JPH0299537A - Aqueous resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition capable of forming a coating film having performances of excellent mechanical strength, water resistance, solvent resistance and adhesivity to substrate, curing at room temperature in a short time, containing a specific polymer and an oxazoline group-containing polymer as essential components. CONSTITUTION:(A) 100 pts.wt. one or more of polyester resin, polyurethane resin and polyolefin resin which have a functional group to be reacted with oxazoline group and are soluble in water, capable of diluted in water or water dispersible are blended with (B) 1-500 pts.wt. polymer comprising >=5wt.% (in the component B) addition polymerizable oxazoline shown by the formula (R1-R4 are H, halogen, alkyl, phenyl or substituted phenyl; R5 is noncyclic organic group containing addition polymerizable saturated bond) and optionally one or more other polymer and optionally (C) <=1,000 pts.wt. (calculated as solid content) aqueous latex to give the aimed composition.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel aqueous resin composition, and more specifically,
Cures quickly even at room temperature and has excellent mechanical strength.
The present invention relates to an aqueous resin composition capable of forming a film having various properties such as water resistance, solvent resistance, heat resistance, durability, and adhesion to substrates.

[Problems that the prior art and invention attempt to improve]

Because water-soluble, water-dilutable, or water-dispersible polyester resins, polyurethane resins, and polyolefin resins are water-based, there is no risk of fire, work environment, or contamination, and their films have excellent mechanical strength. It has the characteristics of flexibility and solvent resistance, and is widely used as a resin component in paint 1 surface treatment agents, coating agents, adhesives, sealants, etc.; In order to make it more durable, it is necessary to include multiple parent wood bases, which poses problems, especially in terms of water resistance and durability. In recent years, attempts have been made to improve the various properties of the film by blending amine blast resins (e.g., water-soluble melamine resins), epoxy resins, aziridine compounds, etc. as hardening agents to overcome these drawbacks, but these efforts are still insufficient. The current situation is that no significant results have been obtained.

(JP-A-47-27241, JP-A-54-41940
(No. 55-184244) [Means and effects for solving the problem] In view of the current situation, the present inventors have developed a material that cures in a short time even at room temperature and has an excellent cured film. As a result of intensive research to develop a water-based resin composition with excellent water resistance and durability,
It was discovered that the above object could be achieved by an aqueous resin composition containing a specific polymer (A) having a functional group capable of reacting with an oxazoline group and a polymer (B) having an oxazoline group as essential components, and the present invention was completed. It is something that

That is, the present invention provides one or more polymers selected from the group of water-soluble, water-dilutable, or water-dispersible polyester resins, polyurethane resins, and polyolefin resins having a functional group that can react with an oxazoline group. (A), -Sakura (I) (In the formula, R1, R2, R3, and Nu are each independently hydrogen,
It is a halogen, alkyl, phenyl or substituted phenyl group, and R9 is an acyclic organic group having an addition-polymerizable unsaturated bond. ) Addition-polymerizable oxazoline (a)
and, if necessary, at least one other monomer (b
) and, if necessary, an aqueous latex (C).

Since the composition of the present invention cures even at room temperature, it does not require extensive equipment such as a heating device during curing, and the cured film has excellent mechanical strength, water resistance, solvent resistance, heat resistance, durability, Because it has various performances such as adhesion to the base material,
It can be suitably used in fields such as paints, surface treatment agents, coating agents, adhesives, and sealants.

In the present invention, the polymer (A) is one or more selected from the group of water-soluble or water-dispersible polyester resins, polyurethane resins, and polyolefin resins having a functional group that can react with an oxazoline group. Any polymer can be used without particular restriction.

Examples of functional groups that can react with the oxazoline group contained in the polymer (A) include carboxyl groups and
Examples include salts of carboxylic acid anhydrides, sulfonic acid groups and their salts, mercapto groups, amine groups, etc., and these can also be used in combination, but from the viewpoint of reactivity with oxazoline groups, carboxyl groups, carboxylic anhydrides, etc. Acid groups and sulfonic acid groups are particularly preferred.

The amount of the functional group is not particularly limited and may be selected as appropriate, but it is preferable to contain the functional group in a proportion such that the molecular weight per equivalent of the functional group is 100 to 20,000, preferably 500 to 10,000. If there are too many functional groups, the cured film tends to become hard and stiff, impairing its water resistance and adhesion to the substrate.On the other hand, if there are too few functional groups, the degree of curing will be insufficient, resulting in poor durability.
Water resistance etc. tend to be impaired.

In the present invention, a wide variety of known polymers can be used as the polymer (A). For example, Sofrane) AE-10, Sofrane) AE-40 (all manufactured by Nippon Sofrane Kako Co., Ltd.)
, Hytran HW-110.

Hytran HW-131, Hytran HW-135, Hytran HW-320, Pondick 72070 (all manufactured by Dainippon Ink & Chemicals Co., Ltd.) Boyz 710. Boyz 720 (both manufactured by Kao Corporation), Norsi 525. Merci 585. Merci 414. Water-dispersible polyurethane resin such as Merci 455 (all manufactured by Toyo Polymer Co., Ltd.); Pyronal MD-1200, Pyronal MD-140
0, Pyronal MD-1930 (both Toyobo ■
water-dispersible polyester resins such as WD3652, WJL6342 (all manufactured by Eastman Chemical Company);
Isopan-10, Isopan-06, Isopan-04 (all manufactured by Clarei Sobrene Chemical Co., Ltd.), Primacol 5981. Primacol 5983, Primacol 59
90. Examples include water-soluble, water-dilutable, or water-dispersible polyolefin resins such as Primacol 5991 (both manufactured by Dow Chemical Company).

The polymer (B) used in the present invention is obtained by polymerizing addition-polymerizable oxazoline (a) and, if necessary, at least one other monomer (b).

In the present invention, the addition-polymerizable oxazoline (a) has the general formula (I) Rζ (wherein R1, R2, R3, & are each independently hydrogen,
It is halogen, alkyl, aralkyl, phenyl or substituted phenyl, and R5 is an acyclic organic group having an addition polymerizable unsaturated bond. ).

Specific examples include 2-vinyl-2-oxazoline, 2-
Vinyl-4-methyl-2-oxazoline, ? -Vinyl-5-methyl-2-oxazoline, 2-impropenyl-
2-oxazoline, 2-impropenyl-4-methyl-
2-oxazoline, 2-isopropenyl-5-ethyl-
2-oxazoline can be mentioned, and one type or a mixture of two or more types selected from these groups can be used. Among them, 2-impropenyl-2-oxacillin is suitable because it is industrially easily available. The amount of addition polymerizable oxazoline (a) used is not particularly limited, but it is preferably 5% by weight or more in the polymer (B). If the amount is less than 5% by weight, the degree of curing is insufficient;
Durability, water resistance, etc. tend to be impaired.

The other monomer (b) used in the present invention is not particularly limited as long as it is a monomer that does not react with the oxazoline group and is copolymerizable with the addition-polymerizable oxazoline (a). For example,
(Meth) such as methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.
Acrylic esters; Unsaturated nitriles such as (meth)acrylonitrile; (meth)acrylamide, N-
Unsaturated amides such as methylol (meth)acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; vinyl chloride, vinylidene chloride, Halogen-containing α, β-unsaturated motumers such as vinyl fluoride; styrene,
Examples include α,β-unsaturated aromatic heptanomers such as α-methylstyrene, and one type or a mixture of two or more of these can be used.

Polymer (B) can be produced by polymerizing addition-polymerizable oxazoline (a) and, if necessary, at least one other monomer (b) by a conventionally known polymerization method. The most preferred embodiment is the emulsion polymerization method because it is easy to make it water-based.

In the emulsion polymerization method, conventionally known polymerization catalysts and surfactants are used, and synthesis can be performed by methods such as the so-called monomer dropping method, multistage polymerization method, and pre-emulsion method.

In the present invention, the blending ratio of polymer (A) and polymer CB) is not particularly limited;
The amount of polymer (B) is preferably in the range of 1 to 500 parts by weight per 00 parts by weight.If the amount is less than 1 part by weight, the degree of curing will be insufficient and durability, water resistance, etc. will be impaired.
When the amount exceeds 1 part by weight, the adhesion to the substrate tends to be impaired.

In the present invention, the composition containing the polymer (A) 8 and the polymer (B) is further added with an aqueous latex (C) as necessary.
can be blended. By blending the aqueous latex (C), adhesion to the substrate, coatability, pigment miscibility, etc. may be improved. Water-based latex used (C
), a wide variety of known materials can be used, such as acrylic aqueous dispersions, vinyl acetate aqueous dispersions, styrene-butadiene aqueous dispersions, natural rubber latex, and the like. Such aqueous latex contains carboxyl groups,
Functional groups such as sulfonic acid groups, mercapto groups, and amine groups may be introduced, and so-called carboxyl-modified latexes in which carboxyl groups are introduced are particularly preferred.

The amount of the aqueous latex (C) to be blended is not particularly limited as long as it does not impede the purpose of the present invention. The amount is preferably up to 1000 parts by weight.

The composition of the present invention may contain a solvent, a plasticizer, an inorganic or organic filler, as necessary, to the extent that the object of the present invention is not impaired.
It is also possible to add coloring pigments, dyes, thickeners, dispersants, wetting agents, antifoaming agents, antiseptic and antifungal agents, antirust agents, and the like.

When producing the composition of the present invention, there are no particular limitations,
A wide range of methods commonly used by those skilled in the art can be applied, for example, to an aqueous solution, diluted solution or dispersion of the polymer (A), add the polymer (B), if necessary, the aqueous latex (C) and other additives. All you have to do is add and mix as appropriate, and when using the paint 1 as a surface treatment agent, coating agent, adhesive, sealant, etc., use a roll coater, spray, dipping, brush coating, or other method commonly used in the industry. Just apply it to the material.

〔Effect of the invention〕

The aqueous resin composition according to the present invention cures in a short time even at room temperature, and has various properties such as excellent mechanical strength, water resistance, solvent resistance, heat resistance, durability, and adhesion to substrates. It is capable of forming a film.

Therefore, the aqueous resin composition according to the present invention can be effectively used in various applications such as paints, surface treatment agents, coating agents, adhesives, and sealants.

〔Example〕

The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.

In the examples, unless otherwise specified, % means % by weight and parts means parts by weight.

Reference Example 1 782.4 parts of deionized water and 128 parts of a 15% aqueous solution of Hitenol N-08 (manufactured by Daiichi Kogyo Seiyaku ■) were placed in a flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel. and an appropriate amount of ammonia water (28%)
The pH was adjusted to 9.0, and the mixture was heated to 70° C. while slowly flowing nitrogen gas. 64 parts of a 5% aqueous solution of potassium persulfate was poured into the solution, followed by 3 parts of a monomer mixture of 288 parts of butyl acrylate, 288 parts of styrene, and 64 parts of 2-impropenyl-2-oxazoline. During the 0 reaction, nitrogen gas was blown in and the internal temperature was kept at 1°C for 70 parts.After the 0 dropping was completed, the temperature was kept at the same temperature for 2 hours, and then the internal temperature was raised to 80°C. Stirring was continued for an hour to complete the reaction. Thereafter, it was cooled to obtain an aqueous resin dispersion (1) with a nonvolatile content of 39.8%.

Reference Example 2.3 In Reference Example 1, the same operation as in Reference Example 1 was repeated except that the composition of the polymerizable monomer mixture was changed as shown in Table 1 to obtain aqueous resin dispersion [2] [3] ] was obtained.

ff51 table Examples 1-3. Comparative Examples 1 to 4 Aqueous dispersions were prepared according to the formulations shown in Table 2, and 20 to ±
The film was cast on a Teflon plate under conditions of 0.5° C. and 75±3% RH, and then dried for one day and night to create a film with a thickness of about 0.3 t+w. The obtained film was left under the same conditions for 7 days, and then used as a test piece and subjected to the following tests.

(2) #Solvent A test piece was immersed in acetone at room temperature for 72 hours, and its swelling rate and dissolution rate were calculated according to the following formula.

Swelling rate = size x 100 (%)
Length before soaking Weight before soaking? ) Film strength was measured using an Instron tensile tester at a tensile speed of 10 cm/min.

3) Boiling water resistance The appearance of the film after being immersed in boiling water for 4 hours was observed.

In addition, the water-dispersible polyester resin in Table 2.

The water-soluble melamine resin, epoxy resin, and aziridine compounds are as follows.

・Water-dispersible polyester resin: Pyronal MD-1930 (manufactured by Toyobo Co., Ltd.) ・Water-soluble melamine resin: Sumitex Resin M-3 (manufactured by Sumitomo Chemical) ・Epoxy resin: Epicron 85-75W (Dainippon Ink & Chemicals) Co., Ltd.) Aziridine-based compound: Chemitite DZ-22E (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) Examples 4 to 9. Comparative Example 5.6 Aqueous dispersions were prepared according to the formulations shown in Table 3, and using these, polyolefin sheets for building materials (corona discharge treatment 40.0811 thickness) and type ■ were prepared under the following agreed conditions. It was laminated with plywood (2.7 arms thick).

[Lamination conditions]

Coating t: 12g/30cm2 Coating method 2 Manual roll press conditions: Pressing at 0.5 kg/cm2 for 3 hours (room temperature) Curing: Room temperature for 5 days Normal strength, water resistance strength, heat resistance strength and # Water retention strength was measured according to the following method.

Normal strength = 180 degree beer strength was measured at 20° C. and 60% RH.

Water resistance strength: The product was left in water at 20'C for 20 hours, and the 180 degree peeling strength while wet was measured.

Heat resistance strength: 180 degree peeling strength was measured immediately after being left at 60°C for 1 hour.

Boiling water resistance strength: After immersed in divine water for 4 hours, immersed in water at 20℃ for 3 hours.
The sample was left to stand for 0 minutes, and the 180 degree beer strength while wet was measured.

The beer strength was measured using an Instron tensile tester at a tensile speed of 30 cm/min.

The water-soluble polyolefin resin, water-dispersible polyurethane resin, and vinyl acetate aqueous dispersion in Table 3 are as follows.

Water-soluble polyolefin resin: An aqueous solution obtained by dispersing 100 parts of Isoban-06 (manufactured by Clareisoprene Chemical ■) in 247 parts of water, and then adding 53 parts of 25% aqueous ammonia.

Water-dispersible polyurethane resin: Hydran HW311 (Manufactured by Dainippon Ink & Chemicals) Vinyl acetate aqueous dispersion: Bond CV270L (manufactured by Konishi ■) Table 3

Claims (1)

[Scope of Claims] 1. One or two selected from the group consisting of water-soluble, water-dilutable, or water-dispersible polyester resins, polyurethane resins, and polyolefin resins having a functional group that can react with an oxazoline group. The above polymer (A), general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. and R_5 is an acyclic organic group having an addition-polymerizable unsaturated bond.) Addition-polymerizable oxazoline (a) represented by An aqueous resin composition characterized by containing a polymer (B) formed by: and, if necessary, an aqueous latex (C).