JPH03162408A - Modified polyolefin resin composition and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject composition suitable for coating material, etc., having excellent storing stability, resistance to solvent and properties of coated film at low temperature by subjecting an ethylenic unsaturated monomer to heat polymerization in the presence of a specific urethane-modified polyolefin and a radical-generating catalyst. CONSTITUTION:(A) (i) A hydroxyl group-containing modified chlorinated polyolefin (e.g. esterified product of acid-modified chlorinated polyolefin with polyol) is reacted with (ii) a hydroxy group-containing ethylenic unsaturated monomer [e.g 2-hydroxyethyl (meth)acrylate], (iii) an active hydrogen-containing compound (e.g. polyether polyol) and (iv) a polyisocyanate (e.g. hexamethylene diisocyanate) to form an urethane-modified polyolefin. Then, in the presence of said urethane-modified polyolefin, (B) an ethylenic unsaturated monomer [e.g. (meth)acrylic acid] is polymerized at >=50 deg.C in the presence of a radical- generating catalyst to afford the aimed composition.

Description

[Detailed description of the invention] [Industrial application. Field: The present invention relates to a modified polyolefin resin composition and a method for producing the same.

[Prior Art] Conventionally, compositions made by blending acid-modified chlorinated polypropylene and acrylic resin are generally known (for example, Japanese Patent Publication No. 83-54312).

[Problems to be Solved by the Invention] However, the above composition has a problem of poor coating film properties and solvent resistance at low temperatures.

[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of extensive research into a composition with excellent coating properties and solvent resistance at low temperatures, and a method for producing the same. That is, the present invention provides a urethane-modified polyolefin (A) obtained from a hydroxyl group-containing modified chlorinated polyolefin (a), a hydroxyl group-containing ethylenically unsaturated monomer (b), an active hydrogen-containing compound (c), and a polyisocyanate (d). In the presence of ethylenically unsaturated monomers (
B) A modified polyolefin resin composition obtained by polymerizing B) and a method for producing the same.

In the hydroxyl group-containing modified chlorinated polyolefin (a) used in the present invention, the polyolefin is propylene homopolymer, propylene and ethylene, butene-1
, pentene-11, hexene-11 and hebutene-1, which are co-311 with α-olefin comonomers having usually 2 or more carbon atoms, preferably 2 to B, and the like. The average molecular weight of polyolefin is usually 2,000 to 30,000
, preferably 3,500 to 25,000.

Polyolefins may be obtained by degrading high molecular weight polyolefins by thermal decomposition, such as conventional telomerization (single or copolymerization of propylene).
It may be obtained from Hydroxyl group-containing modified chlorinated polyolefin (a) is an adduct of unsaturated polycarboxylic acid and/or acid anhydride of chlorinated polyolefin (acid-modified chlorine containing carboxyl group and/or carboxylic acid anhydride group) Examples include esterified polyolefins with polyols and/or alkylene oxide adducts of the adducts.

Examples of the unsaturated polycarboxylic acids and/or acid anhydrides used in the acid-modified chlorinated polyolefin include maleic acid, fumaric acid, maleic anhydride, citraconic acid, citraconic anhydride, itaconic acid, and itaconic anhydride. Examples include β-unsaturated polycarboxylic acids or anhydrides thereof.

The amount of unsaturated polycarboxylic acid and/or acid anhydride added to the polyolefin is usually 0.5 to 15%, preferably 1 to 7%. Acid-modified polyolefins modified with unsaturated polycarboxylic acids and/or acid anhydrides are produced by treating polyolefins in an inert gas atmosphere in the presence of aromatic and/or chlorinated solvents, and by treating them with radical-generating catalysts (
Peroxides such as di-tert-butyl peroxide, tert-butyl hydroperoxide, dicumyl peroxide, penzoyl peroxide, tert-
butyl peroxide benzoate, etc., in the presence or absence of an azonitrile (e.g., azobisisobutyronitrile, azobisisovaleronitrile, azobisisopropionitrile, etc.), usually heated to 120°C to 220°C to dissolve the unsaturated It can be obtained by adding polycarboxylic acid and/or acid anhydride in portions or all at once and reacting (graft polymerization). Usually the acid-modified polyolefin is then chlorinated. Chlorination can be carried out using known methods such as modified polio. It can be obtained by heating and dissolving a refin in a chlorine-based solvent such as carbon tetrachloride, and then blowing chlorine gas at a temperature of 50 to 120°C to cause a reaction. In order to accelerate the reaction, the reaction may be carried out by irradiation with ultraviolet rays or under pressure. The amount of bound chlorine in acid-modified chlorinated polyolefin is usually 5 to 50%.
, preferably 10 to 35%. less than 5% and 50
If it exceeds %, the adhesion will deteriorate.

The hydroxyl group-containing modified chlorinated polyolefin (a) is an esterified product of an acid-modified chlorinated polyolefin and a polyol and/or an acid-modified polyolefin having 2 to 2 carbon atoms.
The alkylene oxide adduct of No. 4 is added.

Examples of polyols include the high molecular polyols and low molecular polyols described in the section of the active hydrogen compound (c). Among these, preferred is the molecule Ji 1000
polyols and low molecular weight polyols. The hydroxyl group of the polyol is usually 0.2 equivalent or more, preferably 0.5 to 5 equivalents relative to the carboxyl group. 0
．． If the amount is less than 2 equivalents, the solubility is poor and separation occurs. If the amount exceeds 5 equivalents, the appearance deteriorates and sometimes gelation occurs. The number of moles of alkylene oxide added to the carboxyl group is usually 0.
1 mol, preferably 10 mol. If it is less than 0.1 mol, the solubility is poor and separation occurs. ! When the amount exceeds 0 mol, the appearance deteriorates and sometimes gelation occurs.

As the hydroxyl group-containing ethylenically unsaturated monomer (b), hydroxyl group-containing (meth)acrylates {for example, 2-hydroxyethyl (meth)acrylate, 2-
Hydroxyprobyl (meth)acrylate, ε-1-cabrolactone-2-hydroxyethyl (meth)acrylate adduct, γ-valerolactone-2-hydroxyethyl (
meth)acrylate adduct, glycerol mono(meth)
Acrylate, glycerol di(meth)acrylate}
, allyl alcohols (eg, allyl alcohol, glycerol monoallyl ether, glycerol diallyl ether), and alkylene oxide adducts thereof having 2 to 4 carbon atoms. The number of moles of alkylene oxide added is usually 0 to 100 moles, preferably 0 to 6 moles.
It is 0 mole.・Among these, what is preferable (meta)
It is an acrylate.

The active hydrogen-containing compound (c) is a polymer polyol,
Examples include low molecular weight polyols and polyamines.

Examples of high-molecular polyols include polyether polyol {low-molecular polyol (ethylene glycol, propylene glycol, !・3- or!・4-butanediol, 3-
Methylpentanediol, 1-11i-hexanediol, neopentyl glycol, diethylene glycol,
Difunctional polyols such as cyclohexylene glycol; glycerin, trimethylolpropane, pentaerythritol, and nrubito? trifunctional or higher functional polyols such as chlorine, sucrose, etc.; hydroxycarboxylic acids such as lactic acid, tartaric acid, citric acid, salicylic acid, dimethylolpropionic acid; these and methanol, ethanol, furopanol, butanol, 2-hydroxyethyl (meth) acrylate, some combination with monoalcohols such as 2-hydroxybropyl (meth)acrylate), polyhydric phenols (bisphenols such as bisphenol A)
, ■ and amines (alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine; aliphatic polyamines such as ethylenediamine, hexamethylenediamine, isophoronediamine, diethylenetriamine;
Alkylene oxides of aromatic diamines (e.g. tolylene diamine, diphenylmethane diamine) [2 carbon atoms]
-4 alkylene oxides such as ethylene oxide,
Adduct of one or more types (random and/or block) of propylene oxide, butylene oxide, etc., alkylene oxide? polyester polyols [polycarboxylic acids (aliphatic polycarboxylic acids such as adipic acid, succinic acid, sebacic acid, azelaic acid, fumaric acid, maleic acid and dimerized linoleic acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid) and low molecular weight polyols or
Polyester polyols with a hydroxyl group at the end, lactone polyesters (polycaprolactone diol, etc.), polycarbonate diols, etc.), polybutadiene polyols, hydrogenated polybutadiene polyols, acrylic polyols, polymanyl Polyol [vinyl monomer (acrylonitrile, acrylonitrile,
styrene, etc.), and mixtures of two or more of these.

Among the polymer polyols, preferred are polyether polyols, polyester polyols, and (hydrogenated) polybutadiene polyols.

The OH equivalent of the polymer polyol is usually 200 to 300G,
Preferably it is 250-200G.

Examples of the low-molecular polyol include those similar to the low-molecular polyols explained in the section on polyether polyols. Preferred low-molecular polyols are ethylene glycol, 1-4-butanediol, and 2-ethyl-3-
It is hexanediol.

Examples of polyamines include aliphatic polyamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, diethylene triamine, etc.), alicyclic polyamines [4
・V-diaminodihexylmethane (hydrogenated MBA)
, 1,4-diaminocyclohexane, 4,V-diaminodimethylcyclohexylmethane, isophorone diamine, etc.], aliphatic diamines with aromatic rings (xylylene diamine, tetramethylxylylene diamine, etc.), aromatic polyamines (diphenylene diamine, etc.), Methanediamine, dichlorodiphenylmethanediamine, tolylenediamine, diethyltolylenediamine, benzidine, phenylenediamine, etc.), alkanolamines (septano- or diethanolonoleamine, propanonoleamine, N-hydroxyethylethylenediamine, etc.), polyalkylene oxide Polyamine [The active hydrogen-containing compound has 2 or more carbon atoms]
4 alkylene oxides such as ethylene oxide, .
Terminal OH of polyether polyols such as one or more (random and/or block) adducts of brobylene oxide, butylene oxide, etc., ring-opening polymers of alkylene oxides (boritetramethylene ether glycol), etc. Compounds with a structure in which a group is substituted with an amino group, such as boroxyethylene ether diamine and boroxypropylene ether diamine],
and mixtures of two or more thereof.

Preferred among the polyamines are hexamethylene diamine, inphorone diamine and 4,4'-diaminodicyclohexylmethane.

These active hydrogen-containing compounds are usually used alone or in combination with a high molecular polyol and a low molecular polyol and/or a polyamine.

The weight ratio of high molecular weight polyol to low molecular weight polyol and/or polyamine is usually 1:0 to 1:5, preferably 120 to 1:3. The average active hydrogen (OH1N H2, NH) equivalent of the active hydrogen-containing compound (total) is usually 70 to 2000, preferably 100 to 1300.

The average number of functional groups of the active hydrogen compound is usually 2 to 3, preferably 2 to 2.5.

The polyisocyanate (d) is an aliphatic polyisocyanate having 2 to 12 carbon atoms (excluding carbon in the NCO group);
For example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate} (MD
I), dodecamethylene diisocyanate, 1・B・11
-undecane triisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate, 2,6-diisocyanate methyl caproate, bis(2-incyanatoethyl) fumarate, bis(2
-isocyanate ethyl) carbonate, 2-isocyanate ethyl-2-todiincyanate hexanoate, etc.; alicyclic polyisocyanates having 4 to 15 carbon atoms, such as inphorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MD I
), cyclohexylene diisocyanate, methylhexylene diisocyanate (hydrogenated TDI) bis(2-incyanate ethyl) 4-cyclohexene-l 2-dicarboxylate, etc.; aromatic aliphatic polyester having 8 to 12 carbon atoms Isocyanates, such as xylylene diincyanate,
Tetramethylexylylene diisocyanate, diethynolebenzene diisocyanate, etc.; water-modified products of HDI,
Trimerized products of IPDI and HDI; aromatic polyisocyanates having 8 to 20 carbon atoms, such as tolylene diisocyanate (TDI), crude TD1, diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate (PAPI; crude MDI) ), naphthylene diisocyanate, etc.; and modified products of these polyisocyanates (modified products containing carbodiimide groups, uretdione groups, uretoimine groups, biuret groups, and/or isocyanurate groups, etc.) can be used. Preferred among these are HDI1, IPDI1, hydrogenated MDI and tetramethynolexylylene diisocyanate.

In producing the urethane-modified polyolefin (A), the ratios of the modified chlorinated polyolefin (a), the hydroxyl group-containing ethylenically unsaturated monomer (b), and the active hydrogen-containing compound (c) to the polyisocyanate (d) are varied. Although it can be changed, NGO and active hydrogen group ( O H1N
H2, NH, etc.) is usually 1:1.0.
1-1: 2, preferably! : 1.02~1:
It is 1.5. (a) contained in the urethane-modified polyolefin (A) is usually 5 to 80% by weight, preferably 15 to 80% by weight.
It is 70% by weight. If it is less than 5% by weight, the adhesion to the polyolefin base material will be poor. If it exceeds 80% by weight, the strength of the coating film will be weakened. (b) is usually 0.01 to 15% by weight
, preferably 0.1-10% by weight.

0. If it is less than % by weight of Ol, the stability of the solution is poor and separation occurs.

If it exceeds 15% by weight, it will gel during polymerization. (a),
(b), (c) and (d) may be produced by reacting them all at once, or a stepwise reaction method, {(a),
After reacting at least a portion of (b) and (c) with (d) to form an NCO-terminated prepolymer, (aL
(aL) A method of producing by reacting the remainder of (b) and (c), (aL) by reacting a part of (b) and (c) with part of (d) to form active hydrogen group terminals (OH1 NH2, NH, etc.) It may be manufactured by a method in which a prepolymer is formed and then the remainder of (d) is reacted, a method in which these are combined, etc.

The polyurethane forming reaction is usually carried out at a temperature of 40 to 120°C, preferably BO to 100°C (however, in the case of reacting a polyamine, the reaction temperature is usually 80°C or lower, preferably 0 to 70°C).
temperature).

To accelerate the reaction, amine catalysts (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), tin catalysts (
dibutyltin dilaurate, dioctyltin dilaurate,
(tin octylate), polymerization inhibitors (hydroquinone, hydroquinone monomethylether, P-methoxyphenol, P-penzoquinone, etc.) to prevent the polymerization of monomers, and hydrochloric acid released from chlorinated polyolefins. An epoxy compound may be used as a stabilizer for.

The reaction is carried out using solvents {ketones (acetone, methyl ethyl ketone, methyl imbutyl ketone, etc.), esters (ethyl acetate, butyl acetate, ethylseron rub acetate, etc.), ethers (dioxane, tetrahydrofuran,
Hydrocarbons (n-hexane, n-heptane, cyclohexane, tetralin, decalin, toluene, xylene, etc.) Alcohols (ethylceronelube, butyl cellosolve, propylene glycol monomethyl ether, etc.)
methanol, ethanol, isopropyl alcohol, isobutanol, jerj-butanol, etc.), chlorinated hydrocarbons (dichloroethane, trichloroethane, carbon tetrachloride, dolichlorethylene, barchloroethylene, etc.), etc.). The solvent may be added before, during or after the reaction.

Ethylenically unsaturated monomer (B) polymerized in the presence of (A)
) as (a) (meth)acrylic acid and its derivatives; (meth)
Acrylonitrile; (meth)acrylic acid and salts thereof; alkyl (meth)acrylates such as methyl (meth)acrylate n-butyl (meth)acrylate (the number of carbon atoms in the alkyl group is usually 1 to 20, preferably 1-12)
Esters: hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ε-1-caprolactone-2-hydroxyethyl (meth)acrylate (
The number of carbon atoms in the alkyl group is usually 2 to 4) Esters and their lactone adducts; aminoalkyl (meth)acrylates such as dimethylaminoethyl methacrylate; (meth)acrylic acid amide, glycidyl (meth)acrylate, etc.; Hydrocarbon monomers: Styrene, α-methylestyrene, etc. (3) Vinyl ester monomers: Vinyl acetate, etc. (2) Vinyl ether monomers: Vinyl methyl ether, etc. (2) Vinyl halide monomers: Chloride Vinyl, vinylidene chloride, etc. (f) Olefinic hydrocarbon monomers: ethylene, propylene, butadiene, imbutylene, isoprene, 1,4-pentadiene, etc.;
Examples include combinations of at least two of the following.

Preferred monomers are (a) or (b) and (0 and/or (c)).

When polymerizing ethylenically unsaturated monomer CB) in the presence of urethane-modified polyolefin (A), (A) (
The weight ratio of solids) to (B) can vary over a wide range, but is usually from 9575 to 5/95, preferably from 85/15 to Is/85. When (A) exceeds 95% by weight, solution stability is poor and separation occurs.

If the amount is less than 5% ffi, the adhesion to the polyolefin base material will be poor.

In the present invention, in the presence of the urethane-modified polyolefin (A), in the presence of a polymerization catalyst (radical generator, etc.),
A modified polyolefin resin composition is produced by polymerizing the ethylenically unsaturated monomer (B). The reaction temperature during production is usually 50°C to 170°C, preferably 70°C.
The temperature is 50°C.

As the polymerization catalyst (radical generator) used in the polymerization reaction, the azo compounds, peroxides, persulfates, perborates, etc. described in the section of the acid-modified polyolefin can be used. Oxides are preferred. The amount used is also not particularly limited, and is usually 0.05 to IO% by weight, preferably 0.1 to 5% by weight, based on the ethylenically unsaturated monomer (B).

The polymerization reaction is carried out in the presence or absence of a solvent.

As the solvent, those described in the section for the production of urethane-modified polyolefin (A) can be used.

The concentration of the modified polyolefin resin composition of the present invention is usually 5
-100%, preferably 20-80%.

The viscosity is usually 50 to 500,000, preferably 100 to 1
00000(cI)S/25°C). Molecular weight (number average molecular ffi) is usually 2000 to 3 Q 0 0 0
01 Preferably 5,000 to 200,000.

Furthermore, the above-mentioned acid-modified chlorinated polyolefin may be added to the modified polyolefin resin composition of the present invention, if necessary.

The modified polyolefin resin composition of the present invention may contain auxiliary compounding agents if necessary.

For example, colorants such as dyes and pigments for decorative coloring, inorganic fillers, organic modifiers, various stabilizers to improve light resistance and heat deterioration resistance, plasticizers, surfactants, and antifoaming agents. agents, crosslinking agents, and other additives.

Examples of the dye include direct dyes, acid dyes, basic dyes, reactive dyes, and metal complex dyes.

Pigments include inorganic pigments such as carbon black, titanium oxide, chromium oxide, zinc oxide, iron oxide, mica, and navy blue, as well as coupled azo, condensed azo, anthraquinone, berylene, quinacridone, thioindigo, dioxazine, Examples include organic pigments such as cyanine-based pigments.

Examples of inorganic fillers include calcium carbonate, silica, talc, and glass fiber.

Examples of the organic modifier include fluororesin powder, silicone resin powder, polyamide resin powder, and urethane resin powder.

Hindered is used as a stabilizer. Phenol type, hydrazine type, phosphorus type, penzophenone type, penzotriazole type,
Examples include oxalic acid anilide type and hindered amine type.

Examples of plasticizers include dibutyl phthalate and dioctyl phthalate.

Examples of surfactants (foam stabilizers, etc.) include silicone foam stabilizers such as siloxaneoxyalkylene block copolymers.

Examples of antifoaming agents include silicone-based antifoaming agents such as dimethylsiloxane-based antifoaming agents.

As a crosslinking agent, a polyisocyanate type (such as an adduct synthesized from 1 mol of hatrimethylolbroban and 1 mol of HDI, 1 IPDI, or 3 mol of TDI; a water-denatured product of HDI, a 3ffi product of IPDI and MDI, etc.)
and blocked isocyanates masked with phenol, methyl ethyl ketoxime, ε monolactam, etc.) and organometallic coordination compounds (e.g. organoaluminum coordination compounds such as aluminum trisacetylacetonate, aluminum triisopropoxide, zirconium tetrakis) Examples include organic zirconium coordination compounds such as acetylacetonate and diisopropoxyzirconium bisacetylacetonate, and organic titanium coordination compounds such as titanium tetrakisacetylacetonate and diisopropoxytitanium bisacetylacetonate.

These adjuvants may be added before, during or after the production of the composition of the present invention.

The composition of the present invention can be used as a coating agent, primer, or adhesive for various substrates. Various inorganic materials (iron, tinplate, galvanized iron, aluminum, galvanized steel sheets, etc.) can be used as base materials.
glass, slate tiles, ceramics, etc.) and organic materials (
Wood, paper, cloth [woven fabrics and non-woven fabrics such as natural fibers, chemical fibers, and synthetic fibers, etc.] Rubber [natural rubber, chloroprene rubber, isoprene rubber, neoprene rubber, etc.], plastics [polyethylene, polybrobylene, polystyrene, ABS1, vinyl chloride, polycarbonate] , polyacetal, polyester, polyamide, polyurethane, modified P P O1 polymethyl methacrylate, epoxy resin, phenol resin, melamine resin, etc.]). It is particularly preferred for polyolefin base materials. When the composition of the present invention is used in coating agents, primer adhesives, etc., the coating amount can be varied, for example, from 1 to 200 microns. Application methods include spray coating, brush coating, trowel coating, roll coating, flow coating, and dipping methods. Drying can be done at room temperature or at elevated temperatures (eg 40-140°C for 1-30 minutes). It can be done with.

[Example] The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Parts in the examples are parts by weight.

Production Example 1 Production of modified chlorinated polyolefin (a) (a-1
) ; High molecular weight polypropylene (average molecular weight 125,000)
300 parts of polypropylene with an average molecular weight of 10,000 obtained by thermally decomposing 10,000 parts of polypropylene and 30 parts of maleic anhydride were placed in an apparatus equipped with a reflux tube, and after adding 700 parts of xylene, the apparatus was purged with nitrogen. 150℃ while stirring and introducing a small amount of nitrogen.
After raising the temperature to a uniform temperature and dissolving it uniformly, dicumyl peroxide 1B. After 5 hours of addition, the reaction was continued for another 4 hours, first at normal pressure, then at 180″G, 3m+a1
Xylene and unreacted maleic anhydride were distilled off over a period of 2 hours under a reduced pressure of 1.1 g. The acid-modified polypropylene obtained was a yellow solid with a melt viscosity of 1600 cpss at 180°C and a ring and ball softening point of 154°C, and the amount of maleic anhydride added was 3.8% by weight.

Next, 200 parts of the above acid-modified polypropylene and 800 parts of carbon tetrachloride were charged into a device equipped with a reflux tube, and 65 to 70 parts of
After uniformly dissolving the mixture by heating to .degree. C., 35 parts of chlorine gas per hour was introduced into the reaction solution for 4 hours. After chlorination, residual chlorine and carbon tetrachloride in the reaction solution were first removed at normal pressure and then at IH°C.
, and was distilled off over 2 hours under reduced pressure of 3 mdg. The obtained acid-modified chlorinated polypropylene was heated to 180°C. Melt viscosity 1
12001) 61 was a yellow solid with a ring and ball softening point of 150''C, and the amount of bound chlorine was 21.5%.

300 parts of this acid-modified chlorinated polypropylene was dissolved in 740 parts of toluene, 17 parts of 2-ethyl-1,3-hexanediol was added, and the mixture was reacted at 100°C for 1 hour, resulting in a solid content of 3
A modified chlorinated polyolefin (a-1) with a viscosity of 0% and a viscosity (25° C.) of 150 cps was obtained.

Production of urethane-modified polyolefin (A) (A-1): 1000 parts of the modified chlorinated polyolefin of Production Example (a-1) and 2-hydroxyethyl methacrylate in a four-necked flask! 3 parts, 1000 parts of polybutadiene glycol with a molecular weight of 2000, 127 parts of inphorone diisocyanate, and 1480 parts of toluene were reacted at 80°C for 4 hours in a nitrogen atmosphere, and then 0.5 part of dibutyltin dilaurate was added. The reaction was carried out at 80° C. for 5 hours to obtain a urethane-modified polyolefin (A-1) having a solid content of 40% and a viscosity (25° C., 500 cps).

Production Example 2 Production of modified chlorinated polyolefin (a) (a-2); 300 parts of acid-modified chlorinated polypropylene obtained during the synthesis of Production Example (a-1) was dissolved in 970 parts of toluene to obtain a molecular fi 100G. Add 116 parts of polyptadiene glycol and react at 100"C for 1 hour to obtain a solid content of 30%.
A modified chlorinated polyolefin (a-2) having a viscosity (25° C.) of 210 aps was obtained.

Production of urethane-modified polyolefin (A) (A-2); Modified chlorinated polyolefin 1000 of production example (a-2)
part, 2-hydroxyethyl methacryly} 32.5 parts, polybutadiene glycol with molecule fi100G! 00
0 parts, 73 parts of 2-ethyl-1,3-hexanediol,
355 parts of inphorone diisocyanate and toluene!
From 941 parts, the solid content was reduced to 40 in the same manner as in Production Example (A-1).
% and a viscosity (25°C) of 2,800 cps was obtained.

Example 1 1,000 parts of the urethane-modified polyolefin (A-1) obtained in Production Example 1 was placed in a four-hole flask equipped with a stirrer, a reflux condenser, a nitrogen blowing tube, and a dropping funnel, and the temperature was raised to 105°C while blowing a small amount of nitrogen. Methyl methacrylate in a flask kept at A mixed solution of 220 parts of ester, 111i of 2-ethylhexyl methacrylate, 20 parts of n-butyl methacrylate, 3 parts of azobisisobutyronitrile, 250 parts of toluene, and 250 parts of butyl acetate was added dropwise over 3 hours for polymerization. The reaction was carried out. One hour after the completion of dropping, add 3 parts of azobisisobutyronitrile and 10 parts of toluene.
0 parts of the solution was added dropwise over 3 hours to effect aging and complete the reaction. Appearance translucent solid content 40%, viscosity (25℃) G
500 cps of the composition of the invention was obtained.

Example 2 Urethane-modified polyolefin (A-
A composition of the present invention having a translucent appearance was obtained in the same manner as in Example 1, except that 1) was replaced with the urethane-modified polyolefin (A-2) obtained in Production Example 2.

Example 3 Urethane-modified polyolefin (A
-1) 150 parts of methyl methacrylate, 300 parts of 2-ethylhexyl methacrylate, 150 parts of n-butyl methacrylate, 6 parts of azobisisobutyronitrile, 400 g of toluene, and 30 G of butyl acetate to 1000 parts.
One hour later, a solution of 6 parts of azopisisobutyronitrile and 200 parts of toluene was added dropwise over 3 hours to ripen and complete the reaction.

Translucent appearance, solid content 40%, viscosity (25°C) 5000
A composition of the invention of cps was obtained.

Comparative Example 1 In the same manner as in Example 1, parts of toluene IOQO and 250 parts of butyl acetate were charged into a flask, and 550 parts of methyl methacrylate and 400 parts of 2-ethylhexyl methacrylate were charged.
A mixed solution of 50 parts of n-butyl methacrylate, 7.5 parts of azobisisobutyronitrile and 250 parts of toluene was added dropwise over 3 hours, and after 1 hour, 7.5 parts of azobisisobutyronitrile and 250 parts of toluene were added. A portion of the solution was added dropwise over 3 hours to age and complete the reaction. An acrylic resin solution with a transparent appearance, a solid content of 40%, and a viscosity (25° C.) of 7QOOcpS was obtained. To 1000 parts of this solution (a-
A solution in which 400 parts of acid-modified chlorinated polypropylene obtained during the synthesis of 1) was dissolved in 600 parts of toluene was mixed,
Opaque appearance, solid content 40%, viscosity (25℃) 3500c
A comparative example composition of ps was obtained.

Test Example 1 The compositions obtained in Examples 1 to 3 and comparative examples were spray-coated onto a propylene plate degreased with isopropyl alcohol so that the film thickness after drying was 20μ, and dried at 80°C for 30 minutes. A painted board was obtained. This coated board was left to stand for one day, and then the coating film was tested. Table 1 shows the results.
Shown below.

Test method Adhesion: A JIS K54QO cellophane tape test was conducted on the coated surface of the painted board.

Water resistance: The coated board was immersed in warm water at 40°C for 240 hours, dried at room temperature for 1 hour, and then subjected to a cellophane tape test.

Alcohol resistance: After immersing the painted board in ethyl alcohol at 20°C for 24 hours,
After drying at room temperature for 1 hour, a cellophane tape test was performed.

N-hexane resistance: After immersing the coated plate in n-hexane for 20"0124 hours, 1
After drying at room temperature for an hour, a cellophane tape test was performed.

Bending resistance: The painted board was subjected to the JIS K5400 bending test (core rod diameter 2 m).
m) was carried out at -10''C and the coating surface was observed.

Table 1 Test Example 2 The compositions obtained in Examples 1 to 3 and Comparative Example 1 were applied onto a glass plate using an applicator so that the film thickness after drying was 40μ, and after drying at 80°C for 60 minutes. The condition of the coating film was observed. The results are shown in Table 2.

Table 2 Test Example 3 Table 3 shows the storage stability of the compositions obtained in Examples 1 to 3 and Comparative Example 1.

Table 3 [Effects of the invention] The composition and production method of the present invention are significantly superior in storage stability, solvent resistance, and physical properties of the coating film compared to conventional compositions, and the coating film properties are particularly excellent at low temperatures. . The composition of the present invention can be applied as a coating agent, primer, or adhesive for various substrates, but is particularly suitable for polyolefin substrates.

Claims (1)

[Scope of Claims] 1. Hydroxyl group-containing modified chlorinated polyolefin (a
), hydroxyl group-containing ethylenically unsaturated monomer (b)
, a modified polyolefin resin composition obtained by polymerizing an ethylenically unsaturated monomer (B) in the presence of a urethane-modified polyolefin (A) made from an active hydrogen-containing compound (c) and a polyisocyanate (d). 2. Hydroxyl group-containing modified chlorinated polyolefin (a
2. The composition according to claim 1, wherein ) is an esterified product of an adduct of an unsaturated polycarboxylic acid and/or an acid anhydride of a chlorinated polyolefin with a polyol, and/or an alkylene oxide adduct of the adduct. 3. A modified polyolefin characterized by polymerizing an ethylenically unsaturated monomer (B) in the presence of the urethane modified polyolefin (A) according to claim 1 or 2 at 50° C. or higher in the presence of a radical generating catalyst. Method for producing resin composition.