JP7358850B2 - Resin composition, molded body, bonded body, and method for manufacturing the bonded body - Google Patents

Description

The present invention relates to a resin composition, a molded body, a bonded body, and a method for manufacturing the bonded body.

Thermoplastic resins such as polyethylene and polypropylene have traditionally been used to manufacture packaging for pharmaceuticals and foods, encapsulants for solar cell modules, encapsulants for organic EL elements, encapsulants for electronic components, etc. .

Alkoxysilyl groups are introduced into such thermoplastic resins in order to ensure that molded objects such as sheets obtained by molding the resin are bonded well to base materials (adherents) made of materials such as glass and metal. (For example, see Patent Document 1).

Japanese Patent Application Publication No. 2003-72012

However, the technique disclosed in Patent Document 1 is required to suppress deformation of the molded body due to heat (i.e., improve dimensional stability) while bonding the molded body well to the adherend. Ta.

Therefore, an object of the present invention is to provide a new technique that improves the dimensional stability of the molded body while bonding the molded body well to the adherend.

The present inventors have focused on the fact that the above-mentioned requirements are increasing, particularly for thermoplastic resins other than aromatic vinyl compound-chain conjugated diene compound block copolymers. A resin obtained by introducing an alkoxysilyl group into a thermoplastic resin other than an aromatic vinyl compound-chain conjugated diene compound block copolymer (hereinafter sometimes referred to as "alkoxysilyl group-containing thermoplastic resin") As a result of intensive studies to achieve the above objective regarding The present inventors have discovered that by using a predetermined amount of a hydrocarbon polymer, it is possible to improve the dimensional stability of the molded body while bonding the molded body well to the adherend, and have completed the present invention.

That is, the present invention aims to advantageously solve the above problems, and the resin composition of the present invention is a resin composition containing a resin having an alkoxysilyl group and a hydrocarbon polymer. The resin having an alkoxysilyl group is a resin in which an alkoxysilyl group is introduced into a thermoplastic resin other than an aromatic vinyl compound-chain conjugated diene compound block copolymer, and the resin having an alkoxysilyl group is is at least one of an olefin polymer and a hydrogenated olefin polymer, and has a number average molecular weight of 300 to 5000, and the content of the hydrocarbon polymer in the resin composition is It is characterized in that the amount is 0.01 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin having the alkoxysilyl group in the product. Thus, by using a resin composition containing an alkoxysilyl group-containing thermoplastic resin and a hydrocarbon polymer in the above-mentioned quantitative ratio, it can be bonded well to an adherend and has excellent dimensional stability. A molded body can be obtained.

Here, in the resin composition of the present invention, the resin having an alkoxysilyl group is preferably at least one of alkoxysilyl group-containing polyethylene and alkoxysilyl group-containing polypropylene. If alkoxysilyl group-containing polyethylene and/or alkoxysilyl group-containing polypropylene is used as the alkoxysilyl group-containing thermoplastic resin, the molded article can be bonded to the adherend even better.
In the resin composition of the present invention, the hydrocarbon polymer preferably has an iodine value of 2.0 g/100 g or less. By using a hydrocarbon polymer having an iodine value below the above-mentioned value, the light resistance of the molded article can be improved.

Further, the present invention aims to advantageously solve the above problems, and the molded article of the present invention is a molded article containing a resin having an alkoxysilyl group and a hydrocarbon polymer, The alkoxysilyl group-containing resin is a resin in which an alkoxysilyl group is introduced into a thermoplastic resin other than an aromatic vinyl compound-chain conjugated diene compound block copolymer, and the hydrocarbon polymer is It is at least one of an olefin polymer and a hydrogenated olefin polymer, and has a number average molecular weight of 300 to 5000, and the content of the hydrocarbon polymer in the molded product is equal to or less than the content of the hydrocarbon polymer in the molded product. It is characterized by being 0.01 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin having an alkoxysilyl group. As described above, a molded article containing an alkoxysilyl group-containing thermoplastic resin and a hydrocarbon polymer in the above-mentioned quantitative ratio can be bonded well to an adherend and has excellent dimensional stability.

Here, the molded article of the present invention includes a resin molded article containing the resin having the alkoxysilyl group, and a resin film that covers at least a part of the surface of the resin molded article and includes the hydrocarbon polymer. It is preferable. A molded body comprising a resin film containing a hydrocarbon polymer on the surface of a resin molded body containing an alkoxysilyl group-containing thermoplastic resin can be bonded more favorably to an adherend via the resin film.

In the molded article of the present invention, the alkoxysilyl group-containing resin is preferably at least one of alkoxysilyl group-containing polyethylene and alkoxysilyl group-containing polypropylene. If alkoxysilyl group-containing polyethylene and/or alkoxysilyl group-containing polypropylene is used as the alkoxysilyl group-containing thermoplastic resin, the molded article can be bonded to the adherend even better.
In addition, in the molded article of the present invention, it is preferable that the hydrocarbon polymer has an iodine value of 2.0 g/100 g or less. By using a hydrocarbon polymer having an iodine value below the above-mentioned value, the light resistance of the molded article can be improved.

Furthermore, the present invention aims to advantageously solve the above-mentioned problems, and the joined body of the present invention is a joined body formed by joining any of the molded bodies of the present invention described above and a base material. It is characterized by A joined body obtained using any of the molded bodies described above has the molded body and the base material which is the adherend well bonded to each other, and has excellent dimensional stability.

Here, in the joined body of the present invention, it is preferable that the adhesive strength between the molded body and the base material is 4 N/cm or more. If the adhesive strength between the molded body and the base material is 4 N/cm or more, the molded body and the base material are sufficiently well bonded.

Further, the present invention aims to advantageously solve the above-mentioned problems, and the method for manufacturing a joined body of the present invention includes bonding a resin molded body containing a resin having an alkoxysilyl group and a base material. A method for producing a bonded body, wherein the alkoxysilyl group-containing resin is obtained by introducing an alkoxysilyl group into a thermoplastic resin other than an aromatic vinyl compound-chain conjugated diene compound block copolymer. A hydrocarbon polymer, which is a resin and is at least one of an olefin polymer and a hydrogenated olefin polymer and has a number average molecular weight of 300 to 5000, is applied to the surface of at least one of the resin molded body and the base material. , a step of supplying 0.01 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin having an alkoxysilyl group to form a resin film containing the hydrocarbon polymer; The method is characterized in that it includes a step of adhering the above through the resin film. Through such a process, the resin molding containing the alkoxysilyl group-containing thermoplastic resin and the base material can be bonded well (especially even under low temperature conditions) through the resin film containing the hydrocarbon polymer. It is possible to obtain a bonded body in which the molded body and the base material are well bonded. Furthermore, the resulting joined body has excellent dimensional stability.

Here, in the method for producing a bonded body of the present invention, it is preferable that the resin having an alkoxysilyl group is at least one of alkoxysilyl group-containing polyethylene and alkoxysilyl group-containing polypropylene. If alkoxysilyl group-containing polyethylene and/or alkoxysilyl group-containing polypropylene is used as the alkoxysilyl group-containing thermoplastic resin, it is possible to obtain a joined body in which the molded article and the base material are bonded more favorably.
In addition, in the method for manufacturing a bonded body of the present invention, it is preferable that the hydrocarbon polymer has an iodine value of 2.0 g/100 g or less. By using a hydrocarbon polymer having an iodine value below the above-mentioned value, it is possible to improve the light resistance of the molded article and the joined article.

In the method for producing a bonded body of the present invention, the base material is an organic base material, and the adhesive surface of the organic base material to the resin molded body is protected from plasma irradiation, ultraviolet irradiation, corona discharge, and flame spraying. It is preferable that at least one surface treatment selected from the group consisting of: By using an organic base material that has been subjected to any of the above-mentioned surface treatments, it is possible to obtain a bonded body in which the molded body and the organic base material are bonded more favorably.

Further, in the method for manufacturing a joined body of the present invention, it is preferable that the bonding temperature in the bonding is lower than the Vicat softening temperature of the resin having the alkoxysilyl group. According to the manufacturing method of the present invention, even if the bonding is performed at a temperature below the Vicat softening temperature of the alkoxysilyl group-containing thermoplastic resin, it is possible to obtain a bonded body in which the molded body and the adherend are well bonded. Furthermore, by performing the adhesion at a temperature below the Vicat softening temperature of the alkoxysilyl group-containing thermoplastic resin, deformation due to heat can be suppressed.

According to the present invention, it is possible to provide a resin composition that can adhere well to an adherend and form a molded article with excellent dimensional stability.
Further, according to the present invention, it is possible to provide a molded article that can be well adhered to an adherend and has excellent dimensional stability.
According to the present invention, it is possible to provide a bonded body that includes a molded body having excellent dimensional stability and in which the molded body is well bonded to a base material as an adherend.

FIG. 1 is a cross-sectional view showing the structure of an example of a molded article according to the present invention.

Embodiments of the present invention will be described in detail below.
The resin composition of the present invention can be used, for example, to form the molded article of the present invention. Moreover, the molded article of the present invention can be joined to a base material as an adherend to form a joined body of the present invention. The joined body of the present invention can be manufactured using, for example, the method for manufacturing a joined body of the present invention.

(Resin composition)
The resin composition of the present invention contains a predetermined alkoxysilyl group-containing thermoplastic resin and a predetermined hydrocarbon polymer, and optionally contains other components. Here, the resin composition of the present invention needs to contain 0.01 parts by mass or more and 50 parts by mass or less of the hydrocarbon polymer per 100 parts by mass of the alkoxysilyl group-containing thermoplastic resin.
Since the resin composition of the present invention contains the predetermined alkoxysilyl group-containing thermoplastic resin and the predetermined hydrocarbon polymer in the above-mentioned quantitative ratio, it is possible to It is possible to form a molded body that can be bonded well to the adhered body and has excellent dimensional stability.

<Alkoxysilyl group-containing thermoplastic resin>
As mentioned above, the alkoxysilyl group-containing thermoplastic resin is a resin in which an alkoxysilyl group is introduced into a thermoplastic resin other than the aromatic vinyl compound-chain conjugated diene compound block copolymer.
In the present invention, "aromatic vinyl compound-chain conjugated diene compound block copolymer" refers to a polymer block whose main component is a structural unit (repeat unit) derived from an aromatic vinyl compound such as styrene. , a block copolymer having a polymer block whose main component is a structural unit derived from a linear conjugated diene compound (linear conjugated diene compound, branched conjugated diene compound) such as 1,3-butadiene, and the like. means hydride. Here, when a polymer block "contains a certain structural unit as a main component", it means that the proportion of the certain structural unit in all structural units in the polymer block is 70% by mass or more.

[Thermoplastic resin]
Here, the thermoplastic resin constituting the alkoxysilyl group-containing thermoplastic resin is as follows:
Polyethylene, polypropylene, poly-1-butene, poly-4-methylpentene, ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/4-methylpentene copolymer, ethylene/1-octene copolymer Coalescence, ethylene/1-butene/1-octene copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propylene/5-ethylidene-2-norbornene copolymer, ethylene/propylene/5-vinyl-2 - Polyolefins such as norbornene copolymer, ethylene/1-butene/dicyclopentadiene copolymer, ethylene/1-butene/5-ethylidene-2-norbornene copolymer, ethylene/1-butene/vinylnorbornene copolymer, etc. system resin;
Cycloolefin polymers such as ethylene/norbornene copolymers, ethylene/tetracyclododecene copolymers, hydrogenated ring-opening metathesis polymers of norbornene derivatives, and cyclohexadiene polymers;
Examples include ethylene/(meth)acrylic acid ester copolymers such as ethylene/methyl methacrylate copolymer, ethylene/ethyl methacrylate copolymer, ethylene/methyl acrylate copolymer, and ethylene/ethyl acrylate copolymer. olefin/(meth)acrylic acid ester copolymer;
Ionomer resin obtained by reacting an ethylene/unsaturated carboxylic acid random copolymer with a metal compound;
Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate;
Bisphenol A, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)phenylethane, 2,2 -bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis( 3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-hydroxyphenyl)propane , 5-dibromo-4-hydroxyphenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4' - A polycarbonate resin obtained by reacting bisphenols such as dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl oxide, and 9,9-bis(4-hydroxyphenyl)fluorene with a carbonyl compound such as carbonyl chloride;
Styrenic resins such as polystyrene, styrene/methyl methacrylate copolymer, styrene/acrylonitrile copolymer;
(Meth)acrylic ester (co)polymers such as polymethyl methacrylate, polymethyl acrylate, methyl methacrylate/glycidyl methacrylate copolymer, methyl methacrylate/tricyclodecyl methacrylate copolymer;
Ethylene/vinyl acetate copolymer;
Halogen-containing resins such as polyvinyl chloride (vinyl chloride resin), polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, ethylene/tetrafluoroethylene copolymer;
Polyurethane resin;
Aromatic resins such as polyetheretherketone resin, polysulfone resin, polyethersulfone resin, polyarylate resin, polyimide resin, polyetherimide resin;
Examples include polyamide resins such as nylon 6, nylon 66, nylon 11, nylon 12, and nylon 6T.
In the present invention, "(meth)acrylic" means acrylic and/or methacryl, and "(co)polymer" means a homopolymer and/or copolymer.

The above-mentioned thermoplastic resins and alkoxysilyl group-containing thermoplastic resins can be used alone or in combination of two or more. Among these, polyethylene and polypropylene are preferred from the viewpoint of better bonding of the molded body to the adherend. That is, as the alkoxysilyl group-containing thermoplastic resin, alkoxysilyl group-containing polyethylene and alkoxysilyl group-containing polypropylene are preferable.

[Alkoxysilyl group]
Examples of the alkoxysilyl group introduced into the above-mentioned thermoplastic resin include tri(alkoxy)silyl groups having 1 to 6 carbon atoms, such as trimethoxysilyl group and triethoxysilyl group; methyldimethoxysilyl group, methyldiethoxysilyl group, (C1-20 alkyl)di(C1-6 alkoxy)silyl groups such as ethyldimethoxysilyl group, ethyldiethoxysilyl group, propyldimethoxysilyl group, propyldiethoxysilyl group; phenyldimethoxysilyl group, phenyl Examples include (aryl)di(alkoxy having 1 to 6 carbon atoms) silyl groups such as diethoxysilyl groups; Among these, trimethoxysilyl group is particularly preferred from the viewpoint of better bonding of the molded article to the adherend. Further, the alkoxysilyl group may be bonded to the thermoplastic resin via a divalent organic group such as an alkylene group having 1 to 20 carbon atoms or an alkyleneoxycarbonylalkylene group having 2 to 20 carbon atoms.

The amount of alkoxysilyl group introduced into the thermoplastic resin is usually 0.1 parts by mass or more and 10 parts by mass or less, preferably 0.2 parts by mass or more, and more preferably 0. .3 parts by mass or more, preferably 5 parts by mass or less, more preferably 3 parts by mass or less. If the amount of alkoxysilyl groups introduced is below the above upper limit, crosslinking between the alkoxysilyl groups decomposed by trace amounts of moisture will proceed before the alkoxysilyl group-containing thermoplastic resin is melt-molded into the desired shape, resulting in gelation. This makes it less likely that problems such as melting or deterioration of moldability due to decreased fluidity during melting will occur. In addition, if the amount of alkoxysilyl group introduced is equal to or higher than the above lower limit value, the molded product can be bonded particularly well to the adherend.Introduction of alkoxysilyl group can be confirmed by IR spectrum. can do. Further, the amount introduced can be calculated from ¹ H-NMR spectrum.
Further, the method for introducing an alkoxysilyl group into the thermoplastic resin is not particularly limited, and any known method can be used.

From the viewpoint of improving the dimensional stability and mechanical strength of the molded article, the molecular weight of the alkoxysilyl group-containing thermoplastic resin is determined by the weight average molecular weight (Mw ), preferably 10,000 or more, more preferably 15,000 or more, still more preferably 20,000 or more, preferably 250,000 or less, more preferably 200,000 or less, still more preferably 100,000 or less It is.
In addition, the molecular weight distribution (Mw/Mn) is preferably 10.0 or less, more preferably 5.0 or less, and even more preferably 3.0 or less, from the viewpoint of improving the dimensional stability and mechanical strength of the molded article. be.

<Hydrocarbon polymer>
As the hydrocarbon polymer, an olefin polymer or a polymer obtained by hydrogenating an olefin polymer (hydrogenated olefin polymer) can be used. Here, the olefin polymer and the hydrogenated olefin polymer may be used together. In addition, in the present invention, if a certain polymer falls under both "hydrocarbon polymer" and "alkoxysilyl group-containing thermoplastic resin", the polymer is not included in "hydrocarbon polymer". , shall not be included in "alkoxysilyl group-containing thermoplastic resin".

The olefin polymer is not particularly limited as long as it is a polymer in which structural units derived from olefins are linked, and it may be a polymer obtained by artificial polymerization or a natural polymer, A mixture of these may be used.
Here, when an olefin polymer is prepared by artificially polymerizing, the monomer olefin is not particularly limited, and includes isobutene, 1-butene, 4-methylpentene, 1-octene, butadiene, isoprene, etc. chain olefins and various cyclic olefins. These can be used alone or in combination of two or more.
Further, hydrogenation of the olefin polymer is not particularly limited, and can be performed using a known method.

Examples of hydrocarbon polymers include polyisobutylene, polyisobutylene hydride, polybutene, polybutene hydride, poly-4-methylpentene, poly-4-methylpentene hydride, and poly-1-octene. , poly-1-octene hydride, ethylene/α-olefin copolymer, ethylene/α-olefin copolymer hydride, aliphatic hydrocarbon resin, hydride of aliphatic hydrocarbon resin, alicyclic carbonization Examples include hydrogen resins, hydrides of alicyclic hydrocarbon resins, polyisoprene, and hydrides of polyisoprene. These can be used alone or in combination of two or more.
Note that the hydrocarbon polymer may have polar groups such as an alkoxysilyl group, an ester group, a hydroxyl group, an amide group, an amino group, and an acid anhydride group. The hydrocarbon polymer may have one type of these polar groups alone, or may have two or more types of these polar groups.
Further, as the hydrocarbon polymer, a hydrogenated olefin polymer is preferable from the viewpoint of improving the light resistance of the molded article.

<<Properties of hydrocarbon polymer>>
The iodine value of the hydrocarbon polymer is preferably 2.0 g/100 g or less, more preferably 1.0 g/100 g or less, and even more preferably 0.5 g/100 g or less. If the iodine value is below the above upper limit, the light resistance of the molded article will improve.
Note that the "iodine value" is a value (g/100g) expressed in terms of the amount (g number) of iodine that reacts with 100 g of the hydrocarbon polymer. The "iodine value" can be measured by the Wijs method using iodine monochloride in a cyclohexane solution of the hydrocarbon polymer at a concentration of 10% by mass.

The molecular weight of the hydrocarbon polymer needs to be 300 or more and 5000 or less, preferably 350 or more, more preferably 350 or more, as measured by GPC using THF as a solvent. It is 400 or more, more preferably 450 or more, and preferably 4000 or less, more preferably 3000 or less. If the Mn of the hydrocarbon polymer is less than the above lower limit, bubbles are likely to be generated during molding of the resin composition, which is not preferable. Furthermore, if the Mn of the hydrocarbon polymer exceeds the above upper limit, the molded article cannot be bonded well to the adherend.

<<Content of hydrocarbon polymer>>
The content of the hydrocarbon polymer in the resin composition of the present invention needs to be 0.01 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the alkoxysilyl group-containing thermoplastic resin. It is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, even more preferably 3 parts by mass or more, It is particularly preferred that the amount is 5 parts by mass or more. If the content of the hydrocarbon polymer is less than the above lower limit, the molded article cannot be satisfactorily bonded to the adherend. Moreover, when the content of the hydrocarbon polymer exceeds the above upper limit, the dimensional stability of the molded article decreases.

<Other ingredients>
Other components include light stabilizers, ultraviolet absorbers, antioxidants, lubricants, inorganic fillers, and the like. These can be used alone or in combination of two or more. In addition, as these other components, known components, such as those described in International Publication No. 2014/077267, can be used.

<Method for preparing resin composition>
As a method for preparing a resin composition by blending the alkoxysilyl group-containing thermoplastic resin with the above-mentioned hydrocarbon polymer and other optional components, commonly used known methods can be applied.
For example, pellets of alkoxysilyl group-containing thermoplastic resin, hydrocarbon polymer, and other components are mixed evenly using a mixer such as a tumbler, ribbon blender, or Henschel type mixer, and then the mixture is mixed using a twin-screw extruder. A method of melt-mixing and extruding into pellets using a continuous melt kneader such as A resin in which an alkoxysilyl group-containing thermoplastic resin, a hydrocarbon polymer, and other components are uniformly dispersed by melt-kneading, extruding, and pelletizing while continuously adding other components. A composition can be manufactured.

(molded object)
The molded article of the present invention contains a predetermined alkoxysilyl group-containing thermoplastic resin and a predetermined hydrocarbon polymer, and optionally contains other components. Here, the molded article of the present invention needs to contain 0.01 parts by mass or more and 50 parts by mass or less of a hydrocarbon polymer per 100 parts by mass of the alkoxysilyl group-containing thermoplastic resin.
Since the molded article of the present invention contains a predetermined alkoxysilyl group-containing thermoplastic resin and a predetermined hydrocarbon polymer in the above-mentioned quantitative ratio, it can be bonded well to an adherend. , and has excellent dimensional stability.

<Alkoxysilyl group-containing thermoplastic resin, hydrocarbon polymer, and other components>
Here, specific examples, properties, quantitative ratios, etc. of the alkoxysilyl group-containing thermoplastic resin and hydrocarbon polymer contained in the molded article of the present invention, as well as other optionally contained components, are as described above. Since it is the same as the resin composition, the explanation in this section will be omitted.

<Shape of molded object>
The shape of the molded product is not particularly limited, and can be made into any shape such as a sheet shape depending on the desired use.

Here, in the molded article of the present invention, the hydrocarbon polymer may be uniformly dispersed, but it is preferable that it is unevenly distributed on the surface of the molded article. For example, the molded article may include a resin molded article containing an alkoxysilyl group-containing thermoplastic resin and a resin film covering at least a portion of its surface, and the resin film may be a film made of a hydrocarbon polymer. preferable. This is because when the hydrocarbon polymer is unevenly distributed on the surface of the molded article, the molded article can be more effectively bonded to the adherend through the surface where the hydrocarbon polymer is present. .

An example of a molded article in which a hydrocarbon polymer is unevenly distributed on the surface is shown in FIG. The molded body 10 in FIG. 1 is a sheet-shaped molded body, and includes a sheet-shaped resin molded body 20 containing an alkoxysilyl group-containing thermoplastic resin and other optional components, and a resin containing a hydrocarbon polymer. A membrane 30 is provided. In FIG. 1, the resin film 30 is formed on one main surface (the surface having the largest area) 20S of the resin molded body 20. In addition, although the resin film 30 covers the entire main surface 20S of the resin molded body 20 in FIG. 1, it may cover a part of the main surface 20S. The ratio of the resin film to the main surface of the sheet-like resin molded body is not particularly limited, but it is preferably 10% or more, with the area of one main surface (i.e., the area in plan view) being 100%. % or more, still more preferably 50% or more, particularly preferably 70% or more, and most preferably 100%.
In addition, the resin film may contain components other than the hydrocarbon polymer, but the proportion of the hydrocarbon polymer in the resin film is 80% by mass, assuming the mass of the resin film as 100% by mass. % or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and 100% by mass (i.e., the resin film consists only of the hydrocarbon polymer). It is particularly preferable.

In addition, when the molded body is in the form of a sheet, its thickness is not particularly limited, but is preferably 0.02 mm or more, more preferably 0.05 mm or more, still more preferably 0.1 mm or more, and preferably 10 mm or less, More preferably, it is 5 mm or less, and still more preferably 3 mm or less.
The thickness of the sheet-like molded body may be uniform or non-uniform. Further, the sheet-like molded body may have a non-uniform structure such as a concavo-convex pattern, an embossed shape, a step, a groove shape, and a through hole.

<Method for manufacturing molded body>
Here, the method for manufacturing the molded article of the present invention is not particularly limited, but
1) A method for obtaining a molded body using the above-described resin composition of the present invention, and 2) A method for producing a resin molded body by supplying a hydrocarbon polymer to the surface of a resin molded body containing an alkoxysilyl group-containing thermoplastic resin. A method of obtaining a molded body by forming a resin film containing a hydrocarbon polymer on the surface of the molded body can be mentioned.

1) The method of forming a molded article using the resin composition of the present invention is not particularly limited, and any known molding method can be used. Examples of such molding methods include melt extrusion molding, inflation molding, calendar molding, and injection molding. Among these, when the shape of the molded object is a sheet, the melt extrusion method is preferable, and the method of extruding it from a T-die onto the cast roll surface is preferably used because it is relatively economical and allows a high-quality product to be obtained. . Further, conditions during molding (resin temperature, etc.) can be set as appropriate.
As described above, in the molded article obtained by molding the resin composition of the present invention described above, the hydrocarbon polymer is usually in a uniformly dispersed state.

Further, 2) the method of supplying the hydrocarbon polymer to the surface of the resin molded body to form the molded body is not particularly limited, and known supply methods such as coating and dipping can be used. Such supply methods include bar coater method, dipping method, roll coating method, gravure coating method, knife coating method, air knife coating method, roll knife coating method, die coating method, screen printing method, spray coating method, and gravure offset method. Examples include. Among these, the bar coater method is preferably used.
As described above, in a molded product obtained by supplying a hydrocarbon polymer to the surface of a resin molded product to form a resin film, the hydrocarbon polymer is usually unevenly distributed on the surface of the resin molded product. . That is, the molded article includes a resin molded article containing an alkoxysilyl group-containing thermoplastic resin and a resin film containing a hydrocarbon polymer. In addition, in the molded article, a portion of the hydrocarbon polymer may permeate into the resin molded article.

(zygote)
The bonded body of the present invention is formed by bonding the molded body of the present invention described above and a base material as an adherend. Since the joined body of the present invention is formed using the molded body of the present invention, the molded body and the adherend are well bonded, and the joined body has excellent dimensional stability.

<Molded object>
As the molded product, the molded product of the present invention described above can be used.

<Base material>
The base material is not particularly limited, but includes organic base materials and inorganic base materials.

<<Organic base material>>
As the organic base material, base materials made of various resin materials and optionally added other components can be used.

[Resin material]
Here, as the resin material, either a thermoplastic resin or a thermosetting resin can be used.
Examples of the thermoplastic resin include those similar to the thermoplastic resins described above in the section of "alkoxysilyl group-containing thermoplastic resin."
Examples of the thermosetting resin include epoxy resin, urea resin, melamine resin, phenol resin, and unsaturated polyester resin.

These resin materials can be used alone or in combination of two or more.
Among these, polycarbonate resins, polyester resins, and (meth)acrylic acid ester (co)polymers are more preferred from the viewpoint of excellent transparency, mechanical strength, and the like.

When the organic base material has a thermoplastic resin as a main component, the content of the thermoplastic resin in the organic base material is preferably 70% by mass or more, more preferably 80% by mass, based on 100% by mass of the organic base material. The content is more preferably 90% by mass or more.
Further, when the organic base material contains a thermosetting resin, the content of the thermosetting resin in the organic base material is preferably 15% by mass or more, more preferably 20% by mass, with the organic base material being 100% by mass. % or more, more preferably 30% by mass or more.

[Other ingredients]
Other components contained in the organic base material include the light stabilizers, ultraviolet absorbers, antioxidants, lubricants, inorganic fillers, and the like described above in the "resin composition" section. These can be used alone or in combination of two or more.

[Method for manufacturing organic base material]
The method of molding the above-mentioned resin material and optionally added other components to obtain the organic base material is not particularly limited, and the known molding method described above in the section of "molded object" can be used.

[surface treatment]
Here, the organic base material is preferably subjected to at least one surface treatment selected from the group consisting of plasma irradiation, ultraviolet irradiation, corona discharge, and flame spraying. This is because by using an organic base material that has been subjected to at least one of these surface treatments, it is possible to obtain a bonded body in which the organic base material and the molded body are bonded more favorably.

-Plasma irradiation-
Examples of plasma irradiation include normal pressure plasma irradiation, in which plasma irradiation is performed under atmospheric pressure, and reduced pressure plasma irradiation, in which plasma irradiation is performed under reduced pressure. Normal pressure plasma irradiation is preferred from the viewpoint of uniform irradiation more easily.
The normal pressure plasma irradiation is preferably performed under atmospheric pressure in an atmosphere of at least one gas selected from hydrogen, helium, nitrogen, oxygen, and argon. It is more preferable to carry out under a mixed gas atmosphere.
In normal pressure plasma irradiation, the output of plasma irradiation is preferably 0.1 kW or more and 2 kW or less. The irradiation rate of plasma irradiation is preferably 1 cm/min or more and 100 cm/min or less. The distance between the plasma generation source and the organic substrate is preferably 1 mm or more and 20 mm or less.

When plasma irradiation is performed under reduced pressure, it is preferable to perform plasma irradiation using a low pressure gas (such as argon, oxygen, nitrogen, or a mixed gas thereof) of 0.001 kPa or more and 10 kPa or less (absolute pressure).
It is particularly preferable to use a mixed gas of nitrogen and oxygen as the low pressure gas. The mixing ratio of nitrogen and oxygen is preferably 10:1 to 1:10 by volume. In the reduced pressure plasma irradiation, the output of the plasma irradiation is preferably 50 W or more and 500 W or less.

-Ultraviolet irradiation-
The ultraviolet irradiation is preferably performed using an excimer ultraviolet lamp while flowing a mixed gas of nitrogen and dry air or oxygen. The oxygen concentration of the mixed gas is preferably 0.01 volume % or more and 15 volume % or less, more preferably 0.05 volume % or more and 5 volume % or less.
The distance between the excimer ultraviolet lamp and the irradiated surface of the organic base material is preferably 10 mm or less, more preferably 1 mm or more and 5 mm or less.
The intensity of irradiation (illuminance) is preferably 5 mW/cm ² or more and 200 mW/cm ² or less, more preferably 30 mW/cm ² or more and 150 mW/cm ² or less.

-Corona discharge-
Corona discharge is preferably performed in a dry air atmosphere.
The output of the corona discharge is preferably 50 W or more and 1000 W or less, and the amount of discharge current is preferably 20 W/min/m ² or more and 550 W/min/m ² or less. The distance between the electrode and the organic base material is preferably 1 mm or more and 20 mm or less.

-Flame spray-
Flame spraying is performed by spraying a flame of fuel gas onto the surface of the organic base material. The temperature of the flame is preferably 500°C or more and 1,500°C or less, more preferably 550°C or more and 1,200°C or less, and still more preferably 600°C or more and 900°C or less. The temperature of the flame can be adjusted as appropriate depending on the type of fuel gas used and the flow rates of the fuel gas and air.
The flame treatment time is preferably 0.1 seconds or more and 100 seconds or less, more preferably 0.3 seconds or more and 30 seconds or less, and still more preferably 0.5 seconds or more and 20 seconds or less.

The above-mentioned surface treatments can be carried out singly or in combination of two or more. Among these surface treatments, plasma irradiation, corona discharge, and flame spraying are preferable from the viewpoint of stably producing a bonded body in which the molded body and the organic base material are more strongly bonded, and plasma irradiation and corona discharge are preferred. More preferred.

<<Inorganic base material>>
As the inorganic base material, base materials made of various inorganic materials can be used. Here, examples of inorganic materials include glass, copper, iron, stainless steel, aluminum, gold, silver, and platinum. These can be used alone or in combination of two or more.

<Shape of base material>
Here, the shape of the base material is not particularly limited, and can be made into any shape such as a sheet shape or a plate shape depending on the desired use.

In addition, when the base material is sheet-like or plate-like, its thickness is not particularly limited, but is preferably 0.02 mm or more, more preferably 0.05 mm or more, still more preferably 0.1 mm or more, and preferably It is 10 mm or less, more preferably 5 mm or less, even more preferably 3 mm or less.
The thickness of the sheet-like or plate-like base material may be uniform or non-uniform. Further, the sheet-like or plate-like base material may have a non-uniform structure such as a concavo-convex pattern, an embossed shape, a step, a groove shape, and a through hole.

<Properties of zygote>
Here, the adhesive strength between the molded body and the base material is not particularly limited, but is preferably 4 N/cm or more, more preferably 6 N/cm or more, still more preferably 8 N/cm or more, particularly preferably 10 N/cm or more. . If the adhesive strength is 4 N/cm or more, it can be said that the molded article and the base material are sufficiently firmly bonded, and they will not peel off easily. Adhesive strength can be measured by the method of JIS 6854-3:1999 described in Examples.
Note that the upper limit of the adhesive strength between the molded body and the base material is not particularly limited, but is, for example, 30 N/cm or less.
In addition, in a bonded body obtained by adhering a molded body on which a resin film containing a hydrocarbon polymer is formed on the surface and a base material, the hydrocarbon polymer is removed from the molded body and/or the base material over time. It may permeate into the base material (particularly an organic base material) and be dispersed in the molded article and/or the base material.

The structure of the joined body of the present invention is not particularly limited as long as it includes at least one molded body of the present invention and at least one base material. That is, the joined body of the present invention may have a plurality of molded bodies and a plurality of base materials, for example, a two-member joined body (two-layer joined body) consisting of a molded body/base material; a molded body/base material; A three-member assembly (three-layer assembly) consisting of a material/molded body, base material/molded body/substrate, etc.; a four-member assembly (four-layer assembly) consisting of a composition of a molded body/substrate/molded body/substrate, etc. layer assembly); 5-member assembly (5-layer assembly) consisting of a molded body/substrate/molded body/base material/molded body, base material/molded body/base material/molded body/substrate, etc. It can take a structure.
Further, the joined body of the present invention may have a hard coat layer, a metal plated portion, and the like.

In addition, when the joined body of the present invention is used as a laminated glass, the two or more glass plates used may be the same or different in thickness, material, etc. The thickness of the glass plate used is not particularly limited, but is preferably 0.05 mm or more and 10 mm or less. In addition, for example, a combination with excellent penetration resistance, such as a five-layer structure such as glass plate / sheet-shaped molded body / sheet-shaped organic base material made of polycarbonate resin / sheet-shaped molded body / glass plate. Glass (each thickness is, for example, 1 mm (glass plate) / 0.8 mm (molded body) / 2 mm (organic base material) / 0.8 mm (molded body) / 1 mm (glass plate)) etc. .

(Method for manufacturing joined body)
Here, the method for obtaining the zygote of the present invention described above is not particularly limited. For example, the above-mentioned zygote can be manufactured using the zygote manufacturing method of the present invention.
The method for manufacturing a bonded body of the present invention is a method for manufacturing a bonded body by bonding a resin molded body containing a predetermined alkoxysilyl group-containing thermoplastic resin and a base material.
The method for manufacturing a bond of the present invention includes:
Supplying a predetermined hydrocarbon polymer onto the surface of at least one of the resin molding and the base material from 0.01 parts by mass to 50 parts by mass per 100 parts by mass of the alkoxysilyl group-containing thermoplastic resin contained in the resin molding. and a step of forming a resin film containing a hydrocarbon polymer (resin film forming step);
A step of adhering the resin molded body and the base material via a resin film (adhesion step);
Contains at least
After the above-mentioned process, a resin molded article containing an alkoxysilyl group-containing thermoplastic resin can be attached to a base material as an adherend (especially under low temperature conditions) via a resin film containing a hydrocarbon polymer. By adhering well, it is possible to obtain a joined body having excellent dimensional stability and in which the molded body and the base material are well joined.

<Resin film formation process>
In the resin film forming step, a resin film containing a hydrocarbon polymer is formed on at least one surface of a resin molded body containing an alkoxysilyl group-containing thermoplastic resin and a base material.

<<Resin molded body>>
As the resin molding, a resin molding obtained by molding a composition containing an alkoxysilyl group-containing thermoplastic resin and optionally other components can be used.
Here, the alkoxysilyl group-containing thermoplastic resin, other ingredients, molding method, etc. used for molding the resin molding are the same as those described above in the sections of "resin composition" and "molding". Can be used.

<<Base material>>
As the base material, the same materials as those mentioned above in the section of "joint body" can be used.

<<Resin film>>
The hydrocarbon polymer used to form the resin film and the method of supplying the hydrocarbon polymer to the surface of the resin molded product are the same as those described above in the "resin composition" and "molded product" sections. .
In the method for producing a bonded body of the present invention, the amount of the hydrocarbon polymer supplied is 0.01 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the alkoxysilyl group-containing thermoplastic resin contained in the resin molded article. The amount is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, and 3 parts by mass or more. It is even more preferable that the amount is 5 parts by mass or more. If the amount of the hydrocarbon polymer supplied is less than the above lower limit, the molded article cannot be satisfactorily bonded to the base material. Moreover, when the amount of the hydrocarbon polymer supplied exceeds the above upper limit, the dimensional stability of the molded body and the joined body decreases.
In addition, "amount of hydrocarbon polymer supplied" means the total amount when the hydrocarbon polymer is supplied to the surfaces of both the resin molded article and the base material.

<Adhesion process>
In the bonding step, the resin molded body and the base material are bonded via a resin film containing a hydrocarbon polymer supplied to at least one surface of the resin molded body and the base material. Here, as a method for bonding, heat compression bonding is preferable.
There are no particular limitations on the method of heat-press bonding, and for example, the resin molded body and the base material are laminated with a resin film interposed therebetween, and the resulting laminate is placed in a flexible bag (hereinafter referred to as a "bag"). ), and heat and press the bonded product while deaerating the air inside the bag; place the laminate obtained in the same manner as above in a bag, and deaerating the air inside the bag. After that, in an autoclave, the laminate is heat-pressed and bonded together to form a bonded body; The laminate obtained in the same manner as above is heated and pressure-bonded using a heat press device to form a bonded body; In the same manner as above. A method of heat-pressing the obtained laminate using a pressure machine such as a vacuum laminator, vacuum press, or roll laminator can be used.
In addition, the adhesion in the adhesion step is preferably performed within 24 hours, more preferably within 18 hours, even more preferably within 12 hours, particularly preferably within 1 hour from the time of forming the resin film (from the end of the resin film forming step). (In other words, preferably within 24 hours, more preferably within 18 hours, even more preferably within 12 hours, particularly preferably within 1 hour, from the time of forming the resin film, the resin molded body and the base material are contact through the membrane).

The temperature (bonding temperature) at which the resin molded body and the base material are bonded via the resin film is preferably lower than the Vicat softening temperature of the alkoxysilyl group-containing thermoplastic resin contained in the resin molded body. By performing adhesion at a temperature lower than the Vicat softening temperature of the alkoxysilyl group-containing thermoplastic resin, deformation due to heat can be suppressed.
Specifically, the bonding temperature is preferably 40°C or higher, more preferably 50°C or higher, preferably 110°C or lower, and more preferably 100°C or lower. If the bonding temperature is at least the above lower limit, sufficient adhesive strength can be obtained, and if it is at or below the above upper limit, it is possible to sufficiently prevent defects such as bubbles while suppressing thermal deformation.
Note that the Vicat softening temperature can be measured based on the JIS K7206A method. The Vicat softening temperature was measured by applying a test load of 10N to a plastic test piece, raising the temperature of the heat transfer medium at a heating rate of 50°C/hour, and measuring the temperature when the needle indenter penetrated 1 mm from the surface of the test piece. This is done by measuring the temperature of the heat transfer medium. As the measuring device, for example, an HDT (heat distortion tester) device manufactured by Toyo Seiki can be used.

The pressure (thermocompression bonding pressure) when performing thermocompression bonding in an autoclave is preferably 0.1 MPa or more and 1.5 MPa or less, more preferably 0.2 MPa or more and 1.2 MPa or less, and even more preferably 0.3 MPa or more and 1.0 MPa or less. It is as follows. If the heating pressure is equal to or higher than the above lower limit, sufficient adhesive strength can be obtained, and if it is equal to or lower than the above upper limit, it is possible to sufficiently prevent defects such as bubbles while suppressing thermal deformation.
The pressure (thermocompression bonding pressure) when performing heat compression bonding using a heat press device is preferably 0.1 MPa or more and 10 MPa or less, more preferably 0.2 MPa or more and 5 MPa or less, and even more preferably 0.3 MPa or more and 2 MPa or less. be. If the heating pressure is equal to or higher than the above lower limit, sufficient adhesive strength can be obtained, and if it is equal to or lower than the above upper limit, it is possible to sufficiently prevent defects such as bubbles while suppressing thermal deformation.
From the viewpoint of maintaining sufficient productivity, the time for heat-compression bonding in an autoclave (heat-compression bonding time) is preferably 10 minutes or more and 60 minutes or less, more preferably 15 minutes or more and 50 minutes or less, and even more preferably 20 minutes or more. The duration is at least 40 minutes.
From the viewpoint of maintaining sufficient productivity, the time for heat-compression bonding using a heat press device is preferably 0.2 minutes or more and 15 minutes or less, more preferably 0.4 minutes or more. It is 10 minutes or less, more preferably 0.5 minutes or more and 5 minutes or less.

<Other processes>
The method for manufacturing a bonded body of the present invention may include steps other than the resin film forming step and bonding step described above. Other steps include, for example, a step of subjecting the surface of the organic base material to the surface treatment described above in the "Substrate" section.

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the following Examples. Note that "parts" and "%" are based on mass unless otherwise specified.

Evaluation in this example was performed by the following method.
(1) Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn)
The molecular weights of the alkoxysilyl group-containing thermoplastic resin and hydrocarbon polymer were measured at 38° C. as standard polystyrene equivalent values by GPC using THF as an eluent. As a measuring device, HLC8320GPC manufactured by Tosoh Corporation was used.
(2) Adhesive strength A test piece with a length of 200 mm and a width of 25 mm was taken from the obtained bonded body. JIS K6854-3:1999 (Adhesives - Peel adhesion strength test method - Part 3: The molded body and the base material were peeled off at a peeling speed of 100 mm/min using an Autograph (manufactured by Shimadzu Corporation, product name "AGS-X") according to the peel strength (T-shaped peeling). Adhesive strength) was measured.
(3) Dimensional stability Molded bodies (Examples 1 to 10: Resin molded bodies coated with hydrocarbon polymer, Comparative Examples 1 to 3: Resin molded bodies not coated with hydrocarbon polymer), It was sandwiched between two sheets of white glass with a thickness of 3.2 mm, a width of 200 mm, and a length of 200 mm, heated and degassed under reduced pressure at 130°C in a vacuum press machine, and then heated and pressed for 10 minutes to bond them together to form a laminated glass. A test piece was prepared. Using this laminated glass test piece, it was stored in an oven at 90°C for 168 hours using a stand to hold only one glass plate and stand it vertically without holding the other glass plate. The laminated glass test piece was visually observed to evaluate the positional shift due to thermal deformation of the molded body.
Dimensional stability was evaluated as "good" when no positional shift was observed, and "poor" when positional shift was observed.
(4) Light resistance Molded bodies (Examples 1 to 10: Resin molded bodies coated with a hydrocarbon polymer, Comparative Examples 1 to 3: Resin molded bodies not coated with a hydrocarbon polymer) were used. A dumbbell-shaped No. 3 test piece as described in JIS K-6251 was prepared. Using a xenon weather meter, the test piece was set up so that the test piece was irradiated with light through a 3.2 mm thick white glass plate, the black panel temperature was 83°C, the irradiance was 60 W/m ² , and the temperature was 700°C without water exposure. Irradiation was carried out for a certain period of time, and the retention of tensile strength and elongation after irradiation was measured compared to before irradiation.
The light resistance is "good" if the tensile strength after irradiation is 80% or more of the tensile strength before irradiation, and the elongation after irradiation is 80% or more of the elongation before irradiation, and at least one of these two A case where the ratio was less than 80% was evaluated as "poor".

(Example 1)
<Preparation of resin molded body>
An ultraviolet absorber is added to 100 parts of pellets of alkoxysilyl group-containing polyethylene (manufactured by Mitsubishi Chemical Corporation, product name "Linkron (registered trademark) SS732N", Vicat softening temperature 95°C) as an alkoxysilyl group-containing thermoplastic resin. 0.2 part of certain 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (Tinuvin® 329, manufactured by BASF Japan) was added. and mixed evenly. The resulting mixture was passed through a film forming machine (1) consisting of a single-screw extruder equipped with a 20 mm diameter screw, a T-die (width 300 mm), and a sheet take-up machine equipped with a cast roll (width 300 mm) having a satin embossed pattern. A sheet-like resin molded product (thickness 0.40 mm, A width of 230 mm) was produced. The resin molded body was wound up into a roll and collected.

<Preparation of organic base material>
A sheet-like test piece measuring 300 mm long x 200 mm wide was prepared from a polycarbonate resin sheet (manufactured by Teijin Kasei Co., Ltd., product name "Panlite (registered trademark) sheet", PC-2151, thickness 0.5 mm). One side of the test piece was surface treated by corona discharge using a corona surface treatment device (manufactured by Wedge Co., Ltd., product name "A3SW-LW") (output 60W, distance between electrode and sheet 10mm, processing speed 1m/min). ) to prepare an organic substrate made of surface-treated polycarbonate resin.

<Resin film formation process>
Liquid paraffin as a hydrocarbon polymer (product name: Hykol (registered trademark) K350, manufactured by Kaneda Corporation, Mn700, A hydride (iodine value: 0.2, hydride) was applied thereto, and a sheet of 300 mm in length x 200 mm in width was cut out to obtain a molded product. The amount of liquid paraffin applied was 0.9 parts per 100 parts of the alkoxysilyl group-containing thermoplastic resin in the resin molding. The obtained molded body (resin molded body coated with a hydrocarbon polymer) was used to evaluate dimensional stability and light resistance. The results are shown in Table 1.

<Adhesion process>
Within 1 hour from the end of the resin film forming process, the above-mentioned organic base material and the above-mentioned resin molded body coated with a hydrocarbon polymer are bonded to the surface treated surface of the organic base material and the carbonized resin molded body. The laminates were stacked so that the hydrogen-based polymer coated surfaces faced each other to form a laminate. At this time, a release film was sandwiched between 50 mm of the longitudinal ends.
This laminate was placed in a 75 μm thick resin bag having a layered structure of NY (nylon)/adhesive layer/PP (polypropylene). After heat-sealing both sides with a heat sealer, leaving a 200 mm width at the center of the opening of the bag, use a sealing packer (manufactured by Panasonic, product name "BH-951") to degas the inside of the bag. The opening was heat sealed and the laminate was hermetically packaged. Thereafter, the hermetically packaged laminate was placed in an autoclave and heat-pressed at a temperature of 55° C. and a pressure of 0.8 MPa for 30 minutes to produce a bonded body. Adhesive strength was evaluated using the obtained bonded body. The results are shown in Table 1.

(Examples 2 to 4)
The amount of liquid paraffin applied was changed to 0.1 parts (Example 2), 5 parts (Example 3), and 20 parts (Example 4) per 100 parts of the alkoxysilyl group-containing thermoplastic resin in the resin molding. A joined body was manufactured in the same manner as in Example 1 except for the above, and various evaluations were performed. The results are shown in Table 1.

(Example 5)
As the alkoxysilyl group-containing thermoplastic resin, alkoxysilyl group-containing polypropylene (manufactured by Mitsubishi Chemical Corporation, product name "Linkron PK500N", Vicat softening temperature 135°C) was used instead of alkoxysilyl group-containing polyethylene, and liquid paraffin was applied. A bonded body was produced in the same manner as in Example 1, except that the amount was 50 parts per 100 parts of the alkoxysilyl group-containing thermoplastic resin in the resin molded body, and the temperature during thermocompression bonding was 65°C. I did it. The results are shown in Table 1.

(Example 6)
Bonding was carried out in the same manner as in Example 1, except that an inorganic base material made of copper (300 mm long x 200 mm wide x 0.1 mm thick) was used instead of an organic base material made of surface-treated polycarbonate resin. A body was manufactured and various evaluations were conducted. The results are shown in Table 1.

(Example 7)
Instead of the polycarbonate resin sheet, a polyethylene terephthalate sheet (manufactured by Toray Industries, product name "Lumirror (registered trademark) S-10", length 300 mm x width 200 mm x thickness 0.25 mm) was prepared in the same manner as in Example 1. A bonded body was produced in the same manner as in Example 1, except that an organic base material made of surface-treated polyethylene terephthalate was used, and various evaluations were performed. The results are shown in Table 1.

(Example 8)
As the alkoxysilyl group-containing thermoplastic resin, alkoxysilyl group-containing polypropylene (manufactured by Mitsubishi Chemical Corporation, product name "Linklon PK500N", Vicat softening temperature 135°C) was used instead of alkoxysilyl group-containing polyethylene, and the temperature during heat compression bonding was A joined body was manufactured in the same manner as in Example 1 except that the temperature was 65° C., and various evaluations were performed. The results are shown in Table 2.

(Example 9)
The same procedure as in Example 1 was used, except that hydrogenated polybutene (manufactured by NOF Corporation, product name "NOF Polybutene 10SH", Mn 1500, iodine value 0.2) was used as the hydrocarbon polymer instead of liquid paraffin. A joined body was manufactured using the same method, and various evaluations were performed. The results are shown in Table 2.

(Example 10)
Bonding was carried out in the same manner as in Example 1, except that polybutene (manufactured by NOF Corporation, product name "NOF Polybutene 10N", Mn 1000, iodine value 17.7) was used as the hydrocarbon polymer instead of liquid paraffin. A body was manufactured and various evaluations were conducted. The results are shown in Table 2.

(Comparative example 1)
A bonded body was manufactured in the same manner as in Example 1, except that the resin film forming step was not performed (that is, a resin molded body to which no hydrocarbon polymer was applied in the adhesion process was used), and various evaluations were conducted. I did it. The results are shown in Table 2.

(Comparative example 2)
Using a resin molded article prepared as follows, an inorganic base material made of glass (300 mm long x 200 mm wide x 0.5 mm thick) was used instead of an organic base material made of surface-treated polycarbonate resin. Example 1 except that the resin film forming step was not carried out (that is, a resin molded body to which no hydrocarbon polymer was applied in the adhesion step was used), and the temperature during thermocompression bonding was 65°C. A joined body was manufactured in the same manner as in Example 1, and various evaluations were performed. The results are shown in Table 2.
<Preparation of resin molded body>
The ultraviolet absorber 2-(2H- 0.2 part of benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (Tinuvin® 329, manufactured by BASF Japan) was evenly mixed. The resulting mixture was passed through a film forming machine (1) consisting of a single-screw extruder equipped with a 20 mm diameter screw, a T-die (width 300 mm), and a sheet take-up machine equipped with a cast roll (width 300 mm) having a satin embossed pattern. Using liquid paraffin as a hydrocarbon polymer (product name: "Hycor K350", manufactured by Kaneda Corporation, Mn 700, iodine value 0.2) using a liquid addition pump A sheet-like resin molded body (thickness: 0.40 mm, width: 230 mm) was produced under the following molding conditions: molten resin temperature of 160°C, T-die temperature of 160°C, and cast roll temperature of 60°C while adding 55 parts of hydride). did. The resin molded body was wound up into a roll and collected.

(Comparative example 3)
Comparative Example 2 was carried out in the same manner as in Comparative Example 2, except that hydrogenated polybutene (manufactured by NOF Corporation, product name "NOF Polybutene 10SH", Mn 1500, iodine value 0.2) was used as the hydrocarbon polymer instead of liquid paraffin. A joined body was manufactured using the same method, and various evaluations were performed. The results are shown in Table 2.

In addition, in Tables 1 and 2 shown below,
"Si-PE" indicates polyethylene containing alkoxysilyl groups,
"Si-PP" indicates alkoxysilyl group-containing polypropylene,
"PC" indicates polycarbonate resin,
"PET" indicates polyethylene terephthalate,
"Cu" indicates copper,
"Amount used [parts by mass]" indicates "amount used [parts by mass] per 100 parts by mass of the alkoxysilyl group-containing thermoplastic resin."

From Tables 1 and 2, it can be seen that in Examples 1 to 10, in which the resin molding containing the alkoxysilyl group-containing thermoplastic resin and the base material were bonded using a predetermined hydrocarbon polymer in an amount within a predetermined range, It can be seen that a joined body with excellent strength and dimensional stability was obtained.
On the other hand, it can be seen that in Comparative Example 1, in which adhesion was performed without using a predetermined hydrocarbon polymer, the adhesive strength decreased. Furthermore, it can be seen that in Comparative Examples 2 and 3, in which the amount of the predetermined hydrocarbon polymer used exceeds the predetermined upper limit, the dimensional stability decreases. Furthermore, it can be seen that in Comparative Examples 2 and 3, the adhesive strength decreases.

According to the present invention, it is possible to provide a resin composition that can adhere well to an adherend and form a molded article with excellent dimensional stability.
Further, according to the present invention, it is possible to provide a molded article that can be well adhered to an adherend and has excellent dimensional stability.
According to the present invention, it is possible to provide a bonded body that includes a molded body having excellent dimensional stability and in which the molded body is well bonded to a base material as an adherend.

10 Molded body 20 Resin molded body 20S Main surface 30 Resin film

Claims (10)

A molded article containing a resin having an alkoxysilyl group and a hydrocarbon polymer,
The molded body includes a resin molded body containing the resin having the alkoxysilyl group, and a resin film that covers at least a part of the surface of the resin molded body and contains the hydrocarbon polymer,
The resin having an alkoxysilyl group is a resin in which an alkoxysilyl group is introduced into a thermoplastic resin other than an aromatic vinyl compound-chain conjugated diene compound block copolymer,
The hydrocarbon polymer is at least one of an olefin polymer and a hydrogenated olefin polymer, and has a number average molecular weight of 300 to 5000, and
A molded product, wherein the content of the hydrocarbon polymer in the molded product is 0.01 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the alkoxysilyl group-containing resin in the molded product. The molded article according to claim 1 , wherein the resin having an alkoxysilyl group is at least one of an alkoxysilyl group-containing polyethylene and an alkoxysilyl group-containing polypropylene. The molded article according to claim 1 or 2 , wherein the hydrocarbon polymer has an iodine value of 2.0 g/100 g or less. A joined body formed by joining the molded article according to any one of claims 1 to 3 and a base material. The joined body according to claim 4 , wherein the adhesive strength between the molded body and the base material is 4 N/cm or more. A method of manufacturing a bonded body by bonding a resin molded body containing a resin having an alkoxysilyl group and a base material, the method comprising:
The resin having an alkoxysilyl group is a resin in which an alkoxysilyl group is introduced into a thermoplastic resin other than an aromatic vinyl compound-chain conjugated diene compound block copolymer,
A hydrocarbon polymer, which is at least one of an olefin polymer and a hydrogenated olefin polymer and has a number average molecular weight of 300 to 5000, is applied to the surface of at least one of the resin molded body and the base material, and the alkoxysilyl supplying 0.01 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin having the group to form a resin film containing the hydrocarbon polymer;
A method for manufacturing a bonded body, including a step of bonding the resin molded body and the base material via the resin film. 7. The method for producing a bonded body according to claim 6 , wherein the resin having an alkoxysilyl group is at least one of an alkoxysilyl group-containing polyethylene and an alkoxysilyl group-containing polypropylene. 8. The method for producing a zygote according to claim 6 , wherein the hydrocarbon polymer has an iodine value of 2.0 g/100 g or less. the base material is an organic base material,
Any one of claims 6 to 8 , wherein the adhesive surface of the organic base material with the resin molding is subjected to at least one surface treatment selected from the group consisting of plasma irradiation, ultraviolet irradiation, corona discharge, and flame spraying. A method for producing a zygote according to claim 1. The method for producing a bonded body according to any one of claims 6 to 9 , wherein the bonding temperature in the bonding is lower than the Vicat softening temperature of the alkoxysilyl group-containing resin.

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