JP2003103728A - Decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative material excellent in interlaminar adhesion from an initial stage, exerting no effect on environment and extremely low in yellowing when exposed to ultraviolet rays. SOLUTION: In the decorative material wherein a surface sheet 1' comprising a transparent olefinic resin is laminated on a substrate sheet 1 comprising an olefinic resin through an adhesive layer 2, the adhesive layer 2 comprises cured matter of a humidity curable hot melt adhesive containing a urethane prepolymer formed by reacting a polyol compound with norbornane diisocyanate and having an isocyanate group at its terminal.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cosmetic material which has extremely low yellowing when exposed to ultraviolet rays and is useful as a building material such as furniture and fittings, and a surface decoration material for automobiles, vehicles, aircrafts and the like. .

[0002]

2. Description of the Related Art Conventionally, for example, vinyl chloride resin has been used as a decorative sheet for building materials, but a decorative sheet using a vinyl chloride resin uses vinyl chloride resin as a material, and therefore is discarded or discarded. There was a problem that toxic chlorinated compounds were generated during combustion. Therefore, a decorative sheet using an olefin resin which is a non-vinyl chloride resin has been proposed. Since an olefin resin is excellent in terms of environment, but has poor adhesiveness, a decorative sheet laminated with an olefin resin is, for example, a substrate obtained by extruding a molten olefin resin and applying an anchor coating agent or an adhesive layer. A method of laminating to a sheet, a method of sticking a base sheet and an olefin resin sheet (top sheet) using a normal heat-sealing adhesive, and a two-component curing type of a base sheet and an olefin resin sheet It is manufactured by a method such as dry lamination using a urethane resin adhesive layer.
Further, as a method of coating a decorative sheet with a polyolefin resin sheet such as polypropylene, for example, immediately after extrusion molding of a two-layer sheet consisting of a polypropylene layer and a polyethylene layer containing an ethylene-α-olefin copolymer, At least the surface portion of the two-layer sheet, the polyethylene layer surface containing the ethylene-α-olefin copolymer in a molten state, subjected to ozone treatment of blowing a gas containing ozone at a constant rate, then the two-layer sheet Anchor coating agent (adhesive)
There is also known a method for producing a laminate in which layers are adhered to each other (see Japanese Patent Publication No. 62-60970, etc.). Among these conventional methods, in particular, by extrusion molding an olefin resin,
The method of laminating and bonding via an adhesive layer (or an anchor coating layer) is widely used because a decorative sheet having a relatively strong adhesive strength can be obtained.

However, the adhesive used in this method is a solvent-diluted adhesive, and the solvent component volatilizes during the production of the decorative sheet, which does not have a bad effect on the environment such as a bad odor or solvent poisoning. In addition, there is a problem that equipment for drying the solvent is required, and in order to improve the production efficiency, the solvent drying capacity is restricted and an extra cost such as a manufacturing space and an electricity cost is required. Further, if the drying is insufficient and the residual solvent is present, so-called swelling may occur between the sheet layers, or the adhesive performance may be adversely affected. In addition, these adhesives are liquid at 2
The liquid curing resin solves the problem of solvent drying, but on the other hand, the initial adhesive force until the curing reaction is completed becomes weak, and there is a problem that post-processing cannot be performed until the curing reaction is completed. .

Therefore, the present inventors have solved these problems, and have an adhesive layer formed by using a moisture-curable hot melt adhesive from the beginning as a decorative sheet having excellent interlayer adhesion and being environmentally friendly. As a decorative material in which sheets made of an olefinic resin are laminated, JP-A No. 11-246830 has been proposed. By the way, as a moisture-curable hot melt adhesive, conventionally, an isocyanate group-terminated urethane prepolymer capable of efficiently developing the initial adhesive strength and imparting heat resistance by three-dimensionally crosslinking by causing a moisture curing reaction. Moisture curable hot melt adhesives of the system are common. As the isocyanate component constituting such a moisture-curable hot melt adhesive, free monomer isocyanate, which is a safety and health problem when heat-melted during use, is generated as mist.
It is essential to select a diisocyanate that produces less mist of free monomer isocyanate. From this viewpoint, it is widely used as a moisture-curable hot melt adhesive composed of a urethane prepolymer using an aromatic diisocyanate, especially methylenediphenyldiisocyanate (MDI).

However, the urethane prepolymer has a tendency to yellow when exposed to ultraviolet rays. Particularly, the urethane prepolymer using an aromatic diisocyanate has a large yellowing because it has an aromatic ring. There is a problem,
The conventional cosmetics using a moisture-curable hot melt adhesive cannot be applied to applications where yellowing is a problem, such as applications exposed to ultraviolet rays or applications requiring transparency. Therefore, considering yellowing, it is conceivable to use an aliphatic diisocyanate having no aromatic ring as the isocyanate component of the urethane prepolymer. As the aliphatic diisocyanate, for example, hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are known. However, when hexamethylene diisocyanate (HDI) is used, the amount of mist generation of free monomer isocyanate is large, and safety and health problems occur. On the other hand, isophorone diisocyanate (IPDI) has a reactivity of two isocyanate groups in one molecule. Therefore, the reaction operation is difficult and a problem occurs in curing reactivity.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has excellent interlayer adhesion from the beginning and does not affect the environment. Further, yellowing when exposed to ultraviolet rays is extremely high. The purpose is to provide a low cosmetic material.

[0007]

Means for Solving the Problems The present inventor has conducted extensive studies to solve the above problems. As a result, by using a moisture-curable hot melt adhesive containing a urethane prepolymer obtained by using a specific polyol compound and a specific diisocyanate compound, the yellowing when exposed to ultraviolet rays is reduced. The inventors have found that it can be suppressed and completed the present invention. That is, the decorative material according to the present invention is a decorative material in which a surface sheet made of a transparent olefin resin is laminated on a base material sheet made of an olefin resin via an adhesive layer. ,
It is characterized by comprising a cured product of a moisture-curable hot melt adhesive containing a urethane prepolymer having a terminal isocyanate group formed by reacting a polyol compound with norbornane diisocyanate.

[0008]

1 to 4 are views showing a typical example of a cross-sectional structure of a decorative material according to an embodiment of the present invention. The present invention is characterized by an adhesive used for laminating resin sheets, but can be applied to a decorative material having a structure as described below. In the structure shown in FIG. 1, an adhesive layer 2 is formed on the upper surface side (front surface side) of a base sheet 1, and a transparent surface sheet 1 ′ is laminated via the adhesive layer 2. In the structure shown in FIG. 2, the pattern layer 3 is laminated on the upper surface side (front surface side) of the base sheet 1, and the adhesive layer 2 is formed on the pattern layer 3.
The topsheet 1'is laminated via the.

In the structure shown in FIG. 3, the pattern layer 3 is laminated on the upper surface side (front surface side) of the base sheet 1, and the surface sheet 1'is laminated on the pattern layer 3 via the adhesive layer 2. Further, an uneven pattern 4 is formed on the surface of the surface sheet 1 ', and the coloring material 5 is filled in the concave portions of the uneven pattern 4.
In the structure shown in FIG. 4, the pattern layer 3 is laminated on the upper surface side (front surface side) of the base sheet 1, and the surface sheet 1 ′ is laminated on the pattern layer 3 with the adhesive layer 2 interposed therebetween. The transparent protective layer 6 is laminated on 1 ', and the base sheet 1, the pattern layer 3, the adhesive layer 2, the surface sheet 1', and the transparent protective layer 6 are laminated.
Has a concavo-convex pattern 4, and the coloring material 5 is filled in the concave part of the concavo-convex pattern 4 of the surface sheet 1 '.

In the present invention, the pattern layer 3 is preferably laminated as shown in FIGS. The pattern layer 3 can give a desired appearance. In addition,
The pattern layer 3 and the adhesive layer 2 are turned upside down, that is, the adhesive layer 2 is first laminated on the upper surface side of the base sheet 1,
The pattern layer 3 may be laminated thereon. In the present invention, instead of laminating the pattern layer 3 for makeup as shown in FIGS. 2 to 4, a colored layer may be laminated for makeup, or separately from the base sheet 1. The base sheet 1 itself may be colored, instead of being laminated with the colored layers described above. By using the base sheet 1 as a coloring sheet,
When printing on a coloring sheet, there is an advantage that it is easy to determine whether the color tone is printed as intended or as the original. This is because, in the field of decorative materials, conventionally, it is often the case that a special color ink having a specific hue of 1 to 3 colors is printed on a colored sheet colored with a highlight color. When the base sheet 1 is a colored sheet and printing is performed on the back side of the topsheet 1 ',
After printing, the color tone can be determined by viewing the base sheet 1 in an overlapping manner. When printing is performed with a plate of three colors or four colors including black, as in normal printing, printing may be performed on the base material sheet 1 or on the lower surface side of the surface sheet 1 ′. When the base material sheet 1 is colored, in many cases, a filler is added in addition to the colorant, but when the base material 1 is formed, the filler is deposited near the slit of the extrusion port. However, since it may cause problems, it is preferable to coat the both surfaces of the layer containing the filler with a layer not containing the filler so as to form a film by co-extrusion, which does not cause any trouble due to the deposition of the filler. . In this case, the base sheet 1 has three layers, that is, a back layer containing no filler, a center layer containing a filler and a colorant, and a front layer containing no filler, which are sequentially laminated.

In the present invention, an uneven pattern 4 may be formed as shown in FIGS. 3 and 4. Due to the uneven pattern on the outermost surface, it is possible to obtain a decorative material having a three-dimensional effect and a sense of reality. Also, it is possible to fill the concave portion with the coloring material 5,
It is preferable because it can be a cosmetic material with an increased three-dimensional effect. For example, if the base material sheet 1 is a white plain sheet and the unevenness pattern 4 of the cloth is provided on the surface of the surface sheet 1 ′, the cloth feels soft and gives a calm atmosphere, and the surface sheet 1'provides depth and gloss. The concavo-convex pattern 4 gives a more complicated impression when used in combination with the pattern layer 3, for example, the pattern layer 3 having a wood grain pattern.
By combining with the fine uneven pattern 4 on the surface of the plate, it is possible to generate a three-dimensional effect that is close to that of real wood grain, which cannot be obtained only by printing. Furthermore, by combining the three elements of stacking the pattern layer 3 and the transparent protective layer 6 and forming the concavo-convex pattern 4, the depth and authenticity are further increased. Further, the pattern layer 2 and the coloring layer are not laminated, and instead, the uneven pattern 4 is provided on the outermost surface, whereby a makeup can be obtained. Although it is not necessary to fill the concave portion of the concave-convex pattern 4 with the coloring material 5, when filled, the three-dimensional effect can be increased due to the difference in hue in addition to the physical unevenness.

In the present invention, as shown in FIG. 4, a transparent protective layer 6 may be laminated on the uppermost surface of the decorative material. Further, the transparent protective layer 6 may be formed independently without the uneven pattern 4, the pattern layer 2 and the coloring layer. In the present invention, the makeup in the decorative material means the pattern layer 2 as described above.
It means that a colored layer is laminated and that the uneven pattern 4 is formed. A typical makeup is lamination of the pattern layers 2 by printing or the like, but a decorative material having only the pattern layers 2 tends to have a flat feeling. Therefore, when a transparent surface sheet 1'and a transparent protective layer 6 are further laminated on the pattern layer 2, the appearance depth is increased due to the transparent layer on the pattern layer 2.

The base sheet 1 and the top sheet 1 ', the adhesive layer 2, the pattern layer 3, the uneven pattern 4, the transparent protective layer 6, and the coloring material 5 will be described below. The base sheet 1 and the top sheet 1'are sheets made of polyolefin resin. The surface sheet 1'is a sheet made of transparent polyolefin resin. The thickness of each of the base sheet 1 and the top sheet 1'is 20
The thickness is preferably 100 μm to 100 μm. More specifically, the polyolefin-based resins suitable for use as decorative materials include
Broadly classified, there are two types: a non-elastomer polyolefin resin and a polyolefin thermoplastic elastomer.

Specific examples of the non-elastomer polyolefin resin include polyethylene (low density or high density), polypropylene (isotactic type, syndiotactic type, or a mixture thereof), polymethylpentene, polybutene. , Ethylene / propylene copolymers, propylene / butene copolymers, and the like, which are highly crystalline. On the other hand, as the polyolefin-based thermoplastic elastomer, specifically, there are the following (1) to (8). (1) A material whose main raw material is high-density polyethylene having a hard segment, isotactic polypropylene or the like, and further an elastomer as a soft segment and, if necessary, an inorganic filler added. Here, examples of the elastomer include diene rubber, hydrogenated diene rubber, and olefin elastomer.
More specifically, examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene / butadiene rubber. Hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of the double bond of the above-mentioned diene rubber molecule, and suppresses crystallization of polyolefin resin (in the present invention, high density polyethylene or polypropylene), It has improved flexibility. Two or three types of olefin elastomers
It is an elastic copolymer in which at least one polyene copolymerizable with at least one type of olefin is added, and ethylene, propylene, α-olefin, etc. are used as the olefin, and 1,4-hexadiene, cyclic diene is used as the polyene. , Norbornene, etc. are used. Examples of preferable olefin-based copolymer rubber include elastic copolymers containing olefin as a main component, such as ethylene / propylene copolymer rubber. In addition, these elastomers may be cross-linked in an appropriate amount by using a cross-linking agent such as an organic peroxide or sulfur, if necessary.

(2) Those in which the hard segment is isotactic polypropylene and the soft segment is atactic polypropylene, and the latter ratio is preferably less than 5% by weight (described in Japanese Patent Publication No. 6-23278). (3) A copolymer of ethylene / propylene / butene, which contains, as butene, one of three structural isomers of 1-butene, 2-butene, or isobutylene. The following (3a) to (3c) are typical. (3a) A random terpolymer of ethylene / propylene / butene, in which propylene in the monomer is preferably 90% by weight (described in JP-A-9-111055). (3b) Amorphous compound consisting of terpolymer of ethylene / propylene / butene having a propylene component content of 50% by weight or more and crystalline polypropylene (described in JP-A-5-77371). . (3c) A low crystalline substance having a propylene and / or 1-butene content of 50% by weight or more and a crystalline polyolefin such as isotactic polypropylene, and 0.5% by weight of an oil gelling agent. Those added (described in JP-A-7-316358).

(4) The hard segment is polyethylene,
A crystalline compound such as polypropylene or polymethylpentene, which is a monoolefin copolymer rubber such as ethylene / propylene non-conjugated diene terpolymer rubber partially soft-crosslinked (described in Japanese Patent Publication No. 53-21021). ). (5) One in which an olefin copolymer (crystalline) as a hard segment and an uncrosslinked monoolefin copolymer rubber as a soft segment are heated and subjected to shear stress to be partially crosslinked (Japanese Patent Publication No. 53- 34210). (6) Peroxide-decomposing olefin polymer whose molecular weight decreases and fluidity increases when mixed and heated with peroxide, for example, isotactic polypropylene, propylene / ethylene copolymer, or propylene / butene-1 copolymer The coalesced product is used as a hard segment, and a peroxide-crosslinking type monoolefin polymer whose fluidity is reduced by the same operation, such as ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated diene terpolymer rubber, is soft. A segment, which is obtained by mixing and heating a non-peroxide type non-crosslinking type hydrocarbon rubber which does not crosslink by the same operation and does not change in fluidity in the presence of a peroxide (Japanese Patent Publication No. 56- 15741 gazette).

(7) Ethylene / styrene / butadiene copolymer (described in JP-A-2-139232). (8) The above (1) having a hydroxyl group or a carboxyl group
~ (7) olefin elastomer. It is preferable to add an ultraviolet absorber or a light stabilizer to the polyolefin resin for the purpose of avoiding adverse effects of ultraviolet rays such as sunlight. If the UV absorber or the light stabilizer can be polymerized with the polyolefin-based monomer, it is used as it is, and if it is not polymerized by itself, it is blended with a compound having a polymerizable functional group such as an acryloyl group. It is more preferable that the base sheet 1 and the top sheet 1 ′ are constituted by producing a polymer and using the obtained copolymer resin as a main component.

As the ultraviolet absorber, for example, the following ones (1) to (5) can be used. (1) Benzophenone-based; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid, etc. . (2) Benzotriazole-based; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2-
(2'-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2 '
-Hydroxy-3 ', 5'-di-t-butylphenyl)-
5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) phenylbenzotriazole, 2- (2'-hydroxy-3'-dodecyl-
5'-methylphenyl) benzotriazole, 2,2'-
Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl)
Phenol], etc.

(3) Acrylate type; ethyl-2-cyano-3,3'-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and the like. (4) Salicylate system; phenyl salicylate, 4-t
-Butylphenyl salicylate and the like. (5) Oxanilide type; 2-ethoxy-2′-ethyl oxalic acid bisanilide, 2-ethoxyne-5
t-butyl-2'-ethyl oxalic acid bis anilide and the like.

As the light stabilizer, for example, a hindered amine-based light stabilizer (commonly known as HALS) can be used.
Specifically, bis- (2,2,6,6-tetramethyl-
4-piperidinyl) sebacate, bis- (N-methyl,
2,2,6,6, -tetramethyl-4-piperidinyl)
Sebacate, [dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine] condensate, poly {[6- (1,1,
3,3-Tetramethylbutyl) imino] -1,3,5-
Triazine-2,4-diyl [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)
Iminol]} and the like.

The mixing ratio of the ultraviolet absorber or the light stabilizer is preferably in the range of 0.1 to 2% by weight based on the total resin content of the layer to be added. 0.
If it is less than 1% by weight, the effect of addition is poor, and if it exceeds 2% by weight, the effect is not improved. It should be noted that the ultraviolet absorber and the light stabilizer are effective even when they are used alone, but the combined use improves synergistically, and therefore it is desirable to use them together. Moreover, since the bleeding during use is unavoidable by simply mixing the ultraviolet absorber and the light stabilizer, 4- (meth) acryloyloxy-2 is used in place of the hindered amine light stabilizer. , 2,
6,6-Tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-1-propyl-2,2,6,6- Tetramethylpiperidine, 4-
(Meth) acryloyloxy-1-butyl-2,2,2
A compound having a (meth) acryloyloxy group such as 6,6-tetramethylpiperidine, or 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4
-Crotonoyloxy-1-propyl-2,2,6,6
It is more preferable to prevent bleeding by using a resin obtained by graft-copolymerizing a compound having a crotonoyloxy group such as tetramethylpiperidine.

In the base sheet 1 and / or the surface sheet 1 ', it is preferable that an adhesive polyolefin resin layer is previously laminated on the surface of the base sheet 1 and / or the surface sheet 1'which is in contact with another layer. It is preferable for improving the property. Here, the adhesive polyolefin-based resin layer is, for example, polyethylene, polypropylene, ethylene / propylene copolymer, or a polyolefin in a broad sense that is a copolymer of these with other α-olefins, vinyl acetate, or the like,
A layer of a resin obtained by graft-copolymerizing one of maleic acid, acrylic acid and fumaric acid (preferably maleic acid) in the range of 10 ⁻⁴ to 10% by weight, preferably 10 ^{−3 to} 5% by weight. Is. The lamination of such an adhesive polyolefin-based resin layer is performed by a melt extrusion method in which one polyolefin resin layer is simultaneously extruded from one T-die, or after forming one resin layer, the other resin layer is formed. Is preferably laminated by extrusion coating.

In the present invention, a corona discharge treatment is applied to one or both sides of the base sheet 1 and / or the top sheet 1 ', if necessary, for the purpose of improving the adhesiveness to the base sheet 1 or the top sheet 1'. May be performed, a primer layer may be formed, or an adhesive layer for laminating another layer may be formed. As the resin constituting the primer layer, polyester resin, polyurethane resin, acrylic resin, polycarbonate resin, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral resin, nitrocellulose resin, etc. can be used, as well as alkyl titanate type and ethylene imine type. Compounds of can also be used. These resins and compounds are used alone or in a mixture to form a coating composition or an ink composition, and a primer layer is formed by using an appropriate coating means or printing means.

The back surface of the topsheet 1 ', that is, the bottom surface of the decorative material, is intended to be easily attached to a general adhesive, assuming that the decorative material is attached to another substrate or article. A primer layer may be laminated. Further, an adhesive resin layer may be previously laminated on the lower surface of the topsheet 1'to increase the adhesive force. In this case, a method of forming a film by co-extrusion at the time of manufacturing the surface sheet 1'is preferable, or a method of melt-extruding the adhesive resin and immediately laminating it on one surface of the once formed film of the surface sheet 1 '. The adhesive layer 2 is formed of a cured product of the following moisture curable hot melt adhesive.

The moisture-curable hot melt adhesive contains a urethane prepolymer having an isocyanate group at the terminal, and the urethane prepolymer is obtained by reacting a diisocyanate compound and a polyol compound. Hereinafter, the urethane prepolymer will be described in detail. In the present invention, the diisocyanate compound is norbornane diisocyanate (NB
DI) is important. Norbornane diisocyanate (NBDI) has a structure represented by the following formula (1), and specifically, 2,5-bis (isocyanatomethyl) bicyclo [2,2,1] heptane and / or 2, It is 6-bis (isocyanatomethyl) bicyclo [2,2,1] heptane.

[0026]

[Chemical 1]

By using such a norbornane diisocyanate (NBDI) as the diisocyanate compound, yellowing when exposed to ultraviolet rays can be suppressed, and at the same time, good moisture curability can be exhibited, and moreover, when it is melted. It is possible to suppress the amount of mist generation of free monomer isocyanate to an allowable range that does not cause a problem in safety and hygiene. In the present invention, the polyol compound has a number average molecular weight of 2,000 to 5,000 1,6-
Copolyester polyol resin of hexane glycol and sebacic acid 30 to 60% by weight and number average molecular weight of 20
Copolyester polyol resin 30 to 60 of 1,0-5,000 1,6-hexane glycol and adipic acid
It is preferably composed of 5% by weight and 5 to 10% by weight of saturated polyester resin. By using such a polyol compound, the obtained urethane prepolymer melts at the time of heating and solidifies at the time of cooling, and at the same time, has crystallinity and exhibits a good hot melt property.

The ratio of the diisocyanate compound to the polyol compound is the equivalent ratio (-NCO) of all isocyanate groups (-NCO) of the diisocyanate compound to all hydroxyl groups (-OH) of the polyol compound.
The range is preferably such that // OH) is 1.5 to 2.5 (molar ratio). Equivalent ratio (-NCO / -OH) is 1.5
If it is less than (molar ratio), thickening or gelation due to chain extension reaction tends to occur, while if it exceeds 2.5 (molar ratio), the amount of residual diisocyanate monomer increases and harmful mist is generated. May lead to The urethane prepolymer in the present invention is not particularly limited as long as it is obtained from the polyol compound and the diisocyanate compound as raw materials, and about the reaction method when reacting the polyol compound and the diisocyanate compound A conventionally known method can be adopted. The reaction conditions and the like are also not particularly limited and may be set appropriately.

The content of the urethane prepolymer in the moisture-curable hot melt adhesive is preferably 50% by weight or more. If the content of the urethane prepolymer is less than 50% by weight, the curing reactivity and the heat resistance of the cured product may decrease. From the viewpoint of moisture curability, it is preferable that the moisture curable hot melt adhesive further contains a curing catalyst together with the urethane prepolymer. As the curing catalyst, an organometallic catalyst is preferable, and a tertiary amine catalyst cannot be used. This is because the cured product of the tertiary amine-based catalyst turns yellow by ultraviolet rays. Examples of the organometallic catalysts include stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercuride, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin mercurtide, dioctyltin thiocarboxylate, and the like. To be Even if only one of these curing catalysts is used, 2
It may be more than one species. The content of the curing catalyst is preferably 1 part by weight or less with respect to 100 parts by weight of the urethane prepolymer.

It is preferable that the moisture-curable hot melt adhesive further contains an ultraviolet absorber together with the urethane prepolymer, because the yellowing can be suppressed more effectively. As the ultraviolet absorber, for example,
Examples include salicylic acid-based, benzophenone-based, and benzotriazole-based derivatives. These UV absorbers may be used alone or in combination of two or more. The content of the ultraviolet absorber is preferably 1 part by weight or less based on 100 parts by weight of the urethane prepolymer. Further, the moisture-curable hot melt adhesive may be blended with various conventionally known additives as long as the effects of the present invention are not impaired. As the additive, for example, a filler, a coloring agent,
Examples include plasticizers, stabilizers, antioxidants, and the like. In addition,
These additives may be used alone or in combination of 2
You may use together more than one kind.

The moisture-curable hot melt adhesive is 1
Melt viscosity at 2000-120 ℃ is 20000mP ・ s
It should be: Preferably 5000-20000
mP · s. When the melt viscosity is higher than the above range, applicability by an applicator tends to deteriorate. The moisture-curable hot melt adhesive has a softening point of 60-80.
It should be in ° C. When the softening point is higher than the above range, the melting rate is lowered and it becomes difficult to handle. On the other hand, when the softening point is lower than the above range, cold flow or the like occurs depending on the temperature, and stickiness is likely to occur.

The adhesive preferably has an isocyanate concentration value of 1.0 to 2.5%. If the isocyanate concentration value is higher than the above range, foaming of the cured product may occur, while if it is lower than the above range, uncured product may occur due to decreased reactivity, or the heat resistance of the cured product tends to decrease. There is. The moisture-curable hot melt adhesive is usually applied by roll coating or gravure roll coating, and the application amount is 2 to 20 g / m in terms of solid content.
^It is preferably about ² . In addition, laminating may be performed using an ordinary dry laminator or extrusion coater.

The pattern layer 3 is for giving the decorative material of the present invention a value in terms of appearance and design, and is usually formed by a printing method using ink. The picture pattern of the pattern layer 3 may be arbitrary and may be selected according to the application, for example, wood grain, stone grain, cloth grain, sand grain, tile pasting pattern,
Examples include brickwork patterns, leather patterns, geometric patterns, letters, symbols, and solid patterns. As a printing method, a gravure printing method is suitable, but a method other than this may be used. Electrophotographic methods, ink jets, and the like have not been used in the field of decorative materials, but in principle, they can be used as means for forming the pattern layer 3.

From the viewpoint of protecting the pattern layer 3, the printing position is preferably either the upper surface side of the base sheet 1 or the lower surface side of the topsheet 1 '. In the case of printing on the lower surface side of the topsheet 1 ', it is preferable to use a so-called reverse plate, which is created by reversing the left and right, for the picture pattern with left and right distinction. Printing on the upper surface side of the surface sheet 1'or the upper surface side of the transparent protective layer 6 is possible, but if it is a decorative material used for a long time, the base material sheet 1 and the surface sheet 1 '
Between and is appropriate. In order to express a feeling of unevenness, in the case of printing a portion that is desired to appear as if it is a concave portion with ink having a matte effect, it may be printed on the upper surface side of the transparent protective layer 6.

When forming the pattern layer 3 by the printing method, it is necessary to consider the adhesiveness with the base sheet 1 or the top sheet 1 '. The ink used for printing the pattern layer 3 includes a vehicle such as a binder, a colorant such as a pigment or a dye, and various additives as necessary. As the binder, vinyl chloride / vinyl acetate copolymer, acrylic resin,
Polyurethane resin, polyamide resin, polystyrene resin, phenol resin, unsaturated polyester resin, epoxy resin, cellulosic resin, etc. are preferable, but in consideration of adhesion, chlorinated polypropylene type, acryl urethane type and vinyl polymer type resins are preferable. It is preferable to use
It is preferable to use it as a one-pack type of resin containing a crosslinkable portion and a two-pack type in which a crosslinking agent is added at the time of use. As the colorant, titanium white, zinc white, carbon black, iron black,
Rouge, chrome vermillion, cadmium red, ultramarine,
Inorganic pigments such as cobalt blue, yellow lead, titanium yellow,
Organic pigments (or dyes) such as phthalocyanine blue, induslen blue, isoindolinone yellow, benzidine yellow, quinacridone red, polyazo red, berylylene red, aniline black, aluminum,
Metallic pigments such as scale-like foil powder such as brass, titanium dioxide-coated mica, pearlescent pigment such as scale-like foil powder such as shells, and the like are used. When the pattern layer 3 is formed of ink, the coloring agent such as a pigment or dye contained in the ink tends to have a negative effect on the adhesiveness. Therefore, the pattern layer 3 is formed on the surface of the pattern layer 3. If a colorless reducer (also called an extender, medium, etc.) containing the same binder as that of the ink used for, and containing no colorant is applied to form the transparent resin layer, the pattern layer 3 is formed. Adhesion is improved, which is preferable.

The transparent protective layer 6 may be coated with a paint of a thermoplastic resin, but for the purpose of protecting the surface, the transparent protective layer 6 is coated with a paint of a thermosetting resin or an ionizing radiation curable resin composition to provide a transparent protection. Layer 5 is preferably laminated. Specifically, it is formed by using an acrylic urethane-based resin composition or an ionizing radiation-curable resin composition that is cured by irradiation with ultraviolet rays or electron beams, and applying a curing means according to each. The transparent protective layer 6 may contain an antiwear agent for the purpose of improving the scratch resistance of the surface and a matting agent for the purpose of adjusting the gloss of the surface. Examples of antiwear agents include alumina, silica, calcium carbonate and the like, and examples of matting agents include silica, calcium carbonate, shirasu balloon, resin beads and the like.

For example, in the case of a decorative material made by imitating a real thing, the uneven pattern 4 is formed by taking a surface shape such as wood grain, cloth grain, stone grain, etc. Alternatively, the roll mold suitable for industrial production may be manufactured by connecting or increasing the area, and the concavo-convex pattern may be formed by the roll mold. The roll type is usually made of metal, and when used, the target sheet is heated and softened in advance, and a predetermined pressure is applied to transfer the uneven pattern on the surface of the roll type to the sheet. In addition, when applying a coating on the surface, a shaped film is often used. Even when the shaped film is used, the uneven pattern itself provided on the surface of the decorative material is the same as when the roll type is used. An uneven pattern is formed on a paper or plastic film with a relatively hard material, and the paint is cured while it remains on the painted surface of the paint, and the patterning film is peeled off to form the pattern of unevenness on the patterning film. Can be transferred.

In addition, various methods for imparting an uneven pattern have been conventionally known, and a method of forming an uneven pattern by changing the degree of curing of the coating material on the surface to cause the resin to flow, and an area for repelling the coating material. A method of forming a concave portion due to the paint being repelled and forming a concave portion, a method of uncuring a part of the coating material and peeling off the uncured portion, or dissolving and removing a solvent etc. The part you want to look like is formed with matte and / or dark color, and the part you want to look like is formed with glossy and / or light color so that it looks as if there is a concavo-convex pattern visually. Method, etc., and any method can be applied to the decorative material of the present invention.

When the coloring material 5 is filled in the concave portions of the concave-convex pattern 4, a hue difference is generated in addition to the height difference of the concave-convex patterns, so that the three-dimensional effect can be increased. For example, the colorant is applied near the top of the convex portion of the roll having the convex portion,
It is possible to apply a method of coloring at the same time as forming the uneven pattern, but once forming the uneven pattern, while applying the paint,
A method (so-called wiping coating method) of filling the coloring material only in the concave portions and removing the coloring material in the flat portion by scraping with a squeegee can also be applied. However, when the coloring material 5 is filled in the concave and convex portions, the coloring material 5 appears on the outermost surface in that portion. Therefore, depending on the required degree of physical and chemical properties, the coloring material 5 may be used as a main component, for example, polyol. It may be necessary to consider that the material is a curable type such as a two-component curable urethane resin having a valent isocyanate as a cross-linking agent. Therefore, the material may be selected according to the application. Acrylic polyols, polyester polyols, polycarbonate polyols and the like are used as the polyols constituting the two-component curing type urethane resin, and polyvalent isocyanates are aromatic isocyanates such as 2,4-tolylene diisocyanate and xylene diisocyanate, 1,6- and the like. Aliphatic (or alicyclic) isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate and hydrogenated tolylene diisocyanate are used.

The decorative material of the present invention can be used by being laminated on various adherends. As the adherend, three-dimensional articles of various materials, plate materials such as flat plates and curved plates, and articles of various shapes such as sheets (or films) are targeted. Materials used for any of three-dimensionally shaped articles, plate materials or sheets (films) include wood veneer, wood plywood, perticle board, wood material such as wood fiber board such as medium density fiber board (MDF), iron, Metals such as aluminum, acrylic resin, polycarbonate resin, ethylene / vinyl acetate copolymer,
Resins such as ethylene vinyl acetate, polyester resin, polystyrene, polyolefin resin, ABS, phenol resin, polyvinyl chloride, cellulosic resin, rubber, etc., exclusively as plate materials, or as materials used as three-dimensional shaped articles, such as glass, ceramics, etc. Ceramics, ALC
Cement such as (foam lightweight concrete), non-cement ceramic material such as calcium silicate, gypsum, etc., as a material used exclusively as a sheet (or film), high-quality paper,
Examples include paper such as Japanese paper, non-woven fabric or woven fabric made of fibers such as carbon, asbestos, potassium titanate, glass, and synthetic resin.

As a method for laminating these various adherends,
For example, 1) a method of laminating by pressing with a pressure roller on a plate-shaped substrate with an adhesive layer interposed therebetween, 2) JP-B-50-1913.
As described in Japanese Patent Publication No. 2 and Japanese Patent Publication No. 43-27488, etc., a decorative sheet is inserted between both male and female molds for injection molding, both molds are closed, and molten resin is injected from the male mold gate. After filling and cooling, a resin sheet is molded, and at the same time a decorative sheet is adhesively laminated on the surface thereof, a so-called injection molding simultaneous laminating method, 3) JP-B-56-45768, JP-B-60-58014, etc. As described in, the decorative sheet is opposed to or placed on the surface of the molded article via the adhesive layer between them, and the decorative sheet is laminated on the surface of the molded article by a pressure difference due to vacuum suction from the molded article side, So-called vacuum press lamination method, 4) Japanese Patent Publication No. 61-5895, Japanese Patent Publication 3-2.
As described in Japanese Patent No. 666, etc., while a decorative sheet is supplied in the long axis direction of a columnar base material such as a cylinder or a polygonal column via an adhesive layer, a plurality of rollers with different orientations form a columnar shape. A decorative sheet is sequentially pressure-bonded and laminated on a plurality of side faces constituting a body, which is a so-called lapping method, 5) Jikkendai 15-31122, JP-A-48-47972, and the like. First, the decorative sheet is laminated on the plate-shaped substrate via the adhesive layer, and then the surface of the plate-shaped substrate opposite to the decorative sheet reaches the interface between the decorative sheet and the plate-shaped substrate. A so-called V-cut or U-cut process in which a groove having a V-shaped or U-shaped cross section is cut, an adhesive is then applied to the groove, and then the groove is bent to form a box or columnar body. There are methods, etc.

The decorative material of the present invention is laminated on various adherends, subjected to predetermined molding and the like, and used for various purposes. For example,
Interior decoration of buildings such as walls, ceilings, floors, surface makeup of fittings such as window frames, doors, handrails, surface makeup of furniture or cabinets of low-light / OA equipment, vehicle interiors such as automobiles and trains, aircraft interiors, ship interiors, For example, makeup for window glass.

[0043]

EXAMPLES Examples and comparative examples according to the present invention will be described below, but the present invention is not limited to the examples. The characteristics of the hot melt adhesive obtained in Production Examples were measured and evaluated by the following methods. [Melt Viscosity] The melt viscosity at 120 ° C. and 100 ° C. was measured with a Thermocell viscometer (manufactured by Brookfield). [Softening Point] The softening point was measured by the Ring and Ball method.

[Isocyanate Concentration Value] JIS-K-
According to 7301, the hot melt adhesive composition is dissolved in dehydrated toluene, excess di-n-butylamine solution is added and reacted, and then unreacted di-n-butylamine is back titrated with hydrochloric acid standard solution. Sought by. (Production Example 1) A separable flask was charged with 2 at both ends of the molecule.
Copolyester resin of 1,6-hexane glycol having one primary hydroxyl group and sebacic acid (number average molecular weight 35
00) 50 parts by weight, 40 parts by weight of a copolyester resin of 1,6-hexane glycol having two primary hydroxyl groups at both ends of the molecule and adipic acid (number average molecular weight 3500), and a saturated polyester resin (Toagosei Co., Ltd.). Chemical Co., Ltd.
Made "PES-120L") 10 parts by weight, 110
It was heated to 0 ° C. and dissolved. Subsequently, dehydration was performed at the same temperature under reduced pressure (1.01 × 10 ⁵ Pa) for about 3 hours to remove water in the system. Then, the system is replaced with nitrogen gas,
After returning to normal pressure, norbornane diisocyanate (NB
DI) has an equivalent ratio of isocyanate groups (-NCO) to all hydroxyl groups (-OH) of the above resin is -NCO /
It was added so that -OH (molar ratio) = 2.0. Then, it was made to react at 95 to 100 ° C. for 2 hours to obtain a urethane prepolymer.

Next, 0.05 wt% of dibutyltin dilaurate as a curing catalyst was added to the obtained urethane prepolymer (total amount of the above reaction product) and mixed, and the mixture was decompressed (1.01 × 10 ^5). Degas in Pa),
A moisture curable hot melt adhesive was obtained. When the physical properties of the obtained adhesive were measured, the melt viscosity at 120 ° C was 5000 mPa · s and the melt viscosity at 100 ° C was 9800 m.
Pa · s, softening point 74 ° C, isocyanate concentration value 2.0
It was 0%. (Production Example 2) A moisture-curable hot melt adhesive was obtained in the same manner as in Production Example 1 except that the curing catalyst dibutyltin dilaurate was not added.

When the physical properties of the obtained adhesive were measured,
Melt viscosity at 120 ℃ is 5000mPa ・ s, 100 ℃
Melt viscosity at 9800 mPa · s, softening point at 74 ° C,
The isocyanate concentration value was 2.00%. <Examples 1 and 2> As a base sheet, 100 parts by weight of a hard segment made of isotactic polypropylene, 100 parts by weight of a soft segment made of styrene-butadiene rubber, an inorganic filler (calcium carbonate powder)
Pigment 1 consisting of 30 parts by weight, titanium white, red iron oxide and yellow lead
A polyolefin resin sheet having a thickness of 80 μm, which was obtained by melt-kneading a mixture of 0 parts by weight and then extruding, was prepared and subjected to corona discharge treatment on both sides.

Next, an acrylic urethane resin and hexamethylene diisocyanate were added to this base sheet, and the acrylic urethane resin: hexamethylene diisocyanate =
A concealable colored solid layer was formed by gravure printing using a concealable colored solid ink obtained by adding titanium white, rouge and yellow lead to a binder resin mixed at a ratio of 10: 1 (weight ratio). Using a pattern printing ink that adds a valve pattern and carbon black as a pigment to the resin,
A pattern print layer having a grain pattern was formed by gravure printing to obtain a print sheet. On the other hand, as the surface sheet, a mixture of 60 parts by weight of a hard segment made of isotactic polypropylene and 40 parts by weight of a soft segment made of atactic polypropylene to which 0.2% by weight of a benzotriazole-based UV absorber is added is used. An 80 μm-thick polyolefin resin sheet prepared by melt-kneading and then extruding was prepared and subjected to corona discharge treatment on both sides.

Next, the adhesive obtained in Production Example 1 in Example 1 and the adhesive obtained in Production Example 2 in Example 2 were applied to the printing surface of the above printing sheet by roll coating. Then, 3 g / m ^{2 was} applied to each, the above-mentioned surface sheet was superposed on the applied surface, and pressure was applied between nip rollers to laminate. Then, it was cured at 40 ° C. for 3 days to obtain a cosmetic material. The peel strength of the laminated portion of the decorative material obtained by using either of the adhesives (1) and (2) was 2.5 kgf / 25 mm 72 hours after the lamination.
It was wide and had excellent interlayer adhesion. Further, the decorative materials obtained by using either of the adhesives (1) and (2) showed no discoloration visually even when exposed to ultraviolet rays for 72 hours immediately after lamination, and very yellowing was observed. It was low. Furthermore, the obtained decorative material is
The weather resistance and heat resistance were also good and there were no problems.

[0049]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide a cosmetic material which has excellent interlayer adhesion from the initial stage, does not affect the environment, and has extremely low yellowing when exposed to ultraviolet rays.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a decorative material of the present invention.

FIG. 2 is a cross-sectional view showing another example of the decorative material of the present invention.

FIG. 3 is a cross-sectional view showing still another example of the decorative material of the present invention.

FIG. 4 is a cross-sectional view showing still another example of the decorative material of the present invention.

[Explanation of symbols]

1 Base sheet 1'top sheet 2 Adhesive layer 3 pattern layers 4 uneven pattern 5 coloring materials 6 Transparent protective layer

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F100 AA00A AK03A AK03B AK07A                       AK07B AK25C AK51C AK51G                       AK73A AL05B AL05G BA02                       BA03 BA07 BA10A BA10C                       CA07G CA13A CA13C CA23A                       CB02 CC00C DD01C EC18                       EJ55 GB08 GB31 GB32 GB81                       HB00C HB01C JA07G JA11A                       JA11B JB12G JK06 JL08G                       JN01B JN28 YY00G                 4J040 EF111 EF301 HA026 HA046                       HA136 HA356 HB19 HC06                       HC25 HC26 HD16 JB01 JB04                       JB08 KA14 KA16 KA29 KA35                       KA42 LA01 LA07 MA11 MB03                       NA02 NA05 PA30

Claims (7)

[Claims] 1. A decorative material in which a surface sheet made of a transparent olefin resin is laminated on a base material sheet made of an olefin resin via an adhesive layer, wherein the adhesive layer comprises a polyol compound and norbornane. A cosmetic material comprising a cured product of a moisture-curable hot melt adhesive containing a urethane prepolymer having an isocyanate group at an end, which is reacted with diisocyanate. 2. A copolyester polyol resin 30 of 1,6-hexane glycol and sebacic acid, wherein the polyol compound has a number average molecular weight of 2000 to 5000.
-60% by weight, 30-60% by weight of a copolyester polyol resin of 1,6-hexane glycol and adipic acid having a number average molecular weight of 2000-5000, and 5-10% by weight of a saturated polyester resin. Cosmetic material described in. 3. The decorative material according to claim 1, wherein the moisture-curable hot melt adhesive further contains a curing catalyst. 4. The decorative material according to claim 1, wherein the moisture-curable hot melt adhesive further contains an ultraviolet absorber. 5. The decorative material according to claim 1, wherein the base sheet and the topsheet are laminated with a pattern layer interposed therebetween. 6. The decorative material according to claim 1, wherein the topsheet has irregularities. 7. The decorative material according to claim 6, wherein the unevenness is filled with a coloring material.