JPH09176218A - Method for curing (meth)acrylic resin composition and cured product therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a crack-free cured product having a high hardness within a short time by curing a (meth)acrylic resin composition (A) by using an organic peroxide (B), a solution (C) of a vanadium compound in an acid-group-containing phosphoric acid ester and a tert. amine (D). SOLUTION: Component A comprises a (meth)acrylic ester, a polyfunctional monomer [e.g. ethylene glycol di(meth)acrylate ] and a viscosity modifier comprising a homopolymer of a (meth)acrylic ester or a copolymer of two or more (meth)acrylic esters. Component B is, for example, t-butylperoxy-2-ethyl hexanoate. Component C is a solution prepared by dissolving a vanadium compound (e.g. vanadium pentoxide) in an acid-group-containing phosphoric ester (e.g. acid ethyl phosphate). Component D is, for example, N,N-dimethylaniline. The mixing ratio is such that 0.1-5 pts.wt. B, 0.0001-1 pt.wt. C and 0.001-3 pts.wt. D are used per 100 pts.wt. A.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is used for coating floors and wall surfaces or marking roads (meta).
The present invention relates to a method for curing an acrylic resin composition and a cured product thereof. More specifically, the present invention relates to a method for curing a (meth) acrylic resin composition and a cured product thereof, which enables to obtain a cured product which is free from cracks, has little coloring, and has a high degree of curing at room temperature in a short time.

[0002]

2. Description of the Related Art A method of curing a (meth) acrylic resin composition at room temperature is roughly classified into a method of using a low temperature decomposition type organic peroxide alone and a redox reaction of an organic peroxide and a decomposition accelerator. It can be divided into two methods. The former is, for example, a method in which diisopropyl peroxydicarbonate is used as a low-temperature decomposition type organic peroxide and is cast and cured at 40 to 50 ° C. The latter is, for example, a method of combining a ketone peroxide and an organic acid salt of cobalt, or a method of combining dibenzoyl peroxide and dimethylaniline.

As a method other than the above, a method of combining a metal salt of a hemiperoxy ester of maleic acid and an oxo acid salt of a sulfur activator in the presence of an alumina hydrate (Japanese Patent Publication No. 59-53282) or an organic method. A method for curing an acrylic resin in which a peroxide, an acid group-containing phosphate ester such as dibutyl phosphate, and α-hydroxyketone are combined (West German Patent No. 1158707) has been reported.

[0004]

The method using low-temperature decomposable diisopropyl peroxydicarbonate has a problem that if it is hardened in a short time, abrupt heat is generated and a myriad of cracks are formed in the hardened material. Further, the method of combining ketone peroxide and an organic acid salt of cobalt is effective for curing an unsaturated polyester resin, but when curing a (meth) acrylic resin, the curing speed is extremely slow and is not practical. In the case of the method of combining dibenzoyl peroxide and dimethylaniline, the curing rate is good, but there is a problem that the cured product is colored due to the redox reaction and cannot be used in a light-colored system. Furthermore, the method disclosed in Japanese Examined Patent Publication No. 59-53282 does not achieve a sufficiently high degree of curing, and there is a problem that the abrasion resistance is poor when used for road marking, for example. Further, the method of West German Patent No. 1158707 also has a problem that the curing speed is insufficient.

The object of the present invention is to solve the problems of the prior art,
A cured product with no cracks, little coloring, and a high degree of curing can be obtained at room temperature in a short time (meta).
It is intended to provide a method for curing an acrylic resin composition and a cured product thereof.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have confirmed that the problems can be solved by using a specific curing accelerator in combination with an organic peroxide. Then, the present invention was completed. That is, the first invention is characterized by using an organic peroxide, a phosphoric acid ester solution containing an acid group of a vanadium compound, and a tertiary amine when the (meth) acrylic resin composition is cured (meth). It is a method of curing an acrylic resin composition. The second invention is
0.1 to 5 parts by weight of an organic peroxide, 100 parts by weight of a (meth) acrylic resin composition, and vanadium metal 0.0 contained in an acid group-containing phosphate ester solution of a vanadium compound.
001 to 1 part by weight and 0.001 to 3 parts by weight of a tertiary amine are used in the method for curing a (meth) acrylic resin composition. Moreover, 3rd invention is 1st or 2nd.
A cured product of the (meth) acrylic resin composition obtained by the curing method described in the invention.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in more detail below. Examples of the organic peroxide used in the present invention include tertiary butylperoxy-2-ethylhexanoate, tertiary amylperoxy-2-ethylhexanoate, and tertiary hexylperoxy-2-ethylhexanoate. , Tertiary butyl peroxybenzoate, tertiary amyl peroxybenzoate, tertiary hexyl peroxybenzoate, tertiary butyl peroxyisopropyl monocarbonate, tertiary amyl peroxyisopropyl monocarbonate, tertiary hexyl peroxyisopropyl monocarbonate, tertiary Tertiary butylperoxy-3,3,5-trimethylhexanoate, tertiary amylperoxy-3,3,5-trimethylhexanoate, tertiary hexylperoxy-3,3,5-trimethylhexanoate, 2,2-dimethyl 2,5
Examples thereof include peroxyesters such as (2-ethylhexylperoxy) hexane and hydroperoxides such as cumene hydroperoxide. Among these organic peroxides, the curing rate is high, the curing degree is high, and the coloring degree is low. Therefore, tertiary butylperoxy-2-ethylhexanoate, tertiary butylperoxybenzoate,
Tertiary hexyl peroxybenzoate, tertiary butyl peroxymonocarbonate and cumene hydroperoxide are preferred. The organic peroxides can be used alone or in combination of two or more. The proportion of the organic peroxide used is 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the (meth) acrylic resin composition. If the amount is less than 0.1 parts by weight, the curing rate will not be sufficient, and if it exceeds 5 parts by weight, the curing rate will not increase, which is economically disadvantageous.

The acid group-containing phosphate ester solution of the vanadium compound used in the present invention is a solution obtained by dissolving the vanadium compound in the acid group-containing phosphate ester. Examples of the vanadium compound include vanadium pentoxide, vanadyl-3-chloride, vanadyl-4-chloride, vanadyl-p-toluenesulfonate, vanadyl acetate, vanadyl octoate, vanadine of acetylacetone and vanadyl complex compounds. . Among these, vanadium pentoxide, vanadyl-3-chloride and vanadyl acetate are preferable from the viewpoint of solubility in the acid group-containing phosphate ester. Examples of the acid group-containing phosphoric acid ester include phosphoric acid, polyphosphoric acid, pyrophosphoric acid and phosphorous acid esters. For example, methyl acid phosphate, dimethyl acid phosphate, ethyl acid phosphate, diethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, 2-ethylhexyl acid phosphate, diethyl phosphate. Etc. Among these, from the viewpoint of solubility of vanadium compound and solubility in (meth) acrylic resin composition, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl acid phosphate,
Is preferred. The concentration of vanadium in the acid group-containing phosphate ester solution varies depending on the solubility of the vanadium compound in the acid group-containing phosphate ester, but is usually 0.01 to 10% by weight. The acid group-containing phosphoric acid ester solution of the vanadium compound can be used after diluting it with a solvent such as phthalic acid ester, acetylacetone or acetoacetic acid ester, if necessary. The vanadium compound is added in an amount of 0.0001 to 1 part by weight as vanadium metal, preferably 0.1 part by weight based on 100 parts by weight of the (meth) acrylic resin composition.
0002 to 0.2 parts by weight. If the amount is less than 0.0001 parts by weight, the curing rate will not be sufficient, and if it exceeds 1 part by weight, the curing rate will not increase, which is economically disadvantageous.

The tertiary amine used in the present invention includes
Examples thereof include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, phenyldiethanolamine, phenylethylethanolamine and m-tolyldiethanolamine. Among these, N, N-dimethylaniline, N, N-dimethyl-p-toluidine and phenyldiethanolamine are preferable because of their fast curing speed and little coloration on the cured product. These tertiary amines can be used alone or in combination of two or more. The addition amount of the tertiary amine is (meth)
0.001 to 100 parts by weight of the acrylic resin composition
3 parts by weight, preferably 0.01 to 1 part by weight. If it is less than 0.001 part by weight, the curing rate is not sufficient, and if it exceeds 3 parts by weight, the cured product is colored, which is not preferable.

In the present invention, the (meth) acrylic resin composition comprises a (meth) acrylic acid ester and a polyfunctional monomer as a polymerizable component, and a (meth) acrylate as a viscosity modifier.
It is composed of a homopolymer of acrylic acid ester or a copolymer of two or more kinds of (meth) acrylic acid ester.

Here, as the (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, primary butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, etc. are mentioned. Of these, methyl (meth) acrylate is preferable from the viewpoint of hardness, heat resistance and weather resistance of the final cured product. The (meth) acrylic acid ester in the polymerizable component is 80 to 99.5.
The amount of methyl (meth) acrylate is preferably 30% by weight or more. If the amount of methyl (meth) acrylate is less than 30% by weight, the above performance of the final cured product is not sufficient.

As the polyfunctional monomer, alkane diol di (meth) acrylate such as ethylene glycol di (meth) acrylate, 1,2-propylene glycol (meth) acrylate and 1,6-hexanediol di (meth) acrylate. , Polyoxyalkylene glycol di (meth) acrylates such as diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) ) Acrylate, divinylbenzene and triallyl isocyanate. Among these, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate and divinylbenzene are preferable from the viewpoint of the crosslink density of the final cured product. . These can be used alone or in combination of two or more. Further, the ratio of the polyfunctional monomer in the polymerizable component,
It is 0.5 to 20% by weight. If it is less than 0.5% by weight, the cross-linking density of the final cured product is not sufficient, and if it exceeds 20% by weight, heat generation during polymerization makes temperature control difficult. The amount of the polymerizable component in the (meth) acrylic resin composition in the present invention is 50 to 95% by weight. If it is less than 50% by weight, the physical properties of the final cured product will be poor, and if it exceeds 95% by weight, the workability during curing will be poor.

The homopolymer or copolymer of (meth) acrylic acid ester used as a viscosity modifier is the above-mentioned (meth)
One or two or more kinds of acrylic acid esters may be used in combination at a desired ratio to obtain an ordinary polymerization. However, from the viewpoint of hardness, heat resistance and weather resistance of the final cured product, a methyl (meth) acrylate component is used. It is preferable to contain 30% by weight. The total proportion of the homopolymer and the copolymer in the (meth) acrylic resin composition is appropriately determined according to the desired viscosity, but is usually 5 to 50% by weight. If it is less than 5% by weight, there is no viscosity adjusting effect, and if it exceeds 50% by weight, the viscosity becomes high and the workability becomes poor.

In the present invention, the (meth) acrylic resin composition contains, in addition to the above-mentioned polymerizable components and viscosity modifiers, if necessary, bone, such as sand, silica sand, quartz sand, clay, calcium carbonate, aluminum stearate. , Fillers such as glass beads, thixotropic agents such as Aerosil, pigments and dyes such as titanium oxide and cobalt blue, ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, release agents such as zinc stearate and cracks. And a low-shrinking agent that prevents shrinkage can be added and cured.

[0015]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these. In the examples,% means% by weight, and part means part by weight. The abbreviations of the materials used in the table are as follows. Organic peroxide b-O: tertiary butyl peroxy-2-ethylhexanoate (trade name: Perbutyl O, manufactured by NOF CORPORATION) b-Z: tertiary butyl peroxybenzoate (trade name: Perbutyl Z) , NOF Co., Ltd. hZ: tertiary hexyl peroxybenzoate (trade name: Perhexyl Z, NOF Co., Ltd.) b-I: tertiary butyl peroxyisopropyl monocarbonate (trade name: Perbutyl I) , Nippon Oil & Fats Co., Ltd. CHP: Cumene Hydroperoxide (Brand name: Park Mill H, Nippon Oil & Fats Co., Ltd.) IPP: Diisopropyl Peroxydicarbonate (Brand Name: Perloyl IPP, Nippon Oil & Fats Co., Ltd.) BPO: Benzoyl Peroxide (Brand name: Niper B, NOF Corporation)

Tertiary amine DMA: N, N-dimethylaniline (manufactured by Samsung Chemical Research Institute) DMPT: N, N-dimethyl-p-toluidine (manufactured by Nippon Fine Chemical Co., Ltd.)

The curing test method and evaluation items (shown by abbreviations in the table) are as follows. Curing test method: A (meth) acrylic resin composition, an organic peroxide, an acid group-containing phosphate ester solution of a vanadium compound, and a tertiary amine were placed in a test tube having an inner diameter of 18 mm equipped with a thermocouple according to JIS-K-6901. Preparation 2
Cured at 5 ° C. Evaluation item GT: Gelation time (time until the temperature of the cured product reaches the test temperature plus 5 ° C. after adding all components) CT: Curing time (the temperature of the cured product is maximum heat generation after adding all components) Time until the temperature is reached) PET: Maximum exothermic temperature Curing degree: The hardness after 1 day is measured by a Barcol hardness tester (934-1).
Type, manufactured by Barber Coleman). Coloring: Visual appearance

Examples 1 to 8 and Comparative Examples 1 to 7 First, 30 parts of a homopolymer of methyl methacrylate (trade name: Dianal BR-83, manufactured by Mitsubishi Rayon Co., Ltd.) was added to 44 parts of methyl methacrylate and 19 parts of butyl acrylate.
Parts and a solution consisting of 7 parts of ethylene glycol dimethacrylate, solid content 30%, viscosity 3 poise (25
(° C) (meth) acrylic resin composition (in the table, described as (meth) acrylic resin composition). On the other hand, 0.36 part of vanadium pentoxide (manufactured by Shinko Chemical Co., Ltd.) was dissolved in 36 parts of dibutyl phosphate (manufactured by Daihachi Chemical Co., Ltd.) at 120 ° C. for 3 hours, and after cooling, 54 parts of dibutyl phthalate and acetoacetic acid. An acid group-containing phosphate ester solution (described as E (vanadium compound) in the table) was obtained by diluting with 10 parts of methyl. The vanadium metal content in this solution was 0.2%. Next, 100 parts of the (meth) acrylic resin composition was charged with an organic peroxide, a phosphoric acid ester solution containing an acid group, and a tertiary amine at a compounding ratio (parts) shown in Tables 1 to 3 to obtain a cured product. . A JIS curing test was carried out using it, and the results are shown in Tables 1-3.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

In Examples 1 to 3, the organic peroxide (b-
O), the acid group-containing phosphate ester solution (E) and the tertiary amine (DMPT) combined use system showed the curing results, but the curing rate was fast, and the cured product was neither colored nor cracked. On the other hand, in Comparative Example 1, the procedure was carried out according to Example 1 except that the acid group-containing phosphate ester solution (E) was not used, but the curing rate was very slow, the maximum exothermic temperature (PET) was low, and The result was low. Further, in Comparative Example 2, the procedure was performed according to Example 1 except that the tertiary amine (DMPT) was not used, but the curing rate was slower than that of Example 1.

In Example 4, the tertiary amine (DMPT)
The curing was carried out in the same manner as in Example 1 except that the tertiary amine (DMA) was used in place of the above, but as in Example 1, good curing results were obtained. In Example 5, the organic peroxide (b-I), the acid group-containing phosphate ester solution (E), and the third
The results of curing the combined use system of a primary amine (DMPT) are shown. Good results were obtained as in Example 1. In the sixth embodiment,
Instead of the organic peroxide (b-O), the organic peroxide (b-
The procedure of Example 1 was repeated except that Z) was used, but as in Example 1, good curing results were obtained. On the other hand, Comparative Example 3 was carried out according to Example 5 except that the amount of the acid group-containing phosphate ester solution (E) added was 1.0 part and no tertiary amine (DMPT) was used. The result was that the curing speed was slower than that of Example 5. Further, in Comparative Example 4, the procedure was performed according to Example 6 except that the tertiary amine (DMPT) was not used, but the curing rate was slower than that of Example 6.

Example 7 was carried out in the same manner as in Example 6 except that the organic peroxide (hZ) was used instead of the organic peroxide (bZ). Good results have been obtained. Further, in Example 8, an organic peroxide (hZ)
Example 7 was repeated except that an organic peroxide (CHP) was used in place of, but good results were obtained as in Example 7. On the other hand, in Comparative Example 5, the tertiary amine (DM
Example 8 was repeated except that (PT) was not used, but the curing rate was slower and the maximum exothermic temperature was lower than in Example 8. Further, in Comparative Example 6, the result of curing using only the organic peroxide (IPP) is shown. Although the curing speed was high, numerous cracks were generated in the cured product.
Further, in Comparative Example 7, the curing result of the combined use system of the organic peroxide (BPO) and the tertiary amine (DMA) was shown. The curing rate was slower than in the examples, and the cured product was colored reddish brown.

Example 9 A phosphoric acid ester solution containing an acid group obtained by using 6.1 parts of vanadyl-3-chloride instead of vanadium pentoxide in Example 1 was used, and 70 parts of titanium oxide and 1 glass bead were also used. Parts and 1 part of aluminum stearate were mixed, and curing was performed according to Example 1. As a result, GT,
CT, PET and curing degree are 3.0 minutes and 11.8 respectively
Min, 171 ° C. and 40, and a white cured product that can be used for road marking materials with little coloring or cracking was obtained.

As described above, it was confirmed that the examples of the present invention gave a cured product having a faster curing rate than the comparative example, less coloring of the cured product, and no cracks.

[0027]

As described in detail above, the present invention has the following excellent effects. According to the method for curing a (meth) acrylic resin composition of the first invention, the (meth) acrylic resin composition can be cured to a high hardness in a short time without cracks. According to the second invention, the effect of the first invention can be further improved. The cured product of the (meth) acrylic resin composition of the third invention is free from cracks, has little coloring, and has a high degree of curing, and is useful as a coating material for floors and wall surfaces and a marking material for roads.

Claims (3)

[Claims] 1. A (meth) acrylic resin composition comprising an organic peroxide, an acid group-containing phosphate ester solution of a vanadium compound, and a tertiary amine when the (meth) acrylic resin composition is cured. How to cure things. 2. A vanadium metal 0.0001 to 1 contained in an acid group-containing phosphoric ester solution of a vanadium compound in an amount of 0.1 to 5 parts by weight of an organic peroxide based on 100 parts by weight of a (meth) acrylic resin composition. Parts by weight and tertiary amine 0.
001-3 weight part is used, The hardening method of the (meth) acrylic resin composition characterized by the above-mentioned. 3. A cured product of a (meth) acrylic resin composition obtained by the curing method according to claim 1.