JP4182693B2 - Antifouling cosmetic material - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a decorative material for use in surface makeup of interior and exterior materials of buildings such as houses, building materials such as construction materials and fittings, furniture fixtures, housing equipment, and home appliances. In particular, quasi-exterior applications such as exterior materials for eaves and entrance doors that are somewhat affected by wind and rain, and children's rooms and kitchens that require wiping, water repellency, contamination resistance, etc. for magic pens and household contaminants, etc. -The present invention relates to a cosmetic material having stain resistance suitable for uses such as a canteen and a washroom.
[0002]
[Prior art]
The cosmetic materials (including decorative plates, decorative paper, decorative sheets, etc.) used in the various applications described above are required to have durability and weather resistance that can withstand long-term use of a decade, and rainwater is in use during use. Contamination resistance is required to prevent the contaminants from sticking firmly so that they can be easily wiped off even if contaminants adhere to the surface due to natural action such as dust or dirt, or due to carelessness of the user. . Especially in kitchens, canteens, and children where spilled or splashed food-related contaminants such as oils and fats such as salad oil and tempura oil, and colored condiments such as soy sauce and sauces, children can wear it on their limbs and clothes. In children's rooms where mud, crayons, magic pens, and other graffiti, etc. that are attached to the outside are likely to adhere, toilets, washrooms, laundry rooms, etc. where water or soap solution is easily splashed by urine water washing, hand washing, washing, etc. However, it is required to have a higher level of contamination resistance against living pollutants than in a normal living room, bedroom, etc., and ordinary urethane coatings cannot be used for ordinary cosmetics.
[0003]
As a method for imparting a high degree of stain resistance to the surface of a decorative material, for example, a method of forming an antifouling layer coated with a silicone resin or fluorine resin having a low surface tension on the surface (Japanese Patent Laid-Open No. 11-58614) However, there are problems such that the surface is extremely slippery and the tactile sensation and handleability are deteriorated, and the surface hardness is insufficient, so that it is vulnerable to scratches and wear. In view of this, a method of adding a silicone oil to a normal paint film made of urethane resin or the like to form an antifouling layer (Japanese Patent Application Laid-Open No. 10-58611 etc.) has been used relatively widely. This is because the main component of the paint film is a normal paint for cosmetics such as urethane resin, and has sufficient surface properties such as scratch resistance, abrasion resistance, weather resistance, etc., and part of the silicone oil in the paint film Oozes out on the surface of the coating film to form an oil film, and this oil film exhibits contamination resistance by preventing the adhesion of contaminants, and has an extremely excellent effect.
[0004]
However, this oil film is wiped away when the contaminants are wiped off, and while the silicone oil is sufficiently contained in the coating film, this oil film oozes out to form an oil film. However, if the silicone oil in the coating film is lost after a long period of time and repeated wiping, the stain resistance will no longer be manifested, so there was a problem with the durability of the stain resistance. . In particular, in the case of cosmetics supplied in a wound state, such as decorative paper, decorative sheets, wallpaper, etc., the silicone oil that has exuded to the surface of the coating film has transferred to the back surface of the decorative material, and the base material or base surface There is also a problem that the adhesive may be repelled when adhering to the adhesive, resulting in adhesion inhibition.
[0005]
As a means of imparting anti-staining properties with excellent long-term durability while ensuring sufficient surface properties on the surface coating film of cosmetic materials, the main component resin of the coating film and the silicone component for imparting anti-staining properties are chemically treated. Various methods have already been studied for bonding to the. A typical example is a two-component crosslinking reaction type resin (Japanese Patent Laid-Open Nos. 5-2222819, 5-246001, etc.) containing an acrylic resin as a main component and a silicone compound as a curing agent, which is compared with the original acrylic resin. If this is the case, the contamination resistance is improved due to the decrease in the surface tension due to the introduction of the silicone component, but the silicone component is bound by two acrylic skeletons as a cross-linking agent and may not move freely. The effect of improving the stain resistance is not as good as that of the case.
[0006]
There is also a proposal of a method using a (meth) acrylate ionizing radiation curable resin blended with a silicone (meth) acrylate compound (JP-A-5-86306, etc.). However, since this uses a special curing system such as an electron beam or ultraviolet rays, it requires expensive equipment and is applicable to special shapes where uniform irradiation is difficult, and problems such as deterioration of the substrate due to irradiation, etc. In addition, in addition to the limited range of application, ionizing radiation curable resins have a very high crosslinking density, and the molecular movement of the silicone component is hindered by the extremely rigid three-dimensional crosslinked structure of the cured product. For this reason, it is difficult to obtain a sufficient effect of improving contamination resistance.
[0007]
In addition to the above, block co-polymerization of a poly (meth) acrylate block unit (acrylic block) having an active hydrogen group such as a hydroxyl group in the side chain as an acrylic component and a polydimethylsiloxane block unit (silicone block) as a silicone component There is also a proposal of a method using a two-component curable resin having an active hydrogen-containing acrylic-silicone block polymer as a main component and a polyisocyanate as a curing agent (JP-A-9-296150, etc.). However, even with this resin, the crosslinking by the curing agent occurs only in the acrylic block portion containing active hydrogen, and the silicone block portion remains in a non-crosslinked state. With regard to the relationship between the reactivity and the antifouling performance, if the ratio of the silicone block portion is high, the ratio of the acrylic block containing active hydrogen is low, so the reactivity with isocyanate is reduced, and stain resistance is exhibited. Although it takes time, the contradictory phenomenon that the contamination resistance is absolutely reduced when the ratio of the silicone block part is low occurs, so it is difficult to design a molecule that combines various physical properties and contamination resistance, and the difference in molecular skeleton Control of various physical properties and stain resistance by blending due to poor compatibility with ordinary acrylic resins that do not contain silicone block parts Difficult, etc., there are many problems.
[0008]
[Problems to be solved by the invention]
The present invention has been made in order to solve the above-described problems in the prior art, and the object of the present invention is, of course, excellent anti-contamination property against various life pollutants. Excellent long-term stain resistance that hardly deteriorates due to changes and repeated wiping, various surface properties such as scratch resistance and wear resistance, and excellent reactivity during resin curing Another object of the present invention is to provide a stain resistant cosmetic material having an antifouling layer that can easily control various surface properties and stain resistance by molecular design or blending.
[0009]
[Means for Solving the Problems]
  The antifouling cosmetic material of the present invention is the antifouling cosmetic material in which an antifouling layer is provided on a substrate, wherein the antifouling layer has an acrylic polyol compound and a terminal hydroxyl group.With a molecular weight in the range of 300-700An organopolysiloxane alkylol compound and a polyisocyanate compound are mixed and applied, and the hydroxyl groups of the acrylic polyol compound are crosslinked and cured through the polyisocyanate compound, and at the same time, a part of the hydroxyl groups of the acrylic polyol compound is cured. An organopolysiloxy group is attached to the side chain of the acrylic urethane resin by a method of bonding with a terminal hydroxyl group of the organopolysiloxane alkylol compound via a polyisocyanate compound.ofIt consists of an introduced silicone-modified acrylic urethane resin.
[0011]
  In particular, the silicone-modified acrylic urethane resin is composed of an acrylic polyol compound in which a carboxyl group is introduced into a side chain by adding an unsaturated carboxylic acid such as acrylic acid or methacrylic acid as a copolymerization component, and a terminal. Is bonded to the hydroxyl group of an organopolysiloxane alkylol compound having a hydroxyl group by an esterification reaction to obtain a silicone-modified acrylic polyol compound in which an organopolysiloxy group is introduced into the side chain. By cross-linking through an isocyanate compound to the side chainThe molecular weight is in the range of 3000 to 6000 (siloxane bond number 40 to 80).Organopolysiloxy groupofIt consists of an introduced silicone-modified acrylic urethane resin.
[0012]
Further, in particular, hard particles made of a material having a hardness higher than that of the silicone-modified acrylic urethane resin are added to the antifouling layer.
[0013]
In particular, an ultraviolet absorber and / or a light stabilizer is added to the antifouling layer.
[0014]
In particular, at least the surface of the base material in contact with the antifouling layer is made of a polyolefin resin.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the stain-resistant cosmetic material of the present invention will be described in detail with reference to the drawings. FIG. 1 is a side sectional view showing an embodiment of the contamination-resistant cosmetic material of the present invention.
[0016]
In the present invention, the material and configuration of the base material 1 are not particularly limited, and any base material for general cosmetics can be applied. Specifically, for example, paper such as thin paper, titanium paper, high-quality paper, surface-treated paper, resin-impregnated paper, resin-mixed paper, inter-paper reinforced paper, fibrous base materials such as woven or non-woven fabric, polyolefin-based, Polyester, acrylic, polystyrene, polyamide, polyvinyl and other thermoplastic resin films and molded products, synthetic resin substrates such as fiber reinforced plastic, wood veneer, plywood, laminated wood, medium density fiberboard, particles Wood base materials such as boards, glass, ceramics, gypsum board, calcium silicate board, slag cement board, wood wool cement board, lightweight foam concrete board, glass fiber reinforced concrete board and other inorganic base materials, steel sheet, brass board, Any metal base such as stainless steel plate, aluminum plate, duralumin plate, etc., or multiple types of these composites, laminates, etc. It can be adopted.
[0017]
In particular, the present invention can be suitably applied to flexible decorative paper or a decorative sheet that can be continuously mass-produced by a winding method using paper or a thermoplastic resin film as a base material 1. This decorative paper or decorative sheet is a non-colored or colored plain sheet made of a single layer of paper or a thermoplastic resin film, or a design imparting process such as pattern layer 13 printing or emboss 16 on one side thereof. 1 may be used, or as shown in FIG. 1, a transparent thermoplastic resin film with a pattern layer 13 on a base sheet 12 made of paper or a thermoplastic resin film. It may be a decorative sheet having a multilayer structure in which the top sheet 15 is laminated.
[0018]
In the multi-layered decorative sheet, as is conventionally known, a primer for coloring the base sheet 12 in a concealing manner or for facilitating adhesion of the back of the base sheet 12 to a wooden board or the like. Layer 11, easy adhesion treatment such as corona discharge treatment or primer treatment on the printed surface of the pattern layer 13 of the base sheet 12 in advance, a concealing layer on the back side of the pattern layer 13, If necessary, the adhesive layer 14 may be interposed between the surface sheet 15, the emboss 16 may be applied to the surface of the surface sheet 15, or the concave portion of the emboss 16 may be colored by a wiping method or the like. It can be implemented arbitrarily. In addition, these decorative papers or decorative sheets are not limited to the form of continuous winding, but may be in the form of single sheets.
[0019]
As a kind of the thermoplastic resin which comprises the surface sheet 15, for example, polyolefin resin, polyester resin, acrylic resin and the like are arbitrary and are not particularly limited in the present invention. In order to effectively prevent contamination due to permeation, it is desirable to employ a resin having excellent solvent resistance, oil resistance, chemical resistance, etc., and from this viewpoint, it is most desirable to employ a polyolefin resin. . This is not limited to the case of a decorative sheet having a multilayer structure, but also applies to a general decorative material, and it is desirable that at least the surface of the base material 1 in contact with the antifouling layer 2 is made of a polyolefin resin.
[0020]
In the antifouling cosmetic material of the present invention, the antifouling layer 2 made of a silicone-modified acrylic urethane resin in which an organopolysiloxy group is introduced into the side chain of an acrylic urethane resin is formed on the surface of various base materials 1 as described above. It is formed. The method for introducing an organopolysiloxy group into the side chain of the acrylic urethane resin is not particularly limited in the present invention, but it is preferable to use one of the following two methods.
[0021]
(1) An acrylic polyol compound, an organopolysiloxane alkylol compound having a hydroxyl group at the terminal, and a polyisocyanate compound are mixed and applied, and the hydroxyl groups of the acrylic polyol compound are crosslinked through the polyisocyanate compound and cured. At the same time, a method in which a part of the hydroxyl group of the acrylic polyol compound is bonded to the terminal hydroxyl group of the organopolysiloxane alkylol compound via the polyisocyanate compound.
[0022]
(2) An organopolysiloxane alkylol having a carboxyl group in the side chain and a hydroxyl group at the terminal by adding an unsaturated carboxylic acid such as acrylic acid or methacrylic acid as a copolymerization component. A method in which the hydroxyl group of a compound is bonded by an esterification reaction to obtain a silicone-modified acrylic polyol compound in which an organopolysiloxy group is introduced into a side chain, and thereafter, the hydroxyl groups are crosslinked via a polyisocyanate compound.
[0023]
According to these methods, it is not necessary to use an organopolysiloxane alkylol compound having a very high molecular weight, so there is not much problem of incompatibility with an acrylic polyol compound or a polyisocyanate compound, and the composition is homogeneous. It is possible to obtain the resin efficiently with good reactivity. In addition, unlike the case of the block copolymer described above, since there is little bias in the crosslinking point of the acrylic polyol compound, which is the basic skeleton, a cured film having high physical properties that is uniformly crosslinked as a whole can be obtained.
[0024]
In the second method, in order to balance various surface properties and stain resistance, a silicone-modified acrylic polyol compound can be blended with a normal acrylic polyol compound not modified with silicone. . At that time, since both have the same basic skeleton, they are highly compatible. Therefore, unlike the case of the block copolymer described above, the balance between various surface properties and stain resistance is adjusted in accordance with the intended use of the cosmetic material. Therefore, there is an advantage that the degree of freedom in material design is expanded.
[0025]
In the present invention, the organopolysiloxane alkylol compound used for introducing an organopolysiloxy group into the side chain of the acrylic urethane resin increases the molecular weight of the side chain and increases the contamination resistance as the molecular weight increases. Although it is advantageous, even if the molecular weight is too high, the compatibility with the acrylic polyol compound and the like is reduced, and the reaction is inhibited. On the other hand, if an extremely low molecular weight is used, the stain resistance becomes insufficient. Therefore, it is necessary to design appropriately in consideration of compatibility / reactivity and contamination resistance.
[0026]
In the case of the above first method, since a composition in which the three of the acrylic polyol compound, the organopolysiloxane alkylol compound and the polyisocyanate compound are mixed is applied onto the base material, The compatibility of the three is important, and the upper limit of the molecular weight of the organopolysiloxane alkylol compound is determined from that viewpoint. The specific numerical value depends on the type and blending ratio of other components, the kind and blending ratio of the solvent, etc., but generally the upper limit is about 1000 molecular weight of the organopolysiloxy group, usually 300 to Good results can be obtained at about 700.
[0027]
On the other hand, in the case of the second method, an organopolysiloxane alkylol compound is reacted with an acrylic polyol compound in which a carboxyl group is previously introduced into a side chain, and a silicone-modified acrylic in which an organopolysiloxy group is introduced into the side chain. Since it is in the form of a polyol compound and then this is converted into a paint, even if a higher molecular weight organopolysiloxane alkylol compound is used than in the case of the first method, an acrylic polyol is used as the basic skeleton in forming the paint. Therefore, the compatibility with the polyisocyanate compound and the solvent can be sufficiently ensured, and the restriction on the molecular weight of the organopolysiloxy group from the viewpoint of coating suitability is relatively small. Specifically, although depending on various conditions, the molecular weight of the organopolysiloxy group can be up to about 8000, and generally about 3000 to 6000 (the number of siloxane bonds is about 40 to 80) is good. Results are obtained.
[0028]
As described above, the second method is advantageous in terms of contamination resistance because an organopolysiloxy group having a higher molecular weight can be introduced. In addition, in the first method, not all of the organopolysiloxane alkylol compound is bonded to the acrylic polyol compound via the polyisocyanate compound. Depending on the blending composition and curing conditions, the organopolysiloxane alkylol compound In contrast to the fact that low molecular weight components such as unreacted substances and dimers via the polyisocyanate compound remain and cause problems of bleeding (bleeding) to the surface, According to the second method, the silicone-modified acrylic polyol compound in which the organopolysiloxy group is introduced into the side chain has many reactive groups and is highly reactive, and since it reacts quickly with the polyisocyanate compound and crosslinks, it has a low molecular weight. The silicone component does not remain, there is no problem of bleeding, and the cross-linking is made more uniform. There is an advantage that it is possible to obtain a coating film excellent in physical properties.
[0029]
The organopolysiloxane group in the organopolysiloxane alkylol compound is not particularly limited in the present invention, but one of the polydimethylsiloxy group, the polymethylphenylsiloxy group, and the methyl group of the polydimethylsiloxy group is another alkyl group. And those substituted with an allyl group or the like can be used as appropriate. Among them, a polydimethylsiloxy group is the most common. Moreover, as an alkylol group, for example, a methylol group, an ethylol group, a propylol group, a butyrol group, etc. are arbitrary, but an ethylol group or a propylol group is the most common.
[0030]
In the present invention, the molecular weight and cross-linking point density of the acrylic polyol compound or the silicone-modified acrylic polyol compound are the same as those in a general acrylic urethane resin that has been widely used in conventional cosmetics. In general, those having a weight average molecular weight of about 15,000 to 80,000 and an average molecular weight between cross-linking points of about 600 to 1500 can be preferably used.
[0031]
In the present invention, various additives can be added to the antifouling layer 2 as necessary. For example, if the surface of the antifouling layer 2 is scratched, it is not desirable in terms of design, and contaminants are buried in the recesses of the scratches, making it difficult to wipe off, thereby causing apparent stain resistance to decrease. There is. Therefore, by adding hard particles made of a material having a hardness higher than that of the silicone-modified acrylic urethane resin constituting the antifouling layer 2 such as silica, alumina, glass beads, and crosslinked acrylic beads to the antifouling layer 2, the antifouling layer 2 is added. By improving the scratch resistance of the layer 2, the durability of the stain resistance can be further increased.
[0032]
By adding such hard particles, fine irregularities are generated on the surface of the antifouling layer 2, and in the case of coating with a normal acrylic urethane resin, it may cause a decrease in the stain resistance. However, in the present invention, due to the excellent antifouling effect of the silicone-modified acrylic urethane resin that constitutes the antifouling layer 2, depending on the fine irregularities that are much gentler than the concave portions due to scratches, Contamination is hardly diminished and practically sufficiently excellent contamination resistance can be exhibited.
[0033]
Further, in such a decorative material, generally, weather resistance is also an important factor in performance. For example, the base material 1 and / or the antifouling layer 2 may deteriorate due to the action of ultraviolet rays, and fine cracks may occur. Then, contaminants enter the cracks, making it difficult to wipe off, and this causes a decrease in apparent stain resistance. Therefore, in order to prevent the deterioration phenomenon, it is desirable to add an ultraviolet absorber and / or a light stabilizer to the antifouling layer 2. Of course, if possible, it is desirable to give the base material 1 the same weathering prescription. Examples of ultraviolet absorbers include organic types such as benzotriazole, benzophenone, and salicylate, inorganic types such as cerium oxide and zinc oxide, and hindered amines and nickel complexes as light stabilizers. If both are used together, the effectiveness is higher.
[0034]
In addition, for example, conventionally known additives such as colorants such as dyes or pigments, fillers, matting agents, lubricants, flame retardants, antistatic agents, antibacterial agents, and antifungal agents may be optionally added. . Examples of the method for forming the antifouling layer 2 include gravure coating, roll coating, rod coating, kiss coating, knife coating, air knife coating, die coating, lip coating, spray coating, flow coating, The dip coating method can be performed by any conventionally known coating method.
[0035]
【Example】
Hereinafter, specific examples and comparative examples of the contamination-resistant cosmetic material of the present invention will be described in detail.
[0036]
Example 1
On the surface of a decorative sheet substrate made of olefin resin having a thickness of 0.2 mm, on which a printed layer and a transparent polypropylene resin film are laminated on a colored polypropylene resin film coated with a urethane primer layer on the back surface, An esterification reaction product of 80 parts by weight of an acrylic polyol having a carboxyl group in the side chain and 20 parts by weight of a polydimethylsiloxane propirole having a polydimethylsiloxy group having a weight average molecular weight of about 4500 (average number of siloxane bonds of about 60). 50 weight parts of a silicone-modified acrylic polyol having a polydimethylsiloxy group in the side chain having a weight average molecular weight of about 25,000 and an average number of hydroxyl groups per molecule of about 25, a weight average molecular weight of about 50,000 and an average number of hydroxyl groups of about 30 per molecule. Acrylic polyol 50 parts by weight, hexamethylene diiso Coating amount after drying paint consisting Aneto based mixed composition of the curing agent 10 parts by weight by a gravure coating method 3 g / m²The coating sheet was dried and cured by curing to form an antifouling layer, thereby producing a decorative sheet which is a stain-resistant cosmetic material of the present invention.
[0037]
Example 2
In Example 1 above, 10 parts by weight of glass beads having an average particle size of about 3 μm are added to the paint for forming the antifouling layer, and the others are the same as in Example 1 above with the antifouling cosmetic material of the present invention. A decorative sheet was prepared.
[0038]
Example 3
In Example 1 above, 0.3 parts by weight of a benzotriazole UV absorber and 0.2 parts by weight of a hindered amine light stabilizer were added to the paint for forming the antifouling layer, and the others were the same as in Example 1 above. In the same manner, a decorative sheet, which is a stain-resistant cosmetic material of the present invention, was produced.
[0039]
Example 4
In Example 1 above, the coating material for forming the antifouling layer is a polydimethylsiloxane polymer having a weight average molecular weight of about 25,000, an acrylic polyol having an average number of hydroxyl groups of about 25 parts by weight of 100 parts by weight, and a weight average molecular weight of about 500. A coating sheet comprising a mixed composition of 10 parts by weight of pyrrole and 10 parts by weight of a hexamethylene diisocyanate curing agent is used, and the rest is the same as in Example 1 above, and a decorative sheet which is a stain-resistant cosmetic material of the present invention is produced. did.
[0040]
Comparative Example 1
In Example 4 above, 20 parts by weight of non-reactive silicone oil (viscosity of about 0.5 Pa · s) was blended in place of polydimethylsiloxane propirole in the coating for forming the antifouling layer. A decorative sheet was prepared in the same manner as in 1.
[0041]
Comparative Example 2
In Comparative Example 1, the amount of the silicone oil was changed to 10 parts by weight, and the rest was prepared in the same manner as in Comparative Example 1 above.
[0042]
Comparative Example 3
In Comparative Example 1, the amount of silicone oil was changed to 5 parts by weight, and the rest was prepared in the same manner as in Comparative Example 1 above.
[0043]
Comparative Example 4
In Comparative Example 1, a cosmetic sheet was prepared in the same manner as in Comparative Example 1 except that no silicone oil was blended.
[0044]
Performance comparison
For each of the decorative sheets of Examples 1 to 4 and Comparative Examples 1 to 3, several sheets of a sheet sample cut into a 10 cm square shape are stacked so that the front surface and the back surface overlap each other, and 100 kg is measured with a blocking tester. After applying a load and curing for 72 hours in an atmosphere of 60 ° C., select one sheet from the sheet sample that was in contact with the surface of another sheet, and use a commercially available modified vinyl acetate emulsion adhesive (center BA-10L manufactured by Rika Kogyo Co., application amount 100g / m²Wet) was adhered to the surface of the plywood to produce a decorative board. About these decorative boards, after writing on the surface using a commercially available black oil-based pen (Magic ink manufactured by Teranishi Chemical Industry Co., Ltd.), repeat the operation of wiping with tissue paper, and stain resistance with the number of repetitions when wiping marks remain Sex was evaluated. Moreover, about these decorative boards, the peeling strength of the decorative sheet was measured on the conditions of temperature 23 degreeC and peeling speed 200mm / min with the tensile tester. The results of these tests are shown in the following table.
[0045]
List of test results
Contamination resistance Peel strength Peel state
Example 1> 100 times 1250 N / m Plywood breakage
Example 2> 100 times 1290 N / m Plywood breakage
Example 3> 100 times 1250 N / m plywood breakage
Example 4> 100 times 1100 N / m Plywood breakage
Comparative Example 1 10 times 200 N / m Interfacial peeling
Comparative Example 2 5 times 590 N / m Interfacial peeling
Comparative Example 3 3 times 780 N / m Plywood breakage
Comparative Example 4 1 time 1250 N / m Plywood breakage
[0046]
However, the interfacial peeling is peeling at the interface between the primer layer and the adhesive layer on the back surface of the decorative sheet. Moreover, the contamination resistance once means that a mark remained after the first wiping.
[0047]
As is apparent from the above table, the stain-resistant cosmetic material of the present invention has significantly greater stain resistance against repeated wiping compared to conventional cosmetic materials having a silicone-free or silicone oil-added surface coating. In addition, even when additives such as hard particles and weathering agents are added, the stain resistance is not significantly reduced. In addition, the silicone component does not ooze out on the surface, and even if wound or stacked and stored, the silicone component does not transfer to the back surface. Maintaining sex.
[0048]
【The invention's effect】
As described above in detail, the antifouling cosmetic material of the present invention has the same antifouling property as the initial state of the cosmetic material having the antifouling layer of the conventional silicone oil addition type, and the silicone component changes with time. It can withstand repeated repeated wiping and maintain excellent contamination resistance for a long period of time without oozing out on the surface and being lost by wiping. There is no problem, and there is an excellent effect that it can be satisfactorily processed without causing an adhesion hindrance with the adhesive at the time of adhesion processing on the back surface.
[Brief description of the drawings]
FIG. 1 is a side sectional view showing an embodiment of a stain-resistant cosmetic material of the present invention.
[Explanation of symbols]
1 Base material
11 Primer layer
12 Substrate sheet
13 Pattern layer
14 Adhesive layer
15 Surface sheet
16 Emboss
2 Antifouling layer

Claims (5)

In the antifouling cosmetic material in which an antifouling layer is provided on a substrate, the antifouling layer comprises an acrylic polyol compound, an organopolysiloxane alkylol compound having a hydroxyl group at the end and a molecular weight of 300 to 700 , A mixture with a polyisocyanate compound is applied, and the hydroxyl groups of the acrylic polyol compound are cured by crosslinking through the polyisocyanate compound, and at the same time, a part of the hydroxyl groups of the acrylic polyol compound is organolated through the polyisocyanate compound. stain decorative material, characterized in that it consists of introducing silicone-modified acrylic urethane resins organopolysiloxanes siloxy group in the side chain of the acrylic urethane resin by a method of bonding with the hydroxyl group at the end of the polysiloxane alkylol compounds. In the antifouling cosmetic material provided with an antifouling layer on the base material, the antifouling layer has a carboxyl group in the side chain by adding an unsaturated carboxylic acid such as acrylic acid or methacrylic acid as a copolymerization component. The carboxyl group of the introduced acrylic polyol compound is bonded to the hydroxyl group of an organopolysiloxane alkylol compound having a molecular weight of 3000 to 6000 (siloxane bond number 40 to 80) having a hydroxyl group at the terminal by an esterification reaction. Thus, a silicone-modified acrylic polyol compound having an organopolysiloxy group introduced into the side chain is obtained, and thereafter, the hydroxyl group is cross-linked through a polyisocyanate compound to form an organopolysiloxy group on the side chain of the acrylic urethane resin . Consists of introduced silicone-modified acrylic urethane resin Anti-pollution decorative material which is characterized.   The antifouling cosmetic material according to claim 1 or 2, wherein the antifouling layer further contains hard particles made of a material having a hardness higher than that of the silicone-modified acrylic urethane resin.   The antifouling cosmetic material according to any one of claims 1 to 3, wherein the antifouling layer is further added with an ultraviolet absorber and / or a light stabilizer.   The antifouling cosmetic material according to any one of claims 1 to 4, wherein at least a surface of the base material in contact with the antifouling layer is made of a polyolefin resin.

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