not preferable. Therefore, compounds having 2 to 50 carbon atoms and 2 to 4 OH groups are more preferably employed.

The amount of the above-mentioned non-blocked polyisocyanate compound (I) can be selected from a wide range. If the amount used is small, the recovery of water and oil repellency will be poor when the treated textile fabric is washed or dry cleaned, and conversely, if it is used in a large amount, the texture of the treated textile fabric will change significantly. This may cause problems such as deterioration of water and oil repellency. Therefore, the amount of the compound to be used is preferably 10 weight percent or more, particularly preferably 50 to 200 weight percent, based on the total solid content in the target water and oil repellent.

The treatment method using the water and oil repellent treatment agent of the present invention can be carried out using, for example, an emulsion or solvent containing a fluorine-based water and oil repellent agent and the blocked polyisocyanate compound (I) in an amount of 0.1 to 4 weight 4 [solid content]. A solution is prepared, and the fiber fabric is immersed in this bath for 5 seconds or more, preferably 10 to 60 seconds, so that a resin solid content ranging from 0.1 to 4 weight range is attached to the fabric, and then pulled out of the bath for 50 seconds. Squeezing until the squeezing rate is ~150m, then pre-drying at 80-120℃ for 1-3 minutes, followed by 2
A heat treatment or curing method is carried out at 00°C or lower, preferably 100 to 180°C, particularly preferably 140 to 180'C, for 30 seconds to 2 minutes. Here, curing at a temperature lower than 140° C. does not provide sufficient air-drying recovery, and curing at a temperature higher than 180° C. damages the fiber material, which is not preferable.

Therefore, the treatment agent of the present invention includes, as an essential component, the above-mentioned compound having 2 to 50 carbon atoms and at least two or more OH groups in one molecule; Although it contains a blocked incyanate compound produced from a reinocyanate compound and a fluorine-based water and oil repellent, why is it that the textile fabric is water and oil repellent treated by the combination of these two essential components? Although it is unclear whether washing or dry cleaning improves the subsequent recovery of water and oil repellency, the present inventors speculate as follows.

In other words, in order for a fluorine-based water and oil repellent to exhibit its performance, fluoroalkyl groups or fluoroalkenyl groups must be arranged on the surface of textiles, etc., but as mentioned above, this fluorine-based water and oil repellent If heat treatment is performed using only oil, alignment will occur immediately, but alignment will be delayed without heat treatment.

However, when the specific pro- or polyisocyanate compound (I) coexists here, the active isocyanate groups dissociated and regenerated by heat treatment are activated by the functional groups in the other water and oil repellent or the active groups in the fiber fabric. (For example, a hydroxyl group, an amino group, or an amide 9 group) to form a crosslinking bond, and as a result, the frame or skeleton of the water and oil repellent that connects the fluoroalkyl (alkenyl) groups becomes strong. This is thought to be because these fluoroalkyl (alkenyl) groups become easier to arrange.

Even if there is no functional group in this fluorine-based water and oil repellent, what is the crosslinking bond in the polymer type water and oil repellent? Interpening with remer chains (Interpen)
A similar effect can also be expected by using (@tration), but in this case, the presence of active groups in the fiber fabric is a prerequisite.

The treatment agent of the present invention can be applied in any form such as an emulsion, a solvent solution, or an aerosol. For example, the blocked polyisocyanate compound (I) can be prepared as an aqueous emulsion by a conventional method and used in combination with an aqueous emulsion type water and oil repellent, or a solvent solution type one can be used. Not only water and oil repellents obtained by solution polymerization, but also (co)polymers obtained by bulk polymerization and emulsion polymerization can be dissolved in one or a mixture of two or more suitable organic solvents. If it is okay to use the blocked polyisocyanate compound (I) that is soluble in these organic solvents, it may be used in combination with the blocked polyisocyanate compound (I) that is soluble in these organic solvents. A processing agent may be prepared, and then a propellant such as dichlorotetrafluoroethane, dichlorodifluoromethane or monofluorotrichloromethane may be added thereto, and the mixture may be filled into a suitable container for use. Preferably it is an aqueous emulsion.

The substrates for treatment to which the treatment agent of the present invention obtained by peeling can be applied include commonly used fiber textile materials, as well as materials used for many types of rafts, such as paper, wood, leather,
These include fur, plasti, wood, paint-coated surfaces, and glazed materials. Typical textile materials mentioned here include natural fibers such as cotton, linen, wool, or silk; polyamide, polyester, polyurethane, and polyvinyl. Synthetic fibers such as alcohol, polyacrylonitrile or polyvinyl chloride; or semi-synthetic fibers such as rayon or acetate. Of course, it can also be used for fiber fabric materials made by mixing these materials, and also for products such as kaite, raw yarn, raw cotton, etc.

Further, the treatment agent of the present invention can treat the various base materials mentioned above, especially fiber fabrics, etc., and it is obvious that the purpose of the present invention can be fully achieved through such treatment. There is no problem in using other fiber processing resins in combination, and this combination will impart water and oil repellency to textiles, etc. while also imparting other properties. In this case, it can be said that it is rather preferable.Here, the following are representative examples of fiber processing resins that can be used in combination.

Urea-formalin initial condensation resin; [Beccamin DS-1
] Cellulose-reactive resins such as ethylene urea, uron, or glyoxol, typified by (glyoxydel-based fiber treatment agent manufactured by Dainippon Ink & Chemicals Co., Ltd.);
"Condensation hardening finishing agent represented by Beckamin J-101, MA or APMJ (melamine fiber treatment agent manufactured by the same company); "Water-soluble acrylic resin represented by Beckamin R-25J (product of the same company); [? Nko) R-332
Acrylic emulsion represented by 0J (product of the same company);
These include urethane emulsions, such as those exemplified by (a product of the same company); or silicone or wax-based softeners.

Furthermore, in order to further improve the stability of the treatment agent of the present invention, the treatment agent must be kept within a range that does not impair the original water and oil repellency or the ability to recover water and oil repellency after washing or dry cleaning. A known and commonly used heat stabilizer, ultraviolet light stabilizer, monostabilizer, etc. may also be added.

Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the following, all parts and units are based on weight unless otherwise specified.

The water repellency and oil repellency data shown in Examples and Comparative Examples are based on the following measurement methods and evaluation scales.

First, water repellency is measured by the Sdale method according to JISL-1005 and is expressed as a "water repellency point" as shown in Table 1. On the other hand, oil repellency is measured by the "water repellency point" as shown in Table 2. Various solvents are dropped onto the test object, and the droplets are heated for 30 minutes.
AATC, which observes the state of penetration when held for seconds.
When indicating ``poor oil repellency'' as shown in Table 2 when measured by a method according to C-118-1975 (Hydrocarbon Resistance Test), there is no infiltration even after the above-mentioned fixed holding time has elapsed. The highest number (&) of the standard test solution that was not recognized was taken as its oil repellency.

Table 2 Example 1 500.2 parts (2 moles) of diphenylmethane diisocyanate are dissolved in 1044.3 parts of toluene and 404 parts (2 moles) of methyl isobutyl ketoxime are added dropwise at 60° C. over 1 hour. Then, triethylene glycol 140.
One part (1 mole) was processed and reacted at 80° C. for 6 hours to obtain a blocked polyisocyanate compound (referred to as compound (I)).

Fluorine-based CH as a water and oil repellent.

08F1,5o2NCH2CH200CCH-CH2's 75 wa and CH2fuCHCOOCH2CHCH2CH2C
10 parts of an emulsion containing a copolymer (copolymer) consisting of 234 H2CH and 2H5CH2-CHCONHCH20H and having a solid content of 20 was added and mixed uniformly. This product was diluted with water to a total solid content of 11.

The cotton cloth was then immersed in this diluted emulsion bath for 30 seconds, then pulled up and squeezed to a squeezing rate of approximately 85 inches, pre-dried at 100°C for 2 minutes, and then at 160°C for 2 minutes. Cured @ The fabric thus treated has a water repellency of 100 and an oil repellency of 6.
Met.

Next, JIS L-0217-10 was applied to this treated cloth.
Washed 10 times according to method 3 or JIS L-1018
・Dry cleaned 10 times according to method E-2.

The water and oil repellency performance after air drying is shown in Table 3.

Comparative Example 1 Table 3 summarizes the performance of a cotton fabric treated in the same manner as in Example 1, except that no compound (I) was used.

Examples 2 to 21 and Comparative Examples 2 to 3 Example 1 with each water and oil repellent treatment agent and fiber material having the composition shown in Tables 3 and 4 and the composition shown in Table 5.
A pro-chlorinated isocyanate compound (produced in the same manner as
Using I) to αQ, treatments such as dipping, squeezing, and curing were performed in the same manner as in Example 1, and the water and oil repellency of the cloth immediately after the curing treatment (after processing) was evaluated, and the water and oil repellency of the cloth was evaluated 10 times. Table 3 summarizes the water and oil repellency of the fabric when air-dried after dry cleaning a or 10 times. 3 at 140℃
The water and oil repellency of the cloth was measured after ironing for 0 seconds, and these results are also summarized in Table 3.Table 4 Example 22 Block composition shown in Table 5 Add C, Fl, 5o2N as a fluorine-based water and oil repellent to 10 parts of a 20% solids trichloroethane solution containing polyisocyanate compound CI3.
A copolymer consisting of 75 mm of CH2CH200CC-CH2 and 25 mm of HSC,8H,,0OCC-CH2 (a trichloroethane solution with a solid content of 20% containing q)
0 parts were added and mixed uniformly. This product was diluted with trichloroethane so that the total solid content was 0.8.

Next, the cotton cloth was immersed in the treatment bath thus obtained for 30 seconds, then the cloth was taken out of the bath, the liquid was thoroughly shaken off, and the cloth was air-dried at room temperature, followed by curing at 160° C. for 2 minutes. Water and oil repellency of the fabric treated in this way and washing II as in Example 1
! As shown in Table 6, the performance when air-dried after dry cleaning was excellent in washing resistance and dry cleaning resistance.

Comparative Example 4 Table 6 summarizes the performance of cotton cloth treated in the same manner as in Example 22, except that the blocked polyisocyanate compound having the composition shown in Table 5 was not used at all. Shown.

Examples 23 to 27 and Comparative Examples 5 to 6 In the same manner as in Example 22, using each water and oil repellent treatment agent and fiber material having the composition shown in Tables 3, 4 and 6. The results of the treatment are summarized in Table 6.

As is clear from the results shown in Tables 3 and 6, the treatment agent of the present invention has better air-drying recovery of water and oil repellency after washing and dry cleaning than conventional treatment agents. It can be seen that it is in good condition.

Examples 28 to 32 and Comparative Examples 7 to 9 Table 7 shows the solubility and emulsion stability of blocked polyisocyanate solutions and emulsified dispersions thereof obtained in the same manner as in Example 1 using methyl imbutyl ketone as a solvent. show.

It is clear that the blocked polyisocyanate compound obtained by the present invention has excellent solvent solubility and emulsion stability.

Table 7 Note: ○; Remains stable for more than 1 month.

Claims (1)

[Scope of Claims] 1. A blocked polyisocyanate compound comprising a compound having 2 to 50 carbon atoms and containing at least two OH groups in one molecule, an oxime compound, and an aromatic polyisocyanate compound. 2. A blocked polyisocyanate compound (I) produced from a compound having 2 to 50 carbon atoms and at least two OH groups in one molecule, an oxime compound, an aromatic polyisocyanate compound, and a fluorine-based repellent. A water- and oil-repellent treatment agent for textile fabric materials, comprising a water-oil repellent (II). 3. Contains a fluorine-based water and oil repellent, a compound having 2 to 50 carbon atoms and having at least two OH groups in one molecule, and a blocked polyisocyanate compound produced from an oxime compound and an aromatic polyisocyanate compound. A water- and oil-repellent treatment method characterized by immersing a fiber fabric in a treatment solution, then pulling it out of the bath, squeezing it, drying it if necessary, and then heat-treating it at 200°C or less.