JP2656130B2 - Aqueous resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial application field) Recently, graft block polymers have been widely used in industry. In particular, it is being actively developed in the field of polymer alloys. In the field of dyes, research on graft block polymers is also active in order to impart polymer functionality. The present invention provides α, β using a high molecular urethane initiator obtained by reacting a diol containing an azo group with a diisocyanate in aqueous conversion of a urethane resin.
It relates to an aqueous resin composition obtained by polymerizing a water-soluble monomer having an unsaturated double bond, a plastic base,
The present invention provides industrially extremely useful materials that can be applied to a wide range of uses, such as metal, paper, cloth, woodwork, and inorganic base materials.

(Prior Art) Conventionally, a method of using a water-soluble raw material as a polyol component of a urethane resin has been used for making a urethane resin aqueous. For example, a method in which a water-soluble oligomer such as polyethylene glycol is used as a raw material polyol, a method in which a sulfonic acid group-containing compound such as aminosulfonic acid is used, a method in which a carboxylic acid group-containing compound such as polyhydroxycarboxylic acid is used There is a method of introducing a tertiary amino group and neutralizing with an acid, or using a compound that is converted into a quaternary ammonium salt with a quaternizing agent, but a water-soluble raw material is used as a polyol component of the urethane resin. Because of the method used, there was a drawback that the resin design was limited. Also known are a method of blocking a urethane prepolymer having a terminal isocyanate group with bisulfite, and a method of producing a high-molecular-weight urethane in a solvent system, forcibly emulsifying the urethane with an appropriate emulsifier, and appropriately collecting the solvent. ing.
However, in these methods, the bisulfite method has poor stability. In addition, the emulsification method has a drawback such as an extreme decrease in water resistance due to an emulsifier or the like.

[Configuration of the invention]

(Means for Solving the Problems) The present invention improves the above-mentioned drawbacks, and uses a high molecular urethane initiator obtained by reacting a diol containing an azo group with a diisocyanate to form a carboxylic acid group or an amino group with an α, β non-alkyl group. The present invention relates to a method for producing an aqueous resin, characterized in that a water-soluble monomer having a saturated double bond is polymerized and made aqueous by alkali or quaternization. The present invention also provides an α, β-unsaturated double using a polymeric urethane initiator obtained by reacting 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) propioamide) with diisocyanate. The present invention relates to a method for producing an aqueous resin, which comprises polymerizing a water-soluble monomer having a bond.
This is because a highly reactive diisocyanate is used so that it can be polymerized by reliably reacting with a diol containing an azo group. That is, it is characterized in that a high molecular urethane initiator is first produced before polymerizing an acrylic monomer, and a diol containing an azo group is used as a diol component of a urethane resin. The method of introduction may be such that the diisocyanate is reacted with a diol containing an azo group, and then, if necessary, is reacted with another diol component to extend the chain. Further, after a urethane prepolymer is produced from a general diol and diisocyanate in advance, a diol containing an azo group may be reacted. The present invention is directed to a method for producing an aqueous resin in which a water-soluble monomer having an α, β unsaturated double bond is polymerized using these polymeric urethane initiators. An object of the present invention is to provide a novel water-based resin having characteristics such that flexibility is obtained despite high film hardness.

Examples of the diisocyanate in the present invention include aliphatic, aromatic, alicyclic and diisocyanates. For example, diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), naphthalene diisocyanate, p-phenylene diisocyanate, trans-1,
4-cyclohexane diisocyanate (CHDI), 1,3-bis- (isocyanatomethyl-benzene, 4,4′-dicyclohexylmethane diisocyanate (H ₁₂ MDI), 1,3-
Bis- (isocyanatomethyl) -cyclohexane (H ₆ XD
I), hexamethylene diisocyanate (HDI), 3-isocyanatomethyl-3,5,5'-trimethylcyclohexyl isocyanate (IPDI), meta-tetramethyl xylene diisocyanate or para-tetramethyl xylene diisocyanate (m-TMVDI, p- TMXDI) and the like, but are not limited thereto. For applications where the weatherability of the cured polymer is important, for example, CH
_{DI, H 12 MDI, H 6} XDI, HDI, IPDI, m-DMXDI or, p
-It is preferred to use aliphatic or cycloaliphatic diisocyanates such as TMXDI.

The azo group-containing diol used in the present invention for producing a high molecular urethane initiator includes 2,2'-azobis (2-cyanopropanol) and 2,2'-azobis (2-
Methyl-N- (2-hydroxyethyl) -propioamide) and azo-bis-isobutyric acid-di-2-hydroxyethylamide, but are not limited thereto. Any diol containing an azo group can be used.

It is also possible to use a general diol as a chain extender. These diols have at least two hydrogen atoms capable of reacting with isocyanates and generally have a molecular weight of 10
Up to 000 compositions. For example, ethylene glycol, propylene glycol, butylene glycol, 1,6
Diols such as hexanediol, 1,8-octanediol, neopentyl glycol, cyclohexanedimethanol, pentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyether glycol, polyester glycol, and liquid polyolefins having hydroxyl groups at both ends. In addition, silicon diol, fluorodiol, and the like can be used to increase the weather resistance. For example, 1,3-bis (2-hydroxyhexafluoroisopropyl) benzene, 1,4
-Bis (2-hydroxyhexafluoroisopropyl)
Benzene, 1,1,2,3,3, pentahydroperfluoroundecane-1,2, -diol, 1,1,2,3,3-pentahydroperfluorononane-1,2-diol, hexafluorobisphenol A, X-22-160AS, X-22-60A, X-22-160B, X-
22-160C (Shin-Etsu Chemical Co., Ltd.), PS197, PX1
01 (all manufactured by Chisso Corporation) and the like, but are not limited thereto.

As the water-soluble monomer having an α, β unsaturated double bond, those having a carboxylic acid group, an amino group, a sulfonic acid group, a hydroxyl group, and an amide group can be used.

Examples of the water-soluble monomer having a carboxylic acid group include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, crotonic acid, and the like.
The monomer is not necessarily limited to these, and may be any monomer that can be easily made aqueous with an alkali such as ammonia, an organic amine, or sodium hydroxide.

Allylamine, N, N-dimethylaminoethyl methacrylate, N, N-
Examples include diethylaminoethyl methacrylate, but are not necessarily limited thereto, and may be any as long as they can be quaternized and made aqueous. For example, those which can be quaternized by reacting an organic amine with vinylpyridine or glycidyl methacrylate may be used.

Depending on the application, other water-soluble monomers or functional monomers can be used, and a monomer having an α, β unsaturated double bond can be used if necessary. Specifically, the following are mentioned.

Examples of the monomer having an α, β unsaturated double bond include acrylic acid (C 1-22) esters: for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, Methacrylic acid esters (1 to 22 carbon atoms) such as ethylhexyl acrylate, glycidyl acrylate, and methyl glycidyl acrylate: for example, methyl methacrylate, ethyl methacrylate, n-
Butyl methacrylate, iso-butyl methacrylate, t
hydroxyl-containing vinyl monomers such as ert-butyl methacrylate, 2-ethylhexyl methacrylate, and glycidyl methacrylate: other monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate: styrene; Monomers having an α, β unsaturated double bond, such as vinyltoluene, acrylonitrile, vinyl chloride, vinyl acetate, vinylidene chloride, vinylpyrrolidone, etc., may be mentioned, but any polymer which is basically polymerized by a radical may be used. It is not something to be done. In use, there is no problem as long as one or more of these can be copolymerized with the above-mentioned water-soluble monomer having an α, β unsaturated double bond to form an aqueous solution.

The reason that a polymer obtained by polymerizing a water-soluble monomer using a high molecular weight urethane initiator can be made water-soluble is not always clear, but the acrylic urethane block copolymer generated by the high molecular weight urethane initiator is composed of an acrylic resin and a urethane resin. It is presumed that the compatibility with water is improved and that the water-soluble acrylic resin acts as an emulsifier.

An amino resin and / or an epoxy resin can be further added to the aqueous resin obtained by the production method of the present invention, if necessary. Such an added resin acts as a crosslinking agent, forms a stronger film, and can impart water resistance, alkali resistance, acid resistance, and solvent resistance. Examples of the amino resin include conventionally known urea-formaldehyde polycondensates modified with monohydric alcohols such as methanol and butanol, and monomeric and polymeric melamine resins and benzoguanamine resins. Further, the epoxy resin is cross-linked by an addition reaction between an epoxy group in the molecule and a hydroxyl group or an amine group in the resin, so that a stronger film can be formed. Such epoxy resins include polyphenol glycidyl ethers having an average molecular weight of at least about 350 or more, preferably about 350 to 3000 and an epoxy equivalent of 150 to 3000, preferably 200 to 2000. The mixing ratio of the amino resin and / or the epoxy resin to the aqueous resin is 40/60 to 5/95, preferably 30/70 to 10/90 in weight percentage. If the amount of the amino resin and / or the epoxy resin exceeds the above range, the physical properties tend to decrease. If the amount is less than the above range, the effect as a crosslinking agent is not sufficient. Furthermore, additives such as pigments, fillers, plasticizers, pigment dispersants, thickener defoamers, and leveling agents can be used in combination.

Examples will be described below. However, all figures indicate parts by weight.

Example 1 1) Duranate D-101 (Note 1) 15 parts 2) Ethylene glycol 2.34 parts 3) Dibutyltin dilaurate 0.01 parts 4) Dioxane 300 parts 5) 2,2'-azobis (2-cyanopropanol) 1
Part 6) 0.74 parts of n-butanol 7) 20 parts of N, N-dimethylaminoethyl methacrylate 8) 10 parts of ethyl acrylate 9) 14.1 parts of acetic acid 10) 200 parts of water 1) to 4) are reflux condenser, stirrer, internal Place in a four-necked flask equipped with a thermometer and nitrogen
Incubate at ℃ for 1 hour. Thereafter, the mixture was cooled to room temperature, and 5) was added, followed by a reaction for 8 hours. Then 6), 7),
8) is added, the temperature is raised to 90 ° C., and the mixture is stirred for 3 hours. Thereafter, 9) and 10) are added to make aqueous. The solvent was removed to obtain a stable aqueous resin having a solid content of about 30%. The molecular weight of the resin thus obtained was about Mw = 38000. The obtained film was a flexible and transparent film.

(Note 1) Bifunctional hexamethylene diisocyanate-based urethane oligomer (manufactured by Asahi Chemical Industry Co., Ltd.) Example 2 1) 15 parts of duranate D-201 2) 2.34 parts of 1,6 hexanediol 3) 0.01 part of dibutyltin dilaurate 4) dioxane 300 parts 5) 2,2'-azobis (2-cyanopropanol) 1
Part 6) 0.74 parts of isopropyl alcohol 7) 20 parts of methacrylic acid 8) 10 parts of ethyl acrylate 9) 14.1 parts of cold water 10) 200 parts of water 1) to 4) are supplied with a reflux condenser, a stirrer, an internal thermometer, and a nitrogen inlet pipe. Into a four-necked flask equipped with
Incubate at ℃ for 1 hour. Thereafter, the mixture was cooled to room temperature, and 5) was added, followed by a reaction for 8 hours. Then 6), 7),
8) is added, the temperature is raised to 90 ° C., and the mixture is stirred for 3 hours. Thereafter, 9) and 10) are added to make aqueous. Then, the solvent was removed to obtain a stable aqueous resin having a solid content of about 30%. The molecular weight of the resin thus obtained was about Mw = 41,000. The obtained film was a flexible and transparent film.

Example 3 1) 15 parts of isophorone diisocyanate 2) 5.56 parts of 1,6 hexanediol 3) 0.01 part of dibutyltin dilaurate 4) 300 parts of dioxane 5) 2,2'-azobis (2-methyl-N- (2-hydroxyethyl) ) -Propionamide 1 part 6) Isopropyl alcohol 0.74 part 7) Methacrylic acid 20 parts 8) β-hydroxyethyl methacrylate 10 parts 9) Ethyl acrylate 10 parts 10) Ammonium (28%) 7.7 parts 11) Water 200 parts 1) ~ 4) into a four-necked flask equipped with a reflux condenser, a stirrer, an internal thermometer, and a nitrogen inlet tube, and
Incubate at ℃ for 1 hour. Thereafter, the mixture was cooled to room temperature, and 5) was added, followed by a reaction for 8 hours. Then 6), 7),
8) and 9) are added, the temperature is raised to 90 ° C., and the mixture is stirred for 3 hours.
Thereafter, 10) and 11) are added to make aqueous. The solvent was removed to obtain a stable aqueous resin having a solid content of about 30%. The molecular weight of the resin thus obtained was about Mw = 52,000. The obtained film was a flexible and transparent film.

Example 4 1) 15 parts of duranate D-101 2) 1.53 parts of ethylene glycol 3) 0.01 part of dibutyltin dilaurate 4) 300 parts of dioxane 5) 2,2'-azobis (2-cyanopropanol) 1
Part 6) n-butanol 0.74 part 7) N, N-dimethylaminoethyl methacrylate 20 parts 8) ethyl acrylate 10 parts 9) acetic acid 7.7 parts 10) water 200 parts 11) Epon 828 (Note 2) 10 parts 1)- 4) into a four-necked flask equipped with a reflux condenser, a stirrer, an internal thermometer, and a nitrogen inlet tube, and
Incubate at ℃ for 1 hour. Thereafter, the mixture was cooled to room temperature, and 5) was added, followed by a reaction for 8 hours. Then 6), 7),
8) is added, the temperature is raised to 90 ° C., and the mixture is stirred for 3 hours. Thereafter, 9) and 10) are added to make aqueous. The solvent was removed to obtain a stable aqueous resin having a solid content of about 30%. The molecular weight of the resin thus obtained was about Mw = 38000. 11) was added to 50 parts of the obtained aqueous resin, and a film was formed in an atmosphere at 50 ° C. The obtained film was a flexible and transparent film.

(Note 2) Bisphenol A type epoxy resin (manufactured by Ciba Geigy) Comparative Example 1 1) 15 parts of duranate D-101 2) 1.53 parts of ethylene glycol 3) 0.01 part of dibutyltin dilaurate 4) 300 parts of dioxane 5) 0.74 part of n-butanol 6) 20 parts of N, N-dimethylaminoethyl methacrylate 7) 10 parts of ethyl acrylate 8) 0.4 part of 2,2'-azoisobutyronitrile 9) 7.7 parts of acetic acid 10) 200 parts of water 1) -4) Into a four-necked flask equipped with a stirrer, stirrer, internal thermometer, and nitrogen inlet tube.
Incubate at ℃ for 1 hour. After that, 5),
6), 7) and 8) are added, the temperature is raised to 90 ° C., and the mixture is stirred for 3 hours. Thereafter, 9) and 10) are added to make aqueous. Then, the solvent was removed to obtain an aqueous resin having a solid content of about 30%. This immediately separated into two layers. The molecular weight of this resin is about
Mw = 32000. The resulting film was flexible but opaque.

Comparative Example 2 1) 15 parts of duranate D-101 2) 5.56 parts of 1,6 hexanediol 3) 0.01 part of dibutyltin dilaurate 4) 300 parts of dioxane 5) 0.74 part of n-butanol 6) 20 parts of methacrylic acid 7) ethyl acrylate 10 Part 8) 2,2'-azoisobutyronitrile 0.4 part 9) cheap water (28%) 14.1 part 10) water 200 parts 1) to 4) are reflux condenser, stirrer, internal thermometer, nitrogen inlet pipe Into a four-necked flask equipped with
Incubate at ℃ for 1 hour. After that, 5),
6), 7) and 8) are added, the temperature is raised to 90 ° C., and the mixture is stirred for 3 hours. After that, 9) and 10) were added to make it aqueous,
It quickly aggregated and could not be made aqueous.

[Effects of the present invention] Since the aqueous resin obtained by the production method of the present invention is aqueous, there is no danger of fire, plastic base materials, metals,
It is considered to be an industrially useful material that can be applied to a wide range of uses such as paper, cloth, woodwork, and inorganic base materials.

Claims (3)

(57) [Claims] 1. A water-soluble monomer having a carboxylic acid group or an amino group and an α, β unsaturated double bond is polymerized using a high molecular urethane initiator obtained by reacting a diol containing an azo group with a diisocyanate. A process for producing an aqueous resin, which comprises converting the aqueous resin to an aqueous solution by alkali, quaternization, or the like. 2. The method for producing an aqueous resin according to claim 1, wherein 2,2′-azobis (2-cyanopropanol) is used as the diol containing an azo group. (3) 2,2'-azobis (2-methyl-N- (2
-Hydroxyethyl) propioamide) and diisocyanate using a high molecular urethane initiator,
A method for producing an aqueous resin, comprising polymerizing a water-soluble monomer having an α, β unsaturated double bond.