JPH0425454A - Laminated molding and manufacture thereof - Google Patents

Abstract

PURPOSE:To bond a crosslinking methacryl resin coated layer having a specific composition firmly with a decorative member, and to improve light resistance, heat resistance, solvent resistance and scuff resistance by forming a base material and the coated layer and positioning a decorative member between the base material and the coated layer. CONSTITUTION:A decorative member is arranged onto a base material, and a methacryl resin material is placed on the member and heated under pressure. A partial crosslinked gel-shaped polymer, in which a mixture composed of (A) a 1-60wt.% crosslinking monomer and (B) a 99-40wt.% unsaturated monomer, which mainly comprises alkyl methacrylate and may dissolve and contain the polymer, is polymerized partially in the presence of a polymerization initiator and which is increased at 4-62wt.% more than the content of the polymer of said mixture within a range that total polymer content does not exceed 80wt.%, is used as the resin material.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a laminate molded product and a method for manufacturing the same, and more specifically to a laminate molded product that has excellent design, durability, and has a large degree of freedom in shape. Regarding the manufacturing method.

[Prior Art] Generally, laminated molded products used in the fields of automobile parts, building materials, decorations, furniture, etc. are coated with a transparent or translucent coating on the surface in order to protect the surface or improve the appearance. Often layered.

Various methods have been proposed in the past to perform such a coating treatment, including (a) a method of bonding glass onto a decorative member bonded to a base material, and (2) a method of bonding glass onto a decorative member bonded to a base material. (C) A method of laminating a resin film on the decorative member adhered to the base material; (d) A method of laminating the decorative member adhered to the base material with the decorative member facing inward; A method of assembling a cast polymerization cell between a base material and glass, etc., and polymerizing a desired monomer on the member; (e) setting the base material to which the decorative member is adhered in an injection mold; and then injection molding a desired resin onto the member.
A method of obtaining a decorative sheet by placing a colored sheet on the back side of a thin veneer impregnated with methyl methacrylate yarn threads and a silub made of its linear polymer, and heating and compressing the sheet (Japanese Unexamined Patent Publication No. 49-94804) etc.

[Problem to be solved by the invention]

However, in the method (a), the resulting laminate is heavy and the coating layer is easily broken (there is a problem that the shape is limited).In the method (b), a predetermined coating thickness is ensured. In order to achieve this, it is necessary to apply several layers of paint,
Moreover, in order to improve the adhesion of each layer and the smoothness of the paint film, it is necessary to sand before applying the next layer, and the surface of the final finishing layer may be polished, making the process complicated. Not only that, but even if the shape is similar to a flat plate, the coating thickness is thinner near the periphery, and curved surfaces are difficult to apply uniformly, and there are also limitations to the shape, and it is difficult to thicken the coating due to durability issues. was there.

In addition, methods (C) and (e) require high temperatures and high pressures, and there are problems in that the decorative member is likely to tear or deform, and the adhesion between the coating layer and the decorative member is insufficient. In method (d), the adhesion between the coating layer and the decorative member is sufficient, but not only is the process complicated, but the material may be in contact with the monomer for a long time, resulting in deterioration, and the thickness of the coating layer may be reduced. There were problems such as difficulty in controlling the In the method of (Matage), the decorative material number is pre-filled with monomer,
There was a problem that the process was complicated because it had to be impregnated with silver slag, etc., and the coating layer could not be made thick. In addition, the coating layer applied by each of the above methods has light resistance, solvent resistance,
There were problems such as often lacking in durability such as heat resistance.

Therefore, it is an object of the present invention to solve the above-mentioned problems and provide a laminate molded product with excellent design, durability, and a large degree of freedom in shape, and a method for manufacturing the same. To provide a laminate molded product that can be freely controlled and thickened, and a method for manufacturing the same.

[Means to solve the problem]

As a result of intensive studies on various materials for the above-mentioned problem to be solved, the present inventors have developed a cross-linked methacrylic resin molding material described in JP-A No. 60-202128, JP-A No. 62-1705, etc. It was discovered that a composition with improved fluidity is extremely useful as a coating material, and that by using it, a laminate molded product with excellent durability and a thick coating layer can be obtained, and the present invention was completed. did.

That is, according to the present invention, the above-mentioned object is a laminate molded product having a base material and a methacrylic resin coating layer, and a decorative member is present between them, in which the coating layer contains (A) a crosslinkable monomer. The polymer content of a mixture consisting of 1 to 60% by weight and 99 to 40% by weight of an unsaturated monomer mainly composed of (B,) alkyl methacrylate and which may contain dissolved polymers is the total polymer content. is 4 to 6% higher than the polymer content in the mixture without exceeding 80% by weight.
This is achieved by a laminate molded product having a crosslinked methacrylic resin coating layer formed by polymerizing a partially crosslinked gel-like polymer increased by 2% by weight.

Further, according to the present invention, the above object is achieved in a method for manufacturing a laminate molded product in which a decorative member is arranged on a base material, and then a methacrylic resin material is placed on the member and heated under pressure, as the resin material: A mixture consisting of (A) 1 to 60% by weight of a crosslinkable monomer and (B) 99 to 40% by weight of an unsaturated monomer mainly composed of alkyl methacrylate and which may contain a dissolved polymer thereof is used as a polymerization initiator. Use a partially crosslinked gel-like polymer which has been partially polymerized in the presence of a mixture to increase the total polymer content by 4 to 62% by weight over the polymer content of the mixture, provided that the total polymer content does not exceed 80% by weight. This is achieved by a method for manufacturing a laminate molded product characterized by the following.

The present invention will be explained in detail below.

The base material of the present invention has heat resistance that can withstand the molding temperature and pressure during the formation of the coating layer, is not easily affected by the heptamers contained in the gel-like crosslinked methacrylic resin molding material that is the raw material for forming the coating layer, and is further Any base material molded from metal, synthetic resin, or other material that is not easily affected by commercially available polishing agents, Wanx, etc. used for ejecting laminated molded products, etc., gets around the sides of the molded product. Although not subject to any restrictions, a base material made of a synthetic resin material is preferably used in terms of mass productivity and freedom of shape. Such resin materials include, for example, crystalline resins such as polyamide, polybutylene terephthalate, and polyethylene terephthalate, or the above-mentioned crystalline resins and acrylonitrile-butadiene-styrene copolymers, acrylonitrile-special acrylic rubber-styrene copolymers. , acrylonitrile/ethylene-propylene rubber/styrene copolymer, acrylonitrile/styrene monomer, and alloyed materials with non-grade resins such as polyphenylene ether. These resin materials can also contain inorganic fillers such as talc, mica, wollastenite, calcium carbonate, and glass fiber.

The thickness of the base material is not particularly limited, but is preferably 0.1 to 15 mm, particularly preferably 0.5 to 10 mm.

The decorative member used in the present invention is a gel-like crosslinked methacrylic resin molding material that is interposed between the base material and the crosslinked methacrylic resin coating layer to enable various decorative expressions, and is a raw material for the coating layer. There is no particular restriction as long as the material is not easily affected by the monomers contained therein, but examples of such materials include wood, paper, cloth, and leather. If the decorative member is wood, thinly sliced 0, 1 to 0.
A 5 mm veneer is preferably used.

The thickness of the decorative member is not particularly limited as long as it is thick enough for decorative expression, but a thickness of 0.01 to 2.0 mm is preferably used. If it is thinner than 0.01 plate, the appearance will be easily affected by the color of the base material, etc., and it will be difficult to take it, which is undesirable.
If it is thicker than I11, it is not only difficult to adhere to a base material having a complicated shape such as a curved surface, but also there is no economic advantage, which is not preferable. If the decorative member is thin, it can be reinforced by backing it with a nonwoven fabric, resin film, or the like. Further, the decorative member may be dyed or patterned in advance, or may be treated after being fixed to a base material to enhance the decorative effect. These decorative members are placed on the base material, but may be fixed to the base material by dots with adhesive so that they do not shift due to the flow of the molding material. It may be used by being fixed over the entire surface of the base material. Such an adhesive can bond decorative members and base materials, withstand the molding temperature during the formation of the covering layer,
There are no particular restrictions on materials that are not affected even if the methacrylate molding material contained in the cross-linked methacrylic resin molding material permeates through the decorative member; for example, urea-based, phenol-based, resol-based, urethane-based and epoxy adhesives.

The crosslinked methacrylic resin coating layer of the present invention has excellent light resistance, solvent resistance, heat resistance, and scratch resistance, and not only improves the durability of the laminate molded product, but also allows the coating layer to be colored. Since it can be made into various thicknesses, various decorative expressions can be created by combining the color and thickness of the coating layer and the type, color, pattern, etc. of the decorative member, which is advantageous in terms of design. In addition, the monomer and/or polymer contained in the gel-like crosslinked methacrylic resin molding material, which is the raw material for forming the coating layer, is filled into the minute gaps of the decorative member, so that the coating layer firmly adheres to the decorative member. This not only makes it possible to improve the durability of the laminated molded product, but also makes it possible to thicken the coating layer. The thickness of such a coating layer is not particularly limited as long as it is thick enough to protect the surface of the decorative member and provide decorative expression, but is preferably 0.3 to 2 mm. If the thickness is less than 0.3 mm, the protective effect of the decorative member will be insufficient and the quality of the resulting laminate molded product will deteriorate, which is not preferable.

The crosslinked methacrylic resin coating layer of the present invention comprises (A) 1 to 60% by weight of a crosslinkable monomer and (B) an unsaturated monomer consisting mainly of alkyl methacrylate and optionally containing dissolved polymer thereof. A partially crosslinked gel-like polymer in which the polymer content of the mixture consisting of ~40% by weight is increased by 4 to 62% by weight over the polymer content in the mixture, provided that the total polymer content does not exceed 80% by weight. It is obtained by polymerizing and solidifying the coalesce.

Here, the amount of crosslinkable monomer (A) used is 1 to 60% by weight, preferably 2 to 50% by weight, more preferably 3 to 50% by weight.
However, if the amount used is less than 1% by weight, the solvent resistance and heat resistance of the coating layer of the finally obtained laminate molded product will not be sufficiently improved, while if it exceeds 60% by weight,
This is undesirable because not only the coating layer of the finally obtained laminate molded product becomes brittle, but also the flow of the coating material tends to be poor.

In addition, the polymer content of the partially crosslinked gel polymer is 4 to 62% by weight relative to the polymer content in the mixture so that the total polymer content does not exceed 80% by weight, preferably 62% by weight. , preferably 10-62% by weight, most preferably 1
This value is an increase of 5 to 62% by weight. If the increase in the polymer content of the partially crosslinked gel-like polymer relative to the polymer content in the mixture is less than 4% by weight, the product will not exhibit a gel-like appearance and will be inconvenient to handle as a coating material. On the other hand, if the value increases by 62% by weight or more, or if it exceeds the upper limit of 80% by weight, it tends to not show good flow during molding and is not preferred as a coating material.

Such a crosslinked methacrylic resin may contain colored materials such as dyes and pigments, ultraviolet absorbers, organic/inorganic fillers, etc., if necessary.

The partially crosslinked gel polymer used to obtain the crosslinked methacrylic resin coating layer of the present invention is
Methacrylic molding materials described in JP-A-202128 and JP-A-62-1705 can be used, including (A) 1 to 60% by weight of a crosslinkable monomer and (B)
A mixture consisting mainly of alkyl methacrylate and optionally containing dissolved polymers of 99 to 40% by weight of unsaturated monomers is polymerized by heating in the presence of a polymerization initiator. It can be obtained by stopping the reaction at a stage where only a portion of the monomer has reacted without the entire amount reacting.

In this case, the content of the polymer present in the partially crosslinked gel polymer is determined by the content of the unsaturated monomer mainly consisting of a crosslinking agent and alkyl methacrylate, or the unsaturated monomer containing a crosslinking agent and a polymer of alkyl methacrylate dissolved therein. 4 to 62% by weight, preferably 1% by weight of the polymer content in the mixture with saturated monomers
0 to 62% by weight, most preferably 15 to 62% by weight, and the total polymer content does not exceed 80% by weight, preferably 62% by weight. Forms of partially crosslinked gel-like polymers include sheets, rondos, pellets, etc.
It is preferable to crush or knead for the purpose of improving fluidity.

Furthermore, 29211-29211-29211, which is mainly composed of alkyl methacrylate, and may contain a dissolved polymer thereof, based on 100 parts by weight of the partially crosslinked gel-like polymer obtained as described above.
Add 100 parts by weight and knead substantially uniformly to improve fluidity,
A molding material with improved adhesiveness and the like can be used, and by using this, the following favorable effects can be imparted.

(i) Fluidity is further improved and processing can be performed at low pressure.

(ii) Appropriate tackiness can be imparted.

(ji) When the total polymer content is relatively high, the adhesion of the coating layer can be improved.

(IV) When coloring the coating layer, dyes and pigments can be mixed into the sill and colored uniformly, and running patterns and uneven spot patterns do not occur.

If the amount of the above-mentioned silica added exceeds 100 parts by weight, the shape retention of the composition will not be maintained, which is not preferable.

In addition, the above-mentioned silica which is mainly composed of alkyl methacrylate and may contain a dissolved polymer thereof means silica containing a polymer of alkyl methacrylate or a monomer mixture containing alkyl methacrylate as the main component,
It preferably has a viscosity of 4 to 50 voids, more preferably 6 to 20 voids at 25°C, and may contain up to 50% by weight of a crosslinking agent if necessary, to form a partially crosslinked gel. It is desirable to contain the same concentration of crosslinking agent as the polymer. As a method for adding this shirub and kneading it substantially uniformly, if the partially crosslinked gel polymer is not crushed, it can be carried out using a kneader or a pulverizer.
On the other hand, if the mixture is crushed, it can be carried out using a mixing agitator such as a super mixer or a Henshil mixer.

Here, ``kneaded substantially uniformly'' means that the silica kneaded into the coating composition by the above-mentioned kneading method is kneaded to such an extent that it does not separate and flow out when left at room temperature for a short time. This state can be achieved by stirring and mixing using a stirrer for several minutes to about 15 minutes.

The crosslinking agent used as a raw material for the above-mentioned partially crosslinked gel polymer and silica has at least two (meth)acryloyl groups in the molecule, and the number of carbon atoms between the (meth)acryloyl groups is 10. The monomers are as follows, preferably monomers represented by (1) to (3) below, and most preferably 2,2-dimethylolpropane dimethacrylate in terms of transparency and fluidity.

MA O(CHz)I, OMA...
・(1) (Here, n is an integer of 3 to 6, and MA represents a methacryloyl group.) R, R3 (M)A OCHZ CCHO(M)8
...(2) [Here, R1 is H, CH3, C2H5, C) + 20H; R2 is H, CH3, CH20COC=CH2 (R4 is H
, CH,) A CH20H group, R3 represents H and CH3 groups, R+, Rz and R4 are not hydrogen at the same time, and (M)A represents a methacryloyl group or an acryloyl group. ] (M)A 0)CHzCHz(g)1-(month)A
...(3) (where n is 1 or 2,
(M) A represents a methacryloyl group or an acryloyl group. ) Similarly, the alkyl methacrylate may be methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, lauryl methacrylate, etc. alone or as a mixture, with methyl methacrylate being particularly preferred.

In the laminate molded product of the present invention, after placing the decorative member on the base material,
In the manufacturing method of a molded article in which a methacrylic resin material is placed on the member and heated under pressure, the resin material is composed mainly of (A) 1 to 60% by weight of a crosslinkable monomer and (B) alkyl methacrylate. Partial polymerization of a mixture consisting of 99 to 40% by weight of an unsaturated monomer which may have a polymer dissolved therein in the presence of a polymerization initiator so that the total polymer content does not exceed 80% by weight. It can be produced by using a partially crosslinked gel-like polymer whose polymer content is increased by 4 to 62% by weight compared to the polymer content of the mixture. After fixing, it is placed in a mold, then a molding material made of a partially crosslinked gel polymer is placed on top of the member to form a mold, and molding can be performed using a simple method such as pressurizing and heating. It is. These moldings are carried out at 90-160°C, preferably 100-150°C.
It is carried out at a temperature of C and under pressure of 5 to 250 kg/afT, preferably 10 to 200 kg Z-. The molding material placed on the decorative member flows as the mold is closed and is subjected to the above pressure, but the shear rate during the flow is slow and the decorative member does not break. In addition, the monomer and/or polymer contained in the partially crosslinked gel polymer penetrates into the minute gaps of the decorative member under heat and pressure, and the coating layer made of the partially crosslinked gel polymer and the decorative member are firmly bonded. Therefore, it is possible to increase the coating thickness and control it to an arbitrary thickness, and it is also possible to improve durability.

When wood or veneer is used as a decorative member, the microscopic irregularities on the surface create the three-dimensional effect inherent to natural wood, but when a cross-linked methacrylic resin molding material is directly applied under pressure and heat, the microscopic unevenness is crushed and the three-dimensional effect is created. In order to prevent this, an acrylic paint film with good adhesion to cross-linked methacrylic resin can be provided as a protective layer on the surface of the wood or veneer. This has the effect that the protective layer that penetrates into minute gaps and firmly adheres to the decorative member and the covering layer are firmly adhered to each other. In addition, if it is difficult for the nitrate contained in the molding material to penetrate into the minute gaps of the decorative component, a protective layer is formed using an acrylic paint that easily penetrates into the decorative component, and the coating layer and the decorative component are separated from each other by forming a protective layer. Adhesion can be improved. In addition, monomers contained in the molding material,
If the decorative component is excessively penetrated, the decorative component may become wet and the color of the underlying base material or adhesive of the decorative component may be visible, but due to the protective layer of the acrylic coating, Since excessive penetration of monomers etc. can be prevented, the above phenomenon can be prevented.

Examples of such acrylic paints include cross-linked polymerizable coating compositions mainly containing polyfunctional (meth)acrylic compounds, such as cross-linked coating compositions having at least two (meth)acryloyloxy groups per molecule. A coating composition consisting of a polymerizable compound, a mixture of the crosslinked polymerizable compound with other polymerizable monomers containing 30% by weight or more, or a partial polymer thereof is preferably used. A coloring agent and an organic/inorganic filler can be added to the acrylic paint as necessary.

Furthermore, since the above-described molding method is used, the shape of the laminated molded product is not particularly limited as long as it can be set in a mold, and the degree of freedom in shape is large.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Evaluations and tests in Examples and the like were conducted in the following manner.

(A) Measurement of polymer content of partially cross-linked gel polymer; 1 part of hydroquinone methyl ether in a Soxhlet extractor
Dichloromethane 150n/dissolved with 1000pp
! After putting 15 g of the gel polymer in strips into an extraction cylindrical mouthpiece and extracting under reflux in a constant temperature water bath kept at 50°C for 20 hours, the extract was poured into 1200 mff1 of methanol. The polymer component was separated and the polymer component was combined with the polymer component in the opening paper and dried under reduced pressure at 55°C until a constant weight was obtained.The weight W of the polymer was determined using the following formula.

(B) Light resistance evaluation: Using a Sunshine Carbon Arc Fade Meter (manufactured by Suga Test Instruments), the black panel temperature was 83°C.
After 00 hours of exposure, the appearance and discoloration of the coating layer were visually evaluated.

(C) Heat resistance test: The laminate molded product was placed in a hot air circulating type opener preheated to 90°C, heated for 1 hour, and then taken out and left to cool naturally to room temperature. This operation was repeated 10 times to determine the appearance and molded product. The adhesion status of each layer was visually evaluated.

(D) Solvent resistance evaluation: A few drops of Henzhen were dropped on the surface of the coating layer of the laminate molded product, covered with a watch glass and left for 5 days, and then the Henzhen was wiped off and the condition of the surface was visually judged.

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)-P-
Menthagene 0.01 weight, 2.2'-azobis(4-
Methoxy-2,4-dimethylvaleronitrile) 0.0
030 parts by weight and 0.3 parts by weight of 2.2bis(1-butylperoxy)butane, 0 parts by weight of di-butylperoxide
．． 2 parts by weight and 0.1 part by weight of 2-(5-methyl-2-hydroxyphenyl)henzotriazur were mixed and dissolved.
The mixture was injected into a cell assembled with glass plates and gaskets at 10 mm intervals, and polymerized at 60°C for about 2 hours to obtain a partially crosslinked gel polymer. The polymer content of this partially crosslinked gel polymer was 30%.

Reference example 2. Production of partially crosslinked gel polymer C] The polymer obtained in Reference Example 1 was extruded using an extruder with a screw diameter of 50 mm and L/D = 8 to obtain a composition crushed to a maximum particle size of 2 mm or less. Ta.

Reference Example 3 [Modification of partially crosslinked gel polymer] Contains 80 parts by weight of the composition obtained in Reference Example 2 and the same concentration of neopentyl glycol dimethacrylate as this composition contains, and has an average viscosity of Polymethyl methacrylate with a degree of polymerization of 10,000 and 20 parts by weight of methyl methacrylate silica with a viscosity of 8 poise were placed in a super mixer (manufactured by Kawata) and stirred and mixed for about 5 minutes to create a sticky composition. I got something.

Reference example 4. [Production of partially crosslinked gel polymer] The amount of methyl methacrylate monomer used was 95 parts by weight, the amount of neopentyl glycol dimethacrylate used was 5 parts by weight, 2
．． A partially crosslinked gel polymer with a polymer content of 38% was prepared in the same manner as in Reference Example 1, except that the amount of 2'-azobis(4methoxy-2,4-dimethylvaleronitrile) used was 0.01 parts by weight. After obtaining, it was crushed in the same manner as in Reference Example 2 to obtain a composition.

Reference example 5. [Coating composition for forming a protective layer] 40 parts by weight of caprolactone-modified dipentaerythritol hexaacrylate (DPCA-20 manufactured by Nippon Kayaku), 18 parts by weight of neopentyl glycol diacrylate, special urethane diacrylate (UAS- manufactured by Nedo Kogyo) 10) A coating composition was obtained by mixing and dissolving 18 parts by weight of methyl methacrylate, 24 parts by weight of methyl methacrylate, and 1.5 parts by weight of hydroxycyclohexylphenyl ketone (Irgacure 184 manufactured by Chipa Geigy).

Example 1 (1) Preparation of substrate; A decorative member made by reinforcing a 0.1 mm thick camphor tree veneer with a 0.1 mm thick polyester nonwoven fabric was
48mm, width 198=, thickness 5mm acrylonitrile.
A substrate was obtained by adhering to a flat plate of an alloyed material made of a butadiene-styrene copolymer and a polyamide resin using a resol adhesive.

The coating composition obtained in Reference Example 5 was applied to the decorative member of the substrate thus obtained to a thickness of about 100 μm after curing.
After spray painting, it was cured at room temperature by irradiating it with a 40W chemical lamp from a distance of 180m.

(2) Lamination molding: The substrate obtained in (1) above was heated to 135°C with N250rfm and a mold core of 200 mm width.
The decorative member surface was placed facing the cavity side. Next, 60 g of the composition obtained in Reference Example 3 was placed on the decorative member, the mold was closed, and the mold was pressurized at a pressure of 10 kg/cT1 for 1 minute, and then kept at a pressure of 100 kg/c++1 for 20 minutes. Take it out, @1250mm, width 2001m+1,
A laminate molded product with a coating layer thickness of about 1 inch was obtained.

(3) Evaluation: The thickness of the coating layer of the laminated molded product obtained as described above is uniform, the surface is smooth and has a beautiful appearance, and the three-dimensional effect of the beautiful wood grain of natural wood is maintained. Each layer was strongly integrated. The results of various evaluations were good as shown in Table 2.

Example 2.3 A laminate molded product was obtained in the same manner as in Example 1, except that the decorative member, adhesive, coating layer thickness, and protective layer were changed as shown in Table 1. The obtained laminated molded product was as good as Example I except for the three-dimensional effect of the wood grain, and the results of various evaluations were also good as shown in Table 2.

Table 1 Example 4 (1) Preparation of the substrate; 2 mm thick Japanese paper was coated with thermosetting acrylic on a flat plate of alloyed material made of polyphenylene ether resin and polyamide resin, N248 mm, 198 plates wide, and 0.5 mm thick. A substrate was obtained by bonding using a base adhesive.

(2) Lamination molding: The substrate obtained in (1) above is placed on the core surface of a mold with a length of 250 mm and a width of 200 mm, which has been heated to 135°C in advance.
The decorative member surface was placed facing the cavity side. Subsequently, 60 g of the crushed composition obtained in Reference Example 4 was placed on the decorative member, the mold was closed, and the pressure was applied at a pressure of 10) cg/cd for 1 minute, and then at 200 kg/cj for 20 minutes. Hold the pressure, cool to 100"C, remove from the mold, and
A laminate molded product was obtained with a diameter of 0 mm, a width of 200 mm, and a coating thickness of about 11 m1.

(3) Evaluation: The laminate molded product obtained as described above was good as in Example 1, and the results of various evaluations were also good as shown in Table 2.

Example 5 The decorative member was made by lining 0.05 m Japanese paper with a polyester nonwoven fabric 0.1 mm thick, and the base material thickness was 1 mm.
A coating layer with a thickness of about 1 m was prepared in the same manner as in Example 4, except that instead of using 0111I11, the composition of Reference Example 4 was used in the form of a sheet measuring 248 mm in length and 198 mm in width.
A laminated molded product of +a was obtained.

The obtained laminated molded product was good as in Example 1, and the results of various evaluations were also good as shown in Table 2.

Example 6 (1) Preparation of the substrate; The decorative member was made of leather with a thickness of 0.5 mm, and the thickness of the base material was 5 mm.
11II+, a substrate was obtained in the same manner as in Example 4 except that a thermosetting acrylic urethane adhesive was used, and then a protective layer was provided in the same manner as in Example 1.

(2) Laminate molding: The pressure in the mold was kept at a constant pressure of 20 kg/a+1 for 20 minutes, and the composition of Reference Example 4 was molded to a length of 248 ann without crushing.
A laminate molded product having a coating layer thickness of 1 mm was obtained in the same manner as in Example 4, except that it was used in the form of a sheet with a width of 198 mm.

(3) Evaluation: The laminate molded product obtained as described above was good as in Example 1, and the results of various evaluations are shown in Table 2.

Example 7 The shape of the base material was changed to a pen plate with a length of 50 mm, a width of 150 mm, a depth of 10 mm, and a thickness of 2 mm, and a cloth with a thickness of 0.5 cm was glued to the outer surface to form the pen plate shape. A laminate molded product with a coating layer thickness of 2 m was obtained in the same manner as in Example 2 except that the mold was used.

The thickness of the coating layer of the obtained laminated molded product was uniform on both the bottom surface and the vertical wall surface of the pen tray, and the appearance etc. were good as in Example 1, and various evaluations were also good as shown in Table 2.

Comparative Example 1 A decorative member similar to that in Example 1 was adhered to an aluminum substrate of @1250a, width 200 mm, and thickness 2 holes using an epoxy adhesive, and then a polyester paint was applied to a thickness of 1 m.

The thickness of the resulting coating layer was non-uniform and the smoothness was poor, so polishing of the surface of the coating layer was necessary.

Furthermore, as a result of heat resistance evaluation, cracks occurred in the coating layer.

Comparative Example 2 A polyester paint was applied to the pen tray-shaped substrate obtained in Example 7 with a target thickness of 2+m+, but the paint applied to the bottom of the pen tray ran and it was difficult to recoat. Furthermore, the paint film on the vertical wall of the pen tray was thin and uneven.

〔Effect of the invention〕

As described above, the present invention is a laminate molded product that has a base material and a crosslinked methacrylic resin coating layer, and a decorative member is present between them, so that the coating layer firmly adheres to the decorative member. In addition, it exhibits excellent light resistance, heat resistance, welt resistance, and scratch resistance, so the laminate molded product as a whole has high durability and can be used in harsh environments.

In addition, the laminated molded product of the present invention can be used with various decorative members, and the thickness and color of the coating layer can be freely adjusted, so the type, thickness, and pattern of the decorative member can be adjusted. Various decorative expressions are possible by combinations of selection, thickness of the coating layer, color tone, etc. In addition, it is possible to form a thick and durable coating layer that cannot be achieved with other methods such as painting, which gives the laminated molded product a luxurious feel and increases its commercial value. It is possible to increase

Since the laminated molded product has excellent decorativeness, design, and durability, it can be used in various fields such as automobile parts, building materials, ornaments, and furniture.

Furthermore, the present invention provides a laminate molded product characterized in that after a decorative member is placed on a base material, a methacrylic resin material made of a partially crosslinked gel polymer is placed on the member and heated under pressure. Since this is a manufacturing method, it is possible to easily and easily manufacture laminate molded products having various shapes and a coating layer having an arbitrary thickness and a uniform thickness, which is useful.

Patent applicant RiRashi Co., Ltd. 〃 Honda motor industry stock company

Claims (4)

[Claims] (1) In a laminate molded product having a base material and a methacrylic resin coating layer and a decorative member present therebetween, the coating layer contains (A) 1 to 60% by weight of a crosslinkable monomer and (B ) The polymer content of a mixture consisting mainly of alkyl methacrylate and 99 to 40% by weight of an unsaturated monomer which may contain a dissolved polymer thereof, within a range in which the total polymer content does not exceed 80% by weight. A laminate molded article characterized in that it is a crosslinked methacrylic resin coating layer formed by polymerizing a partially crosslinked gel-like polymer whose polymer content is increased by 4 to 62% by weight compared to the polymer content in the mixture. (2) The molded article according to claim 1, wherein the decorative member is wood, cloth, paper, or leather. (3) The molded article according to claim 1, wherein the decorative member is a veneer and is fixed onto the base material via an adhesive layer. (4) In a method for manufacturing a laminate molded product in which a decorative member is placed on a base material, a methacrylic resin material is placed on the member and heated under pressure, as the resin material, (A) a crosslinkable monomer is used. In the presence of a polymerization initiator, a mixture consisting of 1 to 60% by weight and 99 to 40% by weight of an unsaturated monomer mainly composed of (B) alkyl methacrylate and optionally containing a dissolved polymer thereof is partially polymerized in the presence of a polymerization initiator. 4 to 6% higher than the polymer content of the mixture, provided that the total polymer content does not exceed 80% by weight.
A method for producing a laminate molded article, characterized by using a partially crosslinked gel polymer increased by 2% by weight.