WO2008018589A1

WO2008018589A1 - Water-compatible reactive resin and process for producing the same

Info

Publication number: WO2008018589A1
Application number: PCT/JP2007/065723
Authority: WO
Inventors: Tetsuo Sakurai
Original assignee: National Starch And Chemical Investment Holding Corporation
Priority date: 2006-08-11
Filing date: 2007-08-10
Publication date: 2008-02-14
Also published as: JP2009143969A; CN101511890A

Abstract

A water-compatible reactive resin giving a film which is equal in gloss, transparency, solvent resistance, and adhesion to films obtained from conventional water-compatible acrylic resins but is improved in water resistance, especially resistance to blushing with water; and a process for producing the resin. The water-compatible reactive resin is obtained by polymerizing (B) one or more polymerizable unsaturated monomers in the presence of (A) a water-compatible urethane resin having (a1) a reactive silyl group capable of forming a crosslinked structure and (a2) an anionic group. The urethane resin (A) preferably contains the reactive silyl group (a1) in an amount of 0.1-10 wt.% in terms of silicon amount and contains the anionic group (a2) in an amount of 0.01-1.1 meq/g. The monomers (B) preferably comprise an alkyl (meth)acrylate and a polymerizable silane monomer (C). The water-compatible reactive resin can form a film having a change in the value of resistance to blushing with water (ΔL) of 10 or lower.

Description

Specification

Water-based reactive resin and method for producing the same

Technical field

The present invention relates to an aqueous reactive resin containing a urethane resin and a bull resin (preferably an acrylic resin) and a method for producing the same, and the aqueous reactive resin is a base (or binder) such as an aqueous coating agent and an adhesive. ) Is preferably used.

Background art

As an aqueous coating resin, an acrylic resin has been conventionally used for various coating applications due to its excellent weather resistance and toughness. Water-based acrylic resins can be easily manufactured in various forms, from emulsion types to microemulsion types, and are generally excellent in weather resistance, gloss, alkali resistance, transparency, solvent resistance and adhesion. Although it has the advantage of providing a film (coating or coating), it is inadequate in terms of bending resistance, impact resistance, wear resistance, etc., and at the same time has good adhesion to both polyester and polyolefin substrates. There is also a problem that this is extremely difficult.

[0003] In addition to acrylic resins, one of the resins used as coating resins is urethane resin. Urethane resins have a problem that they are excellent in adhesion to both polyester and polyolefin substrates, are balanced and expensive, and have insufficient weather resistance.

[0004] By the way, when an ionic group and / or a hydrophilic group is introduced in order to impart water-solubility or water-dispersibility to a urethane resin, a coating film obtained as compared with a solvent-type urethane resin paint is obtained. The water resistance and hot water resistance can be low. However, considering the impact on the environment, urethane-based paints and urethane-based adhesives are also in a time when it is strongly desired to be water-based rather than solvent-based.

[0005] Patent Document 1 discloses a urethane resin and its emulsion (aqueous solution or aqueous dispersion) blended in a water-based paint or water-based adhesive. As described above, the urethane emulsion is excellent in storage stability and water resistance, but the urethane resin is insufficient in weather resistance and the like as compared with the acrylic resin. In addition, urethane resin is cheaper than acrylic resin. Therefore, it is not preferable from the viewpoint of cost to contain a large amount of such urethane emulsion in the water-based paint.

[0006] Since demands for coating agents, such as higher quality required for coatings and lower costs, have been diversifying and highly functional, in order to meet such demands, The approach using a single material is considered difficult to meet the requirements. For this reason, various proposals using a plurality of materials having different characteristics have been made.

[0007] For example, Patent Document 2 discloses an adhesive composition in which a urethane resin and an acrylic resin are mixed. However, when the film is formed, the resulting mixture of urethane resin and acrylic resin is not sufficiently stable with time, phase separation may occur. Furthermore, Patent Document 3 and Patent Document 4 disclose urethane polymer dispersions obtained by emulsion polymerization of acrylic monomers in the presence of water-based urethane resins. The urethane bur polymer dispersions disclosed in Patent Documents 3 and 4 are insufficient in terms of water resistance and solvent resistance capable of forming a film having excellent physical properties. According to the study by the present inventors, it was recognized that the urethane butyl polymer dispersion disclosed in Patent Documents 3 and 4 was coated on a substrate to form a film, and the film was whitened when immersed in water. Because the film is whitened, the film obtained from the urethane butyl polymer dispersion described in Patent Documents 3 and 4 cannot be said to have sufficient water resistance, and the solvent resistance, which is an advantage of acrylic resin, is the effect of urethane resin. It is recognized that it has declined.

Patent Document 1: Japanese Patent Laid-Open No. 9241349 (Patent No. 3618882)

Patent Document 2: Japanese Patent Laid-Open No. 5-117611

Patent Document 3: Japanese Patent Laid-Open No. 5-132535

Patent Document 4: Japanese Patent Laid-Open No. 6-80930

Disclosure of the invention

Problems to be solved by the invention

[0009] The present invention has been made to solve the above-described problems, and the object of the present invention is to obtain gloss, transparency, solvent resistance and adhesion from a conventional aqueous acrylic resin. While maintaining at least the same performance as film, it is water resistant, especially immersed in water. Another object of the present invention is to provide an aqueous reactive resin that exhibits high water resistance that does not substantially whiten, that is, provides a film with improved water whitening resistance, and a method for producing the same.

Means for solving the problem

[0010] As a result of diligent studies to solve the above-mentioned problems, the present inventor has obtained an aqueous reactive resin obtained by polymerizing a polymerizable unsaturated monomer in the presence of a specific aqueous urethane resin. Surprisingly, it has been found that a film capable of solving the above-mentioned problems is provided, and the present invention has been completed.

[0011] That is, according to one aspect of the present invention, a new aqueous reactive resin is provided, which polymerizes (B) a polymerizable unsaturated monomer in the presence of (A) an aqueous urethane resin. The (A) aqueous urethane resin is obtained by hydrolyzing a reactive silyl group (hydrolyzable silyl group and hydrolyzable silyl group that can form a crosslinked structure). And (a2) an aqueous reactive resin having an anion group.

In one embodiment of the present invention, (A) the water-based urethane resin has (al) a reactive silyl group capable of forming a crosslinked structure as “Si”, based on the solid content of the water-based urethane resin. Aqueous reaction containing 0.;! To 10% by weight in the resin and containing (a2) anion groups in the aqueous urethane resin based on the solid content of the aqueous urethane resin from 0.01 to 1; 1. lmeq / g Provide functional resin.

[0013] In another embodiment of the present invention, (A) the water-based urethane resin comprises an organic polyisocyanate component, a polyol component, and a compound having at least one active hydrogen and an anion group in the molecule; Provided is a water-based reactive resin obtained by reacting a compound having at least one active hydrogen and a hydrolyzable silyl group in a molecule to obtain a urethane prepolymer, and subjecting the urethane prepolymer to a chain extension reaction.

[0014] In a further embodiment of the present invention, the weight ratio (A) / (B) between (A) the water-based urethane resin and (B) the polymerizable unsaturated monomer is 2/8 to 8 in terms of solid content. An aqueous reactive resin that is / 2 is provided.

[0015] In a preferred embodiment of the present invention, the polymerizable unsaturated monomer (B) provides an aqueous reactive resin comprising a (meth) acrylic acid alkyl ester.

[0016] In another preferred embodiment of the present invention, (B) the polymerizable unsaturated monomer further comprises (C) polymerization. An aqueous reactive resin comprising a reactive silane monomer is provided.

[0017] Further preferred embodiment of the present invention! /, And embodiment! Provided is a water-based reactive resin that forms a film having a change in water whitening value (ΔL) measured by a color difference meter of 10 or less. To do.

In a still further preferred embodiment of the present invention, an aqueous reactive resin composition comprising the above-mentioned aqueous reactive resin is provided.

[0018] In another aspect of the present invention, a method for producing the above-described aqueous reactive resin is provided, which comprises (B) polymerizing a polymerizable unsaturated monomer in the presence of (A) an aqueous urethane resin. The (A) water-based urethane resin comprises (al) a reactive silyl group capable of forming a cross-linked structure (a hydroxysilyl group obtained by hydrolyzing a hydrolyzable silyl group and a hydrolyzable silyl group). And (a2) a method for producing an aqueous reactive resin having a cation group.

[0019] In another embodiment of the present invention, an organic polyisocyanate component, a polyol component, a compound having at least one active hydrogen and a cation group in the molecule, and at least a molecule. A urethane prepolymer is obtained by reacting one active hydrogen and a compound having a hydrolyzable silyl group. After mixing the urethane prepolymer and the (B) polymerizable unsaturated monomer, the urethane prepolymer is chain-lengthened. Provided is a production method in which (A) an aqueous urethane resin is obtained by an extension reaction, and then (B) a polymerizable unsaturated monomer is polymerized.

[0020] In a preferred embodiment of the present invention, the organic polyisocyanate component, the polyol component, a compound having at least one active hydrogen and an anion group in the molecule, and at least one active hydrogen and a hydrolyzable in the molecule. A urethane prepolymer is obtained by reacting a compound having a silyl group, and the urethane prepolymer is subjected to a chain extension reaction to obtain (A) an aqueous urethane resin, and then (B) a polymerizable unsaturated monomer is mixed. And (B) a production method for polymerizing a polymerizable unsaturated monomer.

[0021] In a preferred aspect of the present invention, a coating agent comprising the above-mentioned aqueous reactive resin composition is provided.

In a further aspect of the present invention, an adhesive comprising the above-mentioned aqueous reactive resin composition is provided.

In the present invention, “aqueous” means a state where the resin is present in the aqueous medium, which means that the resin is dissolved in the aqueous medium! Re! Taste.

Furthermore, in the present invention, the “aqueous medium” refers to general water such as tap water, distilled water, or ion exchange water, but is a water-soluble or water-dispersible organic solvent, such as a monomer. An organic solvent having poor reactivity with the raw material of the resin relating to the present invention, for example, acetone, ethyl acetate and the like, and further water-soluble or water-dispersible monomer, oligomer, prepolymer and / or resin, etc. In addition, as described later, it contains an emulsifier, a polymerizable emulsifier, a polymerization initiator, a chain extender and / or various additives that are usually used in the production of water-based resins or water-soluble resins. But you can do it.

The invention's effect

[0023] The aqueous reactive resin of the present invention is (A) an aqueous reactive resin obtained by polymerizing a polymerizable unsaturated monomer in the presence of an aqueous urethane resin, (A) Since the water-based urethane resin has (al) a reactive silyl group capable of forming a crosslinked structure and (a2) ayuon group, gloss, transparency, solvent resistance and adhesion can be obtained from conventional water-based acrylic resins. While maintaining at least the same performance as acrylic film, it exhibits water resistance, especially high water resistance that does not substantially whiten even when immersed in water, i.e. improved water whitening resistance. It is possible to provide an aqueous reactive resin that provides

[0024] Further, with respect to the aqueous reactive resin of the present invention, (A) the aqueous urethane resin has (al) a reactive silyl group capable of forming a crosslinked structure as "Si", based on the solid content of the aqueous urethane resin. Contained in water-based urethane resin from 0.;! To 10% by weight, and contains (a2) anion group in water-based urethane resin based on solid content of water-based urethane resin, from 0.01 to; 1. lmeq / g In this case, water resistance and solvent resistance are further improved.

[0025] Further, regarding the aqueous reactive resin of the present invention, (A) the aqueous urethane resin includes an organic polyisocyanate component, a polyol component, a compound having at least one active hydrogen and an ionic group in the molecule, When a urethane prepolymer is obtained by reacting a compound having at least one active hydrogen and a hydrolyzable silanol group therein, and the urethane prepolymer is obtained by a chain length extension reaction, water resistance and solvent resistance are (Further) improved.

[0026] Furthermore, regarding the aqueous reactive resin of the present invention, the weight ratio (A) / (B) between (A) the aqueous urethane resin and (B) the polymerizable unsaturated monomer is 2 in terms of solid content. / 8 to 8/2, water resistant , Solvent resistance, film transparency and water whitening resistance are further improved.

[0027] With regard to the aqueous reactive resin of the present invention, when the (B) polymerizable unsaturated monomer comprises (meth) acrylic acid alkyl ester, water resistance, solvent resistance and water whitening resistance are Further improved.

[0028] Regarding the aqueous reactive resin of the present invention, when the (B) polymerizable unsaturated monomer further comprises (C) a polymerizable silane monomer, the solvent resistance is further improved.

[0029] Regarding the aqueous reactive resin of the present invention, when a film having a change in water whitening value (ΔL) force S10 or less measured with a color difference meter is formed, a denser film is formed.

Furthermore, since the aqueous reactive resin composition according to the present invention comprises the above-mentioned aqueous reactive resin, gloss, transparency, solvent resistance and adhesion can be obtained from conventional aqueous acrylic resin compositions. While maintaining at least the same performance as acrylic film, water resistance, especially high water resistance that does not cause whitening even when immersed in water, ie, excellent water whitening resistance Can do.

[0030] The method for producing a water-based reactive resin of the present invention is (A) a method for polymerizing a polymerizable unsaturated monomer in the presence of a water-based urethane resin, and (A) a water-based urethane. Since the resin is a production method having (al) a reactive silyl group capable of forming a bridge structure and (a2) ayuon group, gloss, transparency, solvent resistance and adhesion are obtained from conventional aqueous acrylic resins. While maintaining at least equivalent performance as compared to the allyl film, water resistance, particularly high water resistance that does not substantially whiten even when immersed in water, that is, excellent water whitening resistance. The manufacturing method of the water-system reactive resin shown can be provided.

[0031] The production method of the present invention relates to an organic polyisocyanate component, a polyol component, a compound having at least one active hydrogen and an anion group in the molecule, and at least one active hydrogen and water in the molecule. A urethane prepolymer is obtained by reacting a compound having a decomposable silyl group, and after mixing the urethane prepolymer and (B) a polymerizable unsaturated monomer, the urethane prepolymer is subjected to a chain extension reaction (A) an aqueous urethane. In the case of a production method in which a resin is obtained and then (B) a polymerizable unsaturated monomer is polymerized, water resistance, solvent resistance, film transparency and water whitening resistance are further improved.

[0032] The production method of the present invention relates to an organic polyisocyanate component, a polyol component, and a molecule. A urethane prepolymer is obtained by reacting a compound having at least one active hydrogen and an anion group in the molecule with a compound having at least one active hydrogen and a hydrolyzable silyl group in the molecule. In the case of a production method in which (A) a water-based urethane resin is obtained by an extension reaction and then (B) a polymerizable unsaturated monomer is mixed and (B) the polymerizable unsaturated monomer is polymerized, the water resistance, Solvent properties, film transparency and water whitening resistance are further improved.

[0033] Since the coating agent according to the present invention is a coating agent containing the above-mentioned aqueous reactive resin composition, the coating agent obtained from the conventional aqueous resin composition has gloss, transparency, solvent resistance and adhesion. While maintaining at least the same performance as compared to the above, it can exhibit water resistance, particularly high water resistance that does not substantially whiten even when immersed in water as a film, that is, excellent water whitening resistance. .

[0034] Since the adhesive according to the present invention is an adhesive containing the above-described aqueous reactive resin composition, the adhesive obtained from the conventional aqueous resin composition has high brightness, transparency, solvent resistance and adhesion. While maintaining at least the same performance as compared with the above, it is possible to exhibit water resistance, particularly high water resistance that does not substantially whiten even when the film is immersed in water, that is, excellent water whitening resistance.

BEST MODE FOR CARRYING OUT THE INVENTION

[0035] The aqueous reactive resin according to the present invention is an aqueous reactive resin obtainable by polymerizing (B) a polymerizable unsaturated monomer in the presence of (A) an aqueous urethane resin, “(A) Aqueous urethane resin” has “(al) a reactive silyl group capable of forming a crosslinked structure” and “(a2) an anion group”.

[0036] The "(A) water-based urethane resin" according to the present invention has "(a 1) a reactive silyl group capable of forming a crosslinked structure" and "(a2) an anion group" There is no particular limitation as long as the aqueous reactive resin targeted by the present invention can be obtained.

The “reactive silyl group capable of forming a crosslinked structure” includes a hydrolyzable silyl group and a hydroxysilyl group obtained by hydrolysis of a hydrolyzable silyl group.

Here, the “hydrolyzable silyl group” refers to a functional group containing silicon that gives a hydroxyl group (Si—OH) that is bonded to silicon by hydrolysis, for example, trimethoxysilyl group. And alkoxysilyl groups such as trimethoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, methoxysilyl group, monoethoxysilyl group, and monomethoxysilyl group. An ethoxysilyl group, a dimethoxysilyl group, and a methoxysilyl group are preferred! /.

As the “hydrolyzable silyl group”, more specifically, for example,

Formula (I): Si (X) (Y)

[Y is 10 CH or 10 CH or 10 (CH) —〇 (CH) — H (where n and p are integers from 1 to 3),

X is one (CH) one H (where q is an integer from 0 to 3),

a is an integer from 0 to 2. ]

The functional group shown by can be illustrated.

[0038] Here, "hydroxysilyl group" means Si— (OH), -Si (X)-(OH) Si (X)-

(OH) is shown. X is one (CH 3) — H (where q is an integer from 0 to 3) or H. It is thought that a hydroxysilyl group produced by hydrolysis of a hydrolyzable silyl group is bonded to each other to form a siloxane bond to form a crosslinked structure.

[0039] The hydrolyzable silyl group is preferably "Si" and contained in the aqueous urethane resin in an amount of 0.;! To 10% by weight based on the solid content of the aqueous urethane resin. ~ 1.0 wt% It is more preferable that it is contained 0.15 to 0.60 wt% is particularly preferable.

The hydrolyzable silyl group may be a single species or a combination of two or more thereof.

Yes

In this specification, “anion group” refers to a functional group having a negative charge (eg, COO— and SO—), a functional group in which the negative charge is electrically neutralized by a counter cation (eg, COO—Na ⁺ and SO—K ^+, etc.) and functional groups that can release hydrogen ions in water to form negatively charged functional groups (for example, COOH and SOH). It goes without saying that these functional groups can be easily converted into each other by changing the state surrounding each functional group, for example, pH. Regarding the “anion group” in the present invention, these functional groups are used alone or in combination of two or more thereof, depending on the characteristics of the water-based urethane resin. They can be used in combination.

Here, “functional group having negative charge” and “functional group in which negative charge is electrically neutralized by a counter cation” include, for example, carboxylate groups (—COO— and —COOM ¹ ), Sulfonate groups (one SO— and SO M ² ), and phosphate groups (one PO H—, —PO ² and

4 4

PO and M ⁴ is an alkali metal, alkaline

It is an earth metal or ammonium (M ³ and M ⁴ may be either hydrogen. In addition to ammonium NH ⁺ , triethylenolamine may be used as the ammonium.

Four

Etc.) based on organic amines, etc.)].

Furthermore, “functional groups capable of releasing a hydrogen ion in water to form a negatively charged functional group” include, for example, a carboxyl group (one COOH), a sulfonic acid group (or sulfo group) (one SO H

Three

), And a phosphate group (one PO H).

4 2

[0042] As the anion group, a carboxyl group neutralized with a base is preferable. More specifically, a carboxyl group (COO-M ⁺ ) in which a carboxyl group (COOH) is neutralized with a base is preferable. It may be a combination of a carboxyl group and a carboxylate base neutralized with a base.

[0043] The anion group is preferably contained in the aqueous urethane resin in an amount of 0.0 ;! to 1.lmeq / g based on the solid content of the aqueous urethane resin. 0.044—1. It is more preferable than S, more preferably 0.1 to 0.8 meq / g, and most preferably 0.2 to 0.6 meq / g.

[0044] "meq / g" indicates the number of millimoles contained per lg of the aqueous urethane resin solid content. If the diion group is less than 0 · Olmeq / g, the particle size of the (A) water-based urethane resin can be increased, resulting in a significantly unstable dispersion, which can be insufficient as a water-based urethane resin. 1. If it exceeds lmeq / g, the hydrophilicity of the water-based urethane resin becomes too high, which may cause problems such as a decrease in the water resistance of the formed film and an increase in the viscosity of the aqueous resin solution (dispersion).

Yes

[0045] The specific (A) water-based urethane resin according to the present invention includes an "organic polyisocyanate component", a "polyol component", and a "compound having at least one active hydrogen and an anion group in the molecule". And "having at least one active hydrogen and hydrolyzable silyl group in the molecule" Reacting the compound to obtain a urethane prepolymer,

The urethane prepolymer can be obtained by chain extension reaction.

[0046] "Urethane prepolymer" is a reaction between "organic polyisocyanate component", "polyol component" and "compound having at least one active hydrogen and anion group in the molecule" in an NCO-excess state. Next, it is preferable to obtain a part or all of NCO of the terminal NCO-containing urethane prepolymer obtained by reacting with “a compound having at least one active hydrogen and hydrolyzable silanol group in the molecule”. .

The obtained “urethane prepolymer” is preferably dissolved or dispersed in an aqueous solution containing a basic compound and subjected to a chain length extension reaction. If necessary, a chain extender made of a low molecular weight compound having at least two active hydrogens in the molecule may be used.

[0047] If the urethane prepolymer is dispersed or dissolved in water with NCO remaining without using a chain extender, water can act as a chain extender. Urethane prepolymers can have a strong lpoxyl group (COOH), but the carboxyl group (COOH) is converted into anion (one COO) by a basic substance, so even if the chain length is extended, the prepolymer is converted to a high molecular weight. Even if it becomes, it can be easily dispersed in water.

[0048] (A) As the "organic polyisocyanate component" used for the production of the water-based urethane resin, those generally used for the production of the urethane resin can be used. As long as the conductive resin can be obtained, there is no particular limitation. Specific examples thereof include aliphatic diisocyanates such as ethylene diisocyanate, 2,2,4 trimethylhexamethylene diisocyanate 1,6 xamethylene diisocyanate; hydrogenated 4,4'-diphenyl Cycloaliphatic diisocyanates, naphthalene diisocyanates such as enylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexane xylene diisocyanate, isophorone diisocyanate Aromatic diisocyanates such as Of these, aliphatic and / or cycloaliphatic diisocyanates are preferably used alone or in combination for those that should be considered for discoloration over time. It is particularly preferred to use 6-hexamethylene diisocyanate and / or isophorone diisocyanate. [0049] (A) As the "polyol component" used in the production of an aqueous urethane resin, those generally used in the production of a urethane resin can be used, and an aqueous reactive resin intended by the present invention can be obtained. However, there is no particular limitation as long as possible. Examples of such polyols include polyester polyols, polyether polyols, and polycarbonate polyols. As the polyester polyol, at least one kind of dicenolevonic acid such as succinic acid, dartaric acid, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, ethylene glycol, propylene glycol, 1, 4 1 of polyhydric alcohols such as butanediol, 1,3-butanediol, 1,6-hexanediol, neopentinoglycol, 1,8-octanediol, 1,10-decanediol, diethylene glycol, trimethylolpropane, etc. Examples thereof include those obtained by condensation polymerization of more than one species and those obtained by ring-opening polymerization of latatones. As polyether polyols, water and polyhydric alcohols used for the synthesis of the above polyester polyols, bisphenols — phenols such as A, or primary and secondary amines such as ethylene oxide, propylene oxide, oxetane, A product obtained by ring-opening addition polymerization of a cyclic ether such as tetrahydrofuran can be used. Polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, bisphenol A and at least propylene oxide or ethylene oxide. Examples thereof include one obtained by ring-opening addition polymerization (in the case of a copolymer, either a block copolymer or a random copolymer). Examples of the polycarbonate-polynoole include polybutylene carbonate polyol, polyhexamethylene carbonate polyol, and poly (3-methyl-1,5-pentylene) carbonate polyol.

In addition to these, polybutadiene polyol, polyisoprene polyol, polyolefin polyol, and polyacrylic ester polyol can be used alone or in combination as a polyol.

[0050] (A) "A compound having at least one active hydrogen and a cation group in a molecule" used for the production of an aqueous urethane resin means a functional group having at least one active hydrogen in the molecule (for example, Hydroxyl group, amino group, thiol group, etc.) and the above-described anion group, and any compound that can obtain the water-based reactive resin intended by the present invention. It is not limited to. Examples of such compounds include dimethylolpropionic acid, dimethylolbutanoic acid, carboxyl group-containing polyprolatathone diol, sulfate-containing polyester polyol, and di (/ 3-hydroxyethyl) isophthalic acid-5-sulfur. Examples thereof include phonic acid. From the viewpoint of the stability of the aqueous solution or dispersion of the resulting aqueous reactive resin and the colorability of the film formed from the aqueous reactive resin, a compound having a strong lpoxyl group (COOH) as an anion group is preferred. More preferred are methylolpropionic acid, dimethylolbutanoic acid, and carboxyl group-containing poly strength prolatatone diol.

Yes

[0051] "A compound having at least one active hydrogen and an anion group in the molecule" means that the anion group is 0. Olmeq / g in the solid content of the water-based urethane resin (for example, in the case of COOH, in the solid content of the urethane resin) It is usually used so that lOOg contains 45 mg) or more as “COOH”. When using polyols such as general polyesters and polyethers as the polyol component, the anion group is 0.044 meq / g in the aqueous urethane resin solid content lOOg (for example, `` COOH '' in the case of a carboxyl group). 200mg) or more is preferable. If the amount of the anion group is less than 0. Olmeq / g in the aqueous urethane resin solids, the particle size of the (A) aqueous urethane resin can be increased, resulting in an unstable dispersion, which may be unqualified. On the other hand, when the amount of anion groups increases with respect to the solid content of the aqueous urethane resin, (A) the particle size of the aqueous urethane resin decreases and the drying property, glossiness, and transparency are improved, but the water resistance of the resulting film is increased. Solvent resistance can be reduced. If the content of the anion group exceeds 1. lmeq / g, the hydrophilicity of the water-based urethane resin becomes too high, which may cause problems such as a decrease in water resistance of the film and an increase in the viscosity of the resin aqueous solution (dispersion).

[0052] In this specification, (A) the particle diameter of the water-based urethane resin is measured by a dynamic light scattering method using "PARIII" (L ASER PARTICLE ANALYZER) manufactured by Otsuka Electronics Co., Ltd. The average particle diameter of emulsions obtained by analysis by the method. The particle diameter (ie, average particle diameter) of the (A) water-based urethane resin is 50 to 200 nm, preferably S, 50 to 150 nm, and particularly preferably 50 to 120 nm. .

[0053] The content of the anion group is determined in consideration of the balance with the hydrophilicity of the polyol component or the like. For example, if polyoxyethylene glycol is used as the polyol, Since it itself has hydrophilicity, the content of the functional group should be set low, but when a hydrophobic polyol is used, it should be set high.

[0054] The "compound having at least one active hydrogen and hydrolyzable silyl group in the molecule" according to the present invention means a functional group containing at least one active hydrogen and hydrolyzable silyl group in the molecule. The compound is not particularly limited as long as it is a compound having a desired water-based reactive resin. Examples of the “functional group containing active hydrogen” include a hydroxyl group, an amino group, and a thiol group. Examples of the “hydrolyzable silyl group” include the hydrolyzable silyl groups described above. For example, the hydrolyzable silyl group is preferably an alkoxysilyl group. S Desirably, it is any of mono-, di-, and tri-alkoxysilyl groups. May be. Examples of alkoxysilyl groups include methoxysilyl groups and ethoxysilyl groups.

[0055] "Compound having at least one active hydrogen and hydrolyzable silyl group in the molecule"

_Ethoxysilane , _{ΊMercaptopropylmethyljetoxysilane} , _Ν— / 3 -— (Aminoethyl) γ—Aminopropyltrimethoxysilane, Ν— / 3— (Aminoethyl) _γ —Aminopropyl methyldimethoxysilane, _Ί -Aminopropyl Examples include triethoxysilane, Νphenyl- _l -aminopropyltrimethoxysilane, and the like.

In the present invention, these can be used alone or in combination of two or more thereof, but a compound having a trialkoxysilyl group is a more preferred aminotrialkoxysilane _γ − Aminopropyltrimethoxysilane is particularly preferred.

[0056] "A compound having at least one active hydrogen and a hydrolyzable silyl group in the molecule" has a hydrolyzable silyl group as "Si" in 10 mg of aqueous urethane resin per 100 g of aqueous urethane resin solids ( (O.01 wt%) or more is usually used, and the hydrolyzable silyl group is expressed as `` Si '' in an amount of 200 mg per 100 g of aqueous urethane resin solids (0 (2wt%) or more is preferred. When the hydrolyzable silyl group is “Si” and less than 10 mg per 100 g of aqueous urethane resin solid content, the crosslinking density may be low, and the normal effect may be insufficient. In addition, If the water-decomposable silyl group is “Si” and exceeds 10 wt% in the solid content of the water-based urethane resin, the crosslink density in the film becomes too high, and the coating film may become brittle. These hydrolyzable silanol groups, preferably alkoxysilyl groups, are contained in the (A) water-based urethane resin and generally react with water to form hydroxysilyl groups in an aqueous medium.

[0057] (A) A chain extender consisting of "a low molecular weight compound having at least two active hydrogens in a molecule" optionally used in the production of a water-based urethane resin is a functional group containing active hydrogens in the molecule. It is not particularly limited as long as it is a chain extender composed of a compound having at least two and can obtain the target aqueous reactive resin of the present invention. As such “low molecular weight compounds having at least two active hydrogens in the molecule”, low molecular weight dallicols typified by ethylene glycolol, propylene glycolol, 1,4 butanediole, trimethylololepan pan, etc .; ethylenediamine, Propylene diamine, butylene diamine, hexamethylene diamine, 2, 2, 4 trimethyl hexamethylene diamine, isophorone diamine, dicyclohexyl methane 4, 4'-diamine, bisaminodipropylamine, bisaminoger Examples include amines such as tyramine and piperazine; and diethanolamine and hydrazine and derivatives thereof. Of these, the chain extension reaction is usually carried out after the urethane prepolymer has been dispersed in water. For this reason, for example, amines such as hydrazine and other isocyanates having a higher reactivity than water S are effective. It is preferable because it can be used for chain extension reaction. More specifically, for example, piperazine hexahydrate can be more suitably used.

[0058] Further, as the "basic compound", for example, triethylamine, triethanolamine, ammonia, sodium hydroxide, potassium hydroxide and the like can be used. When using the basic compound, it is preferable to determine the amount of the basic compound so that the resulting aqueous urethane resin solution or urethane resin dispersion has a pH of 6-10. If the pH force is less than, the stability of the urethane resin aqueous solution or urethane resin dispersion may be insufficient. On the other hand, when the pH exceeds 10, the stability of the urethane resin aqueous solution or the urethane resin dispersion is good, but the urethane resin may be hydrolyzed, and there is a side chain of the urethane resin! Since the hydrolyzable silyl group incorporated in the terminal can react with each other in an aqueous medium, there may be a problem in storage stability. [0059] Further, in the present invention! /, (A) in the production method of the water-based urethane resin !, in any step! /, And when synthesizing a general urethane resin as necessary Various stabilizers such as antioxidants and UV absorbers, and various surfactants for improving the stability of aqueous urethane resins in aqueous solvents may be added. Furthermore, when producing a film using a water-based urethane resin, if necessary, a crosslinking agent such as a water-soluble isocyanate, a water-soluble epoxy resin, an aziridine compound, or an oxazoline compound may be used in combination.

[0060] Incidentally, (A) the water-based urethane resin can be obtained in the form of a composition present in the aqueous medium by the above-described production method. That is, it can be obtained in the form of an aqueous urethane resin composition (for example, urethane resin aqueous solution, dispersion, suspension or emulsion). Usually, (A) water-based urethane resin is in the form of a composition contained in this aqueous medium, and is adjusted to a desired solid content, viscosity, pH, etc. as necessary. Used for body polymerization.

[0061] The water-based urethane resin composition according to the present invention described above preferably has a solid content of 25 to 50% by weight, more preferably 30 to 45% by weight, more preferably 30 to 40% by weight. Is particularly preferred. Here, solid content refers to the percentage of the weight of the composition after heating for 3 hours in an oven at 105 ° C., based on the weight of the composition before heating.

The aqueous urethane resin composition according to the present invention described above preferably has a viscosity of 10 to 500 mPa's, more preferably 10 to 200 mPa's, and more preferably 10 to 100 mPa's. Particularly preferred. Here, the viscosity means a value measured at 60 ° C. at 30 ° C. using a rotor No .;

The aqueous urethane resin composition according to the present invention described above preferably has a pH force of 6.5 to 8.5, more preferably 7 to 8.5, and particularly preferably 7 to 8. preferable. Here, pH refers to a value measured using a pH meter.

The water-based urethane resin composition according to the present invention has a particle size of 50 to 200 nm, preferably << 50, more preferably 150 nm, and more preferably 50 to 120 nm. Here, the particle diameter refers to the average particle diameter of the emulsion obtained by the measurement by the dynamic light scattering method as described above and the analysis by the curant method.

[0062] (A) In the presence of an aqueous urethane resin, (B) a polymerizable unsaturated monomer The water-based reactive resin which this invention aims at can be manufactured by polymerizing a body.

In the present invention, “(B) polymerizable unsaturated monomer” is a monomer having an ethylenic double bond, and can obtain an aqueous reactive resin intended by the present invention. If there is, there is no particular limitation. The “ethylenic double bond” refers to a carbon atom double bond capable of radical polymerization. Examples of such a functional group having an ethylenic double bond include a bur group (CH 2 = CH 2), a (meth) aryl group (CH 2 = CH-CH 2 and CH 2 = C 2 (

2 2 2 2

CH) — CH—), (meth) atarioxy group (CH 2 = CH—COO and CH 2 = C (CH 2))

3 2 2 2 3

—COO), and one COO—CH═CH—COO. Specific examples include styrene and derivatives thereof, carboxylic acid and esters thereof, and the like.

Carboxylic acid is an acid having a carboxyl group (COOH), and carboxylic acid ester means an ester of carboxylic acid. Carboxylic acids include saturated carboxylic acids and unsaturated rubonic acids. Examples of saturated carboxylic acids include alkanoic acids. Examples of unsaturated carboxylic acids include (meth) acrylic acid, phthalic acid, maleic acid, and phthalic anhydride. And maleic anhydride.

Specific examples of “alkanoic acid” include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, and 2-pentapentanoic acid. The term “alkanoic acid ester” means an ester of an alkanoic acid, and specifically includes (B) a polymerizable unsaturated monomer, and specifically includes butyl acetate, ethylene acetate butyl, propionate butyl, and butyl acetate butyl acetate. Etc. can be illustrated.

[0063] "(Meth) acrylic acid" refers to both acrylic acid and methacrylic acid, and includes acrylic acid, methatalic acid, and combinations of acrylic acid and methacrylic acid.

“(Meth) acrylic acid ester” refers to an ester of (meth) acrylic acid, ie, (meth) acrylate. (Meta) attalate refers to both attalate and metatalate, and includes talate, metatalate, and combinations of attalate and metatalate.

[0064] Specific examples of (meth) acrylate include methyl (meth) acrylate and ethyl (meth) acrylate.

, 2-ethyl hexyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) (Meth) acrylate, (meth) acrylate behenyl and docosyl (meth) acrylate alkyl esters such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxyhydroxyalkyl Examples include esters. These can be used alone or in combination of two or more. (B) (meth) acrylic acid alkyl ester is preferred as the polymerizable unsaturated monomer, and more specifically, methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (Meth) atalylate is preferred in the present invention.

[0065] Examples of "styrene and derivatives thereof" include styrene, methylstyrene, dimethylstyrene, and the like, and styrene is preferable.

(B) As the polymerizable unsaturated monomer, at least one selected from the group consisting of methyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate and styrene is more preferable. preferable.

[0066] The water-based reactive resin according to the present invention has a weight ratio of (A) water-based urethane resin and (B) polymerizable unsaturated monomer ((A) / (B)) in terms of solid content. Considering the balance of the performance of the water-based reactive resin that is preferably / 8 to 8/2, (A) I (B) is particularly preferably 3/7 to 6/4. (A) When the proportion of the water-based urethane resin ((AV (B)) is greater than 8/2, the gloss and transparency, which are the advantages of the resin part obtained from (B) the polymerizable unsaturated monomer, can be maintained. (A) When the proportion of water-based urethane resin ((AV (B)) is less than 2/8, (A) Adhesiveness of base material, which is an advantage of water-based urethane resin, is reduced. Can

Yes

[0067] (A) When (B) the polymerizable unsaturated monomer is polymerized in the presence of an aqueous urethane resin, (B) the polymerizable unsaturated monomer is further converted into (C) a polymerizable silane monomer. It preferably includes a body. That is, it is preferable that the aqueous reactive resin has a silyl group derived from the (C) polymerizable silane monomer. (C) By polymerizing the polymerizable silane monomer, the water whitening resistance of the film obtained from the resulting water-based reactive resin is improved, and further, the substrate adhesion is also improved.

[0068] (C) The polymerizable silane monomer is a silane compound having an ethylenic double bond and having at least one alkoxy group, and obtains an aqueous reactive resin intended by the present invention. There is no particular limitation as long as it can be used. That is, butyltrimethoxysilane, Vinylenotriethoxysilane, Vinylenotripropoxysilane, Vinylenotriisopropoxysilane, Burmethyletoxysilane, Burmethyldipropoxysilane, Buturis (β-methoxyethoxy) silane, γ-Methacryloxypropyltrimethoxysilane , Γ-methacryloxypropyl triethoxysilane, γ _methacryloxypropyl tripropoxysilane, γ _metatali

) Silane and the like can be exemplified. These can be used alone or in combination of two or more. As the alkoxysilane having an ethylenic double bond, a dialkoxysilane having an ethylenic double bond and a trialkoxysilane having an ethylenic double bond are preferable.

Further, trialkoxysilane having an ethylenic double bond is more preferable. Γ_methacryloxy is preferable. The (C) polymerizable silane monomer may be the same as (i) “compound having at least one active hydrogen and hydrolyzable silyl group in the molecule” for producing a water-based urethane resin. Useful! /

[0069] In the present invention, (i) the polymerization of the polymerizable unsaturated monomer can be exemplified by the following embodiments:

After mixing (Α) the urethane prepolymer of the water-based urethane resin and (Β) the polymerizable unsaturated monomer, the urethane prepolymer is subjected to chain extension reaction (Α) to obtain the urethane prepolymer, and then (Β Polymerizing polymerizable unsaturated monomers; and

The urethane prepolymer is subjected to chain extension reaction (i) to obtain an aqueous urethane resin, and then (ii) a polymerizable unsaturated monomer is mixed, and (ii) a polymerizable unsaturated monomer is polymerized.

[0070] In any of the embodiments, when performing the chain extension reaction of the urethane prepolymer, as described above, the urethane prepolymer is dissolved or dispersed in an aqueous solution that may contain a basic compound, and the chain is thus obtained. An extended reaction can be performed. Before the chain extension reaction, (ii) the urethane prepolymer of the water-based urethane resin and (ii) the polymerizable unsaturated monomer are mixed, the obtained mixture is dissolved or dissolved in an aqueous solution that may contain a basic compound. When dispersed, (ii) a chain extension reaction of the urethane prepolymer can be carried out in the presence of the polymerizable unsaturated monomer.

[0071] In both embodiments, (i) a polymerizable unsaturated monomer is polymerized to form a core, and at least part of the force around the core S (A) is covered with an aqueous urethane resin. Core shell It is presumed that composite fine particles having a structure can be obtained.

[0072] The aqueous reactive resin of the present invention comprises (B) a polymerizable unsaturated monomer (in some cases, (C) a polymerizable silane monomer in the presence of the above-mentioned (A) aqueous urethane resin. It can be obtained by radical polymerization of YO! /,). Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

Of these polymerizations, emulsion polymerization is particularly preferred. Emulsion polymerization is radical polymerization using an emulsifier using water as a medium, and a known method can be used. Examples of the emulsion polymerization method include (B) a method in which a polymerizable unsaturated monomer and an emulsifier are charged and polymerized in an aqueous medium, and (B) a continuous or intermittent polymerization in the polymerizable unsaturated monomer and the emulsifier. (B) An emulsion is prepared by adding water to a polymerizable unsaturated monomer and an emulsifier, and this is dropped continuously or intermittently into the aqueous medium. And a method of polymerizing them.

The emulsifier has a monomer emulsifying power, and forms micelles in the process of emulsion polymerization to provide a place for polymerization to the monomer, and is immobilized on the surface of the polymer particles during or after the polymerization to improve the dispersion stability of the particles. Examples of the emulsifier include an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and a polymer surfactant.

In order to improve water resistance, alkali resistance and waterproofness, it is preferable to use a `` reactive surfactant '' having a double bond capable of radical polymerization in one molecule of the emulsifier! / ヽ

[0073] Examples of anionic surfactants include alkali metal alkyl sulfates such as sodium dodecyl sulfate and potassium dodecyl sulfate; ammonium dodecyl polyglycol ether sulfate; ammonium alkyl sulfate such as ammonium dodecyl sulfate; sodium sulfosinoate; Alkyl sulfonates such as alkali metal salts of sulfonated paraffins and ammonium salts of sulfonated paraffins; fatty acid salts such as sodium laurate, trialtal amine oleate, and triethal amine abiate; sodium dodecylbenzene sulfonate, alkaline phenol hydroxy Alkyl aryl sulfonates such as ethylene metal sulfates; high alkyl naphthalenes Examples thereof include sulfonates; naphthalene sulfonic acid formalin condensates; dialkyl sulfosuccinates; polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts.

In the present invention, as an anionic surfactant, dialkylsulfosuccinate

Perex OT-P (manufactured by Kao Corporation) which is (sodium salt) is preferred.

[0074] Nonionic surfactants include, for example, polyoxyethylene alkyl ethers; polyoxyethylene alkyl aryl ethers; sorbitan fatty acid esters; polyoxyethylene sorbitan fatty acid esters; fatty acid monoglycerides such as monolaurate of glycerol; Examples thereof include ethyleneoxypropylene copolymers; condensation products of ethylene oxide and aliphatic amines, amides or acids.

[0075] Examples of the cationic surfactant include monoalkyl ammonium salts, dialkyl ammonium salts, ethylene oxide addition type alkyl ammonium salts, and the like. Examples of amphoteric surfactants include amidopropyl betaine and amino acetate betaine.

Examples of the polymer surfactant include polybulal alcohol; poly (meth) acrylate sodium, potassium poly (meth) acrylate, poly (meth) acrylate ammonium; poly (meth) acrylate, and the like.

[0076] Examples of reactive surfactants include polyoxyethylenearyl glycidyl nourenyl ether sulfates (Adekaria soap SE series, manufactured by Asahi Denka Kogyo Co., Ltd.), a-sulfo ω- (1 (alkoxy) methyl-2 — (2-propenyloxy) ethoxy) Ammonium salt of poly (oxy 1,2-ethaneyl) (Adekaria soap SR series, manufactured by Asahi Denka Kogyo Co., Ltd.), polyoxyethylene (or alkylene) alkyl (or alkenyl) ether sulfate Ammonium salt (PD series, manufactured by Kao Corporation), sulfosuccinic acid type reactive activator (Latemul 180 series, manufactured by Kao Corporation), alkylaryl sulfosuccinate sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries), polyoxy Ethylene nonylpropenyl phenyl ether sulfate ammonium salt Aqualon HS Series, manufactured by Daiichi Kogyo Kusurisha), polyoxyethylene 1 (§ Lil O carboxymethyl) alkyl ether sulfates S. Teruanmoniumu salt (Aqualon ΚΗ series, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Poriokishechire Na Li glycidyl Roh loose phenyl ether (ADEKA Reasoap NE Series manufactured by Asahi Denka Engineering Gosha), polyoxyethylene nonyl Pro Bae vinyl ether (Aqualon RN series, manufactured by Daiichi Kogyo Seiyaku), _a - hydro - _omega - - ( alkoxy) methyl - ₂ - (propenyl Niruo) ethoxy) poly (Okishi 1, 2- Etanjiiru) (ADEKA REASOAP ER series, may be exemplified by Asahi Denka Co., Ltd.).

These may be used alone or in combination of two or more. Of these, alkylarylsulfosuccinic acid sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries) and alkyl etherole sulfate ester ammonium salt (Aqualon® series, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) are preferred.

[0077] Upon polymerization, (i) a polymerization initiator is used to polymerize the polymerizable unsaturated monomer. Examples of the polymerization initiator include water-soluble or oil-soluble persulfates, peroxides, and azobis compounds. For example, potassium persulfate (KPS), sodium persulfate, ammonium persulfate, diisopropylbenzenehydride peroxide, cumenehydride peroxide, t-butylnodide peroxide (Perbutyl H69 manufactured by Nippon Oil & Fats Co., Ltd.) , T-butylenoperoxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydride chloride, 2,2azobis (2,4 dimethylvaleronitrile), etc. The agent can be further exemplified. In addition, sodium bisulfite, sodium formaldehyde sulfoxylate (Superlite C manufactured by Mitsubishi Gas Chemical Company, Inc.), L-ascorbic acid, thiourea dioxide (Techlite manufactured by Asahi Chemical Industry Co., Ltd.), ferrous chloride, A redox initiator combined with a reducing agent such as an organic amine can also be used.

[0078] In emulsion polymerization, a chain transfer agent can be used as necessary to adjust the molecular weight of the resin.

Examples of the chain transfer agent include n-dodecyl mercaptan, t-decyl mercaptan, n-butyl mercaptan, 2-ethylhexylthioglycolate, 2-mercaptoethanol, trichlorobromomethane and the like.

[0079] The aqueous reactive resin according to the present invention can be obtained in the form of a composition present in an aqueous medium in the above-described production method. That is, it can be obtained in the form of an aqueous reactive resin composition (for example, an aqueous reactive resin solution, dispersion, suspension or emulsion). it can. Usually, the water-based reactive resin is used in the form of a composition contained in the aqueous medium after adjusting to a desired solid content, viscosity, pH, etc. as necessary.

[0080] The solid content of the aqueous reactive resin composition according to the present invention is preferably 30 to 55% by weight, more preferably 30 to 50% by weight, and more preferably 35 to 50% by weight. Especially preferred. The method for measuring the solid content is the same as the method described above.

Further, the water-based reactive resin composition according to the present invention preferably has a viscosity power S of 30 ° C, 5 to 2000 mPa's, more preferably 5 to 1000 mPa's, and 5 to 500 mPa's. Particularly preferred is s. The “viscosity” of the aqueous reactive resin composition refers to a value obtained by measurement by the method described above. For the rotor, No .;

[0081] In the film (or film) formed from the aqueous reactive resin according to the present invention obtained as described above, the change in the water whitening value measured with a color difference meter can usually be 10 or less.

Yes

Here, “change in water whitening value (ΔL)” refers to “change in water whitening value” obtained by the method described in Examples.

If the value of A L exceeds 10, it may be insufficient for various uses such as paints for building materials and exterior paints. As the water-based reactive resin, if the AL value of the formed film is 10 or less, a resin having a force AL value of 3 to 8 that can be used for the above applications is practically preferable, and Δ L A resin with a value of 3-4 is particularly preferred!

The aqueous reactive resin of the present invention having a small AL value (excellent in water whitening resistance) of the formed film is useful as a coating agent and an adhesive described later.

[0082] Furthermore, the film (or film) formed from the aqueous reactive resin according to the present invention obtained as described above may preferably have "transparency".

Here, “transparency” refers to “transparency” obtained by the method described in Examples. The “transparency” of the film is more preferably “fully transparent”, more preferably “substantially transparent”.

[0083] Further, the film (or film) formed from the aqueous reactive resin according to the present invention obtained as described above may preferably have "gloss".

Here, “gloss” means “gloss” obtained by the method described in Examples. More preferably, the “gloss” of the film is “very glossy”, preferably “shiny”.

[0084] Furthermore, the film (or film) formed from the aqueous reactive resin according to the present invention obtained as described above may preferably have "solvent resistance".

Here, “solvent resistance” refers to the solvent resistance obtained by the method described in the Examples.

The “solvent resistance” of the membrane should be “almost unchanged” for both toluene and acetone. S is preferable, and “no change” is more preferable!

[0085] Further, the film (or film) formed from the aqueous reactive resin according to the present invention obtained as described above may preferably have a substrate "adhesion".

Here, the base material “adhesion” refers to the base material “adhesion” obtained by the method described in the examples. The base material of the film “transparency” is preferably “initially hardly peeled” and water-resistant “nearly peeled off! /,” For both PET and glass. It is more preferable than S to be water resistant “almost exfoliating! /,” And is particularly preferable to be initial “no exfoliating! /,” And water resistant “not exfoliating at all! /,”! .

[0086] In another aspect, the present invention further provides a coating agent containing the aqueous reactive resin composition. Moreover, this invention provides the adhesive agent containing the said water-system reactive resin composition in a preferable summary.

For the coating agent and adhesive, the water-based reactive resin composition according to the present invention requires a known facial material, antifungal agent, thickener, dispersant, antifoaming agent, antiseptic agent, film forming aid, and the like. It can be obtained by adding S accordingly.

[0087] The pigment is not particularly limited as long as it is usually a pigment. Pigments are usually classified into organic pigments and inorganic pigments.

Examples of organic pigments include, for example, insoluble azo pigments such as Fastero, Gazo Yellow, Gazo Orange, and Naphtho Red, phthalocyanine pigments such as copper phthalocyanine, dye rakes such as Juan rake, tannin lake, and katanol, and isoindolino erogrees And isoindolino pigments such as isoendolino yellow dish, quinacridone pigments, perylene pigments such as perylene cut and perylene maroon, and the like. Examples of inorganic pigments include carbon black, white lead, red lead, yellow lead, silver vermilion, ultramarine blue, and oxide oxide. Examples include nonreto, titanium dioxide, titanium yellow, strontium chromate, molybden red, molybten white, iron black, ritbon, emerald green, guinea green and cobalt blue.

[0088] The filler refers to a substance added for the purpose of improving performance and reducing costs, and is not particularly limited as long as it is normally used as a filler. Specific examples include calcium carbonate, magnesium carbonate, silica, talc, clay, and alumina.

An antifungal agent is a substance added to suppress corrosion of a material, and is not particularly limited as long as it is usually used as an antifungal agent. For example, red lead, white lead, zinc lead, basic white sulfate, basic lead chromate, calcium lead, zinc chromate, cyanate lead, powder, dichloromate, normochromate, sodium nitrite, Examples include dicyclohexylammonium nitrile, cyclohexylamine carbonate, and mildew oil.

[0089] Furthermore, other resins can be mixed in the coating agent and the adhesive as necessary for the purpose of improving various performances. Examples of the other resin include xylene resin, alkyd resin, urethane resin, epoxy resin, acrylic resin, tackifier, wax emulsion and the like.

[0090] In the present invention, the coating agent is preferably used as a top coating agent, particularly as a top coating agent, and a power that can be used as a base coating agent (including an intermediate coating agent and a so-called sealer). Here, the “top coat” is also called a top coat, which is a paint applied on the outermost side, and is applied for the purpose of improving the appearance, glossing, water resistance, weather resistance, etc. It refers to paint. On the other hand, “undercoat” refers to paints other than topcoats, and is mainly used for the purpose of improving waterproofness, moisture proofing, adhesion to the substrate, etc. In some cases, it is also called a primer), and an intermediate coating agent is applied mainly for the purpose of improving waterproofness, moisture resistance, blister resistance, etc., connecting between the topcoat and the sealer.

In the present invention, the adhesive refers to both an aqueous solution type adhesive and a water dispersion type adhesive. The water-based reactive resin of the present invention is used not only as a coating agent or adhesive but also as a component of ink, sealing material, cosmetics and the like.

[0092] As described above, the present invention has an excellent effect. It is thought that it is based on such reasons.

As a result of intensive studies in order to solve the above-mentioned problems, the present inventor whitens a film formed from emulsion by immersing it in water and water is formed at the interface of a plurality of particles constituting the film. I guessed it was caused by Then, if a specific urethane resin and a bull resin are combined with each other using a specific method in which a specific urethane resin and a vinyl resin (preferably an acrylic resin) are not simply mixed, then it can be obtained. We thought that it would be possible to obtain an aqueous reactive resin that does not allow water to enter the interface between the particles constituting the film.

[0093] That is, (al) a reactive silyl group capable of forming a crosslinked structure and (a2) a cation group (A) (A) radical polymerization of a polymerizable unsaturated monomer in the presence of an aqueous urethane resin As a result, the specific water-based urethane resin and the vinyl resin obtained by radical polymerization of the polymerizable unsaturated monomer (B), preferably an acrylic resin, are combined in a simple combination. A resin can be obtained. When radical polymerization is carried out in an aqueous medium, (A) the water-based urethane resin can act as a protective colloid, and (B) the polymerizable unsaturated monomer is polymerized to have a high molecular weight and the surroundings. It is considered that at least a part is covered with (A) water-based urethane resin. As a result, it is considered that a core-shell structure can be formed in which (A) the water-based urethane resin is the shell and (B) the bull-based resin polymerized with the polymerizable monomer is the core. The water-based reactive resin having such a core-shell structure is formed by bonding (A) water-based urethane resins of the shell to each other by forming a cross-linked structure with (al) reactive silyl groups. It is considered that water enters the water and, as a result, the water whitening resistance of the film obtained from the obtained water-based reactive resin is excellent. (B) The force that the bull resin formed from the polymerizable unsaturated monomer is considered to form the core S, and the property based on this bull resin has a much undesirable effect from the urethane resin that forms the shell. It is thought that it can be maintained without receiving.

[0094] The water-based reactive resin of the present invention is characterized in that the water whitening value of the formed film changes (AU is usually 10 or less. AL shows a small value, that is, water whitening resistance. It is considered that the shell of the aqueous reactive resin of the present invention indirectly indicates that the shell of the water-based reactive resin is a highly water-resistant (Α) urethane resin. The (al) crosslink of silyl groups that can form a cross-linked structure forms a shell with a core chenole structure. (A) Water hardly enters between water-based urethane resins, and as a result, the water-based resin is formed into a film. It is considered that even when immersed in water, it does not become white, that is, water whitening resistance is improved.

Hereinafter, the present invention will be described using examples and comparative examples for the purpose of explaining the present invention in more detail and more specifically. These examples are for explaining the present invention and do not limit the present invention.

Example

[0095] (A) Production of water-based urethane resin

Manufacture of water-based urethane resin (A-I)

In a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, and reflux condenser, isophorone diisocyanate (IPDI, manufactured by Sumika Bayer) 66.6 g, polyester diol (Nippon Polyurethane Industry Co., Ltd.) (Nipporan 4073 MW2000) 150g, dimethylolpropionic acid (DMPA) 12.lg, add 150g of ethyl acetate as solvent, 25g of N-methylolene 2-pyridone, and heat to 80 ° C using an oil bath. For 4 hours. Thereafter, the temperature was lowered to 60 ° C., 9.9 g of γ-aminopropyltrimethoxysilane (GE SILQUEST A1100 manufactured by Toshiba Silicone Co., Ltd.) was added, and the mixture was reacted for 20 minutes. After cooling to 50 ° C, 8.3 g of triethylamine was added and stirred for 10 minutes. Next, the prepolymer in which the NCO group remains is dispersed in 343 g of water and immediately piperazine hexahydrate (Ρζ 6Η 0) 11.6 g

An aqueous solution in which 2 was dissolved in 70 g of water was added, and a chain extension reaction was carried out at 50 ° C. for 3 hours to increase the molecular weight. Ethyl acetate was removed from the liquid thus obtained with a rotary evaporator to obtain a resin dispersion having a solid content of 35%.

[0096] Manufacture of water-based urethane resin (A-II)

In a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 66.6 g of isophorone diisocyanate (IPDI, manufactured by Sumika Bayer Co., Ltd.), polyhexamethylene carbonate diol (Japan) Nippon Polyurethane Industry Co., Ltd. Nipponran 980N MW2000) 150 g, dimethylolbutanoic acid (DMBA) 13.3 g is added, 150 g of ethyl acetate and 25 g of N-methyl-1-pyrrolidone are added as a solvent, and an oil bath is used. Heat to ° C for 4 hours I adapted it. Thereafter, the temperature was lowered to 60 ° C., 9.9 g of γ-aminopropyltrimethoxysilane (GE SILQUEST A1100 manufactured by Toshiba Silicone Co., Ltd.) was added and reacted for 20 minutes. After cooling to 50 ° C, 8.3 g of triethylamine was added and stirred for 10 minutes. Next, disperse the prepolymer with the NCO group remaining in 345 g of water, immediately add an aqueous solution of piperazine hexahydrate (（ζ 6Η 0) 11. 6 g in 70 g of water, and add 50 ° C. At 3 hours chain length extension

2

To increase the molecular weight. Ethyl acetate was removed from the liquid thus obtained with a rotary evaporator to obtain a resin dispersion having a solid content of 35%.

[0097] Manufacture of water-based urethane resin (A III)

In a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 6-6 g of isophorone diisocyanate (manufactured by IPDI Sumika Bayer Co., Ltd.), polytetramethylene glycol (Mitsubishi Chemical ( PTMG2000 MW2000) 150g, dimethylololebutanoic acid (DMBA) 13.3g was added, 25g of N-methyl-2-pyrrolidone was added as a solvent, and heated to 80 ° C using an oil bath and reacted for 4 hours. . Thereafter, the temperature was lowered to 60 ° C., and 9.9 g of γ aminopropyltrimethoxysilane (GE Toshiba Silicone Co., Ltd. SILQUEST A1100) was added and allowed to react for 20 minutes. After cooling to 50 ° C, 8.3 g of triethylamine and 163 g of methyl methacrylate HMMA (corresponding to (B) polymerizable unsaturated monomer) were added and stirred for 10 minutes. Next, disperse the prepolymer with the NCO group remaining in 464 g of water, and immediately add an aqueous solution of 11.6 g of piperazine hexahydrate (Ρζ 6Η 0) dissolved in 70 g of water.

2

In addition, a chain extension reaction was performed at 50 ° C. for 3 hours to increase the molecular weight, and a resin dispersion having a solid content of 25% was obtained.

[0098] Manufacture of water-based urethane resin (A—IV)

In a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 66.6 g of isophorone diisocyanate (IPDI Sumika Bayer Co., Ltd.), polyester diol (manufactured by Nippon Polyurethane Industry Co., Ltd.) (Nipporan 4073 MW2000) 150g, dimethylolbutanoic acid (DMBA) 8.9g, ethyl acetate 150g, N-methylolene 2 pyrrolidone 25g as a solvent, heated to 80 ° C using an oil bath, reacted for 4 hours I let you. Thereafter, the temperature was lowered to 60 ° C., and 3.3 g of γ-aminopropyltrimethoxysilane (GE Toshiba Silicone Co., Ltd. SILQUEST A1100) was added and reacted for 20 minutes. Then cool down to 50 ° C Then, 6. lg of triethylamine was added and stirred for 10 minutes. Next, the prepolymer in which the NCO group remains is dispersed in an aqueous solution in which 6.7 g of PELEX OTP, which is an emulsifier, is dissolved in 334 g of water, and immediately piperazine hexahydrate (Ρζ 6 11 0) 11 An aqueous solution in which 6g is dissolved in 70g of water

2

And a chain length extension reaction was performed at 50 ° C. for 3 hours to increase the molecular weight. Ethyl acetate was removed from the liquid thus obtained with a rotary evaporator to obtain a resin dispersion having a solid content of 35%.

[0099] Manufacture of water-based urethane resin (A—V)

In a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 66.6 g of isophorone diisocyanate (IPDI Sumika Bayer Co., Ltd.), polyester diol (manufactured by Nippon Polyurethane Industry Co., Ltd.) (Nipporan 4073 MW2000) 150 g, dimethylolbutanoic acid (DMBA) 8.9 g, add 150 g of ethyl acetate and 25 g of N-methylolene 2-pyrrolidone as solvent, and heat to 80 ° C using an oil bath. The reaction was performed for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and 3.3 g of γ-aminopropyltrimethoxysilane (GE SILQUEST A1100 manufactured by Toshiba Silicone Co., Ltd.) was added and reacted for 20 minutes. After cooling to 50 ° C, 6. lg of triethylamine was added and stirred for 10 minutes. Next, the prepolymer with the NCO group remaining was dispersed in an aqueous solution of 18.7 g of KH1025 (Daiichi Kogyo Seiyaku Co., Ltd.), an emulsifier, in 322 g of water, and immediately piperazine 6 Hydrate (Ρζ · 6Η 0) 11.6g water 70g

2

An aqueous solution dissolved in was added, and a chain extension reaction was carried out at 50 ° C. for 3 hours to increase the molecular weight. Ethyl acetate was removed from the liquid thus obtained with a rotary evaporator to obtain a resin dispersion having a solid content of 35%.

[0100] Manufacture of water-based urethane resin (Α'-VI)

Except for not reacting with γ -aminopropyltrimethoxysilane, water-based urethane resin (A—I

), A resin dispersion having a solid content of 35% was obtained.

[0101] Manufacture of water-based urethane resin (Α'-VII)

Except for not reacting with γ -aminopropyltrimethoxysilane, water-based urethane resin (Α—

A resin dispersion having a solid content of 35% was obtained in the same manner as in V).

[0102] Tables 1 and 2 show the production of water-based urethane resin (Α-I) to water-based urethane resin (Α'-VII) and the properties of the obtained water-based resin (or resin dispersion). In the table, the solid content, viscosity and The method for measuring pH and the like is as described above. The particle diameter is an average particle diameter.

[table 1]

[Table 2]

Component A-V A'-VI A'-¾a

IPDI ISO 66.6 66.6 66.o

: Tsu * 'run 4073 150 150 150

Run 980N%

PTMG2000

At least one activity in the DMPA molecule 12.1

Dissociates into neutral hydrogen and anions

DMBA 8.9 8.9

Compound with various functional groups

At least one activity in the molecule

Hydrogen and ¾ water-decomposable silica

A1100 3.3

Compound having a ru group

Amihanlan (crosslinking agent)

Acetic acid: 150 150 150

匪 A solvent

MP 25 25 25 i Thiamin Basic compound (neutralized) 6.1 8.3 6.1 Water 322 325 316. Lex OTP alligator surfactant

KH1025 Reactive wrinkle 7 Wrinkle surfactant 18.7 18.7 Water 70 70 70

Pz-6H20 Chain extender 11.6 11.6 11.6 Solids (wt%) 35 35 35

25 35 30 ρΗ 7.5 7.4 7.4 Particle size (nm) 105 60 110 A: ON group (meq / g) 0.26 0.39 0,27

Si amount (wt¾) 0.18 0 0 Example 1

In a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, add 100 g of aqueous urethane resin (AI), raise the temperature to 70 ° C, and replace the system thoroughly with nitrogen. did. Next, anionic reactive surfactant (Eleminol JS2 manufactured by Sanyo Kasei Co., Ltd.) 0.2g, water 6.7g, methinoremethacrylate (MMA) 15.3g, 2-ethylhexyl acrylate (2EH A) 8g 30.2 g of the emulsion consisting of was dropped with a dropping funnel over 2 hours. At the same time, 69% butyl hydride peroxide aqueous solution (Perbutyl H69 manufactured by Nippon Oil & Fats Co., Ltd.) 0.09 g of oxidizer dissolved in water 2.7 g and sodium formaldehyde sulfoxylate (Superlite C Mitsubishi Gas Chemical Co., Ltd.) )) A reducing agent in which 0.03 g was dissolved in 4.7 g of water was dropped from a dropping funnel over 2 hours. After completion of the emulsified liquid droplets, the polymerization was completed by maintaining at 70 ° C. for 1 hour to obtain an aqueous reactive resin emulsion having a solid content of 39%. [0105] Example 2

In a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, add 100 g of aqueous urethane resin (AI), raise the temperature to 70 ° C, and replace the system thoroughly with nitrogen. did. Next, anionic surfactant (Perex OTP Kao Co., Ltd.) 0 · 2g, water 6 · 7g, methyl methacrylate (MMA) 15g, 2-ethylhexyl acrylate (2EHA) 8g, metatalyloxypropyltrimethoxysilane 30.2 g of an emulsion composed of (SZ-6030 manufactured by Toray Dow Coung Silicone Co., Ltd.) was added dropwise over 2 hours with a dropping funnel. In addition, 69% butyhydride peroxide aqueous solution (Perbutyl H69, manufactured by Nippon Oil & Fats Co., Ltd.) Oxygen dissolved in 2.7 g of water in 0.09 g and thiourea dioxide (Techlite manufactured by Asahi Denka Kogyo Co., Ltd.) ) A reducing agent in which 4.7 g of water was dissolved in 0.03 g was dropped from the dropping funnel over 2 hours. After completion of emulsifying droplets, hold at 70 ° C for 1 hour to complete the polymerization, and water-based reactive resin with a solid content of 39%

[0106] Example 3

A four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser was charged with 100 g of aqueous urethane resin (AI) and 17.8 g of water, and the temperature was raised to 70 ° C. Was sufficiently replaced with nitrogen. Next, a reactive reactive surfactant (Eleminol JS2 Sanyo Kasei Co., Ltd.) 0.3g, water 10g, styrene (St) 5g, methinoremethacrylate (MMA) 15g, 2-ethylenohexylatari 45.3 g of an emulsion consisting of 5 g of rate (2EHA), 5 g of butyl acrylate (BA), and 5 g of butyl metatalylate (BMA) was added dropwise over 2 hours using a dropping funnel, together with 69% Iodine Peroxide Aqueous Solution (Perbutyl H69 manufactured by Nippon Oil & Fats Co., Ltd.) Oxidizing agent prepared by dissolving 0.13 g in 4 g of water and thiourea dioxide (Techlite Asahi Denka Kogyo Co., Ltd.) 0.05 g in 7 g of water The dissolved reducing agent was dropped from the dropping funnel over 2 hours, and after completion of the emulsified droplets, the polymerization was completed by holding at 70 ° C for 1 hour to obtain an aqueous reactive resin emulsion having a solid content of 40%. .

[0107] Example 4

A four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser was charged with 85.7 g of aqueous urethane resin (A-11) and 79. lg of water, and the temperature was raised to 70 ° C. The system was thoroughly replaced with nitrogen. Next, methyl methacrylate (HMMA) 6.5 g, 2-ethylhexyl ateryl (2EHA) 63 g and methacryloxyprovir trimethoxysilane (SZ-6030, manufactured by Toray Dawco Iyung Silicone Co., Ltd.) 0.5 g of a mixed solution 70 g was added dropwise over 2 hours with a dropping funnel. At the same time, 69% butyl hydride peroxide solution (perbutyl H69 manufactured by Nippon Oil & Fats Co., Ltd.) 0.15 g of oxidant dissolved in 5 g of water and thiourea dioxide (Tetsukrite Asahi Denka Kogyo Co., Ltd.) 0 A reducing agent in which 06 g was dissolved in 10 g of water was dropped from the dropping port over 2 hours. After completion of the emulsified droplets, the polymerization was completed by maintaining at 70 ° C. for 1 hour to obtain an aqueous reactive resin emulsion having a solid content of 40%.

[0108] Example 5

A four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser was charged with 85.7 g of water-based reactive urethane (A-II) and 61. lg of water, and the temperature was raised to 70 ° C. The system was thoroughly replaced with nitrogen. Next, reactive nonionic anionic surfactant (AQUALON KH1025 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5g, water 18g, methylmetatalylate (MMA) 46.2g, 2-ethylhexyl acrylate (2EHA) 28.3 g of an emulsion composed of 23.3 g and methacryloxypropylmethyldimethoxysilane (Y-9910, manufactured by Toray Dow Coung Silicone Co., Ltd.) was added dropwise over 2 hours using a dropping funnel. In addition, 69% butyl hydride peroxide aqueous solution (Perbutyl H69, manufactured by Nippon Oil & Fats Co., Ltd.) 0. 15 g of oxidizer dissolved in 5 g of water and thiourea dioxide (Techlite manufactured by Asahi Denka Kogyo Co., Ltd.) 0 A reducing agent in which 06 g was dissolved in 10 g of water was dropped from the dropping funnel over 2 hours. After completion of the emulsified liquid droplets, the polymerization was completed by holding at 70 ° C. for 1 hour to obtain an aqueous reactive resin emulsion having a solid content of 40%.

[0109] Example 6

In a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 200 g of aqueous urethane resin (A-III) was added and heated to 75 ° C. did . Next, an aqueous solution in which 2 g of potassium persulfate (KPS) O. was dissolved in 10 g of water was added to react with methyl methacrylate HMMA contained in the aqueous urethane resin (A-III). After the MMA reaction, hold at 80 ° C for 1 hour to complete the polymerization, and an aqueous reactive resin emma with a solid content of 40%

[0110] Example 7

In a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, After adding 100 g of a retane resin (A-IV) and 17.8 g of water and raising the temperature to 70 ° C., the inside of the system was sufficiently substituted with nitrogen. Next, anionic surfactant (manufactured by PELEX OTP Kao Co., Ltd.) 0.2 g, water 10 g, methyl metatalylate (MMA) 26.2 g, 2-ethyl hexyl acrylate (2ΕΗΑ) 8 · 6 g, methacrylate Roxypropinoremethinoresinmethoxysilane (Y-9910, Toray Dow Corning Silicone Co., Ltd.) 4 · 2 g of an emulsion consisting of 0 · 2 g was added dropwise over 2 hours using a dropping funnel. At the same time, 69% butyl hydride peroxide solution (perbutyl H69 manufactured by Nippon Oil & Fats Co., Ltd.) 0.13 g of oxidant dissolved in 4 g of water and thiourea dioxide (Techlite Asahi Denka Kogyo Co., Ltd.) A reducing agent prepared by dissolving 0.05 g in 7 g of water was dropped from the dropping funnel over 2 hours. After completion of the emulsified droplet dropping, the polymerization was completed by maintaining at 70 ° C. for 1 hour to obtain an aqueous reactive resin emulsion having a solid content of 40%.

[0111] Example 8

A four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser was charged with 100 g of aqueous urethane resin (AV) and 17.8 g of water. Was sufficiently substituted with nitrogen. Next, reactive nonionic anionic surfactant (AQUALON KH1025, Daiichi Kogyo Seiyaku Co., Ltd.) 0.5g, water 10g, styrene (St) 5g, methyl methacrylate ク) 6 · lg, 2-ethylhexyl talylate (2EHA) 18.6g, Butylmethalylate (BMA) 5g, Methacryloxypropyltrimethoxysilane (SZ-6030, manufactured by Toray Dawco Ibushiri Silicone Co., Ltd.) 0.3g of emulsion 45.5g was added dropwise. It was dripped in a funnel over 2 hours. In addition, a 69% butyl hydride peroxide solution (perbutyl H69 manufactured by Nippon Oil & Fats Co., Ltd.) was dissolved in 0.13 g of water in 4 g of water and thiourea dioxide (Techlite Asahi Denka Kogyo Co., Ltd.). (Manufactured) A reducing agent prepared by dissolving 0.05 g in 7 g of water was dropped from the dropping funnel over 2 hours. After the completion of the emulsified droplet dropping, the polymerization was completed by holding at 70 ° C. for 1 hour to obtain an aqueous reactive resin emulsion having a solid content of 40%.

[0112] Example 9

A four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser was charged with 57. lg of aqueous urethane resin (A-1) and 63.9 g of water, and the temperature was raised to 70 ° C. The system was thoroughly replaced with nitrogen. Next, ayu-reactive surfactant (Eleminol JS2 manufactured by Sanyo Kasei Co., Ltd.) 0 · 7g, water 2 · 9g, methinoremethacrylate MMA (MMA) 50g, 2-tuccinorehexinole creire (2EHA) 29.5 g, Methacryloxyprovir trimethoxysilane (SZ-6030, Toray Dow Coung Silicone Co., Ltd.) 0 · 5 g of emulsified solution 103 · 6 g was added dropwise over 2 hours using a dropping funnel. did. At the same time, 69% butyl hydride peroxide aqueous solution (Perbutyl H69 manufactured by Nippon Oil & Fats Co., Ltd.) Oxidizing agent prepared by dissolving 0.3g in 9g of water and thiourea dioxide (Techlite manufactured by Asahi Denka Kogyo Co., Ltd.) A reducing agent prepared by dissolving 0.1 g of water in 16 g of water was dropped from the dropping funnel over 2 hours. After completion of the emulsified droplets, the polymerization was completed by maintaining at 70 ° C. for 1 hour to obtain an aqueous reactive resin emulsion having a solid content of 40%.

[0113] Comparative Example 1

An aqueous resin emulsion having a solid content of 39% was obtained in the same manner as in Example 1 except that the aqueous urethane resin (ウレタン '-VI) was used.

Comparative Example 2

An aqueous resin emulsion having a solid content of 39% was obtained in the same manner as in Example 2 except that the aqueous urethane resin (ウレタン '-VI) was used.

Comparative Example 3

In the same manner as in Example 8 except that methacryloxypropyltrimethoxysilane (SZ-6030 manufactured by Toray Dow Cowing Silicone Co., Ltd.) was not reacted with water-based urethane resin (Α'-VII), 39% aqueous resin emulsion was obtained.

Comparative Example 4

An aqueous resin emulsion having a solid content of 40% was obtained in the same manner as in Example 8, except that the aqueous urethane resin (Α'-VII) was used.

[0114] Comparative Example 5

In a four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser tube, 0.5 g of anionic reactive surfactant (Eleminol JS2 manufactured by Sanyo Kasei Co., Ltd.) and 104.5 g of water were added. After raising the temperature to 80 ° C, the system was sufficiently purged with nitrogen. Next, anionic reactive surfactant (Eleminol JS2 manufactured by Sanyo Kasei Co., Ltd.) 2.5g, water 30g, styrene (St) 40g, methinomethacrylate (MMA) 24.3g, 2-ethylhexyl An emulsion (132.5 g) consisting of 35 g of attalylate (2EHA) and 0.7 g of methacryloxypropyltrimethoxysilane (SZ-6030, manufactured by Toray Dow Cowing Silicone Co., Ltd.) was added dropwise over 2 hours using a dropping funnel. At the same time Then, an aqueous solution in which 0.5 g of potassium persulfate was dissolved in 15 g of water was dropped from the dropping funnel over 2 hours. After completion of the emulsified liquid droplets, the polymerization was completed by maintaining at 80 ° C. for 1 hour to obtain an aqueous acrylic resin emulsion having a solid content of 40%.

Comparative Example 6

The aqueous acrylic resin emulsion obtained in Comparative Example 5 and the aqueous urethane resin (AI) were mixed at a ratio of 4 to 6 to obtain an aqueous resin emulsion having a solid content of 37%.

Comparative Example 7

The aqueous acrylic resin emulsion obtained in Comparative Example 5 and the aqueous urethane resin (Α′-VI) were mixed at a ratio of 6: 4 to obtain an aqueous resin emulsion having a solid content of 37%.

The aqueous resin emulsions obtained for the above use are summarized in Tables 3-6. The methods for measuring solid content, viscosity, ρΗ and the like are as described above.

[Table 3]

Four]

Ingredients Example 5 Example 6 Example 7 Example 8 Example 9

A-l 57.1

A-11 (A) Urethane resin 85.7

A I II (Shirame-Contained) Aqueous dispersion 200

A-! V 100

A V 100

Water 61.1 17.8 17.8 63.9

St 5

匪 46.2 26.2 6.1 50

2EHA (B) polymerizable unsaturated monomer 23.3 8.6 18.6 29.5

BA

BMA 5

(G) Polymerizable silane monomer 0.3 0.5

S2-6030

Taku ¹ river Kishifu 'E3 pin birds Kishishiran

(C) polymerizable silane monomer

Y-9910 METAKU ¹ jn xif '0 tisshi' methoxy 0.5 0,2

Silane

I Remi / One ¾ ^ S2 To anionic reactive surfactant 0.7. Lex OTP dione surfactant 0, 2

Reactivity Wow surface activity 0, 5

KH1025 0.5

Agent

Water 18 10 10 22.9 酸化 Oxidizer 0.15 0.13 0.13 0.30 Water 5 4 4 9

KPS oxidizing agent 0.2

Water 10

Su-Λ'-Light C base agent

water

Thiourea dioxide Reduced soot 0,06 0.05 0.05 0, 1 Water 10 7 7 16 Solid content (wt%) 40 40 40 40 40 Viscosity 10

12 15 10 10

(mPas)

1

ρ H 7.1 7.2 7.1 Urethane / 7 Scale ¹ ) Ratio 3/7 6/4 5/5 5/5 2/8 Acrylic calculation Tg 13

2 105 40 -22

(.C) 5] Ingredients Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4

A 'VI (Α)' Urethane resin 100 100

(Sila / not contained) Water dispersion

A '-VI I 100 100 D; ωr

Water 17.8 17.8

St 5 5 醫 A 15.3 15 6.1 6.1

2EHA (B) polymerizable unsaturated monomer 8 8 18.6 18.6

BA

BMA 5 5

(G) Polymerizable silane monomer

SZ-6030 0— 3 0.3 Coxyf n n Pitoxysilane

(G) Polymerizable silane monomer

Y-9910

Uriloxif 'a rumethylsi' methoxysilane

Anionic anti-IS surfactant 0.2 0.2

H'Rex OTP ANWA surfactant

H1025 Reactive On 7-on surfactant 0.5 0.5 Water 6.7 6.7 10 10

H69 Oxidizing agent 0.09 0.09 0.13 0.13 Water 4.7 4.7 4 4 PS Oxidizing agent

water

Suha 'Lai G G Powder 0.03 0.03

Water 4.7 4.7

Chile dioxide urea ia glaze 0.05 0.05 Water 7 7 Solid (wt%) 39 39 40 40

15 15 10 10 pH 7.4 7.3 7.2 7.1 Urethane / 7krill ratio 6/4 6/4 5/5 5/5 out

18 18 21 —22 (° C) 6]

Comparative Example 5 Comparative Example 6 Comparative Example 7

(Ak ^ Resin)

(A) Urethane resin 60

A-l

(Containing silanol) aqueous dispersion

(A) 'Urethane resin 60

A '-VI

(-Not contained) aqueous dispersion

Comparative Example 5 7 Kryl resin aqueous dispersion 40 40

: E-remino-ol JS2 anionic reactive surfactant 0.5

Water 104.5

St 40

關 A 24.3

2EHA (B) polymerizable unsaturated monomer 35

BA

BMA

(C) polymerizable silane monomer

SZ-6030 0.7

Tacri axif 'B pi) 1 Limethoxysilane

I Remile JS2 Phionic Reactive Surfactant 2.5

Wed 30

KPS oxidizing agent 0.5

Wed 15

Solid content (wt%) 40 37 37

50 35 35 ρΗ 3.2 7.2 7.2 Urethane / 1W ratio 0/10 5.7 / 4.3 5.7 / 4.3 Acrylic calculation Tg

17 17 17 (° C.) The glass transition temperature (Tg) of the acrylic resin part described in Tables 3 to 6 was obtained by calculation using the following Fox formula. The Tg values of homopolymers of each monomer used to calculate Tg are shown in parentheses. For acrylic resins containing methacryloxypropyltrimethoxysilane (SZ-6030) and methacryloxypropylmethyldimethoxysilane (Y-9910), the Tg calculated excluding these is the glass transition temperature of the acrylic resin. And

Fox formula:

∑ (Wn / Tgn) / 100

[Wn: wt% of monomer n contained in acrylic resin

Tgn: Tg of each monomer's homopolymer (absolute temperature)]

St: Styrene (105 ° C), MMA: Methyl methacrylate (105 ° C)

2EHA: 2-ethylhexyl acrylate (70 ° C) BMA: n-Butylmetatalylate (20 ° C)

BA: n-Butyl acrylate (156 ° C)

[0120] The water-based resin emulsions of Examples 1 to 9 and Comparative Examples 1 to 7 were evaluated for transparency, gloss, solvent resistance, and adhesion. The evaluation method is described.

Apply a resin dispersion on a glass plate using a 5 mil (125 m) applicator, dry at 105 ° C for 5 minutes, leave the resulting film at room temperature for 1 hour, and visually check the transparency of the film. Observed with.

◎: Completely transparent

○: almost transparent

△: Slightly opaque

X: Completely opaque

[0121] <Glossy>

Apply a resin dispersion on a glass plate using a 5 mil (125 m) applicator, dry at 105 ° C for 5 minutes, leave the resulting film at room temperature for 1 hour, and visually check the gloss of the film. More observed.

◎: Very shiny

Y: Shiny

△: not very glossy

X: No gloss

[0122] <Solvent resistance>

The resin dispersion was applied onto a glass plate using a 5 mil (125 m) applicator and dried at 105 ° C. for 5 minutes. The obtained films were left at room temperature for 1 hour, then immersed in toluene or acetone for 24 hours, and the state of each film was visually observed.

◎: No change

○: Almost no change

Δ: Whitening is observed

X: Whitening and swelling are observed [0123] <Water whitening resistance>

The resin dispersion was applied onto a glass plate using a 5 mil (125 m) applicator and dried at 105 ° C. for 5 minutes. The obtained film is allowed to stand at room temperature for 1 hour, and is attached with a black acrylic plate (N = L. 89 a = -0.0.06 b = —0. 10 made by Nippon Test Panel) with a color difference meter and L value (L0) Measured. Next, the obtained film is immersed in warm water of 40 ° C, and after 24 hours, the glass plate is taken out immediately, wiped off moisture, and within 1 minute after taking out the glass plate, the color difference ( L1) was measured. The A L value of water whitening resistance was calculated from the following equation.

Water whitening resistance Δ L = L 1— L0

[0124] <Adhesion>

The resin dispersion was applied to a PET film (Diafoil O300E Mitsui Chemicals Polyester Film) and a glass plate with a 3 mil applicator and dried at 105 ° C for 5 minutes. Next, a peel test was performed with Cellotape (registered trademark) to examine the initial adhesion. Next, immerse in warm water at 40 ° C, quickly remove the glass plate after 24 hours, wipe off the moisture, dry for 30 minutes at room temperature, perform a cello tape (registered trademark) test, and adhere after being immersed in warm water. Properties, that is, water-resistant adhesion was examined.

A: Not peeled at all

○: hardly peeled

Δ: Peel slightly

X: Exfoliates considerably

[0125] The evaluation results are shown in Table 7 below.

[Table 7]

Adhesion Adhesion Solvent resistance Solvent resistance

Transparency Gloss Water whitening (PET)

卜 Ruen (glass)

Initial / Waterproof Initial / Waterproof Example 1 @ o ○ 4 ® / o @ / © Example 2 © @ ◎ 3 ® / o © / © Example 3 ◎ @ o ○ 4 ◎ / O © / © Example 4 ® @ © ® 3 © / 0 © / © Example 5 @ © 0 0 3 ◎ / 〇 @ / © Example 6 ◎ ® @ ◎ 4 ◎ / O © / © Example 7 0 0 7 © / © ® / o Example 8 ◎ @ @ 8 © / © © / 〇 Example 9 ◎ oo 9 © / 0 @ / o Comparative Example 1 © XX 31 ® / x ◎ / χ Comparative Example 2 © © 厶厶 25 © / 厶 ® / χ Comparative example 3 XX 25 ® / x ® / χ Comparative example 4 ◎ Δ Δ 5 © / 厶 ® / χ Comparative example 5 © © oo 17 © / x ® / @ Comparative example S 0 〇厶厶 15 ® / Δ ◎ / © Comparative Example 7 o ○ XX 25 @ / χ © / 厶 As is clear from Table 7, the water-based reactive resins of Examples;! To 9 have excellent water whitening resistance (AL is 10 or less). Other properties (transparency, gloss, solvent resistance, adhesion) are also excellent in balance of performance. On the other hand, Comparative Examples 1 to 7 have insufficient performance balance. In Comparative Example 4, although water whitening resistance is excellent (AL is 5), solvent resistance and adhesion are insufficient. Comparative Examples 1, 2, 3, 5, 6, and 7 all have insufficient water whitening resistance (AL is considerably high).

Claims

The scope of the claims

[1] (A) An aqueous reactive resin obtained by polymerizing a polymerizable unsaturated monomer (B) in the presence of an aqueous urethane resin,

(A) An aqueous urethane resin is an aqueous reactive resin having (al) a reactive silyl group capable of forming a crosslinked structure and (a2) an anion group.

[2] (A) The water-based urethane resin has (al) a reactive silyl group capable of forming a cross-linked structure as “Si” in the water-based urethane resin based on the solid content of the water-based urethane resin. 2. The aqueous reactive resin according to claim 1, comprising: 10% by weight and containing (a2) anion groups in the aqueous urethane resin in an amount of 0.01 to 1; lmeq / g based on the solid content of the aqueous urethane resin.

[3] (A) Water-based urethane resin

An organic polyisocyanate component, a polyol component, a compound having at least one active hydrogen and an anion group in the molecule, and a compound having at least one active hydrogen and a carohydrolyzable silyl group in the molecule are reacted. Get urethane prepolymers,

The water-based reactive resin according to claim 1, which is obtained by subjecting the urethane prepolymer to a chain extension reaction.

[4] The weight ratio (A) / (B) between (A) the water-based urethane resin and (B) the polymerizable unsaturated monomer is 2/8 to 8/2 in terms of solid content. The water-system reactive resin in any one of.

[5] The aqueous reactive resin according to any one of [1] to [4], wherein the polymerizable unsaturated monomer (B) comprises an alkyl (meth) acrylate.

[6] The polymerizable unsaturated monomer (B) further comprises (C) a polymerizable silane monomer.

The water-system reactive resin in any one of -5.

[7] The water-based reactive resin according to any one of [6] to [6], wherein a film having a change in water whitening value (ΔL) measured by a color difference meter of 10 or less is formed.

[8] An aqueous reactive resin composition comprising the aqueous reactive resin according to any one of Claims! To 7.

[9] (A) A claim wherein (B) a polymerizable unsaturated monomer is polymerized in the presence of an aqueous urethane resin;

A method for producing the aqueous reactive resin according to any one of 7;

(A) A water-based urethane resin comprises (al) a reactive silyl group capable of forming a crosslinked structure and (a2) A method for producing an aqueous reactive resin having an on group.

[10] An organic polyisocyanate component, a polyol component, a compound having at least one active hydrogen and an anion group in the molecule, and a compound having at least one active hydrogen and a hydrolyzable silyl group in the molecule. React to obtain urethane prepolymer,

After mixing the urethane prepolymer and (B) a polymerizable unsaturated monomer, the urethane prepolymer is subjected to a chain length extension reaction to obtain (A) an aqueous urethane resin, and then (B) a polymerizable unsaturated monomer. 10. The production method according to claim 9, wherein the body is polymerized.

[11] An organic polyisocyanate component, a polyol component, a compound having at least one active hydrogen and an anion group in the molecule, and a compound having at least one active hydrogen and a hydrolyzable silyl group in the molecule. React to obtain urethane prepolymers,

The urethane prepolymer is subjected to chain extension reaction to obtain (A) an aqueous urethane resin, and then (B) a polymerizable unsaturated monomer is mixed, and (B) the polymerizable unsaturated monomer is polymerized. 9. The production method according to 9.

[12] A coating agent comprising the aqueous reactive resin composition according to claim 8.

[13] An adhesive comprising the aqueous reactive resin composition according to claim 8.