JPH11255847A - Low malodorous hardenable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low malodorous hardenable resin composition which keeps properties of a vinyl ester resin and emits less malodor due to the absence of styrene. SOLUTION: A low malodorous hardenable composition is obtained by dissolving a vinyl ester comprising (i) an epoxy compound (A) having a viscosity of not more than 1,000 mpa.s at 25 deg.C and at least two epoxy groups in the molecule; (ii) an epoxy compound (B) having a viscosity of more than 1,000 mpa.s at 25 deg.C, an epoxy equivalent of not more than 500 and at least two epoxy groups in the molecule (wherein an equivalent ratio (A):(B)=1090:90-10; (iii) an unsaturated monobasic acid (C); and (iv) a vinyl ester (E) comprising a saturated dibasic acid (D) in a polymerizable (meth)acrylate (F).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-odor curable resin composition containing no styrene, and particularly to various lining materials such as anticorrosive materials, waterproof materials, floor materials, FRP molded products, paints, putties, The present invention relates to a low odor curable resin composition used for applications such as an adhesive.

[0002]

2. Description of the Related Art Vinyl ester resin is a material excellent in water resistance, acid resistance, alkali resistance, solvent resistance, heat resistance, etc., and is made of FRP tanks, waterproof materials, various lining materials as anticorrosion materials, putty materials. Widely used for corrosion resistance applications such as adhesives.

However, styrene is contained in a vinyl ester resin for corrosion resistance as a polymerizable monomer. Styrene has excellent properties as a cross-linking material for unsaturated polyester resins and vinyl ester resins, but has high volatility and a very strong odor. For this reason, styrene has been designated as a Class 2 organic solvent under the Occupational Safety and Health Act and a designated substance under the Odor Control Act. In particular, styrene odor is a major obstacle to work in urban areas, construction of food factories that dislike odor, and construction in places where ventilation is not sufficient.

As a countermeasure against such styrene odor, a method of reducing the content of styrene or a method of blending a special additive to reduce the volatilization amount of styrene has been adopted, but all of them are resins containing styrene. This has not led to a fundamental solution to the odor. Under such circumstances, the emergence of a vinyl ester resin containing no styrene and usable for anticorrosion applications has been strongly desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a styrene-free low odor curable resin composition which retains the properties of a vinyl ester resin and solves the above-mentioned problems of the prior art. is there.

[0006]

That is, the present invention provides: (i) a viscosity at 25 ° C. of 1,000 mpa · s or less;
And an epoxy compound (A) having at least two epoxy groups in the molecule; (ii) having a viscosity at 25 ° C. of more than 1000 mpa · s, an epoxy equivalent of 500 or less, and at least two epoxy groups in the molecule. (B) (where the equivalent ratio of the epoxy compound is (A) :( B) = 1)
(Iii) an unsaturated monobasic acid (C); and (iv) a vinyl ester (E) composed of a saturated dibasic acid (D) with a polymerizable (meth) acrylate ( The present invention provides a low odor curable resin composition dissolved in F).
In the present invention, the equivalent ratio of the unsaturated monobasic acid (C) and the saturated dibasic acid (D) is (C) :( D) = 80 to 20:20.
The present invention provides the above-mentioned low odor curable resin composition having a viscosity of from 80 to 80. Further, the present invention provides the low odor curable resin, wherein the polymerizable (meth) acrylate (F) has a vapor pressure (mmHg / 20 ° C.) of 0.1 or less and a viscosity at 25 ° C. of 100 mpa · s or less. It provides a composition. Still further, the present invention provides the above-mentioned low odor curable resin composition further containing a wax.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. Epoxy compound (A) The epoxy compound (A) has a viscosity of 1000 mp at 25 ° C.
a · s or less and having at least two epoxy groups in the molecule. Examples thereof include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. Ether, polypropylene glycol diglycidyl ether, resorcin diglycidyl ether and the like may be mentioned, and these may be used in combination.

Epoxy compound (B) The epoxy compound (B) has a viscosity of 1000 mp at 25 ° C.
It exceeds a · s, has an epoxy equivalent of 500 or less, and has at least two epoxy groups in the molecule. Examples thereof include known epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, and brominated bisphenol type epoxy resin. You may. Commercially available ones can also be used, for example, Epicron 83 which is a bisphenol A type epoxy resin.
0 (manufactured by Dainippon Ink and Chemicals, Inc.), EPOMIC R301 (manufactured by Mitsui Petrochemical Industries, Ltd.), a bisphenol A type epoxy resin, Epototo YDF170 (manufactured by Toto Kasei Co., Ltd.), a bisphenol F type epoxy resin, bromine Epicron 152 (manufactured by Dainippon Ink and Chemicals, Inc.), which is a bisphenol type epoxy resin, and Epicron N740 (manufactured by Dainippon Ink and Chemicals, Inc.), which is a phenol novolac type epoxy resin.

Examples of the unsaturated monobasic acid (C) include acrylic acid and methacrylic acid, and these may be used in combination.

The saturated dibasic acid (D) includes, for example, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, adipic acid, phthalic anhydride and the like. Further, a half-ester carboxylic acid obtained by the reaction of trimethylolpropane diallyl ether with the above-mentioned phthalic anhydride can also be used.

The epoxy compound used in the production of the vinyl ester (E) is such that the equivalent ratio of the epoxy compound (A) to the epoxy compound (B) is (A) :( B) = 10-9.
0: 90 to 10 and the sum of components (A) and (B) is 10
Adjust so that it becomes 0 equivalent. If the amount of the epoxy compound (A) is more than 90 equivalents, the curability and the drying property of the coating film are inferior.

The equivalent ratio of the unsaturated monobasic acid (C) to the saturated dibasic acid (D) used in the production of the vinyl ester (E) is (C) :( D) = 80-20: 20-80 (The total of the components (C) and (D) is adjusted to be 100 equivalents). According to this range, good curability and coating film drying property can be obtained.

The production of the vinyl ester (E) is usually carried out by mixing a mixture of the epoxy compound (A), the epoxy compound (B), the unsaturated monobasic acid (C) and the saturated dibasic acid (D) with 100 parts.
The reaction is performed at a temperature of about 140 ° C. for about 2 to 10 hours. These reactions can be carried out in the presence of a polymerization inhibitor, a reaction catalyst, a polymerizable (meth) acrylate (F) or the like, if necessary.

Examples of the polymerization inhibitor include known ones such as hydroquinone, methylhydroquinone, and phenothiazine. The amount of the polymerization inhibitor depends on the amount of component (A), component (B), component (C), and component (D). The range of 0.001 to 2 parts by weight with respect to 100 parts by weight in total is preferred.

Examples of the reaction catalyst include tertiary nitrogen-containing compounds such as triethylamine, pyridine derivatives, imidazole derivatives and imidazole derivatives; amine salts such as tetramethylammonium chloride and triethylamine; or trimethylphosphine and triphenylphosphine. And the like. The amounts of the reaction catalyst used are as follows: component (A), component (B), component (C), and component (D).
Is preferably in the range of 0.001 to 2 parts by weight with respect to 100 parts by weight in total.

The polymerizable (meth) acrylate (F) used in the present invention includes, for example, dicyclopentenyl (meth) acrylate having a (meth) acryloyl group, dicyclopentenyloxy (meth) acrylate and the like. Monoacrylates; diol (meth) acrylates such as ethylene glycol di (meth) acrylate and propylene glycol di (meth) acrylate; diethylene glycol di (meth) acrylate, polyethylene glycol Polyalkylene glycol di (meth) acrylates such as (meth) acrylate and polypropylene di (meth) acrylate; trimethylolpropane tri (meth) acrylate; and the like, alone or in combination. be able to. The polymerizable (meth) acrylate (F) preferably has a vapor pressure (mmHg / 20 ° C) of 0.1 or less and a viscosity at 25 ° C of 100 mpa · s or less.

The vinyl ester (E) obtained by the reaction is dissolved in the polymerizable (meth) acrylate (F) to obtain the low odor curable resin composition of the present invention. The proportion of the polymerizable (meth) acrylate (F) in the composition is from 20 to
About 80% by weight, preferably 20 to 50% by weight
It is about.

The composition of the present invention preferably contains a wax. Examples of the wax include paraffin waxes and polar waxes, which can be used alone or in combination.

Known paraffin waxes having various melting points can be used. Further, the polar waxes have both a polar group and a non-polar group in the structure. Specifically, NPS-8070, NPS-9125 (manufactured by Nippon Seiro Co., Ltd.), Emanone 3199, 3299 ( Kao Corporation).

The amount of the wax compounded is 0.05 to 4 parts by weight, preferably 0 to 4 parts by weight, based on 100 parts by weight of the total amount of the vinyl ester (E) and the polymerizable (meth) acrylate (F). 0.1 to 2.0 parts by weight.

The low odor curable resin composition thus obtained is usually used by blending a curing agent and a curing accelerator.

Examples of the curing agent to be used include organic peroxides such as ketone peroxides such as methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide; cumene hydroperoxide and tert-butyl hydroperoxide. Hydroperoxides such as tert-butylperoxyoctoate and tert-butylperoxybenzoate; dialkyl peroxides such as dicumylperoxide; lauroyl peroxide and benzoyl peroxide.
Diacyl peroxides such as oxide, and the like;
These may be used in combination.

Examples of the curing accelerator include salts of organic metal salts, for example, salts such as cobalt such as naphthenic acid and octylic acid, manganese, vanadium and copper, and quaternary ammonium salts such as dimethylbenzylamine and β-acetone such as acetylacetone. Diketones, dimethylaniline, N, N-dimethyl-P-
Amines such as toluidine;

The low odor curable resin composition of the present invention may be, if necessary, an FRP lining impregnated with glass fiber, carbon fiber, aramid fiber or the like as a fiber reinforcing material; 3-8 as bone
Resin mortar lining made by adding talc, silica, etc. as inorganic compounds, such as silica sand and crushed ceramics; and glass flake lining made by adding glass flakes and inorganic compounds can be used.

[0025]

The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The percentages and parts in the examples are on a weight basis. The abbreviations and quality characteristics used in the examples and comparative examples are as shown in Tables 1 to 3 below.

[0026]

Table 1 Abbreviations Epoxy viscosity equivalent (g) (mpa · s) Epoxy compound (A) 1,6-hexanediol diglycidyl ether HDDGE 150 21 neopentyl glycol dichrysidyl ether NPDGE 140 15 resorcin diglycidyl ether Ter LDGE 118 305 Epoxy compound (B) Epicron 830 EP830 188 3620 Epomic R301 EP301 473 Solid Epotote YDF170 EP170 170 3550 Epicron 152 EP152 359 Solid Epicron N740 EP740 182 Semi-solid comparative epicoat 1004 EP1004 Epoxy Bisphenol A type epoxy resin)

[0027]

[Table 2]

[0028]

[Table 3] Abbreviations Polymerizable (meth) acrylate (F) (viscosity at 25 ° C) (vapor pressure) (mPa · S) (mmHg / 20 ° C) Ethylene glycol dimethacrylate EGDMAa 3 0.1 or less Diethylene glycol dimethacrylate G DEGDMAa 5 0.1 or less Trimethylolpropane Trimethacrylate TMPTMAa 42 0.1 or less Dicyclopentenyl oxymethacrylate DCPOMAa 20 0.1 or less Styrene monomer SM 0.7 4.9

(Synthesis of half ester carboxylic acid) Stirrer,
In a reactor equipped with a thermometer, a nitrogen inlet tube and a reflux condenser, 2140 g of trimethylolpropane diallyl ether (1
0 mol) and 1520 g (10 mol) of THPA.
The reaction was carried out at 100 to 130 ° C. for 2.5 hours in a nitrogen gas atmosphere to synthesize a half-ester carboxylic acid (TH-1) having an acid value of 153.

Example 1 A container equipped with a stirrer, a thermometer, a reflux condenser, and a gas inlet tube was provided with 1692 g of EP830, 150 g of HDDGE,
608 g of THPA, 172 g of MAa, 8 g of triethylamine and 0.8 g of hydroquinone were charged and reacted at 130 ° C. for 3.5 hours while flowing air. When the acid value was 4.8, 1748 g (40%) of DCPOMAa and 125 g of 125 were obtained.
゜ F paraffin (8.7 g) was added, and the resin composition (e-
1) was obtained.

Example 2 473 g of EP301, 1260 g of NPDGE were placed in a container equipped with a stirrer, thermometer, reflux condenser and gas inlet tube.
732 g of TH-1, 576 g of Aa, 9.1 g of triethylamine and 0.9 g of hydroquinone were charged, and reacted at 130 ° C. for 2.5 hours while flowing air to obtain an acid value of 8.7.
2027 g (40%) of EGDMAa at the time of
１０F paraffin 10 g was added, and the resin composition (e-2) was added.
I got

Example 3 In a vessel equipped with a stirrer, thermometer, reflux condenser and gas inlet tube, 1530 g of EP170, 118 g of LDGE,
656 g of MTHPA, 172 g of MAa, 7.4 g of triethylamine, and 0.74 g of hydroquinone were charged.
The mixture was reacted at 130 ° C. for 3.5 hours while flowing air, and when the acid value was 4.1, 1651 g of TMPTMAa (40
%) And 8.2 g of 125 ° F paraffin were added to obtain a resin composition (e-3).

Example 4 In a vessel equipped with a stirrer, thermometer, reflux condenser and gas inlet tube, 252 g of EP152, 42 g of NPDGE, TH
292 g of A-1, 14 g of Aa, 1.8 g of triethylamine and 0.18 g of hydroquinone were charged and reacted at 125 ° C. for 4 hours while flowing air, and 400 g (40%) of DEGDMAa was obtained at an acid value of 4.3. 125 ° F
2 g of paraffin was added to obtain a resin composition (e-4).

Example 5 In a vessel equipped with a stirrer, thermometer, reflux condenser and gas inlet tube, 1456 g of EP740, 300 g of HDDGE,
608 g of THPA, 172 g of MAa, 7.6 g of triethylamine, and 0.76 g of hydroquinone were charged and reacted at 120 ° C. for 3 hours while flowing air to obtain an acid value of 4.8.
At the time of EGDMAa was 1691 g (40%), 125
8.5 g of F paraffin was added, and the resin composition (e-
5) was obtained.

Example 6 A container equipped with a stirrer, a thermometer, a reflux condenser, and a gas inlet tube was charged with 188 g of EP830, 1350 g of HDDGE,
732 g of TH-1, 576 g of Aa, 8.5 g of triethylamine and 0.85 g of hydroquinone were charged, and reacted at 130 ° C. for 3.5 hours while flowing air to obtain an acid value of 5.
At the time of 6, 1897 g (40%) of DCPOMAa, 1
9.5 g of 25 ° F paraffin was added, and the resin composition (e
-6) was obtained.

Comparative Example 1 910 g of EP1004 and 1260 of NPDGE were placed in a vessel equipped with a stirrer, thermometer, reflux condenser and gas inlet tube.
g, 732 g of TH-1, 576 g of Aa, 10.4 g of triethylamine, and 1 g of hydroquinone, and reacted at 130 ° C. for 3.5 hours while flowing air to obtain an acid value of 5.
At the time of 4, 2319 g (40%) of EGDMAa, 12
11 g of 5 ° F paraffin was added, and the resin composition (c-
1) was obtained.

COMPARATIVE EXAMPLE 2 A vessel equipped with a stirrer, thermometer, reflux condenser and gas inlet tube was charged with 1880 g of EP830, 608 g of THPA,
172 g of Aa, 8 g of triethylamine and 0.8 g of hydroquinone were charged, and the mixture was added at 130 ° C. while flowing air.
The reaction was carried out for 5 hours. At the time of the acid value of 3.9, 1773 g (40%) of DCPOMAa and 8.8 g of 125 ° F paraffin were obtained.
Was added to obtain a resin composition (c-2).

Comparative Example 3 1504 g of EP830 and 300 g of HDDGE were placed in a container equipped with a stirrer, thermometer, reflux condenser and gas inlet tube.
860 g of MAa, 8 g of triethylamine, and 0.8 g of hydroquinone were charged and reacted at 130 ° C. for 4.5 hours while flowing air, and when the acid value reached 6.6, DCPOMA was added.
a at 1776 g (40%), 125 ° F. paraffin
9 g was added to obtain a resin composition (c-3).

Comparative Example 4 A container equipped with a stirrer, a thermometer, a reflux condenser, and a gas inlet tube was filled with 1530 g of EP170, 118 g of LDGE,
656 g of MTHPA, 172 g of MAa, 7.4 g of triethylamine, and 0.74 g of hydroquinone were charged.
The reaction was carried out at 130 ° C. for 4 hours while flowing air, and the acid value was 5.
At the time of 1, 619 g (20%) of SM and 6.2 g of 125 ° F paraffin were added to obtain a resin composition (c-4).

The resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were subjected to a viscosity test, a curing property test, an odor test, and a coating film drying test.

Viscosity test method Brookfield test method for liquid unsaturated polyester resin
The viscosity of the resin composition of the example thermometer and the viscosity of the resin composition of the comparative example were measured in accordance with the Ludo type viscometer method (JIS K6901 4.4). Table 5 shows the results of the resin compositions of Examples and Table 6 shows the results of the resin compositions of Comparative Examples.

Curing Characteristics Test Method According to the room temperature curing characteristics (JIS K69014.7) of the liquid unsaturated polyester resin test method, a curing agent 328E manufactured by Kayaku Akzo Co., Ltd. was added to the resin compositions of Examples and Comparative Examples.
And 1% each of 6% cobalt naphthenate were blended, and the curing characteristics were measured. Table 5 shows the results of the resin compositions of Examples and Table 6 shows the results of the resin compositions of Comparative Examples.

Odor test method An odor sensor type XP329 manufactured by New Cosmos Electric Co., Ltd. was attached to a sealed container having an internal capacity of 18 liters, and 10 g of each of the resin compositions of Examples and Comparative Examples was allowed to stand at the bottom of the container.
The odor sensitivity value after 60 minutes was measured. At the same time, the odor sensory test was measured based on a six-step odor display method. The evaluation criteria of the six grades are shown in Table 4 below. Table 5 shows the results of the resin compositions of Examples and Table 6 shows the results of the resin compositions of Comparative Examples.

[0044]

[Table 4] Six-step odor intensity indication ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Odor intensity evaluation ━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 0 Odorless 1 Smell that can be sensed at last (detection threshold concentration) 2 Know what smell is Weak odor (cognitive threshold concentration) 3 Easy to detect odor 4 Strong odor 5 Strong odor ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━

Test Method for Drying of Coating Film Resin compositions 328E and 6% cobalt naphthenate manufactured by Kayaku Akzo Co., Ltd. were added to the resin compositions of Examples and Comparative Examples in an amount of 1% each.
Combine, 300μ on a 25mm × 350mm glass plate
m. The coated glass plate was set on an RC type paint drying time measuring device manufactured by Taiyo Kiki Co., Ltd., and the drying time was measured. Table 5 shows the results of the resin compositions of Examples and Table 6 shows the results of the resin compositions of Comparative Examples.

[0046]

[Table 5]

[0047]

[Table 6]

From the comparison between the above embodiment and the comparative example, the following matters are apparent. 1. A suitable viscosity used for normal work is 2000
(Mpa · s / 25 ° C) or less. The resin compositions c-1 and 2 of Comparative Examples 1 and 2, which deviate from the scope of the present invention, have a defect that work cannot be performed due to high viscosity. 2. Normally, if the coating film drying time is within 5 hours, there is no problem in the work, but the coating film does not dry even after 24 hours. 3 is clearly inferior to the resin composition of the example. 3. Resin composition c- of Comparative Example 4 which deviates from the scope of the present invention
No. 4 is clearly inferior to the resin composition of the example in the odor sensitivity value and has a strong pungent odor. 4. It is apparent that the resin compositions e-1 to 6 of the examples according to the present invention have appropriate viscosity and coating film drying property, have low odor sensitivity, and have low odor without pungent odor.

[0049]

According to the low odor curable resin composition of the present invention, odor is suppressed without containing styrene, and further, since it has appropriate viscosity and coating film drying property, the FRP lining material, Gin mortar lining material, FRP molding material,
It can be used in a wide variety of applications such as putty materials, paint materials, and the like.

Claims (4)

[Claims] (1) The viscosity at 25 ° C. is 1000 mpa · s
(Ii) an epoxy compound having a viscosity of not more than 1000 mpa · s at 25 ° C., an epoxy equivalent of not more than 500, and at least 2 Epoxy compound (B) having two epoxy groups (provided that the equivalent ratio of the epoxy compound is (A) :( B) = 1
(Iii) an unsaturated monobasic acid (C); and (iv) a vinyl ester (E) composed of a saturated dibasic acid (D) by polymerizing a (meth) acrylate ( A low-odor curable resin composition dissolved in F). 2. The equivalent ratio of the unsaturated monobasic acid (C) and the saturated dibasic acid (D) is (C) :( D) = 80 to 20:20.
The low odor curable resin composition according to claim 1, which has a molecular weight of from 80 to 80. 3. The polymerizable (meth) acrylate (F) has a vapor pressure (mmHg / 20 ° C.) of 0.1 or less;
The low odor curable resin composition according to claim 1, which has a viscosity at 5 ° C of 100 mpa · s or less. 4. The low odor curable resin composition according to claim 1, further comprising a wax.