JP3457781B2 - Resin composition for paint - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for coatings.
And more specifically,
Also relates to resin compositions for coatings that form coatings with excellent properties
It is. [0002] Conventionally, solvent-based paints have been mainly used as paints.
However, solvent-based paints can cause inflammation and poisoning.
And there is a risk of environmental pollution,
In recent years, the transition to water-based paints is progressing rapidly. But water
Paints have lower water resistance and other film properties than solvent-based paints.
And there are many issues to be solved. [0003] There has been much research into improving the performance of water-based paints.
Aldehyde groups or keto groups
Emulsion of resin containing carbonyl group based on
Organic hydrazine compounds having two or more hydrazine residues
No. 54-144432 discloses a resin composition comprising
It is disclosed in reports. This resin composition is coated at room temperature
It can be formed and can be used as a one-part type
Excellent characteristics, but insufficient water resistance of the resulting coating
And the stain resistance is not sufficient.
No. A water-based paint for improving the water resistance of a coating film
Various developments have been made, one of which is emulsion polymerization.
Acrylic having a hydrolyzable silyl group obtained therefrom
Emulsions of resins are known. But this is
Hydrolysis and condensation of hydrolyzable silyl groups promoted during emulsion polymerization
Agglomerates are formed in the emulsion,
The reaction system easily gels during polymerization, producing an emulsion
There is a problem of poor stability. [0005] As a method of solving these problems, for example,
For example, Japanese Unexamined Patent Publication No. 2-67324 discloses a free radio
-Polymerizable functionality and silane functionality capable of self-condensation crosslinking
Silane monomer containing both cations and cations
It is now possible to use a linear polysiloxane precursor as an essential component.
And Japanese Patent Application Laid-Open No. 3-22712 discloses a
Has a specific alkyl methacrylate and a specific functional group
It is disclosed that an acrylic ester to be made is an essential component
JP-A-3-227313 discloses an emulsifying weight.
It is possible to use a polymerizable monomer having a cyano group when joining
Although it is disclosed, it is difficult to make the emulsion high solid
Difficult to control the emulsion composition and emulsion polymerization conditions.
It has the disadvantage of being large. [0006] On the other hand, water-based paints
Various developments of polysiloxane-based water-based paints have been carried out.
ing. Become a raw material for such silicone-based water-based paints
Polysiloxane resins offer heat resistance, water repellency and weather resistance
It is excellent and has useful features as a resin for paint. Only
And water-based paint containing polysiloxane resin as a main component
There are still some issues to be solved when
Has not yet been widely used for
It is. For example, Japanese Patent Publication No. 63-23212 discloses
Indicates that there are multiple alcoholic hydroxyl groups on the side chain of the polysiloxane.
Production method of water-soluble paint using resin introduced
ing. However, the type that completely dissolves in water like this
Paint using polysiloxane improves the film properties
It is necessary to increase the molecular weight of the polysiloxane resin
In this case, the paint viscosity increases and the paintability decreases.
Has the disadvantage of In addition, formed from this paint
Coated film has a large amount of hydrophilic functional groups.
Has the disadvantage of low water repellency and low water resistance. An object of the present invention is to provide excellent water resistance and stain resistance.
To provide a coating resin composition that forms a coated film.
You. Means for Solving the Problems The present inventors have made the above-mentioned application
Water-based resin composition for paints in view of the problems of conventional technology
As a result of intensive studies, the present invention has been accomplished. That is, the gist of the present invention is as follows.
Polymer block containing dimethylsiloxane as a repeating unit
(A), a vinyl polymerizable monomer as a repeating unit,
Water-decomposable silyl groups, hydroxyalkyl groups,
A carbonyl group based on a hydr group or a keto group
Polymer block (B) containing at least one polymer, and the polymer
Block (A) and copolymerized with the polymer block (B)
A graph composed of a silicon-containing graft crossing unit (C)
Emulsion of ftblock copolymer (I) and two
Organic hydrazine compound having the above hydrazine residue
(II) A resin composition for coatings characterized by comprising
is there. DETAILED DESCRIPTION OF THE INVENTION The resin composition for coatings of the present invention (hereinafter referred to as “resin composition”)
Below, referred to as a resin composition) is water containing a surfactant.
Emulsified dispersion of graft block copolymer (I) in conductive medium
Two or more hydrazines in the emulsion
Containing an organic hydrazine compound (II) having a residue
It is a thing. [0013] Grafts constituting the resin composition of the present invention
The lock copolymer (I) is formed by repeating dimethylsiloxane.
Polymer block (A) (hereinafter referred to as polymer block)
(Referred to as block (A)), a vinyl polymerizable monomer
And a hydrolyzable silyl group hydroxyalkyl group,
A carbonyl group based on a aldehyde group or a keto group, respectively
A polymer block (B) containing at least one polymer (hereinafter referred to as polymer
Block (B)) and silicon-containing graft crossover
Unit (C) (hereinafter referred to as graft-crossing unit (C))
Wherein the graft-crossing unit (C) comprises one or more
Polymer block (A) and polymerization via oxane bond
It is copolymerized in both of the body blocks (B). Graft crossing unit (C) and polymer block
The copolymerization with (B) is carried out with the raw material of the graft crossing unit (C).
And / or a vinyl polymerizable functional group in the graft crosslinking agent
Mercapto group and vinyl as raw material of polymer block (B)
By radical copolymerization with
Can be achieved. The graft block copolymer (I) of the present invention
Is a polymer block (A)
Dimethyldia such as silane and dimethyldiethoxysilane
Lucoxysilanes, hexamethylcyclotrisiloxa
Octamethylcyclotetrasiloxane, decamethyl
Cyclopentasiloxane, dodecamethylcyclohexacyclo
Loxane, tetradecamethylcycloheptasiloxane,
Dimethyl cyclics
Dimethylsiloxane cyclics such as sesame trimer mixture)
Using oligomers and dimethyldichlorosilane as raw materials
Can be synthesized. Raw material price and available resin
Considering the performance such as thermal stability, the polymer block (A)
The most suitable raw material for
It is an oligomer. The graft block copolymer (I) of the present invention
Is a hydrolyzable silyl
Group, hydroxyalkyl group, aldehyde group or keto group
Is characterized by containing at least one carbonyl group based on
It has a sign. These functional groups are
(B) coexist with water resistance and water resistance of the coating film.
It can improve contamination and solvent resistance.
In particular, a coating film having excellent water resistance can be formed.
These functional groups are vinyl having a hydrolyzable silyl group.
Polymerizable monomer, vinyl containing hydroxyalkyl group
Based on polymerizable monomers and aldehyde or keto groups
Use a vinyl polymerizable monomer having a carbonyl group.
And can be introduced into the polymer block (B).
Wear. The water contained in the polymer block (B)
Examples of the decomposable silyl group include a halogenosilyl group,
Acyloxysilyl group, amidosilyl group, aminosilyl
Group, alkenyloxysilyl group, aminoxysilyl group,
Oximesilyl group, alkoxysilyl group, thioalkoxy
There are silicyl group, silanol group, etc.
Considering ease of handling, cost, etc., alkoxy
Silyl groups are preferred. Used as a constituent of the polymer block (B)
Vinyl polymerizable monomer having a hydrolyzable silyl group
As the monomer, for example, vinylmethyldimethoxysila
, Vinyl trimethoxy silane, vinyl triethoxy
Vinylsilanes such as orchids, 3-methacryloxypropyl
Trimethoxysilane, 3-methacryloxypropyl methyl
Rudimethoxysilane, 3-methacryloxypropyltri
Methacryloxyalkylsilanes such as ethoxysilane,
3-acryloxypropyltrimethoxysilane, 3-A
Acryloxypropylmethyldimethoxysilane, 3-act
Acryloxy such as riloxypropyltriethoxysilane
Alkyl silanes and the like;
Considering reactivity, cost, etc., methacryloxyalkyl
Silanes and acryloxyalkylsilanes are particularly preferred.
Good. These components may be used alone or as needed.
Two or more can be used in combination. Vinyl polymerizable compound having hydrolyzable silyl group
The content of the monomer is 0.5 to 3 in the polymer block (B).
It is preferably in the range of 0% by weight. This is vinyl
If the content of the polymerizable monomer is less than 0.5% by weight,
Water resistance and stain resistance of the coating film tend to decrease.
If it exceeds 30% by weight, the graft block
Polymerization stability of the polymer (I) and the obtained aqueous resin composition
This is not preferred because storage stability tends to decrease. Better
More preferably, it is in the range of 1 to 20% by weight. Single content
% Or more, the water resistance and stain resistance of the resulting coating film
It becomes extremely good, and when it is 20% by weight or less, the graph
Stability of the Toblock Copolymer (I) and the Aqueous Solution Obtained
The storage stability of the resin composition becomes extremely good. Used as a constituent of the polymer block (B)
Used, vinyl polymerizable with hydroxyalkyl group
Examples of the monomer include 2-hydroxy methacrylate.
Ethyl, 2-hydroxypropyl methacrylate, methac
3-Hydroxypropyl acrylate, 4-hydr methacrylate
Roxybutyl, 6-hydroxyhexyl methacrylate, etc.
Hydroxyalkyl methacrylate, acrylic
2-hydroxyethyl acid, 2-hydroxypropyl acrylate
Ropyr, 3-hydroxypropyl acrylate, acrylic
4-hydroxybutyl acid, 6-hydroxyacrylate
Hydroxyalkyl acrylates such as xyl
Among them, considering cost, water resistance of coating film
When put, 2-hydroxyethyl methacrylate, methacrylate
2-Hydroxypropyl acrylate, 3-hydr methacrylate
Roxypropyl, 4-hydroxybutyl methacrylate,
2-hydroxyethyl acrylate, 2-hydric acrylate
Roxypropyl, 3-hydroxypropyl acrylate,
4-Hydroxybutyl acrylate is particularly preferred. this
These components may be used alone or in combination of two or more as necessary.
Can be used for Vinyl polymerization having hydroxyalkyl group
The content of the water-soluble monomer is from 3 to 30 in the polymer block (B).
Preferably it is in the range of weight%. This is hydroxy
The content of the vinyl polymerizable monomer having a silalkyl group is
If it is less than 3% by weight, the water resistance of the resulting coating film tends to decrease.
If it exceeds 30% by weight, it is not preferable.
Tendency of polymerization stability of triblock copolymer (I)
Is not preferred. More preferably, 5 to 20% by weight
Range. When the content is 5% by weight or more,
The water resistance of the coated film becomes extremely good, and is not more than 20% by weight.
In the case, the polymerization stability of the graft block copolymer (I)
And the storage stability of the aqueous resin composition becomes extremely good. Al contained in the polymer block (B)
Carbohydrate groups include carbonyl groups based on dehyde or keto groups.
It does not include xyl, ester and amide groups. Polymer
Aldehyde used as a component of block (B)
Polymerization with carbonyl group based on carboxylic or keto group
Examples of the reactive monomer include acrolein, diacetate
Acrylamide, formyl styrene, vinyl methyl
Ketone, vinyl ethyl ketone, vinyl isobutyl ketone
Vinyl alkyl ketones having 4 to 7 carbon atoms such as
Acetone acrylate, diacetone methacrylate
G, acetonyl acrylate, acryloxyalkyl
Propenal, methacryloxyalkyl propenal
But polymerization reactivity, crosslinking reactivity, cost, etc.
Taking into account, diacetone acrylamide,
Lorain and vinyl methyl ketone are preferred. These components
Minutes may be used alone or in combination of two or more as necessary.
Can be used. Carbonyl based on aldehyde or keto group
Content of the vinyl polymerizable monomer having a
It is preferably in the range of 1 to 30% by weight in the lock (B).
New This is because the content of the vinyl polymerizable monomer is 1% by weight.
If it is less than 1, the water resistance, solvent resistance, etc. of the obtained coating film are reduced.
Unfavorably, and when it exceeds 30% by weight,
Means that the effect of improving the coating film performance cannot be obtained anymore,
The water resistance of the resulting coating film tends to decrease, which is not preferable.
More preferably, it is in the range of 1 to 10% by weight. This example
, The water resistance and solvent resistance of the coating film are particularly good.
You. Used for constituting the polymer block (B)
Examples of other vinyl polymerizable monomers include, for example,
Methyl methacrylate, ethyl methacrylate, methacryl
N-butyl acid, i-butyl methacrylate, methacrylic acid
t-butyl, 2-ethylhexyl methacrylate, methacrylic acid
N-lauryl acrylate, n-stearyl methacrylate,
Alkyl methacrylates such as cyclohexyl acrylate
Stele, methyl acrylate, ethyl acrylate, acrylic
N-butyl acrylate, i-butyl acrylate, t-acrylate
-Butyl, 2-ethylhexyl acrylate, acrylic acid
n-lauryl, n-stearyl acrylate, acrylic acid
Alkyl acrylates such as cyclohexyl, styrene
Aromatic vinyl monomers such as
Tacrylamide, acrylamide, crotonamide, N
An amide group-containing vinyl monomer such as methylol acrylamide;
Monomer, methacrylic acid, acrylic acid, crotonic acid, fumaric acid
Carboxy acids such as acid, maleic acid, itaconic acid and sorbic acid
Nitriles such as sil-containing vinyl monomers and acrylonitrile
And a vinyl monomer having a hydroxyl group. These ingredients
May be used alone or in combination of two or more as necessary.
Can be used. The polymer block (B) is a graft block.
Content in the range of 50 to 98% by weight in the copolymer (I).
Preferably. When the content of the polymer block (B) is 5
When less than 0% by weight, a coating film formed from the resin composition
Hardness and strength tend to decrease.
The polymer block ( B ) Exceeds 98% by weight
In such cases, the stain resistance and flexibility of the coating film tend to decrease.
There is not preferred. More preferably, 70-95 weight
% Range. The graft block copolymer (I) of the present invention
The graft crossing unit (C) constituting
A structural unit required to ensure transparency, and
Graft crossover in graft block copolymer (I)
The content of the unit (C) is the same as the graft block copolymer of the present invention.
1 to 50 mol based on the silicon atom in the coalescence (I)
% Is preferable. This is the graft crossover
When the content of the unit (C) is less than 1 mol%, it is obtained.
The transparency of the resin coating film tends to decrease.
Beyond that, in addition to being disadvantageous in terms of raw material costs,
By-products such as alcohol that are eliminated when combined
Stability and handleability of the
It is unfavorable because it is in the opposite direction. More preferably, 1.5 to 15
Mol% range. When the content is 1.5 mol% or more
Has extremely good transparency of the obtained coating film, and contains
If the amount is less than 15 mol%, the latex during emulsion polymerization
S stability is improved. Constituting the graft crossing unit (C) of the present invention
As a graft crossing agent, one or more
A decomposable silyl group, and one or more vinyl polymerizable functional groups or
Compounds containing a mercapto group can be mentioned.
Hydrolyzable silyl groups include polymerization reactivity and handling
Considering easiness and cost, alkoxysilyl groups are preferred.
Good. Specific examples of the graft crosslinking agent include vinyl methyl
Rudimethoxysilane, vinyltrimethoxysilane, vinyl
Vinylsilanes such as rutriethoxysilane, 3-methac
Riloxypropyltrimethoxysilane, 3-methacryloyl
Xypropylmethyldimethoxysilane, 3-methacrylo
Methacryloxya such as xyloxypropyltriethoxysilane
Alkylsilanes, 3-acryloxypropyltrimethoxy
Sisilane, 3-acryloxypropylmethyldimethoxy
Silane, 3-acryloxypropyltriethoxysilane
Acryloxyalkylsilanes such as 3-mercaptop
Ropirtrimethoxysilane, 3-mercaptopropylmeth
Tyldimethoxysilane, 3-mercaptopropyltrie
Toxysilane, 3-mercaptopropylmethyldiethoxy
And mercaptoalkylsilanes such as silane.
However, among others, consider vinyl polymerization reactivity, cost, etc.
And methacryloxyalkylsilanes and acryloxya
Especially alkylsilanes and mercaptoalkylsilanes
preferable. These components may be used alone or as necessary.
Can be used in combination of two or more. The resin composition of the present invention comprises the above graft copolymer.
Aqueous medium containing a surfactant in the presence of a lock copolymer (I)
In the emulsion emulsified and dispersed in the body, two or more
Organic hydrazine compound having a hydrazine residue (I)
By containing I), the emulsion for paints and
Can be used. Organic hydrazine compound used in the present invention
(II) is an alkanol in the graft block copolymer (I).
Number of moles of carbonyl group based on aldehyde group or keto group
(I) and hydrazi in the organic hydrazine compound (II)
The ratio of the number of moles of the residue (ii) is 0.05 ≦ (ii) /
(I) It is preferable to add them so as to satisfy the range of ≦ 5. When (ii) / (i) is less than 0.05
In some cases, the progress of the crosslinking reaction becomes insufficient and the coating film formed
Water resistance and solvent resistance tend to be insufficient.
The remaining unreacted organic hydrazine compound
Tends to adversely affect the appearance and water resistance of the coating film.
You. More preferably, 0.5 ≦ (ii) / (i) ≦ 2.
It is an enclosure. Within this range, the appearance, water resistance and dissolution resistance of the coating film
The agent properties become extremely good. Specific examples of the organic hydrazine compound (II)
Contains from 2 to 10, especially from 4 to 6, carbon atoms
Dicarboxylic acid dihydrazide such as oxalic acid dihydride
Razide, malonic dihydrazide, succinic dihydrazide
, Glutaric dihydrazide, adipic dihydrazide
, Sebacic dihydrazide, maleic dihydrazide
, Fumaric dihydrazide and itaconic dihydrazide
And water-soluble aliphatic dihydrogens having 2 to 4 carbon atoms
Drazines, for example ethylene-1,2-dihydrazine,
Propylene-1,3-dihydrazine, butylene-1,4
-Dihydrazine and the like. Among these
But adipic dihydrazide, isophthalic dihydrazide
, Sebacic dihydrazide and succinic dihydrazide
preferable. These may be used in combination of two or more. In the resin composition of the present invention, the graft
The block copolymer (I) exists as emulsion particles.
Exist. The emulsion particle size depends on the choice of manufacturing conditions.
The average particle size is usually 0.01 to
It is about 1.0 μm. The resin component content in the resin composition of the present invention is
It can be arbitrarily selected, but consider the coating workability, coating film performance, etc.
Considering this, a content of 30 to 60% by weight is preferred. [0034] The resin composition of the present invention comprises a graft block.
Two or more hydrazines are added to the emulsion of the copolymer (I).
An organic hydrazine compound (II) having an amino acid residue
It can be obtained by doing. Emulsion of graft block copolymer (I)
A manufacturing method that can produce suitable applications
As described below, this method is not particularly limited.
Absent. The graft block copolymer emulsion of the present invention
The cyclic dimethylsiloxane oligomer and
Poly (meth) yl containing a polymerizable functional group and / or a mercapto group.
Graft cross-linking agent consisting of functional alkoxysilane
After emulsion polymerization and neutralization in the presence of
Silyl group-containing vinyl polymerizable monomer, hydroxya
Vinyl polymerizable monomer containing alkyl group, aldehyde group
Or vinyl polymerization containing carbonyl groups based on keto groups
Radicals and other vinyl polymerizable monomers
By graft copolymerization in the presence of a polymerization initiator
It can be suitably manufactured. A cyclic dimethylsiloxane oligomer and
The total amount of the grafting agent and the ratio of water can be arbitrarily selected.
However, the weight ratio is preferably in the range of 1: 1 to 1: 9. The acidic emulsifier is a cyclic dimethylsiloxane
It is not particularly limited as long as it can open the ligomer.
However, an example of an acidic emulsifier suitable for polymerization is dodecyl
Benzenesulfonic acid. Preferred of acidic emulsifier
The amount used is the particle size and solid content of the desired emulsion.
Varies depending on the amount, polymerization temperature, and combination of other surfactants.
However, in order to accelerate the polymerization of siloxane,
Of cyclic dimethylsiloxane oligomer and grafting agent
It is preferable to use 0.5% by weight or more based on the total amount. Cyclic dimethylsiloxane oligomer and graphene
The emulsion polymerization temperature of the ft-crossing agent is not particularly limited.
In order to increase the conversion and promote the polymerization more quickly,
It is preferable to receive a heat history of 60 ° C or more at least once.
More preferably, it is 75 ° C. or higher. The resulting siloxane polymer emulsion
The particle size is determined by the degree of preliminary dispersion of the raw materials, the amount of emulsifier, and the polymerization temperature.
It can be controlled by the degree and raw material supply method. Smaller
Emulsions with a large particle size use raw materials and water as emulsifiers.
In the presence of a high-share generator such as a homogenizer
Pre-emulsify, or drop the raw material or pre-emulsion into water
Or increase the emulsifier or increase the polymerization temperature
Either method or a combination of these methods as appropriate
Can be obtained. Emulsion of the obtained siloxane polymer
Is strongly acidic, neutralized after siloxane polymerization
There is a need to. Basic compounds used for neutralization are
Although not limited to, for example, sodium hydroxide, hydroxide
Potassium, ammonia, triethylamine, etc.
You. Emulsify these basic compounds directly or in aqueous solution.
And neutralize. An acid such as methacrylic acid is added to the vinyl polymerizable monomer.
If components are included, neutralize them after the end of polymerization.
This can increase the storage stability of the emulsion.
Wear. Containing a hydrolyzable silyl group to be subsequently performed
Vinyl polymerizable monomer containing hydroxyalkyl group
Vinyl polymerizable monomers, aldehyde groups or keto groups
A vinyl polymerizable monomer containing a carbonyl group,
Used for graft copolymerization of other vinyl polymerizable monomers
Known radical polymerization initiators can be used. Concrete
Typically, azobisisobutyronitrile, 2,2'-azo
Azo compounds such as bis (2,4-dimethylvaleronitrile)
Substances, ammonium persulfate, potassium persulfate, sodium persulfate
Inorganic peroxides such as lithium, benzoyl peroxide, t-butyl
Dihydroperoxide, di-t-butyl peroxide
And organic peroxides such as cumene hydroperoxide
Potassium sulfate or ammonium persulfate and sodium bisulfite
Combination of lium or Rongalite, t-butyl hydride
Such as loperoxide and cumene hydroperoxide
Of metal peroxide and sodium hydrogen sulfate or Rongalite
Redox catalysts and the like represented by combination
You. The amount of the radical polymerization initiator to be added is usually
0.01 to 10% by weight based on the total amount of the nyl polymerizable monomer
But taking into account the progress of polymerization and control of the reaction.
Then, the range of 0.1 to 5% by weight is preferable. Also, polymerization
Divalent iron ions such as iron sulfate for imparting initiator activity
-Containing compounds and disodium ethylenediaminetetraacetate
Chelating agents can be used. The method for charging the vinyl polymerizable monomer is,
Not limited, batch preparation, dripping, or partial
After pre-charging, drop the rest afterwards
It may be a method. When dripping, just drop
May be dropped after pre-emulsification in the presence of an emulsifier.
No. Further, at the time of graft copolymerization of a vinyl polymerizable monomer or
An emulsifier may be additionally added at the end of the graft copolymerization.
The polymerization temperature is not particularly limited, but is usually in the range of 40 to 90 ° C.
It is an enclosure. Emulsifier used for preliminary emulsification or additional addition
Can be used in the known manner.
Sodium sulfonate, lauryl sulfonate
Anionic emulsification such as sodium and sodium lauryl sulfate
Emulsifier, anionic emulsifier containing polyoxyethylene groups,
Lioxyethylene nonyl phenyl ether, polyoxy
Nonionic emulsifiers such as ethylene lauryl ether, molecules
Among them are reactive emulsifiers having vinyl polymerizable double bonds.
I can do it. The resin composition of the present invention has an improved coating film forming property.
Co-solvent can be added as needed to improve
You. Specific examples include methanol, ethanol, 2-p
Lopanol, ethylene glycol, propylene glycol
2,2,4-trimethyl-1,3-pentanedio
Lumonoisobutyrate, ethyl cellosolve, butyl cello
Solve, propylene glycol monomethyl ether,
Propylene glycol mono n-butyl ether and the like.
It is. Further, the resin composition of the present invention has
A curing catalyst to accelerate the curing of the reactive silyl group
Is also good. Specific examples of curing catalysts include isopropyl tri
Isostearoyl titanate, isopropyl tri
Organic seeds such as octyl pyrophosphate) titanate
Acetoalkoxyaluminum diisoproate
Organic aluminum compounds such as pyrate, dioctylic acid
Tin, dibutyltin dilaurate, dibutyltin malate, etc.
Carboxylic acid type tin compounds, dibutyltin oxide, dioctyl
Dialkyltin oxides such as tin oxide, monomethyl acid
Phosphate ester, dimethyl acid phosphate ester, die
Acid phosphates such as tyl acid phosphate
Carboxylic acids such as pinic acid, maleic acid, citric acid and the like
Anhydrides, 3-aminopropyltrimethoxysilane, etc.
Amines such as minosilane and triethylamine and salts thereof
Is mentioned. These curing catalysts can be used alone if necessary.
Or two or more of them can be used in combination.
The amount of the curing catalyst to be added is usually the graft block of the present invention.
0.001 to 20% by weight based on the copolymer (I)
It is. Oily catalysts may compromise emulsion stability
Use water-soluble catalyst or water-dispersed catalyst
Is preferred. The resin composition of the present invention may contain a face if necessary.
Additives, UV absorbers, antioxidants, heat resistance improvers, reveri
Includes various additives such as anti-sagging agents, anti-sagging agents and matting agents
However, other emulsion resins, water-soluble resins,
Viscosity controlling agents, even when used in combination with curing agents such as melamines
Good. The resin composition of the present invention can be used for brush coating, roll
It can be applied by painting, spray painting, etc.
Cured by leaving at room temperature or heating to 50-200 ° C
Can be done. The present invention will be described in more detail with reference to the following examples.
I will tell. In the examples, “parts” are “parts by weight” and “%”.
Indicates "% by weight". The performance of the examples and comparative examples was
The evaluation was performed using the following method. (1) Hardness Using Mitsubishi Pencil Uni (screw the coating film at an angle of 45 degrees
(2) Immersion in warm water of 50 ° C. for 5 days, visual judgment of the appearance of the coating film ○: no change ×: decrease in gloss and significant whitening (3) 20 parts of stain resistant carbon black and water Mix well at a weight ratio of / 80
Apply the carbon paste to the coating and apply
After heating for minutes, wash with running water and remove the carbon
It was visually determined. ◎: Almost no trace remains ○: A thin trace remains ×: A marked trace remains (4) Solvent-resistant methyl ethyl ketone was immersed in gauze and rubbed 100 times
Thereafter, the appearance of the coating film was visually determined. ：: scarcely scratched ×: coating film peeled to expose substrate [Preparation Example 1] Dimethyl cyclics (hereinafter referred to as DMC,
Dimethylsiloxane oligomer tri- to heptamer mixture) 8
5 parts, 3-methacryloyloxypropyltrimethoxy
Silane (hereinafter KBM-503) (graft crosslinker) 15
Parts, water 300 parts and sodium dodecylbenzenesulfonate
From 0.7 parts of lithium (hereinafter referred to as DBSNa) (surfactant)
Premixed with a homomixer,
350kg / cm by Nizer ^Two Shear at high pressure, strong
The emulsion was emulsified to obtain a silicone raw material emulsion. Then, 100 parts of water and dodecylbenze
Agitate 5 parts of sulfonic acid (DBSA) (acidic emulsifier)
Equipment, condenser, temperature controller and drip pump
And keep the temperature inside the flask at 85 ° C.
3 hours for the above silicone raw material emulsion
Was dropped. After dropping, heat and stir for an additional hour.
After continuing, the resulting emulsion is cooled to room temperature and
Decylbenzenesulfonic acid in sodium hydroxide
To obtain a silicone emulsion (hereinafter referred to as SEm-1)
Was. The solid content of the obtained emulsion was 18%. [Production Example 2] 90 parts of DMC, KBM-
The same procedure as in Production Example 1 was carried out except that the amount of 503 was changed to 8 parts.
18% silicone emulsion (hereinafter SEm-
2) was obtained. Example 1 SEm-1 62 parts, water 85 parts and persulfurization
Stirrer, condenser, temperature control of 0.6 part of potassium acid
In a flask equipped with a device, a drip pump and a nitrogen inlet tube
After charging and heating to 70 ° C, the mixture was stirred under a nitrogen atmosphere.
While 2 parts of KBM-503, diacetone acrylic
3 parts of amide (hereinafter DAAm), 2-hydromethacrylic acid
10 parts of xyethyl (hereinafter HEMA), methyl methacrylate
(Hereinafter MMA) 30 parts, n-butyl methacrylate (hereinafter
Lower BMA) 30 parts, 2-ethylhexyl acrylate (hereinafter referred to as “BMA”)
Lower EHA) 23 parts and methacrylic acid (hereinafter MAA) 2
Part of the mixture was polymerized dropwise over 4 hours. After dropping,
Hold at 70 ° C for 1 hour, then raise to 80 ° C for 1 hour
Held. Cool the reaction solution to room temperature and add ammonia water.
Neutralized to obtain a graft block copolymer emulsion.
Was. Polymerization proceeds stably, with no formation of aggregates
Was. The solid content of the obtained emulsion was 44%.
Each of the obtained emulsions has a resin solid content of 100 parts.
On the other hand, 20 parts of butyl cellosolve (BC)
Acid dihydrazide (hereinafter ADH) to be 1.8 parts
To the bar coater No. 40
Apply to the electrodeposited water-coated board with electrodeposition and dry at room temperature for 30 minutes.
After heating at 70 ° C. for 1 hour, a test coating film was prepared. Trial
Table 2 shows the evaluation results of the test coating films. Examples 2 to 5 The charge was changed to the composition shown in Table 1.
Except for the above, the graft block copolymerization is performed in the same manner as in Example 1.
A body emulsion was obtained. All polymerizations proceed stably
Was. Further, BC and ADH have the compositions shown in Table 2.
Of Test Coatings Prepared Using Mixtures
The results are shown in Table 2. COMPARATIVE EXAMPLE 1 122 parts of water, 0.5 parts of DBSNa, and
Stirrer, condenser, temperature control for 0.6 part of potassium sulfate
A flask equipped with a control device, a drip pump and a nitrogen inlet tube
, And heated to 70 ° C, and then stirred under a nitrogen atmosphere.
Meanwhile, 2 parts of KBM-503, 3 parts of DAAm, HE
MA10, MMA30, BMA30, EHA23
Parts and 2 parts of MAA were added dropwise over 4 hours.
At this time, the reaction solution thickened and solidified immediately before the end of the dropping. Silico
Polymerization progresses stably in systems without emulsion
Did not. Comparative Example 2 The monomers were changed to the compositions shown in Table 1.
Except for the above, drop polymerization was carried out in the same manner as in Comparative Example 1. Dripping weight
After the combination, the same operation as in Examples 1 to 5
I got Lushon. Preparation of test coating film in the same manner as in Examples 1 to 5
The evaluation results are shown in Table 2. [Table 1] KBM-502: 3-methacryloxypro
Pyrmethyldimethoxysilane Table 2 1) Ratio to 100 parts of solids (parts) (Note) The numbers in parentheses indicate the number of moles of
In moles of carbonyl group based on aldehyde group or keto group
The resin composition for paints of the present invention has water resistance,
Gives a coating film with excellent stain resistance and is used for water-based emulsion paint
It can be used as a fat in various paint applications.
It is industrially very useful.

──────────────────────────────────────────────────続 き Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI // C08G77 / 442 C08G77 / 442 (56) References JP-A-4-214747 (JP, A) JP-A-8-3253 JP-A 8-3512 (JP, A) JP-A 8-92334 (JP, A) JP-A 9-40912 (JP, A) JP-A 9-40913 (JP, A) Kaihei 9-137124 (JP, A) JP 5-21139 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 183/10 C08F 283/00 C08F 285/00 C08L 83/00 C09D 151/00 C08G 77/00

Claims (1)

(57) [Claim 1] A polymer block (A) having dimethylsiloxane as a repeating unit, a vinyl polymerizable monomer as a repeating unit, a hydrolyzable silyl group and a hydroxyalkyl group. A polymer block (B) containing at least one carbonyl group based on an aldehyde group or a keto group,
And a silicon-containing graft crosslinking unit (C) copolymerized with the polymer block (A) and the polymer block (B).
A resin composition for a coating, comprising: an emulsion of a graft block copolymer (I) composed of: and an organic hydrazine compound (II) having two or more hydrazine residues.