JPH0959329A - Curing-type resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curing-type resin composition consisting of a specific unsaturated polyester resin, a vinyl ether-based monomer and a radical generating-type photopolymerization initiator, rapid in curing excellent in air-drying property and physical properties of cured membrane and useful for paint, adhesive, etc. SOLUTION: This curing-type resin composition consists of (A) an unsaturated polyester resin having >=4000 weight averaged molecular weight and (i) 5-50mol% cyclopentadiene and/or dicyclopentadiene-based unit, and/or (ii) 2-40mol% polyhydric alcohol allyl ether unit such as pentaerythritol triallyl ether based on a polybasic acid component such as maleic anhydride, (B) a vinyl ether-based monomer such as triethylene glycol divinyl ether and (C) a radical generating-type photopolymerization initiator such as 4- phenoxydichloroacetophenone, and further preferably (D) styrene monomer. Further, The blending ratios of components A to C are preferably such that the components A/B is in the range of 100/(40/80), and the components A/C is in the range of 100/(5-10).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an air-drying unsaturated polyester resin-based curable resin composition which is cured by irradiation with active energy rays such as ultraviolet rays.

[0002]

2. Description of the Related Art Conventionally, unsaturated polyester resins containing a polyhydric alcohol allyl ether component or dicyclopentadiene have air-drying properties and are preferred to have a glossy and flesh-like feeling. It is used for paints (for woodworking), sealing materials, adhesives, molded products, etc. The curable resin composition containing such an unsaturated polyester resin as the main component is added to the unsaturated polyester resin as described above in order to impart air-drying property, to the polyhydric alcohol allyl ether component, cyclopentadiene or dicyclopentadiene compound. The unsaturated polyester resin introduced with is used for practical use by further mixing the unsaturated polyester resin with a crosslinkable monomer, an initiator, a curing aid and the like.

[0003]

However, the curable resin composition of such an air-drying (non-wax type) unsaturated polyester resin has a curing rate extremely higher than that of a general acrylic urethane type ultraviolet curable resin. It is slow, and further, the physical properties of the cured film such as cold heat resistance are inferior, and the curing speed and the physical properties of the cured film (cold heat resistance, etc.) equivalent to those of general acrylic urethane UV curable resins are desired.

[0004]

Therefore, as a result of intensive studies by the present inventors, 5 to 50 mol% of cyclopentadiene and / or dicyclopentadiene-based unit (A1) and / or polybasic acid component and / or Or a curable resin comprising an unsaturated polyester resin (A) having 2 to 40 mol% of a polyhydric alcohol allyl ether unit (A2), a vinyl ether monomer (B) and a radical-generating photopolymerization initiator (C) It has been found that the composition has a significantly faster curing rate than the conventional air-drying polyester resin and a cured film physical property equivalent to that of a general acrylic urethane ultraviolet curing resin, and has completed the present invention. In addition, the content mol% of the above (A1) or (A2) is each ratio to 1 mol of the polybasic acid component, and 50 mol% means 0.5 mol to 1 mol of the polybasic acid component. Means

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The cyclopentadiene and / or dicyclopentadiene-based unit (A1) in the present invention means cyclopentadiene,
Examples thereof include dicyclopentadiene and derivatives thereof. Examples of the derivatives include tricyclodecenyl maleate, tricyclodecenyl fumarate, tricyclodecenyl adipate, and tricyclodecenyl phthalate. , Tricyclodecenyl isophthalate, tricyclodecenyl trimellitate, ethylene glycol tricyclodecenyl ether, diethylene glycol tricyclodecenyl ether, propylene glycol tricyclodecenyl ether, 1,4-butanediol tricyclodecane Cenyl ether, 1,6-hexanediol tricyclodecenyl ether, neopentyl glycol tricyclodecenyl ether, glycerin tricyclodecenyl ether, trimethylolpropane tricyclodecenyl ether, hydroxylated dicyclopenta Ene, and the like.

The cyclopentadiene and / or dicyclopentadiene unit (A1) is present in an amount of 5 to 50 mol%, more preferably 15 to 40 mol% based on the polybasic acid in the unsaturated polyester resin (A). However, if it is 5 mol% or less, sufficient air-drying property cannot be obtained, and if it is 50 mol% or more, quick-drying property is deteriorated, which is not practical. To introduce the cyclopentadiene and / or dicyclopentadiene-based unit (A1) into the unsaturated polyester resin (A), basically, at least one of cyclopentadiene, dicyclopentadiene and their derivatives is polybasic. A condensation reaction is carried out by charging it with an acid, but when the cyclopentadiene and / or dicyclopentadiene-based unit is present in the main chain of the unsaturated polyester resin rather than in the main chain of the resin, when it is applied to the paint, etc. Since the physical properties tend to be excellent, it is desirable to charge at least one of cyclopentadiene, dicyclopentadiene and derivatives thereof in the initial stage of condensation in order to produce such a resin.

Specific examples of the polyhydric alcohol allyl ether unit (A2) include pentaerythritol triallyl ether, trimethylolpropane diallyl ether, glycerin monoallyl ether, trimethylolethane diallyl ether and glycerin diallyl ether. To be All are ethers containing at least one hydroxyl group in the molecule. The content of the allyl group is 2 to 40 mol%, preferably 10 to 30 mol% as a polyhydric alcohol allyl ether with respect to the polybasic acid component, and if it is 2 mol% or less, sufficient air-drying property cannot be obtained. ,
Moreover, the air-drying property is also reduced. On the other hand, even if it is introduced in an amount of 40 mol% or more, no remarkable improvement is observed in comparison with the amount. The introduction of the polyhydric alcohol allyl ether unit (A2) into the unsaturated polyester resin may be carried out in the same manner as in the case of the above cyclopentadiene and / or dicyclopentadiene type unit (A1). The blending ratio in the case of using the above (A1) and (A2) together is not particularly limited, as long as the blending mol% of each of (A1) and (A2) to the polybasic acid component as described above is controlled. Good.

As the polybasic acid used in the production of the unsaturated polyester resin (A), an unsaturated acid is usually used, and a saturated acid is used in combination if necessary. Examples of unsaturated acids include maleic anhydride, maleic acid, fumaric acid,
Itaconic anhydride, itaconic acid, etc. may be mentioned, and saturated acids include phthalic anhydride, phthalic acid, terephthalic acid, isophthalic acid, het acid, adipic acid, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, trimellitic acid. , Trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 6-methyl-4-cyclohexene-1,2,
3 tricarboxylic acid anhydride etc. are mentioned.

As the polyhydric alcohol polycondensed with the acid, ethylene glycol, propylene glycol, diethylene glycol, triethylene 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,
Examples thereof include glycerin, pentaerythritol, cyclohexanedimethanol and the like.

In the production of the unsaturated polyester resin (A), the above components may be used in a conventional manner to carry out a condensation or addition reaction in an inert gas atmosphere at a temperature of about 150 to 250 ° C. The unsaturated polyester resin (A) thus obtained usually has an acid value of about 10 to 30 KOHmg / g, and preferably has an acid value of 10 by promoting esterification.
To about 20 KOHmg / g, and the weight average molecular weight of the unsaturated polyester resin is preferably 4000 or more, and more preferably 6000 to 120.
00 is preferable, and when the weight average molecular weight is less than 4000, the curing rate tends to be slow.

The weight average molecular weight of the present invention is measured by gel permeation chromatography (GPC). For example, a column of KF-806 is used in a Showdex system (manufactured by Showa Denko KK) and tetrahydrofuran is used as a solvent. Can be measured using polystyrene as a standard. Examples of the vinyl ether-based monomer (B) of the present invention include triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, propenyl ether propylene carbonate, and the like, among which triethylene glycol divinyl ether. Hydroxybutyl vinyl ether is preferably used.

Further, the radical-generating photopolymerization initiator (C) of the present invention is not particularly limited as long as it generates a radical by the action of light, and specifically, 4-phenoxydichloroacetophenone, 4 -T-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylenephenyl) -2-hydroxy-2-methylpropan-1- On, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl 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, etc., and triethanolamine, triisopropanolamine as auxiliary agents thereof. 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethyl benzoic acid, ethyl 4-dimethylaminobenzoate, (n-butoxy) ethyl 4-dimethylaminobenzoate, 4-dimethylamino benzoin It is also possible to use isoamyl, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like, among these radical-generating photopolymerization initiators. Then, 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-one is preferably used.

In the present invention, the above (A) to (C) are used.
In the composition obtained by blending, the blending ratio is not particularly limited, but in order to efficiently obtain the effect of the present invention,
The compounding weight ratio of (A) :( B) is 100: 20 to 100.
(Preferably 100: 40 to 80), the blending weight ratio of (A) :( C) is 100: 2 to 20 (preferably 100: 5).
In the case of (10) to (A), if the amount of (B) mixed is smaller than the above, the reaction rate is slower. If the amount is less than the above, the reaction rate is slow, and conversely if the amount is more than the above, the reaction rate does not increase and problems such as odor generation occur, which is not preferable.

In addition to the above-mentioned (A) to (C), it is also very useful to add a styrene monomer (D) from the viewpoint of improving the strength of the cured film. The compounding amount of 40 to 70 parts with respect to 100 parts by weight of the above (A)
About parts by weight is preferable. Further, in addition to the styrene monomer (D), a known crosslinking monomer for unsaturated polyester resin such as vinyltoluene, monochlorostyrene, diallyl phthalate, methyl methacrylate, vinyl acetate, glycidyl methacrylate may be used in combination. Is also possible.

The method of curing the curable resin composition of the present invention obtained by such a compounding is not particularly limited as long as it is a method of activating the above radical-generating photopolymerization initiator (C), and it is not limited. Examples include ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, X-rays, electromagnetic waves such as γ-rays, electron beams, proton beams, methods of irradiating active energy rays such as neutron rays, and curing, A curing method by irradiation with ultraviolet rays is advantageous in view of availability of the radiation irradiating device, price, and the like, and 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 lamps. And a method of irradiating with a chemical lamp.

The curable resin composition of the present invention thus obtained can be widely used as a coating agent (paint) for various substrates, a putty / sealing agent, an adhesive agent, etc. Pigment (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.) (Calcium carbonate, kaolin, clay, talc, mica, alumina, asbestos powder, fine powder silica,
Barium sulfate, lithopone, gypsum, zinc stearate,
Perlite etc.), leveling agents (silicone, cellulose acetate butyrate, surfactants etc.), stabilizers, thermoplastic resins (high density, medium density, low density various polyethylene, polypropylene, polybutene, polypentene etc. homopolymers, Polyethylene resin such as ethylene-propylene copolymer, nylon-6, 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-dripping agents (hydrogenated castor oil, fine particle silicic acid anhydride, etc.), matting agents (fine silica powder, paraffin wax, etc.), and abrasives (zinc stearate etc.). The compounding amount is 2 to 20% by weight, the compounding amount of the filler is 2 to 50% by weight, the compounding amount of the leveling agent is 0.001 to 5% by weight, and the compounding amount of the thermoplastic resin is 5 to 3%.
0% 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 1 to 1%.
It is appropriately selected from the range of 0% by weight. Further, as a diluent, ethyl acetate, toluene, xylene, butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cellosolves, diacetone alcohol, etc.
It is also possible to add about 10% by weight.

[0017]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, "%" and "part" mean
Unless otherwise specified, the weight standard is shown. The unsaturated polyester resins (A-I to VI and A-i to iv) were manufactured in the following manner. (AI) A reactor equipped with a stirrer, a rectification column, a nitrogen inlet tube, and a vacuum device was charged with 0.15 mol of dicyclopentadiene (A1), 1 mol of fumaric acid, and 50 ppm of cobalt acetate, and then heated at 150 ° C. After 2 hours of addition reaction, 0.3 mol of ethylene glycol and 0.7 mol of diethylene glycol were charged, and further, 3% of xylene and 0.02% of hydroquinone (polymerization inhibitor) were charged (the charge amounts are all condensation components. 21) while injecting nitrogen gas
After conducting the condensation reaction at 0 ° C. for 5 hours, 5 to 50 mmHg,
The reaction was continued at 150 ° C. for 1 hour and xylene was distilled off to obtain an unsaturated polyester resin (AI) having an acid value of 15 KOHmg / g and a weight average molecular weight of 10,000.

(A-II) The same as in the production of A-I except that 0.25 mol of dicyclopentadiene (A1), 0.45 mol of diethylene glycol and 0.2 mol of propylene glycol were added. Then, an unsaturated polyester resin (A-II) having an acid value of 10 KOHmg / g and a weight average molecular weight of 8000 was obtained. (A-III) In the same manner as in the production of AI above, dicyclopentadiene (A1) was 0.4 mol, ethylene glycol was 0.2 mol, and diethylene glycol was 0.6 mol. , Acid value 12KOHmg /
An unsaturated polyester resin (A-III) having a weight average molecular weight of 8,000 was obtained.

(A-i; Comparative Resin) The same procedure as in the production of A-I above was repeated except that dicyclopentadiene (A1) was changed to 0.03 mol and ethylene glycol was changed to 0.45 mol. An unsaturated polyester resin (Ai) having a valency of 12 KOHmg / g and a weight average molecular weight of 8000 was obtained. (A-ii; Comparative resin) In the above production of AI, except that dicyclopentadiene (A1) was 0.6 mol, ethylene glycol was 0.1 mol, and diethylene glycol was 0.45 mol. Same as above, acid value 15
An unsaturated polyester resin (A-ii) having KOH mg / g and a weight average molecular weight of 9000 was obtained.

(A-IV) Stirrer, rectification column, nitrogen inlet pipe,
In a reactor equipped with a vacuum device, 0.2 mol of trimethylolpropane diallyl ether (A2), 1 mol of maleic acid,
Charge 0.6 mol of ethylene glycol and 0.6 mol of diethylene glycol, and further charge 3% of xylene and 0.02% of hydroquinone (polymerization inhibitor) (the charge amount is based on the total amount of the condensation component) while blowing nitrogen gas. After conducting the condensation reaction at 200 ° C for 5 hours, 5 to 50 mm
The reaction was continued at Hg, 150 ° C for 1 hour, xylene was distilled off, the acid value was 12 KOHmg / g, and the weight average molecular weight was 9000.
To obtain unsaturated polyester resin (A-IV).

(A-V) Stirrer, rectification column, nitrogen inlet pipe,
In a reactor equipped with a vacuum device, pentaerythritol triallyl ether (A2) 0.15 mol, maleic acid 0.8
Mol, phthalic acid 0.2 mol, ethylene glycol 1 mol, diethylene glycol 0.2 mol were charged, and xylene 3% and hydroquinone (polymerization inhibitor) 0.0
An acid value of 10% was obtained by charging 2% (the amount of charge is based on the total amount of the condensation component) in the same manner as in A-IV above.
An unsaturated polyester resin (AV) having KOH mg / g and a weight average molecular weight of 8000 was obtained.

(A-VI) Pentaerythritol triallyl ether (A2) was mixed with 0.1% in the above production of AV.
Acid value 15 KOHmg /
An unsaturated polyester resin (A-VI) having a weight average molecular weight of 10,000 was obtained. (A-VII) The same process as in the above-mentioned A-I was carried out except that 0.05 mol of pentaerythritol triallyl ether (A2) was further added and the reaction was carried out to obtain an acid value of 12 KOHm.
An unsaturated polyester resin (A-VII) having g / g and a weight average molecular weight of 8000 was obtained.

(A-iii; Comparative Resin) The production of A-IV was carried out in the same manner except that the compounding amount of trimethylolpropane diallyl ether (A2) was 0.01 mol, and the acid value was 10 KOHmg / g. , Weight average molecular weight 9000
To obtain unsaturated polyester resin (A-iii). (A-iv; Comparative resin) In the production of A-IV, 0.5 parts of trimethylolpropane diallyl ether (A2) was used.
Except that diethylene glycol was adjusted to 0.45 mol, the unsaturated polyester resin having an acid value of 10 KOHmg / g and a weight average molecular weight of 10,000 (A-i
got v).

Example 1 20 parts of hydroxybutyl vinyl ether (B) and 3 parts of styrene were added to 50 parts of the above unsaturated polyester resin (AI).
0 part, and 4 parts of Irgacure 651 (manufactured by Ciba-Geigy, benzyl dimethyl ketal) as a radical-generating photopolymerization initiator (C) were added to give a viscosity of 150 cps / 2.
A curable resin composition of the present invention at 0 ° C. was obtained. The following evaluation was performed about the obtained curable resin composition. (Curability) The obtained curable resin composition was applied onto a glass plate with an applicator, and 20 cm under a high pressure mercury lamp of 80 W / cm was repeatedly passed at a speed of 5 m / min to give traces of scratches by a nail. The number of times of passage until it was not observed was examined. (Cold heat resistance) The obtained curable resin composition was applied to a plywood (1
(50 × 150 cm) by spraying at 200 g / m ² and then repeating the curing operation until no trace of scratches is observed in the same manner as in the above-mentioned evaluation of curability. Further, cold cycles were repeated with -20 ° C x 2 hours as one cycle, and the number of cycles (times) until cracking occurred in the surface-hardened film was examined.

Example 2 In Example 1, the unsaturated polyester resin (AI) was used.
Except that unsaturated polyester resin (A-II) was used instead of hydroxybutyl vinyl ether (B), 10 parts of triethylene glycol divinyl ether (B) was used instead of 20 parts of hydroxybutyl vinyl ether (B), and 40 parts of styrene was used. It carried out like Example 1 and evaluated it similarly.

Example 3 In Example 1, the unsaturated polyester resin (AI) was used.
In place of the unsaturated polyester resin (A-III),
Further, the same evaluation as in Example 1 was carried out except that the hydroxybutyl vinyl ether was replaced with triethylene glycol divinyl ether.

Example 4 In Example 1, the unsaturated polyester resin (AI) is used.
The same evaluation as in Example 1 was carried out except that the unsaturated polyester resin (A-IV) was used instead of.

Example 5 In Example 2, the unsaturated polyester resin (A-II)
The same evaluation as in Example 2 was carried out except that the unsaturated polyester resin (A-V) was used instead of.

Example 6 In Example 1, the unsaturated polyester resin (AI) is used.
The same evaluation as in Example 1 was carried out except that the unsaturated polyester resin (A-VI) was used instead.

Example 7 In Example 1, the unsaturated polyester resin (AI) is used.
The same evaluation as in Example 1 was carried out except that the unsaturated polyester resin (A-VII) was used instead.

Comparative Examples 1 to 4 The unsaturated polyester resin (Ai; Comparative Example 1),
The curable resin composition was evaluated in the same manner as in Example 1 using (A-ii; Comparative Example 2), (A-iii; Comparative Example 3) and (A-iv; Comparative Example 4).

Comparative Example 5 Except that the hydroxybutyl vinyl ether (B) was omitted from Example 1 and the amount of styrene was increased to 50 parts,
The same evaluation as in Example 1 was performed. Table 1 shows the evaluation results of the examples and comparative examples.

[0033]

[Table 1]

[0034]

The air-drying curable resin composition of the present invention is
Since a specific unsaturated polyester resin is blended with vinyl ether-based monomer, the curing speed is faster than that of conventional air-drying polyester resin (or the irradiation time of ultraviolet rays is shorter), and the physical properties of cured film (cold resistance) Etc.), and is useful as a coating agent (paint) for various substrates, putty / sealing agent, adhesive, etc.

Claims (3)

[Claims] 1. A cyclopentadiene and / or dicyclopentadiene-based unit (A1) of 5 to 50 mol% and / or a polyhydric alcohol allyl ether unit (A2) of 2 to 40 mol% based on the polybasic acid component. A curable resin composition comprising the unsaturated polyester resin (A), a vinyl ether-based monomer (B) and a radical-generating photopolymerization initiator (C). 2. The curable resin composition according to claim 1, wherein the unsaturated polyester resin (A) has a weight average molecular weight of 4000 or more. 3. The curable resin composition according to claim 1, further comprising a styrene monomer (D).