JPH1192546A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which can be cured by merely letting it standing at a room temperature and has excellent storage stability by mixing a resin obtained by the Michael addition reaction of a specified (meth)acryl- containing compound with an aminic active hydrogen containing compound with a resin having non-aminic active hydrogen atoms and epoxy-containing compound. SOLUTION: This composition comprises a resin (A) having a weight-average molecular weight of 1,000-1,000,000 and prepared by the Michael reaction of 20-95 wt.% compound (a) having at least two acrylic or methacrylic groups in the molecule and having a weight-average molecular weight of below 1,000 with 5-80 wt.% compound having at least two aminic active hydrogen atoms in the molecule, a resin (B1) having non-aminic active hydrogen atoms and an epoxy-containing compound (C). B1 and C may be replaced by a resin (B2) having non-aminic active hydrogen atoms and epoxy groups. The non-aminic active hydrogen atom is exemplified by a hydroxylic or carboxylic one.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition which is used for paints, adhesives, adhesives, inks, fillers and molding materials and which cures at room temperature after being applied or poured into a mold.

[0002]

2. Description of the Related Art A curable resin composition utilizing active hydrogen such as a carbonyl group represented by an acetoacetoxy group is disclosed in U.S. Pat. No. 4,408,018, JP-A No. 1-12.
No. 1341, JP-A-1-204919, US
P5,017,649, JP-A-6-167355
And JP-A-7-173262. These are each characterized by a curing catalyst, but none of the curing catalysts are mixed with the resin, do not show sufficient curing at room temperature, or remain in the state of a coating liquid before application for one week or more. There was a problem that it could not be saved.

[0003]

SUMMARY OF THE INVENTION The present inventors have found that a mixture of an epoxy compound and a resin obtained by reacting an amine-based active hydrogen with a (meth) acrylic group causes the reaction between the active hydrogen and the (meth) acrylic group to proceed. It has been found that it significantly accelerates. And using this, just leave it at room temperature,
An object of the present invention is to provide a resin composition which is curable and has excellent storage stability.

[0004]

According to the present invention, there is provided 20 to 95% by weight of a compound (a) having two or more acrylic or methacrylic groups in one molecule and having a weight average molecular weight of less than 1,000, and one molecule. The compound (b) having two or more amino active hydrogens therein has a weight-average molecular weight of from 1,000 to 1,000,000 obtained by Michael addition reaction of 5 to 80% by weight.
000, a resin (B1) having an active hydrogen other than an amino group, and a curable resin composition comprising a compound (C) having an epoxy group. In addition, one molecule has two or more acrylic or methacrylic groups,
Compounds (a) 20 to 9 having a weight average molecular weight of less than 1000
5% by weight, and 2 amino active hydrogens per molecule
(B) having a weight-average molecular weight of 1,000 to 1.0 obtained by subjecting 5 to 80% by weight of a compound (b) having a number of
The present invention relates to a curable resin composition comprising a resin (A) of 0.00000 and a resin (B2) having an active hydrogen other than an amino group and an epoxy group. The active hydrogen other than the amino group is independently selected from a carbonyl group, a carboxyl group, a carbamoyl group, a cyano group, and a nitro group.
The present invention relates to the above curable resin composition, which is methine hydrogen or methylene hydrogen substituted with one or three functional groups. Further, the present invention relates to the curable resin composition, wherein the curable resin composition contains 1 to 80% by weight of the compound (a) based on the whole resin composition.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION As the compound (a) having two or more acryl groups or methacryl groups in one molecule and having a weight average molecular weight of less than 1,000, the compound (a) used in the present invention is, for example, a polyfunctional alcohol or Poly (meth) acrylate of polyfunctional phenol may be mentioned.

More specifically, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, tetrapropylene glycol, polyethylene glycol, polypropylene glycol, butanediol, 2,2-dimethyl Di (meth) acrylates of bifunctional alcohols such as propanediol, pentanediol and hexanediol;

[0007] Di (meth) acrylate, trimellitic acid, pyromellitic of polyalkylene glycol modified or epichlorohydrin modified bifunctional carboxylic acid such as phthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, malonic acid, hexanedioic acid Poly (meth) acrylate of polyalkylene glycol-modified or epichlorohydrin-modified carboxylic acid having a valency of 3 or more such as acid, hexahydropyromellitic acid, di (meth) acrylate of epichlorohydrin-modified bisphenol A derivative, and di (meth) acrylate of isocyanuric acid derivative Polyalkylene glycol-modified poly (meth) acrylate,

Polyfunctional alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, mannitol and sorbitol, or polyalkylene glycol-modified or epichlorohydrin-modified poly (meth) acrylates, catechol, resorcinol, hydroquinone , Poly (meth) acrylates of polyfunctional phenols such as phloroglysin, pyrogallol and the like. These may be used in combination of two or more.

The compound (b) having two or more amino active hydrogen atoms in one molecule used in the present invention includes, in addition to ammonia, methylamine, ethylamine,
Propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine,
An alkylene chain such as octylamine, methylhydrazine, ethylhydrazine, benzylamine, phenethylamine, N, N-dimethylpropylamine, and an amine having one primary amino group, methoxyethoxyethoxyethylamine, methoxypropylpropylamine, methoxypolyethyleneoxy Amines having two or more primary amino groups such as polyalkylene chains such as ethylamine, and amines having one primary amino group, ethylenediamine, propylenediamine, 1,6-hexadiamine, diethylenetriamine, triethylenetetramine, and melamine; Amines having two or more secondary amines such as N, N'-dimethylethylenediamine; cyclic amines such as piperazine; amines having an unsaturated double bond such as allylamine; Examples thereof include amines having a functional group such as min. Further, an amine having two or more primary amines obtained by substituting a part of active hydrogens with, for example, ethyl acrylate or methyl chloride, etc.
A compound having two or more secondary amines may be used. Two or more of these amines may be used.

The resin (A) used in the present invention has at least two acrylic or methacrylic groups in one molecule, and has a weight average molecular weight of less than 1,000.
% By weight, and one or more primary amino groups in one molecule,
Or a compound (b) 5 having two or more secondary amino groups
~ 80% by weight is reacted. This reaction is a polymerization reaction by Michael addition between the (meth) acryl group of the compound (a) and the amino group of the compound (b). As is generally known, the Michael addition reaction involves reacting compound (a) and compound (b) with stirring or vibration in a vessel at normal pressure. Resin (A)
It can be synthesized in the absence of a solvent, but amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylphosphorustriamide, alcohol solvents such as methanol, ethanol, propanol and butanol, diethyl ether, When an ether solvent such as dioxane or tetrahydrofuran or a solvent such as water is used, the reaction rate is improved.

When the compound (a) contains an acryl group, it reacts at room temperature to form a resin (A), but is left at room temperature to improve the molecular weight, and then heated to the reflux temperature of the solvent. May be. The reaction is performed under the conditions of about 5 minutes to 3 days. The obtained resin (A) is preferably purified by precipitation with petroleum ether, hexane or the like to remove low molecular weight components, because physical properties after curing are improved.

The weight average molecular weight of the resin (A) is, for example,
It is preferably 1,000 to 1,000,000 in terms of styrene by GPC (gel permeation chromatography). More preferably, it is 3,000 to 500,000. If it is smaller than this, curing may be poor due to low molecular weight components. If it is larger than this, the compatibility with the resin (B) becomes poor. In order to make the weight average molecular weight of the resin (A) 1000 or more, a compound having three or more (meth) acryl groups in one molecule as the compound (a) or a compound (b) in one molecule. It is recommended to use a compound having three or more amino active hydrogens in combination.

When synthesizing the resin (A), the compounding ratio of the compound (a) to the compound (b) is, theoretically, the chemical equivalent of the (meth) acryl group of the compound (a) and It should be preferred that the chemical equivalents of the amino active hydrogens of compound (b) be equal. However, actually, there is an influence of the viscosity of the reaction solution and the like, and the ratio of the chemical equivalent is not necessarily related to the curability. Therefore, in order to make the weight molecular weight of the resin (A) 1000 or more, the compounds (a) 20 to 95
% By weight and between 5 and 80% by weight of compound (b)
The optimum value of the combination will be selected.

Next, the resin (B1) having an active hydrogen other than the amino group used in the present invention, and the active hydrogen other than the amino group of the resin (B2) having an active hydrogen other than the amino group and the epoxy group are used. Examples thereof include a hydroxyl group, a mercapto group, a carboxyl group and active hydrogen represented by the general formula 1. -X-CH (Y) -Z- (general formula 1) (where X, Y, and Z are not particularly limited, but at least one is a carbonyl group, a carboxyl group, a carbamoyl group, a cyano group, or Shows a functional group selected from nitro groups.)

An active hydrogen is selected from a carbonyl group, a carboxyl group, a carbamoyl group, a cyano group or a nitro group.
Particularly preferred is methine hydrogen or methylene hydrogen substituted with two or more independently selected functional groups. This is a case where at least two of X, Y, and Z have the above functional group in the above general formula 1. Examples of such active hydrogen include a malonic acid residue (X, Z = carboxyl group, Y = H), an acetoacetyl group (X = carbonyl group, Y = H, Z = carboxyl group), and an acetocarbamoyl group (X = carbonyl group). Group, Y = H, Z = carbamoyl group), cyanoacetic acid residue (X = cyano group, Y = H, Z = carboxyl), nitroacetic acid residue (X = nitro group, Y =
H, Z = carboxyl group) and the like.

In order for the resin (B1) or the resin (B2) to have these active hydrogens, there is a method in which a monomer having these active hydrogens is polymerized. For example, 2-
Hydroxyethyl (meth) acrylate, 2-mercaptoethyl (meth) acrylate, (meth) acrylic acid,
There is a method of vinyl polymerizing a (meth) acrylate having active hydrogen such as acetoacetoxyethyl (meth) acrylate.

In addition to the above (meth) acrylates having active hydrogen, vinyl monomers such as styrene, vinylpyridine, vinylpyrrolidone and vinyl acetate, alkyl (meth) acrylates, poly (meth) acrylates Copolymers with (meth) acrylic monomers such as alkyloxy) esters are also suitably used.

In the case of the resin (B2), it is necessary to further copolymerize a monomer having an epoxy group such as glycidyl (meth) acrylate.

Other examples of the resin (B1) include an epoxy resin having a hydroxyl group at the terminal, a phenoxy resin, and a polymer of a bisphenol derivative and an epichlorohydrin derivative having a hydroxyl group in a repeating unit. Further, the resin (B1) and the resin (B2) may be used as a mixture.

The weight average molecular weight of the resin (B) is, for example,
It is preferably 1,000 to 2,000,000 in terms of styrene by GPC (gel permeation chromatography). More preferably, 10,000 to 1,000,000
00. If it is smaller than this, curing may be poor due to low molecular weight components. On the other hand, if it is larger than this, the compatibility with the resin (A) becomes poor.

The compound (C) having an epoxy group used in the present invention includes epichlorohydrin, phenyl glycidyl ether, styrene oxide, cyclohexene oxide, butene oxide, glycidyl (meth) acrylate, glycidyl cinnamate, allyl phenyl ether, vinylcyclohexene Monoepoxide, 1,3-
Butadiene monoepoxide and the like. These may be used in combination of two or more.

The compound (C) comprises a resin (A) and a resin (B)
1) or 1 to 10 with respect to the entire resin (B2).
It is preferable to use it at a ratio of 0% by weight. Resin (B
When 2) is used, compound (C) is not essential,
It is preferably used. In this case, the sum of the epoxy monomer of the resin (B2) and the compound (C) is 1 to the entire resin.
It is preferable to use it at a ratio of 100% by weight.

In order to improve the curability of the resin composition of the present invention, the compound (a) is used in an amount of 1 to 80 with respect to the whole resin.
It is preferable to use it in a ratio of% by weight.

Resin (A), resin (B1) or resin (B
2), and if necessary, compound (C) or compound (a) is stirred, rotated, or vibrated in a container to be mixed to form a resin composition. At this time, heat of 150 ° C. or less may be applied to promote uniform mixing. Colorants such as titanium white and various pigments, lubricants, and the like may be added. In the case of light treatment, various sensitizing dyes may be further added.

Although the resin composition of the present invention cures at room temperature, curing may be accelerated by heat, light or electron beam treatment. When performing the heat treatment, it is heated at 250 ° C. or less. Although there is no particular limitation on the heat source, a heat circulation oven or a heating roll is generally used. When performing the light treatment, the light source is not particularly limited, and examples thereof include a mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, an incandescent lamp, and various lasers. When processing with an electron beam, various medium-to-low voltage electron accelerators are used.

[0026]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1) Butylamine (BA) 3.6
5 g, 5.31 g of 2,2-dimethylpropane 1,3-diol diacrylate (NP) and 7.41 g of trimethylolpropane triacrylate (TMP) were stirred at room temperature overnight in 15.0 g of methanol. Thus, a resin (A-1) solution was obtained. The weight average molecular weight is shown in Table 2. (Synthesis Examples 2 to 5) Instead of butylamine of Synthesis Example 1,
The compound (b) shown in Table 1 was replaced with the compound (a) shown in Table 1 in place of 2,2-dimethylpropane 1,3-diol diacrylate in Synthesis Example 1 to obtain a resin solution (A-
1) to (A-10) were obtained. Table 2 shows the weight average molecular weight.
It was shown to. In the table, HA is hexylamine, OA octylamine, 9EG is polyethylene glycol diacrylate (manufactured by Kyoeisha Chemical), BP is propylene oxide-modified bisphenol A diacrylate (manufactured by Kyoeisha Chemical), and DCP is hydrogenated dicyclopentadienyl. Diacrylate (manufactured by Kyoeisha Chemical), PE3 indicates pentaerythritol triacrylate, PE4 indicates pentaerythritol tetraacrylate, and DPE indicates dipentaerythritol hexaacrylate.

Table 1-----------------------Example of synthesis (resin solution) Compound (a) Compound (b) The number in g is the number of g. The number in () is the number of g. ---------- BA (3.65) NP (5.31) TMP (7.41) 2 (A-2) BA (3.65) NP (6.37) TMP (5.93) 3 (A-3) BA (3.65) 9EG (13.06) PE3 (7.45) 4 (A-4) HA (5.06) BP (14.22) PE4 (8.81) 5 (A-5) OA (6.46) DCP (7.55) DPE (14.46) --------------- −−−−−−−−−−−−−−−−−−−−

Table 2-------------------------Example of synthesis (resin solution) Weight average molecular weight in terms of styrene--- ---------------------------- 1 (A-1) 3.0 × 10 3 2 (A-2) 2.5 × ^{10 3 3 (A-3)} 2.0 × 10 3 4 (A-4) 3.5 × 10 3 5 (A-5) 4.0 × 10 3 ------------ −−−−−−−−−−−−−−−−−−−−−−

(Synthesis Example 6) 50 g of 2-acetoacetoxyethyl methacrylate (AAEM), 50 g of methyl methacrylate (MMA), and 3 g of azobisisobutyronitrile were dissolved in 100 g of ethyl acetate. The reaction was carried out for an hour to obtain a resin solution (B1-1). (Synthesis Examples 7 to 10) Instead of acetoacetoxyethyl methacrylate of Synthesis Example 6 and methyl methacrylate,
Using the monomers shown in Table 3, resin solutions (B1-2) to
(B2-2) was obtained. The weight average molecular weight is shown in Table 4. In the table, ST is styrene, CAEM is 2-cyanoacetoxyethyl methacrylate, BMA is butyl methacrylate, GMA is glycidyl methacrylate,
HEMA stands for 2-hydroxyethyl methacrylate.

Table 3 ———————————————————————————— Synthetic Example (Resin Solution) Monomer ------------------------------------------------------------------------- 6 (B1-1) AAEM (50) MMA (50) 7 (B1-2) AAEM (50) ST (50) 8 (B1-3) CAEM (50) BMA (50) 9 (B2-1) AAEM (50) MMA (45) GMA (5) 10 (B2-2) HEMA (5) MMA (90) GMA (5) ------------------------------------------

Table 4-------------------------Example of synthesis (resin solution) Weight average molecular weight in terms of styrene--- ---------------------------- 6 (B1-1) 4.7 × 10 4 7 (B1-2) 5.4 × ^{10 4 8 (B1-3) 4.6 ×} 10 4 9 (B2-1) 6.0 × 10 4 10 (B2-2) 6.5 × 10 4 ------------ −−−−−−−−−−−−−−−−−−−−−−

Example 1 Resin (A-1) Solution 100
g, 100 g of the resin (B1-1) solution, and 20 g of phenylglycidyl ether (PGE) were stirred and mixed at room temperature for 3 hours, and then cast and coated on a glass plate to a thickness of 50 μm.
After drying overnight at room temperature, it was immersed in ethyl acetate for 30 minutes. Table 4 shows the state of the mixed resin solution. (Examples 2 to 9) Instead of the resin (A-1) solution of Example 1, the resin solution shown in Table 5 was used instead of the resin (B1) of Example 1.
-1) Using the resin solution shown in Table 5 instead of the solution,
After that, the same operation as in Example 1 was performed. Table 6 shows the results. (Examples 10 and 11) The same operations as in Example 1 were performed except that the compound (C) shown in Table 5 was used instead of the PGE of Example 1. Table 6 shows the results. (Examples 12 and 13) In Example 1, the resin (A-1)
The same operation as in Example 1 was performed with the amounts of the solution and the resin (B1-1) being the amounts shown in Table 5. Table 6 shows the results. (Example 14) To the composition of Example 1, 20 g of trimethylolpropane triacrylate (TMP) was further added, and the same operation as in Example 1 was performed. The results are shown in Table 6.

(Comparative Examples 1 to 3) The results of operations performed by the same evaluation method as in Example 1 with the compositions shown in Table 5 are shown in Table 6.
Indicated according to

Table 5----------------Example Resin (A) solution Resin (B) solution Compound ( C)-------------------------------------1 (A-1) (B1-1) PGE 2 (A-1) (B1-2) PGE 3 (A-1) (B1-3) PGE 4 (A-1) (B2-1) PGE 5 (A-1) (B2-2) None 6 (A-2) ( B1-1) PGE 7 (A-3) (B1-1) PGE 8 (A-4) (B1-1) PGE 9 (A-5) (B1-1) PGE 10 (A-1) (B1- 1) GMA 11 (A-1) (B1-2) GMA 12 (A-1) (B1-1) PGE 13 (A-1) (B1-1) PGE 14 (A-1) (B1-1) PGE Comparative Example 1 A-1) None PGE Comparative Example 2 None (B1-1) PGE Comparative Example 3 (A-1) (B1-1) None ------------------------------------ −−−−−−−−−−−−−

Table 6----------------------Example Example Remaining amount of ethyl acetate (%) One week later State of Coating Liquid ------------------------------------------------------------------------------------------- 90 Excellent 2 88 Good 3 90 Good 4 85 Good Good 685 good 7 80 good 8 80 good 9 80 good 10 85 good 11 80 good 12 80 good 13 80 good 14 95 good comparative example 1 0 good comparative example 2 0 good comparative example 3 0 good ----------- --------------------------------------------------------

According to the present invention, a resin composition having excellent storage stability and curable at room temperature is provided.

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Claims (4)

[Claims] 1. A compound (a) having two or more acrylic or methacrylic groups in one molecule and having a weight average molecular weight of less than 1000, 20 to 95% by weight, and amino active hydrogen in one molecule. Compound (b) 5-80 having two or more
(A) a resin having a weight average molecular weight of 1,000 to 1,000,000 obtained by a Michael addition reaction, a resin (B1) having an active hydrogen other than an amino group, and a compound (C) having an epoxy group. A) a curable resin composition comprising: 2. A compound (a) having two or more acrylic or methacrylic groups in one molecule and having a weight average molecular weight of less than 1000, 20 to 95% by weight, and amino active hydrogen in one molecule. Compound (b) 5-80 having two or more
Curable resin comprising a resin (A) having a weight-average molecular weight of 1,000 to 1,000,000 obtained by subjecting a weight% to a Michael addition reaction, and a resin (B2) having an active hydrogen other than an amino group and an epoxy group Composition. 3. A methine hydrogen or methylene in which active hydrogen other than an amino group is substituted by two or three functional groups independently selected from a carbonyl group, a carboxyl group, a carbamoyl group, a cyano group and a nitro group. The curable resin composition according to claim 1, wherein the curable resin composition is hydrogen. 4. The composition according to claim 1, further comprising 1 to 80% by weight of the compound (a) based on the whole resin composition.
4. The curable resin composition according to any one of items 1 to 3.