JPS6231738B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a sizing composition whose main ingredient is a cationic emulsion obtained by a specific production method. More specifically, during the polymerization of fatty acid vinyl esters that are emulsion polymerized in the absence of a cationic polymer, the following general formula (However, R ¹ and R ² represent an alkyl group having 1 to 20 carbon atoms, and R ³ represents an alkyl group having 1 to 20 carbon atoms.
Represents an alkyl group having 20 carbon atoms or an aromatic or alicyclic group having 6 to 15 carbon atoms, and R represents an aliphatic hydrocarbon group having 2 to 6 carbon atoms and 1 ethylene bond. where X represents a chlorine or bromine atom. ), which is obtained by continuously adding and copolymerizing a monomer containing as at least one component a polymerizable quaternary ammonium salt shown in The present invention relates to a glue composition containing a cationic emulsion with a strong cationic emulsion as a main ingredient. Conventionally, cationic emulsions obtained by polymerizing vinyl monomers in the presence of cationic emulsifiers have rarely been produced on an industrial scale, although they can be used for various purposes such as glue compositions. The current situation is that this is not the case. There are various reasons for this, but one is that it lacks stability throughout the entire polymerization process and tends to generate a large amount of coagulum. Although it is not impossible to solve this problem, the cationic emulsifier selected for this purpose is highly toxic and may cause problems in the treatment of emulsion waste liquid. Also, cationic emulsions obtained by polymerizing vinyl monomers in the presence of a cationic emulsifier or emulsions obtained by polymerizing vinyl monomers in the presence of a nonionic emulsifier or using a hydrophilic polymer substance as a protective colloid. Cationic emulsions obtained by adding cationic emulsifiers often have serious deficiencies when used to take advantage of their cationic properties. That is, upon adsorption to an anionic substance, the cationic emulsifier is preferentially removed from the surface of the emulsion particles, causing destabilization of the emulsion particles. As a result, homogeneous adsorption of the emulsion particles to the anionic substance does not occur, making it impossible to achieve the intended purpose when used as a sizing composition, for example. Furthermore, emulsions obtained by using cationic polymers or mixtures of cationic and nonionic polymers as protective colloids do not have the toxicity problems of cationic emulsifiers, but all emulsion particles are cationic. In some cases, the adsorption capacity is not sufficient when adsorbing onto the above-mentioned anionic substance, and the purpose of the adhesive composition cannot be achieved. In view of the above-mentioned shortcomings of the prior art, the inventors of the present invention have conducted intensive studies on a glue composition based on a stable cationic emulsion that has remarkable adsorption ability to negatively charged substances. During the polymerization of fatty acid vinyl esters which are emulsion polymerized in the absence of polymers, the following general formula (However, R ¹ and R ² represent an alkyl group having 1 to 20 carbon atoms, and R ³ represents an alkyl group having 1 to 20 carbon atoms.
R represents an alkyl group having 20 carbon atoms or an aromatic or alicyclic group having 6 to 15 carbon atoms, and R has 2 to 6 carbon atoms and 1 ethylene bond.
represents an aliphatic hydrocarbon group having X, and X represents a chlorine or bromine atom. ) has achieved the above-mentioned intended purpose. We have discovered that it is possible to do this, and have completed the present invention. Specific examples of the polymerizable quaternary ammonium salt represented by the above general formula include 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, 2-hydroxy-3-acryloxypropyltrimethylammonium chloride,
2-hydroxy-3-methacryloxypropyl triethylammonium bromide, 2-hydroxy-3-methacryloxypropyltributylammonium chloride, 2-hydroxy-
3-methacryloxypropylmethylethylbutylammonium chloride, 2-hydroxy-
3-methacryloxypropyldimethylphenylammonium chloride, 2-hydroxy-3
-methacryloxypropyldimethylcyclohexylammonium chloride, etc. These can be used alone or in combination of two or more, and 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride is particularly preferred. Examples of monomers that can be used simultaneously with the above polymerizable quaternary ammonium salt include acrylamide, N-methylolacrylamide, N,N-dimethylacrylamide, hydroxyethylacrylamide, methacrylamide, methyl acrylate, methyl methacrylate, and acrylonitrile. can be mentioned. Of course, the amounts used must be kept within a range that can achieve the purpose of the present invention. In addition, fatty acid vinyl esters used in emulsion polymerization to obtain the cationic emulsion forming the main ingredient of the glue composition of the present invention include:
Vinyl acetate, vinyl propionate, substituted vinyl versatate, etc., and these alone,
Alternatively, two or more types can be used in combination, and vinyl acetate is most preferably used. In addition, styrene, substituted styrene, esters of acrylic acid or methacrylic acid with alcohols having 1 to 12 carbon atoms, acrylonitrile, butadiene, isoprene, ethylene, isobutene, acrylamide, N
-Methyloacrylamide, N,N-dimethylmethacrylamide, methacrylonitrile, divinylbenzene, ethylene glycol dimethacrylate, etc. may be copolymerized without any problem. Examples of the emulsion polymerization method employed to obtain the cationic emulsion forming the main ingredient of the adhesive composition of the present invention include the following. First, in the case of a method in which the fatty acid vinyl ester to be emulsion polymerized is charged all at once, polymerization is started in the presence of a protective colloidal water-soluble polymer such as polyvinyl alcohol or ethyl cellulose, or a nonionic emulsifier, and then the polymerizable quaternary ammonium salt is immediately added. A monomer having at least one component of is continuously added to the polymerization system. The same applies to methods in which fatty acid vinyl ester to be emulsion polymerized is charged in portions or continuously. It can be added to the polymerization system. In other words, no matter what polymerization method is used, it is necessary to continuously add a monomer containing at least one component of a polymerizable quaternary ammonium salt to the polymerization system in conjunction with the polymerization of the fatty acid vinyl ester to be emulsion polymerized. It is essential. As the polymerization initiator, any compound that generates cationic or nonionic free radicals can be used, such as 2,2'-azobis(2-amidinopropane) hydrochloride, hydrogen peroxide, or reduction thereof. Examples include a combination with a reducing agent, kyumene hydroperoxide, t-butyl hydroperoxide, or a combination of these with a reducing agent. When obtaining the cationic emulsion that forms the main ingredient of the glue composition of the present invention, the cationic monomers that are continuously added in the polymerization system include 0.005 to 10 parts by weight per 100 parts by weight of fatty acid vinyl ester to be emulsion polymerized; It is preferably used in an amount of 0.01 to 2 parts by weight. If this amount is too small, the properties as a cationic emulsion will not be fully exhibited, and if it is too large, it will work in the direction of impairing the stability of the polymerization system. Therefore, it is preferable to use it within the above-mentioned range. The effects of the adhesive composition of the present invention will be described in detail below. Traditionally, water-soluble household glues based on polyvinyl alcohol or carboxymethyl cellulose have been used in large quantities because they are inexpensive, but when these glues are applied to clothing, etc., the starched clothing, etc. The current situation is that the fabric has become so hard that it feels like paper, resulting in an extremely poor texture and impairing the feel of the garment. In particularly severe cases, it can cause severe irritation of the skin in areas that come into direct contact with clothing and the like. This is because the polymer used as the main ingredient has a very high glass transition point.
This is thought to be because it is an extremely hard polymer. In addition, these starches adhere to clothing in a low amount, and the polymers that do not adhere to them are discarded, which is uneconomical, and they are also discharged into sewers as wastewater, causing river pollution. In addition, household glues containing polyvinyl acetate emulsions as a main ingredient have recently been used for the reason that they give suitable texture to clothing, but they have various defects. In other words, if the emulsifier used to produce the emulsion is nonionic or anionic, it will have very poor adhesion to negatively charged clothing, etc., and will have a low gluing effect. However, there are many emulsion particles that are not attached, which is extremely uneconomical. On the other hand, when an emulsion containing a cationic emulsifier is used as the main ingredient, the cationic emulsifier in the emulsion separates from the emulsion particles and adheres to the clothing because the clothing is negatively charged when it is pasted. This makes the emulsion unstable and reduces the adhesion of emulsion particles to clothing, etc. In addition, cationic emulsifiers are more or less toxic and toxic to the human body. In addition, a paste based on a cationic emulsion produced using a cationic polymer as a protective colloid or a part of the protective colloid does not have the problems mentioned above in the case of an emulsion polymerized using a cationic emulsifier. As mentioned above, the presence of non-cationized particles may result in insufficient selective adsorption to clothing, which is a major feature of starches based on cationic emulsions. However, the glue composition containing cationic emulsion as a main ingredient obtained by the specific production method of the present invention improves this point, and allows a large amount of polymer to adhere to clothing even at a low concentration of glue. , sufficient bending resistance can be obtained. The paste composition of the present invention may contain an antifoaming agent, an antifungal agent, a fragrance, a fluorescent whitening agent, and the like, if necessary. In particular, plasticizers such as dibutyl phthalate are sometimes added to give starched clothing good hardness and texture. The plasticizer may be added either at the stage of producing the cationic emulsion as the main ingredient or at the stage of blending the emulsion with other additives. In addition, since the cationic emulsion which is the main ingredient in the present invention is extremely stable, the above-mentioned various compounded chemicals can be added without impairing the stability of the emulsion, and a highly stable adhesive composition can be obtained. It will be done. The glue composition obtained in this way is extremely stable, exhibits extremely strong cationic properties, and is composed of an emulsion with a relatively large particle size, so it can be used as a glue component of an extremely excellent household glue. be able to. In other words, the cationic emulsion used as the main ingredient has excellent stability, so it can be used for a long period of time, and when glued, it adheres uniformly to clothing, etc., and it is easy to immerse clothing, etc. in the starch solution.
The size liquid is stable even after repeated pulling operations.
In addition, since this household glue composition has a cationic emulsion as its main ingredient, it easily adheres to negatively charged clothing, etc., and even at low concentrations, the amount of adhesion is large and it is economical. In addition, since the particle size of the cationic emulsion used as the main ingredient is relatively large, it adheres to the intertwined parts of the fibers that make up clothing, and has a positive effect on the hardness and texture of clothing after being glued and ironed. . It also has the advantage that it does not contain cationic emulsifiers that cause problems such as toxicity and coloring during ironing, and does not cause color cast. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples at all. In addition, in the examples, “department”
means "parts by weight" unless otherwise specified. [Example of production of cationic emulsion which constitutes the main ingredient of the glue composition of the present invention] Cationic emulsion No. 1 A portion with a degree of polymerization of 500 and a degree of saponification of 88 mol% was placed in a separable flask equipped with a stirrer and a nitrogen introduction tube. Saponified polyvinyl alcohol (manufactured by Kuraray Co., Ltd.:
After weighing 8 parts of PVA-205) and purging with nitrogen, 100 parts of ion-exchanged water that had been purged with nitrogen was added and dissolved at 90°C. After dissolving, cool to room temperature and use a 50% aqueous solution of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride monomer (Blenmar, manufactured by NOF Corporation).
QA) 0.01 part, acrylamide monomer 0.085 part,
10 parts of vinyl acetate monomer were added. After raising the temperature to 70°C, an aqueous initiator solution consisting of 0.5 parts of 2,2'-azobis(2-amidinopropane) hydrochloride and 10 parts of ion-exchanged water was added. 1.0 hours after the start of polymerization, 2-hydroxy-3 was added to 90 parts of nitrogen-substituted vinyl acetate monomer and 20 parts of ion-exchanged water.
-A monomer aqueous solution containing 0.3 part of a 50% aqueous solution of methacryloxypropyltrimethylammonium chloride monomer (Blenmar QA, manufactured by NOF Corporation) and 0.25 part of acrylamide monomer was added continuously over 3 hours. After the addition was completed, polymerization was carried out for 2 hours to complete the polymerization.
The obtained emulsion (No. 1) exhibited good stability and had a solid content concentration of 47.3%. Cationic emulsion No. 2 Partially saponified polyvinyl alcohol with a degree of polymerization of 500 and a degree of saponification of 88 mol% (manufactured by Kuraray Co., Ltd.) in a separable flask equipped with a stirrer and a nitrogen inlet tube.
After weighing 8 parts of PVA-205) and purging it with nitrogen, 100 parts of ion-exchanged water that had been purged with nitrogen was added and dissolved at 90°C. After dissolving, cool to room temperature,
Add 10 parts of vinyl acetate monomer, raise the temperature to 70°C, and add an aqueous initiator solution consisting of 0.5 parts of 2,2'-azobis(2-amidinopropane) hydrochloride and 10 parts of ion-exchanged water to start polymerization. I let it happen. Immediately after the start of polymerization, a 50% aqueous solution of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride monomer (Blenmar, manufactured by NOF Corporation)
Polymerization was continued while continuously adding a monomer aqueous solution prepared by dissolving 0.002 parts of QA) and 0.013 parts of N-methylolacrylamide monomer in 2 parts of ion-exchanged water over 1.0 hour. Next, 90 parts of nitrogen-substituted vinyl acetate monomer and 18 parts of ion-exchanged water were added to
50 aqueous solution of hydroxy-3-methacryloxypropyltrimethylammonium chloride monomer (manufactured by NOF Corporation: Bremmer QA) 0.018
and N-methylol acrylamide monomer
Polymerization was continued by continuously adding 0.117 parts of a monomer aqueous solution over 3 hours. After the addition was completed, polymerization was carried out for 2 hours to complete the polymerization. The resulting emulsion (No. 2) exhibited good stability and had a solids concentration of 47.5%. Cationic emulsion No. 3 Partially saponified polyvinyl alcohol with a degree of polymerization of 500 and a degree of saponification of 88 mol% (manufactured by Kuraray Co., Ltd.) in a separable flask equipped with a stirrer and a nitrogen inlet tube.
After weighing 8 parts of PVA-205) and purging with nitrogen, 100 parts of ion-exchanged water that had been purged with nitrogen was added and dissolved at 90°C. After dissolving, cool to room temperature,
-Hydroxy-3-methacryloxypropyltrimethylammonium chloride monomer (manufactured by NOF Corporation: Blenmar QA) 0.01 part, acrylamide monomer 0.085 part, and vinyl acetate monomer 10 parts were added. After raising the temperature to 70℃, 2,
2'-azobis(2-amidinopropane) hydrochloride
An initiator aqueous solution consisting of 0.5 parts and 10 parts of ion-exchanged water was added, and after polymerization for 1.0 hours, 90 parts of nitrogen-substituted vinyl acetate monomer and 20 parts of ion-exchanged water were added to 2-hydroxy-3-. A monomer aqueous solution containing 0.03 part of a 50% aqueous solution of methacryloxypropyltrimethylammonium chloride monomer (manufactured by NOF Corporation: Blenmar QA) and 0.25 part of acrylamide monomer was dissolved in 3 parts.
Continuous additions were made over time to continue polymerization. After the addition was completed, polymerization was carried out for 2 hours to complete the polymerization. The obtained emulsion (No. 3) exhibited good stability and had a solid content concentration of 47.2%. Cationic Emulsion Nos. 4 to 6 2-Hydroxy-3-methacryloxypropyltrimethylammonium chloride monomer (Blenmer, manufactured by NOF Corporation: Blenmer) was prepared in the same manner as shown in the production example of Cationic Emulsion No.
The results shown in Table 1 were obtained by changing only the amounts of QA) and acrylamide monomer.

[Production example of cationic emulsion as a comparative example]

Cationic emulsion No. 9 A solid content concentration of 47.3% was obtained using the same method as shown in the production example of cationic emulsion No. 1, except that the 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride monomer and acrylamide were not used. An emulsion (No. 9) was obtained. Cationic Emulsion No. 10 Partially saponified polyvinyl alcohol with a degree of polymerization of 500 and a degree of saponification of 88 mol% (manufactured by Kuraray Co., Ltd.) in a separable flask equipped with a stirrer and a nitrogen inlet tube.
Weighed out 8 parts of PVA-205), purged it with nitrogen, added 100 parts of ion-exchanged water that had been purged with nitrogen, and dissolved it at 90°C. After dissolving, cool to room temperature and use a 50% aqueous solution of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride monomer (Blenmar, manufactured by NOF Corporation).
QA) 0.4 parts, acrylamide monomer 0.335 parts,
10 parts of vinyl acetate monomer were added. After raising the temperature to 70°C, an aqueous initiator solution consisting of 0.15 parts of 2,2'-azobis(2-amidinopropane) hydrochloride and 10 parts of ion-exchanged water was added, and polymerization was carried out for 0.5 hours. Subsequently, 90 parts of nitrogen-substituted vinyl acetate monomer was continuously added over 3 hours. After the addition was completed, polymerization was continued for 2 hours to complete the polymerization. The obtained emulsion (No. 10) had a solid content concentration of 47.4%. Cationic Emulsion No. 11 After purging a separable flask equipped with a stirrer and a nitrogen inlet tube with nitrogen, a 50% aqueous solution of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride monomer (manufactured by NOF Corporation: Bremmer QA) ) and 0.75 parts of acrylamide monomer were added to ion-exchanged water that had been replaced with nitrogen in advance and dissolved at room temperature. After heating to 70℃, 2,2′-azobis(2-amidinopropane)
An aqueous initiator solution consisting of 0.20 parts of hydrochloride and 10 parts of ion-exchanged water was added, and polymerization was carried out for 1 hour. followed by 3.5
After adding 91.5 parts of vinyl acetate monomer and polymerizing for 30 minutes, 91.5 parts of vinyl acetate monomer was continuously polymerized for 100 minutes. During the process, 30 minutes after the start of addition of vinyl acetate monomer, 20 parts of partially saponified polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) aqueous solution with a concentration of 10% by weight was continuously added, and the vinyl acetate monomer was added. I made it end at the same time. After the addition was completed, polymerization was carried out for 2 hours to complete the polymerization. Obtained emulsion (No.11)
The solid content concentration was 50.1%. Cationic emulsion No. 12 Partially saponified polyvinyl alcohol with a degree of polymerization of 500 and a saponification degree of 88 mol% (manufactured by Kuraray Co., Ltd.) in a separable flask equipped with a stirrer and a nitrogen inlet tube.
After weighing 8 parts of PVA-205) and purging with nitrogen, 100 parts of ion-exchanged water that had been purged with nitrogen was added and dissolved at 90°C. After dissolving, cool to room temperature and dissolve 2-methacryloxyethylbenzyldimethylammonium chloride monomer. 0.01 part of acrylamide monomer, 0.085 part of acrylamide monomer, and 10 parts of vinyl acetate monomer were added. After heating to 70℃, 2,2′-azobis(2-amidinopropane)
An aqueous initiator solution consisting of 0.5 parts of hydrochloride and 10 parts of ion-exchanged water was added. Vinyl acetate monomer 90 was further replaced with nitrogen after 1.0 hour had passed after the start of polymerization.
0.3 parts of 2-methacryloxyethylbenzyldimethylammonium chloride monomer and 0.25 parts of acrylamide monomer to 20 parts of ion-exchanged water.
An aqueous monomer solution in which 50% of the monomer was dissolved was continuously added over 3 hours. After the addition was completed, polymerization was carried out for 2 hours to complete the polymerization. The obtained emulsion (No. 12) was unstable, with 7.2% (based on the weight of vinyl acetate monomer) coagulated material observed, and could not be used as a glue composition. Cationic emulsion No. 13 Partially saponified polyvinyl alcohol with a degree of polymerization of 500 and a degree of saponification of 88 mol% (manufactured by Kuraray Co., Ltd.) in a separable flask equipped with a stirrer and a nitrogen inlet tube.
After weighing 8 parts of PVA-205) and purging with nitrogen, 100 parts of ion-exchanged water that had been purged with nitrogen was added and dissolved at 90°C. After dissolving, cool to room temperature and separately polymerize a polymer of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride [[η] in 0.4M NaCl water = 0.65
(dl/g)] were added. Subsequently, 0.01 part of a 50% aqueous solution of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride monomer (Blenmar QA, manufactured by NOF Corporation), 0.085 part of acrylamide monomer, and 10 parts of vinyl acetate monomer were added. After raising the temperature to 70°C, an aqueous initiator solution consisting of 0.5 parts of 2,2'-azobis(2-amidinopropane) hydrochloride and 10 parts of ion-exchanged water was added. 1.0 hours after the start of polymerization, a 50% aqueous solution of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride monomer (manufactured by NOF Corporation: Blenmar) was added to 90 parts of nitrogen-substituted vinyl acetate monomer and 20 parts of ion-exchanged water. QA) 0.3 parts and acrylamide monomer
An aqueous monomer solution in which 0.25 part was dissolved was continuously added over 3 hours. After the addition was completed, polymerization was carried out for 2 hours to complete the polymerization. The obtained emulsion (No. 13) had a solid content concentration of 47.3%. Examples 1 to 8 and Comparative Examples 1 to 5 (Evaluation of performance as a sizing agent) The above-mentioned cationic emulsion No. 1 of the present invention.
Solid content of emulsions No. 1 to No. 8 and cationic emulsions No. 9 to No. 11 and No. 13 as comparative examples
Dibutyl phthalate was added in an amount of 7.5 parts per 100 parts and diluted to a solid content of 0.8% to obtain a thickening solution. Add this paste solution to a bath ratio of 1:20, and
20cm cotton broadcloth and ester/cotton (E/C)
Broad (65% ester) was soaked for 1 minute to form a starch, and after being dehydrated by a household dehydrator for 1 minute, the fabric was air-dried to obtain a starched cloth. Performance evaluation was performed by ironing the starched cloth and cutting it into 2cm x 15cm pieces.
Two types of sensory tests were conducted: bending resistance, which indicates hardness, using the cantilever method, and texture, which is the feeling of thickness of the pasted cloth. (Table 2)

【table】

[Table] As is clear from Table 2, the household pastes of Examples 1 to 8 have greater bending resistance than commercially available products, appropriate hardness, and excellent texture. Next, selective adsorption to cloth, which is the most characteristic property of cationic glues, was compared and studied using the following method for the glues listed in Table 2. Thickness concentration 0.01
% and the E/C broad was immersed so that the bath ratio was 100 (the emulsion solid content was 1.0% by weight based on the cloth), and the adsorption behavior under stirring was investigated from the change in the concentration of the thickener. Changes in the concentration of the glue were determined from a turbidity-concentration calibration curve prepared in advance. Since the pastes of Examples 1 to 8 and Comparative Examples 2 to 4 were all cationic, selective adsorption was observed.
Only the pastes of Examples 1 to 8 showed complete adsorption after 10 hours of immersion, whereas complete adsorption did not occur even after 24 hours of immersion with the pastes of Comparative Examples 2 to 4, and the amount of adsorption was 80%.
It was ~95%. Furthermore, since the pastes of Comparative Examples 1 and 5 (commercially available products) were not cationic, changes in the paste concentration were only observed within the range of error.
It is presumed that the reason why complete adsorption was achieved in this way is that all the emulsion particles in the cationic emulsion, which is the main ingredient of the thickening composition of the present invention, are cationized, which indicates the usefulness of the present invention. is understood.

Claims (1)

[Scope of Claims] 1. During the polymerization of fatty acid vinyl ester that is emulsion polymerized in the absence of a cationic polymer, a monomer containing a polymerizable quaternary ammonium salt represented by the following general formula as at least one component is continuously added. A glue composition whose main ingredient is a cationic emulsion obtained by copolymerizing the cationic emulsion. (However, R ¹ and R ² represent an alkyl group having 1 to 20 carbon atoms, and R ³ represents an alkyl group having 1 to 20 carbon atoms.
R represents an alkyl group having 20 carbon atoms or an aromatic or alicyclic group having 6 to 15 carbon atoms, and R has 2 to 6 carbon atoms and 1 ethylene bond.
represents an aliphatic hydrocarbon group having X, and X represents a chlorine or bromine atom. 2. The adhesive composition according to claim 1, wherein the polymerizable quaternary ammonium salt is used in an amount of 0.01 to 2 parts by weight per 100 parts by weight of the fatty acid vinyl ester.