JP2000103825A - Low-odor curable resin composition having high surface curability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low-odor curable resin composition used as a flooring material, etc., having a high surface tack-free property (dry tack property) at curing. SOLUTION: A thermosetting resin oligomer, dicyclopentenyloxyethyl(meth) acrylate, an organic hydroperoxide, a cobalt salt, benzaldehyde optionally possessing a tertiary amino group in its benzene ring and a tertiary aminobenzene optionally possessing an alkyl group in its benzene ring are used together.

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 used as a flooring material having excellent surface tack-free properties (dryness to the touch) during curing.

[0002]

2. Description of the Related Art Concrete and mortar structures mainly contain urethane resin, unsaturated polyester resin, epoxy (meth) acrylate resin and the like for the purpose of improving functions such as waterproofness, chemical resistance and abrasion resistance. Coating material and FR by coating method and combination with fiber reinforcement
It is applied by the P lining method. In particular, unsaturated polyester resins and epoxy (meth) acrylate resins are overwhelmingly used for renovation and renovation of food factories, chemical factories, and the like because of the short time required to release walking.

[0003]

SUMMARY OF THE INVENTION In a thermosetting resin composition having a polymerizable double bond such as an unsaturated polyester resin or an epoxy (meth) acrylate resin, a thermosetting resin composition is used for the purpose of improving a working method and impregnation. Polymerizable monomers such as styrene and methyl methacrylate are blended as a viscosity reducing agent. However, the use of these monomers produces a strong odor at the construction site, which can cause discomfort and possibly poisoning to workers and those entering the site.
In addition, when the construction site is a place where food is handled, such as a food factory, a refrigerator, or a kitchen, odor may be transferred to the food and the commercial value of the food may be impaired. In order to overcome this drawback, it has been proposed to use dicyclopentenyloxyethyl (meth) acrylate as a monomer (JP-A-3-79609, JP-A-8-217837 and JP-A-9-362053). When these monomers are used, although the generation of odor is greatly reduced as compared with the case where styrene or methyl methacrylate is used,
There is a problem that the tackiness of the surface layer of the coating film is maintained for a long time, and the time required to release walking is prolonged. This surface hardening delay is not improved by increasing the amount of hardener,
Although the inside of the coating layer is completely cured, the phenomenon that only the surface is sticky forever occurs. As a means for solving this problem, a method has been proposed in which poly (allyl glycidyl ether) is used for dicyclopentenyloxyethyl (meth) acrylate (JP-A-9-137080). However, even in this method, the hardening of the surface layer of the coating film is considerably delayed from the hardening of the inner layer, and has not yet been put to practical use.

[0004]

Means for Solving the Problems The present inventors have found that the odor at the time of construction is low and the composition cures in a short time even at a low temperature, the shrinkage upon curing is small, the water resistance and the hot water resistance are excellent, and the inner layer is cured. As a result of intensive studies to obtain a curable resin composition in which the surface layer hardens almost without delay, in addition to organic hydroperoxide as a curing agent and organic acid cobalt salt as a curing accelerator, tertiary amino The inventors have found that the above problems can be completely overcome by using a benzaldehyde which may have a group and a tertiary aminobenzene, and have completed the present invention. That is, the present invention provides (1) a thermosetting resin oligomer (A), dicyclopentenyloxyethyl (meth) acrylate (B), a benzaldehyde (C) which may have a tertiary amino group on a benzene ring, Low odor curable resin excellent in surface curability, containing a tertiary aminobenzene (D) optionally having an alkyl group on a benzene ring, an organic hydroperoxide (E) and a cobalt salt (F). Composition, (2) (A)
The weight ratio of the pair (B) is 5 to 95:95 to 5,
(C) is 0.1 to 10 parts by weight, (D) is 0.001 to 0.2 parts by weight, and (E) is 0.1 to 5 parts by weight based on 100 parts by weight of the total of (A) and (B). (1) the composition according to the above (1), wherein (F) is 0.006 to 0.15 parts by weight of cobalt, and (3) (A) is an epoxy (meth) acrylate resin oligomer. ) Or (2), wherein (4) (C) is (N, N-dimethylamino)
The composition according to (1) or (2), which is parabenzaldehyde; (5) the composition according to (1) or (2), wherein (D) is N, N-dimethylaniline;
(E) the composition according to (1) or (2) above, wherein (E) is cumene hydroperoxide; (7) the composition according to (1) or (2) above, wherein (F) is cobalt naphthenate or cobalt octylate. And (8) the composition according to (1) or (2), further comprising an organic diisocyanate.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Typical examples of the thermosetting oligomer (A) used in the present invention include unsaturated polyester resin or epoxy (meth) acrylate resin oligomer. The unsaturated polyester resin oligomer is obtained by reacting an acidic component with an alcohol component, and in some cases, a modified component. Usually, it is obtained by reacting an α, β-unsaturated dibasic acid and / or an anhydride thereof with a polyhydric alcohol, but if necessary, further reacting with a saturated polybasic acid. Examples of the α, β-unsaturated dibasic acid and its anhydride include maleic acid,
Fumaric acid, itaconic acid, citraconic acid, maleic anhydride and the like. These may be used in combination of two or more. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol,
Dipropylene glycol, 1,3-butanediol, 1,
6-hexanediol, neopentyl glycol, 1,
Examples thereof include dihydric alcohols such as 4-cyclohexanediol and hydrogenated bisphenol A, and tetrahydric alcohols such as petaerythritol. These may be used in combination of two or more.

[0006] Saturated polybasic acids optionally used include, for example, phthalic acid, phthalic anhydride, trimellitic anhydride, succinic acid, azelaic acid, adipic acid, tetrahydrophthalic anhydride, rosin-maleic anhydride addition Things. These may be used in combination of two or more. The method for producing the unsaturated polyester resin is not particularly limited. For example, the unsaturated polyester resin is subjected to a condensation reaction between the acid component and the alcohol component, and water generated when both components react is eliminated from the system. As the epoxy (meth) acrylate resin, for example, a resin obtained by reacting an epoxy resin, an unsaturated monobasic acid, and, if necessary, a polybasic acid is used. The epoxy resin is not particularly limited, and ordinary bisphenol-type epoxy resins and novolak-type epoxy resins are used. As the unsaturated monobasic acid to be reacted with the epoxy resin, for example, acrylic acid, methacrylic acid, crotonic acid and the like can be used. Examples of the polybasic acid used as needed include phthalic anhydride, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride,
Glutaric acid, adipic acid, dimer acid and the like can be mentioned. The epoxy resin, the unsaturated monobasic acid and the optional polybasic acid are used at 60 to 150 ° C., preferably at 7 ° C.
When reacted at a temperature of 0 to 130 ° C., an epoxy (meth) acrylate resin is obtained. The number average molecular weight of the thermosetting resin oligomer (A) used in the present invention is usually from 200 to 200.
It is 1,500, preferably 300-1,000.

The dicyclopentenyloxyethyl (meth) acrylate (B) used in the present invention is disclosed in
As described in JP-A-43337, ethylene glycol is added to dicyclopentadiene and the resulting ethylene glycol monodicyclopentenyl ether is esterified with methacrylic acid or transesterified with methyl methacrylate. Can be manufactured. It is also possible to replace this methacrylic acid or methyl methacrylate with acrylic acid or methyl acrylate. Further, as described in JP-A-57-200331, it can also be produced by adding ethylene glycol monomethacrylate or ethylene glycol monoacrylate to dicyclopentadiene. The weight ratio of component (A) to component (B) is 5 to 95:95 to 5, preferably 10 to 95:95.
65: 90 to 35. If the proportion of (A) is 5 or less, the curability of the composition will be poor, and if it is 95 or more, the viscosity of the composition will be high and the curing of the surface during curing will be delayed. Examples of the benzaldehyde (C) which may have a tertiary amino group on the benzene ring used in the present invention include benzaldehyde and di-C ₁ such as dimethylamino group and diethylamino group at an arbitrary position on the benzene ring. _{And a} benzaldehyde which may have a _-3 alkylamino group. Specific compounds include, for example, benzaldehyde,
(N, N-dimethylamino) parabenzaldehyde,
(N, N-diethylamino) parabenzaldehyde and the like.

The tertiary aminobenzene (D) which may have an alkyl group on the benzene ring used in the present invention includes an alkyl group, preferably a C _1-3 alkyl group, at any position on the benzene ring. Is a tertiary aminobenzene which may have 1 to 3, preferably 1, and the tertiary amino group is the same as the amino group of the component (C) described above. Specific compounds include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyltoluidine, N, N-diethyltoluidine and the like. The amount of the component (C) is usually 0.1 to 10 parts by weight, preferably 1 to 6 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). When the amount is less than 0.1 part by weight, the surface dryness of the composition becomes poor. When the amount is more than 10 parts by weight, the surface dryness of the composition also reaches a plateau, but the storage stability of the composition becomes poor. The amount of the component (D) is usually 0.000 based on 100 parts by weight of the total of the components (A) and (B).
It is 1 to 0.2 part by weight, preferably 0.01 to 0.1 part by weight. If the amount is less than 0.001 part by weight, there is no effect on curability, and if it is more than 0.2 part by weight, the storage stability of the composition becomes poor. The organic hydroperoxide (E) used in the present invention serves as a reaction initiator and includes, for example, cumene hydroperoxide, tertiary butyl hydroperoxide, paramenthane hydroperoxide, diisopropylbenzene hydroperoxide, Tertiary hexyl hydroperoxide and the like can be used in an amount of usually 0.3 to 3.0 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of the total of the components (A) and (B). 0.0 parts by weight.

The cobalt salt (F) as a curing accelerator used in the present invention is, for example, an organic acid cobalt salt such as naphthenic acid or octylate of cobalt, or cobalt acetylacetonate. ) 0.006 to 0.15 parts by weight, preferably 0.01 to 0.1 parts by weight of cobalt based on 100 parts by weight of the total of the component (B) and the component (B).
Parts by weight. The composition of the present invention may contain, if necessary, a curing agent such as an organic diisocyanate, an air barrier agent such as a wax, a low shrinkage material such as a thermoplastic resin, a filler, a reinforcing material, and a coloring agent. Examples of the organic diisocyanate include diphenylmethane diisocyanate (MDI), polymeric MDI, hexamethylene diisocyanate, xylylene diisocyanate, and tolylene diisocyanate. These are particularly effective when the resin composition is used as a primer to be directly applied to concrete before casting mortar without using a filler or a reinforcing material. Examples of the waxes that are air barrier agents include natural and synthetic hydrocarbon waxes having a melting point higher than the use temperature, modified products and oxides thereof, and mineral, animal and plant waxes and modified products thereof. Among them, paraffin wax is preferred from the viewpoint of purity and stability of quality. Although paraffin waxes having various melting points can be obtained, those suitable for the purpose of the present invention are preferably those having a melting point of 5 to 40 ° C. higher than the use temperature. If the temperature is lower than the temperature at the time of use, the film is uncured because it dissolves in the resin and does not precipitate on the surface of the film after coating. If the melting point is higher than the temperature at the time of use by 40 ° C. or more, uniform spreading of the wax on the surface of the coating film cannot be obtained. If the amount of these waxes is less than 0.1 part by weight based on 100 parts by weight of the composition, the wax does not spread uniformly on the surface of the coating film, and therefore becomes partially uncured.

Examples of the thermoplastic resin include polymethyl methacrylate, polystyrene, polycaprolactone,
Examples include polyvinyl acetate, polyethylene, and butadiene rubber. The amount used is determined in consideration of the surface hardness, smoothness, gloss, etc. of the coated floor surface, and is not particularly limited. Examples of the filler include inorganic fillers such as silica sand, calcium carbonate, and talc clay. These fillers may be pre-colored with glaze or the like. As the reinforcing material, glass fiber, carbon fiber, various synthetic fibers and the like can be used, and glass fiber is generally used. These reinforcing materials are used in the form of continuous fibers, woven fabrics, non-woven fabrics and the like.
As a coloring agent, inorganic pigments such as titanium oxide, titanium yellow, yellow iron oxide, iron oxide, cobalt blue, iron black, graphite, molybdenum red, carbon black, condensation azo,
Known coloring pigments are used as organic pigments such as quinacridone, isoindolinone, phthalocyanine, and perylene pigment. INDUSTRIAL APPLICABILITY The coated flooring material of the present invention can be used for improving the functions such as waterproofness, chemical resistance, and abrasion resistance of concrete and mortar structures, and a polymerizable monomer comprising the component (A) and the component (B). In order to dissolve in the body, the components (D) and (F) are added to the resin solution in which the component (C) is dissolved, and the component (E) is added to a resin solution obtained by mixing a thermoplastic resin or a filler as necessary. Using a trowel, a spatula, or a brush roller, application can be performed on the concrete and mortar structure that have been mixed and subjected to primer treatment and unevenness adjustment as required.

[0011]

The present invention will be described more specifically below with reference to examples and comparative examples. In addition, the number of parts in an example shows a weight part. Example 1 Isophthalic acid, maleic acid, diethylene glycol,
30 parts of an unsaturated polyester resin oligomer (A1) containing 1,3-butanediol as a main component (Polymer 9015, manufactured by Takeda Pharmaceutical Co., Ltd.) was mixed with 30 parts of dicyclopentenyloxyethyl acrylate (B1) (Fanacryl FA-
512A, manufactured by Hitachi Chemical Co., Ltd.)
2 parts of (N, N-dimethylamino) parabenzaldehyde (C2) was dissolved therein. N, N
0.03 parts of dimethylaniline, 3 parts of toner (Psycha Color, manufactured by Aika Chemical Co., Ltd.), JIS No. 5 silica sand 4
00 parts, paraffin wax having a melting point of 130 ° F. 0.3
Parts, 6% cobalt naphthenate (Polymer P-106,
0.5 part of Takeda Pharmaceutical Co., Ltd.) was mixed and mixed well with a twin-screw mixer. Cumene hydroperoxide (Parkmill H-80, manufactured by NOF Corporation) 1.0 was added to the obtained mortar. Add 5 parts and stir well before placing 5
mm. The viscosity (25 ° C., mPa · s) of the resin solution obtained by dissolving (B1) in (A1), and the storage stability of the resin solution before adding cumene hydroperoxide (50
° C, days), the mortar gel time (25 ° C, minutes), the time until tack-free on the mortar surface (25 ° C, minutes), and the odor during work were observed. The results are shown in Table 1 together with the ingredients used. Was.

Examples 2 to 7 Using the components shown in Table 1, mortars were prepared according to Example 1, and their physical properties were measured in the same manner as in Example 1. The results are shown in [Table 1]. In addition, [in the table], Example 1
The components other than those used in are as follows. A2: Bisphenol A-based epoxy methacrylate resin oligomer (MCIVE ZZV-01, manufactured by MC Industry Co., Ltd.) B2: Dicyclopentenyloxyethyl methacrylate (QM-657, manufactured by Rohm and Haas Company) B3: Crude dicyclopentenyloxy Ethyl methacrylate (QM-57T, manufactured by Rohm and Haas Company) B4: Styrene C1: Benzaldehyde C2: (N, N-dimethylamino) parabenzaldehyde Polymeric MDI (MC AN-74P, manufactured by MC Industry Co., Ltd.)

[0013]

[Table 1]

Comparative Examples 1 to 10 Using the components shown in [Table 2], mortars were prepared according to Example 1, and their physical properties were measured in the same manner as in Example 1. The results were shown in [Table 2]. Indicated.

[Table 2]

As apparent from Table 1, Examples 1 to
In No. 7, the resin (A) + (B) has an appropriate viscosity and storage stability, and has an appropriate gel time of about 15 to 20 minutes after the preparation of the composition. Further, the surface of the coating layer becomes tack-free within 50 minutes, and the odor during the operation is weak. On the other hand, Comparative Example 2 has a high resin viscosity of (A) + (B), and Comparative Examples 5 and 7 lack storage stability. Comparative Example 1,
The gel times of 3, 6, and 8 are too long, and the comparative example 9 is too short, and all of them have poor workability. Comparative Examples 2, 4, and 8 have poor surface tack-free properties. Comparative Example 10 has a strong odor.

[0016]

The curable resin composition of the present invention has a low odor during application, cures in a short time even at a low temperature, has a small shrinkage at the time of curing, has excellent water resistance and hot water resistance. The surface hardening speed is remarkably improved such that the surface layer becomes tack-free with almost no delay in hardening of the inner layer of the coating layer after the application.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08L 67/06 C08L 67/06 C09D 4/02 C09D 4/02 (72) Inventor Shinichiro Takenouchi Osaka Prefecture 2-17-85 Jusanhoncho, Yodogawa-ku, Osaka-shi Takeda Pharmaceutical Co., Ltd.Chemicals Research Laboratory (72) Inventor Minoru Miki 18 Tsubota, Oshinya, Kashiwara-cho, Hikami-gun, Hyogo MCC Industry Co., Ltd. (72) Invention Person Shotoku Takamura 18 Tsubota, Oshinya, Kashiwara-cho, Hikami-gun, Hyogo Prefecture Inside M-C Industry Co., Ltd. (72) Inventor Noriyuki Moriyama 18 Tsubota, Oshin-ya, Kashiwara-cho, Hikami-gun, Hyogo Prefecture F-term (reference) 4J027 AB02 AB06 AB07 AB08 AB15 AB17 AB18 AB19 AB23 AB24 AB25 AE02 BA17 CA02 CA03 CA04 CA05 CA06 CA08 CA12 CA14 CA18 CA19 CA25 CA28 CA29 CA34 CA36 CA38 CB03 CC01 4J038 D B211 DD181 DD191 DG261 FA131 JA06 JA31 JA47 JA66 NA04 NA14 NA27 PB05 PC04

Claims (8)

[Claims] 1. A thermosetting resin oligomer (A), dicyclopentenyloxyethyl (meth) acrylate (B),
Benzaldehyde (C) optionally having a tertiary amino group on a benzene ring, tertiary aminobenzene (D) optionally having an alkyl group on a benzene ring, organic hydroperoxide (E), and cobalt A low odor curable resin composition containing a salt (F) and having excellent surface curability. 2. The weight ratio of (A) to (B) is 5 to 95:
(C) is 0.1 to 10 parts by weight, and (D) is 0.001 relative to 100 parts by weight of the total of (A) and (B).
2. The composition according to claim 1, wherein the amount of (E) is from 0.1 to 5.0 parts by weight and (F) is from 0.006 to 0.15 parts by weight of cobalt. 3. The composition according to claim 1, wherein (A) is an epoxy (meth) acrylate resin oligomer. 4. The composition according to claim 1, wherein (C) is (N, N-dimethylamino) parabenzaldehyde. 5. The composition according to claim 1, wherein (D) is N, N-dimethylaniline. 6. The composition according to claim 1, wherein (E) is cumene hydroperoxide. 7. The composition according to claim 1, wherein (F) is cobalt naphthenate or cobalt octylate. 8. The composition according to claim 1, further comprising an organic diisocyanate.