JPH0711106A - Resin composition for water-permeable pavement material - Google Patents

Abstract

PURPOSE:To obtain a resin composition capable of giving a water-permeable pavement which is free from defects over long, such as the debonding of in organic aggregate particles caused by external stress, by mixing a liquid epoxy resin with an amine hardener and a xylene/formaldehyde resin. CONSTITUTION:A liquid epoxy resin (A) (e.g. a liquid bisphenol A epoxy resin) is mixed with an amine hardener (B) (e.g. a xylylenediamine modified with acrylonitrile) and a xylene/formaldehyde resin (C) to produce the objective composition. The amount of the ingredient (C) is preferably 3-50 pts.wt. per 100 pts.wt. the sum of the ingredients (A) and (B). A curing accelerator (e.g. hydroquinone), an antioxidant, a thixotropic agent, etc., may further be incorporated. Since this composition has a high initial strength and a high tensile elongation at break and is reduced in deterioration by weathering, a waterpermeable pavement which does not suffer troubles such as cracking over long can be laid with the composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition for a water-permeable pavement material. More specifically, the initial strength of the resin is high and the weathering resistance is low, so there is little chipping of the inorganic granular aggregate due to external stress, and there is little cracking due to the large elongation of the resin and its excellent followability with the ground. The present invention relates to a resin composition for wood.

[0002]

2. Description of the Related Art Conventionally, as a resin for a water-permeable pavement material, a resin is mixed with tar to give flexibility (JP-A-55-36223), and the epoxy resin may be modified with urethane. Those that impart flexibility (Japanese Patent Laid-Open No. 61-1)
No. 57521) is known.

[0003]

However, with these water-permeable pavement resin, the initial strength of the resin is insufficient,
Or, the inorganic granular aggregate often falls off due to external stress due to large weather resistance deterioration. On the other hand, even if the strength is sufficient, the elongation of the resin is insufficient and the followability to the substrate is poor. Therefore, cracks often occurred on the pavement surface.

[0004]

As a result of intensive studies, the present inventors have found that resin strength, that is, inorganic particulates, can be obtained by adding xylene formaldehyde resin as a non-reactive component in addition to ordinary epoxy resin and amine curing agent. It is possible to dramatically increase the elongation of the resin without lowering the adhesive strength of the aggregate, and further, the composition of the present invention is excellent in weather resistance deterioration as compared with a composition in which a usual plasticizer is added as a flexibility-imparting agent. They have found the present invention and reached the present invention. That is, the present invention is
A resin composition for a water-permeable pavement material, which comprises a liquid epoxy resin (A), an amine curing agent (B), and a xylene formaldehyde resin (C).

The liquid epoxy resin (A) used in the present invention includes bisphenol type liquids such as bisphenol A type liquid epoxy resin, bisphenol F type liquid epoxy resin and bisphenol AD type liquid epoxy resin. Epoxy resin, glycidyl ester type liquid epoxy resin such as diglycidyl phthalate, glycidyl ether of aniline, glycidyl ether of o-toluidine, glycidyl amine type liquid epoxy resin such as tetraglycidyl diaminodiphenylmethane, 1,6 hexamethylene glycol glycol Glycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane Glycidyl - Porigurishijirue such ether - ether type liquid epoxy resin and the like, which may be used in alone or in combination.

As the amine-based curing agent (B) used in the present invention, araliphatic amines such as xylylenediamine, ethylenediamine, tetramethylenediamine,
Alkylenediamine such as hexamethylenediamine, polyethylene (alkylene carbon number 2 to 6) polyamine such as alkylenediamine such as hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, bis (hexamethylene) triamine, or epoxide of the above amine Examples thereof include adducts of unsaturated compounds (acrylonitrile, etc.), reaction products with methylol compounds, and the like, and one or more kinds of these can be mixed and used. Preferred is an acrylonitrile modified product of diamine, and more preferred is a modified product of 0.3 to 1.6 mol of acrylonitrile with respect to 1 mol of araliphatic diamine.

The modified product of araliphatic diamine with acrylonitrile is prepared by stirring a predetermined amount of acrylonitrile at a liquid temperature of 60 while stirring the aromatic diamine under a nitrogen atmosphere.
It is possible to carry out the reaction at 60 ° C. for 90 minutes after adding dropwise while controlling so that the temperature becomes not higher than ° C.

The xylene formaldehyde resin (C) used in the present invention is a condensate of xylene with formaldehyde, and examples thereof include Nikanol DS, Nikanol DL-15, Nikanol LLL, Nikanol LL, Nikanol L, Nikanol H, Nikanol HH, Examples thereof include Nikanol G, Nikanol M, Nikanol H-80 [trade names, manufactured by Mitsubishi Gas Chemical Co., Inc.] and the like, and those having a number average molecular weight of 200 to 750 are preferable.

The ratio of (A) to (B) is such that the active hydrogen group of (B) is (0.8 to 1) to 1 equivalent of the epoxy group of (A).
1.5). The amount of (C) is usually 3 to 50 parts by weight based on 100 parts by weight of the total of (A) and (B). Outside this range, chipping or cracking is likely to occur.

A curing accelerator is usually added to the composition of the present invention to adjust the curing rate. Examples of these are bisphenol A, phenol, alkylphenol, catechol, resorcin, hydroquinone and xylenol. The content in these compositions is usually 5
-40% by weight. In addition, various kinds of additives may be added to the composition of the present invention, for example, an antioxidant, an ultraviolet absorber and a thixotropic agent may be added. The content in these compositions is usually 0 to 3% by weight.

As an antioxidant, octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, triethylene glycol-bis [3-
(3-t-Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2 , 4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-
Butylanilino) -1,3,5-triazine, pentaerystyryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,
2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate],
2,2-thiobis (4-methyl-6-t-butylphenol), N, N'-hexamethylenebis (3,5-di-
t-butyl-4-hydroxy-hydrocinnamamide),
3,5-di-t-butyl-4-hydroxy-benzyl phosphate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-
4-hydroxybenzyl) benzene, tris (3,5-
Di-t-butyl-4-hydroxybenzyl) isocyanurate and the like, and preferred is octadecyl-3.
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate.

As the ultraviolet absorber, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2 -[2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-
t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2-
(3,5-di-t-amyl-2-hydroxyphenyl)
Benzotriazole, 2-ethoxy-2'-ethyl oxalic acid bisanilide, 2-ethoxy-5-t
-Butyl-2'-ethyl oxalic acid bisanilide and the like are preferable, and 2- (3,5-di-
t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole.

Further, the antioxidant and the ultraviolet absorber may be used in combination, and the most preferable combination is octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate. 2- (3,5-di-t-
Butyl-2-hydroxyphenyl) -5-chlorobenzotriazole.

By forming a layer obtained by curing the mixture of the composition of the present invention and the inorganic granular aggregate on the surface of artificial ground such as concrete pavement or asphalt pavement, the initial strength of the resin is high and the weathering resistance is low. Therefore, the inorganic granular aggregate is less likely to drop off due to an external stress, and the curing shrinkage is small, and the followability with the base is excellent, so that the water-permeable pavement with less cracks can be applied. This construction method will be described below.

The inorganic granular aggregate is put into a mortar mixer, and the mixture is kneaded for 1 minute, then the resin composition of the present invention which has been well kneaded in advance is put therein, and the mixture is further kneaded for 2 minutes and then taken out.
The kneaded product is freed from adhering substances, and uniformly stretched to a predetermined thickness using a plastering iron on a sufficiently dried base, and then cured for a predetermined time to obtain a water-permeable pavement surface.

The composition of the present invention is used as a water-permeable pavement by mixing with the inorganic granular aggregate by the above-mentioned method and curing, but the inorganic granular aggregate is not particularly limited,
Examples include natural stone, crushed stone, fired ceramic grains, silica sand, and mixtures thereof.

The mixing ratio of the inorganic granular aggregate and the resin composition is
Usually, resin composition 2 to 100 parts by weight of inorganic granular aggregate is used.
15 parts by weight.

[0018]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The parts in the text represent parts by weight.

Production Example 1 Bisphenol A type epoxy resin [trade name Epicoat 8
28, Yuka Shell Epoxy Co., Ltd.] 620 parts, 1.6
-Hexanediol diglycidyl ether [Product name SR
-16H, Sakamoto Yakuhin Kogyo Co., Ltd.] 200 parts, xylene formaldehyde resin [trade name Nikanol DS, Mitsubishi Gas Chemical Co., Ltd.] 170 parts, octadecyl-3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate [trade name Irganox 1076, manufactured by Ciba Geigy Ltd.] 5 parts, 2- (3,5-di-t-butyl-2)
-Hydroxyphenyl) -5-chlorobenzotriazole [trade name: Tinuvin 327, manufactured by Ciba Geigy] 5
A part was uniformly dissolved to obtain a viscous liquid. This is the main agent (1).

Production Example 2 500 parts of Epicoat 828, 330 parts of diglycidyl ether of bisphenol A propylene oxide 3 mol adduct [trade name Glyciere BPP-350, manufactured by Sanyo Chemical Industry Co., Ltd.], Nikanol DS [trade name Mitsubishi Gas] 170 parts manufactured by Kagaku Co., Ltd. were uniformly dissolved to obtain a viscous liquid. This is the main agent (2).

Production Example 3 500 parts of Epicoat 828, Glicier BPP-3
330 parts of 50 were uniformly dissolved to obtain a viscous liquid. This is the main agent (3).

Production Example 4 500 parts of Epicoat 828, Glicier BPP-3
330 parts of 50 and 170 parts of dibutyl phthalate were uniformly dissolved to obtain a viscous liquid. This is the main agent (4).

Production Example 5 A reaction product of 603 parts of an acrylonitrile 1-mole modified product of m-xylylenediamine (hereinafter referred to as XDA-AN) and 67 parts of Epikote 828 was added to nonylphenol [manufactured by Sanyo Chemical Industry Co., Ltd.]. 165 parts and 1 bisphenol A
65 parts and were uniformly dissolved to obtain a viscous liquid. This is designated as a curing agent (1).

Production Example 6 60 parts of m-xylylenediamine [trade name MXDA, manufactured by Mitsubishi Gas Chemical Co., Inc.], 600 parts of XDA-AN, 100 parts of nonylphenol, and 240 parts of bisphenol A were uniformly dissolved to obtain a viscous liquid. Obtained. This is designated as a curing agent (2).

Production Example 7 100 parts of MXDA, 590 parts of XDA-AN, 242 parts of bisphenol A and 48 parts of phenol were uniformly dissolved,
A viscous liquid was obtained. This is used as a curing agent (3).

Production Example 8 603 was used as an equimolar reaction product of MXDA and ethylene oxide.
165 parts of nonylphenol and 165 parts of bisphenol A were uniformly dissolved in a reaction product of 1 part and 67 parts of Epicoat 828 to obtain a viscous liquid. This is designated as a curing agent (4).

Example 1 100 parts of inorganic granular aggregate [granite (average diameter: 5 mm), manufactured by Nakasu crushed stone industry Co., Ltd.] to 100 parts of main agent (1) and hardening agent (1)
2: 1 (weight ratio) 6 parts of the mixture were added and sufficiently kneaded to prepare a water-permeable paving material mortar, and then JIS R 5201 was used.
A bending test sample was prepared according to the above. Separately, a tensile test sample was prepared according to JIS K 6911 using the above resin mixture. The curing was at 25 ° C. for 1 week.

Example 2 Bending test and tensile test samples were prepared in the same manner as in Example 1 using a 3: 1 (weight ratio) mixture of the main agent (2) and the curing agent (2).

Example 3 Using the 3: 1 (weight ratio) mixture of the main agent (2) and the curing agent (3), samples for bending test and tensile test were prepared in the same manner as in Example 1.

Comparative Example 1 Bending test and tensile test samples were prepared in the same manner as in Example 1 using a 5: 2 (weight ratio) mixture of the main agent (3) and the curing agent (2).

Comparative Example 2 A sample for bending test and tensile test was prepared in the same manner as in Example 1 using a 3: 1 (weight ratio) mixture of the main agent (4) and the curing agent (2).

Comparative Example 3 A sample for bending test and tensile test was prepared in the same manner as in Example 1 using a 3: 1 (weight ratio) mixture of the main agent (1) and the curing agent (4).

Using the resin-hardened pieces of Examples 1 to 3 and Comparative Examples 1 to 3, the bending strength as an index of chipping off of inorganic granular aggregate as a resin for water-permeable pavement material and the bending after weathering deterioration promoting test Table 1 shows the results of measuring the tensile elongation at break, which is an index of the strength and the conformability to the substrate, and the tensile elongation at break after the weathering deterioration test.

The weathering-deteriorated accelerated test piece was a cured piece after curing at 25 ° C. for 1 week, and was a sunshine weather meter [Model W
EL-SUN-HCH type manufactured by Suga Test Instruments Co., Ltd.] 20
It was irradiated for 0 hours and created.

[0035]

[Table 1]

Table 2 shows the rate of change (*) in initial physical properties and physical properties after accelerating weathering deterioration.

[Table 2] * Change rate = [(physical properties after accelerated weathering deterioration)-(initial properties)]
× 100 / (initial physical properties)

As is clear from Tables 1 and 2, the resin for water-permeable pavement material according to this example shows a well-balanced high value of flexural strength and tensile elongation at break, and has little change in physical properties due to weathering deterioration. I understand.

[0038]

EFFECT OF THE INVENTION The resin for water-permeable pavement material of the present invention has high initial strength and tensile elongation at break, and has little weathering deterioration. Therefore, it is possible to prevent chipping or cracking of the inorganic granular aggregate due to external stress over a long period of time. A water-permeable pavement that does not occur can be applied.

Claims (4)

[Claims] 1. A resin composition for a water-permeable pavement material, which comprises a liquid epoxy resin (A), an amine curing agent (B), and a xylene formaldehyde resin (C). 2. The composition according to claim 1, wherein (B) is an acrylonitrile-modified diamine. 3. The composition according to claim 1 or 2, wherein (B) is a modified product of 0.3 to 1.6 mol of acrylonitrile with respect to 1 mol of the araliphatic diamine. 4. The composition of (C) comprises 3 to 50 parts by weight with respect to 100 parts by weight of (A) and (B) in total.
3. The composition according to any one of 3 above.