JPS58164656A - Improved coating composition - Google Patents

Abstract

PURPOSE:To provide a coating compsn. which has excellent adhesion to substrates and can impart water and oil repellency, stain resistance and low frictional properties to the surface of a coating film, by dissolving a specified hydrophobic graft polymer and a specified hydrophilic graft polymer in an org. solvent soln. of a film-forming resin. CONSTITUTION:0.1-10wt% hydrophobic graft polymer (B) having a moiety contg. 10-80wt% fluorine or silicon and a moiety compatible with film-forming resin, such as a fluoroalkyl acrylate/methyl methacrylate comb polymer, and 0.01-10wt% hydrophilic graft polymer (C) having a moiety having carboxyl groups and a moiety compatible with film-forming resin, such as a methacrylate ester-terminated copolymer of a macro monomer and acrylic acid, are blended with a soln. of a film-forming resin such as PE in an org. solvent such as toluene, each amount of components B and C being based on the solid in the soln. A.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides water and oil repellency, stain resistance, and low friction properties to the surface of coatings obtained from paints such as air-dry paints, car coats, and baked-on enamels. Regarding coating compositions with improved adhesion to substrates, more specifically organic solvents for film-forming resins such as air-drying lacquers and baking enamels, hydrophobic graft polymers containing fluorine or silicone in the molecular chain, and carboxyl. The present invention relates to a coating composition with improved coating surface and adhesion properties, which is obtained by dissolving a wood-philic graft polymer containing a group in its molecular chain.

In recent years, there has been a strong interest in saving energy and resources, and there are great expectations for the emergence of higher-performance paints, especially those that impart water and oil repellency, stain resistance, and low friction properties to the coating surface. For the purpose of improving the adhesion of the paint film to the substrate, the method described above is being studied.

For improving the coating surface, examples include graft polymerization of monomers onto the coating surface by radiation, light, or plasma irradiation, coating the coating surface with a coupling agent such as an oligomer polymer or silane, and silicone resin. Methods such as adding polymers with low surface energy such as fluorine resins and fluororesins to paints have been used.

Among these methods, the graft polymerization method on the surface of the paint film using radiation, light, or plasma irradiation requires special equipment, and the paint film with an improved surface is expensive.
In the method of coating the coating surface with a coupling agent such as an oligomer, polymer, or silane, the modification of the coating surface is temporary and the modification effect on the coating surface does not last, and the coated material is easily removed, and it is difficult to form a five-layer coating film, which poses many problems.

Furthermore, even with methods of adding polymers with low surface energy such as silicone resins and fluororesins to paints, the sustainability of the modification effect on the paint film surface is never satisfactory (although it is not possible to achieve a sufficient modification effect on the paint film surface). In order to maintain this, a large amount of addition is required, which may impair the original performance of the coating film.In particular, the adhesion between the coating film and the substrate becomes worse.

On the other hand, in order to improve the adhesion of paint films to the substrate, methods such as the use of primers and the addition of special adhesion improvers to paints have been developed. In the method of using primer ~ -, it is necessary to develop a primer that is suitable for the paint used and the base used, and if the primer is not used properly, the adhesive strength between the paint film and the base cannot be obtained. Slurp. An increase in the number of primer treatment steps for 4IK underpainting leads to an increase in costs.

In the method of adding special adhesion improvers to paints,
First of all, it is necessary to select an adhesion improver that is suitable for the target paint and substrate, and because it requires a relatively large amount of addition to obtain sufficient adhesion, it may even impair the original performance of the paint film. be.

The present invention has been achieved as a result of intensive research in view of these conventional techniques.

The present invention is made by dissolving a hydrophobic graft polymer and a hydrophilic graft polymer in an organic solvent solution (hereinafter referred to as an organic solvent type paint) of a film-forming resin, and the hydrophobic graft polymer is dissolved in 7.1. It consists of a certain part that is compatible with the resin, and the parent tree and
'(5 The part where the graft poly(1-) has a carboxyl group
- An improved coating composition consisting of a portion compatible with 1 minute and film-forming resins.

The present invention is directed to the use of parts containing fluorine or silicone as polymeric additives to improve the surface-modifying effect and sustainability of coatings obtained with organic solvent-based paints such as air-drying 1119 paints and baking enamels. Film-forming resin (hereinafter referred to as paint polymer) in organic solvent 1lIlk (A hydrophobic graft polymer with a special structure consisting of a part of a soluble anchor is useful), and has an adhesive effect on the base of the paint film. Due to its excellent durability, hydrophilic graft polymers with a special structure consisting of a carboxyl group-containing part and a Toya anchor part that is compatible with paint polymers are useful as molecular additives. It is good to do it based on this.

The present invention uses hydrophobic graft polymers and hydrophilic graft polymers in which the anchor is the same component as the paint polymer or a moiety that is compatible with four paint molecules, and an organic solvent solution (a typical example is an air-drying lid lacquer). There are coating compositions such as baking-type enamels) A small amount of K is added and dissolved, without impairing the original performance of the resulting coating film, coating film II! It imparts excellent water and oil repellency, stain resistance, and low friction to the surface, and at the same time significantly improves the adhesion between the coating film and the substrate. The concentrated graft polymer does not easily separate from the surface of the coating film or the underlying surface of IklI, and maintains the effect of modifying the surface of the coating film and the underlying surface of the coating film.

Coating film surface obtained from the improved coating composition of the present invention Wi
During O modification, for modifying the base surface of the coating film (improving adhesion between the coating film and the substrate), K provides an environment suitable for migration and concentration of the hydrophobic graft polymer to the coating surface and coating of the hydrophilic graft polymer. It is important to create an environment suitable for migration and concentration of the film to the underlying surface, but the surface of the paint film can be kept in a normal air-KIL state. The # family used in ordinary paints is sufficient.

In other words, if this application is applied to a polar base, the solvent is volatilized in the atmosphere, and then an appropriate horizontal reaction is carried out according to the application fee, the resulting coating film is free from air. The hydrophobic graft polymer is concentrated on the KH surface, and it exhibits excellent water and oil repellency, stain resistance, and low friction. The adhesion between the paint film and the substrate is significantly deteriorated.

Next, the organic solvent-based paint used in the present invention will be described.

The organic solvent-based paint used in the present invention includes α-, β-
Organic solvent-based multipolymers of ethylenically unsaturated monomers, α, β-ethylene, unsaturated carboxylic acids, and derivatives thereof Organic solvent-based polymers obtained by single polycondensation reaction or organic solvent-based polymers obtained by polyaddition reaction One of the organic solvent-based multipolymers used in the present invention, such as the air-drying lacquer or baked-on enamel, is one of the main components of organic solvent-based coating, i.e., α and β used in the production of paint polymers. Ethylenically unsaturated monomers include styrene, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride,
Vinyl monomers used in general synthetic resin paints such as vinyl acetate are used, and α,β-ethylenically unsaturated carzeno acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, etc. Examples include monovalent to divalent carboxylic acids. g, β-, which are also preferably used
Derivatives of ethylenically unsaturated carboxylic acids include alkyl esters of acrylic acid or methacrylic acid, such as methyl (meth)acrylate (hereinafter this expression refers to both methyl methacrylate and methyl acrylate), ethyl,
Propyl, butyl, octyl, 2-ethylhexyl, tesyl, dodecyl, etc., and 11' (meth)acrylic acid hydroxyethyl ester, 1-hydroxypropyl'' ester, Alkyl with hydroxyl group in hydroxybutyl ester
Poisonous esters, aminoalkyl esters of (meth)acrylic acid such as dimethylaminoethyl ester and diethylaminoethyl ester; other derivatives include acrylamide, methacrylic acid amide, and derivatives thereof such as methylolamide and alkoxymethylamide. can give.

By combining and polymerizing these monomers, an air-drying varnish lacquer or a stoving clear enamel can be synthesized.

These monomers may be mixed with hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, ketone #I agents such as methyl ethyl ketone and diethyl ketone, or alcohol solvents such as butanol and octatool. Polymerization is performed in a solvent or a mixed solvent of one or more organic solvents such as methyl cellosolve, cellosolve, butyl cellosolve, etc., to obtain an organic solvent-based multi-component polymer.

Examples of organic solvent-based polymers obtained by polycondensation reactions include linear polyesters, alkyd resins, polyamides, epoxy resins, etc. obtained by ordinary polycondensation reactions dissolved in organic solvents.

Examples of organic solvent-based polymers produced by polyaddition reactions include those in which polyurethane, polyurea, etc. obtained by ordinary polyaddition reactions are mixed with an organic solvent [11%].

Furthermore, in order to adapt the agent Il as a coating composition, a regular lacquer may be prepared by combining cellulose 11114 such as ethyl cellulose, butyl cellulose, nitrocellulose, benzyl cellulose, and cellulose acetate. In addition, butylbenzyl phthalate, butyl octyl phthalate,
In some cases, a plasticizer such as butyl carpitol acetate, an antifoaming agent, a leveling agent, etc. are used in combination.

As an organic fIjjiIII paint, it is a baking type paint in which an aminoplast resin is blended with a crosslinkable polymer containing a functional monomer such as alkoxymethyl acryl oxide in a hydroxyalkyl ester of (meth)acrylic acid, a carboxylic acid or Preferably used are two-component resin coatings in which a polyfunctional epoxy resin is blended with a crosslinkable polymer containing an amino ester, and a two-component resin coating in which a diisocyanate resin is blended with a crosslinkable polymer containing a hydroxyalkyl ester.

Furthermore, inorganic pigments such as titanium oxide, clay, calcium carbonate, chromic acid, strontium, and Bungara, as well as organic materials such as phthalocyanine blue and 7-thalocyanine/green are added to these organic molten copper lid paints, and colored materials are also used. be able to.

Methods for synthesizing the hydrophobic and hydrophilic graft polymers used in the present invention include conventionally known chain transfer methods, radiation grafting methods, mechanical or organic chemical reaction methods,
The polymer initiator method, the prepolymer bonding method, the macromonomer method which has recently been attracting attention, etc. can also be preferably used.

Regarding the synthesis of the hydrophobic graft polymer preferably used in the present invention, the macromonomer method (synthesis method) of the hydrophobic graft polymer containing fluorine in the molecular chain can be mentioned, for example, methacrylic wrought methyl etc. Radical polymerization in the coexistence of thioglycolic acid with a molecular weight of 1000-10
A macromonomer having a methacrylic forged ester end group was obtained by obtaining a carboxylic acid prepolymer with one end of 0.00 and reacting it with glycidyl methacrylate.

Fluoroacrylate (CF, +CF, )n-CH is used as a copolymerization component for this macro-7mer.

CM, 0COCH=CH,, n=4-1201L compound)
By using this method, a gluft polymer can be obtained in which the trunk is a hydrophobic component and the branches are polymethacrylic stirrup methyl.

In addition, as methods for synthesizing hydrophobic graft polymers containing silicone in the molecular chain, there are several conventionally proposed methods:
The following method can be used.

ya□'' Example #i%'tk@5.・°・・``6896・Special'j
``B47-16199, Y-1 @ 48-2858?, etc.) As stated in each publication, active groups are formed by abstracting hydrogen from a lower alkyl group bonded to one elementary atom of K and silicone. , a method to obtain a silicone-based graft polymer by grafting an organic polymer thereon,
As seen in Japanese Patent Publication No. 46-9555, a method for obtaining a silicone-based graft polymer by reacting a silicone having an active group with a living polymer obtained by anionic polymerization, as seen in Japanese Patent Publication No. 52-155191, A method of synthesizing a polysiloxane polyester containing maleic acid in its main chain, mixing it with maleic acid and an electron-donating heptamer that easily forms a charge transfer complex, and graft polymerizing the mixture to obtain a silicone-based graft polymer.
Silicone is produced by radical copolymerization of acrylic-modified silicone obtained by condensation reaction from 0.25 to 1 mole of r-methacryloxyglobylmethyldichlorosilane per mole of a,ω-dihydroxydimethylborisiloxane and a monomer having radical polymerization ability. There are several methods for obtaining graft polymers (hereinafter referred to as radical copolymerization of acrylic-modified silicone and 7-mer), which have excellent solubility in organic solvents and which modify the surface of the coating film. Among these production methods, a method based on radical copolymerization of an acrylic modified silicone and a monomer is superior as a highly effective method for producing a silicone-based graft polymer.

The fluorine or silicone content in these hydrophobic graft polymers is 10 to 10%.
It is preferable to synthesize the BO by weight, preferably 20 to 70% by weight. (Here, the fluorine content in the hydrophobic graft polymer is determined by the amount of fluorine-containing monomer according to the NMR spectrum of the fluorine-based graft polymer (for example, see Reference Example 2 for the amount of fluoroalkyl acrylate), and the silicone content is The silicone-based graft polymer is fired and the silicone is determined as 8i0. It is a friend analysis value.) The fluorine content is the coating composition obtained when a hydrophobic graft polymer with a silicone content of less than 10% by weight is used in the coating composition. If a hydrophobic graft polymer with a fluorine or silicone content of more than 80% by weight is used in the coating composition, the solubility in organic solvents will be poor. Furthermore, the resulting hydrophobic graft polymer is expensive.

This is because most of the cost of raw materials for the hydrophobic graft polymer used in the present invention is accounted for by the price of raw materials containing fluorine and silicone.

It is a brat copolymer in which the silicone-based graft copolymer obtained by K is combined with a polymer obtained from a radically polymerizable monomer as a trunk and silicone as branches, and the number of branch points is determined by the number of branches. This can be determined by the molecular weight of the acrylic-modified silicone, the molecular weight of the radically weighted monomer, the molecular weight of the silicone-7 graft copolymer, and the silicone content in the silicone graft copolymer.

Can be done.

On the other hand, the macromonomer method is a method for synthesizing the hydrophilic raft polymer preferably used in the present invention.
For example, if acrylic acid is used as a synthetic component together with a monomer having a polymethacrylic acid ester end group obtained by the above method, the trunk is a hydrophilic component and the branches are polymethacrylic acid. Acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, etc. can be used as the polymer having a carboxyl group from which a methyl graft polymer can be obtained.

These can be used alone or in combination of two or more. Among these monomers having a carboxyl group, acrylic acid and methacrylic acid are particularly preferred. The amount of carboxyl groups in the hydrophilic graft polymer is 3 to 80% by weight, preferably acrylic acid or methacrylic acid in the hydrophilic graft polymer. is 5
~50wt. A composition 1゛□, coated with a hydrophilic graft polymer comprising less than 3 parts by weight of acrylic acid or methacrylic acid.

If a hydrophilic graft polymer with an acrylic acid or methacrylic acid content of more than 80% by weight is used in the coating composition, the excellent adhesion effect between the resulting coating film and the substrate cannot be expected. Poor solubility in solvents.

These hydrophobic graft polymers and hydrophilic kraft poly 1
- Graft polymers whose trunks or branches are made of polymethyl methacrylate can be used to improve the coating surface and the adhesion between the coating and the substrate, which can be obtained with organic solvent-based paints containing polymethyl methacrylate as the main or one component. Not only is it effective for modified JL, but it is also effective for modifying the surface of the coating film obtained by organic solvent-based paints such as polyvinyl chloride, polyethylene terephthalate, and epoxy resins that have an affinity with polymethyl methacrylate. Base adhesion improvement JiLK% is effective.

The amount of the hydrophobic graft polymer used in the present invention added to the organic solvent-based paint is determined by the non-volatile content of the organic solvent-based paint (
Solid content) K: 101 to 10% by weight, preferably LO: 5 to 5%, and is extremely effective. In a coating composition in which the amount of the hydrophobic graft polymer added is less than α01 weight, the surface modification effect of the resulting coating film is not sufficiently exhibited, and as the amount of the hydrophobic graft polymer added is increased, the resulting coating composition The relationship between the surface modification effect of the membrane (water repellency/oil repellency, stain resistance, low friction) is that when the hydrophobic graft polymer exceeds a few weights, the surface modification effect stops improving and remains almost constant. It becomes a value. Moreover, if a hydrophobic graft polymer is added in large quantities, it will have a negative effect on the inherent performance of the coating film and will also increase the cost.

Therefore, the upper limit of the amount of hydrophobic graft polymer added to the coating composition is 10% by weight relative to the non-volatile content of the organic*MW paint.

The method for adding the hydrophobic graft polymer to the organic 178M111 paint is to add the hydrophobic graft polymer to the organic solvent-based paint, add the hydrophobic graft polymer to an appropriate solvent, and add the resulting solution to the organic III! 1@i
Any method such as adding it to a paint may be used. At the same time, the amount of the hydrophilic graft polymer added to the organic solvent-based paint is determined based on the non-volatile content of the organic solvent IIIk material (as opposed to Q,
01-10 heavy weight, preferably α05-5 weight-
is valid. -The amount of water-based graft polymer added is α0
If it is less than 1% by weight, it will not be possible to obtain sufficient adhesion between the coating film and the base, while if it exceeds 10% by weight, the original performance of the coating film will be affected and the cost will increase. The upper limit of the amount added to a solvent-based paint is 10% by weight based on the nonvolatile content of the organic solvent-based paint.

Hydrophilic graft polymer organic #111pl! 1. As with the case of hydrophobic graft polymers,
Direct addition method, 7tll obtained by dissolving in a suitable solvent
Any method such as adding a liquid may be used.

The thus obtained coating composition of the present invention can be preferably used for commonly used coating materials such as metals, ceramics, wood, and polar plastics.

As mentioned above, a very small amount of hydrophobic graphite
- imparts water richness, oil repellency, stain resistance, and low friction properties to the surface of the film, and a very small amount of hydrophilic graft polymer significantly improves the adhesion of the paint film to the base, without impairing the original performance of the paint film. A coating composition with excellent durability of the modification effect on the surface of the coating film and excellent durability of adhesion to the substrate is provided, but in addition, as in the present invention, a combination of a hydrophobic graft polymer and a hydrophilic craft polymer is provided. (6) The modification effect on the coating surface is greater than the modification effect on the coating surface when using a single K11ll amount of hydrophobic graft polymer.
Better. The amount of the hydrophobic graft polymer used in the present invention may be smaller than that required to obtain the same surface modification effect as when the hydrophobic graft polymer is used alone.

In addition, the coating film obtained from the coating composition of the present invention does not impair the original performance of the coating film, and has excellent water and oil repellency on the coating film surface.
It not only provides stain resistance and low friction (especially when silicone-based graft polymers are used, the low friction effect is remarkable), but also provides excellent adhesion to the base of the coating film.
1.

Next, in order to clarify the present invention in more detail, Reference Examples, Examples, and Comparative Examples are listed.

Note: - in each example represents weight, and parts represent parts by weight.

A reference example was prepared using a glass flask equipped with a stirrer, a reflux condenser, one dropping funnel, a temperature needle, and a gas inlet. 10 parts of ζ methyl methacrylate (hereinafter abbreviated as MMA) and acetone (17
, 51G)-) 83 parts of a toluene mixed solvent were charged, and after entering NJ University, 5 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN) α as a polymerization initiator and 52 parts of thioglycol λ acid α as a chain transfer agent were added under reflux. In addition, polymerization was initiated. Over the next 45 hours, 90 parts of MMA was continuously added dropwise, 1.122.88 parts of thioglycol was dissolved in 7 parts of toluene, and added in 9 portions every 30 minutes. Polymerization was carried out by adding 3 times at different times. Thereafter, the mixture was refluxed for 2 hours to complete the polymerization, and a polymer solution having the following structural formula (1) was obtained.

The reaction temperature was 77-87°C. A part of the reaction solution was converted into n-
After reprecipitation with hecanane and drying, the acid value was measured and found to be α340 hour equivalent/9.

CH3 (1) H-(CH, -C-8-CH, -COOH
薯COO-CH.

Next, after distilling off a portion of a7ton from the above reaction solution, triethylamine n, s* was added as a catalyst.

Add 200 ppm of hydroquinone 7-methyl ether (as a polymerization inhibitor), add glycidyl methacrylate in an amount of 12 times the molar amount based on the acid value, and heat under reflux (approximately 110°C).
) K11 hour reaction was carried out.

The reaction rate determined from the decrease in acid value was 96-.

The reaction solution was poured into 10 times the amount of n-hexane, precipitated, and then dried under reduced pressure at 80° C. to obtain macromonomer 90s having the following structural formula (it). Polystyrene conversion using Gel Permeability Co., Ltd. (hereinafter referred to as GPC),
The calculated molecular weight was 2.840 (number average) and 0 (weight average). Also, the hydroxyl value is α35. O'? -equivalent/9°C.

Reference N 2. Synthesis of fluorine-based graft polymer by macromonomer method Synthesis of fluoroalkyl acrylate (trunk)/methyl methacrylate (branch) -< I, m graft polymer The macromonomer obtained in Reference Example 1 was placed in the same apparatus as in Reference Example 1. 70 parts and the following structural formula [30 parts of button fluoroalkyl acrylate = trifluorotoluene (C, HsCF
s) Prepare 270 parts and 55 parts of MuIBNα, introduce the island,
The reaction was carried out at 11° under reflux (approximately 100°C) for 5 hours (CiM) CF, GCF, icH, C! H, -0CO-
CH=CH.

A mixture of n-=4 to 12 (average value of n: about 7) was saponified and dried under reduced pressure at 80°C to obtain 67 parts of a graft polymer.

This product showed a single peak by GPC, and the polystyrene equivalent molecular weight was IQ, 800 (number average) and 21,
700 (weight average).

In addition, trifluorotoluene was added as an internal standard substance, and an -NMR spectrum was measured in a CD C1s@ medium, and the H of trifluorotoluene and MMA in the polymer were measured.
The content of the MMA unit in the graft polymer was determined from the peak area ratio of the unit -〇-CH5 to H.
It was 60-. The remaining 40- was made into fluoroalkyl acrylate. In this way, a fluorine-based graft polymer having a fluorine content of 40 inches was obtained. Also, by changing the amount of fluoroalkyl acrylate and performing the same operation, the fluorine content was 61-121-1, and the molecular weight was about 10,000 (number average).
A fluorine-based graft polymer was also synthesized.

Reference example 3 Synthesis of hydrophilic graft polymer Acrylic acid +
Synthesis of MMmu (trunk)/MMA (branch)-comb-shaped graft polymer. Into the same apparatus as in Reference Example 1, 40s of the macromonomer obtained in Reference Example 1 was added. J Le 1N511, MMA4
5 parts, 270 parts of ethanol (25 Vol-)-tetrahydrofuran mixed solvent, and 178 parts of AIBN1 were charged.
3, and the reaction was carried out under reflux (52-66°C) for 6 hours.

This reaction solution was poured into 10 times the volume of n-hexane, allowed to settle, and dried under reduced pressure at 80°C to obtain 55 parts of a graft polymer.

This product showed a single peak from GPCK, and the integrated polystyrene molecular weights were 8,700 (number average) and 24,800 (weight average).

Further, al- was t'52 equivalent/2.

Reference example 4 Synthesis of silicone-based graft polymer (Part 1)
) α,ω-dihydroxydimethylborisiloxane CH.

(To a solution in which α12 morn was dissolved in 400 mK of dizthyl;-thyl, a 10% dizthyl ether bath solution containing 16 g (0.05 mol) of r-methacryloxyglobylmethyldichlorosilane was gradually added dropwise over 20 minutes at room temperature.

The reaction proceeded immediately and white crystals of pyridine hydrochloride precipitated. After the addition was completed, the mixture was further stirred at room temperature for 1 hour, and the crystals of pyridine hydrochloride were removed by filtration. Next, add this liquid to Separation Ro)K.

Further, 500 g of water was added and shaken thoroughly to perform washing with water. After washing with water, the separatory funnel was allowed to stand still to separate the upper ether layer and the lower aqueous layer, and the obtained ether 1ilK anhydrous powder was added and left overnight at room temperature to dehydrate. □1゛1 Thereafter, anhydride was removed by filtration, and the resulting filtrate was distilled under reduced pressure to remove ether, yielding 225 g of colorless and transparent acrylic modified silicone.

Next, the acrylic modified silicone and MMA were copolymerized. For copolymerization, 50 parts of the acrylic modified silicone, MM
A50 parts, azobisisobutyronitrile t0111. )
500 parts of rugone was placed in a flask equipped with a condenser and a stirrer, and reacted in a nitrogen atmosphere at a temperature of 80° C. for 24 hours.

After the reaction, toluene and unreacted MMA were removed by vacuum distillation to obtain a solid reaction product. Next, unreacted acrylic-modified silicone was extracted from the scissors reaction product with n-hexane, and dried under reduced pressure to form a white powdery silicone-based graft polymer 81.
part was obtained.

This silicone-based graft polymer was soluble in toluene, xylene, and thinner.

Moreover, as a result of analysis, the amount of silicone contained in this silicone-based graft polymer was found to be dimethyl borosilicate.

40- as resiloxane, polystyrene
The number average molecular weight in terms of 1 ton was 90,000.

Silicone analysis uses silicone in a platinum crucible.

Approximately Q, 29 of the graft polymer was accurately weighed, approximately 6-chain sulfuric acid was added, and the mixture was placed in an electric furnace and heated at 700°C for 2 hours to obtain silicone as 8i0 weight.

Yo Moreover, the molecular weight is a value used in liquid chromatography.

Reference example 5. Synthesis of silicone-based graft polymer (Part 2) 67 parts of acrylate and 75 parts of sheet butyl peroxide were placed in a flask equipped with a condenser and a stirrer, and reacted in a nitrogen atmosphere at a temperature of 122°C for 7 hours.

A small amount of unreacted upper material was removed at 80 DEG C. and under a reduced pressure of 1 H9. The reaction product was a white highly viscous oil.

Even when the reaction product was attempted to be slowly dissolved in toluene, xylene, and/or solvent, there were some undissolved substances, resulting in a cloudy solution.

Further, as a result of analysis, the amount of silicone contained in this silicone-based graft polymer was 45- as dimethylpolysiloxane.

The silicone-based graft polymer contained a small amount of styrene homopolymer, butyl acrylate homopolymer, and styrene/butyl acrylate copolymer in addition to the graft polymer grafted onto silicone.

Examples and Comparative Examples 1, 2, and 5° A 10s trifluorotoluene solution of a fluorine-based graft polymer with a fluorine content of 61 as shown in Reference Example 2 (hereinafter abbreviated as fluorine-based graft polymer solution), and Reference Example A 10-acetone/toluene mixed solvent solution (hereinafter abbreviated as hydrophilic graft polymer solution) of the carboxyl group-containing hydrophilic graft polymer shown in No. 3 was prepared. The obtained fluorine-based graft polymer solution and the hydrophilic graft polymer solution (20Is thinner solution of MMA and ethyl acrylate copolymer), an air-drying acrylic paint, and the fluorine-based graft polymer were added to the acrylic clear paint. The coating composition of the present invention was prepared by adding one dose of each to the nonvolatile content of .

Next, this coating composition of the present invention was coated onto a glass plate using a bar coater. After air drying in a fume hood for one day, a transparent coating film with a thickness of 50 μm was obtained.

The surface of the coating film was smooth and free of pinholes.

The results of the contact angle of the coating film surface with water, stain resistance, and adhesion between the coating film and the glass plate are shown in Table 1 as Example 1.

Also, the fluorine-based graft polyester! The physical properties of the phosphor film obtained from the acrylic clear paint containing only - (the content of the fluorine-based graft polymer is the same as in Example 1) are also shown in Table 1 as Comparative Example 1. The physical properties of the coating film obtained from the acrylic clear paint containing only the 7m hydrophilic graft polymer (the content of the hydrophilic graft polymer is the same as in Example 1) are shown in Table IK Comparative Example 2. In addition, the physical properties of the coating film obtained only from the acrylic clear paint are also listed.
1 as Comparative Example 3.

Table 1 (1) Air surface contact angle Contact angle of water on the surface of the paint film in contact with air (constant at 20°C using a contact angle measuring device with a goniometer) (2) Stain resistance 5-water slurry of activated carbon, +, (α2
- Drop onto the surface of the paint film that is in contact with the air and let it air dry.

After washing with water using a spatula With a collection of mushroom activated charcoal evaluated.

The judgment criteria O to × are as follows. cage ◎: No activated carbon remains at all.

O: A little bit of ・ is attached.

4 It looks like an eagle.

×: # remains attached It's black with Ru.

(3) Adhesion (survival rate of goban test) 2 with a knife
Make a cut in the shape of a gobang on the bow and remove the gobang with cellophane tape.

evaluated. Remaining rate is expressed as - I did.

As shown in Table 1, it can be seen that the surface of the coating film obtained from the coating composition of the present invention was greatly modified, and the surface was extremely excellent in water repellency and stain resistance, and the adhesion was also significantly improved.

In addition, when only fluorine-based graft polymer is added to the ratio (
Compared to Comparative Example 1), when a fluorine-based graft polymer and a hydrophilic graft polymer were simultaneously added as in the coating composition of the present invention (Example 1), the contact angle was significantly larger, indicating that the surface modification effect was even greater. It shows that it is big.

Examples 2, 3 and Comparative Example 45.6 10% trifluorotoluene solution of the fluorine-based graft polymer with a fluorine content of 40 g obtained in Reference Example 2 and the same hydrophilic graft polymer solution used in Example 1 The underarm fluorine graft polymer and the hydrophilic graft polymer are added to an air-drying acrylic clear paint (ethyl acrylate, butyl acrylate), a 25s thinner solution of a copolymer of MMA), and the amount of the hydrophilic graft polymer is 1% relative to the nonvolatile content of the acrylic clear paint. Two types of coating compositions of the present invention were prepared by adding them in the proportions shown in Table 2. Next, these coating compositions of the present invention were coated on a glass plate using a K/(- coater. After being air-dried for one day in a fume hood, a transparent film with a thickness of 50 μm was obtained. The surface of the coating film was All of them were smooth with no pinholes. Table 2 shows the results of the contact angle of the coating film surface with water, the stain resistance of the coating film surface, and the adhesion between the coating film and the glass plate for Examples 2 and 3. It was shown as

In addition, the physical properties of the coating films obtained from the acrylic clear paint containing only the fluorine-based graft polymer are also shown in Table 2 as Comparative Examples 4 and 5.

In addition, the physical properties of the coating film obtained only from the acrylic clear paint are also shown in Table 2 as Comparative Example 6.

The contact angle, stain resistance, and adhesion shown in Table 2 were determined in the same manner as in Example 1.

Table 2 Example 4 and Comparative Example 7 10 of the silicone-based graft polymer obtained in Reference Example 4
-) Luene St......The same hydrophilic graft polymer solution used in Example 1 was added to the same air-drying acrylic clear paint as used in Example 1, and the scissors silicone-based A coating composition of the present invention was prepared by adding the graft polymer and the axillary aqueous graft polymer to the nonvolatile content of the wrinkled acrylic clear paint so as to give α5-.

Next, this coating composition of the present invention was coated onto a glass plate using a bar coater. After air drying in a fume hood for one day, a transparent coating film with a thickness of 50 seconds was obtained.

The surface of the coating film was smooth and free of pinholes.

Contact angle of the paint film surface with water, stain resistance of the paint film surface, *
The results of the adhesion between g and gate ballast plate and the angle of friction on the surface of the coating film are shown in Example 4 in -13. In addition, the physical properties of the coating film obtained only from the acrylic clear paint are also shown in Table 5 as Comparative Example 7.

Contact angle, stain resistance, and adhesion were measured using the methods described in Table 5. The measurement method is to attach a sample formed on a glass plate to this friction angle measuring device, attach this sample, and measure the m! of this sample. A cube weighing 100 g (vertical x horizontal x height = 25 x 25 x 20 am) with a soft polyvinyl chloride sheet attached to the bottom was placed on the membrane surface, and the tilt speed was 27°/
The sample was tilted in seconds to obtain the angle at which the cube began to slide on the coating surface.

Table 6 As shown in Table 5, the surface of the coating film obtained from the coating composition of the present invention was significantly modified, and it was found that it was endowed with excellent water repellency, stain resistance, and low friction properties. It can also be seen that the adhesion was significantly improved.

Example 5 and Comparative Example 8 The silicone graft polymer obtained in Reference Example 5, the same hydrophilic graft polymer as used in Example 1, and the same air-drying acrylic clear paint as used in Example 1 were used. A coating composition of the present invention was prepared in the same manner as in Example 4.

Next, this coating composition of the present invention was applied onto a β lath board using a percoater. After air drying in a fume hood for one day, a transparent coating film with a thickness of 50 μm was obtained.

The surface of the coating film was smooth and free of pinholes.

The results of the contact angle of the coating film surface with water, stain resistance, and adhesion between the coating film and glass are shown in Table 4 as Example 5.

In addition, the physical properties of the coating film obtained from the acrylic clear paint containing only the silicone graft polymer (the content of the silicone graft polymer is the same as in Example 5) are also shown in Table 4 as Comparative Example 8. .

Table 4 Example 6 and Comparative Example 9.10 101) of the fluorine-based graft polymer with a fluorine content of 40s obtained in Reference Example 2! j Fluorotoluene solution and the same hydrophilic graft polymer solution used in Example 1 were used to create a baking-type thermosetting acrylic clear paint made from a copolymer of MMA/hydroxyethyl acrylate/styrene/acrylic acid/butyl acrylate and melamine resin. A coating composition of the present invention was prepared by adding 2% CL of the synthetic polymer and 1% of the axillary hydrophilic graft polymer.

Next, this coating composition of the present invention was coated onto a glass plate using a bar coater. Air dry in a draft for one day at 200℃
After baking for 30 minutes, a transparent coating film with a thickness of 50 seconds was obtained. The surface of the coating film was smooth and free of pinholes.

Contact angle of the paint film surface with water, stain resistance of the paint film surface, l
The results of the adhesion between the ll1 film and the glass plate are shown in Table 5 as Example 6.

Table 5 also shows the physical properties of the coating film obtained from the acrylic clear paint containing only the 7 bulky graft polymer (the content of the fluorine graft polymer is the same as in Example 6).
This is shown as Comparative Example 9. In addition, the physical properties of the coating film obtained only from the acrylic clear paint are also shown in Table 5 as Comparative Example 1o.

The methods for measuring the contact angle, stain resistance, and adhesion shown in Table 5 are the same as in Example 1.

Table 5 Example 7 and Comparative Examples 11 and 12゜101s trifluoro-based toluene solution of the fluorine-based graft polymer with a fluorine content of 21-2 obtained in Reference Example 2 and the same 611 aqueous graft as used in Example 1 A two-component reaction-curing acrylic urethane paint (product name: Aroncoat FC Deluxe (white)) using a polymer solution.
The base agent is a 60S thinner solution, the hardener is a 50X toluene solution, and the method of use is to mix the base agent/hardener so that the weight ratio is 7/1. A coating composition of the present invention was prepared by adding one part of the graft polymer and one part of the cough-related graft polymer. That is, the core coating composition of the present invention is composed of a base material containing a fluorine-based graft polymer and a hydrophilic graft polymer (hereinafter abbreviated as "base composition of the coating composition of the present invention"), and a curing agent.

Next, 7 parts of the main ingredient of the product III of the present invention and 1 part of the curing agent were mixed and immediately coated on a glass plate using a bar coater. If left in a draft for 4 days, the thickness will be 5.
A white coating film of 0μ was obtained.

The surface of the coating film was smooth and free of pinholes.

The results of the contact angle of the coating film surface with water, stain resistance, and adhesion between the coating film and the glass plate are shown in Table 6 as Example 7.

In addition, the physical properties of the coating film obtained from the armpit acrylic urethane paint containing only the nuclear fluorine-based graft polymer (the content of the fluorine-based graft polymer is the same as in Example 7) are also shown in Table 6 as Comparative Example 11. In addition, the physical properties of the coating film obtained only from the acrylic urethane paint are also shown in Table 6 for Comparative Example 12.

The contact angle, stain resistance, and adhesion measurement methods in Table 6 are as follows:
This is the same as in the first embodiment.

Comparative Example 16 According to the method of Reference Example 2, a fluorine-based graft polymer having a fluorine content of 7.0 and a number average molecular weight of about 20,000 was synthesized. A 10-trifluorotoluene solution of a fluorine-based graft polymer was prepared, a coating composition was prepared in the same manner as in Example 1, and the coating composition was coated on a glass plate using a coater. Air-dried in a fume hood for one day. Then the thickness is 50μ
A transparent coating film was obtained.

The adhesion between the coating film and the glass plate did not pass the goblin test.

Comparative Example 14 □1 A fluorine-based graft polymer having a fluorine content of 85 and a number average molecular weight of approximately 25,000 was synthesized according to the method of Reference Example 2. It does not dissolve in fluorotoluene or thinner and cannot be added to paints.

Procedural amendment 1981 (Mon. 2ξ, Director General of the Japan Patent Office Shima 1) Haruki Tono 1, Indication of the case 1988 Patent Application No. GE, S: "7, 2-7 No. 2 Name of the invention Improved coating composition Item 3. Relationship with the case of the person making the amendment Patent applicant address: 1-14-1 Nishi-Shinbashi, Minato-ku, Tokyo Column 5 of the detailed explanation of the invention in the specification, Contents of the amendment (1) Specification No. 301 Equivalent to line Kr0.3401/l
” should be corrected to “ro, 34011 Toki/l” (2) “Paint” and rMM in the second line from the bottom of page 30 of the specification
Add "(" between AJ.

(3) Add "and the hydrophilic graft polymer" between "fluorine graft polymer" and "the acrylic type" on page 30, line 1 of the specification.

(4) Delete the text “Attach this sample” on page 37, lines 4-5 of the specification 0 (5) “Paint” and rMMAJ on page 30, line 10 of the specification
Add "(" in between.

Claims (1)

[Claims] t A hydrophobic graft polymer and a hydrophilic graft polymer are dissolved in an organic solvent solution of a film-forming resin, and the hydrophobic graft polymer is dissolved in 7. The hydrophilic graft polymer is composed of a portion having a silicone unit or a silicone unit and a portion compatible with the film-forming resin, and the hydrophilic graft polymer is composed of a portion having a carboxyl group and a portion compatible with the film-forming resin. Coating composition.