JP3508030B2 - Aqueous resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a polyurethane resin and
Details on aqueous resin compositions containing acrylic and acrylic resins.
Or, as an acrylic resin, a copolymerizable unsaturated bond
Polymerization or emulsion polymerization in the presence of a reactive emulsifier
By using what was obtained by doing
And has excellent storage stability.
Gives a film with excellent water resistance, chemical resistance, film strength, etc.
Water-based resin composition. [0002] BACKGROUND OF THE INVENTION Problems to be Solved by the Invention
Synthetic resins such as urethane resin and acrylic resin are used for various paints,
Used for adhesives, etc., paper, fiber, woven, non-woven
Processing agents for paper or textile products, sizing agents for glass fibers,
Used in a wide variety of applications, such as rutal modifiers and floor polishes
I have. Conventionally, in these applications, synthetic resins are dissolved in organic solvents.
It was used as a solvent-based varnish.
The varnish contains the toxicity of organic solvents, fire hazard, and environmental pollution.
It has drawbacks such as dyeability, and in recent years, water has been used instead of organic solvents.
Water-based resins are becoming mainstream. The water-based resin is a polyurethane resin.
Water in which synthetic resins such as fats and acrylic resins are emulsified and dispersed in water
Urethane and acrylic emulsion are typical
This eliminates the disadvantages of the solvent-based varnish described above.
You. However, aqueous urethane has film-forming properties and elasticity.
(Strength, elongation), abrasion resistance, cold resistance and
Excellent adhesion, hydrolysis resistance, alkali resistance, resistance
It has the disadvantage of poor adhesion to stains and non-polar substances,
In addition, acrylic emulsion has hardness, hydrolysis resistance
To alkaline, alkali and stain resistant, glossy and non-polar substances
Has excellent adhesion, but has poor film-forming properties.
Is not only essential, but also elastic (strength, elongation),
Abrasion resistance, water resistance (especially hot water resistance), solvent resistance and extreme
However, there is a disadvantage that the adhesiveness to the conductive material is poor. To compensate for these disadvantages, polyurethane
Water-based tree using resin and acrylic resin as film-forming components
It has been proposed to use a fat composition. These resins
Combined use of the components provides mechanical strength, adhesion,
Abrasion and other properties are improved to some extent, but water resistance, especially hot water
The effect of improving the resistance and chemical resistance is not sufficient.
And both drawbacks are common.
won. [0005] Water resistance and chemical resistance of such an aqueous resin composition
The cause of adverse effects on product properties is that the unsaturated monomer is emulsified
Used to produce acrylic resin emulsions
Is known to be an emulsifier,
It is difficult to produce an acrylic resin emulsion without
Yes, conventionally, reduced amount of emulsifier
Selection of agent, acrylic resin emulsion in aqueous urethane
Attempt to improve these properties by means such as manufacturing
An attempt was being made. For example, JP-A-63-132975
Polyoxyethylene-styrenated polyethylene
By using phenyl ether as an emulsifier,
Has been proposed to solve the drawbacks of
JP-A-54-77795, JP-A-59-1382
No. 11, JP-A-59-138212,
59-210978, JP-A-62-230863
JP, JP-A-4-222802, JP-A-5-3
No. 20299, etc., disclose acrylic acrylic in aqueous urethane.
Polymerizing ethylenically unsaturated monomers such as
Therefore, proposals have been made to eliminate the above disadvantages.
You. Also, a polyurethane resin and an acrylic resin are chemically
Try to solve the above disadvantages by combining
Some proposals have been made, for example,
No. 2 discloses a polyurethane polymer having an ethylenic end group.
For grafting ethylenic monomers to chromamonomers
A method has been proposed and disclosed in JP-A-3-195737.
Can react with the reactive group in aqueous urethane having a reactive group
Proposes a method for polymerizing ethylenic monomers having a functional group
Have been. [0007] However, these methods are also resistant.
The effect of improving water and chemical resistance is still insufficient.
In some cases, polyurethane resin and acrylic resin
Non-uniform, resulting in non-uniform and opaque film
Storage stability and lack of storage stability.
It wasn't enough. [0008] Therefore, an object of the present invention is to provide an excellent storage stability.
And excellent in water resistance, chemical resistance, film strength, etc.
To provide an aqueous resin composition that gives [0009] The present inventors have conducted various studies.
As a result, polyurethane resin and acrylic resin
In the aqueous resin composition containing, the acrylic resin milk
As an emulsifier used in chemical polymerization, copolymerizable unsaturated
Polymerization by using a reactive emulsifier having a sum bond
Almost emulsifier remaining in the acrylic emulsion after
Despite the lack of water, water-based trees using this acrylic resin
Fat composition, both polyurethane resin and acrylic resin
That the above purpose can be achieved without impairing the characteristics of
Was found. The present invention has been made based on the above findings.
1-85% by weight of polyurethane resin and acrylic resin
Resin containing 1 to 85% by weight of fat and a total of both
An aqueous resin composition containing 2 to 90% by weight of solids.
And the acrylic resin is represented by the following general formula (I):
Reactive emulsification having a copolymerizable unsaturated bond represented by
Glycidyl methacrylate in the presence of an agent or
0.1 to 50% by weight of glycidyl acrylate
YesDoAcrylic unsaturated monomer(However, carboxyl group
Excluding acrylic unsaturated monomers withWeight of the mixture
It is characterized by being obtained by combining
The present invention provides an aqueous resin composition. Embedded image Hereinafter, the aqueous resin composition of the present invention will be described in detail.
Will be described. The polyurethane resin used in the present invention comprises:
It can be produced by known methods, for example, polyisocyanate
Compound, polyol, carboxyl group or sulfo
Other polyols containing acid groups or basic groups in the molecule
With other polyols that are inert to the reaction and
Urethanation in an organic solvent with high compatibility
And then neutralize and extend the prepolymer.
And made by adding water to aqueous urethane.
It is. The above polyurethane resin (aqueous urethane) is
A polyisocyanate compound used to produce
Aliphatic, cycloaliphatic and aromatic polyisocyanates
And specifically, 2,4-tolylenediisobenzene
Anate, 2,6-tolylene diisocyanate, 4,4
-Diphenylmethane diisocyanate, phenylene diisocyanate
Socyanate, xylylene diisocyanate, tetrame
Tylxylylene diisocyanate, tetramethylene dii
Socyanate, hexamethylene diisocyanate, lysine
Diisocyanate ester, 1,4-cyclohexyl
Diisocyanate, 4,4'-dicyclohexyl meta
Diisocyanate, 3,3'-dimethoxy-4,4 '
-Biphenylene diisocyanate, 1,5-naphthalene
Diisocyanate, 1,5-tetrahydronaphthalenedi
Isocyanate, isophorone diisocyanate, etc.
Can be Use amount of the above polyisocyanate compound
Is a polyol, a carboxyl group or a sulfol described below.
Activity of other polyols and chain extenders with phonic acid groups
Preferably 0.8 to 3 equivalents to the total amount of hydrogen, furthermore
Preferably it is 1-2 equivalents. 0.8 times the above usage
If less than the equivalent, excess polyol etc. will remain
And, if it exceeds 3 equivalents, water is added
Urea bonds are generated in large quantities during
In such a case, the characteristics may be deteriorated. In addition, the above polyurethane resin is produced.
Polyols used for
Glycol, diethylene glycol, triethylene glycol
Cole, 1,2-propylene glycol, 1,3-pro
Pyrene glycol, 1,2-butylene glycol, 1,
3-butylene glycol, 1,4-butylene glycol
, Hexamethylene glycol, hydrogenated bisphenol
A, ethylene oxide of bisphenol A and / or
Is a low molecular weight polyol such as propylene oxide adduct,
Polyethylene glycol, polypropylene glycol,
Polyethylene / propylene glycol, polytetramethyl
Polyether polyols such as len glycol;
Molecular weight polyol and succinic acid, glutaric acid, adipic acid,
Sebacic acid, phthalic acid, isophthalic acid, terephthalic acid,
Tetrahydrophthalic acid, Endomethylene tetrahydroph
Polybasic acids such as tallic acid and hexahydrophthalic acid or charcoal
Polyester polyol, polycarbonate which is a condensate with acid
Bonate polyol, polycaprolactone, etc.
Can be Further, the above-mentioned polyurethane resin is produced.
Carboxyl or sulfonic acid groups used for
As other polyols having, for example, 2,2-dimethyl
Tyrolpropionic acid, 2,2-dimethylolbutyric acid,
2,2-dimethylolvaleric acid, 1,4-butanediol
-2-sulfonic acid and the like. In addition, the urethane
Having a basic group in the molecule used to produce
Other polyols include, for example, methyl diethanol
Amine, butyldiethanolamine, triethanolamine
Basic in molecules such as min, triisopropanolamine
And a polyol having a group. Of these,
Especially when a polyol having a carboxyl group is used
Polyurethane resin (water-based urethane) with excellent dispersibility is obtained
Is preferred. The above carboxyl group or sulfonic group
Having a basic group in another polyol or molecule having
The amount of other polyols used is
Depending on the type of compound and the polyol, usually
Applies to all the reaction components that make up the polyurethane resin.
0.5 to 50% by weight, preferably 1 to 30% by weight
is there. If the amount used is less than 0.5% by weight, the storage stability is low.
Inferior, and when used in excess of 50% by weight, adversely affect properties
May have an effect. In addition, the above polyurethane resin is produced.
Inert to the reaction and has high affinity for water
Examples of the organic solvent include acetone and methyl ethyl ketone.
Ton, dioxane, tetrahydrofuran, N-methyl-
2-pyrrolidone and the like can be mentioned. The above organic solvent
Is usually used to produce the prepolymer.
The raw materials used (polyisocyanate compound, poly
Having all, carboxyl or sulfonic acid groups
Other polyols or other polyols with basic groups in the molecule
10% by weight to 100% by weight of R.I. Further, in producing the above polyurethane resin,
At this time, as a neutralizing agent for neutralizing the prepolymer,
For example, trimethylamine, triethylamine, trip
Ropylamine, tributylamine, N-methyldiethanol
Organic amines such as tolueneamine and triethanolamine, water
Inorganic such as sodium oxide, potassium hydroxide, ammonia
Bases are mentioned, and the amount of the neutralizing agent used is
The amount is sufficient to neutralize the groups or sulfonic acid groups. Further, in producing the above polyurethane resin,
In this case, as a chain extender for chain extending the above prepolymer
Is, for example, ethylene glycol, propylene glycol
Polyols, ethylenediamine, propylene
Diamine, hexamethylenediamine, tolylenediamine
, Xylylenediamine, diaminodiphenylmeta
, Diaminocyclohexylmethane, piperazine, 2
-Methylpiperazine, isophoronediamine, melamine,
Succinic dihydrazide, adipic dihydrazide, lid
Amines such as luic dihydrazide and water;
You. The amount of the above chain extender depends on the target polyurethane.
Usually, depending on the molecular weight of the resin,
On the other hand, it is 0.5 to 10% by weight. The above polyurethane resin used in the present invention
Is manufactured as aqueous urethane from the above raw materials as described above.
It is well known that
Manufactured by changing or dividing and charging
It is also possible. The above polyurethane resin is usually a resin solid.
1 to 90% by weight, preferably 5 to 80% by weight
Is adjusted as follows. As the above-mentioned polyurethane resin, commercially available
Water-based urethane can be used as is
For example, "Adeka Bonta" manufactured by Asahi Denka Kogyo Co., Ltd.
Iter ”series,“ Olesta ”manufactured by Mitsui Toatsu Chemicals, Inc.
ー ”series,“ Bon ”manufactured by Dainippon Ink and Chemicals, Inc.
Dick series, Hydran series, Bayer
"Impraniel" series, Soflan Japan
"Sofranate" series manufactured by Kao Corporation
"Poise" series, "Sump" manufactured by Sanyo Chemical Industries, Ltd.
Ren series, Hoizaya Chemical Industry Co., Ltd.
Series ”and“ Daiichi Kogyo Seiyaku Co., Ltd. “Super”
Flex series and Zeneca Corporation
The "Tsu" series and the like can be used. Next, the acrylic resin used in the present invention
Is a specific reactive emulsification with copolymerizable unsaturated bonds
Polymerizes a mixture of acrylic unsaturated monomers in the presence of
It was obtained by having Then,
The mixture of acryl unsaturated monomers is glyceryl methacrylate.
Gill ester or glycidyl acrylate
Containing 0.1 to 50% by weightIs. Where
Reactive Emulsifiers Having Copolymerizable Unsaturated Bonds
Means copolymerizable with the mixture of acrylic unsaturated monomers.
It has a functional unsaturated bond. In addition, the above polymerization
Can be polymerized by emulsification or dispersion in an aqueous solvent.
preferable. The above acrylic resin is used to produce
In mixtures of acrylic unsaturated monomers
Acid esters or methacrylic esters includeGuri
In addition to sidyl esters,Methyl, ethyl, propyl, a
Isopropyl, butyl, isobutyl, sec-butyl, tert-butyl
Chill, amyl, hexyl, cyclohexyl, octyl,
Isooctyl, 2-ethylhexyl, nonyl, decyl,
Dodecyl, octadecyl, 2-hydroxyethylRuWhich
Esters are mentioned. The above acrylate or methacryl
The acid ester content isGlycidyl methacrylate
Ter or glycidyl acrylate
(Total mixture of acrylic unsaturated monomers)
50% by weight, preferably 1 to 30% by weight.
On conditionCan be set arbitrarily, but usually allAll over the body30 layers
% Or more, preferably 50% by weight or more. the aboveAku
Of lylic acid esters or methacrylic acidContent is 30 weight
% Is less than acrylic acid ester or methacrylic acid ester.
The effect of using tel becomes difficult to manifest. Ma
Was,UpGlycidyl methacrylate or acrylic
Uses unsaturated monomer containing glycidyl luate
This significantly improves the water resistance and chemical resistance of the film.
Is done. In the mixture of the above-mentioned acrylic unsaturated monomers,
Is the acrylate or methacrylate ester
Together with other unsaturated monomers.
Other unsaturated monomers can be copolymerized. above
Other unsaturated monomers include, for example, ethylene and propylene.
Len, butene, isobutene, butadiene, vinyl chloride,
Aliphatic unsaturated hydrocarbons such as vinylidene chloride and halogen
Aliphatic unsaturated hydrocarbons, styrene, α-methylstyrene
Aromatic unsaturated hydrocarbons such as
Other acids such as tonic acid, itaconic acid, fumaric acid, maleic acid, etc.
Esters of saturated carboxylic acids (alcohols constituting the esters)
Acrylic acid and methacrylic acid
The alcohol component constituting ter is exemplified), benzoic acid
Vinyl esters such as vinyl acid and vinyl acetate, and acrylic
Mid, methacrylamide, N-methylolacrylamide
, N-methylol methacrylamide, acrylonitrile
And nitrogen-containing vinyl monomers such as The mixture of the above-mentioned acrylic unsaturated monomers is
It can be charged at the beginning of the reaction,
It is possible to feed continuously, and if necessary
Chain transfer agents such as mercaptans.
Wear. Further, in producing the above acrylic resin,
The polymerization initiator can be used.
Is not particularly limited and is used for ordinary emulsion polymerization.
Uses water-soluble initiators as well as oil-soluble initiators
can do. As the polymerization initiator, for example,
Potassium persulfate, ammonium persulfate, azobiscyano
Valeric acid, azobisisobutyronitrile, tert-butyl high
Dropper oxide, dicumyl peroxide, peroxide
Benzoyl and the like, and these polymerization initiators
Consists of a combination of sulfites and sulfoxylates
A so-called redox catalyst can also be used. The amount of the above polymerization initiator used is
The type of unsaturated monomer in the mixture of the systemically unsaturated monomers,
It varies depending on the concentration, reaction temperature, etc.
Preferably 0.01 to 10% by weight, more preferably
Preferably, it is 0.1 to 5% by weight. The above polymerization initiators are added all at once.
Or adding in portions or continuously
You can also. In addition, the reaction in producing the acrylic resin is
The reaction temperature depends on the mixture of the acrylic unsaturated monomers.
Types of unsaturated monomers and the above-mentioned polymerization initiators
And usually varies from 0 ° C to 100 ° C.
It is. [0033] [0034] [0035] [0036] As the above-mentioned reactive emulsifier, water resistance and the like are particularly preferable.
And a film with excellent chemical resistance can be obtained.
(Chemical3Using a compound represented by the general formula (I)You. [0038] Embedded imageIn the above general formula (I), R_TwoRepresented by
As the hydrocarbon group having 6 to 30 carbon atoms, for example,
Xyl, octyl, isooctyl, 2-ethylhexyl
, Nonyl, isononyl, decyl, isodecyl, unde
Syl, dodecyl, tridecyl, isotridecyl, tetra
Decyl, hexadecyl, octadecyl, eicosyl, de
Alkyl such as Kosyl, Tetracosyl and Triacontyl
Group, octenyl, decenyl, dodecenyl, octadecenyl
Alkenyl groups such as octylphenyl, nonylphen
Alkylphenyl groups such as phenyl, dinonylphenyl, etc.
FluffBe. An A having 2 to 4 carbon atoms represented by A
As the alkylene group, ethylene, 1,2-propylene,
1,3-propylene, 1,2-butylene, 1,3-butylene
Len and 1,4-butylene. [0041] [0042] [0043] [0044] [0045] [0046] The amount of the reactive emulsifier used is
0.1 to the mixture of the unsaturated monomer
20% by weight. If the above amount is less than 0.1% by weight
In this case, the emulsion stability is insufficient, and 20% by weight
Of the coating obtained from the aqueous resin
The properties may be adversely affected. In producing the above acrylic resin,
Together with the above reactive emulsifier, a small amount of a non-reactive emulsifier
It is also possible to use an emulsifier that remains in the system.
Can adversely affect the properties of the coating,
Should be as small as possible. The aqueous resin composition of the present invention comprises
Contains urethane resin and acrylic resin
However, there are no particular restrictions on the adjustment method, and
Aqueous urethane (polyurethane resin) and acrylic emulsion
Method of mixing John (acrylic resin)
Mixture and reactivity of acrylic unsaturated monomers with urethane
Either method of adding an emulsifier and polymerizing can be used.
Can be. The above separately prepared aqueous urethane and aqueous
In the method of mixing the rill emulsion, the order of mixing is
There are no particular restrictions on conditions such as introduction, temperature, etc.
For example, add aqueous urethane little by little in the acrylic emulsion
Acrylic emulsion in aqueous urethane
And mixing both at once.
Any method may be used.
Even when one or both are hot or under heat
May be mixed. In particular, glycidyl methacrylate
Or an unsaturated monomer containing glycidyl acrylate
Using acrylic emulsion obtained from monomer mixture
If necessary, mix with aqueous urethane at 50-100 ° C
Or in aqueous urethane at 50-100 ° C
Obtained by polymerizing a mixture of
By using the aqueous resin composition of the present invention,
There is a tendency for the properties of the formed film to be improved. This
Use of an aqueous resin composition produced at high temperatures such as
It is obvious why the properties of the film formed by
However, the carbohydrate contained in the polyurethane resin
Xyl group or sulfonic acid group and contained in acrylic resin
Glycidyl group reacts with the
Bonding occurs and the uniformity of both resins is improved.
It is estimated that. In the aqueous resin composition of the present invention,
The content of the urethane resin and the acrylic resin is
Although it can be changed over a wide range according to the purpose of use,
Usually, 1-85% by weight of polyurethane resin, acrylic resin
Fatty acid is 1 to 85% by weight, and the total of both is resin
With a solid content of 2-90% by weight, preferably 5-80% by weight
is there. If the resin solids content is less than 2% by weight, it can be dried.
It takes time and more than 90% by weight
Not only is it inconvenient to handle due to its high viscosity,
Qualitative properties may be reduced. Further, in the aqueous resin composition of the present invention,
The ratio of the polyurethane resin and the acrylic resin,
Although there is no particular limitation, it is usually 1:10 to 1 by weight.
0: 1. If the above ratio is out of this range,
Reduces the amount of urethane resin or acrylic resin
In many cases, desired characteristics cannot be obtained. Further, the aqueous resin composition of the present invention has
Depending on the antioxidant, UV absorber, colorant, wax
Type, preservative, defoamer, plasticizer, solvent, film forming aid, dispersion
Conventional additives such as agents, thickeners, and fragrances can also be added.
You. The aqueous resin composition of the present invention can be used for fabric, paper, leather
Leather, metal, wood, plastics molded products, slate board, etc.
For impregnating paints, fibers, woven fabrics, etc. used for coatings
, Adhesives, floor polishes, glass fiber sizing agents, etc.
It can be used for various purposes. [0056] The present invention will be described below by way of Production Examples and Examples.
As will be described in more detail, the present invention is limited by these.
It does not receive. In the production examples and examples,
Parts are parts by weight unless otherwise specified.
You. Production Example 1 [Polyurethane resin (aqueous urethane
Production example) Polypropylene glycol having an average molecular weight of 1000 (PP
G1000) 49 parts, dicyclohexylmethanediisosi
176 parts of anate (hydrogenated MDI), dimethylol propyl
70 parts of ononic acid and 196 parts of N-methylpyrrolidone
In a reaction vessel, react at 80-100 ° C
Thus, a prepolymer was produced. Next, 48 parts of triethylamine were added.
After neutralization, 5 parts of hexamethylenediamine was added, and water was added.
Perform the crosslinking reaction at 35 ° C or less while adding
456 parts of water is added to the mixture, and the resin solid content is 35% by weight.
A urethane resin (aqueous urethane A) was produced. Production Example 2 [Polyurethane resin (aqueous urethane
Production example) Propylene oxide of bisphenol A having an average molecular weight of 790
140 parts of side adduct (BPAPO), xylylene diiso
151 parts of cyanate and N-methylpyrrolidone 120
Part in a reaction vessel and the NCO content is 1 at 80 to 85 ° C.
React to 0.3% by weight to produce prepolymer
did. Then, 14 parts of dimethylolpropionic acid
And 25 parts of 1,4-butylene glycol.
The cross-linking reaction is carried out at
After reacting until the absorption of the phosphate group disappears, triethyl
Neutralize by adding 12 parts of amine and 538 parts of water.
Aged for 1 hour, resin solids content 34% by weight polyurethane
A resin (aqueous urethane B) was produced. Production Example 3 [Polyurethane resin (aqueous urethane
Production example) Terephthalic acid and isophthalic acid as dibasic acid components
(Weight ratio 1: 1), and use ethylene glycol as the glycol component.
Glycol and diethylene glycol (weight ratio 2:
Polyester polyol having a molecular weight of 1000 using 3)
(Polyester polyol 1) 100 parts, isophorone di
107 parts of isocyanate and methyl ethyl ketone 90
The reaction mixture was placed in a reaction vessel and mixed well at 75 ° C.
Add 20 parts of methylolpropionic acid, and at 12 hours at 70 ° C
Reaction. 60 parts of 5% ammonia water was added for neutralization.
Thereafter, methyl ethyl ketone was distilled off under reduced pressure, and water was added.
Polyurethane resin with a resin solid content of 23% by weight (aqueous urethane
C) was prepared. By the same operation as in Production Example 1 above,
Poly obtained by the compounds (amount used) shown in [Table 1]
Urethane resins (aqueous urethanes DG) were produced. still,
Compounds used for producing the above aqueous urethanes A to C (uses
Amount) is also shown in [Table 1] below. [0063] [Table 1]Production Example 4 [Acrylic resin (acrylic emulsion)
John) Production Example] 100 parts of ion-exchanged water and represented by the following formula
Take 2 parts of reactive emulsifier (emulsifier A) and heat to 70 ° C
Then, 0.6 parts of ammonium persulfate was added. here
In addition, methyl methacrylate 45 parts, n-butyl acryle
45 parts, glycidyl methacrylate 10 parts, emulsifier
A mixed emulsion comprising 1 part of A1 and 30 parts of ion-exchanged water
The solution was added dropwise over 3 hours, and after the addition was completed,
Allowed to react for hours. Then, the pH is adjusted to 8 to 9 with aqueous ammonia.
Adjusted to 44% by weight of acrylic resin
Ril emulsion A) was prepared. [0065] Embedded image By the same operation as in Production Example 4, the following
The compounds obtained by using the compounds (amount used) shown in [Table 2]
Lil resins (acrylic emulsions BF) were prepared.
The compound used in the production of the acrylic emulsion A was used.
The products (amount used) are also shown in [Table 2] below. [0067] [Table 2]Production Examples 5 to 9 [Acrylic resin (acrylic resin)
Production example of Marjon) The reactive emulsifier is converted from emulsifier A to1
0Reactive emulsifiers B, C and D represented by the formulaAnd E
Except for the change,
Resin (Acrylic Emma El John G, H, IAnd J)
Was manufactured. [0069] Embedded image [0070] Embedded image [0071] Embedded image [0072] Embedded image [0073] Example 1 [PolyCUrethane resin (aqueous urethane
) And acrylic resin (acrylic emulsion)
Production of aqueous resin composition by Aqueous urethane according to the formulations shown in the following [Table 3] to [Table 5]
And the acrylic emulsion mixed at 30 ° C for 2 hours
Aqueous resin composition No. 1No.14 and No.17 to No.20To
It was adjusted. The obtained aqueous resin composition was placed on a glass plate.
Apply so that the film thickness at the time of drying becomes 0.5 mm.
After air drying all day and night, dry at 80 ° C for 5 minutes
A film was formed, and the obtained specimen was subjected to the following conditions.
Therefore, water resistance, alkali resistance, acid resistance and transparency
The test was performed. The results are shown in the following [Table 3] to [Table 5]
Shown in Water resistance is immersed according to JIS K5400
Time is 30 days, alkali resistance is 3.5% hydroxylated
Soak in sodium aqueous solution at 60 ° C for 1 hour.
The immersion time was 24 hours according to ISK5400.
The results were evaluated according to the following criteria. A: No change from before test. ：: No wrinkles, swelling or peeling, but slight discoloration
You. Δ: Wrinkling, swelling or peeling was observed, and there was discoloration. ×: Wrinkling, swelling or peeling was observed, and discoloration was significant.
No. The transparency of the film was visually observed, and was evaluated according to the following criteria.
evaluated. ：: The whole is transparent. C: Turbidity is partially observed. ×: cloudy. Further, these aqueous resin compositions are heated at 50 ° C.
Check the storage stability (storage stability) when stored for 30 days.
It was determined visually. The results are evaluated according to the following criteria:
Was. ：: No increase in viscosity, and no phase separation was observed. Δ: Viscosity increase or phase separation observed, but usable
Noh. X: Not usable because of significant increase in viscosity or phase separation. [0079] [Table 3] [0080] [Table 4][0081] [Table 5] Example 2 [Polyurethane resin (aqueous urethane
Aqueous resin set by polymerization of acrylic monomer
Production of products) 126 parts of ion exchange water, 3 parts of emulsifier A, aqueous urethane E
200 parts were taken and heated to 60 ° C. Shown in [Table 6] below
100 parts of a mixture of unsaturated monomers composed of
Amount) and 10% of tertiary butyl hydroperoxide
4 parts of the aqueous dispersion was added dropwise over 3 hours. 7 after dropping
The polymerization reaction was completed by maintaining at 0 ° C. for 1 hour,
7% by weight of an aqueous resin composition (aqueous resin composition No.twenty four~ 2
7) Manufactured. Using the obtained water-based resin composition,
The same test as in Example 1 was performed. The results are shown in Table 6 below.
Shown in [0084] [Table 6]Embodiment 3 The effect of producing an aqueous resin composition at high temperature was examined.
The operation was the same as in Example 1 except that the mixing was performed at 70 ° C.
Water-based resin composition No. 5, No. 6 and No. 12
An aqueous resin composition having the same composition (aqueous resin composition N
o.28-30) were prepared. The resulting aqueous resin composition has a film thickness when dried.
Coated to a thickness of 150 μm, the tensile strength of the resulting film
Degree (Kgf / cm^Two), Elongation (%) and 100% modulus
(Kgf / cm^Two) And the results are shown in [Table 7] below.
You. The water resistance, alkali resistance, acid resistance and permeability of the film
About lightness and storage stability of aqueous resin composition,
There is no difference between when manufactured at high temperature and when manufactured at high temperature.
I was not able to admit. [0087] [Table 7] The results obtained using the aqueous resin compositions Nos. 1 to 7
Use an acrylic resin polymerized using a reactive emulsifier.
If so, change the composition of the polyurethane resin to be combined.
Even when changed, water resistance, alkali resistance, acid resistance, etc.
Film with excellent transparency and water-based resin composition
It is clear that the storage stability of the product is also good. Similarly, a polyurethane resin and an acrylic resin
When the combination ratio of water is changed (aqueous resin composition No. 5
And 8-11), when the composition of acrylic resin is changed
(Aqueous resin composition No. 5 and 13 ~14), Reactivity used
When the type of emulsifier was changed (aqueous resin composition No. 5
And 17 ~20) Or acrylic resin in aqueous urethane
Polymerized in aqueous solution (aqueous resin composition No.24, 26 and
And 27) also have water resistance, alkali resistance, acid resistance and transparent
A film with excellent water resistance can be obtained, and the aqueous resin composition can be stored.
It is clear that the stability is also good. [0090] On the other hand, the aqueous resin composition No. 5 and the aqueous resin composition No. 5
Resin composition No.12,AhOr water-based resin composition No. 24
Aqueous resin composition No.25 toFrom the comparison with the case where
Water resistance and alkali resistance when a reactive emulsifier is used
Not only insufficient and acid resistance, but also uniformity of film
(Transparency) and storage stability tend to be poor
It is clear that. Further, as shown in Table 7 above,
An aqueous resin composition using the reactive emulsifier of the invention is produced at a high temperature.
If manufactured, adversely affect the water resistance and chemical resistance of the film.
Strength and elongation are improved without shrinking
When a reactive emulsifier is used, its improvement effect is almost
Mostly not. [0093] The aqueous resin composition of the present invention is free
Excellent storage stability despite little residual agent
It was a thing. In addition, the aqueous resin composition of the present invention
The film to be formed has water resistance, chemical resistance (alkali resistance,
Acidity) and excellent transparency as well as strength
And has the characteristic of high elongationYou.In addition, the present invention
The aqueous resin composition is obtained using a specific reactive emulsifier.
By containing acrylic resin, water resistance and
Gives a film with excellent chemical propertiesYou.Further, the aqueous resin of the present invention
The composition comprises a mixture of certain acrylic unsaturated monomers.
By containing the acrylic resin obtained by combining
Provides a film with excellent water and chemical resistanceYou.Therefore, the book
The water-based resin composition of the present invention includes paints, binders, adhesives, etc.
Very suitable for use as

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-192616 (JP, A) JP-A-6-136164 (JP, A) JP-A-7-207217 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 33/04-33/17 C08L 75/04 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claim 1] It contains 1 to 85% by weight of a polyurethane resin and 1 to 85% by weight of an acrylic resin, and contains 2 to 90% by weight of a total resin solid content of both. An aqueous resin composition, wherein the acrylic resin is glycidyl methacrylate or glycidyl methacrylate in the presence of a reactive emulsifier having a copolymerizable unsaturated bond represented by the following general formula (I): 0.1-5 glycidyl acrylate
Acrylic unsaturated monomer containing 0% by weight (however,
Water-based resin composition obtained by polymerizing a mixture of acrylic unsaturated monomers having a voxyl group) . Embedded image