JPH0130956B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a modifier for synthetic or semi-synthetic fibers. Synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyolefin, and polyacetate are homogeneous and have strength, durability,
Due to its excellent physical properties such as chemical resistance, its production and demand have increased in recent years.
It has physical property problems that require further improvement and modification, such as the inertness of the fiber surface, dyeing agents due to the denseness of the internal structure, and insufficient adhesion. Various attempts and proposals have been made to improve these synthetic fibers for a variety of purposes and uses, but none have been found to be satisfactory. For example, among synthetic fibers, polyester fiber has a particularly dense structure and has few functional groups, so it cannot be dyed with ionic dyes or reactive dyes, and even disperse dyes, which can be dyed at temperatures higher than 130℃. It was possible to dye only under such high temperatures. In this regard, easy dyeing has been devised to enable boil dyeing by copolymerization of anionic group-containing dibasic acids or their derivatives, cationic dye-dyeable polyesters, polyethylene oxide chain-containing glycols, etc. Polyester fibers such as polyester fibers have been introduced, but these increase costs due to the use of special raw materials, reduce physical properties such as strength, and even if they can be dyed at low temperatures, they are practically dyed at temperatures of 100 to 120℃. The reality is that high-temperature dyeing is performed. Furthermore, when synthetic fibers such as polyester and polyolefin are used as reinforcing materials in the production of heavy fabrics and synthetic leather, various types of At present, it has poor adhesion with resins, which is often a problem. The present invention chemically modifies the surface of synthetic fibers or semi-synthetic fibers without impairing their original properties, improving dyeability of synthetic fibers or semi-synthetic fibers, affinity for other substances, and even heat melting. It modifies gender, etc. The present invention uses synthetic fibers, especially polyester surfaces, to
Since it is coated with the heat-reactive blocked product of the present invention, it is possible to impart hydroxyl groups to the polyester surface, making it possible to dye with dyes that can be dyed at temperatures below 100°C, such as reactive dyes, and also with polyvinyl alcohol, It facilitates adhesion to resins or drugs having hydroxyl groups such as starch, and further improves the friction or thermal melting properties of synthetic fibers. That is, a water-soluble or water-dispersible and heat-reactive urethane compound having an isocyanate group obtained by reacting a polysaccharide derivative obtained by adding an alkylene oxide to a polysaccharide with an organic polyisocyanate and blocking the isocyanate group. The present invention provides a modifier for synthetic fibers or semi-synthetic fibers, which is characterized in that the blocked product is processed into a synthetic fiber or semi-synthetic fiber fabric, and then the fabric is heat-treated. In the present invention, a water-soluble or water-dispersible isocyanate group-containing urethane compound obtained by reacting a polysaccharide derivative obtained by adding an alkylene oxide to a polysaccharide and an organic polyisocyanate, with blocked isocyanate groups, And a heat-reactive blocked product is used. Examples of the polysaccharides include starch, dextrin, tamarind, guar gum, cellulose,
Examples include, but are not limited to, chitosan. A natural polysaccharide derivative is produced by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, etc. to the polysaccharide by a conventional method. Specific examples of polysaccharide derivatives in which alkylene oxide is added to cellulose include those in the form of hydroxyalkyl cellulose such as hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxybutyl cellulose. Various cellulose derivatives have been used. The organic polyisocyanate used in the present invention can be prepared by mixing an organic polyisocyanate monomer or a compound containing two or more active hydrogens, which is generally used in urethane production, with an organic polyisocyanate monomer in a ratio of isocyanate groups/active hydrogen groups by a conventional method. However, there is a prepolymer having isocyanate groups obtained by reacting such that the isocyanate groups are in excess. Examples of the compound containing two or more active hydrogens include polyether polyols obtained by addition polymerization of alkylene oxide, polyester polyols, polyols containing tertiary amino groups, or quaternized cations in the same molecule. base 1
For example, a polyol containing tertiary amino group-containing polyether obtained by addition-polymerizing alkylene oxide to triethanolamine or N-methyldiethanolamine, quaternizing the tertiary amino group with diethyl sulfate, or the same molecule. Polyols containing one or more anionic groups therein, such as dimethylolpropionic acid, more particularly organosilicone polyols,
Examples include, but are not limited to, organic fluorine polyols. The organic polyisocyanate monomers used include aromatic isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, which are generally used in urethane production, aromatic aliphatic isocyanates such as xylylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and hexane diisocyanates. Examples include aliphatic isocyanates such as methylene diisocyanate. A urethane compound having an isocyanate group is produced from the above-mentioned polysaccharide derivative and organic polyisocyanate, but during production, an organic solvent may be used as necessary from the viewpoint of viscosity, uniformity, solubility, etc. of the reaction system. You may do so. The organic solvent used must not react with isocyanate groups, and hydrophilic solvents such as dioxane, methyl ethyl ketone, dimethyl formamide, dimethyl sulfoxide, N-methylpyrrolidone, and pyridine are particularly preferred. The isocyanate group of the urethane compound produced in this way is a free radical and is prone to self-polymerization or gelation due to reaction with moisture, moisture, or an active hydrogen compound. Therefore, in order to protect the isocyanate group, for example, , secondary or tertiary alcohols, compounds having active methylene, phenols, halogenated phenols, oximes, lactams, imidazoles, bisulfites, etc., using a blocking agent that regenerates isocyanate groups by heat treatment. In this way, a water-soluble or water-dispersible and heat-reactive blocked product [hereinafter referred to as the blocked product used in the present invention] is produced. The blocked products used in the present invention include a type in which all the isocyanate groups contained in the urethane compound are blocked with a blocking agent that is not water-soluble or water-dispersible, and a type in which the isocyanate groups are blocked with the above-mentioned blocking agent. , a type in which part of the free isocyanate group is added with a compound containing a water-soluble or water-dispersible group that does not dissociate, and a type in which part or all of the free isocyanate group is blocked with bisulfite, and the remaining part is water-soluble or water-dispersible. There are types that are blocked with blocking agents that do not contain Next, blocking of the urethane compound used in the present invention will be specifically explained. For example, as a blocking agent that is not water-soluble or water-dispersible, it is particularly preferable to use one that can react with the urethane compound and form a block at temperatures above room temperature and below 100°C. Examples of such blocking agents include secondary or tertiary alcohols, compounds having active methylene, phenols, halogenated phenols, oximes, lactams, imidazoles, etc. As is generally known, the reaction with the urethane compound is carried out in the presence of a conventional urethanization catalyst or a catalyst such as an alkali metal alcoholate, or in the absence of a catalyst. The urethane compound used in the present invention is blocked with a blocking agent as described above, and contains one or more active hydrogen atoms and an anionic salt-like group or an anionic salt-forming group in the same molecule, which does not partially dissociate due to heat. It may also be reacted with compounds such as aminocarboxylic acids or aminosulfonic acids. The anionic salt-like group or anionic salt-forming group may be a lithium salt,
It is used in the form of sodium salt, potassium salt, ammonium salt, etc. On the other hand, when bisulfite is used as a blocking agent, all of the isocyanate groups in the urethane compound used in the present invention may be blocked using an aqueous bisulfite solution, or some of the isocyanate groups may be made water-soluble or water-dispersible. The remaining isocyanate groups may be blocked using an aqueous bisulfite solution. When blocking isocyanate groups,
Preferably, a hydrophilic solvent such as dioxane, methyl ethyl ketone, dimethylformamide, methanol, ethanol, isopropyl alcohol, etc. is added. Furthermore, when producing a blocked product using a blocking agent that is not water-soluble or water-dispersible, in addition to the above method, at least one isocyanate of an organic polyisocyanate monomer or a prepolymer having free isocyanate groups may be used. After blocking the groups, the remaining isocyanate groups may be reacted with natural polysaccharide derivatives.
In this case, the molar ratio of isocyanate groups to hydroxyl groups of the polysaccharide derivative can be freely selected within 1.0. The blocked product synthesized as described above and used in the present invention is stable even when diluted with water because the isocyanate groups are blocked. therefore,
Even when the blocked product used in the present invention is made into an aqueous solution or an aqueous dispersion, it can be stored for a long period of time. The aqueous solution or aqueous dispersion is applied to synthetic fibers or semi-synthetic fiber fabrics made from polyester fibers, polyamide fibers, polyacrylic fibers, polyolefin fibers, polyacetate fibers, or blends of these and natural fibers, and By heating at 240° C., the blocking agent is dissociated, and the isocyanate groups are regenerated, react, and crosslink, thereby achieving the durable processing of the present invention. To impart water-solubility or water-dispersibility of the heat-reactive blocked product of the present invention to the fabric, a dipping method, a coating method, or the like can be applied. Next, the reason why the present invention provides modification properties will be explained. Regarding durability, this is because the heat-reactive blocked product of the present invention regenerates isocyanate groups by heat treatment and undergoes reaction crosslinking. Regarding dyeability and affinity modification with other base materials and other substances, since the heat-reactive blocked product of the present invention coats the synthetic fiber surface, in other words, the synthetic fiber surface is coated with functional groups [of the polysaccharide derivatives mentioned above]. This is thought to be due to the addition of a hydroxyl group. This makes it possible to dye with anionic dyes, reactive dyes, etc., and improve or enable affinity with other substrates and reactivity with other substances. Regarding the modification of the heat-meltability of synthetic fibers, the heat-reactive blocked material of the present invention, which does not have heat-meltability, undergoes a crosslinking reaction by heat treatment and is exerted because it coats the surface of the synthetic fibers. Furthermore, the surface feel and texture of the processed fabric to which the heat-reactive blocked material of the present invention has been applied is cotton-like. In addition, when implementing the present invention, various additives such as softeners, antistatic agents, penetrants, etc. may be used in combination. Furthermore, in order to accelerate the curing of the blocked isocyanate groups, it is preferable to use sodium methylate, triethylamine or a general urethanization catalyst in combination. The present invention will be specifically explained below using examples. Synthesis Example 1 Isocyanate obtained by reacting polypropylene glycol (molecular weight 400) and hexamethylene diisocyanate with 100 parts (parts by weight, the same applies hereinafter) of a cellulose derivative having one glucose unit of cellulose and adding 6 moles of propylene oxide. Adding 433.0 parts of a prepolymer containing 11.3% groups followed by 100 parts of dioxane,
The reaction was carried out at an internal system temperature of 85° C. for 90 minutes to obtain a urethane compound containing 4.4% of isocyanate groups based on the total amount of the cellulose derivative and the prepolymer. Next, 50 parts of ethanol was added at 45℃, cooled, and 30% sodium bisulfite was added at a system temperature of 35℃.
After adding 194.0 parts, the mixture was stirred and mixed at 35 to 40°C for 60 minutes, and diluted with water to obtain a transparent and viscous reactive urethane composition with a resin content of 25% (wt%, same hereinafter). Synthesis Example 2 Same cellulose derivative used in Synthesis Example 1
100 parts, polyethylene glycol (molecular weight 1000)
786.0 parts of a prepolymer containing 6.1% isocyanate groups obtained by reacting the cellulose derivative and hexamethylene diisocyanate were added, and the reaction was carried out at a system internal temperature of 90°C for 120 minutes to convert the isocyanate groups into the cellulose derivative and the prepolymer. A urethane compound containing 2.80% of the total amount was obtained. Next, 37.0 parts of methyl ethyl ketoxime was added to the obtained urethane compound and reacted at 80° C. for 120 minutes to obtain a blocked product containing 0.75% of isocyanate groups based on the total amount of the cellulose derivative and the prepolymer. Furthermore, the system internal temperature is 35
67.0 parts of a 35% taurine soda aqueous solution was added at 35% Celsius, stirred and mixed for 30 minutes at an internal system temperature of 35 to 45°C, and then diluted with water to form a transparent, low-viscosity reactive urethane composition with a resin content of 15%. I got it. Synthesis Example 3 100 parts of polybutylene glycol (molecular weight 400) and 84.0 parts of hexamethylene diisocyanate were reacted to produce a prepolymer containing 11.0% of isocyanate groups. Add 23.0 parts of methyl ethyl ketoxime to the obtained prepolymer and heat at 85°C.
A blocked product containing 4.0% of isocyanate groups based on the prepolymer was obtained. To the obtained blocked product, 108 parts of a starch derivative in which 6 mol of propylene oxide was added per amylose unit of starch was added, and 100 parts of dioxane was further added, and the reaction was carried out at an internal temperature of 90°C to form an isocyanate group. After confirming that it had disappeared, it was diluted with water to obtain a transparent and viscous reactive urethane composition with a resin content of 20%. Synthesis Example 4 After adding 50 parts of dioxane to 20 parts of hexamethylene diisocyanate, 22.3 parts of phenol and 0.1 part of triethylamine were added, and the system temperature was
The reaction was carried out at 70°C for 30 minutes to obtain a blocked isocyanate containing 25.3% isocyanate groups based on hexamethylene diisocyanate. Thereafter, 51.3 parts of a starch derivative in which 6 moles of ethylene oxide were added per amylose unit of starch was added to the obtained blocked isocyanate, and the reaction was carried out at a system temperature of 80°C, and the isocyanate group disappeared. After confirming this, it was diluted with water to obtain a cloudy, low-viscosity reactive urethane composition with a resin content of 15%. Examples 1 to 4 A catalyst [Elastron Catalyst-32 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)] was added to the compositions obtained in Synthesis Examples 1 to 4 in an amount of 10% based on the resin content, and
Further, a treatment liquid was prepared by diluting with water so that the resin content was 4%. Polyester jersey is immersed in the resulting treatment bath and squeezed with a mangle (squeezing rate 100%)
Baking machine at 120℃ for 2 minutes, then 150℃
Heat treatment was performed for 2 minutes at . The number of rotations of the processed cloth
Contact pressure on a wooden roll (made of cherry wood) rotating at a speed of 1500rpm roller surface speed of 7m/min
A processed cloth was brought into contact with 1.0 kg, and the frictional melting time until holes were formed was measured. The results are shown in Table-1. Note that Examples 1 to 4 are Synthesis Examples 1 to 4, respectively.
This composition uses the following composition. Examples 5 to 6 A polyester jersey white cloth was soaked in the treatment solution obtained in Examples 3 and 4, squeezed with a mangle (squeezing ratio 100%), and heated in a baking machine at 120°C for 2 minutes, then Heat treatment was performed at 150°C for 2 minutes.
Furthermore, the treated polyester jersey white fabrics were subjected to dyeing tests using reactive dyes.
Furthermore, the polyester jersey fabric dyed by the above procedure was subjected to a durability test by washing under the following conditions. The results are shown in Table-2. Note that Examples 5 and 6 correspond to the compositions of Synthesis Examples 3 and 4. Dyeing conditions using reactive dyes Bath ratio 1:50 Anhydrous sulfur salt 30g/Dye [Mikcacion Brilliant Red B] (manufactured by Mitsubishi Kasei Corporation) 4% OWF Soda ash 10% OWF Dyeing heat conditions Anhydrous sulfur dye/processed fabric →35℃ → (20 minutes) → 80℃ (60 minutes)
→ Hot water washing soda ash washing conditions Using a washing bath containing 2 g of neutral detergent, bath ratio 1:
It was rinsed, dehydrated, and dried for 60 minutes at 40°C using a household washing machine at 30°C. The results are shown in Table-2. Table 2 shows that the fabrics were dyed with reactive dyes by the reactive blocked compound treatment of the present invention, and were also durable against washing. Examples 7-8 Nylon taffeta was immersed in the treatment solution of Examples 3-4, and squeezed with a mangle (squeezing ratio 70%) at 120° C. and dried for 3 minutes. Next, one side of the nylon taffeta treated above is coated with a 20% polyvinyl alcohol aqueous solution (solid content 10 g/m ² coating), and a nylon taffeta treated with the same composition is laminated on the coated side. After heating at 150°C for 10 minutes, peel strength was measured. For comparison, the peel strength when treated only with polyvinyl alcohol was measured, and the results are shown in Table 3 using an index when this was used as a blank (100). Note that Examples 7 and 8 are Synthesis Examples 3 and 4.
This corresponds to the one using the composition. From Table 3, it can be confirmed that the present invention clearly provides strong adhesion to the blank. Examples 9-10 Polyacetate knit white cloth was immersed in the same treatment bath as in Examples 5-6, heat treated in the same manner as in Examples 5-6, and then washed in the same manner as in Examples 5-6. The results are shown in Table-4. In addition, Example 9~
No. 10 corresponds to the compositions of Synthesis Examples 3 and 4. From Table 4, it can be confirmed that the polyacetate knit fabric can be dyed with a reactive dye by the heat-reactive block treatment of the present invention and has durability against washing.

【table】

[Table] 〓Note〓 Dyeing condition: Best ◎ ← → × Poor (not dyed at all)

【table】

[Table] 〓Note〓 Dyeing condition: Best ◎ ← → × Poor (not dyed at all)

Claims (1)

[Claims] 1 A water-soluble or water-dispersible and heat-reactive urethane compound having isocyanate groups obtained by reacting a polysaccharide derivative obtained by adding an alkylene oxide to a polysaccharide and an organic polyisocyanate with blocked isocyanate groups. A modifier for synthetic fibers or semi-synthetic fibers, which comprises processing a blocked product into a synthetic fiber or semi-synthetic fiber fabric, and then heat-treating the fabric.