JPH09291252A - Resin composition and paint - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition suitable for paint excellent in adhesion to plastic difficult to be coated and in resistance to gasoline and acid. SOLUTION: This resin composition contains a vinyl-modified chlorinated polyolefin polymer which is prepared by polymerizing, in the presence of (A) a chlorinated polyolefin resin of >=50wt.% chlorine content, (B) a mixture of (b1) an unsaturated organosilane of the formula (X is a group bearing a copolymerizable double bond, Y is a hydrolyzable group or a halogen atom, R is an inactive organic group, m is an integer of 0-2, n is an integer of 1-3 where m and n sum up to 3), (b2) a hydroxyl group-bearing polymerizable monomer, (b3) a carboxyl group-bearing polymerizable monomer and (b4) a polymerizable monomer bearing unsaturated double bond containing an unsaturated double bond-bearing polyester-polyol. This paint comprises this resin composition and a curing agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition and a paint.

[0002]

2. Description of the Related Art In recent years, synthetic resins such as polyolefins have been widely used in place of metals for reduction of weight, rust prevention, and other purposes in automobiles, home appliances, and various other industrial fields. In this case, since the surface of the molded product is usually coated, good paintability on the surface of the molded product is required. However, it is known that a coating film applied to a plastic molded article made of polyolefin such as polyethylene or polypropylene is generally inferior in adhesion, solvent resistance and the like. However, if this adhesion is attempted to be secured, other performances such as vinyl chloride plasticizer migration resistance and alcohol resistance deteriorate. Therefore, in order to improve coating properties such as adhesion to plastic molded articles made of polyolefin, storage stability of varnish, migration resistance to PVC plasticizer, solvent resistance, weather resistance, many attempts have been proposed in the past. Came. For example, a method of improving the adhesion by degreasing the surface of these molded products, surface treatment such as chromic acid treatment has been proposed, and the surface of the molded product is chlorinated polyolefin or maleic acid or its anhydride. A method has also been proposed in which a polyolefin modified with a substance is applied in a solution state or a dispersed state, a primer treatment is performed, and then a coating material having excellent coating film performance is applied (JP-A-58-83042, JP-A-58-30442). 58-118809 and JP-A-59
-30830).

On the other hand, as a coating composition for improving the adhesion of a coating film on a polyolefin molded product, an epoxy resin,
An epoxy composition comprising a curing agent for an epoxy resin and a polyolefin or polyethylene copolymer having a functional group that reacts with an epoxy group has been proposed (JP-A-56-56).
72053, JP-A-56-50971, and JP-A-58-101122). An acrylic-modified chlorinated polyolefin resin composition comprising an acrylic resin and a chlorinated polyolefin has also been proposed (JP-A-58-183718 and JP-A-58-19495).
No. 9).

However, the above surface treatment method cannot sufficiently improve coating film performance such as adhesion. Further, in the method of applying the primer treatment, although there are some that can obtain a coating film having excellent adhesion depending on the type of the chlorinated polyolefin and the modified polyolefin, the operation of applying the primer is complicated, and the primer treatment is often used. There are problems such as requiring time and labor, and eventually increasing the coating cost. Further, the epoxy composition described above does not have sufficient adhesion to a plastic molded product such as polyolefin. Further, the acrylic modified chlorinated polyolefin composition has an adhesiveness that depends on the amount of the chlorinated polyolefin, and it is necessary to increase the amount of the chlorinated polyolefin in order to obtain sufficient adhesiveness. Therefore, it is difficult to simultaneously improve chemical resistance (acid resistance) and gasoline resistance in addition to adhesion, and in addition to improving these performances, storage stability, weather resistance, and other performances are also improved. Is more difficult.

[0005]

SUMMARY OF THE INVENTION The invention according to claim 1 provides a resin composition suitable for a coating which is excellent in adhesion to a plastic which is difficult to coat, gasoline resistance and acid resistance. The invention described in claim 2 provides a resin composition suitable for a coating having excellent storage stability and weather resistance in addition to the effect of the invention described in claim 1. The invention described in claim 3 provides a resin composition suitable for a paint having excellent coating film appearance and water resistance, in addition to the effect of the invention described in claim 1 or 2. In addition to the effect of the invention of claim 3, the invention of claim 4 provides a resin composition suitable for a coating which is more excellent in storage stability. The invention according to claim 5 provides a coating material which is excellent in adhesion to difficult-to-paint plastics, gasoline resistance and acid resistance.

[0006]

Means for Solving the Problems The present invention includes the following (1) to
Regarding (5). (1) (A) In the presence of a chlorinated polyolefin resin having a chlorine content of 50% by weight or less, (B) (b1) general formula (I)

Embedded image (In the formula, X represents a group having a copolymerizable double bond,
Y represents a hydrolyzable group or a halogen atom, R represents an inactive monovalent organic group, m is an integer of 0 to 2,
n is an integer of 1 to 3, and the sum of m and n is 3), an unsaturated organosilane compound represented by (b2) a polymerizable monomer having a hydroxyl group, and (b3) a polymerization having a carboxyl group. Containing a vinyl-modified chlorinated polyolefin-based polymer obtained by polymerizing a polymerizable monomer mixture having an unsaturated double bond, including a polymerizable monomer and (b4) a polyester polyol having an unsaturated double bond Resin composition.

(2) The polymerizable monomer mixture having an unsaturated double bond (B) further comprises (b5) the general formula (II).

Embedded image (In the formula, R ′ represents a hydrogen atom or a methyl group, R ″ represents a divalent organic group, and k is an integer of 0 or 1), an alkyl acrylate, an acrylic acid Acid cycloalkyl ester, methacrylic acid alkyl ester, methacrylic acid cycloalkyl ester, acrylic acid aminoalkyl ester, methacrylic acid aminoalkyl ester, styrene monomer, vinyl derivative and dialkyl ester of unsaturated dibasic acid The resin composition according to (1) above, which contains at least one kind of a monomer as described above.

(3) (b4) A polyester polyol having an unsaturated double bond is a reaction product of a polyester polyol having a hydroxyl group at a terminal and a compound having a group capable of reacting with the hydroxyl group and an unsaturated double bond. The resin composition according to (1) or (2) above. (4) The resin composition according to (3), wherein the polyester polyol having a hydroxyl group at the terminal is an aliphatic polyester polyol having an alicyclic structure. (5) A coating obtained by combining the resin composition according to any one of (1) to (4) and a curing agent.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The chlorinated polyolefin resin having a chlorine content of 50% by weight or less in the present invention includes, for example, a chlorinated polyethylene resin and a chlorinated polypropylene resin having a chlorine content of 50% by weight or less. Chlorinated ethylene-propylene copolymers, chlorinated ethylene-vinyl acetate copolymers and the like can be mentioned. When the chlorine content exceeds 50% by weight, the adhesiveness of the resin composition or the coating material containing the same to the polyolefin-based substrate is deteriorated.

The chlorine content is appropriately determined in consideration of various desired coating performances, and the lower limit thereof is not particularly limited as long as the coating performance is not significantly deteriorated, but the coating performance and the polyolefin are not limited. From the viewpoint of the adhesion of the resin composition or the coating material containing the same to the base material and the balance of the polymerizability of the polymerizable monomer mixture having an unsaturated double bond which is the component (A) and the component (B), It is preferably 15 to 40% by weight, and more preferably 15 to 35% by weight.
If the chlorine content is less than 15% by weight, the polymerizability of the components (A) and (B) tends to decrease. In this specification, the chlorine content is a value measured by a combustion method.

The polymerizable monomer mixture having an unsaturated double bond (B) in the present invention contains the components (b1), (b2), (b3) and (b4) as essential components. Is. The component (b1) has the general formula (I)

Embedded image (In the formula, X represents a group having a copolymerizable double bond,
Y represents a hydrolyzable group or a halogen atom; R represents an inert organic group; m is an integer of 0 to 2;
-3, and the sum of m and n is 3).

In the general formula (I), the group having a copolymerizable double bond of X is, for example, an alkenyl group,
Examples thereof include a cycloalkenyl group, an unsaturated acyloxyalkyl group, an unsaturated acyloxyalkoxy group and a group represented by the following chemical formula 6.

[Chemical 6]

Examples of the alkenyl group include groups having 2 to 6 carbon atoms such as vinyl group, allyl group and butenyl group. Examples of the cycloalkenyl group include cyclohexenyl group, cyclopentadienyl group and cyclohexyl group. Examples thereof include a group having 3 to 18 carbon atoms such as a sadienyl group, and examples of the unsaturated acyloxyalkyl group include a group having 3 to 10 carbon atoms such as a γ-methacryloxypropyl group. The alkoxy group is, for example, a γ-methacryloxyethylpropyl ether group or the like having 3 to 3 carbon atoms.
Ten groups are included. Among these groups, from the viewpoint of adhesiveness, the number of carbon atoms such as γ-methacryloxypropyl group is 3 to
An unsaturated acyloxyalkoxy group having 3 to 10 carbon atoms such as an unsaturated acyloxyalkyl group having 10 and a γ-methacryloxyethylpropyl ether group is preferable.

In the general formula (I), the hydrolyzable group of Y includes, for example, a group which is hydrolyzed to form a hydroxyl group, and the halogen atom includes fluorine, chlorine and
Examples include bromine and iodine. Examples of the group that forms a hydroxyl group by hydrolysis include an alkoxy group, an acyloxy group, an oximo group, an alkylamino group, and an arylamino group.

Among these groups or halogen atoms, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 1 to 6 carbon atoms, and a carbon number of 1 from the viewpoint of adhesion and compatibility with a chlorinated polyolefin resin. An oximo group having 14 to 1 carbon atoms
An alkylamino group having 6, an arylamino group having 3 to 10 carbon atoms and chlorine are preferred. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group and butoxy group, and examples of the acyloxy group having 1 to 6 carbon atoms include formyloxy group, acetoxy group, propyleneoxy group and the like. Examples of the oximo group having 1 to 14 carbon atoms include groups represented by the following chemical formula 7,

Embedded image Examples of the alkylamino group having 1 to 6 carbon atoms or the arylamino group having 3 to 10 carbon atoms include a group represented by the following chemical formula 8 and the like.

Embedded image In the general formula (I), when n is 2 or 3, a plurality of Y
May be the same or different.

In the general formula (I), the inert monovalent organic group for R is, for example, an alkyl group, an aryl group,
And monovalent hydrocarbon groups such as aralkyl groups. Examples of the alkyl group include an alkyl group having 1 to 18 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a tetradecyl group, and an octadecyl group. . Examples of the aryl group include an aryl group having 3 to 18 carbon atoms, and examples of such an aryl group include a phenyl group and a tolyl group. The aralkyl group includes, for example, an aralkyl group having 7 to 18 carbon atoms, and the aralkyl group includes, for example, a benzyl group.

Specific examples of the unsaturated organosilane compound represented by the general formula (I) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane and vinyltri (2-
Methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltri (2-methoxyethoxy) silane, γ- Acryloxypropyltrimethoxysilane, vinyltrichlorosilane, γ-methacryloxylaurylpropoxydimethoxysilane, γ-methacryloxyhexyltriethoxysilane, vinyldimethylmethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-acryloxyethylmethoxyethoxy Butoxysilane, γ-acryloxyoctylbutoxymethoxysilane, γ-acryloxybutylmethoxydibutoxysilane and the like.

In the general formula (I), the hydrolyzable group or halogen atom represented by Y reacts with water in the raw material or polymerization solvent used, and undergoes hydrolysis or substitution reaction to have a hydroxyl group or the like. It is considered that the functional groups such as hydroxyl groups undergo a crosslinking reaction during the polymerization reaction or when the coating material is dried. Among the components (b1), γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane are preferable from the viewpoint of adhesion, and γ-methacryloxypropyltrimethoxysilane is more preferable. The component (b1) is used alone or in combination of two or more.

The component (b2) is a polymerizable monomer having a hydroxyl group, such as hydroxyalkyl acrylate,
Examples thereof include hydroxyalkyl methacrylate and lactone-modified products thereof. Examples of hydroxyalkyl acrylates include hydroxyalkyl acrylates having an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate. Can be mentioned. Examples of the hydroxyalkyl methacrylate include hydroxyalkyl methacrylate having an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. Can be mentioned. Further, specific examples of the lactone-modified product of the hydroxyalkyl acrylate and hydroxyalkyl methacrylate include lactone-modified 2-hydroxyethyl acrylate and lactone-modified 2-hydroxyethyl methacrylate. Among these compounds, 2-hydroxyethyl methacrylate is preferable from the viewpoint of adhesion. The component (b2) is used alone or in combination of two or more.

The component (b3) is a polymerizable monomer having a carboxyl group, and the carboxyl group may be contained as an acid anhydride group. Examples of the component (b3) include unsaturated acids, unsaturated dibasic acids, and acid anhydrides thereof. Examples of the unsaturated acid include acrylic acid and methacrylic acid, and examples of the unsaturated dibasic acid include maleic acid and phthalic acid, and examples of the acid anhydride include maleic anhydride. And phthalic anhydride. The component (b3) is used alone or in combination of two or more.

The component (b4) is a polyester polyol having an unsaturated double bond. For example, a reaction between a polyester polyol having a hydroxyl group at the terminal and a compound having a group capable of reacting with this hydroxyl group and an unsaturated double bond. Products. The polyester polyol having a hydroxyl group at the terminal is obtained, for example, by subjecting an aliphatic or alicyclic polybasic acid component having two or more bases to an aliphatic or alicyclic dihydric or more polyhydric alcohol component for condensation reaction. Examples thereof include polyester polyols. Examples of the polybasic acid component include adipic acid, azelaic acid, sebacic acid,
Examples thereof include dodecanedioic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, methylhexahydrophthalic acid and their anhydrides. Examples of the polyhydric alcohol component include ethylene glycol, diethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, and cyclohexanedimethanol.

When the aliphatic or alicyclic polybasic acid component having two or more bases and the aliphatic or alicyclic dihydric or more polyhydric alcohol component are subjected to a condensation reaction, the mixing ratio of both components is such that the resulting polyester polyol is obtained. There is no particular limitation so long as it has a hydroxyl group at the terminal. Among the polyester polyols having a hydroxyl group at the terminal, an aliphatic polyester polyol having an alicyclic structure is preferable, and a linear one is more preferable, from the viewpoint of excellent storage stability of the resulting coating, and a branched structure and an aromatic Those having no ring structure are more preferable. Further, from the viewpoint that the resulting coating composition gives good coating properties, the number average molecular weight of the polyester polyol having a hydroxyl group at the terminal is preferably 100 to 500, more preferably 150 to 400, and
It is more preferable to set it to 0 to 350.

Examples of the group capable of reacting with the hydroxyl group include an isocyanate group and a carboxyl group. Examples of the compound having an isocyanate group and an unsaturated double bond include a reaction product of a divalent or higher polyvalent isocyanate compound and a polymerizable monomer having a hydroxyl group, a polymerizable monomer having an isocyanate group, and the like. Is mentioned. Examples of the divalent or higher polyvalent isocyanate compound include diisocyanate compounds having isocyanate groups having different reactivity, and specific examples thereof include 2,2,4-
Examples include trimethylhexamethylene diisocyanate and tetramethylxylylene diisocyanate. Examples of the polymerizable monomer having a hydroxyl group include the above-mentioned (b
2) The compounds exemplified as the component are included.

As the polymerizable monomer having an isocyanate group, for example, isocyanate alkyl acrylate,
Examples of the isocyanate alkyl methacrylate and the like, as the isocyanate alkyl acrylate, for example, isocyanatomethyl acrylate, isocyanatoethyl acrylate, isocyanate butyl acrylate, and the like, and as the isocyanate alkyl methacrylate,
Examples thereof include isocyanatomethyl methacrylate, isocyanatoethyl methacrylate, and isocyanatobutyl methacrylate. In addition, examples of the compound having a carboxyl group and an unsaturated double bond include acrylic acid and methacrylic acid.

The polyester polyol having a hydroxyl group at the terminal and the compound having a group capable of reacting with the hydroxyl group and an unsaturated double bond are used as the hydroxyl group of the polyester polyol from the viewpoint of stability during polymerization, adhesion and solvent resistance. The ratio of the number of moles of the above to the number of moles of the group capable of reacting with the hydroxyl group is preferably such that the former / the latter is 0.05 / 1 to 0.7 / 1, and 0.2 / 1 to 0 It is more preferable to mix them in a ratio of 0.5 / 1. The said (b4) component is used individually or in combination of 2 or more types.

The component (B) in the present invention improves the compatibility of the polymerizable monomer mixture and the chlorinated polyolefin resin during the synthesis of the vinyl-modified chlorinated polyolefin polymer, and the resin thus obtained. It is preferable that the composition contains the component (b5) in addition to the components (b1) to (b4) since the composition has excellent storage stability and the resulting coating composition has excellent weather resistance.

The component (b5) has the general formula (II)

Embedded image (In the formula, R ′ represents a hydrogen atom or a methyl group, R ″ represents a divalent organic group, and k is an integer of 0 or 1), an alkyl acrylate, an acrylic acid Acid cycloalkyl ester, methacrylic acid alkyl ester, methacrylic acid cycloalkyl ester, acrylic acid aminoalkyl ester, methacrylic acid aminoalkyl ester, styrene monomer, vinyl derivative and dialkyl ester of unsaturated dibasic acid Is at least one type of monomer.

In the general formula (II), the carbon number of the divalent organic group of R ″ is preferably 1 to 18 and more preferably 2 to 12 from the viewpoint of the balance between adhesion and storage stability. It is more preferable, and it is even more preferable to set it to 2 to 4.
Such a divalent organic group has, for example, 1 to 1 carbon atoms.
An alkylene group having 18 carbon atoms, a group having 4 to 18 carbon atoms, represented by the general formula (III)

Embedded image (In the formula, Z and Z'independently represent an alkylene group having 2 or more carbon atoms, and j is a repeating number and is an integer of 1 or more) and the like. Examples of the alkylene group having 1 to 18 carbon atoms include a methylene group and an ethylene group.

Specific examples of the monomer represented by the general formula (II) include, for example, tricyclodecyloxyalkyl acrylate, tricyclodecyloxyalkyl methacrylate, polyalkylene glycol tricyclodecyl monoether acrylate and polyacrylate. Methacrylate of alkylene glycol tricyclodecyl monoether and the like can be mentioned.

Examples of tricyclodecyloxyalkyl acrylate include, for example, tricyclodecyl acrylate,
Examples thereof include tricyclodecyloxyethyl acrylate and tricyclodecyloxypropyl acrylate, and examples of the tricyclodecyloxyalkyl methacrylate include tricyclodecyl methacrylate, tricyclodecyloxyethyl methacrylate, tricyclodecyloxypropyl methacrylate and the like. As the acrylate of polyalkylene glycol tricyclodecyl monoether, for example, acrylate of diethylene glycol tricyclodecyl monoether and the like, and as the methacrylate of polyalkylene glycol tricyclodecyl monoether, for example, diethylene glycol tricyclo Examples include decyl monoether methacrylate.

Examples of the alkyl acrylate include alkyl acrylates having an alkyl group having 1 to 20 carbon atoms, and specific examples thereof include methyl acrylate, ethyl acrylate, butyl acrylate, and the like. Examples thereof include isobutyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate. Examples of the acrylic acid cycloalkyl ester include an acrylic acid cycloalkyl ester whose cycloalkyl group has 3 to 20 carbon atoms, and specific examples thereof include cyclohexyl acrylate. Examples of the alkyl methacrylate include alkyl methacrylates having 1 to 20 carbon atoms in the alkyl group. Specific examples thereof include, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and isobutyl methacrylate. , 2-ethylhexyl methacrylate, lauryl methacrylate and the like. Examples of the cycloalkyl methacrylate include cycloalkyl methacrylates having a cycloalkyl group having 3 to 20 carbon atoms, and specific examples thereof include cyclohexyl methacrylate. Examples of the aminoalkyl acrylate include aminoalkyl acrylates having 1 to 20 carbon atoms in the alkyl group. Specific examples thereof include, for example, aminomethyl acrylate, N-methylaminomethyl acrylate, N, N-diethylaminoethyl acrylate is exemplified. Examples of the aminoalkyl methacrylate include aminoalkyl methacrylates having 1 to 20 carbon atoms in the alkyl group, and specific examples thereof include, for example, aminomethyl methacrylate, N-methylaminomethyl methacrylate, N, N-diethylaminoethyl methacrylate is exemplified. Examples of the styrene-based monomer include styrene, vinyltoluene, α-methylstyrene, and the like. Examples of the vinyl derivative include vinyl chloride, vinylidene chloride, vinyl acetate, isopropenyl acetate, glycidyl methacrylate, glycidyl acrylate, methacrylamide, acrylamide, and the like. Examples of the dialkyl ester of an unsaturated dibasic acid include dimethyl maleate, diethyl maleate, dimethyl phthalate, diethyl phthalate, and the like.

Among the above-mentioned components (b5), the monomer represented by the general formula (II) is preferable because of excellent coating properties such as adhesion, alcohol resistance, and vinyl chloride plasticizer migration resistance. body,
It is preferable to use at least one polymerizable monomer selected from alkyl acrylate, cycloalkyl acrylate, alkyl methacrylate and cycloalkyl methacrylate.

The component (B) in the present invention is the above (b)
In addition to the components 1) to (b4) or the components (b1) to (b5), other polymerizable monomer may be contained. Examples of the other polymerizable monomer include monomers having two or more unsaturated double bonds, and examples thereof include divinylbenzene, ethylene glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol. Diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, etc. Can be mentioned.

In the resin composition of the present invention, the blending amount of the component (A) is from the viewpoint of the balance of weather resistance, gasoline resistance, storage stability and adhesion to a polyolefin substrate.
3 for 100 parts by weight of the total of the components (A) and (B)
˜20 parts by weight, preferably 5 to 15 parts by weight, more preferably 5 to 10 parts by weight. If the amount is less than 3 parts by weight,
The adhesiveness of the obtained resin composition and the coating material containing the same to the polyolefin substrate tends to decrease, and when it exceeds 20 parts by weight, the weather resistance, gasoline resistance and storage of the obtained resin composition and the coating material containing the same are improved. Stability tends to decrease.

On the other hand, the blending amount of the component (B) is 100 weight% of the total amount of the component (A) and the component (B) from the viewpoint of the balance of weather resistance, gasoline resistance, storage stability and adhesion to the polyolefin base material. The amount is preferably 80 to 97 parts by weight, more preferably 85 to 95 parts by weight, and even more preferably 90 to 95 parts by weight.
If the compounding amount is less than 80 parts by weight, the weather resistance, gasoline resistance and storage stability of the resulting resin composition and the coating composition containing the resin composition tend to decrease, and if it exceeds 97 parts by weight, the resin obtained is increased. Composition The adhesion of a coating material containing the composition to a polyolefin substrate tends to decrease.

The blending amount of the component (b1) in the component (B) is a balance between the adhesiveness and storage stability of the resulting resin composition and the coating composition containing the same, and the suppression of gelation of the resulting polymer. Therefore, it is preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the total amount of the component (B), and 0.3 to 2
More preferably, the amount is more preferably 0.3 to 1.5 parts by weight. If the amount is less than 0.1 part by weight, the adhesiveness and storage stability of the resulting resin composition and the coating material containing the resin composition tend to decrease.
If the amount is more than parts by weight, the hydrolyzable group is hydrolyzed during the polymerization to cause a crosslinking reaction, and the resulting polymer tends to gel during the polymerization. The blending amount of the component (b2) in the component (B) is 1 to 2 with respect to 100 parts by weight of the total amount of the component (B) from the viewpoint of balance between gasoline resistance, weather resistance and adhesion.
It is preferably 5 parts by weight, more preferably 3 to 20 parts by weight, still more preferably 3 to 10 parts by weight. If the amount is less than 1 part by weight, the gasoline resistance and weather resistance tend to be poor, and if it exceeds 25 parts by weight, the adhesion tends to be poor.

The blending amount of the component (b3) in the component (B) is 0.1 with respect to 100 parts by weight of the total amount of the component (B) from the viewpoint of balance between gasoline resistance, storage stability and adhesion.
It is preferably 1 to 4 parts by weight, more preferably 0.5 to 3 parts by weight, and even more preferably 0.5 to 2 parts by weight. If the amount is less than 0.1 part by weight, gasoline resistance tends to be poor, and if it exceeds 4 parts by weight, storage stability and adhesion tend to be inferior.
The blending amount of the component (b4) in the component (B) is (B)
When the component (b5) is not contained as a component, from the viewpoint of the hardness of the resulting coating film, the adhesion of the coating film and the balance of the appearance, 68 to 9 relative to 100 parts by weight of the total amount of the component (B).
It is preferably 8.8 parts by weight. This compounding quantity is 68
If it is less than parts by weight, the adhesion and appearance of the resulting coating film will tend to be poor, and if it exceeds 98.8 parts by weight, the hardness of the resulting coating film will tend to be reduced.

On the other hand, when the component (b5) is contained as the component (B), the blending amount of the component (b4) is from the viewpoint of the hardness of the obtained coating film, the adhesion of the coating film and the balance of the appearance. , (B) is preferably 5 to 30 parts by weight, more preferably 5 to 20 parts by weight, and further preferably 5 to 10 parts by weight, relative to 100 parts by weight. If the amount is less than 5 parts by weight, the adhesion and appearance of the resulting coating film tend to be poor, and if it exceeds 30 parts by weight, the hardness of the resulting coating film tends to decrease.

When the component (b5) is added to the component (B), the amount of the component (b5) to be blended is 1 from the viewpoint of the balance of storage stability, weather resistance and adhesion.
It is preferably 38 to 93.8 parts by weight, more preferably 40 to 90 parts by weight, and further preferably 50 to 80 parts by weight, relative to 00 parts by weight. If the amount is less than 38 parts by weight, the storage stability and weather resistance tend to be poor, and if it exceeds 93.8 parts by weight, the adhesion tends to be poor.

As a method for polymerizing the polymerizable monomer mixture in the presence of the chlorinated polyolefin resin, a general radical polymerization method can be used, and the method is not particularly limited. In the radical polymerization method, as the organic solvent, for example, an aromatic solvent, a ketone solvent, an ester solvent, a chlorine solvent, or the like can be used. As the aromatic solvent, for example, toluene,
Xylene and the like, as ketone solvents, for example, methyl ethyl ketone, methyl isobutyl ketone, and the like, as ester solvents, for example, ethyl acetate, butyl acetate and the like, as a chlorine-based solvent, for example, And carbon tetrachloride.

In the radical polymerization method, as the polymerization initiator, for example, an organic peroxide, an azobis compound or the like can be used. Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, dibutyl peroxide and the like, and examples of the azobis compound include 2,2′-azobisisobutyronitrile and azobisvaleronitrile. Etc. In the polymerization, each of the polymerizable monomers may be added to the reaction system after being mixed beforehand, or may be added separately to the reaction system, and the mixture may be divided into reaction systems. You may add.

As described above, the vinyl-modified chlorinated polyolefin polymer can be obtained by polymerizing the polymerizable monomer mixture in the presence of the chlorinated polyolefin resin. The obtained vinyl-modified chlorinated polyolefin polymer can be dissolved in an organic solvent to form a resin composition. As the organic solvent, for example, those described above can be used. This resin composition can be used, for example, in the production of paint.

The coating composition of the present invention is a combination of the resin composition and a curing agent. Examples of the curing agent include amino resins, polyisocyanates, blocked polyisocyanates, and the like. Examples of the amino resin include compounds obtained by addition condensation of an amino compound and an aldehyde, and etherified amino resins obtained by reacting these compounds with a lower alcohol. Examples of the amino compound include benzoguanamine, urea, and melamine. Examples of the aldehyde include formaldehyde and acetaldehyde. Examples of the lower alcohol include methanol, butanol, isobutanol and the like.

Specific examples of the amino resin include, for example, n
-Butyl etherified melamine resin, isobutyl etherified melamine resin, methyl etherified melamine resin and the like. Among the above amino resins, it is preferable to use an n-butyl etherified melamine resin or an isobutyl etherified melamine resin because the paint can be baked at a relatively low temperature. The amino resins are used alone or in combination of two or more.

Examples of the polyisocyanate include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, xylylene diisocyanate, a burette formed from 3 mol of hexamethylene diisocyanate and 1 mol of water, and isophorone diisocyanate containing an isocyanurate ring. Body, a compound having two or more isocyanate groups remaining produced by the reaction of these isocyanates with a polyhydric alcohol, and the like. Examples of the polyhydric alcohol include propanediol, hexanediol, polyethylene glycol, trimethylolpropane, and pentaerythritol. Examples of the blocked polyisocyanate include compounds obtained by blocking the polyisocyanate with phenol, ethyl acetoacetate, cyclohexanol, ε-caprolactam, acetoxime, diisobutylketoxime, and the like.

These curing agents are used alone or in combination of two or more kinds. When using the amino resin alone as a curing agent, the compounding amount of the amino resin,
The amino resin is used in an amount of 15 to 40 parts by weight per 100 parts by weight of the total of the components (A) and (B), though it is appropriately selected depending on the properties required for the coating composition. When the polyisocyanate is used alone as a curing agent, the equivalent ratio (OH / NCO) of the hydroxyl groups of the vinyl-modified chlorinated polyolefin polymer to the isocyanate groups of the polyisocyanate is 1 from the viewpoint of the adhesion of the coating material to the substrate.
The polyisocyanate is preferably used in a ratio of /0.5 to 1 / 1.5, and more preferably in a ratio of 1/1.

When the blocked polyisocyanate is used alone as the curing agent, the equivalent ratio of the hydroxyl group of the vinyl-modified chlorinated polyolefin polymer to the isocyanate group of the blocked polyisocyanate is taken into consideration from the viewpoint of the adhesion of the coating material to the substrate. (OH / NCO) is 1 / 0.5-1 /
The blocked polyisocyanate is preferably used in a ratio of 1.5, and more preferably 1/1. When the amino resin and the blocked polyisocyanate are used in combination as a curing agent, the component (A) and the component (B) are used in view of the adhesion of the coating material to the substrate.
15 parts by weight of the amino resin is added to 100 parts by weight of the total components.
It is preferable to use ˜40 parts by weight and 1 to 20 parts by weight of the blocked polyisocyanate.

The coating material of the present invention may contain an inorganic pigment, an organic pigment or the like, if necessary. Examples of the inorganic pigment include titanium white and carbon black, and examples of the organic pigment include a phthalocyanine pigment and an azo pigment. As a method for incorporating these inorganic pigments, organic pigments and the like, for example, a usual pigment dispersion method can be used. Further, the paint of the present invention, if necessary, various additives, for example, aluminum paste, plasticizer, resin for strengthening the coating film, dispersant, coating surface adjuster, ultraviolet absorber, ultraviolet stabilizer, antioxidant, It may contain a crosslinking reaction accelerator or the like.

The coating composition of the present invention can be applied for coating according to a usual coating method. When painting, for example,
An air spray machine, an airless spray machine, an electrostatic coating machine, a dipping, a roll coating machine, a brush, etc. can be used. The coating material of the present invention can be used for directly coating a polyolefin base material in a polyolefin-based molded product, sheet, film or the like, and can be used as a top clear, enamel coating, metallic coating, primer or the like.

In the coating material of the present invention, when at least one of amino resin and blocked polyisocyanate is used as a curing agent, it is necessary to heat after coating to crosslink and cure the coating film. The heating conditions are appropriately selected in consideration of the thermal deformation temperature of the substrate and the like.
It is preferable to cure by heating for 00 minutes. When a polyisocyanate is used as a curing agent, a sufficiently cured coating film can be obtained at room temperature, but the coating film can be quickly cured by heating. The heating conditions are appropriately selected in consideration of the thermal deformation temperature of the substrate and the like, but from the viewpoint of the balance between the curability of the coating film and the heat resistance of the substrate, 50 to 100
It is preferable to cure by heating at a temperature of 1 ° C. for 1 to 60 minutes.

[0051]

The present invention will be described below with reference to examples. In addition, part and% show a weight part and weight%, respectively. Production Examples 1 to 4 In a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, the compounding ratios shown in Table 1 were used, and the total was 11
Chlorinated polypropylene resin, polyester polyol and toluene were charged to 0 parts by weight and heated to 80 ° C. Subsequently, α-methacryloyloxyether isocyanate having a blending ratio shown in Table 1 was mixed with toluene so that the total amount was 20 parts by weight, and this mixed solution was dropped into the four-necked flask over 30 minutes, and 110 Heated to ° C. Then, the blending ratios (b1) to (b
A mixture was prepared by uniformly dissolving 3) and (b5) components and 1 part by weight of 2,2'-azobisisobutyronitrile, and the mixture was added dropwise to the four-neck flask over 2 hours while keeping the same temperature. The temperature was kept at the same temperature for 1 hour. Furthermore, toluene 1
5,2 parts of 2,2'-azobisisobutyronitrile was added to 5 parts by weight.
A mixture in which 2 parts by weight was uniformly dissolved was prepared, and the mixture was added dropwise to the four-necked flask over 1 hour while keeping the same temperature.
Then, the temperature was kept at the same temperature for 2 hours. Then, the four-necked flask was left to stand and cooled to room temperature, and toluene was added so that the heating residue of the reaction product was 40% by weight, and the resin compositions (R-1) to (R-4) were added. Obtained.

The resulting resin compositions (R-1) to (R-
4) was allowed to stand at 50 ° C. or 5 ° C. for 10 days, and the storage stability of the resin composition was examined. As shown in Table 1, all the resin compositions are good without any change while maintaining a uniform solution state, and the resin compositions (R-1) to (R-4) have good storage stability. Was excellent.

[0053]

[Table 1]

Production Examples 5 to 8 Resin compositions (R-R) were prepared according to the methods described in Production Examples 1 to 4 except that the components were blended in the proportions shown in Table 2.
5)-(R-8) were obtained. The obtained resin composition (R-
Regarding 5) to (R-8), the storage stability was examined in the same manner as in Production Examples 1 to 4 above. As shown in Table 2, in each of the resin compositions (R-5) and (R-6), unreacted chlorinated polyolefin resin is precipitated in the solution to form particles, and the resin composition (R-5) and (R-6) were inferior in storage stability. Further, as shown in Table 2, in both the resin compositions (R-7) and (R-8), the resin gelled during the synthesis of the resin composition, and the storage stability could not be examined. It was

[0055]

[Table 2]

Examples 1 to 16 and Comparative Examples 1 to 8 Resin compositions (R-1) obtained in the above Production Examples 1 to 4
Using (R-4), the other components were blended in the blending ratios shown in Tables 3 and 4, and each component was dispersed according to a conventional method to obtain a coating material. Thinner (toluene / xylene / methyl isobutyl ketone / butyl cellosolve 10/50/20 /
The resulting coating composition was diluted with Ford cup # 4 at 15 seconds / 20 ° C. to obtain a polypropylene film having no surface treatment and a dry film thickness of 30. Spray coating was performed so as to have a thickness of ˜35 μm, the mixture was allowed to stand at room temperature for 10 minutes, and then baked and dried to obtain a coated plate. Here, the baking conditions when the amino resin or the blocked polyisocyanate are used alone or in combination as the curing agent are 120 ° C. and 30 minutes, and the baking conditions when the polyisocyanate is used alone are 80 ° C. , 30 minutes.

Similarly, the resin compositions (R-5) and (R-6) obtained in the above Production Examples 5 to 8 were mixed with other components at the compounding ratio shown in Table 5 to prepare coating compositions. A coated plate was prepared.

[0058]

[Table 3]

[0059]

[Table 4]

[0060]

[Table 5]

Evaluation The coated plate obtained was measured according to the following method for glossiness, adhesion (initial adhesion), acid resistance, gasoline resistance, water resistance (appearance of coating film and adhesion after hot water treatment) and weather resistance. Was examined, and the evaluation results are shown in Tables 6, 7, and 8.

Glossiness According to JIS K-5400, the glossiness was determined by measuring the reflectance at a reflection angle of 60 °.

Adhesion (Initial Adhesion) According to JIS K-5400, an eyelet test method. Draw 10 lines each on the coating film with a knife at 2mm intervals, 10 lines each
Zero gobangs were formed, a cellophane tape was adhered thereon, the tape was peeled off, and the number of gobangs remaining on the coating film was measured and evaluated according to the following criteria. 100/100: Good adhesion 51-99 / 100: Adhesion is slightly inferior 50/100 or less: Adhesion is significantly inferior

An acid resistant 10% sulfuric acid aqueous solution was dropped on the coating film, the coated plate was heated to 60 ° C., left to stand for 40 minutes to be naturally cooled, and the coating film surface was observed and evaluated according to the following criteria. ○: No trace △: Slight trace ×: Trace

Gasoline resistance Gauze is impregnated with commercially available gasoline, and the surface of the coating film is strongly
After rubbing 0 times, the coating film surface was observed and evaluated according to the following criteria. ◯: Poor adhesion and no loss of gloss of coating surface Δ: Poor adhesion and almost no loss of gloss of coating surface ×: Poor adhesion and conspicuous coating surface

Water resistance (Appearance of coating film and adhesion after hot water treatment) The coated plate was immersed in warm water at 40 ° C for 240 hours, washed with water, and the appearance of the coating film was observed and evaluated according to the following criteria. on the other hand,
With respect to this coating film, the adhesion was evaluated according to the evaluation method of the initial adhesion. ◯: No change Δ: Slight gloss disappeared ×: Blister (blister) occurred

Weather resistance Sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd., W
EL-SUN-HCH type) was used, and the results are shown by the gloss retention rate (%) of the coating film surface after 1000 hours.

[0068]

[Table 6]

[0069]

[Table 7]

[0070]

[Table 8]

According to Table 8, the evaluation results in the column of gasoline resistance of the paints obtained in Comparative Examples 1 to 8 are x (poor adhesion and conspicuous coating film surface), and the water resistance The evaluation result in the column of coating appearance is also × (blisters occur), and the evaluation result in the column of adhesion after water-resistant hot water treatment is 0/100 or 20/100 (adhesion is The paints obtained in Comparative Examples 1 to 8 were inferior in gasoline resistance and water resistance (appearance of coating film and adhesion after hot water treatment). On the other hand, according to Tables 6 and 7, the evaluation results in the column of gasoline resistance of the paints obtained in Examples 1 to 16 are ◯ (no adhesion failure and no gloss on the coating surface). In addition, the evaluation result in the column of water-resistant coating appearance is also ○ (no change at all), and the evaluation result in the column of adhesion after water-resistant hot water treatment is 100/100 (adhesion The paints obtained in Examples 1 to 16 were excellent in gasoline resistance and water resistance (coating appearance and adhesion after hot water treatment).

Further, according to Tables 6 and 7, Examples 1 to
16, the glossiness of the paint obtained, the adhesiveness (initial adhesiveness),
The evaluation results in the columns of acid resistance and weather resistance are 90 or more, 100/100 (good adhesion), ○ (no trace) and 89, respectively.
As described above, the coating materials obtained in Examples 1 to 16 are
It was also excellent in glossiness, adhesion (initial adhesion), acid resistance and weather resistance. As described above, the resin composition of the present invention is excellent in storage stability, and the coating composition of the present invention has glossiness, adhesiveness (initial adhesion), acid resistance, gasoline resistance, water resistance (coating appearance). And adhesion after hot water treatment) and weather resistance.

[0073]

EFFECT OF THE INVENTION The resin composition according to the first aspect is suitable for a coating having excellent adhesion to a plastic which is difficult to coat, gasoline resistance and acid resistance. The resin composition according to claim 2,
The resin composition according to the first aspect of the present invention is suitable for a coating material that exhibits the effects and is excellent in storage stability and weather resistance. Claim 3
The resin composition described above exhibits the effects of the resin composition according to claim 1 or 2, and is suitable for a coating material having excellent coating film appearance and water resistance. The resin composition according to the fourth aspect exhibits the effects of the resin composition according to the third aspect, and is suitable for a coating material which is more excellent in storage stability. The coating composition according to claim 5 is excellent in adhesion to a difficult-to-paint plastic, gasoline resistance and acid resistance.

Claims (5)

[Claims] (A) In the presence of a chlorinated polyolefin resin having a chlorine content of 50% by weight or less, (B) (b1) a compound of the general formula (I) (In the formula, X represents a group having a copolymerizable double bond,
Y represents a hydrolyzable group or a halogen atom, R represents an inactive monovalent organic group, m is an integer of 0 to 2,
n is an integer of 1 to 3, and the sum of m and n is 3), an unsaturated organosilane compound represented by (b2) a polymerizable monomer having a hydroxyl group, and (b3) a polymerization having a carboxyl group. Containing a vinyl-modified chlorinated polyolefin-based polymer obtained by polymerizing a polymerizable monomer mixture having an unsaturated double bond, including a polymerizable monomer and (b4) a polyester polyol having an unsaturated double bond Resin composition. 2. The polymerizable monomer mixture having an unsaturated double bond (B) further comprises (b5) the general formula (II): (In the formula, R ′ represents a hydrogen atom or a methyl group, R ″ represents a divalent organic group, and k is an integer of 0 or 1), an alkyl acrylate, an acrylic acid Acid cycloalkyl ester, methacrylic acid alkyl ester, methacrylic acid cycloalkyl ester, acrylic acid aminoalkyl ester, methacrylic acid aminoalkyl ester, styrene monomer, vinyl derivative and dialkyl ester of unsaturated dibasic acid 1. At least one kind of monomer to be contained is contained.
The resin composition as described in the above. 3. The (b4) polyester polyol having an unsaturated double bond is a reaction product of a polyester polyol having a hydroxyl group at a terminal and a compound having a group capable of reacting with the hydroxyl group and an unsaturated double bond. The resin composition according to claim 1 or 2. 4. The resin composition according to claim 3, wherein the polyester polyol having a hydroxyl group at the terminal is an aliphatic polyester polyol having an alicyclic structure. 5. A paint comprising the resin composition according to claim 1 and a curing agent in combination.