JPH06206979A - Thermosetting resin aqueous dispersion and fiber finishing agent - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin aqueous dispersion excellent in preservability, etc., by dispersing in an aqueous medium a copolymer prepared from a monomer and a blocked isocyanate group-contg. ethylenic unsaturated monomer formed by reaction among a blocking agent, a specific polyisocyanate and an active hydrogen atom-contg. monomer. CONSTITUTION:The dispersion can be obtained by dispersing in an aqueous medium a copolymer prepared by copolymerization between (A) a blocked isocyanate group-contg. ethylenic unsaturated monomer formed by reaction among (1) a blocking agent (pref. ketone oxime), (2) a secondary or tertiary isocyanate group-bearing polyisocyanate (pref. tetramethylxylylene diisocyanate) and (3) an active hydrogen atom-contg. monomer (e.g. hydroxyethyl (meth) acrylate) and (B) another copolymerizable monomer (e.g. methyl (meth)acrylate) at the weight ratio A/B of pref. (90:10) to (50:50).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aqueous thermosetting resin dispersion and a fiber treating agent.

[0002]

2. Description of the Related Art As an aqueous dispersion of a thermosetting resin, an acrylic resin emulsion to which a blocked isocyanate emulsion is added and blended is known. This type has a drawback that it takes time to mix the two liquids.

On the other hand, examples of the thermosetting resin aqueous dispersion which does not require the trouble of mixing two different kinds of liquids include, for example, polyisocyanates having only a primary isocyanate group such as tolylene diisocyanate and diphenylmethane diisocyanate, and a block. It is known to use a copolymer obtained by polymerizing a monomer obtained by reacting an agent with an active hydrogen atom-containing monomer (A3) as an essential component with another copolymerizable monomer (B). Has been.

[0004]

However, the above-mentioned thermosetting resin aqueous dispersion has advantages and disadvantages, and one in which the blocking agent dissociates at low temperature has poor storage stability, and one having excellent storage stability does not have high temperature. There was a drawback that the blocking agent did not dissociate.

[0005]

The inventors of the present invention have made diligent studies in view of the above situation. As a result, a polymer having a blocked isocyanate group in the skeleton is obtained from a polyisocyanate having a secondary isocyanate group. Was
It has been found that the use of a polymer having a blocked isocyanate group in the skeleton makes it possible to have both storage stability and low-temperature dissociation property.

On the other hand, when it was used as a fiber finish, it was found that the adhesiveness was more remarkably exhibited as compared with other base materials, and the present invention was completed.

That is, the present invention provides a copolymer obtained by polymerizing an ethylenically unsaturated monomer (A) having a blocked isocyanate group and another copolymerizable monomer (B) as essential components. In a thermosetting resin aqueous dispersion liquid dispersed in an aqueous medium, as a monomer (A), a blocking agent (A1), a polyisocyanate having a secondary isocyanate group (A2), and an active hydrogen atom-containing single monomer. Quantum (A
The present invention provides a thermosetting resin aqueous dispersion characterized by using a monomer obtained by reacting with 3) as an essential component, and a fiber treating agent comprising the same.

The present invention provides a blocking agent (A) as an ethylenically unsaturated monomer having a blocked isocyanate group.
1), a polyisocyanate having a secondary isocyanate group (A2), and an active hydrogen atom-containing monomer (A3) are reacted as essential components [hereinafter, abbreviated as monomer (A). To do. ] Is the feature.

The monomer (A) used in the present invention may have any molecular weight, but the number average molecular weight is from 1000 to 60.
It is preferably about 00.

The monomer (A) used in the present invention can be produced, for example, as follows. Polyisocyanate (A2-1) having two isocyanate groups per mol of polyol (A4) having (2 + n) hydroxyl groups (where n is an integer of 1 or more) in the molecule.
(2 + n) moles of are added to obtain a polyisocyanate having (2 + n) secondary or tertiary isocyanate groups, to which an active hydrogen atom-containing monomer (A3) and a blocking agent (A1) are added. Method of adding reaction respectively.

1 mol of a polyisocyanate (A2-1) having two isocyanate groups and an active hydrogen atom-containing monomer (A3) were used to prepare NCO groups / active hydrogen atoms = 2:
A secondary or tertiary isocyanate group-containing ethylenically unsaturated monomer is obtained by reacting at a ratio of 1, while the blocking agent (A1) and the polyisocyanate (A2-1) are NCO group number / activity. The reaction is carried out at a ratio of the number of hydrogen atoms = 2: 1 to obtain an isocyanate in which a secondary or tertiary isocyanate group is blocked with a blocking agent (A1), and a mixture of these has (2 + n) hydroxyl groups. With polyol,
The former / the latter = (2 + n) / n (molar ratio of NCO / OH)
Method of reacting at the ratio of.

The blocking agent (A1) used in the present invention is a compound that seals the secondary or tertiary isocyanate group of the polyisocyanate (A2). This blocking agent (A
In 1), it is dissociated by heating, and an active isocyanate group is reproduced.

Examples of the blocking agent (A1) include phenol, sodium hydrogen sulfite, methylethylketoxime, acetone oxime, and methylisobutylketoxime. Of these, ketone oxime is preferable.

The polyisocyanate (A used in the present invention
2) is a polyisocyanate having at least one secondary or tertiary isocyanate group. The secondary isocyanate group means that the carbon atom to which the isocyanate group is directly bonded has one hydrogen atom,
The primary isocyanate group means that the carbon atom to which the isocyanate group is directly bonded does not have a hydrogen atom.
The primary isocyanate group means that the carbon atom to which the isocyanate group is directly bonded has two hydrogen atoms.

Examples of the polyisocyanate (A2) include tetramethyl xylylene diisocyanate (meta), tetramethyl xylylene diisocyanate (para), lysine diisocyanate, glycerin 1 mol-tetramethyl xylylene diisocyanate 3 mol adduct,
Trimethylolpropane 1 mol-tetramethylxylylene diisocyanate 3 mol adduct, pentaerythritol 1 mol-tetramethylxylylene diisocyanate 4
Examples thereof include a molar adduct and a trimethylolpropane 1 mol-lysine diisocyanate 3 mol adduct. You may use together other polyisocyanate as needed.

The active hydrogen atom-containing monomer (A3) is an ethylenically unsaturated monomer having an active hydrogen atom, for example, hydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate-ethylene oxide 4 mol addition. And hydroxyethyl (meth) acrylate-propylene oxide 4 mol adduct, hydroxyethyl (meth) acrylate-ethylene oxide propylene oxide random adduct, and the like.

Examples of the polyol (A4) having three or more hydroxyl groups in the molecule include glycerin, trimethylolpropane, polyoxyethylenetriol, pentaerythritol, sorbitol and dipentaerythritol. The polyol (A4) includes various diols, for example, low molecular weight diols such as 1,4-butanediol and propylene glycol, polyester diols, polyether diols, polycarbonate diols, polyether ester diols, polymers such as polycaprolactone diols and polyamide diols. A diol may be used in combination.

The ratio of the blocked isocyanate group and the ethylenically unsaturated double bond contained in the monomer (A) is not particularly limited, but is usually 80/20 to 20 /.
Among the 80, it is preferable that the relationship of the number of blocked isocyanate groups in one molecule ≦ the number of ethylenically unsaturated double bonds in one molecule is satisfied.

The copolymer in the present invention is a copolymer of the above-mentioned monomer (A) and another monomer (B) copolymerizable therewith.

As the monomer (B), various known and commonly used ethylenically unsaturated monomers can be used. Examples of the monomer (B) include methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl ( (Meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, acrylonitrile, acrylamide, N-vinylpyrrolidone, vinyl acetate, vinyl propionate, styrene, vinyltoluene, etc. And monofunctional monomers, conjugated dienes such as butadiene and chloroprene, and the like.

Further, a carboxyl group-containing ethylenically unsaturated monomer such as (meth) acrylic acid or maleic anhydride, a polyorganosiloxyl group, a fluoroalkyl group, a phosphoric acid group, an ethylenically unsaturated monomer containing a halogen atom. A monomer may be used.

In addition to the above-mentioned monomers, for example, N-methylol acrylamide, diacetone acrylamide, N
-Butoxymethyl (meth) acrylamide, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and other crosslinkable monomers may be used in combination.

The copolymerization ratio of the monomer (A) and the monomer (B) is not particularly limited, but usually 90/10 to 50/50.
Is.

The thermosetting resin aqueous dispersion of the present invention contains, for example, the monomer (A) and the monomer (B) in the presence of an emulsifier or a polymerization initiator, if necessary, in an aqueous medium. It can be easily obtained by emulsion polymerization. The reaction temperature and time are not limited, but usually 40 to 90 ° C. and 30 minutes to 12 hours.

As the emulsifier used at this time, any known emulsifier can be used. For example, nonionic surfactants such as polyoxyethylene nonylphenol ether, polyoxyethylene polyoxypropylene random adduct monoalkyl ether, and the like, Anionic surfactants such as sodium dodecylbenzene sulfonate may be mentioned. A self-emulsifying polyurethane resin or a self-emulsifying epoxy resin may be used as an emulsifier.

As the polymerization initiator, any conventionally known one can be used, and examples thereof include potassium persulfate, ammonium persulfate, azobisisobutyronitrile and azobisisovaleronitrile. Further, a redox-based initiator system composed of a persulfate, a reducing sulfoxy compound and / or an iron salt may be used.

A chain transfer agent may be additionally used in order to adjust the molecular weight of the obtained copolymer. Examples of the chain transfer agent include lauryl mercaptan, dodecyl mercaptan, mercaptoglycerin, and thioglycolic acid.

In the above polymerization, an organic solvent may be used together with water, if necessary. The aqueous dispersion obtained as described above may be further added with water to remove the organic solvent and unreacted monomers or to adjust the solid content, if necessary.

The method for producing an aqueous dispersion by the emulsion polymerization method has been described above. For example, the monomer (A) and the monomer (B) are copolymerized in an organic solvent to form an organic solvent solution. Alternatively, it may be obtained by another method in which the phase-inverted emulsion is obtained and the organic solvent is removed. The solid content concentration of the aqueous dispersion of the present invention is not particularly limited, but is usually 40 to 60% by weight.

The aqueous dispersion of the present invention can be used as it is as a fiber finish, but if necessary, a water repellent, a water and oil repellent, a flame retardant, an antioxidant, a colorant, a light fastness stabilizer,
By using an adsorbent or the like in combination, a fiber finish having various functionalities can be obtained. Incidentally, the antioxidant and the light resistance stabilizer can be added not only to the dispersion liquid later, but also in the presence thereof, the monomer (A) and the monomer (B) can be emulsion-polymerized.

Of course, if a perfluoroalkyl group-containing ethylenically unsaturated monomer is used as the main component as the monomer (B), the copolymer obtained will be suitable as a water and oil repellent, and the bromine atom The use of a containing monomer or a phosphoric acid group-containing monomer makes it suitable as a flame retardant finishing agent, and a hard monomer as a main component can be used as a hard finish agent.

As the fiber base material when the aqueous dispersion of the present invention is used as a fiber finishing agent, any of the known and conventional ones can be used. For example, natural fibers such as cotton and hemp, rayon, nylon, polyester and polyurethane. Artificial and synthetic fibers such as acrylic, blended fiber and glass fiber,
Inorganic fibers such as carbon fibers can be used. As the fibrous base material, one having an active hydrogen atom in its material is preferred because the adhesion with the copolymer becomes better. In addition, the effects of the present invention are sufficiently exerted on a base material that does not have very good high-temperature durability.

When the aqueous dispersion of the present invention is used as a fiber finishing agent, a treatment bath containing the fiber finishing agent is prepared in advance, and the fiber base material is dipped and impregnated in the treatment bath to obtain the required adhesion amount. It may be squeezed with a mangle roll or the like so as to be dried.

The drying conditions at this time may be the temperature and the time at which the blocking agent of the blocked isocyanate group in the copolymer is dissociated, but the ambient temperature of 80 to 120 ° C. may be used in advance.
~ After drying for 5 minutes to evaporate most of the water, 130 ~
It may be dried at an ambient temperature of 150 ° C. for 2 to 4 minutes.

In the second drying step, it is preferable that the blocking agent for the blocked isocyanate group in the copolymer is dissociated so that the blocked isocyanate group becomes an active isocyanate group. By doing so, the reaction with the fiber base material and the self-crosslinking reaction between the isocyanate groups proceed, and the adhesion between the fiber base material and the fiber finish becomes better. A metal compound such as a tertiary amine or a tin-based metal may be added to promote dissociation.

An example of using the aqueous dispersion of the present invention as a fiber treating agent has been described in detail above. This aqueous dispersion contains, for example, a monomer (B) containing a monomer having 4 or more carbon atoms as a main component. The pressure-sensitive adhesive can be obtained by using the copolymer obtained as described above, or as the carpet backing agent by using the copolymer obtained by using the conjugated diene as the monomer (B). It can be used.

Further, a filler such as titanium oxide, alumina or calcium carbonate may be mixed and used as a paint.

[0038]

EXAMPLES The present invention will now be described in detail with reference to Examples and Comparative Examples. Unless otherwise specified, all parts are by weight, and% by weight.
Indicates "% by weight".

Reference Example 1 (Synthesis of Urethane Acrylate A) 3-Methylpentane adipate 150 having a molecular weight of 500 was placed in a 4-necked flask equipped with a stirrer, a condenser and a thermometer.
Add 0 parts, 134 parts trimethylolpropane, and 1464 parts tetramethylxylylene diisocyanate.
Then, the mixture is heated to 100 ° C. and reacted for 5 hours to give a polyfunctional terminal isocyanate prepolymer (NCO content ratio 4.1.
%) Was obtained.

Next, the temperature of this product is set to 60 ° C., and β
-174 parts of hydroxyethyl methacrylate was added and reacted for 2 hours. Thereafter, 130 parts of methyl ethyl ketoxime was further added and the reaction was continued for 2 hours to obtain a blocked isocyanate group-containing urethane acrylate A.

Reference Example 2 (Synthesis of Urethane Acrylate B) Polyoxypropylene triol 3 having a molecular weight of 3000 was placed in a 4-necked flask equipped with a stirrer, a condenser and a thermometer.
000 parts, tetramethyl xylylene diisocyanate 7
Add 32 parts. After that, the mixture is heated to 100 ° C. and reacted for 5 hours to obtain a polyfunctional terminal isocyanate prepolymer (NC
O content was 3.0%).

Next, the temperature of this product is set to 60 ° C., and β
-116 parts of hydroxyethyl methacrylate was added and reacted for 2 hours. Thereafter, 174 parts of methyl ethyl ketoxime was further added and the reaction was continued for 2 hours to obtain a blocked isocyanate group-containing urethane acrylate B.

Reference Example 3 (Synthesis of Urethane Acrylate C) The same operation as in Reference Example 2 was carried out except that 732 parts of tetramethylxylylene diisocyanate was replaced with 522 parts of tolylene diisocyanate to obtain urethane acrylate C containing a blocked isocyanate group. It was

Reference Example 4 (Synthesis of Urethane Acrylate D) Tetramethylxylylene diisocyanate 7 of Reference Example 2
A blocked isocyanate group-containing urethane acrylate D was obtained by performing the same operation except that 32 parts was replaced with 522 parts of tolylene diisocyanate and 174 parts of methyl ethyl ketoxime was replaced with 208 parts of sodium bisulfite.

Example 1 (Synthesis of aqueous dispersion of thermosetting resin) To a beaker was added 125 parts of ion-exchanged water, and 10 parts of Neugen EA190D [nonionic surfactant manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] was stirred. 15 parts of Prysurf A-215E [anionic surfactant manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] is added and uniformly dissolved. Then, 130 parts of urethane acrylate A of Reference Example 1 above, 250 parts of ethyl acrylate,
100 parts of butyl acrylate, 10 parts of N-methylol acrylamide, and 10 parts of acrylic acid were added, and these monomers were completely emulsified in water to obtain a monomer premix 1.

Stirrer, two dropping funnels, condenser,
A cylindrical flask equipped with a thermometer is completely replaced with nitrogen. Next, 250 parts of ion-exchanged water was added to this, and 1 part of PRYSURF A-215E was added with stirring,
Heat to 70 ° C and add Monomer Premix 1 to 20
Added some. After 15 minutes, 25 parts of a 5% aqueous sodium persulfate solution was added to initiate polymerization for 15 minutes.

Continuing, the remaining monomer premix 1 of 6
30 parts and 5 parts of a 5% aqueous sodium persulfate solution were added dropwise to the mixture over 3 hours to carry out polymerization. After 30 minutes from the completion of the dropping, 50 parts of a 5% sodium persulfate aqueous solution was further added dropwise over 1 hour. After that, the mixture was cooled and filtered through a 200-mesh wire net to obtain Emulsion 1. This emulsion 1
The nonvolatile content was 50%, the viscosity was 300 cps, and the pH was 2.5.

Emulsion 1 was poured into a mold and dried at room temperature to obtain a sheet having a thickness of 0.3 mm. This sheet 10
Dry with hot air for 3 minutes at 0 ° C and 2 minutes at 140 ° C.
Then, the film elongation and the area swelling ratio after immersion in a solvent were measured. The results are shown in Table-1.

The emulsion 1 was diluted with water to a solid content concentration of 15%. A T / C (= 65/35) cotton broad cloth was dipped in this 15% solution, squeezed to 70% solid content by a mangle roll, and then further 1 minute at 100 ° C.
It was dried with hot air at 40 ° C. for 2 minutes. The bending resistance of the obtained work cloth and the bending resistance after 3 times of dry cleaning were measured, and the results are also shown in Table 1.

Example 2 The same procedure was performed except that the urethane acrylate A was replaced with the urethane acrylate B, and the monomer premix 2 was prepared.
Got A similar emulsion 2 was obtained by using this monomer premix 2 in place of the monomer premix 1.
This emulsion 2 has a nonvolatile content of 50% and a viscosity of 240c.
ps, pH 2.4.

A sheet and a work cloth were obtained in the same manner as in Example 1 by using this emulsion 2, and the same test was performed. The results are shown in Table-1.

Comparative Example 1 A monomer premix 3 was obtained in the same manner as in Example 2 except that the urethane acrylate B was replaced with the urethane acrylate C. A similar emulsion 3 was obtained by using this monomer premix 3 in place of the monomer premix 2.

A sheet and a work cloth were obtained in the same manner as in Example 1 using this emulsion 3, and the same test was conducted. The results are shown in Table-1. Comparative Example 2 A monomer premix 4 was obtained by performing the same operation as in Example 2 except that the urethane acrylate B was replaced with the urethane acrylate D. A similar emulsion 4 was obtained by using this monomer premix 4 instead of the monomer premix 2.

A sheet and a work cloth were obtained in the same manner as in Example 1 using this emulsion 4, and the same test was conducted. The results are shown in Table-1.

[0055]

[Table 1]

[0056]

[Table 2]

The test method is as follows. 1) Measurement of sheet physical properties An aqueous dispersion is poured onto a glass plate provided with a mold so that the sheet thickness is 1 mm, and dried at 40 ° C. for 2 days.
Then, the sheet is hot-air dried at a predetermined temperature for a predetermined time and subjected to a test.

2) Bending Resistance of Work Cloth An aqueous dispersion is diluted with water to prepare a resin liquid having a concentration of 15%. Then, cotton broad is impregnated into this solution and squeezed with a mangle roll so that the amount of resin adhered becomes 10% of the weight of the base cloth. Then, it is dried at 100 ° C. for 2 minutes and then at 170 ° C. for 1 minute.

Then, according to JIS, the cantilever method is performed after the bending resistance and dry cleaning.

3) 400 ml of the aqueous dispersion is added to a 500 ml glass container and immersed in a constant temperature water bath adjusted to 40 ° C. ± 2 ° C. to trace changes in the contents.

As can be seen by comparing Example 2 with Comparative Examples 1 and 2, it can be seen that the aqueous dispersion of the present invention has both good storage stability and low-temperature dissociation property. It can be seen that the agent gives a treated cloth having excellent solvent resistance and cleaning resistance.

[0062]

Industrial Applicability The aqueous dispersion of the present invention is of the secondary or tertiary type.
Since a copolymer using a blocked isocyanate group-containing monomer in which the primary isocyanate group is blocked with a blocking agent is used, the dispersion liquid is more stable and has a particularly remarkable effect that it can be processed at a low temperature. Play.

Moreover, when it is used as a fiber finish, a treated cloth having good solvent resistance can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location D06M 13/395 15/564

Claims (6)

[Claims] 1. A copolymer obtained by polymerizing an ethylenically unsaturated monomer having a blocked isocyanate group (A) and another copolymerizable monomer (B) as essential components in an aqueous medium. In a thermosetting resin aqueous dispersion liquid dispersed in, as a monomer (A), a blocking agent (A1), a polyisocyanate (A2) having a secondary or tertiary isocyanate group, and an active hydrogen atom-containing An aqueous thermosetting resin dispersion, comprising a monomer obtained by reacting the monomer (A3) as an essential component. 2. A monomer (A) having a polyol (A4) having three or more hydroxyl groups in the molecule, a polyisocyanate (A2) having a secondary isocyanate group, and a hydroxyl group-containing monomer (A3). The dispersion according to claim 1, which is a monomer having a structure obtained by reacting with a blocking agent (A1). 3. The dispersion according to claim 1, wherein the monomer (A) is a monomer satisfying the relationship of the number of blocked isocyanate groups in one molecule ≦ the number of ethylenically unsaturated double bonds in one molecule. liquid. 4. The dispersion according to claim 1, wherein the polyisocyanate (A2) is tetramethylxylylene diisocyanate. 5. The dispersion according to claim 1, wherein the copolymerization ratio of the monomer (A) and the monomer (B) is 90/10 to 50/50 (weight ratio). 6. A fiber finish comprising the dispersion according to claim 1.