JPS585371A - Resin composition for coating - Google Patents

Abstract

PURPOSE:To provide an internally plasticized resin compsn. for coating contg., as a film-forming component, an acryl-modified chlorinated polyolefin obtained by polymerization of chlorinated polyolefin and acrylic monomer and having excellent resistance to weathering and impact. CONSTITUTION:70-10pts.wt. chlorinated polyolefin and 30-90pts.wt. one acrylic monomer (e.g. methyl acrylate or isobutyl acrylate) or mixture of two or more acrylic monomers, are dissolved in a solvent. A polymerization initiator (e.g. benzoyl peroxide) and a chain transfer agent (e.g. laurylmercaptan) are added to the soln. and suspension polymerization is effected in water at about 40- 100 deg.C. The compsn. is prepared by using the acryl-modified chlorinated polyolefin as a film-forming component and adding pigment, dye, stabilizer, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides polyolefins such as natural rubber, synthetic isoprene rubber, polypropylene, polyethylene, etc. Generally the chlorine water content is 5
s ~ 75 weight sound, preferably t! Chlorinated polyolein (hereinafter abbreviated as CPO) that has been chlorinated to a weight of 60 to 70% has excellent solubility in anti-solvents, and its dry film has chemical resistance.
Paints, printing inks, etc. have excellent weather resistance.
It is widely used in the adhesive field. However, these CPOO
The single film is hard and brittle, so in practical use it is often necessary to use a plasticizer in combination.
Typical plasticizers include dioctyl heptatarate and h&i salt bulked paraffin. Since these plasticizers are all low molecular weight substances, their migration or escape into the atmosphere can cause deterioration of the CPO paint film properties over time, i.e. cracking, staining, and yellowing of the film over time. It is generally said that this happens.

The present inventors #i It is necessary to improve the hard and brittle physical properties of CPO, which necessitates the use of low molecular weight plasticizers (C
As a result of various studies for the purpose of internal plasticization of PO,
We succeeded in synthesizing acrylic-modified CPO in which CPO was internally plasticized with acrylic resin, and proposed a method for its production in Japanese Patent Application No. 111855-66156.Furthermore, the present inventors have proposed a method for producing the same in Japanese Patent Application No. 111855-66156. As a result of continued research and application development, we developed acrylic modified CPO into a coating film I!
It was discovered that bulky paints have even better weather resistance and impact resistance, which led to the present invention.The acrylic-modified cpoFi natural rubber used in the present invention, synthetic inbrene rubber, polypropylene, polyethylene, and other olefins or Polymers of olefins are generally classified by chlorine content (weight) [
Produced by homogeneous chlorination to 55-75% weight, preferably 60-70% R,#'i hydrogen or methyl group, R,#'i
(i represents an alkyl group having 1 to 8 carbon atoms) One or more mixed monomers of alkyl esters of acrylic acid or methacrylic acid 1 Specifically, methyl acrylate, methyl methacrylate, ethyl acrylate,
Ethyl methacrylate, n-butyl acrylate, n
-butyl memethacrylate, inbutyl acrylate,
Inbutyl methacrylate, octyl acrylate,
A uniform solution of octyl memethacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, etc. is suspended in water in the presence of a dispersion stabilizer such as polyvinyl alcohol, and the polymerization temperature is 40~ Z
It is produced by polymerization reaction at OO°C, preferably F170-90°C. At this time, a polymerization initiator such as benzoyl peroxide, dialkyl peroxide, ketone peroxide, benzoyl hydroperoxide, t-butyl hydroperoxide, trizopisbutyronitrile, t-butyl peroxybenzoate, etc. is added to the acrylic monomer.
0.00 parts by weight, 0.05 to 'Lθ parts and a chain transfer agent of laurelmercabutan, h-butylmercabutane, and bromotrichloromethane were added
0.01-! to 0 parts by weight! LOI! The polymerization reaction is carried out by adding it.

Furthermore, FC a part of the alkyl ester monomer of acrylic acid or methacrylic acid is used as an acrylic monomer having a functional group such as an OH group, a COOH group, or an EBO group within a range that provides a uniform toluene solution. In addition to changing the structure, it is also possible to introduce a functional group into the product to impart crosslinking properties and adhesion to the nuclear modified product.

After the polymerization reaction is completed, this layered liquid polymerization solution is cooled to room temperature, and the polymerization reaction product is separated from water by a filtration method such as centrifugal dehydration.

l! Next, the product is washed and dried to obtain the desired acrylic-modified CPO.

This acrylic-modified CPO has a granular form and is easy to handle because it does not have mating properties.

#i Regarding the type and composition of the paint, there are no particular limitations, but the acrylic modified CPO can be used alone as the main component for forming a paint film, or CPO or a resin such as A or Kito can be used in combination.4 It gets cloudy. If necessary, various pigments, dyes, stabilizers, chicken agents, leveling agents, wetting agents, anti-settling agents, etc. may be used in combination as appropriate. resin,
It can also be used in combination with ketone resin, etc. As intermediate coating or top coating, thermoplastic acrylic resin, vinyl chloride-vinyl acetate copolymer resin,
May be used in combination with vinyl chloride resin, etc.;
A detailed explanation of the present invention is given based on aK. Example 1.

A 30 flask with a capacity of 2 tO and a stirrer was charged with 210F (n-butyl acrylate) and 9 t of methyl methacrylate, and chlorinated polyethylene (hereinafter CP) was added to the mixed monomer.
After homogeneously dissolving 3002 (abbreviated as E) at room temperature, benzoyl peroxide 3F and bromotrichloromethane 6F were added to obtain a homogeneous solution. To this solution, Kuraray Bovar (Note: Dispersion stabilizer ■ Kuraray Manufacturing Co., Ltd.) was added. ) PVA-205
Pour 600 tons of a homogeneous aqueous solution containing 31. Thereafter, the temperature inside the system was raised to 80° C. using a water pass, and the reaction was continued for 2 hours while stirring was continued. After the reaction was completed, the reaction product was cooled to room temperature, filtered, washed, dehydrated, and dried at 45°C for 72 hours to obtain a granular reaction product of 597.5 f (hereinafter abbreviated as acrylic modified CPE). Table 2 shows the results of a practical test of paints based on the formulation of modified CPE shown in Table 1. For comparison, the results of a normal CPE @ material O test using chlorinated paraffin are also listed @ 1!1. Paint formulation (parts by weight) After kneading the formulation in Table 1 for 3 hours in a sand kil, the paint viscosity was adjusted to a constant value (72 KU) and used as a sample for a practical paint test. The test piece used was a polished steel plate treated with wash brimer, and both were painted so that the dry coating thickness was 80μ. Pigment volume content) and CPE/plasticizer ratio are different.
As a result of paint tests, increasing the amount of plasticizer causes contamination of the paint film, and decreasing the amount of plasticizer causes cracking of the paint film.However, the paint film of the present invention has excellent weather resistance. Because it is internally plasticized by 14i1, it has excellent weather resistance and bending resistance, and there is no change in weight over time (presence or absence of volatile components), and it exhibits much superior physical properties compared to conventional CPE paints. There is.

Example λ Using the apparatus of Example 1, n-butyl acrylate 210
F and cyclohexyl methacrylate) 90F were added, and the monomer IIccPE3oor was uniformly dissolved at room temperature, and then 2.4t1 of benzoyl peroxide and 12F of bromotrichloromethane were added to obtain a homogeneous solution. After that, when I performed the same operation as Ill, 598t was obtained.
Obtaining a granular resin tube 90 Example 3 Using the apparatus described in Ill, 210 t of basezyl acrylate and 90 t of methyl methacrylate were added to 2-ethyl.
After uniformly dissolving CPE30 (l) in the mixed monomer at room temperature, the same operation as in Example 112 was performed.
98 tons of granular reaction products were obtained from Yu-Mitsu m@2 and implementation 1.
The acrylic modified CPE obtained in Example 13 was subjected to a paint test based on the paint formulation shown in Table 3 using the same procedure as in Example 111. The results are shown in Table 4.

Example 4 For the combined system of the Acryl-modified CPE and salt-accumulated polyethylene produced in Example 1, a paint test was conducted based on the formulation shown in Table 5 and in the same manner as in Example fl11 for the purpose of improving the conventional formulation. The results are shown in Table 6.

Table 6 Imperial Examination Results From the above results, it can be seen that the combination of acrylic modified CPE has a synergistic effect compared to the conventionally formulated plasticized coating film using only chlorinated paraffin (comparative formulation Φ■ in Table 2).

Example & Using the apparatus of Example 1, n-butyl acrylate 210
Add t and methyl methacrylate 90F to the mixed monomer to form a salt-accumulated compound (similar to dipropylene (abbreviated as CPP)) 3
After homogeneously dissolving 0 (l) at room temperature, the same operation as in Example 1 was performed to obtain 59610 granular reaction product.

Implementation fl16゜Using the equipment of Implementation@1, n-butyl ac number route 210
After adding F and 90f of methyl methacrylate and uniformly dissolving 300t of chlorinated rubber (hereinafter abbreviated as OR) in the mixed monomer at room temperature, the same operation as in Example 1 was carried out.
However, a granular reaction product of 597f was obtained in Example 6. A paint test was conducted using the acrylic-modified CPP and acrylic-modified CR obtained in Example 6 and Example 6, based on the formulations shown in Table 7. The results are shown in Table 8. As a comparison, the test results for normal CPP using chlorinated paraffin and t, kLg are also listed.

Table 8 Paint test results

Claims (1)

[Claims] 70 to 10 parts by weight of chlorinated polyolefin and 30 to 90 parts by weight of one or more acrylic monomers are mixed and dissolved, and #Ic is prepared in the presence of a polymerization initiator and a chain transfer agent.
An acrylic-modified chlorinated polyolein produced by subjecting an armpit solution to a suspension polymerization reaction in water in the presence or absence of a dispersion stabilizer to form a coating film. system paint composition.