JPH03220268A - Matte coating composition - Google Patents

Abstract

PURPOSE:To improve the curability, the weatherability of a coating film, and the matte effect by compounding a specific vinylic resin with a matting agent comprising a weather-resistant high polymer powder and/or a finely powdered synthetic silica. CONSTITUTION:A vinylsilane monomer having a hydrolyzable group is copolymerized with another vinylic monomer to give a vinylic resin which has a mol.wt. of 1000-80000, a main chain virtually comprising a vinylic polymer, and at least one hydrolyzable silyl group at the terminal or in the side chain in the molecule. 100 pts.wt. said vinylic resin is compounded with 1-50 pts.wt. matting agent comprising a weather-resistant high polymer powder having a mean particle diameter of 0.05-100mum and selected from the group consisting of vinylidene fluoride polymer tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, etc., and/or a synthetic, hydrophobic silica powder having a means particle diameter of 0.01-20mum and a di-n-butylamine adsorption, i.e., degree of hydrophobicity, of pref. 100meq/kg or lower.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a novel matte coating composition, and more specifically,
It has excellent weather resistance, can form a matte coating film, and has good curing properties, making it suitable for use in outdoor structures and architectural exteriors.1. % of the matte coating composition.

[Prior Art] Since weather resistance is required for top coats of outdoor structures, building exteriors, automobiles, etc., weather-resistant paints are used as the most commonly used paints.

In recent years, paints using acrylic silicone resins have been developed and are beginning to be used as paints with excellent weather resistance. This acrylic silicone resin (well, the main chain is essentially made of a vinyl polymer, and one or more hydrolyzable silyl groups are introduced into each molecule at the terminal or side chain, so it is not self-crosslinking or The silyl groups are hydrolyzed by the curing catalyst to form siloxane bonds between molecules, which are crosslinked and cured to form a film.

On the other hand, for architectural exteriors, paints that provide a matte coating are often preferred from the standpoint of design.

As this matte coating, coating compositions to which inorganic fine powder such as silica or organic fine powder such as polyethylene resin are added are conventionally known.

However, when fine silica powder is added as a matting agent to the acrylic silicone resin in an attempt to obtain a coating film with excellent weather resistance and a matte finish, curing failure occurs and sufficient physical properties of the coating film cannot be obtained. Or polyethylene M
Addition of F-fat fine powder inevitably causes a problem in that the weather resistance of the coating film is significantly reduced.

[Problem to be Solved by the Invention 1] The present invention was made for the purpose of providing a coating composition that has excellent weather resistance, can form a coating film with sufficient matte effect, and has good curability. It is something.

[Means for Solving the Problems 1] As a result of intensive research aimed at developing a coating composition having the above-mentioned favorable properties, the present inventors found that a predetermined amount of vinyl resin containing a hydrolyzable silyl group was added to the vinyl resin containing a hydrolyzable silyl group. It was discovered that the objective could be achieved by a coating composition containing weather-resistant polymer particles and fine particulate synthetic silica, and based on this knowledge, the present invention was completed.

That is, the present invention provides (a) a vinyl resin 100 whose main chain is substantially composed of a vinyl polymer and which has one or more hydrolyzable silyl groups in one molecule at the terminal and/or side chain;
Based on the weight part, (b) at least 1 m or more selected from weather-resistant polymer particles and fine particulate synthetic silica1
50 parts by weight of the matte coating composition is provided.

The present invention will be explained in detail below.

In the composition of the present invention, the vinyl resin used as component (a) has a main chain substantially composed of a vinyl polymer, and has one or more hydrolyzable polymers in one molecule at the terminal or side chain. Those having a silyl group are used. This thing is
Those obtained by copolymerizing a vinyl type silane monomer having a hydrolyzable group with another vinyl type monomer and having a molecular weight in the range of 1000 to so, ooo are preferably used. If this molecular weight is less than 1,000, the resulting coating film will not have sufficient weather resistance, and if it exceeds 80,000, the viscosity of the solution will increase when dissolved in a solvent.
The solid content concentration must be lowered, which makes coating difficult and tends to cause uneven gloss, which is undesirable.

The hydrolyzable silyl group introduced into the end or side chain of this vinyl resin includes a hydrolyzable group such as a halogen atom, an alkoxy group, a thioalkoxy group, an acyloquine group, a phenoxy group, an iminooxy group, and an alkenylokyne group. Among these, alkoxysilyl groups are preferred from the viewpoint of handling stability and economical efficiency in resin production.

Such a vinyl polymer having a hydrolyzable silyl group is crosslinked by self-crosslinking or by forming siloxane bonds between molecules using a curing catalyst to provide a cured coating film.

In the composition of the present invention, the vinyl resin having a hydrolyzable silyl group at the terminal or side chain and used as the component (a) is easily available as a commercial product.

Examples of commercially available products include Kaneriki Zemlak [manufactured by Kaneshiro Kagaku Kogyo Co., Ltd., trade name], Acryday 7ri C Inu Nippon Ink Kagaku Kogyo Co., Ltd.! ! , trade name j, and Kriyamar [manufactured by Sanyo Chemical Industries, Ltd., trade name].

These are generally dissolved in a solvent and sold as a solution.

Original F! In Composition A, weather-resistant polymer particles or particulate synthetic silica are used as the matting agent (b). As for the former weather-resistant polymer particles,
For example, vinylidene fluoride 1i polymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, chlorotrifluoroethylene-ethylene copolymer, methacryl Examples include particles such as acid methyl polymers.

One type of these weather-resistant polymer particles may be used, or two or more types may be used in combination. In addition, these weather-resistant polymer particles have an average particle diameter of 0.05 to
Those within the range of 100 μm are preferable; if this average particle diameter is less than 0.05 μm, it is difficult to obtain a matte coating film, and if it exceeds 100 μm, the uniform color and smoothness of the coating film will deteriorate. This is not desirable.

The shape of the polymer particles is not particularly limited and may be spherical or irregular in shape, but spherical or nearly spherical shapes are preferred.

On the other hand, examples of fine particulate synthetic silica include those obtained by the reaction of sodium silicate and an acid, those obtained by the hydrolysis of alkoxine silane, and those obtained by the reaction of calcium silicate and an acid. This fine particulate synthetic silica has an average particle diameter of 0.01~
Preferably, the thickness is in the range of 20 μm.

The fine particulate synthetic silica used in the composition of the present invention is produced by reacting the silanol groups on its surface with halosilane, alkoxysilane, silazane, siloxane, etc. to chemically bond organic substances to the silanol groups, making the surface hydrophobic. Hydrophobic synthetic silica having a hydrophobicity of 1k (hereinafter referred to as DBA value) of di-n-butylamine adsorption of 100 meq/kg or less is particularly suitable.

Specific examples of hydrophobic synthetic silica made by chemically bonding an organic substance to the silanol groups on the surface include those that are generally commercially available as hydrophobic synthetic silica, such as cyholobic [Fuji Davison Chemical Co., Ltd. ), product g
l, Njpsil SS [manufactured by Nippon Sirikani Co., Ltd.,
Product name], AERLO5IL R972rEi manufactured by Hon Aerosil Co., Ltd., and product name Ko.

In the composition of the present invention, the fine particulate synthetic silica is 1
A species may be used, or two or more species may be used in combination.

In the composition of the present invention, as the matting agent of the component (b), only the weather-resistant polymer particles described above or only the fine particulate synthetic silica may be used; May be used in combination.

In the composition of the present invention, the matting agent consisting of weather-resistant polymer particles and/or fine particulate synthetic silica as component (b) is added in an amount of 1 to 100 parts by weight per 100 parts by weight of the vinyl resin as component (a). It is necessary to mix it in a proportion of 50 parts by weight. If the amount is less than 1 part by weight, the matting effect will not be sufficiently exhibited, and if it exceeds 50 parts by weight, the mechanical strength of the coating film will decrease.

In the composition of the present invention, a curing catalyst can be used as desired. There are no particular limitations on this curing catalyst, and any catalyst can be selected from those conventionally used as curing catalysts for hydrolyzable silyl group-containing vinyl polymers.

Examples of such curing catalysts include alkyl titanates; acidic compounds such as phosphoric acid, p-toluenesulfonic acid, and phthalic acid; aliphatic diamines such as ethylenediamine and hexamethylenediamine; diethylenetriamine, triethylenetetramine, and tetraethylene. Amine compounds such as aliphatic polyamines such as pentamine, heterocyclic amines such as piperidine and piperazine, ethanolamines, triethylamine, and various modified amines used as curing agents for epoxy resins: (n-CJ*)zsn( OCOC+ 1H23-11)
2, Cn-Cans)xsn(OCOCH=CflCO
OCH3)2, (n-Cans)2sIl(OCOCH
”CHCOOC*L-n)2, (11-Csll+y)
:5n(OCOC+ 1H23-D)2, (n-C61
(+7)2sn(OCOCH=C)IcOOcII3
)2, (n-Cafl+y)zsn(QC(lcIl=
cRc(IQcJs-11)z, (n-Cs[l+t
)zsll(OCOCtl=CI(COOCa■IT-
Organotin carboxylates such as 1sO)2.5o(OCOCaH+ 7-n)2, (n-C4)1s)zsn(SCH2COO), (++
-C, ■5)xsn(SCH2COOC@H+y-IS
O)z, (II-CaLy)zsn(SCH2COO)
, (II-Ca[117)2Sn(SCH2COOCJ
17-1sO)2.

(11-CsL,)2sn(SCJCOOCH2CM
zOCOLS), (n-CJ+ 7) 2511 (SCH
2CH2COO), (n-CaLy)zsn(SC)
12C00CHzCHzCH2CLC[130CO[2
S), (n-Cs11+7)zsn(SCt12COO
C+2Bzs-n)2, (n-C4Hs):5n(SC
II, C00C, H, 7-iso) (n-C+Hs)z
Mercaptide-type organotin compounds such as sll (SC112COOCal (+ y-iso), (n -C4+I
* ) Sulfide-type organic tin compounds such as Sn:S / (D-CaL) Sn=S (o-C@H+□) (n-C4L)-SngS (n-C4Hs)-5n-5, (II-C4 !II) 2SDO% (n-CJ+y)z
sn.

and (n-C4Hs)SnOl(II-CsH+ r)Sn
.

Organic tin compounds such as reaction products of organic tin oxides such as ethyl silicate, ethyl silicate 40, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, etc. can be mentioned.

These curing catalysts may be used alone, or
Two or more types may be used in combination, and the blending amount is as follows:
Usually, the amount is selected from o, oos to 10 parts by weight, preferably from 0.1 to 8 parts by weight, based on 100 parts by weight of the hydrolyzable silyl group-containing vinyl resin of component (a).

Furthermore, a stabilizer may be added to the composition of the present invention as desired in order to improve the stability of the resin. Alcohols, hydrolyzable esters, etc. are preferably used as the stabilizer, and the alcohols include alcohols with an alkyl group of 1 to 10 carbon atoms, such as methanol, ethanol, impropatol, n-7'tanol, 5e
C-butanol, n-amyl alcohol, in-amyl alcohol, hexyl alcohol, octyl alcohol,
Examples include cellosolve.

On the other hand, examples of hydrolyzable esters include silanes such as silane, dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, and tetraethoxysilane, vinyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Examples include silane coupling agents such as silane, γ-glyndoxypropyltrimethoxysilane, and γ-ureidopropyltriethoxysilane, and formic acid esters such as methyl orthoformate and ethyl orthoformate.

These stabilizers may be used alone or
Two or more types may be used in combination, and the blending amount is as follows:
Usually 0.01 to 20 parts by weight, preferably 0.1 to 20 parts by weight, per 100 parts by weight of the silyl group-containing vinyl resin of component (a).
The amount is selected within the range of 10 parts by weight.

Furthermore, an adhesion improver can be added to the composition of the present invention in order to improve the adhesion of the coating film to various materials. Examples of the adhesion improver include aminoalkyl alkoxysilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-aminopropylmethyljethoxysilane, and aminoalkyl alkoxysilanes represented by the formula %))). Examples include alkylene polyaminoalkylalkoxysilanes such as γ-anilinopropyltrimethoxysilane, piperazinoalkylalkoxysilanes such as anilinoalkylalkoxysilanes such as γ-anilinopropyltrimethoxysilane, and reaction products of γ-aminopropyltriethoxysilane and ethylene oxide. Among these, Etkin silanes are preferred.

The composition of the present invention includes, to the extent that it does not impair the purpose of the present invention,
If desired, general resins other than the above component (a) or (b)
Matting agents other than the ingredients can also be included;
, additive components conventionally used in paint compositions, such as coloring pigments such as titanium white and iron oxide, extender pigments such as carbonic acid, solvents such as xylene, or pigment dispersants,
Antifoaming agent, dehydrating agent, thickener, plasticizer, surfactant, anti-settling agent, anti-sagging agent, anti-color separation agent, leveling agent, anti-skin agent, anti-scratch agent, anti-mold agent, ultraviolet absorption agent,
Additives such as antioxidants and antistatic agents can be added.

The matte coating composition of the present invention can be applied directly or as an undercoat to objects to be coated such as metal, wood, plastic, glass fiber reinforced plastic, concrete, slate, etc. by brushing, roller coating, spraying, etc. A matte coating film with excellent curability and weather resistance can be formed by applying the coating and then drying it naturally or by heating.

[Example] Next, the present invention will be explained in more detail with reference to production examples, working examples, and comparative examples, but the present invention is not limited to these examples in any way.

Production Examples 1 to 4 Production of hydrolyzable silyl group-containing vinyl resins Using the types and amounts of vinyl monomers, polymerization modifiers, and polymerization initiators shown in Table 1, the reaction conditions shown in Table 1 were followed. Polymerization was carried out to obtain a hydrolyzable noryl group-containing vinyl resin solution. The molecular weight of the vinyl resin and the heating residue of the vinyl resin solution (JI
Measured in accordance with SK-5400 8.2)
Shown in the table. Note that xylene was used as a reflux solvent for the polymerization.

(Left below) Example 1 Resin solution of Production Example 1 (heating residue 49.1 wt%) 204
Polyhnylidene fluoride particles A [Neoflon VP-850. Manufactured by Daikin Industries, Ltd., product name] 40
After adding parts by weight and dispersing in a sand mill for 30 minutes,
A coating composition was prepared by adding 0.5 parts by weight of dioctyltin malate and further diluting with xylene to a viscosity of 20 seconds (7 Ord Cup #4.25°C).

Next, this coating composition was applied to chemical conversion treated steel sheet PB-3114.
M [J Is G-3141 standard product, manufactured by Nihon Testoba Furuuegyo Co., Ltd., trade name] was painted with air spray, set at room temperature for 5 minutes, and then baked in a dryer at 140°C for 30 minutes. Created a painted board.

Example 2 Polytetrafluoroethylene particles B [Luburon L-2: manufactured by Daikin Co., Ltd., product name] were added to 175 parts by weight of the resin solution of Production Example 2 (heating residue 57.1 wL%) in the same manner as in Example 7ffi@l. After adding 3 parts by weight and dispersing for 30 fi in a sand mill, 1 part by weight of dibutyltin dilaurate was added and the viscosity was further reduced to 20 seconds (7 Ordkatug #4.25°C).
Prepare the paint composition by diluting with xylene to give .

Next, a coated board was prepared in the same manner as in Example 1 using this coating composition.

Example 3 Resin solution obtained in Production Example 3 (heating residue 55.9 wt%) 1
Polymethyl methacrylate particles C [MP
-3100: manufactured by Souken Kagaku Co., Ltd., trade name: 310 parts by weight was added and dispersed in a sand mill for 30 minutes; then, 0.5 parts by weight of dioctyltin malate was added, and the viscosity was reduced to 2.
A coating composition was prepared by diluting with xylene to 0 sec (7 odocassop #4.25°C).

Next, a coated board was created in the same manner as in Example 1 using this coating composition.

Example 4 Resin solution obtained in Production Example 4 (heating residue 50.7 wt%) 1
98 parts by weight, polymethyl methacrylate particles D [G
L-300: manufactured by Souken Kagaku Co., Ltd., trade name] After adding 10 parts by weight and dispersing for 30 minutes in a sand mill, 0.3 parts by weight of dibutyltin dilaurate and 0.05 parts by weight of p-toluenesulfonic acid were added, A coating composition was then prepared by diluting with xylene to a viscosity of 20 seconds (Ford Cup #4.2'5°C).

Next, a coated board was created in the same manner as in Example 1 using this coating composition.

Example 5 Resin solution obtained in Production Example 2 (heating residue 57.1 wt%) 1
75 parts by weight, 60 parts by weight of titanium oxide L [CR-90 manufactured by Nikishihara Sangyo Co., Ltd., trade name] and 110 parts by weight of polymethyl methacrylate particles C [MP-3100: manufactured by Souken Kagaku Co., Ltd., trade name]. In addition, after dispersing in a sand mill for 30 minutes, 0.4 parts by weight of dioctyltin malate and 0.1 parts by weight of ethylenediamine were added, and then the viscosity was adjusted to 20 seconds (
A coating composition was prepared by diluting with xylene to give a coating composition of 25° C.).

Next, a coated board was created in the same manner as in Example 1 using this coating composition.

Example 6 Resin solution obtained in Production Example 1 (heating residue 49.1 wt%) 2
04 parts by weight, fine particulate synthetic silica E [N1 ps i
l 5S-10: Manufactured by Nihon Shirikanigyo Co., Ltd., product name,
DBA value Ome q/9] 40 parts by weight was added and dispersed in a sand mill for 30 minutes, then 0.5 parts by weight of dioctyltin malate was added and the viscosity was reduced to 20 seconds (7 Ord Cup #4.25°C). A coating composition was prepared by diluting with xylene to give

Next, a coated board was created in the same manner as in Example 1 using this coating composition.

Example 7 Resin solution obtained in Production Example 2 (heating residue 57.1 wt%) 1
To 75 parts by weight, fine particulate synthetic silica F [Cyholobic 200: manufactured by Fuji Davison Chemical Co., Ltd., trade name, DB
A value 70meq/kg] After adding 8 parts by weight and dispersing in a sand mill for 30 minutes, 1 part by weight of dibutyltin dilaurate was added, and then xylene was added so that the viscosity was 20 seconds (Ford cup #4.25'C). A coating composition was prepared by diluting with.

Next, a coated board was created in the same manner as in Example 1 using this coating composition.

Example 8 Resin solution obtained in Production Example 3 (heating residue 55.9 wt%) 1
79 parts by weight of fine particulate synthetic silica G [AERLO3I
L R972: Manufactured by Nippon Aerosil Co., Ltd., product name, D
After adding 10 parts by weight of BA value 49 meq/9] and dispersing in a sand mill for 30 minutes, 0.5 parts by weight of dioctyltin malate was added, and then the viscosity was reduced to 20 seconds (7 Ord Cup #4.25°C). A coating composition was prepared by diluting with xylene to give the following.

Next, a coated board was created in the same manner as in Example 1 using this coating composition.

Example 9 Resin solution obtained in Production Example 4 (heating residue 50.7 wt%) 1
To 98 parts by weight, fine particulate synthetic silica F [Cyholobic 200: manufactured by Fuji Davison Chemical Co., Ltd., trade name, DB
After adding 1'0 part by weight of A value 70 m e Q / and dispersing for 30 minutes in a sand mill, 0.3 part by weight of dibutyltin dilaurate and 0.05 part by weight of p-toluenesulfonic acid were added, and then the viscosity was A coating composition was prepared by diluting with xylene such that the temperature was 20 seconds (7 od cup #4.25°C).

Next, a coated board was created in the same manner as in Example 1 using this coating composition.

Example 10 I obtained in Production Example 2; Resin solution (heating residue 57.1 wt%)
175 parts by weight, 360 parts by weight of titanium oxide L [CR-90: manufactured by Mihara Sangyo Co., Ltd., trade name] and fine particulate synthetic silica F
[Cyholobic 200: Fuji Davison Chemical Co., Ltd.
product, trade name, DBA value 70me q/Jn] was added and dispersed for 30 minutes in a sand mill, and then 0.4 parts by weight of dioctyltin malate and 0.1 parts by weight of ethylenediamine were added, and then the viscosity was 20 Coating compositions were prepared by diluting with xylene to give a total of 25° C. (7 ord cup #4.25° C.).

Next, a coated board was created in the same manner as in Example 1 using this coating composition.

Example 11 Acrylic Noricone + Δ (fat solution M [Rikifukazemurasoku AM1226: manufactured by Kanekabuchi Chemical Co., Ltd., trade name, non-volatile content 50wt%] 80 parts by weight and Q [Rikifakazemurasoku YC
7209: Manufactured by Kanebuchi Chemical Industry Co., Ltd., product name, non-volatile content 6
0 wt% and 1100 parts by weight of polyvinylidene fluoride particles A [Neoflon VP-850: manufactured by Daikin Industries, Ltd., trade name] was added thereto, and after milling in a sand mill for 30 minutes, dioctyl A coating composition was prepared by adding 0.5 parts by weight of tin malate and further diluting with xylene to a viscosity of 20 seconds (Ford Cup #, 4.25°C).

Next, a coated board was created in the same manner as in Example 1 using this coating composition.

Example 12 Acrylic silicone resin solution M [Kanekazemlac AM
1226: Manufactured by Kanebuchi Chemical Industry Co., Ltd., trade name, non-volatile content 5
0wt%] 100 parts by weight and R [Clearamer〇A40:
Manufactured by Sanyo Chemical Industries, Ltd., product name, non-volatile content 50wt%]
100 parts by weight of polytetrafluoroethylene particles B [Rubron Shi-2: Daikin Industries, Ltd.]
After adding 13 parts by weight of the product manufactured by the company, trade name, and dispersing for 30 minutes in a sand mill, 1 part by weight of dibutyltin dilaurate was added, and then the viscosity was reduced to 20 seconds (Ford force, tube #4.25).
A coating composition was prepared by diluting with xylene so that

Next, a coated board was created in the same manner as in Example 1 using this coating composition.

Example 13 Acrylic silicone resin solution N [Kaneki Zemluck AM1532: manufactured by Kanejiri Chemical Co., Ltd., trade name, non-volatile content 50 wt%] 90 parts by weight and P [Kaneki Zemluck YC]
7531: Manufactured by Kanebuchi Chemical Industry Co., Ltd., trade name, non-volatile content 5
5 wt%] were mixed, 110 parts by weight of polymethyl methacrylate particles C (MP-3100: manufactured by Souken Kagaku Co., Ltd., trade name) were added thereto, and 30 parts by weight were mixed in a sand mill.
After dispersing for a minute, 0.5 parts by weight of dioctyl tin malate was added and then the viscosity
．． A coating composition was prepared by diluting with xylene to a temperature of 25°C.

Next, using this coating composition, a coated board was prepared in the same manner as in Example 1.

Example 14 Acrylic silicone resin solution Q [Rikikazemuranoku YC
7209 Manufactured by Kanebuchi Chemical Industry Co., Ltd., product name, non-volatile content 60
wL%] 167 parts by weight, polymethyl methacrylate particles D [GL-300: manufactured by Souken Kagaku Co., Ltd., trade name]
After adding 10 parts by weight and dispersing in a sand mill for 30 minutes, 0.3 parts by weight of siftyl tin laurate, p -
A coating composition was prepared by adding 0.05 parts by weight of t/reninsulfonic acid and then diluting with xylene to a viscosity of 20 seconds (Ford cup $4.25°C).

Next, a coated board was created in the same manner as in Example 1 using this coating composition.

Example 15 Acrylic silicone resin solution M [Rikikazemlac AM
1226: Manufactured by Kanebuchi Chemical Industry Co., Ltd., trade name, non-volatile content 5
0 wt%] 90 parts by weight and P
31: Manufactured by Kanebuchi Chemical Industry Co., Ltd., product name, non-volatile content 55w
t%] and 100 parts by weight of titanium oxide L[
CR-90 manufactured by Nikishihara Sangyo Co., Ltd., trade name] 60 parts by weight and polymethyl methacrylate particles C [MP-3100:
After adding 10 parts by weight of Souken Kagaku Co., Ltd. (trade name) and dispersing it in a sand mill for 30 minutes, 0.4 parts by weight of dioctyltin malate and 7001 parts by weight of ethylenediamine were added, and then the viscosity was reduced to 20 seconds (7 parts by weight). Eau de cup/pu #4.25
A coating composition was prepared by diluting with xylene so that

Next, a coated board was created in the same manner as in Example 1 using this coating composition.

Example 16 Resin solution obtained in Production Example 2 (heating residue 57.1 wt%) 1
To 75 parts by weight, polyvinylidene fluoride particles A [Neoflon VP-850: manufactured by Daikin Industries, Ltd., trade name 1
10 parts by weight and fine particulate synthetic silica E (Nipsil
5S-10: Manufactured by Nippon Silica Kogyo Co., Ltd., trade name, DBA
320 parts by weight of Om eq /kg was added and dispersed in a sand mill for 30 minutes, and a coated board was prepared in the same manner as in Example 1.

Example 17 Acrylic 7 silicone resin solution M [Kanekazemura/RiAM
1226: Manufactured by Kanebuchi Chemical Industry Co., Ltd., trade name, non-volatile content 5
0wt% 380 parts by weight and Q [Kaneryoku Zemurasoku YC72
09: Manufactured by Kanebuchi Chemical Industry Co., Ltd., product name, non-volatile content 60w
t%] and 100 parts by weight of polymethyl methacrylate particles C [MP-3100': manufactured by Souken Kagaku Co., Ltd., trade name 11O and particulate synthetic silica F [Cyholobic 200: Fuji Davison]. Manufactured by Kagaku Co., Ltd.
Product name, DBA value 70 m eq /&g] 8 parts by weight were added and dispersed in a sand mill for 30 minutes, and a coated board was prepared in the same manner as in Example 1.

Example 18 Acrylic Noricone Resin Solution N [Kanekazem Lac AM
1532: Manufactured by Kanebuchi Kagaku Kogyo Co., Ltd., product name, Fumunhabun 5
0wt%] 90 parts by weight and P [Kaneryoku Zem Rank YC75
31: Manufactured by Kanebuchi Chemical Industry Co., Ltd., product name, non-volatile content 55w
t%] and 100 parts by weight of polymethyl methacrylate particles D [GL-300: Souken Kagaku Co., Ltd.
Co., Ltd., trade name 35 parts by weight and fine particulate synthetic silica G [AE
RLO5I LR972: manufactured by Nippon Aerosil Co., Ltd., trade name, DBA value 49me Q/12g] 10 parts by weight was added and dispersed in a sand mill for 30 minutes, and the following Example 1 was prepared.
A painted board was created using the same method.

Comparative Example 1 Resin solution obtained in Production Example 2 (heating residue 57.1 wt%) 1
Polymethyl methacrylate particles C [MP
-3100: manufactured by Soken Kagaku Co., Ltd., trade name 10.1 parts by weight was added and dispersed in a sand mill for 30 minutes, and the following Example 1
A painted board was created using the same method.

Comparative Example 2 Resin solution obtained in Production Example 2 (heating residue 57.1 wt%) 1
To 75 parts by weight, 180 parts by weight of polytetrafluoroethylene particles B [Lubloon L-2: manufactured by Daikin Industries, Ltd., trade name] was added and dispersed in a sand mill for 30 minutes, and then coated in the same manner as in Example 1. Created a board.

Comparative Example 3 Obtained in Production Example 2: Resin solution (heating residue 57.1 wt%)
To 175 parts by weight, 50 parts by weight of polyethylene particle fraction product H Liofuranoto W-2563T: manufactured by Toyo Ink Mfg. Co., Ltd., trade name, heating residue 20 wt%] was added and dispersed in a sand mill for 30 minutes, and the following examples were prepared. A painted board was created in the same manner as in 1.

Comparative Example 4 Resin solution obtained in Production Example 2 (heating residue 57.1 wt%) 1
75 parts by weight, silica powder■ [Thyroid 244: manufactured by Fuji Davison Chemical Co., Ltd., trade name, DBA value 500m
10 parts by weight of eq/jigl was added and dispersed in a sand mill for 30 minutes, and a coated board was prepared in the same manner as in Example 1.

Comparative Example 5 Resin solution obtained in Production Example 2 (heating residue 57.1 wt%) 1
75 parts by weight, silica powder J [Thyroid TP-10
315: Manufactured by Fuji Davison Chemical Co., Ltd., trade name, DBA
8 parts by weight of 118 meq/kg was added and dispersed in a sand mill for 30 minutes, and a coated board was prepared in the same manner as in Example 1.

Comparative Example 6 Resin solution obtained in Production Example 2 (heating residue 57.1 wt%) 1
75 parts by weight, silica powder K [Thyroid TP-103
15: Manufactured by Fuji Davison Chemical Co., Ltd., trade name, DBA value 367me Q/9] 8 parts by weight was added and dispersed in a sand mill for 30 minutes, and a coated board was prepared in the same manner as in Example 1 below. .

Comparative Example 7 Resin solution obtained in Production Example 2 (heating residue 57.1 wt%) 1
To 75 parts by weight, fine particulate synthetic silica F [Cyholobic 200: manufactured by Fuji Davison Chemical Co., Ltd., trade name, DB
A value of 70 meq/8 parts by weight of Thg was added and dispersed in a sand mill for 30 minutes, and a coated board was prepared in the same manner as in Example 1.

Comparative Example 8 Resin solution obtained in Production Example 2 (heating residue 57.1 wt%) 1
To 75 parts by weight, fine particulate synthetic silica F [Cyholobic 200: manufactured by Fuji Davison Chemical Co., Ltd., trade name, DB
A value of 70 meQ/J+g] 0.1 part by weight was added and dispersed in a sand mill for 30 minutes, and a coated board was prepared in the same manner as in Example 1.

Comparative Example 9 Acrylic silicone resin solution N [Rikikazemurasoku AM
1532: Manufactured by Kanebuchi Chemical Industry Co., Ltd., trade name, non-volatile content 5
0wt%] 90 parts by weight and P [Rikikazemlac YC75
31: Manufactured by Kanebuchi Chemical Industry Co., Ltd., product name, non-volatile content 55w
t%] were mixed, 50 parts by weight of polyethylene particle dispersion amount H [Liofura/T W-2563T: manufactured by Toyo Ink Mfg. Co., Ltd., trade name, heating residue 20 wt%] was added, and the mixture was placed in a sand mill. After dispersion, a coated board was prepared in the same manner as in Example 1.

Comparative Example 10 Acrylic silicone resin solution N [Kanekazemlac AM
1532: Manufactured by Kanebuchi Chemical Industry Co., Ltd., trade name, non-volatile content 5
0 wt%] 90 parts by weight and P [Rikikazemlac YC75
31: Manufactured by Kanebuchi Chemical Industry Co., Ltd., product name, non-volatile content 55w
t%] and 100 parts by weight of silica powder I.
[Thyroid 244: manufactured by Fuji Davison Chemical Co., Ltd., trade name] 10 parts by weight was added and dispersed in a sand mill, and a coated plate was prepared in the same manner as in Example 1.

Comparative Example 11 Acrylic silicone resin solution N [Rikikazemlac AM
1532: Manufactured by Kanebuchi Chemical Industry Co., Ltd., trade name, non-volatile content 5
0wt%] 90 parts by weight and P [Kafu Kazemlac YC75
31: Manufactured by Kanebuchi Chemical Industry Co., Ltd., product name, non-volatile content 55w
t%] and 11 parts by weight of polymethyl methacrylate particles C [MP-3100: manufactured by Souken Kagaku Co., Ltd., trade name 1O] were added thereto and dispersed in a sand mill. Create a painted board using this method.

Comparative Example 12 Acrylic silicone resin solution N [Kaneiki Zemura 7ri AM
1532: Manufactured by Ubube Chemical Industry Co., Ltd., trade name, non-volatile content 5
0 wt% Co90 parts by weight and P
31: Manufactured by Kanebuchi Chemical Industry Co., Ltd., product name, non-volatile content 55w
t%] and 100 parts by weight of polytetrafluoroethylene particles B (Luburon Shi-2: manufactured by Daikin Industries, Ltd., trade name) were added to 80 parts by weight and dispersed in a sand mill. A painted board was created in the same manner as in 1.

Table 2 shows the formulation composition of each coating composition.

Table 3 shows the results of evaluating the curing properties, weather resistance, and coating performance of the temporary coatings prepared in Examples 1 to 18 and Comparative Examples 1 to 12.

As is clear from Table 3, the coating films of Examples 1 to 18 based on the matte coating composition of the present invention all showed good results in terms of curability, weather resistance, and matte effect. , Comparative Examples 1 to 12 all showed insufficient results in terms of curability, weather resistance, and matte effect.

In addition, the symbol of each component in Table 2 means the following.

(1) Resin M: Kaneki Zemurasoku AM1226; Manufactured by Kanebuchi Chemical Industry Co., Ltd. acrylic silicone resin, Molecule 1 approximately 10,00O N: Kaneki Zemluck AM1532゜ Manufactured by Kazube Chemical Industry Co., Ltd. acrylic silicone resin, Molecule 1 approx. 10,000 P: Kaneki Zemluck YC7531; Manufactured by Kanebuchi Chemical Industry Co., Ltd. acrylic silicone resin, Molecule 1 about io, oo.

Q: Rikikazemrak YC7209; Manufactured by Kanebuchi Chemical Industry Co., Ltd. acrylic silicone resin, Molecule 1 approx. 10,000 R: Clearmar UA-40; Manufactured by Sanyo Chemical Industries, Ltd. acrylic silicone resin, Molecule 1 approx. 7.000 (2) Matting agent A: Neo 707VP-850- Manufactured by Daikin Industries, Ltd. polyvinylidene fluoride particles B Nilbronshi-2; Manufactured by Daikin Industries, Ltd. polytetrafluoroethylene particles CAMP-3100; Manufactured by Souken Kagaku Co., Ltd. polymethyl methacrylate particles D: GL-300° Manufactured by Souken Kagaku Co., Ltd. polymethyl methacrylate particles E: N1psil 5S-10; Manufactured by Nippon Sirikani Gyo Co., Ltd. hydrophobic synthetic silica, DBA value Om eq 7kg F: Saihorobi 7ri 200; Manufactured by Fuji Davison Chemical Co., Ltd. hydrophobic synthetic silica, DBA value 70meq/9 G: AERLO5IL R972; Manufactured by Nippon Aerosil Co., Ltd. hydrophobic synthetic silica, DBA4’1meq/11g H: Rio Flat W-2563T.

Manufactured by Toyo Ink Mfg. Co., Ltd., polyethylene particle dispersion ■ = Psioid 244; manufactured by Fuji Davison Chemical Co., Ltd., silica powder, DBA value 5
00meQ/9 J Cothyroid TP-10315; manufactured by Fuji Davison Chemical Co., Ltd., silica powder, DBA value 1
18meQ/&g K: Thyroid TP-10311; manufactured by Fuji Davison Chemical Co., Ltd., silica powder, DBA value 3
67meq/Ju9 (3) Titanium oxide L: CR-90; manufactured by Mihara Sangyo Co., Ltd. (4) Catalyst DOTM Nidioctyltin Maleate DBTDL Nidibutyltin dilaurate PTS: p-
Toluenesulfonic acid EDA: Ethylenediamine [Effects of the Invention] The matte coating composition of the present invention has characteristics such as excellent weather resistance, the ability to form a matte-like coating film, and good curability. However, it is suitable for use in outdoor structures and architectural exteriors.

Claims (1)

[Scope of Claims] 1(a) 100 weight of a vinyl resin whose main chain consists essentially of a vinyl polymer and which has one or more hydrolyzable silyl groups per molecule at the terminal and/or side chain. For part (b
) A matte coating composition comprising 1 to 50 parts by weight of at least one selected from weather-resistant polymer particles and particulate synthetic silica. 2 The weather-resistant polymer particles are vinylidene fluoride polymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-
The matte according to claim 1, which is at least one selected from hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, chlorotrifluoroethylene-ethylene copolymer, and methyl methacrylate polymer. Paint composition. 3. The matte coating composition according to claim 1, wherein the fine particulate synthetic silica is a hydrophobic synthetic silica formed by chemically bonding an organic substance to the silanol groups on its surface. 4. The matte coating composition according to claim 3, wherein the hydrophobic synthetic silica has a degree of hydrophobicity of a di-n-butylamine adsorption amount of 100 meq/kg or less.