JPH08127968A - Warp sizing agent for fiber - Google Patents

Abstract

PURPOSE: To obtain a warp sizing agent for fibers containing a specific modified PVA as a main component, exhibiting cohesiveness and adhesiveness to filaments and excellent in fuzz-preventing property, abrasion resistance and smoothness to short fibers and excellent in a paste-dropping property. CONSTITUTION: This warp sizing agent for fibers having high usefulness is obtained by blending 100 pts.wt. of a new modified PVA-based resin obtained by copolymerizing (A) 0.1-20mol% of an ethylenic unsaturated dicarboxylic acid monoamide whose amide component is a branched acrylamide of the formula (R1 is H, an alkyl or an aryl; R2 to R4 are each H, an alkyl or an aryl and >=2 groups of R2 to R4 are not simultaneously H and total number of carbon number of R1 to R4 is >=4) with (B) 80-99.9mol% of a vinyl ester, preferably vinyl acetate and saponifying the reactional product with 0-200 pts.wt. of an acrylic sizing agent. The degree of polymerization of the modified PVA-based resin is preferably 500-1000 when used to filaments and preferably 1000-200 when used to short fibers. The component A is synthesized from maleic anhydride and tert-octylamine, tert-amylamine, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a warp sizing agent for fibers using polyvinyl alcohol (hereinafter abbreviated as PVA). The present invention relates to a warp sizing agent for fibers, which is excellent in abrasion resistance, fluff prevention, adhesion, and weaving efficiency.

[0002]

2. Description of the Related Art Conventionally, warp sizing agents used in the production of fibrous materials are mainly PVA or modified PVA, to which oil agents and auxiliaries are appropriately added, and acrylic copolymers and starches. An aqueous solution prepared by mixing is widely used. However, such conventional fiber sizing agents often have insufficient adhesiveness, cannot completely prevent falling glue and fluffing, have low binding force, and have poor weavability. It was In order to solve this drawback,
The applicant of the present invention has proposed a method of blending saccharides with PVA (JP-A-52-
No. 81191), a method of blending an anionic surfactant with low-saponified PVA (JP-A-53-86890), and a method of using PVA that does not exhibit a cloud point (JP-A-54-160882). And sulfonic acid modified PVA
And a method of using an alkali metal salt of an organic acid (JP-A-54-1)
No. 60883).

[0003]

However, with recent improvements in the performance of looms, market demands have become even more stringent, and in filament yarns, improvements in tying force, stickiness, tackiness, and weaving efficiency are required. In spun yarn, it is desired to prevent fluffing, improve abrasion resistance, smoothness, and improve weaving efficiency.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above drawbacks, the present inventors have found that the ethylenically unsaturated dicarboxylic acid monoamide (A) is contained as a copolymerization component in an amount of 0.1 to 20 mol%. A polyvinyl alcohol-based resin, wherein the amide component of the ethylenically unsaturated dicarboxylic acid monoamide (A) is a novel PVA-based resin whose main component is a polyvinyl alcohol-based resin represented by the following chemical formula 1, The present invention has been accomplished by finding that when used as an agent, it satisfies various performances required for a warp sizing agent for fibers in filament yarns and spun yarns as described above.

Embedded image (However, R ₁ is hydrogen or an alkyl group or aryl (ary
1) group, R _{2 to} R ₄ are hydrogen, an alkyl group or aryl
(aryl) groups are shown, two or more of which are not hydrogen at the same time, and the total number of carbon atoms of R _{1 to} R ₄ is 4 or more. )

The present invention will be described in detail below. The modified PVA (hereinafter sometimes simply referred to as modified PVA) -based resin of the present invention contains the (A) unit as an essential component as described above, and the (A) unit is a branched alkylamide component represented by the above chemical formula 1. containing ethylenically unsaturated dicarboxylic acid monoamide units are those having the functional group of R ₁ to R _4, stable modifying groups during the saponification is less than the number of carbon atoms of functional groups R ₁ to R ₄ is 4 And the storage stability of the aqueous solution are poor, and the carbon number is preferably 4 to 16.

The copolymerizable monomer containing the (A) unit includes N-tert-octyl maleic acid monoamide, N-tert-amyl maleic acid monoamide, and N-tert-amyl maleic acid monoamide.
-1,3-Dimethylbutyl maleic acid monoamide, N-
1,2,2-Trimethylpropyl maleic acid monoamide, N-1-methylhexyl maleic acid monoamide, N
-1-Ethylpentyl maleic acid monoamide, N-1-
Methylheptyl maleic acid monoamide, N-1,5 dimethylhexyl maleic acid monoamide, N, N-ethylisopropyl maleic acid monoamide, N, N-diisopropyl maleic acid monoamide, N, N-methyl-tert
-Butyl maleic acid monoamide, N, N-isopropyl-tert-butyl maleic acid monoamide, N, N-di-
sec-Butyl maleic acid monoamide, N-1-methylbutyl maleic acid monoamide, N-1-ethylpropyl maleic acid monoamide, N-1,2-dimethylpropyl maleic acid monoamide, N-diphenylmethyl maleic acid monoamide, N-1 , 2-Diphenylethyl maleic acid monoamide, N-1-methyl-2-phenylethyl maleic acid monoamide, N-1-methyl-3-phenylpropyl maleic acid monoamide, N, N-methyl-1-methyl-2-phenyl Ethyl maleic acid monoamide, N,
N-isopropyl-benzylmaleic acid monoamide,
N, N-tert-butyl-benzyl maleic acid monoamide, N-1,1-dimethyl-2-phenylethyl maleic acid monoamide, N-1-propylbutyl maleic acid monoamide, N-1-phenylethyl maleic acid monoamide.

N-tert-octyl fumaric acid monoamide, N-tert-amyl fumaric acid monoamide, N-
1,3-dimethylbutyl fumaric acid monoamide, N-1,
2,2-Trimethylpropyl fumaric acid monoamide, N-
1-methylhexyl fumarate monoamide, N-1-ethylpentyl fumarate monoamide, N-1-methylheptyl fumarate monoamide, N-1,5 dimethylhexyl fumarate monoamide, N, N-ethylisopropyl fumarate monoamide, N , N-diisopropyl fumarate monoamide, N, N-methyl-tert-butyl fumarate monoamide, N, N-isopropyl-tert-butyl maleic acid monoamide, N, N-di-sec-butyl fumarate monoamide, N-1-methylbutyl fumarate Acid monoamide,
N-1-ethylpropyl maleic acid monoamide, N-
1,2-Dimethylpropyl fumarate monoamide, N-diphenylmethyl fumarate monoamide, N-1,2-diphenylethyl fumarate monoamide, N-1-methyl-2
-Phenylethyl fumaric acid monoamide, N-1-methyl-3-phenylpropyl fumaric acid monoamide, N, N-
Methyl-1-methyl-2-phenylethyl fumarate monoamide, N, N-isopropyl-benzyl fumarate monoamide, N, N-tert-butyl-benzyl fumarate monoamide, N-1,1-dimethyl-2-phenylethyl fumarate Acid monoamide, N-1-propylbutyl fumaric acid monoamide, N-1-phenylethyl fumaric acid monoamide.

N-tert-octylitaconic acid monoamide, N-tert-amylitaconic acid monoamide, N
-1,3-Dimethylbutyl itaconic acid monoamide, N-
1,2,2-Trimethylpropyl itaconic acid monoamide, N-1-methylhexyl itaconic acid monoamide, N
-1-Ethylpentylitaconic acid monoamide, N-1-
Methylheptyl itaconic acid monoamide, N-1,5 dimethylhexyl itaconic acid monoamide, N, N-ethylisopropyl itaconic acid monoamide, N, N-diisopropyl itaconic acid monoamide, N, N-methyl-tert
Butyl itaconic acid monoamide, N, N-isopropyl-
tert-Butyl itaconic acid monoamide, N, N-di-s
ec-Butylitaconic acid monoamide, N-1-methylbutylitaconic acid monoamide, N-1-ethylpropylitaconic acid monoamide, N-1,2-dimethylpropylitaconic acid monoamide, N-diphenylmethylitaconic acid monoamide, N-1 , 2-diphenylethylitaconic acid monoamide, N-1-methyl-2-phenylethylitaconic acid monoamide, N-1-methyl-3-phenylpropylitaconic acid monoamide, N, N-methyl-1-methyl-2-phenyl Ethylitaconic acid monoamide, N, N
-Isopropyl-benzyl itaconic acid monoamide, N,
N-tert butyl-benzyl itaconic acid monoamide,
N-1,1-dimethyl-2-phenylethylitaconic acid monoamide, N-1-propylbutylitaconic acid monoamide, N-1-phenylethylitaconic acid monoamide.

N-tert-octyl citraconic acid monoamide, N-tert-amyl citraconic acid monoamide, N-1,3-dimethylbutyl citraconic acid monoamide, N-1,2,2-trimethylpropyl citraconic acid monoamide, N-1 -Methylhexyl citraconic acid monoamide, N-1-ethylpentyl citraconic acid monoamide, N-1-methylheptyl citraconic acid monoamide,
N-1,5 dimethylhexyl citraconic acid monoamide,
N, N-ethylisopropyl citraconic acid monoamide,
N, N-diisopropylcitraconic acid monoamide, N,
N-methyl-tert-butyl citraconic acid monoamide,
N, N-isopropyl-tert-butylcitraconic acid monoamide, N, N-di-sec-butylcitraconic acid monoamide, N-1-methylbutylcitraconic acid monoamide, N-1-ethylpropylcitraconic acid monoamide,
N-1,2-dimethylpropyl citraconic acid monoamide, N-diphenylmethyl citraconic acid monoamide, N
-1,2-diphenylethylcitraconic acid monoamide,
N-1-methyl-2-phenylethyl citraconic acid monoamide, N-1-methyl-3-phenylpropyl citraconic acid monoamide, N, N-methyl-1-methyl-2-
Phenylethyl citraconic acid monoamide, N, N-isopropyl-benzyl citraconic acid monoamide, N, N-
tert butyl-benzyl citraconic acid monoamide, N
-1,1-dimethyl-2-phenylethyl citraconic acid monoamide, N-1-propylbutyl citraconic acid monoamide, N-1-phenylethyl citraconic acid monoamide and the like can be mentioned, preferably Nt-octyl maleic acid monoamide. It is preferably used. The carboxylic acid component in the unit (A) of the modified PVA-based resin of the present invention is a free carboxyl group or a salt thereof.

Usually, in order to produce the PVA resin of the present invention, the vinyl ester copolymer obtained by copolymerizing (A) and the vinyl ester (B) is saponified. Examples of (B) include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, and the like, and vinyl acetate is preferable from the economical viewpoint.

The ratio of each unit of the modified PVA resin is
From the viewpoint of film-forming property and economical efficiency, 0.1 to 20 mol% of the ethylenically unsaturated dicarboxylic acid monoamide unit (A) containing the N-branched alkylamide component represented by Chemical Formula 1 above,
Preferably, 0.1 to 10 mol% of the vinyl ester unit (B) and the vinyl alcohol unit (C) are 80 in total.
The range of ˜99.9 mol% is suitable. In addition, the saponification degree (vinyl alcohol unit (D) relative to the total amount of vinyl ester unit (C) and vinyl alcohol unit (D))
Is 50% from the viewpoint of the productivity of the modified PVA-based resin.
It is preferably at least mol%, and particularly preferably in the range of at least 70 mol%.

The modified PVA resin used in the present invention preferably has a degree of polymerization of 200 to 3000, and a degree of polymerization of 200.
If less than 3,000, the film strength after gluing becomes weaker, and conversely 3000
If it exceeds, the viscosity tends to be high and the workability tends to decrease. Also, 200 to 100 for sizing of filament yarn
0, more preferably 500 to 1000 is used, and for sizing the spun yarn, 500 to 3000, more preferably 1000 to 2000 is used. Next, the modified P of the present invention
A method of manufacturing the VA resin will be described.

The modified PVA-based resin of the present invention is obtained by saponifying a copolymer of the above-mentioned ethylenically unsaturated dicarboxylic acid monoamide (A) monomer containing a branched alkylamide component represented by Chemical Formula 1 and a vinyl ester. It is obtained by doing. Such an ethylenically unsaturated dicarboxylic acid monoamide (A) is an ethylenically unsaturated dicarboxylic acid such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid or citraconic anhydride, or an anhydride thereof. Alternatively, these acid halides are reacted with the primary amine or secondary amine represented by Chemical formula 2 in the presence of no catalyst or an appropriate acid catalyst (protonic acid such as sulfuric acid, hydrochloric acid, P-toluenesulfonic acid). Is obtained by

Examples of such amines include tert-octylamine, tert-amylamine, 1,3-dimethylbutylamine, 2-amino-3,3-dimethylbutane, 2-aminoheptane, 3-aminoheptane and 1-methyl. Heptylamine, 1,5-dimethylhexylamine, N-ethylisopropylamine, diisopropylamine, N-methyl-tert-butylamine, N-te.
rt-butylisopropylamine, di-sec-butylamine, 1-methylbutylamine, 1-ethylpropylamine, 1,2-dimethylpropylamine, aminodiphenylmethane, 1,2-diphenylethylamine, 1-
Methyl-2-phenylethylamine, 1-methyl-3-
Phenylpropylamine, N-methyl-1-methyl-2
-Phenylethylamine, N-isopropylbenzylamine, N- (tert-butyl) benzylamine, α,
Examples include α-dimethyl-β-phenylethylamine, 1-propylbutylamine, 1-phenylethylamine and the like.

Embedded image (However, R ₁ is hydrogen, an alkyl group or an allyl group, R ₂ ~
R ₄ represents hydrogen, an alkyl group, or an allyl group, respectively, and is not 2 or more hydrogens at the same time, and the total number of carbon atoms of R _{1 to} R ₄ is 4 or more. )

In this polymerization, other unsaturated monomers copolymerizable with the monomers other than the above two components, for example, alkyl vinyl ether, methacrylamide, ethylene, propylene, as long as the gist of the present invention is not impaired. ,
Olefins such as α-hexene, α-octene, α-dodecene and α-octadodecene, nitriles such as acrylonitrile and methacrylonitrile, alkyl acrylates, methacrylic acid alkyl esters, crotonic acid alkyl esters, maleic acid dialkyl esters, itacone A small amount of acid dialkyl ester, citraconic acid dialkyl ester, fumaric acid dialkyl ester and the like may be copolymerized.

The copolymerization reaction is a known polymerization method in radical polymerization, for example, bulk polymerization, solution polymerization, emulsion polymerization,
Although it can be arbitrarily selected from suspension polymerization and the like, solution polymerization is preferable from an industrial viewpoint. Any method such as batch polymerization and continuous polymerization can be selected. There is no particular limitation on the charging method of the monomers during the polymerization, batch charging,
Any method such as divided preparation and continuous preparation is adopted,
The divided charging method or the continuous charging method is advantageous in that the ethylenically unsaturated dicarboxylic acid monoamide can be uniformly introduced into PVA.

As a catalyst for the copolymerization, known radical polymerization catalysts such as azoisobutyl nitrile, acetyl peroxide, benzoyl peroxide and lauryl peroxide, and low temperature active radical catalysts such as azobisdimethylvaleronitrile and azobismethoxydimethylvaleronitrile. Etc. are used. Further, the reaction temperature is not particularly limited and is appropriately selected from the range well known to those skilled in the art.

The copolymer obtained by such a method is then saponified. As the saponification method, any method such as kneader saponification, continuous saponification, and pearl saponification can be adopted. In the saponification step, the residual monomer is expelled as necessary, and then saponification is performed according to a conventional method. To be done. That is, in saponification, the copolymer is dissolved in alcohol or hydrous alcohol, neutralized with alkali, and then saponified with an acid catalyst or an alkali catalyst. As alcohol, methanol, ethanol, propanol, t
Examples include ert-butanol, but methanol is particularly preferably used. The concentration of the copolymer in alcohol is appropriately selected depending on the viscosity in the system, and is usually selected from the range of 10 to 60% by weight. As the catalyst used for saponification,
An alkali catalyst such as an alkali metal hydroxide or alcoholate such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate or potassium methylate, or an acid catalyst such as sulfuric acid or hydrochloric acid is used.

The saponification reaction temperature is not particularly limited and is usually selected in the range of 10 to 60 ° C, preferably 20 to 50 ° C. After completion of the saponification reaction, the target modified P is neutralized, washed with alcohol and the like if necessary, and dried.
A VA resin is obtained.

Next, the preparation of a warp sizing agent for fibers using the obtained modified PVA resin will be described. In the preparation of the sizing agent, the above-mentioned effect does not change even if another sizing agent such as an acrylic sizing agent, starch, modified starch, or carboxymethylcellulose is used in combination with the modified PVA resin. In some cases, the effect may be even greater.

Particularly, it is important to use it together with an acrylic sizing agent, and by using this together, an extremely excellent warp sizing agent for fibers can be obtained. The acrylic paste is an alkaline substance which is a copolymer of a hydrophobic monomer mainly composed of acrylic acid ester or methacrylic acid ester and an ethylenically unsaturated carboxylic acid such as acrylic acid or methacrylic acid or sulfonic acid. It is made to be water-soluble or water-dispersible. The mixing ratio when the acrylic sizing agent is used in combination is preferably selected so as to fall within a range of 0 to 200 parts by weight with respect to 100 parts by weight of the PVA resin, and optimally 20 to 100.
It is in the range of parts by weight, and when the blending ratio of the acrylic sizing agent is too small, it is difficult to expect a synergistic effect due to the combined use,
On the other hand, if the blending ratio is too high, the adhesiveness of the sizing yarn becomes high, the fallen sizing gums up on the loom, and the warp threads stick together due to the warp beam, and the open state deteriorates, which is also a cost disadvantage. Is not preferable.

Further, like other sizing agents, it is extremely useful to use an oil agent in combination, and as the oil agent, natural wax (animal wax such as whale wax, plant wax such as wood wax, petroleum paraffin, etc.) is used. And synthetic wax (paraffin derivative,
Synthetic fatty alcohol and acid, synthetic fatty acid ester, etc.) and a mixture of surfactants (anionic, nonionic, etc.) and the like. Specifically, for filament yarn,
"Citex T-190" (manufactured by Mutual Chemical Co., Ltd.,
35% by weight of active ingredient), "Citex T-290"
(Myocon Chemical Co., Ltd., active ingredient 35% by weight), etc. For spun yarn, "Merconol TS253" (Matsumoto Yushi-Seiyaku Co., Ltd., active ingredient 100%), "Merconol TS222" (Matsumoto Yushi-Seiyaku) Co., Ltd., active ingredient 10
0%), "Solvill Wax 135" (manufactured by Yushiro Chemical Co., Ltd., 100% active ingredient) and the like are preferably used.

The mixing ratio of the oil agent is the PVA resin 1
It is preferable to select it so as to be in the range of 1 to 40 parts by weight with respect to 00 parts by weight, optimally in the range of 5 to 10 parts by weight, and when the blending ratio of the oil agent is too low, the smoothness is If the blending ratio is too large, on the contrary, the tackiness of the film becomes large, and the amount of glue drops, which is not preferable. Furthermore, in the present invention, within the range that does not impair the effects of the present invention, known smoothing agents for warp sizing, softening agents,
There is no problem even if an appropriate amount of penetrant, antistatic agent, defoaming agent, etc. is added. Further, the resin content concentration in the paste solution is 2 to 13
It is usual to control the amount by weight.

The warp sizing agent for fibers of the present invention thus prepared is used for sizing filament yarn, spun yarn (spun yarn), wooly processed yarn, etc. It can also be used as a finishing agent.

[0025]

The function of the warp sizing agent for fibers of the present invention is to provide a specific modified PVA.
It is highly useful as a warp sizing agent for fibers because it contains a system resin as a main component. Especially, in filament yarns, it improves cohesiveness, stickiness, tackiness and weaving efficiency, and in spun yarns it prevents fluffing. It is possible to improve abrasion resistance, smoothness and weaving efficiency.

[0026]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, "%" and "parts" mean weight basis unless otherwise specified. (Production of modified PVA-based resin) maleic anhydride 50.0
And 65.9 parts of tert-octylamine were charged into a flask, and the reaction was carried out at 60 ° C. for 2 hours while stirring. After completion of the reaction, the reaction product was recrystallized to obtain the compound represented by Chemical formula 3.

Embedded image The yield was 95%.

A polymerization vessel equipped with a reflux condenser, a dropping funnel, and a stirrer was charged with 1000 parts of vinyl acetate and 450 parts of methanol, and the temperature was raised under a nitrogen stream while stirring to obtain 0.6 of azobisisobutyronitrile at 62 ° C. A solution prepared by dissolving 1 part in 19.4 parts of methanol was added to initiate polymerization.
Polymerization was carried out while continuously adding dropwise 272 parts of a methanol solution in which 27.2 parts of the compound N-tert-octylmaleic acid monoamide obtained above from the polymerization initiation point were dissolved for 5 hours, and the polymerization rate of vinyl acetate was 50. The polymerization was terminated when the percentage reached. Then, the unreacted vinyl acetate monomer was removed out of the system by a method of blowing methanol vapor to obtain a methanol solution of the copolymer. Then, the solution was diluted with methanol to adjust the concentration to 30% and charged in a kneader, and sodium hydroxide was added to neutralize while keeping the solution temperature at 35 ° C. To this, sodium hydroxide was further added in an amount of 30 mmol with respect to the vinyl acetate unit in the polymer and kneaded. As the saponification reaction proceeded, a saponified product was deposited and finally became a particulate form. The resulting modified PVA-based resin was filtered, washed well with methanol, and dried in a hot air drier to obtain the desired product. The modified PVA resin thus obtained was washed by extraction with methanol using a Soxhlet extractor.
As a result of ¹ H-NMR analysis of the degree of modification with -tert-octyl maleic acid monoamide, the degree of modification was 2.0 mol%. The saponification degree of the modified PVA-based resin was 98 mol% when analyzed by quantifying the amount of alkali consumption required for hydrolysis of the residual vinyl acetate unit. still,
The viscosity of a 4% aqueous solution of this modified PVA-based resin measured by a B-type viscometer was 6 cps / 20 ° C.

Further, the IR spectrum and ¹ H-NMR spectrum of the obtained modified PVA resin are shown below. ^{IR: 3350cm -1, 1100cm -1 -OH} 2950cm -1, 1420cm -1 -C-H 1650cm -1 -C = O ( amide I absorption ^{band) 1585cm -1 -COONa 1 H-NMR} : 1.0ppm -C (CH ₃ ) methyl proton 1.6 ppm —CH ₂ —CH— methylene proton | 2.1 ppm —O—CO—CH ₃ methyl proton 4.0 ppm —CH ₂ —CH— methine proton |

Example 1 Polyester filament yarn was pasted with a sizing liquid containing the modified PVA-based resin as a main component, and the obtained yarn was woven as follows. (Paste solution composition) 100 parts of the above-mentioned modified PVA-based resin-Acrylic paste agent 100 parts (Plus size 780, manufactured by Kyoo Kagaku Kogyo Co., Ltd., acrylic acid ester copolymer sodium salt, 25% solution) -Oil agent 5 parts ( Cytex T-190, manufactured by Kyoo Kagaku Kogyo Co., Ltd., containing wax and nonionic activator, 35% solution) -Water 2000 parts

(Gluing conditions) Target yarn Polyester filament yarn (75 denier / 36 filament, untwisted) Gluing machine KS-J type warping slasher manufactured by Tsudakoma Co., Ltd. Gluing conditions 180% to 260 kg drawing liquid temperature 50 ° C paste liquid temperature Drying temperature Chamber 120 ° C × 2 Cylinder 100 ° C × 2 Winding speed 95m / min Adhesion amount 12.1%

Next, in the above (manufacture of modified PVA-based resin), the same procedure was performed except that the amount of methanol charged was 250 parts. The viscosity of a 4% aqueous solution measured by a B-type viscometer was 30%.
A modified PVA-based resin having a degree of polymerization of 1500 at cps / 20 ° C. was obtained, and a polyester spun yarn was pasted with the following sizing liquid containing the resin as a main component, and the obtained yarn was woven as follows. I went like this. (Paste liquid composition) 100 parts of the above-mentioned modified PVA-based resin-Acrylic paste agent 2 parts (Marposol TS-189, manufactured by Matsumoto Yushi-Seiyaku Co., Ltd., acrylic acid ester copolymer sodium salt, 25% solution) -Oil agent 8 parts (Maconol TS-797, manufactured by Matsumoto Yushi-Seiyaku Co., Ltd., wax and 99% salt containing nonionic activator) -corn starch 10 parts-water 1000 parts

(Adhesion Conditions) Target Thread Polyester Spun Thread (40th Number) Adhesion Machine, Baba Sangyo Co., Ltd., 2B0X12C Adhesion Conditions Total drawing load 500-800 kg Paste liquid temperature 85 ° C Drying temperature Cylinder (1-6) 120 ° C. Cylinder (7 to 12) 110 ° C. Winding speed 60 m / min Loading amount 13%

(Weaving conditions) Weaving was performed under the following conditions using the sizing polyester filament yarn or sizing polyester spun yarn obtained under the above sizing conditions. In the case of sizing polyester filament yarn, the woven fabric is taffeta, the total number of warp yarns is 4600 yarns, the weaving width is 38 inches, the warp yarn density is 118 yarns / inch, the weft yarn density is 90 yarns / inch, and the weaving machine is an automatic loom 160 rpm, and one sack is 50m. As each, 10 braids were woven. In the case of sizing polyester spun yarn,
The woven fabric has a total warp yarn count of 4100, a weaving width of 39 inches, a warp density of 104 yarns / inch, a weft yarn density of 92 yarns / inch, and a loom has an air jet loom (AJL) of 600 rpm and 1
Each of the 10 nits was woven with 00 m as one nit. At the time of sizing and weaving, for filament yarn, binding force, dropability, adhesiveness, open state, weaving efficiency, and for spun yarn, fluffiness, abrasion resistance, dropability, warp stopping property, Weaving efficiency was examined by the following methods.

Coupling force The average number of times of rubbing of the sizing yarn after sizing after the sizing is rubbed at a load of 100 g / 10 and an angle of 145 ° by using a TM tying degree tester (manufactured by Matsui Seiki) Was measured.・ Detachability The sizing thread after sizing is entwined with a metal needle (diameter 1 mm) and 1
The glued yarn is rubbed on the side surface of the needle so as to form an angle of 20 degrees, and the amount of glue dropped at this time is divided into 5 levels (1st class (small) to 5th class).
It was divided into grades (most) and evaluated relatively. Note that the sizing yarn was rubbed for 10 m at a pulling speed of 10 cm / min during rubbing.・ Adhesiveness The sizing thread after sizing is wound around a bobbin, 35 ℃, 80% R
After standing for 1 week in H, the resistance when pulling out the yarn was examined. The evaluation criteria are as follows. ◎ −−− There is no resistance ○ −−− There is a little resistance × −−− The resistance is large and it is difficult to pull it out.

-Opening state The degree of opening of the thread between the mating roll and the heddle on the loom is set to 5
Relative evaluation was performed by dividing into stages (1st grade (large opening) to 5th grade (almost no opening)). -Weaving efficiency The ratio of the target weaving time based on the number of revolutions of the loom and the weft driving density during weaving and the actual weaving time was expressed in%.・ Fuzziness The number of fluffs of the sizing thread after sizing (3 mm or more in length) (book /
m) was measured using a fluff counter (Toray Industries, Inc.). -Abrasion resistance The sizing yarn after sizing is 1000 with a load of 400 g / 10 using a TM type tie tester (manufactured by Matsui Seiki Co., Ltd.).
The fluffing state of the yarn after being rubbed twice was divided into 8 grades (1st grade (no fluffing) to 8th grade (strong fluffing, weaving impossible)) and relatively evaluated.・ Warp stopability The number of times the loom was stopped due to warp fluff, fluff entanglement, and yarn breakage during weaving was measured.

Examples 2 to 8 and Comparative Examples 1 to 6 Copolymerization with vinyl acetate and saponification by the same procedure as the above (Production of modified PVA-based resin) with the components and charging amounts shown in Tables 1 and 2. Various modified PVA as shown in Table 3
Manufacture resin (for filament yarn and spun yarn),
A sizing agent was prepared in the same manner as in Example 1 using the PVA-based resin, and the same evaluation as in Example 1 was performed. The evaluation results of Examples and Comparative Examples are shown in Table 4 (evaluation of filament yarn) and Table 5.
(Evaluation of spun yarn) is shown.

[0037]

[Table 1] Synthetic conditions of ethylenically unsaturated dicarboxylic acid monoamide Synthetic monoamic acid amine Temperature time Yield (parts) (parts) (℃) (hr) (%) Nt-OMMAm Maleic anhydride tert-octylamine 60 2 96 Nt-OIMAm Itaconic anhydride tert-Octylamine 60 2 94 Nt-AMMAm Maleic anhydride tert-Amylamine 60 2 97 N-DMHMMAm Maleic anhydride 1,5 Dimethylhexylamine 60 2 95 N-DMPEMMAn Maleic anhydride α, α- Dimethylhexylamine 60 2 95 Nt-BMMAm Maleic anhydride tert-Butylamine 60 2 96 N-n-OMMAm Maleic anhydride n-octylamine 60 2 90 Note) Nt-OMMAm is N-tert-octylmaleic acid monoamide. Nt-OIMAm is N-te
rt-Octylitaconic acid monoamide. Nt-AMM
Am is N-tert-amyl maleic acid monoamide.
N-DMHMMAm is N-1,5-dimethylhexyl maleic acid monoamide. N-DMPEMMAN is N-
1,1-Dimethylphenylethyl maleic acid monoamide. Nt-BMMAm is N-tert-butyl maleic acid monoamide. Nn-OMMAm is Nn-octyl maleic acid monoamide.

[0038]

[Table 2] Modified species during polymerization with vinyl acetate, charged amount and polymerization rate (A) Monomer charged amount Polymerization rate (mol%) (%) Example 1 Nt-OMMAm (2.0) 50 Example 2 Nt-OMMAm (0.5) 59 Example 3 Nt-OMMAm (8.0) 48 Example 4 Nt-OIMAm (2.0) 49 Example 5 Nt-AMMAm (2.0) 53 Example 6 N -T-MMAm (2.0) 50 Example 7 N-DMHMMAm (2.0) 50 Example 8 N-DMPEMMAm (2.0) 45 Comparative Example 1 Nt-BMMAm (2.4) 51 Comparative Example 2 Nn-OMMAm (2.5) ) 52 Comparative Example 3 VeoVa-10 (3.0) 50 Itaconic Acid (1.0) Comparative Example 4 MRM (3.0) 55 Comparative Example 5 AMPS (2.0) 55 Comparative Example 6 3M (2.0) 60

Note) The value in parentheses () represents the mole fraction of the monomer (A) charged relative to the total amount of the monomer charged. Abbreviations are as follows. Nt-OMMAm is N-tert-octyl maleic acid monoamide. Nt-OIMAn is N-
tert-Octylitaconic acid monoamide. Nt-A
MMAm is N-tert-amyl maleic acid monoamide. N-DMHMMAm is N-1,5 dimethylhexyl maleic acid monoamide. N-DMPEMMAm is N
-1,1-Dimethylphenylethyl maleic acid monoamide. Nt-BMMAm is N-tert-butyl maleic acid monoamide. Nn-OMMAm is Nn-octyl maleic acid monoamide. 3M is monomethyl maleate. MRM is mono (diisopropylmethyl) malate. VeoVa-10 is a monomer represented by the following chemical formula 4.

[Chemical 4] R ₁ , R ₂ and R ₃ are hydrogen or an alkyl group. The total carbon number of R ₁ , R ₂ and R ₃ is 10 on average. AMPS is sodium N-sulfoisobutylene acrylamide.

[0040]

TABLE 3 denaturation P V A saponification degree (A) monomer of 4% viscosity degree of polymerization content (cps) (mol%) (mol%) ab ab Example 1 98 2.0 6 30 500 1500 Example 2 98 0.5 6 30 500 1500 Example 3 98 7.9 4 20 400 1400 Example 4 98 2 0.0 6 30 500 1600 Example 5 98 2.0 6 30 30 500 1700 Example 6 80 2.0 5 25 500 1500 Example 7 98 2.0 6 30 500 1500 Example 8 98 2.0 2.0 7 35 700 2000 Comparative Example 1 98 2.0 6 30 500 1700 Comparative Example 2 98 2.0 7 40 600 2300 Comparative Example 3 98 2.0 (VeoVa-10) 6 30 500 1700 1.0 (itaconic acid) Comparative Example 4 98 2 0.06 30 500 1500 Comparative Example 5 98 2.0 6 30 500 1500 Comparative Example 6 98 2.0 6 30 500 1700

The modified PVs obtained in Examples 2 to 8 above
Assignments of IR spectrum and ¹ H-NMR (D ₂ O) spectrum of the A-based resin are shown below. (Modified PVA Example ^{2) IR: 3350cm -1, 1100cm} -1 -OH 2950cm -1, 1420cm -1 -C-H 1650cm -1 -C = O ( amide I absorption band) 1585cm ^-1 -COONa ¹ H -NMR: 1.0ppm -C (CH ₃₎ methyl protons 1.6 ppm -CH ₂ -CH- methylene protons │ of 2.1ppm -O-CO-CH ₃ methyl protons 4.0 ppm -CH ₂ -CH- Methine proton │

[0042] (Example 3 of modified ^{PVA) IR: 3350cm -1, 1100cm} -1 -OH 2950cm -1, 1420cm -1 -C-H 1650cm -1 -C = O ( amide I absorption band) 1585 cm ^-1 - COONa ¹ H-NMR: 1.0 ppm —C (CH ₃ ) methyl proton 1.6 ppm —CH ₂ —CH— methylene proton | 2.1 ppm —O—CO—CH ₃ methyl proton 4.0 ppm —CH ₂ -CH-methine proton │

[0043] (Example 4 of Modified ^{PVA) IR: 3350cm -1, 1100cm} -1 -OH 2950cm -1, 1420cm -1 -C-H 1650cm -1 -C = O ( amide I absorption band) 1585 cm ^-1 - COONa ¹ H-NMR: 1.0 ppm —C (CH ₃ ) methyl proton 1.6 ppm —CH ₂ —CH— methylene proton | 2.1 ppm —O—CO—CH ₃ methyl proton 4.0 ppm —CH ₂ -CH-methine proton │

[0044] (Example 5 of Modified ^{PVA) IR: 3350cm -1, 1100cm} -1 -OH 2950cm -1, 1420cm -1 -C-H 1650cm -1 -C = O ( amide I absorption band) 1585 cm ^-1 - COONa ¹ H-NMR: 0.9 ppm —CH ₂ —CH ₃ methyl proton 1.6 ppm —CH ₂ —CH— methylene proton | 2.1 ppm —O—CO—CH ₃ methyl proton 4.0 ppm —CH ₂ -CH-methine proton │

[0045] (modified PVA in Example ^{6) IR: 3350cm -1, 1100cm} -1 -OH 2950cm -1, 1420cm -1 -C-H 1650cm -1 -C = O ( amide I absorption band) 1585 cm ^-1 - COONa ¹ H-NMR: 1.0 ppm —C (CH ₃ ) methyl proton 1.6 ppm —CH ₂ —CH— methylene proton | 2.1 ppm —O—CO—CH ₃ methyl proton 4.0 ppm —CH ₂ -CH-methine proton │

[0046] (Example 7 of the modified ^{PVA) IR: 3350cm -1, 1100cm} -1 -OH 2950cm -1, 1420cm -1 -C-H 1650cm -1 -C = O ( amide I absorption band) 1585 cm ^-1 - COONa ¹ H-NMR: 0.9 ppm —CH (CH ₃ ) ₂ methyl proton 1.6 ppm —CH ₂ —CH— methylene proton | 2.1 ppm —O—CO—CH ₃ methyl proton 4.0 ppm —CH _2- CH-methine proton │

[0047] (modified PVA of Example ^{8) IR: 3350cm -1, 1100cm} -1 -OH 2950cm -1, 1420cm -1 -C-H 1650cm -1 -C = O ( amide I absorption band) 1585 cm ^-1 - COONa ¹ H-NMR: 1.6 ppm —CH ₂ —CH— methylene proton | 2.1 ppm —O—CO—CH ₃ methyl proton 4.0 ppm —CH ₂ —CH— methine proton | 7.2 ppm C ₆ H ₅ protons

[0048]

[Table 4] Evaluation results of filament yarns Cohesion strength Degradability Adhesiveness Open state Weaving efficiency (times) (class) (class) (%) Example 1 35 2 ◎ 1-292 〃 2 352 2 ○ 1-2 90 〃 3 20 2 ◎ 1 to 2 93 〃 4 50 2 ○ 3 90 〃 5 35 2 ◎ 1 to 2 92 〃 6 30 2 ○ 3 92 〃 7 35 2 ◎ 1 to 2 93 〃 8 40 2 ◎ 1-2 93 Comparative Example 1 20 5 ◎ 1-2 84 〃 2 352 2 × 4-5 81 〃 3 40 2 × 4-5 81 81 〃 4 25 3 ○ 1 to 2 87 〃 5 25 3 ○ 1 to 2 85 〃 6 20 5 ○ 1-284

[0049]

[Table 5] Evaluation results of spun yarn Fluffing resistance, abrasion resistance, dropability, warp stopability, weaving efficiency (books / m) (class) (class) (times / day) (%) Example 1 0.2 21 10 95 〃 2 0.3 2 1 1 10 90 〃 3 0.4 3 2 3 13 90 〃 4 0.3 3 3 3 11 90 〃 5 5 0.4 3 2 13 13 90 〃 6 0.3 3 2 1 10 90 90 〃 7 .3 2 1 10 90 〃 8 0.3 2 1 10 95 Comparative Example 1 1.2 3 4 20 85 〃 2 1.0 3 1 1 8 88 〃 3 1.0 3 1 15 15 87 〃 4 1.2 5 3 18 86 〃 5 1.3 5 5 4 19 85 〃 6 1.2 5 4 20 20 85

[0050]

The warp sizing agent for fibers of the present invention is highly useful as a warp sizing agent for fibers because it contains a specific modified PVA resin as a main component. It is possible to improve sizing, tackiness and weaving efficiency, and to prevent fluffing, abrasion resistance, smoothness and weaving efficiency in spun yarn.

Claims (2)

[Claims] 1. A polyvinyl alcohol-based resin containing 0.1 to 20 mol% of an ethylenically unsaturated dicarboxylic acid monoamide (A) as a copolymerization component, which is an amide of the ethylenically unsaturated dicarboxylic acid monoamide (A). A warp sizing agent for fibers, which comprises a polyvinyl alcohol-based resin represented by the following chemical formula 1 as a main component. Embedded image (However, R ₁ is hydrogen or an alkyl group or aryl (ary
1) group, R _{2 to} R ₄ are hydrogen, an alkyl group or aryl
(aryl) groups are shown, two or more of which are not hydrogen at the same time, and the total number of carbon atoms of R _{1 to} R ₄ is 4 or more. ) 2. The warp yarn sizing agent for fibers according to claim 1, wherein the acrylic sizing agent is blended in an amount of 0 to 200 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin.