JP2001240632A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition exhibiting a low smelling property, curing property, tenacity, endurance, etc., and a resin mortar composition obtained by using the same. SOLUTION: This curable resin composition contains (I) an epoxy (meth) acrylate consisting of a reaction material of an epoxy compound obtained by reacting 1.5-3.5 mol aliphatic diglycidyl ether type epoxy compound having <=300 epoxy equivalent with 1.0 mole bisphenol A and/or F', with (meth)acrylic acid and (II) a polymerizable (meth)acrylic monomer having >=160 molecular weight and <=100 mPa.s viscosity at 25 deg.C, and consists of 20-80 mass % (I) and 80-20 mass % (II) based on the total mass of the above (I) and (II). Also, the resin mortar composition contains 0.4-20 pt. mass inorganic aggregates and/or inert powdery material based on 1 pt. mass above described curable resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a curable resin composition,
And a resin mortar composition using the same. More specifically, it is excellent in low odor and curability, and the cured product is excellent in toughness, strength, durability, water resistance, chemical resistance,
Curable resin compositions usable for various anticorrosive materials, waterproof materials, covering materials such as floor materials, and fiber-reinforced plastics, and anticorrosive materials, waterproof materials, covering materials and repair materials for floor materials, etc. using the same. And a resin mortar composition useful as an application of the resin.

[0002]

2. Description of the Related Art Conventionally, unsaturated polyester resins, vinyl ester resins, acrylic resins, and the like have been widely used as curable resins curable by radical polymerization at room temperature. In these resins, a styrene monomer is generally used as an unsaturated polyester resin and a vinyl ester resin as a polymerizable diluent, and a volatile monomer such as methyl methacrylate is used as an acrylic resin. However, these monomers have a high volatility and a strong odor, which poses a problem at the time of construction or molding and limits the use.

In the case where a low-volatile acrylic monomer is used instead of the above-mentioned monomers such as styrene and methyl methacrylate, the viscosity becomes high and the workability becomes poor. That is, in such a case, the use of the monomer increases, and in any case, it is extremely difficult to satisfy all the properties of the cured product such as odor and toughness, and strength and durability. .

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the conventional curable resins, and provides a curable resin having excellent properties such as low odor, curability, toughness and durability. An object of the present invention is to provide a resin composition and a resin mortar composition using the same, which is useful as a coating material such as an anticorrosive material, a waterproof material, a floor material, and a repair material.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have used specific epoxy (meth) acrylate and (meth) acrylic monomers, and Finding that the problem can be solved by blending in the ratio,
The present invention has been completed.

That is, the present invention relates to (1) bisphenol A (a) and / or bisphenol F (b).
Aliphatic diglycidyl ether type epoxy compound (c) having an epoxy equivalent of 300 or less per 0 mol (c) 1.5 to 3.5
An epoxy compound (A) obtained by reacting
Epoxy (meth) acrylate (I) comprising a reaction product with (meth) acrylic acid (B); and a polymerizable (meth) acrylic monomer (II) having a molecular weight of 160 or more and a viscosity at 25 ° C of 100 mPa · s or less. ) And based on the total mass of (I) and (II) above,
(I) is 20 to 80% by mass, (II) is 80 to 20% by mass.
The curable resin composition according to (1), wherein the (2) polymerizable (meth) acrylic monomer (II) is a cyclic monofunctional (meth) acrylic monomer. The curable resin composition according to (1) or (2), further comprising (3) a curing agent, and (4) the curable resin composition according to (3). It is a resin obtained by curing a curable resin composition, and (5) 1 part by mass of the curable resin composition according to any one of (1) to (3) above, with respect to an inorganic aggregate and / or an inorganic aggregate. The present invention relates to a resin mortar composition comprising 0.4 to 20 parts by mass of active powder.

[0007]

DETAILED DESCRIPTION OF THE INVENTION First, the epoxy (meth) acrylate (I) in the curable resin composition of the present invention is obtained by reacting bisphenol A and / or F with an aliphatic diglycidyl ether type epoxy compound (c). (A) and a reaction product thereof with (meth) acrylic acid (B).

In the present invention, the aliphatic diglycidyl ether type epoxy compound (c) is a diglycidyl ether type epoxy compound of an aliphatic bifunctional alcohol, and the epoxy equivalent thereof is 300 or less. Specific examples include 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (di) glycerol (poly) glycidyl Ether and polytetramethylene glycol diglycidyl ether.

In the present invention, the amount of the aliphatic diglycidyl ether type epoxy compound (c) used in forming the epoxy compound (A) is bisphenol A (a).
The amount is usually in the range of 1.5 to 3.5 mol, and more preferably 2.0 to 3.0 mol, per 1.0 mol of bisphenol F (b). When the amount is less than 1.5 mol, the viscosity of the obtained curable resin composition becomes high and the workability tends to be poor, and when it exceeds 3.5 mol, the curable resin composition obtained is cured. None of them is preferable because the toughness of the product is likely to be inferior.

In the present invention, an aromatic polyfunctional epoxy resin can be used in combination with the aliphatic diglycidyl ether type epoxy compound (c), if necessary.
The aromatic polyfunctional epoxy resin is a polyfunctional epoxy resin having an aromatic ring in a molecule, and when used in combination, a resin having an epoxy equivalent of 600 or less is preferable.
The following are more preferred.

Specific examples of the aromatic polyfunctional epoxy resin include phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alkylphenol type epoxy resin, and resorcinol type epoxy resin. , N-glycidylamine type epoxy resin, brominated bisphenol A type epoxy resin and the like. Among them, bisphenol type epoxy resin is preferable. The amount used is up to 60 mol%, more preferably up to 40 mol%, in the epoxy compound (c) to be reacted with bisphenol A and / or bisphenol F. If this amount exceeds 60 mol%, the viscosity of the resulting curable resin composition will be high, workability will be poor, and the tensile elongation of the cured product will be low, resulting in poor toughness. Is not preferred.

In the present invention, bisphenol A (a)
And / or bisphenol F (b) and the aliphatic diglycidyl ether type epoxy compound (c) are reacted with bisphenol A (a) and / or bisphenol F
This is a reaction between the phenolic hydroxyl group of (b) and the epoxy group of the aliphatic diglycidyl ether type epoxy compound (c), and is usually performed at a temperature of 100 to 200 ° C.
In this reaction, an inorganic base such as sodium hydroxide, potassium hydroxide or lithium hydroxide, or an organic base such as triethylamine may be used as a catalyst, and an inorganic base is particularly preferable.

In the present invention, the reaction is carried out in an amount of 1.5 to 3.5 moles of the aliphatic diglycidyl ether type epoxy compound with respect to 1.0 mole of bisphenol A (a) and / or bisphenol F (b). (C) reacts, and in the present invention, since this (c) is in excess,
The epoxy compound (A) obtained by the reaction usually contains an unreacted aliphatic diglycidyl ether type epoxy compound (c).

In the present invention, the epoxy (meth) acrylate (I) comprises a reaction product of the epoxy compound (A) obtained by the above reaction and (meth) acrylic acid (B). Is usually in the range of 0.9: 1.1 to 1.1: 0.9 by molar ratio.

In the present invention, as the epoxy compound (A), an aromatic polyfunctional epoxy resin may be used in combination, if necessary. The amount used is in the range of 60 mol% or less in the epoxy compound (A), and more preferably 30 mol% or less.

In the present invention, the reaction between the epoxy compound (A) and the (meth) acrylic acid (B) is usually carried out at 80 ° C. to 1 ° C.
The reaction is performed at 30 ° C., and a tertiary amine such as triethylamine or dimethylaniline, a quaternary ammonium salt such as trimethylbenzylammonium chloride or pyridinium chloride, or an inorganic salt such as lithium hydroxide or lithium chloride is used as a reaction catalyst. A polymerization inhibitor is used if necessary. Examples of the polymerization inhibitor include hydroquinones such as hydroquinone and methylhydroquinone, benzoquinones such as benzoquinone and methyl-p-benzoquinone, catechols such as t-butylcatechol, and 2,6. Phenols such as -di-t-butyl-4-methylphenol and 4-methoxyphenol; phenothiazine;

In the present invention, as the polymerizable (meth) acrylic monomer (II), those having a molecular weight of 160 or more and a viscosity at 25 ° C. of 100 mPa · s or less are used. When a resin having a molecular weight of less than 160 is used, the resulting curable resin composition tends to have a high odor, and the viscosity is 100 mPa · s.
When using more than one, the viscosity of the obtained curable resin becomes high, and the workability is likely to be deteriorated.

Polymerizable (meth) acrylic monomer (II)
As a specific example, monofunctional alkyl (meth) such as butyl (meth) acrylate and hexyl (meth) acrylate
In addition to monofunctional (meth) acrylates such as acrylates and cyclic monofunctional (meth) acrylates described below, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, bisphenol A alkylene oxide di (Meth) acrylate,
Examples thereof include polyfunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, and these may be used alone or in combination.

In the present invention, a cyclic monofunctional (meth) acrylate monomer is more preferably used as the polymerizable (meth) acrylic monomer (II). More specifically, it is a monofunctional (meth) acrylate compound having a cyclic structure in the molecule, such as cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, isobornyl methacrylate, dicyclopentenyloxyethyl methacrylate, phenoxyethyl methacrylate. And the like. Among these, dicyclopentenyloxyethyl methacrylate and phenoxyethyl methacrylate are more preferably used in view of low odor and physical properties of the cured product.

In the curable resin composition of the present invention, the ratio of the epoxy (meth) acrylate (I) and the polymerizable (meth) acrylic monomer (II), which are essential components constituting the curable resin composition, is based on the total mass of these. (I)
Is in the range of 20 to 80% by mass, and (II) is in the range of 20 to 20% by mass.
It is preferably in the range of mass%. That is, in this case, if (I) is less than 20% by mass, the resulting curable resin composition tends to have poor chemical resistance and toughness, and if it exceeds 80% by mass, the cured product tends to have poor surface properties. Further, the workability is likely to be poor due to the high viscosity, so that the above range is preferable.

The curable resin composition of the present invention may contain a curing accelerator, a polymerization inhibitor, an antifoaming agent and the like, if necessary. Examples of the curing accelerator include metal soaps such as cobalt naphthenate, manganese naphthenate, copper naphthenate, potassium naphthenate, calcium naphthenate, and cobalt octylate, dimethylaniline, N, N-dimethyltoluidine, N, N Amines such as -diethylaniline and N, N-di (hydroxy) -4-methylaniline; β-diketones such as acetylacetone, ethyl acetoacetate and N, N-dimethylacetoacetamide; β-ketoesters and β-ketoamides Is mentioned. Examples of the polymerization inhibitor include hydroquinones such as hydroquinone and methylhydroquinone, benzoquinones such as benzoquinone and methyl-p-benzoquinone, catechols such as t-butylcatechol, and 2,6-di-t-butyl-4-methylphenol. And phenols such as 4-methoxyphenol, phenothiazine and the like. Examples of the antifoaming agent include a commercially available polymeric antisaturant and other additives in addition to the silicone type and the like.

The curable resin composition of the present invention may contain, in addition to a coloring agent such as a pigment and a toner, a thixotropic agent such as fumed silica, and an inorganic filler such as calcium carbonate, silica and talc, if necessary. Can also be blended.

Further, it is recommended to add a wax to the curable resin composition of the present invention in order to avoid poor curing of the air contact surface. Examples of the wax include petroleum waxes such as paraffin wax and microcrystalline wax, olefinic waxes such as polyethylene and polypropylene, and polar waxes having a polar group introduced therein. As the amount of the wax added, it is necessary to exhibit excellent barrier properties and curability, and not to deposit wax without lowering the solubility. It is preferably in the range of 02 to 2% by mass.

The curable resin composition of the present invention can be cured by adding a curing agent. Examples of the curing agent include methyl ethyl ketone peroxide, acetylacetone peroxide, cumene hydroperoxide, t-butyl perbenzoate, t-butyl peroctoate, benzoyl peroxide, bis (4-t
-Butylcyclohexyl) peroxydicarbonate, t
A polymerization initiator such as an organic peroxide such as -hexylperoxy-2-ethylexanoate is used. As the amount of the curing agent, with respect to 100 parts by mass of the curable resin composition,
Usually, 0.5 to 5 parts by mass is used.

The curable resin composition of the present invention can be used alone, but in particular, 1 part by mass of the curable resin composition of the present invention is preferably used in an amount of 0.1% by weight of inorganic aggregate and / or inert powder. The composition containing 4 to 20 parts by mass can be suitably used particularly as a composition for resin mortar.

The above-mentioned inorganic aggregate includes silica sand, silica, clay, bentonite, aluminum hydroxide, alumina,
Inorganic powders such as talc and calcium carbonate;
Examples of the inert powder include thermoplastic resins such as polyethylene, polypropylene, and polystyrene; thermosetting resins such as acrylic resins, polyester resins, phenol resins, and urethane resins; powders such as rubber and wood; Things.

In the resin mortar composition of the present invention,
When the mixing ratio of the inorganic aggregate and / or the inert powder is too small, the viscosity of the obtained composition is too low, and further, the strength and rigidity after curing are low, and the mixing ratio is low. If the amount is too large, the viscosity is too high and the workability is poor, and further the surface properties after curing tend to be poor, so the above-mentioned mixing ratio, that is, 1 part by mass of the curable resin composition of the present invention , Inorganic aggregate and / or inert powder 0.4-20
It is preferable to use a resin mortar composition composed of parts by mass.

[0028]

The present invention will be described in more detail with reference to the following examples. In the following, “%” and “parts” are all based on mass.

Synthesis Example 1 1.0 mol of bisphenol A and 1,6-hexanediol diglycidyl ether (Denacol EX21
2: trade name, manufactured by Nagase Kasei Co., Ltd.) 2.5 mol of 20% potassium hydroxide 0.02% was added and reacted at 140 ° C. to 180 ° C. for 5 hours to obtain an epoxy compound (A1) having an epoxy equivalent of 345. Was. This epoxy compound (A1) and 2.95 mol of methacrylic acid were mixed with 0.2% of triethylamine,
In the presence of 0.01% of phenothiazine,
The reaction was carried out at a temperature of 00 to 120 for 3 hours to obtain an epoxy methacrylate (I-1) having an acid value of 2.

Synthesis Example 2 1.0 mol of bisphenol A, 1.6 mol of 1,6-hexanediol diglycidyl ether (Denacol EX212: trade name, manufactured by Nagase Kasei Co., Ltd.), and bisphenol A epoxy resin (Epomic R140: trade name) 20% potassium hydroxide 0.0 in 0.9 mol
2% was added and reacted at 140 ° C. to 180 ° C. for 5 hours,
Epoxy compound (A2) having an epoxy equivalent was obtained. This epoxy compound (A2) and 2.95 mol of methacrylic acid were mixed with 0.2% of triethylamine and 0.0% of phenothiazine.
The reaction was carried out at a temperature of 100 to 120 for 3 hours in the presence of 1% in an air stream to obtain an epoxy methacrylate having an acid value of 2 (I
-2) was obtained.

Synthesis Example 3 1.0 mol of bisphenol A and bisphenol A
20% potassium hydroxide 0.02% in 2.5 moles of epoxy resin (Epomic R140: trade name, manufactured by Mitsui Chemicals, Inc.)
Was added and reacted at 140 ° C. to 180 ° C. for 5 hours to obtain an epoxy compound (A3) having an epoxy equivalent of 400. The epoxy compound (A2) and 2.95 mol of methacrylic acid were mixed with 0.2% of triethylamine and 0.1% of phenothiazine.
The reaction was carried out at a temperature of 100 to 120 for 3 hours under an air stream in the presence of 01% to obtain an epoxy methacrylate (I-3) having an acid value of 2.

Examples 1 to 3 and Comparative Example 1 The components shown in Table 1 were mixed to prepare a curable resin composition.

(Description of Materials Used) [Polymerizable (meth) acrylic monomer (II) component] QM57T: (trade name, manufactured by Rohm and Haas Co.) dicyclopentenyloxyethyl methacrylate light ester PO: (product, manufactured by Kyoeisha Chemical Co., Ltd.) Name) phenoxyethyl methacrylate

[0034]

[Table 1]

(Test Method) The viscosities of the curable resin compositions of Examples 1 to 3 and Comparative Example 1 at 25 ° C. were measured according to JISK.
Measured with a Brookfield viscometer according to the method of 6901. Table 2 shows the results. Further, to 100 parts of each of the curable resin compositions, 1.0 part of 6% cobalt naphthenate and 2.0 parts of a curing agent 328E manufactured by Kayaku Akzo Co. were added, and then 260 mm × 260 mm × 3 m
m, and after curing for 3 hours at room temperature,
Further, it was post-cured in a curing oven at 60 ° C. for 2 hours to prepare a casting plate. These were subjected to a tensile test of the cast plate according to the method of JIS K7113. Table 2 shows the results. From the results in Table 2, the tensile elongation rates of Examples 1 to 3 are:
This shows an extremely high value, indicating that the toughness is high.

[0036]

[Table 2]

Also, 100 parts of each of the curable resin compositions obtained in Examples 1 to 3 were combined with 0.025 part of hydroquinone monomethyl ether as a polymerization inhibitor and paraffin waxes 120 and 130 manufactured by Nippon Seiro Co., Ltd. as waxes. 14
0 (trade name), 0.1 part of each, 1 part of 8% cobalt octylate, 0.4 part of N, N-dimethyltoluidine and 200 parts of silica sand as a curing accelerator were added and mixed.
Resin mortar composition.

Next, each of the above resin mortar compositions was
As a curing agent, 1.0 part of Percure K manufactured by NOF Corporation was added and mixed, and formed into a 3 mm thickness using a spatula on a 300 mm × 300 mm concrete surface. As a result of conducting a sensory evaluation of the odor at a distance of 10 cm from the surface before curing the applied resin composition, compared to the strong pungent odor of volatile monomers such as styrene and methyl methacrylate, It was an extremely weak odor that could somehow be perceived. In addition, the time required for the surface of the applied resin composition to cure at room temperature was within 1 hour in each case, and the surface curability was also very good.

Next, Example 3 was further used as an overcoating agent.
In the curable resin composition obtained in the above, 0.025 parts of hydroquinone monomethyl ether as a polymerization inhibitor and paraffin waxes 120 and 13 manufactured by Nippon Seiwa Co., Ltd. as waxes
0, 140 (trade name) 0.1 part each, 8 as a curing accelerator
% Of cobalt octylate, 0.4 part of N, N-dimethyltoluidine, and 1.0 part of Percure VI manufactured by NOF Corporation as a curing agent were added and mixed. This was applied to the cured surface of the resin mortar composition of Examples 1 to 3 to a thickness of 0.4 mm using a brush and cured at room temperature to obtain test pieces of Examples 1 to 3.

Absorbent cotton containing a chemical solution shown in Table 3 was placed on each of the test pieces of Examples 1 to 3, and an inner diameter of 50 m was placed thereon.
m, and a chemical resistance test was performed. After 48 hours, the presence or absence of abnormalities such as blisters and cracks was observed. Table 3 shows the results. From the results in Table 3, Example 1
It can be seen that the test pieces of Nos. To 3 have no abnormality and show strong corrosion resistance.

[0041]

[Table 3]

[0042]

As is clear from the results of the above Examples and Comparative Examples, the curable resin composition and the resin mortar composition having the constitution of the present invention have low odor and excellent curability, and the cured product Is extremely excellent in any of the tests such as toughness, durability, and corrosion resistance, and is extremely useful for various anticorrosive materials, waterproof materials, coating materials such as flooring materials, and fiber-reinforced plastics.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // (C08L 63/10 (C08L 63/10 101: 00) 101: 00) C04B 111: 54 C04B 111: 54 (72) Inventor Hideo Sakai 1900 Togo, Mobara City, Chiba Prefecture Inside Mitsui Chemicals Co., Ltd. (72) Inventor Takumi Shimizu 1900 Togo, Togo Mobara City, Chiba Prefecture Mitsui Chemicals Co., Ltd. (72) Inventor Tatsuya Shibata Mobara, Chiba Prefecture 1900 Togo Mitsui Chemicals F-term (reference) 4J002 AC002 AH002 BB032 BB122 BC032 BG002 CC032 CD201 CF002 CK022 DE146 DE236 DJ016 DJ036 DJ046 FD012 FD016 GL00 4J027 AC03 AC04 AC06 AE01 AE02 AJ06 CD02 CA02 CD07 4J036 AA01 AB01 AJ01 AJ05 CA07 CA21 DA04 DB29 FA01 FB02 FB03 FB06 FB07 FB10 FB11 FB18 JA13

Claims (5)

[Claims] 1. An aliphatic diglycidyl ether type epoxy compound (c) having an epoxy equivalent of 300 or less, 1.5 to 3.5 mol per 1.0 mol of bisphenol A (a) and / or bisphenol F (b). Epoxy compound (A) obtained by reaction and (meth) acrylic acid (B)
And a polymerizable (meth) acrylic monomer (II) having a molecular weight of 160 or more and a viscosity at 25 ° C. of 100 mPa · s or less, and A curable resin composition comprising 20 to 80% by mass of (I) and 80 to 20% by mass of (II) based on the total mass of (I) and (II). 2. A polymerizable (meth) acrylic monomer (I)
The curable resin composition according to claim 1, wherein I) is a cyclic monofunctional (meth) acrylic monomer. 3. The curable resin composition according to claim 1, further comprising a curing agent. 4. A resin obtained by curing the curable resin composition according to claim 3. 5. A resin mortar comprising 1 part by mass of the curable resin composition according to claim 1 and 0.4 to 20 parts by mass of an inorganic aggregate and / or an inert powder. Composition.