JP3378101B2 - Low solvent type resin composition, coating composition using the same, and coating method thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a low solvent type resin composition,
The present invention relates to a low-solvent type coating composition containing such a low-solvent type resin composition as a binder, and a coating method for the low-solvent type coating composition. In particular, the present invention is a low-solvent resin composition having excellent coating film properties such as scratch resistance, gasoline resistance, and acid resistance, and capable of controlling the amount of the coatable organic solvent at 25 ° C. to 0 to 30%. The present invention relates to a product, a low-solvent coating composition using the same, and a method for coating the low-solvent coating composition.

[0002]

2. Description of the Related Art In recent years, in paints using an organic solvent, strict restrictions are imposed on the release of the organic solvent in order to prevent the environment from being polluted by vaporization of the organic solvent constituting the paint. It is in. For this reason, water-based paints that do not use or practically do not use organic solvents,
Although powder coatings, UV-curable coatings, etc. have been widely studied, satisfactory coatings have not been obtained. On the other hand, in an organic solvent type coating composition, a method for further reducing the solvent has been earnestly studied. For example, as disclosed in JP-A-58-108259, an alkoxymelamine resin,
A polyol and an oligomer having a specific hydroxyl value,
A high solids coating composition configured to increase the solid resin content at the time of coating and reduce the amount of organic solvent by lowering the molecular weight by blending an acidic catalyst with a specific ratio has been proposed. . However, when lowering the molecular weight, the amount of hydroxyl groups has to be increased in order to compensate for insufficient curing, and since the polarity of hydroxyl groups is large, it has not always been possible to achieve low viscosity. Further, when a resin having a high hydroxyl value is cured with melamine, there has been a problem that the coating film performance such as acid resistance of the coating film is extremely lowered.

[0003]

Therefore, the present invention has excellent coating film characteristics such as scratch resistance, gasoline resistance, and acid resistance, and the amount of the organic solvent which can be coated at 25 ° C. is 0. To provide a low solvent type resin composition which can be reduced to -30%, a low solvent type coating composition containing such a low solvent type resin composition as a binder, and a method for coating such a low solvent type coating composition. To aim.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventor has (1) hydroxyl group, blocked hydroxyl group, blocked carboxyl group, blocked phosphate group and acid anhydride It contains a first functional group selected from the group consisting of groups as an essential functional group and has a number average molecular weight of 6
00-1500, weight average molecular weight 600-3000,
And a vinyl polymerized oligomer having a weight average molecular weight / number average molecular weight ratio of 1.0 to 2.0 and a total functional group amount of 2.5 to 5.0 mol / kg resin, and a second functional group comprising (2) a vinyl (thio) ether group. Contains a plurality of groups as essential functional groups,
Number average molecular weight is 400 to 1500, weight average molecular weight is 4
And a vinyl (thio) ether group-containing compound having a weight average molecular weight / number average molecular weight ratio of 1.0 to 2.0 and a total functional group amount of 2.5 to 10.0 mol / kg resin. The inventors have found that the above object can be achieved and arrived at the present invention. That is, the present invention is
The present invention relates to the following inventions. 1. (1) It contains a first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group, a blocked carboxyl group, a blocked phosphate group and an acid anhydride group as an essential functional group, and has a number average molecular weight of 600 to 1500. A vinyl polymerized oligomer having a weight average molecular weight of 600 to 3000, a weight average molecular weight / number average molecular weight ratio of 1 to 2 and a total functional group amount of 2.5 to 5.0 mol / kg resin, and (2) vinyl ( A plurality of second functional groups consisting of thio) ether groups as essential functional groups, having a number average molecular weight of 400 to 1500, a weight average molecular weight of 400 to 3000, and a weight average molecular weight / number average molecular weight ratio of 1.0 to 2 A vinyl (thio) ether group-containing compound having a total amount of functional groups of 2.5 to 10.0 mol / kg resin and a coatable organic solvent amount at 25 ° C. of 0 to 30% by weight. Low-solvent type resin composition which is characterized by certain. 2. (1) It contains a first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group, a blocked carboxyl group, a blocked phosphate group and an acid anhydride group as an essential functional group, and has a number average molecular weight of 600 to 1500. , The weight average molecular weight is 600 to 3000, and the weight average molecular weight / number average molecular weight ratio is 1.0 to 2.0, and the total functional group amount is 2.5 to 5.0.
A vinyl polymerized oligomer that is a mol / kg resin and (2) a plurality of second functional groups consisting of vinyl (thio) ether groups are contained as essential functional groups and have a number average molecular weight of 400 to 150.
Vinyl (thio) having a weight average molecular weight of 400 to 3000, a weight average molecular weight / number average molecular weight ratio of 1.0 to 2.0, and a total functional group amount of 2.5 to 10.0 mol / kg.
A low-solvent type coating composition comprising an ether group-containing compound and (3) an acidic catalyst, wherein the amount of the coatable organic solvent at 25 ° C is 0 to 30% by weight.

3. A method for coating the surface of an article to be coated with the low-solvent type coating composition according to 2 above, wherein the surface of the article to be coated is rotatably supported about a substantially horizontal axis in a normal vertical direction. On the extending surface, the coating material is applied to a thickness that causes sagging, and then the sagging of the coating material applied to the surface of the coating object begins to rotate about the horizontal axis before the sagging of the coating material occurs due to gravity, and A speed at which the rotation at least shifts the surface of the coating object from a substantially vertical state to a substantially horizontal state before the sagging of the applied paint is caused by gravity, and is slower than the speed at which the sagging of the paint is caused by the centrifugal force due to the rotation. A method for coating a low-solvent type coating composition, characterized in that the coating composition is rotated. 4. A method for coating the surface of an article to be coated with the low-solvent coating composition according to 2 above, which comprises applying 3
A method for coating a low-solvent type coating composition, which comprises coating at 0 to 80 ° C. 5. 3. A low-solvent type coating composition, characterized in that the low-solvent type coating composition according to the above 2 is applied to the surface of an object to be coated and then heat-cured to form a coating film on the surface of the object to be coated. How to paint.

The present invention will be described in detail below.
The first functional group used in the present invention is selected from the group consisting of a hydroxyl group, a blocked hydroxyl group, a blocked carboxyl group, a blocked phosphate group and an acid anhydride group. here,
The hydroxyl group is a functional group represented by --OH. The blocked hydroxyl group is a functional group represented by the following structure. --O--Z Here, Z is a block group derived from a blocking agent bonded to a hydroxyl group, and a silyl block group or a vinyl (thio) ether block group represented by the following formula is mentioned as a preferable group. be able to. [1] Silyl Block Group As the silyl block group, a silyl block group represented by the following formula (1) can be exemplified.

[0007]

[Chemical 1]

R ^{1 to} R ³ in the above formula (1) are each independently an alkyl group or an aryl group. Examples of the alkyl group include linear or branched alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, s-butyl group, t-butyl group, pentyl group. And lower alkyl groups having 1 to 8 carbon atoms such as hexyl group are particularly preferable. The aryl group includes a phenyl group which may have a substituent, a naphthyl group, an indenyl group and the like, and a phenyl group is particularly preferable. Examples of the silyl block group represented by the formula (1) include a trimethylsilyl group,
Diethylmethylsilyl group, ethyldimethylsilyl group, butyldimethylsilyl group, butylmethylethylsilyl group,
Examples thereof include a phenyldimethylsilyl group, a phenyldiethylsilyl group, a diphenylmethylsilyl group and a diphenylethylsilyl group. In particular, the smaller the molecular weight of R ^{1 to} R ^3, the easier it is for the blocking group to come off, and the more preferable it is. As a blocking agent for forming such a silyl block group, halogenated silane can be preferably used. Examples of the hagen atom contained in the halogenated silane include chlorine atom and bromine atom. Specific examples of the blocking agent include trimethylsilyl chloride, diethylmethylsilyl chloride, ethyldimethylsilyl chloride, butyldimethylsilyl bromide, butylmethylethylsilyl bromide, and the like. [2] Vinyl (thio) ether block group As the vinyl (thio) ether block group, a vinyl (thio) ether block group represented by the following formula (2) is exemplified.

[0009]

[Chemical 2]

R ¹ , R ² and R ³ in the above formula (2) are each independently a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. R ⁴ is a hydrocarbon group having 1 to 18 carbon atoms. Y is an oxygen atom or a sulfur atom. Also, R ³ and R ⁴
And may combine with each other to form a heterocycle having Y as a heteroatom. As the hydrocarbon group in the above formula,
Examples thereof include an alkyl group, a cycloalkyl group and an aryl group. As the alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, s-butyl group, t-butyl group,
A lower alkyl group having 1 to 8 carbon atoms such as a pentyl group and a hexyl group is particularly preferable. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. The aryl group may have a substituent,
Includes phenyl group, naphthyl group, anthracene group, etc.,
Particularly, a phenyl group is preferable. Such vinyl (thio) ether blocking groups can be formed by reacting an aliphatic vinyl ether or thioether or a cyclic vinyl ether or thioether with a hydroxyl group. As the aliphatic vinyl (thio) ether, for example,
Examples thereof include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether and the like, or vinyl thioether corresponding thereto. Examples of the cyclic vinyl (thio) ether include 2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydro-
2H-pyran, 3,4-dihydro-2H-pyran, 3,
4-dihydro-2-methoxy-2H-pyran, 3,4-
Dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran,
Examples include sodium 3,4-dihydro-2H-pyran-2-carboxylate and the like and corresponding cyclic vinyl thioethers.

The blocked carboxyl group as the first functional group is a functional group represented by the following formula. --COO--Z Here, Z is a blocking group derived from a blocking agent bonded to a hydroxyl group of a carboxyl group, and the silyl blocking group or vinyl (thio) ether blocking group is preferable. You can The blocked phosphate group is a functional group represented by the following formula.

[0012]

[Chemical 3]

Here, Z is a block group derived from a blocking agent bonded to the hydroxyl group of a phosphoric acid group, and the above silyl block group or vinyl (thio) ether block group can be mentioned as a preferable example. n is 1 or 2. In addition, n is 2, and it is preferable that all the hydroxyl groups are blocked in terms of stability during storage and reduction of the viscosity of the oligomer. The blocking group of the blocked hydroxyl group, the blocked carboxyl group and the blocked phosphate group is preferably deprotected by the presence of heat (moisture or water in the atmosphere) or heat in the presence of an acidic catalyst. It is a functional group that separates to release a hydroxyl group, a carboxyl group and a phosphoric acid group. Moreover, since the polarities of the hydroxyl group, the carboxyl group and the phosphate group are suppressed by blocking, the amount of the organic solvent can be reduced. In particular, the carboxyl group and the phosphate group have a strong polarity in the free state,
If it is used as it is as a functional group of a paint component, it requires a large amount of an organic solvent to dissolve the resin, so that it is difficult to prepare a low solvent paint composition as in the present invention. Furthermore, the acid anhydride group as the first functional group has the formula:
It is a functional group represented by CO--O--CO--.

The vinyl polymerized oligomer (1) used in the present invention has a number average molecular weight (Mn) of 600 to 1500. When the number average molecular weight is less than 600, the coating film forming ability is lowered, the strength of the obtained coating film is lowered, and the gasoline resistance and the scratch resistance are lowered. On the other hand, if the number average molecular weight is more than 1500, the viscosity of the coating material becomes too large, which is not suitable. The preferred number average molecular weight is
700 to 1200, and particularly preferably 800 to
It is 1000. The weight average molecular weight / number average molecular weight (Mw / Mn) of the vinyl polymerized oligomer (1) is 1.0 to 2.0.
Is. When the weight average molecular weight / number average molecular weight is more than 2.0, a relatively large amount of vinyl polymerized oligomers having too large a molecular weight or a vinyl polymerized oligomer having a too small molecular weight is contained, and the molecular weight is too large or too small. The problem occurs in. The lower limit is theoretically 1.0, and the smaller the molecular weight of the vinyl-polymerized oligomer, the easier it is to approach the theoretical value, and a coating composition having extremely uniform properties can be obtained. A preferred weight average molecular weight / number average molecular weight is 1.0 to 1.8, and particularly preferred is 1.0 to 1.6. The weight average molecular weight (Mw) of the vinyl polymerized oligomer (1) used in the present invention is 600 to 3000 corresponding to the above number average molecular weight and the weight average molecular weight / number average molecular weight ratio. A preferred weight average molecular weight is 700 to 2400, and particularly preferred is 80.
0 to 2000.

The vinyl polymerized oligomer (1) used in the present invention comprises a first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group, a blocked carboxyl group, a blocked phosphoric acid group and an acid anhydride group. It is obtained by polymerizing or copolymerizing a monomer having a polymerizable unsaturated bond (hereinafter, simply referred to as “polymerization”). For example, when the vinyl polymerized oligomer (1) is synthesized from the acrylic acid or methacrylic acid monomer having the first functional group, it becomes an acrylic oligomer. In the vinyl polymerized oligomer (1) used in the present invention, the first functional group such as a hydroxyl group, a blocked hydroxyl group, a blocked carboxyl group, a blocked phosphoric acid group and an acid anhydride group has the same vinyl polymerized oligomer (1). ), Or in separate vinyl polymerized oligomers (1) in various combinations. The number of the first functional groups contained in one molecule of the vinyl polymerized oligomer (1) used in the present invention is
Depending on the molecular weight of the vinyl polymerized oligomer (1) used, the number is preferably 2 to 5, more preferably 2.5 to 4. If the number of first functional groups is less than two,
It is not preferable because the strength of the coating film tends to decrease. On the other hand, the first
If the number of functional groups exceeds 5, the viscosity becomes too high and the coating becomes brittle, which is not preferable.

The number of all functional groups in one molecule of the vinyl polymerized oligomer (1) used in the present invention is preferably 2.
0 to 5.0 mol / kg resin, particularly preferably 3.0 to 4.0 mol / kg resin. If the total number of functional groups is less than 2.0 mol / kg resin, the crosslink density becomes small, and thus the coating film properties such as scratch resistance and gasoline resistance are deteriorated. On the other hand, if the total number of functional groups is more than 5.0 mol / kg resin, the viscosity becomes too high, which is not preferable. When selecting the total number of functional groups, it is necessary to particularly consider the relationship with the molecular weight of the vinyl-polymerized oligomer (1). That is, when the molecular weight of the vinyl polymerized oligomer (1) is small, unless the total number of functional groups is increased, the vinyl polymerized oligomer (1) having no functional group in one molecule is produced, so that the coating film performance is sufficiently exhibited. It is not possible. Also,
When the vinyl polymerized oligomer (1) has a large molecular weight, the viscosity itself becomes large, which is not preferable. In any case, a suitable combination of molecular weight and all functional groups is
It can be easily determined by those skilled in the art experimentally within the scope of the present invention. The glass transition temperature of the vinyl polymerized oligomer (1) used in the present invention is preferably −3.
5 to 40 ° C, particularly preferably -10 to 30 ° C.
If the glass transition temperature is higher than 40 ° C, the viscosity of the coating material becomes too high, which is not preferable. On the other hand, when the glass transition temperature is lower than -35 ° C, the coating film becomes too soft and the gasoline resistance is lowered, which is also not preferable.

The vinyl polymerized oligomer (1) used in the present invention can be prepared by polymerizing a monomer having a first functional group and a polymerizable unsaturated bond as described above. The method of polymerizing these monomers can be carried out by a known conventional means. For example, the polymerization can be performed by anionic polymerization, ionic polymerization such as cationic polymerization, or radical polymerization. In the present invention, radical polymerization is preferred from the viewpoint of ease of polymerization. However, in the present invention, since it is necessary to produce a low-molecular weight vinyl-polymerized oligomer, during the polymerization, a mercaptoethanol such as mercaptoethanol, thioglycerol, lauryl mercaptan or the like, so that the vinyl-polymerized oligomer can be produced at a low molecular weight, or A method of using a chain transfer agent, a method of reacting at 60 to 180 ° C.,
Alternatively, it is desirable to adopt a method of reacting at a low monomer concentration. When a monomer having a hydroxyl group, a carboxyl group or a phosphate group blocked with a vinyl (thio) ether group is polymerized, it is preferable to carry out the polymerization at 60 to 100 ° C. When the polymerization is carried out at a temperature higher than 100 ° C, the block group is easily dissociated. Further, the molecular structure of the vinyl polymerized oligomer (1) is not particularly limited, and for example,
It may have various structures such as a linear shape, a comb shape, a block shape, a star shape, and a star burst shape.

The radical polymerization is preferably carried out in a solution. As a solvent used for such radical solution polymerization, a solvent conventionally used for polymerization of a vinyl polymerizable monomer such as an acrylic monomer can be used without limitation. Examples of such a solvent include toluene, xylene, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, Solvesso (manufactured by Exxon) and the like. As the radical reaction initiator used in radical solution polymerization, a reaction initiator conventionally used in radical polymerization can be used without limitation. Examples of such a reaction initiator include benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, peroxides such as t-butyl peroxy-2-ethylhexanol, and azobisvaleronitrile,
Examples thereof include azo compounds such as azobisisobutyronitrile and azobis (2-methylpropionitrile). As the hydroxyl group-containing monomer, a monomer having a hydroxyl group and a radically polymerizable unsaturated bond group is preferably used. The radical-polymerizable unsaturated bond group is preferably a radical-polymerizable vinyl bond (CHR ¹ = CR ² — (R ¹ and R ² are each a hydrogen atom, an alkyl group or a single bond). The alkyl group includes a linear or branched alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group or the like having 1 to 2 carbon atoms.
An alkyl group of 0 is preferred. As such a hydroxyl group-containing monomer, a monomer represented by the following formula (3) can be preferably mentioned.

[0019]

[Chemical 4]

In the above formula, R ¹ is a hydrogen atom or a methyl group. R ² is an alkylene group, a cycloalkylene group or an arylene group. Y is -COO-, -CO-, a single bond or -O-. X is a hydroxyl group. Where, in particular,
Acrylic monomers in which Y is -COO- are preferred. The alkylene group has a linear or branched carbon number of 1 to 1.
8 alkylene groups are included, for example, methylene group, ethylene group, propylene group, butylene group, isobutylene group,
Examples thereof include lower alkylene groups having 1 to 6 carbon atoms in a hexamethylene group. As the cycloalkylene group, for example,
Examples thereof include cycloalkylene groups having 5 to 18 carbon atoms, such as cyclopentylene groups and cycloalkylene groups having 5 to 8 carbon atoms such as cyclohexylene groups. Examples of the arylene group include an ortho, meta or para-phenylene group, a naphthalene group, a fluorene group, an indole group, an anthracene group, a furan group and a thiophene group. Specific preferred hydroxyl group-containing monomers include hydroxyl group-containing acrylic monomers, for example,
2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like and those modified with a lactone compound can be mentioned. As the blocked hydroxyl group-containing monomer, a monomer obtained by blocking the hydroxyl group in the above hydroxyl group-containing monomer with the above block group can be mentioned as a preferable example.

Examples of the monomer having a blocked carboxyl group include a monomer having a blocked carboxyl group and a radically polymerizable unsaturated bond group. As such a monomer, for example, a monomer obtained by blocking a monomer having a carboxyl group and the above radically polymerizable unsaturated bond group with the above blocking agent is mentioned as a preferable monomer. The monomer having such a carboxyl group and a radically polymerizable unsaturated bond group may include a plurality of carboxyl groups. As the monomer having one carboxyl group in the molecule, for example, (meth) acrylic acid is preferable. Examples of the monomer having two carboxyl groups in the molecule include itaconic acid, maleic acid, mesaconic acid, fumaric acid and the like. Alternatively, an acid anhydride such as maleic anhydride or itaconic anhydride may be reacted with an alcohol or amine having 1 to 18 carbon atoms. Examples of such alcohols include alcohols such as methanol, ethanol, propanol and butanol. However, if the alcohol has more than 18 carbon atoms, the plasticity of the coating film becomes too high, which is not preferable. Examples of such amines include aliphatic amines such as dibutylamine, dihexylamine, methylbutylamine, ethylbutylamine and n-butylamine, and aromatic amines such as aniline and toluidine. Furthermore, as the monomer having a carboxyl group,
It can be produced by reacting a monomer having a hydroxyl group and a radically polymerizable unsaturated bond group with an acid anhydride. For example, it can be produced by reacting hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate with 4-methylhexahydrophthalic anhydride, succinic anhydride, trimellitic anhydride, phthalic anhydride or the like. it can.

As the monomer having a blocked phosphoric acid group, a vinyl polymerizable monomer having the above-mentioned blocked phosphoric acid group and the above radically polymerizable unsaturated bond group can be mentioned as a preferable monomer. As such a monomer, for example, a monomer obtained by blocking a monomer having a phosphoric acid group and the above radical polymerizable unsaturated bond group with the above blocking agent can be mentioned as a preferable monomer. As the vinyl polymerizable monomer having such a phosphoric acid group and a radically polymerizable unsaturated bond group, a vinyl polymerizable monomer in which X is a phosphoric acid group in the above formula (3) is preferred. You can A particularly preferred blocked phosphoric acid group-containing vinyl polymerizable monomer is an acrylic monomer in which Y is -COO-. Typical examples of such acrylic monomers include monomers represented by the following formulas (4), (5) and (6).

[0023]

[Chemical 5]

As the acid anhydride group-containing monomer, a monomer having an acid anhydride group and the above radical polymerizable unsaturated bond group is preferably used. As the monomer having such an acid anhydride and a radically polymerizable unsaturated bond group,
For example, a monomer that forms an acid anhydride group in the molecule such as maleic anhydride or itaconic anhydride, or a monomer having a radical-polymerizable unsaturated bond and one carboxyl group in one molecule In addition, a monomer obtained by condensing a compound having one carboxyl group by dehydration or dealcoholization reaction can be mentioned. The compound having one carboxyl group in one molecule may or may not have a radical polymerizable unsaturated bond in the molecule. Examples of such a monomer include a monomer obtained by condensing a monoester of a divalent polybasic acid such as methacrylic acid anhydride or monoalkyl maleate or monoalkyl itaconate by dealcoholation reaction.

When the vinyl polymerized oligomer (1) used in the present invention is produced, other polymerizable monomers such as α, β-ethylenically unsaturated monomers may be used in combination, if necessary. As such α, β-ethylenically unsaturated monomer, for example, the following monomers can be used. (1) Acrylic acid or methacrylic acid ester: For example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, methacrylic acid C1-18 alkyl group esters of acrylic acid or methacrylic acid such as ethyl, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate; methoxybutyl acrylate, methacrylic acid Acid such as methoxybutyl acrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, etc., having 2 to 18 carbon atoms. Lucoxyalkyl ester; alkenyl ester of acrylic acid or methacrylic acid such as allyl acrylate or allyl methacrylate having 2 to 8 carbon atoms; acrylic acid or methacrylic acid such as allyloxyethyl acrylate or allyloxyethyl methacrylate having 3 carbon atoms ~ 18 alkenyloxyalkyl esters.

(2) Vinyl compounds: for example, vinyl acetate, hexafluoropropylene, tetrafluoropropylene, styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene. (3) Polyolefin compound: For example, butadiene, isoprene, chloroprene. (4) Allyl ethers: hydroxyethyl allyl ether and the like. (5) Others: For example, methacrylamide, acrylamide, diacrylamide, dimethacrylamide, acrylonitrile, methacrylonitrile, methyl isopropenyl ketoin, vinyl acetate, vinyl propionate, vinyl pivalate, acrylic acid, methacrylic acid, N, N -Dialkylaminoalkyl (meth) acrylate, perfluorovinyl ether such as trifluoromethyl vinyl ether, vinyl ether such as hydroxyethyl vinyl ether and hydroxybutyl vinyl ether.

As the vinyl ether group or vinyl thioether group used in the vinyl (thio) ether group-containing compound used in the present invention, those represented by the following formulas can be mentioned as preferable ones. —X——CH═CH ——— Y (7) In the formula, X is an oxygen atom or a sulfur atom, and Y is a hydrogen atom or a single bond. That is, in the above formula (7), when Y is a hydrogen atom, it is an aliphatic vinyl ether group or a vinyl thioether group, while when Y is a single bond, it is a cyclic vinyl ether group or a vinyl thioether group. . Examples of the cyclic vinyl (thio) ether group when Y is a single bond include, for example, 2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydro-2H-pyran and 3,4-dihydro-. 2H-pyran,
3,4-dihydro-2-methoxy-2H-pyran, 3,
4-dihydro-4,4-dimethyl-2H-pyran-2-
Preferred examples include groups derived from on, 3,4-dihydro-2-ethoxy-2H-pyran, sodium 3,4-dihydro-2H-pyran-2-carboxylate, or a sulfur-containing compound corresponding thereto. be able to. As the vinyl (thio) ether group-containing compound, any compound having a plurality of the above vinyl (thio) ether groups, even if it is a polymer, is not polymerized (compound)
May be However, from the viewpoint of design freedom and the like, a polymer, for example, an oligomer such as a vinyl polymerization oligomer is preferable.

The vinyl (thio) ether group-containing compound has a number average molecular weight of 400 to 1500, preferably 400 to
It is 1200. When the number average molecular weight is less than 400, the blocking groups of the blocked hydroxyl group, the blocked carboxyl group and the blocked phosphoric acid group are removed during the curing reaction, and the vinyl (thio) ether group is released, the hydroxyl group, the carboxyl group and the phosphoric acid. Since the reactivity of reacting with the group becomes small, the curing reaction does not proceed. On the other hand, the number average molecular weight is 15
When it is greater than 00, the viscosity of the compound increases. The weight average molecular weight / number average molecular weight ratio of the vinyl (thio) ether group-containing compound is 1.0 to 2.0, and preferably 1 to 1.8. When the weight average molecular weight / number average molecular weight ratio is larger than 2.0, there are problems when the molecular weight is large and problems when the molecular weight is small. Further, corresponding to the number average molecular weight and the weight average molecular weight / number average molecular weight ratio, the weight average molecular weight of the vinyl (thio) ether group-containing compound used in the present invention is 400 to 3000, preferably 400 to 2400. is there. The total amount of functional groups of the vinyl (thio) ether group-containing compound used in the present invention is 2.5
It is -10.0, Preferably it is 3-7. If the total amount of functional groups is less than 2.5 mol / kg resin, the crosslink density is lowered and the gasoline resistance is lowered. On the other hand, when the amount of all the functional groups is as high as 10.0 mol / kg resin, the crosslinking becomes too dense and cracks easily. The number of vinyl (thio) ether groups contained in one molecule of the vinyl (thio) ether group-containing compound may be plural, but is usually 2 to 6, and preferably 2 to 4. When the number of vinyl (thio) ether groups is 2 or less, the crosslinking reaction does not occur, and thus the coating properties are very poor.
On the other hand, when the number of vinyl (thio) ether groups is 6 or more, the cross-linking density becomes too large and the coating film becomes brittle, resulting in poor properties such as gasoline resistance and scratch resistance.

The vinyl (thio) ether group-containing compound used in the present invention can be produced by reacting, for example, a polyol with vinyl halide when Y is a hydrogen atom in the above formula (7). it can. Examples of the polyol used here include diols such as ethylene glycol, propylene glycol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, and cyclohexanedimethanol, trimethylolpropane, and trimethylol. Examples include trihydric alcohols such as ethane and glycerin, pentaerythritol, and tetrahydric alcohols such as diglycerin. Specific aliphatic vinyl (thio) ether groups include, for example, propanediol divinyl (thio) ether, butanediol divinyl (thio) ether, trimethylolpropane trivinyl (thio) ether, trimethylolethane trivinyl (thio). ) Ether, glycerin trivinyl (thio) ether and the like can be mentioned as preferable compounds. Further, a preferable aliphatic vinyl (thio) ether group-containing compound is the above vinyl (thio) group when a vinyl polymerizable monomer having a hydroxyl group or a functional group such as a carboxyl group or a phosphoric acid group is polymerized.
An aliphatic vinyl (thio) ether group-containing vinyl polymerized oligomer obtained by reacting an ether group-containing compound is mentioned. On the other hand, the cyclic vinyl (thio) ether group-containing compound in which Y is a single bond in the above formula (7) reacts with a compound containing a dihydrofuran ring or a dihydropyran ring to form a plurality of cyclic compounds in one molecule. A compound having a vinyl (thio) ether group can be synthesized. For example, by reacting an alcohol containing a cyclic vinyl (thio) ether group with a carboxylic acid containing a cyclic vinyl (thio) ether group, 1
Ester compounds having a plurality of cyclic vinyl (thio) ether groups in the molecule can be produced. Examples of such compounds include, for example, 2,3-dihydro-2H-
Furan-2-ylmethyl 2,3-dihydro-2H-furancarboxylate, 3,4-dihydro-2H-pyran-2-ylmethyl 3,4-dihydro-2H-pyrancarboxylate and the like can be mentioned. For example, 3,4-dihydro-2H-pyran-2-ylmethyl 3,4-dihydro-2H-pyrancarboxylate is a compound having a structure represented by the following formula.

[0030]

[Chemical 6]

Further, as a preferable cyclic vinyl (thio) ether group-containing compound, the above vinyl (thio) ether is used when polymerizing a vinyl polymerizable monomer having a hydroxyl group or a functional group such as a carboxyl group or a phosphoric acid group. Examples thereof include vinyl (thio) ether group-containing vinyl polymerized oligomers obtained by reacting a group-containing compound. The proportion of the vinyl polymerizable monomer (1) and the vinyl (thio) ether group-containing compound (2) used is 0 to
70/30 to 100% by weight. When the vinyl ether group-containing compound is less than 30, the functional group of the oligomer becomes small, the cross-linking when cured becomes insufficient, and the gasoline resistance decreases.

In the present invention, the blocking group is dissociated from the blocked hydroxyl group, the blocked carboxyl group and the blocked phosphate group, and the free hydroxyl group, the free carboxyl group and the free phosphate group and the vinyl (thio) ether group are used. An acidic catalyst is used as a catalyst for catalyzing the reaction with. As such an acidic catalyst, for example, a strongly acidic catalyst or a weakly acidic catalyst is used. As a strong acid catalyst,
Examples thereof include inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, organic acids such as sulfonic acid, and salts thereof such as esters, ammonium salts and onium salts thereof. Particularly, as the strongly acidic catalyst, sulfonic acid, its ester or amine salt, benzoic acid, trichloroacetic acid and the like are preferable. Specifically, examples of the sulfonic acid include aliphatic sulfonic acids such as methanesulfonic acid and ethanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenedisulfonic acid, dinonylnaphthalenesulfonic acid, and dinonyl. Examples thereof include aromatic sulfonic acids such as naphthalene disulfonic acid. As the strongly acidic catalyst, aromatic sulfonic acid or its ester is preferable, and specifically, dodecylbenzene sulfonic acid and dinonylnaphthalene disulfonic acid are particularly preferable because they improve the water resistance of the coating film.

On the other hand, examples of the weakly acidic catalyst include phosphoric acid, phosphoric acid monoester, phosphorous acid ester, and unsaturated group-containing phosphoric acid ester. As the weakly acidic catalyst, phosphoric acid or its ester is particularly preferable. As such phosphoric acid or its ester, for example, phosphoric acid,
Examples thereof include pyrophosphoric acid and the like, phosphoric acid mono- or diester and the like. Examples of the phosphoric acid monoester include monooctyl phosphate, monopropyl phosphate, monolauryl phosphate and the like. As the phosphoric acid diester, for example,
Dioctyl phosphate, dipropyl phosphate, dilauryl phosphate and the like can be mentioned. Further, mono (2- (meth) acryloyloxyethyl) acid phosphate can be mentioned. The acidic catalyst is used in a catalytic amount, and is used in an amount of 0.001 to 10%, preferably 0.001 to 5%, based on the weight of the vinyl polymerized oligomer (1) and the vinyl (thio) ether group-containing compound. It

The low-solvent type resin composition of the present invention may be used as it is or, if necessary, various pigments (for example, color pigments and brightening agents) and anti-sagging agents conventionally used in the field of paints. Alternatively, a low-solvent type coating composition can be prepared by appropriately adding an anti-sedimentation agent, a reverig agent, a dispersant, a defoaming agent, an ultraviolet absorber, a light stabilizer, an antistatic agent, a thinner and the like. Examples of the pigment or glittering agent include titanium oxide, carbon black, precipitated barium sulfate, calcium carbonate, talc, kaolin, silica, mica, aluminum, red iron oxide, lead chromate, lead molybdate,
Chromium oxide, cobalt aluminate, azo pigments, phthalocyanine pigments, anthraquinone pigments and the like can be preferably used. As an anti-sagging agent or an anti-settling agent,
For example, bentonite, castor oil wax, amide wax, microgel, aluminum acetate and the like can be preferably used. Examples of the leveling agent include silicon-based ones such as KF69, KP321 and KP301 (manufactured by Shin-Etsu Chemical Co., Ltd.), Modaflow (manufactured by Mitsubishi Monsanto), BYK358 (manufactured by Big Chemie Japan) and Dia-Aid AD9001 (manufactured by Mitsubishi Rayon). Etc. can be preferably used.

As the dispersant, for example, Anti-Terra U or Anti-Terra P and Disperbyk-101 (above, manufactured by Big Chemie Japan) can be preferably used.
As the defoaming agent, for example, BYK-O (manufactured by BYK Chemie Japan) or the like can be preferably used. Examples of UV absorbers include benzotriazole-based UV absorbers such as TINUVIN 900, TINUVIN 384, and TINUVIN P (all manufactured by Ciba Geigy), and anilide oxalate UV absorbers such as SANDBA-3206 (manufactured by Sand). It can be preferably used. Examples of the light stabilizer include sanol
Hindered amine light stabilizers such as LS292 (manufactured by Sankyo) and sand bar 3058 (manufactured by Sand) can be preferably used. Examples of the thinner include aromatic compounds such as toluene, xylene, and ethylbenzene, alcohols such as methanol, ethanol, propanol, butanol, and isobutanol, acetone, methyl isobutyl ketone, and the like.
Methyl amyl ketone, cyclohexanone, isophorone,
A ketone such as N-methylpyrrolidone, an ester compound such as ethyl acetate, butyl acetate, methyl cellosolve, or a mixture thereof can be used. As the antistatic agent, for example, Esocard C25 (manufactured by Lion Armor) or the like can be preferably used.

The low solvent type coating composition of the present invention is particularly useful as a clear coating, an intermediate coating, a base coating, a solid color coating and the like used for coating automobiles. The low-solvent type coating composition of the present invention is particularly useful as a clear coating. The low solvent type coating composition of the present invention,
It is particularly excellent as a clear coating used for 2 coat 1 bake, 3 coat 2 bake or overcoat. Further, the low solvent type coating composition of the present invention, each of the following,
It can be applied as an intermediate coating composition, a base coating composition and a clear coating composition, or a solid color coating composition and a clear coating composition. Furthermore, the low-solvent type coating composition of the present invention uses this as an intermediate coating composition, and a base coat coating composition consisting of a conventionally known organic solvent-based coating composition or a water-based coating composition can be further applied thereon by wet-on-wet. . It is also possible to use the coating composition of the present invention as a base coat coating and to apply a conventionally known clear coating thereon. Furthermore, a conventionally known base coat paint may be applied, and then a clear paint as the paint composition of the present invention may be applied thereon by wet on wet. In this case, the base coat paint may be an organic solvent type paint or an aqueous paint. As the organic solvent type paint, for example, it is preferable to use a paint composition containing an oligomer having a hydroxyl group and a weight average molecular weight of 6000 or less, and a melamine resin. Further, the base coat coating composition preferably has a coating solid content of 35% by weight or more, particularly 40% by weight or more.

The low-solvent type coating composition of the present invention can reduce the viscosity of the coating composition although the amount of the organic solvent is small. That is, it is possible to maintain the viscosity suitable for the paint, even though the solid content of the paint can be greatly improved as compared with the conventional case. The low-solvent type coating composition of the present invention is generally applied to an object to be coated in a predetermined amount,
By setting (drying) and then baking,
Coating film formation is preferably performed. The setting (drying) is generally 5 to 30 minutes, preferably 10 to 15 minutes and is carried out at room temperature or ambient temperature. The baking is performed at 60 to 200 ° C., preferably 80 to 160 ° C. for 1 to 60 minutes, preferably 10
It is preferable to carry out ~ 40 minutes. The low solvent type coating composition of the present invention can be applied with a coating by hot spraying while further reducing the amount of solvent. Such a hot spray is, for example, a process from a tank storing a low solvent type coating composition to a step immediately before spraying at a predetermined temperature, generally 30 to 80 ° C., preferably 35 to 50 ° C.
It can be performed by keeping the temperature at 70 ° C. In the low-solvent coating composition of the present invention, the characteristics of the coating film to be formed, for example, gasoline resistance, scratch resistance, in various characteristics such as acid resistance, while having excellent quality, the amount of organic solvent, It can be much lower than before. For example, the amount of organic solvent is 30% or less, preferably 2
It can be reduced to 0% or less, more preferably 15% or less. Therefore, the problem of environmental pollution due to the release of the organic solvent can be significantly reduced. The lower limit is
5% is preferable.

[0038]

The present invention will be described in more detail with reference to Reference Examples and Examples, but the scope of the present invention is not limited to these Reference Examples and Examples.
However, in the following, "%" or "part" means "% by weight" and "part by weight" unless otherwise specified. Reference Example 1 Synthesis of Cyclic Vinyl Ether Group-Containing Monomer D 600 ml of methyl ethyl ketone and 224 parts of 2-hydroxyethyl methacrylate were placed in a four-necked flask equipped with a dropping funnel, stirrer, inert gas inlet, and thermometer. , Stirred. At room temperature, a mixture of 200 parts of 3,4-dihydro-2H-pyran-2-yl-methyl-3,4-dihydro-2H-pyran-2-carboxylate and 5 parts of paratoluenesulfonic acid over 30 minutes. And dropped into the flask. After dropping, the mixture was reacted at room temperature for 24 hours, then the reaction solution was transferred to a separating funnel, and 10% aqueous sodium hydrogencarbonate solution was added to the separating funnel to carry out alkali washing. After washing, washing with 200 parts of deionized water was repeated until the pH of the washing solution reached 7. Next, molecular sieve 4A / 16 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the organic layer,
After drying at room temperature for 3 days, methyl ethyl ketone was removed under reduced pressure to obtain a monomer D. Reference Example 2 Synthesis of Aliphatic Vinyl Ether Group-Containing Monomer E A 4-necked flask equipped with a dropping funnel, stirrer, inert gas inlet, and thermometer was charged with 600 parts of methyl ethyl ketone and 284 parts of 2-hydroxyethyl methacrylate. It was put and stirred. At room temperature, a mixture of 260 parts of butanediol divinyl ether and 5 parts of paratoluenesulfonic acid was added dropwise to the flask over 30 minutes. After dropping, the mixture was reacted at room temperature for 24 hours, then the reaction solution was transferred to a separating funnel, and 10% aqueous sodium hydrogencarbonate solution was added to the separating funnel to carry out alkali washing. After washing, washing with 200 parts of deionized water was repeated until the pH of the washing solution reached 7.
Next, Molecular Sieve 4A / 16 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the organic layer and dried at room temperature for 3 days, and methyl ethyl ketone was removed under reduced pressure to obtain a monomer E.

[0039]Reference Examples 3 to 26 Hydroxyl group, Blocked hydroxyl group, Blocked carboxyl
Containing vinyl groups, blocked phosphate groups or acid anhydride groups
Synthesis of polymerized oligomer (1) Equipped with stirrer, inert gas inlet, thermometer and cooler
In a four-necked flask, the following Table 1 (item of "synthetic raw material")
As shown in, charge 674 parts of xylene, and
℃ reaction temperature (however, vinyl polymerization oligomer B4, B
In the case of the synthesis of P2 and BC2, the reaction temperature is 80
The temperature is raised to ℃) and shown in Table 1 (item of "Synthetic raw material").
A monomer composed of monomers having a predetermined functional group in proportion.
-Mixture and a certain amount of perbutyl O (peroxide catalyst,
This oil and fat company) and xylene were added dropwise. Moreover, the opposite
The reaction continued at the reaction temperature, and the solid content became 26%.
After confirming that, the synthesis was stopped and xylene was distilled off under reduced pressure.
The vinyl weight having the characteristics and the amount of functional groups shown in Table 1 is
Combined oligomer (1) was prepared.

[0040]

TABLE 1 TABLE 1 O B1 B2 B3 B4 BOO1 BOO2 A1 number characteristic of the vinyl polymer cage Goma average molecular weight 1020 865 1040 1373 1060 1120 1065 1050 (Mn) The weight average molecular weight 1369 1033 1265 2334 1365 1860 1432 1680 (Mw) Mn / Mw 1.3 1.2 1.2 1.7 1.3 1.7 1.3 1.6 Functional group amount (mol / kg resin) OH group ^* 3.0 2.0 1.0 BOH group ^* 3.0 2.8 2.8 3.0 1.0 2.0 ACa group ^* 3.0 Synthetic raw material xylene 674 674 674 674 674 674 674 674 674 2- Hydroxy 98 65 33 Ethylmethacrylate Trimethylsiloxy 152 122 122 51 102 Ethyl methacrylate Monomer A ^* 152 Styrene 52 38 48 48 38 44 45 50 n-Butyl acryl 50 30 40 40 30 45 40 75 Rate 2-Ethylhex 50 30 40 40 30 45 30 50 Lumethacrylate Itaconic anhydride 75 Polymerization initiator Perbutyl-O 23 26 23 21 22 23 23 Xylene 53 50 53 55 44 54 53 53 Azoisobutyl 17 Nitrile Azoisovalero 17 Nitrile Note) Table Among them, the OH group represents a hydroxyl group, the BOH group represents a blocked hydroxyl group, and the ACa group represents an acid anhydride group. Further, the monomer A is a vinyl polymerizable monomer represented by the following formula.

[0041]

[Chemical 7]

[0042]

TABLE 2 TABLE 1 (Continued) BP1 BP2 BPO BPBO BPBC BPBCO BC1 BC2 vinyl polymer sediment characteristics Number-average molecular weight of Goma 1000 1150 866 980 1020 1050 1035 1256 (Mn) The weight average molecular weight 1500 1840 1300 1274 1430 1575 1656 2135 (Mw ) Mn / Mw 1.5 1.6 1.5 1.3 1.4 1.5 1.6 1.7 Functional group amount (mol / kg resin) OH group 1.0 1.0 BOH group 1.0 BCa group ^* 1.0 1.0 3.0 3.0 BPh group ^* 3.0 3.0 2.0 2.0 2.0 1.0 Synthetic raw material xylene 674 674 674 674 674 674 674 674 674 2-hydroxy 33 33 ethyl methacrylate trimethylsiloxy 51 ethyl methacrylate styrene 3 3 52 34 35 55 42 41 n-butyl acrylate 50 50 rate 2-ethylhex 11 40 50 50 rumethacrylate monomer B ^* 247 165 165 165 165 83 Monomer C ^* 247 Trimethylsilyl 39 39 108 Methacrylate monomer F ^* 109 Polymerization initiator Perbutyl-O 23 27 23 23 23 23 Xylene 53 46 49 53 53 53 53 53 48 Azoisobutyl 15 14 Nitrile Azoisovalero 15 14 Nitrile Note) In the table, the BCa group represents a blocked carboxyl group, and the BPh group represents a blocked phosphate group. The monomers B, C and F are vinyl polymerizable monomers having the following structures, respectively.

[0043]

[Chemical 8]

[0044]

[Table 3] Table 1 (continued)BCO BCBO BCBOO ABO ABCBO BPBCBO ABPBO A2 Vinyl polymerizationGomer characteristics   Number average molecular weight 1133 967 1000 1022 1050 1165 965 1460     (Mn)   Weight average molecular weight 1700 1450 1500 1533 1680 1733 1448 2482     (Mw)Mn / Mw 1.5 1.5 1.5 1.5 1.6 1.5 1.5 1.7 Functional group amount(Mol / kg resin)   OH group 1.0 1.0   BOH group 1.0 1.0 1.5 1.0 1.0 1.0   BCa group 2.0 2.0 1.0 1.0 1.0   BPh group 1.0 1.0ACa group 1.5 1.0 1.0 3.0 Raw material for synthesis   Xylene 674 674 674 674 674 674 674 674   2-hydroxy 33 33     Ethylmethac     Related   Trimethylsiloxy 51 51 77 51 51 51     Ethyl methacrylate     rate   Styrene 45 37 40 45 48 50 30 50   n-Butyl acryl 50 45 45 45 45 20 75     rate   2-ethylhex 50 45 45 45 45 27 38 50     Lemethacrylate   Itaconic anhydride 38 25 28 75   Monomer B 83 83   Trimethylsilyl 72 72 36 36 39Lemethacrylate Polymerization initiator   Perbutyl-O 23 23 23 23 23 23 23 23 20 Xylene 53 53 53 53 53 53 53 56

Reference Examples 27 to 30 Synthesis of vinyl ether group-containing vinyl polymerizable monomer In a four-necked flask equipped with a stirrer, an inert gas inlet, a thermometer and a cooler, the following Table 2 ("Synthetic raw material") was used. item)
As shown in, charge 674 parts of xylene at 80 ° C.
Up to the reaction temperature of Table 2 (the item of “Synthetic raw materials”)
In the proportion shown in (1), a monomer mixture consisting of monomers having a predetermined functional group, a predetermined amount of perbutyl O (peroxide catalyst, manufactured by NOF CORPORATION) and xylene were added dropwise. Furthermore,
At the reaction temperature, the reaction was continued, the solid content was confirmed to be 26%, the synthesis was stopped, xylene was distilled off under reduced pressure, and vinyl ether group-containing vinyl polymerization having the properties shown in Table 2 was obtained. Oligomers V1-3 were prepared.

Reference Example 31 Synthesis of compound containing vinyl ether group In a flask, 134 parts of trimethylolpropane, 3,
4-dihydro-2H-pyran-2-yl-methyl-3,
384 parts of 4-dihydro-2H-pyran-2-carboxylate (vinyl ether compound) and 100 parts of n-butyl acetate were added to prepare a suspension. To this suspension, 3 parts of dodecylbenzenesulfonic acid was added and reacted at room temperature for 24 hours. After filtering the reaction mixture, n-butyl acetate was removed under reduced pressure to obtain a vinyl ether group-containing compound V4 having the characteristics shown in Table 2.

[0047]

Table 4 Table 2 V1 V2 V3 V4 characteristic number average molecular weight of the vinyl polymer cage Goma 1368 1190 869 425 (Mn) The weight average molecular weight 2533 1700 1204 486 (Mw) Mn / Mw 1.9 1.4 1.4 1.1 functionality (molar / kg resin) vinyl ether group 2.6 3.0 3.0 7.8 synthetic material xylene 674 674 674 acetate n- butyl 100 trimethylol 134 propane vinyl ether 384 compounds styrene 20 46 46 monomer D 230 monomer E 204 204 Dodeshiruben Zensuruhon acid 3 initiator xylene 10 10 10 Azoisobuchiru 25 30 40 nitrile t- Buchirupa 50 50 50 Okishipiba rate

[0048]Comparative Reference Examples 1-7 Hydroxyl group, Blocked hydroxyl group, Blocked carboxyl
Group, blocked phosphoric acid group, acid anhydride group, or vinyl ether
Synthesis of Vinyl Polymerization Oligomer Containing Ter Group

TABLE 5 TABLE 3 HO HB HCO1 HV HCO2 HA HBP vinyl polymer sediment characteristics Number-average molecular weight of Goma 1863 1900 1850 1832 580 1890 2030 ( Mn) The weight average molecular weight 3620 3900 3350 3400 870 3660 3859 ( Mw) Mn / Mw 1.9 2.1 1.8 1.9 1.5 1.9 1.9 Amount of functional group (mol / kg resin) OH group 3.0 BOH group 3.0 BCa group 3.0 3.0 BPh group 3.0 ACa group 3.0 Vinyl ether group 2.6 Synthetic raw material xylene 374 374 374 674 374 674 674 2-hydroxy 121.5 ethylmethacrylate trimethyl white 188 Kishiechirume methacrylate styrene 64.5 47 52 20 52 50 3 n- Buchiruakuri 62 37 62 62 75 rate 2-ethylhexyl 62 37 62 62 50 Shirumetakuri rate itaconic anhydride 75 monomer D 230 monomer B 247 trimethylsilyl 134 134 methacrylate polymerization initiator Perbutyl-O 19 19 19 30 18 18 Xylene 30 30 30 45 40 30 30 Azoisobutyl 20 Nitrile t-Butyl Per 40 Okishipiba rate

Application Example A. Preparation of clear coating material A clear coating composition was prepared based on the composition shown in Table 4 below. In addition, in Table 4, compounds represented by trade names and the like are as follows. -Tinuvin 384 means a benzotriazole-based ultraviolet absorber manufactured by Ciba Geigy. -Sanol LS292 means a light stabilizer made by Ciba Geigy. -KP321 means a silicon-based surface conditioner manufactured by Shin-Etsu Silicon. The clear coating material prepared as described above was diluted with an 8/2 mixture of Solvesso 150 / Solvesso 100 at 100 ° C. at 25 ° C. to obtain a clear coating composition. B. Evaluation of paint performance The obtained clear paint was applied to the surface of a test piece as described below to form a paint film, and the paint film performance was measured in the following manner.

1. Preparation of coated plate OTO850 (intermediate coating paint manufactured by Nippon Paint Co., Ltd.) was coated on the electrodeposition plate and baked at 140 ° C. for 30 minutes. Then O
TO520 (Nippon Paint Co., Ltd. base coat paint)
Was applied and baked at 140 ° C. for 10 minutes, and then a clear paint (CC1 to 26) or a comparative clear paint (CN1 to 8) shown in Table 4 below was applied and baked at 140 ° C. for 30 minutes. 2. Performance evaluation method (1) Dilute with a mixed solution of Solvesso 100 / xylene = 1/1 so that the coating composition becomes 100 cps at the solvent contents of 25 ° C and 60 ° C,
Bake at 140 ° C. for 30 minutes and measure the volatile content of the paint.
Here, those having a volatile content of more than 30% were evaluated as x, those having a volatile content of more than 15% and not more than 30% were evaluated as o, and those having a volatile content of 15% or less were evaluated as o. (2) Acid resistance test 0.2% of 5% sulfuric acid aqueous solution was dripped on the coating film, and it was 30 at 40 ℃.
After drying for a minute, the state of the coating film is visually observed. When there was a trace, it was marked with X, and when there was no trace, it was marked with ◯. (3) The scratch resistance felt was soaked with a 5% amount of cleanser, and a 1 kg load was applied, and the cloth was reciprocated 30 times, and then the gloss retention rate was measured. Here, if the gloss retention rate is 70% or more, ◎, 60
% To less than 70% is represented by O, and less than 60% is represented by X. (4) Solvent resistance After rubbing the coating film 10 times with a felt soaked with xylene, the state of the coating film is visually observed. The case where there is no swelling is indicated by ◯, the case where swelling occurs slightly is indicated by Δ, and the case where swelling is indicated by x. The results of these tests are shown together in Table 4 below.

[0051]

[Table 6] Table 4 CC1 CC2 CC3 CC4 CC5 CC6 CC7 CC8 CC9 CC10 O 50 40 B1 50 40 B2 50 B3 50 B4 50 BOO1 50 BOO2 50 A1 40 40 BP1 50 V1 54 V2 50 50 50 50 50 40 40 50 V3 50 Monophosphate 4 4 4 4 4 4 4 4 4 4 Octyltinuvin 384 4 4 4 4 4 4 4 4 4 4 Sanol 2 2 2 2 2 2 2 2 2 2 LS 292 KP321 (X10 ² ) 5 5 5 5 5 5 5 5 5 5 Solvent content 25 ℃ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 60 ℃ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Scratch resistance ◎ ◎ ○ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Solvent resistance ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Acid resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

[0052]

[Table 7] Table 4 (continued) CC11 CC12 CC13 CC14 CC15 CC16 CC17 CC18 CC19 CC20 BP2 50 BPO 50 BPBO 50 BPBC 50 BPBCO 50 BC1 50 BC2 50 BCO 50 BCBO 50 BCBOO 50 V2 50 50 50 50 50 50 50 50 50 50 Monophosphate 4 4 4 4 4 4 4 4 4 4 Octyltinuvin 384 4 4 4 4 4 4 4 4 4 4 Sanol 2 2 2 2 2 2 2 2 2 2 LS 292 KP321 (x10 ³ ) 5 5 5 5 5 5 5 5 5 5 Solvent content 25 ° C ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 60 ℃ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Scratch resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Solvent resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Acid resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

[0053]

[Table 8] Table 4 (continued) CC21 CC22 CC23 CC24 CC25 CC26 O 20 13 ABO 40 ABCBO 40 BPBCBO 50 ABPBO 44 A2 50 BPBO 78 V1 50 V2 40 40 50 50 V4 30 Monophosphate 4 4 4 4 4 4 Octyl tinuvin 384 4 4 4 4 4 4 Sanol LS292 2 2 2 2 2 2 KP 321 (x10 ² ) 5 5 5 5 5 5 Solvent content 25 ℃ ◎ ◎ ◎ ◎ ◎ ○ ◎ 60 ℃ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Scratch resistance ◎ ◎ ◎ ◎ ○ ◎ Solvent resistance ◎ ◎ ◎ ◎ ○ ◎ Acid resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎

Comparative Application Example Preparation of Comparative Clear Paint A comparative clear paint was prepared in the same manner as above according to the formulation shown in Table 5 below.

[0055]

[Table 9] Table 5 CN1 CN2 CN3 CN4 CN5 CN6 CN7 CN8 HO 52 HB 52 HBCO1 52 HBCO2 52 52 HA 52 HBP 52 HV 60 60 60 60 50 V1 60 60 60 50 Monophosphate 4 4 4 4 4 4 4 4 4 Octyl Tinuvin 384 4 4 4 4 4 4 4 4 4 Sanol 2 2 2 2 2 2 2 2 LS 292 KP321 (x10 ² ) 5 5 5 5 5 5 5 5 Solvent content 25 ℃ × × × ◎ × × ◎ × 60 ° C ○ ◎ ○ ◎ ○ ○ ◎ ◎ ◎ Scratch resistance ○ ○ ○ × ○ ○ × ○ Solvent resistance △ △ △ × △ △ × △ Acid resistance ○ ○ ○ ○ ○ ○ ○ ○

[0056]

EFFECTS OF THE INVENTION According to the present invention, a coating film having a coating solvent having a limit solvent amount at 25 ° C. of 30% or less and having excellent coating properties such as scratch resistance, acid resistance and solvent resistance can be obtained. can get. Moreover, since the coating composition of the present invention is used with an organic solvent content of 30% or less, it is very useful for preventing pollution.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroyuki Uemura 3-1, Shinchi Fuchu-cho, Aki-gun, Hiroshima Prefecture Mazda Co., Ltd. (72) Inventor Kazuyo Koga 3-3 Shinchi, Fuchu-cho, Aki-gun, Hiroshima Mazda Incorporated (72) Inventor Mika Osawa 3-1, Shinchi, Fuchu-cho, Aki-gun, Hiroshima Mazda Ltd. (56) Reference JP-A-4-175376 (JP, A) JP-A-57-190038 (JP) , A) JP-A-55-157663 (JP, A) JP-A-4-325565 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C09D 5/00-201/10 B05D 1/00-1/40

Claims (5)

(57) [Claims] (1) A number average compound containing a first functional group selected from the group consisting of a hydroxyl group, a blocked hydroxyl group, a blocked carboxyl group, a blocked phosphoric acid group and an acid anhydride group as an essential functional group. The molecular weight is 600 to 1500, the weight average molecular weight is 600 to 3000, the weight average molecular weight / number average molecular weight ratio is 1.0 to 2.0, and the total functional group weight is 2.
Vinyl polymerized oligomer which is 5 to 5.0 mol / kg resin,
(2) It contains a plurality of second functional groups consisting of vinyl (thio) ether groups as essential functional groups and has a number average molecular weight of 400 to
Vinyl (thio) ether having a weight average molecular weight of 1500, a weight average molecular weight of 400 to 3000, a weight average molecular weight / number average molecular weight ratio of 1.0 to 2.0, and a total functional group amount of 2.5 to 10.0 mol / kg resin. A low-solvent type resin composition containing a group-containing compound and having a coatable organic solvent amount at 25 ° C. of 0 to 30% by weight. 2. A number-average compound containing a first functional group selected from the group consisting of (1) a hydroxyl group, a blocked hydroxyl group, a blocked carboxyl group, a blocked phosphoric acid group and an acid anhydride group as an essential functional group. The molecular weight is 600 to 1500, the weight average molecular weight is 600 to 3000, the weight average molecular weight / number average molecular weight ratio is 1.0 to 2.0, and the total functional group weight is 2.
Vinyl polymerized oligomer which is 5 to 5.0 mol / kg resin,
(2) It contains a plurality of second functional groups consisting of vinyl (thio) ether groups as essential functional groups and has a number average molecular weight of 400 to
Vinyl (thio) ether having a weight average molecular weight of 1500, a weight average molecular weight of 400 to 3000, a weight average molecular weight / number average molecular weight ratio of 1.0 to 2.0, and a total functional group amount of 2.5 to 10.0 mol / kg resin. A group-containing compound, (3) an acidic catalyst,
And the amount of organic solvent that can be coated at 25 ° C is 0
A low-solvent type coating composition, which is 30% by weight. 3. A method for coating the surface of an article to be coated with the low solvent type coating composition according to claim 2, wherein the surface of the article to be coated is rotatably supported about a substantially horizontal axis. On the surface that normally extends in the vertical direction, apply paint to a film thickness that causes sagging,
Next, before the sagging of the paint applied to the surface of the object to be coated is caused by gravity, the object to be coated is started to rotate about a horizontal axis, and the rotation is at least before the sagging of the applied material is caused by the force of gravity. A low-solvent type coating composition characterized in that it is rotated at a speed such that the surface of the article to be coated is changed from a substantially vertical state to a substantially horizontal state, and at a speed slower than the speed at which the coating sags due to the centrifugal force caused by the rotation. How to paint. 4. A method of coating the surface of an article to be coated with the low solvent type coating composition according to claim 2, wherein the low solvent type coating composition is coated at 30 to 80 ° C. A method for coating a low solvent type coating composition. 5. A low-solvent type coating composition according to claim 2 is applied to the surface of an article to be coated and then heat-cured to form a coating film on the surface of the article to be coated. A method for coating a solvent type coating composition.