JPH0742078A - Paste composition and spray-type paste article - Google Patents

Abstract

(57) [Summary] [Structure] Polymer and / or monomer of N-vinyl-2-pyrrolidone monomer (hereinafter referred to as monomer (A))
A copolymer of (A) with at least one vinyl monomer other than the monomer (A) capable of copolymerizing with the monomer (A) or a salt thereof (provided that the mole fraction of the monomer (A) is 30% or more. And a 0.5 to 15.0% by weight of the polymer and / or copolymer or a salt thereof in the composition. In addition, a spray type paste article obtained by filling the size agent composition in a spray container such as a trigger type spray container. [Effect] Even after long-term storage, clogging is less likely to occur,
In addition, even if it occurs, it is possible to easily recover the clogging even in a general household and to spray it again by immersing and cleaning the spray components of the spray container in water, lukewarm water, or the like. In addition, when treated with a sizing agent, it imparts sufficient tension to the clothing, and because the sizing agent has good heat resistance, it does not burn even when ironed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sizing agent composition and a spray type sizing agent article obtained by filling the sizing agent composition in a spray container.

[0002]

BACKGROUND OF THE INVENTION There are powder type, liquid type, gel type or spray type of sizing agent for clothes used at home, and many products utilizing each characteristic are commercially available.
Of these, the spray type sizing agent is particularly convenient because it can be used partially and easily on the object to be treated with the sizing agent.

As a spray-type fiber sizing agent, JP-A-53-12
In 2890, a polysaccharide emulsion, a copolymer emulsion of polyvinyl alcohol and vinylpyrrolidone is used as an essential component, and a sizing agent that has an effect of preventing sizing of the paste (precipitation of the sizing agent on the surface of the treated fiber in white) is disclosed. Proposed. However, when this spray agent is filled into a spray container and used, after being used for a long period of time or under low humidity, the sprayed part of the spray container or the passage connecting the paste agent and the spray port is opened. Phenomenon in which it becomes clogged and as a result cannot be sprayed (hereinafter, "clogging")
Say. ) Is likely to occur, and once clogging occurs, it is difficult to recover the clogging and spray again.

An object of the present invention is to prevent clogging even after long-term storage, and even when clogging occurs, spray components (spray port and the liquid in the container and the spray port are connected to water, lukewarm water, etc.). By dipping and washing the parts to be sewn, it is possible to easily recover the clogging even in general households and to spray it again. Furthermore, when treated with a sizing agent, sufficient tension can be imparted to clothing. Also, to provide a paste composition and a spray-type paste article, which have good heat resistance and do not cause charring etc. when ironed with a garment-treated garment, and are particularly suitable for filling and using in a spray container. Is.

[0005]

Under these circumstances, the present inventor has conducted diligent research in order to solve the above-mentioned problems, and as a result, a polymerized product of N-vinyl-2-pyrrolidone monomer and / or its copolymer was obtained. It was found that this object can be achieved by using an aqueous solution of a polymer (salt), and the present invention has been completed.

That is, the present invention provides the following polymer (1) and / or
Alternatively, a paste composition containing an aqueous solution of the polymer (2), wherein the total amount of the polymer (1) and / or the polymer (2) in the entire composition is 0.5 to 15.0% by weight. I will provide a. Polymer (1): A polymer of N-vinyl-2-pyrrolidone monomer (hereinafter referred to as monomer (A)). Polymer (2): A copolymer of the monomer (A) and at least one vinyl monomer other than the monomer (A) capable of copolymerizing with the monomer (A) (hereinafter referred to as the monomer (B)), or a copolymer thereof. Salt (however, in the monomer composition of the copolymer or the salt thereof, the mole fraction of the monomer (A) is 30% or more). The present invention also provides a spray-type paste product obtained by filling the paste composition in a trigger-type spray container, a pump-type spray container, or a pressure-accumulation-type spray container. The present invention will be described below.

<Polymer (1)> Polymer used in the present invention
(1) is a polymer of the monomer (A), and its weight average molecular weight is preferably 1,000 to 6,000,000, more preferably
It is 2,000 to 1,000,000. Polymer (1) has a molecular weight of 1,00
When it is less than 0, sufficient tension performance is not obtained in the garment treated with sizing agent, and when it is more than 6,000,000, the sprayability when spraying the sizing agent obtained (fog condition when sprayed ) Is not good and as a result
It is not preferable because the sizing agent causes a phenomenon such as unevenness on clothing to be treated.

Examples of the polymer of the monomer (A) include PVP K homopolymer series PVP K-15, K-30, K-60 and K-90 (all are trademarks) of ISPE Japan Co., Ltd. . Their chemical structures are, for example:

[0009]

[Chemical 3]

<Polymer (2)> In the present invention, a copolymer of the monomer (A) and the monomer (B) or a salt thereof can also be used [polymer (2)]. In this case, for the preferable range of the molecular weight of the polymer (2) and the reason for this, <Polymer (1)>
Is as described in the explanation.

Examples of the monomer that can be used as the monomer (B) include a water-soluble vinyl monomer, a water-insoluble vinyl monomer, and a mixed monomer of both. Here, as the water-soluble vinyl monomer, specifically, at least one selected from the monomer group consisting of the following (a) to (k) is used. (a) Acrylic acid and its salts (b) Methacrylic acid and its salts (c) Maleic acid and its salts (d) Maleic anhydride (e) 2-Hydroxyethyl acrylic acid and its salts (f) 2-Hydroxyethyl methacryl Acid and its salt (g) 2-Hydroxypropylacrylic acid and its salt (h) 2-Hydroxypropylmethacrylic acid and its salt (i) Acrylamide, methacrylamide, N, N-dialkylacrylamide and N, N-dialkylmethacrylamide (Alkyl group: alkyl group having 1 to 4 carbon atoms) (j) Monomer represented by formula (I), acid salt thereof and quaternary ammonium salt thereof

[0012]

[Chemical 4]

[In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹ and R ^{2 are the} same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyethyl group, or a hydroxypropyl group. x: shows the number of 1-5. ] (K) Monomer represented by general formula (II), its acid salt and its quaternary ammonium salt

[0014]

[Chemical 5]

[Wherein R, R ¹ and R ^{2 have the} above-mentioned meanings] y: shows the number of 1-5. ].

In this case, specific examples of the monomer represented by the general formula (I) include N, N-dimethylaminopropylacrylic acid (or methacrylic acid) amide, N, N-dimethylaminomethylacrylic acid (or methacrylic acid). )
Examples thereof include amide, N, N-dimethylaminoethyl acrylic acid (or methacrylic acid) amide, N, N-dimethylaminobutyl acrylic acid (or methacrylic acid) amide, and the like.

When the monomer represented by the general formula (I) is used as an acid salt, for example, an inorganic acid salt such as HCl, H ₂ SO ₄ , H ₃ PO ₄ , or p-toluenesulfonic acid salt, glycolic acid, When an organic acid salt such as citric acid or succinic acid is used, or when it is used as a quaternary ammonium salt, the monomer represented by the general formula (I) is converted into CH ₃ Cl, (CH ₃ ) by a conventionally known method. _A quaternary ammonium salt of an alkylating agent such as ₂ SO ₄ is used.

As examples of the monomer represented by the general formula (II), acrylic acid-N, N-dimethylaminoethyl, acrylic acid-N, N-dimethylaminomethyl, acrylic acid-N, N
-Dimethylaminobutyl, acrylic acid-N, N-dimethylaminopropyl, methacrylate-N, N-dimethylaminoethyl, methacrylate-N, N-dimethylaminomethyl,
Methacrylic acid-N, N-dimethylaminobutyl, methacrylic acid-N, N-dimethylaminopropyl, acrylic acid-N,
N-diethylaminoethyl, acrylic acid-N, N-diethylaminomethyl, acrylic acid-N, N-diethylaminobutyl, acrylic acid-N, N-diethylaminopropyl, methacrylic acid-N, N-diethylaminoethyl, methacrylic acid-N, N-diethylaminomethyl, methacrylic acid-N, N
-Diethylaminobutyl, methacrylic acid -N, N-diethylaminopropyl and the like can be mentioned.

Further, the monomer represented by the general formula (II) can be used as an acid salt or a quaternary ammonium salt as in the case of the monomer represented by the general formula (I).

Examples of the water-insoluble monomer in the monomer (B) include vinyl acetate and N-vinyl-2-
Caprolactam, ethylene, propylene, n-butylene, isobutylene, n-pentene, isoprene, 2-methyl-1-butene, n-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl- 1-
Examples include pentene and 2-ethyl-1-butene. Of these, vinyl acetate and N-vinyl-2-caprolactam are particularly preferable.

In the monomer composition of the polymer (2) composed of two kinds of monomers as described above, the molar fraction of the monomer (A) is 30% or more, preferably 40% or more, and more preferably
50% or more. In the monomer composition of the polymer (2), in the case of a copolymer or a salt thereof in which the mole fraction of the monomer (A) is less than 30%, good solubility in water is not achieved and, as a result, in the paste composition. The object of the present invention cannot be achieved.

As the monomer (B), a water-soluble vinyl monomer, a water-insoluble vinyl monomer or a mixed monomer of both are used, but the use of a water-soluble vinyl monomer is preferable for the copolymer or its salt against water. It is preferable because it achieves high solubility.

Polymer (2) which is the main component of the sizing agent of the present invention
As the salt, a salt of a copolymer of the monomer (A) and the monomer (B) can be used. Examples of such salts include metal salts such as lithium, sodium and potassium, ammonium salts as monovalent salts, and organic amine salts such as mono-, di- or triethanolamine, morpholine, ethylamine and butylamine. Examples of the salt include alkaline earth metal salts such as calcium, magnesium and barium, organic amine salts such as ethylenediamine and hexamethylenediamine, and examples of trivalent salts include aluminum salts, organic amine salts such as diethylenetriamine, and polyethyleneimine. Examples include polyvalent organic amines. As the salt, a sodium salt is particularly preferable from the viewpoint of solubility of the copolymer salt in water and production economy.

The copolymer of the monomer (A) and the monomer (B) can be obtained by a conventionally known radical polymerization or the like under normal pressure or under pressure. Acetone as a polymerization solvent
As the polymerization initiator, azobisisobutyronitrile or the like can be used. The polymerization temperature and time vary depending on the combination of the polymerization solvent and the monomer used, but generally 40
Suitable is 90 ° C for 5-20 hours.

The polymer (2) used in the present invention can also be obtained as a commercial product, for example, PVP / VA copolymer series PVP / VA735 of ISPE Japan Co., Ltd.
(Both are trademarks) and the chemical structures are as follows, for example.

[0026]

[Chemical 6]

[Wherein q, r: q + r represents the degree of polymerization, p
/ Q = 7/3 (p is the polymerization degree of the monomer (A)). ]
In addition, the company's copolymer series Copolymer 845, Copo
lymer 937, Copolymer 958 (both are trademarks) and the like, and their chemical structures are, for example, as follows.

[0028]

[Chemical 7]

Further, GAFQUAT 734, GAFQUAT 755N (both are trade marks manufactured by ISPE Japan Co., Ltd.) and the like can be mentioned, and their chemical structures are, for example, as follows.

[0030]

[Chemical 8]

The followings are also exemplified (all are trademarks of ISPE Japan Co., Ltd.).

[0032]

[Chemical 9]

<Sizing Agent Composition> The sizing agent composition of the present invention contains an aqueous solution of the polymer (1) and / or the polymer (2) and contains the polymer (1) and / or the polymer in the composition. The total amount of objects (2) is 0.5
It is characterized in that it is about 15% by weight. If the total amount is less than 0.5% by weight, sufficient tension cannot be obtained, while 15% by weight
If it exceeds, the composition has a high viscosity and the spraying properties are not good when sprayed, and it is disadvantageous from an economical point of view. The fact that these polymers are in the state of an aqueous solution means that they are a light scattering photometer (eg, Otsuka Electronics Co., Ltd. light scattering photometer ELS-70).
0) (Measurement wavelength 633 nm) confirms that particles with a particle size of 10 nm or more are not detected.

In the present invention, when the aqueous solution of the polymer (1) and / or the polymer (2) is not used, for example, when it exists in an emulsion state, the aforementioned clogging occurs when the paste composition is used. If this phenomenon occurs, it is difficult to recover and it becomes impossible to spray again.

When the polymer (1) and the polymer (2) are used in combination, the weight ratio thereof is not limited, but [polymer (1)] /
[Polymer (2)] = 100/0 to 0/100, preferably 100
/ 0 to 5/95, and more preferably 95/5 to 10/90.

The sizing agent composition of the present invention further comprises, as optional components, polyvinyl alcohol, modified starch, cellulose derivative (carboxymethyl cellulose, hydroxyalkyl cellulose, etc.), water-soluble vinyl polymer (polystyrene sulfonate, etc.). The polymer can be blended in an amount of 0 to 50% by weight in order to improve the tension.

As an iron adhesion preventive agent, an organic acid (citric acid, malic acid, benzoic acid, tartaric acid, etc.), polyethylene glycol, glycerin, polypropylene glycol, etc. should be blended in the paste composition in an amount of 0 to 10% by weight. Further, as an iron slip agent or an antifoaming agent, silicone or the like can be blended in the composition in an amount of 0 to 10% by weight, and as a penetrating agent, lower alcohol (ethyl alcohol, propyl alcohol, etc.), polyoxyethylene alkyl ether, etc. Can be added to the paste composition in an amount of 0 to 10% by weight.

In addition, additives such as fluorescent dyes, bactericides, fragrances, and fragrance solubilizers (ethylene glycol, propylene glycol, dipropylene glycol, etc.) may be added.

<Spray-type sizing agent article> The sizing agent composition of the present invention is a trigger-type spray container (a type in which the air pressure in the container is increased by operating the trigger of the container to inject the liquid in the container to the outside). Container), a pump type spray container (a type of container in which the air pressure in the container is increased by operating the pump of the container to inject the liquid in the container to the outside), a pressure accumulating spray container (a container equipped with a pressure accumulator) However, by increasing the air pressure in the container via a pressure accumulator, a container of a type that injects the liquid in the container to the outside), or an aerosol spray container (liquefied propane, liquefied butane, and a mixture thereof, or A container in which a propellant such as dimethyl ether is filled in a container, and the pressure of the propellant is used to fill a container in which the liquid in the container is ejected to the outside), It is use. Among these, the trigger type spray container, the horn type spray container, and the pressure accumulating type spray are particularly preferable in terms of safety because a combustible propellant is not used.

When an aerosol type spray container is filled with the paste composition of the present invention to prepare a spray type paste article, the weight ratio of the propellant to the paste composition of the present invention is (propellant) /
(Sizing agent composition of the present invention) = (3/97) to (40/60) is preferable, and (5/95) to (30/70) is more preferable.

[0041]

EFFECTS OF THE INVENTION According to the present invention, clogging is unlikely to occur even after long-term storage, and even if clogging occurs, it can be clogged even in ordinary households by immersing and washing the sprayed parts in water, lukewarm water, etc. A spray-type adhesive article that can be easily recovered and sprayed again can be obtained. Furthermore, when the spray-type sizing agent article of the present invention is capable of imparting sufficient tension to the garment when treated with the sizing agent, and the heat resistance of the sizing agent is good, when the sizing agent-treated clothing is ironed Does not cause charring.

[0042]

EXAMPLES Examples will be shown below to more specifically describe the present invention, but the present invention is not limited to these examples.

<Preparation of paste composition> Monomers (A) and monomers (B) shown in Tables 1 and 2 were (co) polymerized at a molar ratio shown in Tables 1 and 2 (using acetone as a solvent and using azobisiso Using butyronitrile as an initiator, polymerization temperature 40-90 ℃, polymerization time 5
Polymerization or copolymerization product obtained by polymerizing for ~ 20 hours) is dissolved in water to prepare an aqueous solution having a concentration of 5.0% by weight,
Various paste compositions were obtained.

<Evaluation of Tensile Performance> A trigger type container was filled with the sizing agent composition prepared as described above, and the polyester / polyester /
Cotton = 65/35 (%) Broad 60th cloth with 100% owf (of
The sizing composition was sprayed evenly to give a weight fabric), the temperature scale of the iron was changed to "cotton", and the iron was ironed and dried. After conditioning the humidity at 20 ° C for 12 hours at 65% relative humidity, the tension performance was evaluated by the cantilever method (JIS L 1096).

<Evaluation of Spray State> The spray state was visually evaluated. The score has the following six levels. 1 It becomes a very uniform mist. 2 It becomes a uniform mist. 3 It becomes a fog, but partly becomes coarse droplets. 4 It becomes fog, but it becomes partly streaky. 5 It doesn't become fog. 6 Cannot spray.

<Evaluation of Clog Recoverability of Glue Treatment Article> Clog property: after spraying under the conditions of 30 ° C. and 20% relative humidity,
Leave for 1 week → Repeat the spraying cycle 10 times. The spray state at the 10th cycle was visually evaluated. The score was the same as in the above-mentioned 6-stage evaluation of the spray state.・ Recovery: 40 ° C for sizing agent products evaluated for clogging
The sprayed parts were immersed in the above water for 30 minutes and then sprayed, and the sprayed state was visually evaluated. The score is 6 of the above evaluation of the spray state.
Same as step.

<Evaluation of heat resistance of sizing agent> Using the sizing agent of the present invention, 100% owf (of weight) was applied to cotton broad # 60 cloth.
5 sprays and 5 irons each
Repeated times, but no charring occurred.

[0048]

[Table 1]

[0049]

[Table 2]

Note) * 1: Light scattering photometer (Otsuka Electronics Co., Ltd. light scattering photometer ELS
The particle size of the particles in the product of the present invention was measured at -700, measurement wavelength 633 nm), and no particles having a particle size of 10 nm or more were detected. * 2: Molecular weight was measured by Gel Permeation Chromatography.

[Procedure amendment]

[Submission date] October 26, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 3

[Correction method] Change

[Correction content]

[Chemical 1] [In formula, R: A hydrogen atom or a C1-C4 alkyl group is shown. R ¹ and R ^{2 are the} same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyethyl group or a hydroxypropyl group. x: shows the number of 1-5. ] (K) Monomer represented by general formula (II), its acid salt and its quaternary ammonium salt

[Chemical 2] [In the formula, R ¹ , R ¹ and R ² are as defined above. y: shows the number of 1-5. ]

Claims (4)

[Claims] 1. The following polymer (1) and / or polymer
A paste composition comprising the aqueous solution (2), wherein the total amount of the polymer (1) and / or the polymer (2) in the entire composition is 0.5 to 15.0% by weight. Polymer (1): A polymer of N-vinyl-2-pyrrolidone monomer (hereinafter referred to as monomer (A)). Polymer (2): A copolymer of the monomer (A) and at least one vinyl monomer other than the monomer (A) capable of copolymerizing with the monomer (A) (hereinafter referred to as the monomer (B)), or a copolymer thereof. Salt (however, in the monomer composition of the copolymer or the salt thereof, the mole fraction of the monomer (A) is 30% or more). 2. In the monomer composition of the monomer (B),
The paste composition according to claim 1, which contains at least one water-soluble vinyl monomer. 3. The water-soluble vinyl monomer has the following (a) to
The mold paste composition according to claim 2, which is at least one selected from the group of monomers consisting of (k). (a) Acrylic acid and its salts (b) Methacrylic acid and its salts (c) Maleic acid and its salts (d) Maleic anhydride (e) 2-Hydroxyethyl acrylic acid and its salts (f) 2-Hydroxyethyl methacryl Acid and its salt (g) 2-Hydroxypropylacrylic acid and its salt (h) 2-Hydroxypropylmethacrylic acid and its salt (i) Acrylamide, methacrylamide, N, N-dialkylacrylamide and N, N-dialkylmethacrylamide (Alkyl group: alkyl group having 1 to 4 carbon atoms) (j) Monomer represented by formula (I), acid salt thereof and quaternary ammonium salt thereof [In formula, R: A hydrogen atom or a C1-C4 alkyl group is shown. R ¹ and R ^{2 are the} same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyethyl group or a hydroxypropyl group. x: shows the number of 1-5. (K) Monomer represented by the general formula (II), its acid salt and its quaternary ammonium salt [In the formula, R ¹ , R ¹ and R ² are as defined above. y: shows the number of 1-5. ] 4. A spray type paste article obtained by filling the size agent composition according to claim 1 in a trigger type spray container, a pump type spray container or a pressure accumulating type spray container.