JPH09169818A - Self-crosslinkable polymer emulsion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a self-crosslinkable polymer emulsion composition which can give a coating film having a high crosslinking degree and being excellent in toughness, heat resistance, chemical resistance, water resistance, weather resistance, etc., at relatively low temperatures by modifying a polymer emulsion obtained from an ethylenically unsaturated carbonyl monomer (A) and an ethylenically unsaturated monomer (B) with a modifier (C) having a silicone structure and mixing the modified product with a specified semicarbazide curing agent and/or a terminal-blocked product thereof (D). SOLUTION: Component A has a least one also or keto group in the molecule. Component B is exemplified by an acrylic ester. An emulsion obtained by emulsion-polymerizing 0.1-50wt.% component A and 50-99.9wt.% component B in an aqueous medium is modified with component C (e.g. cyclic silane). The modified product is mixed with component D represented by formula I (wherein R<1> is a 2-20C alkylenediisocyanate or the like; R<2> is a 2-20C alkylene or the like; R<3> is H or the like; (n) is 0 or 1; and (l) and (m) are each 0 or a positive integer).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to toughness using a semicarbazide compound as a curing agent, stain resistance, water resistance, weather resistance, pigment dispersibility, gloss retention, adhesion, rust resistance, and water permeation resistance. The present invention relates to a self-crosslinking polymer emulsion composition capable of forming a film having excellent properties and hardness. More specifically, it is obtained by copolymerizing an ethylenically unsaturated carbonyl group-containing monomer modified with silicone and having at least one aldo group or keto group in the molecule with another ethylenically unsaturated monomer. The polymer emulsion prepared,
The present invention relates to a self-crosslinking polymer emulsion composition using a curing agent as a semicarbazide system obtained by reacting a polyisocyanate compound having three or more -NCO groups in one molecule with a hydrazine derivative.

A coating film obtained from the composition of the present invention is useful as a coating material, a base treatment material or finishing material for building materials, an adhesive, a pressure-sensitive adhesive, a paper processing agent, and a finishing agent for textile fabrics, and particularly, a coating material. Concretely, concrete, cement mortar, slate board, silica board, gypsum board, extruded board, inorganic building materials such as foam concrete, building materials based on woven or non-woven fabrics It is useful as a paint for various foundations such as metal building materials or as a building finishing material, as a multilayer coating material, synthetic resin emulsion paint such as gloss paint, metal coating material, plastic coating material, wood part coating material, roof tile coating material.

[0003]

2. Description of the Related Art A polymer emulsion obtained by emulsion polymerization as a resin for water-based paints is widely used because it forms a film at room temperature or under heat drying to form a film having relatively good durability. However, when exposed outdoors, the film was contaminated by adhesion of dust, soot, sand, etc., and the gloss value was rapidly reduced by light, heat, rain, etc., and the level of gloss retention was low. As a result, the glossy appearance immediately after the application of the paint resulted in a very dirty and dull film due to contamination over time and a decrease in gloss value. In particular, there was a disadvantage that the aesthetic appearance immediately after painting could not be maintained because the coating film became white or brittle due to rain or condensation.

In order to solve the above problems, Japanese Patent Publication No. 46
Use of a room temperature cross-linkable polymer emulsion, which is a mixture of a carbonyl group-containing polymer emulsion and a hydrazide compound, as disclosed in JP-A-200553, JP-B-1-150101, JP-B-63-51180 and the like. In the case of a water-based paint, the rate of decrease in the gloss value of the film is slightly slower than in the past, but it is not sufficient. This decrease in gloss value results in insufficient water resistance of the film when exposed outdoors for a long period of time and facilitates water penetration into the film, which accelerates decomposition of the polymer. As described above, the room temperature crosslinkable polymer emulsion, which is a conventional mixture of a carbonyl group-containing polymer emulsion and a hydrazide compound, has insufficient gloss retention, weather resistance and water resistance. Further, the hydrazide compound is inferior in stability over time as a curing agent, and in particular, the hydrazide compound is a compound containing an ethylenically unsaturated carbonyl group-containing monomer having at least one aldo group or keto group in the molecule and other monomers. When added to a polymer emulsion obtained by copolymerizing with an ethylenically unsaturated monomer, the hydrazide compound changes with time, and the film obtained by drying exhibits sufficient curing performance. I couldn't. Further, when a hydrazide compound is added to the polymer emulsion,
Since the compatibility is poor, the water resistance of the crosslinked film obtained by drying is very poor. Therefore, it is desired to provide a coating composition which is excellent in low-temperature curability and storage stability as a curing agent, and can obtain a film excellent in water resistance, stain resistance, hardness and the like.

A polymer emulsion obtained by emulsion-polymerizing an ethylenically unsaturated monomer disclosed in JP-A-2-301159, JP-A-6-256522 and the like, and having a copolymerization weight thereof A polymer emulsion in which an organopolysiloxane formed from a hydrolyzable silane compound coexists or is chemically bound in the coalescence, or a film obtained from the production method has excellent gloss retention when exposed outdoors. However, since the water resistance is not sufficient, the film becomes white or becomes fragile due to rain and dew condensation.

That is, when exposed outdoors, the film obtained from the conventional polymer emulsion is contaminated by the adhesion of dust, soot, sand, etc., and further, the decrease of the gloss value is rapid due to light, heat, rain, etc. The level of gloss retention was low. As a result, the glossy appearance immediately after the application of the paint resulted in a very dirty and dull film due to contamination over time and a decrease in gloss value. Especially, there is a drawback that the aesthetics cannot be maintained because the film becomes white or becomes brittle due to rain or dew condensation.

[0007]

DISCLOSURE OF THE INVENTION The present invention uses a semicarbazide compound as a curing agent toughness, stain resistance, and
It is an object of the present invention to provide a self-crosslinking polymer emulsion composition capable of forming a film excellent in water resistance, weather resistance, pigment dispersibility, gloss retention, adhesion, rust prevention, water permeability, and hardness. It is a thing.

[0008]

[Means for Solving the Problems] The present inventors have made diligent studies in order to solve the above-mentioned problems, and have developed a film which exhibits water resistance and gloss retention of a film which could not be predicted in the past. The invention was completed. That is, in the present invention, an ethylenically unsaturated carbonyl group-containing monomer [A] having at least one aldo group or keto group in the molecule and another ethylenically unsaturated monomer [B] are used as an aqueous medium. A polymer emulsion obtained by subjecting the polymer emulsion to emulsion polymerization, wherein the polymer emulsion is silicone-modified with a modifier [C] having a silicone structure during or after the emulsion polymerization, and The present invention relates to a self-crosslinking polymer emulsion composition comprising a semicarbazide type curing agent represented by the formula (1) and / or its terminal blocker [D].

[0009]

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(Wherein R ¹ is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms, or 1 carbon atom)
C8 to C8 cycloalkylene diisocyanate substituted with an alkoxy group or a C1 to C6 alkylene group, unsubstituted or C1 to C1
An alkylene group having 8 to 8 carbon atoms or an arylene diisocyanate having 6 to 20 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms, and an unsubstituted or alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms A polyisocyanate residue having no terminal isocyanate group, which is derived from a trimer to 20mer oligomer of at least one diisocyanate selected from the group consisting of C6 to C20 noaralkylene diisocyanate substituted with a group, Alternatively, R ¹ represents a triisocyanate residue having no terminal isocyanate group, which is derived from an alkylene diisocyanate having 2 to 20 carbon atoms and is substituted with an isocyanatoalkyl group having 1 to 8 carbon atoms; R ² represents A linear or branched alkylene group having 2 to 20 carbon atoms, 5 to 20 carbon atoms
Or a C 6-10 arylene group which is unsubstituted or substituted with a C 1-18 alkyl group or a C 1-8 alkoxy group; each R ³ is Each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; n is 0 or 1
And l and m are each 0 or a positive integer, provided that 3 ≦ (l + m) ≦ 20. ) Further, the terminal blocker of the semicarbazide-based curing agent represented by the above formula (1) has a terminal group H ₂ NR ³ N in the formula (1).
At least one of — has a blocking end group represented by the formula R ⁵ R ⁴ C═NR ³ N— (in the formula, R ⁴ and R ⁵ are each independently a hydrogen atom, a straight chain or Branched carbon number 1-2
An alkyl group of 0, a cycloalkyl group of 5 to 20 carbon atoms,
Or, it represents an aryl group having 6 to 10 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and R ⁴ and R ^4
In some cases, ⁵ may jointly form a cyclic structure. ).

In a preferred embodiment of the present invention, the modifier [C] having a silicone structure contains a self-crosslinking heavy chain containing at least one silane compound (I) having a silicone structure represented by the formula (I). It is a combined emulsion composition. _{^{R 6 -Si- (R 7) 3}} ···· (I) ( wherein, R ⁶ is a hydrogen atom, an aliphatic hydrocarbon group of 1 to 16 carbon atoms, an aryl group having 5 to 10 carbon atoms, carbon Number 5-6
Is a cycloalkyl group, a vinyl group, an alkyl acrylate group having 1 to 10 carbon atoms, or an alkyl methacrylate group having 1 to 10 carbon atoms, and each R ⁷ is independently an alkoxy group having 1 to 8 carbon atoms. Group, acetoxy group or hydroxyl group. In the present invention, the ethylenically unsaturated carbonyl group-containing monomer [A] having at least one aldo group or keto group in the molecule is an ethylenic unsaturated carbonyl group containing an aldo group or keto group. It refers to a saturated monomer, and excludes an ethylenically unsaturated monomer containing a carbonyl group of carboxylic acids and esters. Specifically, acrolein, diacetone acrylamide, diacetone methacrylamide, formyl styrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone,
Examples thereof include acryloxyalkylpropanals, methacryloxyalkylpropanals, diacetone acrylate, diacetone methacrylate, acetonyl acrylate, 2-hydroxypropyl acrylate acetyl acetate, butanediol acrylate acetyl acetate.

Further, the other ethylenically unsaturated monomer [B] in the present invention will be specifically shown. In some cases, it may be expressed as an acrylic acid ester or a methacrylic acid ester [hereinafter simply referred to as (meth) acrylic acid ester]. . 〕,styrene,
Aromatic monomers such as vinyltoluene, vinyl esters such as vinyl acetate, vinyl propionate and vinyl persaticate, vinyl cyanides such as (meth) acrylonitrile, vinyl halides such as vinyl chloride and vinylidene chloride, butadiene And various functional monomers,
For example, (meth) acrylamide, vinylpyrrolidone,
2-hydroxyethyl (meth) acrylate, N-methylolacrylamide, N-butoxymethylacrylamide, acid phosphooxyethyl methacrylate, 3-chloro-2-acidphosphooxypropyl methacrylate, methylpropanesulfonic acid acrylamide, divinylbenzene, (Poly) oxyethylene mono (meth) acrylate, (poly) propylene glycol (meth) acrylate, (meth) allyl acrylate, (poly) oxyethylene di (meth) acrylate, trimethylolpropane tri (meth) acrylate, (meth ) Dimethylaminoethyl acrylate, diethylaminoethyl (meth) acrylate and the like are included. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride and itaconic acid, fumaric acid, and half esters of maleic acid.
Examples of the acrylic acid ester or methacrylic acid ester include (meth) methyl acrylate, (meth) ethyl acrylate, (meth) butyl acrylate, (meth) 2-ethylhexyl acrylate, (meth) cyclohexyl acrylate, ( (Meth) Dodecyl acrylate, etc.

In the present invention, the silicone-modified polymer emulsion contains 0.1 to 50 ethylenically unsaturated carbonyl group-containing monomer [A] having at least one aldo group or keto group in the molecule. % By weight, and 50 to 99.9% by weight of other ethylenically unsaturated monomer [B].
Of the ethylenically unsaturated carbonyl group-containing monomer [A] having at least one aldo group or keto group in the molecule is preferably 0.2 to 30. %, And other ethylenically unsaturated monomers [B] are obtained by subjecting 70 to 99.8% by weight to emulsion polymerization in an aqueous medium, more preferably at least one aldo compound in the molecule. Of the ethylenically unsaturated carbonyl group-containing monomer [A] having a group or keto group is 0.5 to 20% by weight, and the other ethylenically unsaturated monomer [B] is 80 to 99.5% by weight. It is obtained by subjecting it to emulsion polymerization in an aqueous medium.

In the present invention, examples of the modifier [C] having a silicone structure include those represented by the above formula (I). In the formula (I), “alkyl acrylate group, alkyl methacrylate group” means
It can be expressed as an alkyl (meth) acrylate group,
A substituent derived from an alkyl (meth) acrylate, in which the alkyl portion has a free bond end, which means "(" to "alkyl group" of the "alkyl (meth) acrylate group"". When "meth) acrylic acid" is expressed as an acyl group, it can be expressed as "(meth) acryloxyalkyl group".

In the above formula (I), R ⁶ is preferably a methyl group, a phenyl group, a vinyl group or a γ- (meth) acryloxypropyl group, and R ^7's are each independently
Methoxy, ethoxy, propoxy, butoxy,
A methoxyethoxy group and a hydroxyl group are preferable. Formula (I)
Preferred specific examples of the silane (I) represented by are methyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, vinylethoxysilane and γ-acryloxypropyl. Trimethoxysilane, γ-acryloxypropyltriethoxysilane, γ
-Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane and the like are preferably used, and one or more of these silanes may be contained.

Further, examples of the modifier [C] having a silicone structure include cyclic silanes, linear siloxanes having a hydrolyzable group, and silanes represented by the formula (II). _{^{(R 8) n ─Si─ (R}} 9) 4-n ···· (II) ( wherein, each R ⁸ is independently a hydrogen atom, an aliphatic hydrocarbon group of 1 to 16 carbon atoms, Aryl group, cycloalkyl group, vinyl group, alkyl acrylate group or alkyl methacrylate group: R ⁹ are each independently an alkoxy group having 1 to 8 carbon atoms, an acetoxy group, a hydroxyl group: n is 0, 2 or 3) As a specific example, tetraethoxysilane and the like can be cited as those in which n in formula (II) is 0, and n in formula (II) is 3
Examples thereof include phenyltriethoxysilane and trimethylmethoxysilane.

When n = 2, a silane represented by the formula (III) can be mentioned. _{^{(R 8) 2 -Si- (R}} 9) 2 ···· (III) ( wherein, R ^8, R ⁹ are as defined above.) Specific examples thereof include dimethyl dimethoxysilane, diphenyl dimethoxysilane, dimethyl Diethoxysilane,
Diphenyldiethoxysilane, methylphenylsilane,
γ-methacryloxypropylmethyldimethoxysilane may be mentioned.

As the cyclic silanes, octamethylcyclotetrasiloxane, octaphenylcyclosiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, tetramethyltetravinylcyclotetrasiloxane and the like can be used. Examples of linear siloxanes having a hydrolyzable group in the molecule include those represented by the following general formula (IV), (V) or (VI).

[0019]

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[0020]

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[0021]

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(In the formula, R ¹⁰ is hydrogen, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group, a cycloalkyl group vinyl group, an alkyl acrylate group or an alkyl methacrylate group: R ¹¹ is 1 to Alkoxy group having 8 carbon atoms, acetoxy group, hydroxyl group, epoxy group, ethylene oxide group: m is a positive integer of 1 to 999.) In each of the above formulas, R ^{10 s} are all the same or partly or totally different. May be. Further, R ^11's may be the same or different in part or in whole. Further, as chlorosilanes, for example, methylchlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenylchlorosilane, vinylchlorosilane, γ- (meth) acryloxypropyltrichlorosilane, γ- (meth) acrylosilane. Roxypropyldichloromethylsilane and the like are also included.

In the present invention, the modifier [C] having a silicone structure preferably contains at least one silane compound (I) having a silicone structure represented by the formula (I). The modifier [C] having a silicone structure may contain at least one selected from the group consisting of the above cyclic silanes, siloxanes having a hydrolyzable group, and the silane compound represented by the formula (II). You can
The molar ratio of the silane compound (I) represented by the formula (I) to at least one selected from the group consisting of the cyclic silanes, hydrolyzable group-containing siloxanes and the silane compound (II) is at least 10 / 100, preferably 35/100 or more.

Further, the modifier [C] having a silicone structure is at least 1 selected from the group consisting of the above cyclic silanes and the silane compound represented by the formula (III).
And a molar ratio of the silane compound (I) to at least one selected from the group consisting of the cyclic silanes and the silane compound (II) is at least 10/100, preferably 35/100. The above is preferable.

As the modifier [C] having a silicone structure, at least one kind of the silane compound (I) represented by the formula (I), a cyclic silane and a silane compound (III) represented by the formula (III) are used. It is particularly preferable to contain at least one selected from the group consisting of this is,
At least one silane compound (I) represented by formula (I)
By using a seed and at least one selected from the group consisting of a cyclic silane and a silane compound (III) represented by formula (III), the crosslink density of the silicone polymer formed by the modifier is lowered, This is because it is possible to prevent the structure of the polymer from becoming complicated, and thereby it is possible to impart flexibility to the coating film provided from the silicone-modified polymer emulsion.

In the present invention, the total weight of the ethylenically unsaturated carbonyl group-containing monomer [A] having at least one aldo group or keto group in the molecule and the other ethylenically unsaturated monomer [B]. And the weight ratio of the modifier [C] having a silicone structure are represented by the following formula (a), and the range of the ratio is preferably in the range of 1/2 to 99/1. More preferably, it is in the range of 1 to 98/2.

{[A] + [B]} / [C] ... (a) In the present invention, a silicone-modified polymer emulsion produced by using a modifier [C] is used. A film obtained from a self-crosslinking polymer emulsion comprising a semicarbazide curing agent and / or its end-blocking compound [D] has improved gloss retention during long-term exposure to the outdoors, and a film having high weather resistance is obtained for the first time. be able to. The presence of these silicone condensates can be known by ²⁹ SiNMR ( ²⁹ Si nuclear magnetic resonance spectrum). The condensate of the general formula (I) is ²⁹ S
It can be identified by the iNMR chemical shift showing a peak at −50 to −70 PPM. In addition, the general formula (III) or a condensate of cyclic silane is ²⁹ SiNMR
It can be identified by showing a peak in the chemical shift of −16 to −26 PPM.

The radical polymerization catalyst in the present invention is one which causes radical decomposition by heat or a reducing substance to cause addition polymerization of an ethylenically unsaturated monomer, and is a water-soluble or oil-soluble persulfate or a persulfate. Oxides, azobis compounds and the like can be used. Examples thereof include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis. (2-diaminopropane)
Hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like are used, and particularly water-soluble ones are preferably used, and the amount thereof has at least one aldo group or keto group in the molecule. Usually, 0.1 to 1% by weight is blended with respect to the total amount of the ethylenically unsaturated carbonyl group-containing monomer and the other ethylenically unsaturated monomer. When it is desired to accelerate the polymerization rate and to carry out the polymerization at a low temperature, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, Rongalit or the like is used in combination with the radical polymerization catalyst. Further, in order to adjust the molecular weight, it is possible to add a chain transfer agent such as dodecyl mercaptan.

In the present invention, an ordinary surfactant as an emulsifier for emulsion polymerization, such as fatty acid soap, alkyl sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate, polyoxyethylene alkylaryl sulfate, p Anionic surfactants such as styrene sulfonate, nonionic surfactants such as polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, oxyethyleneoxypropylene block copolymer, etc. are used, but the composition of the present invention is used. In order to improve the water resistance of the film obtained from the product, at least one of the surfactants is an anionic reactive surfactant,
That is, 0.05 to 20 parts by weight of an ethylenically unsaturated monomer having a sulfonic acid group or a sulfonate group is used as an ethylenically unsaturated carbonyl group-containing monomer having at least one aldo group or keto group in the molecule. It is preferable to use [A] and the other ethylenically unsaturated monomer [B] for each 100 parts by weight in total. Specifically, for example, there are Elyominol (trademark) JS-2 and JS-5 manufactured by Sanyo Kasei Co., Ltd., and Latemur (trademark) S-120 and S- manufactured by Kao Corporation.
180A, S-180, Aqualon (trademark) HS-10 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Adecaria Soap (trademark) SE-1025N manufactured by Asahi Denka Co., Ltd., methacrylic acid sulfoalkyl ester salt, p- There are styrene sulfonic acid salts and the like, and these are used alone or in combination of two or more kinds, or are used in combination with a usual surfactant or a nonionic reactive surfactant.

In the present invention, in order to produce a silicone-modified polymer emulsion, an ordinary emulsion polymerization method can be adopted. Specifically, after the modifier [C] is added to the reaction system, it is simply added. A method of emulsion-polymerizing the monomers [A] and [B] in the reaction system, or a modifier [C] for the reaction system.
There is a method in which the monomers [A] and [B] are introduced at the same time, and it is possible to carry out by combining them, but it is not particularly limited thereto.

In the present invention, the hydrogen ion concentration (pH) during emulsion polymerization is usually pH 4.0 or lower, preferably pH 3.0 or lower. In the present invention, after the completion of emulsion polymerization, as a curing catalyst during film formation, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, tin octylate, tin laurate, iron octylate, lead octylate, tetrabutyl titanate. Metal salts of organic acids such as can be added to the compositions of the present invention.

When using these curing catalysts, it is desirable to emulsify them with a surfactant and water. In the present invention, the semicarbazide-based curing agent (1) represented by the formula (1) has —N in one molecule.
It is obtained by reacting a polyisocyanate compound having three or more CO groups with a hydrazine derivative. When a compound obtained by reacting a diisocyanate compound having two -NCO groups in one molecule with a hydrazine derivative is used as a curing agent, the obtained film has low crosslinking efficiency, is tough and is water resistant. No excellent film can be obtained.

In the present invention, the polyisocyanate compound which can be used for the production of the semicarbazide type curing agent represented by the formula (1) has a --NCO group of 3 to 2 in one molecule.
A polyisocyanate compound having 0, for example,
A polyisocyanate compound obtained by oligomerizing diisocyanates with a buret bond, a urea bond, an isocyanurate bond, a urethane bond, an allophanate bond, a uretdione bond, and further 1,8-diisocyanato-
4-isocyanatomethyl octane and a combination thereof are included.

The polyisocyanate compound having 3 to 20 --NCO groups in one molecule can be obtained by using the following diisocyanate compound. As such a diisocyanate compound, a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a carbon number C5-C20 cycloalkylene diisocyanate substituted with 1-6 alkylene group, carbon not substituted or substituted with C1-C18 alkyl group or C1-C8 alkoxy group From the group consisting of arylene diisocyanate having 6 to 20 carbon atoms and aralkylene diisocyanate having 8 to 20 carbon atoms which is unsubstituted or substituted by an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. It is at least one diisocyanate compound selected.

Examples of the diisocyanate compound include alkylene diisocyanates such as hexamethylene diisocyanate (HDI); 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), dimethylcyclohexane diisocyanate (hydrogenated). XDI) and other cycloalkylene diisocyanates; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and mixtures thereof (TDI), diphenylmethane-4,4′-
Diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3-dimethyl-4,4
-Biphenylene diisocyanate (TODI), crude T
DI, polymethylene polyphenyl diisocyanate, crude MDI, arylene diisocyanate such as phenylene diisocyanate, xylylene diisocyanate (XD
Aralkylenediisocyanates such as I) and the like, and combinations thereof.

Among these diisocyanate compounds, alkylene diisocyanate and cycloalkylene diisocyanate are preferable from the viewpoints of heat-resistant yellowing, weather resistance and the like of the film using the semicarbazide compound produced. As described above, a polyisocyanate compound which is at least one trimer to 20mer oligomer of these diisocyanates is preferable, and the polyisocyanate compound is reacted with hydrazine or a derivative thereof to obtain the semicarbazide curing agent. In this case, R ¹ in equation (1) is
The polyisocyanate residue does not have a terminal isocyanate group.

In the present invention, from the viewpoint of compatibility with the silicone-modified polymer emulsion, a polyisocyanate compound having 3 to 20 —NCO groups in one molecule, which is obtained by oligomerizing a diisocyanate compound, is obtained. Is preferably used. This is because the semicarbazide curing agent obtained by using a polyisocyanate compound having 3 to 20 —NCO groups in one molecule is polyfunctional, and thus the film obtained from the self-crosslinking polymer emulsion has high crosslinking ability. It can provide a tough film. When the number of —NCO groups in one molecule of polyisocyanate exceeds 20, the number of semicarbazide groups becomes excessive, so that the viscosity of the semicarbazide curing agent becomes high and handling becomes difficult.

In the present invention, a semicarbazide type curing agent represented by the following formula (2) obtained by reacting these isocyanurate type polyisocyanates with hydrazine or a derivative thereof or an end-capped product thereof is preferable. preferable.

[0039]

[Chemical 6]

(In the formula, A ¹ , A ² and A ³ are each independently a linear or branched alkylene group having 2 to 20 carbon atoms, unsubstituted or having 1 to 18 carbon atoms. Alkyl group, C1-C8 alkoxy group or C1-C6
C5-C20 cycloalkylene group substituted with an alkylene group, which is not substituted or has a carbon number of 1-
An arylene group having 6 to 20 carbon atoms, which is substituted with an 18 alkyl group or an alkoxy group having 1 to 8 carbon atoms, or an unsubstituted or alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms Represents an aralkylene group having 8 to 20 carbon atoms, which is substituted with a group; and X ¹ ,
X ² and X ³ each independently represent a group represented by the following formula (3) or formula (4).

[0041]

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(In the formula, R ¹² is a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, or unsubstituted or having 1 to 18 carbon atoms. An alkyl group or an arylene group having 6 to 10 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms; each R ¹³ independently represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms; ; N is 0 or 1.)

[0043]

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(In the formula, R ¹³ is the same as above.) The semicarbazide-based curing agent end-capped product in which the semicarbazide group of the semicarbazide-based curing agent represented by the above formula (2) is blocked as a semicarbazone group is represented by the formula: (3) or have a terminal group H ₂ NR ³ N-at least 1 Exemplary ethynylphenylbiadamantane derivatives ^{R 5 R 4 C = NR 3} N- in blocked terminal group represented in (4) (wherein, R ^4, R ⁵ is independently a hydrogen atom,
Linear or branched alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 5 to 20 carbon atoms, or unsubstituted or alkyl group having 1 to 18 carbon atoms or 1 carbon atom
It represents an aryl group having 6 to 10 carbon atoms which is substituted with an alkoxy group having from 8 to 8, and R ⁴ and R ⁵ may jointly form a cyclic structure. ).

Another preferred example of the polyisocyanate compound is a polyisocyanate compound having a biuret bond (biuret type isocyanate) obtained by reacting a diuret with a biuretizing agent such as water, t-butanol or urea. . In the present invention,
A semicarbazide-based curing agent represented by the following formula (5) obtained by reacting a biuret type isocyanate with hydrazine or a derivative thereof or an end-capped product thereof is preferable.

[0046]

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(Wherein A ¹ , A ² , A ³ , X ¹ , X ² ,
X ³ is the same as above. The semicarbazide type curing agent obtained by using the above-mentioned isocyanurate type polyisocyanate and biuret type polyisocyanate has good compatibility with the polymer emulsion. Therefore, when a self-crosslinking polymer emulsion composition containing at least one selected from the isocyanurate type polyisocyanate and the semicarbazide type curing agent obtained using the biuret type polyisocyanate is applied to the substrate, A film excellent in hardness, water resistance, chemical resistance, weather resistance, heat resistance, and appearance can be obtained.

Further, as another preferable example of polyisocyanate, the following formula (6) obtained by reacting urethane type polyisocyanate with hydrazine or its derivative is given.
It is preferably a semicarbazide type curing agent represented by The semicarbazide type curing agent obtained by using the urethane type polyisocyanate has good compatibility with the polymer emulsion, and contains at least one selected from the semicarbazide type curing agent obtained by using the urethane type polyisocyanate. When the self-crosslinking polymer emulsion composition as described above is applied to a substrate, a film having excellent hardness, flexibility, water resistance, heat resistance and the like can be obtained.

[0049]

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(Wherein A ¹ , A ² , A ³ , X ¹ , X ² ,
X ³ is the same as above, B has a hydroxyl group derived from an aliphatic triol having 1 to 20 carbon atoms, an alicyclic triol having 5 to 20 carbon atoms or an aromatic triol having 6 to 20 carbon atoms. Represents a non-triol residue; i, j, and k are integers of 0 to 50, respectively, provided that i, j, and k satisfy the relationship of (i + j + k) ≧ 1. ) Examples of the hydrazine derivative used in the present invention include hydrazine and hydrates thereof; monoalkyl-substituted hydrazine compounds such as monomethylhydrazine, monoethylhydrazine, monobutylhydrazine; ethylene-1,2-dihydrazine, propylene-1,3. -Dihydrazine, butylene-
Dihydrazine compounds such as 1,4-dihydrazine; oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide.
Dicarboxylic acid dihydrazides such as isophthalic acid dihydrazide and phthalic acid dihydrazide; tricarboxylic acid trihydrazides such as trimellitic acid trihydrazide, carbonic acid dihydrazides represented by the following general formula (7), represented by the following general formula (8) Examples thereof include bissemicarbazides and the like, and combinations thereof.

[0051]

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(In the formula, x represents an integer of 0 or 1.)

[0053]

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(In the formula, R ¹⁴ is a linear or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms, or unsubstituted or having 1 to 18 carbon atoms. Represents an arylene group having 6 to 10 carbon atoms which is substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms.) In the present invention, a semicarbazide curing agent or a polyisocyanate compound as a raw material thereof is hydrazine or its For the purpose of preventing the derivative from polymerizing due to chain extension, hydrazine or a derivative thereof may be reacted with a monoaldehyde or monoketone represented by the following formula (9) to block it as a hydrazone group.

R ¹⁵ R ¹⁶ C═O (9) (In the formula, R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or 5 carbon atoms. ~ 20 cycloalkyl group, or unsubstituted or alkyl group having 1 to 18 carbon atoms or 1 to carbon atoms
It represents an aryl group having 6 to 10 carbon atoms, which is substituted with an alkoxyl group having 8 atoms, and R ¹⁵ and R ¹⁶ may jointly form a cyclic structure. In this case, the resulting semicarbazide-based curing agent is a semicarbazide group in which the semicarbazide group is blocked as a semicarbazone group. The elimination of the monoaldehyde or monoketone used as a blocking agent from the semicarbazide curing agent may be carried out by hydrolysis before being mixed with the silicone-modified polymer emulsion, and may be used as a curing agent as it is. After the self-crosslinking polymer emulsion composition is applied to the surface of the substrate, it may be spontaneously released during the curing process. Therefore, a monoketone having a boiling point of 30 to 200 ° C. (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) is preferable as the blocking agent.

In the production of the semicarbazide type curing agent used in the present invention, the -NCO group of the polyisocyanate compound having three or more -NCO groups in one molecule and the terminal group represented by the following formula (10) in the hydrazine derivative: And the equivalent ratio with the total of the blocked end groups derived therefrom is 1: 1.5 to 1:
It is 100, preferably 2: 5 to 1:50. —NR ¹⁷ NH ₂ (10) (In the formula, R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) Further, after the completion of the reaction, the excess hydrazine derivative may be distilled or extracted as necessary. Can be removed.

The reaction for obtaining the semicarbazide type curing agent used in the present invention can be carried out under any condition in the presence or absence of a solvent. Solvents which are inert to the NCO groups or less active than the reaction components can be used. Specifically, ketone-based solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone cyclohexanone; ether-based solvents such as dioxane, tetrahydrofuran and diethylene glycol dimethyl ether; amide-based solvents such as dimethylformamide and dimethylacetamide; N-methyl-2-pyrrolidone and the like. Lactam solvents, sulphoxide solvents such as dimethylsulfoxide, ester solvents such as ethyl acetate and cellosolve acetate, alcohols such as t-butanol and diacetone alcohol, aromatic hydrocarbon solvents such as toluene and xylene, n- Examples thereof include aliphatic hydrocarbon solvents such as hexane and the like, and their combined use.

Further, the semicarbazide-based curing agent represented by the formula (1) and / or the semicarbazide-based curing agent end-capped product in which the semicarbazide group is blocked as a semicarbazone group assists dispersion stability and solubility in an aqueous medium. For this purpose, a hydrophilic group-containing compound represented by the following formula (11) and at least one selected from the group consisting of compounds in which a semicarbazide group thereof is blocked as a semicarbazone group can be mixed and used.

[0059]

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(Wherein R ¹⁸ is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or an alkyl group having 1 to 18 carbon atoms, or 1 carbon atom)
C8 to C8 cycloalkylene diisocyanate substituted with an alkoxy group or a C1 to C6 alkylene group, unsubstituted or C1 to C1
An alkylene group having 8 to 8 carbon atoms or an arylene diisocyanate having 6 to 20 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms, and an unsubstituted or alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms A polyisocyanate residue having no terminal isocyanate group, which is derived from a trimer to 20mer oligomer of at least one diisocyanate selected from the group consisting of aralkylene diisocyanates having 8 to 20 carbon atoms, which is substituted with a group, or, R ¹⁸ is derived from alkylene diisocyanates having 2 to 20 carbon atoms which is substituted with isocyanatoalkyl group having 1 to 8 carbon atoms, it represents a triisocyanate residue free of having a terminal isocyanate group; R ¹⁹ is , A linear or branched alkylene group having 2 to 20 carbon atoms, or 5 to 2 carbon atoms
0 cycloalkylene group, or unsubstituted or alkyl group having 1 to 18 carbon atoms or 1 to 8 carbon atoms
Represents an arylene group having 6 to 10 carbon atoms substituted with an alkoxy group; each R ²⁰ independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; and n is 0 or 1. And p and q are each 0 or a positive integer, r is a positive integer, and 0 ≦ (p + q) and 2 ≦
(P + q + r) ≦ 20. ) In the compound represented by the formula (11) in which the semicarbazide group of the semicarbazide curing agent is blocked as a semicarbazone group, at least one of the terminal groups H ₂ NR ³ N- in the formula (11) has the formula R ⁵ R ⁴ C. = NR ³ N- having a blocked terminal group (in the formula, R ⁴ and R ⁵ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, Represents a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms which is unsubstituted or substituted by an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. , R ⁴ and R ⁵ may jointly form a cyclic structure).

That is, at least one selected from the semicarbazide curing agent represented by the formula (1) and the end-blocked body thereof, and at least the hydrophilic group-containing compound represented by the formula (11) and the end-blocked body thereof. The composition containing one of these can be advantageously used as a curing agent for a polymer emulsion obtained by silicone modification. The semicarbazide curing agent and its end capping used in the present invention include
As described above, at least one state selected from the group consisting of dispersion in an aqueous medium and dissolution in an aqueous medium is preferable so that it can be easily mixed with the silicone-modified polymer emulsion.

In some cases, the semicarbazide curing agent and its end-blocking agent used in the present invention may have the above formula (1).
Other surfactants than the hydrophilic group-containing compound represented by 1) and the compound in which the semicarbazide group is blocked as a semicarbazone group may be added. Examples of such surfactants include fatty acid soap, alkyl sulfonic acid,
Anionic surfactants such as alkyl succinic acid, polyoxyethylene alkyl sulfate, polyoxyethylene alkylaryl sulfate, polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, oxyethyleneoxypropylene block copolymer, and ethylene oxide Nonionic surfactants such as known reaction products with phosphoric acids, cationic surfactants containing quaternary ammonium salts, etc., polymeric dispersion stabilizers such as polyvinyl alcohol, partially saponified polyvinyl alcohol, and the like, and combinations thereof Is mentioned.

However, the surfactant is represented by the formula (11)
And a compound in which the semicarbazide group is blocked as a semicarbazone group are particularly preferred because of their high affinity with the semicarbazide curing agent and the terminal blocker. And in particular, at least one selected from the semicarbazide curing agent represented by the formula (1) and the end-blocked body thereof, and at least one selected from the hydrophilic group-containing compound represented by the formula (11) and the end-blocked body thereof. At least one selected from the semicarbazide curing agent represented by the formula (1) and the end-capped product thereof, and the hydrophilic group-containing compound represented by the formula (11) and the end-capped product thereof When a composition having a weight ratio with at least one selected from the range of 99/1 to 10/90 is used as a curing agent for a silicone-modified polymer emulsion, it is particularly stable and excellent in curing performance. A self-crosslinking polymer emulsion composition is obtained.

In the present invention, at least one selected from the semicarbazide curing agent represented by the formula (1) and the end-blocked body thereof, and the hydrophilic group-containing compound represented by the formula (11) and the end-blocked body thereof are selected. As a specific method for obtaining a composition containing at least one of the following, the following two methods can be mentioned. [I] An active hydrogen compound having a polyisocyanate compound having three or more —NCO groups in one molecule and a nonionic hydrophilic group and / or an ionic hydrophilic group (including one that can be converted into an ionic system later) And a method of reacting with a hydrazine derivative after reacting with an excess of -NCO group, and [ii] semicarbazide curing agent (1) and formula (11)
Can be obtained by a method of separately synthesizing and mixing the hydrophilic group-containing compound represented by, etc., but it is also possible to carry out by combining the above-mentioned methods, and in addition to the above-mentioned two methods only. It is not limited.

First, the method [i] will be described in detail. As a polyisocyanate compound having three or more —NCO groups in one molecule, a polyisocyanate compound as an example of the raw material used in the production of the above-mentioned semicarbazide curing agent (1) is used. The ones mentioned are listed. Further, among the active hydrogen compounds having a nonionic hydrophilic group and / or an ionic hydrophilic group (including one which can be converted into an ionic system later) used in the method [i],
Examples of the nonionic hydrophilic group include polyethylene glycol, polyoxyethylene-oxypropylene (random and / or block) glycol, polyoxyethylene-oxytetramethylene (random and / or
Or block) glycols and other polyether polyols, but preferably the following general formula (12)
Polyethylene glycol monoalkyl ethers represented by

[0066]

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(In the formula, R ²¹ represents an alkyl group having 1 to 25 carbon atoms, and n represents an integer of 5 to 80.) As the ionic hydrophilic group, a tertiary amine salt of carboxylic acid is used. And anionic groups such as quaternary ammonium salts. Examples of the active hydrogen compound having an anion group (or a group which can be converted into an anion group later) include, for example, α, α′-dimethylolpropionic acid, α,
Examples include α, α′-dimethylolalkanoic acids such as α′-dimethylolacetic acid, and the like, preferably lactic acid, glycolic acid, 4-hydroxybutyric acid, monohydroxycarboxylic acids such as p-phenolcarboxylic acid; glycine, alanine, Amino acids such as aspartic acid and β-alanine;
Examples thereof include monohydroxy sulfonic acids such as p-phenol sulfonic acid; amino sulfonic acids such as taurine; and combinations thereof. The acid groups of these active hydrogen compounds are
The hydrophilic polyisocyanate reaction product can be converted into an anionic group by neutralization with a base during the synthesis, or during emulsification or solubilization in an aqueous medium, but it is preferably used during the synthesis of the hydrophilic polyisocyanate reaction product. Specific examples of the base include, for example, triethylamine, ammonia, diethanolamine, dimethylaminoethanol,
Examples thereof include amine compounds such as methyldiethanolamine and dibutylamine; hydroxides of alkali metals such as KOH, NaOH and LiOH, and combinations thereof.

Examples of the active hydrogen compound having a cationic group (or a group which can be converted into a cationic group later) include, for example, N-alkyldialkanolamines such as N-methyldiethanolamine and N-butyldiethanolamine, and the like. Examples of the alkylene oxide (ethylene oxide, propylene oxide, etc.) adduct having 2 to 4 carbon atoms include N, N such as N, N-dimethylethanolamine and N, N-diethylethanolamine.
-Dialkyl monoalkanolamines and the like, as well as combinations thereof. 3 of these active hydrogen compounds
The primary amino group can be converted into a cationic group by neutralizing with an acid or quaternizing with an alkylating agent during the synthesis of a hydrophilic polyisocyanate compound or during emulsification or solubilization in an aqueous medium. Examples of the acid used for neutralization include acetic acid, lactic acid, hydrochloric acid, phosphoric acid, sulfuric acid and the like, and combinations thereof. Examples of the alkylating agent include dimethylsulfate, diethylsulfate, methyl chloride, methyl iodide, benzyl chloride and the like.

Polyisocyanate compound having three or more --NCO groups in one molecule and nonionic hydrophilic group and / or ionic system (including those which can be converted to ionic system later)
The reaction with an active hydrogen compound having a hydrophilic group is about 20 ° C.
At a temperature of about 130 ° C. under substantially anhydrous conditions,
Equivalent ratio of -NCO group to active hydrogen group capable of reacting with -NCO group is 1.1 / 1 to 500/1, preferably 2/1 to 10
Perform at 0/1.

Further, these reactions can be carried out without solvent or in a solvent, if necessary, using a catalyst. The solvent is inert to the -NCO group,
Alternatively, one having lower activity than the reaction component can be used. Specifically, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether-based solvents such as dioxane, tetrahydrofuran and diethylene glycol dimethyl ether; amide-based solvents such as dimethylformamide and dimethylacetamide; N-
Lactam solvents such as methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; ester solvents such as ethyl acetate and cellosolve acetate; alcohols such as t-butanol and diacetone alcohol; aromatic hydrocarbons such as toluene xylene. System solvents; aliphatic hydrocarbon solvents such as n-hexane and the like, and combinations thereof.

Specific examples of the above catalyst include, for example,
Dibutyltin dilaurate, stannous octoate, lead octylate, and other salts of organic and inorganic acids, and organic metal derivatives; organic tertiary amines such as triethylamine and triethylenediamine; diazabicycloundecene catalysts, etc. Can be mentioned. In the method of [i], 1 obtained in this way
Reaction of a polyisocyanate compound having three or more -NCO groups in the molecule with an active hydrogen compound having a nonionic hydrophilic group and / or an ionic hydrophilic group (including one that can be converted into an ionic system later) From the semicarbazide curing agent represented by the formula (1) used in the present invention and the end-capped product thereof, the compound is reacted with the hydrazine derivative described above according to the reaction conditions in the production of the semicarbazide curing agent (1). At least one selected and the formula (1
A composition containing the hydrophilic positive group-containing compound represented by 1) and at least one selected from the end-capped compounds thereof is obtained.

Next, the method [ii] will be described in detail. The hydrophilic group-containing compound represented by the formula (11) and the end-capped compound thereof are poly-containing compounds having two or more -NCO groups in one molecule. Reacting an isocyanate compound with the above-mentioned active hydrogen compound having a nonionic hydrophilic group and / or an ionic hydrophilic group (including one which can be converted into an ionic system later) and, if necessary, the above hydrazine derivative Obtained by

As the polyisocyanate compound having two or more -NCO groups in one molecule, the polyisocyanate compound having three or more -NCO groups in one molecule used for the production of the semicarbazide curing agent (1) and the polyisocyanate compound thereof Examples of the raw material include the diisocyanate compounds described above. In the synthesis of the hydrophilic group-containing compound represented by the formula (11) and the end-capped compound thereof, 2 —NCO groups are included in one molecule.
The reaction of the polyisocyanate compound having at least one with an active hydrogen compound having a nonionic hydrophilic group and / or an ionic hydrophilic group (including one which can be converted into an ionic system later) is carried out by -NCO group and -NCO group. Is carried out at an equivalence ratio of 1 to 10: 1 with an active hydrogen group capable of reacting with. Other reaction conditions follow the method of [i].

In the present invention, the ratio of the semicarbazide curing agent and the terminal blocker [D] thereof to the silicone-modified polymer emulsion in the self-crosslinking polymer emulsion composition is represented by the formula (1) ) At least one selected from the semicarbazide curing agent and the end-blocked body thereof, or at least one selected from the semicarbazide curing agent represented by the formula (1) and the end-blocked body and the formula (11) The ratio of the composition containing the hydrophilic positive group-containing compound and at least one selected from the end-capped compounds thereof to the silicone-modified polymer emulsion is 0.1 / 99.9 to 90/10.
It is preferred that

In the present invention, the silicone-modified polymer emulsion or the self-crosslinking polymer emulsion composition is preferably adjusted to have a pH in the range of 3 to 10 in order to keep the emulsion stable for a long period of time.
It is more preferable to adjust the pH to the range of 6-9.
In the composition of the present invention, it is optional to add components that are usually added to and mixed with water-based paints, such as thickeners, defoamers, pigments, dispersants, dyes and preservatives.

[0076]

[Pigment dispersion]

Water 82.5 parts Poise 530 (Note 1) 7.5 parts 5% aqueous solution of sodium tripolyphosphate 7.5 parts Daicel HEC SP-600 3% aqueous solution (Note 2) 25.0 parts Nopco 1497VD (Note 3) 2.5 parts Taipaque CR-97 (* 4) 375.0 parts (* 1) Dispersant: Kao Corporation (* 2) Thickener: Daicel Chemical Industries (* 3) Defoamer : Sannopco Co., Ltd. (Note 4) Rutile titanium oxide: Ishihara Sangyo Co., Ltd. [Let Down] Emulsion of each Example and Comparative Example (solid content conversion) 460.0 parts Ethylene glycol monobutyl ether 60.0 parts Ethylene glycol mono 2-ethylhexyl ether 10.0 parts Water 30.0 parts Nopco 1497VD 1.0 parts Water resistance of paint film The above coating composition B was wire coater No. Using No. 50, it was applied to a sulfated alumite plate and dried at room temperature for 2 hours. After further drying at 50 ° C. for 2 days, it was immersed in water at 40 ° C. for 30 days, and the state was visually determined. [Criteria] ◎: No blister or gloss is observed. ○: There is slight blistering, but no gloss is visible. Δ: Blisters and gloss are observed. ×: The entire surface is blistered and gloss is remarkable.

[0077]

Reference Example 1 <Preparation of Polymer Emulsion Modified with Silicone> [Synthesis Example of Emulsion (1)] 8 parts of methacrylic acid was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer. Diacetone acrylamide 3 parts, methyl methacrylate 34 parts, butyl acrylate 40 parts, cyclohexyl methacrylate 15 parts, water 300 parts, Latemur S
-180A (sulfosuccinic acid diester ammonium salt having a double bond copolymerizable with an ethylenically unsaturated monomer in the molecule: 20 parts of a 20% aqueous solution manufactured by Kao Co., Ltd. was added, and the temperature in the reaction vessel was adjusted. After raising the temperature to 78 ° C., 0.5 part of ammonium persulfate was added and kept for 1 hour, whereby the seed latex of the first stage was prepared, and the hydrogen ion concentration was measured to be pH 1.8. Methacrylic acid 3 parts, diacetone acrylamide 12 parts, methyl methacrylate 165 parts, butyl acrylate 160 parts,
Mixture of 60 parts of cyclohexyl methacrylate, 330 parts of water, 20 parts of 20% aqueous solution of Latemur S-180A, 1.0 part of ammonium persulfate, 2.5 parts of γ-methacryloxypropyltrimethoxysilane, 25 parts of dimethyldimethoxysilane. , And a mixed solution of 25 parts of methyltrimethoxysilane are allowed to flow into the reaction vessel from separate dropping tanks for 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured and found to be 2.1. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.02% of the total monomer. The obtained emulsion has a solid content of 44.0% and an average particle size of 1080Å
It was.

[0078]

Reference Example 2 <Preparation of polyisocyanate compound> [Synthesis example of polyisocyanate compound A] 222 parts of isophorone diisocyanate, 168 parts of hexamethylene diisocyanate, and 2.4 parts of water as a buretizing agent,
It was dissolved in 130 parts of a mixed solvent of ethylene glycol methyl ether acetate and trimethyl phosphate at a ratio of 1: 1 (weight ratio), and reacted at a reaction temperature of 160 ° C. for 1.5 hours. The obtained reaction solution was 1.0 m for the first time using a thin film distillation can.
The second time is 0.1 mmHg /
Excessive isophorone diisocyanate and hexamethylene diisocyanate, and the solvent were distilled off and recovered by a two-step treatment under the condition of 200 ° C.

The polyisocyanate compound A thus obtained is
Cobourette-type polyisocyanate of isophorone diisocyanate and hexamethylene diisocyanate, the remaining isophorone diisocyanate is 0.7% by weight,
0.1% by weight of remaining hexamethylene diisocyanate,
The NCO content is 19.6% by weight and the viscosity is 20,000 (±
3000) mPa. s / 40 °, number average molecular weight is about 80
0 (± 100) with an average -NCO functionality of about 3.
It was 7. The polyisocyanate compound A was a 79.6% solution with ethyl acetate.

[0080]

[Reference Example 3] <Preparation of semicarbazide curing agent or end-capped product thereof> [Synthesis example of semicarbazide curing agent and end-capped product A] 23 parts of acetone in a reactor having a reflux condenser, a thermometer and a stirrer Polyisocyanate compound A obtained in Reference Example 2 (79.6% ethyl acetate solution, NCO group content 1
5.6% by weight) 23 parts, "UNIOX (trademark) M10
00 "(manufactured by Nippon Oil & Fats Co., Ltd., polyoxyethylene methyl ether having a hydroxyl value of 56.9) and 0.001 part of dibutyltin dilaurate as a catalyst were added and reacted at 60 ° C for 4 hours. Then hydrazine 1 was added to 421 parts of acetone placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer.
74 parts of the hydrate was added with stirring at room temperature over 30 minutes, and the mixture was further stirred for 1 hour. The reaction product obtained above was added to this reaction solution with stirring at 40 ° C. over 1 hour, and then further stirred at 40 ° C. for 4 hours. Thereafter, 1183 parts of water was added at 40 ° C. over 30 minutes, and stirring was continued for another 30 minutes. Acetone, ethyl acetate, hydrazine, a reaction product of acetone and hydrazine, water, and the like in the obtained reaction solution were distilled off under reduced pressure by heating to obtain an aqueous dispersion of a semicarbazide-based composition having a solid content of 25%.

The infrared absorption spectrum of this product is shown in FIG. 100 parts of cyclohexanone was added to 50 parts (solid content: 10 parts) of an aqueous dispersion of the obtained semicarbazide composition, and the mixture was shaken at 150 rpm for 5 hours, and then 10,000 rpm
and centrifugation at 10 m for 10 minutes. 6.7 parts of a hydrophilic group-containing compound having a polyisocyanate A skeleton in which a polyoxyethylene methyl ether group is introduced as a hydrophilic group is present in the lower aqueous phase, and a polyisocyanate A skeleton is present in the upper cyclohexanone phase. 3.3 parts of the semicarbazide-based curing agent and its terminal blocker were present. [Synthesis example of semicarbazide curing agent B] Tetrahydrofuran 22 parts, polyisocyanate A (79.6% ethyl acetate solution, NCO group content 15.6% by weight) in a reactor having a reflux condenser, a thermometer and a stirrer. ) 23 parts, "UNIOX (trademark) M1000" (manufactured by NOF CORPORATION)
Polyoxyethylene methyl ether having a hydroxyl value of 56.9] 10 parts, dibutyltin dilaurate as a catalyst 0.0
01 parts were added and reacted at 60 ° C. for 4 hours. Then, 147 parts of tetrahydrofuran were placed in a reactor equipped with a reflux condenser, a thermometer and a stirring device, and 7.3 parts of hydrazine monohydrate was added.
Part at room temperature over 30 minutes with stirring and then 1 more
Stirred for hours. The reaction product previously obtained was added to this reaction solution at 40
Stir at ℃ for 1 hour and then add 40 more
The mixture was stirred at 0 ° C for 4 hours. Then 182 parts of water was added over 30 minutes at 40 ° C. and stirring was continued for another 30 minutes. Tetrahydrofuran, ethyl acetate, hydrazine, water and the like in the obtained reaction solution were distilled off under reduced pressure by heating to obtain an aqueous dispersion of a semicarbazide-based curing agent having a solid content of 30%.

The infrared absorption spectrum of this product is shown in FIG.

[0083]

Example 1 100 parts of the polymer emulsion (1) modified with silicone synthesized in Reference Example 1 was added to a semicarbazide curing agent obtained in Reference Example 3 and an aqueous dispersion 12.4 of the terminal blocker (A) thereof. After adding and mixing parts, the mixture was made into a mixture according to the formulation A or the formulation B, and then subjected to each test. Table 1 shows the results.

[0084]

[Example 2] 12.4 parts of an aqueous dispersion of the semicarbazide curing agent (B) obtained in Reference Example 3 was added to 100 parts of the silicone-modified polymer emulsion (1) synthesized in Reference Example 1, After mixing, a mixture was prepared according to the formulation A or the formulation B, and then subjected to each test. Table 1 shows the results.

[0085]

COMPARATIVE EXAMPLE 1 100 parts of the silicone-modified polymer emulsion (1) synthesized in Reference Example 1 was made into a mixture according to the formulation A or the formulation B, and then subjected to each test. Table 1 shows the results.

[0086]

Comparative Example 2 In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 8 parts of methacrylic acid, 37 parts of methyl methacrylate, 40 parts of butyl acrylate, 15 parts of cyclohexyl methacrylate, 300 parts of water. Latemur S-180A (sulfosuccinic acid diester ammonium salt having a double bond in the molecule capable of copolymerizing with an ethylenically unsaturated monomer: 20 parts of a 20% aqueous solution manufactured by Kao Co., Ltd. was added to the reaction vessel. Was increased to 78 ° C., and then 0.5 part of ammonium persulfate was added and kept for 1 hour, whereby a seed latex of the first stage was prepared, and the hydrogen ion concentration was measured to be pH 1.8. Next, 3 parts of methacrylic acid, 177 parts of methyl methacrylate, 160 parts of butyl acrylate, 60 parts of cyclohexyl methacrylate.
Solution, 330 parts of water, 20 parts of 20% aqueous solution of Latemur S-180A, 1.0 part of ammonium persulfate, and γ-
2.5 parts of methacryloxypropyltrimethoxysilane,
A mixture of 25 parts of dimethyldimethoxysilane and 25 parts of methyltrimethoxysilane is allowed to flow into the reaction vessel from separate dropping tanks for 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured and found to be 2.1. 25%
After adjusting the pH to 8 by adding aqueous ammonia solution,
It was filtered through a wire mesh of 0 mesh. The dry weight of the filtered agglomerates was very low, 0.02% of the total monomer. The solid content of the obtained emulsion was 44.0%, and the average particle size was 1080Å. This emulsion was made into a mixture according to the above-mentioned formulation A or formulation B, and then subjected to each test. Table 1 shows the results.

[0087]

Comparative Example 3 To 100 parts of the emulsion obtained in Comparative Example 2, 12.4 parts of the water dispersion of the semicarbazide curing agent (B) obtained in Reference Example 3 was added and mixed, and then the mixture A or the mixture B was added. The composition was prepared according to the above, and then subjected to each test. Table 1 shows the results.

[0088]

Comparative Example 4 8 parts of methacrylic acid, 3 parts of diacetone acrylamide, 34 parts of methyl methacrylate were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer.
Part, butyl acrylate 40 parts, cyclohexyl methacrylate 15 parts, water 300 parts, Latemul S-180A (sulfosuccinic acid diester ammonium salt having a double bond copolymerizable with an ethylenically unsaturated monomer in the molecule: Kao 20 parts of a 20% aqueous solution manufactured by Co., Ltd. was added, the temperature in the reaction vessel was raised to 78 ° C., and then ammonium persulfate was added to 0.
Add 5 parts and keep for 1 hour. Thus, a seed latex of the first stage was prepared, and the pH was 1.8 when the hydrogen ion concentration was measured. Next, 3 parts of methacrylic acid,
Diacetone acrylamide 12 parts, methyl methacrylate 165 parts, butyl acrylate 160 parts, cyclohexyl methacrylate 60 parts, water 330 parts, Latemur S-180
20 parts of a 20% aqueous solution of A and a mixed solution of 1.0 part of ammonium persulfate are allowed to flow into the reaction vessel from separate dropping tanks for 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured and found to be 2.1. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.02% of the total monomer. The obtained emulsion has a solid content of 44.0% and an average particle size of 1080Å
It was. 12.4 parts of an aqueous dispersion of the semicarbazide-based curing agent (B) obtained in Reference Example 3 was added to 100 parts of this emulsion, and after mixing, the mixture was made into a mixture according to the formulation A or the formulation B, and then subjected to each test. did. Table 1 shows the results.

[0089]

Comparative Example 5 0.67 parts of adipic acid dihydrazide was added to 100 parts of the silicone-modified polymer emulsion (1) synthesized in Reference Example 1 and mixed, and then a compound was prepared according to Formula A or Formula B. After that, it was subjected to each test. Table 1 shows the results.

[0090]

[Example 3] To a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 290 parts of water and 10 parts of ADEKA RIASOAP SE-1025N (manufactured by Asahi Denka Kogyo Co., Ltd.) were charged to react. After raising the temperature in the container to 80 ° C., 10 parts of a 2% aqueous solution of ammonium persulfate was added, and then 5
After a minute, as a first step, 4 parts of methacrylic acid, 10 parts of diacetone acrylamide, 40 parts of methyl methacrylate, 86 parts of 2-ethylhexyl acrylate, 60 parts of cyclohexyl methacrylate, 96 parts of water, ADEKA REASOAP SE-1
025N 10 parts, 2% aqueous solution of ammonium persulfate 3
An emulsion mixture consisting of 0 parts and a mixture consisting of 0.5 part of γ-methacryloxypropyltrimethoxysilane, 10 parts of dimethyldimethoxysilane and 10 parts of methyltrimethoxysilane were charged into a reaction vessel from separate dropping tanks. Time 2
Allow to flow over 0 minutes. The temperature of the reaction vessel is kept at 80 during inflow.
Keep at ° C. After the inflow is completed, set the temperature of the reaction vessel to 80 °
And keep it for 30 minutes. When the hydrogen ion concentration at the end of the first step was measured, it was pH 2.0.

Next, as the second step, methacrylic acid 10
Parts, 5 parts of diacetone acrylamide, 20 parts of methyl methacrylate, 15 parts of 2-ethylhexyl acrylate, 50 parts of cyclohexyl methacrylate, 48 parts of water, 5 parts of ADEKA REASOAP SE-1025N, 15 parts of a 2% aqueous solution of ammonium persulfate. And the emulsified mixed solution consisting of are introduced into the reaction vessel from the dropping tank over 40 minutes. The temperature of the reaction vessel is maintained at 80 ° C during the inflow. After the inflow is completed, the temperature of the reaction vessel is maintained at 80 ° C. for 30 minutes. When the hydrogen ion concentration at the end of the first step was measured, it was pH 1.9.

Further, as a third step, 4 parts of methacrylic acid,
Emulsifying 10 parts of diacetone acrylamide, 49 parts of methyl methacrylate, 37 parts of 2-ethylhexyl acrylate, 100 parts of cyclohexyl methacrylate, 96 parts of water, 10 parts of ADEKA REASOAP SE-1025N, and 30 parts of a 2% aqueous solution of ammonium persulfate. The mixed solution and a mixed solution consisting of 0.5 part of γ-methacryloxypropyltrimethoxysilane, 10 parts of dimethyldimethoxysilane and 10 parts of methyltrimethoxysilane were put into a reaction vessel from separate dropping tanks over 1 hour and 20 minutes. Inflow. The temperature of the reaction vessel is maintained at 80 ° C during the inflow. After the inflow is completed, the temperature of the reaction vessel is kept at 80 ° C. and kept for 2 hours. After cooling to room temperature, the hydrogen ion concentration was measured and found to be 2.0. 25%
After adjusting the pH to 8 by adding aqueous ammonia solution,
It was filtered through a wire mesh of 0 mesh. The dry weight of the filtered agglomerates was very small, 0.04% based on the total monomers. The solid content of the obtained emulsion was 44.4%, and the average particle size was 970Å. To 100 parts of the obtained silicone-modified polymer emulsion, 20.6 parts of the aqueous dispersion of the semicarbazide curing agent (B) obtained in Reference Example 3 was added, mixed, and then blended according to Formulation A or Formulation B. After making it into a thing, it used for each test. Table 2 shows the results.

[0093]

Example 4 8 parts of methacrylic acid, 9 parts of diacetone acrylamide, 28 parts of methyl methacrylate were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer.
Part, butyl acrylate 40 parts, cyclohexyl methacrylate 15 parts, water 300 parts, Latemul S-180A (sulfosuccinic acid diester ammonium salt having a double bond copolymerizable with an ethylenically unsaturated monomer in the molecule: Kao 20 parts of a 20% aqueous solution manufactured by Co., Ltd. was added, the temperature in the reaction vessel was raised to 78 ° C., and then ammonium persulfate was added to 0.
Add 5 parts and keep for 1 hour. Thus, a seed latex of the first stage was prepared, and the pH was 1.8 when the hydrogen ion concentration was measured. Next, 3 parts of methacrylic acid,
Diacetone acrylamide 36 parts, methyl methacrylate 141 parts, butyl acrylate 160 parts, cyclohexyl methacrylate 60 parts, water 330 parts, Latemur S-180
A mixed solution of 20 parts of a 20% aqueous solution of A and 1.0 part of ammonium persulfate, and a mixed solution of 2.5 parts of γ-methacryloxypropyltrimethoxysilane, 25 parts of dimethyldimethoxysilane and 25 parts of methyltrimethoxysilane. Flow into the reaction vessel from separate dripping tanks over 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured to be 2.1.
Met. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very small, 0.07% based on the total monomers. The solid content of the obtained emulsion was 44.1% and the average particle size was 1120Å. The resulting silicone-modified polymer emulsion 10
36 parts of an aqueous dispersion of the semicarbazide-based curing agent (B) obtained in Reference Example 3 was added to 0 parts, mixed and made into a composition according to the composition A or the composition B, and then subjected to each test. Table 2 shows the results.

[0094]

[Table 1]

[0095]

[Table 2]

[0096]

As is clear from the above results, the film obtained from the self-crosslinking polymer emulsion comprising the semicarbazide curing agent and the silicone-modified polymer emulsion according to the present invention has a high crosslink density and is tough. Thus, a film having excellent heat resistance, chemical resistance, water resistance and weather resistance can be obtained at a relatively low temperature.

Therefore, according to the present invention, it can be used in various applications such as paints, base treatment materials or finishing materials for building materials, adhesives, pressure-sensitive adhesives, paper processing agents, and finishing agents for textiles. A coating is provided.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum diagram of an example of a compound used in the present invention.

FIG. 2 is an infrared absorption spectrum diagram of another example of the compound used in the present invention.

Claims (2)

[Claims] 1. An ethylenically unsaturated carbonyl group-containing monomer [A] having at least one aldo group or keto group in the molecule and another ethylenically unsaturated monomer [B] in an aqueous medium. A polymer emulsion obtained by subjecting the polymer emulsion to emulsion polymerization, wherein the polymer emulsion is silicone-modified with a modifier [C] having a silicone structure during or after the emulsion polymerization, and the following formula: A self-crosslinking polymer emulsion composition comprising a semicarbazide type curing agent represented by (1) and / or a terminal blocker [D] thereof. Embedded image (Wherein R ¹ is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a carbon number A cycloalkylene diisocyanate having 5 to 20 carbon atoms substituted with an alkylene group having 1 to 6 carbon atoms not substituted or substituted with an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; From the group consisting of arylene diisocyanates of numbers 6 to 20, and aralkylenediisocyanates of 8 to 20 carbon atoms which are unsubstituted or substituted by an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. Polyimide having no terminal isocyanate group, derived from at least one selected from trimer to 20-mer oligomer of diisocyanate Cyanate residues or,, R ¹
Represents a triisocyanate residue having no terminal isocyanate group, which is derived from an alkylene diisocyanate having 2 to 20 carbon atoms and is substituted with an isocyanatoalkyl group having 1 to 8 carbon atoms; R ² represents a linear chain Or a branched C2-C20 alkylene group, a C5-C20 cycloalkyllene group, or an unsubstituted or substituted C1-C18 alkyl group or a C1-C8 alkoxy group Represents an arylene group having 6 to 10 carbon atoms; each R ³ independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; n is 0 or 1; Each m is 0 or a positive integer, provided that 3 ≦ (l + m) ≦ 20. ) In the end-capped compound of the semicarbazide-based curing agent represented by the above formula (1), at least one of the terminal groups H ₂ NR ³ N- in the formula (1) is represented by the formula R ⁵ R ⁴ C = NR ³ N-. It has a blocked terminal group represented by the formula (in the formula, R ⁴ and R ⁵ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or 5 to 20 carbon atoms). A cycloalkyl group, or an aryl group having 6 to 10 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and R ⁴ and R ⁵ are In some cases, they may jointly form a cyclic structure). 2. A modifier having a silicone structure [C].
The self-crosslinking polymer emulsion composition according to claim 1, characterized in that it contains at least one silane compound having a silicone structure represented by formula (I). _{^{R 6 -Si- (R 7) 3}} ···· (I) ( wherein, R ⁶ is a hydrogen atom, an aliphatic hydrocarbon group of 1 to 16 carbon atoms, an aryl group having 5 to 10 carbon atoms, carbon atoms A cycloalkyl group having 5 to 6 vinyl group, an alkyl acrylate group having 1 to 10 carbon atoms, or an alkyl methacrylate group having 1 to 10 carbon atoms, and each R ⁷ independently has 1 to 1 carbon atoms. 8 is an alkoxy group, an acetoxy group or a hydroxyl group.)