JP5865662B2 - Bathtub with washing area and manufacturing method thereof - Google Patents

Description

  The present invention relates to a bathtub with a washing place in which a bathtub and a washing place are integrally formed.

  Fiber Reinforced Plastics (FRP) are processed and molded into a wide variety of products and are often used as housing equipment. In particular, it is used for a bathtub such as in a bathroom, for example, a floor of a unit bath, a bathtub, a wall or a panel of a bathroom vanity.

  In a bathtub exposed to water or moisture, slimy deposits having a pink or brown color are generated depending on the environmental conditions, and black or brown mold is easily generated on a bathroom wall, floor, ceiling or the like. In particular, bathrooms are easily soiled by various factors such as scales, sebum, and metal soap. Furthermore, mold and bacteria may be generated by using these soils as nutrients.

Conventional fiber reinforced plastics and the like show adhesion of scales, sebum, soap scum, etc. under the use conditions such as bathroom. At this time, in order to remove the adhered dirt in order to keep the bathroom or the like clean, long time cleaning is required. Moreover, since moisture tends to remain in the bathroom and the like, molds and the like were easily generated.
On the other hand, in recent years, in order to prevent dirt such as kitchen walls and tiles, a technique for fluorine coating the resin surface or laminating functional members having antifouling properties has been disclosed (for example, Patent Document 1). In addition, a resin composition containing a silicone oil and a resin not having a reactive group, a resin composition containing a silicone oil and a resin having a reactive group, and the like are disclosed (for example, see Patent Documents 2 to 7). ).

  On the other hand, for bathroom washrooms, many techniques are used to improve the drying property by suppressing the formation of a puddle due to the shape effect, making it difficult to retain water and improving drainage. Moreover, about the washing place, the technique which improved drainage property, slip prevention property, etc. is proposed, for example (for example, patent documents 8-11).

JP-A-10-137149 JP-A-10-310760 JP 2001-234079 A JP 2001-89651 A JP 2002-69378 A JP 2002-293969 A JP 2008-184487 A Japanese Patent No. 4230411 JP 2006-68279 A JP 2004-208928 A JP 2004-162514 A

However, in order to coat the resin surface that is the base material or to laminate functional members on the resin, specialized equipment is required, and uniform coating is difficult if the resin surface shape is complicated. Yes, the adhesion of the functional member to the resin surface may be weakened.
In addition, when the silicone oil contained in the resin composition does not have a reactive group, the silicone oil is removed together with the use of a bathtub formed by molding the resin composition, and the effect such as antifouling performance becomes weak with time. May be.
On the other hand, although the resin composition containing the silicone oil having a reactive group can suppress deterioration in performance over time, it cannot exhibit excellent antifouling properties.

  Further, even in the same bathroom, the performance required for water (water droplets) differs between the bathtub part and the washing place part. For example, with respect to the bathtub, it is preferable from the viewpoint of antifouling properties to make it easy for water droplets to fall from the side of the bathtub. On the other hand, regarding the washing place, from the viewpoint of drainage, it is preferable to eliminate the puddle by the shape effect so that water droplets cannot be formed, and to make it difficult for water to remain. For example, in Patent Document 8, the resin material in the vicinity of the drainage portion of the bathroom floor is made of a material having higher hydrophilicity than other portions, thereby avoiding remaining water droplets around the drainage portion. Moreover, in patent document 9, the hydrophilic coating film is formed in the horizontal surface of a bathtub, and the water-repellent coating film is formed in the vertical surface. As described above, the performance required for the bathtub and the washing place is different. For example, if the bathtub and the washing place are integrally formed using a fiber reinforced plastic that has been subjected to antifouling treatment and imparted water repellency, the repellent property of the material is reduced. The aqueous property may cancel out the drainage of the washing area enhanced by the shape effect.

However, conventionally, when integrally forming a bathtub with a washing place, a single material is usually used, and in order to impart surface characteristics suitable for each member, means such as forming a coating film may be used. Many have been made. In this case, when special equipment is required and the shape of the resin surface is complicated, uniform coating is difficult, and the adhesion of the functional member between the coating film and the resin surface may be weakened.
In this way, a bathtub with a washing area has been developed that can integrally mold the bathtub and the washing area with existing equipment, has excellent durability, and has both the antifouling property of the bathtub and the drying property of the washing area. It wasn't.

  In order to solve the above-mentioned problems, the present invention has an object to provide a bathtub with a washing place in which a bathtub part having excellent antifouling properties and a washing place part having excellent drying property are integrally formed and have excellent durability. And

The bathtub with a washing place of the present invention has a bathtub part provided with a bathtub, and a washing part formed using a material different from the material of the bathtub part integrally with the bathtub part, and the bathtub The water contact angle of the material constituting the water and the water contact angle of the material constituting the washing area satisfy the relationship of the following formula (1).
Formula (1): A> B (A: contact angle of water of material constituting the bathtub, B: contact angle of water of material constituting the washing area)

  In the bathtub with a washing place of the present invention, the bathtub part and the washing place part are integrally formed, and the materials having different water contact angles are used as the respective materials. Specifically, using a material with a high water contact angle as the material for the bathtub, improving the water repellency and improving the antifouling property, while using a material with a small water contact angle as the material for the washing area Drying is improved by improving drainage. That is, dirt is less likely to adhere due to water repellency in the bathtub, and water is unlikely to remain as water droplets in the washing area. Furthermore, since the bathtub with a washing place of the present invention uses different materials for the bathtub part and the washing place part, the coating film or the like is adhered to the coating film as in the case of imparting hydrophilicity or water repellency to the surface. It is also excellent in durability because it is not necessary to consider properties and missing coatings.

  The bathtub with a washing area of the present invention can be configured such that the washing area has an uneven pattern.

  According to the bathtub with a washing place of the present invention, by providing a concavo-convex pattern in the washing place, it is possible to suppress the formation of a puddle due to the shape effect of the pattern, and to increase the drainage of the washing place by making it difficult for water to remain. Can do. Thereby, the drying property of the washing-room part in the bathtub with a washing-room of this invention can be improved.

  The bathtub with a washing place of the present invention is configured such that the contact angle of water of the material constituting the bathtub is 90 ° or more, and the contact angle of water of the material constituting the washing place is smaller than 90 °. can do.

  According to the bathtub with a washing place of the present invention, by making the contact angle of water of the material constituting the bathtub 90 ° or more, the water repellency of the bathtub is further enhanced and the water of the material constituting the washing place is in contact with water. By making the angle smaller than 90 °, the drainage of the washing area can be further enhanced. Thereby, the bathtub with a washing place of this invention can further improve the antifouling property of a bathtub and the drying property of a washing place.

  The bathtub with a washroom of the present invention has a number average molecular weight of 5 to 4 parts by mass with respect to 100 parts by mass of the base resin containing at least an unsaturated resin and 100 parts by mass of the base resin as a material constituting the bathtub. The fiber reinforced plastic composition containing a silicone compound having a reactive group at one end can be used.

According to the bathtub with a washing place of the present invention, the number average molecular weight of 2 to 4 parts by mass with respect to 100 parts by mass of the base resin containing at least an unsaturated resin and 100 parts by mass of the base resin as a material constituting the bathtub. Is 5,000-20,000, and the contact angle with respect to the water of a bathtub can be enlarged by using the fiber reinforced plastic composition containing the silicone compound which has a reactive group in one terminal.
According to the method for manufacturing a bathtub with a washing place of the present invention, a pair of upper and lower molds composed of an upper mold and a lower mold, and at least a bathtub portion is formed when the mold is in a clamped state. And a second molding space for forming a washing area, and the bathtub portion is configured in a portion corresponding to the first molding space in the lower mold. An antifouling material is placed, and a material having a smaller contact angle with respect to water than the antifouling material is placed on a portion corresponding to the second molding space, and then the mold is clamped The
In the method for manufacturing a bathtub with a washing place according to the present invention, the mold has a third molding space for forming an apron when the mold is in a clamped state, and the lower mold The antifouling material constituting the apron portion can be placed on the portion corresponding to the third molding space, and then the mold can be clamped.

  ADVANTAGE OF THE INVENTION According to this invention, the bathtub part excellent in antifouling property and the washing place part excellent in drying property are shape | molded integrally, and the bathtub with a wash place excellent in durability can be provided.

It is a perspective view which shows the bathtub with a washing place which concerns on one Embodiment of this invention. It is sectional drawing which shows the mold open state of the metal mold | die used for the formation process of the bathtub with a washroom of this invention. It is sectional drawing which shows the clamping state of the metal mold | die used for the formation process of the bathtub with a washroom of this invention.

The bathtub with a washing place of the present invention has a bathtub part provided with a bathtub, and a washing part molded integrally with the bathtub part. The contact angle of water of the material constituting the bathtub and the washing part are The water contact angle of the constituent material satisfies the relationship of the following formula (1).
Formula (1): A> B (A: contact angle of water of material constituting the bathtub, B: contact angle of water of material constituting the washing area)

  Here, “water contact angle” means a contact angle when 1.5 μL of distilled water is brought into contact with a molded article of each material, and indicates an average value of three measurement results. The contact angle can be measured by, for example, a contact angle measuring device manufactured by Kyowa Interface Science.

  The bathtub with a washing place of the present invention has a bathtub part provided with a bathtub and a washing part molded integrally with the bathtub part. In the bathtub with a washing place of the present invention, the contact angle (A) of water of the material constituting the bathtub and the contact angle (B) of the material constituting the washing place have a relationship of formula (1): A> B. . In the bathtub with a washing place of the present invention, materials having different water contact angles are used as the material constituting the bathtub and the material constituting the washing place, respectively. That is, a material having a large water contact angle is used as the material constituting the bathtub, and a material having a small water contact angle is used as the material constituting the washing area. By using a material having a large water contact angle for the bathtub, the water repellency of the bathtub can be increased. Thereby, the antifouling property of a bathtub can be improved. On the other hand, by using a material with a small contact angle of water for the washing area, water drainage can be enhanced, so that water is not likely to remain in the washing area as water droplets. Thereby, the drying property of a washing place part can be improved.

If the contact angle (B) of the material constituting the washing area is larger than the contact angle (A) of the material constituting the bathtub, the water repellency of the washing area becomes too large, and the water in the washing area becomes water droplets. It becomes difficult to flow and drainage performance is reduced.
The water contact angle of the material (A) constituting the bathtub is preferably 90 ° or more. When the contact angle of water of the material (A) constituting the bathtub is 90 ° or more, the water repellency can be further improved.

Moreover, it is preferable that the material which comprises the said bathtub has a small fall angle with respect to water, for example, it is preferable that the fall angle is 40 degrees or less. When the falling angle of the material constituting the bathtub is 40 ° or less, the rolling property of water is excellent. Here, “water rolling property” is evaluated by tilting the surface of a product on which water droplets are placed and measuring the angle (falling angle) at which the water droplets begin to roll. Even on the surface of a product that tends to have a large water contact angle and high water repellency, the falling angle may be large. That is, it is considered that the rolling property (falling angle) of water is an evaluation standard for antifouling properties that is stricter than the contact angle evaluation that is generally an evaluation index for water repellency or antifouling properties. By forming the bathtub with a material having high water rolling property, long-term antifouling property of the bathtub can be realized.
The sliding angle can be measured by various contact angle measuring devices (for example, a fully automatic contact angle meter manufactured by Kyowa Interface Science Co., Ltd.) as well as the contact angle.
The material having a small sliding angle will be described later.

  Moreover, it is preferable that the contact angle of water of the material constituting the washing place is smaller than 90 °. If the contact angle of water is smaller than 90 °, the water repellency of the washing area can be reduced, the water drainage effect of the washing area can be increased, and the drying property can be improved.

  Moreover, the bathtub with a washing place of this invention has an apron part further, and can be comprised so that the said bathtub part and the said washing place part may be continued via the said apron part. Although there is no limitation in particular as the material which comprises the said apron part, The antifouling property of an apron part can be improved by using the thing similar to the material which comprises the said bathtub.

  Furthermore, as described later, the bathtub with a washing place of the present invention is a pair of upper and lower molds composed of, for example, an upper mold and a lower mold, and at least when the mold is brought into a clamped state, A lower mold using a mold having a first molding space for forming a part, a second molding space for forming a washing area, and a third molding space for forming an apron part. An antifouling material (for example, a water repellent FRP composition to be described later) constituting the bathtub and the apron portion is placed on the part corresponding to the first molding space and the part corresponding to the third molding space. Furthermore, it can be manufactured by placing a material having a smaller contact angle with respect to water than the antifouling material in a portion corresponding to the second molding space, and then clamping the mold. .

  Hereinafter, the structure of the bathtub with a washing place of the present invention will be described with reference to the drawings, and then the material constituting the bathtub and the material constituting the washing place portion will be described.

  First, the bathtub with a washing place of the present invention will be described with reference to FIG. FIG. 1 is a perspective view showing a bathtub 12 with a washing area according to an embodiment of the present invention. However, the present invention is not limited to the following embodiments.

  As shown in FIG. 1, the bathtub 12 with a washing area includes a washing area 14, a bathtub section 16 having a bathtub 20, and an apron section 18. The apron portion 18 is integrally formed with the washing area 14 and the bathtub portion 16. In this invention, the material which has the contact angle of water larger than the contact angle of the water of the material which comprises the washing place part 14 is used for the material which comprises the bathtub part 16 containing the bathtub 20. As shown in FIG. Moreover, as a material which comprises the apron part 18, the same material as the material which comprises the bathtub part 16 can be used. Thereby, like the bathtub part 16, the antifouling property of the apron part 18 can be improved.

  A material having a water contact angle smaller than the water contact angle of the material constituting the bathtub portion 16 is used for the washing area 14. That is, in FIG. 1, the bathtub portion 16 and the apron portion 18 are formed of the same material, and the water contact angle of the material constituting the bathtub portion 16 and the apron portion 18 is the water of the material constituting the washing area 14. It is larger than the contact angle. In FIG. 1, the washing area 14 is formed in a substantially flat plate shape and serves as a washing area for bathers. Although omitted in FIG. 1, an uneven pattern is formed in the washing area 14.

  As described above, in the bathtub with a washing place of the present invention, an uneven pattern can be provided in the washing place 14 in order to improve drainage. As such a concavo-convex pattern, for example, a cross-sectional shape formed on the surface of a bathroom floor panel described in JP-A-2006-336423 can be employed.

  As for the bathtub part 16, the bathtub 20 and the flange part 22 of the upper end are integrally formed. Further, an apron portion 18 is integrally formed between the washing place portion 14 and the bathtub portion 16 (flange portion 22), whereby a washing place that continues from the bathtub portion 16 through the apron portion 18 to the washing place portion 14 is attached. A bathtub 12 is configured.

  In the washing section 14 and the bathtub section 16, flange sides 24 are formed upward from three sides (6 sides in total) other than the sides that are continuous with the apron section 18, and the washing section 14 and the bathtub section 16. The rigidity is improved. When the bathtub 12 with a wash basin is installed in the bathroom, the flange side 24 is located outside the bathroom inner wall (not shown) and acts as a water return.

  Next, the material which can be used for a bathtub and a washing place part is demonstrated. Moreover, it is preferable to use the material similar to the said bathtub also when comprising an apron part. In the present invention, each material can be appropriately selected and used as long as it satisfies the relationship of the contact angle of water described above, as long as the effects of the present invention are not impaired. For example, a base resin containing at least an unsaturated resin And a fiber reinforced plastic composition containing fibers can be used. When the fiber reinforced plastic composition is provided with, for example, silicone oil, the contact angle of water can be increased when formed into a molded product. That is, water repellency can be imparted to the fiber-reinforced plastic resin by the addition of silicone oil.

  For this reason, for example, a water-repellent fiber-reinforced plastic composition containing at least silicone oil, a base resin containing an unsaturated resin, and fibers is used as a material constituting the bathtub, and silicone oil is used in the washing area. By using a fiber reinforced plastic composition containing at least a base resin containing an unsaturated resin and fibers without adding, the bathtub with a washing place of the present invention can be formed. The fiber reinforced plastic is also abbreviated as FRP (Fiber Reinforced Plastics), and the fiber reinforced plastic composition may be referred to as “FRP composition”.

<Water repellent fiber reinforced plastic composition>
As a water-repellent fiber reinforced plastic that can be used as a material constituting the bathtub or apron part, a base resin containing at least an unsaturated resin and 2 parts by mass to 4 parts by mass with respect to 100 parts by mass of the base resin A fiber reinforced plastic having a number average molecular weight of 5,000 to 20,000 and having a reactive group at one end can be used (hereinafter referred to as the fiber reinforced plastic). The composition is referred to as “water-repellent FRP composition”).
Hereinafter, a silicone compound having a number average molecular weight of 5,000 to 20,000 and having a reactive group at one end is also referred to as a “specific silicone compound”.

  When the water-repellent FRP composition is molded to produce a bathtub, the water repellency and water-rolling property of the water product are improved, it is inexpensive, and can be applied to complicated shapes such as curved surfaces. It is excellent in durability and can exhibit a good antifouling effect even indoors where ultraviolet rays hardly enter, such as a bathroom. The reason for this is not clear, but is presumed to be due to the following reason.

Since the specific silicone compound has a reactive group at one end of the molecule, it is used together with a base resin containing an unsaturated resin, so that the double bond portion of the unsaturated resin, the reactive group of the specific silicone compound, and It is considered that a reaction occurs between the base resin and the specific silicone compound. Furthermore, in order to improve the water repellency and water rolling property of the bathtub or apron part, which is a molded product of the water repellent FRP composition, the siloxane portion of the polysiloxane molecule obtained by combining the base resin and the silicone compound However, it is considered necessary to be unevenly distributed on the surface side without leaving the base resin.
At this time, if the molecular chain of the silicone compound is too long, the unsaturated resin and the silicone compound contained in the base resin are difficult to be compatible with each other, so that it is considered that the silicone compound is difficult to bind to the unsaturated resin. On the other hand, if the molecular chain of the silicone compound is too short, conversely, even if the silicone compound is too mixed with the base resin and the silicone compound and the unsaturated resin react with each other, the siloxane portion derived from the silicone compound does not react with the base resin. It is thought that it is hard to be unevenly distributed on the surface.
In addition, the ratio of the silicone compound to the base resin is greatly related to the uneven distribution of the siloxane portion on the surface of the base resin, and if the ratio of the silicone compound to the base resin of the silicone compound is small, the water repellency and the water rolling property cannot be expressed. Conceivable. On the other hand, when the ratio of the silicone compound to the base resin is large, when the bathtub or apron part is formed, the silicone compound remaining without reacting with the unsaturated resin is raised, causing a problem in the surface properties, water repellency and water It is considered that the rolling property is impaired.

In general, the molecular chain length of the polymer compound is related to the molecular weight of the compound, the number average molecular weight of the silicone compound is 5,000 to 20,000, and 2 to 4 mass of the silicone compound with respect to 100 mass parts of the base resin. By setting the ratio of the part, when the silicone compound having a reactive group at one end and the unsaturated resin contained in the base resin react and bind, it is considered that the siloxane part is unevenly distributed on the surface of the base resin. .
As a result, it is considered that not only water repellency but also a bathtub and an apron part excellent in water rolling property can be manufactured, and long-term antifouling performance can be expressed.
Thus, the water-repellent FRP composition is a composition containing an unreacted unsaturated resin and a specific silicone compound, and reacts the unsaturated resin in the composition with the specific silicone compound, What was made into siloxane composite resin can be made into the material which comprises a bathtub.

  Hereinafter, the specific silicone compound, the base resin, and other components constituting the fiber-reinforced plastic composition will be described.

[Silicone compound]
The water repellent FRP composition has a number average molecular weight of 5,000 to 20,000 and can contain a silicone compound having a reactive group at one end (specific silicone compound).
The details of the chemical structure of the silicone compound will be described later. One end means, for example, one end of a silicone compound having a molecular chain (main chain) having a siloxane moiety as a repeating unit, and is in the middle of the main chain. That is, it does not include a reactive group in the side chain.

  When a specific silicone compound having a reactive group is blended and cured in a fiber reinforced plastic composition containing an unsaturated resin as a matrix resin, the reactive group reacts with a double bond of the unsaturated resin, thereby causing no reaction. It is estimated that a functional polysiloxane moiety remains. Since the remaining polysiloxane portion is incompatible with the unsaturated resin, it is considered that the concentration of the non-reactive polysiloxane portion is selectively increased on the outermost surface of the obtained molded product. Since this polysiloxane portion exhibits high water repellency and water rolling property, it is considered that dirt and bacteria are difficult to adhere to the surface of the product around the water, and that the adhered dirt and bacteria are easily removed.

  The water-repellent FRP composition prevents the occurrence of non-reactive and highly water-repellent polysiloxane portions on the surface of the molded article by the reaction between the unsaturated resin double bond and the reactive group of the specific silicone compound. In order to obtain soiling properties, straight silicone oils consisting only of non-reactive polysiloxanes that do not have reactive groups can provide water repellency if they are added to fiber-reinforced plastics without increasing the number of parts. Absent.

The water-repellent FRP composition only contains a specific silicone compound in a normal fiber reinforced plastic composition, and there is no problem of an increase in material cost, and there is no problem of an increase in molding process and post-processing process. Provided at low cost. In addition, there is no need for a large amount of blending that affects the moldability, and it can be sufficiently applied to complex shaped products. Furthermore, since it is not by post-processing like a coating film, it is excellent also in antifouling durability, and good antifouling properties can be obtained without being affected by the external environment such as ultraviolet rays. .
That is, a water-repellent FRP composition is used as a material constituting the bathtub in the present invention, and a normal FRP composition (one not compounded with a specific silicone compound) is used as a material constituting the washing area, which is integrally molded. Thus, it is possible to easily form a bathtub with a washing area having a bathtub and a washing area having different water contact angles.

  Examples of the reactive group possessed by the specific silicone compound include a functional group containing a double bond (ethylenically unsaturated bond group), an isocyanate group, a block isocyanate group, an epoxy group, an oxetanyl group, an amino group, and a carboxy group. Etc. Among them, a functional group containing a double bond is preferable, and more specifically, a group containing an acryloyl group represented by the following general formula (1) and a group containing a methacryloyl group represented by the following general formula (2). At least one is mentioned.

Ra in the general formula (1) and Rb in the general formula (2) each independently represent a single bond or a divalent linking group. Examples of the divalent linking group represented by Ra or Rb include an alkylene group, an alkenylene group, an arylene group, and combinations thereof.
Among these, an alkylene group is preferable, and 1 to 6 carbon atoms are preferable. For example, a methylene group, an ethylene group, a propylene group, a butylene group and the like can be mentioned, and among them, a propylene group is preferable. When the divalent linking group can be further substituted, the divalent linking group may have a monovalent substituent such as a hydrocarbon group, a halogen atom, or a hydroxy group.

The specific silicone compound has a reactive group as described above at one end of a molecular chain (main chain) having a siloxane moiety as a repeating unit.
Examples of the silicone compound having a reactive group at one end of the molecular chain include those represented by the following general formula (3).

In general formula (3), R ^{1 to} R ⁷ each independently represents a monovalent non-reactive substituent, and n represents the amount of the repeating unit [wherein, represented by general formula (3) Q represents a reactive group, which represents an amount selected within a range where the number average molecular weight of the compound is 5,000 to 20,000.

Examples of the monovalent non-reactive substituent represented by R ^{1 to} R ⁷ in the general formula (3) include a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group. R ^{1 to} R ⁷ may all be the same or different. Moreover, several R < ⁴ > in repeating units and R < ⁵ > may be the same, or may differ.
Among these, a hydrogen atom or an alkyl group is preferable.
The alkyl group is preferably a linear, branched, or cyclic alkyl group, and examples thereof include a methyl group, an ethyl group, an isopropyl group, a butyl group, a tert-butyl group, a hexyl group, and a cyclohexyl group. As for carbon number of an alkyl group, 1-6 are preferable, More preferably, it is 1-4.

Q in the general formula (3) represents a reactive group, and examples thereof include a group containing an acryloyl group represented by the general formula (1) and a group containing a methacryloyl group represented by the general formula (2).
In the present invention, the reactive group possessed by the specific silicone compound is located at one end of the molecular chain, and the silicone compound having a reactive group at the side chain of the molecular chain or both ends of the molecular chain is included in the specific silicone compound. I can't. Incidentally, those having a reactive group in the side chain of the molecular chain, for example, if the silicone compound is represented by the general formula (3), refers to the case at least one of R ⁴ and R ⁵ is a reactive group. Further, those having a reactive group at both ends of the molecular chain, if the silicone compound is represented by the general formula (3), in addition to Q, at least one of R ¹ to R ³ is a reactive group Refers to cases.

Among the above, the specific silicone compound is represented by the general formula (3), R ^{1 to} R ⁷ are all methyl groups, and Q is a compound represented by the general formula (1) or the general formula (2). Preferably there is.

  The number average molecular weight (also referred to as Mn) of the specific silicone compound is 5,000 to 20,000 from the viewpoint of reactivity with the unsaturated resin contained in the base resin and uneven distribution of the specific silicone compound on the base resin surface. Yes, it is preferably 6,000 to 15,000. As described above, when the number average molecular weight (Mn) of the specific silicone compound exceeds 20,000, the unsaturated resin and the silicone compound contained in the base resin are separated from each other without being compatible with each other, and selectively to the surface. When the molecular weight is less than 5,000, the silicone compound is too compatible and the silicone compound is not unevenly distributed on the surface of the base resin, so that excellent water repellency and water rollability cannot be expressed.

  The property of the specific silicone compound having the number average molecular weight is not particularly limited, and may be in a solid state or an oil state at room temperature, but may be a polysiloxane molecule formed by reaction with a base resin. From the viewpoint of easy transfer to the outermost surface of the product, it is preferably oily at room temperature (for example, 25 ° C.).

  Moreover, it is preferable that content of the specific silicone compound in a water-repellent FRP composition is 2 mass parts-4 mass parts with respect to 100 mass parts of base resin. When the content of the specific silicone compound is 2 parts by mass or more, the effect of imparting water repellency is sufficient, and the antifouling property can be sufficiently exhibited. Moreover, when the content of the specific silicone compound is 4 parts by mass or less, when the fiber reinforced plastic composition is used as a bathtub or an apron part, the silicone compound is raised on the surface of the bathtub wall or the like, or the surface property of the bathtub is impaired. There is nothing.

[Base resin]
The water repellent FRP composition contains a base resin containing at least an unsaturated resin.
The base resin contains at least an unsaturated resin as a matrix resin, and when the water repellent FRP composition is molded by SMC, TMC, or BMC, which will be described later, may further contain a low shrinkage agent or the like. . Therefore, when the base resin contains only the unsaturated resin, the content of the specific silicone compound in the water-repellent FRP composition is a ratio with respect to 100 parts by mass of the unsaturated resin, and the base resin is less than the unsaturated resin. In the case of a resin composition containing a shrinkage agent, the content of the specific silicone compound in the water-repellent FRP composition is a ratio relative to 100 parts by mass of the unsaturated resin and the low shrinkage agent.

-Unsaturated resin-
The unsaturated resin contained in the base resin is not particularly limited as long as the resin contains a double bond in the molecule. For example, from unsaturated polyester resin, vinyl ester resin, polyamide resin, phenol resin alone or a mixture thereof. The unsaturated resin which becomes.
Of these, unsaturated polyester resins are preferably used.
The unsaturated polyester resin can be obtained by esterifying a dicarboxylic acid component containing an unsaturated dicarboxylic acid and a glycol component. The unsaturated polyester resin is preferably a polymer having a number average molecular weight of about 500 to 5,000.

As the matrix resin, a liquid containing an unsaturated polyester resin may be used.
A liquid containing an unsaturated polyester resin is obtained by dissolving an unsaturated polyester resin obtained by esterifying a dicarboxylic acid component containing an unsaturated dicarboxylic acid and a glycol component in a liquid vinyl monomer. .
As the unsaturated dicarboxylic acid, maleic anhydride or fumaric acid is usually used. The liquid vinyl monomer functions as a solvent for the unsaturated polyester resin and functions as a crosslinking agent. As the liquid vinyl monomer, a styrene monomer is generally used, but other monomers such as methyl methacrylate, vinyl toluene, α-methyl styrene, divinylbenzene, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meta ) A polyfunctional monomer such as acrylate can be used depending on the purpose.
These liquid vinyl monomers may be used singly or in combination of two or more, and the blending amount is not particularly limited and is appropriately selected depending on the situation. Is selected in the range of 10 to 150 parts by mass, preferably 15 to 80 parts by mass with respect to 100 parts by mass in total of the unsaturated polyester resin and the low shrinkage agent described later.

-Low shrinkage agent-
Low shrinkage agents include polymethyl methacrylate resin, polystyrene resin, polyvinyl acetate resin, powdered polyethylene resin, saturated polyester, styrene-butadiene copolymer, styrene-methacrylic acid copolymer, polycaprolactone, polybutadiene, etc. Examples thereof include a plastic resin, and among them, a polystyrene resin is preferable. These may be used individually by 1 type, and may be used in combination of 2 or more types.
The amount of the low shrinkage agent may be selected in consideration of the shrinkage rate, surface smoothness, surface gloss, etc. of the fiber-reinforced plastic obtained, and the mass ratio of the matrix resin and the low shrinkage agent is Usually, it is selected in the range of 90:10 to 50:50, preferably 80:20 to 60:40.

[Other additive components]
The water-repellent FRP composition can be blended in the same manner as a conventional general fiber-reinforced plastic composition except that the specific silicone compound is blended with the base resin. In addition, as for each additive component which a fiber reinforced plastic composition contains, all may be used individually by 1 type, and may be used in combination of 2 or more types.
The fiber reinforced plastic is obtained by blending fibers (preferably glass fibers) as a reinforcing material in a base resin. Examples of the fiber include carbon fiber, and organic fiber such as carbon fiber, polyester fiber, nylon fiber, and aramid fiber.
Generally, glass fibers as a reinforcing material are classified into E-glass (non-alkali glass), S-glass (High Strength glass), and the like, and glass roving, chopped strand mat, roving cloth, etc. are used. The

When a roving-shaped fiber is used as the glass fiber, a long fiber and a short fiber obtained by cutting the roving are usually used. The long fiber has a length of usually 15 to 100 mm, preferably 20 to 50 mm, and the short fiber has a length of usually 3 mm or more and less than 15 mm, preferably 6 to 13 mm. .
The roving is usually obtained by bundling about 50 to 4000 single fibers having a fiber diameter of 5 to 25 μm with a bundling agent such as polyvinyl acetate, polyester, epoxy resin or polyurethane.
Examples of other additive components include the following various components such as a curing catalyst, an internal mold release agent, and a filler.

-Curing catalyst-
Examples of the curing catalyst include organic peroxidation such as t-butyl peroxybenzoate, t-butyl peroxy-2-hexanoate, methyl ethyl ketone peroxide, acetylacetone peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, and the like. Things are used. The curing catalyst is commonly used as a so-called polymerization initiator.

-Internal release agent-
As the internal release agent, for example, zinc stearate is used.

-Filler-
Examples of the filler include inorganic compounds such as calcium carbonate, aluminum hydroxide, silica, talc, barium sulfate, leh, mica, hollow balloon (glass, shirasu, cement), ferrite, and zinc white. Of these, calcium carbonate is preferred. The filler can be subjected to a surface treatment in order to improve dispersibility.

-Thickener-
As a thickener, for example, an oxide or hydroxide of an alkaline earth metal such as MgO or Mg (OH) ₂ that can react with a carboxyl group in an unsaturated polyester resin, or an oxide of an alkali metal such as K ₂ O or KOH In general, magnesium oxide is used.

-Colorant-
Examples of the colorant include toner and pigment.

-Curing accelerator-
Examples of the curing accelerator include cobalt naphthenate; cobalt octoate; N, N-dimethylaniline; N, N-diethylaniline; N, N-dimethyl-p-toluidine; acetylacetone; ethyl acetoacetate.

-Polymerization inhibitor-
Examples of the polymerization inhibitor include hydroquinone; p-benzoquinone; methylhydroquinone; trimethylhydroquinone; t-butylhydroquinone; catechol; t-butylcatechol; 2,6-di-t-butyl-4-methylphenol. .

(Amount of additive component)
In the water-repellent FRP composition, the preferred blending of additive components other than the specific silicone compound varies depending on the molding method, application, etc., but generally has the following blending ratio, and the fibers (preferably glass fibers) are: It mix | blends in the ratio of about 20-50 mass% in the fiber reinforced plastic composition containing these.
The content of other additive components that can be contained in the water-repellent FRP composition is preferably in the following range with respect to 100 parts by mass of the base resin (matrix resin and low shrinkage agent).
Curing catalyst: 0.2-2 parts by weight Internal mold release agent: 1.0-10 parts by weight Filler: 10-200 parts by weight Thickener: 0.5-10 parts by weight

  In addition to those exemplified above, other additives conventionally used in fiber reinforced plastic compositions, such as antioxidants, ultraviolet absorbers, antifoaming agents, thixotropic agents, and the like can be blended as desired. .

  As above-mentioned, the bathtub with a washroom of this invention can be shape | molded using a water-repellent FRP composition. In particular, the above-mentioned water-repellent FRP composition is used as a bathtub or an apron portion, and a normal FRP composition (one that does not contain water repellency-imparting components such as silicone oil) is used as a wash-place portion. A bathtub can be formed.

  Here, there are many molding methods for fiber reinforced plastics, which are classified into SMC (Sheet Molding Compound), BMC (Bulk Molding Compound), TMC (Thick Molding Compound) and the like depending on the molding material.

In SMC, a composition in which a thickener is mixed with a mixture obtained by kneading a base resin with a filler, a release agent, a curing catalyst, and the like is applied onto a polyethylene film, and fibers (for example, glass fibers) are laid on the polyethylene film. Both are compression impregnated and rolled into a sheet to make it tack free.
BMC is a mixture of the above-mentioned base resin mixed with a release agent, a curing catalyst, and the like, and a filler is kneaded with a kneader, and then a thickener is mixed. Aged in the size and shape.
TMC is a mixture of a base resin mixed with a filler, a release agent, a curing catalyst, etc., and a composition in which a thickener is mixed, and a fiber (for example, glass fiber) between at least a pair of opposed rollers. Is passed, and the product mixture is scraped off into a desired shape such as a rod shape, a lump shape, or a sheet shape by high-speed rotation of a rotating body that is arranged close to the roller and provided with a gap.

  In addition, when obtaining sheet-like SMC thru | or TMC in SMC shaping | molding or TMC shaping | molding, the thickness of the said sheet | seat is 1-10 mm normally from surfaces, such as the permeability to the glass fiber of the mixture containing base resin, Preferably Can be 1-5 mm.

  The bathtub with a washing place of the present invention can be produced by SMC, BMC, TMC molding or the like using each FRP composition according to a conventional method. At this time, materials having different water contact angles are used for the bathtub and the washing area. The water-repellent FRP composition described above is cured and molded to react the unsaturated resin and the specific silicone compound having a reactive group. The obtained water repellent FRP composition has a siloxane portion unevenly distributed and fixed on the surface of the base resin, so that the molded product (tub) has high water repellency and high water rolling property, and is excellent. Antifouling property can be maintained for a long time.

  Moreover, one mode in the case of integrally molding the bathtub with a washing place of the present invention will be described with reference to FIGS. FIG. 2 is a cross-sectional view showing a mold open state of a mold used in the molding process of the bathtub with a washing place of the present invention. FIG. 3 is a cross-sectional view showing a mold clamping state of a mold used in the molding process of the bathtub with a washing place of the present invention. In addition, the same code | symbol is attached | subjected to the site | part which is common in FIG.2 and 3, and description is abbreviate | omitted.

  FIG. 2 shows a pair of upper and lower molds 28 composed of an upper mold 30 and a lower mold 32. For example, the upper mold 30 and the lower mold 32 can be configured such that one of them is a fixed mold and the other is a movable mold so that the movable mold moves up and down, and the mold is opened and clamped. .

  As shown in FIGS. 2 and 3, the upper mold 30 and the lower mold 32 include a first molding space 34 for forming a bathtub portion in the bathtub with a washing area according to the present invention when the mold 28 is in a clamped state. The second molding space 36 for forming the washing section and the third molding space 38 for forming the apron section are configured in pairs. In order to form the bathtub with a washing place of the present invention using the mold 28, for example, as shown in FIG. 2, first, a portion corresponding to the first molding space 34 in the lower mold 32 and the third molding are performed. The antifouling SMC 40 made of the above-mentioned water-repellent FRP composition is placed in a portion corresponding to the space 38, and the contact angle with respect to water is higher than the antifouling SMC in the portion corresponding to the second molding space 36. A small SMC 42 is placed. Next, the mold 28 is clamped, and pressure is applied and then cooled, so that the water contact angle of the material constituting the bathtub (and the apron part) and the water contact angle of the material constituting the washing area are obtained. Thus, the bathtub with a washing place of the present invention can be manufactured in which the bathtub part and the washing place part are integrally formed through the apron part.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the following, “part” and “%” are based on mass unless otherwise specified.

<Preparation of FRP composition (FRP1)>
The components shown in Table 1 were mixed to prepare an FRP composition (FRP1).
Specifically, silicone compound 1 described later was blended in a proportion (2 parts) shown in Table 2 with respect to 100 parts of the base resin. A glass fiber chopped strand mat was impregnated with the components shown in Table 1 except for the base resin, the silicone compound, and the glass fiber. A plastic composition) was obtained.

<Production of water products>
The obtained FRP1 was molded into a sheet to obtain SMC1.
Next, the obtained SMC1 was cured at a curing temperature of 140 ° C. to prepare a plate sample of FRP1 glass fiber reinforced plastic.

1. Water repellency evaluation (contact angle of water with plate-like sample)
The contact angle when 1.5 μL of distilled water was brought into contact with the surface of the obtained plate-like sample was measured, and the results are shown in Table 2. The contact angle of water was measured by a contact angle measuring device manufactured by Kyowa Interface Science, and the average value of three measurement results was recorded.

2. Evaluation of water rollability (water drop angle with respect to the surface of plate-like sample)
The falling angle when 30 μL of distilled water was attached to the surface of the obtained plate-like sample was measured, and the results are shown in Table 2. The falling angle of water was measured by a contact angle measuring device manufactured by Kyowa Interface Science, and the average value of three measurement results was recorded.

[Preparation of FSP2]
FRP composition 2 was prepared in the same manner as the preparation of FRP 1 except that the content of the silicone compound in the FRP composition was changed to the amount shown in the “Content” column of Table 2.

  Next, a plate-like sample was produced using the obtained FRP2, and the contact angle and the water falling angle were measured by the same method as described above. The measurement results are shown in Table 2.

-Silicone compound-
As the silicone compound in the composition shown in Table 1, the following product (silicone compound 1) was used. The silicone compound is oily at room temperature.
Silicone compound 1; manufactured by Chisso Corporation, FM0725 (Mn = 14,972)
The number average molecular weight (Mn) of the silicone compound 1 is a value measured by GPC measurement under the following conditions. Mw (weight average molecular weight) obtained simultaneously with Mn measurement was 16,089, Mp (peak top molecular weight) was 16,176, and Mw / M was 1.07. These numerical values are all in terms of polystyrene.
(conditions)
・ Measuring instrument: Water perm, gel permeation chromatograph (GPC)
・ Column: Tosoh Corporation, TSKgelSuperH2000 + TSKgelSuperH3000
・ Solvent: Tetrahydrofuran (THF)
Column temperature: 40 ° C
・ Flow rate: 0.5ml / min

(Examples and Comparative Examples)
Using the FRPs 1 and 2 obtained from the above, the bathtubs with washing places of Examples and Comparative Examples were integrally molded according to Table 3 below. In addition, an uneven pattern was formed on the surface of the washing area of each bathtub with a washing area to improve drainage.

<Evaluation>
1. The degree of soiling of the bathtub The degree of soiling after use for one month was visually observed according to the following criteria. The results are shown in Table 3 below.
○: No adhesion of dirt was observed.
X: Adherence of dirt was recognized.

2. Drying property of washing place About the obtained bathtub with a washing place, the dry condition of the washing place 5 hours after use was observed visually according to the following reference | standard. The results are shown in Table 3 below.
○: Almost no water droplets remained on the floor surface of the washing area, and the drying property was excellent.
X: Many water droplets were observed on the floor surface of the washing place.

  As can be seen from Table 3, the bathtub with washing place of the example had no stain on the bathtub and was excellent in antifouling property, and furthermore, the drying property of the washing place was also good. Further, as shown in Table 3, it was found that when FRP 2 having a water contact angle of less than 90 ° was used as the material for the washing area, the drying property of the washing area was excellent. On the other hand, Comparative Example 1 using the same material (FRP1) in the bathtub and the washing area was excellent in the antifouling property of the bathtub, but was inferior in the drying property of the washing area. Further, Comparative Example 2 using the same material (FRP2) in the bathtub and the washing place was inferior in the antifouling property of the bathtub although it was excellent in the drying property of the washing place.

DESCRIPTION OF SYMBOLS 12 Bath tub with washing place Washing place part 16 Bath part 18 Apron part 20 Bathtub 22 Flange part 24 Flange side 28 Mold 30 Upper mold 32 Lower mold 34 First molding space 36 Second molding space 38 Third molding space 40 Prevention Antifouling SMC
42 SMC

Claims (6)

A bathtub section provided with a bathtub,
A washing place molded using a material different from the material of the bathtub portion integrally with the bathtub portion ,
The bathtub with a wash basin where the contact angle of water of the material composing the bathtub and the contact angle of water of the material composing the washing section satisfy the relationship of the following formula (1).
Formula (1): A> B (A: contact angle of water of material constituting the bathtub, B: contact angle of water of material constituting the washing area)   The bathtub with a washing area according to claim 1, wherein the washing area has an uneven pattern.   The bathtub with a washing place according to claim 1 or 2, wherein a contact angle of water of a material constituting the bathtub is 90 ° or more, and a contact angle of water of a material constituting the washing place is smaller than 90 °.   The material constituting the bathtub has a number average molecular weight of 5,000 to 20,000 with respect to 100 parts by mass of the base resin containing at least an unsaturated resin and 100 parts by mass of the base resin. The bathtub with a washroom of any one of Claims 1-3 containing the fiber reinforced plastic composition containing the silicone compound which has a reactive group in one terminal. A pair of upper and lower molds composed of an upper mold and a lower mold, and at least a first molding space for forming a bathtub portion when the mold is in a mold-clamped state, and a washing place portion are formed A mold having a second molding space, and placing an antifouling material constituting the bathtub portion in a portion of the lower mold corresponding to the first molding space; A method for manufacturing a bathtub with a washing place, in which a material having a smaller contact angle with water than the antifouling material is placed on a part corresponding to the molding space, and then the mold is clamped. The mold has a third molding space for forming an apron portion when the mold is in a clamped state, and a portion corresponding to the third molding space in the lower mold. The manufacturing method of the bathtub with a washroom of Claim 5 which mounts the antifouling material which comprises the said apron part, and clamps the said metal mold | die after that.