JPS6354747B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composition comprising a vinyl resin containing a hydrolyzable silyl group at the terminal or side chain, an acrylic resin, and/or a cellulose compound, and is useful as a coating or a paint. The present inventors discovered that a vinyl resin containing a silyl group having a hydrolyzable group at the terminal or side chain is
In addition to the excellent characteristics of vinyl resins such as high gloss, weather resistance, and discoloration resistance, the hydrolyzable silyl group improves adhesion to inorganic substances, and it also has excellent resistance to crosslinking at room temperature due to moisture, especially moisture in the atmosphere. discovered that the resin forms a dense network structure and has excellent solvent resistance, water resistance, heat resistance, high hardness, and weather resistance, and filed a patent application (Japanese Unexamined Patent Application Publication No. 1983-1999).
36395). The present inventors further investigated silyl group-containing vinyl resins and discovered various advantages by mixing them with acrylic resins and/or cellulose compounds, leading to the present invention. The advantage of the composition of the present invention of a silyl group-containing vinyl resin and an acrylic resin is that it improves workability and physical properties of the coating film, such as solvent resistance, adhesion, and weather resistance. One type of acrylic resin is room temperature drying acrylic resin, but while paints made from this resin have excellent weather resistance and gloss retention, they have problems with workability due to their high molecular weight and are resistant to solvents. However, by adding a silyl group-containing vinyl resin, the solvent resistance is improved by curing the silyl group-containing vinyl resin in the composition. Excellent coating film properties can be obtained even with room-temperature drying acrylic resins, and the drawbacks of high molecular weight acrylic resins, such as workability and sticky feeling, can be improved.
At the same time, it is possible to improve the physical properties of the coating film, such as adhesion and weather resistance. Also, when a silyl group-containing vinyl resin is added to a composition of a thermosetting acrylic resin, which is an acrylic resin, and a melamine resin, the silyl group-containing vinyl resin in the composition may be heated at room temperature or low temperature. Since it is cured at low temperature, it is possible to obtain a coating film with excellent physical properties such as solvent resistance even when heated at low temperatures, and at the same time, it is possible to improve adhesion, weather resistance, etc. The advantage of the composition of the present invention of a silyl group-containing vinyl resin and a cellulose compound is improved drying properties. Cellulose compounds are added to various natural resins and synthetic resins and used as quick-drying lacquers. Similarly, by adding cellulose compounds to silyl group-containing vinyl resins, solvent separation can be prevented. An improved and quick-drying lacquer is obtained. The lacquer obtained by the present invention is quick-drying and at the same time has excellent physical properties of the silyl group-containing vinyl resin, so it is a highly hard coating with excellent weather resistance, solvent resistance, water resistance, and adhesion compared to general lacquers. Forms a film. The advantages of the composition of the present invention of a silyl group-containing vinyl resin, an acrylic resin, and a cellulose compound are improvements in solvent resistance, weather resistance, adhesion, and drying properties. Compositions made of acrylic resin and cellulose compounds are used as quick-drying lacquers, but
Although it has excellent weather resistance, it has problems with poor solvent resistance and adhesion, but by adding silyl group-containing vinyl resin, a coating film with improved solvent resistance and adhesion and weather resistance can be created. available. The silyl group-containing vinyl resin used in the present invention has at least one, preferably two or more, silyl groups having a hydrolyzable group in one molecule, and most of the silyl groups are

[Formula] (X is a hydrolyzable group, R ₁ and R ₂ are hydrogen or an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, and n = an integer of 1.2.3.) It will be done. The production of the silyl group-containing vinyl resin of the present invention includes:
Carbon-
Industrially effective methods include a hydrosilylation reaction using a vinyl resin having a carbon double bond and hydrosilane, and a method involving copolymerization of a vinyl compound and a silyl compound having a polymerizable double bond. The details will be explained below. The silyl group-containing vinyl resin of the present invention is easily produced by reacting a hydrosilane compound with a vinyl resin having a carbon-carbon double bond in the presence of a group transition metal catalyst. The hydrosilane compound used in the present invention has the following general formula. (In the formula, R ₁ is 1 selected from alkyl groups, aryl groups, and aralkyl groups having 1 to 10 carbon atoms.
valent hydrocarbon group, X is halogen, alkoxy,
A group selected from acyloxy, aminoxy, phenoxy, thioalkoxy, and amino groups, and n is an integer from 1 to 3. ) Specific examples of hydrosilane compounds included in this general formula include methyldichlorosilane,
Halogenated silanes such as trichlorosilane, phenyldichlorosilane; Alkoxysilanes such as methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethoxysilane, triethoxysilane; methyldiacetoxysilane, phenyldichlorosilane; Examples include acyloxysilanes such as acetoxysilane and triacetoxysilane; various silanes such as methyldiaminoxysilane, triaminoxysilane, methyldiaminosilane, and triaminosilane. The amount of hydrosilane compound used is determined based on the carbon-carbon double bond contained in the vinyl resin.
Although any amount can be used, it is preferable to use 0.5 to 2 moles. Although this does not preclude the use of a larger amount of silane, it will simply be recovered as unreacted hydrosilane. Furthermore, in the present invention, halogenated silanes, which are inexpensive basic raw materials and have high reactivity, can be easily used as the hydrosilane compound. The silyl group-containing vinyl resin obtained using halogenated silanes is
When exposed to air, it hardens rapidly at room temperature while generating hydrogen chloride, but it can only be used in limited applications due to problems with the irritating odor and corrosion caused by hydrogen chloride. It is desirable to convert it to other hydrolyzable functional groups. The vinyl resin used in the method is not particularly limited, except for vinyl compounds containing hydroxyl groups, and includes methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate,
Esters of acrylic acid and methacrylic acid such as 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate; carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and fumaric acid; and acid anhydrides such as maleic anhydride; glycidyl acrylate , epoxy compounds such as glycidyl methacrylate; amino compounds such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether; acrylamide, methacrylamide, itaconic acid amide, α-ethylacrylamide,
Amide compounds such as crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide; acrylonitrile, styrene,
A resin whose main component is a copolymer selected from α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate, etc. is suitable. When producing these vinyl compounds alone or as copolymers, by radical copolymerizing some allyl acrylate, allyl methacrylate, diallyl phthalate, etc., carbon-carbon doubles for hydrosilylation reaction are created in the vinyl resin. It is possible to introduce bonds. The amount of monomer necessary for this purpose can be arbitrarily determined depending on the number of silyl groups in the target resin. Furthermore, n
The molecular weight can be adjusted by adding a chain transfer agent such as -dodecylmercaptan or t-dodecylmercaptan. When polymerizing these vinyl compounds, a solvent may or may not be used, but when used, it is preferable to use a non-reactive solvent such as ethers, hydrocarbons, and acetic esters. In the present invention, a transition metal complex catalyst is required in the step of reacting a hydrosilane compound with a carbon-carbon double bond. As the transition metal complex catalyst, group transition metal complex compounds selected from platinum, rhodium, cobalt, palladium and nickel are effectively used. This hydrosilylation reaction is achieved at any temperature between 50 and 150 °C,
The reaction time is about 1 to 10 hours. Another method of the invention is based on the formula

[Formula] (In the formula, R ₁ is an alkyl group having 1 to 10 carbon atoms,
A monovalent hydrocarbon group selected from an aryl group and an aralkyl group, R ₂ is an organic residue having a polymerizable double bond, and X is a group selected from a halogen, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, and amino group. , n is an integer of 1.2.3. ) It is produced by radical polymerization of the silane compound shown in the following and various vinyl compounds. Examples of the silane compounds used in the present invention include: etc. These silane compounds are synthesized by various methods, but for example, acetylene, allyl acrylate, allyl methacrylate, diallyl phthalate and methyldimethoxysilane, methyldichlorosilane, trimethoxysilane, trichlorosilane are synthesized under a group transition metal catalyst. It can be produced by reaction. Vinyl compounds used in the present invention include:
It is possible to use compounds used in the synthesis of vinyl resins in the above method, but in addition to those described in the method, 2-hydroxyethyl acrylate,
Vinyl compounds containing hydroxyl groups such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxy vinyl ether, N-methylolacrylamide, Aronix 5700 (manufactured by Toagosei Co., Ltd.) are also possible. . Synthesis of these copolymers of vinyl compounds and silane compounds is carried out using a normal solution polymerization method, in which a vinyl compound, a silane compound, a radical initiator,
In addition, n-dodecyl mercaptan,
A chain transfer agent such as t-dodecyl mercaptan is added and the reaction is carried out at 50-150°C. Even if the solvent is used,
It is not necessary, but if used, ethers,
Preferably, non-reactive solvents such as hydrocarbons and acetic acid esters are used. In the silyl group-containing vinyl resin thus obtained, the hydrolyzable group can be converted into another hydrolyzable group by a known method. In this way, a silyl group-containing vinyl resin whose main chain is substantially composed of a vinyl polymer and which has at least one silicon group bonded to a hydrolyzable group in an end or side chain in one molecule. It can be grown. The silyl group-containing vinyl resin used in the present invention is not particularly limited, but when used in fields where weather resistance and yellowing resistance of coating films are required, styrene contained in the silyl group-containing vinyl resin may be used. The amount is 0-5
Weight percent is preferred. The acrylic resin used in the present invention is not particularly limited, and is a commonly used acrylic resin obtained by copolymerizing a vinyl compound other than the silane compound used to synthesize the silyl group-containing vinyl resin of the present invention. Acrylic resin is used. In particular, when used in fields where weather resistance and yellowing resistance of coating films are required, the amount of styrene contained in the acrylic resin is preferably 0 to 5% by weight. The cellulose compounds used in the present invention include:
Nitrified cotton, acetyl cellulose, cellulose acetate butyrate, cellulose acetate propionate, ethyl cellulose, benzyl cellulose, etc. are used. The compatibility of the composition of the present invention can be improved by changing the composition of the silyl group-containing vinyl resin and the acrylic resin. The composition of the present invention comprises 5 to 99.9 parts by weight of a silyl group-containing vinyl resin, 1 to 95 parts by weight of an acrylic resin, and/or 0.1 to 80 parts by weight of a cellulose compound,
Preferably, a composition consisting of 5 to 99 parts by weight of a silyl group-containing vinyl resin and 1 to 95 parts by weight of an acrylic polymer, 20 to 99.9 parts by weight of a silyl group-containing vinyl resin and 0.1 to 80 parts by weight of a cellulose compound. A composition consisting of
Silyl group-containing vinyl resin 5 to 99 parts by weight, acrylic resin 1 to 95 parts by weight, and cellulose compound 0.1 to 80 parts by weight
The composition consists of parts by weight. If the silyl group-containing vinyl resin is less than 5 parts by weight, the curing properties of the composition of the present invention at low temperatures such as room temperature will be insufficient, and if it exceeds 99.9 parts by weight, drying properties and coating workability will not be improved. If the amount of acrylic resin is less than 1 part by weight, drying properties will not be improved, and if it exceeds 95 parts by weight, curing properties will be insufficient. Furthermore, if the cellulose compound is less than 0.1 part by weight, the drying properties and gasoline resistance of the coating film will be insufficient, and if it exceeds 80 parts by weight, the curing performance will be insufficient. The composition of the present invention forms an excellent resin at room temperature or by heating, and in this case, a curing accelerator may or may not be used. When using a curing accelerator, carboxylic acid metal salts such as alkyl titanate, tin octylate, dibutyltin dilaurate, lead octylate; sulfide type such as monobutyltin sulfide, dibutyltin di-octyl mercaptide, Mercaptide-type organotin compounds; acidic promoters such as p-toluenesulfonic acid and phthalic acid; tetraethylenepentamine, triethylenediamine, N
Amines such as -β-aminoethyl-γ-aminopropyltrimethoxysilane and alkaline accelerators such as potassium hydroxide and sodium hydroxide are effective. The amount of these curing accelerators added is preferably 0.001 to 10% by weight based on the solid content of the silyl group-containing vinyl resin. The silyl group-containing vinyl resin composition of the present invention is
Depending on the type of acrylic resin and cellulose compound contained, it forms a coating film with excellent adhesion, solvent resistance, weather resistance, and quick drying. It is useful as a top coat, top coat, and metallic base paint. It is also possible to improve physical properties such as surface hardness by adding a compound such as ethyl silicate that can be co-condensed with the silyl group-containing vinyl resin of the present invention. It can also be blended with various resins currently used as paints and coatings, such as lacquer paints, alkyd paints, melamine paints, epoxy paints, etc., in appropriate proportions. It is possible to improve the physical properties such as adhesion and weather resistance of these paints and coating agents currently in use. The silyl group-containing vinyl resin of the present invention can contain various fillers, pigments, and the like. Fillers and pigments include various silicas, calcium carbonate, magnesium carbonate, titanium oxide, iron oxide,
Various materials such as glass fiber can be used. In this way, it is useful not only for the above-mentioned uses, but also as a coating composition for aircraft, buildings, automobiles, glass, etc., a sealing composition, and a surface treatment agent for various inorganic materials. Next, the present invention will be specifically explained using examples. Synthesis Example 1 In 90 g of xylene solvent heated to 90°C, 30 g of styrene, 16 g of allyl methacrylate, 20 g of methyl methacrylate, 19 g of n-butyl methacrylate, 14 g of butyl acrylate, 2 g of maleic anhydride, 4 g of acrylamide, n- dodecyl mercaptan 2
A solution of 2 g of azobisisobutyronitrile dissolved in 10 g of g,n-butanol was added dropwise and reacted for 10 hours to obtain a vinyl polymer containing an allylic unsaturated group with a molecular weight of 8,000. In the infrared absorption spectrum of this product, absorption due to carbon-carbon double bond at 1648 cm ^-1 and absorption of acid anhydride at 1780 cm ^-1 were observed. 40 g of solvent is removed from the resulting polymer solution under reduced pressure to remove most of the n-butanol. A solution of 1.5 g of methyldimethoxysilane and 0.0005 g of chloroplatinic acid dissolved in isopropanol was added to 16 g of the obtained vinyl copolymer solution containing an allylic unsaturated group, and the mixture was reacted at 90° C. for 6 hours under sealed conditions. In the infrared absorption spectrum of this product, the absorption at 1648 cm ^-1 disappeared, and a silyl group-containing vinyl polymer was obtained. Synthesis Example 2 22 g of γ-methacryloxypropyltrimethoxysilane, 52 g of methyl methacrylate, and 15 n-butyl methacrylate in 70 g of xylene heated to 70°C
g, a solution of 2 g of azobisisobutyronitrile dissolved in 18 g of n-butyl acrylate, 2 g of acrylamide, 10 g of n-butanol, and 1 g of n-dodecyl mercaptan was added dropwise and reacted for 10 hours to determine the molecular weight.
A vinyl resin containing 14,000 silyl groups was obtained. Synthesis Example 3 Styrene 30 in 70g xylene heated to 90℃
g, _CH2 =C( _CH3 )COO( _CH2 ) _3Si ( _OCH3 ) ₃ 22
g, methyl methacrylate 22g, methacrylic acid n-
A solution of 2 g of azobisisobutyronitrile dissolved in 15 g of butyl, 18 g of n-butyl acrylate, 2 g of acrylamide, 10 g of n-butanol, and 1 g of n-dodecyl mercaptan was dropped and reacted for 10 hours to contain a silyl group with a molecular weight of 12,000. A vinyl resin was obtained. Synthesis Example 4 Styrene 30g in 70g xylene heated to 90℃
g, _CH2 =C( _CH3 )COO( _CH2 ) _3Si ( _OCH3 ) ₃ 22
g, methyl methacrylate 22g, methacrylic acid n-
A solution of 2 g of azobisisobutyronitrile dissolved in 15 g of butyl, 18 g of n-butyl acrylate, and 1 g of n-dodecyl mercaptan was added dropwise and reacted for 10 hours to obtain a silyl group-containing vinyl resin with a molecular weight of 12,000. Synthesis Example 5 Add 30% styrene to n-butyl acetate heated to 90°C.
g, methyl methacrylate 20g, methacrylic acid n-
A solution of 0.1 g of azobisisobutyronitrile dissolved in 30 g of butyl and 20 g of n-butyl acrylate was added dropwise and reacted for 10 hours to obtain an acrylic resin with a molecular weight of 25,000. Synthesis Example 6 A solution of 50 g of methyl methacrylate, 20 g of n-butyl methacrylate, and 0.1 g of azobisisobutyronitrile dissolved in 30 g of n-butyl acrylate was added dropwise to n-butyl acetate heated to 70°C for 10 hours. The reaction produced an acrylic resin with a molecular weight of 30,000. Example 1 Nitrified cotton RS1/2 (manufactured by Daicel Chemical Industries, Ltd.) solution and CAB551-0.2 (manufactured by Kodatsu Corporation) were added to the silyl group-containing vinyl resin solution obtained in Synthesis Example 1.2.3, respectively.
company) solution at a solid content ratio of 10:1 and 10:2, respectively.
In addition, 2 parts of ONJ-IF (manufactured by Sankyoki Co., Ltd.) as a hardening accelerator was added to the solid content of the silyl group-containing vinyl resin, and after diluting with Lutzker thinner, it was applied to a polished mild steel plate. It was applied and the drying properties were measured. Similarly, the acrylic resin solution obtained in Synthesis Example 6 and the CAB551-0.2 solution were added to the silyl group-containing vinyl resin solution obtained in Synthesis Example 2 at a solid content ratio.
In addition to the ratio of 10:2:1, as a curing accelerator.
Two parts of ONJ-IF was added to the solid content of the silyl group-containing vinyl resin, diluted with Lutzker thinner, and then applied to a polished mild steel plate to measure drying properties. As a comparative example, a case in which nitrified cotton CAB is not included is shown. Dry to touch time (20℃) Synthesis example 1 + RS1/2 7 minutes Synthesis example 1 15 minutes Synthesis example 2 + CAB551-0.2 5 minutes Synthesis example 2 10 minutes Synthesis example 3 + CAB551-0.2 5 minutes Synthesis example 3 10 minutes Synthesis example 2 + Synthesis example 6 + CAB551 -0.2 8 minutes Synthesis Example 2 + Synthesis Example 6 20 minutes From the above, it can be seen that the drying properties are improved by adding the cellulose compound. Example 2 The silyl group-containing vinyl resin solution obtained in Synthesis Example 2 was added to the acrylic resin solution obtained in Synthesis Example 6 at a solid content ratio of 10:1, and titanium oxide was added at a solid content ratio of 30:1. Synthesize white enamel by mixing it in a ball mill so that it becomes the same color, apply it to a polished mild steel plate, and heat it at 80℃.
After heat treatment for 30 minutes, gasoline resistance was measured one day later. Similarly, the silyl group-containing vinyl resin solution obtained in Synthesis Example 4 and the CAB551-0.2 solution were added to the acrylic resin solution obtained in Synthesis Example 5 at a solid content ratio of 10:
Add to the ratio 1:2 and apply white enamel in the same way.
It was painted and its gasoline resistance was measured. As a comparative example, a case where the silyl group-containing vinyl resin is not included is shown.

[Table] From the above, it can be seen that gasoline resistance is improved by adding a silyl group-containing vinyl resin.

Claims (1)

[Claims] 1. A silicon group whose main chain consists essentially of a vinyl polymer and which is bonded to a hydrolyzable group at the terminal or side chain: (X is a hydrolyzable group, R ₁ and R ₂ are hydrogen or an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, and n is an integer of 1, 2, or 3.) in one molecule. 5 to 99.9 parts by weight of a vinyl resin containing at least one silyl group and 1 to 99.9 parts by weight of an acrylic resin.
A composition comprising 95 parts by weight and/or 0.1 to 80 parts by weight of a cellulose compound. 2 Silyl group-containing vinyl resin is 5 to 99 parts by weight,
2. The composition according to claim 1, wherein the acrylic polymer comprises 1 to 95 parts by weight. 3. The composition according to claim 1, comprising 20 to 99.9 parts by weight of the silyl group-containing vinyl resin and 0.1 to 80 parts by weight of the cellulose compound. 4 Silyl group-containing vinyl resin is 5 to 99 parts by weight,
Claim 1 consisting of 1 to 95 parts by weight of acrylic resin and 0.1 to 80 parts by weight of cellulose compound
Compositions as described in Section. 5. The composition according to claim 1, wherein the cellulose compound is nitrified cotton. 6. The composition according to claim 1, wherein the cellulose compound is cellulose acetate butyrate. 7 Silyl group-containing vinyl resin is 0 to 5% by weight
A composition according to claim 2, comprising styrene. 8. The composition according to claim 2, wherein the acrylic resin contains 0 to 5% by weight of styrene.