JPH0128149B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel sizing agent for textile products (excluding warp sizing agents), and more specifically, the present invention relates to a novel sizing agent for textile products (excluding warp sizing agents), and more specifically, it contains at least one compound represented by the following general formula (), (), (), or () in the molecule. The present invention relates to a sizing agent (excluding warp sizing agent) which is made of cationic group-modified polyvinyl alcohol (hereinafter referred to as PVA) containing 0.1 to 3 mol% of polymerized units and has excellent adhesion efficiency and a high sizing finishing effect. (Here, R ¹ , R ² , R ³ are hydrogen atoms or lower alkyl groups, B is

[expression] or

[Formula] R ⁴ and R ⁵ are hydrogen atoms or lower alkyl groups, R ⁶ is lower alkyl groups (which may contain substituents), X ^- is an anion, A is the nitrogen atom in B and the nitrogen atom of the amide group. Each means a connecting group. ) (Here, R ⁷ , R ⁸ , and R ⁹ each represent a hydrogen atom, a lower alkyl group, or a phenyl group, R ¹⁰ represents a lower alkyl group (which may contain a substituent), and X ⁻ represents an anion. ) (Here, B is

[expression] or

[Formula] R ⁴ and R ⁵ are hydrogen atoms or lower alkyl groups, R ⁶ is lower alkyl groups (which may contain substituents), X ^- is an anion, and D is a fatty acid that connects the nitrogen atom and oxygen atom in B. They each mean the group's group. ) Conventionally, sizing agents have been aqueous solutions such as starch, PVA, or carboxymethylcellulose, or cationic emulsions obtained by emulsion polymerization of vinyl monomers using polyvinyl acetate emulsions or cationic polymers. Emulsion type products have been used. Among these, PVA is currently widely used because it does not have to worry about rotting and has a crisp texture, but it lacks adhesive strength for polyester fiber products such as cotton fabric, and when dehydrated after gluing. They have the disadvantage that they fall off from fibers and have a low adsorption rate, and emulsion-type adhesives are generally said to have poor adhesive removal when washed. As a result of intensive research into improving the performance of PVA as a sizing agent for textile products (excluding warp sizing agents), the present inventors found that modified PVA with a specific amount of specific cationic groups introduced into the molecule When this product is used as a sizing agent for textile products (excluding warp sizing agent), it has excellent adsorption power to textile products, and extremely good sizing effect can be obtained even for polyester textile products. In addition to this discovery, we also established an industrially advantageous method for introducing cationic groups into PVA.
This completes the present invention. The technology of cationically modifying water-soluble polymers such as starch or polyacrylamide has been known and has been produced industrially, but the concept of using PVA modified with cationic groups as a sizing agent is completely unknown. Not yet. Although several methods have been proposed to simply introduce cationic groups into PVA, all of them had drawbacks in their modification methods and were difficult to produce industrially, so cationic group-modified PVA This is presumed to be because it was unthinkable to apply it to adhesives. The methods for producing cation-modified PVA that have been reported so far include a method in which vinyl pyridine and vinyl acetate are copolymerized and then saponified, N-vinylphthalimide or N-vinyl succinimide and vinyl acetate are copolymerized and then saponified, and then alkali Alternatively, a method of decomposing the imide group with hydrazine, a method of converting PVA into aminoacetal or aminobenzacetal under an acid catalyst, a method of converting PVA to alkoxydimethylamine, glycidyltrimethylammonium hydrochloride or 3-chloro-2-hydroxypropyltrimethyl Known methods include a method in which ammonium hydrochloride is reacted, and a method in which acrylamide is added to PVA with microspheres, and then an amino group is introduced by Hoffman decomposition. However, these methods for producing cation-modified PVA have various problems in the cationization step itself, which are difficult to implement industrially. Furthermore, when used as a sizing agent for textile products, it is still unsatisfactory. On the other hand, the following general formula (),
Cation group-modified polyvinyl alcohol containing 0.1 to 3 mol% of at least one kind of copolymerized unit represented by (), () or () not only exhibits cationic activity, but also can be used industrially depending on the introduction of cationic groups and purposes. Both of these methods can be carried out stably and easily to obtain a saponification degree, and when used as a sizing agent, they exhibit extremely excellent effects. (Here, R ¹ , R ² , R ³ are hydrogen atoms or lower alkyl groups, B is

[expression] or

[Formula] R ⁴ and R ⁵ are hydrogen atoms or lower alkyl groups, R ⁶ is lower alkyl groups (which may contain substituents), X ^- is an anion, A is the nitrogen atom in B and the nitrogen atom of the amide group. Each means a connecting group. ) (Here, R ⁷ , R ⁸ , and R ⁹ each represent a hydrogen atom, a lower alkyl group, or a phenyl group, R ¹⁰ represents a lower alkyl group, and X ⁻ represents an anion.) (Here, B is

[expression] or

[Formula] R ⁴ and R ⁵ are hydrogen atoms or lower alkyl groups, R ⁶ is lower alkyl groups (which may contain substituents), X ^- is an anion, and D is a fatty acid that connects the nitrogen atom and oxygen atom in B. They each mean the group's group. ) Modified PVA containing copolymerized units represented by the above general formulas () to () can be produced using vinyl esters, especially vinyl acetate, and the following formulas (a) to (d). CH ² = CH-O-D-B (d) (here, R ¹ to ^{R 3} , R ⁷ to R ¹⁰ , X ^- , A, B,
The meaning of D is the same as above. ) in the presence of a radical polymerization initiator, and then an alkali or acid catalyst is applied to the alcohol solution of the copolymer to form vinyl ester units in the copolymer. It can be effectively and easily produced by partially or highly saponifying it to form vinyl alcohol units depending on the purpose. R ¹ and R ² in the monomer represented by general formula (a)
is a hydrogen atom or a lower alkyl group, usually a hydrogen atom or a methyl group is preferred, and a hydrogen atom is more preferred since the polymerization rate in the copolymerization reaction with vinyl acetate is high. R ³ is also a hydrogen atom or a lower alkyl group, but usually a hydrogen atom or a methyl group is preferred. B is an amino group

[Formula] or quaternary ammonium salt

[Formula], R ⁴ and R ⁵ are hydrogen atoms or lower alkyl groups, R ⁶ is a lower alkyl group which may contain a substituent, and X ^- is an anion.
For normal purposes, R ⁴ , R ⁵ , and R ⁶ are all preferably methyl groups, but for special purposes, they may be lower alkyl groups such as ethyl or propyl groups, methylol groups, or amino groups for the purpose of increasing the density of cationic groups. Lower alkyl groups containing substituents such as alkyl groups are also used. X is a halogen atom such as chlorine, silium, iodine, CH ₃ OSO ₃ or
_{CH3C6H4SO3 is preferred .} When B is in the form of a quaternary ammonium salt, the effects of the present invention can be exhibited even with primary to tertiary amines, which are preferable for ease of handling in the production of modified PVA. A is a group that connects the nitrogen atom in the amino group B and the nitrogen atom in the amide group
Any group containing a stable bond can be used, but a linear or branched aliphatic group is usually used. Among the monomers represented by the above general formula (A), the following are specific examples of monomers in the form of tertiary amines. N-(2-dimethylaminoethyl)acrylamide, N-(2-dimethylaminoethyl)methacrylamide, N-(3-dimethylaminopropyl)acrylamide, N-(3-diethylaminopropyl)acrylamide, N-(3-dimethyl aminopropyl) methacrylamide, N-(3-
diethylaminopropyl) methacrylamide, N
-(1,1-dimethyl-3-dimethylaminopropyl)acrylamide, N-(1,1-dimethyl-3-dimethylaminopropyl)methacrylamide, N-(1,1-diethyl-3-dimethylaminobutyl)acrylamide , N-(1-methyl-
1,3-diphenyl-3-diethylaminopropyl)methacrylamide, N-(3-dimethylaminohexyl)acrylamide, N-(3-methylethylaminopropyl)methacrylamide, N-
Methyl-N-(3-dimethylaminopropyl)acrylamide, N-(2,2-dimethyl-3-dimethylaminopropyl)acrylamide, N-
(2,2-dimethyl-3-dimethylaminopropyl)methacrylamide, N-(2,2-dimethyl-3-dimethylaminopropyl)crotonic acid amide, N-(3,3-dimethyl-4-dimethylaminobutyl) Acrylamide, N-(3,3-dimethyl-4-dimethylaminobutyl)methacrylamide, N-(3,3-dimethyl-4-dimethylaminobutyl)crotonic acid amide. Among the monomers represented by the above general formula (a), those in the form of quaternary ammonium can be easily obtained by quaternizing the above-mentioned tertiary amine type monomer with the following quaternizing agent. be able to. Dialkyl sulfate, e.g. dimethyl sulfate, diethyl sulfate, dipropyl sulfate, alkyl or aryl sulfonic acid C ₁ ~
C ₄ -esters, e.g. methyl-, ethyl-, propyl- or butyl esters, such as methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid, benzyl halides, e.g. benzyl chloride or benzyl bromide, alkyl halides, e.g. methyl chloride. , methyl bromide, methyl iodide, ethyl chloride, ethyl bromide or ethyl iodide. Among the various examples mentioned above as monomers represented by the general formula (A), the following four types of monomers are important in terms of polymerization rate, stability of amide groups, monomers, etc. It is excellent from the viewpoint of economic efficiency during mass production. N-(1,1-dimethyl-3-dimethylaminopropyl)acrylamide trimethyl-(3-acrylamide-3,3-
dimethylpropyl) ammonium chloride N-(3-dimethylaminopropyl)methacrylamide Trimethyl-(3-methacrylamidopropyl)ammonium chloride Furthermore, examples of the monomer shown in (b) above include the following. 1-vinylimidazole, 1-vinyl-2-methylimidazole, 1-
Vinyl-2-ethylimidazole, 1-vinyl-
2-phenylimidazole, 1-vinyl-2,
4,5-trimethylimidazole. Further, the monomer represented by the above general formula (c) can be easily obtained by quaternizing the monomer represented by the above general formula (b) with the above-mentioned quaternizing agent. Examples of the monomer represented by the above general formula (2) include dimethylaminoethyl vinyl ether, dimethylaminopropyl vinyl ether, quaternized products thereof, and vinyloxyethylamine. The amount of cationic groups in the modified PVA is required to be 0.1 to 3 mol%. The degree of saponification or degree of polymerization of modified PVA is appropriately selected depending on the purpose and is not particularly limited, but a good gluing effect can usually be obtained when the degree of saponification is selected from the range of 70 to 100 mol%. Also, the degree of polymerization is usually 300~
Selected from a range of 3000. The sizing agent for textile products of the present invention (excluding the warp sizing agent) has the features of an excellent adsorption rate in sizing operations and a high sizing finishing effect even when used alone. . Although the reason why such performance is exhibited is not fully elucidated, the modified PVA that constitutes the present invention
It is presumed that excellent performance is exhibited by the effect of the action of specific cationic groups in the material, which increases the adsorption power for textile products that tend to be negatively charged in water. A sizing agent made of modified PVA of the present invention (however,
Excludes warp glue. ) is effective with modified PVA alone in most cases, but if necessary, other sizing agents such as starch, modified starch (cation-modified starch, carboxymethylated starch, etc.), PVA, modified
PVA (carboxyl group-containing modified PVA, acrylamide modified PVA), carboxymethylcellulose, water-soluble polyester resin, polyethylene glycol, etc. may be used in combination, and if necessary, fragrances, fluorescent paints, pigments, preservatives, and antifungal agents may be used. , a softener may be added. When sizing textile products after washing, the sizing agent of the present invention (excluding warp sizing agent) has a pure content of 0.2 to 5 ml based on the textile product.
It is preferable to use it within a range of % by weight. Compared to conventional PVA-based sizing agents, a good sizing effect can be obtained even when diluted with a sufficient amount of water. It also provides a good finishing agent when used together with dimethyl ether as an aerosol type sizing agent. In addition to laundry starch, it can also be used as a finishing agent for nonwoven fabrics, hard finishing, resin processing (combined with thermosetting resin), etc., and exhibits good adhesion to textile products. Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts and percentages are based on weight unless otherwise specified. Example 1 Trimethyl-(3-acrylamide-3,3-
A copolymer of dimethylpropyl) ammonium chloride and vinyl acetate was saponified to form trimethyl-(3-acrylamide-3,3) as a cationic group.
- Contains 1 mol% of dimethylpropyl) ammonium chloride units, and has a saponification degree of vinyl acetate units.
The viscosity of a 95 mol%, 4% aqueous solution at 20°C (as measured by a Burckfield viscometer; the same applies hereinafter) is
A cationic group-modified PVA of 28.0 cp (centipoise) was obtained. A 1% aqueous solution of this modified PVA was prepared and a gluing test was conducted. Sizing was carried out on both cotton fabric (broad, basis weight 125 g/m ² ) and polyester-cotton blend fabric (polyester/cotton = 65/35, cloth for dress shirts). After soaking each fabric in the size solution, kneading it by hand for 1 minute. , then lightly dehydrated and air-dried. After drying
After ironing at 130℃ and controlling the humidity at 20℃ and 65% RH, the amount of glue adhered was measured by weight measurement, and the bending resistance was determined by the cantilever method according to JIS-1005-1959 (the higher the number, the harder it is). ) was measured.
The results are shown in Table 1. Comparative Examples 1, 2 In place of the cationic group-modified PVA of Example 1, the following
Example 1 except that PVA or modified PVA was used
In the same manner as above, the adhesion amount and bending resistance of the sizing agent were measured. The results are also shown in Table 1. PVA used in Comparative Example 1: PVA with a degree of saponification of 95 mol% and a 4% aqueous solution having a viscosity of 28.0 cp at 20°C. Modified PVA used in Comparative Example 2: Contains 1 mol% of maleic acid units obtained by saponifying a copolymer of monomethyl maleate and vinyl acetate, and the degree of saponification of vinyl acetate units is 95 mol%, 4
% aqueous solution with a viscosity of 28.1 cp at 20℃
PVA. Table 1 shows that the sizing agent of the present invention has a high adsorption rate to cloth and is excellent in sizing effect.

[Table] Examples 2 to 8 In place of the cationic group-modified PVA of Example 1,
Evaluation as a sizing agent was carried out in the same manner as in Example 1 except that the cationic group-modified PVA shown in the table was used. The results are shown in Table 2. Comparative Examples 3 and 4 In place of the cationic group-modified PVA of Example 1, the second
Evaluation as a sizing agent was carried out in the same manner as in Example 1 except that the cationic group-modified PVA shown in the table was used. The results are shown in Table 2. Modified PVA used in Comparative Example 3: Trimethyl (3-crotonamide-2,2-
Contains 4 mol% of dimethylpropyl) ammonium chloride units, and the degree of saponification of vinyl acetate units is 88.
Mol%, viscosity of 4% aqueous solution at 20℃ is 25.1cp
modified PVA. Modified PVA used in Comparative Example 4: Trimethyl (3-crotonamide-2,2-
dimethylpropyl) ammonium chloride unit
Contains 0.05 mol%, and the degree of saponification of vinyl acetate units is
The viscosity of an 88 mol%, 4% aqueous solution at 20℃ is
26.0 cp modified PVA.

[Table] Example 9 Trimethyl-(3-acrylamide-3,3-
A copolymer of dimethylpropyl) ammonium chloride and vinyl acetate was saponified to form trimethyl-(3-acrylamide-3,3) as a cationic group.
- Contains 1 mol% of dimethylpropyl) ammonium chloride units, and has a saponification degree of vinyl acetate units.
The viscosity of a 98 mol%, 4% aqueous solution at 20℃ is
A cationic group-modified PVA of 5.6 cp was obtained. This degeneration
An aerosol type sizing agent was prepared from 100 parts of a 4% aqueous solution of PVA and dimethyl ether. When this aerosol type glue was used to spray glue onto the collar and cuffs of a polyester/cotton blend dress shirt, it had a suitable hardness and smooth finish, and the glue was in good condition.

Claims (1)

[Claims] 1. At least one copolymer unit represented by the following general formula (), (), () or () is contained in the molecule.
A sizing agent for textile products comprising 0.1 to 3 mol% of cationic group-modified polyvinyl alcohol (excluding warp sizing agent). (Here, R ¹ , R ² , R ³ are hydrogen atoms or lower alkyl groups, B is [Formula] or [Formula] R ⁴ , R ⁵ are hydrogen atoms or lower alkyl groups, R ⁶ is lower alkyl group (substituted ), X ^- means an anion, and A means a group connecting the nitrogen atom in B and the nitrogen atom of the amide group.) (Here, R ⁷ , R ⁸ , and R ⁹ each represent a hydrogen atom, a lower alkyl group, or a phenyl group, R ¹⁰ represents a lower alkyl group (which may contain a substituent), and X ⁻ represents an anion. ) (Here, B is [Formula] or [Formula] R ⁴ , R ⁵ is a hydrogen atom or lower alkyl group, R ⁶ is a lower alkyl group (which may contain a substituent), X ^- is an anion, and D is B (respectively means an aliphatic group that connects the nitrogen atom and oxygen atom of)