JPH03106939A - Production of integral molding - Google Patents

Abstract

PURPOSE:To obtain an integral molding composed of a molding and a metathesis polymer by polymerizing and curing a metathesis-polymerizable monomer in the presence of a metathesis polymerization catalyst in contact with the coating surface of another molding coated with a specified adhesive layer. CONSTITUTION:A metathesis-polymerizable monomer (e.g. dicyclopentadiene) is polymerized and cured in the presence of a metathesis polymerization catalyst (e.g. tungsten hexachloride) in contact with the coating surface of another molding coated with an adhesive layer mainly consisting of a base polymer selected from among a poly(ethylene/vinyl acetate) copolymer, a poly(ethylene/acrylic ester) copolymer and a lowly crystalline polyolefin (e.g. atactic polypropylene) and a hydrocarbon tackifying resin (e.g. terpene resin or petroleum resin) to form an integral molding composed of said molding and the metathesis polymer molding. According to the above process, an integral molding can be easily produced.

Description

[Detailed Description of the Invention] a. Industrial Application Field The present invention is directed to the industrial application of a monolithic molded product of a polymer molded product obtained by simultaneously polymerizing and molding a metasense polymerizable monomer in the presence of a metasense polymerization catalyst system and another molded product. It concerns a manufacturing method that can be easily implemented. More specifically, the metasense polymer molded product is brought into contact with the coated surface of another molded product coated with a specific hot melt adhesive to produce a molded product that is integrated with the other molded product. Regarding the method. b. Prior Art It is known that strained cyclic olefins undergo ring-opening polymerization using a metasense polymerization catalyst system. The metasense polymerization catalyst system consists of two components, a main catalyst component and an activator component, and a monomer containing each of these two components A method has been proposed in which a reactive solution of 100% is poured into a mold immediately after mixing, and bulk polymerization is performed therein to perform polymerization and molding in one step (for example, Japanese Patent Laid-Open No. 58-1
(See Publication No. 29013). According to this method, large molded products can be obtained using inexpensive molds, so it has the potential to be used for a wide range of applications. However, in practical use, such molded products are often required to be used as an integral structure with molded products made from other materials.
For example, there are a wide variety of products, including those with a foam core, metal insert moldings and joint parts, and resin moldings whose surfaces are covered with a decorative film. A common method for manufacturing such a one-piece molded product is to join the two after molding, but this is time-consuming and depending on the form, for example,
In some cases, it is impossible to join the core shape after molding, so the industrial method is to mold one side and then join it to the other molded product at a predetermined position when molding the other. can be said to be a more advantageous method. By the way, the metasense polymer is generally a polymer of cyclic olefin, but after molding, the surface is oxidized by oxygen in the air and polar groups are formed, so it cannot be used with commonly used polar adhesives such as epoxy and polyurethane. Although good adhesion can be obtained depending on the agent,
Immediately after molding, it is non-polar and has very low surface energy.
Generally, it is characterized by poor adhesion. In the case of molding, this property means that the molded product has a metal surface or a resin surface such as epoxy, and both types of molds have good flame retardancy, and this property can be used to advantage for molded products. That means you are doing it. However, when it is used for one-piece molding as described above, the adhesion with other molded products is extremely poor. In fact, even if a metasense polymer with the same composition is molded in contact with a molded product obtained from the same metasense polymer, the former will be oxidized and will not adhere at all. As mentioned above, there are few molded products that have a surface with good affinity in terms of surface energy, and in the case of one-piece molding as described above, it naturally comes into contact with the metasense polymerizable monomer, which eventually hardens and forms a polymer. In the case of molded products, there will be some shrinkage due to shrinkage.
Even if there is affinity, good adhesion cannot be obtained due to the strain at the interface. Therefore, the above 1
For body molding, it is expected that it is necessary to apply an adhesive to the contact surface of the previously obtained molded product with the later metasense polymer molded product to ensure good adhesion. ．． C. SUMMARY OF THE INVENTION Therefore, the inventors of the present invention have endeavored to find an adhesive that can be satisfactorily used for this purpose, thereby realizing the ability to obtain a good integral molded product with a wide range of other molded products by the method described above. As a result of our studies, we have arrived at the present invention. In other words, although such an adhesive has an affinity for cycloolefins of metasense polymerizable monomers, it does not substantially inhibit metasense polymerization and moderately reduces the strain on the adhesive surface that occurs during the molding process. It is necessary to satisfy the requirements that the base polymer is composed of chains that are flexible enough to be relaxed, and that it can be softened and bonded by the heat generated during molding due to metasense polymerization. The present inventor has proposed that an adhesive composed of a base polymer selected from poly(ethylene-vinyl acetate) copolymer, poly(ethylene-acrylic acid ester) copolymer, and low-crystalline polyolefin, and a tackifying resin is applied. We have discovered that it can be used for this purpose. That is, the present invention provides a base polymer selected from poly(ethylene-vinyl acetate) copolymer, poly(ethylene-acrylic acid ester) copolymer, and low-crystalline polyolefin, and a hydrocarbon-based tackifier resin. A metasense polymerizable monomer was polymerized and cured in the coexistence of a metasense polymerization catalyst in contact with the coated surface of another molded product coated with the main adhesive layer, thereby integrating the molded product and the metasense polymer molded product. This is a method for producing a one-piece molded product. At least one of the above three types is used as the base polymer of the adhesive forming the adhesive layer used in the present invention. As the poly(ethylene-vinyl acetate) copolymer, one having a vinyl acetate content of 18 to 35% by weight and a melt index (MI) of 3 to 300 is used. In particular, those with low vinyl acetate content and low polarity, such as
18 to 25 wt% is preferably used. (Ethyl acrylate and imbutyl acrylate are used as the acrylic ester constituting the ethylene-acrylic ester copolymer, but ethyl acrylate is particularly preferably used.Acrylate content is generally 18 to 32% by weight. The melt index used is one in the range of 2 to 100.As the polyolefin, polyolefins that do not have large crystallinity are preferably used, such as atactic polypropylene, ethylene-propylene copolymer, etc. Depending on the performance of the adhesive layer required for the body molded product, it is only necessary to select a material with properties suitable for it. Problems such as compatibility arise when blending different types of such base polymers. Generally, one type of base polymer is used, but there is no problem in adjusting the properties by blending the same type of polymer or those with different molecular weights.The above-mentioned pace polymer alone In this case, it is necessary to coexist with a hydrocarbon-based tackifying resin because the tackiness as an adhesive is insufficient and adhesiveness can only be imparted under extremely special conditions.As such tackifying resin, there are They can be classified into hydrocarbon-based adhesives and oxygen-containing polar adhesives.In the case of general hot-melt adhesives, polar adhesives have good adhesion, and those with polar adhesives as their main ingredients are prized. However, for the purposes of the present invention, such polar compounds, especially those containing a large number of carboxyl groups containing active hydrogen and hydroxyl groups, are difficult to use because they inhibit metasense polymerization; The former hydrocarbon-based ones are preferred. Examples of the former include terpene resins, petroleum-based resins, styrene resins, indene resins, etc. To explain in more detail, terbene resins generally include pine resin. Among the cationic polymers of α-pinene or β-pinene obtained from essential oils, β-pinene-based terbene resins are particularly preferred and can be suitably used in the present invention. Terpene resins obtained from synthetic terbene oils are also suitable. Petroleum resins can be broadly classified into aliphatic petroleum resins, aromatic petroleum resins, dicyclobentadiene petroleum resins, hydrogenated petroleum resins, etc. Aliphatic petroleum resins are also known as C!1. Also called petroleum resin, it is made by polymerizing a mixture of C and olefins such as 1-bentene, 1,3-pentadiene and isoprene, and is made by enriching dienes such as 1,3-pentadiene and isogrene. Quantification t! K-polymerized products can be mentioned. Aromatic petroleum resin is also called C, petroleum resin.
C! Aromatic unsaturated hydrocarbons of l to Clo, such as indene, methylindene, vinyltoluene, α-methylstyrene. It is a resin made by polymerizing a mixture of β-methylstyrene, etc. Furthermore, dicyclobentadiene resin refers to a product obtained by polymerizing an alicyclic olefin mixture whose main component is dicyclopentadiene. Hydrogenated petroleum resin is made by hydrogenating the unsaturated bonds in the resin by catalytic reduction of the petroleum resins mentioned above, and changing them to saturated bonds.In addition to being colorless and transparent in appearance, The compatibility with the base polymer changes. Therefore, depending on the selection of the base polymer, hydrogenated resins are preferred because they are advantageous and tend to have fewer metasense polymerization-inhibiting groups. Styrenic resins include styrene and α-methylstyrene.
Styrene such as vinyltoluene or styrene derivatives with similar polymerizability to styrene are made into polymers with a relatively low degree of polymerization by cationic polymerization, etc., singly or as a suitable mixture. Able to use things and use them favorably. Indene-based resin is generally produced by polymerizing a mixture of coumaron, indene, styrene, etc. that has been fractionally distilled from coal tar as coumaron-indene resin, and because it contains coumaron residues, it is no longer a pure hydrocarbon. It has low polarity and can be considered a non-polar hydrocarbon resin. On the other hand, oxygen-containing monopolar resins include rosin resins such as rosin, hydrogenated rosin, esterified rosin, and rosin-modified xylene resin, and phenolic resins such as terbenphenol resin, alkylphenol resin, and alkylphenol-modified xylene resin. Broadly divided. These polar types, except for completely esterified esterified rosin, have carboxylic acid in the rosin component, a phenolic hydroxyl group in the phenolic resin, and a polar group with active hydrogen, which can be used as a metasense polymerization catalyst. Since it has an inhibiting effect and is too polar, it is generally not desirable to use it in the adhesive of the present invention, but it must be used in a limited amount. Furthermore, in addition to the base polymer and tackifier resin as essential components, the adhesive of the present invention also contains waxes and antioxidants as important components. Furthermore, if necessary, feelers, plasticizers, softeners, etc. are added. Waxes are often preferably added for the purpose of improving workability during adhesive application and bonding. However, among such waxes, hydrocarbon waxes are preferred, and waxes obtained from petroleum such as paraffin wax and microcrystalline wax. Examples include synthetic waxes such as polyethylene wax and polypropylene wax. It is preferable to select the necessary amount from the viewpoint of workability; in general, adding too much is not preferable as it will reduce the adhesive strength. As the antioxidant, hindered phenols are preferred. Regarding the distribution of each precept of the adhesive as described above, good adhesion is generally possible over a wide range on the metasense polymer side, but the selection should be made depending on the surface properties of the other molded product. It is also necessary to consider the required performance such as heat resistance, and the optimal composition must be selected according to the required conditions. On the other hand, preferred specific examples of the metasense polymerizable cycloolefin monomer as the metasense polymerizable cycloolefin compound used in the present invention include dicyclobentadiene, tricyclobentadiene, cyclobentadiene-methylcyclobentadiene codimer. body, 5-ethylidenenorbornene, norbornene. norbornadiene, 5-cyclohexenylnerbornene, 1,4,5.8-dimethano-1,4.4a,5, 6,7,8,8,8a-octahydronaphthalene, 1,4-methanol 1.4 ,4a
,5, 6,7,8,8,8a-octahydronaphthalene. 6-ethylidene-1.4,5.8-dimethanol 1.
4.4a,5,6,7,8,8a-heptahydronaphthalene, 6-methyl-1.4,5.8-dimethano-1,
4,4a,5,6,7,8.8a-hegutahyde-naphthalene,1,4,5.8-dimethano-1,4,4a,5
,8,8a-hexahydronaphthalene, ethylenebis(
Examples include one or a mixture of two or more of cyclic olefins having 1 to 3 norbornene groups, such as (5-norbornene), but dicyclobentadiene or a monomer mixture mainly composed of dicyclobentadiene is particularly preferably used. It will be done. Furthermore, if necessary, a metasense polymerizable cyclic compound containing a different element such as oxygen or nitrogen can also be used. Such polar monomers, which are often used in copolymerization with dicyclopentadiene and the like, preferably have a norbornene structural unit, and the polar groups include ester groups, ether groups, etc. Cyano group. N-substituted imides and the like are preferred. Specific examples of such copolymerizable monomers include 5-methoxycarbonylnorbornene, 5-(2-ethylhexyloxy)carbonyl-5-methylnorbornene, 5-phenyloxymethylnerbornene, 5-cyanonorbornene,
6-cyano-1.4,5.8-dimethano-1.4,4a
,5,6,7,8,8a-octahydronaphthalene,N
-butylnadic acid imide, etc. As mentioned above, the metasense polymerizable monomer is required to contain as few impurities as possible that would inactivate the metasense polymerization catalyst. Tungsten is the main catalyst component in the metasense polymerization catalyst system used in the present invention. Salts such as halides such as rhenium, tantalum, and molybdenum are used, but compounds of tungsten and molybdenum are preferred, and tungsten compounds are particularly preferred. Such tungsten compounds include tungsten halide,
Tungsten oxyhalide and the like are preferred, and more specifically tungsten hexachloride, tungsten oxychloride and the like are preferred. Additionally, organic ammonium tungstate and the like can also be used. Such tungsten salt compounds are known to immediately start cationic polymerization when added directly to monomers, which is not preferable. Therefore, tungsten salt compounds are used in inert solvents such as benzene and toluene. It is preferable to use it by suspending it in advance in chlorobenzene, etc., and solubilizing it by adding a small amount of an alcoholic compound or phenolic compound. Further, in order to prevent undesirable polymerization as described above, it is preferable to add about 1 to 5 moles of Lewis base or chelating agent per mole of the tungsten compound. Examples of such additives include acetylacetone, acetoacetic acid alkyl esters, tetrahydrofuran, and penzonitrile. Thus, the monomer solution containing the catalyst component (solution A) is
It has sufficient stability for practical use. On the other hand, the activator component in the metasense polymerization catalyst system is
Preferred are organometallic compounds mainly consisting of alkylated metals of group Ⅰ, especially tetraalkyl tin, alkylaluminum compounds, and alkylaluminum halide compounds, specifically diethylaluminum chloride, ethylaluminum dichloride. Examples include trioctylaluminum, dioctylaluminum iodide, tetrabutyltin, and tributyltin hydride. By dissolving these organometallic compounds as activator components in the mixed monomer, the other solution (referred to as solution B) is prepared.
is formed. In the present invention, it is also possible, but preferred, to obtain a polymer molded product by sequentially adding catalyst components to the metasense polymerizable monomers as described above. Basically, it is preferable to take a method of obtaining a crosslinked polymer molded product by mixing the solutions A and B. However, if the above composition is used as it is, the polymerization reaction will start very quickly, so hardening may occur before it has sufficiently flowed into the mold, which often causes problems. It is preferable to use an agent. As such regulators, Lewis bases are generally used, especially ethers. Esters, nitriles, etc. are used. Specific examples include ethyl benzoate, butyl ether, and diglyme. Such regulators can be added to both solutions, but generally the effect may be greater if added to the side of the solution containing the organometallic compound activator. As mentioned above, when a monomer having a Lewis space group is used, it can also serve as a regulator. The amount of the metasense polymerization catalyst system to be used is, for example, when a tungsten compound is used as a catalyst component, the ratio of the tungsten compound to the raw material monomer is about 1 on a molar basis.
000:1 to 15000:1, preferably 2000:1
In addition, when an alkyl aluminum is used as the activator component, the ratio of the aluminum compound to the raw material monomer is about 100:1 to about 30 on a molar basis.
00:1, preferably around 300:1 to about 1000:1. Furthermore, as described above, the masking agent and regulating agent can be appropriately adjusted and used depending on the amount of the catalyst system to be used through experiments. In practical use, various additives can be added to the metasense polymer used in the present invention in order to improve or maintain its properties. Such additives include:
Fillers, pigments. Antioxidant. These include light stabilizers, B-burning agents, and polymer modifiers. Similar to the inorganic filler in the present invention, it is impossible to add such additives after a molded product is obtained at the same time as polymerization, so when adding them, they must be added to the raw material solution described above in advance. It is necessary to keep it. The easiest method is to use the solution A and solution B.
One method is to add it to either or both of the above in advance, but in that case, it is necessary to add the compound to either or both of the liquids, but in this case, it does not react with the highly reactive catalyst component or activator component in the liquid to a practical extent, and It must not inhibit polymerization. If the reaction cannot be avoided, but coexistence does not substantially inhibit polymerization, it is possible to mix it with the monomer, condition the third liquid, and use it immediately before polymerization. can. Further, it is preferable to add an antioxidant to the metasense polymer used in the present invention, and therefore it is desirable to add a phenol-based or amine-based antioxidant to the solution in advance. Specific examples of these antioxidants include 2
．． 6-t-butyl-P-cresol, N,N'-diphenyl-P-phenylenediamine. Examples include tetrakis[methylene(3.5-di-t-butyl-4-hydroxycinnamate)]methane. Further, other polymers can be added to the metasense polymer used in the present invention when it is in the monomer solution state. As mentioned above, the addition of an elastomer as such a polymer additive is effective in increasing the impact resistance of the molded product and controlling the viscosity of the solution. Elastomers used for this purpose include styrene-butadiene rubber, styrene-butadiene-styrene triblock rubber,
Styrene-isoprene-styrene triblock rubber, polybutadiene. Polyisograin, butyl rubber. A wide range of elastomers can be mentioned, including ethylene propylene dienterpolymer and mononitrile rubber. Furthermore, if a large amount of residual monomer remains in the polymer used in the present invention, a characteristic odor may be emitted. α,α,α-trichlorotoluene is used as such a residual monomer reducing agent. Trichloroacetic acid ester, phthalic acid chloride, benzoic anhydride,
Examples include phosphorus oxychloride and benzenesulfonic acid chloride. The polymer used in the present invention is produced by simultaneously performing polymerization and molding, as described above. As mentioned above, such molding methods include mixing the catalyst and raw material monomer with a simple mixer such as a static mixer, a resin injection method in which a pre-mixed premix is flowed into a mold, and a two-way catalyst system. The RIM method can be used, in which solution A and solution B, which are separated into two, are collided and mixed in the head and poured directly into the mold. In particular, the RIM method is commonly used. In either case, the injection pressure into the mold can be relatively low, making it possible to use inexpensive molds. Furthermore, once the polymerization reaction inside the mold starts, the temperature inside the mold rises rapidly due to the reaction heat, and the polymerization reaction ends in a short time. As with polyurethane-RIM, it is easy to release from the mold and often does not require a special mold release agent. In the present invention, when forming a polymer as described above, another molded product is brought into contact with a surface coated with a specific adhesive as described above, and this other molded product and the metasense polymer molded product are bonded together. A one-piece molded product is obtained. Examples of such other molded products include plastic molded products and metal molded products for obtaining metasense polymer molded products and integral molded products. When bonding large molded items together with considerable dimensions, the stresses that occur under usage conditions due to differences in the coefficients of thermal expansion of the materials used to form the two molded items, differences in dimensional changes upon moisture absorption, etc. Since it will touch the adhesive surface, it is necessary not to make it too large, or to devise a form that can withstand even if it is large. Therefore, the one-piece molded product of the present invention can be advantageously used in a form where such stress does not become too large. Such formats include (1) Another molded product is a film-like material that covers half, all, or a part of the surface of the metasense polymer; ■ Another molded product is a foam-like material that covers the metasense polymer, especially as a 7-form core. It is covered entirely or with only a portion of the surface covered with polymer. Another example is a molded product, preferably cylindrical, inserted into a metasense polymer. 0) protects the surface of the metasense polymer molded product by covering it with such a film, and has other functions depending on the properties of the film, such as imparting a pattern by using a printed film or imparting conductivity by using a conductive layer. It is possible to do this. In the case of (2), an elliptical shape is provided that allows weight reduction while maintaining the rigidity of the molded product. (1) can be made into an advantageous structure for actual use by inserting other plastic or metal screws, rods, etc. into the metasense polymer molding. As can be easily surmised, in (1) to (1) above, even if the properties of the two materials combined are different as described above, the structure is such that large interfacial stress is not likely to be applied, and good adhesion is achieved. It is possible to maintain the surface and is particularly advantageous as a one-piece molded product of the present invention. In order to carry out integral molding in the present invention, another molded article coated with an adhesive is generally installed in the mold for obtaining the metasense polymer molded article, and the integral molded article is then placed in the mold. You will get In this case, the other molded product does not shrink, but the metasense polymer molded product generates heat as polymerization progresses.
Shrinkage occurs as the molded product is converted into a polymer, especially as the molded product cools. At this time, consideration must be given to the form so that such shrinkage does not occur in the direction of peeling off the adhesive layer. The above-mentioned one-piece molded product is characterized in that it is generally obtained in a form in which the metasense polymer molded product is taken out after molding and adhered at the same time, and can be obtained with extremely high productivity. d. Effects of the Invention Thus, the one-piece molded product according to the present invention has the features of a metasense polymer molded product suitable for obtaining large-sized molded products, as well as the ability to form a one-piece molded product that is integrated and bonded with other molded products at the same time as the molding. Since molded products can be obtained, it can be used in a wide range of applications, such as components for various transportation vehicles on land, on water, on snow, in the air, and as construction and civil engineering materials. It can be used for mechanical parts in factories, housings for electronic equipment, etc. e. EXAMPLES The present invention will be described in detail with reference to Examples and Comparative Examples. In addition,
The examples are intended to be illustrative and not limiting. Examples 1 to 3 Preparation of adhesive-coated polyvinyl chloride sheet> An adhesive as shown in the table below was melt-coated onto a 0.3 m thick polyvinyl chloride sheet to form a 0.2 cm thick adhesive. I created a sheet with one layer on one side. Preparation of liquid for metasense polymerization> (1) [Preparation of catalyst component solution] 20 parts by weight of tungsten hexachloride was added to 70 parts by volume of dry toluene under a nitrogen stream, and then nonylphenol 2
A 0.5 M tungsten-containing catalyst solution was prepared by adding a solution consisting of 1 part by weight and 16 parts by volume of toluene, and the solution was purged with nitrogen gas overnight to react with tungsten hexachloride and nonylphenol. The generated hydrogen chloride gas was removed, and 1 part by volume of acetylacetone was added to 10 parts by volume of the solution to prepare a polymerization catalyst solution. 95 parts by weight of purified dicyclopentadiene. For a monomer mixture consisting of 5 parts by weight of purified ethylidene norbornene,
3 parts by weight of ethylene-propylene-ethylidenenorbornene copolymer rubber with an ethylene content of 70 mol%. The above polymerization catalyst solution was added to a solution containing 7022 parts by weight of Ethanox 702 as an oxidation stabilizer until the tungsten content was O. OQI M
A catalyst component solution (solution A) was prepared. +2] [Preparation of activator component solution] trioctyl aluminum 85. A mixed solution of a polymerization activator prepared by mixing 15 parts of dioctyl aluminum iodide and 100 parts of diglyme in a molar ratio was mixed with 95 parts by weight of purified dicyclopentadiene, 5 parts by weight of purified ethylidene norbornene, and the same ethylene-propylene-ethylidene norbornene copolymer rubber as above. An activator component solution (solution B) was prepared by mixing the activator component solution (solution B) with a mixture consisting of 3 parts by weight at a ratio such that the aluminum content was 0.003 M. [Creation of one-piece molded product] The adhesive layer created above The attached sheet was placed horizontally and attached to the bottom of a cantergate-type plaque mold with a thickness of 3 mm, with the adhesive layer facing upward. A mix head of a reaction injection molding machine was attached to the gate of this mold, and solution A. Inject solution B, 1
Polymerization was carried out in a large mold to obtain a molded product consisting of a PVC sheet and a metasense polymer. The liquid temperature at the time of injection is 30℃, and the mold is below! The test was carried out at 185°C and 60°C above. The PVC sheet adheres very well to the metasense polymer. In order to measure the degree of adhesion, the above plaque was cut into strips with a width of 25 mm and tested using a tensile tester at a rate of 50 m/min.
The T-peel strength was measured at a tensile speed of . Example 1 12St+r/25m, Example 2
11.5kg/25m solid tumor case 3 12.5kg/2
It showed a good adhesive strength of 5 m, and cohesive failure was observed on all peeled surfaces. Examples 4 to 6 The adhesive layer-attached PVC sheet used in Examples 1 to 3 was molded by vacuum molding into a box shape with the adhesive layer on the inside and one side open. This box shape was modified by T degrees, and the above box-shaped PVC sheet was attached to the side gate side of a side gate mold that had a side with dimensions and was capable of molding a similar box shape with a thickness of 31 mm. The same reaction solutions A and B as in cases 3 to 3 were mixed and injected into the mold and hardened. A box-shaped one-piece molded product whose outer surface was covered with a PVC sheet was obtained. It was confirmed that the PVC sheet and metasense polymer were bonded very strongly. In this case, the liquid temperature is 30℃, and the mold is 90℃ on the show side. Molding was carried out at 60°C on the core side. Written amendment (voluntary) 1. Case Indication Patent Application No. 1 242934 2. Title of the invention (1) "Good flame retardancy" on page 4, line 1 of the specification is corrected to "good releasability."

(2) On page 11, line 14 of the same text, ``takaka kake'' is corrected to ``tada kake''.

(3) “Mixed head” on page 27, lines 10-11.
is corrected as "mixing head".

that's all Method for manufacturing one-taikai type objects

Claims (1)

[Claims] Apply an adhesive layer consisting mainly of a base polymer selected from poly(ethylene-vinyl acetate) copolymer, poly(ethylene-acrylic acid ester) copolymer, and low-crystalline polyolefin, and a hydrocarbon-based tackifier resin. A metasense polymerizable monomer is polymerized and cured in the coexistence of a metasense polymerization catalyst in contact with the coated surface of another molded product, and the molded product and the metasense polymer molded product are integrated. A method for manufacturing a body molding.