JP3488175B2 - Resin composition for paint - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating resin composition comprising an unsaturated polyester resin and a urethane (meth) acrylate resin, more specifically, a coating resin composition excellent in heat resistance and crack resistance. It is about things.

[0002]

2. Description of the Related Art Conventionally, radical curable resins such as unsaturated polyester resins have been used for coating furniture, interior materials, household products, sealing materials, adhesives, molded products and the like. A coating film composed of such an unsaturated polyester-based resin has excellent properties in terms of drying property, coating film hardness, etc., but in order to impart a higher air-drying property, an allyl ether group is usually contained in the resin. Is being introduced. When the allyl ether group was introduced into the unsaturated polyester resin, the amount of the allyl ether group introduced was naturally limited due to restrictions in terms of production such as gel formation during resin production.

As a countermeasure against this, Japanese Patent Publication No. 2-57806.
In the publication, air-drying property is good, flexibility of coating film, weather resistance,
(A) unsaturated polyester resin, in order to improve water resistance,
(B) to 100 parts by weight of at least one radical-curable resin selected from urethane acrylic resin, polyester acrylic resin and epoxy acrylic resin
(A) Diisocyanate compound, (b) Polyester polyol or polyhydric alcohol, (c) Allyl ether of polyhydric alcohol, and (d) (meth) acrylic monomer 1.5-4.0 mmol / g of an allyl ether group and 0.4 to 2.0 mmol / g of a (meth) acryloyl group having a molecular weight of 450 to 700, 5 to 60 parts by weight of a urethane acryl oligomer, and (C) an ethylenically unsaturated monomer. An air-drying resin composition comprising 5 to 60 parts by weight of (D) a polymerization initiator of 0.1 to 10 parts by weight has been proposed.

[0004]

However, in the technology disclosed in Japanese Patent Publication No. 2-57806, although the air-drying property is good, the heat resistance and cracking resistance of the coating film are still unsatisfactory. Further improvement is desired. Therefore, in such a background under the present invention, it is an object to provide a coating for <br/> resin composition for forming the heat resistance, a coating film excellent in resistance to cracking.

[0005]

However, as a result of intensive studies conducted by the present inventors in view of such circumstances, at least one selected from a cyclopentadiene unit, a dicyclopentadiene type unit and a polyhydric alcohol allyl ether unit.
Coating resin unsaturated polyester resin (A) and a weight average molecular weight which has units of species consisting of urethane (meth) acrylate resin (B) represented by the following general formula 3,000 to 40,000 (1) We have found that the composition meets the above objectives and completed the present invention.

[0006]

[Chemical 2] Here, R ₁ is a urethane bond residue of hydroxy (meth) acrylate , R ₂ is a urethane bond residue at both ends of a polyisocyanate compound, R ₃ is a urethane bond residue at both ends of a polyol, and m is an integer of 1 to 20. .

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The unsaturated polyester-based resin (A) used in the present invention is not particularly limited, and is usually an unsaturated acid, an acid component (a1) containing a saturated acid if necessary, and a polyhydric alcohol (a2). Any condensation product may be used.

Examples of the unsaturated acid in the acid component (a1) include maleic acid, fumaric acid, itaconic acid, citraconic acid and their anhydrides. As the saturated acid, phthalic anhydride, phthalic acid, Terephthalic acid, isophthalic acid, het acid, adipic acid, sebacic acid, succinic acid,
Azelaic acid, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 6
-Methyl-4-cyclohexene-1,2,3 tricarboxylic acid anhydride and the like can be mentioned.

As the polyhydric alcohol (a2), ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hydrogenated bisphenol A, bisphenol A dioxypropoxy ether, bisphenol A dipolyoxypropoxy ether, bisphenol A Dioxyethoxy ether, bisphenol A dipolyoxyethoxy ether, 1,9-nonanediol, polypropylene glycol, polyethylene glycol, polytetramethylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene Glycol, 1,
6-hexanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentane-diol, neopentyl glycol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, glycerin, Examples thereof include diglycerin, pentaerythritol, cyclohexanedimethanol and the like.

In the present invention, at least one unit selected from cyclopentadiene-based units, dicyclopentadiene-based units and polyhydric alcohol allyl ether units is contained as the constitutional unit of the unsaturated polyester resin (A). It is necessary that the cyclopentadiene-based unit and the dicyclopentadiene-based unit include cyclopentadiene, dicyclopentadiene, and derivatives thereof, and examples of the derivative include tricyclodecenyl maleate, Tricyclodecenyl fumarate, tricyclodecenyl adipate, tricyclodecenyl phthalate, tricyclodecenyl isophthalate, tricyclodecenyl trimellitate, ethylene glycol tricyclodecenyl ether, diethylene glycol Tricyclodecenyl ether, Pyrene glycol tricyclodecenyl ether, 1,4-butanediol tricyclodecenyl ether, 1,6-hexanediol tricyclodecenyl ether, neopentyl glycol tricyclodecenyl ether, glycerin tricyclodecenyl ether, trimethylol Examples thereof include propane tricyclodecenyl ether and hydroxylated dicyclopentadiene.

Specific examples of the polyhydric alcohol allyl ether unit include glycerin monoallyl ether, glycerin diallyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, trimethylolethane monoallyl ether and trimethylolethane. Diallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, 1,2,6-hexanetriol monoallyl ether, 1,2,6-hexanetriol diallyl ether, sorbitan monoallyl ether, sorbitan diallyl Examples thereof include ethers, all of which are ethers having at least one hydroxyl group in the molecule.

The composition ratio of at least one unit selected from the cyclopentadiene type unit, the dicyclopentadiene type unit and the polyhydric alcohol allyl ether unit in the unsaturated polyester resin (A) is the resin composition of the present invention. When the curable resin composition is cured at room temperature or by heating, it is 10 to 50 mol% with respect to the acid component (a1).
Is more preferable. Particularly, in the case of a cyclopentadiene-based unit or a dicyclopentadiene-based unit, 20 to 5
It is more preferable that 0 mol% be present, and if such a ratio is less than 20 mol%, sufficient air-drying property cannot be obtained, and if it exceeds 50 mol%, rapid drying property is deteriorated, which is not preferable.

In the case of a polyhydric alcohol allyl ether unit, it is more preferable that it is present in an amount of 10 to 40 mol%, and if it is less than 10 mol%, sufficient air-drying property cannot be obtained. It is not preferable because no remarkable improvement was observed in comparison with the amount.

When the resin composition of the present invention is to be a curable resin composition which is cured by irradiation with active energy rays, it is more preferable to use 2 to 40 mol% with respect to the acid component (a1). In particular, in the case of cyclopentadiene-based units or dicyclopentadiene-based units, it is more preferable that the content is 15 to 30 mol%. If the ratio is less than 15 mol%, sufficient air-drying property cannot be obtained, and if it exceeds 30 mol%. The curability is lowered, which is not preferable.

In the case of a polyhydric alcohol allyl ether unit, it is more preferable that it is present in an amount of 10 to 40 mol%, and if it is less than 10 mol%, sufficient air-drying property cannot be obtained, and air-drying property is lowered, while 40 mol% Even if it is introduced in excess of%, it is not preferable because no remarkable improvement is seen in comparison with the amount.

The above-mentioned mol% is the respective proportions with respect to 1 mol of the acid component, and 50 mol% means 0.5 mol per 1 mol of the acid component.

In order to introduce such a cyclopentadiene-based unit or dicyclopentadiene-based unit into the unsaturated polyester resin (A), basically at least one of cyclopentadiene, dicyclopentadiene and derivatives thereof is treated with an acid. The condensation reaction is carried out by charging with the component (a1) and the polyhydric alcohol (a2), but the cyclopentadiene-based unit and the dicyclopentadiene-based unit are present in the main chain of the unsaturated polyester resin rather than at the terminal thereof. In this case, since the physical properties of the coating tend to be superior when applied to a coating or the like, in order to produce such a resin, at least one of cyclopentadiene, dicyclopentadiene and derivatives thereof is charged at the initial stage of condensation. Is desirable.

Further, the polyhydric alcohol allyl ether unit may be introduced into the unsaturated polyester resin (A) in the same manner as in the case of the above cyclopentadiene unit or dicyclopentadiene unit.

In the production of the unsaturated polyester resin (A), the above components may be used in accordance with a conventional method to carry out a condensation or addition reaction in an inert gas atmosphere at a temperature of about 150 to 250 ° C., The obtained unsaturated polyester resin (A) usually has an acid value of 10 to 40 KOHmg / g.
The acid value is preferably in the range of about 10 to 30 KOHmg / g by promoting esterification.

The weight average molecular weight of the unsaturated polyester resin (A) is preferably 5,000-40,000, more preferably 10,000-3.
10,000, more preferably 15,000 to 25,000
0, particularly preferably 15,000 to 20,000. When the weight average molecular weight is less than 5,000, the physical properties of the cured product are low and the curability is slow. On the contrary, when it exceeds 40,000, the viscosity becomes high and a large amount of diluting monomer is required, and the cured film becomes brittle, which is not preferable. .

The urethane (meth) acrylate resin (B) used in the present invention is not particularly limited as long as it has the structure represented by the general formula (1), and the polyol (b1) and the polyisocyanate ( It is a urethane (meth) acrylate resin obtained by reacting b2) with hydroxy (meth) acrylate (b3).

The polyol (b1) is not particularly limited and includes, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1 , 4-butanediol, polybutylene glycol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, poly Pentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, polytetramethylene glycol, etc. Polyhydric alcohol, polyethylene oxide, polypropylene oxide, polyether polyol having at least one structure of block or random copolymerization of ethylene oxide / propylene oxide, polyhydric alcohol or polyether polyol and maleic anhydride, maleic acid, Fumaric acid, itaconic anhydride, itaconic acid, adipic acid, polyester polyols that are condensation products with polybasic acids such as isophthalic acid, caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol, polyolefin-based polyols, hydrogenated polybutadiene polyols, etc. Examples of the polybutadiene-based polyol include

Particularly, the molecular weight is 200 to 10,000.
It is preferably 0, preferably 500 to 10,0
00, and more preferably 1,000 to 4,000.
If the molecular weight is less than 200, the crack resistance is reduced and
If it exceeds 10,000, the curability is lowered and the coating film becomes sticky, which is not preferable.

The polyisocyanate (b2) is not particularly limited, and examples thereof include aromatic, aliphatic, cycloaliphatic, and alicyclic polyisocyanates, among which tolylene diisocyanate ( TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (crude MDI),
Modified diphenylmethane diisocyanate (modified MD
I), hydrogenated xylylene diisocyanate (H-XD
I), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), trimethyl hexamethylene diisocyanate (TMXDI), tetramethyl xylylene diisocyanate (m-TMXD)
I), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (H ₆ XDI)
And the like, or a trimer compound of these polyisocyanates, reaction products of these polyisocyanates and polyols, and the like are preferably used. The molecular weight of the polyisocyanate compound (b2) is preferably less than 500, and when it exceeds 500, the reactivity with the diol decreases, which is not preferable.

Hydroxy (meth) acrylate (b3)
Is not particularly limited, and is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 4-butylhydroxy. (Meth) acrylate, 2- (meth) acryloyloxyethyl-2-
Hydroxypropyl phthalate, glycerin di (meth)
Acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, caprolactone modified 2
-Hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, and the like, among which 2-hydroxyethyl (meth) acrylate, 2-Hydroxypropyl (meth) acrylate is preferably used.

Regarding the method for producing the urethane (meth) acrylate resin (B), the polyol (b1),
The method is not particularly limited as long as it is a method of reacting the polyisocyanate (b2) and the hydroxy (meth) acrylate (b3), and a known method is adopted. For example, (1) a method in which three components of a polyol (b1), a polyisocyanate (b2), and a hydroxy (meth) acrylate (b3) are mixed together and reacted, (2) a polyol (b1) and a polyisocyanate (b2) To react 1 per molecule
A method of forming a urethane isocyanate intermediate containing one or more isocyanate groups and then reacting the intermediate with hydroxy (meth) acrylate (b3), (3) polyisocyanate (b2) and hydroxy (meth) acrylate (b3) To form a urethane (meth) acrylate intermediate containing one or more isocyanate groups per molecule, and then the intermediate and the polyol (b1)
And the like. Among them, the method (2) is preferable in terms of stability of reaction control and reduction of production time.

For example, the polyol (b1) and the polyisocyanate (b2) are n: n + 1 (molar ratio) (theoretical value).
(N is an integer of 1 or more), and then the reaction product is further reacted with hydroxy (meth) acrylate at a reaction molar ratio of 1: 2 (molar ratio) (theoretical value). It is preferable to react. (In the actual charging, an error of about several percent is allowed) In the above reaction, it is also preferable to use a catalyst such as dibutyltin dilaurate for the purpose of promoting the reaction.

Thus, the urethane (meth) acrylate resin (B) can be obtained. In the present invention, the urethane (meth) acrylate resin (B) has a weight average molecular weight of 3,000 to 4 in terms of standard polystyrene molecular weight.
It is necessary to be 50,000, preferably 5,000
~ 30,000, particularly preferably 10,000-27,
It is 000. If the weight average molecular weight is less than 3,000, the coating film becomes too hard and brittle, and if it exceeds 40,000, the curability deteriorates and stickiness occurs.

The above-mentioned weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and is measured by high performance liquid chromatography (Showa Denko KK, "Shodex").
GPC system-11 type "), column: Sh
odex GPC KF-806L (exclusion limit molecular weight:
2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number:
It is measured by using three series of 10,000 stages / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm).

The coating resin composition of the present invention comprises the unsaturated polyester-based resin (A) having the above-mentioned specific structural unit and the above-mentioned specific urethane (meth) acrylate-based resin (B). The unsaturated polyester resin (A) and the urethane (meth) acrylate resin (B) are contained in the unsaturated polyester resin (A).
The urethane (meth) acrylate resin (B) is preferably 5 to 100 parts by weight with respect to 100 parts by weight,
More preferably 10 to 90 parts by weight, particularly preferably 15
~ 80 parts by weight. When the content of the urethane (meth) acrylate-based resin (B) is less than 5 parts by weight, heat resistance,
The crack resistance is inferior, and if it exceeds 100 parts by weight, the cured coating film is too soft and inferior in abrasiveness, which is not preferable.

The resin composition for coating thus obtained is
Either a curable resin composition that is cured at room temperature or by heating or a curable resin composition that is cured by irradiation with an active energy ray may be used, but particularly 3
From the viewpoint of curability in thick film coating such as 100 to 400 μm, it is preferable to use a room temperature or heat curable resin composition.

When the coating resin composition of the present invention is used as a curable resin composition which is cured at room temperature or by heating, it is preferable to use a heat-induced radical generator (C). Examples of the radical generator (C) include methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, t-butyl perbenzoate, and the like, and octenoic acid as an auxiliary agent for these. Cobalt, cobalt naphthenate, manganese octenoate, manganese naphthenate, various amine compounds, and the like can be used in combination, and methyl ethyl ketone peroxide and cobalt octenoate are preferably used in combination.

The radical generator (C) is used in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of the total amount of the unsaturated polyester resin (A) and the urethane (meth) acrylate resin (B). Preferably a part,
More preferably 0.5 to 10 parts by weight, particularly preferably 1
~ 6 parts by weight. If the amount is less than 0.5 parts by weight, the curability will be slow, and if it exceeds 15 parts by weight, the curability will not be improved and it is wasteful. The amount of the auxiliary compounded is preferably 1 part by weight or less, and more preferably 100 parts by weight of the total amount of the unsaturated polyester resin (A) and the urethane (meth) acrylate resin (B). It is 0.5 parts by weight or less.

In addition to the above (A), (B) and (C), it is also possible to use an antifoaming agent, a flame retardant, an antistatic agent, a plasticizer and the like in combination.

When the coating resin composition of the present invention is used as a curable resin composition which is cured by irradiation with active energy rays, it is preferable to further use a radical-generating photopolymerization initiator (D) in combination, The photopolymerization initiator (D) is not particularly limited as long as it generates a radical by the action of light, and specifically, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxy. Acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylenephenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) 2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-pro Pill) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1
-[4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether,
Benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid,
Methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4 '
-Methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-
Chlorthioxanthone, 2-methylthioxanthone,
2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosuberone, 2-
Ethylanthraquinone, 4 ', 4 "-diethylisophthalophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxy Rate, benzyl, 9,10-phenanthrenequinone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, and the like.

Further, as these auxiliary agents, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,
4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, (n-butoxy) ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid 2 It is also possible to use -ethylhexyl, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like in combination.

Among these radical-generating photopolymerization initiators (D), benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy)-
Phenyl (2-hydroxy-2-propyl) ketone, 2
-Hydroxy-2-methyl-1-phenylpropane-1
-ON is preferably used.

The amount of the photopolymerization initiator (D) blended is 2 to 10 parts by weight based on 100 parts by weight of the total amount of the unsaturated polyester resin (A) and the urethane (meth) acrylate resin (B). Is more preferable, 2 to 6 parts by weight is more preferable, and 3 to 5 parts by weight is particularly preferable. If the blending amount is less than 2 parts by weight, the curing rate in the case of ultraviolet curing will be extremely slow, and if it exceeds 10 parts by weight, the curability will not be improved and it is wasteful.

In addition to the above (A), (B) and (D), it is also possible to use an antifoaming agent, a flame retardant, an antistatic agent, a plasticizer and the like in combination.

The method for curing the active energy ray-curable resin composition obtained as described above is not particularly limited as long as it is a method for activating the above radical-generating photopolymerization initiator (D), and it is not limited. Ultraviolet, ultraviolet, near-ultraviolet, infrared rays, X-rays, electromagnetic waves such as γ-rays, electron beams, proton rays, and a method of irradiating active energy rays such as neutron rays to cure may be mentioned. A curing method by irradiation with ultraviolet rays is advantageous in view of availability of an irradiation apparatus, price, and the like. The ultraviolet rays mainly include light in a wavelength range of 150 to 450 nm, and are high-pressure mercury lamps, metal halide lamps, and xenon. A method of irradiating with a lamp, a chemical lamp or the like can be mentioned.

If necessary, an ethylenically unsaturated monomer (E) is added to the above (A), (B) and (C) or (A), (B) and (D). It is preferable that the ethylenically unsaturated monomer has one or more ethylenically unsaturated groups in one molecule, and a monofunctional monomer, a bifunctional monomer, a trifunctional or more functional monomer is used. Can be mentioned.

Examples of monofunctional monomers include styrene, vinyltoluene, chlorostyrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, vinyl acetate, 2-hydroxyethyl (meth) acrylate, and the like. 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate Dicyclopentenyl (meth) acrylate, n- butyl (meth) acrylate, n- stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide-modified (n =
2) phthalates such as (meth) acrylate, nonylphenol propylene oxide-modified (n = 2.5) (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate Acid derivative half (meth) acrylate, furfuryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, N-methylol (meth) acrylamide, N -Vinylpyrrolidone, 2-
Vinyl pyridine etc. are mentioned.

Examples of the bifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate. , Dipropylene glycol di (meth)
Acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Ethylene oxide modified bisphenol A type di (meth)
Acrylate, propylene oxide-modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Examples thereof include acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, and hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate.

Examples of trifunctional or higher functional monomers include, for example:
Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxy Examples thereof include trimethylolpropane and glycerin polyglycidyl ether poly (meth) acrylate. These may be used alone or in combination of two or more.

The thus obtained resin composition for coatings of the present invention (curable resin composition) can be widely used in paint or the like for various substrates, especially useful as an interior coating material.

Depending on the above-mentioned application, pigments (titanium white, cyanine blue,
Watching red, red iron oxide, carbon black, aniline black, manganese blue, iron black, ultramarine blue, Hansa red, chrome yellow, chrome green, etc., filler (calcium carbonate, kaolin, clay, talc, mica, alumina, asbestos powder) , Fine silica, barium sulfate, lithopone, gypsum, zinc stearate, perlite, etc., leveling agent (silicone,
Cellulose acetate butyrate, surfactants, etc., stabilizers, thermoplastic resins (high density, medium density, low density various polyethylene, polypropylene, polybutene, homopolymers such as polypentene, ethylene-propylene copolymer, nylon- 6, nylon-based resin such as nylon-6,6,
Vinyl chloride resin, nitrocellulose resin, vinylidene chloride resin, acrylic resin, acrylamide resin, styrene resin, vinyl ester resin, polyester resin, etc.), reinforcing agent (glass fiber, carbon fiber, etc.),
It is also possible to add anti-sagging agents (hydrogenated castor oil, fine particle silicic acid anhydride, etc.), matting agents (fine silica powder, paraffin wax etc.), grinding agents (zinc stearate etc.) and the like.

In this case, the pigment content is 2 to 20% by weight, the filler content is 2 to 50% by weight, the leveling agent content is 0.001 to 5% by weight, and the thermoplastic resin content is 5 to 30% by weight, the content of the anti-sagging agent is 1 to 5% by weight, the content of the matting agent is 1 to 10% by weight, and the content of the abrasive is appropriately selected from the range of 1 to 10% by weight. .

As a diluent, ethyl acetate, toluene, xylene, methanol, ethanol, butanol,
Acetone, methyl isobutyl ketone, methyl ethyl ketone, cellosolves, diacetone alcohol and the like can be mentioned, and it is also possible to add about 1 to 10% by weight.

Thus , the resin composition for coating of the present invention is
An unsaturated polyester-based resin (A) having a specific structural unit and a specific urethane (meth) acrylate-based resin (B), resulting in excellent drying properties, as well as excellent heat resistance and crack resistance of the coating film. the Ru der those shown.

[0050]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, "%" and "parts" are based on weight unless otherwise specified.

Unsaturated polyester resins (A-1 to 3) were produced in the following manner. -Unsaturated polyester resin (A-1) In a reactor equipped with a stirrer and a reflux condenser, maleic anhydride 7.3 mol, propylene glycol 5.3 mol, diethylene glycol 2.6 mol, pentaerythritol allyl. 2.4 mol of ether and 0.02% of hydroquinone (polymerization inhibitor) were charged (the charge amount is based on the total amount of the condensation component) and condensed at 195 ° C. until the acid value reached 6 mgKOH / g while blowing nitrogen gas. The reaction is carried out to obtain an unsaturated polyester resin (A-
1) was obtained.

-Unsaturated polyester resin (A-2) In a reactor equipped with a stirrer and a reflux condenser, maleic anhydride 7.7 mol, ethylene glycol 6.0 mol, 1,3-
2.0 mol of butylene glycol, 3.3 mol of trimethylolpropane diallyl ether, and 0.02% of hydroquinone (polymerization inhibitor) were charged (the charging amount was all with respect to the total amount of the condensation component), while blowing nitrogen gas.
A condensation reaction was carried out at 5 ° C. until the acid value became 3 mgKOH / g to obtain an unsaturated polyester resin (A-2) having a weight average molecular weight of 14,000.

3. Unsaturated polyester resin (A-3) , a reactor equipped with a stirrer and a reflux condenser, maleic anhydride 5.0 mol, dicyclopentadiene 2.0 mol, water 4.
3 mol, diethylene glycol 3.3 mol, pentaerythritol allyl ether 0.8 mol, bisphenol A propylene oxide 2 mol adduct 0.05 mol, propylene glycol 0.5 mol, and further hydroquinone (polymerization inhibitor) 0.02 % While charging the nitrogen gas while blowing nitrogen gas to 19%.
A condensation reaction was carried out at 5 ° C. until the acid value became 20 mgKOH / g to obtain an unsaturated polyester resin (A-3) having a weight average molecular weight of 20,000.

Urethane (meth) acrylate resins (B-1 to 3) were produced in the following manner. -Urethane acrylate resin (B-1) In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port, 66.6 g (0.3 mol) of isophorone diisocyanate and a polyol having an average molecular weight of 2000 ( A condensate of ethylene glycol / 1,4-butanediol / adipic acid, "Adeka New Ace V14-90" manufactured by Asahi Denka Co., Ltd., 400 g (0.2 mol), and ethyl acetate 74.3 g were charged, and the mixture was put under nitrogen atmosphere at When the residual isocyanate group became 2.5%, the temperature was lowered to 60 ° C., and 23.2 g (0.2 mol) of 2-hydroxyethyl acrylate was added and reacted to make the residual isocyanate group 0. The reaction was terminated when the content became 0.3% to obtain a urethane acrylate resin (B-1) solution. The obtained urethane acrylate resin (B-1) had a resin content of 79.6% and an isocyanate content of 0.3.
%, And the weight average molecular weight was 20,000.

Urethane acrylate resin (B-2) 200 g of 1,3-bisisocyanatomethylcyclohexane (1.0 mol) in a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port. ), A polyol having an average molecular weight of 1725 (“Adeka New Ace YG-226” manufactured by Asahi Denka Co., Ltd.), 400 g (0.23 mol),
72 g (0.7 mol) of neopentyl glycol and 300 g of toluene were charged and reacted at 75 ° C. under a nitrogen atmosphere, and when the residual isocyanate group became 2.5%,
The temperature was lowered to 60 ° C., 27 g (0.23 mol) of 2-hydroxyethyl acrylate was added and reacted, and the reaction was terminated when the residual isocyanate group became 0.3%, and the urethane acrylate resin (B-2 ) A solution was obtained. The urethane acrylate resin (B-2) thus obtained had a resin content of 70%, an isocyanate content of 0.3%, and a weight average molecular weight of 20,000.

・ Urethane acrylate resin (B-3) 230 g of 1,3-bisisocyanatomethylcyclohexane (1.15 mol) in a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port. ), A polyol having an average molecular weight of 1725 (“Adeka New Ace YG-226” manufactured by Asahi Denka Co., Ltd.), 343 g (0.2 mol),
300 g of ethyl acetate was charged and reacted at 75 ° C. under a nitrogen atmosphere. When the residual isocyanate group became 2.5%, the temperature was lowered to 60 ° C. and 46 g (0.4 mol) of 2-hydroxyethyl acrylate was added. The reaction was terminated by addition reaction, and the reaction was terminated when the residual isocyanate group became 0.3% to obtain a urethane acrylate resin (B-3) solution. The urethane acrylate resin (B-3) thus obtained had a resin content of 70%, an isocyanate content of 0.3%, and a weight average molecular weight of 14,000.

Urethane acrylate resin (B-4) A mixture of dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate (KAYRAD) was placed in a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas blowing port. DPHA) 934
g (1.8 mol) and isophorone diisocyanate 66 g
(0.3 mol) was added and reacted, and when the residual isocyanate group became 0.3%, the reaction was terminated to obtain a urethane acrylate resin (B-4) solution. The resin content of the obtained urethane acrylate resin (B-4) was 99.5.
%, The isocyanate content was 0.3%, and the weight average molecular weight was 2,000.

Examples 1 to 9 and Comparative Examples 1 to 3 As shown in Table 1, unsaturated polyester resin (A) and urethane (meth) acrylate resin (B) were mixed with styrene and 6% cobalt octenoate. 0.4 parts and 1.2 parts of methyl ethyl ketone peroxide were added to obtain a room temperature curable resin composition. The following evaluation was performed about the obtained resin composition.

(Heat resistance) The obtained resin composition was applied onto a polypropylene plate with a 500 μm applicator to give a film thickness of 200 μm.
After the test sample was coated so as to have a thickness of m, cured, and the polypropylene plate was peeled off, the color difference ΔE of the coating film after standing at 100 ° C. for 200 hours was measured.

(Heat and crack resistance) A substrate (15) in which the obtained resin composition was applied to a veneer of a plywood with a wood sealer
(0 × 150 cm) with a flow coater to a film thickness of 200 μm.
After heat treatment for 40 hours, -40 ° C x 16 hours and 80 ° C x 8
The heat cycle test is conducted by setting the time as one cycle,
The number of cycles (times) until the coating film cracked was examined.

[Table 1] Unsaturated Polyurethane Urethane (Meth) Acrylate Styrene Resin (A) Resin (B) Type Content (part) Type Content (part) Content (part) Example 1 A-1 45 B-1 28 27 〃 2 A-1 56 B-2 10 34 〃 3 A-1 56 B-3 10 34 〃 4 A-2 45 B-1 28 27 〃 5 A-2 56 B-2 10 34 〃 6 A-2 56 B-3 10 34 〃 7 A-3 39 B-1 28 33 33 〃 8 A-3 49 B-2 10 41 〃 9 A-3 46 B-3 15 39 Comparative Example 1 --- 0 B-1 70 30 〃 2 A-1 75 --- 0 25 〃 3 A-1 45 B-425 Thirty

Example 10 60 parts of unsaturated polyester resin (A-1), 40 parts of urethane acrylate resin (B-1), 4 parts of Irgacure 651 and 10 parts of tripropylene glycol triacrylate were added, An ultraviolet curable resin composition was obtained. About the obtained resin composition, except that the coating film was cured using a high pressure mercury lamp with an output of 80 W / cm ²
Evaluation was carried out in the same manner as in Example 1. The results of Examples and Comparative Examples are shown in Table 2.

[0063] Note) In Comparative Example 1, the hardness was insufficient and polishing was impossible.

[0064]

The coating resin composition of the present invention comprises the unsaturated polyester resin (A) and the specific urethane (meth) acrylate resin (B), and therefore has excellent drying property and heat resistance of the coating film. It exhibits excellent properties and crack resistance, and is useful as a coating agent (paint ) for various base materials, and is particularly useful as an interior paint.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-11-240931 (JP, A) JP-A-54-54192 (JP, A) JP-A-55-90522 (JP, A) JP-A-55- 155011 (JP, A) JP 10-30012 (JP, A) JP-B 2-57806 (JP, B2) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09D 167/06 C08F 290 / 00-290/14 C08F 299/00-299/08 C09D 175/16

Claims (6)

(57) [Claims] 1. An unsaturated polyester resin (A) having at least one unit selected from a cyclopentadiene unit, a dicyclopentadiene type unit and a polyhydric alcohol allyl ether unit, and a weight average molecular weight of 3,000 to.
A resin composition for coating material, which comprises 40,000 urethane (meth) acrylate resin (B) represented by the following general formula (1). [Chemical 1] Here, R ₁ is a urethane bond residue of hydroxy (meth) acrylate, R ₂ is a urethane bond residue at both ends of a polyisocyanate compound, R ₃ is a urethane bond residue at both ends of a polyol, and m is an integer of 1 to 20. . 2. The content ratio of the unsaturated polyester resin (A) and the urethane (meth) acrylate resin (B) is
The urethane (meth) acrylate resin (B) is 5 to 10 parts by weight with respect to 100 parts by weight of the unsaturated polyester resin (A).
The resin composition for paints according to claim 1, wherein the resin composition is 0 parts by weight. 3. A process according to claim 1 or 2 coating resin composition, wherein the weight average molecular weight and wherein it is from 5,000 to 40,000 of the unsaturated polyester resin (A). 4. A resin composition coating resin composition according to any one of claims 1-3, characterized in that the cold-curable. 5. A coating resin composition according to any one of claims 1 to 3, wherein the resin composition is an ultraviolet-curable. 6. The resin composition for coating composition according to claim 1, further comprising an ethylenically unsaturated monomer.