JPS62275048A - Acrylic resin concrete composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an acrylic resin concrete composition, and particularly to an acrylic resin concrete using colored aggregate as its aggregate. In addition, the diameter is approximately 5'IRx
When larger aggregates are coarse aggregates and aggregates smaller than about 5N are fine aggregates, concrete is generally made of coarse aggregate and fine aggregate, and concrete is made of only fine aggregates. is called mortar, but Lennon concrete here is broadly defined to include resin mortar. [Prior art] Types of resin concrete, which uses synthetic resin as a binder and mixes aggregate into it and cures it, include evoquinone, unsaturated polyester, and
There are acrylic types, etc. Incidentally, in such resin concrete, the aggregates thereof are colored in order to improve the aesthetic appearance and identify the concrete. As an example, in Japanese Patent Publication No. 59-27816, silica sand whose particle size has been adjusted is heated at 80 to 120°C, preferably 10°C.
A method is described in which a pigment and an aqueous emulsion of a curable epochino resin composition are added while stirring with a mixer after heating to 0° C. or higher, and the mixture is stirred and mixed to produce a colored bone oat. [Problems to be Solved by the Invention] However, when acrylic resin concrete manufactured by this method is used, hot water resistance and initial bending strength are poor. The cause of this is that destruction occurs in the colored component covering the aggregate. In order to solve this problem, we used a silane coupling agent that has the ability to chemically bond organic polymers and inorganic materials to increase the adhesion between the aggregate and the coloring component and renon. It is possible to increase the strength at By the way, an example of using aggregate treated with a silane coupling agent in acrylic renone concrete is disclosed in U.S. Patent No. 3.
, 575,785. However, this publication does not mention colored aggregate, and from this description it cannot be recognized that the strength of the colored component portion is improved by the silane coupling agent. In addition, since the 7-rankanopuring agent chemically bonds an organic polymer and an inorganic material, if a silane coupling agent is used to solve the above problem, those skilled in the art will be able to use a silane coupling agent. It is expected that some people will decide that it is sufficient to first treat the aggregate with a chemical agent and then bake the coloring component into the aggregate. Based on this prediction, the inventors conducted experiments and found that although this method improved the adhesion between the aggregate and the coloring component, there was a problem with the adhesion between the coloring component and the resin, and fracture occurred at the interface. It was found that the initial bending strength was poor and the hot water resistance was also poor. Therefore, we tried baking a silane coupling agent after baking a coloring component into the aggregate, but in this case as well, the adhesion between the aggregate and the coloring component was poor and fracture occurred at the interface, resulting in poor initial bending strength and heat resistance. It was found that neither the aqueous solution nor the aqueous solution was improved. The present invention has been made in view of the above, and is a technical endeavor to improve the physical properties of acrylic resin concrete compositions by using colored aggregate treated with a silane coupling agent. This is an issue to be addressed. [Means for Solving the Problems] In order to solve the above-mentioned technical problems, the present invention takes the following technical means. That is, in an acrylic resin concrete composition whose main components are at least one monomer component selected from (meth)acrylic acid and its ester, a polymer that can be dissolved or swelled by the monomer component, and aggregate. As the aggregate, a colored aggregate was used, in which a colored layer of a mixed component consisting of a silane coupling agent, a pigment, and a binder component was formed partially over the entire surface. [Function] The acrylic resin concrete of the present invention will be described in more detail below.

[Lenone component]

The acrylic resin concrete of the present invention has at least II selected from (meth)acrylic acid and its ester.
If the main components are a monomer component and a polymer that can be dissolved or swelled in the monomer component, any type of polymer can be used without discrimination. An example of such an acrylic renone concrete includes (a) a monomer of (meth)acrylic acid and/or its ester, (b) a swellable polymer that is soluble in the monomer component, and (c) m. a plasticizer soluble in the monomer component; and (d) at least 2 plasticizers in one molecule.
An example is a compound having 2 polymerizable unsaturated bonds. Monomers (a) include alkyl (meth)acrylates such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate, acrylic acid, methacrylic acid, 2-hydroquinethyl acrylate, and methacrylate. 2-Hydroquinoethyl, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hequin Lenglycolno(meth)acrylate, 2.
2-His[4-(meth)acryloyloxyphenyl:
Propane, 2,2-bis[4-(meth)acryloyloxycyclohexyl]propane, 2,2-bis[3-(
Examples include meth)acryloyloxy-2-hydroxypropoxyphenyl]propane, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and noventaerythritol hexa(meth)acrylate. Examples of the polymer (b) include homopolymers or copolymers of the above-mentioned monomers, particularly (meth)acrylic acid esters, and examples of the plasticizer (C) include dimethyl phthalate, knobdel phthalate, dicyclohexyl phthalate, and dioctyl phthalate. Representative examples include phthalic acid esters such as , dioctyl phthalate, no-2-ethylhexyl phthalate, dioctyl phthalate, and prylbenzyl phthalate. Further, α is copolymerizable with (a) such as noethyl maleate, dibutyl maleate, dioctyl maleate, dibutyl fumarate, and dioctyl fumarate. Internal plasticizers such as β-unsaturated carboxylic acid esters may be mentioned. Representative examples of the polymerizable unsaturated bond compound (d) include ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, I , alkanediol di(meth)acrylates such as 4-butylene glycol di(meth)acrylate, 2,2-bis[3-(meth)acryloyloxy-
Examples include 2-human C-xypropoquinophenyl]propane and (meth)acrylic acid modified products of Evokin resin such as Lipoxy VR-60 or Ribokin VR-90 manufactured by Showa Kobunshi Co., Ltd. Generally, the blending ratio of each of these components is 45 to 85 wt% of the monomer component (a) and 5 to 20 wt% of the polymer (b).
%, the plasticizer (c) is 1 to 25 wt%, and the remainder is (d). It is possible to harden the acrylic resin concrete using the colored aggregate of the present invention by adding a polymerization initiator and, if necessary, amines as a room-temperature faeces accelerator. Such polymerization initiators include dian ruberoxide, alkyl peroxide, aralkyl peroxide, peracid,
Peroxides such as peracid esters, azo compounds, and the like can be used, but among these, diacyl peroquinide is preferably used. Specific examples of cyatul peroxide include nobenzoyl peroxide, diacyl peroxide, tsucapryl peroxide, dilauroyl peroxide, and distearoyl peroxide. As the amines, either primary amines or tertiary amines can be used, but tertiary amines are preferably used. Specifically, aniline, toluidine, xolidine,
phenylene diamine, N. N-dimedylaniline, N, N-noedylaniline, N
, N-di(β-hydroquinethyl)aniline, N,N-
Dimethyltoluidine, N,N-diethyl J, It/
Iノ'/+1J anti-)ノ壬11ノニツ・ノ゛ノ NN-dimethylanidine, N,N-dimethyl-p
−

[-Butylaniline, N, IN-diethyl-pt-
Examples include butylaniline, N,N-dimethyl-p-chloroaniline, nophenylamine, N,N-(β-hydroquinethyl)-p-1 ruinone, and the like. Among these are N,N-trimethyl-p-toluidine, N
, N-trimethyl-p-butylaniline, N,N-dimethylanidine, N,N-dimethyl-p-chloroaniline, N,N-bis(β-hydroquinethyl)-p-toluidine and the like. Tertiary amines having an electron donor substituent at the p-position of N are preferred. N-dimethyl-p-toluidine, N,N~dimedyl-p
-t-butylaniline is particularly preferred. The blending ratio of the polymerization initiator and amines to the resin concrete is approximately 0.1 to 2 of the former per 100 polymerized parts of the resin concrete consisting of the above (a) to (d).
0 parts by weight, and 0.1 to 20 parts by weight of the latter. Further, in order to prevent the surface curing reaction from proceeding sufficiently due to radical scavenging by oxygen in the air, it is preferable to add solid paraffin, preferably paraffin wax having a melting point of 40 to 60°C. The blending ratio of this paraffin to the resin concrete is 0.1-1.0 parts by weight for 100 parts by weight of the resin concrete made of the above (a) to (d).
Parts by weight. [Raw materials for colored aggregate] <Aggregate> Any inorganic particulate material such as silica sand may be used, and it does not matter whether the diameter of the particles is larger or smaller than 5 sv. Pigments> Both organic and inorganic pigments can be used. Organic pigments include benzidine yellow, Hansa yellow,
Lysol Red, Alizarin Lake, Pigment Scarlet 3B, Brilliant Carmen 6B, Permanent Ret F-5R, Permanent Reved 4R, Rhodamine Lake B, Rhodamine Lake Y, Lake Red C, Rose Red, Peacock Blue Lake, Phthalocyanine Blue, Aniline Black, permanent yellow) IR, P
Examples include V Violet BL, quinacridone, perinone, anthraquinone, Ria Moftar Elo-6G, Ria Moftar Elo-3G, and Cromophtar Elo R. Inorganic pigments include titanium oxide, zinc white, lithopone, lead white, cadmium yellow, yellow lead, titanium yellow, zinc chromate, ocher, chrome vermilion, red pigment, amber, yellow iron oxide, red iron oxide, cadmium red,
There are lead red, navy blue, ultramarine blue, cobalt blue, chrome oxide green, mineral violet, carbon black, iron black, etc. Both organic and inorganic pigments can be used, but the pigment selection is based on the resin of resin concrete. Compatibility with ingredients should be considered. Binder> As the binder component, an emulsion or solution of epoxy resin, urethane resin, acrylic urethane resin, etc. is used. Silane coupling agent> As a silane coupling agent, vinyltrimethquine 7
Ran, vinyltriethquinsilane, vinyltris (β-
Preferred are methoxymethoxysilane, vinyltriacetyltonane, and γ-methoxysilane, and vinyltrichlorosilane, γ-
N-(β-methacryloquinoethyl)-N,N-dimethylammonium (chloride)propyltrimethoxy7ran, etc. can be used.

[Coloring component coating method]

<First coating method> After heating the aggregate to a high temperature, for example, about 120°C, put it in a mixer, add a coloring component and stir it for about 5 minutes, add a binder and stir it for another 2 minutes, take it out from the mixer and put it on a board. Spread the mixture on top and let it cool naturally, then pass it through a sieve to adjust the particle size. Second coating method> After heating the aggregate to a relatively low temperature, for example 50 to 60°C, put it in a mixer, add a coloring component and stir for about 5 minutes,
Add binder and dryer = ql + nM l
-*I l1bF! IP3t? ? tl! l-1Or
After curing in the oven for about 2 hours, remove from the mixer and cure at room temperature for 24 hours, and finally pass through a sieve to adjust the particle size. Note that the coloring component may be coated using other coating methods. The point is that it is sufficient if the coloring component can be attached to the aggregate.

[Production method of colored aggregate used in the present invention]

The method for producing the colored aggregate used in the acrylic resin concrete of the present invention involves baking the aggregate in the presence of a silane coupling agent at the same time as coating the colored component. More specifically, in the first coating method, the second coating method, etc., a silane coupling agent is added together with a coloring component, that is, a pigment, and is baked onto the surface of the aggregate. As a result, the molecular chains of the silane coupling agent grow in the colored component and bind to the aggregate, and are also exposed on the surface of the colored component, so that if it is used in Renon concrete in the future, it will bond to the resin part. It is assumed that [Effects of the Invention] The acrylic resin concrete composition of the present invention uses colored aggregate on which a colored layer of a mixed component consisting of a silane coupling agent, a pigment, and a binder component is formed partially but not over the entire surface. By doing so, it is possible to obtain good hot water resistance and initial bending strength. [Examples and Comparative Examples] Examples of the present invention will be described below while comparing them with comparative examples. <Example 1> A colored aggregate was obtained by simultaneously baking a pigment, a silane coupling agent, and an emulsion-based epoxy resin onto the aggregate using a second coating method. Here, the aggregate is silica sand, the pigment is red iron oxide, the silane coupling agent is γ-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBE 503), and the amount of each raw material is silica sand. 2QO
Q9, pigment 49, silane coupling agent 5g, emulsion type epoxy resin 409. This colored aggregate was used in acrylic resin concrete to measure its bending strength and hot water resistance. Here, the composition of acrylic resin concrete is methyl methacrylate 5
Five layers! 161E, 20 parts by weight of polymethyl methacrylate, 5 parts by weight of 1.4-butylene glycol dimethacrylate, 15 parts by weight of dibutyl maleate, 2 parts by weight of dicyclohexyl phthalate, 0.3 parts by weight of paraffin wax, 2 parts by weight of polymerization initiator. , hardening accelerator 0.7 heavy machinery parts. In addition, the hot water resistance was measured by immersing the resin concrete in hot water at 95°C and measuring the change in compressive strength over time. The results are shown in Table 1. <Example 2> Same as Example 1 except that a solution-based epoxy resin was used instead of an emulsion-based epoxy resin. Comparative Example I> After treating the aggregate with a silane coupling agent, it was colored by the second coating method described above to obtain a colored aggregate, which was used in acrylic resin concrete to measure bending strength and hot water resistance. Other conditions such as the type of aggregate were the same as in Example 1. Comparative Example 2 This is the same as Comparative Example 1 except that the aggregate was colored by the second coating method and treated with a silane coupling agent to obtain colored aggregate. The results are shown in Table 1. Comparative Example 3> Aggregate was coated with pigment and emulsion-based epoxy resin using the second coating method to obtain colored aggregate that was not treated with a silane coupling agent, and used in acrylic resin concrete to improve bending strength, Hot water resistance was measured. The types and amounts of aggregates and pigments are the same as in Example t. The results are shown in Table 1. Comparative Example 4 The same as Comparative Example 3 except that the first coating method was used instead of the second coating method and the amount of pigment was 2 g. The results are shown in Table 1. <Reference example! 〉 After adding water and a silane coupling agent to the aggregate and stirring and mixing with a mixer, heat treatment was performed at 110°C for 10 to 20 minutes,
It was air-dried for 3 days to obtain uncolored aggregate, which was used in acrylic resin concrete to measure bending strength and hot water resistance. 2QOO9 was used as aggregate, 100 g of water, and 5 g of silane coupling agent. The results are shown in Table 1. <Comparative study of Examples, Comparative Examples, etc.> As is clear from Table 1, when a silane coupling agent is simultaneously present in the coloring component and baked into the aggregate,
Both the bending strength and the compressive strength in hot water resistance are good, and the compressive strength in particular gets better as time passes. On the other hand, the colored aggregate of the comparative example has problems such as low bending strength and deterioration of compressive strength over time.

Claims (2)

[Claims] (1) An acrylic resin concrete composition whose main components are at least one monomer component selected from (meth)acrylic acid and its ester, a polymer that can be dissolved or swelled by the monomer component, and aggregate. In,
An acrylic resin concrete composition characterized in that the aggregate is a colored aggregate on which a colored layer of a mixed component consisting of a silane coupling agent, a pigment, and a binder component is formed over the entire surface or partially on the surface. (2) The acrylic resin concrete composition according to claim 1, which contains a plasticizer or a crosslinking agent.