JP2824109B2 - Decorative molded article and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a decorative molded article and a method for producing the same, and more particularly, to a molded article having scratch resistance and excellent in decorativeness and fashionability and a method for producing the same.

[Conventional technology]

In general, (meth) acrylic resins are used for decorative applications such as lighting covers, automobile parts and decorative articles due to their excellent weather resistance, transparency and outstanding appearance, and particularly excellent appearance such as excellent surface properties. Since a high finish can be expected, articles obtained by coating various decorative materials with (meth) acrylic resin are also used in the various fields. Conventionally, various methods for performing these coating treatments have been proposed. For example, (a) a colored sheet substrate is coated on the back surface of a thin veneer impregnated with a syrup composed of a methyl methacrylate monomer and a linear polymer thereof. Placing, heating and compressing to obtain a decorative sheet (JP-A-49-94804)
(B) A method in which a methacrylic resin formed into a sheet is pressure-bonded under heat and pressure to a decorative sheet having a printed sheet disposed on a substrate to obtain a coated molded article (Japanese Patent Application Laid-Open No. 47-11396). )
A method in which a film-formed methacrylic resin is brought into contact with the surface of a semipolymer containing a polymerizable monomer and a solvent, and the uncured material is cured by heating to obtain a coated product (JP-A-57-135,122). A) A method in which a decorative material is fixed on a substrate with an adhesive or the like, and a (meth) acrylic paint is applied thereto.

[Problems to be solved by the invention]

However, in the methods (a) to (c), since the coating layer made of a methacrylic resin is a linear polymer, the surface of the coated product has insufficient heat resistance, solvent resistance, etc. However, there has been a drawback in that the application to decorative materials and the adhesiveness are not sufficient. Further, the coating layer has insufficient scratch resistance, and in order to improve the scratch resistance, a coated molded product is formed once and then subjected to a hard coating treatment, or the surface of a film used as a coating material is subjected to a hard coating treatment in advance. Therefore, there is a problem that not only the process is complicated but also it is difficult to obtain sufficient scratch resistance.

Further, the method of applying the (meth) acrylic paint of (d) has a problem that the surface of the coating layer is easily affected by irregularities of the decorative material.

Therefore, the present invention, in order to solve the above problems, heat resistance, solvent resistance, abrasion resistance multifunctional acrylic coating layer, decorative material layer and methacrylic resin substrate integrated decorativeness The purpose of the present invention is to provide a molded article having excellent fashionability and durability and a method for producing the same, and furthermore, a decorative material is disposed between the base material and the coating layer without using an adhesive, and each layer is firmly adhered. An object is to provide an integrated molded product and a method for producing the same.

[Means for Solving the Problems] The present inventors have conducted intensive studies to solve the above problems, and as a result, formed a thin film of a scratch-resistant coating composition on the inner surface of the mold, and placed a porous decorative material thereon. By filling and molding the gel-like methacrylic polymer therein, it was found that the gel-like methacrylic polymer was filled in the minute gaps of the decorative material layer and the coating layer and the resin substrate were firmly joined. Was.

Therefore, according to the present invention, a scratch-resistant polyfunctional acrylic coating formed from a coating composition containing a crosslinked polymerizable compound having a molecular weight of 150 or more and having at least two (meth) acryloyloxy groups per molecule as a main component. A molded article having a decorative material in at least a portion between the layer and the methacrylic resin base material, and is filled in the minute gaps of the porous decorative material layer even in a portion where a porous decorative material layer of 10 to 1000 μm is interposed. A decorative molded article in which the coating layer and the resin base material are adhered via the methacrylic resin.

The decorative molded article is obtained by curing a coating composition comprising a crosslinked polymerizable compound having a molecular weight of 150 or more and having at least two (meth) acryloyloxy groups per molecule as a main component, and drying the composition to the touch. 10 to 10 between the thin film and the methacrylic resin molding material composed of a gel polymer
It can be manufactured by heating under pressure with a porous decoration material of 00 μm interposed.

 Hereinafter, the present invention will be described in detail.

Scratch resistant polyfunctional acrylic coating layer (hereinafter referred to as abrasion resistance) formed from a coating composition containing a crosslinked polymerizable compound having a molecular weight of 150 or more and having at least two (meth) acryloyloxy groups per molecule as a main component. ), The molecular weight of the cross-linkable polymerizable compound is preferably from 200 to 2000, most preferably from 200 to 1200, and the compound is a mixture with up to 70% by weight of another polymerizable monomer. Or a mixture thereof with a partially polymerized product. The average number of functional groups of the crosslinked polymerizable compound or mixture as a main component of the coating is 2.0 to 6.0,
Preferably it is 2.5-5.5. If the average number of functional groups is less than 2.0, sufficient abrasion resistance cannot be obtained, and if it exceeds 6.0, it is difficult to promote the reaction sufficiently, and the weather resistance is reduced. Here, the average number of functional groups is represented by the following formula.

In the cross-linkable polymerizable compound, the residue binding the (meth) acryloyloxy group is a hydrocarbon or a derivative thereof, and the molecule contains an ether bond, a thioether bond, an ester bond, an amide bond, a urethane bond, or the like. And those having an isocyanuric acid skeleton or a melamine skeleton.

Examples of such compounds include trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol diacrylate hydroxypivalate, and dipentaerythritol hexaacrylate (hereinafter, referred to as "dipentaerythritol hexaacrylate").
DPHA), improved products of the DPHA (for example, DPCA-20, 30, 60, etc., manufactured by Nippon Kayaku Co., Ltd.), urethane acrylate,
Trisacryloyloxy cyanurate, (meth) acryloyloxy compound having an isocyanuric acid skeleton,
Epoxy acrylate, polyester acrylate and the like can be mentioned.

The “other polymerizable monomer” that forms the scratch-resistant film includes methyl methacrylate, butyl methacrylate, butyl acrylate, tetrahydrofurfuryl acrylate, ethyl carbitol acrylate, phenyl carbitol acrylate, hydroxyethyl acrylate, -Hydroxy-3-phenoxypropyl acrylate and the like.

The thickness of the abrasion-resistant coating is not particularly limited as long as it protects the decorative material, sufficiently exerts the abrasion-resistance performance, and does not impair the appearance, but is preferably 5 to 800 μm,
-100 μm is particularly preferred. If it is less than 5 μm, not only is the scratch resistance insufficient, but also the smoothness of the coating surface is easily affected by the surface properties of the decorative material, which is not preferred. On the other hand 800μ
Exceeding not only has no economic merit, but also tends to cause defects in durability performance, which is not preferable.

The abrasion-resistant coating described above may contain a leveling material, a dye / pigment, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a filler, an organic solvent, and the like, if necessary.

The methacrylic resin used in the present invention is not particularly limited as long as it is a resin that is filled in the minute gaps of the porous decoration material layer and adheres to the coating layer even in the portion where the decoration material layer is interposed, but is not particularly limited. Methacrylic resin and crosslinked methacrylic resin containing at least 50% by weight of methacrylic acid are preferably used, and crosslinked methacrylic resin is particularly preferable in view of heat resistance, solvent resistance, chemical resistance, and weather resistance.

The crosslinked methacrylic resin which is a preferred embodiment of the present invention is mainly composed of methyl methacrylate, and is selected from a group of monofunctional unsaturated monomers containing methyl methacrylate.
30% to 98% by weight of one or more monofunctional unsaturated monomers
And a polymer of an unsaturated monomer comprising 2 to 70% by weight of a polyfunctional unsaturated monomer. The polyfunctional unsaturated monomer is 1
A compound having two or more unsaturated bonds in the molecule, at least two of these unsaturated bonds must be capable of copolymerizing with a monofunctional unsaturated monomer mainly composed of methyl methacrylate. . Examples of such polyfunctional unsaturated monomers include, but are not limited to, polyesters of acrylic acid and / or methacrylic acid and polyhydric alcohols, divinylbenzene, triacrylisocyanurate, and the like. Not something. Two or more polyfunctional unsaturated monomers can be used in combination.

Among the polyfunctional unsaturated monomers described above, a polyester of methacrylic acid and a polyhydric alcohol is preferable for the purpose of improving heat resistance. In particular, the minimum number of atoms connecting two methacryloyl groups is 10 The following are particularly preferred. Examples of such are ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1 , 6-hexanediol dimethacrylate, tetramethylolmethanetetramethacrylate, trimethylolethanetrimethacrylate, trimethylolpropanetrimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, and the like.

The amount of the polyfunctional unsaturated monomer used is 2 to 70% by weight, preferably 2 to 70% by weight, based on the total amount of the monofunctional unsaturated monomer mainly composed of methyl methacrylate and the polyfunctional unsaturated monomer. It is 5 to 50% by weight, more preferably 5 to 30% by weight. If the amount of the polyfunctional unsaturated monomer is less than 2% by weight, the heat resistance is insufficient, and if it exceeds 70% by weight, the composition becomes brittle.

Further, the proportion of methyl methacrylate in the monofunctional unsaturated monomer containing methyl methacrylate as a main component and containing methyl methacrylate is 50% by weight or more, preferably
It is at least 70% by weight, more preferably at least 90% by weight. The monofunctional unsaturated monomer that can be used in combination with the methyl methacrylate may be any polymer or copolymerizable one,
There is no particular limitation. Examples of such an ester include an ester of a monohydric alcohol having 2 to 18 carbon atoms in one molecule and methacrylic acid, a monohydric alcohol having 1 to 18 carbon atoms in a molecule and acrylic acid Monoester of a dihydric alcohol having 2 to 4 carbon atoms in one molecule with acrylic acid or methacrylic acid, acrylic acid, methacrylic acid, maleic anhydride, acrylonitrile, methacrylonitrile, acrylamide, methacrylic acid Amides, maleimides, metal acrylates, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, ethylene, glycidyl methacrylate, vinyl triethoxysilane, γ-methacryloxypropyl trimethoxysilane, etc. I can give it.

Such a crosslinked methacrylic resin does not necessarily need to be composed of one kind of polymer, and may be a mixture of polymers having different compositions or different molecular weights.

The methacrylic resin of the present invention can contain coloring agents such as dyes and pigments, heat stabilizers, lubricants, ultraviolet absorbers, light stabilizers, and inorganic or organic fillers.

The thickness of the methacrylic resin substrate is not particularly limited, but is preferably 0.1 to 15 mm. When the thickness of the substrate is small, another substrate may be laminated for the purpose of imparting rigidity.

The decorative molded article of the present invention, without using an adhesive,
It is a molded article in which the base material and the scratch-resistant coating layer are fixed via the methacrylic resin filled in the minute gaps of the porous decoration material layer. That is, in the molded article of the present invention, for example, a methacrylic resin molding material composed of a gel polymer constituting a base material is filled into the minute gaps of the porous decorative material layer and reaches the scratch-resistant coating layer, It is characterized in that it is polymerized and / or diffused with the components constituting the abrasion film and is firmly bonded and integrated.

Therefore, in the porous decorative material used in the present invention, the methacrylic resin molding material constituting the base material reaches the scratch-resistant coating substantially through the decorative material and does not dissolve in the molding material or There is no particular limitation as long as the material is difficult to dissolve, but the thickness needs to be 10 to 1000 μm. Preferably 50-600 μm wood, paper,
Cloth, non-woven fabric, glass fiber cloth, leather, a film or metal foil having a large number of pores from the front to the back, organic and inorganic fine powders arranged in layers and the like, wood in terms of decorative properties, Paper, cloth, nonwoven fabric, glass fiber cloth, leather and the like are preferably used. These decorative materials can be pre-patterned. The minute gap referred to in the present invention is a gap from the front surface to the back surface, and has a size that allows a molding material formed of a gel polymer or a monomer / partial polymer contained in the molding material to pass therethrough. Means Further, in a normal form, for a decorative material having substantially no effective micro-gap as described above, a micro-gap is substantially provided by providing a large number of pores from the front surface to the back surface. Can be used for 1 to 10
0 .mu.m ^2, preferably pores 10 to 10 ⁴ of the size of 1 to 9 m ²
Pcs / cm ² are preferably used.

When the thickness of these decorative materials is less than 10 μm, the handleability is poor, while when the thickness exceeds 1000 μm, the methacrylic resin is not sufficiently filled, and the adhesion between the scratch-resistant coating layer and the base material is unfavorably reduced. .

The decorative material used in the present invention can be used without any pretreatment, but may be used after being impregnated with a solvent or monomer containing a surfactant in advance for the purpose of improving wettability.

Further, the decorative material can cover the entire surface of the methacrylic resin base material, but can also cover locally and / or discontinuously. Furthermore, several kinds of decorative materials can be used in combination.

As described above, since the decorative molded article of the present invention can arrange various decorative materials without using an adhesive, the type, thickness, and pattern of the decorative material, and the thickness and color tone of the scratch-resistant film can be arranged. Various decorative expressions are possible by combining the color tone of the base material. Moreover, since the substrate, decorative material and coating are firmly bonded and integrated, not only has excellent durability, but also the coating has scratch resistance, heat resistance, solvent resistance, chemical resistance,
Because of its excellent weather resistance, it can be used in harsh environments. If a crosslinked methacrylic resin is used as the methacrylic resin base material, the heat resistance, solvent resistance, chemical resistance, and weather resistance of the base material are improved, so that it is more advantageous as a decorative molded product.

The decorative molded article of the present invention has a scratch-resistant composition which is obtained by curing a coating composition containing a crosslinked polymerizable compound having a molecular weight of 150 or more and having at least two (meth) acryloyloxy groups per molecule as a main component and drying it by touch. It can be produced by a method in which a porous decorative material is interposed between a morphologically-forming thin film and a methacrylic resin molding material made of a gel polymer, and heated under pressure.

The scratch-resistant formed thin film must be dry to the touch. In addition to this requirement, the number of (meth) acryloyloxy groups in the crosslinked polymerizable compound or mixture which is a main component of the coating (see above) X and the degree of polymerization y of the thin film satisfy the formula (I) or (II) y ≦ 70 (2 ≦ x ≦ 3.5) (I) y ≦ −7.5x ² + 52x-18 (3.5 <x ≦ 6) It is preferable that (II) is satisfied. If the touch is not dry, the thickness of the film cannot be adjusted, which is not preferable. Touch dryness refers to a state in which a finger does not feel sticky as normally used (tack-free state), and varies depending on the average number of functional groups in a cross-linkable polymerizable compound or mixture which is a main component of the coating. , Usually 10-68%, preferably 30
It has a polymerization rate of about 68%.

As shown in Japanese Patent Application Laid-Open No. Sho 62-20513, this polymerization rate is expressed as a percentage of the amount of residual double bonds measured from the height of the absorption band peak due to C = C appearing around 1620 nm by an infrared method. It is calculated by subtracting the remaining double bond amount from 100.

As a method of adjusting the polymerization rate, the coating composition may be applied to the inner surface of the mold in advance before charging the resin base material, and may be polymerized by heat or light in the presence of a polymerization initiator, or may be a synthetic resin. It may be preliminarily polymerized on the film surface.

As an initiator for polymerizing the coating composition, a low-temperature active catalyst and a high-temperature active catalyst can be used, and a photopolymerization initiator can be used.

As the low-temperature active polymerization initiator, a radical polymerization initiator of a peroxide and an azo compound having a decomposition temperature of 50 ° C. or lower, preferably 26 to 45 ° C. for obtaining a half-life of 10 hours is preferably used. The amount used is 0.5 to 5% by weight, preferably 1 to 4% by weight, based on the mixture with the crosslinkable polymerizable compound or polymerizable monomer. If the amount used is less than 0.5% by weight, the polymerization of the scratch-resistant coating is delayed, so that sufficient abrasion resistance cannot be obtained, which is not preferable. On the other hand, if it exceeds 5% by weight, the polymerization starts before being applied uniformly. It is not preferable because a smooth film cannot be obtained.

High temperature active polymerization initiator, the decomposition temperature is 60 ~ 220 ℃,
Preferably, a radical polymerization initiator of a peroxide and an azo compound at 70 to 170 ° C is used. The amount used is based on the crosslinkable polymerizable compound or the polymerizable monomer mixture.
It is 0.5 to 5% by weight, preferably 1 to 4% by weight. When the amount is less than 0.5% by weight, sufficient polymerization is not performed within the molding time, and the scratch resistance tends to decrease. On the other hand, when the amount exceeds 5% by weight, curing is slow. It is not preferable because the adhesiveness to the resin substrate may be insufficient.

The photopolymerization initiator is not particularly limited, but may be, for example, Irgacure 184 or Irgacure 6 manufactured by Ciba-Geigy Japan KK
51, Benzophenone manufactured by Kawaguchi Pharmaceutical Co., Ltd., Darocure 1116, Darocure 1173 manufactured by Merck Japan Co., Ltd., Kayacure DETX, CTX, RTX, Nippon Kayaku Co., Ltd., MBP, BP, DMBI, E
There is PA etc. The amount used depends on the output of the lamp generating the ultraviolet rays, but is 0.2 to 1% by weight, preferably 0.3 to 0.
6% by weight. If the amount used is less than 0.2% by weight, it is not preferable that a fine uneven surface appears on the film and a smooth surface is hardly obtained, while if it exceeds 1.0% by weight, curing is fast, and the film and the methacrylic resin via the laminated material are hardened. It is not preferable because the adhesiveness to the substrate may be insufficient.

The methacrylic resin molding material used in the present invention is not particularly limited as long as it is a gel polymer that can be easily filled into the minute gaps of the porous decoration material layer under pressure and has a shape retention property and is easy to handle. However, a partially crosslinked gel polymer is preferable in terms of heat resistance and the like and ease of production. The gel fraction of the partially crosslinked gel polymer is preferably in the range of 4 to 62%, more preferably 15 to 62%. The form is not limited to sheets, rods, pellets and the like, and may be formed for the purpose of improving fluidity. It is preferred to crush or knead before. Examples of the method for producing a methacrylic resin molding material that is a partially crosslinked gel polymer include, for example, methods described in JP-A-60-202128 and JP-A-62-1705, and the methyl methacrylate is used. Monofunctional unsaturated monomer as a main component or 30 to 98% by weight of a syrup mainly containing the monomer and optionally containing a polymer dissolved therein and 2 to 70% by weight of a polyfunctional unsaturated monomer % By partially polymerizing the polymer so as to increase the polymer content by 4 to 62% by weight over the polymer content in the mixture within a range not to exceed 62% by weight. be able to.

In addition, the present inventors, based on 100 parts by weight of the partially crosslinked gel polymer produced by the above method, syrup 1 containing methyl methacrylate as a main component and containing the polymer dissolved therein.
It has been found that a molding material which is added to 100 parts by weight, preferably 10 to 50 parts by weight and kneaded substantially uniformly can be used. The syrup containing the polymer mainly containing the methyl methacrylate and dissolved therein means a syrup containing a polymer of methyl methacrylate or a monomer mixture containing methyl methacrylate as a main component, and if necessary.
It may contain up to 50% by weight of a polyfunctional unsaturated monomer.

As a method of interposing a porous decorative material between the scratch-resistant formed thin film and the methacrylic resin molding material, heating under pressure, and simultaneously forming the methacrylic resin molding material and forming the scratch-resistant coating layer, (1) The coating composition is previously applied to a mold such as a press molding machine by spraying, rolling, etc.,
After polymerizing and curing in the above range, a method of placing a decorative material, further introducing a molding material into a mold and molding, (2) coating a coating composition on a film of a synthetic resin or the like in advance to obtain a desired polymerization After polymerizing to a degree, a decorative material and a molding material are placed thereon, and then put into a mold and molded. These moldings are performed at 90-160 ° C., preferably at 100 ° C.
It is performed under pressure at a temperature of 150 ° C. Further, after this, in order to further improve the heat resistance of the molding substrate, 120 to 140 ° C.,
It can be heated at normal pressure for 2 to 12 hours.

An example of the configuration of the decorative molded product obtained in this way is schematically shown in FIGS. FIG. 1 shows an example in which a decorative material is entirely laminated between a scratch-resistant coating layer and a methacrylic resin base material, and FIGS. 2 and 3 show a part of the coating layer and the resin base material. And a molded article having a decorative material layer.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

 Evaluations and tests in Examples and the like were performed by the following methods.

(A) Polymer content measurement of partially cross-linked gel polymer; 150 ml of dichloromethane in which 1000 ppm of hydroquinone monomethyl ether was added and dissolved was placed in a Soxhlet extractor, and 15 g of the gel polymer was cut into a strip of cylindrical paper for extraction. After refluxing for 20 hours in a constant temperature water bath maintained at 50 ° C, the extract was put into 1200 ml of methanol to separate the polymer component. The polymer was dried under reduced pressure until the weight was reduced, and the weight W of the polymer was obtained and calculated by the following equation.

(B) Scratch resistance evaluation; A jig equipped with $ 000 steel wool was pressed against the surface of the scratch-resistant coating of the decorative molded product under a constant load (100 g / cm ² ) and reciprocated 50 times at a constant speed. Thereafter, the scratches before and after the main abrasion test were visually judged.

(C) Evaluation of adhesiveness: A bending test sample piece was cut out so that the portion where the decorative material of the decorative molded product was arranged was almost at the center, and a bending load was applied in accordance with the bending test method (ASTM D790). The adhesiveness was evaluated by visually observing the fracture surface of the decorative molded product.

When peeling occurred at the interface between the abrasion-resistant coating and the decorative material and / or at the interface between the decorative material and the methacrylic resin, it was determined that the adhesion was poor.

(D) Evaluation of weather resistance: Using a sunshine carbon arc weather meter (manufactured by Suga Test Instruments Co., Ltd.), after exposure for 1000 hours at a black panel temperature of 63 ° C., the appearance and adhesion were evaluated.

(E) Heat resistance test: The decorative molded article was placed in a hot-air circulation oven preheated to 110 ° C and heated for 400 hours, and then the appearance and adhesiveness were evaluated.

(F) Evaluation of chemical resistance: The decorative molded article was immersed in a 2% aqueous solution of sodium carbonate at 80 ° C. for 200 hours, and then the appearance and adhesion were evaluated.

(G) Evaluation of solvent resistance: A few drops of benzene were dropped on the surface of the scratch-resistant coating of the decorative molded product, covered with a watch glass and allowed to stand for 5 days, and then the benzene was wiped off to visually determine the condition of the surface.

Reference Example 1. [Production of partially crosslinked gel polymer] 70 parts by weight of methyl methacrylate monomer, 30 parts by weight of neopentyl glycol dimethacrylate, 1,4 (8)-
0.01 parts by weight of P-menthadiene, 0.0030 parts by weight of 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and 0.3 part by weight of 2,2-bis (t-butylperoxy) butane, di-t- 0.2 parts by weight of butyl peroxide, 2-
0.1 part by weight of (5-methyl-2-hydroxyphenyl) benzotriazole is mixed and dissolved, poured into a cell assembled with two glass plates and a gasket at 10 mm intervals, and polymerized at 60 ° C. for 2 hours to form a portion. A crosslinked gel-like polymer was obtained. The polymer content of this partially crosslinked gel polymer was 30%.

In the measurement of the polymer content, the polymer content remaining on the extraction cylindrical mouthpiece was 29.9%, and the polymer content separated by pouring the extract into methanol was 0.1%.

Reference Example 2. [Production of partially crosslinked gel-like polymer] The polymer obtained in Reference Example 1 was screwed with a diameter of 50 mm and L / D
= 8 to obtain a composition pulverized to a maximum particle size of 2 mm or less.

Reference Example 3. [Production of partially crosslinked gel polymer] 90 parts by weight of the composition obtained in Reference Example 2, containing the same concentration of neopentyl glycol dimethacrylate as contained in this composition, and having a viscosity average 10 parts by weight of methyl methacrylate syrup having a viscosity of 8 poise and containing polymethyl methacrylate having a polymerization degree of 10,000 were mixed with a super mixer (Co., Ltd.).
(Manufactured by Kawata Co., Ltd.) and stirred and mixed for about 5 minutes to obtain a highly adhesive composition.

Reference Example 4. (Production of partially crosslinked gel polymer) 95 parts by weight of methyl methacrylate monomer was used,
The amount of neopentyl glycol dimethacrylate used was 5
3 parts by weight of a partially crosslinked gel having a polymer content of 34% in the same manner as in Reference Example 1 except that the amount of 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) was changed to 0.1 part by weight. After obtaining a polymer in the form of a powder, the composition was crushed in the same manner as in Reference Example 2 to obtain a composition.

Example 1. (1) Preparation of coating composition; 50 parts by weight of caprolactone-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .: DPCA20), tris (acryloxyethyl) isocyanurate (Toa Gosei Chemical Industry Co., Ltd.) ): M315) 30 parts by weight, 1,6-hexanediol diacrylate (hereinafter abbreviated as HDDA) 20 parts by weight,
To 10 parts by weight of methyl methacrylate were added 4% by weight of t-butylperoxyisopropyl carbonate, 2% by weight of benzoyl peroxide, and 0.1% by weight of 2- (5-methyl-2-hydroxyphenyl) benzotriazole, mixed and dissolved to obtain an average functionality. A coating composition having a radix of about 3.4 was obtained.

(2) Molding of decorative molded products: The coating composition of (1) above is spray-coated on the inner surface of a cavity of a 250 mm long and 200 mm wide mold pre-heated to 135 ° C., and cured by heating to a thickness of 30 μm to polymerize. A film with a rate of 65% is formed, and a thickness of 100 μm, a length of 248 mm and a width of 19
An 8 mm camphor veneer was placed, and then 300 g of the composition obtained in Reference Example 2 was placed thereon. The mold was closed, and the mixture was pressed at a temperature of 135 ° C. and a pressure of 10 kg / cm ² for 1 minute. , And the pressure was maintained at 200 kg / cm ² for 20 minutes, followed by taking out from the mold. Then, it was heated in a hot air oven at 140 ° C. for 10 hours to obtain a decorative molded product having a length of 250 mm, a width of 200 mm and a thickness of about 5 mm.

(3) Evaluation: A scratch-resistant coating of the decorative molded product obtained as described above,
In addition, the surface of the substrate had a smooth and beautiful appearance, and the coating, the decorative material, and the substrate were completely bonded and integrated. The results of various evaluations and tests were good as shown in Table 1.

Examples 2 to 6 A decorative molded product was obtained in the same manner as in Example 1 except that the decorative material was changed as follows.

The appearance and adhesion state of the decorative molded product were as good as in Example 1, and the results of various evaluations and tests were also as shown in Table 1.

Examples 7 and 8 The partially crosslinked gel polymer was prepared by cutting the composition obtained in Reference Example 1 into a plate shape having a length of 245 mm, a width of 195 mm, and a weight of 300 g. Except to change to
A decorative molded product was obtained in the same manner as in Example 1.

The appearance and adhesion state of the decorative molded product were as good as in Example 1, and the results of various evaluations and tests were also as shown in Table 1.

Example 9 A decorative molded article was obtained in the same manner as in Example 7, except that the thickness of the scratch-resistant film was 50 μm, and aluminum powder having an average particle size of 5 μm was laminated as a decorative material to a thickness of 20 μm.

The appearance and adhesion state of the decorative molded product were as good as in Example 1, and the results of various evaluations and tests were also as shown in Table 1.

Example 10. (1) Preparation of coating composition: 65 parts by weight of DPHA (manufactured by Nippon Kayaku Co., Ltd.), 20 parts by weight of M315 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), 15 parts by weight of HDDA, 10 parts by weight of methyl methacrylate 3 parts by weight of t-butyl peroxyisopropyl carbonate, 1.5% by weight of benzoyl peroxide and 0.1% by weight of 2- (5-methyl-2-hydroxyphenyl) benzotriazole were added and mixed and dissolved to obtain an average number of functional groups of about 4.0. Was obtained.

(2) Molding of decorative molded product: The coating composition of (1) is spray-coated on the inner surface of a cavity of a 250 mm long and 200 mm wide mold previously heated to 135 ° C., and cured by heating to a thickness of 20 μm to polymerize. A film having a rate of 60% is formed, and a thickness of 600 μm, length of 248 mm and width of 19 is formed on the film.
8 mm of Japanese paper was placed, and 42 g of the composition obtained in Reference Example 3 was placed on the entire surface of the Japanese paper almost uniformly. Then, the mold was closed, and a temperature of 135 ° C. and a pressure of 10 kg / cm ² were added. After pressurizing for 20 minutes, the pressure was maintained at 200 kg / cm ² for 20 minutes, and the product was taken out of the mold. Then heat in a hot air oven at 140 ° C for 10 hours,
A decorative molded product having a length of 250 mm, a width of 200 mm and a thickness of about 0.8 mm was obtained.

(3) Evaluation; The appearance and adhesion of the decorative molded product obtained as described above were as good as in Example 1, and the results of various evaluations and tests were as shown in Table 1. .

Example 11. (1) Preparation of coating composition: 40 parts by weight of DPHA (manufactured by Nippon Kayaku Co., Ltd.), 40 parts by weight of M315 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), 20 parts by weight of HDDA, 10 parts by weight of isobutyl acrylate In parts, cumyl peroxy neodecanoate 2% by weight, cumyl peroxy octoate 1.5%
% By weight, 2- (5-methyl-2-hydroxyphenyl)
0.1% by weight of benzotriazole was added and mixed and dissolved to obtain a coating composition having an average number of functional groups of about 3.4.

(2) Molding of decorative molded article: A metal temperature of 120 ° C., a coating having a thickness of 100 μm and a polymerization rate of 65% were formed on the inner surface of the cavity using the coating composition of (1), and the composition of Reference Example 4 was used. Use 900g of goods,
Except that the dwell time at 200 kg / cm ² was 40 minutes and the temperature of the hot air oven was 115 ° C.,
A decorative molded product having a size of 50 mm, a width of 200 mm and a thickness of about 15 mm was obtained.

(3) Evaluation; The appearance and adhesion of the decorative molded product obtained as described above were as good as in Example 1, and the results of various evaluations and tests were as shown in Table 1. .

Example 12. (1) Preparation of coating composition; 100 parts by weight of DPHA and 10 parts by weight of methyl methacrylate
Cumyl peroxy neodecanoate 2% by weight, cumyl peroxy octoate 1.5% by weight, 2- (5-methyl-
0.1% by weight of 2-hydroxyphenyl) benzotriazole was added and mixed and dissolved to obtain a coating composition having an average number of functional groups of about 5.5.

(2) Molding of decorative molded article; 10 μm thick using the coating composition of (1).
m, a coating having a polymerization rate of 40% was formed on the inner surface of the cavity, and a 200 μm-thick Japanese paper was used as a decorative material in the same manner as in Example 11 except that 600 g of the composition of Reference Example 4 was used.
A decorative molded product having a length of 250 mm, a width of 200 mm and a thickness of about 10 mm was obtained.

(3) Evaluation; The appearance and adhesion of the decorative molded product obtained as described above were as good as in Example 1, and the results of various evaluations and tests were as shown in Table 1. .

Comparative Example 1. A decorative molded product was obtained in the same manner as in Example 1 except that the thickness of the decorative material was changed to 1200 µm.

The scratch-resistant coating of the obtained molded article, and the surface of the substrate were smooth and beautiful, but the adhesion between the coating and the decorative material was poor. Separation occurred at the interface.

Comparative Example 2. A decorative molded product was obtained in the same manner as in Example 1 except that the thickness of the scratch-resistant coating was changed to 1 µm.

On the surface of the scratch-resistant coating of the obtained molded article, irregularities considered to be caused by the surface properties of the decorative material were observed. In the “evaluation of scratch resistance”, generation of scratches was observed.

Comparative Example 3. A decorative molded product was obtained in the same manner as in Example 1 except that the thickness of the scratch-resistant film was changed to 1200 µm. The appearance of the obtained molded product had a thick surface and the three-dimensional effect of the grain was impaired.

Comparative Example 4. A methyl methacrylate syrup having a viscosity of 8 poise and containing 0.5 parts by weight of 2,2-bis (t-butylperoxy) butane and a polymethyl methacrylate having a viscosity average degree of polymerization of 10,000 was applied to a 300 μm thick veneer veneer. A paper having a thickness of 1 mm was placed on the back surface and heated and pressed at a temperature of 130 ° C. and a pressure of 3 kg / cm ² for 20 minutes to obtain a laminated molded product.

When the surface of the example of a single veneer was evaluated for abrasion resistance, a scratch was generated and it reached the single veneer. When the surface was evaluated for solvent resistance (benzene), the surface was altered.

[Effects of the Invention] The methacrylic resin base material not only exhibits excellent adhesion durability by firmly bonding and integrating with the decorative material and the coating layer, but also the coating layer has excellent heat resistance, solvent resistance, chemical resistance, Weatherability,
Shows scratch resistance and can be used in harsh environments.

When a crosslinked methacrylic resin is used as the base material,
The heat resistance, solvent resistance, chemical resistance, and weather resistance of the base material have also been improved,
The durability of the whole molded article is improved, which is more advantageous.

Since the molded article of the present invention can use various decorative materials and can adjust the thickness of the coating layer, the type, thickness and pattern of the decorative material can be selected, and the thickness of the coating layer can be adjusted. Various decorative expressions are possible by combination of selection of color and color tone, selection of base material color tone and pattern, and the like.

Since it is a decorative molded product with excellent decorativeness, fashionability and durability, it can be used in various fields such as industrial members, decorative products, sundries, tableware, decorative panels, etc., both indoors and outdoors. It is possible.

Since the methacrylic resin base material is firmly bonded to the decorative material and the coating layer via the methacrylic resin filled in the minute gaps of the porous decorative material, the decorative material is applied to the base material in advance using an adhesive. It is useful because a molded article with a beautiful appearance and good durability can be easily and easily provided without requiring any treatment such as attaching.

The gel polymer used in the present invention is suitable for the purpose of the present invention, for example, it can be easily filled under pressure into the minute gaps of the decorative material and has a shape retention property at normal pressure. The gel polymer is particularly excellent in handleability, and is advantageous in terms of ease of production and heat resistance of the obtained molded article.

[Brief description of the drawings]

FIG. 1, FIG. 2 and FIG. 3 are schematic sectional views of a decorative molded product according to an embodiment of the present invention. 1 ... scratch-resistant coating layer, 2 ... decorative material layer, 3 ... methacrylic resin base material.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-U 52-72576 (JP, U) (58) Fields investigated (Int. Cl. ⁶ , DB name) B32B 33/00 B32B 27/10 B32B 27 / 12 B32B 27/30

Claims (3)

(57) [Claims] (1) a molecular weight of 150 or more and at least 2 per molecule;
At least a portion between the scratch-resistant multifunctional acrylic coating layer formed from a coating composition containing a crosslinked polymerizable compound having a (meth) acryloyloxy group as a main component and a methacrylic resin base material; A molded article having a porous decorative material layer having a thickness of about 1000 μm, wherein the coating layer and the resin are interposed via a methacrylic resin filled in minute gaps of the porous decorative material layer even in a portion where the decorative material layer is interposed. A decorative molded article characterized by being fixed to a substrate. 2. The molded article according to claim 1, wherein the methacrylic resin is a crosslinked methacrylic resin. 3. A compound having a molecular weight of 150 or more and at least 2 per molecule.
A coating composition containing a crosslinked polymerizable compound having a (meth) acryloyloxy group as a main component, and a scratch-resistant thin film formed by touching and drying, and a methacrylic resin molding material comprising a gel polymer; A method for producing a decorative molded product, wherein a porous decorative material having a thickness of 10 to 1000 μm is interposed therebetween and heated under pressure.