JP2000351805A - Preparation of composite resin emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a preparation process of a composite resin emulsion of a polyurethane and an ethylenically unsaturated monomer polymer which has an excellent dispersion stability and yields a coated film, etc., showing an excellent transparency, solvent resistance, flexibility, mechanical properties, wear resistance, weather resistance, flexing resistance, hydrolysis resistance, etc. SOLUTION: In the presence of 100 pts.wt. polyurethane in a polyurethane emulsion which satisfies the following conditions (1)-(4), from 10 to 90 pts.wt. ethylenically unsaturated monomer is emulsion polymerized to prepare a composite resin emulsion. (1) The emulsion is prepared by allowing an isocyanate- terminated urethane prepolymer to react with a chain extender in an aqueous solution in the presence of a surfactant, (2) the polyurethane has from 1 to 20 mmol ethylenically unsaturated group per 100 g polyurethane, (3) the polyurethane has from 3 to 30 mmol neutralized carboxyl group and/or sulfonate group per 100 g polyurethane, (4) the emulsion contains from 0.5 to 10 g surfactant per 100 g polyurethane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a composite resin emulsion of a polyurethane and an ethylenically unsaturated monomer polymer, a composite resin emulsion obtained thereby, and a method of adding a thermosensitive gelling agent to the composite resin emulsion. The present invention relates to a thermosensitive gelling composite resin emulsion obtained. More specifically, the present invention is excellent in dispersion stability, the polyurethane and the ethylenically unsaturated monomer polymer form a good composite form and are emulsified and dispersed in an aqueous dispersion medium in granular form, and when dried, Transparency, solvent resistance, flexibility,
A method for producing a composite resin emulsion capable of forming a film having excellent properties such as mechanical properties, abrasion resistance, weather resistance, bending resistance, and hydrolysis resistance with good polymerization stability, and a composite obtained thereby. The present invention relates to a resin emulsion and a composite resin emulsion obtained by adding a heat-sensitive gelling agent to the composite resin emulsion and having excellent thermal gelation properties.

[0002]

2. Description of the Related Art The strength and abrasion resistance of polyurethane,
The purpose is to obtain a composite resin that has properties such as solvent resistance and the properties of a polymer composed of an ethylenically unsaturated monomer, particularly a weather resistance, hydrolysis resistance, and low cost of a (meth) acrylic acid derivative polymer. It has been proposed to produce a composite resin emulsion by emulsion polymerization of an ethylenically unsaturated monomer in the presence of a polyurethane-based emulsion (JP-A-62-241902, JP-A-5-32.
0299, JP-A-10-30057). In these prior arts, an emulsion of a so-called ionomer type "self-emulsifying polyurethane" is used, in which the polyurethane itself has an emulsifying property, in which the polyurethane forming reaction is carried out without using a surfactant, as the polyurethane emulsion. It is useful as a substitute for a self-emulsifying polyurethane emulsion.

On the other hand, as an alternative to a forced emulsion type polyurethane emulsion dispersed and stabilized by a surfactant, a forced emulsion type composite resin obtained by emulsion polymerization of an ethylenically unsaturated monomer in the presence of a forced emulsion type polyurethane emulsion is used. Emulsions are preferred. For example, when a woven or knitted fabric or the like is impregnated with an emulsion to perform a texture process or the like, the emulsion may be provided with a thermosensitive gelling property so that the resin uniformly adheres to the woven or knitted fabric or the like. However, self-emulsifying emulsions have difficulty in imparting heat-sensitive gelling properties, and a phenomenon called so-called migration in which a resin moves to the surface of a woven or knitted fabric in a drying step occurs, and only a poorly textured product can be obtained. There is. For these reasons, the production of a forced emulsion type composite resin emulsion is desired.However, when emulsion polymerization of an ethylenically unsaturated monomer is performed in the presence of a forced emulsion type polyurethane emulsion, gelation may occur during the polymerization. Alternatively, there is a problem that particles composed only of a polymer from the ethylenically unsaturated monomer are generated in large quantities, and the physical properties of the obtained composite resin are reduced.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a composite compound of polyurethane and an ethylenically unsaturated monomer polymer which has excellent dispersion stability and is emulsified and dispersed in an emulsion. Particles consisting only of the unsaturated monomer polymer are hardly present in the emulsion, and when dried, transparency, solvent resistance, flexibility, mechanical properties, abrasion resistance, weather resistance, flex resistance, and water resistance Provided is a composite resin emulsion of a polyurethane and an ethylenically unsaturated monomer polymer capable of forming a film having excellent properties such as decomposability, and a method for producing the composite resin emulsion smoothly with good polymerization stability. It is to be. Further, an object of the present invention is to provide a thermosensitive gelling agent which, when added, maintains a fluid state without coagulation immediately, forms a gel when heated, and has excellent handling properties and thermogelling properties. Another object of the present invention is to provide a composite resin emulsion to which a thermosensitive gelling agent has been added, wherein the thermosensitive gelling property can be easily adjusted and can be effectively used for imparting a feeling to a substrate such as a fabric.

[0005]

The present inventor has made intensive studies to achieve the above object. As a result, in producing an emulsion of a composite resin of polyurethane and an ethylenically unsaturated monomer polymer, instead of using the conventional emulsion of a self-emulsifiable polyurethane described above as a polyurethane-based emulsion, a specific amount of a surfactant is used. Forced emulsification having a specific amount of neutralized carboxyl groups and / or sulfonic acid groups and a specific amount of ethylenically unsaturated groups in a polyurethane skeleton obtained by reacting a chain extender with an isocyanate-terminated urethane prepolymer in the presence When a polyurethane emulsion of the type is used, the polyurethane and the ethylenically unsaturated monomer polymer are stably dispersed in the emulsion in the form of particles of a good composite form without phase separation, and are transparent and flexible when dried. , Mechanical properties, abrasion resistance, weather resistance, bending resistance, melting resistance Sex, found that composite resin emulsion capable of forming a like film having excellent properties such as hydrolysis resistance is obtained.
Furthermore, the present inventors have found that the addition of the heat-sensitive gelling agent to the composite resin emulsion obtained above maintains the flowability without coagulation or the like by merely adding the heat-sensitive gelling agent, and is excellent in handleability. The present inventors have found that gelation occurs quickly upon heating, and based on those findings, completed the present invention.

That is, the present invention relates to: (1) an ethylenically unsaturated monomer (B) in the presence of a polyurethane-based emulsion (A) is added to 100 parts by weight of the polyurethane in the polyurethane-based emulsion (A); In the method for producing a composite resin emulsion by performing emulsion polymerization using the saturated monomer (B) at a ratio of 10 to 900 parts by weight, the following requirements are required as the polyurethane emulsion (A); A polyurethane-based emulsion prepared by reacting a chain extender with an isocyanate-terminated urethane prepolymer in the presence of an agent.
An emulsion of a polyurethane having an ethylenically unsaturated group in a ratio of 1 to 20 mmol, in the polyurethane, per 100 g of the polyurethane,
An emulsion of a polyurethane having a neutralized carboxyl group and / or a sulfonic acid group at a ratio of 3 to 30 mmol, and a surfactant of 0.5 to 100 g per 100 g of the polyurethane.
A method for producing a composite resin emulsion, characterized by using a polyurethane emulsion satisfying the following:

In the present invention, the above-mentioned requirements
Is essential, but it is preferable to employ at least one of the following conditions (2) to (7). (2) The ethylenically unsaturated group in the polyurethane is a (meth) acryloyl group or a vinyl group, (3)
(4) the ethylenically unsaturated monomer (B) is present on a side chain of a polyurethane skeleton;
Is an ethylenically unsaturated monomer having a (meth) acrylic acid derivative as a main component, and (5) the polymerization of the ethylenically unsaturated monomer (B) is performed in two stages, and the acrylic acid derivative is obtained in the first stage polymerization. After the use of the ethylenically unsaturated monomer (B1) whose main component is the ethylenically unsaturated monomer (B2) whose main component is a methacrylic acid derivative and / or an aromatic vinyl compound in the second stage polymerization, In this case, the weight ratio of (B1) and (B2) is (B1) / (B2)
(6) that at least a part of the surfactant contained in the polyurethane emulsion (A) is an anionic surfactant, (7)
Performing the emulsion polymerization using an oil-soluble polymerization initiator,

Further, the present invention is a composite resin emulsion obtained by such a production method, and the present invention is obtained by adding a thermosensitive gelling agent to the composite resin emulsion obtained by the above production method. It is a thermosensitive gelling composite resin emulsion.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, the polyurethane emulsion (A)
The above-mentioned requirement (a polyurethane-based emulsion prepared by reacting a chain extender with an isocyanate-terminated urethane prepolymer in the presence of a surfactant in an aqueous liquid) and the requirement (polyurethane 10 in polyurethane)
A point that the emulsion is a polyurethane having ethylenically unsaturated groups in a proportion of 1 to 20 mmol per 0 g), and a requirement (3 to 30 mmol of carboxyl groups and / or sulfonic acid groups neutralized per 100 g of polyurethane in the polyurethane). And the requirements (polyurethane 100
It is necessary to use a polyurethane emulsion which satisfies (point of being a polyurethane emulsion having a surfactant in a ratio of 0.5 to 10 g per g).

That is, the polyurethane emulsion (A) used in the present invention must first satisfy the above requirements, and if the requirements are not satisfied (the urethane isocyanate-terminated urethane without using a surfactant). In the case of a polyurethane emulsion obtained by reacting a prepolymer with a chain extender), the dispersion stability in an aqueous liquid is extremely poor.

Although not limited, examples of preferred methods for preparing the polyurethane emulsion (A) used in the method for producing a composite resin emulsion of the present invention include:
(I) a polymer polyol, a compound containing an ethylenically unsaturated group and having at least one active hydrogen atom reactive with an isocyanate group, containing at least one of a carboxyl group and a sulfonic acid group and reacting with an isocyanate group Reacting a compound having at least one active hydrogen atom of the formula (I) and an organic polyisocyanate to produce an isocyanate-terminated urethane prepolymer containing an ethylenically unsaturated group and a carboxyl group and / or a sulfonic acid group in the skeleton; (Ii) converting a carboxyl group and / or a sulfonic acid group in the isocyanate-terminated urethane prepolymer (hereinafter sometimes referred to as “urethane prepolymer”) obtained in (i) to a tertiary amine or an alkali metal hydroxide; After neutralization with a basic substance such as (iii) a predetermined amount of surfactant A method in which a polyurethane-based emulsion (A) is prepared by reacting a chain extender with a urethane prepolymer in a state in which the neutralized urethane prepolymer is emulsified in an aqueous liquid by forced stirring or the like. it can.

The above-mentioned polymer polyol used in the production of the urethane prepolymer for preparing the polyurethane emulsion (A) [step (i)] includes polyester polyol, polycarbonate polyol,
Examples thereof include polyester polycarbonate polyols and polyether polyols, and one or more of these can be used. Among them, one or more of polyester polyol, polycarbonate polyol and polyether polyol are preferably used.

The above-mentioned polyester polyol can be prepared by a conventional method, for example, a polycarboxylic acid, an ester thereof,
It can be produced by directly esterifying or transesterifying a polycarboxylic acid component such as an ester-forming derivative such as an anhydride with a polyol component, or by ring-opening polymerization of a lactone using a polyol as an initiator. it can.

As the polycarboxylic acid component that can be used in the production of the polyester polyol for producing the urethane prepolymer, a polycarboxylic acid component generally used in the production of a polyester polyol can be used. For example, succinic acid, glutaric acid , Adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-
Methylpentanedioic acid, 2-methyloctaneedioic acid, 3,8
Aliphatic dicarboxylic acids such as -dimethyldecandioic acid and 3,7-dimethyldecandioic acid; aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, phthalic acid and naphthalenedicarboxylic acid; fats such as 1,4-cyclohexanedicarboxylic acid Cyclic dicarboxylic acids; tricarboxylic acids such as trimellitic acid and trimesic acid; ester-forming derivatives thereof; and the like, and one or more of these can be used. Among them, the polyester polyol is mainly composed of an aliphatic dicarboxylic acid or an ester-forming derivative thereof as a polycarboxylic acid component, and optionally contains a small amount of a trifunctional or more polycarboxylic acid or an ester-forming derivative thereof. It is preferably manufactured.

As the polyol component which can be used in the production of the polyester polyol for producing the urethane prepolymer, those generally used in the production of the polyester polyol can be used. For example, ethylene glycol, propylene glycol, 2- Methyl-
1,3-propanediol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,7-heptanediol, 1,8-
Aliphatic diols such as octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and 1,10-decanediol; alicyclic diols such as cyclohexanedimethanol and cyclohexanediol; glycerin, trimethylol Examples thereof include trifunctional or more functional polyols such as propane, butanetriol, hexanetriol, trimethylolbutane, trimethylolpentane, and pentaerythritol, and one or more of these can be used. Among them, the polyester polyol is composed of an aliphatic diol as a polyol component, and a small amount of 3
It is preferably produced using a polyol component containing a functional or higher functional polyol.

Examples of the lactone which can be used in the production of the polyester polyol for producing the urethane prepolymer include ε-caprolactone, β-methyl-δ-valerolactone and the like.

Examples of the polycarbonate polyol which can be used for producing the urethane prepolymer include those obtained by reacting a polyol with a carbonate compound such as dialkyl carbonate, alkylene carbonate, diaryl carbonate and the like. As the polyol constituting the polycarbonate polyol, the polyol exemplified above as the constituent component of the polyester polyol can be used. Examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate, examples of the alkylene carbonate include ethylene carbonate, and examples of the diaryl carbonate include diphenyl carbonate.

Examples of the polyester polycarbonate polyol which can be used for producing the urethane prepolymer include those obtained by simultaneously reacting a polyol, a polycarboxylic acid and a carbonate compound, and those obtained by reacting a previously prepared polyester polyol and a carbonate compound. What was obtained by reacting, a product obtained by reacting a pre-produced polycarbonate polyol with a polyol and a polycarboxylic acid, a product obtained by reacting a pre-produced polyester polyol and a polycarbonate polyol, etc. Can be mentioned.

Examples of the polyether polyol which can be used for producing the urethane prepolymer include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.
Species or two or more can be used.

The high molecular polyol used in the production of the urethane prepolymer preferably has a number average molecular weight of 500 to 10,000, more preferably 700 to 5,000, from the viewpoint of ease of production. Preferred, 7
More preferably, it is 50 to 4,000. Also,
The high molecular polyol used in the production of the urethane prepolymer has a hydroxyl group number f per molecule of 1.0 ≦ f ≦ 4.0.
, And more preferably 2.0 ≦ f ≦ 3.0.

The polyurethane emulsion (A) used in the present invention satisfies the above-mentioned requirements, that is, a polyurethane emulsion having 1 to 20 mmol of ethylenically unsaturated groups per 100 g of polyurethane in the polyurethane. It is necessary. In the polyurethane emulsion (A), polyurethane 1
The content of ethylenically unsaturated groups per 1 gram is 1 mmol
If it is less than 1, the polyurethane and the ethylenically unsaturated monomer polymer are likely to undergo phase separation when the composite resin emulsion is dried, and the solvent resistance and strength of the composite resin are reduced. On the other hand, when the content of the ethylenically unsaturated group per 100 g of polyurethane is more than 20 mmol, the polymerization stability when the ethylenically unsaturated monomer (B) is emulsion-polymerized in the presence of the polyurethane emulsion (A) decreases. However, the strength and the like of the obtained composite resin are also reduced. The polyurethane in the polyurethane emulsion (A) contains 2 to 18 ethylenically unsaturated groups per 100 g of the polyurethane.
It is preferable that the compound has a mmol ratio in terms of stability during emulsion polymerization, solvent resistance and strength of the obtained composite resin.

In order to obtain a polyurethane emulsion (A) which satisfies the above requirements, at the time of production of the urethane prepolymer, as described above, it has an ethylenically unsaturated group together with the polymer polyol and has a reactivity with the isocyanate group. It is preferable to use a compound having at least one active hydrogen atom of the above [Step (i)]. Examples of the compound having such an ethylenically unsaturated group and having one or more active hydrogen atoms reactive with an isocyanate group include, for example, 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
-Hydroxypropyl, 2-hydroxybutyl (meth) acrylate, allyl alcohol, trimethylolpropane diacrylate, pentaerythritol triacrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2-hydroxy-1-acryloxy-3 -Methacryloxypropane, 1: 2 adduct of ethylene glycol diglycidyl ether and (meth) acrylic acid, 1: 2 adduct of diethylene glycol diglycidyl ether and (meth) acrylic acid, propylene glycol diglycidyl ether and (meth) acryl 1: 2 adduct of acid, 1: 2 adduct of neopentyl glycol diglycidyl ether and (meth) acrylic acid, 1: 2 adduct of 1,6-hexanediol diglycidyl ether and (meth) acrylic acid, bisphenol Diglycidyl ether and (meth)
1: 2 adduct of acrylic acid, 2,3-butenediol,
Examples thereof include polycondensates of butanediol and succinic acid, and one or more of these can be used.

Among these, reactions such as a 1: 2 adduct of ethylene glycol diglycidyl ether and (meth) acrylic acid, and a 1: 2 adduct of 1,6-hexanediol diglycidyl ether and (meth) acrylic acid are exemplified. When a compound having two or more active hydrogen atoms and the ethylenically unsaturated group is a (meth) acryloyl group or a vinyl group is used, the presence of the ethylenically unsaturated group in the side chain of the polyurethane makes the polyurethane Molecular weight does not decrease,
When the ethylenically unsaturated monomer (B) is emulsion-polymerized, the ethylenically unsaturated group in the polyurethane skeleton and the ethylenically unsaturated monomer (B) are easily copolymerized. The characteristics are particularly excellent and preferred.

The polyurethane emulsion (A) used in the present invention has the above-mentioned requirements, ie, 3 to 30 mmol of carboxyl groups and / or sulfonic acid groups neutralized per 100 g of polyurethane in polyurethane.
It is necessary to satisfy the point of being a polyurethane emulsion having a ratio of In the polyurethane-based emulsion (A), the content of neutralized carboxyl groups and / or sulfonic acid groups per 100 g of polyurethane (the total amount of both neutralized carboxyl groups and sulfonic acid groups when both have neutralized carboxyl groups and sulfonic acid groups) is When the amount is less than 3 mmol, the dispersion stability of the polyurethane-based emulsion is reduced, and the system tends to gel when the ethylenically unsaturated monomer (B) is emulsion-polymerized in the presence of the polyurethane-based emulsion. On the other hand, when the content of the neutralized carboxyl group and / or sulfonic acid group per 100 g of polyurethane is more than 30 mmol, when the ethylenically unsaturated monomer (B) is emulsion-polymerized in the presence of the polyurethane-based emulsion, Stability is reduced, and the thermosensitive gelling properties of the obtained composite resin emulsion are lost or deteriorated. When a thermosensitive gelling agent is added, troubles such as gelation immediately before heating are likely to occur. . The polyurethane in the polyurethane emulsion (A) is
Percentage of 5-27 mmol of neutralized carboxyl groups and / or sulfonic groups per 100 g of polyurethane is the stability at the time of emulsion polymerization, the stability of the obtained composite resin emulsion, and the heat-sensitive gelling property. It is preferable from the point of view. Further, the polyurethane in the polyurethane emulsion (A) may have a non-neutralized carboxyl group and / or sulfonic acid group.

In order to obtain a polyurethane emulsion (A) which satisfies the above requirements, as described above, at the time of production of the urethane prepolymer, it has a carboxyl group and / or a sulfonic acid group together with a high molecular weight polyol and isocyanate group. [Step (i)] using a compound having one or more active hydrogen atoms reactive with the above [Step (ii)] of neutralizing a carboxyl group and / or a sulfonic acid group. A compound having a carboxyl group and / or a sulfonic acid group and having at least one active hydrogen atom reactive with an isocyanate group [hereinafter referred to as a “carboxyl group and / or A sulfonic acid group-containing isocyanate-reactive compound ”may be mentioned, for example, as 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid,
Carboxyl group-containing compounds such as 2-bis (hydroxymethyl) valeric acid and derivatives thereof; sulfonic acid groups such as 1,3-phenylenediamine-4,6-disulfonic acid and 2,4-diaminotoluene-5-sulfonic acid Included compounds and the like. Further, as a part of the polyol component to be reacted with the polycarboxylic acid component at the time of producing the polyester polyol used for producing the above-mentioned urethane prepolymer, 2,2-bis (hydroxymethyl) is used.
Polyester polyol produced using a carboxyl group-containing compound such as propionic acid, 2,2-bis (hydroxymethyl) butyric acid, 2,2-bis (hydroxymethyl) valeric acid or a derivative thereof, or the like can also be used.
One or more of these can be used.

The organic polyisocyanate used for producing the urethane prepolymer [that is, the urethane prepolymer for preparing the polyurethane emulsion (A)] includes:
Any of organic polyisocyanates conventionally used in the production of polyurethane emulsions can be used, but one or more of alicyclic diisocyanates, aliphatic diisocyanates, and aromatic diisocyanates having a molecular weight of 500 or less are preferred. used. Examples of such organic diisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, 4,4
'-Dicyclohexylmethane diisocyanate, 2,4
-Tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate and the like. Or 2
More than one species can be used.

In producing a urethane prepolymer containing a carboxyl group and / or a sulfonic acid group in the molecule, the proportion of each component used is such that the molecular terminals of the resulting prepolymer are blocked with isocyanate groups. It is generally necessary that the molar ratio of [total amount of active hydrogen atoms reactive with isocyanate groups]: [isocyanate groups] is 1: 1.1 to 5 It is preferred to carry out the reaction. The temperature during the production of the urethane prepolymer is not particularly limited, but is usually 20 to
A temperature of 150 ° C. is preferably employed.

The urethane prepolymer obtained as described above is treated with a basic compound such as a tertiary amine such as triethylamine and trimethylamine, and an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide. Carboxyl groups and / or sulfonic groups in the urethane prepolymer molecule can be neutralized. The neutralization treatment of the carboxyl group and / or sulfonic acid group can be easily performed by adding a basic compound to the system after the production of the urethane prepolymer is completed or at the time of emulsification.

Next, the neutralized urethane prepolymer having a carboxyl group and / or a sulfonic acid group obtained above is added to an aqueous liquid in the presence of a surfactant,
The polyurethane-based emulsion (A) used in the present invention is prepared by reacting a chain extender (requirement).

As the chain extender, any chain extender conventionally used in the preparation of a polyurethane emulsion can be used, but it has a molecular weight having two or more active hydrogen atoms reactive with isocyanate groups in the molecule. 400 or less low molecular weight compounds are preferably used. Specific examples of preferably used chain extenders include hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, nonamethylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine, xylenediamine,
Diamines such as adipic dihydrazide and isophthalic dihydrazide; triamines such as diethylene triamine; ethylene glycol, propylene glycol;
1,4-butanediol, 1,6-hexanediol,
1,4-bis (β-hydroxyethoxy) benzene,
Diols such as 1,4-cyclohexanediol, bis (β-hydroxyethyl) terephthalate and xylylene glycol; triols such as trimethylolpropane; pentaols such as pentaerythritol; amino such as aminoethyl alcohol and aminopropyl alcohol Alcohols and the like can be mentioned, and one or more of these can be used.

The amount of the chain extender used is such that the molar ratio of [isocyanate group in prepolymer]: [active hydrogen atom reactive with isocyanate group in chain extender] is 1: 0.5 to 2
Is preferably in the range of 1: 0.7 to
More preferably, the amount falls within the range of 1.5. In reacting the chain extender with the urethane prepolymer, the chain extender may be added alone to the aqueous emulsion of the urethane prepolymer, but the chain extender may be dissolved in water or mixed with water. It is preferable that the polyurethane-based emulsion (A) is dissolved in a mixed solvent with a hydrophilic organic solvent and added to the aqueous emulsion of the urethane prepolymer, whereby the reaction between the urethane prepolymer and the chain extender proceeds well. Can be prepared smoothly. Further, a part of the chain extender may be reacted before emulsification of the urethane prepolymer.

In preparing the polyurethane emulsion (A), the surfactant is used in an amount such that the surfactant is in the range of 0.5 to 10 g per 100 g of polyurethane formed by the reaction of the urethane prepolymer and the chain extender. It is necessary to carry out the chain elongation reaction using the above (the above requirements), and it is preferable to carry out the chain elongation reaction using a surfactant in an amount within the range of 0.7 to 7 g. If the amount of the surfactant is less than 0.5 g per 100 g of the polyurethane in the polyurethane-based emulsion, the dispersion stability of the polyurethane-based emulsion is reduced, and the emulsion polymerization of the ethylenically unsaturated monomer (B) is carried out. The stability is reduced, and gelation is likely to occur. On the other hand, when the amount of the surfactant per 100 g of the polyurethane in the polyurethane emulsion is more than 10 g, the polymerization stability at the time of emulsion polymerization of the ethylenically unsaturated monomer (B) is reduced, and the ethylenically unsaturated monomer is further reduced. The polymer particles composed only of (B) are generated, and the composite resin particles are hardly generated, so that an emulsion of the target composite resin cannot be obtained, and the film or the like obtained by drying the composite resin emulsion becomes cloudy and transparent. Sex is impaired. In some cases, a small amount of the surfactant (preferably 20% or less of the surfactant) may be used in combination with the urethane prepolymer and the chain extender as long as the dispersion stability when reacting the urethane prepolymer with the chain extender can be ensured. May be added to the polyurethane emulsion. However, also in this case, it is necessary to adjust the amount of the surfactant to be finally in the range of 0.5 to 10 g per 100 g of the polyurethane in the polyurethane emulsion (A).

Examples of the surfactant used when preparing the polyurethane emulsion (A) (ie, during the chain extension reaction of the urethane prepolymer) include, for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium polyoxyethylene tridecyl ether acetate, dodecyl Anionic surfactants such as sodium benzenesulfonate, sodium alkyldiphenyletherdisulfonate, sodium di (2-ethylhexyl) sulfosuccinate;
Nonionic surfactants such as polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene-polyoxypropylene block copolymer can be exemplified. , One or more of these can be used. Among them, it is preferable that at least a part of the surfactant is composed of an anionic surfactant from the viewpoint of polymerization stability at the time of emulsion polymerization of the ethylenically unsaturated monomer (B). More preferably, it is a surfactant. In particular, one or two of sodium lauryl sulfate, ammonium lauryl sulfate, and sodium polyoxyethylene tridecyl ether acetate
More than one species is preferably used.

The urethane prepolymer may be diluted with an organic solvent to facilitate emulsification and dispersion. Examples of the organic solvent include acetone, methyl ethyl ketone, and the like.
Examples thereof include toluene, ethyl acetate, tetrahydrofuran, and dimethylformamide. The organic solvent used for diluting the urethane prepolymer can be removed from the emulsion before or after the emulsion polymerization of the ethylenically unsaturated monomer (B).

The method for dispersing the urethane prepolymer in the aqueous liquid in the presence of the surfactant is not particularly limited, and any method may be employed as long as the urethane prepolymer can be uniformly emulsified and dispersed in the aqueous liquid. Among them, a method of emulsifying and dispersing a urethane prepolymer in an aqueous liquid while applying a strong shearing force such as strong stirring is preferably employed.

In the polyurethane emulsion (A),
When the average particle diameter of the particles contained in the emulsion is measured by a dynamic light scattering method and determined by analysis by a cumulant method, it is 500 nm or less from the viewpoint of the production stability of the composite resin emulsion and the like. Preferably 400 nm
It is more preferably at most 300 nm, more preferably at most 300 nm. If the average particle size of the particles in the polyurethane emulsion (A) exceeds 500 nm, gelation of the system is likely to occur when the ethylenically unsaturated monomer (B) is emulsion-polymerized in the presence of the polyurethane emulsion (A). Become.

In the polyurethane emulsion (A),
Based on the weight of the emulsion, the content of polyurethane (resin solids) is preferably 5 to 60% by weight, from the viewpoints of dispersion stability of the emulsion, formation of the composite resin emulsion, productivity and the like. More preferably, it is 50% by weight.

In producing the composite resin emulsion by emulsion polymerization of the ethylenically unsaturated monomer (B) in the presence of the polyurethane emulsion (A) satisfying the above requirements, the polyurethane emulsion (A) When the ethylenically unsaturated monomer (B) is used in a proportion of 10 to 900 parts by weight with respect to 100 parts by weight of the polyurethane, dispersion stability of the obtained composite resin emulsion, strength of the composite resin, abrasion resistance and weather resistance It is preferable from the viewpoints of properties, hydrolysis resistance, cost and the like, and it is more preferable to use the ethylenically unsaturated monomer (B) at a ratio of 25 to 400 parts by weight. The use ratio of the ethylenically unsaturated monomer (B) is 10 per 100 parts by weight of the polyurethane.
When the amount is less than part by weight, the weather resistance and hydrolysis resistance of the obtained composite resin are apt to decrease, and the cost is increased. On the other hand, when the amount exceeds 900 parts by weight, the strength and abrasion resistance of the obtained composite resin are liable to decrease. .

In the production of the composite resin emulsion, the ethylenically unsaturated monomer (B) is supplied to the polymerization system in the first stage by supplying the whole amount of the ethylenically unsaturated monomer (B). Alternatively, a continuous addition method, a multi-stage supply (multi-stage polymerization) method in which the monomer composition is changed at each polymerization stage, a power feed method in which the monomer composition is continuously changed, or the like can be used. The amount of the polyurethane emulsion (A) charged to the polymerization system and the amount of the ethylenically unsaturated monomer (B) supplied are determined by the solid content (composite resin) content in the composite resin emulsion obtained by emulsion polymerization. 10 to 60% by weight, especially 20 to 50% by weight, based on the weight of the composite resin emulsion
The amount is preferably within the range of from the viewpoints of polymerization stability, dispersion stability of the obtained composite resin, handleability of the composite resin emulsion, physical properties of the composite resin, and the like.

The ethylenically unsaturated monomer (B) used in the production of the composite resin emulsion includes methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, (Meth) acrylic acid such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate or derivatives thereof; styrene, α- Aromatics such as methylstyrene and p-methylstyrene Amides of unsaturated carboxylic acids such as (meth) acrylamide and diacetone acrylamide; maleic acid, fumaric acid, itaconic acid or derivatives thereof; heterocyclic vinyl compounds such as vinylpyrrolidone; vinyl chloride, acrylonitrile, vinyl ether And vinyl compounds such as vinyl ketone and vinyl amide; and α-olefins such as ethylene and propylene. One or more of these can be used. Among them, as the ethylenically unsaturated monomer (B), an ethylenically unsaturated monomer having a (meth) acrylic acid derivative as a main component, that is, an ethylenically unsaturated monomer having a proportion of (meth) acrylic acid derivative of 50% by weight or more is used. Saturated monomers are preferably used from the viewpoint of the weather resistance of the obtained composite resin, and the proportion of the (meth) acrylic acid derivative is 60% by weight or more, and more preferably 70% by weight.
The above ethylenically unsaturated monomers are more preferably used. Furthermore, in the present invention, the polymerization of the ethylenically unsaturated monomer (B) is carried out in two stages, and in the first stage polymerization,
After using the ethylenically unsaturated monomer (B1) having an acrylic acid derivative as a main component, an ethylenically unsaturated monomer (B2) having a methacrylic acid derivative and / or an aromatic vinyl compound as a main component is obtained in a second stage polymerization. The weight ratio between (B1) and (B2) was (B1) / (B2) = 5.
When the ratio is 0/50 to 99/1, the resulting composite resin is more preferably excellent in solvent resistance, mechanical properties, abrasion resistance, weather resistance and the like.

In the production of the composite resin emulsion, a bifunctional or higher polyfunctional ethylenically unsaturated monomer may be used in combination, if necessary. Specific examples of the polyfunctional ethylenically unsaturated monomer include ethylene Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth)
Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Di (meth) acrylates such as dimethylol tricyclodecane di (meth) acrylate and glycerin di (meth) acrylate; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth)
Tri (meth) acrylates such as acrylate; tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate; polyfunctional aromatic vinyl compounds such as divinylbenzene and trivinylbenzene; allyl (meth) acrylate, vinyl ( Two or more different ethylenically unsaturated bond-containing compounds such as meth) acrylate; a 2: 1 addition reaction product of 2-hydroxy-3-phenoxypropyl acrylate and hexamethylene diisocyanate; a 2: 1 addition product of glycerin dimethacrylate and tolylene diisocyanate The molecular weight of the addition reaction product is 1500
The following urethane acrylates and the like can be mentioned,
One or more of these can be used. When a polyfunctional ethylenically unsaturated monomer is used, it is preferably at most 20% by weight, more preferably at most 15% by weight, based on the total weight of the ethylenically unsaturated monomer (B). It is more preferred that the content be not more than% by weight.

The emulsion polymerization of the ethylenically unsaturated monomer (B) in the presence of the polyurethane emulsion (A)
This is performed using a polymerization initiator. The polymerization initiator may be added to the polymerization system by any of batch addition, divisional addition and continuous addition. Specific examples of the polymerization initiator that can be used in the present invention include benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide. Oil-soluble peroxides such as oxides; oil-soluble azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis- (2,4-dimethylvaleronitrile); hydrogen peroxide, persulfuric acid Water-soluble peroxides such as potassium, sodium persulfate, and ammonium persulfate; azobiscyanovaleric acid;
Examples include water-soluble azo compounds such as 2,2'-azobis- (2-amidinopropane) dihydrochloride, and one or more of these can be used. Further, a redox initiator system using a reducing agent and, if necessary, a chelating agent together with the polymerization initiator described above may be used. Examples of the reducing agent include alkali metal formaldehyde sulfoxylates such as Rongalit (sodium formaldehyde sulfoxylate); sulfites such as sodium sulfite and sodium bisulfite; pyrosulfites such as sodium pyrosulfite; sodium thiosulfate Thiosulfate; phosphorous acid,
Phosphorous acid such as sodium phosphite or a salt thereof; pyrophosphite such as sodium pyrophosphite; mercaptans; ascorbic acid or a salt thereof such as ascorbic acid or sodium ascorbate; erythorbic acid;
Erythorbic acid such as sodium erysorbate or salts thereof; saccharides such as glucose and dextrose; and metal salts such as ferrous sulfate and copper sulfate. Examples of the chelating agent include sodium pyrophosphate and ethylenediaminetetraacetate.

In the present invention, among the above polymerization initiators,
It is excellent in polymerization stability, and a composite resin composed of a polyurethane and an ethylenically unsaturated monomer (B) can be smoothly obtained without almost producing polymer particles composed only of the ethylenically unsaturated monomer (B). An oil-soluble polymerization initiator such as cumene hydroperoxide is preferably used. In particular, a redox initiator system in which a reducing agent and / or a chelating agent is combined with an oil-soluble polymerization initiator is more preferably used.

The amount of the polymerization initiator used depends on the type of the ethylenically unsaturated monomer (B), the ratio of the ethylenically unsaturated monomer (B) to the polyurethane in the polyurethane emulsion (A), the type of the polymerization initiator, Although it can be adjusted according to the polymerization temperature and the like, it is generally desired that the ratio is 0.01 to 1% by weight based on the weight of the ethylenically unsaturated monomer (B). Is preferred because it can be obtained smoothly. When a redox initiator in which a reducing agent and / or a chelating agent is combined with a polymerization initiator is used, the amounts of the reducing agent and the chelating agent can be adjusted according to each situation. 0.1 to 1 reducing agent based on the weight of initiator
000% by weight and a chelating agent of 0 to 100%.
It is preferred to use 0% by weight. The method of supplying the polymerization initiator to the polymerization system is not particularly limited, and can be performed in the same manner as in the conventionally known emulsion polymerization of an ethylenically unsaturated monomer, and among them, the polymerization initiator is dissolved or dissolved in an aqueous liquid. A method of adding to the polymerization system in a dispersed state is preferably employed.

The polymerization conditions for producing the composite resin emulsion are not particularly limited, and the polymerization can be carried out in the same manner as conventionally known emulsion polymerization of an ethylenically unsaturated monomer. It is preferable to perform emulsion polymerization in an active gas atmosphere from the viewpoint of polymerization stability, physical properties of the obtained composite resin, and the like. Further, a surfactant may be further added as needed at the time of production of the composite resin emulsion as long as the object of the present invention is not hindered.

The composite resin emulsion of the present invention obtained by emulsion polymerization of the ethylenically unsaturated monomer (B) in the presence of the polyurethane emulsion (A) has excellent dispersion stability. Films formed when dried have excellent properties such as transparency, flexibility, mechanical properties, weather resistance, and bending resistance. Utilizing these properties, film forming materials, paints, and coating agents It can be effectively used as a fiber treating agent, an additive for ink, an adhesive, a glass fiber sizing agent, a modifier for other resin emulsions, and the like.

Furthermore, the heat-sensitive gelling agent added to the composite resin emulsion of the present invention obtained as described above maintains fluidity and is excellent in handleability unless heating is performed. The composite resin emulsion of the present invention to which the heat-sensitive gelling agent is added easily gels by heating.
Therefore, the composite resin emulsion of the present invention to which a heat-sensitive gelling agent is added can be effectively used as a film forming material, a paint, a coating agent, a fiber treatment agent, an adhesive, a glass fiber sizing agent, and the like.

The heat-sensitive gelling agent to be added to the composite resin emulsion of the present invention includes, for example, inorganic salts, polyethylene glycol type nonionic surfactant, polyvinyl methyl ether, polypropylene glycol, silicone polyether copolymer, polysiloxane and the like. And one or more of these can be used. Among them, a thermosensitive gelling agent obtained by combining an inorganic salt and a polyethylene glycol type nonionic surfactant is preferably used because it has a high gelation rate when heated, has good storage stability, and is inexpensive. Can be Examples of the inorganic salts in that case include, for example, sodium carbonate, potassium carbonate, sodium sulfate, calcium sulfate, sodium chloride, potassium chloride, calcium chloride, zinc chloride, aluminum chloride, magnesium chloride, sodium nitrate, and lead nitrate. Can,
One or more of these can be used. Examples of the polyethylene glycol type nonionic surfactant include ethylene oxide adducts of higher alcohols, ethylene oxide adducts of alkyl phenols, ethylene oxide adducts of fatty acids, and ethylene oxide adducts of fatty acid esters of polyhydric alcohols. Examples thereof include an ethylene oxide adduct of an alkylamine and an ethylene oxide adduct of a polypropylene glycol, and one or more of these may be used. The amount of the heat-sensitive gelling agent is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight, based on 100 parts by weight of the composite resin emulsion.

The composite resin emulsion of the present invention, and the heat-gelling composite resin emulsion of the present invention obtained by adding a heat-sensitive gelling agent thereto, may further contain other additives such as a light stabilizer, if necessary. , Antioxidants, ultraviolet absorbers, penetrants, leveling agents, thickeners, fungicides, water-soluble polymer compounds such as polyvinyl alcohol and carboxymethyl cellulose, dyes, pigments, fillers, coagulation regulators, etc. Or you may contain 2 or more types.

[0050]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by the following examples. In the following examples, the average particle size of the particles in the polyurethane emulsion, the polymerization stability when the ethylenically unsaturated monomer is emulsion-polymerized, and the transparency and solvent resistance of the film obtained by drying the composite resin emulsion , And the thermal gelation temperature of the composite resin emulsion were measured or evaluated as follows.

(1) Average particle size of particles in polyurethane emulsion: "ELS-800" manufactured by Otsuka Electronics Co., Ltd.
The particles in the polyurethane emulsion were measured by the dynamic light scattering method and analyzed by the cumulant method (described in “Colloid Science Vol. IV, Colloid Science Experiment Method”, page 103, published by Tokyo Chemical Dojinsha). Was determined.

(2) Polymerization stability at the time of emulsion polymerization: A composite resin emulsion obtained by emulsion polymerization of an ethylenically unsaturated monomer in the presence of a polyurethane-based emulsion is filtered through a 20-mesh filter, and placed on a filter. The remaining aggregates are collected and dried, and the weight (Wb) is measured, and the weight% of the composite resin solid content in the composite resin emulsion (dry weight) (Wa) Ｗ (Wb / W)
a) × 100 ° is determined, and when the value is less than 1% by weight, the polymerization stability is good (○). When the value is 1% by weight or more and less than 5% by weight, the polymerization stability is slightly poor (△), 5%. When the amount was not less than% by weight, the polymerization stability was evaluated as poor (x).

(3) Transparency and tackiness of the film: The thickness 1 obtained by drying the composite resin emulsion at 50 ° C.
The 00 μm film was visually observed to evaluate whether it was transparent or cloudy.

(4) Solvent resistance of the film: A 100 μm thick film obtained by drying the composite resin emulsion at 50 ° C. was heat-treated at 130 ° C. for 10 minutes.
A test piece was prepared by cutting into a size of 3 cm × 3 cm, and 90
Film (test piece) immersed in toluene at ℃ for 1 hour
The elution rate and the area swelling rate were determined from the following formulas, respectively, and thereby the solvent resistance was evaluated.

Dissolution rate (%) = {(W0−W1) / W0} × 100 [where W0 is the weight (mg) of the test piece before immersion in toluene, and W1 is the test piece after immersion in toluene. Shows the weight (mg) of. ]

Area swelling ratio (%) = {(S1-S0) / S0} × 100 [where S0 is the area of the test piece before immersion in toluene (cm2), and S1 is the test after immersion in toluene. The area (cm2) of the piece is shown. ]

(5) Thermal gelation temperature of the composite resin emulsion: 10 g of the composite resin emulsion was weighed into a test tube.
The temperature was raised while stirring in a constant temperature hot water bath at 90 ° C., and the temperature at which the composite resin emulsion lost its fluidity and became a gel was defined as the thermosensitive gelling temperature of the composite resin emulsion.

The abbreviations and contents of the polymer diols used in the following examples are as follows. PTMG1400: polytetramethylene glycol having a number average molecular weight of 1400 PHC2000: polyhexamethylene carbonate diol having a number average molecular weight of 2,000 PMPA2000: polyester diol having a number average molecular weight of 2,000 (3-methyl-1,5-pentanediol and adipic acid) Produced by the reaction of

Reference Example 1 [Preparation of Polyurethane Emulsion (PU Emulsion)] (1) In a three-necked flask, PT was used as a polymer diol.
150.0 g of MG1400 and 1 of PHC2000
50.0 g, 6.00 g of a 1: 2 adduct of 1,6-hexanediol diglycidyl ether and acrylic acid (containing two acryloyl groups in the diol side chain), 68.51 g of 2,4-tolylene diisocyanate and 2 8.83 g of 2,2-bis (hydroxymethyl) propionic acid was weighed and stirred at 90 ° C. for 2 hours under a dry nitrogen atmosphere to quantitatively react the hydroxyl groups in the system, thereby obtaining an isocyanate-terminated urethane prepolymer. Manufactured. (2) After adding 202.4 g of 2-butanone to the isocyanate-terminated urethane prepolymer obtained in (1) above and uniformly stirring, the temperature in the flask was lowered to 40 ° C.
6.66 g of triethylamine was added and stirred for 10 minutes. Then, sodium lauryl sulfate as an emulsifier 4.
An aqueous solution in which 06 g and ECT-3NEX (an anionic surfactant manufactured by Nippon Surfactant Industry Co., Ltd.) was dissolved in 296.2 g of distilled water was added to the urethane prepolymer solution, followed by stirring with a homomixer for 1 minute. Immediately after emulsification, 6.34 g of diethylenetriamine
5.23 g of isophorone diamine and distilled water 513.
An aqueous solution dissolved in 3 g was added, and the mixture was stirred for 1 minute with a homomixer to perform a chain extension reaction. (3) Next, 2-butanone was removed by a rotary evaporator to obtain a polyurethane emulsion having a solid content of 35% by weight (hereinafter referred to as “PU emulsion”). The PU emulsion thus obtained has a proportion of 8.1 mmol of ethylenically unsaturated groups, 16.4 mmol of neutralized carboxyl groups per 100 g of polyurethane in polyurethane, and 2 surfactant per 100 g of polyurethane. 0.0g, and the average particle size of the particles was 150 nm.

Reference Example 2 [Preparation of Polyurethane Emulsion (PU Emulsion)] (1) PM was added as a polymer diol to a three-necked flask.
300.0 g of PA2000 and a 1: 2 adduct of ethylene glycol diglycidyl ether and methacrylic acid (containing two methacryloyl groups in the diol side chain) 1.5
0 g, 70.90 g of 2,4-tolylene diisocyanate
Then, 7.90 g of 2,2-bis (hydroxymethyl) propionic acid was weighed and reacted in the same manner as in (1) of Reference Example 1 to produce an isocyanate-terminated urethane prepolymer. (2) After adding 200.2 g of 2-butanone to the isocyanate-terminated urethane prepolymer obtained in the above (1) and stirring uniformly, the temperature in the flask was lowered to 40 ° C.
5.96 g of triethylamine was added and stirred for 10 minutes. Then, sodium lauryl sulfate 1 was used as an emulsifier.
An aqueous solution in which 2.03 g was dissolved in 293.2 g of distilled water,
After adding to the urethane prepolymer solution and stirring with a homomixer for 1 minute to emulsify, immediately 6.04 g of diethylenetriamine and 4.99 g of isophoronediamine were obtained.
Was dissolved in 507.4 g of distilled water, and the mixture was stirred with a homomixer for 1 minute to perform a chain extension reaction. (3) Next, 2-butanone was removed by a rotary evaporator to obtain a polyurethane emulsion having a solid content of 35% by weight (hereinafter referred to as “PU emulsion”). The PU emulsion thus obtained has 2.2 mmol of ethylenically unsaturated groups, 14.8 mmol of neutralized carboxyl groups per 100 g of polyurethane, and 3 surfactant per 100 g of polyurethane. 0.0g, and the average particle size of the particles was 140 nm.

Reference Example 3 (1) In a three-necked flask, PT was used as a polymer diol.
150.0 g of MG1400 and 1 of PHC2000
50.0 g, 2,4-tolylene diisocyanate
08 g and 2,2-bis (hydroxymethyl) propionic acid 8.14 g were weighed and reacted in the same manner as in (1) of Reference Example 1 to produce an isocyanate-terminated urethane prepolymer. (2) After adding 196.3 g of 2-butanone to the isocyanate-terminated urethane prepolymer obtained in (1) above and uniformly stirring, the temperature in the flask was lowered to 40 ° C.
6.14 g of triethylamine was added and stirred for 10 minutes. Next, sodium lauryl sulfate was used as an emulsifier.
93 g and ECT-3NEX 3.93 g in distilled water 28
The aqueous solution dissolved in 7.3 g was added to the urethane prepolymer solution and stirred for 1 minute with a homomixer to emulsify. Immediately, 6.13 g of diethylenetriamine and 5.06 g of isophoronediamine were dissolved in 497.9 g of distilled water. The resulting aqueous solution was added, and the mixture was stirred with a homomixer for 1 minute to perform a chain extension reaction. (3) Next, 2-butanone was removed by a rotary evaporator to obtain a polyurethane emulsion having a solid content of 35% by weight (hereinafter referred to as “PU emulsion”). The PU emulsion thus obtained has no ethylenically unsaturated groups in the polyurethane, has 15.6 mmol of neutralized carboxyl groups per 100 g of polyurethane, and contains a surfactant per 100 g of polyurethane. The content was 2.0 g, and the average particle size of the particles was 140 nm.

Reference Example 4 [Preparation of Polyurethane Emulsion (PU Emulsion)] (1) PT was used as a polymer diol in a three-necked flask.
150.0 g of MG1400 and 1 of PHC2000
50.0 g, 18.00 g of a 1: 2 adduct of 1,6-hexanediol diglycidyl ether and acrylic acid (containing two acryloyl groups in the diol side chain), 74.19 g of 2,4-tolylene diisocyanate and 2 8.65 g of 2,2-bis (hydroxymethyl) propionic acid was weighed and reacted in the same manner as in (1) of Reference Example 1 to produce an isocyanate-terminated urethane prepolymer. (2) After adding 211.2 g of 2-butanone to the isocyanate-terminated urethane prepolymer obtained in (1) above and uniformly stirring, the temperature in the flask was lowered to 40 ° C.
6.52 g of triethylamine was added and stirred for 10 minutes. Then, sodium lauryl sulfate as an emulsifier 4.
23 g and 4.23 g of ECT-3NEX in 30 parts of distilled water.
The aqueous solution dissolved in 9.3 g was added to the urethane prepolymer solution and stirred for 1 minute with a homomixer to emulsify. Immediately, 6.43 g of diethylenetriamine and 5.31 g of isophoronediamine were dissolved in 535.4 g of distilled water. The resulting aqueous solution was added, and the mixture was stirred with a homomixer for 1 minute to perform a chain extension reaction. (3) Next, 2-butanone was removed by a rotary evaporator to obtain a polyurethane emulsion having a solid content of 35% by weight (hereinafter referred to as “PU emulsion”). The PU emulsion thus obtained has 23.3 mmol of ethylenically unsaturated groups, 15.4 mmol of neutralized carboxyl groups per 100 g of polyurethane in polyurethane, and a surfactant per 100 g of polyurethane. Was contained at a ratio of 2.0 g, and the average particle size of the particles was 160 nm.

<< Reference Example 5 >> [Preparation of Polyurethane Emulsion (PU Emulsion)]
A polyurethane emulsion having a solid content of 35% by weight (hereinafter referred to as “PU emulsion”) was prepared in the same manner as in (1) to (3) of Reference Example 1 except that 4.33 g and 24.33 g of ECT-3NEX were used. I got The PU emulsion thus obtained has 8.1 m of ethylenically unsaturated groups per 100 g of polyurethane in the polyurethane.
mol, 16.4 mmol of neutralized carboxyl groups
And a surfactant was contained in a proportion of 12.0 g per 100 g of polyurethane, and the average particle diameter of the particles was 130 nm.

Reference Example 6 [Preparation of Polyurethane Emulsion (PU Emulsion)] (1) to (3) of Reference Example 1 except that sodium lauryl sulfate and ECT-3NEX were not used in (2) of Reference Example 1. ), And the solid content is 35% by weight.
(Hereinafter referred to as “PU emulsion”). The PU emulsion thus obtained has, in the polyurethane, 8.1 mmol of ethylenically unsaturated groups and 16.4 mmol of neutralized carboxyl groups per 100 g of polyurethane, does not contain a surfactant, and The average particle size of the particles was 970 nm.

Reference Example 7 [Preparation of Polyurethane Emulsion (PU Emulsion)] (1) In a three-necked flask, PT was used as a polymer diol.
150.0 g of MG1400 and 1 of PHC2000
50.0 g, 6.00 g of a 1: 2 adduct of 1,6-hexanediol diglycidyl ether and acrylic acid (containing two acryloyl groups in the diol side chain) and 60.40 g of 2,4-tolylene diisocyanate were weighed. The mixture was reacted in the same manner as in (1) of Reference Example 1 to produce an isocyanate-terminated urethane prepolymer. (2) After adding 191.7 g of 2-butanone to the isocyanate-terminated urethane prepolymer obtained in the above (1) and stirring uniformly, the temperature in the flask was lowered to 40 ° C. Next, ECT-3NEX 15.37 was used as an emulsifier.
g of water dissolved in 279.0 g of distilled water was added to the urethane prepolymer solution, and the mixture was stirred with a homomixer for 1 minute to emulsify. Immediately, 7.28 g of diethylenetriamine and 6.01 g of isophoronediamine were dissolved in 487 g of distilled water. An aqueous solution dissolved in 0.6 g was added, and the mixture was stirred with a homomixer for 1 minute to perform a chain extension reaction. (3) Next, 2-butanone was removed by a rotary evaporator to obtain a polyurethane emulsion having a solid content of 35% by weight (hereinafter referred to as “PU emulsion”). The PU emulsion thus obtained has 8.4 mmol of ethylenically unsaturated groups per 100 g of polyurethane in polyurethane, has no neutralized carboxyl groups, and has 4.0 g of surfactant per 100 g of polyurethane. And the average particle size of the particles was 860 nm.

Reference Example 8 [Preparation of Polyurethane Emulsion (PU Emulsion)] (1) PM as a polymer diol was placed in a three-necked flask.
300.0 g of PA2000 and a 1: 2 adduct of ethylene glycol diglycidyl ether and methacrylic acid (containing two methacryloyl groups in the diol side chain) 1.5
0 g, 2,4-tolylene diisocyanate 94.01 g
Then, 21.12 g of 2,2-bis (hydroxymethyl) propionic acid was weighed and reacted in the same manner as in (1) of Reference Example 1 to produce an isocyanate-terminated urethane prepolymer. (2) After adding 225.3 g of 2-butanone to the isocyanate-terminated urethane prepolymer obtained in (1) above and stirring uniformly, the temperature in the flask was lowered to 40 ° C.
15.93 g of triethylamine was added and stirred for 10 minutes. Next, an aqueous solution in which 4.51 g of sodium lauryl sulfate was dissolved in 328.9 g of distilled water was added to the urethane prepolymer solution, and the mixture was emulsified by stirring with a homomixer for 1 minute, and immediately thereafter, 7.72 g of diethylenetriamine was obtained.
And 6.37 g of isophoronediamine in 572.
An aqueous solution dissolved in 2 g was added, and the mixture was stirred with a homomixer for 1 minute to perform a chain extension reaction. (3) Next, 2-butanone was removed by a rotary evaporator to obtain a polyurethane emulsion having a solid content of 35% by weight (hereinafter referred to as “PU emulsion”). The PU emulsion thus obtained has 2.0 mmol of ethylenically unsaturated groups per 100 g of polyurethane, 35.3 mmol of neutralized carboxyl groups in 100 g of polyurethane, and a surfactant per 100 g of polyurethane. Was contained at a ratio of 1.0 g, and the average particle size of the particles was 90 nm.

The contents of PU emulsions obtained in Reference Examples 1 to 8 are summarized in Table 1 below.

[0068]

[Table 1]

Example 1 [Production of Composite Resin Emulsion] (1) Initial Charge: 240 g of the PU emulsion obtained in Reference Example 1 in a flask equipped with a cooling tube, and 236 distilled water
g, ferrous sulfate heptahydrate (FeSO4.7H2O)
0.020 g, potassium pyrophosphate 0.294 g, Rongalit (formaldehyde sodium sulfoxylate dihydrate) 0.451 g, and ethylenediaminetetraacetic acid disodium salt (EDTA · 2Na) 0.020 g
Was weighed and heated to 40 ° C., and the inside of the system was sufficiently purged with nitrogen. (2) Emulsion polymerization: Then, butyl acrylate 186.2
g, 1,6-hexanediol diacrylate 9.80
g and ECT-3NEX (the same anionic surfactant used in Reference Example 1) (mixture containing ethylenically unsaturated monomers) (1.96 g), cumene hydroperoxide 0.392 g, ECT-3NEX 0.392 g
An emulsion (polymerization initiator-containing emulsion) composed of 25.0 g of distilled water and distilled water was dropped into the flask from a separate dropping funnel over 5 hours, and after completion of the dropping, the temperature was maintained at 50 ° C. for 60 minutes to complete the polymerization. Thus, a composite resin emulsion having a solid content of 40% by weight was obtained.

(3) The polymerization stability of the composite resin emulsion obtained in the above (2) and the transparency and solvent resistance of the film obtained by drying the composite resin emulsion were measured or evaluated by the methods described above. The results are shown in Table 2 below. Further, the composite resin emulsion obtained in the above (2) did not gel even when heated to 90 ° C. by itself (when no heat-sensitive gelling agent was added).

Example 2 [Production of Composite Resin Emulsion] (1) Example 1 was repeated using the PU emulsion obtained in Reference Example 1 and the components shown in Table 2 below in amounts shown in Table 2. Initial charging and emulsion polymerization were carried out in the same manner as in (1) and (2) to produce a composite resin emulsion of Example 2. (2) The polymerization stability of the composite resin emulsion of Example 2 obtained in (1) above, and the transparency and solvent resistance of the film obtained by drying the composite resin emulsion were measured or evaluated by the methods described above. And Table 2 below. In addition, the composite resin emulsion of Example 2 is itself (when no heat-sensitive gelling agent is added).
It did not gel when heated to 90 ° C.

Example 3 [Production of Composite Resin Emulsion] (1) Initial Charge: In a flask equipped with a cooling tube, 320 g of the PU emulsion obtained in Reference Example 2, ferrous sulfate · 7
0.017 g of hydrate (FeSO4.7H2O), 0.252 g of potassium pyrophosphate, Rongalit (dihydrate of sodium formaldehyde sulfoxylate) 0.38
6 g, ethylenediaminetetraacetic acid disodium salt (ED
After weighing 0.017 g of TA · 2Na) and 193 g of distilled water and raising the temperature to 40 ° C., the inside of the system was sufficiently purged with nitrogen. (2) First-stage emulsion polymerization: Then, butyl acrylate 1
43.6 g, 4.54 g of 1,6-hexanediol diacrylate, 3.02 g of allyl methacrylate and E
Mixture of 1.51 g of CT-3NEX (monomer mixture)
And 0.302 g of cumene hydroperoxide, ECT-
An emulsion (polymerization initiator-containing emulsion) composed of 0.302 g of 3NEX and 15.0 g of distilled water was dropped into the flask from separate dropping funnels over 4 hours.
The polymerization was carried out at 40 ° C. for 30 minutes. (3) Second-stage emulsion polymerization: Thereafter, a mixture (monomer mixture) of 16.46 g of methyl methacrylate, 0.336 g of 1,6-hexanediol diacrylate and 0.168 g of ECT-3NEX, and 0.1% of cumene hydroperoxide. No. 034 g, ECT-3NEX 0.034 g and distilled water 2.0 g (polymerization initiator-containing emulsion) were placed in separate flasks for 1 hour 30 from separate dropping funnels.
After completion of the dropwise addition, the mixture was kept at 50 ° C. for 60 minutes to complete the polymerization, thereby obtaining a composite resin emulsion having a solid content of 40 wt%. (4) The polymerization stability of the composite resin emulsion obtained in the above (3) and the transparency and solvent resistance of the film obtained by drying the composite resin emulsion were measured or evaluated by the above-mentioned methods. As shown in FIG. Further, the composite resin emulsion obtained in the above (3) can be used by itself (when no heat-sensitive gelling agent is added).
It did not gel when heated to 90 ° C.

Example 4 [Production of Composite Resin Emulsion] (1) Example 3 was repeated using the PU emulsion obtained in Reference Example 1 and the components shown in Table 2 below in amounts shown in Table 2. The initial charge and emulsion polymerization were carried out in the same manner as in (1), (2) and (3), to produce a composite resin emulsion of Example 4. (2) The polymerization stability of the composite resin emulsion of Example 4 obtained in (1) above, and the transparency and solvent resistance of a film obtained by drying the composite resin emulsion were measured or evaluated by the above-described methods. And Table 2 below. In addition, the composite resin emulsion of Example 4 was used by itself (when no heat-sensitive gelling agent was added).
It did not gel when heated to 90 ° C.

<< Comparative Examples 1 to 3 >> [Production of Composite Resin Emulsion] (1) PU emulsions obtained in Reference Examples 3 to 5
And the initial charge and emulsion polymerization were carried out in the same manner as in (1) and (2) of Example 1 using any one of the components shown in Table 2 in the amounts shown in Table 2. 1 to 3 were prepared respectively. (2) The polymerization stability of each of the composite resin emulsions of Comparative Examples 1 to 3 obtained in (1) above, and the transparency and solvent resistance of a film obtained by drying the composite resin emulsion were measured by the above-described methods. Or, when evaluated, it was as shown in Table 2 below. In addition, none of the composite resin emulsions of Comparative Examples 1 to 3 gelled even when heated to 90 ° C by themselves (when no heat-sensitive gelling agent was added).

<< Comparative Examples 4 and 5 >> Using either of the PU emulsions obtained in Reference Examples 6 and 7 and the components shown in Table 2 below in the amounts shown in Table 2, (1) When initial charging and emulsion polymerization were performed in the same manner as in (2) and (2), gelation (coagulation) of the entire system occurred during emulsion polymerization, and a composite resin emulsion could not be produced.

Comparative Example 6 Production of Composite Resin Emulsion (1) Example 3 was repeated using the PU emulsion obtained in Reference Example 8 and the components shown in Table 2 below in the amounts shown in Table 2. The initial charge and emulsion polymerization were carried out in the same manner as in (1), (2) and (3) to produce a composite resin emulsion of Comparative Example 6. (2) When the polymerization stability of the composite resin emulsion of Comparative Example 6 obtained in (1) above and the transparency and solvent resistance of the film obtained by drying the composite resin emulsion were measured or evaluated by the above-described methods. And Table 2 below. In addition, the composite resin emulsion of Comparative Example 6 itself (when no heat-sensitive gelling agent is added)
It did not gel when heated to 90 ° C.

[0077]

[Table 2]

From the results in Table 2 above, it can be seen that Examples 1 to 4 in which the emulsion polymerization of an ethylenically unsaturated monomer was carried out in the presence of a PU emulsion satisfying all of the above requirements to all the requirements. It can be seen that the film obtained by drying the composite resin emulsion has excellent polymerization stability during emulsion polymerization, and also has excellent transparency and solvent resistance. On the other hand, Comparative Example 1 in which emulsion polymerization of an ethylenically unsaturated monomer was carried out in the presence of the above requirements to PU emulsions lacking any of the above requirements
In the case of Nos. 6 to 6, the polymerization stability during the emulsion polymerization was inferior (Comparative Examples 2 and 6) or gelation occurred and emulsion polymerization was not possible (Comparative Examples 4 and 5), and the composite resin emulsion was dried. The solvent resistance of the obtained film is inferior (Comparative Examples 1 and 3), or the film becomes cloudy and the transparency is inferior (Comparative Example 3).
You can see that it is doing.

Example 5 [Production of a Thermosensitive Gelling Composite Resin Emulsion] A nonionic surfactant (Kao Corporation) was added as a thermosensitive gelling agent to 100 parts by weight of the composite resin emulsion obtained in Example 1. (Emulgen 109P) and 1 part by weight of calcium chloride were added to produce a thermogelling composite resin emulsion. The heat-sensitive gelling composite resin emulsion thus obtained did not gel (at room temperature) as it was, but showed fluidity and was excellent in handleability. The thermosensitive gelling temperature of the obtained thermosensitive gelling composite resin emulsion was measured by the method described above.
9 ° C.

Example 6 Production of Thermosensitive Gelling Composite Resin Emulsion A thermosensitive gelling composite resin emulsion was prepared in the same manner as in Example 5, except that the composite resin emulsion obtained in Example 3 was used. Was manufactured. The heat-sensitive gelling composite resin emulsion thus obtained did not gel (at room temperature) as it was, but showed fluidity and was excellent in handleability. The thermosensitive gelling temperature of the obtained thermosensitive gelling composite resin emulsion was measured by the method described above, and it was 53 ° C.

Comparative Example 7 A thermosensitive gelling composite resin emulsion was prepared in the same manner as in Example 5 except that the composite resin emulsion obtained in Comparative Example 6 was used. Immediately after the addition of the nonionic surfactant and calcium chloride), the entire system gelled, and a thermosensitive gelling composite resin emulsion could not be obtained.

[0082]

According to the present invention, the dispersion stability is excellent, and the polyurethane and the ethylenically unsaturated monomer polymer are dispersed in the emulsion in the form of a well-combined particle. Composite of polyurethane and ethylenically unsaturated monomer polymer capable of forming a film with excellent properties such as solvent resistance, flexibility, mechanical properties, abrasion resistance, weather resistance, bending resistance and hydrolysis resistance A resin emulsion can be produced smoothly with good polymerization stability without causing gelation or the like during emulsion polymerization. The composite resin emulsion obtained by adding a heat-sensitive gelling agent to the composite resin emulsion obtained by the method of the present invention retains fluidity before heat gelation and is excellent in handleability. The composite resin emulsion of the present invention to which the heat-sensitive gelling agent is added easily gels by heating.

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Claims (4)

[Claims] 1. An ethylenically unsaturated monomer (B) is added in the presence of a polyurethane-based emulsion (A), and the ethylenically unsaturated monomer (B) is added to 10 parts by weight of the polyurethane in the polyurethane-based emulsion (A). ~ 90
In the method for producing a composite resin emulsion by carrying out emulsion polymerization using 0 parts by weight, the polyurethane emulsion (A) has the following requirements, and isocyanate-terminated urethane in an aqueous liquid in the presence of a surfactant. A polyurethane emulsion prepared by reacting a chain extender with a prepolymer. In the polyurethane, per 100 g of the polyurethane,
An emulsion of a polyurethane having an ethylenically unsaturated group in a ratio of 1 to 20 mmol, in the polyurethane, per 100 g of the polyurethane,
An emulsion of a polyurethane having a neutralized carboxyl group and / or a sulfonic acid group at a ratio of 3 to 30 mmol, and a surfactant of 0.5 to 100 g per 100 g of the polyurethane.
A method for producing a composite resin emulsion, which comprises using a polyurethane emulsion having a ratio of 10 g. 2. The polymerization of the ethylenically unsaturated monomer (B) is carried out in two stages. The methacrylic acid derivative and / or
Alternatively, an ethylenically unsaturated monomer (B2) having an aromatic vinyl compound as a main component is used, and (B1) and (B
The weight ratio of (2) is (B1) / (B2) = 50/50 to 99.
The production method according to claim 1, wherein the ratio is / 1. 3. A composite resin emulsion obtained by the production method according to claim 1. 4. A thermosensitive gelling composite resin emulsion obtained by adding a thermosensitive gelling agent to the composite resin emulsion according to claim 1 or 2.