JPH0335432B2 - - Google Patents

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, a water and oil repellent for fiber fabric materials such as textile fabrics, carpets, and raw cotton yarns, which has 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-based compounds have 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 due to a structural problem with fluorine-based water and oil repellents, and it is assumed that rearrangement of the fluoroalkyl 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 hassle, and the complicated shape When it comes to things, ironing them is never easy, and there are some items that are not normally ironed, such as diaper covers, so we are waiting for the emergence of water and oil repellent treatments that do not require ironing. Ta. The present inventors have disclosed in Japanese Patent Application Laid-Open No. 165072/1987 that carbon atoms having 2 to 50 carbon atoms and at least 2 or more OH atoms in one molecule.
We have proposed a water and oil repellent finishing method in which only a fluoroalkyl group-containing compound and a polyfunctional isocyanate or its block form are blended without using a compound having a group. However, this water and oil repellent cannot be used as a solvent-based water and oil repellent because the polyfunctional isocyanate block used in combination has poor solvent solubility, and is highly crystalline, so it is stable in storage even when used as an emulsion. In addition, blocks obtained by reacting commercially available trimethylolpropane tolylene diisocyanate adducts, 1,6-hexanediol, adipate tolylene diisocyanate adducts, etc. with methyl ethyl ketoxime contain high molecular weight components and cannot be emulsified and dispersed. The problem was that it lacked storage stability. <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. As a result of intensive research to develop a fluorine-based water and oil repellent treatment agent with excellent storage stability (emulsion stability) and solvent solubility, which eliminates the need for air-dry recovery, we have developed a specific blocked polyisocyanate. The present inventors discovered that a fluorine-based water and oil repellent using the 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 polyisocyanate compound () produced from a compound having 2 to 50 carbon atoms and at least two OH groups in one molecule, an oxime compound, and an aromatic polyisocyanate compound; Fluorine-based water and oil repellent ()
A water and oil repellent treatment agent for textile fabric materials, comprising:
and a blocked polyisocyanate compound produced from a fluorine-based water and oil repellent, a compound having 2 to 50 carbon atoms and at least two OH groups in one molecule, an oxime compound, and an aromatic polyisocyanate compound. Immerse the fiber fabric in the treatment solution,
The object of the present invention is to provide a water and oil repellent treatment method, which is characterized in that it is then lifted out of the bath and squeezed, dried if necessary, and then heat-treated at 200°C or less. According to the present invention, after many washings or dry cleanings, almost the original water and oil repellency can be restored 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 a _C3 to _C20 , preferably
It has a C ₆ - _{C 12} fluoroalkyl group or fluoroalkenyl group, is insoluble in water (solubility is 1% by weight or less at 25℃), and has a main transition temperature, melting point, glass transition point, or softening point of 20℃. above, preferably 50 to 160°C, preferably with a molecular weight of about 700
A non-adhesive organic fluorine-based compound having a molecular weight of about 200,000 is suitable, and the fluorine-based water and oil repellent is
It must also contain 5% by weight, preferably 10 to 50% by weight, of fluorine atoms in its molecule and have water and oil repellency. Representative examples of such organic fluorine compounds are as follows. (1) First, there are homopolymers of vinyl monomers having _C3 to _C20 fluoroalkyl groups or fluoroalkenyl groups, or copolymers of these with vinyl monomers that do not contain fluorine. The following are representative examples of the vinyl monomer having a fluoroalkyl group or a fluoroalkenyl group. C ₇ F ₁₅ CH ₂ OCOCH=CH ₂ ,
C ₁₀ F ₁₉ OCH ₂ CH ₂ OCOCH=CH ₂ ,
C ₈ F ₁₇ CH ₂ CH ₂ OCOCH=CH ₂ , C ₈ F ₁₇ SO ₂ N(C ₃ H ₇ ) CH ₂ CH ₂ OCOCH=
CH ₂ , C ₈ F ₁₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ )=
CH ₂ , On the other hand, typical examples of the fluorine-free vinyl monomers include ethylene, propylene, butylene, butadiene, isoprene, chloroprene, vinyl chloride, vinylidene chloride, styrene,
Esters or amides of (meth)acrylic acid and alcohols or alkyl amines (all _C20 or less), diacetone acrylamide, N-
Examples include methylol acrylamide, acrylonitrile, acrylamide, vinyl acetate, and vinyl compounds having 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 is generally preferably 3000 or more. (2) Next, a C ₃ to C ₃₀ monohydric or polyhydric alcohol having a C ₃ to _{C 20} fluoroalkyl group or a fluoroalkenyl group, and a C ₄ to _{C 20} monohydric alcohol even if fluorinated. or a (poly)ester with a polycarboxylic acid, preferably having a molecular weight of 1000 or more, and a monohydric or polyhydric alcohol of C ₂ to _{C 20} , which may be fluorinated, and a fluorocarbon of C ₃ to C ₂₀ . preferably with a _C3 to _C30 mono- or polycarboxylic acid having an alkyl group or a fluoroalkenyl group.
There are (poly)esters with a molecular weight of 1000 or more, and typical examples of component compounds used to obtain these (poly)esters are: C ₆ F ₁₃ CH ₂ CH ₂ OH, C _{7 F15CH2OH ,}
C ₇ F ₁₅ CH ₂ CH ₂ OH, C ₈ F ₁₇ CH ₂ CH ₂ OH, C ₆ F ₁₃ SO ₂ N (CH ₃ )
CH ₂ CH ₂ OH, C ₈ F ₁₇ SO ₂ (C ₃ H ₇ ) CH ₂ CH ₂ OH, C ₈ F ₁₇ SO ₂ N
( _{CH2CH2OH ) 2} , _{C8F17SO2N ( C2H5 ) CH2CH2 (} OH _)
CH2OH , _{C10F19N ( C2H5 ) CH2CH2OH ,}
C ₇ F ₁₅ COOH, _{C8F17SO2N ( C2H7 ) CH2COOH ,} Examples include benzoic acid, adipic acid, sebacic acid, phthalic acid, maleic acid, trimellitic acid, ethylene glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol, glycerin, polypropylene glycol, 2-ethylhexanol, and stearyl alcohol. (3) In addition, a _C3 to _C30 monohydric or polyhydric alcohol having a _C3 to _C20 fluoroalkyl group or a fluoroalkenyl group (in some cases, a fluorine-free monohydric or polyhydric alcohol) (may be mixed) and an organic mono- or polyisocyanate, such as phenyl isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, preferably with a molecular weight of 700 or more. Typical (poly)urethane compounds having a fluoroalkyl group or fluoroalkenyl group include the following. (4) Epoxide monomers having _C3 - _C20 fluoroalkyl or fluoroalkenyl groups, e.g. and preferably a homopolymer having a molecular weight of 3,000 or more, and a combination of these epoxide monomers and preferably a fluorine-free epoxy compound such as propylene oxide or epichlorohydrin.
A copolymer with a molecular weight of 3000 or more. The fluorine-containing water and oil repellent, which is an essential component of the treatment agent of the present invention, includes the above-mentioned fluorine-containing compounds, and in particular various fluorine-containing (poly)urethane compounds as listed in (3) above, The fluorine-containing vinyl compound (1) is preferably used. In this case, the fluorine-containing urethane compound may be used alone or in combination, or the fluorine-containing urethane compound may be further added with (1), (2) and the like mentioned above.
Of course, it may be used in a blend with other fluorine-based water and oil repellents (fluorine-based compounds) such as (4). In that case, they are mixed at a weight ratio of 1/9 to 9/1. On the other hand, the blocked polyisocyanate compound, which is the other essential component of the treatment agent of the present invention, has 2 to 50 carbon atoms and contains at least two OH groups in one molecule, such as triethylene glycol, glycerin, trimethylolethane,
Trimethylolpropane, ethylene oxide (preferably 5 mol or less adduct) or/or propylene oxide (preferably 5 mol or less adduct) adduct of trimethylolpropane, bisphenol A, bisphenol A ethylene oxide (preferably 5 mol or less) following additions) or/
or propylene oxide (preferably 5 moles or less of adduct) adduct, pentaerythritol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,
3-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3,5-pentanediol, 3-methyl-1,5-pentanediol, N,N,N',N'- Examples include tetra(2-hydroxypropyl)ethylenediamine, sucrose, fructose, and the like. In addition, the oxime compound is an oxime compound having 7 or less carbon atoms, such as acetoxime,
Examples include methyl ethyl ketoxime, cyclohexanone oxime, methyl isobutyl ketoxime and the like. The aromatic polyisocyanate compound is one to which no polyol is added, for example,
Examples include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate, tris(4-phenyl isocyanate) thiophosphate, and the like. The blocked polyisocyanate compound is a compound having 2 to 50 carbon atoms and at least two OH groups in one molecule, which is added to 2 equivalents of an aromatic polyisocyanate compound in an organic solvent under anhydrous conditions.
It is produced by adding 0.9 to 1.1 equivalents and 0.9 to 1.1 equivalents of an 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 carried out by adding the oxime compound to the aromatic polyisocyanate compound and then adding the OH group-containing compound. Although it is unclear why such blocked polyisocyanate compounds () have excellent solvent solubility and emulsion stability, the present inventors speculate as follows. That is, by introducing an appropriate hydrophilic unit, hydrophobic unit, 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 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 greater than 50 increases hydrophobicity, resulting in a decrease in oil repellency.
Further, the use of a compound having a hydrophilic unit (ethylene oxide unit) among the OH group-containing compounds having a carbon number of more than 50 is not preferable because the hydrophilicity increases and the water repellency decreases. In addition, the use of the above-mentioned 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 fluorine-free blocked polyisocyanate compound () as described above 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 disadvantages such as deterioration of water and oil repellency. Therefore, the amount of the compound to be used is preferably 10% by weight or more, particularly preferably 50 to 200% by weight, 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 includes, for example, an emulsion or a solvent solution containing 0.1 to 4% by weight (solid content) of the fluorine-based water and oil repellent agent and the blocked polyisocyanate compound (). Adjust the fiber fabric in this bath for at least 5 seconds, preferably 10 to 60 minutes.
Dip for 0.1 to 4% by weight of resin solids to the textile product, then remove from the bathtub and soak for 50 to 40 minutes.
Squeeze until the squeezing rate is 150%, then 80-120℃
Pre-drying for 1 to 3 minutes at
A method of heat treatment or curing is performed 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 processing agent of the present invention contains as essential components:
Compounds having at least two OH groups in one molecule with 2 to 50 carbon atoms as described above, oxime compounds, blocked isocyanate compounds produced from aromatic polyisocyanate compounds, and fluorine-based repellents Although it contains a water and oil repellent, the combination of these two essential components improves the recovery of water and oil repellency after washing and dry cleaning of textiles etc. that have been treated with water and oil repellents. Although it is unclear whether or not this will improve, 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. If the oil repellent alone is used, the alignment will be immediate if heat treatment is performed, but alignment will be delayed without heat treatment. However, when a specific blocked polyisocyanate compound () coexists here, the active isocyanate groups dissociated and regenerated by heat treatment,
A water repellent that links fluoroalkyl (alkenyl) groups as a result of reaction with functional groups in the other water and oil repellent or active groups (e.g. hydroxyl, amino, or amide groups) in the fiber fabric to form a crosslinking bond. The trunk or skeleton of the oil repellent becomes strong, and these fluoroalkyl (alkenyl)
This is thought to be because the groups become easier to arrange. Even if there are no functional groups in this fluorine-based water and oil repellent, similar effects can be expected in polymer-type water and oil repellents due to crosslinking and interpenetration of polymer chains. Yes, 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 () can be prepared as an aqueous emulsion by a conventional method and used in combination with an aqueous emulsion type water and oil repellent; In addition to water and oil repellents obtained by polymerization, (co)polymers obtained by bulk polymerization or emulsion polymerization are dissolved in one or more suitable organic solvents. If it is acceptable to use a water- and oil-repellent treatment agent, it may be used in combination with the blocked polyisocyanate compound () which is soluble in these organic solvents. may be prepared, and then a propellant such as dichlorotetrafluoroethane, dichlorodifluoromethane or monofluorotrichloromethane is added thereto, and the mixture is filled into a suitable container and used. Preferably it is an aqueous emulsion. The thus obtained treatment agent of the present invention can be applied to a wide variety of substrates, including commonly used textile materials, such as paper, wood, leather, fur, plastics, and paint coatings. Examples include construction surfaces and plaster, but
Typical textile materials mentioned here include natural fibers such as cotton, hemp, wool, or silk; synthetic fibers such as polyamide, polyester, polyurethane, polyvinyl alcohol, polyacrylonitrile, or polyvinyl chloride; or rayon or acetate. There are semi-synthetic fibers such as Of course, it can also be used for fiber fabric materials that are a mixture of these, and also for products such as carpets, 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. Sometimes, there is no problem in using other fiber processing resins in combination, and by using such a combination, water and oil repellency is imparted to fiber fabrics, etc., and at the same time, other properties are also imparted. In this sense, it can be said to be rather preferable. Here, the following are representative examples of fiber processing resins that can be used in combination. Urea-formalin initial condensation resin;
Cellulose-reactive resins such as ethylene urea, uron, or glyoxal, represented by DS-1 (a glyoxal fiber treatment agent manufactured by Dainippon Ink and Chemicals Co., Ltd.); condensation-based hardening finishing agent represented by "APM" (a melamine-based fiber treatment agent made by the same company); water-soluble acrylic resin represented by "Betsukamine R-25" (a product of the same company); "Boncourt R-3320" (product of the same company); urethane emulsion such as "BONDIX 1610NS" (product of the same company); and 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, PH stabilizer, etc. can also be added. Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the following, all parts and percentages 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 a spray method according to JIS L-1005, and the "water repellency" as shown in Table 1 is measured.
On the other hand, for oil repellency, various solvents with different surface tensions as shown in Table 2 are dropped onto the test object, and the state of penetration is observed when the droplet is held for 30 seconds. When displaying the "Oil Repellency No." as shown in Table 2, measured by a method (hydrocarbon resistance test) in accordance with AATCC-118-1975, even after the above-mentioned fixed retention time has elapsed. The highest number (No.) of the standard test solution in which no penetration was observed was considered the oil repellency.

【table】

[Table] Example 1 500.2 parts (2 mol) of diphenylmethane diisocyanate was dissolved in 1044.3 parts of toluene, and 404 parts (2 mol) of methyl isobutyl ketoxime was dissolved at 60°C.
Drop it in 1 hour. Next, 140.1 parts (1 mol) of triethylene glycol was added and the reaction was carried out at 80°C for 6 hours to obtain a blocked polyisocyanate compound (referred to as compound (1)). Obtained blocked polyisocyanate compound
(1) Add 10 parts of stearyltrimethylammonium chloride to 290 parts of water to 200 parts of the solution and emulsion it with a homomixer.

75% of [formula] 10 parts of an emulsion with a solid content of 20% containing a copolymer (copolymer (A)) consisting of 23% of CH ₂ =CHCONHCH 2 OH and 2% of CH 2 =CHCONHCH ₂ OH were added and mixed uniformly. This material was diluted with water so that the total solid content was 1%. A cotton cloth is then placed in this diluted emulsion bath.
After soaking for 30 seconds, the cloth was pulled up and squeezed to a squeezing rate of about 85%, pre-dried at 100°C for 2 minutes, and then cured at 160°C for 2 minutes. The thus treated fabric had a water repellency of 100°C and an oil repellency of 6. Next, JIS L-0217-103 was applied to this treated cloth.
Washed 10 times according to the law or JIS L-1018/E-
Table 3 shows the water and oil repellency when air-dried after dry cleaning 10 times according to the two methods. Comparative Example 1 Example 1 except that no use of compound (1) was used.
Table 3 summarizes the performance of cotton fabrics treated in the same manner as above. Examples 2 to 21 and Comparative Examples 2 to 3 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 were prepared in the same manner as in Example 1. Using the produced blocked isocyanate compounds (1) to (16), treatments such as dipping, squeezing and curing were carried out in the same manner as in Example 1, and the fabrics immediately after the curing treatment (after processing) were obtained. Water and oil repellency, and
Table 3 summarizes the water and oil repellency of the fabric when air-dried after washing or dry-cleaning 10 times, and in addition, in the case of each comparative example, the treated fabric after washing or dry-cleaning 10 times. to 140℃
After ironing for 30 seconds, the water and oil repellency of the fabric was measured, and the results are summarized in Table 3.

【table】

【table】

【table】

【table】

[Table] Example 22 As a fluorine-based water and oil repellent, 10 parts of a 20% solids trichloroethane solution containing the blocked polyisocyanate compound (13) having the composition shown in Table 5 was added.

75% of [formula]

Trichloroethane solution with solid content of 20% containing copolymer (C) consisting of 25% of [formula] 10
1 part was added and mixed uniformly. This material was diluted with trichloroethane so that the total solid content was 0.8%. Next, a cotton cloth was placed in the treatment bath thus obtained.
After soaking for 30 seconds, remove the cloth from the bath, shake off the liquid thoroughly, and let it air dry at room temperature.
Curing was performed at 160°C for 2 minutes. The water repellency and oil repellency of the fabric treated in this way, as well as its performance when air-dried after washing or dry cleaning in the same manner as in Example 1, are shown in Table 6. It was excellent. Comparative Example 4 Except that the blocked polyisocyanate compound (13) having the composition shown in Table 5 was not used at all,
Table 6 summarizes each performance of the cotton fabric treated in the same manner as in Example 22. 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.

【table】

【table】

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[Table] 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 isobutyl ketone as a solvent. Shown below. It is clear that the blocked polyisocyanate compound obtained by the present invention has excellent solvent solubility and emulsion stability.

【table】

【table】

Claims (1)

[Claims] 1. A blocked polyisocyanate compound () produced from 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.
and a fluorine-based water and oil repellent (). 2 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 textile fabric in a treatment solution, then pulling it out of the bath and squeezing it, drying it if necessary, and then heat-treating it at 200°C or less.