JPH1030012A - Activation-energy ray setting resin composition and coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an activation-energy ray setting resin composition able to provide coating films and cured articles which have excellent cold-crack resistance and curing characteristic from a specific urethane (meth)acrylate, air dryness-imparting unsaturated polyester and ethylenic unsaturated monomer. SOLUTION: This activation-energy ray setting resin composition comprises (A) an urethane (meth)acrylate using an aromatic polyether polyol, (B) at least one or more of (i) an air dryness-imparting unsaturated polyester, (ii) unsaturated polyester, and (iii) epoxy(meth)acrylate (preferably containing a component (i) as the essential component) at a [component (i)]:[component (ii)] ratio of (100:0)-(20:80). This composition provides excellent coating films for metals, woods, plastics, etc., and is especially useful for paint of UV ray curing type, and paints for metals and woodwork.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable resin composition capable of producing a coating film and a cured product having excellent resistance to cold cracking and curability, and a coating material thereof.

[0002]

2. Description of the Related Art In recent years, demands for higher performance paints suitable for resource saving and energy saving have been increasing due to social needs.

As such a coating material, an active energy ray-curable resin is used because of its advantages such as (1) quick curing, (2) low energy cost, and (3) non-pollution. Have been.

For example, as an unsaturated polyester resin, an active energy ray-curable type is widely used for woodworking paints because it can be formed into a thick film and is inexpensive. However, when such paints are instantaneously cured by active energy rays,
There is a disadvantage that cracks are easily generated under severe cold conditions due to large internal strain. In order to improve such disadvantages, (1) a method of lowering the crosslink density of the cured product to make the coating film softer (2) a method of imparting a terminal carboxyl group-containing unsaturated polyester to
A method of adding a compound having a reactive double bond (3) A method of introducing a flexible skeleton into a resin molecule (4) A method of blending a flexible resin as a second component has been performed.

[0005] However, there has not yet been obtained a material which can satisfy both the cold crack resistance and the curability.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an active energy ray-curable resin composition and a coating material capable of providing a coating film and a cured product having excellent resistance to cold cracking and curing. That is.

[0007]

Means for Solving the Problems The present inventors have made intensive studies on these problems and as a result have completed the present invention.

That is, the present invention relates to (A) a urethane acrylate using an aromatic polyether polyol;
At least one or more of the air-drying imparting type unsaturated polyester (B1), the unsaturated polyester (B2), and the epoxy acrylate (B3) are composed of (C) an ethylenically unsaturated monomer; (B1) / (B2 + B3) A resin composition characterized by containing the components (B) and (C), preferably the component (B) contains an air-drying imparting unsaturated polyester (B1) as an essential component. ) Is 1 by weight
00/0 to 20/80, preferably the aromatic polyether polyol is obtained by adding an alkylene oxide to an aromatic diol, and preferably the weight ratio of component (A) / component (B) is 30 / 70-90 /
10, an air-drying type unsaturated polyester (B
1) The unsaturated polyester (B2) contains at least 30% by weight of maleic acid and / or fumaric acid residues in the polyester, preferably the epoxy acrylate (B) has an epoxy equivalent of 100 to 1000, In particular, the present invention provides a coating material characterized by using one or more of 180 to 600 epoxy compounds, and using these resin compositions as main components.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The urethane (meth) acrylate (A) of the present invention is preferably a polyisocyanate, an aromatic polyether polyol and a hydroxyl group-containing (meth).
It is obtained by reacting with acrylate.

The aromatic polyether polyol referred to herein is preferably an aromatic diol to which an alkylene oxide has been added. Preferably number average molecular weight 4
More than 00, particularly preferably 700 to 1700. For example, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, tetrahydrofuran adduct of bisphenol A, ethylene oxide-propylene oxide random adduct of bisphenol A, ethylene oxide-propylene oxide block adduct of bisphenol A, bisphenol F ethylene oxide adduct, bisphenol F propylene oxide adduct, bisphenol F tetrahydrofuran adduct, bisphenol F ethylene oxide-propylene oxide random adduct, bisphenol F ethylene oxide-
Propylene oxide block adduct, bisphenol AD ethylene oxide adduct, bisphenol AD
Propylene oxide adduct, bisphenol AD tetrahydrofuran adduct, bisphenol AD ethylene oxide-propylene oxide random adduct, bisphenol AD ethylene oxide-propylene oxide block adduct, and the like.

Examples of the polyisocyanate include 2,4-tolylene diisocyanate and its isomer or a mixture of isomers (hereinafter abbreviated as TDI), diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate. Isocyanate, dicyclohexylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, Vernock D-750, Crisbon NX (product of Dainippon Ink and Chemicals, Inc.), Desmodur L (product of Nippon Polyurethane Co., Ltd.), Takenate D1
02 (manufactured by Takeda Products) and Isonate 143L (manufactured by Mitsubishi Kasei). TDI is particularly preferably used.

Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
-Hydroxypropyl (meth) acrylate, 2-hydroxy-3phenoxypropyl (meth) acrylate,
Examples include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate.

The urethane (meth) acrylate (A) preferably has a double bond concentration of at least 0.8 mmol / g.
2 mmol / g or less. When it is less than 0.8 mmol / g, the active energy ray curability is poor, and when it is more than 2.2 mmol / g, the cold heat crack resistance is poor.

The air-drying type unsaturated polyester (B1) of the present invention is obtained by synthesizing an acid component, a glycol component and an air-drying component by an ester reaction. Examples of the air-drying component include those using allyl ethers as the glycol component, those using tetrahydrophthalic anhydride and methyltetrahydrophthalic acid as the acid component, those using linseed oil and tung oil as the drying oil, and those containing dicyclopentadiene. And / or a compound using the compound, but considering surface curability, it is preferable to use allyl ethers, tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride alone or in combination.

As the allyl ethers, known and commonly used allyl ethers can be used, and typical examples thereof include, for example, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, and polyethylene glycol. Monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether,
1,2-butylene glycol monoallyl ether, 1,
Examples include allyl ether compounds of polyhydric alcohols such as 3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether, glycerin diallyl ether, and pentaerythritol triallyl ether. And allyl ether compounds having one hydroxyl group are preferred.

The acid component is mainly maleic acid, maleic anhydride or fumaric acid, but other acid components can be used as long as the object of the present invention is not impaired. For example, α, β-
Examples of unsaturated dibasic acids or acid anhydrides include itaconic acid, citraconic acid, chlormaleic acid and esters thereof, and examples of aromatic saturated dibasic acids or acid anhydrides include phthalic acid and phthalic anhydride. , Isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic acid, halogenated phthalic anhydride, and esters thereof, and the like. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid and malon. There are acids, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride and esters thereof, and these are used in combination.

As the glycol component, ethylene glycol, propylene glycol, diethylene glycol,
Dipropylene glycol, 1,3-butanediol,
1,4-butanediol, 2-methylpropane-1,3
-Diol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4- (Hydroxypropoxydiphenyl) propane and the like, and these are used alone or in combination. In addition, adducts such as ethylene oxide and propylene oxide can also be used. Polycondensates such as polyethylene terephthalate can also be used as part of the glycols and the acid component.

The unsaturated polyester (B2) is obtained by using an unsaturated polyester raw material excluding the above components for imparting dryness. The unsaturated polyester (B1) and the unsaturated polyester (B2) imparting air-drying property preferably contain maleic acid and / or fumaric acid residues in an amount of at least 30% by weight, particularly preferably 30% by weight or more in the polyester.
６３63% by weight.

The epoxy (meth) acrylate (B3) used in the present invention refers to a bisphenol type epoxy resin alone or a mixture of a bisphenol type epoxy resin and a novolak type epoxy resin and an unsaturated monobasic acid. Epoxy vinyl ester obtained by reacting in the presence of an esterification catalyst.

Here, a typical example of the bisphenol-type epoxy resin is glycidyl having two or more epoxy groups in one molecule obtained by reacting epichlorohydrin with bisphenol A or bisphenol F. Ether type epoxy resin, dimethyl glycidyl ether type epoxy resin obtained by reacting methyl epichlorohydrin with bisphenol A or bisphenol F, or epoxy resin obtained from alkylene oxide adduct of bisphenol A and epichlorohydrin or methyl epichlorohydrin. . Typical examples of the novolak type epoxy resin include an epoxy resin obtained by reacting phenol novolak or cresol novolac with epichlorohydrin or methyl epichlorohydrin.

Representative examples of the unsaturated monobasic acids include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid,
Monomethyl malate, monopropyl malate, monobutene malate, sorbic acid or mono (2-ethylhexyl) malate are examples. These unsaturated monobasic acids may be used alone or in combination of two or more. The reaction between the epoxy resin and the unsaturated monobasic acid is preferably performed at a temperature of 60 to 140 ° C, particularly preferably 80 to 120 ° C, using an esterification catalyst.

Examples of the esterification catalyst include triethylamine, N, N-dimethylbenzylamine, N, N
-A known catalyst such as a tertiary amine such as dimethylaniline or diazabicyclooctane, or diethylamine hydrochloride can be used as it is.

The epoxy (meth) acrylate (B)
3) preferably has an epoxy equivalent of 100 to 1000,
Particularly preferably, one or more of 180 to 600 epoxy resins are used.

The component (B) of the present invention preferably contains an air-drying imparting unsaturated polyester (B1) as an essential component.
1) and the mixing ratio of the unsaturated polyester (B2) and the epoxy (meth) acrylate (B3), that is, B1 /
(B2 + B3) The weight ratio is preferably 100/0 to 20/80. If the (B2 + B3) component is more than 80, the curability will be poor.

The aromatic polyether urethane (meth) acrylate (A), the air-drying type unsaturated polyester (B1), the unsaturated polyester (B2) and the epoxy (meth) acrylate (B3) of the present invention. The weight ratio of (A) / (B) to at least one or more (B) is 3
It is preferably 0/70 to 90/10. If the amount of the component (B) is less than 10, the curability will be poor, and
If it is more than 70, the cold crack resistance will be poor.

The ethylenically unsaturated monomer (C) of the present invention may be any known and commonly used one. Among them, particularly typical ones are shown below.
Styrene, α-methylstyrene, vinyltoluene, vinyl acetate, diallyl phthalate, diallyl isophthalate
And a triallyl isocyanurate, preferably styrene, and a monomer or oligomer having a (meth) acryloyl group, and particularly preferably a (meth) acrylate monomer.

As the monomer having a (meth) acryloyl group, any monomer may be used as long as it is a known and commonly used monomer. Among them, particularly typical ones are exemplified by 2-ethylhexyl (meth) Acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, β -Ethoxyethyl (meth) acryle-
Cyclohexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) ) There are acrylates and the like.

As the monomer used in the component (C), a compound having at least two polymerizable double bonds in one molecule can also be used. 0
５０50% by weight, preferably 0-20% by weight. The compound having at least two polymerizable double bonds in one molecule, that is, the polyfunctional unsaturated monomer is preferably a polyfunctional (meth) acrylate monomer, for example, 1,6-hexanediol (Meth) acrylate, 1,9-nonanediol- (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and the like. Are used alone or in combination of two or more.

The aromatic polyetherurethane (meth) acrylate (A) component of the present invention and at least one or more of the air-drying imparting type unsaturated polyester and unsaturated polyester and epoxy (meth) acrylate Preferred mixing ratio [(A + B) / C] of polymer component (A + B) to which component (B) is added and ethylenically unsaturated monomer (C)
Is 5/5 to 8/2 on a weight basis. (A + B) is 5
If it is smaller, the curability and the resistance to cold cracking will be poor. When it is larger than 8, the viscosity of the composition becomes high and handling becomes difficult.

As the photoinitiator to be used in the resin composition of the present invention, all known and common photoinitiators can be used. Among them, benzoin, benzoin methyle -Ter, benzyl, benzyl dimethyl ketal, diphenyl disulfide and the like.

The addition amount is a commonly used amount, and is preferably 0.1 to 100 parts by weight of the resin composition.
It is 1 to 10 parts by weight.

The coating material of the present invention is a material which is applied to an object to be coated such as metal, wood, plastic, paper and the like and is cured by an active energy ray such as an ultraviolet ray or an electron beam.

The present invention relates to an energy ray-curable resin composition having excellent resistance to cold cracking and hardening, and as a coating material, coating of woodwork products such as floors, interior materials, furniture, musical instruments, iron plates, steel plates, and the like. It can be widely used as a coating material for metal products such as copper plates and as a printing material such as ink.

[0034]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples, where "parts" and "%" are by weight unless otherwise specified.

Synthesis Example 1 [Urethane acrylate (UA-
Preparation of 1)] 2.0 mol of tolylene diisocyanate and 8 mol of bisphenol A ethylene oxide in a 1 liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet, and a reflux condenser. 1.0 mol was charged and reacted at 80 ° C. for 5 hours under a nitrogen atmosphere. Since the NCO equivalent was 480, which was almost the same as the theoretical value and was stable, the system was cooled to 40 ° C., and then 2-hydroxyethyl acrylate was added to 2.N.
0 mol was added and reacted at 80 ° C. for 4 hours in an air atmosphere.
After confirming that the NCO% became 0.1% or less, 100 ppm of trihydroquinone was added to obtain an aromatic polyetherpolyurethane acrylate resin composition. Its double bond concentration was 1.7 mmol / g.

Synthesis Example 2 [Urethane acrylate (UA-
Preparation of 2)] 2.0 mol of tolylene diisocyanate and 18 mol of bisphenol A ethylene oxide in a one-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet, and a reflux condenser. 1.0 mol was charged and reacted at 80 ° C. for 5 hours under a nitrogen atmosphere. NCO equivalent of 745
It became almost the same value as the theoretical value and became stable.
Then, 2.0 mol of 2-hydroxyethyl acrylate was added and reacted at 80 ° C. for 4 hours in an air atmosphere. After confirming that the NCO% became 0.1% or less, 100 ppm of trihydroquinone was added to obtain an aromatic polyetherpolyurethane acrylate resin composition. The double bond concentration of this is 1.2 mmol
/ G.

Synthesis Example 3 [Preparation of air-drying type unsaturated polyester (UP-1)] Dipropylene was placed in a 1-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. Glyco-
2 mol, diethylene glycol 7.5 mol, maleic anhydride 10 mol, pentaerythritol triallyl ether
Ter 2 moles, and an acid value 2
The reaction is terminated at 0 or less, and trihydroquinone is 200 pp.
m was added to obtain an air-drying unsaturated polyester resin composition.

Synthesis Example 4 [Unsaturated polyester (UP-
Preparation of 2)] A 1-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser was charged with 8 mol of diethylene glycol, 2 mol of dipropylene glycol, and 10 mol of maleic anhydride. Acid value 2 at 215 ° C under nitrogen atmosphere
The reaction is terminated at 0 or less, and trihydroquinone is 200 pp.
m was added to obtain an unsaturated polyester resin composition.

Synthesis Example 5 [Epoxy acrylate (EA-
Preparation of 1)] In a 1-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet, and a reflux condenser, bisphenol A diglycidyl ether (manufactured by Dainippon Ink and Chemicals, Inc.) Epiclone 1050] epoxy equivalent 45
0) 1 mol, 2 mol of acrylic acid, triethylamine
0.3%, trihydroquinone 300ppm,
The reaction was performed at 110 ° C. for 6 hours in an air atmosphere. The reaction was terminated at an acid value of 5 or less to obtain an epoxy acrylate resin composition.

Comparative Synthesis Example 1 [Urethane acrylate (U
Preparation of A-3)] In a 1-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet, and a reflux condenser, 3.0 mol of tolylene diisocyanate and “MN700” [Mitsuhito Trifunctional polypropylene glycol manufactured by Toshikagaku Co., Ltd.] 1.0
A mole was charged and reacted at 80 ° C. for 5 hours under a nitrogen atmosphere. The NCO equivalent was 407, which was almost the same as the theoretical value, and was stabilized. After cooling to 40 ° C, 3.0 mol of 2-hydroxy-3-phenoxypropyl acrylate was added, and the mixture was reacted at 80 ° C in an air atmosphere for 4 hours. Was. NCO%
Was confirmed to be 0.1% or less, and 100 ppm of trihydroquinone was added to obtain a polyether urethane acrylate resin composition. Its double bond concentration was 1.6 mmol / g.

Comparative Synthesis Example 2 [Unsaturated polyester (UP
Preparation of -3)] In a 1-liter four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 2.5 mol of propylene glycol, 2.5 mol of ethylene glycol, Fumaric acid 4
And a solid content acid value of 2 at 215 ° C. under a nitrogen atmosphere.
0 was obtained. Then, after cooling this intermediate 1 to 90 ° C., 1.5 mol of phthalic anhydride was added and reacted at 140 ° C. in a nitrogen atmosphere to obtain an intermediate 2 having a solid content acid value of 130. Intermediate 2 was cooled to 80 ° C., 1.5 mol of glycidyl methacrylate was added in an air atmosphere, and the mixture was heated at 80 ° C. to terminate the reaction at an acid value of 4 or less.
By adding 00 ppm, an unsaturated polyester resin composition was obtained.

<Test Method and Evaluation><CurabilityTest> The following composition was applied to a glass plate using a 10-mile applicator, and thereafter, an ultraviolet curing device Dicure (manufactured by Dainippon Ink and Chemicals, Inc.) 80w / 1 high pressure mercury lamp, conveyor speed 6m / min,
UV curing is performed using a light source height of 15 cm. In the evaluation of the curability, the number of passes required until it can be determined that the composition was cured by touch with the finger was used as the value of the curing speed.

<Cold heat crack resistance test>
One piece of vinyl tape (thickness: 11) as a spacer on 8 mm Rawan plywood sanded with 320 sandpaper
0 μm) and apply with a glass rod. This is cured by ultraviolet light under the same conditions as the curing speed value (number of passes) determined above. Thereafter, the coating film is sanded with # 320 sandpaper. One piece of a gum tape (250 μm in thickness) is attached to this as a spacer, and is applied with a glass rod so as to have a coating thickness of 250 μm. This is UV-cured under the same conditions as above and for the same number of passes. The paint and the coating film thus obtained were subjected to a heat-cooling cycle test in which + 80 ° C. × 2 hours and −20 ° C. × 2 hours as one cycle, and the number of cycles until cracks occurred in the coating film was measured and judged.

<Blending composition> Resin composition 100 parts by weight Irgacure 651 3 parts by weight

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

The active energy ray-curable resin composition of the present invention is excellent in cold crack resistance and curability in a well-balanced manner, and can provide an excellent coating film on metals, woods, plastics and the like. is there. Particularly, it is extremely useful as a UV-curable paint and a metal / woodwork paint.

Claims (8)

[Claims] 1. A urethane (meth) acrylate using an aromatic polyether polyol, (B) an air-drying type unsaturated polyester (B1), an unsaturated polyester (B2), an epoxy (meth) acrylate (A) An active energy ray-curable resin comprising at least one or more of B3), (C) an ethylenically unsaturated monomer, and the components (A), (B) and (C). Composition. 2. The resin composition according to claim 1, wherein the component (B) contains an air-drying imparting type unsaturated polyester (B1) as an essential component. 3. The resin composition according to claim 1, wherein (B1) / (B2 + B3) is 100/0 to 20/80 in weight ratio. 4. The resin composition according to claim 1, wherein the aromatic polyether polyol is obtained by adding an alkylene oxide to an aromatic diol. 5. The weight ratio of component (A) / component (B) is 30.
/ 70 to 90/10
4. The resin composition according to any one of 3. 6. An air-drying type unsaturated polyester (B)
1) The polyester according to claim 1, wherein the unsaturated polyester (B2) contains at least 30% by weight of maleic acid and / or fumaric acid residues in the polyester.
The resin composition according to any one of the above. 7. Epoxy (meth) acrylate (B3)
Has an epoxy equivalent of 100 to 1000, particularly 180 to 60
The resin composition according to any one of claims 1 to 4, wherein one or two or more epoxy compounds are used. 8. A coating material comprising the resin composition according to claim 1 as a main component.