JPS581230B2 - Japanese serpent serpent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a warp sizing agent that can be removed from the size extremely easily in a solvent-based scouring method using percrene or the like.

An object of the present invention is to provide a non-polluting warp sizing agent that can be applied to closed process equipment that uses nonflammable solvents such as perchloromethane in the fiber sizing process and scouring process.

Conventionally, so-called aqueous systems using aqueous solutions of appropriate chemicals and auxiliaries have been mainly used for pasting, scouring, dyeing and finishing of fibers.

That is, it is a completely aqueous system in which a water-soluble polymer compound is used as the sizing agent and an aqueous solution of the auxiliary agent is used for its removal.

However, in recent years, pollution of rivers by wastewater has started to cause major social problems.

Although great efforts are being made to prevent the occurrence of such pollution, it is said that the best method is to employ a solvent-based closed process using perchloren or the like.

Recently, research has progressed particularly on solvent-based processes for scouring knits and wool and dyeing synthetic fibers, and commercialization is gradually progressing.

Incidentally, it is said that the solvent used in this solvent-based process is generally good if it has the following properties.

(Reference: Textile processing Vol. 22, A. 6, p. 38, 1
970) (1) Does not damage fibers.

(2) Chemically stable and does not damage processing equipment.

(3) The solubility of the processing agent is low.

(4) Dries quickly, does not burn, and is not explosive. (5) Recovery and regeneration is easy, and the specific gravity of steam is high.

(6) Low toxicity.

(7) It is inexpensive. Chlorinated hydrocarbons are commonly used as solvents that meet these conditions, and Table 1 shows the physical properties of perchlorene, trichlorene, 1,1,1-trichloroethane, and water.

Therefore, although percrene has a lower ability to dissolve acrylic resins than other chlorinated solvents, other than this point, it can be said to be the most suitable solvent for solvent-based processes.

By adopting a closed process using percrene, the solvent can be recovered and recycled.
Compared to conventional water-based systems, operating costs are lower, efficiency is improved by shortening processing time, and the quality of fiber products is expected to be improved with less damage to the fibers.

Furthermore, advantages such as no problem of river pollution caused by factory waste liquid are found.

These advantages can be expected not only in the scouring and dyeing finishing processes but also in the warp sizing process.

Solvent-based processes have many advantages as described above, and many industries are trying to illegally adopt them.

However, in order to employ the solvent-based scouring method, it is necessary that the sizing agent adhering to the textile fabric be dissolved in a solvent, and it must also be easily and completely dissolved and removed.

Most of the sizing agents conventionally used for sizing the warp yarns prior to weaving are water-soluble polymer compounds, and it is well known that they are poorly soluble or insoluble in percrene and the like.

Therefore, if a solvent-based process is applied only to the scouring process for gray fabric (kipata) that has been pasted and woven using conventional water-soluble sizing agents, the scouring process will naturally be poor, resulting in dyeing in the subsequent dyeing process. It is predicted that it will cause unevenness, poor texture, and various other problems.

Therefore, the industry is currently eagerly awaiting the emergence of a sizing agent to which a solvent-based scouring method using percrene or the like can be applied.

However, it is not enough just to dissolve it in percrene, etc. Of course, the film must have the appropriate adhesion to fibers, hardness, strength, elongation, smoothness, etc. required by Kiku as a warp sizing agent. Must be.

(Normally these can be estimated from laboratory data of glass transition temperature, tack, conjugation and % friction.

) Particularly regarding hardness, the solvent-based scouring method is difficult to use for hardness, which has a high glass transition temperature (i.e.,
Since starch (hard), polyvinyl alcohol, etc. cannot be used in combination, the main component polymer of the sizing agent is preferably one that is harder than conventional water-soluble polymer compound films.

As a result of intensive research, the present inventors succeeded in obtaining a warp sizing agent that can be practically applied to a solvent-based scouring method using percrene or the like.

That is, the present invention comprises [a total of at least 58% by weight of a component selected from methacrylic esters of aliphatic alcohols having 2 to 8 carbon atoms, preferably 4 to 6 carbon atoms, preferably 70% by weight or more, and whose glass transition temperature is 10°C ~ 80'C
Preferably, the method is replaced by a "perculene scouring warp sizing agent" which is mainly composed of a polymer soluble in perclene at a temperature of 10°C to 50°C.

In addition, the "glass transition temperature" mentioned here refers to Vibron D
Using DV-1 type 1 (Toyo Baldwin KK product), the measurement conditions were a frequency of 110 cycles and a temperature increase rate of approximately 1°C.
/min, refers to the glass transition temperature measured at a room temperature of 25°C and a humidity of 65% RH.

As mentioned above, the solvent scouring warp sizing agent of the present invention requires that the glass transition temperature of the polymer is in the range of -10°C to 80°C, preferably 10°C to 50°C.

This is based on the temperature range of the textile factory during weaving.
If the glass transition temperature of the polymer is outside this range, the glue film is either too hard and a large amount of glue scum is generated during weaving, or the fabric is cracked or wrinkled, or the glue film is too soft. It lacks smoothness, and its tackiness tends to cause problems such as thread breakage, clogging of reeds, and poor weaving due to poor opening during the gluing and weaving processes, making it impractical.

Even if the glass transition temperature of the polymer is 80° C. or lower, in special cases when it is too high, an appropriate plasticizer may be used in combination.

Examples of monomers accounting for 49% by weight or less in the polymer of the present invention include copolymerizable carboxylic acids and their amine neutralized products, methacrylic esters of various alcohols having 9 or more carbon atoms, and various acrylic esters. Examples include copolymerizable monomers such as vinyl acetate, vinyl ethers, acrylonitrile, styrene, vinyltoluene, and methyl methacrylate.

However, among these, copolymerizable carboxylic acids and their amine neutralized products, methyl methacrylate, methyl acrylate, vinyl acetate, acrylonitrile, etc. have the effect of improving adhesion to fibers, but they have a negative effect on the solubility of percrene. Since it is effective, it is necessary to avoid including it in an amount larger than necessary.

In addition, methacrylic acid esters of aliphatic alcohols having 2 to 4 carbon atoms have the effect of increasing the cohesive force of the glue film;
In order to further enhance the binding property of the warp yarns, a highly polar monomer may be copolymerized as necessary.

Examples of highly polar monomers include copolymerizable carboxylic acids such as acrylic acid, methacrylic acid, and itaconic acid, acrylamide and its derivatives, and nitrogen-containing monomers such as acrylonitrile and dimethylaminoethyl methacrylate. Particularly effective.

Incidentally, by neutralizing part or all of the carboxylic acid contained in the copolymer with an amine, the binding property of the warp yarns can be improved.

However, since these highly polar monomers have a negative effect on solubility in perchloromethane, polymers containing large amounts of them cannot be applied to solvent-based scouring.

Therefore, acrylic acid, etc. in the polymer is 6% by weight or less, acrylamide is 2% by weight or less, and other nitrogen-containing monomers are 30% by weight or less.
It is necessary to keep the copolymerization ratio below % by weight, and if the above components are contained in duplicate, sufficient solubility for percrene cannot be obtained unless the copolymerization ratio is further reduced.

The method for producing the polymer of the present invention is not particularly limited, but known methods such as emulsion polymerization, solution polymerization, and suspension polymerization can be applied.

Among these, the solution polymerization method is particularly economical and advantageous in terms of process.

In any case, the polymer is diluted with percrene to form a sizing agent.

In addition to the polymer of the present invention, antistatic agents, plasticizers, smoothing agents, and other polymers may be added as necessary unless otherwise noted.

The sizing agent of the present invention thus produced is suitable for sizing various synthetic and natural (particularly cellulose-based) fibers, particularly filament-based fibers, by a solvent-based process.

The warp glued with the sizing agent of the present invention has sufficient cohesiveness and smoothness, so it can achieve weaving efficiency comparable to conventional products, and has extremely excellent water resistance, so it can be used in conventional looms. It can also be applied to water jet looms.

By using the sizing agent of the present invention, a solvent-based closed process using perchloren solvent can be applied, and both the sizing process and the scouring process can be carried out economically and efficiently, and the pollution of rivers by factory waste liquid can be prevented. I can do it.

Furthermore, by using the sized yarn according to the present invention, it can be applied not only to ordinary looms but also to water jet looms, making it possible to weave efficiently and economically without any problems, and at the same time, it can be applied to solvent-based weaving machines. High-quality textile products can be obtained by reducing damage to the fibers through application, eliminating dyeing defects due to poor scouring, and producing gray fabric with a hard, soft, compressed texture. .

Next, the present invention will be explained in detail with reference to Examples.

Example 1 Sample rAJ ~ “J” consisting of the monomer composition listed in Table 2
was synthesized.

Among these, "A" to "D" are examples within the present invention,
"E" to "J" are comparative examples outside the present invention.

For "A", "B", "C", "E", "F", and "H", the monomer mixture listed in Table 2 is polymerized in a 1:1 mixed solvent of isopropyl alcohol and toluene. Using benzoyl peroxide as an initiator, the polymerization reaction was carried out at 78°C in nitrogen gas for 10 hours.

Note that "B" is the acrylic acid used after the polymerization reaction, in which 20% of the acrylic acid was neutralized with triethanolamine.

For "D", "G", "I" and "J", the monomer mixture listed in Table 2 was added to N as a polymerization initiator in Tokuso Percrene (trade name Percrene, a product of Tokuyama Soda KK). , N-azobisisobutyronitrile at 71°C.
A polymerization reaction was carried out for 10 hours in nitrogen gas.

The glass transition temperature of the obtained polymer was measured and reported in Table 2.

Example 2 A film was prepared from the sample obtained in Example 1, and the dissolution rate of perchloren was measured.

In addition, as comparison products, polyvinyl alcohol (trade name Poval 205: a product of Kuraray Co., Ltd.) and water-soluble acrylic resin (polyacrylic acid ester partially saponified sodium salt - trade name Finetex MD-) 20: Inuhi Moku Ink Chemical Industrial KK products) were also measured.

The measurement results are shown in Table 3.

The dissolution rate was determined by creating a film with a thickness of 0.05 mm and a size of 2 x 2 cm, heat-treating it at 170°C for 2 minutes, then immersing it in 100 cc of Perclean at 40°C, and stirring gently with a magnetic stirrer. , the time required for complete dissolution is measured and expressed in seconds, and the smaller the value, the better the solubility.

In addition, if it does not dissolve within 600 seconds, this is indicated in Table 3 as "
Insoluble.

As shown in Table 3, both polyvinyl alcohol and water-soluble acrylic resin, which are typical types of conventional water-soluble sizing agents, are insoluble in percrene, and the comparative examples "B", "E", and "F","H","■", and "J" were also difficult to dissolve.

Example 3 Film adhesion was measured for samples “A” to “J” obtained in Example 1, polyvinyl alcohol, and a mixed system of polyvinyl alcohol and water-soluble acrylic resin (mixing ratio 1:1). From each of the 6 samples compared, the size 1 × 1
Make a film with a thickness of 0 cm and 0.10 to 0.12 mm, and
Heat treatment was performed at 0°C for 2 minutes.

Align the directions of the obtained specimens, stack them in two, and weigh 100g.
After applying a load of /cm for 30 minutes, the peeling strength was measured and the adhesive was removed.

Sampling, conditioning, and peeling strength measurements were performed in a measurement room adjusted to 25°G and 65%RH.

In addition, the wet tackiness was measured in the same manner as above after immersing the sample film obtained as above in water at 25°C for 10 minutes and lightly wiping the moisture on the film surface with P paper. In the table, since the poval type is water-soluble, the film tackiness in wet conditions could not be measured.

Example 4 Samples “A” to “E”, “H” to “J” obtained in Example 1
” (resin concentration 6% by weight) and a mixed system of polyvinyl alcohol and water-soluble acrylic resin (concentration 8% by weight), which is one of the formulations currently commonly used as a comparative example (mixing ratio 45: Using 5.5), glue the polyester filament type (75dX36f),
The binding force, which is one of the typical tests for weavability, was measured.

Both dry and wet conjugation were measured to determine suitability for plain looms and water jet looms.

The conjugation strength during drying is 25°C, 65%RH, and a load of 10g.
The value measured using a TM type conjugation force tester at /75d,
The wet binding strength is a value measured by the same method after immersing the sized yarn in water at 25° C. for 15 minutes, and in both cases, the larger the value, the better.

Example 5 Samples “A” to “J” obtained in Example 1 (resin concentration 4
Using cupra rayon yarn (75
dX54f Bemberg (manufactured by Asahi Kasei Industries, Ltd.) was pasted, and the binding force and friction coefficient, which are typical test methods for weavability, were measured.

Poval 205 was also measured as a comparative sample.

As shown by the above results, the uninvented sizing agent has properties that are fully satisfactory for solvent-based processes, while the comparative ones are inferior in some properties and are suitable for solvent-based processes. cannot be provided.

Claims (1)

[Claims] 1. A total of at least 58% by weight of components selected from methacrylic esters of aliphatic alcohols having 2 to 8 carbon atoms.
or more and its glass transition temperature is -10°C to 80°C
A percolene scouring warp sizing agent whose main component is a polymer soluble in percolene solvents.