JP4741269B2 - Antifouling resin product and manufacturing method thereof - Google Patents

Description

  The present invention relates to an antifouling resin product and a method for producing the same.

  For example, artificial marble generally used as a resin product includes a resin matrix such as an acrylic resin and a polyester resin, and a filler such as aluminum hydroxide dispersed in the matrix (for example, Patent Documents 1 to 3). This artificial marble is suitably used for sink kitchen countertops and the like.

  However, when artificial marble made of a matrix and a filler is used in a kitchen, toilet, bathroom, etc., there is a problem that dirty oil or water adheres to the surface and it is difficult to wipe it even after cleaning. For this reason, for example, in the technique disclosed in Patent Document 1, the surface of a base material composed of a matrix and a filler is roughened, and an antifouling agent having both oil repellency and water repellency is applied in the recess. Yes. The artificial marble thus obtained is composed of a base material composed of a matrix and a filler, and an antifouling layer made of an antifouling agent formed on the surface of the base material. The artificial marble provided with this antifouling layer can exhibit antifouling properties based on water repellency and oil repellency as compared with the artificial marble whose base material is exposed. The rough surface of the substrate is considered to function in that the substrate and the antifouling layer are firmly fixed.

JP 2002-255672 A JP 2002-3260 A Japanese Patent Laid-Open No. 11-130504

  However, according to the test results of the inventors, an antifouling resin product such as artificial marble in which an antifouling layer is directly formed on a substrate made of a matrix and a filler is peeled off from the substrate by long-term use. It is easy and lacks antifouling durability. In the technique disclosed in Patent Document 1, the antifouling layer is firmly fixed to the base material by the rough surface of the base material, but a cleaning operation was performed to wipe the dirt by rubbing the surface with a sponge. In some cases, it still lacks antifouling durability.

  This invention is made | formed in view of the said conventional situation, Comprising: It is set as the problem which should be solved to provide the antifouling resin product which can exhibit durable antifouling property.

  The inventors have intensively studied to solve the above problems. When aluminum hydroxide is used as a filler dispersed in the base material, an underlayer containing an aluminum chelate compound and a silicon component is provided between the base material and the silicone surface layer exhibiting antifouling properties. Then, it discovered that the surface layer was hard to peel from a base material, and came to complete this invention.

That is, the antifouling resin product of the present invention comprises a matrix made of a resin and a base material comprising a filler dispersed in the matrix,
In an antifouling resin product comprising an antifouling layer formed on the surface of the substrate,
The filler includes aluminum hydroxide, and the antifouling layer is formed on the substrate side, and includes an underlayer containing an aluminum chelate compound and a silicon component, and a silicone-based surface formed on the surface side of the underlayer And a layer.

Further, the method for producing an antifouling resin product of the present invention comprises preparing a base material comprising a resin matrix and a filler containing aluminum hydroxide dispersed in the matrix, an aluminum chelate compound, and a silicon component A first step of preparing a first antifouling agent and a silicone-based second antifouling agent,
A second step of forming an underlayer by applying the first antifouling agent to the surface of the substrate;
And a third step of forming a surface layer by applying the second antifouling agent to the surface side of the foundation layer.

  According to the test results of the inventors, the antifouling resin product of the present invention has a highly durable antifouling property as compared with the bare substrate and the surface layer only formed on the surface of the substrate. It has been confirmed that it works.

  In the antifouling resin product of the present invention, it is considered that the aluminum hydroxide filler and the aluminum chelate compound chemically react at the interface between the base material and the base layer, and the base material and the base layer are firmly fixed to each other. Further, since the surface layer is the same type of silicon as the base layer, the surface layer is also firmly fixed to the base layer. For this reason, in the antifouling resin product of the present invention, the antifouling layer is hardly peeled off.

  Therefore, the antifouling resin product of the present invention can exhibit durable antifouling properties. Moreover, since this antifouling resin product has a silicone surface layer, it can also exhibit excellent chemical resistance.

  The antifouling resin product of the present invention comprises a base material and an antifouling layer.

  The substrate is composed of a resin matrix and fillers dispersed in the matrix. As the matrix, for example, an acrylic resin, a polyester resin, a vinyl ester resin, an epoxy resin, or the like can be used. The antifouling resin product of the present invention contains aluminum hydroxide as a filler, but may contain fine silica sand, calcium carbonate, glass frit, talc, glass fiber and the like as other fillers. In addition, a base material can contain a thickener, a hardening | curing agent, a mold release agent, etc. other than these matrices and fillers.

  The antifouling layer is formed on the surface of the substrate. The antifouling layer has a base layer and a surface layer.

  The underlayer is formed on the substrate side and contains an aluminum chelate compound and a silicon component. As a 1st antifouling agent which forms a base layer, what consists of a chelate compound of alkoxysilane, alkoxysiloxane, and aluminum is employable, for example. The underlayer can be formed by hydrolysis and dehydration condensation polymerization of a layer-forming element containing one of alkoxysilane, organoalkoxysilane, a hydrolyzate thereof, and a dehydration condensation polymerization product thereof. Here, as alkoxysilane and organoalkoxysilane, for example, tetramethoxysilane, phenyltrimethoxysilane, n-propylmethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, n-propyltriethoxysilane Dimethyldimethoxysilane, diethyldimethoxysilane, phenylethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, phenylmethyldiethoxysilane, and the like, and mixtures thereof.

  Aluminum chelate compounds include ethyl acetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate), etc. , And mixtures thereof can be used.

  The surface layer is a silicone type having an antifouling function formed on the surface side of the underlayer. The silicone-based surface layer may be fluorosilicone-based or alkyl-modified silicone-based. This surface layer can be formed by hydrolysis and dehydration condensation polymerization of a layer-forming element including one of alkoxysilane, perfluoroalkylsilane, alkyl-modified silane, a hydrolyzate thereof, and a dehydration condensation polymerization product thereof. Polysiloxanes such as polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, and the like, and mixtures thereof can be used. As the fluorosilicone and the alkyl-modified silicone antifouling agent, a perfluoroalkyl group or a modified silicone having an alkyl group, and a mixture thereof can be used.

  It is also possible to provide an intermediate layer between the underlayer and the surface layer. This intermediate layer may have an inclined component from the underlayer to the surface layer, or may be a primer component. The intermediate layer is not limited to one layer, and may be two or more layers.

  The manufacturing method of this invention will produce an antifouling resin product in a factory, when performing 1st-3rd processes in a factory.

  Moreover, the manufacturing method of this invention can also perform a 2nd process and a 3rd process with respect to the resin product by which construction or an assembly was already performed. In this case, it becomes possible to change the resin product that has already been constructed or assembled to the antifouling resin product of the present invention.

  Furthermore, the manufacturing method of this invention can also perform a 2nd process and a 3rd process with respect to the antifouling resin product by which construction or assembly was already performed. In this case, it becomes possible to recycle the antifouling resin product of the present invention that has already been constructed or assembled into a new antifouling resin product of the present invention.

  The production method of the present invention is preferably performed while heating at least one of the second step and the third step. As a result, it is possible to shorten the time from when at least one of the base layer and the surface layer is applied to curing. When the second step and the third step are performed on a resin product or an antifouling resin product that has already been constructed or assembled, a hair dryer or the like can be used.

  Hereinafter, the example which materialized the present invention in artificial marble is described with reference to drawings with comparative examples 1-3.

  First, as the first step, the base material 1, the first antifouling agent and the second antifouling agent shown in FIG.

  As shown in FIG. 2, the base material 1 is composed of a matrix 1a made of acrylic resin and a filler 1b containing aluminum hydroxide dispersed in the matrix 1a. This base material 1 is a well-known artificial marble. In addition, a base material can contain a thickener, a hardening | curing agent, a mold release agent, etc. other than these matrices and fillers.

  The first antifouling agent is a mixture comprising 45% by mass of alkoxysilane, 45% by mass of alkoxysiloxane and 10% by mass of an aluminum chelate compound.

  The second antifouling agent is light aliphatic naphtha 45 to 55% by mass, aromatic petroleum distillate 30 to 40% by mass, 1,2,4-trimethylbenzene 5 to 10% by mass, 1,3,5-trimethyl. It is a mixture comprising less than 5% by weight of benzene, less than 5% by weight of xylene and 1-5% by weight of dimethyl silicone oil.

  Then, as a second step, as shown in FIG. 1 (B), the first antifouling agent is applied to the surface of the substrate 1 with a trowel or a brush, and then wiped off with a waste cloth. And if it is in a factory, it will harden at normal temperature with respect to the base material 1 which has already been constructed or assembled by the heater on a line. Moreover, in order to accelerate | stimulate hardening, you may make it harden | cure for 30 minutes at 60 degreeC with a hair dryer. Thereby, the volatile component of a 1st antifouling agent volatilizes and solid content hardens early. Thus, the base layer 2 having a thickness of about 0.1 to 0.2 μm is formed. The underlayer 2 can have a thickness of about 0.01 to 10 μm. The underlying layer 2 closes the unevenness 1c on the surface of the substrate 1.

  Then, as a 3rd process, as shown in FIG.1 (C), a 2nd antifouling agent is apply | coated to the surface side of the base layer 2 with a trowel or a brush, and it is wiped off with a waste cloth. And if it is in a factory, it will harden at normal temperature with respect to the base material 1 which has already been constructed or assembled by the heater on a line. Moreover, in order to accelerate | stimulate hardening, you may make it harden | cure for 30 minutes at 60 degreeC with a hair dryer. Thereby, the volatile component of a 2nd antifouling agent volatilizes and solid content hardens early. Thus, the surface layer 3 having a thickness of about 0.05 to 0.3 μm is formed. The surface layer 3 may have a thickness of about 0.01 to 1 μm.

  In this way, the artificial marble of Example 1 is obtained. This artificial marble includes a base material 1 and an antifouling layer 4 formed on the surface of the base material 1. The antifouling layer 4 comprises a base layer 2 formed on the substrate 1 side and a surface layer 3 formed on the surface side of the base layer 2.

Comparative Example 1

  The artificial marble of Comparative Example 1 is composed only of the base material 1 as shown in FIG. Other conditions are the same as in the first embodiment.

Comparative Example 2

  The artificial marble of Comparative Example 2 includes a base material 1 and a surface layer 3 formed on the surface of the base material 1 as shown in FIG. Other conditions are the same as in the first embodiment.

Comparative Example 3

The artificial marble of Comparative Example 3 is obtained by making the underlayer 2 in the artificial marble of Example 1 different. The undercoat layer of Comparative Example 3 is composed of an antifouling agent comprising about 45% by weight alkoxysilane, about 45% by weight alkoxysiloxane and about 10% by weight phosphoric acid. Other conditions are the same as in the first embodiment.
(Evaluation 1, 2)
A wet sponge is placed on the artificial marble of Example 1 and Comparative Examples 1 to 3 with a load of 1 kgf and slid a certain number of times. After this wear, commercially available salad oil was dropped, the salad oil was blotted with a dry kitchen towel, and the condition of flipping the salad oil was visually observed. Further, commercially available oleic acid was dropped on the artificial marble after initial wear and after wear, and the oil repellency was evaluated by the contact angle (°). These results are shown in Table 1.

  From Table 1, the artificial marble of Example 1 is extremely durable compared to that of Comparative Example 1 in which the substrate 1 is bare and that of Comparative Example 2 in which only the surface layer 3 is formed on the surface of the substrate 1. It turns out that it has high oil repellency. In the artificial marble of Example 1, as shown in FIG. 2, the filler 1b of aluminum hydroxide and the chelate compound of aluminum chemically react at the interface between the base material 1 and the base layer 2, and the base material 1 and the base layer 2 are firmly fixed to each other. Further, as shown in FIG. 1C, the surface layer 3 is made of silicon based on the same quality as the foundation layer 2, and therefore the surface layer 3 is firmly fixed to the foundation layer 2. For this reason, the antifouling layer 4 is hard to peel off from the artificial marble of Example 1.

  Therefore, the artificial marble of Example 1 can exhibit durable antifouling properties. Further, since this artificial marble has a surface layer 3 made of silicone, it can exhibit excellent chemical resistance.

  Moreover, according to the manufacturing method of Example 1, it is also possible to produce artificial marble in a factory, or to impart or reproduce antifouling property to an artificial marble that has already been constructed or assembled.

  In the above, the present invention has been described with reference to the first embodiment. However, the present invention is not limited to the first embodiment, and it is needless to say that the present invention can be appropriately modified and applied without departing from the spirit of the present invention. .

  The antifouling resin product according to the present invention is artificial marble or the like, and can be used for a kitchen countertop of a sink, a range hood, a kitchen bag, and the like.

The manufacturing method of the artificial marble of Example 1 is shown, FIG. (A) is sectional drawing of a base material, FIG. (B) is sectional drawing of a base material and a base layer, FIG. (C) is a base material, base layer, and surface layer. FIG. 1 is an enlarged cross-sectional view of a main part of an artificial marble of Example 1. FIG. 3 is a cross-sectional view of an artificial marble of Comparative Example 1. FIG. It is sectional drawing of the artificial marble of the comparative example 2.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1a ... Matrix 1b ... Filler 1 ... Base material 4 ... Antifouling layer 2 ... Underlayer 3 ... Surface layer

Claims (7)

A base material comprising a resin matrix and a filler dispersed in the matrix;
In an antifouling resin product comprising an antifouling layer formed on the surface of the substrate,
The filler includes aluminum hydroxide, and the antifouling layer is formed on the substrate side, and includes an underlayer containing an aluminum chelate compound and a silicon component, and a silicone-based surface formed on the surface side of the underlayer An antifouling resin product comprising a layer. The antifouling resin product according to claim 1, wherein the underlayer comprises an alkoxysilane, an alkoxysiloxane, and an aluminum chelate compound. A base material comprising a resin matrix and a filler containing aluminum hydroxide dispersed in the matrix, a first antifouling agent containing an aluminum chelate compound and a silicon component, and a second anti-silicone agent A first step of preparing a soiling agent;
A second step of forming an underlayer by applying the first antifouling agent to the surface of the substrate;
And a third step of forming a surface layer by applying the second antifouling agent to the surface side of the foundation layer. 4. The method for producing an antifouling resin product according to claim 3, wherein the first antifouling agent comprises a chelate compound of alkoxysilane, alkoxysiloxane and aluminum. The method for producing an antifouling resin product according to claim 3 or 4 , wherein the second step and the third step are performed on the base material that has already been constructed or assembled. The antifouling resin product according to any one of claims 3 to 5, wherein the second step and the third step are performed on the antifouling resin product that has already been constructed or assembled. Production method. The method for producing an antifouling resin product according to any one of claims 3 to 6 , wherein at least one of the second step and the third step is performed while heating.

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