JPS62191576A - Modifier for synthetic or semisynthetic fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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-1 are homogeneous and have excellent physical properties such as strength, durability, and chemical resistance, so their production has increased in recent years. Demand has grown to such an extent that it exceeds that of cotton, wool, silk, etc., but it has problems such as insufficient water absorption, lack of hygroscopicity, inertness of the fiber surface, and lack of dyeability and adhesiveness due to the dense internal structure. There are problems with physical properties that require further improvement and modification. ``Various attempts and proposals have been made to improve these synthetic fibers for various purposes and uses, but they have not yet been satisfactory.

For example, it has been proposed to post-process polyester and polyamide fibers with polymerizable compounds mainly consisting of polyethylene oxide chains in order to impart durable water absorption properties, but most of these have been processed using disperse dyes. These compounds have the disadvantage of being accompanied by a significant decrease in color fastness, especially color fastness to rubbing, and these compounds have not been able to substantially impart hygroscopicity.

In addition, 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 the only disperse dye that can be dyed exceeds 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 have appeared, 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 actually have a 100 to 120 The reality is that dyeing is done at a high temperature of ℃.

In addition, when using synthetic fibers such as polyester or polyolefin as reinforcing materials for tire cords, belt cords, heavy fabrics, or synthetic leather production, it is important to note that there are no functional groups on the surface of the fibers, or the surface is dense. Due to its structure, it has poor adhesion with various resins, which is often a problem.

For example, tire cords have poor compatibility with resorcin formalin latex, which is an adhesive with rubber, and various pretreatments have been considered, but none have been fully satisfactory.

The present invention chemically modifies the surface of synthetic fibers or semi-synthetic fibers without impairing the original properties of synthetic fibers or semi-synthetic fibers to improve the moisture absorption, water absorption, and water retention properties of synthetic fibers or semi-synthetic fibers.
It modifies dyeability, affinity for other substances, heat meltability, etc.

For example, the present invention provides water absorption performance, which occurs when attempting to impart water absorption performance to synthetic TA fibers using conventional compounds mainly consisting of polyethylene oxide chains. This was achieved in order to solve the following drawbacks: (1) The color fastness is significantly reduced, and only dyes with good color fastness can be used.

Furthermore, the present invention provides synthetic fibers, especially polyester surfaces.
Since it is cross-linked and 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 a dye that can be dyed at 100°C or less, such as a reactive dye, and For example, it was developed to facilitate adhesion with resorcinol formalin latex. Furthermore, it improves the friction and thermal melting properties of synthetic fibers. That is, the present invention provides water-soluble or water-dispersible isocyanate group-blocked urethane compounds having isocyanate groups obtained by reacting a natural polysaccharide derivative obtained by adding an alkylene oxide to a natural polysaccharide with an organic polyisocyanate. The present invention provides a modifier for synthetic fibers or semi-synthetic fibers, which is characterized in that a heat-reactive blocked substance is applied to the threads of the synthetic fibers or semi-synthetic fibers, and then the chain threads are heat-treated.

In the present invention, a water-soluble or water-dispersible urethane compound containing an isocyanate group obtained by reacting a natural polysaccharide derivative obtained by adding an alkylene oxide to a natural polysaccharide with an organic polyisocyanate is obtained by blocking the isocyanate group. and a thermally reactive blocked product is used.

Examples of the natural polysaccharides include, but are not limited to, starch, dextrin, tamarind, guar gum, cellulose, and chitosan.

A natural polysaccharide derivative is produced by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, etc. to the natural polysaccharide by a conventional method.

Specific examples of natural polysaccharide derivatives in which alkylene oxide is added to cellulose include those in the form of hydroxyalkylcellulose such as hydroxyethylsululose, hydroxypropylcellulose, and hydroxybutylcellulose. Examples include various cellulose derivatives with polyaddition of .

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 amine groups, or polyols containing four or more active hydrogens in the same molecule.
The tertiary amine group of a polyol containing one or more graded cationic groups, such as a tertiary amino group-containing polyether obtained by addition polymerizing an alkylene oxide to triethanolamine or N-methyljetanolamine, with diethyl sulfate or the like. graded polyols or polyols containing one or more anionic groups in the same molecule, such as dimethylolpropionic acid, and more specific examples include organosilicone polyols and organofluorine polyols. It is not limited.

The organic polyisocyanate monomers used include aromatic isocyanates such as tolulene diisocyanate and diphenylmethane diisocyanate, which are generally used in the production of urethane, aromatic aliphatic isocyanates such as xylylene diisocyanate, alicyclic isocyanates such as inphorone 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 natural polysaccharide derivative and an 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. May be used. 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, ,
Using a blocking agent that regenerates isocyanate groups through heat treatment of secondary or tertiary alcohols, compounds with active methylene, phenols, halogenated phenols, oximes, lactams, imidazoles, bisulfites, etc. 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 product used in the present invention includes a type in which all isocyanate groups contained in the urethane compound are blocked with a blocking agent that is not water-soluble or water-dispersible.
The isocyanate group is blocked with the above-mentioned blocking agent, and a part is added with a water-soluble group or water-dispersible group-containing compound that does not dissociate due to heat, and a part or all of the free isocyanate group is blocked with bisulfite. However, there are types in which the remaining portion is blocked with a blocking agent that is neither water-soluble nor water-dispersible.

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 a blocking agent that reacts with the urethane compound at room temperature or higher and 100° C. or lower to form a block.

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 alcoholade, 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, it is preferable to add a wood-philic solvent such as dioxane, methyl ethyl ketone, dimethyl formamide, methanol, ethanol, and inpropyl alcohol.

Furthermore, when producing a blocked product using a blocking agent that is not water-soluble or water-dispersible, in addition to the method described above, at least one isocyanate of an organic polyisocyanate monomer or a prepolymer having free isocyanate groups is 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 natural polysaccharide derivative can be freely selected within 1.0.

The blocked product used in the present invention synthesized as described above 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 or semi-synthetic fibers made from polyester fibers, polyamide fibers, polyacrylic fibers, polyolefin fibers, polyacetate Fa fibers, or blends of these and natural fibers. By application and heat treatment at 100 to 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. In addition, when the processed yarn is made into a fabric after being processed into yarn according to the present invention, the texture of the fabric will be softer than that of a fabric that is subjected to the main processing. Next, the reason why the present invention provides modification properties will be explained.

Regarding durability, it is considered that the heat-reactive blocked product of the present invention regenerates isocyanate groups by heat treatment and undergoes reaction crosslinking.

The water absorption, moisture absorption, and water retention properties are thought to be due to the natural polysaccharide derivative. Furthermore, the advantage of excellent color fastness is thought to be due to the poor affinity between the dye used for dyeing synthetic fibers or semi-synthetic fibers and the natural polysaccharide derivative.

Regarding dyeability, low base material, and affinity modification with other substances, since the heat-reactive blocked product of the present invention coats the surface of synthetic M&fiber or semi-synthetic fiber, in other words, functional groups are added to the surface of synthetic fiber. This is thought to be due to the provision of [hydroxyl group of the natural polysaccharide derivative]. This makes it possible to dye with anionic dyes, reactive dyes, etc., and improve or enable low affinity with base materials and reactivity with other substances.

Regarding the modification of the heat-fusibility of synthetic fibers, the heat-reactive blocked product of the present invention, which does not have heat-fusibility, undergoes a crosslinking reaction by heat treatment and is exerted because it coats the surface of the synthetic fibers.

In addition, when implementing the present invention, various additives such as softeners, antistatic agents, penetrants, etc. may be used in combination. moreover,
In order to accelerate the curing of the blocked isocyanate group, 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 Polypropylene glycol (molecule i400) and hexamethylene diisocyanate were reacted with 100 parts (parts by weight, the same shall apply hereinafter) of a cellulose derivative containing one glucose unit of cellulose and 6 moles of brobylene oxide added thereto. 433.0 parts of a prepolymer containing 11.3% of isocyanate groups was added, and then 100 parts of dioxane was added, and the reaction was carried out at a system temperature of 85°C for 90 minutes to convert the isocyanate groups into the cellulose derivatives. A urethane compound containing 4.4% based on the total amount of the prepolymer was obtained.

Next, 50 parts of ethanol was added at 45°C, cooled, and 30% sodium bisulfite 194 was added at 35°C.
．． After adding 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% (weight %, the same applies hereinafter).

Synthesis Example 2 Prepolymer 786.1 containing 6.1% isocyanate groups was obtained by reacting 100 parts of the same cellulose derivative used in Synthesis Example 1 with polyethylene glycol (molecular weight 1000) and hexamethylene diisocyanate. 0
The mixture was reacted for 120 minutes at a system internal temperature of 90° C. to obtain a urethane compound containing 2.80% of isocyanate groups based on the total amount of the cellulose derivative and prepolymer.

Next, 37.0 parts of methyl ethyl ketoxime was added to the obtained urethane compound and reacted at 80°C for 120 minutes to form a block containing 0.75% of isocyanate groups based on the total amount of the cellulose derivative and the prepolymer. I got a monster. Furthermore, 67.0 parts of a 35% taurine soda aqueous solution was added at a system temperature of 35°C to
After stirring and mixing at 45° C. for 30 minutes, the mixture was diluted with water to obtain a transparent, low-viscosity reactive urethane composition with a resin content of 15%.

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. 23.0 parts of methyl ethyl ketoxime was added to the obtained prepolymer and reacted at 85°C for 60 minutes to obtain a blocked product containing 4.0% of isocyanate groups based on the prepolymer.

1 amylose unit of starch in a blocky product
Add 108 parts of a starch derivative to which 6 moles of propylene oxide have been added per starch derivative, add 100 parts of dioxane to the colander, react at a system temperature of 90°C, and after confirming that the isocyanate group has disappeared, dilute with water. A transparent and viscous reactive urethane composition with a resin content of 20% was obtained.

Synthesis Example 4 20 parts of hexamethylene diisocyanate and 5 parts of dioxane
After adding 0 part, 22.3 parts of phenol and 0.1 part of triethylamine were added and reacted for 30 minutes at a system temperature of 70°C to obtain a mixture containing 25.3% of isocyanate groups based on hexanoethylene diisocyanate. A blocked isocyanate was obtained. 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 an internal temperature of 80°C, so that the isocyanate group disappeared. After confirming that this was the case, the mixture was diluted with water to obtain a cloudy, low-viscosity reactive urethane composition with a resin content of 15%.

[Elastron Catalyst-32 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)] was used in combination at a resin content of 12%, and further diluted with water to a resin content of 10% to prepare a treatment liquid.

With these treatment solutions, polyester filament yarn [75
Denier/36 filament] was coated with a resin content of 4% using a KISS roller and heat-treated in a baking machine under the following conditions.

[Heat treatment conditions] After drying at 100° C. for 3 minutes and curing at 140° C. for 1 minute, the treated polyester filament yarn was finished into a knitted cloth using a tube knitting machine, and the water absorption and washing durability of the knitted cloth were measured. The results are shown in Table-1. In addition, those using the compositions obtained in Synthesis Examples 1 to 4 correspond to Examples 1 to 4, respectively.

[Water absorption] Wide Evaluated by JIS10798 method (Pyrex).

[For durability of water absorption, use a washing bath containing 2 g/l of neutral detergent, wash at 40°C for 60 minutes using a household washing machine at a bath ratio of 1:30, then wash at 40°C.
Rinse for 60 minutes, dehydrate, dry, and evaluate water absorption as described above.

Comparative example 1 CH2= CH-Coo -(CH2CH20) t
.

A treatment bath having the following composition was prepared using a modifier (resin content: 100%) represented by Kaiko6'i so that the resin concentration of the treatment bath was 10%.

(Treatment bath composition) Modifier: 10.0 parts Ammonium persulfate: 0.5 parts Water: 89.5 parts Using the above treatment bath, a resin content of 4% was applied to polyester filaments in the same manner as in Examples 1 to 4. Heat treatment was performed in the same manner as in Examples 1 to 4, and then knitted cloth was prepared in the same manner as in Examples 1 to 4 and evaluated in the same manner as in Examples 1 to 4. Table 1 shows the results.
It was shown to.

Examples 5 to 8 The reactive urethane compositions obtained in Synthesis Examples 1 to 4 were each placed in a Teflon coated inbrader with a diameter of 10 cm, and catalytic treatment 9 [Elastron Catalyst] was applied so that the resin content was 3.0 g. 32] and air-dried at night, dried at 60°C for 3:20pm, and heat-treated at 140°C for 10 minutes to form a cured film. After that, the obtained cured film was heated at 25℃ and humidity 9.
Hygroscopicity at 0% was measured.

The results are shown in Table-2.

[Hygroscopicity] The change in weight of the film over time at 25° C. and 90% humidity was measured and evaluated as hygroscopicity.

Comparative Example 2 A cured film was formed in the same manner as in Example 5 using 3.0 g of the modifier used in Comparative Example 1, 0.15 g of ammonium persulfate, and 10 g of water, and the hygroscopicity was measured. The results are shown in Table-2.

Examples 9-2 Polyester filaments dyed with disperse dyes were processed in the same manner as Examples 1-4 to obtain Examples 1-4.
After heat treatment in the same manner as above, it is finished into a knitted cloth using a tube knitting machine, and the abrasion fastness of the knitted cloth is evaluated according to JIS084.
This was done using the 9 method.

The results are shown in Table-3.

Comparative Example 3 A polyester filament dyed with a disperse dye was processed in the same manner as in Comparative Example 1, heat treated in the same manner as in Comparative Example 1, and finished into a knitted cloth using a tube knitting machine. Evaluation of fastness to rubbing was performed in the same manner as in Examples 9-12. The results are shown in Table-3.

Examples 13-14 The polyester knit fabrics obtained in Examples 3-4 were subjected to a dyeing test using reactive dyes. Briefly, the polyester knit cloth dyed by the above procedure was washed under the washing conditions shown in Example 1. The results are shown in Table-4. Note that Example 14 uses the composition obtained in Synthesis Example 4, and Example 14 uses the composition obtained in Synthesis Example 4.

Dyeing conditions with reactive dyes Bath ratio 1:50 Anhydrous Pouyu 30 g / 1 Dye [Mikcation Br1lliant
Red B Co. (manufactured by Mitsubishi Kasei Corporation) 4% owf Soda ash 10% owf Dyeing heat conditions Anhydrous sulfur dye processing cloth -35℃ (20 minutes) → 8 Soda ash
5° C. (60 minutes)→Hot water washing From Table 4, all processed knit fabrics were dyed with reactive dyes and had durability against washing.

Examples 15 to 16 Nylon coats were immersed in the treatment solutions of Examples 3 to 4 to give a resin content of 2.0%, and then dried at 120° C. for 3 minutes. Next, this dry cord is immersed in RFL (resorcinol-formalin latex), and the RFL solid content is approximately 3.
．． After adjustment to 0%, heat treatment was performed at 200° C. for 2 minutes. Next, this processing code is embedded in natural rubber,
After heating at 15° C. for 30 minutes, peel strength, pull-out strength, and bending hardness were measured. In addition, for comparison, we measured the peel strength, pull-out strength, and bending hardness when treated with only RFL (adhesion amount: 5.0%), and the results are shown based on the index when this is used as a blank (100). -5.

Note that Example 15 used the composition obtained in Synthesis Example 3, and Example 16 used the composition obtained in Synthesis Example 4.

As is clear from Table 5, it can be confirmed that the material according to the present invention can provide flexible and strong adhesion to the blank.

Examples 17-20 The polyester knit fabrics obtained in Examples 1-4 were placed on a wooden roll [made of cherry wood] rotating at a rotation speed of 150 rpm and a roller surface speed of 7 m/mfn at a contact pressure of 1.0 kg. The processed polyester knit cloth was brought into contact and the frictional melting time until holes were formed was measured. The results are shown in Table-6.

Examples 21 to 24 A treatment solution was prepared by the same operation as in Examples 1 to 4, and nylon filament yarn (75 denier/3
6 filament) was coated with a resin content of 4.3% using a KI SS roller, and heat-treated in a baking machine in the same manner as in Examples 1 to 4. The treated nylon filament yarns were finished into knitted fabrics in the same manner as in Examples 1 to 4, and the water absorption and washing durability of the knitted fabrics were measured. Water absorption evaluation and washing conditions were the same as in Examples 1-4. These results are shown in Table-7.

JP-A-62-19157G (9) Procedural amendment dated March 1986, Day 2, Name of the invention: Modifier for synthetic or semi-synthetic fibers 3, Relationship with the person making the amendment Patent applicant 4, Amendment Date of order voluntary amendment 5, number of inventions not increased by amendment 6, subject of amendment 7, content of amendment
7 ~ The present application is amended as follows based on the original specification.

(1) In the 5th line of page 2 of the specification, the phrase ``...has grown...'' has been corrected to ``work, grow...''.

(2) Same, page 5, line 10, page 5, line 11, page 5, line 19, page 5, line 20, ``... natural polysaccharide'' is replaced with ``... polysaccharide.'' Correct it to saccharide J.

(3) Same, page 6, line 7, ``tamarind J'' is corrected to ``tamarind gum''.

(4) Same, page 6, line 10 Same, page 6, line 15, ``...Natural polysaccharide J'' is corrected to ``...Polysaccharide j.''

(5) "Hydroxyethylsululose" on page 6, lines 15 to 16 of the same publication is corrected to "hydroxyethylcellulose J."

(6) Same, page 8, line 6, ``r-toluene diisocyanate'' is corrected to ``r-toluene diisocyanate-1-j.''

(7) Same, page 8, line 13, same, page 12, line 8, same, page 12, line 9, same, page 13, line 13, same, page 13, line 16, same, page 14, line 1 Correct the text ``...Natural polysaccharide A'' to ``...Polysaccharide.''

(8) Amend the claims as shown in the attached sheet.

Claims of the above yIIJ paper: ``A water-soluble or water-dispersible urethane compound having isocyanate groups obtained by reacting a polysaccharide derivative obtained by adding an alkylene oxide to a polysaccharide with an organic polyisocyanate and blocking the isocyanate groups. A modifier for synthetic fibers or semi-synthetic fibers, which is characterized in that a thermally reactive blocked substance is added to the threads of the synthetic fibers or semi-synthetic fibers, and then the chain threads are heat treated.

Claims (1)

[Claims] Water-soluble or water-dispersible and heat-reactive urethane compound containing isocyanate groups obtained by reacting a natural polysaccharide derivative obtained by adding alkylene oxide to a natural polysaccharide with an organic polyisocyanate. 1. A modifier for synthetic fibers or semi-synthetic fibers, characterized in that a blocked product of the above is applied to threads of synthetic fibers or semi-synthetic fibers, and then the threads are heat-treated.