JP7351145B2 - 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.

Structural units derived from aromatic vinyl compounds have traditionally been used to produce packaging for pharmaceuticals and foods, encapsulants for solar cell modules, encapsulants for organic EL elements, encapsulants for electronic components, and laminated glass interlayer films. A polymer (block copolymer) obtained by hydrogenating a block copolymer having a polymer block mainly composed of copolymer hydrides) are used.

Such a hydrogenated block copolymer is usually used for the above-mentioned purposes by mixing it with other components and molding the resulting resin composition into a molded article having a desired shape.
For example, in Patent Document 1, 1 to 50 parts by weight of a hydrocarbon polymer having a number average molecular weight of 300 to 5000 is blended to 100 parts by weight of a predetermined hydrogenated block copolymer into which an alkoxysilyl group has been introduced. A resin composition has been proposed. According to Patent Document 1, a molded article obtained from the resin composition can be bonded well to a base material (adherend) made of a material such as glass or metal.

International Publication No. 2014/077267

However, as a result of study by the present inventor, the resin composition of Patent Document 1 has room for further improvement in terms of suppressing thermal deformation of molded objects (i.e., improving dimensional stability). there were.

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.

As a result of intensive studies to achieve the above object, the present inventors have found that when producing a bonded body by bonding a molded article containing a predetermined block copolymer hydride to a base material as an adherend, It was discovered that by using a predetermined amount of a hydrocarbon polymer having the following properties, it is possible to improve the dimensional stability of the molded body while bonding the molded body well to the adherend, and completed the present invention. reached.

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 hydrogenated block copolymer and a hydrocarbon polymer. The block copolymer hydride is composed of at least two polymer blocks [A] mainly composed of a structural unit [a] derived from an aromatic vinyl compound, and a structural unit [b] derived from a linear conjugated diene compound. ] A block copolymer having at least one polymer block [B] as a main component, wherein the structural unit [a] derived from the aromatic vinyl compound accounts for the mass proportion of the entire block copolymer. The ratio of wa to wb (wa:wb) is 30: 70 to 65:35, in which 90% or more of the carbon-carbon unsaturated bonds derived from the structural unit [b] are hydrogenated, and the hydrocarbon polymer is an olefin at least one of a polymer and a hydrogenated olefin polymer, and has a number average molecular weight of 300 to 5,000, and the content of the hydrocarbon polymer in the resin composition is It is characterized in that the amount is 0.01 part by mass or more and less than 1 part by mass per 100 parts by mass of the block copolymer hydride. In this way, by using a resin composition containing a block copolymer hydride and a hydrocarbon polymer in the above-mentioned quantitative ratio, it is possible to form a molded material that can be bonded well to an adherend and has excellent dimensional stability. You can get a body.

Here, in the resin composition of the present invention, it is preferable that the hydrogenated block copolymer has an alkoxysilyl group. By using a hydrogenated block copolymer having an alkoxysilyl group, 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.

Furthermore, the present invention aims to advantageously solve the above-mentioned problems, and the molded article of the present invention is a molded article containing a hydrogenated block copolymer and a hydrocarbon polymer, The block copolymer hydride comprises at least two polymer blocks [A] each containing a structural unit [a] derived from an aromatic vinyl compound as a main component, and a structural unit [b] derived from a chain conjugated diene compound. A block copolymer having at least one polymer block [B] as a main component, wherein the structural unit [a] derived from the aromatic vinyl compound accounts for a mass fraction in the entire block copolymer. wa, when the mass fraction of the structural unit [b] derived from the linear conjugated diene compound in the entire block copolymer is defined as wb, the ratio of wa and wb (wa:wb) is 30:70 to 65:35, in which 90% or more of the carbon-carbon unsaturated bonds derived from the structural unit [b] are hydrogenated, and the hydrocarbon polymer is an olefin polymer. and at least one of a hydrogenated olefin polymer, and has a number average molecular weight of 300 or more and 5000 or less, and the content of the hydrocarbon polymer in the molded article is at least one of the block copolymer in the molded article. The amount is 0.01 part by mass or more and less than 1 part by mass per 100 parts by mass of the combined hydride. As described above, a molded article containing a hydrogenated block copolymer and a hydrocarbon polymer in the above-described 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 block copolymer hydride, 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 a hydrogenated block copolymer can be more favorably bonded to an adherend via the resin film.

In the molded article of the present invention, the hydrogenated block copolymer preferably has an alkoxysilyl group. By using a hydrogenated block copolymer having an alkoxysilyl group, 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 producing a zygote of the present invention provides at least A block copolymer having two polymer blocks [A] and at least one polymer block [B] mainly composed of a structural unit [b] derived from a linear conjugated diene compound, the block copolymer having the aromatic The mass fraction of the structural unit [a] derived from the group vinyl compound in the entire block copolymer is wa, and the mass fraction of the structural unit [b] derived from the chain conjugated diene compound in the entire block copolymer is wa. 90 of the carbon-carbon unsaturated bonds derived from the structural unit [b] of the block copolymer in which the ratio of wa and wb (wa:wb) is 30:70 to 65:35, where wb is % or more of hydrogenated block copolymer and a base material, the method comprises: bonding a resin molded body containing a block copolymer hydride obtained by hydrogenating % or more of the hydrogenated block copolymer to a base material to produce a bonded body, the surface of at least one of the resin molded body and the base material 0.01 part by mass of 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 per 100 parts by mass of the block copolymer hydrogenation. The method further comprises: supplying less than 1 part by mass to form a resin film containing the hydrocarbon polymer; and bonding the resin molded body and the base material via the resin film. do. Through such a process, the resin molding containing the block copolymer hydride and the base material can be bonded well (especially under low temperature conditions) through the resin film containing the hydrocarbon polymer. Thus, 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 conjugate of the present invention, it is preferable that the hydrogenated block copolymer has an alkoxysilyl group. By using a hydrogenated block copolymer having an alkoxysilyl group, it is possible to obtain a bonded body in which the molded body 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.

Furthermore, in the method for producing a joined body of the present invention, it is preferable that the adhesion temperature in the adhesion is lower than the glass transition temperature of the block copolymer hydride. According to the production method of the present invention, even if adhesion is performed below the glass transition temperature of the block copolymer hydride, it is possible to obtain a bonded body in which the molded body and the adherend are well bonded, Further, by performing the adhesion at a temperature below the glass transition temperature of the hydrogenated block copolymer, 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 hydrogenated block copolymer, a predetermined hydrocarbon polymer, and optionally other components. Here, the resin composition of the present invention needs to contain 0.01 parts by mass or more and less than 1 part by mass of the hydrocarbon polymer per 100 parts by mass of the hydrogenated block copolymer.
Since the resin composition of the present invention contains the predetermined hydrogenated block copolymer and the predetermined hydrocarbon polymer in the above-mentioned quantitative ratio, the resin composition of the present invention can be used to improve adhesion. It is possible to form a molded article that can be bonded well to the body and has excellent dimensional stability.

<Block copolymer hydride>
A hydrogenated block copolymer is a polymer obtained by hydrogenating a predetermined block copolymer.

<<Block copolymer>>
The block copolymer is a precursor of a hydrogenated block copolymer, and is composed of at least two polymer blocks [A] mainly composed of a structural unit [a] derived from an aromatic vinyl compound, and a chain conjugated diene. It is a polymer containing at least one polymer block [B] whose main component is a structural unit [b] derived from a compound.

-Polymer block [A]-
Here, the polymer block [A] is a polymer block whose main component is a structural unit [a] derived from an aromatic vinyl compound. The content of the aromatic vinyl compound-derived structural unit [a] in the polymer block [A] is usually 50% by mass or more, preferably 90% by mass or more, more preferably 95% by mass or more, particularly preferably 99% by mass or more. % by mass or more. The polymer block [A] may contain components other than the structural unit [a] derived from an aromatic vinyl compound. Other components include structural units derived from chain conjugated diene compounds and/or structural units derived from other vinyl compounds. Its content is usually 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, based on the polymer block [A].
If the content of the structural unit [a] derived from the aromatic vinyl compound in the polymer block [A] is too small, the dimensional stability of the molded article may decrease.
The plurality of polymer blocks [A] contained in the block copolymer may be the same or different from each other as long as they satisfy the above range. For example, the composition and/or block length of each structural unit of the plurality of polymer blocks [A] may be the same or different.

-Polymer block [B]-
The polymer block [B] is a polymer block whose main component is a structural unit [b] derived from a chain conjugated diene compound. The content of the structural unit [b] derived from the linear conjugated diene compound in the polymer block [B] is usually 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably It is 90% by mass or more. The polymer block [B] may contain components other than the structural unit [b] derived from the chain conjugated diene compound. Other components include structural units derived from aromatic vinyl compounds and/or structural units derived from other vinyl compounds. Its content is usually 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less, based on the polymer block [B].
It is preferable that the content of the structural unit [b] derived from the chain conjugated diene compound in the polymer block [B] is within the above range because flexibility is imparted to the molded article.
When the block copolymer has a plurality of polymer blocks [B], the polymer blocks [B] may be the same or different from each other. For example, the composition and/or block length of each structural unit of the plurality of polymer blocks [B] may be the same or different.

Aromatic vinyl compounds include styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, Styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, such as 5-t-butyl-2-methylstyrene; halogen atoms as a substituent, such as 4-chlorostyrene, dichlorostyrene, 4-monofluorostyrene, etc. Styrenes having an alkoxy group having 1 to 6 carbon atoms as a substituent, such as 4-methoxystyrene; Styrenes having an aryl group as a substituent, such as 4-phenylstyrene. Among these, from the viewpoint of hygroscopicity, aromatic vinyl compounds that do not contain polar groups, such as styrene and styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, are preferable, and from the viewpoint of easy industrial availability. , styrene is particularly preferred.

Examples of chain conjugated diene compounds (linear conjugated diene compounds, branched conjugated diene compounds) include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, etc. From the viewpoint of hygroscopicity, linear conjugated diene compounds containing no polar group are preferred, and 1,3-butadiene and isoprene are particularly preferred from the viewpoint of industrial availability.

Other vinyl compounds include chain vinyl compounds, cyclic vinyl compounds, unsaturated cyclic acid anhydrides, unsaturated imide compounds, and the like. These compounds may have a substituent such as a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group, or a halogen atom. Among these, from the viewpoint of hygroscopicity, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene, Chain olefins with 2 to 20 carbon atoms such as 4-methyl-1-pentene and 4,6-dimethyl-1-heptene; cyclic olefins with 5 to 20 carbon atoms such as vinylcyclohexane; do not contain polar groups; A chain olefin having 2 to 20 carbon atoms is more preferable, and ethylene and propylene are particularly preferable.

-Properties of block copolymer-
Here, the number of polymer blocks [A] in the block copolymer is usually 3 or less, preferably 2. The number of polymer blocks [B] in the block copolymer is usually 2 or less, preferably 1.

The form of the block of the block copolymer is not particularly limited, and may be either a chain type block or a radial type block, but a chain type block is preferable since it has excellent mechanical strength.
The most preferred form of the block copolymer is a triblock copolymer ([A]-[B]-[A]) in which a polymer block [A] is bonded to both ends of a polymer block [B].

The mass fraction of the structural unit [a] derived from the aromatic vinyl compound in the block copolymer in the entire block copolymer is wa, and the structural unit [b] derived from all the chain conjugated diene compounds in the block copolymer is ] is the mass fraction of the entire block copolymer as wb, the ratio of wa to wb (wa:wb) is 30:70 to 65:35, preferably 40:60 to 58: 42, more preferably 45:55 to 55:45. If there is too much wa, there is a risk that the impact resistance of the molded article will decrease. On the other hand, if wa is too small, the rigidity of the molded article may decrease.
Regarding the "ratio of wa to wb (wa:wb)", in the process of producing the block copolymer, the aromatic vinyl compound, chain conjugated diene compound, and other It can be calculated from the number of parts of the vinyl compound and the polymerization conversion rate of the monomer used at the end of polymerization of each block of the block copolymer measured using gas chromatography (GC). .
In addition, wA is the weight fraction of all the polymer blocks [A] in the block copolymer, and the weight fraction of all the polymer blocks [B] in the whole block copolymer is wA. When wB is, the ratio of wA and wB (wA:wB) is preferably 30:70 to 65:35, more preferably 40:60 to 58:42, even more preferably 45:55 to 55: It is 45. If wA is too large, the impact resistance of the molded article may decrease. On the other hand, if wA is too small, the rigidity of the molded article may decrease.

The molecular weight of the block copolymer is determined in terms of polystyrene, measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, from the viewpoint of improving the dimensional stability and mechanical strength of the molded product. The weight average molecular weight (Mw) is preferably 35,000 or more, more preferably 38,000 or more, even more preferably 40,000 or more, preferably 200,000 or less, more preferably 150,000 or less, and Preferably it is 100,000 or less. In addition, the molecular weight distribution (Mw/Mn) of the block copolymer is preferably 3 or less, more preferably 2 or less, and even more preferably 1.7 or less, from the viewpoint of improving the dimensional stability and mechanical strength of the molded article. It is.

-Production method of block copolymer-
The method for producing the block copolymer is not particularly limited, and any known method can be employed. Specifically, examples of the method for producing the block copolymer include methods described in International Publication No. 2003/018656, International Publication No. 2011/096389, and the like.

<<Hydrogenation>>
A hydrogenated block copolymer can be obtained by hydrogenating at least the carbon-carbon unsaturated bond derived from the chain conjugated diene compound of the block copolymer described above.
Here, the block copolymer hydride may be a polymer in which only the carbon-carbon unsaturated bonds in the main chain and side chain derived from the chain conjugated diene compound of the block copolymer are selectively hydrogenated. It is also possible to use hydrogenated carbon-carbon unsaturated bonds in the main chain and side chain derived from the linear conjugated diene compound of the block copolymer, as well as the carbon-carbon unsaturated bonds in the aromatic ring derived from the aromatic vinyl compound. It may be a molecule or a mixture thereof.

During hydrogenation, the hydrogenation rate of the carbon-carbon unsaturated bonds derived from the structural unit [b] (structural unit derived from a linear conjugated diene compound) of the block copolymer affects the light resistance and dimensional stability of the molded article. From the viewpoint of improvement, it is necessary to be 90% or more, preferably 95% or more, and more preferably 98% or more.

For example, when selectively hydrogenating only the carbon-carbon unsaturated bonds in the main chain and side chains derived from the linear conjugated diene compound of the block copolymer, the carbon-carbon unsaturated bonds in the main chain and side chains are The hydrogenation rate needs to be 90% or more, preferably 95% or more, more preferably 98% or more, and carbon-carbon unsaturation of the aromatic ring derived from the aromatic vinyl compound. The hydrogenation rate of the bond is preferably 15% or less, more preferably 10% or less, even more preferably 5% or less.
By hydrogenating the carbon-carbon unsaturated bonds in the main chain and side chains derived from the linear conjugated diene compound, the light resistance and dimensional stability of the molded article are improved. If the hydrogenation rate of the carbon-carbon unsaturated bonds in the main chain and side chains derived from the linear conjugated diene compound is less than 90%, the light resistance and dimensional stability of the molded product may be poor. Furthermore, by suppressing the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound to 15% or less, it becomes easier to maintain the dimensional stability of the molded article.

For example, when hydrogenating carbon-carbon unsaturated bonds in the main chain and side chain derived from a linear conjugated diene compound of a block copolymer, and carbon-carbon unsaturated bonds in an aromatic ring derived from an aromatic vinyl compound. The hydrogenation rate is preferably 90% or more of all carbon-carbon unsaturated bonds, more preferably 95% or more, and still more preferably 98% or more. By setting the hydrogenation rate to 90% or more, the molded product has excellent light resistance and dimensional stability.

The hydrogenation rate of carbon-carbon unsaturated bonds derived from the chain conjugated diene compound and the hydrogenation rate of carbon-carbon unsaturated bonds derived from the aromatic vinyl compound of the hydrogenated block copolymer are, for example, It can be determined by measuring ¹ H-NMR of a block copolymer and a hydrogenated block copolymer.

The method of hydrogenating unsaturated bonds in the block copolymer, the reaction form, etc. are not particularly limited, and may be carried out according to known methods.
As a method for selectively hydrogenating carbon-carbon unsaturated bonds in the main chain and side chains derived from the linear conjugated diene compound of the block copolymer, for example, the method described in JP-A No. 2015-78090, etc. Known hydrogenation methods may be mentioned.
In addition, as a method for hydrogenating carbon-carbon unsaturated bonds in the main chain and side chain derived from a linear conjugated diene compound of a block copolymer, and carbon-carbon unsaturated bonds in an aromatic ring derived from an aromatic vinyl compound. Examples of the method include methods described in International Publication No. 2011/096389 and International Publication No. 2012/043708.

After the hydrogenation reaction is completed, the hydrogenation catalyst, or the hydrogenation catalyst and the polymerization catalyst are removed from the reaction solution, and then the solvent can be removed from the resulting solution to recover the block copolymer hydride. .
The recovered block copolymer hydride is usually formed into pellets and can be subjected to subsequent alkoxysilyl group introduction reaction and sheet forming processing.

The molecular weight of the block copolymer hydride is preferably a weight average molecular weight (Mw) in terms of polystyrene measured by GPC using THF as a solvent, from the viewpoint of imparting sufficient melt moldability and mechanical strength to the molded product. is 35,000 or more, more preferably 38,000 or more, still more preferably 40,000 or more, preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less.
In addition, the molecular weight distribution (Mw/Mn) of the block copolymer hydride is preferably 3 or less, more preferably 2 or less, and even more preferably It is 1.7 or less.

<<Introduction of alkoxysilyl group>>
It is preferable that the block copolymer hydride has an alkoxysilyl group from the viewpoint of better bonding of the molded article to the adherend.
Here, the method for obtaining the hydrogenated block copolymer having an alkoxysilyl group is not particularly limited. For example, by reacting the above-mentioned block copolymer hydride with an ethylenically unsaturated silane compound in the presence of an organic peroxide, a modified block copolymer hydride into which an alkoxysilyl group has been introduced can be obtained. I can do it.

Examples of alkoxysilyl groups include tri(alkoxy)silyl groups such as trimethoxysilyl group and triethoxysilyl group; methyldimethoxysilyl group, methyldiethoxysilyl group, ethyldimethoxysilyl group, and ethyldiethoxysilyl group. (C1-20 alkyl)di(C1-6 alkoxy)silyl groups such as propyldimethoxysilyl group, propyldiethoxysilyl group; (aryl dimethoxysilyl group, phenyldiethoxysilyl group, etc.); ) di(alkoxy with 1 to 6 carbon atoms) silyl group; and the like. Among these, trimethoxysilyl group is particularly preferred from the viewpoint of better bonding of the molded article to the adherend. Furthermore, the alkoxysilyl group is bonded to the hydrogenated block copolymer 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. Also good.

The amount of alkoxysilyl group introduced into the block copolymer hydride is usually 0.1 parts by mass or more and 10 parts by mass or less, preferably 0.2 parts by mass, based on 100 parts by mass of the block copolymer hydride. As mentioned above, the amount is more preferably 0.3 parts by mass or more, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. If the amount of alkoxysilyl groups introduced is below the above upper limit, crosslinking between alkoxysilyl groups decomposed by trace amounts of moisture will proceed before the resulting modified block copolymer hydrogenated product is melt-molded into the desired shape. Problems such as gelation, decreased fluidity during melting, and decreased moldability are less likely to 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.

The ethylenically unsaturated silane compound to be used is not particularly limited as long as it graft-polymerizes with the hydrogenated block copolymer and introduces an alkoxysilyl group into the hydrogenated block copolymer. Examples of ethylenically unsaturated silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, 3-acrylic Roxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-acryloxypropyltrimethoxysilane, etc. are preferably used.
These ethylenically unsaturated silane compounds may be used alone or in combination of two or more.

The amount of the ethylenically unsaturated silane compound used is usually 0.1 parts by mass or more and 10 parts by mass or less, preferably 0.2 parts by mass or more, more preferably The amount is 0.3 parts by mass or more, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less.

As the organic peroxide, one having a 1-minute half-life temperature of 170° C. or more and 190° C. or less is preferably used. For example, t-butylcumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butyl peroxide, Di(2-t-butylperoxyisopropyl)benzene and the like are preferably used.
These organic peroxides may be used alone or in combination of two or more.
The amount of organic peroxide used is usually 0.05 parts by mass or more and 2 parts by mass or less, preferably 0.08 parts by mass or more, and more preferably 0.05 parts by mass or less, per 100 parts by mass of the hydrogenated block copolymer. The amount is 1 part by mass or more, preferably 1 part by mass or less, and more preferably 0.5 part by mass or less.

The method of reacting the hydrogenated block copolymer and the ethylenically unsaturated silane compound in the presence of an organic peroxide is not particularly limited. For example, an alkoxysilyl group can be introduced into the hydrogenated block copolymer by kneading it at a desired temperature for a desired time using a twin-screw kneader. The kneading temperature using the twin-screw kneader is usually 180°C or higher and 220°C or lower, preferably 185°C or higher, more preferably 190°C or higher, and preferably 210°C or lower, more preferably 200°C or lower. The heat-kneading time is usually 0.1 minutes or more and 10 minutes or less, preferably 0.2 minutes or more, more preferably 0.3 minutes or more, and preferably 5 minutes or less, more preferably 2 minutes or less.
Specifically, the alkoxysilyl group is introduced into the block copolymer hydride, the block copolymer hydride, the ethylenically unsaturated silane compound, and the organic peroxide by keeping the temperature and residence time within the above ranges. All you have to do is knead and extrude the material continuously.

The molecular weight of the modified block copolymer hydride is the weight average molecular weight (Mw) in terms of polystyrene measured by GPC using THF as a solvent, from the viewpoint of improving the dimensional stability and mechanical strength of the molded article. It is 35,000 or more, more preferably 38,000 or more, still more preferably 40,000 or more, preferably 200,000 or less, more preferably 150,000 or less, and still more preferably 100,000 or less.
In addition, the molecular weight distribution (Mw/Mn) is preferably 3.5 or less, more preferably 2.5 or less, and even more preferably 2.0 or less, from the viewpoint of improving the dimensional stability and mechanical strength of the molded product. 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. Note that the olefin polymer and the hydrogenated olefin polymer may be used together.

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 less than 1 part by mass per 100 parts by mass of the hydrogenated block copolymer. .1 part by mass or more, more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, preferably 0.95 parts by mass or less, 0. More preferably, the amount is .9 parts by mass or less. 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, antiblocking agents, 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 above-mentioned hydrocarbon polymer and other optionally used components with a hydrogenated block copolymer, a commonly used known method can be applied.
For example, after uniformly mixing block copolymer hydride pellets, hydrocarbon polymer, and other components using a mixer such as a tumbler, ribbon blender, or Henschel type mixer, the mixture is then mixed using a twin screw extruder or the like. A continuous melt kneading machine is used to melt mix the block copolymer hydride and then extruded to form pellets.A twin screw extruder equipped with a side feeder is used to melt and mix the block copolymer hydride into pellets. A resin composition in which the block copolymer hydride, hydrocarbon polymer, and other components are uniformly dispersed is prepared by melt-kneading, extruding, and pelletizing while continuously adding the components. can be manufactured.

(molded object)
The molded article of the present invention contains a predetermined hydrogenated block copolymer, a predetermined hydrocarbon polymer, and optionally other components. Here, the molded article of the present invention needs to contain 0.01 parts by mass or more and less than 1 part by mass of the hydrocarbon polymer per 100 parts by mass of the hydrogenated block copolymer.
Since the molded article of the present invention contains the predetermined hydrogenated block copolymer and the predetermined hydrocarbon polymer in the above-mentioned quantitative ratio, it can be bonded well to the adherend, It also has excellent dimensional stability.

<Block copolymer hydride, hydrocarbon polymer, and other components>
Here, specific examples, properties, quantitative ratios, etc. of the hydrogenated block copolymer and hydrocarbon polymer contained in the molded article of the present invention, and other components optionally contained in the molded article of the present invention are as follows. Since it is the same as the 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 includes a resin molded article containing a hydrogenated block copolymer and a resin film covering at least a portion of its surface, and the resin film is preferably a film made of a hydrocarbon polymer. . 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 product 10 in FIG. 1 is a sheet-like molded product, and includes a sheet-like resin molded product 20 containing a block copolymer hydride and other optional components, and a resin film containing a hydrocarbon polymer. 30. 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 obtaining a molded body by supplying a hydrocarbon polymer to the surface of a resin molded body containing a hydrogenated block copolymer. Examples include a method of forming a resin film containing a hydrocarbon polymer on the surface to obtain a molded body.

1) The method for forming a molded object using the resin composition of the present invention described above 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 a hydrogenated block copolymer 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.
As a thermoplastic resin,
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.

As a thermosetting resin,
Examples 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.
In the present invention, "(meth)acrylic" means acrylic and/or methacryl, and "(co)polymer" means a homopolymer and/or copolymer.

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.
Further, 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 according to the present invention is a method for manufacturing a bonded body by bonding a resin molded body containing a predetermined hydrogenated block copolymer and a base material.
And, the method for manufacturing a joined body of the present invention includes:
A predetermined hydrocarbon polymer is supplied to the surface of at least one of the resin molding and the base material from 0.01 part by mass to less than 1 part by mass per 100 parts by mass of block copolymer hydride contained in the resin molding. , 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
If the above-mentioned process is carried out, the resin molding containing the hydrogenated block copolymer can be attached to the base material as an adherend (especially under low temperature conditions) through the resin film containing the hydrocarbon polymer. By adhering the molded article to the base material, it is possible to obtain a joined body having excellent dimensional stability and in which the molded article and the base material are well bonded.

<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 a hydrogenated block copolymer and a base material.

<<Resin molded body>>
As the resin molding, a resin molding obtained by molding a composition containing a hydrogenated block copolymer and optionally other components can be used.
Here, the hydrogenated block copolymer, other components, molding method, etc. used for molding the resin molding are the same as those described above in the sections of "resin composition" and "molding". be able to.

<<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 part by mass or more and less than 1 part by mass per 100 parts by mass of the block copolymer hydride 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 0.95 parts by mass. It is preferably at most 0.9 parts by mass, more preferably at most 0.9 parts by mass. 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 at which the resin molded body and the base material are bonded together via the resin film (bonding temperature) is preferably lower than the glass transition temperature of the block copolymer hydride contained in the resin molded body. By performing adhesion at a temperature below the glass transition temperature of the block copolymer hydride, 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 glass transition temperature can be measured by the method described in Examples.

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 block copolymer, hydrogenated block copolymer, 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) Hydrogenation rate The hydrogenation rate of the main chain, side chain, and aromatic ring of the hydrogenated block copolymer was calculated by measuring ¹ H-NMR of the block copolymer and the hydrogenated block copolymer.
(3) Glass transition temperature A block copolymer hydride (modified block copolymer hydride) was press-molded to prepare a test piece with a length of 50 mm, a width of 10 mm, and a thickness of 1 mm. Using this test piece, based on the JIS-K7244-4 method, using a viscoelasticity measuring device (manufactured by TA Instruments Japan, ARES), in the range of -100°C to +150°C, The viscoelastic spectrum was measured at a heating rate of 5° C./min. The glass transition temperature (Tg) was determined from the peak top temperature on the high temperature side of the loss tangent tan δ.
(4) 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.
(5) Dimensional stability Molded bodies (Examples 1 to 6: Resin molded bodies coated with hydrocarbon polymer, Comparative Examples 1 to 2: 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 100°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 misalignment was observed and "poor" when misalignment was observed. (6) Light resistance Molded object (Examples 1 to 6: Hydrocarbon polymer Using the coated resin moldings (Comparative Examples 1 and 2: resin moldings not coated with hydrocarbon polymer), dumbbell-shaped No. 3 test pieces as described in JIS K-6251 were 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 modified block copolymer hydride>
<<Preparation of block copolymer>>
550 parts of dehydrated cyclohexane, 25.0 parts of dehydrated styrene, and 0.475 parts of n-dibutyl ether were placed in a reactor equipped with a stirring device and sufficiently purged with nitrogen, and 15 parts of n-butyllithium was added while stirring at 60°C. % cyclohexane solution was added to initiate polymerization.
The reaction was carried out at 60° C. for 60 minutes while stirring. The polymerization conversion rate at this point was 99.5% as measured by gas chromatography.
Next, 50.0 parts of dehydrated isoprene was added and stirring was continued for 30 minutes. At this point, the polymerization conversion rate was 99%.
Thereafter, 25.0 parts of dehydrated styrene was further added and stirred for 60 minutes. The polymerization conversion rate at this point was approximately 100%. Here, 0.096 part of isopropyl alcohol was added to stop the reaction. The weight average molecular weight (Mw) of the obtained block copolymer was 47,200, the molecular weight distribution was 1.05, and wa:wb=50:50.
In addition, the above "wa:wb" indicates that the mass fraction of structural units derived from styrene as an aromatic vinyl compound in the block copolymer is wa, and the structural units derived from isoprene as a chain conjugated diene compound are It represents the ratio of wa and wb (wa:wb), where wb is the mass fraction occupied in the block copolymer.
<<Hydrogenation>>
The polymer solution obtained as described above was transferred to a pressure-resistant reactor equipped with a stirring device, and 0.042 parts of bis(cyclopentadienyl) titanium dichloride was added as a hydrogenation catalyst in 1.0 part of toluene. and 0.122 parts of diethylaluminum chloride were added and mixed. The inside of the reactor was replaced with hydrogen gas, hydrogen was further supplied while stirring the solution, and a hydrogenation reaction was carried out at a temperature of 90° C. and a pressure of 1.0 MPa for 5 hours.
The weight average molecular weight (Mw) of the hydrogenated block copolymer after the hydrogenation reaction was 49,000, and the molecular weight distribution (Mw/Mn) was 1.06.
After the hydrogenation reaction was completed, 0.10 part of water was added to the reaction solution, and the mixture was stirred at 60°C for 60 minutes. Thereafter, it was cooled to below 30°C, and 1.5 parts of activated clay (product name "Galleon Earth (registered trademark)", manufactured by Mizusawa Chemical Industry Co., Ltd.) and talc (product name "Micro Ace (registered trademark)", manufactured by Nippon Talc Co., Ltd.) were added. 1.5 parts of the reaction solution was added and the reaction solution was filtered to remove insoluble matter. A phenolic antioxidant, pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by SONGWON, product name "Songnox1010"), was added to the filtered solution. 1.0 part of a xylene solution in which 1 part was dissolved was added and dissolved.
Next, the above solution was filtered with a metal fiber filter (pore size 0.4 μm, manufactured by Nichidai) to remove minute solids, and then filtered using a cylindrical concentration dryer (product name "Contro", manufactured by Hitachi, Ltd.). ) to remove solvents such as cyclohexane, xylene, and other volatile components from the solution at a temperature of 260°C and a pressure of 0.001 MPa or less, and extrude the molten state into a strand from a die directly connected to a concentration dryer. After cooling, it was cut with a pelletizer to obtain 92 parts of pellets of the hydrogenated block copolymer. The obtained hydrogenated block copolymer had a weight average molecular weight (Mw) of 48,600 and a molecular weight distribution (Mw/Mn) of 1.11. In addition, the hydrogenation rate of carbon-carbon double bonds in the main chain and side chains derived from linear conjugated diene compounds is 99%, and the hydrogenation rate of carbon-carbon double bonds in aromatic rings derived from aromatic vinyl compounds. was less than 5%.
[Introduction of alkoxysilyl group]
2.0 parts of vinyltrimethoxysilane and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane ( 0.2 part of product name "Perhexa (registered trademark) 25B", manufactured by NOF Corporation) was added to obtain a mixture. This mixture was kneaded using a twin-screw extruder (product name "TEM37B", manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 200°C and a residence time of 60 to 70 seconds, extruded into strands, cooled in air, and then pelletized using a pelletizer. The mixture was cut to obtain 97 parts of pellets of a hydrogenated modified block copolymer having an alkoxysilyl group.
10 parts of the obtained pellets of the hydrogenated modified block copolymer were dissolved in 100 parts of cyclohexane, and then poured into 400 parts of dehydrated methanol to coagulate the hydrogenated modified block copolymer and filtered. After filtration, 9.0 parts of crumb of the hydrogenated modified block copolymer was isolated by vacuum drying at 25°C. In the FT-IR spectrum, new absorption bands originating from ₃ Si-OCH groups at 1090 cm ^-1 and ₂ Si-CH groups at 825 cm ^-1 and 739 cm ^-1 are found, compared to those of vinyltrimethoxysilane at 1075 cm ^-1 and 808 cm ^-1 , and 766 cm ^-1 . In addition, in the ¹ H-NMR spectrum (in deuterated chloroform), an absorption band based on the proton of the methoxy group was observed at 3.6 ppm, and from the peak area ratio, 1. It was confirmed that 8 parts were combined. Note that the glass transition temperature of the hydrogenated modified block copolymer was 125°C.

<Preparation of resin molded body>
2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl), which is an ultraviolet absorber, is added to 100 parts of the obtained modified block copolymer hydrogenated pellets. ) 0.2 part of phenol (Tinuvin (registered trademark) 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 body (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 "Hycor (registered trademark) K350", manufactured by Kaneda Corporation, Mn700, iodine value 0.2, hydride) was coated and cut into a sheet shape of 300 mm in length x 200 mm in width to obtain a molded body. The amount of liquid paraffin applied was 0.9 parts per 100 parts of the hydrogenated modified block copolymer 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 (molded body) coated with a hydrocarbon polymer are bonded to the surface treated surface of the organic base material and the resin molded body. The molded bodies were stacked so that the surfaces coated with the hydrocarbon polymer 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 70° 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.

(Example 2)
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.

(Examples 3-4)
Instead of an organic base material made of surface-treated polycarbonate resin, an inorganic base material made of glass (300 mm long x 200 mm wide x 0.5 mm thick) and an inorganic base material made of copper (300 mm long x 0.5 mm wide) were used. A bonded body was manufactured in the same manner as in Example 1, except that a bonded body (200 mm×0.1 mm thick) was used, and various evaluations were performed. The results are shown in Table 1.

(Example 5)
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 1.

(Example 6)
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 1.

(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 1.

(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. A bonded body was produced 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 bonding process was used). We conducted various evaluations. The results are shown in Table 1.
<Preparation of resin molded body>
2-(2H-benzotriazol-2-yl)-4-(1,1, 0.2 part of 3,3-tetramethylbutyl)phenol (Tinuvin (registered trademark) 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-shaped resin molded body (thickness 0.40 mm, width 230 mm) was produced under the following molding conditions: molten resin temperature 170 °C, T die temperature 170 °C, and cast roll temperature 60 °C while adding 15 parts of hydride). did. The resin molded body was wound up into a roll and collected.

In addition, in Table 1 shown below,
"PC" indicates polycarbonate resin,
"PET" indicates polyethylene terephthalate,
"Cu" indicates copper.

From Table 1, in Examples 1 to 6, in which the resin molding containing the block copolymer hydride and the base material were bonded using a predetermined hydrocarbon polymer in an amount within a predetermined range, adhesive strength and dimensions It can be seen that a bonded body with excellent 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 Example 2, in which the amount of the predetermined hydrocarbon polymer used exceeds the predetermined upper limit, the dimensional stability 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 block copolymer hydride and a hydrocarbon polymer,
comprising a resin molded body containing the block copolymer hydride; and a resin film covering at least a portion of the surface of the resin molded body and containing the hydrocarbon polymer,
The block copolymer hydride comprises at least two polymer blocks [A] each containing a structural unit [a] derived from an aromatic vinyl compound as a main component, and a structural unit [b] derived from a chain conjugated diene compound. A block copolymer having at least one polymer block [B] as a main component, wherein the structural unit [a] derived from the aromatic vinyl compound accounts for a mass fraction in the entire block copolymer. wa, when the mass fraction of the structural unit [b] derived from the linear conjugated diene compound in the entire block copolymer is defined as wb, the ratio of wa and wb (wa:wb) is 30:70 to A polymer obtained by hydrogenating 90% or more of the carbon-carbon unsaturated bonds derived from the structural unit [b] of a block copolymer with a ratio of 65:35,
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 part by mass or more and less than 1 part by mass per 100 parts by mass of the block copolymer hydride in the molded product. The molded article according to claim 1 , wherein the hydrogenated block copolymer has an alkoxysilyl group. 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. At least two polymer blocks [A] having a structural unit [a] derived from an aromatic vinyl compound as a main component, and at least one polymer block having a structural unit [b] derived from a linear conjugated diene compound as a main component. A block copolymer having a combined block [B], in which the structural unit [a] derived from the aromatic vinyl compound accounts for a mass fraction wa in the entire block copolymer, and the structural unit [a] derived from the linear conjugated diene compound is A block copolymer in which the ratio of wa to wb (wa:wb) is 30:70 to 65:35, where wb is the mass fraction of the structural unit [b] in the entire block copolymer. A resin molded body containing a hydrogenated block copolymer obtained by hydrogenating 90% or more of the carbon-carbon unsaturated bonds derived from the structural unit [b] of the above and a base material are bonded to produce a bonded body. A method,
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 supplying 0.01 part by mass or more and less than 1 part by mass per 100 parts by mass of the polymer hydride 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 conjugate according to claim 6 , wherein the hydrogenated block copolymer has an alkoxysilyl group. 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 to 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 joined body according to any one of claims 6 to 9 , wherein the adhesion temperature in the adhesion is lower than the glass transition temperature of the block copolymer hydride.

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