JPS6354471A - Paint comprising novel copolymer - Google Patents

Abstract

PURPOSE:To provide a paint which can be rapidly cured at room temp. and gives a coating film having very excellent surface gloss and hardness, consisting of a silylated copolymer of an acrylic or methacrylic ester with diallyl phthalate. CONSTITUTION:The title paint comprises a random copolymer having an MW of 400 to less than 1,000, composed of a structural unit (A) of formula I (wherein R1 is a 1-4C alkyl; and R4 is H or CH3), a structural unit (B) of formula II (wherein R1 is H or a monovalent hydrocarbon group selected from the group consisting of a 1-10C alkyl, an aralkyl and an aryl groups; X is a group selected from the group consisting of a halogen, an alkoxy, an acryloxy, an aminoxy, an N-substd. aminoxy, phenoxy, a thioalkoxy, thiophenoxy and an amino group; and a is 0-2) and a structural unit (C) of formula III in a ratio of A to B of 1-99:1-1-99 (A+B=100) or A:B:C of 1-98:1-98:1-98 (A+B+C=100) by mol%.

Description

[Detailed description of the invention] This invention relates to a coating material comprising a new copolymer.

The paint of this invention has the formula A R4 ■ ÷ca2-0+ ...... A0OR3 (In the formula, R8 represents an alkyl group of 01 to C4, and R4 represents hydrogen or -0H3) (Hereinafter, blank space) 2B ( -CH2-CH+ CH2 CH2 CH2 CH2 ■ 5i-(Rt)a No. 5-a (wherein, R1 is hydrogen or a monovalent hydrocarbon selected from alkyl groups, aralkyl groups, and aryl groups having 1 to 10 carbon atoms) group, X is a group selected from halogen, alkoxy, acyloxy, aminoxy, N-alkyl-substituted aminoxy, phenoxy, thioalkoxy, thiophenoxy, amino group, a represents an integer from θ to 2) Formula 0 -C-CH2 -an-) "CH2 ■ CH2 H CH2 1 to 99 mol% of the structural unit represented by 2A above and 1 to 99 mol% of the structural unit represented by 2B (total of A and B 100 mol%), or 2 Structural unit 1 represented by A
~98 mol%, 1 to 98 mol% of the structural unit represented by NiB, and 1 to 98 mol% of the structural unit represented by the formula C (A
Molecular weight (number average molecular weight by GPc method, same hereinafter) consisting of 100 mol%) 400 ~
It is a paint made of a random copolymer of less than 100%.

Various vinyl copolymers are already well known and used in large quantities as thermoplastic resins, but the copolymer used in the present invention is a copolymer of acrylic ester or methacrylic ester and diallyl phthalate. However, there are no known compounds containing a silyl group.

The paint of the present invention is not only made of the copolymer having a silyl group at the terminal or side chain, but also has improved adhesion as well as excellent weather resistance and gloss of the acrylic ester or methacrylic ester polymer. It also has the characteristic of being able to be cured at room temperature by moisture, especially moisture in the atmosphere.

Furthermore, by including diallylphthalate as a copolymerization component, the hardness of the cured product is also improved. Therefore, it is very convenient as a solvent-free paint or a high solid content paint, for which pollution-free and resource-saving are currently attracting great attention. In particular, the copolymer used in the present invention has a lower molecular weight than conventional vinyl resins, so a major feature is that it can be easily applied to solvent-free or high solids paints for this purpose. .

The copolymer containing a silyl group, which is a copolymerization method of acrylic ester or methacrylic ester and diallyl phthalate used in the present invention, is a new substance, and its structure is based on the manufacturing method and the assay in the examples. It's pretty obvious.

The copolymer of acrylic acid ester or methacrylic acid ester and diallyl phthalate used in the present invention, which also contains a silyl group, is a copolymer containing a hydrosilane compound represented by the formula %. It is easily produced by reacting a copolymer of an acid ester or a methacrylic acid ester with diallyl phthalate in the presence of a group Ⅰ transition metal catalyst.

The hydrosila/compound used in this case has the following general formula.

(Ri)a 1B -4Si Tl (wherein R1 is a monovalent hydrocarbon group selected from an alkyl group, an aryl group, and an aralkyl group having 1 to 101 carbon atoms,
X is halogen, alkoxy, acyloxy, aminoxy,
a group selected from N-alkyl substituted aminoxy, phenoxy, thioalkoxy, thiophenoxy, amino group, aF
(integer from iO to 2) Specific examples of hydrosilane compounds included in this general formula include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, trichlorosilane; Alkoxysilanes such as ethoxysilane, methyljethoxysilane, methyldimethoxysilane, phenyldimethoxysilane; triacetoxysilane,
Examples include acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; various silanes such as triaminoxysilane, methyldiaminooxysilane, and methyldiamino 7-lane.

The amount of the hydrosilane compound to be used can be any amount with respect to the carbon-carbon double bonds contained in the copolymer, but it is preferably used in an amount of 0.5 to 2 times the mole. Although this does not preclude the use of a larger amount of silane, it will simply be recovered as unreacted hydrosilane.

Further, as the hydrosilane compound, non-rogenated 7ranes, which are inexpensive basic raw materials and have high reactivity, can be used. Silyl group-containing copolymers of acrylic esters or methacrylic esters and diallyl phthalate obtained using halogenated silanes harden rapidly at room temperature while generating hydrogen chloride when exposed to air; Since it is prone to problems such as irritating odor and corrosion, and can only be used practically in limited applications, it is desirable to further convert the Rogge/functional group to another hydrolyzable functional group.

Examples of the hydrolyzable functional group include an alkoxy group, an acroxy group, an aminoxy group, an N-alkyl-substituted ami-noxy group, a phenoxy group, a thioalkoxy group, a thiophenoxy group, and an amino group.

Methods for converting halogen functional groups into these hydrolyzable functional groups include: (1) alcohols and phenols such as methanol, ethanol, 2-methoxyethanol, 5ec-butanol, tert-butanol, and phenol; (2) alcohols and phenols; Specific examples include a method of reacting an alkali metal salt of, (2) an alkyl orthoformate such as methyl orthoformate and ethyl orthoformate with a halogen functional group.

Specific examples of the method for converting into an acyloxy group include: (1) reacting carboxylic acids such as acetic acid, propionic acid, and benzoic acid; (2) alkali metal salts of carboxylic acids; and the like with a halogen functional group.

Methods for converting into aminoxy groups include: (1) Hydroxylamines such as N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, N,N-methylphenylhydroxylamine and N-hydroxypyrrolidine; (2) Hydroxylamines such as N-hydroxypyrrolidine; A specific example is a method of reacting an alkali metal salt with a functional group.

Methods for converting into amino groups include: 1) primary and secondary amines such as N,N-dimethylamine, N,N-methylphenylamine and pyrrolidi/; 2) alkali metal salts of primary and secondary amines; A specific example is a method of reacting the like with a halogen functional group.

Examples of methods for converting into thioalkoxy groups include: ■ thioalcohols and thiophenols such as ethyl mercaptan and thiophenol, ■ alkali metal salts of thioalcohols and thiophenols; etc., are reacted with a halogen functional group. Can be mentioned.

With regard to the silyl groups introduced into the vinyl copolymer through the hydrosilylation reaction, only in the case of non-rogen functional groups, the silyl groups are not converted to other hydrolyzable substituents, but are converted to other alkoxy groups, acyloxy groups, etc. In the case of
It can be converted into a hydrolyzable functional group such as an aminoxy group. A suitable temperature for converting the hydrolyzable functional group on the silyl group directly introduced by the hydrosilylation reaction into another hydrolyzable functional group is 50°C to 150°C. Further, these conversion reactions can be accomplished with or without the use of a solvent, but when used, inert solvents such as nityls, hydrocarbons, and acetic esters are suitable.

The copolymer of acrylic ester or methacrylic ester and diallylphthalate used in the present invention is not particularly limited, and includes methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. It is possible to copolymerize various acrylic monomers such as diallyl phthalate alone or as a mixture. Furthermore, it is also possible to partially copolymerize other vinyl monomers such as acrylonitrile, styrene, alkyl vinyl ether, etc. Specific examples of the diallyl phthalate to be used include ortho-diallyl phthalate, iso-diallyl phthalate, and telesiallyl phthalate. The molecular weight of this copolymer is preferably from 300 to less than 1000, and for that purpose n-
A chain transfer agent such as dodecyl mercaptan or t-dodecyl mercaptan may be added as necessary.Furthermore, in the presence of a chain transfer agent, one allyl ester moiety of diallylphthalate remains in the copolymer and is used for hydrosilylation. It is possible to introduce a carbon-carbon double bond, and it can be manufactured very simply and at low cost. Therefore, the number of carbon-carbon double bonds for hydrosilylation can be easily adjusted by varying the amount of diallylphthalate used as a copolymerization component.

Copolymerization of these acrylic esters or methacrylic esters and diallyl phthalate may be carried out with or without the use of a solvent, but if it is used, a non-reactive solvent such as ethers, hydrocarbons, or acetate esters may be used. The use thereof is preferred, and known polymerization initiators such as various azo compounds and peroxides can be used.

A transition metal complex catalyst is required in the step of reacting the hydrosilane compound with the carbon-carbon double bond.

As the transition metal complex catalyst, a Group 1 transition metal complex compound selected from platinum, rhodium, cobalt, palladium and nickel is effectively used. This hydrosilylation reaction is accomplished at any temperature from 50 to 150°C, and a reaction time of about 1 to 4 hours is sufficient.

The copolymer of acrylic ester or methacrylic ester and diallyl phthalate used in the present invention, and the silyl group-containing copolymer, is a random copolymer with a molecular weight of 400 to less than 1,000, and when exposed to the atmosphere, it will react at room temperature. It forms a network and hardens. In this case, the curing rate varies depending on the atmospheric temperature, relative humidity, and type of hydrolyzable group, so the type of hydrolyzable group must be carefully considered when using the resin.

In curing the coating material of the present invention, a curing accelerator may or may not be used. When curing accelerators are used, alkyl titanates, metal salts of carboxylic acids such as tin octylate and diptylstin laurate, amine salts such as dibutylamine-2-hexoate, and other acidic and basic catalysts are used. It is valid. The amount of these curing accelerators added is 0.001 to 10% based on the copolymer used.
Preferably, it is used in % by weight.

As shown in the examples, the paint of the present invention cures rapidly at room temperature and provides a coating film with excellent surface gloss and hardness.

Another feature of the present invention is that the surface hardness can be freely adjusted by adding ethyl silicate to the paint.

The paint of the present invention can contain various fillers, pigments, etc. Fillers and pigments that can be used include various silicas, calcium carbonate, magnesium carbonate, titanium oxide, iron oxide, and glass fibers.

Next, examples will be described.

Synthesis of copolymer Methyl methacrylate 20f1 Diallyl phthalate 2Of
of n-dodecyl mercaptan in 40 g of toluene/solution
f and 0.51 of azobisisobutyronitrile were added and polymerized at 80° for 3 hours to obtain a copolymer (copolymer 1) with a molecular weight of about 600.

The infrared absorption spectrum of the obtained compound shows 1730α-
In addition to the absorption by the ester of 1, 1640c1 due to the carbon-carbon double bond! ! An absorption near 750 m due to the ortho-substituted benzene nucleus was observed. Moreover, the iodine value of this copolymer was 48.

To 839 of the copolymer 1 obtained above, 7.8 f of methyldichlorosilane and 0.000011 chloroplatinic acid were added and reacted under sealed conditions at 90°C for 3 hours. 5 m of methanol after reaction
1 and 5 ay/ml of methyl orthoformate were added, and stirring was continued until I)H in the solution became neutral. In the infrared absorption spectrum of the copolymer (copolymer 2) obtained after the hydrosilylation reaction, the absorption near 164Oax completely disappeared;
The iodine value was 2.5, indicating that more than 90% of the carbon-carbon double bonds had reacted with the hydrosilane. Note that the molecular weight of this copolymer 2 was 750.

When 2% by weight of dibutyltin maleate was added to the copolymer 2 and exposed to the atmosphere, the mixture became tack-free and cured in about 1 hour.

From the above, it can be seen that the obtained copolymer 2 is a copolymer of methyl methacrylate and diallyl phthalate, and is a silyl group-containing copolymer.

The figure shows the infrared absorption spectra of Copolymer 1 and Copolymer 2.

Example 1 (Coating Example) 2 parts of dibutyltin maleate was added to 100 parts of Copolymer 2 obtained above and applied to a mild steel plate, and the film forming ability and physical properties thereof were measured. The results are shown below. The resulting coating film had a thickness ranging from 0.01 to Q, lyttx.

・Additional 30% by weight of ethyl silicate to the paint of Example 1・・Leave at 25°C and 70% humidity for 200 hours using a sarometer

[Brief explanation of the drawing]

Figure 1 shows Copolymer 1 (1 in Figure 1) in the synthesis of copolymers of Examples of the present invention and Copolymer 2 (Figure 1) which is a silyl group-containing diallylphthalate copolymer after hydrosilylation reaction. -1-2) is an infrared absorption spectrum diagram.

Claims (1)

[Claims] (1) Formula A ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・A (In the formula, R_3 is an alkyl group of C_1 to C_4, R_4
represents hydrogen or -CH_3) Formula B ▲Mathematical formulas, chemical formulas, tables, etc. are available▼・・・・・・B (In the formula, R_1 is hydrogen or an alkyl group with 1 to 10 carbon atoms, an aralkyl group, an aryl group a monovalent hydrocarbon group selected from X is halogen, alkoxy, acyloxy, aminoxy, N-alkyl-substituted aminoxy, phenoxy,
A group selected from thioalkoxy, thiophenoxy, and amino groups, where a represents an integer from 0 to 2) Formula C ▲ Numerical formulas, chemical formulas, tables, etc. are available▼・・・・・・C Structure represented by the above formula A 1 to 99 mol% of units and a structural unit represented by formula B 1 to 99 mol% (A and B combined 100 mol%), or 1 to 98 mol% of structural units represented by formula A and a structure represented by formula B 1 to 98 mol% of units and 1 to 98 mol% of structural units represented by formula C (A, B, C combined 100 mol%)
) A paint consisting of a random copolymer having a molecular weight of 400 to less than 1000.