JP3483839B2 - Aqueous resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aqueous resin composition used for forming a film in a wide range of fields such as paint bases, adhesives, fiber processing materials and civil engineering, and a method for producing the same. In particular, it relates to an aqueous resin composition capable of forming a film excellent in durability (weather resistance) against deterioration by light such as ultraviolet rays and visible rays.

[0002]

2. Description of the Related Art Generally, an aqueous resin composition is superior in safety and hygiene to a solvent-based resin composition (using an organic solvent). Widely used in fields such as civil engineering. However, the aqueous resin composition is usually related to the fact that it contains a water-soluble component such as an emulsifier, and the water resistance of the film formed, weather resistance, etc., as compared with a solvent-based resin composition, There is a problem of being inferior.

Therefore, various studies have been conducted in order to improve the water resistance, weather resistance, etc. of the formed film (Japanese Patent Laid-Open No. 8-27349 and Japanese Patent Laid-Open No. 10-120724).
(See Japanese Patent Publication). However, the water resistance, weather resistance, etc. of the film formed from these aqueous resin compositions are not always sufficient, and further improvement is required.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and the weather resistance of the film formed is
At least one selected from water resistance and adhesion,
An object of the present invention is to provide an improved aqueous resin composition as compared with a conventional aqueous resin composition.

[0005]

Means for Solving the Problems As a result of intensive studies by the present inventor, a monomer containing a monomer having an ethylenic double bond and containing a photostable group and / or an ultraviolet absorbing group is used. The mixture of polymers is copolymerized in an organic solvent, the solvent is replaced with an aqueous medium, and then neutralized as necessary, and in the presence of a specific copolymer, an acrylic monomer is polymerized in the aqueous medium. It was found that the water-based resin composition obtained as described above is excellent in the above-mentioned performance.

The present invention provides a new aqueous resin composition,
It is a monomer (A1) containing a light-stable group and / or an ultraviolet-absorbing group and having an ethylenic double bond, (A1)
2) A monomer containing an alkoxysilyl group and having an ethylenic double bond, (A3) a monomer containing an anionic group and having an ethylenic double bond, and (A4) another ethylenic double bond. (A1): 0.1 to 40% by weight, (A2): 0.1 to 20% by weight, (A3): 0.5 to 30% by weight, and (A4): The remaining mixture is copolymerized in an organic solvent, the organic solvent is replaced with an aqueous medium, and neutralized if necessary to obtain a specific (A) copolymer, and (A) copolymer An aqueous resin composition obtained by a production method comprising a step (B) of polymerizing an acrylic monomer in an aqueous medium in the presence of a combination to obtain a polymer, wherein the acrylic monomer / (( (Mixture comprising A1) to (A4)) (weight ratio) is 100 / based on the amount used.
It is an aqueous resin composition of 5 to 100/100. This aqueous resin composition is particularly suitable for forming a film in the fields of paint bases, adhesives, fiber processing materials, and civil engineering.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous resin composition of the present invention is obtained by obtaining a specific (A) copolymer, and then obtaining the specific (A)
It can be produced by obtaining the polymer (B) in the presence of the copolymer.

In the step of obtaining the (A) copolymer, (A
1) A monomer having a light-stable group and / or an ultraviolet absorbing group and having an ethylenic double bond, (A2) A monomer having an alkoxysilyl group and having an ethylenic double bond, (A3) (A1): 0.1 to 40% by weight, comprising (A4) another monomer having an ethylenic double bond and containing an anionic group, and (A4) another monomer having an ethylenic double bond, A2): 0.1 to 20% by weight, (A3): 0.5 to 30% by weight, and (A4): the rest of the mixture are polymerized (radical polymerization) in an organic solvent.

In the present specification, "(A1) a monomer having a light-stable group and / or an ultraviolet-absorbing group and having an ethylenic double bond" (hereinafter also referred to as "(A1) monomer") The term "compound" means a compound that provides a (A) copolymer with a photostable group and / or an ultraviolet absorbing group by a (radical) polymerization reaction.

The "light-stable group" is a functional group having an amino group or a hydroxyl group (so-called hindered amino group or hindered hydroxyl group) around which a substituent having a bulky steric hindrance effect is present. Say.

As used herein, “ethylenic double bond”
The term “double bond between carbon atoms capable of performing a polymerization reaction (radical polymerization)”. As the functional group having such an ethylenic double bond, for example, a vinyl group (CH ₂ ═CH—),
(Meth) allyl group _{(CH 2 = CH-CH 2} - and CH ₂ =
_{C (CH 3) -CH 2 -} ), ( meth) acryloyloxy groups (CH ₂ = CH-COO- and _{CH 2 = C (CH 3)} -
COO-), -COO-CH = CH-COO- and the like can be exemplified.

In the present specification, acrylic acid and methacrylic acid are collectively referred to as "(meth) acrylic acid", and acrylic acid ester and methacrylic acid ester are collectively referred to as "(meth) acrylic acid ester" or Also referred to as "(meth) acrylate". The same applies to the allyl group and the acryloyloxy group.

Therefore, by having both a light-stable group and an ethylenic double bond, for example, the light-stable group is bonded to the ethylenic double bond via an ester bond or an amide bond, and the light stability is improved. A monomer containing a group and having an ethylenic double bond is obtained. Examples of the monomer having a light-stable group and having an ethylenic double bond include so-called hindered amine compounds and hindered alcohol compounds.

The monomer containing a light-stable group and having an ethylenic double bond is

[Of 5] (I): [However, in the formula (I), R ¹ is H or CN,
R ² and R ³ are each H, CH ₃ or C ₂ H ₅ , and may be the same or different, and R ⁴ is H and has 1 to 1 carbon atoms.
18 alkyl or -CO-C of (R ⁵⁾ = CH
(R ⁶⁾ (where, R ⁵ and R ⁶ are each H, a CH ₃ or C ₂ H _5, it may be the same or different.), And X represents an imino group (-NH-) or oxygen Atom (-O-)
Represents ] The hindered amine type compound shown by these is preferable.

Specific examples of the monomer represented by the formula (I) include 4- (meth) acryloyloxy-1,2,2,2.
6,6-Pentamethylpiperidine, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2,2
6,6-Pentamethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-4-cyano-
2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-4-cyano-1,2,2
6,6-Pentamethylpiperidine, 4- (meth) acryloylamino-4-cyano-2,2,6,6-tetramethylpiperidine, and 4- (meth) acryloylamino-4-cyano-1,2,2 , 6,6-Pentamethylpiperidine can be exemplified.

Further, as the monomer represented by the formula (I),
1- (meth) acryloyl-4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 1
-(Meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-
(Meth) acryloyl-4- (meth) acryloyloxy-4-cyano-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6, 6-Tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloyloxy-4-cyano-2,2,6,6-tetramethylpiperidine, and 1- (meth) acryloyl-4-
(Meth) acryloylamino-4-cyano-2,2,2
An example is 6,6-tetramethylpiperidine.

Further, as the monomer represented by the formula (I),
4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,
6-tetramethylpiperidine, 4-crotonoyloxy-1,2,2,6,6-pentamethylpiperidine, 4-
Crotonoylamino-1,2,2,6,6-pentamethylpiperidine, 4-crotonoyloxy-4-cyano-
2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-4-cyano-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6, 6-tetramethylpiperidine, 1
-Crotonoyl-4-crotonoylamino-2,2
6,6-Tetramethylpiperidine, 1-crotonoyl-
4-crotonoyloxy-4-cyano-2,2,6,6
-Tetramethylpiperidine, and 1-crotonoyl-4
-Crotonoylamino-4-cyano-2,2,6,6-
An example is tetramethylpiperidine. Particularly, 4- (meth) acroyloxy-1,2,2,6,6-pentamethylpiperidine is preferable.

The monomers containing a light-stable group and having an ethylenic double bond can be used alone or in combination.

In the present specification, the "ultraviolet absorbing group" absorbs an ultraviolet ray capable of exciting and breaking the chemical bond of the copolymer (A) to be obtained, and as a result, improves the weather resistance of the film. A functional group that contributes. The "ethylenic double bond" is as described above.

By having both an ultraviolet absorbing group and an ethylenic double bond, more specifically, for example, the ultraviolet absorbing group is ethylenic through an ester bond, an amide bond, an alkylene group, an alkyleneoxy group or the like. By combining with a double bond, a monomer containing an ultraviolet absorbing group and having an ethylenic double bond is obtained.

As a monomer containing an ultraviolet absorbing group and having an ethylenic double bond, 2- (2'-hydroxy-5 ')
-Methacryloyloxyethyl-3-tert-butylphenyl) -2H-benzotriazole, 2- (2'-
Hydroxy-5'-methacryloyloxypropyl-3
-Tert-butylphenyl) -5-chloro-2H-benzotriazole, and 3-methacryloyl-2-hydroxypropyl-3- [3 '-(2''-benzotriazolyl) -4-hydroxy-5-tert. Examples thereof include benzotriazole-based compounds such as -butyl] phenylpropionate.

Further, as a monomer containing an ultraviolet absorbing group and having an ethylenic double bond, 2- (2'-hydroxy-5'-methacryloyloxymethylphenyl) -2H is used.
-Benzotriazole, 2- (2'-hydroxy-5 '
-Methacryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-methacryloyloxypropylphenyl) -2H-benzotriazole, and 2- (2'-hydroxy-5'-methacryloyloxyhexylphenyl) ) -2H-benzotriazole can be illustrated.

Further, as a monomer containing an ultraviolet absorbing group and having an ethylenic double bond, 2-hydroxy-4-
[3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone, 2,2'-dihydroxy-
4- [3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone, 2-hydroxy-4-
(Meth) acryloyloxybenzophenone, 2-hydroxy-5- (meth) acryloyloxybenzophenone, 2-hydroxy-4-((meth) acryloyloxy-ethoxy) benzophenone, 2-hydroxy-4-
Examples thereof include benzophenone compounds such as ((meth) acryloyloxy-diethoxy) benzophenone, 2-hydroxy-4-((meth) acryloyloxy-triethoxy) benzophenone, and 2-hydroxy-4-methacryloyloxyethylbenzophenone.

As a monomer having such an ultraviolet absorbing group and having an ethylenic double bond,

## STR00006 ## (II): [However, in the formula (II), R ⁷ is H or C
H ₃ and Y represent an alkylene group having 1 to 6 carbon atoms. ] The compound shown by these is preferable. In particular, 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl)-
2H-benzotriazole is preferred. The monomers containing an ultraviolet absorbing group and having an ethylenic double bond can be used alone or in combination.

The mixture for obtaining the (A) copolymer is
(A1) A monomer containing an ethylenic double bond containing a light-stable group and / or a UV-absorbing group is added in an amount of 0.1 to 4
It preferably comprises 0% by weight, more preferably 1 to 30% by weight, particularly preferably 1 to 20% by weight.

Further, in the present specification, the term "(A2) monomer containing an alkoxysilyl group and having an ethylenic double bond" (hereinafter also referred to as "(A2) monomer") mainly means (A ) A compound which forms a crosslinked structure inside the copolymer or between (A) the copolymers and can contribute to the improvement of weather resistance, water resistance and the like of the film obtained from the aqueous resin composition of the present invention. .

Here, the "alkoxysilyl group" is a silicon-containing functional group that gives a hydroxyl group (Si-OH) bonded to silicon by hydrolysis, such as a trimethoxysilyl group or a triethoxysilyl group, Dimethoxymethylsilyl group, dimethoxymethylsilyl group,
It refers to an alkoxysilyl group such as a diethoxysilyl group, a monoethoxysilyl group, and a monomethoxysilyl group, and a trimethoxysilyl group and a triethoxysilyl group are particularly preferable. The “ethylenic double bond” is as described above.

Examples of the monomer (A2) containing an alkoxysilyl group and having an ethylenic double bond include, for example, (IV): R ¹⁰ Si (OR ¹¹ ) (OR ¹² ) (OR ¹³ ). In IV), R ¹⁰ represents a functional group having an ethylenic double bond, and R ¹¹ , R ¹² and R ¹³ represent an alkyl group having 1 to 5 carbon atoms, which may be the same or different from each other. ] The compound shown by these can be illustrated.

As the functional group having an ethylenic double bond for R ¹⁰ , for example, vinyl group, (meth) allyl group, (meth) acryloyloxy group, 2- (meth) acryloyloxyethyl group, 2- (meth) Acryloyloxypropyl group, 3- (meth) acryloyloxypropyl group,
Examples thereof include a 2- (meth) acryloyloxybutyl group, a 3- (meth) acryloyloxybutyl group, and a 4- (meth) acryloyloxybutyl group.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ¹¹ , R ¹² and R ¹³ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl group. , A t-butyl group, and a linear or branched alkyl group such as an n-pentyl group.

As the monomer (A2) containing an alkoxysilyl group and having an ethylenic double bond, specifically,
(A2-1) vinyl trimethoxy silane, vinyl trialkoxy silane such as vinyl triethoxysilane and vinyl tri -n- butoxysilane; (A2-2) (III): CH 2 = CR 8 -COO-Z
-Si (OR ⁹ ) ₃ [In the formula (III), R ⁸ is H or C
H ₃ and R ⁹ represent an alkyl group having 1 to 3 carbon atoms, and Z represents an alkylene group having 1 to 6 carbon atoms. ] Ω- (meth) acryloyloxyalkyltrialkoxysilane represented by the formula: (A2-3) allyltrialkoxysilane such as allyltriethoxysilane and allyltrimethoxysilane;
And the like can be preferably exemplified.

(A2) As a monomer containing an alkoxysilyl group and having an ethylenic double bond, (A2-2) (III): CH ₂ ═CR ⁸ —COO-Z
-Si (OR ⁹ ) ₃ [In the formula (III), R ⁸ is H or C
H ₃ and R ⁹ represent an alkyl group having 1 to 3 carbon atoms, and Z represents an alkylene group having 1 to 6 carbon atoms. ] Is more preferable.

Specific examples of the compound represented by the formula (III) include 3- (meth) acryloyloxypropyltrimethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane. Particularly, 3- (meth) acryloyloxypropyltrimethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane are preferable.

These (A2) alkoxysilyl group-containing monomers having an ethylenic double bond can be appropriately selected according to the properties of the (A) copolymer and can be used alone or in combination. can do.

The mixture for obtaining the (A) copolymer is
The amount of the monomer (A2) having an alkoxysilyl group and having an ethylenic double bond is preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, and even more preferably 0.1. It is particularly preferable to contain 5 to 10% by weight.

In the present specification, "(A3) monomer containing an anion group and having an ethylenic double bond" (hereinafter also referred to as "(A3) monomer") means an anion group and an ethylenic double bond. A compound having a bond, which provides a copolymer (A) with an anionic group by a polymerization reaction (radical polymerization) to impart hydrophilicity and anionicity.

"Anion group" is a functional group having a negative charge.
A group (for example, -COO^-And -SO₃ ^-Etc.)
Functional groups that are electrically neutralized by cations (eg,
For example, -COO^-Na⁺And -SO₃ ^-K⁺Etc.)) and
Forming a negatively charged functional group by releasing hydrogen ions in water
Functional groups that can be formed (for example, -COOH and -SO₃H
Etc.). These "functional groups having a negative charge" and
"The release of hydrogen ions in water
The “functional group that can be formed” means the state around each functional group, for example,
For example, it can be easily converted to each other by changing pH etc.
It goes without saying that it is Noh. In the present invention,
Regarding the “on group”, depending on the characteristics of the (A) copolymer,
It is possible to use these functional groups alone or in combination.
it can.

Here, as the “functional group having a negative charge (including a functional group in which a negative charge is electrically neutralized by a counter cation)”, for example, a carboxylate group (—COO ⁻ and —COOM ¹ ), sulfonate (-SO ₃ ^- and -S
O ₃ M ^2), and phosphate groups _{^{(-PO 4 H -, -PO 4}} 2- , and -PO ^₄ M ³ M ₄₎ or the like can be exemplified [where, M ^1, M ^2,
M ³ and M ⁴ are alkali metal, alkaline earth metal or ammonium (it is to be noted that either one of M ³ and M ⁴ may be hydrogen)]. Furthermore, examples of the “functional group capable of releasing a hydrogen ion in water to form a functional group having a negative charge” include, for example, a carboxyl group (—COOH), a sulfonic acid group (—SO ₃ H), and a phosphoric acid group (— It can be exemplified PO ₄ H ₂₎ or the like. The “ethylenic double bond” is as described above.

Examples of such a "(A3) monomer containing an anion group and having an ethylenic double bond" include, for example,
The following compounds can be illustrated: (A3-1) acrylic acid, methacrylic acid, itaconic acid,
A compound having a carboxyl group and an ethylenic double bond, such as crotonic acid, fumaric acid, maleic acid, and a half ester of maleic acid, and a compound having a carboxylic acid group and an ethylenic double bond; (A3-2) Acrylic sulfonic acid , Methacryl sulfonic acid, 2-acryloylamino-2-methyl propane sulfonic acid, 2-methacryloyl amino-2-methyl propane sulfonic acid, compounds having a sulfonic acid group and an ethylenic double bond, such as styrene sulfonic acid, and sulfonic acid A compound having a base and an ethylenic double bond; a compound having a phosphate group and an ethylenic double bond, such as (A3-3) (meth) acrylic acid oxyethylamide phosphate, and a phosphate group and an ethylenic double bond A compound having a bond.

(A3) As a monomer containing an anion group and having an ethylenic double bond, (A3-1) a compound having a carboxyl group and an ethylenic double bond, a carboxylate group and an ethylenic double bond Are preferred, and acrylic acid and methacrylic acid are particularly preferred. Incidentally, a carboxylate group, a sulfonate group, and a counter cation of a phosphate group are preferably ammonium ions and alkali metal ions, and particularly, ammonium ions,
Potassium ion and sodium ion are preferred. These monomers containing an anionic group (A3) and having an ethylenic double bond can be used alone or in combination depending on the properties of the target (A) copolymer.

The mixture for obtaining the (A) copolymer is
(A3) The monomer containing an anionic group and having an ethylenic double bond is preferably contained in an amount of 0.5 to 30% by weight, more preferably 2 to 20% by weight, and 2 to 15% by weight. It is particularly preferable to include.

In the present specification, "(A4) other monomer having an ethylenic double bond" (hereinafter also referred to as "(A4) monomer") means other than the above-mentioned (A1) to (A3). A monomer having an ethylenic double bond, which is capable of being copolymerized (radical polymerized) with the above-mentioned (A1) to (A3), and is a target (A) copolymer It can be appropriately used according to the characteristics of. The “ethylenic double bond” is as described above.

Examples of such “(A4) other monomer having an ethylenic double bond” include the following compounds: (A4-1) methyl (meth) acrylate, ethyl (meth) acrylate. , Propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and cyclohexyl (meth). (Meth) acrylic acid alkyl esters such as acrylates (including (meth) acrylic acid cycloalkyl esters); (A4-2) (meth) acrylic acid esters having an epoxy group such as glycidyl (meth) acrylate; (A4-3) Styrene, vinyltoluene, etc. Styrene and styrene derivatives; (A4-4) Alkenes such as ethylene, and dienes such as butadiene and isoprene; (A4-5) Vinyl ester compounds such as vinyl acetate and vinyl propionate; (A4-6) Chlorinated vinyl compounds such as vinyl chloride and vinylene chloride; (A4-7) Compounds having a cyano group-containing ethylenic carbon-carbon double bond such as acrylonitrile.

(A4) As the other monomer having an ethylenic double bond, (A4-1) (meth) acrylic acid alkyl esters are preferable, and (meth) acrylic acid containing (meth) acrylic acid cycloalkyl ester is included. More preferred are acid alkyl esters. These (A4) and other monomers having an ethylenic double bond can be used alone or in combination.

The copolymer (A) can be obtained by copolymerizing a monomer mixture containing (A1) to (A4) in an organic solvent and substituting the organic solvent with an aqueous medium. (A)
If necessary, the copolymer may be neutralized with an alkaline substance depending on the properties such as water solubility of the copolymer.

The monomer mixture containing (A1) to (A4) is (A1): 0.1 to 40% by weight, (A2): 0.1 to 20% by weight, (A3): 0. 5 to 30% by weight, and (A4): the balance, (A1): 1 to 30% by weight, (A2): 0.5 to 15% by weight, (A3): 2 to 20% by weight, and ( A4): preferably the balance, (A1): 1 to 20% by weight, (A2): 0.5 to 10% by weight, (A3): 2 to 15% by weight, and (A4): the balance. Is more preferable.

The acid value of the resulting (A) copolymer is 200.
It is preferably less than mgKOH / g, 160 mgK
More preferably OH / g or less, 120 mg KO
It is particularly preferably H / g or less.

The copolymerization of the monomer mixture containing (A1) to (A4) is carried out by a conventional solution polymerization method using an appropriate catalyst in an organic solvent and the above monomers. It can be performed by polymerizing the mixture (radical polymerization). Here, the "organic solvent" can be used for copolymerization of a monomer mixture containing (A1) to (A4), and does not substantially affect the polymerization reaction and the adhesive property. If it is, it will not be specifically limited. As such an organic solvent, for example, methanol, ethanol,
Examples include lower alcohols such as propanol and esters such as ethyl acetate, and combinations thereof.

Polymerization reaction such as reaction temperature, reaction time, type of organic solvent, type and concentration of monomer mixture, stirring speed, type and concentration of catalyst, etc. for copolymerization of the mixture containing (A1) to (A4) The condition (1) can be appropriately selected depending on the properties of the target (A) copolymer and the like.

The term "catalyst" as used herein means a compound capable of causing copolymerization of a mixture containing (A1) to (A4) by addition in a small amount and used in an organic solvent. Those capable of satisfying are preferable. For example, ammonium persulfate, sodium persulfate, potassium persulfate, t
-Butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile (A
IBN), 2,2-azobis (2-amidinopropane)
Examples thereof include dihydrochloride and 2,2-azobis (2,4-dimethylvaleronitrile), and particularly 2,2-azobisisobutyronitrile (AIBN).
And 2,2-azobis (2-amidinopropane) dihydrochloride are preferred.

Further, a chain transfer agent or the like can be used as appropriate. As a "chain transfer agent" for controlling the molecular weight,
Compounds well known to those skilled in the art can be used, and examples thereof include mercaptans such as n-dodecyl mercaptan and laurylmethyl mercaptan.

After copolymerization, the organic solvent is replaced by the aqueous medium. The replacement with an aqueous medium can be carried out by a conventional method, and examples thereof include a method of distilling off an organic solvent by distillation and then adding an aqueous medium, and a method of adding an aqueous medium and distilling off an organic solvent. In the present specification, the "aqueous medium" mainly refers to so-called water such as distilled water, ion-exchanged water, and pure water, but may appropriately contain a water-soluble organic solvent such as acetone and lower alcohol. . By replacing the organic solvent with an aqueous medium,
(A) A copolymer can be obtained.

It may be neutralized depending on the properties of the (A) copolymer. Here, the "neutralization" can be performed by adding an alkaline substance that is usually used for neutralization. As a result, in particular, the carboxyl groups in the system are neutralized, so that water solubility can be imparted to the target copolymer. But,
The (A) copolymer need not be completely water-soluble. It is sufficient that the specific (A) copolymer has the required water solubility within a range that does not deteriorate the properties of the desired aqueous resin composition, that is, within a range of the desired predetermined properties.

In the present specification, the "alkaline substance" means a substance exhibiting a pH of more than 7 when dissolved in water, and is not particularly limited as long as it is usually called an alkaline substance. The alkaline substance may be in the form of gas, liquid or solid, but is preferably in the form of an aqueous solution dissolved in water because it can be handled and the neutralization reaction can be easily controlled. Examples of such an "alkaline substance" include ammonia, alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, and the like, but ammonia water,
Aqueous sodium and potassium solutions are preferred.

The alkaline substance is preferably added so that the pH of the aqueous medium containing the copolymer (A) becomes 8.0 or more, and the pH becomes 8.0 to 10.0. Is more preferable, and it is particularly preferable to add it so that the pH is 8.5 to 9.5.

The (A) copolymer according to the present invention has a function as a protective colloid in the polymerization of acrylic monomers described later. Therefore, the (A) copolymer has a function required as a protective colloid, for example, a function that emulsion polymerization can be performed without using an emulsifier and an emulsion can be stabilized. Furthermore, the (A) copolymer also provides the ability of the water-based resin composition of the present invention to be absorbed and adhered to the base.

The (A) copolymer is usually handled in a form existing in an aqueous medium, and is not usually handled by the (A) copolymer alone after being isolated from the aqueous medium. In this case, the amount of the (A) copolymer present in the aqueous medium is expressed using the concentration in the aqueous medium. Here, the concentration of the (A) copolymer is 105
After drying in an oven at 0 ° C. for 3 hours, the weight of the remaining portion is shown as a weight percentage with respect to the weight before drying.

In the present specification, "parts by weight" and "% by weight" are based on the weight of the copolymer (A) containing no medium. Therefore, the weight part of the (A) copolymer is based on the weight calculated based on the concentration of the (A) copolymer.

The aqueous resin composition of the present invention has the above-mentioned (A).
It is obtained by polymerizing an acrylic monomer in an aqueous medium in which the copolymer is present. Since the copolymer (A) functions as a protective colloid in an aqueous medium, it is not necessary to add an emulsifier, but an additional emulsifier may be added as appropriate.

5 to 100 parts by weight (A1) based on the amount used
100 parts by weight of the acrylic monomer for obtaining the polymer (B) are polymerized with respect to the mixture containing (A4).
(A1) to (A) per 100 parts by weight of the acrylic monomer.
The mixture comprising 4) is 5-100 parts by weight,
It is more preferably 5 to 80 parts by weight, and particularly preferably 5 to 60 parts by weight.

In the present specification, the "acrylic monomer" is used to produce an aqueous resin composition which is usually used for paints, adhesives, fiber processing, civil engineering, etc.
Monomers having an ethylenic double bond capable of polymerization (radical polymerization) with monomers selected from acrylic acid derivatives and methacrylic acid derivatives, in addition to monomers selected from so-called acrylic acid derivatives and methacrylic acid derivatives Or a mixture containing a plurality of these monomers.

Further, a polymer obtained by directly polymerizing an "acrylic monomer" under the condition that the above-mentioned specific polymer does not exist (hereinafter also referred to as "polymer of acrylic monomer",
The (B) polymer substantially corresponding to the present specification preferably has practical toughness alone at room temperature (20 to 30 ° C.), and more preferably has gloss.

Examples of such acrylic monomers include the following monomers: (B1) methyl (meth) acrylate, ethyl (meth)
Acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, C1-C18 alkyl groups (including cycloalkyl groups) that may have a substituent such as isooctyl (meth) acrylate, isononyl (meth) acrylate, dodecyl (meth) acrylate, and cyclohexyl (meth) acrylate.
(Meth) acrylic acid alkyl ester compounds having: (B2) hydroxyethyl (meth) acrylate, and hydroxypropyl (meth) acrylate-containing (meth) acrylic acid derivatives; (B3) dimethylaminoethyl (meth) ) Acrylate,
(Meth) acrylic acid derivatives containing nitrogen such as N-methylol acrylamide, N-methylol methacrylamide, t-octyl acrylamide, and diethylaminoethyl (meth) acrylate; (B4) ethylene glycol di (meth) acrylate;
Ethylenic double bonds such as diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and tetramethylolmethane tetra (meth) acrylate (B5) Other (meth) acrylic acid derivatives such as glycidyl (meth) acrylate; (B6) Unsaturation such as ethylene, propylene, isobutylene, butadiene, and isoprene Chain hydrocarbon compounds; (B7) Styrene and its derivatives such as α-methylstyrene; and (B8) Vinyl compounds such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyral; (B9) Vinyl chloride, Vinylidene chloride, chloroprene,
And compounds having a chlorine atom and an ethylenic double bond such as α-chlorostyrene; (B10) Monomers having a nitrogen atom and an ethylenic double bond such as acrylamide, acrylonitrile, N-vinylpyrrolidone and vinylpyridine. (B13) Monomers having at least two ethylenic double bonds such as divinylbenzene, divinylsilane, diallylphthalate, cyclopentadiene, methylenebisacrylamide, diallylmaleate, and tetraallyloxyethane; (B14) The above (A1), (A2), and (A3)
etc. These acrylic monomers can be used alone or in combination.

The acrylic monomers are (B1) alkyl (meth) acrylate compounds having an alkyl group (including a cycloalkyl group) having 1 to 18 carbon atoms which may have a substituent, (A1) A monomer having an ethylenic double bond, which contains a photostable group and / or an ultraviolet absorbing group,
And (A2) at least one selected from the monomers having an alkoxysilyl group and having an ethylenic double bond. Further, it is preferable that (B1) a (meth) acrylic acid cycloalkyl ester compound having a cycloalkyl group having 1 to 18 carbon atoms which may have a substituent is included.

Polymerization of acrylic monomers (radical polymerization)
Can be carried out by using an ordinary emulsion polymerization method in an aqueous medium, using an appropriate catalyst or the like. Here, the "aqueous medium" is as described above. Since the (A) copolymer present in the aqueous medium can act as a protective colloid, an emulsifier is not particularly necessary, but an additional emulsifier can be used as appropriate. Reaction temperature, reaction time, type of aqueous solvent, type and concentration of monomer mixture, stirring speed, and conditions of the polymerization reaction such as type and concentration of catalyst, depending on the characteristics of the desired aqueous resin composition, etc. It can be selected.

Surfactants known to the person skilled in the art can be used here as additional "emulsifiers". A water-soluble polymer compound can also be used, and a cellulose derivative such as methyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose, a water-soluble polyurethane resin, a water-soluble acrylic resin, a polyvinylpyrrolidone-based resin, and polyvinyl alcohol can also be used.

In the present specification, "parts by weight" and "% by weight" are based on the weight of the resin containing no medium. Therefore, the parts by weight of the aqueous resin composition is based on the weight calculated based on the concentration of the aqueous resin composition.

Further, in another gist of the present invention, it is obtained by the polymerization of an acrylic monomer in an aqueous medium (B).
At least a part of the polymer, preferably substantially all,
(A1) A monomer having a light-stable group and / or an ultraviolet-absorbing group and having an ethylenic double bond, (A2) a monomer having an alkoxysilyl group and having an ethylenic double bond, (A3) ) A monomer containing an anion group and having an ethylenic double bond, and (A4) other monomer having an ethylenic double bond, (A1): 0.1 to 40% by weight, (A2): 0.1 to 20% by weight, (A3): 0.5 to 30% by weight, and (A4): coated with the (A) copolymer obtained by copolymerizing the balance of the mixture. An aqueous resin composition comprising a resin, wherein (B) polymer / (A) copolymer (weight ratio) is 100/5 to 100/100. I will provide a.

That is, the present invention provides an aqueous resin composition comprising a resin in which at least a part of the polymer (B), and preferably substantially all of the polymer (B), is coated with the copolymer (A). .

(B) Polymer / (A) Copolymer (weight ratio)
Is 100/5 to 100/100, but 100/5
Is more preferably 100/80, more preferably 100/5
It is particularly preferably 100/60.

Furthermore, in a preferred embodiment of the present invention,
(A1) A monomer having a light-stable group and / or an ultraviolet-absorbing group and having an ethylenic double bond, (A2) a monomer having an alkoxysilyl group and having an ethylenic double bond, (A3) ) A monomer containing an anion group and having an ethylenic double bond, and (A4) other monomer having an ethylenic double bond, (A1): 0.1 to 40% by weight, (A2): 0.1 to 20% by weight, (A3): 0.5 to 30% by weight, and (A4): The balance of the mixture is copolymerized in an organic solvent, and then the organic solvent is added to an aqueous medium. Substituting and neutralizing if necessary to obtain a copolymer (A), and polymerizing an acrylic monomer in an aqueous medium in the presence of the copolymer (A), A manufacturing method including a step of obtaining a combined product, comprising: an acrylic monomer /
(Mixture comprising (A1) to (A4)) (weight ratio)
Is 100/5 to 100/100, and at least a part of the polymer (B) obtained by polymerizing the acrylic monomer is coated with the copolymer (A). An aqueous resin composition comprising a resin as described above is provided.

Accordingly, the present invention uses a production method of obtaining a polymer (B) by polymerizing an acrylic monomer in an aqueous medium in the presence of the copolymer (A) in an aqueous medium, ( B) At least a part of the polymer, preferably substantially all of (A)
An aqueous resin composition comprising a resin coated with a copolymer is provided.

The aqueous resin composition of the present invention contains a light stabilizer which is an addition type weathering agent at the production stage or after the production.
An ultraviolet absorber and an antioxidant may be added. Such an additive-type weatherproofing agent gradually bleeds out and is washed away by rain or the like, and is not effective for improving long-term weatherability, but an effect is expected in the initial stage.

The aqueous resin composition of the present invention can be used in the fields of paints, adhesives, fiber processing, civil engineering, etc. by using the conventional method used for forming a film of the aqueous resin composition. Here, the conventional method includes a method of applying to a substrate or the like. Here, "application" means that an appropriate amount of the aqueous resin composition is allowed to be present on a substrate or the like, and examples thereof include coating and coating. The application is preferably performed uniformly on the entire surface of the substrate or the like.

As described above, according to the present invention, the monomers (A1) to (A4) are copolymerized in an organic solvent at a specific ratio to obtain a copolymer (A), and the organic solvent is an aqueous solvent. After substituting the medium, the acrylic monomer is polymerized in the aqueous medium (B).
An aqueous resin composition is obtained by obtaining a polymer. The aqueous resin composition of the present invention can form a film in which at least one selected from water resistance, weather resistance and adhesion is improved as compared with the conventional aqueous resin compositions. Furthermore, it is possible to form a film having preferably improved physical properties (film) such as strength and toughness of the film.

As described above, the aqueous resin composition of the present invention can form a film in which at least one selected from water resistance, weather resistance and adhesion is superior to conventional films. This is considered to be due to the following reasons. In the aqueous resin composition of the present invention, since the (A) copolymer that functions as a protective colloid is used to obtain the aqueous resin composition, the aqueous resin composition obtained by using the emulsifier used in ordinary emulsion polymerization. Compared with, the content of the hydrophilic component contained in the formed film can be reduced. Therefore, since the hydrophilicity of the film formed from the aqueous resin composition of the present invention can be lowered, it is considered that the water resistance and the like of the film formed can be improved.

The (B) polymer, which is the main component of the film, is polymerized in the presence of the (A) copolymer, which is a protective colloid, so that it is compared with a polymer obtained by ordinary emulsion polymerization. The target molecular weight can be high. Therefore, it can contribute to the improvement of the water resistance of the formed film, the high strength,
A tough film can be obtained.

Further, in the aqueous resin composition of the present invention, the copolymer (A) functioning as a protective colloid is
It is considered that (B) the polymer covers at least a part, preferably the whole. Therefore, it is expected as a functional group capable of improving the water resistance, weather resistance and adhesion of the coating,
The light-stabilizing group and / or UV-absorbing group and the alkoxysilyl group introduced into the (A) copolymer can be concentrated on the outside of the (B) polymer by the (A) copolymer.

Therefore, in the aqueous resin composition of the present invention, the (A) copolymer can be formed on the outside of the (B) polymer in a concentrated and efficient manner, so that the above-mentioned functional groups can be formed. It is considered that at least one selected from the water resistance, weather resistance and adhesion of the coating is improved.

Although the aqueous resin composition of the present invention is considered to have excellent properties for the above reasons, the aqueous resin composition of the present invention is not limited by these reasons. .

[0081]

EXAMPLES The present invention will be described specifically and in detail below with reference to Examples and Comparative Examples, but these Examples are merely one aspect of the present invention, and the present invention is in no way limited by these Examples. is not. In the examples, “parts” means “parts by weight”.

(A) Production of Copolymers W1 to W4 The following monomers were used in the production of (A) Copolymers W1 to W4: (A1) Light-stabilizing group and / or UV absorbing group As a monomer containing and having an ethylenic double bond, (a1
-1) 4-methacryloyloxy-1,2,2,6,6
-Pentamethylpiperidine and (a1-2) 2- (2 '
-Hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole; (A2) As a monomer having an alkoxysilyl group and having an ethylenic double bond, (a2-1) 3-methacryloyloxypropyltrimethoxy Silane; (A3) As a monomer having an anionic group and having an ethylenic double bond, (a3-1) methacrylic acid; and (A4) As a monomer having another ethylenic double bond, (a4) -1) Methyl methacrylate and (a4-
2) n-butyl acrylate.

In a four-necked flask equipped with a stirring blade, a thermometer, and a reflux condenser, the monomers (a1-1) to (a1-1) shown in Table 1 were used.
(A4-2) was added at the ratio shown in Table 1, and 2 parts of n was added.
-Dodecyl mercaptan, 300 parts 2-propanol and 1 part 2,2'-azobisisobutyronitrile were added. The mixture was heated to 80 ° C. with stirring. 80
The compound was copolymerized by stirring at ℃ for 5 hours. After cooling the reaction mixture to room temperature, while adding 300 parts of water, aqueous ammonia was added to adjust the pH of the mixture to 9.
2-Propanol was removed by vacuum distillation to obtain a uniform and transparent mixture, that is, (A) copolymers W1 to W4 present in the aqueous medium. The concentration of each of the copolymers (A) W1 to W4 was 25% by weight. The concentration of the copolymers (A) W1 to W4 is the weight percentage of the weight of the portion remaining after drying for 3 hours in an oven at 105 ° C. with respect to the weight before drying.

[0084]

[Table 1] a) The units of (a1-1) to (a4-2) are parts by weight.

Production of Aqueous Resin Compositions of Examples 1 to 3 and Comparative Example 1 As acrylic monomers, (b-1) methyl methacrylate, (b-2) n-butyl acrylate and (a2-1) 3. -Methacryloyloxypropyltrimethoxysilane was used. Incidentally, (b-1) is (a4-1)
And (b-2) is (a4-2).

The (A) copolymers W1 to W4 shown in Table 1 were
90 parts of distilled water was added to the four-necked flask equipped with a stirring blade, a thermometer, and a reflux condenser at a ratio shown in Table 2. The mixture was heated to 80 ° C. with stirring. (B-
1), (b-2), (a2-1) in the proportions shown in Table 2, a mixture containing 0.3 parts of sodium persulfate and 10 parts.
Each of the mixtures containing a part of distilled water was added dropwise to the four-necked flask simultaneously for 3 hours while blowing nitrogen gas.
After dropping, the mixture was further stirred at 80 ° C. for 2 hours to give an emulsion,
That is, the aqueous resin compositions of Examples 1 to 3 and Comparative Example 1 were obtained.

Concentrations of the aqueous resin compositions of Examples 1 to 3 and Comparative Example 1 The concentrations of the aqueous resin compositions of Examples 1 to 3 and Comparative Example 1 were:
The mass of the evaporation residue after heating at 105 ° C. for 3 hours was measured, and the mass% of the mass before heating was shown. The results are shown in Table 2.

[0088]

[Table 2] a) The amounts of W1 to W4 and (b-1) to (a2-1) are parts by weight. b) The amounts of W1 to W4 are values calculated based on the concentrations of W1 to W4, and are values that do not substantially contain an aqueous medium. c) The concentration of the aqueous resin composition is the weight percentage of the portion remaining after drying for 3 hours in an oven at 105 ° C. with respect to the weight before drying.

Production of Aqueous Resin Compositions of Comparative Examples 2-5 As acrylic monomers, (b-1) methyl methacrylate, (b-2) n-butyl acrylate, (a1-
1) 4-methacryloyloxy-1,2,2,6,6-
Pentamethylpiperidine, (a1-2) 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole, (a2-1) 3-methacryloyloxypropyltrimethoxysilane, and (a3-1). ) Methacrylic acid was used. Incidentally, (b-1)
Is (a4-1) and (b-2) is (a4-2).

In a four-necked flask equipped with a stirring blade, a thermometer, and a reflux condenser, 67 parts of distilled water and 1 part of a reactive surfactant (Eleminol JS-2 manufactured by Sanyo Kasei Co., Ltd.) were used.
(Trade name)) was added. The mixture was heated and stirred while blowing nitrogen gas, and the liquid temperature was kept at 75 ° C. On the other hand, 40 parts of distilled water, 4 parts of a reactive surfactant (Eleminol JS-2 (trade name) manufactured by Sanyo Kasei Co., Ltd.) and the monomers shown in Table 3 were used in the proportions shown in Table 3. An aqueous solution containing 0.3 parts of sodium persulfate and 10 parts of distilled water was prepared. About 5% by volume of the mixture and about 10% by volume of the aqueous solution were added to a four-necked flask and stirred to start the emulsion polymerization reaction. Then, the rest of the mixture and the rest of the aqueous solution were simultaneously applied for about 3 hours. Was added dropwise to the four-necked flask. Further, stirring was continued for 1 hour while maintaining the liquid temperature at 75 ° C., and then the obtained reaction mixture was cooled to room temperature. Ammonia water was added to adjust the pH to 9, and thus an emulsion, that is, the target Comparative Example 2
~ 5 aqueous resin compositions were obtained.

Concentrations of the aqueous resin compositions of Comparative Examples 2-5 The concentrations of the aqueous resin compositions of Comparative Examples 2-5 were measured by the method described above. The results are shown in Table 3.

[0092]

[Table 3] a) The amounts of the monomers (b-1) to (a3-1) are parts by weight. b) The concentration of the aqueous resin composition is the weight percentage of the portion remaining after drying for 3 hours in an oven at 105 ° C. with respect to the weight before drying.

Preparation of coatings for coatings formed from the aqueous resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5 Using each of the aqueous resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5 The materials listed in Table 4 were mixed in the proportions listed in Table 4 to prepare coating materials based on the aqueous resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5.

[0094]

[Table 4] a) Parts by weight of material are parts by weight containing solvent, if the material contains solvent (or medium). b) The parts by weight of the aqueous resin composition is the parts by weight containing the aqueous medium.

Weather resistance of film A coating based on each of the above aqueous resin compositions was applied on a slate plate (sealer applied) to a thickness of about 1 mm in a wet state, and sufficiently dried to obtain a film. . J
Using the conditions of accelerated weathering resistance of the sunshine carbon arc lamp type specified in 9.8.1 of IS K5400, the coating was applied in a sunshine weather meter at 200
Hold for 0 hours. The gloss of the film before and after the film was held in the sunshine weather meter was measured using a gonio-gloss meter to obtain a gloss retention rate (60 ° -60 °). Furthermore, the degree of discoloration (ΔE) was measured by measuring the chromaticity of the film before and after holding the film in the sunshine weather meter using a color difference meter.
Got The results are shown in Table 5.

Substrate adhesion of coating film The above coating material was applied to a test substrate defined in JIS A6909, 6.3 (2) so that the thickness was about 1 mm in a wet state, and dried at room temperature for 1 hour. The test body was used. This test body was subjected to a hot and cold repeated test defined in JIS A6909 6.11. The presence or absence of peeling, cracking and swelling of the film was visually observed. The case where the film did not swell was evaluated as ◯, the case where the film swelled was evaluated as Δ, and the case where the film peeled was evaluated as x. The results are shown in Table 5.

Water resistance of the coating Each of the aqueous resin compositions preliminarily plasticized using CS12 (trade name) manufactured by Chisso Co., has a thickness of about 25 on a glass plate.
After coating so as to have a thickness of 0 μm, it was dried at room temperature for one week to obtain a film. The film was immersed in water at 20 ° C for one week. The whitening state of the coating was visually observed. The one that was not whitened was marked with ◯, the one that was slightly whitened was marked with Δ, and the one that was completely whitened was marked with x. The results are shown in Table 5.

[0098]

[Table 5]

The aqueous resin composition of Comparative Example 1 is disclosed in JP-A-8-2.
Almost corresponding to the aqueous resin composition disclosed in 7349, the aqueous resin compositions of Comparative Examples 2 to 4 are disclosed in JP-A-10-12.
It substantially corresponds to the aqueous resin composition disclosed in Japanese Patent No. 0724. The films formed from the aqueous resin compositions of Examples 1 to 3 are excellent as a whole as compared with the films formed from the aqueous resin compositions of Comparative Examples 1 to 5, but particularly excellent in weather resistance. Is understood.

[0100]

Since the present invention has the characteristics described above, it has the following effects. The aqueous resin composition of the present invention is obtained by copolymerizing a monomer mixture containing a monomer having an ethylenic double bond and containing a photostable group and / or an ultraviolet absorbing group in an organic solvent, After substituting the solvent with an aqueous medium and optionally neutralizing it in the presence of a certain specific copolymer, it is obtained by polymerizing an acrylic monomer, so that the weather resistance and water resistance of the formed film are improved. , And at least one selected from adhesion and the like are improved. Preferably, the weather resistance of the coating is improved.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI C08F 220/04 C08F 220/04 220/34 220/34 220/38 220/38 220/58 220/58 220/60 220/60 230/02 230/02 230/08 230/08

Claims (3)

(57) [Claims] 1. An (A1) ethylenic diamine containing a photostable group.
A monomer having a heavy bond and / or a monomer having an ethylenic double bond containing an ultraviolet absorbing group, (A2) a monomer having an ethylenic double bond containing an alkoxysilyl group, (A3) ) A monomer containing an anion group and having an ethylenic double bond, and (A4) another monomer having an ethylenic double bond, (A1): 0.1 to 40% by weight, (A2): 0.1 to 20% by weight, (A3): 0.5 to 30% by weight, and (A4): the balance of the mixture is solution copolymerized in an organic solvent, and the organic solvent is added to an aqueous medium. Substituting to obtain the copolymer (A), and emulsifying and polymerizing the acrylic monomer in the presence of the copolymer (A) to obtain the polymer (B). A water-based resin composition obtained by including: an acrylic monomer / ((A1) to (A4) Comprising mixture) (weight ratio), in use basis 100 / 5-10
0/100 , and (A1) a monomer containing a light-stable group and having an ethylenic double bond.
Is, [Formula 1] (I): [However, in formula (I), R ¹ is, H or CN, R ² and R ³ are met each H, CH ₃ or C ₂ H ₅
And R ⁴ may be the same or different, and R ⁴ is H, an alkyl group having 1 to 18 carbon atoms or —C
^{O-C (R 5) =} CH (R 6) ( where, R ⁵ and R ⁶ are each
H, CH ₃ or C ₂ H ₅ , which may be the same or different
May be. ), And X is an imino group (-NH-) or
Represents an oxygen atom (—O—). ], Which contains a UV-absorbing group and has an ethylenic double bond
Mer, ## STR2 ## (II): [However, in the formula (II), R ⁷ is H or C
H ₃ and Y represent an alkylene group having 1 to 6 carbon atoms. ]so
And (A2) an alkoxysilyl group-containing ethylenic double bond
The monomer having a slip _{is, (III): CH 2 =} CR 8 -COO-Z-Si (O
R ⁹ ) ₃ [However, in the formula (III), R ⁸ is H or C
H ₃ and R ⁹ are alkyl groups having 1 to 3 carbon atoms, Z is the number of carbon atoms
Represents 1 to 6 alkylene groups. ] And (A
3) Single containing anionic group and having ethylenic double bond
The monomer contains a carboxyl group and contains an ethylenic double bond.
A monomer containing a monomer and / or a carboxylate group
An aqueous resin composition which is a monomer having an acidic double bond . 2. At least a part of the polymer (B) obtained by emulsion polymerization of an acrylic monomer has (A1) a light-stable group and an ethylenic double bond.
Monomer having an ethylenic double bond and / or containing an ultraviolet absorbing group, (A2) a monomer having an ethylenic double bond containing an alkoxysilyl group, (A3) an anionic group Containing a monomer having an ethylenic double bond and (A4) another monomer having an ethylenic double bond, (A1): 0.1 to 40% by weight, (A2) : (A) 0.1 to 20% by weight, (A3): 0.5 to 30% by weight, and (A4): resin coated with the (A) copolymer obtained by solution copolymerization of the balance of the mixture. An aqueous resin composition comprising: (B) polymer / (A) copolymer (weight ratio) is 100 /
5 to 100/100 , (A1) contains a light stable group and has an ethylenic double bond
That monomers, embedded image (I): [However, in the formula (I), R ¹ is H or CN,
R ² and R ³ are met each H, CH ₃ or C ₂ H ₅
And R ⁴ may be the same or different, and R ⁴ is H, an alkyl group having 1 to 18 carbon atoms or —C
^{O-C (R 5) =} CH (R 6) ( where, R ⁵ and R ⁶ are each
H, CH ₃ or C ₂ H ₅ , which may be the same or different
May be. ), And X is an imino group (-NH-) or
Represents an oxygen atom (—O—). ], Which contains a UV-absorbing group and has an ethylenic double bond
The isomer has the following structure: (II): [However, in the formula (II), R ⁷ is H or C
H ₃ and Y represent an alkylene group having 1 to 6 carbon atoms. ]so
Shown, (A2) an alkoxysilyl group-containing ethylene
Monomer, having a sexual double bond _{(III): CH 2 = CR} 8 -COO-Z-Si (OR 9) 3 [ where, in formula (III), R ⁸ represents, H or C
H ₃ and R ⁹ are alkyl groups having 1 to 3 carbon atoms, Z is the number of carbon atoms
Represents 1 to 6 alkylene groups. ] And (A
3) Single containing anionic group and having ethylenic double bond
The monomer contains a carboxyl group and contains an ethylenic double bond.
A monomer containing a monomer and / or a carboxylate group
A water-based resin composition, which is a monomer having an acidic double bond . 3. An (A1) ethylenic diamine containing a light-stable group
A monomer having a heavy bond and / or a UV-absorbing group
A monomer containing an ethylenic double bond, (A2) an ethylenic double bond containing an alkoxysilyl group
A monomer having a bond , (A3) having an anionic group and having an ethylenic double bond
And (A4) other monomer having an ethylenic double bond , (A1): 0.1 to 40% by weight, (A2): 0.1 to 20% by weight, (A3): 0.5 to 30% by weight, and (A4): the balance of the mixture is solution-copolymerized in an organic solvent to form an organic solvent.
Is replaced with an aqueous medium to obtain a copolymer (A), and the acrylic monomer is emulsified in the presence of the copolymer (A).
The aqueous resin composition according to claim 2, which is produced by a production method including a step of obtaining a polymer (B) when combined .