JP2000191804A - Acrylic film and laminated acrylic material for interior walling of bathroom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic film for use in an interior walling material for a bathroom which can be prepd. in a fewer manufacturing steps, furnishes a deep transparency, and has a good quality, and to provide a laminated acrylic material for interior walling of a bathroom by using this film. SOLUTION: This acrylic film for use in a laminated acrylic material for interior walling of a bathroom comprises an acrylic resin having dispersed rubber particles with an average particle size of 0.2-0.4 μm, having a pencil hardness of H or more, and having a thickness of 300 μm or less. The laminated acrylic material 8 for interior walling of a bath is obtd. by bonding a decorative sheet 7 onto a substrate 2 by lamination with or without an adhesive layer 4 in-between, the sheet 7 having been obtd. by forming a printed layer 3 on one of the surfaces of an acrylic film 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bathroom interior wall material in which a specific acrylic film is laminated, and an acrylic film used for the purpose.

[0002]

2. Description of the Related Art Conventionally, ceramic tiles, vinyl chloride steel plates, molded panels made of FRP, and the like have been used as bathroom wall materials. A clear layer is generally formed on the outermost surface of these wall materials by a thermosetting resin (diallyl phthalate resin, polyester resin, or the like) or by painting. On the other hand, recently, with the spread of system buses,
There is an increasing need for bathroom interior wall materials that are affordable, easy to handle, and highly designed.

[0003]

The clear layer formed on a conventional bathroom interior wall material has the following problems.

[0004] The pattern that gives the sense of design is under the clear layer and is printed directly on the base material or a special printing paper is attached to the substrate. However, direct printing employs a batch method, which increases the cost, and is not suitable for a place where a high degree of water resistance is required, such as a bathroom, when a special printing paper is attached to a substrate. In addition, a large number of steps, such as applying a pattern before placing the clear layer, also leads to an increase in cost.

[0005] The thermosetting resin-based clear layer does not always have high transparency. Further, the thickness of the clear layer is as thin as 0.1 to 0.2 mm, and several overcoats are required to obtain a deep view. Even when a clear layer is formed by painting, the maximum coating thickness is as thin as about 0.1 mm, multi-layer coating is required to obtain a deep view, and finally polishing is required to obtain a mirror surface. Become.

[0006] The clear layer of the bathroom interior wall material is required to have chemical resistance and various surface properties. For example, since soap and various detergents are frequently used, alkali resistance is required, and stain resistance and chemical resistance to a hair dyeing liquid, a fungicide, and the like are required. However, a thermosetting resin-based clear layer cannot satisfy all of these requirements. In addition, a clear layer made of a coating, particularly a UV coating, has excellent chemical resistance, but is easily contaminated by a hair dyeing solution or the like.

[0007] The present invention has been made to solve each of the above problems. That is, an object of the present invention is to reduce the number of manufacturing steps, have a deep and transparent feeling, and satisfactorily satisfy the quality required for a bathroom wall material, and an acrylic laminated bathroom interior wall material, and the like. An object of the present invention is to provide an acrylic film used for a purpose.

[0008]

According to the present invention, there is provided an acrylic resin in which rubber particles having an average particle size of 0.2 to 0.4 μm are dispersed, the pencil hardness is H or more, and the thickness is 300 μm or less. An acrylic film for an acrylic laminated bathroom interior wall material.

[0009] The present invention is also an acrylic laminated bathroom interior wall material characterized by being laminated with this acrylic film on a substrate.

The acrylic film of the present invention is made of an acrylic resin in which rubber particles having an average particle size of 0.2 to 0.4 μm are dispersed. Thus, by using rubber particles larger than the rubber particles used in the conventional acrylic film, it is possible to satisfactorily satisfy the quality required for a bathroom wall material. In particular, it is possible to use a relatively small amount of rubber particles than before, and it is possible to use stain resistant, chemical resistant,
A film excellent in hot water resistance, surface hardness and the like can be obtained.

In the acrylic film of the present invention, an acrylic resin having excellent transparency is used, and the thickness is as thin as 300 μm or less. Moreover, the acrylic film is superior to the vinyl chloride and polyester films in terms of depth and luxury.

Further, since the acrylic film of the present invention has a sufficient surface hardness (pencil hardness H or more), an operation such as crosslinking for increasing the surface hardness is not required. Therefore,
It is excellent in stretchability and bending workability, and there is no problem in workability in the laminating process of bathroom interior wall material.

In the prior art, when the surface of the wall material is to be clear-coated with a thermosetting resin, this is gel-coated,
It is necessary to further heat cure, and in the case of painting, in order to obtain the thickness of the clear layer until a sufficient depth of view is obtained, it is necessary to apply a coating twice or more of the required film thickness to obtain a mirror surface In addition, it is necessary to polish the film to a required film thickness, resulting in high cost and extremely low productivity. On the other hand, when the acrylic film of the present invention is used, the outermost clear layer having a deep and transparent feeling can be formed in one step. Further, in that step, it is also possible to provide a design such as a color pattern.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below.

The acrylic resin constituting the acrylic film of the present invention contains 0 to 10 parts by weight of a specific thermoplastic polymer (I) and 5.5 to 5.5 parts of a rubber-containing polymer (II) described below.
25 parts by weight, and a thermoplastic polymer (III) 65 to 9
A rubber-containing polymer (I) containing 4.5 parts by weight as a main component.
It is preferable that the amount of the elastic copolymer in I) is 5 to 18 parts by weight [all based on a total of 100 parts by weight of the components (I), (II) and (III)]. The rubber-containing polymer (II) in the acrylic resin has an average particle size of 0.2 to 0.4 as described above.
This corresponds to rubber particles of μm.

Hereinafter, the preferred constitution of each of the components (I) to (III) will be described.

The thermoplastic polymer (I) preferably comprises 50 to 100% by weight of methyl methacrylate and 0 to 50% by weight of at least one other vinyl monomer copolymerizable therewith. The reduced viscosity of the polymer (0.1 g of the polymer dissolved in 100 mL of chloroform and measured at 25 ° C.) is 0.1.
It is a thermoplastic polymer exceeding 2 L / g.

The thermoplastic polymer (I) is a preferable component in that the film formability is good. Specifically, this can improve the melt tension, increase the discharge rate during film formation, enable film formation even at a relatively high resin temperature, improve productivity, and improve film thickness unevenness. Can be reduced.

The reduced viscosity of the thermoplastic polymer (I) is important. When the reduced viscosity exceeds 0.2 L / g, a film having good thickness accuracy can be obtained. The reduced viscosity is usually 2 L / g or less, preferably 1.2 L / g.
g or less.

In the thermoplastic polymer (I), other vinyl monomers copolymerizable with methyl methacrylate include, for example, alkyl acrylates, alkyl methacrylates, aromatic vinyl compounds, vinyl cyanide compounds And the like.

The production of the thermoplastic polymer (I) is preferably carried out by an emulsion polymerization method, and it can be recovered in a powder form by a usual emulsion polymerization method and a post-treatment method.

The rubber-containing polymer (II) preferably contains 50 to 99.9% by weight of an alkyl acrylate and at least one other vinyl monomer copolymerizable therewith.
To 49.9% by weight, and 0.1 to 1 of a copolymerizable crosslinkable monomer.
In the presence of 100 parts by weight of an elastic copolymer having at least one structure obtained by polymerizing a monomer mixture consisting of 0% by weight, 50 to 100% by weight of a methacrylate ester and copolymerizable therewith At least one other vinyl monomer 0
Of the monomer or monomer mixture 10 to 50% by weight
A rubber-containing copolymer having an average particle diameter of 0.2 to 0.4 [mu] m, wherein the polymer layer is bonded to the elastic copolymer one or more times by polymerizing about 400 parts by weight.

The rubber-containing polymer (II) is obtained by, for example, polymerizing the above-mentioned respective components for an elastic copolymer in at least one stage by an emulsion polymerization method or the like to obtain an elastic copolymer. Of methacrylic acid ester and the like in at least one stage in the presence of a methacrylate ester by an emulsion polymerization method or the like. By this polymerization, the methacrylic acid ester and the like are graft-copolymerized to the elastic copolymer to form a crosslinked elastic copolymer having a graft chain. When the polymerization is carried out in two or more stages, it is sufficient that the overall monomer composition is within the above range, not the monomer composition of each stage.

That is, the rubber-containing polymer (II) is a graft copolymer having a multilayer structure containing an alkyl acrylate as a main component of the rubber. The rubber-containing polymer (II) has an effect of imparting excellent impact resistance and elongation to the film.

In the rubber-containing polymer (II), examples of the alkyl acrylate used to form the elastic copolymer include those having 1 to 8 carbon atoms in the alkyl group. In particular, butyl acrylate, acrylic acid 2
-Ethylhexyl and the like are preferred.

In the rubber-containing polymer (II), other vinyl monomers copolymerizable with the alkyl acrylate used as required to form the elastic copolymer include methyl methacrylate and methacrylic acid. Alkyl methacrylates such as butyl and cyclohexyl methacrylate, styrene and acrylonitrile are preferred.

In the rubber-containing polymer (II), the copolymerizable crosslinkable monomer used for forming the elastic copolymer is not particularly limited, but may be ethylene glycol dimethacrylate, butanediol dimethacrylate, acrylic Examples thereof include allyl acid, allyl methacrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, diallyl maleate, trimethylol triacrylate, and allyl cinnamate. These can be used alone or in combination of two or more.

Examples of the methacrylate ester to be grafted on the elastic copolymer include, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like.

The other copolymerizable vinyl monomer to be grafted to the elastic copolymer is not particularly limited, and examples thereof include alkyl acrylates such as methyl acrylate, butyl acrylate and cyclohexyl acrylate, styrene, Acrylonitrile and the like can be mentioned.

The monomer to be grafted or a mixture thereof is preferably used in an amount of 10 parts by weight based on 100 parts by weight of the elastic copolymer.
The polymerization can be carried out in at least one stage using from 400 to 400 parts by weight, more preferably from 20 to 200 parts by weight. When the amount is 10 parts by weight or more, aggregation of the elastic copolymer hardly occurs and transparency is improved.

The average particle size of the rubber-containing polymer (II) is preferably from 0.2 to 0.4 μm, more preferably from 0.2 to 0.4 μm.
25 to 0.35 μm. When the average particle size is 0.2 μm or more, the resulting film does not become brittle and film formation becomes easy. When the thickness is 0.4 μm or less, the transparency of the film is improved.

The thermoplastic polymer (III) is preferably
50 to 100% by weight (more preferably 50 to 99.9) of a methacrylic acid ester having an alkyl group having 1 to 4 carbon atoms
0 to 50% by weight (more preferably 0.1 to 40% by weight), and at least one kind of another vinyl monomer copolymerizable therewith, 0 to 49% by weight.
The reduced viscosity of the polymer (0.1 g of the polymer was dissolved in 100 mL of chloroform and measured at 25 ° C.) was 0.1.
L / g or less.

In the thermoplastic polymer (III), examples of the methacrylate include methyl methacrylate and
Examples include ethyl methacrylate and butyl methacrylate. Particularly, methyl methacrylate is preferred. Examples of the acrylate include methyl acrylate, ethyl acrylate, butyl acrylate and the like.

In the thermoplastic polymer (III), as other copolymerizable vinyl monomers, conventionally known various monomers can be used, and examples thereof include aromatic vinyl compounds and vinyl cyanide compounds. Can be

The reduced viscosity of the thermoplastic polymer (III) is 0.1.
It is preferably at most L / g. This reduced viscosity is set to 0.
When it is 1 L / g or less, the melt viscosity of the acrylic resin does not become so high, and the film forming property becomes good. Further, the reduced viscosity is preferably 0.05 L / g or more. If it is 0.05 L / g or more, the film does not become brittle,
Film breakage during film formation and printing can be prevented.

The method of polymerizing the thermoplastic polymer (III) is not particularly limited, but it can be carried out by usual methods such as suspension polymerization, emulsion polymerization, bulk polymerization and the like. In order to obtain a suitable viscosity, it is preferable to use a chain transfer agent during polymerization. The amount of the chain transfer agent may be appropriately determined depending on the type and composition of the monomer.

If the film is made of an acrylic resin containing the thermoplastic polymer (I), the rubber-containing polymer (II) and the thermoplastic polymer (III) as the main components as described above, it can be used for bathroom interior wall materials. The most suitable film is obtained.

The content of the thermoplastic polymer (I) in the acrylic resin is preferably 0 to 10 parts by weight based on 100 parts by weight of the total of the components (I) to (III). When the content is 10 parts by weight or less, the viscosity of the acrylic resin does not become too high, and the film forming property and the transparency are improved. Although film formation is possible without using the thermoplastic polymer (I), it is more preferable to use 0.1 part by weight or more in order to obtain sufficient film formability.

The content of the rubber-containing polymer (II) in the acrylic resin is preferably 5.5 to 25 parts by weight based on 100 parts by weight of the total of the components (I) to (III). Further, the amount of the elastic copolymer in the rubber-containing polymer (II) is preferably 5 to 18 parts by weight based on 100 parts by weight of the total of the components (I) to (III). When the amount of the elastic copolymer is 5 parts by weight or more, the film does not become brittle, and the film forming property is improved. When the content is 18 parts by weight or less, transparency and surface hardness of the film are improved.

Thermoplastic polymer (III) in acrylic resin
Is preferably 65 to 94.5 parts by weight based on 100 parts by weight of the total of components (I) to (III).

The acrylic film of the present invention may contain, if necessary, general compounding agents such as stabilizers, lubricants, processing aids, plasticizers, impact-resistant aids, foaming agents, fillers, coloring agents, matting agents. , An ultraviolet absorber, an antibacterial agent, and the like.

The heat distortion temperature (measured based on ASTM D648) of the acrylic film of the present invention is preferably 80 ° C. or higher. When the temperature is 80 ° C. or higher, residual stress is unlikely to occur during heating of the interior wall material of the acrylic laminated bathroom, and surface roughness can be prevented. In particular, since the bathroom interior wall material often comes into contact with hot water, the thermal deformation temperature of the acrylic film is more preferably 100 ° C. or higher.

When the acrylic film of the present invention is constituted by using the above-mentioned components (I) to (III), the heat deformation temperature of the film varies depending on the amount of the rubber-containing polymer (II). Is determined by the heat distortion temperature of the thermoplastic polymer (III).

The thermal deformation temperature of the thermoplastic polymer (III) can be adjusted by adjusting the monomer composition of the thermoplastic polymer (III) by a conventionally known method. Although it depends on various conditions, for example, a thermoplastic polymer (II
When methyl acrylate is used as a component of I), the content of methyl methacrylate is set to 88% by weight or more and the heat deformation temperature is set to 1 to obtain a heat deformation temperature of 80 ° C. or more.
In order to increase the temperature to 00 ° C. or higher, it may be set to 95% by weight or more.
When the heat distortion temperature is 80 ° C. or higher or 100 ° C. or higher, the content of methyl methacrylate can be reduced by copolymerizing maleimides such as maleic anhydride and phenylmaleimide.

The amount of residual calcium in the acrylic resin is 5
Preferably, it is 500 ppm. By setting the amount of residual calcium within the above range, whitening of the film at the time of contact with warm water can be favorably prevented.

The acrylic film of the present invention can be obtained by forming the above-described acrylic resin into a film.
As the production method, any method such as a melt casting method, a melt extrusion method such as a T-die method and an inflation method, and a calendar method may be used. In particular, the T-die method is preferable from the viewpoint of economy.

In order to use the acrylic film of the present invention as a clear layer of a wall material for a bathroom interior and to give the wall material a design, it is preferable to print the acrylic film by an appropriate printing method. In this case, it is preferable to perform a one-sided printing process on the acrylic film, and it is preferable that the printing surface side is adhered to the substrate at the time of lamination, from the viewpoint of protection of the printing surface and imparting a sense of quality. In addition, if necessary,
The acrylic film can be matted or colored.

The thickness of the acrylic film of the present invention is 30
0 μm or less. When this becomes thicker than 300 μm,
As the rigidity increases, laminating properties and secondary processing properties deteriorate, and it becomes impossible to use it as a film, and the weight per unit area increases, so it is economically disadvantageous,
Further, it is difficult to form a film, and the film cannot be stably manufactured. In particular, the thickness is preferably from 100 μm to 300 μm. When the thickness is 100 μm or more, a sufficient depth view as the appearance of the wall material can be obtained.

By laminating the above-described acrylic film of the present invention on a substrate, an acrylic laminated bathroom interior wall material can be obtained.

In order to impart a design such as a color pattern to the bathroom interior wall material, a decorated acrylic film (decoration film) is prepared in advance, thereby reducing the number of steps of the bathroom wall material production process. A deep and transparent feeling can be obtained. For example, printing on one side of an acrylic film, with or without an adhesive layer, laminating the printed side to the substrate, laminating another printed film on one side of the acrylic film A method of laminating another printed side of the film to the substrate with or without the interposition of an adhesive layer, coating the acrylic film on one side, and applying the coating with or without the interposition of an adhesive layer There is a method of laminating the formed surface side to the base material.

When another printed film (print film) is used, a resin film having high compatibility with an acrylic resin such as a PVC resin may be directly laminated on the acrylic film. A resin such as an olefin resin, which is incompatible with the acrylic resin, requires an adhesive with the acrylic film. Therefore, a method such as dry lamination may be used.

FIG. 1 is a schematic sectional view showing an example of a bathroom interior wall material produced by bonding the acrylic film of the present invention to a base material. The example shown in FIG.
This is a bathroom interior wall member 8 having a configuration in which a decorative sheet 7 having a printed layer 3 formed on one side of the above is laminated and adhered to the base material 2 via an adhesive layer 4.

As the substrate 2, various conventionally known substrates such as a rock wool board and a calcium silicate plate can be used.

FIG. 2 is a schematic sectional view showing another example. In this example, a coating layer 5 is formed on one side of the acrylic film 1.
1 is different from the example of FIG. 1 in that the decorative sheet 7 is formed.

FIG. 3 is a schematic sectional view showing another example. In this example, a color pattern film having a print layer 3 formed on one side of a PVC film 6 is prepared, and the print layer 3 side of this color pattern film is laminated on one side of an acrylic film 1.
This is different from the example of FIG. 1 in that the decorative sheet 7 is configured.

[0056]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. In the examples, “parts” represents “parts by weight”, and “%” represents “% by weight”. The evaluation of the film composition and the film was performed by the following test methods.

1) Average Particle Size of Rubber Particles [Rubber-Containing Polymer (II)] The obtained film was cut into a suitable size, and the section was immersed in a 0.5% by weight ruthenium tetroxide aqueous solution at room temperature for 15 hours. The rubber particles were dyed. The sample was further cut to a thickness of about 70 nm using a microtome, and photographed with a transmission electron microscope. From this photograph, 50 dyed rubber particle portions were randomly selected, the particle diameter of each was calculated, and the average value was taken as the average particle diameter.

2) Pencil hardness A sample was prepared by laminating a film in the shape of a bathroom wall material, cut out to an appropriate size, and evaluated according to JIS K5400.

3) Amount of Residual Calcium About 2 g of acrylic resin was precisely weighed, placed on a platinum dish, completely incinerated with an electric heater, and then pure water and hydrochloric acid were added.
A test solution was prepared by taking a constant volume in a mL volumetric flask, and the amount of calcium was quantified from the solution by an atomic absorption method.

4) Heat Deformation Temperature (HDT) A pellet of the film composition is subjected to ASTM by injection molding.
Formed into a sample for measuring heat distortion temperature based on D648,
After annealing at 0 ° C for 24 hours, low load (4.6 kg / cm ² )
Measured according to ASTM D648.

5) Warm water resistance A sample was prepared in the same manner as in the evaluation of pencil hardness (2), and a cell was attached to the film surface of the cut sample so that only the surface was contacted with hot water. The sample was immersed in exchange water for 240 hours, and after 240 hours, the sample was taken out of the warm water and immediately observed for the surface (film surface) appearance of the sample. In Tables 1 and 3, "O" means no change in visual appearance and "△" means a slightly rough surface.
Those having discoloration were indicated by "x".

6) Chemical Resistance A sample was prepared in the same manner as in the evaluation of the pencil hardness (2), and a 5% solution of NaOH, a 5% solution of Ca (OH) ₂ , and a mold remover (trade name: mold killer) were added to each sample. After being applied to the surface and allowed to stand at room temperature for 24 hours, the surface was quickly washed with a neutral detergent, and the deterioration and discoloration of the surface were observed. In Table 1,
Those having no change in appearance visually were marked with "O", and those with surface deterioration and discoloration were marked with "x".

7) Stain resistance A sample was prepared in the same manner as in the evaluation of pencil hardness (2), and various hair dyeing solutions and magic inks were applied to the sample surface. Was quickly washed with a neutral detergent, and the state of contamination was observed. In Table 1, those having no visual change in appearance were marked with “○”.

<Example 1> Production of Thermoplastic Copolymer (I) A reaction vessel was charged with 200 parts of ion-exchanged water purged with nitrogen, and 1 part of an emulsifier, potassium oleate, and 0.3 part of potassium persulfate. Subsequently, methyl methacrylate (MMA) 40 parts, butyl acrylate (BuA) 10
And 0.005 part of n-octyl mercaptan (NOM), and the mixture was stirred at 65 ° C. for 3 hours under a nitrogen atmosphere to complete the polymerization. Subsequently, a monomer mixture composed of 48 parts of MMA and 2 parts of BuA was added dropwise over 2 hours, and after completion of the addition, the mixture was maintained for 2 hours to complete the polymerization. The obtained latex was added to a 0.25% sulfuric acid aqueous solution, and the polymer was subjected to acid coagulation, followed by dehydration, washing with water, and drying to collect the polymer in powder form.
A thermoplastic copolymer (I) was obtained. Its reduced viscosity (ηsp /
c) was 0.38 L / g.

[0065] Production of rubber-containing polymer (II) In a reaction vessel, the total amount of raw material (a) and raw material (b) shown below
, And at 90 ° C for 90 minutes in a nitrogen atmosphere.
Polymerization was performed while stirring. Thereafter, the other half of the raw material (b) was continuously added over 90 minutes,
Polymerization was carried out for 1 minute to obtain an elastic latex.

Subsequently, the following raw material (c) was added to this elastic latex and stirred, and then the following raw material (d) was continuously added at 80 ° C. for 45 minutes.
Thereafter, polymerization was further continued at 80 ° C. for 1 hour to obtain a rubber-containing polymer (II) latex.

This rubber-containing polymer (II) latex was subjected to coagulation, coagulation and solidification reactions using calcium chloride, followed by filtration without washing with water and drying, and an average particle size of 0.29 μm.
To obtain a rubber-containing polymer (II).

[Raw material (a)] 300 parts of deionized water 0.5 part of N-acyl sarcosine acid 0.5 part of boric acid 0.1 part of sodium carbonate 0.5 part of sodium formaldehyde sulfoxylate 0.5 part of ferrous sulfate 0.1 part 00024 parts Disodium ethylenediaminetetraacetate 0.000072 parts [Raw material (b)] Butyl acrylate 80.0 parts Styrene 19.0 parts Allyl methacrylate 1.0 part Cumene hydroperoxide 0.3 parts [Raw material (c)] Deionization Water 5 parts N-acyl sarcosine acid 1.2 parts [Raw material (d)] Methyl methacrylate 76.6 parts Ethyl acrylate 3.2 parts n-octylmercaptan 0.28 parts Cumene hydroperoxide 0.24 parts.

[0069] Production of Acrylic Film Methyl methacrylate / methyl acrylate copolymer shown in Table 2 as thermoplastic polymer (I), rubber-containing polymer (II), and thermoplastic polymer (III) obtained as described above A (methyl methacrylate / methyl acrylate = 98 /
2, reduced viscosity 0.06 L / g) were mixed at each ratio shown in Table 1 using a Henschel mixer. Next, φ40
mm screw type extruder (L / D = 26)
The mixture was melt-kneaded at a cylinder temperature of 200 to 260 ° C and pelletized. The obtained pellet is dried at 80 ° C. all day and night,
Using a non-vent screw type extruder equipped with a T die, a film was formed at a cylinder temperature of 200 to 240 ° C. and a T die temperature of 250 ° C. to obtain a hard acrylic film having a thickness of 125 μm.

. Fabrication of decorative sheet (i) Acrylic film back side printed product On the back side of the obtained hard acrylic resin transparent film, a stone-like pattern layer (several μm to several tens μm) was formed by gravure printing.
m) was printed to obtain a decorative sheet 7 as shown in FIG.

(Ii) Acrylic film back side coated product Acrylic / urethane-based paint containing fillers and having a stone-like tone was applied to the back surface of the obtained hard acrylic resin transparent film (coating thickness: 20 to 100 μm). The decorative sheet 7 as shown in FIG.

(Iii) Decorative PVC Laminate A PVC film (thickness: 4) whose surface is decorated with a printed layer
The resulting hard acrylic resin transparent film was laminated on the surface of the printed layer (0 to 50 μm) using a mirror surface heat laminating apparatus to obtain a decorative sheet 7 as shown in FIG.

[0073] Preparation of bathroom interior wall material The surface of rock wool board (base material 2) that has been subjected to surface treatment (sanding and impregnation of sealer, etc.) in advance to improve product surface smoothness and water resistance Back side of decorative sheet 7 (surface opposite to acrylic surface)
Then, a synthetic rubber-based adhesive is applied with a bar coater, and after bonding, a hot plate press method (80 ° C., 10 kg × 5 minutes)
To produce the bathroom interior wall material 8 as shown in FIGS. Note that a similar panel can be manufactured by using a calcium silicate plate or a plastic plate instead of the rock wool board as the base material 2.

Tables 1 and 3 show the evaluation results of this example. The bathroom interior wall material using the hard acrylic film of the present example on the outermost surface had excellent properties shown in Tables 1 and 3 in addition to a deep high-grade appearance.

<Example 2> The thermoplastic polymer (III) was
Methyl methacrylate / methyl acrylate copolymer B shown in Table 2 (methyl methacrylate / methyl acrylate = 87
/ 13, reduced viscosity of 0.05 L / g), except that films, decorative sheets and wall materials were produced in the same manner as in Example 1.
Table 1 shows the evaluation results.

In this embodiment, almost the same good results as in Embodiment 1 were obtained. However, the heat distortion temperature of the film is 8
Since it was less than 0 ° C. (75 ° C.), it was slightly inferior to Example 1 in hot water resistance, and surface roughness occurred when the acrylic laminated bathroom wall material came into contact with hot water.

Example 3 A film and a decorative material were prepared in the same manner as in Example 1 except that the thermoplastic polymer (I) was not used and the amount of the rubber-containing polymer (II) was increased to 20 parts. Sheets and wall materials were produced. Table 1 shows the evaluation results.

In this embodiment, almost the same good results as in Embodiment 1 were obtained. However, since the thermoplastic polymer (I) was not used, the film-forming property of the film was slightly inferior to that of Example 1, and the thickness unevenness of the film was slightly increased.

Example 4 The procedure of Example 1 was repeated, except that magnesium sulfate was used instead of calcium chloride used for coagulating the latex during the production of the rubber-containing polymer (II) of Example 1. A film, a decorative sheet, and a wall material were produced. Table 3 shows the evaluation results.

In this embodiment, since the amount of residual calcium in the acrylic resin is less than 5 ppm (less than 1 ppm), the resistance to warm water tends to be inferior to that in Example 1, and the wall material of the acrylic laminated bathroom comes in contact with hot water. Some whitening was observed.

Comparative Example 1 The procedure of Example 1 was repeated except that the amount of N-acyl sarcosine acid in the raw material (A) was changed to 2.0 parts during the production of the rubber-containing polymer (II). Thus, a rubber-containing polymer having a rubber particle diameter of 0.12 μm was obtained. Using this rubber-containing polymer, a film, a decorative sheet, and a wall material were produced in the same manner as in Example 1. Table 1 shows the evaluation results.

In this comparative example, since a rubber-containing polymer having a particle size of less than 0.2 μm was used, the film-forming property was poor, the film was brittle, and the film was broken.

Comparative Example 2 A film, a decorative sheet, and a wall material were produced in the same manner as in Comparative Example 1, except that the amount of the rubber-containing polymer having a rubber particle diameter of 0.12 μm was changed to 36 parts. Table 1 shows the evaluation results.

In this comparative example, since the amount of the rubber-containing polymer used was increased, the film-forming property was improved as compared with the comparative example 1, but the pencil hardness was reduced to B instead.

Comparative Example 3 The same as Example 1 except that the addition amount of the rubber-containing polymer (II) was changed to 36 parts and the addition amount of the thermoplastic polymer (III) was changed to 62 parts. A film, a decorative sheet, and a wall material were produced. Table 1 shows the results.

In this comparative example, since the amount of the rubber-containing polymer (II) used exceeded 25 parts, the surface hardness was poor and the pencil hardness was B.

[0087]

[Table 1]

[0088]

[Table 2]

[0089]

[Table 3]

[0090]

As described above, when the acrylic film of the present invention is used for an acrylic laminate bathroom interior wall material, the wall material has a deep and transparent feeling and is required as a bathroom wall material. It satisfies the quality well. Also, compared to the case of obtaining the same appearance by conventional clear painting,
The number of steps can be greatly simplified, and a product can be obtained at low cost.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing an example of a bathroom interior wall material produced by bonding an acrylic film of the present invention to a base material.

FIG. 2 is a schematic cross-sectional view showing another example of a bathroom interior wall material produced by bonding the acrylic film of the present invention to a base material.

FIG. 3 is a schematic cross-sectional view showing a further example of a bathroom interior wall material produced by bonding the acrylic film of the present invention to a base material.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Acrylic film 2 Base material 3 Printing layer 4 Adhesive layer 5 Coating layer 6 PVC film 7 Decorative sheet 8 Wall material for bathroom interior

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) // (C08L 33/10 51:04 33:12) F term (reference) 4F071 AA33 AA33X AA77 AA85 AA88 AD02 AF25 AH03 BC01 BC12 4F073 AA32 BA18 BB01 4F100 AK01A AK12A AK15B AK25A AL01A AN00A AT00B BA02 CB00 CC00A DE01A EH17 GB08 HB31A JB16A JK12A JN01 JN01A YY00A 4J002 BG0500 BG06 BG06

Claims (8)

[Claims] 1. Acrylic laminated bathroom interior, comprising an acrylic resin in which rubber particles having an average particle size of 0.2 to 0.4 μm are dispersed, having a pencil hardness of H or more and a thickness of 300 μm or less. Acrylic film for wall materials. 2. The amount of calcium remaining in the acrylic resin is 5
2. The acrylic film according to claim 1, wherein the amount is from 500 to 500 ppm. 3. The acrylic film according to claim 1, wherein the heat distortion temperature (measured based on ASTM D648) is 80 ° C. or higher. 4. The acrylic resin comprises 0 to 10 parts by weight of a thermoplastic polymer (I) shown below, 5.5 to 25 parts by weight of a rubber-containing polymer (II) as rubber particles, and a thermoplastic polymer (I). III) 65 to 94.5 parts by weight as a main component, and the amount of the elastic copolymer in the rubber-containing polymer (II) is 5 to 5
18 parts by weight [all components (I), (II) and (III)
Based on a total of 100 parts by weight]. Thermoplastic polymer (I) Consists of 50 to 100% by weight of methyl methacrylate and 0 to 50% by weight of at least one other vinyl monomer copolymerizable therewith, and the reduced viscosity of the polymer (Polymer 0) 0.1 g dissolved in 100 mL chloroform, measured at 25 ° C.) exceeds 0.2 L / g. Rubber-containing polymer (II) 50 to 99.9% by weight of alkyl acrylate;
0 to 49.9% by weight of at least one other vinyl monomer copolymerizable therewith, and 0.1 to 0.1 of a copolymerizable crosslinkable monomer.
50 to 100% by weight of a methacrylate ester in the presence of 100 parts by weight of an elastic copolymer having at least one structure obtained by polymerizing a monomer mixture consisting of 10% by weight;
A monomer or monomer mixture 1 comprising from 0 to 50% by weight of at least one other vinyl monomer copolymerizable therewith;
A rubber-containing copolymer having an average particle size of 0.2 to 0.4 μm, wherein the polymerized layer is bonded to the elastic copolymer one or more times by polymerizing 0 to 400 parts by weight. Thermoplastic polymer (III) 50 to 100% by weight of a methacrylate having an alkyl group having 1 to 4 carbon atoms, and 0 to 50% of an acrylate
% By weight and at least 1 to 49% by weight of another vinyl monomer copolymerizable therewith. The reduced viscosity of the polymer (0.1 g of the polymer is dissolved in 100 mL of chloroform and measured at 25 ° C.) ) Is 0.1 L / g or less. 5. An interior wall material for an acrylic laminated bathroom, wherein the acrylic film according to claim 1 is laminated on a base material. 6. Printing on one side of an acrylic film,
The acrylic laminate bathroom interior wall material according to claim 5, wherein the printed side is laminated to a substrate with or without an adhesive layer. 7. A method in which another printed film is laminated on one side of an acrylic film, and the printed another film is laminated to a substrate with or without an adhesive layer. Item 6. An acrylic laminated bathroom interior wall material according to Item 5. 8. Applying a coating on one side of the acrylic film,
6. The acrylic laminated bathroom interior wall material according to claim 5, wherein the coated side is laminated to a substrate with or without an adhesive layer.