JP2007152695A - Resin laminate and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a methacrylic resin laminate improved in post processability and having sufficient strength as well as stable quality. <P>SOLUTION: The methacrylic resin laminate is composed of a thermoplastic resin molded product and a polymerized cured matter. The polymerized cured matter is the polymerized cured matter of a mixed liquid comprising 0.1-10 mass% of a compound having at least two isocyanate groups, 100 pts.mass of a polymerizable and curable methacrylic resin raw material including 0.1-30 mass% of a copolymerizable compound having at least one hydroxy group, and 100-300 pts.mass of an inorganic filler with a volume average particle size of 1-50 μm. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminate such as a bathtub obtained by injecting a polymerization curable methacrylic resin raw material and a filler into a cell and polymerizing and curing the raw material, and a method for producing the same.

As an example of a synthetic resin molded body, a methacrylic resin bathtub will be described. Conventionally, after a methacrylic resin sheet is heated and softened, it is formed into a desired bathtub shape by vacuum forming and unsaturated with glass fiber as a reinforcing material for the backing. It is manufactured by spraying a polyester resin with a spray gun or forming a layer of such a reinforcing material by a hand lay-up method, smoothing the layer while defoaming, and then curing. However, since this method uses glass fiber, there are problems that post-processing is difficult and disposal methods are limited. For this reason, a technique is disclosed in which a resin containing a filler is filled between a vacuum-formed thermoplastic resin molded product and a mold, polymerized, cured, and integrated (see Patent Document 1).
JP-A-5-237854

  However, the laminate manufacturing method described in Patent Document 1 has not been sufficiently studied for strength. An object of the present invention is to solve this problem.

  The gist of the present invention is a resin laminate of a thermoplastic resin molded article and a methacrylic polymer cured product, wherein the methacrylic polymer cured product has a compound containing at least two isocyanate groups in an amount of 0.1% by mass to 10% by mass. 100% by mass of a polymer curable methacrylic resin raw material containing 0.1% by mass to 30% by mass of a copolymerizable compound having at least one hydroxyl group and inorganic particles having a volume average particle size of 1 μm to 50 μm It exists in the resin laminated body which is a polymerization hardened | cured material of a liquid mixture with 100 mass parts of fillers-300 mass parts.

  The gist of the present invention is that a thermoplastic resin molded product molded into a predetermined shape in advance is covered with a male mold having substantially the same shape as the thermoplastic resin molded product, with a predetermined interval from the thermoplastic resin molded product, A cell is formed by disposing a female mold on the opposite side of the male mold, and the peripheral portion of the thermoplastic resin molded product and the peripheral portion of the female mold are sealed and clamped, From the female inlet into the cell, 0.1% by mass to 10% by mass of the compound having at least two isocyanate groups and 0.1% by mass to 30% by mass of the copolymerizable compound having at least one hydroxyl group. After pouring a mixed liquid of 100 parts by mass of the polymerization curable methacrylic resin raw material containing 100 parts by mass to 300 parts by mass of the inorganic particle filler having a volume average particle diameter of 1 μm to 50 μm, and then curing this, the male type And from female type In the production method of the resin laminate to the mold.

  According to the present invention, a resin laminate having good post-processability, sufficient strength, and stable quality can be obtained.

  The invention will be described in detail below.

  The resin laminate of the present invention is a resin laminate of a thermoplastic resin molded product and a methacrylic polymer cured product that becomes a reinforcing layer.

  The thermoplastic resin molded product used in the present invention is preferably a thermoplastic resin plate formed into a predetermined shape by thermoforming. Although it does not specifically limit as a thermoplastic resin board, For example, a methacryl resin board, a polystyrene board, an ABS resin board, or these laminated boards etc. are mentioned. Examples of a molding method for molding the thermoplastic resin plate into a predetermined shape include vacuum molding, pressure molding, and press molding. For vacuum or pressure forming, auxiliary forming using a plug or the like can also be performed.

  The thickness of the thermoplastic resin plate is not particularly limited, but is 0.3 mm or more, preferably 0.8 mm or more where the thickness of the molded product is the thinnest. If the plate is thick, cracks due to unreacted raw material compounds remaining in the methacrylic polymer cured product for reinforcement, deformation due to heat generated during curing of the polymer curable methacrylic resin material, and deformation due to injection are less likely to occur. . If necessary, printing can be performed on a thermoplastic resin plate, a film can be laminated, and patterning with a gel coat resin is also possible.

  When the resin laminate is a bathtub, a methacrylic resin plate disclosed in Japanese Patent Publication No. 6-70098 is particularly preferable because it is excellent in thermoforming processability and solvent resistance. That is, when a methacrylic resin plate is produced by polymerizing methyl methacrylate alone or a monomer mixture of methyl methacrylate 60% by mass or more and acrylic acid ester 40% by mass or less in the presence of a polymerization initiator, A syrup is produced by adding 0.01 to 20 parts by mass of a chain transfer agent to 100 parts by mass of the body, and then 0.02 to 1.0 parts by mass of the crosslinked syrup obtained by 100 parts by mass. It is preferable to use a methacrylic resin plate obtained by adding an agent and performing cast polymerization in a mold.

  Examples of the predetermined shape in the present invention include shapes such as a bathtub, a wash bowl, a sink, a shower tray, and a wash counter.

  The mold used in the present invention is not particularly limited, but the following is preferable from the viewpoint of moldability. The male mold having almost the same shape as the thermoplastic resin molded product used in the present invention and the female mold arranged on the opposite side of the male mold with a predetermined distance from the thermoplastic resin molded product include epoxy resin and FRP molds using vinyl ester resin, unsaturated polyester resin, etc., molds made of laminates such as FRP and resin concrete, Ni electroformed molds (FRP surface coated with nickel), metals such as aluminum alloys And those reinforced with a rib structure. Since the liquid mixture of the polymerization curable methacrylic resin raw material and the filler filled in the cell is polymerized and cured, the cured product is released from the female mold. It is preferable to apply a release agent to the film or laminate a material such as Teflon (registered trademark). Since the male mold is a pressing tool, it is preferable that the male mold has substantially the same shape as the thermoplastic resin molded product and is held so as not to deform the thermoplastic resin molded product.

  The interval between the cells constituted by the thermoplastic resin molded product and the female mold in the present invention is the thickness of the desired reinforcing layer when the mixed liquid containing the polymerization curable methacrylic resin raw material is completely filled in the cell. What is necessary is just to be sufficient, and the cell space | interval at the time of liquid mixture injection | pouring does not need to correspond with the thickness of the reinforcement layer of a desired laminated body. That is, in order to reduce the flow resistance of the polymerization curable methacrylic resin raw material at the time of injection, the cell interval at the time of injection may be set to the thickness of the desired reinforcing layer of the laminate +1 to 10 mm. In addition, the cell interval from the start of injection to the completion of filling is controlled so as to gradually increase the clamping pressure of the male and female molds and not to apply a pressure above a certain level, thus suppressing an extreme rise in the resin pressure in the cell. It is desirable. The thickness of the reinforcing layer thus formed is preferably 2 to 20 mm. From the viewpoint of mechanical strength, it is preferably 2 mm or more, and from the viewpoint of workability and handleability, it is preferably 20 mm or less. When the laminate is a bathtub, the thickness of the reinforcing layer is more preferably in the range of 5 to 15 mm. Particularly at the bottom of the bathtub, it is more preferably 6 mm or more in order to obtain sufficient strength.

  Further, the peripheral part of the cell constituted by the thermoplastic resin molded product and the female mold is sealed with packing or the like so that the injected polymerization curable resin material does not leak out of the cell.

  In the present invention, the methacrylic polymerized cured product serving as the reinforcing layer is obtained by polymerizing and curing a mixed solution containing a polymer curable methacrylic resin raw material and an inorganic particle filler.

  The polymerization curable methacrylic resin raw material used in the present invention contains 50 to 99.7% by mass of methacrylic acid alkyl ester. Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate and the like. These may be used alone or in combination. Of these, methyl methacrylate is particularly preferred.

  Examples of the compound having at least two isocyanate groups used in the present invention include 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene 1,5-diisocyanate, paraphenylene diisocyanate, and tetramethylxylylene diene. Isocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, norbornene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate and the like can be used alone or in combination of two or more. The addition amount of the compound having at least two isocyanate groups is 0.1% by mass to 10% by mass in 100% by mass of the polymerization curable methacrylic resin raw material. If it is less than 0.1% by mass, the curability is insufficient, and if it exceeds 10% by mass, cracks are likely to occur.

  Examples of the copolymerizable compound having at least one hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and ethyl (meth) acrylate. Examples include α-hydroxymethyl, 2-hydroxy-3phenoxypropyl (meth) acrylate, para-vinylphenol, and the like. These can be used alone or in combination of two or more. In the present invention, (meth) acryl represents acryl or methacryl.

  The addition amount of the copolymerizable compound having at least one hydroxyl group is 0.1% by mass to 30% by mass in 100% by mass of the polymerization curable methacrylic resin raw material. When it is less than 0.1% by mass, the curability is poor, and when it exceeds 30% by mass, the water resistance is deteriorated.

  The inorganic particle filler must be inorganic particles having a volume average particle diameter of 1 μm to 50 μm, and examples thereof include aluminum hydroxide, calcium carbonate, and silica. Calcium carbonate is preferred. When the volume average particle diameter of the inorganic particle filler is less than 1 μm, the mixture liquid of the polymerization curable methacrylic resin raw material and the inorganic particle filler has a viscosity that is difficult to flow into the mold. In the meantime, the sedimentation of the inorganic particle filler tends to occur.

  The addition amount of the inorganic particle filler needs to be 100 to 300 parts by mass per 100 parts by mass of the polymerization curable methacrylic resin raw material. When the amount exceeds 300 parts by mass, the mixed liquid of the polymerization curable methacrylic resin material and the inorganic particle filler has a viscosity that is difficult to flow into the mold.

  When it is desired to improve the adhesion at the interface between the thermoplastic resin molded product and the methacrylic polymer cured product, at least one of acrylic acid and methacrylic acid is added in an amount of 0.1% by mass in the polymer curable methacrylic resin raw material. It is preferable to add 10 mass%. When it is 0.1% by mass or more, the adhesiveness with the thermoplastic resin molded article is excellent, and when it is 10% by mass or less, the polymerized cured product is excellent in mechanical strength. In particular, when the particle size of the inorganic particle filler is small and the addition amount is large, the adhesiveness at the interface between the thermoplastic resin molded product and the methacrylic polymer cured product is likely to decrease, which is effective.

  The mixed liquid of the polymerization curable methacrylic resin raw material and the inorganic particle filler is preferably adjusted to an appropriate viscosity from the viewpoint of sedimentation of the filler and ease of pouring into the cell. As a method for adjusting the viscosity, a method of combining a plurality of types of fillers having different volume average particle diameters in an appropriate ratio, a method of adding an alkyl methacrylate polymer to a polymerization-curable methacrylic resin raw material, or an alkyl methacrylate ester There are methods such as adding a syrup obtained by polymerizing a part of a monomer having a main component as a main component. Among them, a method of adding an alkyl methacrylate polymer is preferable in terms of workability and quality stability. preferable. In this case, 100 parts by mass of the polymerization curable methacrylic resin material includes an alkyl methacrylate polymer for viscosity adjustment.

  A radical polymerization initiator can be used as a curing agent for polymerizing and curing the mixed solution. Although it does not specifically limit as this radical polymerization initiator, A well-known organic peroxide and an azo compound can be used, What is necessary is just to select suitably according to the desired hardening rate and hardening temperature. Specifically, diacyl peroxides such as benzoyl peroxide, lauroyl peroxide and succinic peroxide, dialkyl peroxides such as di-t-butyl peroxide, t-butylcumyl peroxide and dicumyl peroxide, and t-butyl Peroxyacetates, t-butylperoxypivalate, t-butylperoxybenzoate, peroxyesters such as t-butylmaleic acid hemiperester, hydroperoxides such as t-butylhydroperoxide, cumenehydroperoxide, Organic peroxides typified by bis (4-t-butylcyclohexyl) peroxydicarbonate, peroxydicarbonates such as t-butylperoxyisopropylcarbonate, and ketone peroxides such as methylketone peroxide; Zobisu (2,4-dimethylvaleronitrile) azo compounds such as and the like are exemplified.

  A radical polymerization initiator may be used independently or may be used in mixture of 2 or more types. Further, the blending amount of the radical polymerization initiator may be determined according to the desired curing speed, curing temperature, mechanical strength of the cured body, etc., and is not particularly limited, but 100 mass of the polymerization curable methacrylic resin raw material. 0.1-3 mass parts is suitable with respect to a part.

  Furthermore, you may add a polymerization accelerator and / or a polymerization promotion adjuvant with the said radical polymerization initiator. Specific examples of the polymerization accelerator include mercaptans such as lauryl mercaptan, octyl mercaptan, 2-ethylhexyl mercaptan, glycol dimercaptoacetate, glycol dimercaptopropionate, thioureas such as dibutylthiourea and tetramethylthiourea, and trimethyl. Examples thereof include phosphites and phosphites such as tri-n-butyl phosphite. Specific examples of the polymerization accelerator include salts of organic acids such as naphthenic acid of metals selected from iron, copper, cobalt, nickel, tin, aluminum and antimony, acetylacetone of these metals, phenylacetylacetone and the like. Examples include organometallic complexes and allylic compounds of these metals.

  Moreover, in order to accelerate the crosslinking reaction between the isocyanate group and the hydroxyl group of the compound in the mixed solution as necessary, for example, di-n-butyltin dilaurate, tetramethylbutanediamine, 1,4 diazabicyclo (2,2,2 ) Octane, N, N, N ′, N′-tetramethyl-1,3-butanediamine, dimethyl tin chloride, trimethyl tin hydroxide, second tin chloride, tetra-n-butyl tin, first tin chloride, A catalyst such as cobalt naphthenate or triethylamine can also be used.

  In the mixed solution used in the present invention, additives such as a chain transfer agent, a colorant, a stabilizer, a viscosity modifier, a mold release agent, an antistatic agent, and an antibacterial agent can be blended as necessary.

  In the present invention, the following method is preferred as a method for producing a resin laminate of a thermoplastic resin molded article and a methacrylic polymer cured product.

  A thermoplastic resin molded product molded in a predetermined shape in advance is placed on a male mold having substantially the same shape as the thermoplastic resin molded product, and is opposite to the male mold with a predetermined distance from the thermoplastic resin molded product. A cell is formed by disposing a female mold on the mold, and the peripheral part of the thermoplastic resin molded product and the peripheral part of the female mold are sealed and clamped, and then the female mold is injected from the inlet of the female mold. A resin laminate is obtained by pouring the mixed liquid into the cell, polymerizing and curing the mixture, and releasing the male mold and the female mold.

  In the present invention, when the mixed liquid is poured and cured in the cell, the exothermic peak temperature of the mixed liquid at a position in contact with the thermoplastic resin molded product is preferably in the range of 70 to 130 ° C. When the peak temperature is 70 ° C. or higher, curing in the cell is easily promoted, and the resin laminate is unlikely to undergo large deformation after demolding. Moreover, since it is hard to give a deformation | transformation to a thermoplastic resin molded product as it is 130 degrees C or less, and there is also little residual internal distortion after hardening, it is hard to cause a crack to a resin laminated body after mold release.

  As a method of adjusting the exothermic temperature within this range, the mold (male type, female type) is provided with a temperature control function, and in the initial stage, when the polymerization exotherm of the polymerization curable methacrylic resin raw material increases. Includes a method of cooling, a method of increasing or decreasing the content of the curing agent to be used, a method of adding a chain transfer agent, and the like.

  Hereinafter, the case where a bathtub is manufactured among the suitable examples of this invention is demonstrated.

1) Measuring method of volume average particle diameter of inorganic particle filler The volume average particle diameter was measured using Nikkiso Co., Ltd. make, laser diffraction scattering type micro track particle size distribution measuring device 9320HRA (X-100).

2) Viscosity of liquid mixture The liquid mixture of the polymerization curable methacrylic resin raw material and the inorganic particle filler was marked with a viscosity that could be poured into the cell at 23 ° C.

3) Inorganic particle filler sedimentation The cross-section of the cured laminate was observed, and those where no sedimentation of the inorganic particle filler was observed were marked with ◯ and those where the inorganic particle filler sedimentation was marked with x.

4) Appearance A case where no abnormality was found in the cured resin laminate was rated as ◯, a case where warpage was seen, and a case where cracks were seen was marked as x.

5) Bending test It measured based on JISK7171, and calculated | required the bending elastic modulus and bending strength. A sample is prepared by pouring the polymerization-curable methacrylic resin raw material described in Examples and Comparative Examples described later between a methacrylic resin plate having a thickness of 5 mm and a flat mold, and polymerizing and curing the polymerized cured product having a thickness of 4 mm. A resin laminate having a width of 10 mm and a length of 100 mm was used.

6) Peel test The adhesion at the interface of the resin laminate was evaluated as follows. As the sample, a resin laminate was prepared in the same manner as in the bending test, and the sample was cut into a width of 15 mm and a length of 70 mm. A cutter blade (product number: BL-150P, manufactured by NTT Corporation) was applied to the interface between the methacrylic resin plate and the methacrylic polymer cured product, and was manually peeled off from above. X when peeled at the interface without resistance, △ when there was resistance but easily peeled, ◯ when there was resistance and difficult to peel, and ◎ when there was resistance and the substrate was destroyed and could not be peeled. did.

[Example 1]
In this example, a bathtub using a molded product of a methacrylic resin plate as a thermoplastic resin molded product was manufactured as follows.

  First, as the thermoplastic resin molded product 1, a methacrylic resin plate (Acrylite (registered trademark) PX-200, manufactured by Mitsubishi Rayon Co., Ltd.) having a thickness of 5 mm was formed into a bathtub shape by thermoforming. The shape of the bathtub is a complicated shape having a stool and an armrest as shown in FIG. As the male mold 2, an FRP made of an epoxy resin having substantially the same shape as the inner surface of the thermoplastic resin molded article 1 was used.

  As shown in FIG. 2A, the male mold 2 is covered with a thermoplastic resin molded product 1, and the aluminum alloy female mold 3 is placed at an interval of about 11 mm with respect to the bottom surface (upper surface in the figure) of the thermoplastic resin molded product 1. And put it on. In both the male mold and the female mold, the temperature was controlled by embedding a pipe for circulating hot water inside the mold. Next, the periphery of the thermoplastic resin molded product 1 and the female mold 3 is sealed with an elastic seal packing 4 and pressurized from above and below using an appropriate mold clamping machine, as shown in FIG. 2 (B). A sealed cell 6 was formed. The inlet 5 of the mixed solution provided in the female die 3 is 8 mm in diameter in the sealed cell 6 arranged as shown in FIG. 2B, while the interval between the male die 2 and the female die 3 is narrowed by a mold clamping machine. From 5, a mixture 7 of a polymerization curable methacrylic resin raw material and an inorganic particle filler was injected using a plunger pump. In this case, the mold temperature was set to 80 ° C. for the male mold and 60 ° C. for the female mold.

  As a polymerization curable methacrylic resin raw material, 88.7 parts by mass of methyl methacrylate, 0.3 part by mass of 4,4′-diphenylmethane diisocyanate, 1 part by mass of 2-hydroxyethyl methacrylate, weight average produced by suspension polymerization method After mixing 10 parts by mass of polymethyl methacrylate having a molecular weight of 40,000 and adding 250 parts by mass of aluminum hydroxide having a volume average particle diameter of 3 μm as a filler, di-n-butyltin dilaurate 0 0.05 parts by mass and 0.6 parts by mass of t-hexylperoxypivalate were added and mixed, and degassed under reduced pressure.

  With this injection, as shown in FIG. 2C, the air in the unfilled portion of the mixed liquid 7 of the polymerization curable methacrylic resin raw material and the inorganic particle filler in the cell was exhausted from the exhaust port 8.

  The mixed liquid filled in the cell was heated by polymerization from the mold and polymerized and cured. The exothermic peak at that time was 110 ° C. when measured using a thermocouple at the temperature measurement position 9. Thereafter, the mold was removed to obtain a resin bathtub. Although this bathtub has a complicated shape, it is filled without leaving an unfilled area in the cell, has a good appearance without any air accumulation, and has a small deformation such as warpage. Moreover, since it is not the reinforcement layer which uses the conventional glass fiber, post-processes, such as surface-mounting the attachment part of the leg in the lower part of a bathtub, and grinding | polishing of a repair part, were easy.

  When the bending test of the above-mentioned sample was performed with the methacrylic resin plate portion as the lower surface, the bending elastic modulus was 10.5 GPa and the bending strength was 91 MPa, which was a favorable value.

[Examples 2-4, Comparative Examples 1-2]
Examples 2 to 4 and Comparative Example were the same as Example 1 except that the addition amounts of methyl methacrylate, 4,4′-diphenylmethane diisocyanate and 2-hydroxyethyl methacrylate were as shown in Tables 1 and 2. The laminated body of Examples 1-2 was obtained. The appearances of the laminates of Examples 2 to 4 were good and the deformation such as warpage was small, but the laminate of Comparative Example 1 was insufficiently polymerized and warped after demolding. Further, cracks occurred in the laminate of Comparative Example 2.

  Moreover, when the bottom surface of the bathtub was cut out in the same manner as in Example 1 and a bending test was performed, the laminates of Examples 2 to 4 showed good values for both the flexural modulus and the bending strength as shown in Table 3. As shown in Table 4, Example 1 had an insufficient bending elastic modulus. On the other hand, since Comparative Example 2 could not obtain a good sample due to cracks, a bending test could not be performed.

[Example 5]
Example 1 was used except that hexamethylene diisocyanate was used instead of 4,4'-diphenylmethane diisocyanate, and the addition amount and addition amounts of methyl methacrylate and 2-hydroxyethyl methacrylate were changed as shown in Table 1. Thus, a laminate of Example 5 was obtained. The appearance of the laminate was good, and the bath was small in deformation such as warpage.

  Moreover, when the bathtub bottom face was cut out similarly to Example 1 and the bending test was implemented, as shown in Table 3, the bending elastic modulus showed 10.0 GPa and the bending strength showed a favorable value with 90 MPa.

[Examples 6-7, Comparative Examples 3-4]
Except that the addition amount of methyl methacrylate and polymethyl methacrylate having a weight average molecular weight of 40,000 produced by suspension polymerization and aluminum hydroxide was as shown in Tables 1 and 2, the same as in Example 2, The laminated bodies of Examples 6 to 7 and Comparative Example 3 were obtained. As shown in Tables 3 and 4, the outer appearances of the laminates of Examples 6 to 7 and Comparative Example 3 were good, and the baths were small in deformation such as warpage, but Comparative Example 4 was a polymerization curable resin raw material and filler. The viscosity of the liquid mixture was too high to be poured into the cell.

  Moreover, when the bathtub bottom was cut out and the bending test was implemented similarly to Example 1, the laminated body of Examples 6-7 showed a favorable value with respect to the bending elastic modulus and bending strength as Table 3, comparison. As shown in Table 4, the laminate of Example 3 had an insufficient flexural modulus of 4.9 GPa.

[Examples 8 to 9, Comparative Examples 5 to 6]
Example 2 except that the addition amount of methyl methacrylate and polymethyl methacrylate having a weight average molecular weight of 40,000 produced by suspension polymerization and the volume average particle size of aluminum hydroxide were as shown in Tables 1 and 2. Similarly, the laminated body of Examples 8-9 and Comparative Examples 5-6 was obtained. The outer appearance of the laminates of Examples 8 to 9 was good and the deformation such as warpage was small, but Comparative Example 5 was poured into the cell because the viscosity of the mixture of the polymerization curable resin raw material and the filler was too high. I couldn't. In Comparative Example 6, the filler settled during curing, and a laminate having a uniform polymerized cured product (backup layer) could not be obtained. Moreover, when the bathtub bottom face was cut out similarly to Example 1 and the bending test was implemented, the laminated body of Examples 8-9 showed the favorable value in both the bending elastic modulus and bending strength as Table 3.

[Example 10]
A laminate of Example 10 was obtained in the same manner as Example 7 except that 250 parts by mass of calcium carbonate having a volume average particle diameter of 2 μm was added as a filler. The appearance of the laminate was good, and the bath was small in deformation such as warpage. Post-processing such as chamfering the leg attachment at the bottom of the bathtub and polishing the repaired part was also easy.

  Moreover, when the bathtub bottom face was cut out similarly to Example 1 and the bending test was implemented, as shown in Table 3, the bending elastic modulus was 10.0 GPa and the bending strength showed a favorable value with 71 MPa.

[Comparative Examples 7-8]
The laminated bodies of Comparative Examples 7 to 8 were obtained in the same manner as in Example 1 except that the addition amounts of methyl methacrylate, 4,4′-diphenylmethane diisocyanate, and 2-hydroxyethyl methacrylate were changed as shown in Table 2. It was. All the laminates were insufficiently polymerized and warped after demolding.

  Moreover, when the bathtub bottom face was cut out and the bending test was implemented similarly to Example 1, all the laminated bodies became a value with insufficient bending elastic modulus as Table 4.

[Examples 11 to 12]
Stacking of Examples 11 to 12 in the same manner as in Example 2, except that methyl methacrylate, 4,4′-diphenylmethane diisocyanate, 2-hydroxyethyl methacrylate, and methacrylic acid were added as shown in Table 1. Got the body. As shown in Table 3, the laminate appearance was good, and good adhesion was obtained at the interface between the thermoplastic resin molded product and the polymerization curable methacrylic resin.

Explanation of abbreviations MMA: methyl methacrylate MDI: 4,4′-diphenylmethane diisocyanate HMDI: hexamethylene diisocyanate HEMA: 2-hydroxyethyl methacrylate MAA: methacrylate PMMA: polymethyl methacrylate Weight average molecular weight 40,000 DBTDL: di-n -Butyl tin dilaurate

  The laminate obtained by the production method of the present invention has good productivity, quality stability and post-processability, has sufficient strength, and is suitable for various uses such as a bathtub and a wash bowl.

It is the schematic which shows an example of a thermoplastic resin molded product. It is sectional drawing which shows each process in an example of the manufacturing method of this invention.

Explanation of symbols

1 Thermoplastic resin molded product 2 Male mold 3 Female mold 4 Seal packing 5 Mixture inlet 6 Cell 7 Mixture 8 Air vent 9 Exothermic peak measurement position

Claims (3)

  A resin laminate of a thermoplastic resin molded article and a methacrylic polymer cured product, wherein the methacrylic polymer cured product is 0.1% by mass to 10% by mass of a compound having at least two isocyanate groups, and at least 1 100 parts by mass of a polymerization-curable methacrylic resin raw material containing 0.1% by mass to 30% by mass of a copolymerizable compound having two hydroxyl groups, and 100% by mass to 300% by mass of an inorganic particle filler having a volume average particle diameter of 1 μm to 50 μm. A resin laminate that is a polymerized cured product of a mixed solution with parts by mass.   A thermoplastic resin molded product molded in a predetermined shape in advance is placed on a male mold having substantially the same shape as the thermoplastic resin molded product, and is opposite to the male mold with a predetermined distance from the thermoplastic resin molded product. A cell is formed by disposing a female mold on the mold, and the peripheral part of the thermoplastic resin molded product and the peripheral part of the female mold are sealed and clamped, and then the female mold is injected from the inlet of the female mold. A polymerization curable methacrylic compound containing 0.1% by mass to 10% by mass of a compound having at least two isocyanate groups and 0.1% by mass to 30% by mass of a copolymerizable compound having at least one hydroxyl group in a cell. A mixed liquid of 100 parts by mass of a resin raw material and 100 parts by mass to 300 parts by mass of an inorganic particle filler having a volume average particle diameter of 1 μm to 50 μm is poured, and after this is cured by polymerization, the male mold and the female mold are separated. Resin laminate Manufacturing method.   The manufacturing method of the resin laminated body of Claim 2 which contains 0.1 mass%-10 mass% of at least 1 sort (s) of acrylic acid and methacrylic acid in a polymerization curable methacrylic resin raw material.

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