JP2001129933A - Resin molded object and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin molded object used for a toilet seat part or a privates washing toilet seat part capable of easily removing a stain high in the adhesion force to a base material and difficult to remove such as a fur stain or the like. SOLUTION: A low surface energy layer is formed on the surface of a base material resin by transfer simultaneously with the molding of the base material resin by using a mold coated with a low surface free energy polymer such as a silicone resin, a fluoroplastic resin or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article of a thermoplastic resin such as a toilet seat part having a low surface free energy layer and excellent in antifouling properties, a local cleaning toilet seat part, a member used around water, and the like. It relates to the manufacturing method.

[0002]

2. Description of the Related Art Conventionally, a toilet seat such as a toilet seat sheet, a toilet lid, a main body case, or a part of a local washing toilet seat having a washing nozzle or the like is generally made of acrylonitrile-butadiene-styrene resin (hereinafter abbreviated as ABS resin) or polypropylene. It is mainly composed of a molded article of a thermoplastic resin such as a resin (hereinafter abbreviated as PP resin).

[0003] Many of the exposed components of the toilet seat such as the toilet seat sheet, the toilet seat bottom plate, the toilet lid, and the main body case are in direct contact with the skin, and attention has been paid to the hygiene thereof, and many contrivances have been put to practical use. . For example, when the heating toilet seat member has both antifouling property and antibacterial property, as described in JP-A-9-56642, the toilet seat and the like are made of a resin body in which a silicone resin is dispersed to lower the surface energy and reduce repellency. It improves antifouling performance such as water-based properties, and further imparts antibacterial properties by dispersing an antibacterial agent.

[0004]

In the case of a conventional toilet seat or a local flush toilet seat, when a man urinates, the toilet seat is used mainly with the toilet seat seat raised, so the back of the toilet seat seat or the main body of the local flush toilet seat is used. Urination may be applied to the front part of the case. In the case of stool, the stool that has fallen into the toilet bowl may repel water in the toilet trap, causing dirt and water to adhere to the back surface of the toilet seat sheet. Further, skin dirt such as sebum adheres to the surface of the toilet seat sheet and the toilet lid that come into contact with the skin during use.

[0005] The above AB used as an exposed component of a toilet seat such as a toilet seat sheet, a toilet lid, a main body case or a local cleaning toilet seat.
S resin has relatively large surface free energy. Therefore, there is a drawback that dirt is likely to adhere firmly and dirt is difficult to remove.

[0006] Further, in order to remove the adhered dirt, the surface of each member of the toilet seat is cleaned with a detergent.
The resin was inferior in detergent resistance, and solvent cracks sometimes occurred when repeatedly exposed to the detergent.

[0007] The PP resin has a lower surface free energy than the ABS resin, but is insufficient, and it is difficult to remove strongly adhered dirt such as scale, and a surface having a lower surface free energy is desired. I was

[0008] That is, PP is used to remove stains such as scale from AB.
Although it is easier to remove than S, permeable stains such as gargles and yotin are more likely to penetrate, and once penetrated, it is very difficult to remove the stains.

As described above, toilet seats or local flush toilet seat components are often contaminated when used daily and have poor recovery properties. However, the composition of the stain component and the mechanism by which the resin molded article is stained are complicated and have not been sufficiently elucidated. In general, oils and fats and proteins derived from the human body, stool containing oils and fats, water-soluble components such as urine and urinary stones due to minerals contained in urine, water bouncing from tap water and toilet traps Water scales, dusts, etc., due to the contained minerals. Bacteria, mold stains, etc. are generated using these stains as a nutrient source. These stains do not have a large adhesive force at the initial stage of generation, and are relatively easy to remove.

However, as the soil is used over a long period of time and as the soil dries, the soil itself becomes more cohesive and the soil components are denatured. It grows and becomes difficult to remove. The state can be classified as follows. A state of being buried in the irregularities on the surface of the resin molding. The state due to the intermolecular attraction between the surface molecules of the resin molded article and the dirt molecules The state in which the surface molecules of the resin molded article and the dirt molecules are chemically bonded The state in which dirt has penetrated or diffused inside the resin molded article Electrostatically attached state Adhered by the adhesive component of the dirt component.

On the other hand, in a living environment, it is difficult to create a state in which no dirt is attached, and dirt is hardly attached.
It is important to say that if there is dirt, it is easy to remove the dirt and easy to clean.

[0012] The wettability between the dirt component and the substrate surface is deeply involved in such strong dirt adhesion, and the worse the wettability, the lower the dirt adhesion. In order to reduce the adhesion of dirt, it is effective to lower the surface free energy of the substrate and reduce the wettability of dirt or a liquid containing dirt.

[0013] In general, it is necessary to use Yo
The equation of ung holds. γS = γSL + γLcosθ γS: surface free energy of an individual γSL: surface free energy between liquid and solid γL: surface free energy of liquid θ: contact angle of liquid to solid Wetability is defined by the magnitude of θ. The larger the value, the poorer the wettability, and the smaller θ, the better the wettability. Further, the work Wa for attaching the liquid to the base material is expressed by the following equation. Wa = γS + γL−γSL Wa = γL (1 + cosθ) This adhesion work corresponds to the work of separating dirt from the base material,
The larger θ and the lower the wettability, the smaller the value of the adhesion work (small adhesion). Therefore, by lowering the surface free energy of the substrate and increasing the contact angle of dirt or a liquid containing dirt, it is possible to reduce the adhesion of dirt to the substrate.

From the above, it is generally considered that the following method is effective for ensuring easy removal of the adhered dirt on the resin molded article.

A resin having a small surface free energy, for example, a silicone resin or a fluororesin is blended into the resin molded body to reduce the surface free energy, thereby reducing the adhesion of dirt to the surface.

An antistatic agent is added to prevent contamination of the surface of the resin molded product due to static electricity.

However, in the above method of blending a resin having a small surface free energy, even if a resin having a small surface free energy is blended, most of the resin is present inside the molded body and is exposed to the surface, contributing to the surface characteristics. The ratio of the resin having a small surface free energy is limited, and a large amount of addition is required to reduce the surface free energy. Further, when the resin having a large surface free energy is a base resin, there is a problem that a large amount of a resin having a small surface free energy must be added in order to reduce the adhesion of dirt to the surface.

In addition, the method of (addition of an antistatic agent) has a problem that the effect of preventing contamination other than dust and the like affected by static electricity is small and the effect is not maintained.

Accordingly, the present invention has been made to solve the above-mentioned problems, and a thermoplastic resin molded article having a surface having a small adhesive force of dried and solidified dirt, especially a toilet seat part among thermoplastic resin molded articles, It is an object of the present invention to provide a thermoplastic resin molded article such as a local cleaning toilet seat part, a member used around water, and a method for producing the same.

[0020]

According to a first aspect of the present invention, there is provided a thermoplastic resin molded article having a low surface free energy layer formed of a low surface free energy polymer on a surface thereof. And a surface having a lower surface free energy than the base resin.

In the present invention, by forming a low surface free energy layer on the surface, it is possible to provide a thermoplastic resin molded article having a surface having a small adhesion of dried and solidified dirt.

In order to achieve the above object, the invention according to claim 2 is characterized in that at least one component of a toilet seat such as a toilet seat sheet or a toilet lid has a low surface free energy by a low surface free energy polymer on its surface. By forming a layer, the surface has a surface having a lower surface free energy than that of the base resin.

In the present invention, by forming the low surface free energy layer on the surface, it is possible to provide a toilet seat component having a surface with a small adhesion of dried and solidified dirt.

According to a third aspect of the present invention, at least one of the components of a local cleaning toilet seat such as a toilet seat sheet, a toilet lid, and a main body case has a low surface free energy polymer on its surface. Forming a low surface free energy layer by the method described above, whereby the surface has a surface free energy lower than that of the base resin.

In the present invention, since the low surface free energy layer is formed on the surface, it is possible to provide a local cleaning toilet seat part having a surface having a small adhesion of dried and solidified dirt.

According to a fourth aspect of the present invention, a member used around water forms a low surface free energy layer by a low surface free energy polymer on the surface. It is characterized in that the surface has a surface free energy lower than that of the base resin.

In the present invention, by forming the low surface free energy layer on the surface, it is possible to provide a member used around water having a surface with a small adhesion of dried and solidified dirt.

According to a fifth aspect of the present invention, there is provided a thermoplastic resin molded product according to the first aspect, a toilet seat part according to the second aspect, and a local cleaning toilet seat according to the third aspect. The surface layer formed on the surface of the component, the member used around water according to claim 4 is a silicone resin.

In the present invention, a toilet seat component having a surface with low adhesion of dried and solidified dirt by forming a low surface free energy layer on the surface with a silicone resin,
It is possible to provide a thermoplastic resin molded body such as a local cleaning toilet seat part or a member used around water.

According to a sixth aspect of the present invention, there is provided a thermoplastic resin article according to the first aspect, a toilet seat component according to the second aspect, and a local cleaning toilet seat according to the third aspect. The surface layer formed on the surface of the component, the member used around water according to claim 4 is a fluororesin.

In the present invention, since a low surface free energy layer is formed on the surface with a fluororesin, it can be used in toilet seat parts having a surface with low adhesion of dried and solidified dirt, locally cleaned toilet seat parts, and around water. And a thermoplastic resin molded article such as a member.

In order to achieve the above-mentioned object, the invention according to claim 7 has a surface free energy of 28 dyne /
The surface free energy is 10 dyne / cm or more and 28 dyn on the surface of the base resin having a size of not less than 45 cm
A resin molded article characterized in that a low surface free energy layer is formed from a low surface free energy composition of less than e / cm, and the surface has a surface free energy lower than that of the base resin surface. And

In the present invention, the low surface free energy composition having a surface free energy of 10 dyne / cm or more and less than 28 dyne / cm has a low surface free energy layer formed on the surface, so that the adhesion of dried and solidified dirt is reduced. A resin molded body such as a toilet seat part having a small surface, a local cleaning toilet seat part, or a member used around water can be provided.

The invention described in claim 8 for achieving the above object is a method for producing a thermoplastic resin molded article according to any one of claims 1 to 7, wherein the method comprises forming a low surface free energy layer by molding. A step of applying a low surface free energy polymer to the surface of the mold, and simultaneously molding the base resin with the mold, and transferring the low surface free energy polymer from the mold to the surface of the base resin. A step of forming a low surface free energy layer on the surface.

In the present invention, by transferring a resin layer having a small surface free energy from a mold at the same time as molding of the base resin, the resin layer can be efficiently formed on the base material surface. A surface layer made of a resin having low energy can provide a high surface modification effect regardless of the surface free energy of the substrate.

In the method of coating with a resin having a small surface free energy, the adhesion between the base resin and the coating film is poor.
Although durability was a problem, the resin layer with low surface free energy was transferred from the mold at the same time as the molding of the base resin, so that the adhesion between the base resin surface and the surface layer of the resin with low surface free energy was achieved. However, the physical adhesion due to the anchor effect or the like increases, and the durability is improved.

The present invention also relates to at least one member of a constituent material of an exposed component of a toilet seat such as a toilet seat sheet, a toilet lid, a main body case, and the like. A low surface free energy layer is formed to make the toilet seat excellent in antifouling properties.

In this configuration, since the low surface free energy layer is formed on the surface, it is possible to provide a toilet seat having excellent antifouling property having a surface having a small adhesive force of dried and solidified dirt.

In order to achieve the above object, at least one of the constituent materials of the exposed components of the toilet seat for local cleaning, such as a toilet seat sheet, a toilet lid, a main body case, and a cleaning nozzle, the surface of which is made of a silicone resin, A low surface free energy layer lower than the surface of the base resin of the member was formed to provide a local cleaning toilet seat having excellent antifouling properties.

In this configuration, since the low surface free energy layer is formed on the surface, it is possible to provide a local cleaning toilet seat having excellent antifouling property and having a surface having a small adhesive force of the dried and solidified dirt.

As the base resin, a resin having a surface free energy of at least 28 dyne / cm and less than 45 dyne / cm was used.

Further, a silicone resin containing free silicone may be used as the silicone resin.

Further, a silicone resin containing 5 wt% to 80 wt% in 100 wt% of the silicone resin was used as the free silicone contained in the silicone resin.

Further, an antibacterial agent may be added to the base resin.

[0045] Further, in the toilet seat having excellent antifouling properties described thus far, as the silicone _{^{resin, R 1 p Si (OR 2}} ) q O (4-pq) / 2 or _{^{R 1 p Si (ONR 2)}} q O _{(4-pq) / 2} R ¹ ; organic group, R ² ; hydrogen group or organic group 0 <p <2, 0 ≦ q <4, 0 <p + q <4, antifouling using a silicone represented by the formula: It may be a toilet seat with a property.

As a production method for achieving the above object, a step of applying a silicone resin to the surface of a molding die, a step of casting a base resin, a step of molding the base resin with the molding die, The method includes a step of forming a low surface free energy layer on the surface of the base resin by transferring the silicone resin from the mold to the surface of the base resin.

In this method, the silicone resin layer can be efficiently formed on the surface of the base material by transferring the silicone resin layer from the mold at the same time as the molding of the base resin. A high surface modification effect can be obtained regardless of the surface free energy of the material.

In the method of coating the low surface free energy resin, the adhesion between the base resin and the coating film is poor and the durability is problematic. By transferring from the base material, the adhesion between the base resin surface and the surface layer of the resin with low surface free energy increases due to the anchor effect, physical adhesion due to curing during the molding of the base resin, and the durability is improved. improves.

As a production method for achieving the above object, in the step of applying a silicone resin to the surface of the molding die, the average particle size of the silicone resin after transfer is 50%.
The area ratio of the silicone resin layer that is applied so as to have a uniform particle size of less than
%.

According to this method, a product having a good appearance can be obtained without forming a silicone resin layer on the entire surface of the base resin. Regardless of the energy, a high surface modification effect can be obtained.

Also, the present invention relates to a method for manufacturing a toilet seat having excellent antifouling properties, wherein a silicone resin is dispersed and applied to form a low surface free energy layer to thereby provide the antibacterial performance of the base resin and the base resin. The performance and quality (appearance (gloss, color tone, transparency, etc.), surface hardness, etc.) can be maintained.

It is effective that the amount of the silicone resin to be dispersedly applied is 0.01 mg / cm ² or more.

As a production method for achieving the above object, in the step of applying a silicone resin to the surface of the mold, the surface layer after the transfer of the silicone resin has a thickness of 0.1 mm.
The ratio of the area of the silicone resin layer formed to a thickness of from 02 to 10.00 μm and covering the surface of the base resin was 5% or more.

It is effective that the amount of the silicone resin to be dispersedly applied is 0.01 mg / cm ² or more.

In this method, in order not to impair the performance of the base resin, the compounding agent such as an antibacterial agent is added to the silicone resin layer in some cases, and to the base resin in another case. Can be selected.

Further, in the above-described method for manufacturing a toilet seat having excellent antifouling properties, R ¹ _p Si (OR ² ) _q O _{(4-pq) / 2} or R ¹ _p Si (ONR ₎ may be used as the silicone resin. ² ) _q O _{(4-pq) / 2} R ¹ ; organic group, R ² ; hydrogen group or organic group Using silicone represented by the formula of 0 <p <2, 0 ≦ q <4, 0 <p + q ≦ 4 And a method for manufacturing a toilet seat having antifouling properties.

According to the present invention, the surface energy of exposed components such as a toilet seat sheet, a toilet lid, and a main body case is small and excellent in water repellency, and the effect is maintained. It is easy to remove and clean, and it is possible to provide a toilet seat with excellent antifouling properties.

Since dirt is hardly adhered and dirt can be easily removed and cleaned, there is no need to use a detergent that is strong in cleaning. Even when a resin having poor detergent resistance is used as a base material, generation of solvent cracks and the like due to the detergent is eliminated. .

As the embodiment of the low surface free energy layer described above, in addition to molding by transfer as described above, various forms of coating, painting, and film are possible as described below.

The present invention also provides a blasting treatment, a chemical treatment, a degreasing, a flame treatment, and the like for at least one of the constituent materials of exposed components of a toilet seat such as a toilet seat sheet, a toilet lid, and a main body case.
After performing surface treatments such as oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, and ion treatment, a low surface free energy layer lower than the base resin surface of the member is formed with silicone resin. The toilet seat has antifouling properties.

In this configuration, since a low surface free energy layer is formed on the surface, it is possible to provide an antifouling toilet seat having a surface with a small adhesive force of the dried and solidified dirt.

In order to achieve the above object, at least one of the constituent materials of the exposed components of the toilet seat for local cleaning, such as a toilet seat sheet, a toilet lid, a main body case, and a cleaning nozzle, the surface of which is made of silicone resin, A low-surface free energy layer lower than the base resin surface of the member was formed to provide an antifouling local cleaning toilet seat.

In this configuration, since the low surface free energy layer is formed on the surface, it is possible to provide an antifouling local cleaning toilet seat having a surface with low adhesion of dried and solidified dirt.

A resin having a surface free energy of at least 28 dyne / cm and less than 45 dyne / cm was used as the base resin.

Further, a silicone resin containing free silicone may be used as the silicone resin.

In addition, a silicone resin containing 5 wt% to 80 wt% in 100 wt% of the silicone resin was used as the free silicone contained in the silicone resin.

Further, an antibacterial agent may be added to the base resin.

[0068] Further, in the toilet seat having antifouling properties described thus far, as the silicone _{^{resin, R 1 p Si (OR 2}} ) q O (4-pq) / 2 or _{^{R 1 p Si (ONR 2)}} q O _{(4-pq) / 2} R ¹ ; organic group, R ² ; hydrogen group or organic group 0 <p <2, 0 ≦ q <4, 0 <p + q <4, antifouling using a silicone represented by the formula: It may be a toilet seat with a property.

Further, in the production method according to the present invention, a low surface free energy layer is formed on the surface of the base resin by performing a predetermined surface treatment on the base resin surface and a step of applying a silicone resin. .

As a surface treatment, a discharge treatment such as a corona treatment, a plasma treatment, a corona discharge or an arc discharge is carried out by using an electrode for generating a high-frequency high voltage, a base resin, and a metal disposed on the back side thereof as a facing electrode. It is preferable that any of these discharge treatments can exert the excellent effects of the present invention.

That is, by subjecting the base resin to a discharge treatment, the surface of the base resin can be modified to an optimum state, the wettability and reactivity of the surface can be significantly improved, and The adhesive strength with the silicone resin applied from the above can be significantly improved.

In the present invention, in the step of applying the silicone resin to the base resin, the surface layer of the silicone resin is formed to a thickness of 0.02 to 10.00 μm and the area of the silicone resin layer covering the base resin surface is reduced. 12%
As described above, the maximum particle size was set to 80 μm or less.

In this method, a product having a good appearance can be obtained without forming a silicone resin layer on the entire surface of the substrate resin. Regardless of the energy, a high surface modification effect can be obtained.

A method of manufacturing a toilet seat having antifouling properties, comprising applying a silicone resin to form a low surface free energy layer, thereby improving the antibacterial performance of the base resin, the performance of the base resin and Quality (appearance (gloss, color tone, transparency, etc.), surface hardness, etc.) can be maintained.

It is effective that the amount of the silicone resin dispersed and applied is 0.01 mg / cm ² or more.

In this method, in order not to impair the performance of the base resin, the compounding agent such as an antibacterial agent is added to the silicone resin layer in some cases, and to the base resin in another case. Can be selected.

Further, in the method of manufacturing a toilet seat having an antifouling property described above, the silicone resin may be R ¹ _p Si (OR ² ) _q O _{(4-pq) / 2} or R ¹ _p Si (ONR). ² ) _q O _{(4-pq) / 2} R ¹ ; organic group, R ² ; hydrogen group or organic group Using silicone represented by the formula of 0 <p <2, 0 ≦ q <4, 0 <p + q ≦ 4 And a method for manufacturing a toilet seat having antifouling properties.

According to the present invention, the surface energy of exposed components such as a toilet seat sheet, a toilet lid, and a main body case is small and excellent in water repellency, and the effect is maintained. It is easy to remove and clean, and it is possible to provide an antifouling toilet seat. In addition, a surface treatment is performed in advance for the purpose of improving adhesion and patterning. For example, surface treatments such as blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, and ion treatment can be given.

It is difficult to attach dirt, and the dirt can be easily removed and cleaned. Therefore, there is no need to use a detergent which is strong in cleaning. Even when a resin having poor detergent resistance is used as a base material, generation of solvent cracks and the like due to the detergent is eliminated. .

The present invention also provides a toilet seat having a lower surface than the base resin surface by applying a coating to the surface of at least one of the constituent materials of the exposed components of the toilet seat such as a toilet seat sheet, a toilet lid, and a main body case. A low surface free energy layer was formed to provide an antifouling toilet seat.

In this configuration, since the low surface free energy layer is formed on the surface, it is possible to provide a toilet seat having an antifouling property having a surface with a small adhesion of dried and solidified dirt.

The present invention relates to at least one member of a constituent material of an exposed component part of a local cleaning toilet seat such as a toilet seat sheet, a toilet lid, a main body case, a cleaning nozzle, and the like. A low surface free energy layer lower than the surface of the base resin was formed to provide an antifouling local cleaning toilet seat.

In this configuration, since the low surface free energy layer is formed on the surface, it is possible to provide an antifouling local cleaning toilet seat having a surface with low adhesion of dried and solidified dirt.

The paints used for coating the above members include:
A coating containing silicone resin or fluororesin was used.

As the types of coatings containing the silicone resin, silicone resins, modified silicone resins, polysulfide resins, polyurethane resins, acrylic urethane resins, and acrylic resins are currently widely used. Acrylic urethane-based resin was used from the viewpoint of performance.

Further, an antibacterial agent may be added to the base resin.

[0087] Further, in the toilet seat having antifouling properties described thus far, the as silicone _{^{resin, R 1 p Si (OR 2}} ) q O (4-pq) / 2 R 1; organic group, R ^2; hydrogen Group or Organic Group A toilet seat having antifouling properties may be formed using silicone represented by the formulas of 0 <p <2, 0 ≦ q <4, and 0 <p + q <4.

Alternatively, as the fluororesin, polytetrafluoroethylene (PTFE), perfluoroethylene propene copolymer (PFEP), perfluoroalkoxyalkane (PFA), polychlorotrifluoroethylene (PCTFE),
Polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene-tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (ECTFE), polytetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD) A toilet seat having antifouling properties may be used.

According to the present invention, the surface energy of exposed components such as a toilet seat sheet, a toilet lid and a main body case is small and excellent in water repellency, and the effect is maintained. It is easy to remove and clean, and it is possible to provide an antifouling toilet seat.

It is not necessary to use a strong detergent for cleaning because dirt is hardly adhered and the dirt can be easily removed and cleaned. Even when a resin having poor detergent resistance is used as a base material, generation of solvent cracks and the like due to the detergent is eliminated. .

The present invention also provides a toilet seat sheet, a toilet seat bottom plate,
A film-like or sheet-like resin layer is provided on at least one member of an exposed component of a toilet seat such as a toilet lid or a main body case, preferably an exposed component of a local cleaning toilet seat such as a cleaning nozzle. A low surface free energy layer lower than the resin surface was used.

The method for providing the resin layer of the present invention on the surface of an exposed component of a toilet seat for local cleaning, such as a toilet seat sheet, a toilet seat bottom plate, a toilet lid, a main body case, and a cleaning nozzle, is described below. After being placed in the mold and closing the mold, the molten resin is injected into the mold, and the resin is solidified to bond the resin layer to the resin molded product.

In this manner, the toilet seat of the present invention having the antifouling property having a low surface free energy on the surface of the molded article, and having a high surface hardness and being hardly damaged can be obtained.

Further, a three-layered film- or sheet-shaped resin layer was used, and a transparent clear layer capable of being colored and a pattern ink layer and an adhesive layer were sequentially formed on the transparent layer.

Alternatively, the film-shaped or sheet-shaped resin layer was formed into two layers, and a transparent clear layer capable of being colored and a pattern ink layer were formed on the transparent layer in this order.

Alternatively, the film-shaped or sheet-shaped resin layer was made into a single layer, and the structure was formed only with a transparent transparent layer which could be colored.

The clear layer contained a silicone resin or a fluororesin.

The clear layer contains an antibacterial agent.

In this configuration, since the low surface free energy layer is formed on the surface, it is possible to provide an antifouling local cleaning toilet seat having a surface with low adhesion of dried and solidified dirt.

[0100]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The thermoplastic resin according to the first aspect has a low surface free energy layer formed on the surface of a substrate. A general thermoplastic resin serving as a base material is, for example, AB
S, PP, polyethylene, polystyrene, acrylonitrile / styrene copolymer, polyvinyl chloride, polyvinylidene chloride, polymethylpentene, polyacetal, polymethyl methacrylate, polyamide, polybutylene terephthalate, polycarbonate and the like, but are not limited thereto. Not something. The surface free energy of the general thermoplastic resin is 28 dynes / cm or more and 45 dy.
ne / cm, but a surface free energy of 10 dyne / cm or more and 28 dyne / cm
By forming a low surface free energy layer of less than
The wettability of dirt can be reduced, and the adhesion of dirt can be reduced. Such a surface has a strong adhesion to the substrate, such as water stain, which has been difficult to remove in the past, and can easily remove stains that are difficult to remove.

The components of the toilet seat such as the toilet seat sheet and the toilet lid according to the second aspect have a low surface free energy layer formed on the surface of the base material. The surface free energy of the resin used for general toilet seats is 28 dynes / cm or more and 45 dy.
ne / cm, but a surface free energy of 10 dyne / cm or more and 28 dyne / cm
By forming a low surface free energy layer of less than
The wettability of dirt can be reduced, and the adhesion of dirt can be reduced. Such a surface has a strong adhesion to the substrate, such as water stain, which has been difficult to remove in the past, and can easily remove stains that are difficult to remove.

The components such as the toilet seat sheet, the toilet lid, and the main body case according to the third aspect have a low surface free energy layer formed on the surface of the base material. The surface free energy of resin used for general local toilet seats is 28 dyne /
The substrate has a surface free energy of not less than 10 dyne / cm and not more than 45 dyne / cm.
By forming a low surface free energy layer of less than 8 dyne / cm, the wettability of dirt can be reduced and the adhesion of dirt can be reduced. Such a surface has a strong adhesion to the substrate, such as water stain, which has been difficult to remove in the past, and can easily remove stains that are difficult to remove.

The member used around water according to claim 4 is a member having a low surface free energy layer formed on the surface of a substrate. The surface free energy of a resin used for a member used around ordinary water has a value of 28 dyne / cm or more and less than 45 dyne / cm, and a surface free energy of 10 dyne / cm or more and 28 dy is applied to the surface of the base material.
By forming a low surface free energy layer of less than ne / cm, the wettability of dirt can be reduced and the adhesion of dirt can be reduced. Such a surface has a strong adhesion to the substrate, such as water stain, which has been difficult to remove in the past, and can easily remove stains that are difficult to remove.

In the invention according to claim 5, the low surface free energy polymer forming the surface layer is made of a silicone resin. Silicone resin is 10 dyne / cm or more and 28 dyne / c due to its special molecular structure.
A low surface free energy surface layer of less than m can be obtained.

Examples of the silicone resin include silicone resins such as dimethylpolysiloxane and methylphenylpolysiloxane, and amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, and methacryl-modified silicone resins having an organic group. And modified silicone resins such as mercapto-modified, phenol-modified, polyether-modified, methylstyryl-modified, alkyl-modified and fatty acid ester-modified, but are not limited thereto. In addition, there are silicone resin resins and silicone resin rubbers obtained by a dehydration condensation reaction, an addition reaction, a peroxide reaction, a deoxime reaction, a dealcoholation reaction and the like, and modified resins thereof, but are not limited thereto. Further, there is a silicone-modified organic resin such as an epoxy resin, an acrylic resin, and a polyester resin, but is not limited thereto.

In the invention according to claim 6, the low surface free energy polymer forming the surface layer is made of a fluororesin. Due to the special molecular structure of the fluororesin, a low surface free energy surface layer of 10 dyne / cm or more and less than 28 dyne / cm can be obtained.

Examples of the fluororesin include, but are not limited to, polytetrafluoroethylene, tetrafluoroethylene, perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene and the like.

The invention described in claim 8 is the invention according to claims 1 to 7
In the formation of the surface layer as described above, a step of applying a low surface free energy polymer to the surface of a molding die, and molding the base resin with the molding die, and simultaneously applying the low surface free energy polymer from the molding die to the surface of the base resin. By transferring to
A method for producing a thermoplastic resin article, comprising a step of forming a low surface free energy layer on the surface of a base resin.

In the present invention, the low surface free energy polymer is applied to the mold by adjusting the viscosity to a desired value with a solvent such as a stock solution or a solvent, and then by a method such as spraying or wiping. The application may be applied uniformly over the entire product surface in the mold, or the effect of reducing the adhesion of dirt due to the surface layer having a low surface free energy on the product surface in the mold, It may be applied only to any necessary part. The molding of the thermoplastic resin that is the base resin is performed by a molding die coated with the surface layer forming material,
It is performed by a molding method such as injection molding and press molding.

At the same time as the molding of the base resin, the transfer of the surface layer to the base resin surface is performed. The method of coating with a resin having a low surface free energy has been problematic in terms of durability such as adhesion between a base resin and a coating film. By transferring from the mold, the adhesion between the surface of the base resin and the surface layer of the resin having a small surface free energy is increased by the physical adhesion force due to the anchor effect or the like, and the durability is improved.

Hereinafter, the low surface energy layer of the present invention will be described in detail. The surface energy of the silicone resin in the present invention is generally from 10 dyne / cm to 28 dyne / cm.
It indicates a value less than cm. Therefore, in the present invention, by forming a low surface free energy layer using a silicone resin on the surface of the base material, the wettability of dirt can be reduced and the adhesion of dirt can be reduced. Accordingly, the base resin is not limited, but is not less than 28 dyne / cm 4
It is more effective to use a resin of less than 5 dyne / cm. On such a surface, by forming a low surface free energy layer using a silicone resin, it is difficult to remove the resin such as water stains. It has a strong adhesion to the substrate, and can easily remove dirt that is difficult to remove.

The surface free energy 28d in the present invention
Examples of the resin having a diameter of not less than yne / cm and less than 45 dyne / cm include ABS, PP, polyethylene, polystyrene, acrylonitrile / styrene copolymer, polyvinyl chloride, polyvinylidene chloride, polymethylpentene, polyacetal, polymethyl methacrylate, polyamide, Examples include, but are not limited to, polybutylene terephthalate and polycarbonate.

The silicone resin of the present invention is a resin formed by partially hydrolyzing and polycondensing a hydrolyzable silane derivative monomer and / or an uncured siloxane polymer.

Examples of the silicone resin include silicone resins such as methylphenyl silicone resin and diphenyl silicone resin, and alkyd-modified, polyester-modified, epoxy-modified,
Modified silicone resins such as acryl-modified, phenol-modified, urethane-modified, and melamine-modified are exemplified, but not limited thereto.

Specifically, the general formula R12SiX2 (wherein
R1 is an organic group, and X is chlorine, bromine, or a group having 1 to 4 carbon atoms.
Is an alkoxy group. The same applies to the following), prepared from a hydrolyzable bifunctional silane derivative represented by the general formula R1SiX3, a hydrolyzable trifunctional silane derivative represented by the general formula R1SiX3, and a hydrolyzable tetrafunctional silane derivative represented by the general formula SiX4. .

As the hydrolyzable trifunctional silane derivative,
Methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane,
Methyltriisopropoxysilane, methyltri-t-butoxysilane, ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxy Examples thereof include silane, vinyltriethoxysilane, trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, and triethoxyhydrosilane.

Further, n-propyltrichlorosilane, n
-Propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n- Hexyltriethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-octadecyltrimethoxysilane,
n-octadecyltriethoxysilane, phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3 , 4-Epoxycyclohexyl) ethyltrimethoxysilane, β- (3,
4-epoxycyclohexyl) ethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-
Aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, hepta There are decafluorooctyltrimethoxysilane and heptadecafluorooctyltriethoxysilane.

As the hydrolyzable bifunctional silane derivative,
Diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxy Silane, γ-glycidoxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth)
Acryloxypropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, heptadecafluorooctylmethyldimethoxysilane, heptadecafluorooctylmethyldiethoxysilane, and dimethyldichlorosilane, dimethyldimethylsilane There are bromosilane, dimethyldimethoxysilane and dimethyldiethoxysilane.

The hydrolyzable tetrafunctional silane derivative includes tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and dimethoxydiethoxysilane.

A conventionally known hydrolysis catalyst can be added to the silicone resin.
It is preferable to use one exhibiting acidity. Particularly preferred are acidic hydrogen halides, carboxylic acids, sulfonic acids, acidic or weakly acidic inorganic salts, and solid acids such as ion exchange resins. Preferable examples include hydrogen fluoride, hydrochloric acid, nitric acid, sulfuric acid; organic acids represented by acetic acid and maleic acid; methylsulfonic acid; and cation exchange resins having a sulfonic acid group or a carboxylic acid group on the surface. . The amount of the hydrolysis catalyst was 0.001 per mole of the hydrolyzable group on the silicon atom.
Preferably it is in the range of 5 mol.

The amount of water used for the hydrolysis is 0.001 to 500 mol, preferably 0.01 to 500 mol per mol of the hydrolyzable group on the silicon atom, in consideration of the curability of the coating film and the stability of the liquid.
Preferably it is in the range of 5 to 100 moles. In the hydrolysis reaction, it is preferable to use a polar solvent such as alcohol, ketone, ester or the like, or a non-polar solvent such as toluene or hexane as a solvent. When halogenosilane is used as a raw material, it is necessary to sufficiently wash with water after hydrolysis to remove halogen components.

As the solvent or dispersion medium of the coating composition, a polar organic solvent can be used, and water or lower alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, and the like can be used from the viewpoint of sol stability and availability.
Isobutanol or ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIB)
K) is preferred. Further, water and all organic solvents can be used as a diluent for diluting the coating composition. Alcohols, ketones, esters and ethers are suitable as organic solvents.

A conventionally known curing catalyst can be added to the silicone resin. As a curing catalyst,
For example, basic salts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, sodium formate, potassium acetate, potassium formate, potassium propionate, tetramethylammonium chloride, and tetramethylammonium hydroxide Compounds: n-hexylamine, tributylamine, diazabicycloundecene, ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenebentamine, ethanolamines,
γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ
-Aminopropylmethyldimethoxysilane, γ- (2-
Amine compounds such as aminoethyl) -aminopropylmethyldimethoxysilane; titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate; aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride Aluminum compounds such as; tin acetylacetonate, tin compounds such as dibutyltin octylate; cobalt octylate;
Metal-containing compounds such as cobalt acetylacetonate and iron acetylacetonate; phosphoric acid, nitric acid, phthalic acid,
acidic compounds such as p-toluenesulfonic acid and trichloroacetic acid;

Further, a combination of an acid and a basic compound serving as a buffer for adjusting the pH, for example, acetic acid and sodium acetate, disodium hydrogen phosphate and citric acid may be added. In addition, pigments, dyes, leveling agents, storage stabilizers, and the like can be added for the purpose of imparting excellent film performance.

For improving the stability of the coating solution, known surfactants, titanate coupling agents and silane coupling agents can be added.

Further, metal oxide fine particles may be added in order to improve the hardness and scratch resistance of the cured film and to impart optical functions such as a high refractive index. Examples of the metal oxide include silica, alumina, cerium oxide, tin oxide, zirconium oxide, antimony oxide, iron oxide, iron oxide or titanium oxide doped with zirconium oxide, and rare earth oxides. In particular, it is preferable to add silica to improve the scratch resistance.

As the free silicone in the present invention, not only silicones having the same system as the silicone resin used in the present invention, that is, not only silicones differing only in molecular weight, but also all kinds of silicones can be used.

Examples of the silicone include silicone resins such as dimethylpolysiloxane and methylphenylpolysiloxane, and amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, and methacryl-modified silicone resins having an organic group added to these silicone resins. And modified silicone resins such as mercapto-modified, phenol-modified, polyether-modified, methylstyryl-modified, alkyl-modified and fatty acid ester-modified, but are not limited thereto.

It should be noted that the free silicone is obtained by adjusting the ratio of the silicone resin and the polymer of the silicone so that the silicone does not react when the silicone resin layer is formed on the surface of the base resin, and is free after the formation of the silicone resin layer. It exists in the state where it was done.

Although the silicone resin layer alone has high antifouling properties, the presence of free silicone further improves the antifouling properties.

As the amount of the free silicone increases, the antifouling performance improves, but the durability of the low surface energy layer decreases, such as softening of the silicone resin layer. Therefore, the free silicone contained in the silicone resin is preferably used. 5 wt% of silicone in 100 wt% of silicone resin
% When using a silicone resin containing from 80% by weight to 80% by weight.

The antibacterial agents of the present invention include, as inorganic antibacterial agents, silver nitrate, silver sulfate, silver chloride and the like. Zeolite supporting silver, copper, zinc and tin. Examples include, but are not limited to, silica gel supporting silver, copper, zinc, and tin. About the mixing ratio, based on 100 parts by weight of the base resin
When the amount is less than 0.1 part by weight, no antibacterial property is recognized. When the amount exceeds 5 parts by weight, properties of the resin composition such as coloring and deterioration are significantly impaired. Therefore, it is desirable that the amount be 0.3 to 3 parts by weight.

Examples of the organic antibacterial agent include imidazole derivatives such as 2- (4-thiazolyl) benzimidazole (hereinafter abbreviated as TBZ), N-haloalkylthio compounds such as cyclofluanid, and 10,10'-oxybisphenoxaarsine. Examples include, but are not limited to, phenyl ether derivatives, quaternary ammonium salts such as cetyldimethylethylammonium bromide, and sulfone derivatives such as 2,3,5,6 tetracolor-4- (methylsulfonyl) pyridine.

Regarding the compounding ratio, with respect to the organic fungicide, if the amount is less than 0.02 parts by weight with respect to 100 parts by weight of the base resin, there is almost no fungicidal property, and if it exceeds 5 parts by weight, problems such as blooming will occur. appear. Therefore, 0.
It is desirably in the range of 0.5 to 1 part by weight.

As a method for manufacturing a toilet seat, a step of applying a silicone resin to the surface of a molding die, and molding a base resin with the molding die, and simultaneously transferring the silicone resin from the molding die to the surface of the base resin, A step of forming a silicone resin layer on the surface of the base resin.

In the present invention, the silicone resin is applied to the mold by adjusting the viscosity to an arbitrary value using a stock solution or a solvent such as a solvent, and then applying the solution by a spraying method or a wiping method.

The coating may be applied uniformly over the entire product surface in the mold, or the effect of reducing the adhesion of dirt due to the surface layer having low surface free energy on the product surface in the mold. However, it may be applied only to any particularly necessary part.

The molding of the base resin is performed by a molding method such as injection molding or press molding using a molding die coated with the silicone resin.

At the same time as the molding of the base resin, the transfer of the surface layer to the base resin surface is performed. The method of coating with a resin having a low surface free energy has been problematic in terms of durability such as adhesion between the base resin and the coating film.However, the silicone resin must be transferred from the mold at the same time as the base resin is molded. Due to this, the adhesion between the base resin surface and the surface layer of the silicone resin,
Anchor effect, physical adhesion due to the influence of hardening or the like at the time of molding the base resin increase, and the durability is improved.

For controlling the curing of the silicone resin, a curing-promoting catalyst or the like may be added as long as the curing of the present invention is not impaired. By using these curing agents, catalysts, and the like, it is possible to perform curing suitable for the base resin molding temperature, mold temperature, and the like.

Representative curing accelerator catalysts include fatty acid salts such as zinc, lead, cobalt, tin, iron and zirconium, chelates such as aluminum and titanium, various amines and salts thereof, and amino-based CF silanes. However, the present invention is not limited to this.

Further, in the step of applying the silicone resin to the mold for forming the silicone resin surface layer,
The silicone resin is applied so that the average particle size after the transfer is 50 μm or less in uniform fine particles. The viscosity is adjusted to an arbitrary value with a solvent such as a stock solution or a solvent, and the solution is applied by a spray method or the like. In addition, the coating may be applied uniformly on the entire surface of the product in the mold, or on the product in the mold,
The effect of reducing the adhesion of dirt by the surface layer having a low surface free energy may be applied only to any part particularly required. In this case, when the proportion of the area of the silicone resin layer covering the surface of the base resin is 5% or more, particularly 10% or more, excellent antifouling property is exhibited.

Further, when the silicone resin after transfer has an average particle diameter of 50 μm or more, excellent antifouling properties are exhibited even with a very small amount of application, but there is a drawback that the appearance becomes poor.

The present invention relates to a method for manufacturing a toilet seat having excellent antifouling properties, wherein a low surface free energy layer is formed with a silicone resin, the antibacterial performance of the base resin, and the performance and quality of the base resin. (Appearance (gloss, color tone, transparency, etc.),
Surface hardness etc.) can be prevented from lowering.

Hereinafter, one embodiment (coating) of the low surface energy layer of the present invention will be described in detail. The surface energy of the silicone resin in the present invention is generally 10 dyne / c.
The value is not less than m and less than 28 dyne / cm. Therefore, in the present invention, by applying a discharge treatment to the surface of the base resin, and then applying a silicone resin layer having a small surface free energy, it can be efficiently formed on the base resin surface, and the adhesion of the silicone resin layer can be improved. The surface layer is made of a very small amount of silicone resin and has a low surface free energy, regardless of the surface free energy of the base material. Can be reduced.

Therefore, the base resin is not limited, but is not less than 28 dyne / cm and 45 dyne / cm.
It is more effective to use a resin having a size of less than 1 cm. On such a surface, a low surface free energy layer is formed by using a silicone resin. It has a strong adhesion to the material and can easily remove dirt that is difficult to remove.

The surface free energy 28d in the present invention
As for the resin, silicone resin, and antibacterial agent having a diameter of yne / cm or more and less than 45 dyne / cm, the same ones as described above can be used.

As a method of manufacturing the toilet seat, a low surface free energy layer is formed on the surface of the base resin by performing a predetermined surface treatment on the base resin surface and applying a silicone resin.

In the present invention, the silicone resin is applied to the base resin by adjusting the viscosity to a desired value with a solvent such as an undiluted solution or a solvent, and by a spraying method or a wiping method.

As the surface treatment method for the base resin, in the discharge treatment, corona treatment, plasma treatment, corona discharge or arc discharge is performed by using an electrode for generating a high-frequency high voltage and a metal placed on the back side of the base resin in a facing electrode. It is preferable that a discharge is generated as a result, and the excellent operation and effect of the present invention can be exerted by performing any of these discharge treatments.

That is, by subjecting the base resin to a discharge treatment, the surface of the base resin can be modified to an optimum state, and the wettability and reactivity of the surface can be significantly improved. The adhesive strength with the silicone resin applied from the above can be significantly improved.

Here, as the corona treatment, a method in which an electrode for generating a high-frequency high voltage, a base resin, and a metal disposed on the back side thereof are used as facing electrodes to generate a discharge. Alternatively, the base resin can be modified by a method in which corona discharge or arc discharge is blown to the base resin by a gas flow. As the discharge conditions, the output is usually 10 to 1000 W, and the processing time is about 0.1 to 30 sec.

In the plasma treatment, the surface of the base resin is modified by utilizing ions, electrons, radicals, light, atoms, molecules and the like in the plasma, and a gas of a predetermined pressure (low pressure or atmospheric pressure) is applied. In contrast, a method in which a discharge is generated by a DC or AC electric field, and a discharge treatment is performed by installing a base resin during the discharge or downstream of the gas flow from the discharge. In this case, the discharge conditions are usually such that the pressure is 0.
001 to 1000 Torr, plasma excitation electric field frequency is DC, constant frequency AC such as 50 Hz, 1 to 100 kHz
AC of about z, radio waves such as 13.56 MHz, 2.4
Microwaves such as 5 GHz can be used. As gas, argon gas, oxygen gas, air, nitrogen, helium gas,
CF ₄ or the like is used.

The discharge conditions of the corona discharge or the plasma discharge are such that the discharge portion and the surface of the resin are 0.1 to 100 m apart.
It is preferable that the processing time is about 1 to 60 sec.

The surface treatment may be performed by blasting, chemical treatment, degreasing, flame treatment,
Various treatment methods such as oxidation treatment, steam treatment, ultraviolet irradiation treatment, and ion treatment can be applied.

In the step of applying the silicone resin to the base resin, the surface layer of the silicone resin may
The ratio of the area of the silicone resin layer formed to 10.00 μm and covering the base resin surface was 12% or more, and the maximum particle size was 80 μm or less. That is, the silicone resin is diffused and applied to the surface of the base material, and 12% or more of the entire area is formed as the silicone resin layer.

In this method, a product having a good appearance can be obtained without forming a silicone resin layer on the entire surface of the base resin. Therefore, a very small amount of the surface layer of the silicone resin can be used regardless of the surface free energy of the base resin. And a high surface modification effect can be obtained.

Further, the present invention relates to a method for manufacturing a toilet seat having antifouling properties, wherein the antibacterial performance of the base resin, the performance of the base resin, and the low surface free energy layer are formed by applying a silicone resin. Quality (appearance (gloss, color tone, transparency, etc.), surface hardness, etc.) can be maintained.

It is effective that the amount of the silicone resin to be dispersedly applied is 0.01 mg / cm ² or more.

As a method for applying the silicone resin, a spray method for achieving a uniform particle size and density is preferable, but not limited thereto. Also, the silicone resin may be applied uniformly over the entire product surface,
The effect of reducing the adhesion of dirt by the surface layer having a low surface free energy may be applied only to any part particularly required.

For the control of the curing of the silicone resin, the same control as described above can be used.

Further, in the step of applying the silicone resin to the base resin for forming the silicone resin surface layer, the low surface free energy layer after the application of the silicone resin has a thin thickness of 0.02 to 10.00 μm. Apply in layers. The viscosity is adjusted to an arbitrary value with a solvent such as a stock solution or a solvent, and the solution is applied by a spray method or the like.

The coating may be applied uniformly over the entire surface of the product, or the effect of reducing the adhesion of dirt due to the surface layer having low surface free energy on the product may be applied to any part particularly required. You may apply only. At this time, the ratio of the area of the silicone resin layer covering the base resin surface is 5% or more,
In particular, when the content is 12% or more, excellent antifouling property is exhibited.

[0164] The silicone resin after coating was used in 10.
When a low surface free energy layer having a thickness of 00 μm or more is formed, excellent antifouling properties are exhibited even with a very small amount of application, but there is a disadvantage that the appearance becomes poor. In addition, when a solvent is used for a diluting solution, etc. on the molding cycle,
The cycle can be long.

The present invention relates to a method for manufacturing a toilet seat having antifouling properties, wherein a low surface free energy layer is formed by a silicone resin, and the durability is improved by the effect of a discharge treatment.
In addition, the antibacterial performance of the base resin, the performance and quality of the base resin (appearance (gloss, color tone, transparency, etc.), surface hardness, etc.) can be kept from deteriorating.

Further, in the step of applying the silicone resin to the mold for forming the silicone resin surface layer, the low surface free energy layer after transferring the silicone resin is
It is applied to form a thin layer of 0.02 to 10.00 μm. The viscosity is adjusted to an arbitrary value with a solvent such as a stock solution or a solvent, and the solution is applied by a spray method or the like. The application may be applied uniformly over the entire product surface in the mold, or the effect of reducing the adhesion of dirt due to the surface layer having a low surface free energy on the product surface in the mold, It may be applied only to any necessary part. At this time, when the ratio of the area of the silicone resin layer covering the surface of the base resin is 5% or more, particularly 10% or more, that is, the silicone resin layer is 5% of the total area of the base material on the surface of the base resin.
As described above, particularly, the silicone resin is diffused and transferred so as to have a concentration of 10% or more, so that excellent antifouling properties are exhibited.

Further, the silicone resin after transfer was used in 10.
When a low surface free energy layer having a thickness of 00 μm or more is formed, excellent antifouling properties are exhibited even with a very small amount of application, but there is a disadvantage that the appearance becomes poor. In addition, when a solvent is used for a diluting solution, etc. on the molding cycle,
The cycle can be long.

Hereinafter, another embodiment (painting) of the low surface energy layer of the present invention will be described in detail. The surface energy of the silicone resin or fluororesin in the present invention generally shows a value of 10 dyne / cm or more and less than 28 dyne / cm. Therefore, in the present invention, a surface having a small surface free energy can be formed irrespective of the surface free energy of the base material by coating the base resin surface with a paint containing a silicone resin or a fluororesin. Can be reduced, and the adhesion of dirt can be reduced.

Therefore, the base resin is not limited, but is not less than 28 dyne / cm and 45 dyne / cm.
It is more effective to use a resin of less than 1 cm, and on such a surface, by forming a low surface free energy layer with a silicone resin or a fluororesin, it has been difficult to remove the resin. As described above, the adhesion to the substrate is strong, and dirt that is difficult to remove can be easily removed.

The surface free energy 28d in the present invention
As for the resin, silicone resin, and antibacterial agent having a diameter of yne / cm or more and less than 45 dyne / cm, the same ones as described above can be used.

With respect to the fluororesin, polytetrafluoroethylene (PTFE), perfluoroethylene propene copolymer (PFEP), perfluoroalkoxy alkane (PF
A), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride
(PVF), ethylene-tetrafluoroethylene copolymer
(ETFE), polychlorotrifluoroethylene (ECTF
E), a polytetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD) is preferred.

The mixing ratio of the fluororesin is preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the paint. By blending fluororesin,
The surface energy of the resin molded body decreases, the contact angle with water increases, the dirt component hardly adheres, and the antifouling performance increases, but if the mixing ratio is too high, the physical properties such as mechanical strength deteriorate. However, other characteristics required for the toilet seat such as strength cannot be satisfied.

The paint containing the silicone resin or the fluororesin of the present invention can be toned by further containing a coloring agent such as a pigment or a dye, if necessary.

The pigment that can be used is not particularly limited, and examples thereof include carbon black, quinacridone,
Organic pigments such as naphthol red, cyanine blue, cyanine green, and Hansa yellow; inorganic pigments such as titanium oxide, barium sulfate, red iron oxide, and composite metal oxides; and one or more selected from these groups. Can be used.

The dispersion of the pigment is not particularly limited, and may be a usual method, for example, a method of directly dispersing the pigment powder using a dyno meal, a paint shaker or the like. At that time, a dispersant, a dispersing aid, a thickener, a coupling agent, and the like can be used.

The amount of the pigment to be added is not particularly limited, since the concealing property varies depending on the type of the pigment. Parts, more preferably 10
70 parts by weight. When the amount of the pigment is less than 5 parts by weight, the concealing property tends to deteriorate, and when the amount exceeds 80 parts by weight, the smoothness of the coating film may deteriorate.

The dyes that can be used are not particularly limited, but include, for example, azo dyes, anthraquinone dyes, indicoid dyes, sulfide dyes, triphenylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, quinone imine dyes, and the like.
And thiazole, methine, nitro and nitroso dyes. One kind selected from these groups or a combination of two or more kinds may be used.

The amount of the dye added is not particularly limited since the concealing property varies depending on the type of the dye. For example, it is preferably 5 to 80 parts by weight based on 100 parts by weight of the total solid content in terms of the total condensed compound in the total amount of the paint. Parts, more preferably 10
70 parts by weight. When the amount of the dye is less than 5 parts by weight, the concealing property tends to be deteriorated, and when it exceeds 80 parts by weight, the smoothness of the coating film may be deteriorated.

Note that a leveling agent, metal powder, glass powder,
Antibacterial agents, antioxidants, ultraviolet absorbers and the like may also be included in the paint within a range that does not adversely affect the effects of the present invention. The paint can be used by diluting it with various organic solvents, if necessary, because of the ease of handling, or it may be diluted with the same organic solvent.

The kind of the organic solvent can be appropriately selected according to the kind of the monovalent hydrocarbon group contained in each component of the silicone resin, the molecular weight of each component of the silicone resin, and the like. Such organic solvents are not particularly limited, and include, for example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ethylene glycol,
Ethylene glycol derivatives such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether acetate; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether;
And toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol, etc., and one or more selected from the group consisting of these. Can be used. The dilution ratio in the organic solvent is not particularly limited, and the dilution ratio may be appropriately determined as needed.

The method of applying the paint is not particularly limited, and for example, various common application methods such as brush coating, spraying, dipping (dipping), roll, flow, curtain, knife coating, spin coating and the like are selected. can do. In addition, the coating may be applied uniformly on the entire surface of the product, or may be applied only on any portion where the effect of reducing the adhesion of dirt due to the surface layer having low surface free energy on the product is particularly necessary. You may.

The method of curing the paint film may be a known method, and is not particularly limited. The temperature at the time of curing is not particularly limited, either, and can be in a wide range from room temperature to heating temperature according to the desired performance of the cured film and the heat resistance of the substrate.

The thickness of the cured coating film formed from the coating material is not particularly limited, and may be, for example, about 0.1 to 100 μm. The coating adheres stably for a long time,
In order to be retained and not to cause cracking or peeling, the thickness is preferably from 10 to 80 μm, more preferably from 20 to 60 μm.

The silicone resin after application was 100
When a low surface free energy layer of μm or more is formed,
Although excellent antifouling property is exhibited, it has a drawback that appearance becomes poor such as occurrence of uneven coating. Also, the amount of paint used increases.

When the paint of the present invention is applied to a substrate, depending on the material and surface condition of the substrate, if the paint of the present invention is applied as it is, it may be difficult to obtain adhesion and weather resistance.
If necessary, a primer layer may be previously formed on the surface of the base material before forming the applied cured film of the paint of the present invention.

The primer layer is not particularly limited, but may be a nylon resin, an alkyd resin, an epoxy resin, an acrylic resin, an organically modified silicone resin (eg, an acrylic silicone resin), a chlorinated rubber resin, a urethane resin, a phenol resin, or a polyester. A cured resin layer of an organic primer composition containing at least one organic resin selected from the group consisting of a resin and a melamine resin in a solid content of 10% by weight or more is exemplified.

Although the thickness of the primer layer is not particularly limited, it is preferably, for example, 0.1 to 50 μm, and 0.5 to 50 μm.
-10 μm is more preferred. If the thickness is too small, adhesion and weather resistance may not be obtained. If the thickness is too large, foaming may occur during drying. In addition, a substrate having at least one organic primer layer as described above on its surface is included in the category of the coated substrate. That is, the coating film on the surface of the coating substrate may be the primer layer.

The primer layer may contain a coloring agent such as a pigment or a dye for toning as required. Examples of the colorant that can be used include those described above as those that can be added to the paint. For the preferred numerical range of the amount of the coloring agent to the primer layer, as described above,
The same applies to the case of paint. However, the amount is specified not with respect to 100 parts by weight of the solid content in terms of the total condensed compound but with respect to 100 parts by weight of the total resin solid content in the total amount of the primer composition.

The present invention relates to a toilet seat having an antifouling property, in which a low surface free energy layer is formed by applying a coating containing a silicone resin or a fluororesin, and the quality (appearance (gloss / color tone)・ Transparency, etc.), surface hardness, etc.) cannot be reduced.

Hereinafter, another embodiment (film) of the low surface energy layer of the present invention will be described in detail. The film or sheet-like resin layer of the present invention has a transparent clear layer 14 mainly composed of a thermoplastic resin such as an acrylic resin, and a pattern ink layer 15 and an adhesive layer 16 sequentially formed on the transparent clear layer 14. (FIGS. 16 to 20).

The transparent clear layer 14 mainly composed of an acrylic resin, which constitutes the resin layer of the present invention, can be deformed (stretched) even at a low temperature. Excellent workability. The advantage of the excellent “workability” is that, for example, the shape of the inner surface of the cavity 70 of the injection mold 17 is a complicated shape such as irregularities having a large number of grooves or the like, Even if the resin layer is made of a transparent resin sheet mainly composed of an acrylic resin as the clear layer 14, the resin layer using the transparent resin sheet containing acrylic resin as a main component is heated or vacuum-sucked, and the injection molding die 17 is formed. The shape of the inner surface of the cavity 70 can be changed into a complicated shape or a shape with a deep rise, and an insert molded product having a surface shape similar to the shape of the inner surface of the cavity 70 of the injection molding die 17 can be obtained.

As the clear layer 14, an acrylic film made of a pure acrylic resin such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, etc., or an acrylic resin and another resin (for example, fluorine) Resin, polypropylene resin,
A film mainly composed of a copolymer with a polystyrene resin, a polyvinyl chloride resin, a polyester resin, or the like, or an acrylic film and another plastic film (for example, a fluorine film, a polypropylene film, a polyvinyl chloride film, a polyester film). the film,
Polyethylene vinyl acetate film, polycarbonate film, etc.). As a method of laminating the laminated film, there are various laminating methods such as direct lamination and a heat sealing method.

The clear layer 14 can be colored by adding a coloring agent such as a pigment or a dye as needed. The pigment that can be used is not particularly limited,
For example, organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and Hansa yellow; and inorganic pigments such as titanium oxide, barium sulfate, red iron oxide, and composite metal oxides are preferred. Species or a combination of two or more species may be used.

The dispersion of the pigment is not particularly limited, and may be a usual method, for example, a method of directly dispersing the pigment powder using a dyno meal, a paint shaker or the like. At that time, a dispersant, a dispersing aid, a thickener, a coupling agent, and the like can be used. The amount of the pigment to be added is not particularly limited because the concealing property varies depending on the type of the pigment. For example, the solid content is preferably 5 to 80 parts by weight, based on 100 parts by weight of the total solid content in terms of the total condensed compound in the total amount of the paint. Preferably 10
７０70 parts by weight. When the amount of the pigment is less than 5 parts by weight, the concealing property tends to deteriorate, and when the amount exceeds 80 parts by weight, the smoothness of the coating film may deteriorate.

The dye that can be used is not particularly limited, but examples thereof include azo, anthraquinone, indicoid, sulfide, triphenylmethane, xanthene, alizarin, acridine, quinone imine, and the like.
And thiazole, methine, nitro and nitroso dyes. One kind selected from these groups or a combination of two or more kinds may be used. The amount of the dye added is not particularly limited because the concealing property varies depending on the type of the dye.
It is 80 parts by weight, more preferably 10 to 70 parts by weight.
When the amount of the dye is less than 5 parts by weight, the concealing property tends to be deteriorated, and when it exceeds 80 parts by weight, the smoothness of the coating film may be deteriorated.

The thickness of the clear layer 14 is 10 μm
５００500 μm, but when performing integral molding by film insert, it is required to be 300 μm in order to obtain sufficient workability.
μm or less is preferred.

The pattern of the pattern ink layer 15 includes, but is not limited to, a wood grain pattern, a marble pattern, a granite pattern, letters, symbols, and numbers.

The adhesive layer 16 includes, but is not limited to, acrylic resin, urethane resin, polyester resin, polyamide resin, ethylene butyl alcohol resin, ethylene vinyl acetate copolymer, vinyl chloride / vinyl acetate copolymer, and the like. Absent.

The method for providing the resin layer of the present invention on the surface of an exposed component of a toilet seat for local cleaning, such as a toilet seat sheet, a toilet seat bottom plate, a toilet lid, a main body case, and a cleaning nozzle, is as follows. After being placed in the mold and closing the mold, the molten resin is injected into the mold, and the resin is solidified to bond the resin layer to the resin molded product.

[0200] As another manufacturing method, a sheet-like substrate prepared in advance according to the shape of a molded article and a resin layer attached thereto is arranged in a mold and injection-molded. There is a method such as attaching a resin layer to the surface of a resin molded product.

The injection molding die 17 used in the manufacturing method for providing the resin layer of the present invention on the surface of the exposed component of the toilet seat for local cleaning includes a movable die and a fixed die. When arranging the resin layer in the injection molding die, the sheet-by-sheet resin layer may be sent and arranged one by one, or a necessary portion of the long resin layer may be intermittently sent and arranged. Good. When a long resin layer is used, it is preferable to use a feeding device having a positioning mechanism so that the register between the pattern layer of the resin layer and the molding die coincides with each other. After disposing the resin layer, the resin layer is brought into close contact with the inner surface of the concave portion (cavity) of the movable mold by vacuum suction or heating.

Thereafter, the injection mold is closed to form the cavity 70 (FIG. 18). Injection port 1 provided in fixed mold
8, the molten resin 19 is injected and filled into the cavity 70,
At the same time as the resin is solidified and the resin molded article 10 is formed, a resin layer is adhered to the surface. After cooling the resin molded product 10, the mold for injection molding is opened and the resin molded product is taken out.
In this way, it is possible to obtain a toilet seat having the antifouling property having low surface free energy on the surface of the molded article of the present invention, and having high surface hardness and being resistant to scratching.

The resin used for the injection molding of the resin molded product 10 is acrylonitrile butadiene polystyrene copolymer resin (ABS), polypropylene resin (PP), polyethylene resin (PE), polyethylene terephthalate resin (PET), Butylene terephthalate resin (PB
T), polyethylene naphthalate resin, polyamide resin (PA), polyacetal resin (POM), polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer resin (PF)
EP) tetrafluoroethylene-perfluoroalkylvinyl ether copolymer resin (PFA), and the like, but are not limited thereto.

The clear layer 14 forming the resin layer of the present invention
Is a resin formed by partially hydrolyzing and polycondensing a hydrolyzable silane derivative monomer and / or an uncured siloxane polymer.

Examples of the silicone resin include silicone resins such as methylphenyl silicone resin and diphenyl silicone resin, and alkyd-modified, polyester-modified, epoxy-modified,
Modified silicone resins such as acryl-modified, phenol-modified, urethane-modified, and melamine-modified are exemplified, but not limited thereto.

The compounding ratio is preferably from 0.2 to 15 parts by weight, more preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of the paint. By blending the silicone resin, the surface energy of the resin is reduced and the antifouling performance such as water repellency is improved. However, if the blending ratio is too high, the physical properties such as mechanical strength deteriorate.

The clear layer 14 forming the resin layer of the present invention
As the fluorine resin to be contained, polytetrafluoroethylene (PTFE), perfluoroethylene propene copolymer (PFEP), perfluoroalkoxy alkane (PFA),
Polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PV
F), ethylene-tetrafluoroethylene copolymer (E
TFE), polychlorotrifluoroethylene (ECTFE),
Polytetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD) is preferred.

The compounding ratio is desirably 0.5 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the paint. By blending the fluororesin, the surface energy of the resin molded body is reduced, the contact angle with water is increased, the stain component is less likely to adhere, and the antifouling performance is increased, but if the blending ratio is too high, Physical properties such as mechanical strength are deteriorated, and properties required for the toilet seat such as other strength cannot be satisfied.

[0209] The details of the silicone resin and the antibacterial agent may be the same as those described above.

[0210]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

FIG. 1 shows a local flush toilet seat ((a); toilet seat viewed from above, (b); toilet seat viewed from the side) as an example of an embodiment of the present invention. 1 is a toilet seat sheet, 2 is a toilet lid, 3 is a main body case, 4 is a washing nozzle for washing a local part.

FIG. 2 is a cross-sectional view of a part of a toilet lid, which is a local cleaning toilet seat component as an example of the embodiment of the present invention. A substrate having a surface free energy of less than 28 dyne / cm;
A surface layer containing a silicone resin or the like is covered.

Hereinafter, description will be made with reference to FIG.

Example 1 A silicone resin having a methyl group, diluted 10-fold with heptane, was applied to the product surface of a molding die by a spray method. Using a molding die coated with the silicone resin, a toilet lid as a local cleaning toilet seat part was formed by injection molding with a PP resin.

Example 2 A fluorine resin mainly composed of polytetrafluoroethylene was applied to a product surface of a molding die by a spray method. Using a molding die coated with the fluororesin, a toilet lid as a local cleaning toilet seat part was formed by injection molding with a PP resin.

Example 3 A silicone resin having a methyl group, diluted 10-fold with heptane, was applied to the product surface of a molding die by a spray method. Using a molding die coated with the silicone resin, a toilet lid as a local cleaning toilet seat part was molded by injection molding with an ABS resin.

Comparative Example 1 Using a molding die sufficiently degreased with a solvent such as toluene and alcohols, a silicone resin and a fluororesin were not applied to the die, and PP
The toilet lid, which is a part of the toilet flush toilet seat, was molded by injection molding with resin.

Comparative Example 2 Using a molding die sufficiently degreased with a solvent such as toluene and alcohols, AB resin was applied without applying a silicone resin and a fluororesin to the die.
A toilet lid, which is a local cleaning toilet seat part, was molded by injection molding with S resin. Next, the test will be described.

(1) Contact angle of water: The water repellency of the surface of the molded article was examined based on the contact angle of water. The measurement of the contact angle was performed with a contact angle meter manufactured by Kyowa Interface Science.

(2) Tape peeling test: The adhesiveness of the molded product surface was examined by a tape peeling test. For the tape peeling test, Sumitomo 3M Mending Tape (12m wide)
m) on the surface of the test piece cut out from the molded product
The peeling force at the time of performing a 90 ° peeling at a speed of 0 cm / min was measured.

(3) Adhesion contamination test (ink juice): The adhesion of the artificial soil on the surface of the molded article was examined using a water-soluble artificial soil. Ink was used as a water-soluble artificial waste having adhesive properties.
The ink was applied to the surface of the test piece cut out from the molded article by brush coating, left in an atmosphere of 23 ° C. and 50% RH for 24 hours, and dried. Next, the surface on which the dried ink was adhered was rubbed five times with a dry cotton cloth with a load of 1 kg per 1 cm 2 of the sliding portion, and the degree of the ink removal was visually observed. The evaluation was performed by relative comparison. The case where the ink was completely removed was evaluated as ○, the case where the ink was not removed slightly was evaluated as Δ, and the case where a relatively large amount of ink could not be removed was evaluated as ×.

(4) Adhesion contamination test (scale): The adhesion of scale on the surface of the molded article was examined. Tap water was dropped on the surface of the test piece cut out from the molded product, left for 1 hour in an atmosphere of 40 ° C., and dried. The procedure of drying at 40 ° C. for 1 hour after dropping of tap water was repeated 50 times at the same location on the surface of the test piece, to attach scale to the surface of the test piece. Next, the surface on which the scale was adhered was rubbed five times with a dry cotton cloth under a load of 1 kg per 1 cm 2 of the sliding portion, and the degree of scale removal was visually observed. The evaluation was performed by relative comparison, and the case where the scale was completely removed was evaluated as 、, the case where the scale was not removed slightly was evaluated as Δ, and the case where a relatively large amount of scale could not be removed was evaluated as ×.

According to the test results shown in FIG. 3, the PP resin and the ABS resin molded by using a mold coated with a silicone resin or a fluororesin were molded by a mold not coated with a silicone resin or a fluororesin. It can be seen that the water repellency is high and the wettability is poor as compared with the PP resin and the ABS resin, respectively. Also, in the tape peeling test, the peeling force shows a small value, indicating that the adhesiveness is small. Furthermore, it can be seen that the adhesive force of the fixed dirt between the dried ink and the scale is reduced, and the ink can be removed by wiping with a dry cloth.

As described above, when the low surface free energy layer is formed by transferring the low surface free energy polymer from the mold at the same time as the injection molding of the base resin such as the PP resin or the ABS resin, the wettability is reduced. And the dirt adhesion can be reduced. It can be seen that such a surface has a strong adhesion to the substrate, such as scale stains, which has been difficult to remove in the past, and can easily remove stains that are difficult to remove.

Hereinafter, description will be made with reference to FIG.

Example 4 A silicone resin having a methyl group, diluted ten-fold with heptane, was applied to the product surface of a molding die by a spray method. Using a molding die coated with the silicone resin, a toilet lid as a local cleaning toilet seat part was formed by injection molding with a PP resin. In this example, assuming that the entire amount of the silicone resin applied to the molding die was transferred to the toilet lid molded product, the ratio of the silicone resin to the obtained molded body was 0.02% by weight.

Comparative Example 3 To a PP resin was added 2% by weight of a silicone resin having a methyl group, and the mixture was melt-mixed with a twin-screw extruder to obtain a compound resin pellet. The obtained compound resin pellets were molded in the same manner as in Comparative Example 1 to form a toilet lid as a local cleaning toilet seat part.

The test was performed by the same test method and evaluation method as in Examples 1 to 3 and Comparative Examples 1 and 2.

[0229] From the test results shown in Fig. 4, the PP resin molded by the mold coated with the silicone resin showed that a small amount of the silicone resin formed a surface layer on the surface of the base material, so that a large amount of the silicone resin was obtained. It is understood that the water repellency is high and the wettability is poor as compared with the PP resin which is added to the resin and subjected to ordinary molding. Also, in the tape peeling test, the peeling force shows a small value, indicating that the adhesiveness is small. Furthermore, it can be seen that the adhesive force of the fixed dirt between the dried ink and the scale is reduced, and the ink can be removed by wiping with a dry cloth.

As described above, when the low surface free energy polymer is transferred from the mold at the same time as the injection molding of the base resin, the low surface free energy layer is formed. Even if the surface modification effect is effectively obtained, compared to molded products with a large amount of low surface free energy polymer added, lower wettability,
The dirt adhesion can be reduced. It can be seen that such a surface has a strong adhesion to the substrate, such as scale stains, which has been difficult to remove in the past, and can easily remove stains that are difficult to remove.

Hereinafter, description will be made with reference to FIG.

Example 5 A test piece was cut out from the toilet lid obtained in Example 1, and the surface of the test piece was rubbed 100 times reciprocally with a wet cotton cloth at a load of 1 kg per square cm of the sliding portion.
The surface was dried by leaving it at room temperature for 24 hours.

Comparative Example 4 The silicone resin having a methyl group diluted 10-fold with heptane used in Example 1 was applied to the surface of the toilet lid obtained in Comparative Example 1 by a spray method. A test piece was cut out of the toilet lid coated with the silicone resin, and the surface of the test piece was rubbed 100 times reciprocally with a wet cotton cloth at a load of 1 kg per 1 cm 2 of the sliding portion.
The surface was dried by leaving it at room temperature for 24 hours.

The test was performed by the same test method and evaluation method as in Examples 1 to 3 and Comparative Examples 1 and 2.

According to the test results shown in FIG. 5, the PP resin molded by the mold coated with the silicone resin was rubbed 100 times reciprocally with a wet cotton cloth at a load of 1 kg per 1 cm 2 of the sliding portion. It shows that the water repellency is high and the wettability is poor. Also, in the tape peeling test, the peeling force shows a small value, indicating that the adhesiveness is small. Furthermore, it can be seen that the adhesive force of the fixed dirt between the dried ink and the scale is reduced, and the ink can be removed by wiping with a dry cloth.

On the other hand, even if a silicone resin is applied after molding, the surface of the toilet seat made of a normally molded PP resin is covered with a wet cotton cloth and the surface is slid with a load of 1 kg per 1 cm 2 of the sliding portion.
After rubbing 0 times, it can be seen that the water repellency is reduced, the adhesiveness of the tape is relatively large, and the adhesion of the fixed dirt between ink and scale is large.

As described above, the method of transferring the silicone resin layer from the mold to the surface of the PP resin at the same time as molding is different from the method of coating the surface of the PP resin after molding the silicone resin.
It can be seen that the durability of the surface silicone resin layer has been improved.

By transferring the resin layer having a small surface free energy from a mold at the same time as the molding of the base resin, the adhesion between the base resin surface and the surface layer of the resin having a small surface free energy can be improved by an anchor effect or the like. It can be seen that the thickness increases due to the physical adhesive force of the, and the durability improves.

In this embodiment, by transferring a resin layer having a small surface free energy from a mold at the same time as molding the base resin, the resin layer can be efficiently formed on the base resin surface. With a surface layer made of a resin having a small surface free energy, a surface having a small surface free energy can be formed regardless of the surface free energy of the substrate.

By forming a low surface free energy layer, the wettability of dirt can be reduced, and the adhesion of dirt can be reduced. Such a surface has a strong adhesion to the substrate, such as water stain, which has been difficult to remove in the past, and can easily remove stains that are difficult to remove.

In the method of coating with a resin having a small surface free energy, the adhesion between the base resin and the coating film is poor.
Although durability was a problem, the resin layer with low surface free energy was transferred from the mold at the same time as the molding of the base resin, so that the adhesion between the base resin surface and the surface layer of the resin with low surface free energy was achieved. However, the physical adhesion due to the anchor effect or the like increases, and the durability is improved.

Next, another embodiment (one in which silicone resin is described in detail) will be described.

Hereinafter, description will be made with reference to FIG. FIG. 6 shows the water repellency effect of the surface onto which the silicone resin has been transferred, as evaluated by the contact angle of water, and the ease with which dirt can be removed is evaluated by a tape peeling force, a pseudo dirt adhesion test, and a scale adhesion test.

Example 11 A methylphenylsilicone resin (containing 30% of methylphenylsiloxane with respect to 100% by weight of methylphenylsilicone resin, hereinafter referred to as silicone resin), diluted 10-fold with heptane, was placed on the product surface of a molding die. It was applied by a spray method. Using a molding die coated with the silicone resin, a toilet lid as a local cleaning toilet seat part was molded by injection molding with PP resin.

Example 12 A silicone resin diluted 10 times with heptane was applied to a product surface of a molding die by a spray method. Using a molding die coated with the silicone resin, a toilet lid as a local cleaning toilet seat part was molded by injection molding with ABS resin.

Comparative Example 11 Using a molding die sufficiently degreased with a solvent such as toluene and alcohols, a silicone resin was not applied to the die, but a local cleaning toilet seat part was formed by injection molding with PP resin. The toilet lid was molded.

Comparative Example 12 Using a molding die sufficiently degreased with a solvent such as toluene and alcohol, the silicone resin is not applied to the die, but is used as a local cleaning toilet seat part by injection molding with ABS resin. The toilet lid was molded.

Next, regarding the test, (1) water contact angle,
(2) Tape peeling test, (3) attached matter contamination test (black ink), and (4) attached matter contamination test (scale) are the same as those described above.

[0249] From the test results shown in Fig. 6, the PP resin and ABS molded using a mold coated with silicone resin were used.
It can be seen that the resin has high water repellency and poor wettability, as compared with the PP resin and the ABS resin, respectively, which were molded using a mold not coated with silicone resin. Also,
Also in the tape peeling test, the peeling force shows a small value, indicating that the adhesiveness is small. Furthermore, it can be seen that the adhesive force of the fixed dirt between the dried ink and the scale is reduced, and the ink can be removed by wiping with a dry cloth.

As described above, when the low-surface free energy layer is formed by transferring the silicone resin from the mold at the same time as the injection molding of the base resin, ie, the PP resin or the ABS resin, the wettability is reduced and the contamination is reduced. Adhesion can be reduced. It can be seen that such a surface has a strong adhesion to the substrate, such as scale stains, which has been difficult to remove in the past, and can easily remove stains that are difficult to remove.

Hereinafter, description will be made with reference to FIG. Figure 7 shows the water repellency effect of the surface to which the silicone resin has been transferred and the surface to which the silicone resin has been added, the contact angle of water, and the ease with which dirt can be removed. Evaluation of the water repellency effect of the surface due to the difference in the transferred surface area of the silicone resin with the contact angle of water, the ease with which dirt can be removed, the tape peeling force, the pseudo dirt adhesion test,
The difference in appearance due to the particle size of the silicone resin after transfer was evaluated by a scale adhesion test, and the gloss was evaluated.

Example 13 A silicone resin diluted 10-fold with heptane was applied to a product surface of a molding die by a spray method. Using a molding die coated with the silicone resin, a toilet lid as a local cleaning toilet seat part was molded by injection molding with PP resin. In this example, assuming that the entire amount of the silicone resin applied to the molding die was transferred to the molded toilet stool, the ratio of the silicone resin to the obtained molded body was 0.02% by weight. At this time, the area ratio of the silicone resin layer covering the base resin surface was 22%, the silicone resin surface layer was about 0.1 μm, and the average particle diameter of each silicone resin particle was 35 μm.

Example 14 A silicone resin diluted 10-fold with heptane was applied to a product surface of a molding die by a spray method. Using a molding die coated with the silicone resin, a toilet lid as a local cleaning toilet seat part was molded by injection molding with PP resin. In this example, assuming that the entire amount of the silicone resin applied to the molding die was transferred to the toilet lid molded product, the ratio of the silicone resin to the obtained molded body was 0.01% by weight. At this time, the area ratio of the silicone resin layer covering the surface of the base resin was 10%, the silicone resin surface layer was about 0.2 μm, the particle diameter of the concave portion, and the average particle diameter of each particle of the silicone resin were 35 μm. .

Comparative Example 13 A silicone resin diluted 10-fold with heptane was applied to a product surface of a molding die by a spray method. Using a molding die coated with the silicone resin, a toilet lid as a local cleaning toilet seat part was molded by injection molding with PP resin. In the present example, assuming that the entire amount of the silicone resin applied to the molding die was transferred to the molded toilet stool, the ratio of the silicone resin to the obtained molded body was 0.004% by weight. At this time, the area ratio of the silicone resin layer covering the base resin surface was 3%, the silicone resin surface layer was about 0.2 μm, and the average particle size of each particle of the silicone resin was 33 μm.

Comparative Example 14 A silicone resin diluted 10-fold with heptane was applied to a product surface of a molding die by a spray method. Using a molding die coated with the silicone resin, a toilet lid as a local cleaning toilet seat part was molded by injection molding with PP resin. In this example, assuming that the entire amount of the silicone resin applied to the molding die was transferred to the toilet lid molded product, the ratio of the silicone resin to the obtained molded body was 0.025% by weight. At this time, the ratio of the area of the silicone resin layer covering the surface of the base resin was 19%, the surface layer of the silicone resin layer was 15 μm or more, and the average particle size of each particle of the silicone resin was 98 μm.

Comparative Example 15 A toilet lid as a local cleaning toilet seat part was molded in the same manner as in Comparative Example 1 by mixing 2% by weight of silicone resin with PP resin.

In the test, in addition to the same test method and evaluation method as in Examples 11 to 12 and Comparative Examples 11 to 12, gloss was measured using a gloss meter.

[0258] From the test results shown in Fig. 7, the PP resin molded by the mold coated with the silicone resin showed that a small amount of the silicone resin formed a surface layer on the base material surface, so that a large amount of the silicone resin was obtained. It is understood that the water repellency is high and the wettability is poor as compared with the PP resin which is added to the resin and subjected to ordinary molding. Also, in the tape peeling test, the peeling force shows a small value, indicating that the adhesiveness is small. Furthermore, it can be seen that the adhesive force of the fixed dirt between the dried ink and the scale is reduced, and the ink can be removed by wiping with a dry cloth.

As described above, when the low surface free energy layer is formed by transferring the silicone resin from the mold at the same time as the injection molding of the base resin, even if the amount of the silicone resin is very small, it can be effectively formed. A surface modification effect can be obtained, and the wettability can be reduced and the adhesion of dirt can be reduced as compared with a molded product to which a large amount of silicone resin is added. It can be seen that such a surface has a strong adhesion to the substrate, such as scale stains, which has been difficult to remove in the past, and can easily remove stains that are difficult to remove.

Here, the silicone resin layer covering the surface of the base resin means 0.01 mg / cm ² or more, and the ratio of the area of the silicone resin layer to the surface of the molded article is 1%.
Even at about 0%, excellent antifouling properties are exhibited. Also,
When the silicone resin after transfer has a surface layer of 20 μm or more and an average particle size of 50 μm or more, excellent antifouling properties are exhibited even with a very small amount of application, but the defect such as glossiness becomes poor. It can be seen that

Hereinafter, description will be made with reference to FIG. FIG. 8 shows the difference between the antifouling property and the antibacterial property according to the ratio of the surface onto which the silicone resin has been transferred and the ratio thereof, using a base resin mixed with an antibacterial agent, and evaluated by antifouling tests and antibacterial tests.

Example 15 A silicone resin diluted 10-fold with heptane was applied to a product surface of a molding die by a spray method. Using a molding die coated with the silicone resin, a toilet lid as a local cleaning toilet seat part was molded by injection molding with PP resin. The PP resin contains 0.5 part by weight of silver zeolite as an antibacterial agent. Further, in this example, assuming that the entire amount of the silicone resin applied to the molding die was transferred to the toilet lid molded product, the ratio of the silicone resin to the obtained molded body was 0.02% by weight. At this time, the area ratio of the silicone resin layer covering the base resin surface was 22%, the silicone resin surface layer was about 0.2 μm, and the average particle diameter of each particle of the silicone resin was 35 μm.

Comparative Example 16 A silicone resin diluted 10 times with heptane was applied to the product surface of a molding die by a spray method. Using a molding die coated with the silicone resin, a toilet lid as a local cleaning toilet seat part was molded by injection molding with PP resin. The PP resin contains 0.5 part by weight of silver zeolite as an antibacterial agent. Further, in this example, assuming that the entire amount of the silicone resin applied to the molding die was transferred to the molded toilet stool, the ratio of the silicone resin to the obtained molded body was 0.1% by weight. At this time, the area ratio of the silicone resin layer covering the base resin surface was 95%.

Comparative Example 17 Using a molding die sufficiently degreased with a solvent such as toluene and alcohol, a silicone resin is not applied to the die, but is a local cleaning toilet seat part by injection molding with PP resin. The toilet lid was molded.
The PP resin had silver zeolite 0.1 as an antibacterial agent.
5 parts by weight are blended.

In the test, in addition to the same test methods and evaluation methods as in Examples 11 to 12 and Comparative Examples 11 to 12, evaluation of antibacterial properties was performed. The antibacterial test was also performed on the sample of Comparative Example 1 here.

Next, evaluation of antibacterial properties will be described.

The antibacterial property is described in “Antibacterial test or antibacterial activity of constituents” described in “Voluntary Standards and Antibacterial Test Methods for Silver and Other Inorganic Antibacterial Agents (1995 edition)” issued by the Research Group for Inorganic Antibacterial Agents such as Silver. The antibacterial properties of Escherichia coli and Staphylococcus aureus were evaluated according to “Test method I”. The inoculum was 0.5 ml, the suspension was 1/500 NB, and the storage temperature was 35 ° C.
Film used: 4.5 cm x 4.5 cm square, Recovery liquid: SC
Performed with 10 ml of DLP.

From the test results shown in FIG. 8, according to the present example, it is possible to impart antifouling properties without deteriorating the performance and quality of the base resin, such as the antibacterial performance of the base resin. . From this, in this example, the amount of the antibacterial agent and the like contained in the base resin varies the area of the silicone resin layer covering the base resin that does not impair the performance of the base resin. It was found that it was possible to adjust the optimal amount of silicone resin that exerted antifouling properties without impairing the performance of the base resin. .

Hereinafter, description will be made with reference to FIG. FIG. 9 shows the surface on which the silicone resin has been transferred and the surface on which the silicone resin has been molded and spray-coated after wiping with water for a comparison of durability. Was evaluated by a tape peeling force, a pseudo-dirt adhesion test, and a scale adhesion test.

Example 16 A test piece was cut out from the toilet lid obtained in Example 11, and the surface of the test piece was rubbed 100 times reciprocally with a wet cotton cloth at a load of 1 kg per 1 cm 2 of the sliding portion. To dry the surface.

Comparative Example 18 The same procedure as in Example 11 was carried out.
The silicone resin diluted 10-fold with heptane was applied to the toilet lid surface obtained in Comparative Example 1 by a spray method. A test piece was cut out from the toilet lid coated with the silicone resin, and the surface of the test piece was rubbed 100 times reciprocally with a wet cotton cloth at a load of 1 kg per 1 cm 2 of the sliding portion, and then left at room temperature for 24 hours to dry the surface. Was done.

The test was performed by the same test method and evaluation method as in Examples 11 to 12 and Comparative Examples 11 to 12.

According to the test results shown in FIG. 9, the PP resin molded by the mold coated with the silicone resin was rubbed 100 times with a wet cotton cloth on the surface thereof with a load of 1 kg per 1 cm 2 of the sliding portion. It shows that the water repellency is high and the wettability is poor. Also, in the tape peeling test, the peeling force shows a small value, indicating that the adhesiveness is small. Furthermore, it can be seen that the adhesive force of the fixed dirt between the dried ink and the scale is reduced, and the ink can be removed by wiping with a dry cloth.

On the other hand, even if a silicone resin is applied after molding, the surface of a normally molded PP resin toilet lid is covered with a wet cotton cloth, and the surface is slid with a load of 1 kg per 1 cm 2 of sliding portion.
It can be seen that after rubbing back and forth 00 times, the water repellency is reduced, the adhesiveness of the tape is relatively large, and the adhesion of the fixed dirt between ink and scale is large.

As described above, the method of transferring the silicone resin layer from the mold to the surface of the PP resin at the same time as molding is more durable than the method of coating the surface of the PP resin after molding the silicone resin. You can see that it is doing.

By transferring the resin layer having a small surface free energy from a mold at the same time as the molding of the base resin, the adhesion between the base resin surface and the surface layer of the resin having a small surface free energy can be improved by the anchor effect, It can be seen that the strength increases due to physical adhesion due to curing or the like at the time of molding the base resin, and the durability is improved.

6 to 9 that the structure of the present invention has excellent antifouling properties, and is therefore extremely excellent as a material for toilet seats.

Although the molded articles of the above Examples and Comparative Examples were toilet covers, similar results can be obtained with toilet seat sheets, main body cases, or washing nozzles.

[0279] Various additives can be appropriately added to the base resin to the extent that the effects of the invention are not impaired. Examples include plasticizers, internal mold release agents, hydrolysis inhibitors, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, flame retardants, foaming agents, inorganic pigments, organic pigments, and the like.

As described above, according to the toilet seat of this embodiment, the following effects can be obtained.

In this embodiment, the silicone resin layer having a small surface free energy can be efficiently formed on the surface of the base resin by transferring it from the mold at the same time as the formation of the base resin. With the surface layer made of the silicone resin, a surface having a small surface free energy can be formed regardless of the surface free energy of the substrate.

By forming the low surface free energy layer, the wettability of dirt can be reduced, and the adhesion of dirt can be reduced. Such a surface has a strong adhesion to the substrate, such as urine and scale stains, which were difficult to remove conventionally, and can easily remove difficult-to-remove stains, and has excellent antifouling properties. Toilet seat can be provided.

In the method of coating with a silicone resin having a small surface free energy, the adhesion between the base resin and the coating film is poor and the durability is problematic. By transferring from the mold at the same time as molding, the adhesion between the base resin surface and the surface layer of the resin with low surface free energy is increased by the anchor effect, physical adhesion due to curing during molding of the base resin, etc. Become
The durability is improved.

Further, since antifouling properties can be imparted without impairing the performance and quality of the base resin, such as the antibacterial properties of the base resin,
With both the performance of the base resin and the antifouling property with excellent durability,
A toilet seat with excellent antifouling properties can be provided.

Subsequently, another example (with a silicone resin applied) will be described.

Hereinafter, description will be made with reference to FIG. FIG. 10 shows the water repellency of water-repellent effect of the surface coated with silicone resin after corona discharge treatment, the surface coated with silicone resin after plasma discharge treatment, and the surface coated with silicone resin without discharge treatment. , Easy to remove adhesion stains, tape peeling force, adhesion soil test (ink soup, scale)
In the evaluation, the ease of removal of dirt after actual use was evaluated by a durability test, and the difference in appearance due to the ratio of the area of the silicone resin layer covering the surface of the base resin after application and the particle size were evaluated by appearance.

Example 21 A base resin of a toilet lid as a local cleaning toilet seat part by injection molding is a PP resin, and a corona discharge treatment is applied to the surface of the resin, and a methylphenylsilicone resin diluted 10-fold with heptane is used. (Contains 30% of methylphenylsiloxane with respect to 100% by weight of methylphenylsilicone resin ... hereinafter referred to as silicone resin)
However, the maximum particle size is 12% with respect to the entire base resin surface, and the maximum particle size is 80.
It was applied by a spray method so as to have a thickness of μm.

Example 22 The base resin of the toilet lid, which is a part of the toilet seat for local cleaning by injection molding, is a PP resin. After subjecting the surface to plasma discharge treatment, a silicone resin diluted 10-fold with heptane is used. The coating was performed by a spray method so that the maximum particle size was 12 μm with respect to the entire surface of the base resin and the maximum particle size was 80 μm.

Comparative Example 21 The base resin of the toilet lid, which is a local cleaning toilet seat part by injection molding, was PP resin, and the surface thereof was not subjected to corona discharge treatment, and a silicone resin diluted 10-fold with heptane was used as the base resin. 1 for the entire resin surface
It was applied by a spray method so that the maximum particle size was 2 μm and the maximum particle size was 80 μm.

Comparative Example 22 The base resin of the toilet lid, which is a local cleaning toilet seat part by injection molding, is a PP resin. After subjecting the surface to corona discharge treatment, a silicone resin diluted 10-fold with heptane is used. The composition was applied by a spray method so that the maximum particle diameter became 12 μm with respect to the entire base resin surface.

Comparative Example 23 The base resin of the toilet lid, which is a local cleaning toilet seat component by injection molding, is a PP resin. After subjecting the surface to corona discharge treatment, a silicone resin diluted 10-fold with heptane is used. The coating was performed by a spray method so that the maximum particle diameter was 24 μm with respect to the entire base resin surface and the maximum particle size was 80 μm.

Comparative Example 24 A base resin of a toilet lid which is a local cleaning toilet seat part by injection molding is a PP resin. After subjecting the surface to corona discharge treatment, a silicone resin diluted 10-fold with heptane is used. It was applied by a spray method so that the maximum particle size was 12 μm and the maximum particle size was 50 μm with respect to the entire surface of the base resin.

Comparative Example 25 The base resin of the toilet lid, which is a local cleaning toilet seat part by injection molding, is a PP resin. After subjecting the surface to plasma discharge treatment, a silicone resin diluted 10-fold with heptane is used. The coating was performed by a spray method so that the maximum particle diameter was 24 μm with respect to the entire base resin surface and the maximum particle size was 80 μm.

Comparative Example 26 The base resin of the toilet lid, which is a local cleaning toilet seat part by injection molding, is a PP resin. After subjecting the surface to plasma discharge treatment, a silicone resin diluted 10-fold with heptane is used. It was applied by a spray method so that the maximum particle size was 12 μm and the maximum particle size was 50 μm with respect to the entire surface of the base resin.

Next, regarding the test, (1) the contact angle of water,
(2) Tape peeling test, (3) attached matter contamination test (black ink), and (4) attached matter contamination test (scale) are the same as those described above.

(5) Durability test: The degree of adhesion of the silicone resin to the surface of the molded product was examined. The surface of the test piece cut out from the molded product was rubbed 4000 times with a cotton cloth soaked in tap water at a load of 60 g per 1 cm 2, then dipped for 5 s in pseudo-filament (oil-based), and then pulled up after 60 s Was visually inspected for the repellency of the pseudo-filth. The evaluation was evaluated as ○ when completely repelled the simulated waste, △ when almost half of the filth was repelled, and x when not completely repelled.

(6) Appearance: Appearance of the surface of the molded product was visually observed. In the evaluation, the level at which the applied silicone resin was inconspicuous was evaluated as ○, the level at which the applied silicone resin was slightly noticeable was Δ, and the level at which the applied silicone resin was noticeable and had no gloss was evaluated as ×.

From the test results shown in FIG. 10, the low surface free energy layer formed by applying a discharge treatment to the surface of the base resin and applying a silicone resin has reduced wettability and reduced adhesion of dirt. It can be seen that the durability is maintained by the effect of the discharge treatment. When the ratio of the area of the silicone resin layer covering the base resin surface is 12% and the maximum particle size of the silicone resin is 80 μm, the appearance of the surface of the molded product is good. With such a surface, the adhesion to the substrate, such as scale stains, which has been difficult to remove in the past, is strong, and the stains that are difficult to remove can be easily removed and the effect can be maintained. confirmed.

Hereinafter, description will be made with reference to FIG. FIG. 11 shows the results of evaluating the difference between the antifouling property and the antibacterial property according to the surface coated with the silicone resin and the proportion thereof using a base resin mixed with an antibacterial agent in an antifouling test and an antibacterial test.

Example 23 The base resin of the toilet lid, which is a local cleaning toilet seat part by injection molding, is a PP resin. After subjecting the surface to corona discharge treatment, the methylphenyl silicone resin diluted 10-fold with heptanes (Contains 30% of methylphenylsiloxane with respect to 100% by weight of methylphenylsilicone resin ... hereinafter referred to as silicone resin)
However, the maximum particle size is 12% with respect to the entire base resin surface, and the maximum particle size is 80.
It was applied by a spray method so as to have a thickness of μm. The PP resin contains 0.5 part by weight of silver zeolite as an antibacterial agent.

Comparative Example 27 The base resin of the toilet lid, which is a local cleaning toilet seat component by injection molding, is PP resin. After subjecting the surface to corona discharge treatment, the silicone resin diluted 10-fold with heptane was used. The composition was applied by a spray method so as to be 90% of the entire surface of the base resin. The PP resin had a silver zeolite of 0.5 as an antibacterial agent.
Contains parts by weight.

Comparative Example 28 The base resin of the toilet lid, which is a part of a toilet flush toilet seat part, was PP resin by injection molding, and 0.5 part by weight of silver zeolite was blended as an antibacterial agent. In the test, in addition to the same test methods and evaluation methods as in Examples 21 to 22 and Comparative Examples 21 to 26, evaluation of antibacterial properties was performed. The antibacterial test was also performed on the sample of Comparative Example 1 here.

Next, evaluation of antibacterial properties will be described. The test is as described above.

From the test results shown in FIG. 11, it can be seen that according to this example, the antifouling property can be imparted without deteriorating the performance and quality of the base resin such as the antibacterial performance of the base resin. From this, in this example, the amount of the antibacterial agent and the like contained in the base resin varies the area of the silicone resin layer covering the base resin that does not impair the performance of the base resin. As a result, it was found that the optimum amount of silicone resin to be applied to exhibit the antifouling property can be adjusted without impairing the performance of the base resin.

As described above, from FIGS. 10 and 11, it was found that the configuration of this embodiment is excellent as a material for toilet seats because of its excellent antifouling property.

Although the molded articles of the above Examples and Comparative Examples were toilet covers, similar results can be obtained with toilet seat sheets, main body cases, or washing nozzles.

[0307] Various additives can be appropriately added to the base resin to the extent that the effects of the present invention are not impaired. Examples include plasticizers, internal mold release agents, hydrolysis inhibitors, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, flame retardants, foaming agents, inorganic pigments, organic pigments, and the like.

As described above, according to the toilet seat of this embodiment, the following effects can be obtained.

In this embodiment, after a predetermined surface treatment is performed on the surface of the base resin, a silicone resin layer having a small surface free energy is applied, whereby the base resin surface can be efficiently formed. The silicone resin layer has good adhesion, and a surface layer made of a very small amount of silicone resin can form a surface having a small surface free energy regardless of the surface free energy of the substrate.

[0310] By forming the low surface free energy layer, the wettability of dirt can be reduced, and the adhesion of dirt can be reduced. Such a surface has a strong adhesion to the substrate, such as urine and scale stains, which were difficult to remove conventionally, and can easily remove difficult-to-remove stains, and has excellent antifouling properties. Toilet seat can be provided.

In the method of coating with a silicone resin resin having a small surface free energy, the adhesion between the base resin and the coating film is poor and the durability is problematic. However, the surface of the base resin is subjected to discharge treatment. As a result, a functional group is formed, and the adhesiveness between the surface of the base resin and the surface layer of the resin having a small surface free energy is increased by chemical adhesion, thereby improving the durability.

Further, since the antifouling property can be imparted without impairing the performance and quality of the base resin, such as the antibacterial property of the base resin,
Antifouling with excellent performance and durability of base resin. Next, another example (coated with silicone resin) is shown.

FIG. 12 is a sectional view of a part of a cleaning nozzle for cleaning a local part, which is a local cleaning toilet seat component as an example of the embodiment of the present invention. The surface of the base material is covered with a surface layer of a paint containing silicone resin.

Hereinafter, description will be made with reference to FIG.

Example 31 A base resin of a cleaning nozzle which is a local cleaning toilet seat part by injection molding is an ABS resin.
An acrylic urethane-based resin coating containing a silicone resin was applied to the surface by a spray method.

Comparative Example 31 In Example 1, an acrylic urethane resin paint containing no silicone resin was applied by a spray method.

Comparative Example 32 In Example 1, nothing was applied.

The antifouling performance of the thus obtained washing nozzle was evaluated by the following method. <Evaluation method> (1) Contact angle of water: The water repellency of the surface of the molded article was examined by the contact angle of water. The measurement of the contact angle was performed with a contact angle meter manufactured by Kyowa Interface Science.

(2) Oil contact angle: The oil repellency of the surface of the molded article was examined based on the oil contact angle. The measurement of the contact angle was performed with a contact angle meter manufactured by Kyowa Interface Science.

(3) Pseudo-fouling adhesion test (miso): Adhesion of pseudo-fouling on the surface of the molded article was examined using the pseudo-fouling. Miso was used as a pseudo-filt with adhesive properties. The miso was attached to the surface of the cleaning nozzle, and the degree of the drop was visually confirmed by a self-cleaning mechanism. Evaluation is performed by relative comparison,
The case where the miso was completely removed was rated as ○, the case where the miso was not removed a little was rated as △, and the case where a relatively large amount was not removed was rated as x.

According to the test results shown in FIG. 13, by applying a coating containing a silicone resin to the surface of the base resin, the formed low surface free energy layer has reduced wettability and reduced dirt adhesion. It was confirmed that it would be.

Although the molded articles of the above Examples and Comparative Examples were cleaning nozzles, similar results can be obtained with toilet seat sheets, toilet lids, or main body cases.

In this embodiment, the surface of the base resin is coated with a coating material containing a silicone resin having a small surface free energy, so that the coating surface layer containing the silicone resin can be used regardless of the surface free energy of the base material. A surface with small free energy can be formed.

By forming a low surface free energy layer, the wettability of dirt can be reduced, and the adhesion of dirt can be reduced. With such a surface, dirt that is difficult to remove can be easily removed, and a toilet seat with excellent antifouling properties can be provided.

Next, another embodiment (using a film) will be described. FIG. 14 is a perspective view showing a toilet device provided with a local cleaning toilet seat composed of exposed components of the toilet seat when the resin layer of the present invention is manufactured by film insert molding.

In FIG. 14, a main body case 12 of a local cleaning toilet seat is fixed on the upper surface of the toilet body 11, and a toilet seat 12a and a toilet lid 12b are attached to the main body case 12 so as to be openable and closable. A nozzle device for local cleaning, a hot water supply piping system, a hot air drying device for drying after cleaning, and the like are housed inside the main body case 12, and each functional unit is integrated with the main body case 12. This is performed by the board 12c.

FIG. 15 is a perspective view showing another embodiment of a toilet apparatus provided with a local flush toilet seat integrated with a low tank of a toilet.

The exposed components of the toilet seat for local cleaning provided with the resin layer of the present invention include: 12 main body case, 12a toilet seat, 1
2b toilet lid, 13a nozzle rod, 13b nozzle head,
It is a main body case with a built-in 13c low tank, a 12c operation panel, and the like.

The clear layer 14 of the resin layer is composed of 3 parts by weight of silicone resin with respect to 100 parts by weight of the sheet base resin,
A resin binder consisting of a polyvinyl chloride resin under a clear layer, using a 200 μm thick methyl methacrylate film in which 1 part by weight of an inorganic antibacterial agent zeolite is dispersed with respect to 100 parts by weight of a sheet base resin. And a brown pigment were formed by a gravure printing method. An adhesive layer made of vinyl chloride-vinyl acetate copolymer resin was formed on the base of the pattern ink layer by a gravure printing method to obtain a wood-patterned acrylic resin layer.

The wood-grained acrylic resin layer obtained as described above is placed in a mold for injection molding comprising a movable mold and a fixed mold for manufacturing a toilet seat, and the resin layer is heated at 90 ° C. Vacuum suction was applied to the movable mold so that it was in close contact with the concave part of the movable mold. After closing the mold, maintain the mold temperature at
A molten resin made of an acrylonitrile butadiene polystyrene copolymer resin heated to 30 ° C. to 250 ° C. was injected into a mold, and after the resin was solidified, a part was trimmed to obtain a molded product.

The exposed components of the toilet seat and the toilet seat for local cleaning according to the present embodiment are obtained by providing a resin layer having a clear layer having not only antifouling property such as water repellency but also antibacterial property on the surface of the resin molded product. It is possible to have both good antifouling properties and antibacterial properties without lowering the mechanical strength of the resin molded product. Further, by providing the design ink layer 15 and the adhesive layer 16 on the back surface of the clear layer 14 by making the clear layer 14 of the resin layer transparent, the toilet seat, the toilet lid and the toilet seat for local cleaning can be used without impairing the antifouling property and the antibacterial property. The design can also be applied to the cubic surface of the exposed component. Further, since the material colors of the exposed components of the toilet seat and the toilet seat for local cleaning do not appear in the appearance, a material of an arbitrary color such as a recycled material can be used.

[Brief description of the drawings]

FIG. 1 is an external view of a local cleaning toilet seat showing an example of an embodiment of the present invention ((a); a view of the toilet seat from above,
(B): View of the toilet seat from the side)

FIG. 2 is a sectional view of a part of a toilet lid which is a local cleaning toilet seat part showing an example of an embodiment of the present invention.

FIG. 3 shows the water repellency effect of the surface to which the surface-modified resin was transferred was evaluated by the contact angle of water, and the ease of removal of the adhered dirt was evaluated by a tape peeling force, a pseudo-dirt adhesion test, and a scale adhesion test. Things.

FIG. 4 shows the water repellency effect of the surface to which the surface-modified resin has been transferred and the surface to which the surface-modified resin has been added by the contact angle of water; It was evaluated by a pseudo-dirt adhesion test and a scale adhesion test.

FIG. 5 is a graph showing the effect of water repellency on the surface on which the surface-modified resin is transferred and the surface on which the surface-modified resin is formed by spray coating after molding. The ease of removal of the adhered dirt was evaluated by a tape peeling force, a pseudo dirt adhesion test, and a scale adhesion test.

FIG. 6 is a graph showing the water repellency effect of the surface onto which the silicone resin has been transferred, evaluated by the contact angle of water, and the ease with which dirt can be removed by tape peeling force, pseudo-fouling test, and scale test. is there.

FIG. 7 is a graph showing the water repellency effect of the surface to which the silicone resin has been transferred and the surface to which the silicone resin has been added, the contact angle of water; Evaluated by a scale test, the effect of water repellency on the surface due to the difference in the transferred surface area of the silicone resin is determined by the contact angle of water.
The evaluation was made by a pseudo-dirt adhesion test and a scale adhesion test, and the difference in appearance due to the particle size of the silicone resin after transfer was evaluated by glossiness.

FIG. 8 is a graph showing the results obtained by using a base resin mixed with an antibacterial agent to evaluate the difference between the antifouling property and the antibacterial property depending on the surface to which the silicone resin has been transferred and the ratio thereof by antifouling tests and antibacterial tests. .

FIG. 9 is a diagram showing the relationship between the water-repellent effect and the water-repellent effect obtained by wiping the surface onto which the silicone resin has been transferred and the surface onto which the silicone resin has been molded and spray-painted for comparison of durability. The ease of removal was evaluated by a tape peeling force, a pseudo-dirt adhesion test, and a scale adhesion test.

FIG. 10 shows the water repellency of the surface coated with silicone resin after corona discharge treatment, the surface coated with silicone resin after plasma discharge treatment, and the surface coated with silicone resin without discharge treatment, by the contact angle of water. Evaluation, Ease of removal of adhered dirt evaluated by tape peeling force, Adhesive dirt test (ink soup, scale), Ease of soil removal after actual use evaluated by endurance test, Density and particle size of silicone resin after application The difference in appearance was evaluated in terms of gloss and appearance.

FIG. 11 shows the results of evaluating the difference between the antifouling property and the antibacterial property by the antifouling test and the antibacterial test using the base resin mixed with the antibacterial agent and the surface to which the silicone resin was transferred and the ratio thereof.

FIG. 12 is a cross-sectional view of a part of a cleaning nozzle which is a local cleaning toilet seat part showing an example of an embodiment of the present invention.

FIG. 13 shows the antifouling effect of the surface coated with a paint containing silicone resin on the surface of the base resin, the surface coated with a paint containing no silicone resin, and the surface not coated with anything. Are evaluated by a contact angle of, and the easiness of removing adhered dirt is evaluated by a pseudo-filtration adhesion test (miso).

FIG. 14 is a perspective view of a toilet apparatus equipped with a local cleaning toilet seat composed of exposed components of the present invention.

FIG. 15 is a perspective view showing a toilet device provided with a local flush toilet seat integrated with a low tank of the toilet.

FIG. 16 shows a production process in the case where the film-like or sheet-like resin layer of the present invention is produced by film insert molding.

FIG. 17 is a sectional view showing one embodiment of a toilet seat of the present invention in which a film-like or sheet-like resin layer is manufactured by film insert molding.

FIG. 18 is a cross-sectional view showing one of the manufacturing steps in the case of manufacturing a toilet seat having a film-like or sheet-like resin layer of the present invention by film insert molding.

FIG. 19 is a cross-sectional view showing one of manufacturing steps in the case of manufacturing a toilet seat having a film-like or sheet-like resin layer of the present invention by film insert molding.

FIG. 20 is a cross-sectional view showing a film insert molded product when a toilet seat having a film-like or sheet-like resin layer of the present invention is manufactured by film insert molding.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Toilet seat sheet, 2 ... Toilet lid, 3 ... Body case, 4 ... Cleaning nozzle, 5 ... Operation part, 10 ... Resin molding, 11 ... Toilet bowl,
12: body case, 12a: toilet seat, 12b: toilet lid, 12
c: operation panel, 13a: nozzle rod, 13b: nozzle head, 13c: body case with built-in low tank, 14: clear layer, 15: pattern ink layer, 16: adhesive layer, 17 ...
Injection molding die, 18 ... injection port, 19 ... molten resin

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 11-173314 (32) Priority date June 18, 1999 (June 18, 1999) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. Hei 11-203962 (32) Priority date July 16, 1999 (July 16, 1999) (33) Priority claim country Japan (JP) (31) Priority claim number (32) Priority date August 24, 1999 (August 24, 1999) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. Hei 11-237642 ( 32) Priority Date August 24, 1999 (Aug. 24, 1999) (33) Priority Country Japan (JP) (72) Inventor Minoru Furukoji 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Prefecture No. 72 Totoki Equipment Co., Ltd. Inventor Hiroyuki Togawa 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Prefecture Person Koji Shozuzawa 2-1, 1-1 Nakajima, Kokurakita-ku, Kitakyushu City, Fukuoka Prefecture (72) Inventor Hiroki Fujimura 2-1-1, Nakajima, Kokurakita-ku, Kitakyushu City, Fukuoka Totoki Equipment Co., Ltd. (72) Inventor Koji Kikusui 2-1-1, Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka F-term (reference) in Totoki Kiki Co., Ltd. GB90 JB20B JL06 YY00A YY00B

Claims (43)

[Claims] 1. A thermoplastic material having a low surface free energy layer formed on a surface of a base resin by using a low surface free energy polymer, and having a surface free energy lower than that of the base resin surface. Resin molding. 2. The thermoplastic resin molded article according to claim 1, which is at least one component of a toilet seat such as a toilet seat sheet or a toilet lid. 3. The thermoplastic resin article according to claim 1, wherein the thermoplastic resin article is at least one of components of a local cleaning toilet seat such as a toilet seat sheet, a toilet lid, and a main body case. 4. The thermoplastic resin molded article according to claim 1, which is a member used in a toilet, a bathroom or a lavatory, such as a counter, a basin ball, and a hand-washing ball, which are used around water. Plastic molded article. 5. The thermoplastic resin molded article according to claim 1, wherein the low surface free energy polymer according to claim 1 is a silicone resin. 6. The thermoplastic resin molded article according to claim 1, wherein the low surface free energy polymer according to claim 1 is a fluororesin. 7. A surface free energy of 28 dyne /
The surface free energy is 10 dyne / cm or more and 28 dyn on the surface of the base resin having a size of not less than 45 cm
A resin molded article characterized in that a low surface free energy layer is formed from a low surface free energy composition of less than e / cm, and the surface has a surface free energy lower than that of the base resin surface. 8. In forming a low surface free energy layer, a step of applying a low surface free energy polymer to the surface of a mold, a step of casting a base resin, and a step of molding the base resin with the mold. At the same time, a method for producing a resin molded article, comprising a step of transferring a low surface free energy polymer from a mold to a substrate resin surface to form a low surface free energy layer on the substrate resin surface. 9. A low surface which is at least one member of a constituent material of an exposed component of a toilet seat such as a toilet seat sheet, a toilet lid, and a main body case, the surface of which is lower than a base resin surface of the member by a silicone resin. An antifouling toilet seat characterized by forming a free energy layer. 10. At least one member of a constituent material of an exposed component of a toilet seat for local washing such as a toilet seat sheet, a toilet lid, a main body case, a washing nozzle, and a base resin of the member made of a silicone resin on the surface thereof. A toilet seat for local cleaning with antifouling properties, wherein a low surface free energy layer lower than the surface is formed. 11. The toilet seat with antifouling properties according to claim 9, wherein a resin having a surface free energy of 28 dyne / cm or more and less than 45 dyne / cm is used as the base resin. 12. The silicone resin according to claim 9, wherein the silicone resin comprises free silicone.
A toilet seat having the described antifouling property. 13. The antifouling toilet seat according to claim 12, wherein the free silicone is contained in an amount of 5 wt% to 80 wt% in 100 wt% of the silicone resin. 14. An antifouling toilet seat according to claim 9, wherein an antibacterial agent is blended in the base resin. As claimed in claim 15, wherein the silicone _{^{resin, R 1 p Si (OR 2}} ) q O (4-pq) / 2 or _{^{R 1 p Si (ONR 2)}} q O (4-pq) / 2 R 1; organic group , R ² ; a hydrogen group or an organic group; a silicone represented by the following formula: 0 <p <2, 0 ≦ q <4, 0 <p + q <4; Toilet seat with. 16. A step of applying a silicone resin to the surface of a molding die, a step of casting a base resin, molding the base resin with the molding die, and transferring the silicone resin from the molding die to the surface of the base resin. A method of forming a low surface free energy layer on the surface of the base resin by performing the method. 17. A step of applying a silicone resin to the surface of a mold, a step of casting a base resin, a step of molding the base resin with the mold, and a step of applying the silicone resin from the mold to the surface of the base resin. A method of forming a low surface free energy layer on the surface of a base resin by transferring to a surface of a base resin. 18. In the step of applying a silicone resin to the surface of the mold, the silicone resin is applied so that the average particle size after transfer is 50 μm or less, and the resin covers the base resin surface. 2. A resin layer having an area ratio of 5% or more.
18. The method for producing a toilet seat excellent in antifouling property according to 6 or 17. 19. The method according to claim 18, wherein the silicone resin is dispersedly applied. 20. A silicone resin applied to the surface of a molding die, which is transferred to a molded article so as to form a thin low surface free energy layer having a thickness of 0.02 to 10.00 μm, and covers a surface of a base resin. The method according to claim 16 or 17, wherein the ratio of the area of the layer is 5% or more. 21. The antifouling property according to claim 16, wherein the layer transferred to the surface of the molded article has a concave portion therein, and the concave portion contains the free silicone. Toilet seat and method of manufacturing the same. 22. The method according to claim 16, wherein the amount of the silicone resin to be applied is 0.01 mg / cm ² or more. As claimed in claim 23, wherein the silicone _{^{resin, R 1 p Si (OR 2}} ) q O (4-pq) / 2 or _{^{R 1 p Si (ONR 2)}} q O (4-pq) / 2 R 1; organic group , R ² ; a hydrogen group or an organic group 0 <p <2, 0 ≦ q <4, 0 <p + q ≦ 4, wherein a silicone represented by the following formula is used. The manufacturing method of the toilet seat provided with. 24. A blasting treatment, a chemical treatment, a degreasing, a flame treatment, at least one member of a constituent material of an exposed component of a toilet seat such as a toilet seat sheet, a toilet seat bottom plate, a toilet lid, and a main body case.
After applying surface treatments such as oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, and ion treatment, the silicone resin is applied and adhered.
A toilet seat with antifouling properties, characterized in that a low surface free energy layer lower than the base resin surface of the member is formed. 25. A blasting treatment, a chemical treatment, a degreasing, a flame treatment, an oxidation, etc., at least one of the constituent materials of exposed components of a local cleaning toilet seat such as a toilet seat sheet, a toilet seat bottom plate, a toilet lid, a main body case, and a cleaning nozzle. After applying surface treatment such as treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment, etc., applying and attaching silicone resin, low surface free energy lower than the base resin surface of the member A toilet seat for local cleaning having an antifouling property, wherein a layer is formed. 26. The antifouling toilet seat according to claim 24, wherein a resin having a surface free energy of 28 dyne / cm or more and less than 45 dyne / cm is used as the base resin. 27. The silicone resin according to claim 24, wherein the silicone resin contains free silicone.
6. A toilet seat with antifouling properties according to 6. 28. The antifouling toilet seat according to claim 27, wherein the free silicone is contained in an amount of 5 wt% to 80 wt% in 100 wt% of the silicone resin. 29. The antifouling toilet seat according to claim 24, wherein an antibacterial agent is blended into the base resin. As claimed in claim 30, wherein the silicone _{^{resin, R 1 p Si (OR 2}} ) q O (4-pq) / 2 or _{^{R 1 p Si (ONR 2)}} q O (4-pq) / 2 R 1; organic group , R ² ; a hydrogen group or an organic group; a silicone represented by the following formula: 0 <p <2, 0 ≦ q <4, 0 <p + q <4; Toilet seat with. 31. A step of subjecting at least one member of a constituent material of an exposed component of a toilet seat such as a toilet seat sheet, a toilet seat bottom plate, a toilet lid, and a main body case to a predetermined surface treatment, and applying a silicone resin to a surface of the member. Forming a low surface free energy layer lower than the surface of the base resin of the member by attaching the toilet seat. 32. The surface treatment is a discharge treatment such as a corona treatment or a plasma treatment.
A method for producing a toilet seat having the antifouling property described in the above. 33. The discharge treatment according to claim 31, wherein the discharge treatment is performed by using an electrode for generating corona discharge or arc discharge at a high frequency and a high voltage and a metal disposed on the back side of the base resin as a facing electrode. 32. A method of manufacturing a toilet seat having antifouling properties according to claim 32. 34. A silicone resin layer which is granular and is applied to a molded article so as to form a thin low surface free energy layer having a thickness of 0.02 to 10.00 μm, and covers a base resin surface. Area ratio is 12%
33. The method for producing an antifouling toilet seat according to claim 31, wherein the maximum particle size is 80 μm or less. 35. The method according to claim 31, wherein the amount of the silicone resin to be applied is 0.01 mg / cm ² or more. As claimed in claim 36, wherein the silicone _{^{resin, R 1 p Si (OR 2}} ) q O (4-pq) / 2 or _{^{R 1 p Si (ONR 2)}} q O (4-pq) / 2 R 1; organic group , R ^2; hydrogen group or an organic group 0 <p <2,0 ≦ q < 4,0 < antifouling claim 31 to 35, wherein the using a silicone represented by the formula p + q ≦ 4 The manufacturing method of the toilet seat provided with. 37. A surface which is lower than the surface of the base resin of the member by coating the surface of at least one member of a constituent material of an exposed component of the toilet seat such as a toilet seat sheet, a toilet seat bottom plate, a toilet lid, and a main body case. An antifouling toilet seat characterized by forming a surface free energy layer. 38. A base material for a member by coating at least one of the constituent materials of the exposed constituent parts of the toilet seat for local cleaning such as a toilet seat sheet, a toilet seat bottom plate, a toilet lid, a main body case, and a cleaning nozzle. A toilet seat for local cleaning having an antifouling property, wherein a low surface free energy layer lower than a resin surface is formed. 39. The antifouling toilet seat according to claim 37, wherein the paint used for coating the member contains a silicone resin or a fluororesin. 40. The paint containing the silicone resin, which is any one of a silicone resin, a modified silicone resin, a polysulfide resin, a polyurethane resin, an acrylic urethane resin, and an acrylic resin. The toilet seat with antifouling property according to any one of 37 to 39. 41. The toilet seat with antifouling property according to claim 37, wherein an antibacterial agent is blended into the paint. As claimed in claim 42, wherein the silicone _{^{resin, R 1 p Si (OR 2}} ) q O (4-pq) / 2 R 1; organic group, R ^2; hydrogen group or an organic group 0 <p <2,0 ≦ q The antifouling toilet seat according to any one of claims 37 to 41, wherein a silicone represented by the formula of <4, 0 <p + q <4 is used. 43. As the fluororesin, polytetrafluoroethylene (PTFE), perfluoroethylene propene copolymer (PFEP), perfluoroalkoxyalkane (PFA), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (P
VDF), polyvinyl fluoride (PVF), ethylene-tetrafluoroethylene copolymer (ETFE),
The antifouling toilet seat according to any one of claims 37 to 41, wherein polychlorotrifluoroethylene (ECTFE) or polytetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD) is used. .