JP2001181560A - Novel resin composition for coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for coatings which has excellent coating film qualities such as weather resistance, processibility, adhesion, corrosion resistance, etc., exerts a high solubility to organic solvents such as thinners, etc., shows an excellent shelf stability and ensures safety at working. SOLUTION: The resin composition for coatings contains (a) an alicyclic group-containing compound A of formula 1, wherein R is remaining residue of an organic compound having at least two active hydrogens selected from the group consisting of phenols, amines, aromatic carboxylic acids, aliphatic carboxylic acids having a carbon number of >=4 and alcohols having a carbon number of >=3 which partially or totally leaves out the active hydrogens; X is an unsaturated alicyclic group of formula (1-1); Y is a reactive functional group of formula (1-2); and X+Y is >=1 and (b) a compound B having a functional group which is reactive against the alicyclic group-containing compound A and/or at least one compound (C) which catalyzes the reaction among the alicyclic group-containing compounds A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel resin composition for coatings, and more particularly, to a coating composition having good solubility in organic solvents such as thinner, good workability, and being safe and excellent in weather resistance. The present invention relates to a coating resin composition having excellent film quality. In particular, the present invention relates to a resin composition for paints having suitable performance as a paint for powder coating.

[0002]

2. Description of the Related Art In the field of paints, epoxy resins are widely used in anti-corrosion and undercoat paints because of their excellent adhesion and corrosion resistance. However, due to poor weather resistance, their use in the paint field is limited. It has been done.

On the other hand, various resins having excellent weather resistance are used, but none of them have corrosion resistance and adhesion comparable to epoxy resins, and there is a strong demand for a resin having both weather resistance, corrosion resistance and adhesion. Have been.

[0004] Conventionally, triglycidyl isocyanurate is known as an epoxy resin which gives a cured product having excellent weather resistance. However, it has poor processability as a coating film quality and poor solubility in organic solvents. Furthermore, it has skin sensitization, and if it adheres to the skin during painting work, it may cause rash and there is a safety problem.

[0005] Some of the paints using isocyanates have excellent weather resistance, but have a problem that the pot life is short. To solve this problem, blocked isocyanates are used. In this case, there is a problem that the volatilization of the blocking reagent not only contaminates the heating furnace but also significantly impairs the working environment. In particular, this problem has caused serious problems in application to powder coatings.

In particular, if it is limited to powder coating applications, it has been proposed to use a tetramethoxymethylglycoluril or β-hydroxyalkylamide-based curing agent as a resin having good weather resistance and being safe in the coating operation. . However, there is a problem in that both of them have desorbed substances during the heat curing, which deteriorates the coating film quality and further contaminates the heating furnace.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the needs in the market for a coating composition having both weather resistance and a coating quality comparable to that of an epoxy resin. An object of the present invention is to provide a resin composition for a paint in which the problem has been solved. That is, excellent weather resistance, workability,
An object of the present invention is to provide a coating resin composition having excellent coating film quality such as adhesion and corrosion resistance, good solubility in an organic solvent such as thinner, excellent storage stability, and safe in workability. It is another object of the present invention to provide a resin composition for paints having a performance particularly suitable as a paint for powder coating.

[0008]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a specific novel resin composition has particularly excellent properties, and have completed the present invention.

That is, the present invention provides: (A) Compound (B) having a functional group which reacts with alicyclic group-containing compound (A) represented by the following general formula (1) and (b) alicyclic group-containing compound (A) and / or alicyclic group A novel resin composition for a coating material, comprising one or more compounds (C) having a catalytic action of causing the contained compounds (A) to react with each other;

[0010]

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Wherein R is a phenol, an amine,
Organic compounds having at least two active hydrogen atoms selected from aromatic carboxylic acids, aliphatic carboxylic acids having 4 or more carbon atoms, and alcohols having 3 or more carbon atoms, except for some or all of the active hydrogen atoms Represents a group. Also,
x, y, a, and b represent an integer of 0 or more, and (x + y + a +
b) is 2 or more, and (x + y) represents an integer of 1 or more. X represents an unsaturated alicyclic group represented by the following general formula (1-1).

[0012]

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(Wherein n is an integer selected from 1 and 2, P is hydrogen, Q is a hydrocarbon group having 15 or less carbon atoms which may have an unsaturated double bond, a halogen group, a hydroxyl group, Represents at least one group selected from an amino group and a glycidyl group, p and q represent an integer of 0 to 9, and when n is 1, p + q is 7, and when n is 2, p + q is 9.) Y represents a reactive functional group represented by the following general formula (1-2).

[0014]

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(Wherein m is an integer selected from 1 and 2, P is hydrogen, Q is a hydrocarbon group having 15 or less carbon atoms which may have an unsaturated double bond, a halogen group, a hydroxyl group, Represents an amino group or a glycidyl group, p and q each represent an integer of 0 to 9, and when m is 1, p + q is 7; when m is 2, p + q is 9)

2. The alicyclic group-containing compound (A) represented by the general formula (1) is represented by the following general formula (2). The novel resin composition for coatings described,

[0017]

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(Wherein R is a phenol, an amine,
Organic compounds having at least two active hydrogen atoms selected from aromatic carboxylic acids, aliphatic carboxylic acids having 4 or more carbon atoms, and alcohols having 3 or more carbon atoms, except for some or all of the active hydrogen atoms Represents a group. Also,
x and y are positive integers including 0, and (x + y) is 2
Represents the above integer. X represents an unsaturated alicyclic group represented by the following general formula (2-1).

[0019]

Embedded image (N is an integer selected from 1 and 2) Y represents an alicyclic epoxy group represented by the following general formula (2-2). )

[0020]

Embedded image (M is an integer selected from 1 and 2)

3. In the general formula (1), R is a bisphenol compound residue. Or 2. The novel resin composition for coatings described,

4. In the general formula (1), x is 0 and a is 0. The novel resin composition for coatings described,

5. 2. In the general formula (2), x = 0. Or 3. The novel resin composition for coatings described,

6. The above-mentioned 1., wherein R is a terephthalic acid residue in the general formula (2). Or 5. The novel resin composition for coatings described,

[7] In the general formula (1), when y = 0 and b = 0. The novel resin composition for coatings described,

8. In the general formula (2), 2. Or 3. The novel resin composition for coatings described,

9. The compound (B) having a functional group which reacts with the alicyclic group-containing compound (A) is a polyester resin having a carboxyl group and / or an acrylic resin having a carboxyl group and / or amines. ~
5. The novel resin composition for coatings described,

10. A novel resin for coatings, comprising one or more prepolymers obtained by reacting an alicyclic group-containing compound (A) with a compound (B) having a functional group that reacts with the alicyclic group-containing compound. Composition,

(11) The above-mentioned 1., which contains one or more curing accelerators. -10. 11. The novel resin composition for a coating according to the above, 1. The above-mentioned 1., which contains one or more pigments. ~ 11. 12. The novel resin composition for a coating according to the above, The above-mentioned 1., which contains one or more additives. ~ 12. 13. The resin composition for a novel coating according to the above, 1. The above-mentioned 1., which contains one or more diluents. ~ 13. 14. The novel resin composition for coatings according to the above, 1. ~ 13. Described above. Hereinafter, the present invention will be described in detail.

I. The alicyclic group-containing compound (A) represented by the general formulas (1) and (2) The active hydrogen in the present invention means a hydrogen atom bonded to an oxygen atom, a nitrogen atom, and a sulfur atom. Active hydrogen-containing groups having these active hydrogens, for example, a phenolic hydroxyl group that is a hydroxyl group bonded to an aromatic ring, an alcoholic hydroxyl group that is a hydroxyl group bonded to a carbon atom other than an aromatic ring, an amino group, an imino group, a carboxyl group, The active hydrogen represented by the present invention means a hydrogen atom existing in these functional groups.

In the present invention, the above formulas (1) and (2)
R in the above is an organic compound having at least two active hydrogens selected from phenols, amines, aromatic carboxylic acids, aliphatic carboxylic acids having 4 or more carbon atoms, and alcohols having 3 or more carbon atoms. And a residue excluding a part or all of the active hydrogen.

The phenols, amines, aromatic carboxylic acids, aliphatic carboxylic acids having 4 or more carbon atoms, and alcohols having 3 or more carbon atoms, which are precursors of the residue according to the present invention, have active hydrogen in the molecule. At least one selected from a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, an imino group, and a carboxyl group as the functional group having a containing group
A structure in which at least two or more active hydrogens are present in a molecule by essentially having these kinds of functional groups and further having only these functional groups or simultaneously having these functional groups and other active hydrogen-containing groups. Is required.

The phenols of the present invention are organic compounds having at least two active hydrogens and at least one phenolic hydroxyl group, and may have another active hydrogen group at the same time. To give a concrete example,
Bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1- (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxybenzophenone, 4,4 ′
Bisphenols such as dihydroxybiphenyl, 3,3 ', 5,5'-tetramethylbiphenyl, brominated bisphenol A, bis (4-hydroxyphenyl) sulfone; catechol, resorcinol, hydroquinone,
Mononuclear polyphenols such as pyrogallol; polynuclear polyphenols such as naphthalene diol, resole type phenolic resin and cresol novolak resin; and hydroxyphenyl terminal aromatic polycarbonates, aromatic polyesters and aromatic polysulfones There are polymer-type phenols; other active hydrogen-containing phenols such as aminophenol; and derivatives thereof.

The amines of the present invention are organic compounds having at least two or more active hydrogens and one or more amino groups in the molecule, and may have other active hydrogen groups at the same time. Specific examples include methylamine, isopropylamine, 3,3′-iminobis (propylamine),
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dicyandiamide, 1,3,6
Aliphatic amines such as trisaminomethylhexane, hexamethylenediamine and allylamine; alicyclic amines such as mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane and 3-bisaminomethylcyclohexane Heterocyclic amines such as piperazine and N-aminoethylpiperazine; aromatic amines such as metaxylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, bismethylaminodiphenylamine, aniline and phenylenediamine; Other active hydrogen-containing amines such as -phenyl-4cyclooctenylamine, diethanolamine; and derivatives thereof.

The aromatic carboxylic acids of the present invention are organic compounds having at least two active hydrogens and having at least one carboxyl group directly attached to the aromatic ring in the molecule, and further having another active hydrogen group. At the same time. Specific examples include aromatic polycarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, trimellitic acid, and hemimellitic acid; polynuclear aromatic carboxylic acids such as naphthalene dicarboxylic acid; hydroxybenzoic acid, amino Other active hydrogen-containing aromatic carboxylic acids such as benzoic acid; and derivatives thereof.

The aliphatic carboxylic acids of the present invention refer to a carboxyl group having at least two active hydrogens and directly attached to a saturated and / or unsaturated aliphatic (ring) aliphatic hydrocarbon having 4 or more carbon atoms. Organic compound having at least one active hydrogen group therein, and may further have another active hydrogen group at the same time.
Specific examples include aliphatic dicarboxylic acids such as pimelic acid, suberic acid, azelaic acid, sebacic acid and undecandioic acid; unsaturated aliphatic dicarboxylic acids such as dihydromuconic acid;
Tetrahydrophthalic anhydride, such as dimer acid, 1,2,2
Aliphatic (cyclic) polycarboxylic acids such as 3-propanetricarboxylic acid and 4-methylhexahydrophthalic acid; and other active hydrogen-containing aliphatic (cyclic) carboxylic acids such as aminovaleric acid and oxyundecanoic acid; There are derivatives.

Active hydrogen having 3 or less carbon atoms must be at least 2
In the case of the aliphatic carboxylic acid having more than one, the drying property tends to decrease, and the appearance of the cured coating film tends to decrease.

The alcohols of the present invention are defined as alcohols having at least two active hydrogens and directly attached to a saturated and / or unsaturated aliphatic (ring) group hydrocarbon having 3 or more carbon atoms in one molecule. It is an organic compound having at least one active hydrogen group and may have another active hydrogen group at the same time. Specific examples include propylene glycol, butanediol,
Neopentyl glycol, neopentanediol, isopentylglycol, 1,6-hexanediol, glycerol, trimethylolethane, trimethylolpropane, pinacol, pentanediol, 2-butene-
1. Aliphatic diols such as 4-diol; polyhydric alcohols such as glycerin, erythritol and adunit; alicyclic polyols such as cyclohexanediol, cyclohexanetriol, cyclohexenediol. 1.2.4 Polyhydric nucleus-containing polyols such as trimethylolbenzene; other active hydrogen-containing alcohols such as aminocyclohexanol and hydroxybenzyl alcohol; and derivatives thereof.

Active hydrogen having 2 or less carbon atoms is converted into at least 2
In the case of aliphatic carboxylic acids having more than one, the drying property is poor,
High volatility significantly impairs working environment.

In the present invention, hydroquinone, resorcinol, bisphenols and the like are used as organic compounds which are precursors of the residue because they are very easily industrially available and can provide a sufficiently cured coating film. , Triphenols, aniline, hexamethylenediamine, isophoronediamine, diaminodiphenylmethane, terephthalic acid, isophthalic acid, trimellitic acid can be suitably used,
Particularly, bisphenols, terephthalic acid and trimellitic acid are preferred.

The alicyclic group-containing compound (A) according to the present invention, as represented by the general formula (1), has an unsaturated alicyclic group represented by X and an alicyclic group The formula epoxy group Y, allyl group and glycidyl group are bonded. In the present invention, x, y, a, and b in the formula are positive integers including 0, (x + y + a + b) is 2 or more, and (x + y) is an integer of 1 or more. is there.

In the present invention, (x + y + a + b) is usually in the range of 2 to 3000, preferably in the range of 2 to 2
000, more preferably 2 to 500. (X + y
When + a + b) is less than 2, when used as various cross-linking agents, the cured product obtained has not only low glass transition point and low corrosion resistance, but also low cross-linking point density and sufficient mechanical strength such as hardness and impact strength. This is not desirable because it tends not to be obtained. When (x + y + a + b) exceeds 3000, the melting temperature of the alicyclic group-containing compound (A) of the present invention tends to be high, and the viscosity at the time of melting tends to be high, so that the coating tends to be difficult. is there. Furthermore, (x + y) is 30
If it exceeds 00, it tends to be difficult to dissolve in various solvents, and for example, it tends to be difficult to use it as a solvent-based paint.

In the alicyclic group-containing compound (A) of the present invention, the case represented by the general formula (2), wherein a = 0 and b = 0 in the general formula (1), preferable. In the case of the alicyclic group-containing compound represented by the general formula (2),
The resulting cured product has a higher glass transition point than when an allyl group or a glycidyl group is contained as a reactive functional group.

The alicyclic group-containing compound (A) represented by the general formula (2) of the present invention comprises an unsaturated alicyclic group represented by X and an alicyclic epoxy group represented by Y in the molecule. They may be contained at the same time, or may have only one of the reactive alicyclic groups. In particular, in the present invention, X and Y in the same molecule
It is preferable that the ratio of any of the reactive alicyclic groups is high. Furthermore, a case where only one of the reactive alicyclic groups is present, that is, a case where x = 0 or a case where y = 0 in the general formula (2) is preferable. When the above-mentioned unsaturated alicyclic group and alicyclic epoxy group are simultaneously contained in the molecule, it is necessary to simultaneously use a curing agent and a curing catalyst suitable for each reactive alicyclic group. Need to be performed in two stages for each case, and the process of obtaining a cured product tends to be complicated.

When x = 0 in the general formula (2),
Since it has only an alicyclic epoxy group in the molecule as a crosslinkable reactive group, a crosslinking reaction can be performed only with a curing agent generally used for an epoxy compound.

When y = 0 in the general formula (2), the unsaturated double bond can be subjected to a crosslinking reaction using only a generally used reaction catalyst or reaction initiator.

Further, in the alicyclic group-containing compound (A) of the present invention wherein y = 0 in the general formula (2), various functional groups are introduced into the unsaturated double bond contained in the alicyclic group. By this, many useful compounds can be derived, and by performing an epoxidation reaction of the unsaturated double bond, an alicyclic ring of y = 1 or more or x = 0 in the general formula (2) of the present invention. An alicyclic group-containing compound (A) containing a formula epoxy group can be obtained.

In the present invention, formulas (1-1), (1-2),
N and m shown in (2-1) and (2-2) are 1
Or 2 and the substituents when n and m are 1 and 2 may be present simultaneously in the same molecule. When n and m are 0 or more than 2, when used as a crosslinking agent, the glass transition temperature of the cured product tends to decrease. In the present invention, it is preferable that both n and m are 2, since the glass transition point and the corrosion resistance tend to be high.

P in the above formula is a hydrogen atom, and Q is a hydrocarbon group having 15 or less carbon atoms, which may have an unsaturated double bond, a halogen group, a hydroxyl group, an amino group, a glycidyl group. Represents a group. The halogen means fluorine, chlorine, bromine and iodine. In the formula, p and q are integers of 0 to 9, and when n and m are 1, p + q represents 7, and when n and m are 2, p + q represents 9. In the present invention,
A compound with q = 0 is desirable in that corrosion resistance and weather resistance are improved.

The properties of the alicyclic group-containing compound (A) of the present invention depend on the structure of the above-mentioned residue.
Further, there may be a case of a wax, a solid, a crystalline solid or the like. The structure of the alicyclic group-containing compound (A) of the present invention has been described above, and representative structures thereof will be described below.

[0051]

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The method for producing the alicyclic group-containing compound (A) of the present invention will be described below. First, in the above equation (1), y =
An alicyclic group-containing compound (A) wherein 0 and b = 0
The production method of is described.

In the above formula (1) of the present invention, the alicyclic group-containing compound (A) represented by y = 0 and b = 0 is an organic compound having at least two or more active hydrogens,
It can be obtained by reacting the functional group having active hydrogen with a cycloalkenyl compound having a functional group capable of reacting.

For example, a method of reacting cyclohexenol or cyclopentenol with active hydrogen of the organic compound, or a method of reacting cyclohexene halide, cyclopentene halide or allyl halide with active hydrogen of the organic compound and dehydrohalogenation. There is a method of coupling. Further, in the present invention, if the resulting alicyclic group-containing compound has the structure of the alicyclic group-containing compound (A) of the present invention, R in the above formula (1)
The organic compound serving as a precursor of the residue represented by may have acid chloride as a reactive functional group. In this case, the alicyclic group-containing compound (A) of the present invention may be obtained by subjecting the acid chloride site to a dehydrochlorination reaction using cyclohexenol or cyclopentenol.

Further, a cyclopentyl group or a cyclohexyl group having a hydroxyl group or a halogen group as shown in the following formula is bonded to an organic compound which is a precursor of the residue represented by R in the above formula (1). By performing intramolecular dehydration and intramolecular dehydrohalogenation as a subsequent step,
A method of generating an unsaturated bond so as to have a structure represented by the formula (1-1) may be used.

[0056]

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The alicyclic group-containing compound having y = 0 in the general formula (2) obtained by the above-described synthesis method can be obtained by filtration, solvent extraction, water washing, column separation, distillation, recrystallization (crystal Can be easily purified by combining generally known means such as the case of sex.

Next, a method for producing a compound in which y in formula (1) is at least 1 will be described.

The compound in which y is at least 1 in the above formula (1) is a compound in which y = 0 and b = 0 in the formula (1) obtained by the above method, or a compound of the general formula (2)
In which the carbon-carbon double bond in the alicyclic group and in the allyl group of the compound in which v = 0 is epoxidized using an oxidizing agent, and 3-chloro-1,2 is added to a phenolic hydroxyl group or the like.
-Cyclohexene oxide and / or 3-chloro-1,
A method obtained by reacting 2-cyclopentene oxide, a halohydrin method in which the double bond is formed into a halohydrin structure by hypochlorous acid or the like, and then epoxidized by dehydrochlorination using an alkali such as caustic soda can be employed. .

In the present invention, the production method of or from the viewpoint that the selectivity and the halogen waste can be reduced is preferable. In the case of the above method, unreacted compounds having a halohydrin structure, which are difficult to purify and remove, tend to remain in the subsequent epoxidation step with an alkali, and the purity of the product tends to decrease.

The alicyclic group-containing compound in which y is at least 1 in the formula (1) obtained by the above-described synthesis method is subjected to filtration, solvent extraction, water washing, column separation, distillation, recrystallization (crystal Can be easily purified by combining generally known means such as the case of sex.

II. Compound (B) having a functional group that reacts with alicyclic group-containing compound (A) The resin composition for a novel coating material of the present invention comprises a compound (B) having a functional group that reacts with the alicyclic group-containing compound (A). Specific examples include carboxyl group-containing polyester resin, carboxyl group-containing acrylic resin, carboxyl group-containing silicone resin, carboxyl group-containing fluoro resin, and carboxyl group-containing polycarbonate resin. In the case of these compounds, those containing an acid anhydride as a functional group instead of a carboxyl group are also used as suitable compounds. Particularly preferably,
A carboxyl group-containing polyester resin and a carboxyl group-containing acrylic resin.

Specific examples of the carboxyl group-containing polyester resin include a reaction product of a polyol with a dicarboxylic acid and its acid anhydride or / and a polyvalent carboxylic acid and its acid anhydride. As the polyol, ethylene glycol, 1,3-butanediol, neopentanediol, isopentyl glycol,
Examples include 1,6-hexanediol, glycerol, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, polypropylene glycol, polyethylene glycol, polytetramethylene glycol, and cyclohexanediol.
Suitable dicarboxylic acids and their anhydrides include isophthalic acid, terephthalic acid, phthalic acid and its anhydride, methylphthalic acid and its anhydride, tetrahydrophthalic acid and its anhydride, methyltetrahydrophthalic acid and its acid Anhydrides, cyclohexanedicarboxylic acid, succinic acid and its anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, 4,4-diphenylcarboxylic acid and the like. . Suitable tricarboxylic acids and their anhydrides include 1,2,3-propanetricarboxylic acid, trimellitic acid and its anhydride, hemi-mellitic acid and its anhydride, and the like. Preferred tetracarboxylic acids and their anhydrides include pyromellitic acid and its anhydrides, benzophenone-3,
3 ', 4,4'-tetra-carboxylic acid and acid anhydrides thereof, and the like.

As specific examples of the carboxyl group-containing acrylic resin, acrylic acid or methacrylic acid and styrene, vinyltoluene, acrylic acid or methacrylic acid alkyl esters having 1 to 8 carbon atoms can be used to initiate radical polymerization of peroxide or the like. Copolymers reacted at a temperature of 80C to 150C using the agent. Examples of the alkyl ester of acrylic acid or methacrylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, ( Examples thereof include n-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-octyl (meth) acrylate. However, the above (meth) acrylic acid means acrylic acid or methacrylic acid.

As the compound (B) having a functional group that reacts with the alicyclic group-containing compound (A) in the novel coating resin composition of the present invention, a curing agent for epoxy can be mentioned. Examples thereof include amines, phenols, thiols, polycarboxylic acids and anhydrides thereof, which are used as curing agents for epoxy resins.

Specific examples of amines include ethylenediamine, propane-1,2-diamine, and propane-1,3-diamine.
Diamine, n, n-diethylethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, n- (2-
(Hydroxyethyl)-, n- (2-hydroxypropyl)-and n- (2-cyanoethyl) -diethylenetriamine, 2,2,4-trimethylhexane-1,6-
Diamine, 2,3,3-trimethylhexane-1,6-
Diamines n, n-dimethyl and n, n-diethylpropane-1,3-diamine, ethanolamine, bis (4
-Aminocyclohexyl) methane, 2,2-bis (4-
Aminocyclohexyl) propane, 2,2-bis (4-
Amino-3-methylcyclohexyl) propane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine) and n- (2-aminoethyl) -piperazine, dicyandiamide, polyaminoamide, and Mannich of these amines Modifications such as polyaminoamides prepared from aliphatic polyamines and dimerized or trimerized unsaturated fatty acids, adducts of amines with sub-stoichiometric amounts of polyepoxides such as diglycidyl ether, adipic hydrazide, and thiols such as thiochol And polythiol.

The compound (B) having a functional group capable of reacting with the alicyclic group-containing compound (A) in the novel resin composition for coatings of the present invention includes monomers, oligomers and polymers having a carbon-carbon double bond. And compounds capable of undergoing a Michael addition reaction. Specific examples include styrene, MMA, divinylbenzene, diallyl phthalate, cyclopentadiene derivatives, epoxy acrylates, unsaturated polyesters, unsaturated group-containing acrylic resins, unsaturated group-containing silicone resins, unsaturated group-containing fluorine resins, and unsaturated groups. Examples include a group-containing polycarbonate resin, an unsaturated group-containing urethane resin, and amines.

In the composition of the present invention, the equivalent ratio of the compound having a functional group which reacts with the compound having a functional group which reacts with the alicyclic group-containing compound (A) is in the range of 0.5: 1 to 2: 1. Used.

III. Compound (C) having a catalytic action to cause alicyclic group-containing compounds (A) to react with each other Compound (C) having a catalytic action to cause alicyclic group-containing compounds (A) to react with each other in the novel coating resin composition of the present invention As imidazoles, anionic curing agents for epoxy resins such as tertiary amines,
Boron trifluoride or antimony hexafluoride and complexes thereof, for example, chelates formed by reaction with amines or 1,3-diketones, Al silanol complexes, S
Cationic curing agents for epoxy resins such as nCl ₄ and AlCl ₃ can be mentioned.

Further, in the novel coating resin composition of the present invention, a catalyst for reacting a carbon-carbon unsaturated double bond as a compound having a catalytic action for reacting alicyclic group-containing compounds with each other,
Specific examples include organic peroxides such as ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and percarbonates.

In the composition of the present invention, the compound (C) having a catalytic action of causing the alicyclic group-containing compound (A) 100 represented by the general formula (1) to react with the alicyclic group-containing compound is 0%. 0.11 to 50 parts by weight.

IV. Prepolymer alicyclic group-containing compound (A)
And a compound (B) having a functional group that reacts with the alicyclic group-containing compound. The prepolymer is obtained by heating and reacting the above two components in the presence or absence of a catalyst. In this case, the ratio of the alicyclic group-containing compound and the compound having a functional group that reacts with the alicyclic group-containing compound is such that the alicyclic group-containing compound is in an excess in an equivalent amount, and further the gelation or the molecular weight becomes 50,000 or more. It is selected within a range that does not increase the molecular weight. When the molecular weight is 50,000 or more, the solubility or fluidity of the solvent is extremely poor, and a suitable coating composition cannot be obtained. As specific examples of the compound (B) having a functional group that reacts with the alicyclic group-containing compound, the compounds described in II are suitably used. The composition containing the prepolymer can be obtained by separately reacting in a reaction kettle and then mixing, and a method of adjusting the temperature and the like in a kneader such as an extruder to simultaneously form the prepolymer simultaneously with mixing is also available. Can be adopted.

V. Curing Accelerator In the novel coating resin composition of the present invention, an epoxy resin curing accelerator can be suitably used as a curing accelerator.

Specific examples include a tertiary amine or a salt thereof,
Quaternary ammonium compounds, phosphines, phosphonium salts or alkali metal alkoxides can serve as accelerators. For example, n-benzyldimethylamine,
Examples include 2,4,6-tris (dimethyl-aminomethyl) -phenol, imidazoles, trimethylammonium phenoxide, triphenylphosphine, and ethyltriphenylphosphonium bromide.

Also, boron trifluoride or antimony hexafluoride and its complexes, for example, amines or 1,3-
A chelate formed by a reaction with a diketone, an Al silanol complex, a compound used as a cationic curing agent for an epoxy resin such as SnCl ₄ or AlCl ₃ can be used as an accelerator.

Other accelerators which can be used include metal nitrates, especially magnesium nitrate and manganese nitrate, fluorinated and chlorinated carboxylic acids and their salts (eg magnesium trifluoroacetate, sodium trifluoroacetate, magnesium trichloroacetate) Acetate and sodium trichloroacetate, trifluoromethanesulfonic acid and its salts (eg manganese,
Zinc, magnesium, nickel and cobalt salts) and magnesium perchlorate and magnesium perchlorate and calcium perchlorate.

VI. Pigment As the pigment of the resin composition for a novel coating of the present invention, coloring pigments and extenders generally used for coatings can be used.

Specific examples of color pigments include organic pigments; azo pigments, copper phthalocyanine pigments, basic dye lakes, acid dye lakes, mordant dye pigments, vat dye pigments, quinacridone pigments, dioxazines. Pigments, condensed azo pigments, etc., as carbon black, inorganic pigments; chromates, ferrocyanides, oxides such as titanium white, selenide sulfides, silicates, carbonates, phosphates,
Metal powder and the like.

As the extender, barium sulfate, barium carbonate, powder, gypsum, alumina white, clay, silica, talc, calcium silicate, magnesium carbonate and the like can be used.

VII. Additives Additives used in the novel coating resin composition of the present invention include dryers such as cobalt naphthenate, anti-skinning agents such as methoxyphenol and cyclooxane oxime, highly polymerized linseed oil, organic bentonite, silica and the like. Thickeners, anti-floating agents and color-separation inhibitors such as fatty acids, lecithin and silicone oil, pitting inhibitors such as benzoin, and flow regulators such as modaflow can be suitably used.

VIII. Diluent As the diluent used in the novel coating resin composition of the present invention, an organic solvent which is non-reactive or / and reactive and is preferably used for decreasing the viscosity of the coating composition is used. Is done. Water is also a suitable diluent if a dispersant or emulsifier is used.

Specific examples of non-reactive diluents include: acetone, methyl ethyl ketone, methyl isobutyl ketone,
Toluene, xylene, cellosolve and the like can be mentioned.

As reactive diluents, butyl glycidyl ether, neopentyl diglycidyl ether, 1.
6-hexanediol and the like can be mentioned.

In the novel coating composition of the present invention, the alicyclic group-containing compound (A) and the epoxy compound may be used in combination. That is, the compound (B) having a functional group which reacts with the alicyclic group-containing compound (A) by using the alicyclic group-containing compound (A) alone or in combination with one or more epoxy compounds. Alternatively, if a curing reaction is carried out with a compound (C) having a catalytic effect of causing the alicyclic group-containing compounds to react with each other, an excellent cured resin for paint can be obtained. Examples of the epoxy compound used in combination include phenolic epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, epoxy cresol novolak resin, and epoxyphenol novolak resin;
Glycidyl ester resins such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate and glycidyl dimer; glycidyl amine resins such as diglycidylaniline and tetraglycidyldiaminodiphenylmethane; 1.4 Butanediol diglycidyl ether, trimethylolpropane triglycidyl ether,
Aliphatic epoxy resins such as aliphatic epoxy carboxylate.

The novel coating composition of the present invention is applied to a material to be coated with a spray, a roll, a brush, a roll coater or the like, and then left at an ambient temperature or heat is applied, or a radiation such as UV or electron beam is irradiated. Thereby, a durable coating film can be formed.

The novel coating composition of the present invention is preferably a metal,
The present invention can provide a paint which gives a high-quality coating film with good curability and excellent workability for use in cans, automobiles, ships or construction / construction materials as a protective material for concrete bodies, wood and plastic materials.

A preferred field of application is powder coating applications.
Particularly, a resin composition suitable for a powder coating application applied to a site where weather resistance is required is provided. Hereinafter, the present invention will be specifically described with reference to Synthesis Examples and Examples.

(Synthesis Example 1) Sodium hydride was placed in a 500 ml round bottom flask equipped with a stirrer and a thermometer.
54 g (product containing 40% by weight of oil) was added, 20 g of dehydrated n-hexane was added, and the operation of stirring for 20 minutes and removing the hexane was performed three times to wash and remove the oil attached to the sodium hydride. Then, 260 g of dehydrated dimethylformamide was added, and then 23.5 g of bisphenol A (0.1 g) was slowly added while cooling the flask with water.
03 mol) was added, followed by stirring for 2 hours. During the addition of bisphenol A, bubbles of hydrogen were generated and the liquid turned yellow as the sodium salt of bisphenol A was formed.

After 2 hours, 26.50 of 3-chlorocyclohexene was added using a dropping funnel while stirring the above solution.
g (0.227 mol) was added dropwise over 1 hour, after which stirring was continued. During the dropwise addition and during the stirring after the completion of the dropwise addition, the outside of the flask was water-cooled, and the temperature of the reaction solution was kept in the range of 24 to 45 ° C.

Twenty hours after the completion of the dropwise addition, the reaction mixture was analyzed by liquid chromatography to find that bisphenol A
(Or its sodium salt) peak was not detected, and the conversion of bisphenol A was 100%.

After the completion of the above reaction, 3 ml of water was added to the reaction solution to deactivate excess sodium hydride. Next, 100 ml of n-hexane was added to the reaction solution, and the mixture was vigorously stirred to extract the product into the hexane phase.
I went there. The obtained n-hexane solution was washed five times with 200 ml of distilled water, and then dried over anhydrous magnesium sulfate. Further, after the filtration treatment, the obtained n-hexane solution was evaporated to obtain 38.63 g of a pale yellow viscous transparent liquid (A-1). As a result of analysis by liquid chromatography, the purity of the main product was 96%.
Met.

Next, 300 m equipped with a stirrer and a thermometer
l three-necked flask with sodium tungstate (Na
₂ WO ₄ · 2H ₂ O) and 0.33 g (1 mmol), 31
8.17 g of 85% aqueous hydrogen peroxide, 0.12 of 85% aqueous phosphoric acid solution
g and stirred while cooling the flask with ice water. The pH of the solution thus adjusted was 1.8.
Met.

On the other hand, 10.0 g of toluene, CH ₃ N
[(CH ₂ ) ₇ CH ₃ ] ₃ Cl (manufactured by Aldrich, Aliqua
t 336) 0.30 g and the above viscous transparent liquid 7.00 g
Was prepared, and this was designated as solution B.

While the above solution A was vigorously stirred under cooling with water, the solution B was slowly dropped using a dropping funnel over about 20 minutes. After the completion of the dropping, the mixture was stirred for 40 hours.

After completion of the reaction, the toluene layer was separated using a separating funnel, and a 1N aqueous sodium thiosulfate solution (20 m
l, distilled water 20 ml, 1N aqueous sodium hydrogen carbonate solution 20 ml, and distilled water 20 ml in this order, the toluene solution was washed.

The obtained toluene solution was dried over anhydrous magnesium sulfate, and anhydrous magnesium sulfate was removed by filtration.
The solution was diluted with 100 ml of toluene, and 100 g of dry silica gel was added. After stirring for 1 hour, the silica gel was removed by filtration, and toluene was removed by evaporating the toluene solution obtained as a filtrate to obtain 7.51 g of a pale yellow highly viscous liquid compound which was almost colorless. As a result of analysis by liquid chromatography, the purity of the main product was 98.4%. Moreover, the measurement result of the epoxy equivalent was 215 g / equivalent.

As a result of the elemental analysis of the compound thus obtained, an IR measurement nuclear magnetic resonance spectrum (FIGS. 1 and 2) was analyzed, and an alicyclic group-containing compound (A-1) having a structure represented by the following formula was obtained. ).

[0098]

Embedded image

(Synthesis Example 2) Dimethyl terephthalate
2 g (0.3 mol) and 3-hydroxycyclohexene 5
After performing a transesterification reaction using 8.8 g (0.6 mol), an epoxidation reaction was performed with m-chloroperbenzoic acid,
By performing recrystallization twice, 26.8 g of a white solid was obtained. As a result of analysis by liquid chromatography, the purity of the main product was 99%. In addition, the measurement result of the epoxy equivalent was 180 g / equivalent.

As a result of elemental analysis of the compound thus obtained, an NMR measurement was performed to analyze a nuclear magnetic resonance spectrum, and the compound was identified as an alicyclic group-containing compound (A-2) having a structure represented by the following formula. .

[0101]

Embedded image

(Synthesis Example 3) Trimethyl trimellitate 2
A transesterification reaction was carried out using 5.2 g (0.1 mol) and 38.8 g (0.6 mol) of 3-hydroxycyclohexene, followed by an epoxidation reaction with m-chloroperbenzoic acid to obtain a highly viscous liquid. Was obtained 41.4 g. As a result of analysis by liquid chromatography, the purity of the main product was 98%. In addition, the measurement result of the epoxy equivalent was 169 g / equivalent.

As a result of the elemental analysis of the compound thus obtained, the nuclear magnetic resonance spectrum measured by IR (FIGS. 3 and 4) was analyzed, and an alicyclic group-containing compound (A-3) having a structure represented by the following formula was obtained. ).

[0104]

Embedded image

(Synthesis Example 4) Synthesis of Prepolymer I 210 g of the alicyclic group-containing compound (A-1) obtained in Synthesis Example 1 and 80 g of bisphenol A were added, 0.3 g of a 10% aqueous NaOH solution was added, and 180 ° C. The reaction was performed for 6 hours. The epoxy equivalent of the obtained prepolymer was 970 g / eq.

(Synthesis Example 5) Synthesis of Prepolymer II 180 g of the alicyclic group-containing compound (A-2) obtained in Synthesis Example 2 and 106 g of a carboxyl group-containing polyester having an acid value of 53 (GV230 manufactured by Nippon Yupika Co., Ltd.) In addition, 100 ℃
Reacted for 1 hour. The epoxy equivalent of the obtained prepolymer was 320 g / eq.

Synthesis Example 6 Synthesis of Carboxyl Group-Containing Acrylic Resin 70 g of methyl methacrylate, 23 g of butyl acrylate and 7 g of acrylic acid were dissolved in 400 g of methyl ethyl ketone, 2 g of azobisisobutylnitrile was added, and the mixture was reacted at 80 ° C. for 5 hours. Acid value 55 at 20% solids
Was obtained.

[0108]

Examples (Examples 1 to 3 and Comparative Examples 1 to 3) The compounds shown in Table 1 were mixed with a Henschel mixer and extruded while kneading with an extruder. The extrudate was cooled and ground to about 40 μm to obtain a powder coating. This paint was applied to a mild steel plate by electrostatic spraying and baked at 200 ° C. for 30 minutes to obtain a coating film test piece having a film thickness of 50 to 70 μm.

As shown in the lower part of Table 1, the composition of the present invention was excellent in the initial gloss and the gloss retention after the weather resistance test, and exhibited the same powder coating properties as the bisphenol A type epoxy resin. .

[0110]

[Table 1]

(Examples 4 and 5, Comparative Example 4) The formulations shown in Table 2 were prepared, and the viscosity was adjusted to 20 to 40 seconds with Ford Cup 4 using toluene. The clear paint was sprayed on a mild steel sheet by air spray and heat-cured at 180 ° C. for 30 minutes to obtain a mild steel sheet to be coated having a thickness of 30 to 40 μm.

As shown in the lower part of Table 2, the measurement results show that the composition of the present invention was excellent in the initial gloss and the gloss retention after the weather resistance test, and exhibited the same solvent-type coating properties as bisphenol A type epoxy resin. .

[0113]

[Table 2]

(Examples 6 and 7, Comparative Example 5) The compositions shown in Table 3 were prepared, and 90 to 10 were applied to mild steel plates using an applicator.
It was applied in a film thickness of 0 μm. After curing at room temperature for 7 days, the coating properties were measured.

As shown in the lower part of Table 2, the composition of the present invention is excellent in the initial gloss and the gloss retention after the weather resistance test, and has the same solvent-free paint properties as the bisphenol A type epoxy resin. Was.

[0116]

[Table 3]

[0117]

The present invention provides a coating composition having both weather resistance and coating properties comparable to conventional epoxy resins, that is, coating qualities such as weather resistance, workability, adhesion, and corrosion resistance. The present invention provides a resin composition for coatings which has excellent solubility, good solubility in organic solvents such as thinner, excellent curability, and is safe in workability and excellent in storage stability. In particular, the present invention provides a paint resin composition having suitable performance as a powder coating paint.

[Brief description of the drawings]

FIG. 1 is an IR absorption spectrum of the compound obtained in Synthesis Example 1.

FIG. 2 is a ¹ H-NMR spectrum diagram of the above.

FIG. 3 is an IR absorption spectrum of the compound obtained in Synthesis Example 3.

FIG. 4 is a nuclear magnetic resonance spectrum diagram of the same.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Hideki Date 3-13-1, Shiodori, Kurashiki-shi, Okayama Asahi Kasei Corporation (72) Inventor Mitsuo Konishi 3--13, Shiodori, Kurashiki-shi, Okayama 1 Asahi Kasei Kogyo Co., Ltd. (72) Inventor Yasushi Takahashi 10-66, Miyukicho, Takarazuka-shi, Hyogo Asahi Ciba Co., Ltd. F-term (reference) 4J038 CC001 CC002 CC011 CC012 CC021 CC022 CF101 CF102 CG011 CG012 CG141 CG142 CH031 CH032 CH041 CH042 CL001 CL002 CM001 CM002 CM011 CM012 CP061 CP062 CP111 CP112 CR071 CR072 DB211 DB212 DB261 DB262 DB392 DD001 DD002 DD181 DD182 FA011 FA012 GA01 GA06 GA07 HA126 HA256 HA326 JA66 JB01 JB04 JB05 JB08 JB17 JB32. MA14 NA03 NA07 NA12 NA26 NA27 PA02 PA13 PA14 PA19

Claims (15)

[Claims] 1. An alicyclic group-containing compound (A) represented by the following general formula (1) and (b) an alicyclic group-containing compound (A)
For a new coating material, which contains one or more compounds (C) having a catalytic action of reacting the compound (B) having a functional group which reacts with the compound (B) and / or the compound (A) having an alicyclic group with each other. Resin composition. Embedded image (Wherein R is an organic compound having at least two active hydrogen atoms selected from phenols, amines, aromatic carboxylic acids, aliphatic carboxylic acids having 4 or more carbon atoms, and alcohols having 3 or more carbon atoms) A residue excluding a part or all of the active hydrogen of the compound, and x, y, a, b
Represents an integer of 0 or more, (x + y + a + b) is 2 or more, and (x + y) represents an integer of 1 or more. Also,
X represents an unsaturated alicyclic group represented by the following general formula (1-1). Embedded image (In the formula, n is an integer selected from 1 and 2, P is hydrogen, Q is a hydrocarbon group having 15 or less carbon atoms which may have an unsaturated double bond, a halogen group, a hydroxyl group, an amino group, Represents at least one group selected from glycidyl groups, p and q represent integers of 0 to 9, and when n is 1, p + q is 7,
In the case where n is 2, p + q is 9) and Y represents a reactive functional group represented by the following general formula (1-2). Embedded image (In the formula, m is an integer selected from 1 and 2, P is hydrogen, Q is a hydrocarbon group having 15 or less carbon atoms which may have an unsaturated double bond, a halogen group, a hydroxyl group, an amino group, Represents a glycidyl group, p and q represent an integer of 0 to 9, and when m is 1, p + q is 7, and when m is 2, p + q is 9.) 2. The resin composition for a novel paint according to claim 1, wherein the alicyclic group-containing compound (A) has the following general formula (2). Embedded image (Wherein R is an organic compound having at least two active hydrogen atoms selected from phenols, amines, aromatic carboxylic acids, aliphatic carboxylic acids having 4 or more carbon atoms, and alcohols having 3 or more carbon atoms) Represents a residue excluding a part or all of the active hydrogen of the compound, x and y are positive integers including 0, and (x + y) represents an integer of 2 or more. (It represents an unsaturated alicyclic group represented by the formula (2-1).) (N is an integer selected from 1 and 2) Y represents an alicyclic epoxy group represented by the following general formula (2-2). ) (M is an integer selected from 1 and 2) 3. The resin composition according to claim 1, wherein R is a bisphenol residue in the general formula (1). 4. In the general formula (1), x = 0,
2. The resin composition according to claim 1, wherein a = 0. 5. The resin composition according to claim 2, wherein x = 0 in the general formula (2). 6. The resin composition according to claim 2, wherein R in the general formula (2) is a terephthalic acid residue. 7. In the general formula (1), y = 0.
The resin composition for a novel coating according to claim 1, wherein b = 0. 8. The resin composition according to claim 2, wherein y = 0 in the general formula (2). 9. The compound (B) having a functional group that reacts with the alicyclic group-containing compound (A) is a carboxyl group-containing polyester resin and / or a carboxyl group-containing acrylic resin and / or amines. ~ 6
The resin composition for a novel coating according to the above. 10. A prepolymer obtained by reacting an alicyclic group-containing compound (A) with a compound (B) having a functional group capable of reacting with the alicyclic group-containing compound, comprising one or more prepolymers. New resin composition for paint. 11. The resin composition for a novel coating composition according to claim 1, which comprises one or more curing accelerators. 12. The resin composition for a novel coating according to claim 1, which comprises one or more pigments. 13. The novel resin composition for coatings according to claim 1, which comprises one or more additives. 14. The novel coating resin composition according to claim 1, which comprises one or more diluents. 15. The resin composition for a novel powder coating according to claim 1.