JPH09201918A - Resin laminated body and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide excellent durability, weathering resistance and adhesion by forming a laminated body of a methacrylate resin layer contg. a specified amt. of isotactic methyl methacrylate polymer, a specified amt. of syndiotactrc methyl methacrylate polymer and an inorg. filler and a non-methacrylic resin layer. SOLUTION: This resin laminated body consists of a methacrylic resin layer and a non-methacrylic resin layer. The methacrylic resin layer contains 0.01-48.5 pts.wt. isotactic methyl methacrylate polymer which means that isotacticity with continuation of methyl methacrylate units is at least 50% expressed by triad expression among polymers and 51.5-99.99 pts.wt. syndiotactic methyl methacrylate polymer which means that syndiotacticity with continuation of methylmethacrylate units is at least 50% by triad expression and 0-300 pts.wt. inorg. filler.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to durability, weather resistance,
Further, the present invention relates to a resin laminate having excellent adhesion.

[0002]

2. Description of the Related Art Fiber reinforced plastics (FRPs) utilize their light weight and high strength to make use of boats, septic tanks, tanks,
It is used in various applications such as bathtubs, corrosion-resistant equipment, industrial components, automobiles and electrical components. Among FRP, materials that can be compression molded in the mold, such as sheet molding compound (SMC) and bulk molding compound (BMC), are easy to integrally mold, the molding speed is fast, and it can contribute to the improvement of working environment. , Has replaced conventional hand lay-up molding materials and spray-up molding materials.

[0003] Conventional SMC and BMC containing an unsaturated polyester as a resin component have excellent moldability and strength, but have problems in surface smoothness, coating properties and weather resistance. A method has been proposed. For example, JP-A-59-76255 discloses a conductive resin sheet,
Vinyl chloride sheet, glass fiber reinforced 6 nylon sheet,
A base material formed of a resin material such as an acrylic resin sheet, an ABS resin sheet, or a sheet molding compound, and a surface member formed of the resin material and thinner than the base material are laminated by heating and pressing. A resin molded product is disclosed.

In Japanese Patent Publication No. 64-11652, a crosslinked acrylic syrup (1) obtained by at least partially copolymerizing a vinyl monomer having a carboxyl group, an alkaline earth metal oxide or hydroxide (2), A polymerization initiator (3), a fiber reinforcement (4), and optionally a filler,
A method of producing a sheet-shaped or bulk-shaped molding material in which a compound composed of a component (5) such as a release agent and a colorant is wrapped in a mold-releasing film and aged, and the molding material further comprises an SMC using an unsaturated polyester resin. It is described that a molded product is obtained by compounding with BMC or BMC.

Further, Japanese Patent Publication No. 1-46530 discloses that
Crosslinked acrylic syrup (1) at least partially copolymerized with vinyl monomer having hydroxyl group, organic polyisocyanate (2), group (3) consisting of aluminum alcoholate and acetylacetonate of aluminum alcoholate, fiber reinforcing agent ( 4) and, if necessary, a compound comprising the component (5) such as a filler, a release agent, and a colorant is wrapped with a release film and aged, and a method for producing a sheet-shaped or bulk-shaped molding material further includes this molding. SMC and BMC using unsaturated polyester resin
It is described to obtain a molded product by compounding with.

On the other hand, it is well known that an isotactic methyl methacrylate polymer and a syndiotactic methyl methacrylate polymer form a stereocomplex methyl methacrylate polymer in a methyl methacrylate monomer. The methyl methacrylate monomer solution of this stereocomplex methyl methacrylate polymer exhibits a gel at room temperature and undergoes a sol-gel transition temperature reversibly.

As a method of utilizing the gelation by this stereocomplex, JP-A-6-287394 discloses that acrylic syrup is composed of 25 to 65% by weight and inorganic powder is 75 to 35% by weight, and the acrylic syrup is the total amount of syrup. The unsaturated monomer component containing methyl methacrylate as the main component is 90 to 30% by weight, and the weight ratio is 1:99 to 99: 1 to the isotactic methyl methacrylate polymer and the syndiotactic methacrylic acid. An acrylic premix has been proposed which uses a solution containing 10 to 70% by weight of a polymer component composed of a methyl polymer. In this proposal, by dissolving the isotactic methyl methacrylate polymer and the syndiotactic methyl methacrylate polymer prepared in advance in the monomer, both polymers form a stereocomplex in the obtained syrup. Then, the method of utilizing the phenomenon of thickening is taken.

[0008]

Problems to be Solved by the Invention JP-A-59-7625
According to the method described in Japanese Patent Publication No. 5, it is possible to impart a function to the surface layer while making the best use of the characteristics of the base material, but most of the resin sheets used in this method are various resin sheets made of a polymer. Since the layers are laminated by heating and pressing each other, the adhesion between the base material and the surface member is poor and problems such as peeling occur.

In the method described in JP-B-64-11652, an alkaline earth metal oxide or hydroxide is contained as an essential component as a thickening method. These inorganic substances can be dispersed in acrylic syrup, but they are not completely dissolved and particles remain after molding. Furthermore, since alkaline earth metal oxides and hydroxides are water-absorbing, there is not only the problem that aging is not stable due to the effect of coexisting water, but they are also durable for use in molded products used in water applications. There is a problem in terms of sex.

The method described in Japanese Patent Publication No. 1-46530 is a method of partially forming a urethane bond using an organic polyisocyanate compound. It is generally known that the isocyanate group is susceptible to moisture, and reacts with moisture to form carbamic acid or amine.
Further, since the urethane bond is a covalent bond, there is a problem that the fluidity during molding is not good.

The methods described in JP-B-64-11652 and JP-B-1-46530 each have a step of wrapping the compound after mixing with a release film and aging, Industrially, not only the temperature of these steps but also the humidity must be controlled, which is not a preferable method.

Further, the acrylic syrup used in the methods described in JP-B-64-11652 and JP-B-1-46530 has a total weight of acrylic monomer, hydroxyl group-containing monomer or carboxyl group-containing monomer of 50% of syrup. %, And these monomer components hardly participate in the polymerization during the aging step, so that there is a problem that the odor derived from the monomer component of the SMC or BMC material obtained after aging is significant.

[0013]

In view of such circumstances, the present inventor has diligently studied a resin laminate having excellent durability, weather resistance and adhesiveness, and as a result, a specific amount of isotactic methyl methacrylate polymer has been obtained. By using acrylic syrup or methacrylic molding compound containing syndiotactic methyl methacrylate polymer, methyl methacrylate monomer, etc., and heat-press molding with non-methacrylic molding compound in the mold, It was found that a resin laminate having excellent properties, weather resistance, and adhesion can be easily produced, and the present invention has been completed.

That is, the present invention is as follows. (1) Based on 100 parts by weight of the polymer, the isotactic methyl methacrylate-based polymer is 0.0
1 to 48.5 parts by weight, 51.5 to 99.99 parts by weight of syndiotactic methyl methacrylate polymer and 0 to 300 parts by weight of inorganic filler, and a methacrylic resin layer and a non-methacrylic resin. A resin laminate including layers. (2) A non-methacrylic molding compound is previously molded in a mold to form a base material, and the total amount of the polymer and the monomer is 10
Based on 0 parts by weight, 0.01 to 48.5 parts by weight of isotactic methyl methacrylate polymer, 0 to 48.5 parts by weight of syndiotactic methyl methacrylate polymer, methyl methacrylate monomer An acrylic syrup containing 3 to 99.99 parts by weight, a radical polymerization initiator and 0 to 300 parts by weight of an inorganic filler is injected into the surface of the base material, and heated and pressed in a mold to be molded. (1) The method for producing a resin laminate as described above. (3) Based on 100 parts by weight of the total amount of the polymer and the monomer, the isotactic methyl methacrylate polymer 0.1.
01 to 48.5 parts by weight, syndiotactic methyl methacrylate polymer 48.5 to 70.99 parts by weight, methyl methacrylate monomer 3 to 29 parts by weight, radical polymerization initiator and inorganic filler 0 to The method for producing a resin laminate as described in (1) above, wherein the methacrylic molding compound and the non-methacrylic molding compound containing 300 parts by weight are molded by heating and pressing in a mold. Hereinafter, the present invention will be described in detail.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The isotactic methyl methacrylate polymer in the present invention is a polymer having a methyl methacrylate unit as a main component, and the isotacticity of the methyl methacrylate unit chain is represented by a triad.
It means 0% or more, and includes a copolymer with another monomer which can be copolymerized if necessary.

Other copolymerizable monomers are known. For example, methacrylic acid esters such as ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, acrylic Acrylic acid esters such as 2-ethylhexyl acid and 2-hydroxyethyl acrylate, unsaturated acids such as methacrylic acid and acrylic acid, and monofunctional monomers such as acrylonitrile, methacrylonitrile and styrene. Furthermore, (poly) alkylene glycol di (meth) acrylic acid ester, allyl (meth) acrylic acid ester, trimethylolpropane tri (meth) acrylic acid ester, divinylbenzene, etc., having two or more unsaturated double bonds in the molecule. It is a polyfunctional monomer contained.

The ratio of each monomer unit in the isotactic methyl methacrylate copolymer is 50 to 100 parts by weight, preferably 90 to 100 parts by weight, of methyl methacrylate.
0 to 50 parts by weight, preferably 0 to 50 parts by weight of another copolymerizable monomer
To 10 parts by weight. This is because if the amount of the other copolymerizable monomer exceeds 50 parts by weight, it will be difficult to dissolve in the methyl methacrylate monomer. In particular, a monomer having two or more of these copolymerizable functional groups gives a crosslinked product at the time of copolymerization,
Since the obtained polymer becomes insoluble in the solvent, it should be 1 part by weight or less with respect to 1000 parts by weight of the monofunctional monomer.

The isotactic isotactic methyl methacrylate-based polymer can be produced by a conventionally known method, but it is obtained by anionic polymerization using a Grignard reagent as a polymerization initiator (JP-A-SHO). 61-179210, JP-A-61-1766.
No. 17).

The syndiotactic methyl methacrylate polymer in the present invention is a polymer having a methyl methacrylate unit as a main component, and the syndiotacticity of the methyl methacrylate unit chain is 50% or more in triad display. Means a copolymer with the above-mentioned other copolymerizable monomer, if necessary.

The ratio of each monomer unit in the syndiotactic methyl methacrylate copolymer is 50 to 100 parts by weight, preferably 90 to 100 parts by weight of methyl methacrylate, and other copolymerizable monomers. It is 0 to 50 parts by weight, preferably 0 to 10 parts by weight. 5 other copolymerizable monomers
This is because if it exceeds 0 parts by weight, it becomes difficult to dissolve in the methyl methacrylate-based monomer. In particular, these monomers having two or more functional groups capable of copolymerization give a crosslinked product at the time of copolymerization, and the obtained polymer becomes insoluble in a solvent. It should be 1 part by weight or less.

The syndiotactic methyl methacrylate polymer can be produced by a conventionally known method. The polymerization initiator may be a known initiator for polymerizing a monomer containing methyl methacrylate as a main component. For example, organic peroxide type initiators such as benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxy 2-ethylhexaate; 2,2'-azobisisobutyronitrile, 2,2 ' An azo initiator such as azobis (2,4-dimethylvaleronitrile); a known redox initiator obtained by combining a peroxide initiator with a reducing compound such as amines and mercaptans as a main component; Further, benzoin, benzoin ethers, 1-hydrohexyl phenyl ketone, benzyl dimethyl ketal, acyl phosphenoxide, benzophenone, Michler's ketone, a photopolymerization initiator system in which a photosensitizer is optionally used in combination with thioxanthone, etc. is there.

Further, it can be obtained by anion polymerization using a complex compound of an organic aluminum compound and an organic phosphorus compound or an organic lanthanide complex (Japanese Patent Publication No. 6-89054, JP-A-3-26).
3412).

The monomer containing methyl methacrylate as the main component in the present invention is a monomer mixture containing 50% or more of methyl methacrylate and optionally the above-mentioned other copolymerizable monomer. .

The radical polymerization initiator in the present invention is
A conventionally known radical polymerization initiator may be used for the polymerization of the monomer containing methyl methacrylate as a main component. For example, organic peroxide type initiators such as benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxy 2-ethylhexaate; 2,2'-azobisisobutyronitrile, 2,2 ' An azo initiator such as azobis (2,4-dimethylvaleronitrile); a known redox initiator obtained by combining a peroxide initiator with a reducing compound such as amines and mercaptans as a main component; Further, benzoin, benzoin ethers, 1-hydrohexyl phenyl ketone, benzyl dimethyl ketal, acyl phosphenoxide, benzophenone, Michler's ketone, a photopolymerization initiator system in which a photosensitizer is optionally used in combination with thioxanthone, etc. is there.

The inorganic filler in the present invention is not particularly limited as long as it is insoluble in the methyl methacrylate monomer and does not inhibit the polymerization and curing thereof. Examples thereof include powders of aluminum hydroxide, aluminum oxide, calcium carbonate, calcium silicate, calcium aluminate, calcium sulfate, magnesium hydroxide, silica, talc, clay, etc., but are not limited thereto. Of these, aluminum hydroxide, magnesium hydroxide and silica are particularly preferable. The particle size of the inorganic powder is usually 0.1 to 100 μm.
m, preferably 0.1 to 75 μm. The inorganic powder is added when it is desired to give the laminate a marble-like appearance.

If necessary, an antioxidant, an ultraviolet absorber, a chain transfer agent, a dye or a pigment can be added to the acrylic syrup.

The methacrylic molding compound according to the present invention comprises 0.01 to 48.5 parts by weight of isotactic methyl methacrylate polymer and syndiotactic methacrylic acid based on 100 parts by weight of the total amount of the polymer and the monomer. It contains 48.5 to 70.99 parts by weight of a methyl acid polymer, 3 to 29 parts by weight of a methyl methacrylate monomer, a radical polymerization initiator and 0 to 300 parts by weight of an inorganic filler.

This methacrylic molding compound is usually produced by injecting acrylic syrup into a cell and polymerizing. The composition of the acrylic syrup is based on 100 parts by weight of the total amount of the polymer and the monomer, and the isotactic methyl methacrylate polymer 0.01 to 48.5.
30 parts by weight, syndiotactic methyl methacrylate polymer 0 to 20 parts by weight, methyl methacrylate monomer 31.
5 to 99.99 parts by weight, a radical polymerization initiator and an inorganic filler in an amount of 0 to 300 parts by weight, preferably isotactic methacryl based on 100 parts by weight of the total of the polymer and the monomer. Methyl acid-based polymers 1 to
30 parts by weight, syndiotactic methyl methacrylate polymer 0.01 to 1.9 parts by weight, methyl methacrylate monomer 68.1 to 98.99 parts by weight, radical polymerization initiator and inorganic filler 0 to Containing 300 parts by weight,
Alternatively, based on 100 parts by weight of the total amount of the polymer and the monomer, the isotactic methyl methacrylate polymer 0.
01 to 1 part by weight, syndiotactic methyl methacrylate polymer 1.9 to 8.9 parts by weight, methyl methacrylate monomer 90.1 to 98.09 parts by weight, radical polymerization initiator and inorganic filler It contains 0 to 300 parts by weight.

This acrylic syrup is radically polymerized in a cell, and it is preferable that the acrylic syrup is stirred and deaerated under reduced pressure below the 10-hour half-life temperature of the radical polymerization initiator and then poured into the cell. . This method is not particularly limited, but it is necessary to suppress the total amount of gas dissolved in the monomer remaining in the methacrylic molding compound.

Also when pouring into the cell, if the viscosity of the composition is high and it is difficult, it may be heated to a temperature at which the added radical polymerization initiator is not rapidly decomposed. The temperature is affected by the type and amount of the radical polymerization initiator used, but is preferably 10 hours or less half-life temperature of the polymerization initiator used. More preferably, it is 10 to 50 ° C. or lower than the 10-hour half-life temperature.

The structure of the cell is not particularly limited. For example, 2 made of glass, stainless steel, etc.
It is composed of a single plate and a sealing material such as soft vinyl chloride, and the batch type is fixed by a clamp. A continuous cell can also be used. In addition, it is preferable to stick a film made of a material which is hard to be exposed to the monomer such as polyester, polyethylene, or polypropylene on the inner surface of the cell, because release becomes easy at the time of release. Further, it is also possible to apply various release agents to the inner surface of the cell to perform release treatment.

When the polymerization is carried out after injection into the cell, the polymerization is carried out by heating or irradiation with light. As a heating method, a known method, for example, hot air, hot water, or a heat source such as an infrared heater is used. Moreover, as a light irradiation method,
A high-pressure mercury lamp, a metal halide lamp, a low-wavelength UV lamp, a xenon lamp, a Kuptarc lamp, or the like may be used for irradiation with visible light, ultraviolet light, or the like. These methods may be appropriately selected depending on the type and amount of the polymerization initiator used and are not particularly limited.

In the cell, the above acrylic syrup was polymerized to a range in which the residual amount of the methyl methacrylate monomer was in the range of 3 to 29 parts by weight based on 100 parts by weight of the total amount of the polymer and the monomer. And remove the methacrylic molding compound.

The non-methacrylic molding compound of the present invention is typified by SMC or BMC,
For example, it refers to an unsaturated polyester resin as described in JP-A-54-68892. Specifically, it means a molding material obtained by aging and thickening an unsaturated polyester containing a carboxyl group or a hydroxyl group, a filler, a fiber reinforcing agent and other additives.

The resin laminate of the present invention is produced by using an acrylic syrup or a methacrylic molding compound and heat-pressing in a mold together with a non-methacrylic molding compound.

When the acrylic syrup and the non-methacrylic molding compound are used for the production, the non-methacrylic molding compound is preliminarily heat-pressed in a mold to form a base material, and the acrylic syrup is injected onto the base material. It is formed by heating and pressing in a mold. The molding compound of the unsaturated polyester resin may be molded under the conditions according to the respective SMC and BMC, but the general temperature is 80 to 17
The temperature is 0 ° C. and the pressure is in the range of 30 to ²⁰⁰ kg / cm ² .

Acrylic syrup is poured onto the obtained molded body. The acrylic syrup used is 0.01 to 48.5 parts by weight of an isotactic methyl methacrylate-based polymer and a syndiotactic methyl methacrylate-based polymer based on 100 parts by weight of the total of the polymer and the monomer. Four
8.5 parts by weight, methyl methacrylate monomer 3 to 99.
99 parts by weight, radical polymerization initiator and inorganic filler 0 to
1 to 30 parts by weight of isotactic methyl methacrylate-based polymer, syndiotactic methyl methacrylate-based polymer 0 based on 100 parts by weight of those containing 300 parts by weight, preferably polymer and monomer .01-1.
9 parts by weight, methyl methacrylate monomer 68.1 to 9
8.99 parts by weight, a radical polymerization initiator and 0 to 300 parts by weight of an inorganic filler, or an isotactic methyl methacrylate polymer based on 100 parts by weight of the total of the polymer and the monomer. 0.01 to 1 part by weight, syndiotactic methyl methacrylate polymer 1.9 to
8.9 parts by weight, methyl methacrylate-based monomer 90.1
It contains 98.09 parts by weight, a radical polymerization initiator and an inorganic filler of 0 to 300 parts by weight.

The heating and pressurizing conditions of the acrylic syrup are such that the temperature is 50 to 150 ° C. and the pressure is 3 to 200 kg / cm ² . If the temperature is lower than 50 ° C., it takes time for polymerization and curing, and if it exceeds 150 ° C., problems of decomposition and coloring due to depolymerization and the like occur, which is not preferable. Also, the pressure is 3 kg
If it is lower than / cm ^2, it becomes difficult to suppress the boiling of the contained monomer, and it becomes a factor to generate bubble-like defects, which is not preferable.

To manufacture a resin laminate from a methacrylic molding compound and a non-methacrylic molding compound, both molding compounds are put in a mold at the same time and heated or pressed, or the non-methacrylic molding compound is heated and pressed in a mold in advance. Then, the above-mentioned methacrylic molding compound is charged between the obtained molded body and a mold, and the mixture is heated and pressed again for molding. You.

The molding conditions for the methacrylic molding compound are a temperature of 80 to 150 ° C. and a pressure of 30 to 200 kg / cm ² . Temperature is 80 ℃
If it is lower, good fluidity cannot be obtained. On the contrary, if it exceeds 150 ° C., decomposition caused by not only polymerization reaction but also depolymerization reaction
Alternatively, it is not preferable because it causes a problem such as coloring due to high temperature. It is preferable to perform the molding at the same temperature as the molding temperature of the non-methacrylic molding compound, because the same mold can be used for production without changing the mold temperature. Also, the pressure is 30
When it is less than kg / cm ² , the methacrylic molding compound does not flow sufficiently, which is not preferable.

Polymer 1 having excellent durability, weather resistance and adhesiveness was obtained by taking out from the mold after heat-press molding.
Based on 00 parts by weight, 0.01 to 48.5 parts by weight of isotactic methyl methacrylate-based polymer and 51.5 to 99.99 parts by weight of syndiotactic methyl methacrylate-based polymer among the polymers. And inorganic filler 0-3
A resin laminate comprising a methacrylic resin layer containing 100 parts by weight and a non-methacrylic resin layer is obtained.

[0042]

According to the present invention, a resin laminate comprising a methacrylic resin layer and a non-methacrylic resin layer having excellent durability, weather resistance and adhesion can be easily obtained.

[0043]

EXAMPLES The present invention will be described in detail with reference to examples, but the present invention is not limited thereto. [Evaluation of Adhesion] 4 × 4c from a laminate obtained by molding
A sample having a size of m was cut out. This sample is 90 ℃
The cycle of immersion in warm water for 3 hours and then leaving it at room temperature for 1 hour was repeatedly carried out to examine the state change at the interface.

Example 1 Isotopic methyl methacrylate syndiotactic methyl methacrylate polymer (number average molecular weight 32,900, isotacticity) obtained by anionic polymerization was added to 93.8 parts by weight of a methyl methacrylate monomer. 99%)
5 parts by weight and syndiotactic methyl methacrylate resin obtained by radical polymerization (methyl methacrylate unit 98% by weight, methyl acrylate unit 2% by weight, number average molecular weight 80,000, syndiotacticity 58%) 1 .2
Part by weight was heated to 60 ° C. and dissolved with stirring. To 100 parts by weight of the obtained solution, 2,2'-azobis (2,4
-Dimethylvaleronitrile) (0.25 part by weight) was added and dissolved to homogeneity. After degassing the obtained acrylic syrup, it was poured into a cell constituted by two glass plates and a vinyl chloride resin gasket so that the gap between the glass plates was 3 mm, and polymerized at 30 ° C. for 8 hours. After
After cooling, the methacrylic molding compound was taken out.

Next, width 5 cm, length 12 cm, depth 4 c
Unsaturated polyester SMC in a m-shaped box
(Trade name Polymer Rumat: manufactured by Takeda Pharmaceutical Co., Ltd.) was charged, and press molding was performed for 3 minutes under the conditions of a temperature of 140 ° C. and a pressure of 120 kg / cm ² to prepare a Nishikei body. Open the mold, place 50 g of the above methacrylic molding compound inside the box, close the mold again, and close the box.
A methacrylic molding compound was molded for 10 minutes at a temperature of 70 ° C. and a pressure of 70 kg / cm ² . A resin molded body having a transparent acrylic layer having a thickness of 150 μm on the surface layer was obtained. As a result of performing the adhesion test for 10 cycles, no abnormality was particularly observed.

Example 2 In the same molding die as in Example 1, unsaturated polyester SM was added.
C (trade name Selecty Mat: manufactured by Takeda Yakuhin Co., Ltd.) was charged, and press molding was performed for 30 minutes at a temperature of 90 ° C. and a pressure of 70 kg / cm ² to prepare a molded body. After opening the mold, 50 g of the methacrylic molding compound prepared in the same manner as in Example 1 was charged, the mold was closed again, and the methacrylic molding compound was kept for 30 minutes under the conditions of 90 ° C. and a pressure of 70 kg / cm ^2. Was molded. A resin molded body having a transparent acrylic layer having a thickness of 150 μm on the surface layer was obtained. 10 adhesion tests
As a result of carrying out the cycle, no particular abnormality was found.

Example 3 5 parts by weight of an isotactic methyl methacrylate polymer (number average molecular weight 32,900, isotacticity 99%) obtained by anionic polymerization was dissolved in 95 parts by weight of a methyl methacrylate monomer. The same procedure as in Example 1 was carried out except that the solution was prepared. A resin molded body having a transparent acrylic layer having a thickness of 150 μm on the surface layer was obtained. As a result of performing the adhesion test for 10 cycles, no abnormality was particularly observed.

Example 4 Using the methacrylic molding compound prepared in the same manner as in Example 3, a resin molding was prepared in the same manner as in Example 2. A resin molded body having a transparent acrylic layer having a thickness of 150 μm on the surface layer was obtained. As a result of performing the adhesion test for 10 cycles, no abnormality was particularly observed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location B29K 105: 06

Claims (9)

[Claims] 1. Based on 100 parts by weight of the polymer, 0.01 to 48.5 parts by weight of the isotactic methyl methacrylate-based polymer and 51.50% of the syndiotactic methyl methacrylate-based polymer among the polymers. A resin laminate comprising a methacrylic resin layer and a non-methacrylic resin layer containing 5 to 99.99 parts by weight and 0 to 300 parts by weight of an inorganic filler. 2. A non-methacrylic molding compound is molded in a mold in advance as a base material, and an isotactic methyl methacrylate polymer of 0.01 to 100 parts by weight based on a total of 100 parts by weight of the polymer and the monomer is used. 48.5 parts by weight, syndiotactic methyl methacrylate polymer 0 to 4
8.5 parts by weight, methyl methacrylate monomer 3 to 99.
99 parts by weight, radical polymerization initiator and inorganic filler 0 to
The method for producing a resin laminate according to claim 1, wherein an acrylic syrup containing 300 parts by weight is poured onto the surface of the base material, and the mixture is heated and pressed in a mold to be molded. 3. The amount of isotactic methyl methacrylate polymer, syndiotactic methyl methacrylate polymer, and methyl methacrylate monomer in the acrylic syrup is 100% by weight of the total amount of the polymer and the monomer. The manufacturing method according to claim 2, wherein the amount is 1 to 30 parts by weight, 0.01 to 1.9 parts by weight, and 68.1 to 98.99 parts by weight, respectively, based on parts. 4. The amount of isotactic methyl methacrylate-based polymer, syndiotactic methyl methacrylate-based polymer, and methyl methacrylate-based monomer in the acrylic syrup is 100% by weight of the total of the polymer and the monomer. The production method according to claim 2, wherein the amount is 0.01 to 1 part by weight, 1.9 to 8.9 parts by weight, and 90.1 to 98.09 parts by weight, respectively, based on parts. 5. An isotactic methyl methacrylate-based polymer 0.01 to 48.5 parts by weight, a syndiotactic methyl methacrylate-based polymer 48. based on a total of 100 parts by weight of the polymer and the monomer. 5 to 70.99 parts by weight,
A methacrylic molding compound and a non-methacrylic molding compound containing 3-29 parts by weight of a methyl methacrylate monomer, a radical polymerization initiator and 0-300 parts by weight of an inorganic filler are heated and pressed in a mold to be molded. The method for producing a resin laminate according to claim 1, wherein 6. A non-methacrylic molding compound is preliminarily heated and pressed in a mold to form a molded body, and then a methacrylic molding compound is disposed between the molded body and the mold and heated and pressed to mold. The manufacturing method described. 7. The methacrylic molding compound comprises an isotactic methyl methacrylate polymer of 0.1% by weight based on a total of 100 parts by weight of the polymer and the monomer.
01 to 48.5 parts by weight, syndiotactic methyl methacrylate polymer 0 to 20 parts by weight, methyl methacrylate monomer 31.5 to 99.99 parts by weight, radical polymerization initiator and inorganic filler 0 to 6. An acrylic syrup containing 300 parts by weight is injected into a cell and polymerized until the residual amount of the methyl methacrylate monomer falls within the range of 3 to 29 parts by weight. 6. The manufacturing method according to 6. 8. The amount of isotactic methyl methacrylate-based polymer, syndiotactic methyl methacrylate-based polymer and methyl methacrylate-based monomer in the acrylic syrup is 100 weight% of the total of the polymer and the monomer. The manufacturing method according to claim 7, wherein the amount is 1 to 30 parts by weight, 0.01 to 1.9 parts by weight, and 68.1 to 98.99 parts by weight, respectively, based on parts. 9. The amount of isotactic methyl methacrylate-based polymer, syndiotactic methyl methacrylate-based polymer and methyl methacrylate-based monomer in the acrylic syrup is 100 weight% of the total of the polymer and the monomer. The manufacturing method according to claim 7, which is 0.01 to 1 part by weight, 1.9 to 8.9 parts by weight, and 90.1 to 98.09 parts by weight, respectively, based on parts.