JP2002011821A - Composite sheet and method for manufacturing plastic molding using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plastic molding capable of satisfying both an anti- contamination functional surface and a durable surface. SOLUTION: A composite sheet comprises a mold release layer, a functional inorganic layer containing a hydrophilic inorganic compound, and a polymer layer containing a polymer compound as a final layer on a surface of a support. A method for manufacturing the plastic molding comprises the step of adhering the composite sheet so that the support of the sheet is contacted with an inner surface of a mold, then filling a thermoplastic resin or a thermosetting resin in the mold, molding the resin, and transferring the functional inorganic layer to the surface of the resin, thereby manufacturing the molding.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composite sheet and a method for producing a plastic molded article using the same. The composite sheet of the present invention can impart hydrophilicity to the surface of the plastic molded body and, if necessary, further impart properties such as conductivity and high refractive index.

[0002] Plastic molded articles whose surface is highly functionalized by the composite sheet of the present invention include, for example, various home appliances, bathtubs, bathrooms, vanities, walls, floors, sinks, doors and the like, as well as internally illuminated signboards. , Signs, plastic reflective mirrors, exterior decorative panels, showcase windows, aquarium transparent panels, vending machine covers, windowpane shatterproof films, lighting fixture reflectors, clear face masks, etc.

[0003]

2. Description of the Related Art In a living environment, in particular, plastic moldings for water supply as described above include artificial marble mainly composed of an epoxy-based thermosetting resin, thermosetting resin such as acrylic resin and polypropylene. Plastic resins are often used. Over time, the surface of these plastic molded products is exposed to food residues, oils and organic substances such as proteins and fats discharged from the human body, bacteria that propagate these as nutrients, and tap water. Since soap scum and the like generated by the chemical bond between the contained inorganic substance such as metal ions and the soap adhere as dirt, there is a problem in appearance and hygiene.

[0004] It takes a lot of time and effort to remove these stains from the plastic molded article. Therefore, as a method of imparting an antifouling function to a plastic molded product to prevent the adhesion of dirt, 1) a method of reducing the free energy of the surface of the molded product to make the surface water-repellent, and 2) a method of reducing the free energy of the surface of the molded product. A method of increasing the surface to make the surface hydrophilic has been proposed.

[0005] 1) Means for making the surface of a molded article water-repellent include conventionally applying an antifouling coating agent having a relatively low surface energy such as a fluorine-based coating agent or a silicone-based coating agent to the surface of the molded product. According to the method, a method of forming a water-repellent coat layer on the surface of a molded article is generally performed. However, these antifouling coating agents have surface free energies that are not low enough to satisfy the prevention of fouling in the first place, and they also fall off the surface of molded articles over time, and the fouling prevention function deteriorates. Problem.

On the other hand, 2) As means for making the surface of the molded article hydrophilic, a hydrophilic inorganic compound such as aluminum oxide or titanium oxide photocatalyst is applied to the surface of the molded article to form a coating layer having hydrophilicity on the surface of the molded article. Is formed. However, when a hydrophilic inorganic compound such as aluminum oxide is directly coated on the surface of a molded article, the adhesion between the resin of the molded article and the hydrophilic inorganic compound is not sufficient, and the coating layer peels off during use. It has a problem of durability such as rubbing.

As described above, none of the plastic molded products whose surfaces have been modified by the conventional method can satisfy the antifouling function and the durability in view of the fact that the plastic molded products are frequently used. .

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a plastic molded product which can satisfy both the antifouling function and the durability. further,
An object of the present invention is to provide a plastic molded product which can be colored or printed as required, and further has functions such as antistatic property, high refractive index, and conductivity.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, using a composite sheet having a functional inorganic layer shown below, and forming this into a plastic molding It has been found that a plastic molded product meeting the above-mentioned object can be obtained by transferring the functional inorganic layer so that it appears on the surface of the product, thereby completing the present invention.

That is, the present invention relates to a method of forming a first layer, a release layer, and a second layer
The present invention relates to a composite sheet comprising a functional inorganic layer containing a hydrophilic inorganic compound as a layer, and a polymer layer containing a polymer compound as a final layer.

The composite sheet of the present invention is used for providing a hydrophilic coating layer on the surface of a plastic molded product. The polymer layer of the composite sheet is attached to the surface of the plastic molded product, and then the support of the composite sheet is peeled off from the plastic molded product, and the release layer is removed to remove the hydrophilicity on the surface of the plastic molded product. A coat layer is provided. The hydrophilic coating layer provided on the surface of the plastic molded product in this way is firmly adhered to the molded product surface via the polymer layer and has excellent durability, and the hydrophilic coating layer is hydrophilic. It contains inorganic compounds and can impart strong hydrophilicity, and exhibits an excellent antifouling function.

[0012] Further, contaminants hardly adhere to the surface of the obtained plastic molded article, and even if it adheres, it can be easily washed off by running water, so that a plastic molded article having excellent antifouling properties can be obtained. .

In the composite sheet of the present invention, the function of the release layer is to prevent direct contact between the support and the hydrophilic inorganic compound contained in the functional inorganic layer. It is to suppress that the polymer compound (resin) used wets the surface of the hydrophilic inorganic compound. This release layer is removed from the surface of the molded article after transferring the composite sheet to the surface of the plastic molded article, and the hydrophilic inorganic compound on the surface of the molded article is exposed to the atmosphere.

In the case of a composite sheet having a functional inorganic layer directly provided on a support without a release layer, the support is heat-dissolved during transfer molding and adheres to the functional inorganic layer, Subsequent removal of the support is very difficult. Even if the support can be removed, the functional inorganic layer does not perform its function sufficiently because the support is attached to the surface of the functional inorganic layer. In addition, the polymer layer wraps around the surface of the functional inorganic layer, and the surface exposure rate of the hydrophilic inorganic compound is reduced, so that the function cannot be sufficiently exhibited.

The release layer constituting the composite sheet of the present invention preferably has water solubility or alcohol solubility. The release layer constituting the composite sheet of the present invention preferably has water swellability.

When the release layer exhibits the above properties, the function of the hydrophilic inorganic compound as the functional particles in the functional inorganic layer is not impaired when the support is released, and the release is easy.
When a release material (separator) generally used in which a fluorine-based release agent or a silicone-based release agent is applied to a polyester film or the like as a release layer,
When the composite sheet is transferred to the surface of the plastic molded article, the release material transfers to the functional inorganic layer, so that the function of the hydrophilic inorganic compound cannot be sufficiently exhibited.

The hydrophilic inorganic compound contained in the functional inorganic layer constituting the composite sheet of the present invention includes aluminum, silicon, zinc, tin, lanthanum, samarium, barium, magnesium, strontium, titanium, cerium, zirconium, It is preferably an oxide and / or hydroxide containing at least one element selected from the group consisting of yttrium, potassium and calcium. Such a hydrophilic inorganic compound exhibits an excellent antifouling function.

The polymer compound contained in the polymer layer constituting the composite sheet of the present invention may be at least one selected from the group consisting of an acrylic resin, an epoxy resin and a fluororesin. preferable.

The polymer layer has a function of adhering the functional inorganic layer to the surface of the plastic molded product. The polymer layer has good adhesion to the above-mentioned functional inorganic layer and does not adhere to the release layer. Required. Further, the polymer layer imparts weather resistance, chemical resistance, and aesthetic appearance to the plastic molded product in some cases. From these points, the above resins are preferably used.

As the acrylic resin and / or epoxy resin exemplified as the polymer layer, those containing a silanol group are more preferable. By using a resin having a silanol group for the polymer layer, the adhesion to the functional inorganic layer can be further improved.

In the composite sheet of the present invention, a second functional layer can be provided between the functional inorganic layer and the polymer layer. For example, if a colored layer or a printed layer is provided as the second functional layer, there is no need to color the plastic molded article main body. Therefore, when considering a resin recital, if only the colored portion of the surface is scraped off, the molded article main body can be removed. Since the portion is not colored, it can be reused as it is and the resources can be effectively used. In addition, a functional layer having anti-reflection effect and beautification by interference color can be provided by a functional layer having conductivity, antistatic property and high refractive index.

In producing a plastic molded article using the composite sheet, a support of the composite sheet is attached so as to be in contact with the inner surface of the mold, and then a thermoplastic resin or a thermosetting resin is placed in the mold. It is preferable to adopt a method of injecting the resin, molding the resin, and transferring the functional inorganic layer of the composite sheet to the surface of the resin molded product.

According to the production method of the present invention, it is possible to obtain a molded article excellent in any of the surface hydrophilicity, adhesion and durability, and the production method of the present invention is excellent in productivity. I have.

[0024]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The composite sheet of the present invention will be described below with reference to the drawings. 1 to 4 show cross-sectional views of the composite sheet of the present invention.

In the composite sheet of FIG. 1, a release layer 1 as a first layer, a functional inorganic layer 2 containing a hydrophilic inorganic compound as a second layer, and a polymer compound as a final layer are formed on a support 4. The polymer layer 3 is provided.

Examples of the support 4 include a plastic film such as polyester, polypropylene, polyimide, and acrylic resin, and a metal foil such as iron, stainless steel, and aluminum. For example, a metal foil is used when the composite sheet is used at a high temperature, and a flexible plastic film is used when the composite sheet is transferred onto a curved surface. As the support 4, as a special case, an inorganic material such as ceramics can be used.

The release layer 1 does not dissolve in an organic solvent,
Those that dissolve in water or alcohol, or those that swell with water to weaken the bonds between molecules and easily peel off and fall off the support 4 are preferably used.

Examples of the material constituting the release layer 1 include water-soluble polymers such as cellulose, polyacrylic acid, and polyvinyl alcohol, alumina sol, and the like.
Inorganic polymers such as silica sol, titania sol, zirconia sol, Al, Si, Zr, Ti, Zn, etc., Ce,
Fine particles of oxides or hydroxides of rare earths such as Y or alkaline earth metals such as Mg, Ca and Ba are used.

The particle size of the compound using fine particles of an inorganic polymer or oxide or hydroxide as the material of the release layer 1 is not particularly limited, but when a transparent smooth surface is formed, the particle size may be reduced. It is preferred to make it small, generally 5
１００100 nm. After the transfer of the composite sheet to the surface of the plastic molded product, if the surface of the molded product requires transparency or smoothness, the particle size is preferably 10 nm or less. The fine particles used as the material of the release layer 1 are preferably spherical so that they can swell with water or the like and be easily separated. These materials used for the release layer 1 may be used alone or as a mixture of two or more types. A mixture of a system that dissolves in water or the like and a system that swells and peels with water may be used. Good.

As the hydrophilic inorganic compound contained in the functional inorganic layer 2, various compounds can be used. For example, aluminum, silicon, zinc, tin, lanthanum, samarium, barium, magnesium, strontium, titanium, cerium, zirconium , Yttrium, potassium and calcium oxides or hydroxides, or composite oxides thereof. Preferably, aluminum oxide, cerium oxide, zirconium oxide, silicon oxide, yttrium oxide, potassium oxide, and titanium oxide compounds are used.

These hydrophilic inorganic compounds are used separately from the materials used for the release layer 1. The size of the hydrophilic inorganic compound is not particularly limited as long as it has hydrophilicity, but it is preferable to reduce the size to obtain a transparent and high-gloss molded article. The size of the hydrophilic inorganic compound is 2n
m to 2 μm, more preferably 5 to 100 nm. The hydrophilic inorganic compound may be powdery or granular, but preferably has a fibrous or network structure that does not cause peeling. In addition, the particles may be spherical as long as the particle size is relatively large such that the resin easily permeates as a hydrophilic agent. These hydrophilic inorganic compounds may be used alone or in combination of two or more.

Among the above-mentioned hydrophilic inorganic compounds, titanium oxide is known as a hydrophilic agent utilizing a photocatalytic action. When a composite sheet using the same as a material of the functional inorganic layer 2 is used, the photocatalyst is used. A plastic molded article having on the surface thereof can be produced. When this photocatalyst is formed on the surface of a plastic, deterioration of the base plastic (molded body) due to the photocatalysis becomes a problem.

As described above, when titanium oxide which is a photocatalyst is used as the hydrophilic inorganic compound of the functional inorganic layer 2,
As shown in FIG. 2, the composite sheet of the present invention has a barrier between a functional inorganic layer 2 and a polymer layer 3 that forms an inorganic inert layer or an organic inert layer that is inactive against titanium oxide. Layer 5 can be provided. The inorganic inert layer or the organic inert layer used for the barrier layer 5 generally has poor adhesion to the base plastic (molded body) and is difficult to apply, but by using the composite sheet of the present invention, It is possible to form the barrier layer 5 having excellent adhesion to the base plastic (molded article), and to mold a plastic molded article having a photocatalytic surface having excellent durability. Note that as a material for forming the inorganic inert layer, fine particles used as a hydrophilic agent such as silicon oxide, aluminum oxide, cerium oxide, yttrium oxide, and amorphous titanium oxide, or an inorganic polymer such as silica sol and alumina sol can be used. . Further, a fluorine resin, a silicone resin, or the like can be used as the organic inert layer. Further, the barrier layer 5 may be a mixture of two or more of those used for the inorganic inert layer and the organic inert layer.

When the above-mentioned functional inorganic layer 2 is formed on the support 1, the functional inorganic layer 2 may be formed only of a hydrophilic inorganic compound, and if necessary, a binder and a curing agent for the binder may be used. They can be used together.

Examples of the binder include organic polymers such as unsaturated polyester, vinyl ester, epoxy resin, diallyl phthalate resin, acrylic resin, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, and silicone resin, alumina sol, and the like. Inorganic sols such as silica sol and titania sol are used.

It is preferable that the content of the binder is 50 to 100% in terms of weight%, and the content of the binder is 0 to 50%. More preferably, the hydrophilic inorganic compound is 65 to 100%, and the binder is 0 to 35%.
It is blended in the range. When the content of the hydrophilic inorganic compound is less than 50%, after transferring and peeling the composite sheet to the surface of the plastic molded product, the hydrophilic inorganic compound is less likely to be exposed on the surface of the plastic molded product, and the surface energy does not increase. There is a possibility that the hydrophilic property of the surface, which is an expected function, may be reduced.

The curing agents that may be added as needed include tertiary (abbreviated as t) -butyl peroxybenzoate, benzoyl peroxide, t-butyl novaeoxy isopropyl carbonate, t-hexyl peroxy isopropyl carbonate, Organic peroxides such as t-hexylnos-oxybenzoate, bis (4-t-butylcyclohexyl) peroxydicarbonate or t-hexylperoxydiethylhexanoate, or hexamethylene diisocyanate, tolylene diisocyanate, meta-xylene diisocyanate ,
Examples thereof include phenylene diisocyanate, tetramethylene diisocyanate, bis (isocyanatomethyl) cyclohexane isocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and diphenyl diisocyanate. An appropriate one is selected according to the combination with the binder.

The amount of the curing agent used is an amount generally used depending on the combination of the binder and the curing agent.

Further, in forming the functional inorganic layer 2, a solvent can be used to adjust the viscosity of the forming agent of the functional inorganic layer 2 to facilitate application. As the solvent, benzene, toluene, xylene, styrene, chloroform, chlorobenzene, dichloromethane, dichloroethylene, trichlene, perchloroethylene, ethyl ether, isopropyl ether, tetrahydrofuran,
1,4-dioxane, diglyme, anisole, methanol, ethanol, 2-pronovenol, t-butanol, ethyl cellosolve, butyl cellosolve, phenol, methyl ethyl ketone, methyl isobutyl ketone, 2
-Pentanone, 3-pentanone, ethyl acetate, butyl acetate, triethylamine, piperidine, pyridine, acetonitrile, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorumamide, N-methylpyrrolidone, methyl methacrylate, diotatyl phthalate, Water, acetone, and the like are used, but are not particularly limited thereto.

The amount of the solvent used is not particularly limited, but the total weight of the hydrophilic inorganic compound and the binder is 1 to 7
It is preferable to use it in the range of about 0% by weight.

As a method of preparing the forming agent of the functional inorganic layer 2, there is a method in which a hydrophilic inorganic compound is added to a solvent while stirring, and then a binder and a curing agent are added. The compounding method is not limited. However, when a curing agent is used, it is added last.

Next, the polymer layer 3 will be described. The polymer compound forming the polymer layer 3 has a function of adhering a functional inorganic layer to the surface of a plastic molded product, and the polymer compound used for the polymer layer includes:
It is preferable that the SP value (solubility parameter) is close to the SP value of the resin used for the plastic molded product, and the difference between the SP values is preferably 2 or less.

The polymer compound may be appropriately determined according to the material of the plastic molded article to which the composite sheet is applied. For example, an acrylic resin, an epoxy resin, and a fluorine resin are used. For example, for a molded article made of polypropylene or polystyrene, by applying a composite sheet using an acrylic resin for the polymer layer 3,
The weather resistance and chemical resistance of the surface of the molded article can be improved.

As the acrylic resin and the epoxy resin, those having a silanol group are preferably used because of good adhesion to the functional inorganic layer 2. Such a silanol group can be directly introduced into the polymer compound, or can be introduced by adding a silane coupling agent to the polymer layer 3.

The polymer layer 3 is generally formed by dissolving a polymer compound in an organic solvent such as toluene, xylene, ethyl acetate, or methyl ethyl ketone and applying the solution. If necessary, a curing agent compatible with the polymer compound may be used. The amount of the silane coupling agent and the curing agent is
Usually, it may be an amount generally used, and is not particularly limited.

The polymer layer 3 is required to have good adhesion to the above-mentioned functional inorganic layer 2 and not to adhere to the release layer 1. When a plastic material (water-soluble polymer) is used for the release layer 1, the difference between the SP values of the materials of the two layers should be 0.5 or more in order to improve the releasability from the polymer layer 3. preferable.

FIG. 3 shows that the functional inorganic layer 2 and the polymer layer 3
FIG. 5 shows an example in which the second functional layer 6 is provided between the polymer layers 3.
In FIG. 5, the polymer layers 3 on both sides of the second functional layer 6 may have the same composition or different compositions.

As the second functional layer, for example, a colored layer,
A printing layer, a conductive layer, an antistatic layer, and a high refractive index layer can be provided. As the functional material included in the second functional layer, a coloring agent or a variety of agents for imparting a pattern is used for the coloring layer or the printing layer, and the conductive layer and the antistatic layer are conductive agents. SnO ₂ , In ₂ O ₃ , ATO (S
n-added SnO ₂ ), Au, Ag, Pb, Cu, Pt,
Ni, Cr, or the like can be used. In the high refractive index layer, SnO ₂ , In ₂ O ₃ , ATO, I
TO, TiO ₂ , ZrO _{2 and the} like can be used.

For forming the second functional layer, the polymer layer 3 is usually used.
The same high molecular compound (resin) is used.

Further, it is possible to provide the polymer layer 3 with the second function by adding a functional material exhibiting the above function to the polymer layer 3 without separately providing the second function layer. it can.

Next, a basic method for producing the composite sheet of the present invention will be described.

First, a forming agent for the release layer 1 is applied to one surface of the support 4 and dried. Next, a forming agent for the functional inorganic layer 2 is applied to the surface of the release layer 1 and dried, and then a forming agent for the polymer layer 3 is applied to the surface of the functional inorganic layer 2 and dried to obtain a composite sheet. obtain.

The other barrier layers 5 and the second functional layers 6 are provided as necessary in the same manner as described above. As a coating method, any method such as a roll coating method, a knife coating method, a die coating method, a spray-up method, and a brush coating method can be adopted, and the coating is performed by an appropriate method according to the viscosity of each layer forming agent and the like.

The thickness of the support 4 and the thickness of each layer are also determined appropriately according to the application. Usually support 4:
About 1 to 50 μm, release layer 1: about 1 to 30 μm, functional inorganic layer 2: about 0.5 to 30 μm, polymer layer 3: 1 to 1
The thickness is about 30 μm, the barrier layer 5 is about 50 to 200 nm, and the second functional layer 6 is about 20 nm to 10 μm.

The drying conditions are selected in an appropriate range depending on the polymer compound (resin), curing agent and solvent used, but the temperature is generally about 80 ° C. to 200 ° C., and the time is generally about 1 minute to 30 minutes. It is a target.

Next, a method for producing a plastic molded article having an antifouling function on the surface by transfer using a composite sheet will be described.

The transfer method using the composite sheet is not particularly limited, but in the present invention, after the composite sheet is attached so that the support of the composite sheet is in contact with the inner surface of the mold, a thermoplastic resin or a resin is placed in the mold. After injecting thermosetting resin,
A method in which a thermoplastic resin is cooled or a thermosetting resin is cured and molded, and a functional inorganic layer is transferred to the surface of the resin molded body can be preferably adopted.

As a method for molding the resin, various methods such as injection molding, compression molding, reaction injection molding and injection molding can be employed.

According to this method, the functional inorganic layer is transferred and adhered to the surface of the molded body via the polymer layer. After the resin is molded, the mold is removed and the support on the surface is peeled off. The functional inorganic layer and the release layer are firmly adhered to the surface of the plastic molded product. If the surface of the release layer is removed by washing with water or the like, a functional inorganic layer containing a hydrophilic inorganic compound appears on the surface of the plastic molded product.

As the thermoplastic resin and the thermosetting resin, those used for various molding materials can be used without any particular limitation. Examples of the thermoplastic resin include general-purpose resins such as polypropylene resin, polystyrene resin and acrylic resin. Is raised. As the thermosetting resin, an epoxy resin, a melamine resin, a urea resin, a phenol resin, or the like, or a resin that can be thermoset with a thermopolymerizable diluent such as styrene is used. As the thermosetting resin, a curing agent corresponding to the resin can be used.

The transfer method using the composite sheet is not limited to the above-mentioned method. For example, a method in which the composite sheet is directly adhered to the surface of a plastic molded product, the support is peeled off, and the release layer is removed. Can also.

Incidentally, without using the composite sheet of the present invention, a hydrophilic inorganic compound,
The method of post-coating a composition containing a binder, a solvent, a curing agent, and the like has a problem in terms of adhesion between a coating material and a plastic molded product. Therefore, it is necessary to improve the adhesion and film strength by performing a heat treatment after the post-coating on the surface of the plastic molded product, but if the base plastic does not have heat resistance, the treatment temperature may be sufficiently increased. It is not possible to provide sufficient adhesiveness, and if heated above the heat resistance temperature, the substrate will be damaged. Also, in the method of directly coating the mold and then transferring the resin onto the surface of the plastic molded product by press-fitting, etc., there are problems such as uneven thickness when coated, and the quality is not stable. In order to form a layer, it is necessary to repeatedly perform coating and drying, and it takes a considerable time to form a layer. In addition, a product which can be molded in a short time, such as injection molding, has a problem particularly in productivity.

[0063]

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.

Example 1 (Preparation of Functional Inorganic Layer Forming Agent) Magnesium oxide powder (NanoTek, MgO, manufactured by C-I Kasei Co., Ltd., trade name) as a hydrophilic inorganic compound, vinyl ester (PS-6150, Hitachi, Ltd.) as a binder A functional inorganic layer forming agent was prepared using butyl cellosolve as a solvent (trade name, manufactured by Kasei Kogyo Co., Ltd.). Magnesium oxide and vinyl ester were mixed at a weight ratio of magnesium oxide: vinyl ester = 9: 1, and the mixture was dispersed in butyl cellosolve so as to have a weight ratio of 50% by weight.

(Preparation of Polymer Layer Forming Agent) Epoxy-modified acrylic resin (7800, manufactured by Hitachi Chemical Co., Ltd.)
Product name) with a mixture of water and ethanol (water: ethanol =
7: 3, by weight) and a polymer layer forming agent adjusted so that the resin content was 6% by weight.

(Preparation of Composite Sheet) Polyethylene terephthalate (hereinafter abbreviated as PET) film (25 μm)
A polyvinyl alcohol (hereinafter abbreviated as PVA, release agent S) forming a release layer on the surface of
Colorless, coated with Showa Kogyo Co., Ltd., trade name) 120
And dried by heating at 10 ° C. for 2 minutes (10 μm).
It is applied on the VA layer and dried by heating at 120 ° C. for 2 minutes (2
μm), and then applying the polymer layer forming agent,
The resultant was dried by heating at 0 ° C. for 10 minutes (15 μm), and the dispersion solvent was evaporated to prepare a composite sheet of the present invention.

(Preparation of Thermosetting Resin Composition) As a thermosetting resin composition to be injected into a cavity of a mold, 50% by weight of vinyl ester diluted with styrene (PS615) was used.
0, manufactured by Hitachi Chemical Co., Ltd., trade name) 100 parts by weight,
200 parts by weight of aluminum hydroxide (HBT320, manufactured by Showa Denko KK, trade name) as a filler, bis (4-t-butylcyclohexyl) peroxydicarbonate (Percadox 16S, manufactured by Kayaku Akzo Co., Ltd.) as a curing agent, 0.3 parts by weight of t-hexylperoxydiethylhexanoate (Percure HO, manufactured by NOF CORPORATION, trade name) was mixed and uniformly mixed.

(Production and Molding of Plastic Molded Product) A composite sheet is stuck in a mold, and this mold and the other mold are combined and clamped to form a male-female combined mold cavity. Injecting the thermosetting resin composition,
The molding was performed at a heating temperature of 100 ° C. and a heating time of 30 minutes. At this time, the functional inorganic layer of the composite sheet was transferred to the plastic molded product side. After demolding and peeling off the PET film, it was washed with water, and a plastic molded product (200 mm long, 2 mm wide) constituting a surface layer supporting a hydrophilic inorganic compound was formed.
00 mm).

Example 2 In the preparation of the functional inorganic layer forming agent of Example 1, α-type aluminum oxide powder (AM2
A functional inorganic layer-forming agent was prepared in the same manner as in Example 1 except that 1, (manufactured by Sumitomo Chemical Co., Ltd., trade name) was used.
Thereafter, a polymer layer forming agent was prepared in the same manner as in Example 1, and a composite sheet was produced in the same manner as in Example 1. Further, the same thermosetting resin composition as in Example 1 was prepared, and a plastic molded product was manufactured and molded in the same manner as in Example 1, and the plastic molding constituting the surface layer supporting the hydrophilic inorganic compound was performed. A product (length 200 mm, width 200 mm) was obtained.

Example 3 In the preparation of the functional inorganic layer forming agent of Example 1, silicon oxide powder (NanoTek, S.K.) was used as the hydrophilic inorganic compound.
A functional inorganic layer-forming agent was prepared in the same manner as in Example 1 except that iO ₂ (trade name, manufactured by CI Kasei Co., Ltd.) was used. Thereafter, a polymer layer forming agent was prepared in the same manner as in Example 1, and a composite sheet was produced in the same manner as in Example 1. Further, the same thermosetting resin composition as in Example 1 was prepared, and a plastic molded product was manufactured and molded in the same manner as in Example 1, and the plastic molding constituting the surface layer supporting the hydrophilic inorganic compound was performed. Product (length 200mm, width 20)
0 mm).

Example 4 In the preparation of the functional inorganic layer forming agent of Example 1, yttrium oxide powder (NanoT) was used as a hydrophilic inorganic compound.
ek, Y ₂ O ₃ , C I Kasei Co., Ltd. (trade name) was used in the same manner as in Example 1 to prepare a functional inorganic layer forming agent. Thereafter, a polymer layer forming agent was prepared in the same manner as in Example 1, and a composite sheet was produced in the same manner as in Example 1. Further, the same thermosetting resin composition as in Example 1 was prepared, and a plastic molded product was manufactured and molded in the same manner as in Example 1, and the plastic molding constituting the surface layer supporting the hydrophilic inorganic compound was performed. A product (length 200 mm, width 200 mm) was obtained.

Example 5 In the preparation of the functional inorganic layer forming agent of Example 1, cerium oxide powder (NanoT) was used as the hydrophilic inorganic compound.
ek, CeO ₂ , C I Kasei Co., Ltd. (trade name) was used in the same manner as in Example 1 to prepare a functional inorganic layer forming agent. Thereafter, a polymer layer forming agent was prepared in the same manner as in Example 1, and a composite sheet was produced in the same manner as in Example 1. Further, the same thermosetting resin composition as in Example 1 was prepared, and a plastic molded product was manufactured and molded in the same manner as in Example 1, and the plastic molding constituting the surface layer supporting the hydrophilic inorganic compound was performed. A product (length 200 mm, width 200 mm) was obtained.

Example 6 In the preparation of the functional inorganic layer forming agent of Example 1, titanium oxide powder (NanoTe) was used as the hydrophilic inorganic compound.
k, TiO ₂ , C I Kasei Co., Ltd. (trade name) was used in the same manner as in Example 1 to prepare a functional inorganic layer forming agent. Thereafter, a polymer layer forming agent was prepared in the same manner as in Example 1, and a composite sheet was produced in the same manner as in Example 1. Further, the same thermosetting resin composition as in Example 1 was prepared, and a plastic molded product was manufactured and molded in the same manner as in Example 1, and the plastic molding constituting the surface layer supporting the hydrophilic inorganic compound was performed. Product (length 200mm, width 2)
00 mm).

Comparative Example 1 A composite sheet was prepared in the same manner as in Example 1 except that a hydrophilic inorganic compound was not used in the preparation of the functional inorganic layer forming agent of Example 1. Thereafter, the same thermosetting resin composition as in Example 1 was prepared, and a plastic molded product was manufactured and molded in the same manner as in Example 1 to obtain a plastic molded product (length 200 mm, width 200 mm).

Comparative Example 2 (Preparation of Functional Inorganic Layer Forming Agent and Polymer Layer Forming Agent) In the preparation of the functional inorganic layer forming agent of Example 1, α-type aluminum oxide powder (hydrophilic inorganic compound) was used. AM2
A functional inorganic layer-forming agent was prepared in the same manner as in Example 1 except that 1, (manufactured by Sumitomo Chemical Co., Ltd., trade name) was used.
In the same manner as in Example 1, a polymer layer forming agent was prepared.

(Application to Mold) A PVA for forming a release layer was applied to the inner surface of the mold by spray coating on the inner surface of the mold similar to that in Example 1 and dried by heating at 80 ° C. for 5 minutes (10 μm). The forming agent for the functional inorganic layer is applied by spray coating, and dried by heating (2 μm) at 60 ° C. for 5 minutes. Then, a polymer layer forming agent is applied by spray coating.
After drying by heating at 0 ° C. for 10 minutes (15 μm), the solvent was evaporated to form a hydrophilic layer on the inner surface of the mold.

(Production and Molding of Plastic Molded Product) The mold and the other mold are combined and clamped. The resin composition was injected, and molding was performed at a heating temperature of 100 ° C. and a heating time of 30 minutes. At this time, the functional inorganic layer was transferred to the plastic molded product side. After demolding and peeling off the PET film, it was washed with water to obtain a plastic molded product (200 mm in length and 200 mm in width) constituting a surface layer supporting a hydrophilic inorganic compound.

The plastic molded articles produced in Examples 1 to 6 and Comparative Examples 1 and 2 were subjected to the following Test Examples 1 to 6. Table 1 shows the results.

Test Example 1 (Droplet Diameter) In order to evaluate the hydrophilicity of the surface of the plastic molded product, a water drop was dropped on the surface of the plastic molded product using a Pasteur pipette, and the droplet size was measured with a vernier caliper. In addition, a droplet is 0.03 ml. The larger the droplet diameter, the more hydrophilic the surface.

Test Example 2 (Water wettability) In order to evaluate the water wettability of the surface of a plastic molded product,
Water was applied to the entire surface of the plastic molded product. At this time, the spreading state of the water was observed with eyes, and the water wettability was evaluated according to the following criteria. The better the water wettability, the more hydrophilic the surface. ：: Water spread uniformly over the entire surface of the plastic molded product and was well wetted. ×: Water is repelled to form droplets and adhere to the surface of the plastic molded product.

Test Example 3 (Contact Angle) In order to evaluate the hydrophilicity of the surface of the plastic molded product, the contact angle of the droplet of Test Example 1 was measured. A smaller contact angle indicates that the surface is more hydrophilic. The contact angle was measured using a contact angle meter (CA-X manufactured by Kyowa Interface Science Co., Ltd.).
150 type).

Test Example 4 (Antifouling Property) In order to evaluate the antifouling property of the surface of the plastic molded product, a salad oil in which carbon black was dispersed was used as a contaminant, and this was forcibly adhered to the surface of the plastic molded product. Was. Ten minutes after the adhesion, tap water was allowed to flow down to the soiled surface for 10 seconds, and the degree of stain removal was visually evaluated according to the following criteria. ：: The pollutant was washed down. ×: Contaminants are not washed down.

Test Example 5 (Adhesion) In order to evaluate the adhesion between the functional inorganic layer carrying the hydrophilic inorganic compound on the surface of the plastic molded product and the base resin, the plastic molded product was heated at 90 ° C. with hot water. For 300 hours. This was taken out, and the surface was visually evaluated for swelling or peeling according to the following criteria. ：: No swelling or peeling, no change in the surface condition of the plastic molded product.

×: There is swelling or peeling, and the surface state of the plastic molded article has changed.

Test Example 6 (Smoothness) In order to evaluate the smoothness of a functional inorganic layer having a hydrophilic inorganic compound supported on the surface of a plastic molded product, the gloss of the surface was measured using a gloss meter.

[0086]

[Table 1] As shown in Table 1, the plastic molded products of Examples 1 to 6 had a droplet diameter as large as 10 mm or more, and even in water wettability, water spread evenly and showed a good water wet state. , And the contact angle of the droplets is less than 20 °,
Shows sufficient hydrophilicity. Regarding the antifouling property,
The dirt substance is easily washed away by washing down with water, and has good characteristics, and also has good characteristics without swelling or peeling in adhesion. Further, the gloss is 80 or more, and the surface is glossy. Therefore, the antifouling property and durability of the surface layer of the plastic molded article are excellent, and the gloss is large, the gloss is good, and the clothes are good. On the other hand, the plastic molded product of Comparative Example 1 is inferior in hydrophilicity and does not show an antifouling effect. Further, the plastic molded product of Comparative Example 2 exhibits hydrophilicity but has low gloss and poor smoothness.

Example 7 (Preparation of Functional Inorganic Layer Forming Agent) Ultrafine particles of aluminum oxide (Al ₂ O ₃ , Nano) as a hydrophilic inorganic compound
Tek (trade name) and isopropanol as a solvent to prepare a functional inorganic layer-forming agent. The aluminum oxide was dispersed in isopropanol so as to be 5% by weight.

(Preparation of Polymer Layer Forming Agent) Epoxy resin (Epomic 7301, trade name, manufactured by Hitachi Chemical Co., Ltd.) was mixed with butyl acetate and isopropanol (butyl acetate: isopropanol = 1: 1, weight ratio). In addition, a polymer layer forming agent adjusted to have a resin content of 6% by weight was prepared.

(Preparation of Composite Sheet) PET film (2
Alumina sol (alumina sol 100, manufactured by Nissan Chemical Co., Ltd., trade name) was applied to the surface of 5 μm) using a roll coater, and heated and dried at 120 ° C. for 2 minutes (100 nm).
Next, the formed functional inorganic layer forming agent was applied on the alumina sol layer using a roll coating method,
Heat drying for 2 minutes (2 μm), then apply the polymer layer forming agent, and heat dry at 140 ° C. for 10 minutes (1
5 μm) and the dispersion solvent was evaporated to produce a composite sheet of the present invention.

(Production and Molding of Plastic Molded Product) A composite sheet is stuck in a mold, and this mold and the other mold are combined and clamped to form a male-female combined mold cavity. A commercially available acrylic plate (thermoplastic resin) was melted at 200 ° C. to obtain 200 kg / cm ²
And injection molding was performed. At this time, the functional inorganic layer of the composite sheet was transferred to the plastic molded product side. After demolding and peeling off the PET film, it was washed with water to obtain a plastic molded product (200 mm in length and 200 mm in width) constituting a surface layer supporting a hydrophilic inorganic compound.

Example 8 In the preparation of the polymer layer forming agent of Example 7, an acrylic resin (Hitaloid 216) was used as the polymer compound (resin).
A polymer layer forming agent was prepared in the same manner as in Example 7 except that 0X (trade name, manufactured by Hitachi Chemical Co., Ltd.) was used. Thereafter, a composite sheet was produced in the same manner as in Example 7, using the same functional inorganic layer forming agent as in Example 7. Further, using the same thermoplastic resin as in Example 7,
Production and molding of plastic molded products in the same manner as
A plastic molded article (200 mm long, 200 mm wide) constituting a surface layer supporting a hydrophilic inorganic compound was obtained.

When the plastic molded products produced in Examples 7 and 8 were evaluated in Test Examples 1 to 6, the hydrophilicity was good as in Examples 1 to 6, and the adhesion to the substrate was also good. A plastic molded article excellent in antifouling property and smoothness was obtained.

In Examples 7 and 8, a composite sheet was prepared by using another inorganic polymer sol or oxide fine particles instead of alumina sol to form a release layer. Plastic molded articles were produced and molded in the same manner as in Examples 7 and 8. The obtained plastic molded article was excellent in antifouling properties. Incidentally, the oxide fine particles,
When the particle diameter is 1 μm or more, the gloss on the surface of the plastic molded product becomes 70 or less, and the transparency is further reduced.
Therefore, when a plastic molded product is used with specifications such as a cloudy window, the larger the particle size of the oxide fine particles is, the more effective it is. It is better to reduce the particle size. In addition, even when the oxide fine particles having a large particle diameter were used for the release layer, the gloss and the transparency of the plastic surface after molding were improved when mixed with a water-soluble polymer.

Further, when it is difficult to judge whether or not the release layer has been completely washed with water from the plastic molded product, the release layer can be colored. However, in this case, since organic dyes and organic pigments as a coloring agent may be strongly bonded to the hydrophilic inorganic compound, those having a large particle diameter as the hydrophilic inorganic compound are dispersed in a water-soluble polymer. It was effective to use it white.

Example 9 In the same manner as in Example 7, a functional inorganic layer-forming agent and a polymer layer-forming agent were prepared. Then, as in Example 7, P
Alumina sol (alumina sol 100, manufactured by Nissan Chemical Co., Ltd., trade name) is applied to the surface of the ET film using a roll coater, dried by heating at 120 ° C. for 2 minutes, and then the formed functional inorganic layer-forming agent is prepared. Was applied on the alumina sol layer by a roll coating method, and dried by heating at 120 ° C. for 2 minutes. Next, an appropriate photograph was color-printed on the surface of the functional inorganic layer using an ink jet printer. After that, the polymer layer forming agent was applied,
For 10 minutes, and the dispersion solvent was evaporated to prepare a composite sheet of the present invention. A plastic molded article was manufactured and molded in the same manner as in Example 7 using the same thermoplastic resin as in Example 7, and a plastic molded article (vertical) constituting a surface layer supporting a hydrophilic inorganic compound was prepared. 200m
m, width 200 mm).

When the obtained molded plastic products were evaluated in Test Examples 1 to 6, the hydrophilicity, the antifouling property, the adhesion and the smoothness were good as in Examples 1 to 8, and the printed photographs were also good. There was no gradual or swelling, and transfer was possible without deterioration in image quality as in film printing.

Example 10 (Preparation of functional inorganic layer forming agent) Ultrafine particles of aluminum oxide (Al ₂ O ₃ , Nano) as a hydrophilic inorganic compound
Tek (trade name), fluorinated resin (A
usimont USA, trade name Polymist),
A functional inorganic layer forming agent was prepared using water as a solvent. The mixing ratio of aluminum oxide and fluororesin is aluminum oxide: fluororesin = 8: 2 by weight ratio,
This compounding ratio was dispersed in water so as to be 5% by weight.

(Preparation of Polymer Layer Forming Agent) A fluororesin (manufactured by Elf Atochen, trade name Kynar) was extruded into a sheet shape to obtain a polymer layer forming agent.

(Preparation of Composite Sheet) Aluminum foil (15 μm)
m) Using a roll coater on the surface, apply an alumina slurry (alumina slurry, trade name, manufactured by CI Kasei Co., Ltd.) and heat dry at 120 ° C. for 2 minutes (0.2 μm).
m). Next, the formed functional inorganic layer forming agent is applied on alumina using a roll coating method, and dried by heating at 350 ° C. for 3 minutes (1 μm), and then the polymer layer forming agent is applied thereon. The combined sheet was heated at 350 ° C. for 3 minutes to produce a composite sheet of the present invention.

(Production and Molding of Plastic Molded Product) A composite sheet is stuck in a mold, this mold and the other mold are joined together, and the mold is clamped. , Fluorine resin (ElfAtochen)
(Trade name, Kynar) was injected and molded. At this time, the functional inorganic layer of the composite sheet was transferred to the plastic molded product side. After removing the mold and peeling off the aluminum foil, the aluminum foil was washed with water to obtain a plastic molded product (200 mm in length and 200 mm in width) constituting a surface layer supporting a hydrophilic inorganic compound.

When the obtained plastic molded articles were evaluated in Test Examples 1 to 6, the hydrophilicity, antifouling property, adhesion and smoothness were good as in Examples 1 to 8. However, since the fluororesin having extremely low surface energy was the binder, the hydrophilicity was slightly inferior to those of Examples 1 to 8, but had sufficient performance as the antifouling performance.

Example 11 (Preparation of Functional Inorganic Layer Forming Agent) Ultrafine particles of titanium oxide (TiO ₂ , NanoTek,
(Trade name) and a functional inorganic layer-forming agent were prepared using isopropanol as a solvent. The titanium oxide was dispersed in isopropanol so as to be 5% by weight.

(Preparation of Polymer Layer Forming Agent) Acrylic resin (Hitaloid 2160X, manufactured by Hitachi Chemical Co., Ltd.)
(Trade name) to a mixed solution of butyl acetate and isopropanol (butyl acetate: isopropanol = 1: 1, weight ratio)
A polymer layer forming agent adjusted to have a resin content of 6% by weight was prepared.

(Preparation of Composite Sheet) PET film (2
5 μm) is coated with PVA using a roll coater, dried by heating at 120 ° C. for 2 minutes (15 μm), and then the formed functional inorganic layer forming agent is coated on the PVA using a roll coating method. Then, it was dried by heating at 120 ° C. for 2 minutes (0.5 μm), and then SiO ₂ sol (ASR4
9. Apply Sumitomo Osaka Cement Co., Ltd. product name) 1
Treated at 40 ° C. for 5 minutes. Next, the composition of the polymer layer was applied, dried by heating at 140 ° C. for 10 minutes (50 μm), and the solvent was evaporated to prepare a composite sheet of the present invention.

(Production and Molding of Plastic Molded Product) The composite sheet is stuck in a mold, this mold and the other mold are combined, and the mold is clamped. A commercially available acrylic plate (thermoplastic resin) was melted at 200 ° C. to obtain 200 kg / cm ²
And injection molding was performed. At this time, the functional inorganic layer of the composite sheet was transferred to the plastic molded product side. After demolding and peeling off the PET film, it was washed with water to obtain a plastic molded product (200 mm in length and 200 mm in width) constituting a surface layer supporting a hydrophilic inorganic compound.

When the obtained plastic molded articles were evaluated in Test Examples 1 to 6, the hydrophilicity, antifouling property, adhesion and smoothness were good as in Examples 1 to 8.

Further, titanium oxide functions as a photocatalyst,
Irradiation with ultraviolet light makes it super-hydrophilic and makes the contact angle of water 0 °. Then, when this molded body was left outdoors and exposed to sunlight, in Example 6, the hydrophilicity became better than that of the molded body using titanium oxide as the hydrophilic inorganic compound, and the function as a photocatalyst was also improved. It was found to have.
Further, a low-pressure mercury lamp (intensity: 12 mW / cm ² , wavelength: 254 nm) was irradiated for 12 hours, and durability was examined.
As a result, the molded article of this example did not show any deterioration in strength even after irradiation for 12 hours. As described above, it was found that the present invention is capable of transferring a photocatalyst, and that an excellent photocatalyst molded article without strength deterioration can be produced by using a molding method by transfer.

[0108]

According to the present invention, the composite sheet is obtained by using the composite sheet,
A plastic molded article having a hydrophilic inorganic compound supported on the surface forms a surface layer having excellent durability and antifouling properties. In addition, the method for producing a plastic molded product of the present invention comprises:
After applying the composite sheet to a mold to form a layer, it is a simple process of injecting a thermoplastic resin or a thermosetting resin composition into the mold and molding it. A plastic molded article having a supported surface layer can be produced.

[Brief description of the drawings]

FIG. 1 is an example of an embodiment of a composite sheet of the present invention.

FIG. 2 is an example of an embodiment in which a barrier layer is provided on the composite sheet of the present invention.

FIG. 3 is an example of an embodiment in which a second functional layer is provided on the composite sheet of the present invention.

FIG. 4 is an example of an embodiment in which a second functional layer is provided on the composite sheet of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 support 2 release layer 3 functional inorganic layer 4 polymer layer 5 second functional layer

 ──────────────────────────────────────────────────続 き Continued on front page (72) Inventor Takayuki Hiwa 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation (72) Inventor Takao Ishikawa 7-1- Omika-cho, Hitachi City, Ibaraki Prefecture 1 Hitachi, Ltd. Hitachi Research Laboratory (72) Inventor Daigoro Kamoto 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture F-term in Hitachi Research Laboratory, Hitachi, Ltd. F-term (reference) AA28C AK01D AK17D AK21 AK25D AK42 AK53 AK53D AL06 AT00A AT00E BA04 BA05 BA10A BA10D EC042 EH112 EH312 EH46 GB08 JB05C JB08B JB09B JB10B JB13 JB16 JG01 JL14B JN18 ABB JA18A13B

Claims (8)

[Claims] 1. A release layer as a first layer, a functional inorganic layer containing a hydrophilic inorganic compound as a second layer, and a polymer compound as a final layer, counted from the support surface, on the support surface. A composite sheet characterized by containing a polymer layer. 2. The composite sheet according to claim 1, wherein the release layer exhibits water solubility or alcohol solubility. 3. The composite sheet according to claim 1, wherein the release layer has water swellability. 4. The hydrophilic inorganic compound contained in the functional inorganic layer includes aluminum, silicon, zinc, tin, lanthanum, samarium, barium, magnesium, strontium,
4. An oxide and / or hydroxide containing at least one element selected from the group consisting of titanium, cerium, zirconium, yttrium, potassium and calcium. The composite sheet as described. 5. The polymer compound contained in the polymer layer is at least one selected from the group consisting of an acrylic resin, an epoxy resin, and a fluorine resin. The composite sheet according to any one of the above. 6. The composite sheet according to claim 5, wherein the acrylic resin and / or the epoxy resin contains a silanol group. 7. The composite sheet according to claim 1, further comprising a second functional layer between the functional inorganic layer and the polymer layer. 8. After attaching the composite sheet according to claim 1 such that the support of the composite sheet is in contact with the inner surface of the molding die, a thermoplastic resin or a thermosetting resin is placed in the molding die. A method for producing a plastic molded product, comprising: injecting a resin, molding the resin, and transferring a functional inorganic layer of the composite sheet to a surface of the resin molded product.