JP7230426B2 - Method for manufacturing conjugate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a joined body by adhering a molded article containing a hydrogenated modified block copolymer into which an alkoxysilyl group has been introduced and a resin molded article.

Hydrogenated modified block copolymers into which alkoxysilyl groups have been introduced are useful for adhesion between a glass plate and a resin sheet, adhesion between a metal foil and a resin sheet, and the like. and food packaging, solar cell module encapsulant, organic EL element encapsulant, electronic component encapsulant, laminated glass interlayer film, and the like.

Then, in Patent Document 3, when producing a joined body in which a sheet made of a modified block copolymer hydride to which an alkoxysilyl group is introduced and a thermoplastic resin sheet are adhered, the two sheets are heat-pressed together. Prior to this, it has been proposed that the surface of a thermoplastic resin sheet be subjected to at least one type of activation treatment selected from plasma irradiation, excimer ultraviolet irradiation, and corona discharge to firmly bond these two sheets together. ing.

WO2015/137376 JP 2017-171833 A WO2017/154718

However, as a result of investigation by the present inventors, it has become clear that the activation treatment of Patent Document 3 has a problem that the time for which the effect is maintained is not necessarily long. Therefore, when manufacturing a product in which a sheet made of a hydrogenated modified block copolymer into which an alkoxysilyl group is introduced and a thermoplastic resin sheet are bonded together, both There is a possibility that the above activation treatment is required to be performed immediately before bonding the substrates together, which may lead to restrictions on manufacturing. That is, it is difficult to stably produce a joined body in which a sheet made of a hydrogenated modified block copolymer into which an alkoxysilyl group is introduced and a thermoplastic resin sheet are firmly adhered by the above-described conventional method. there were.

Therefore, the present invention provides a method for stably and firmly adhering a molded article mainly composed of a hydrogenated modified block copolymer into which an alkoxysilyl group is introduced and a resin molded article, thereby forming the molded article and the resin. An object of the present invention is to provide a method for manufacturing a joined body of molded bodies.

As a result of intensive studies aimed at achieving the above object, the present inventors have found that they are the first to bond a resin molded article to a molded article whose main component is a hydrogenated modified block copolymer into which an alkoxysilyl group has been introduced. If the surface of the resin molding is subjected to a surface treatment in which a predetermined surface treatment is performed in the presence of a silicon compound and/or a surface treatment is performed in which a silicon compound is brought into contact with the surface after the predetermined surface treatment, the surface The present inventors have found that a molded article containing a hydrogenated modified block copolymer as a main component and a resin molded article can be stably and firmly adhered to each other even if the bonding is performed after a long time has passed since the treatment. I have perfected my invention.

Thus, according to the present invention, the following methods (1) to (3) for producing a joined body are provided.
(1) Bonded body [H] is formed by bonding molded body [F] mainly composed of hydrogenated modified block copolymer [E] into which alkoxysilyl groups are introduced and resin molded body [G]. A manufacturing method of a joined body, comprising steps 1 and 2 below.
Step 1: Treatment (i) of subjecting the surface of the resin molding [G] to at least one selected from the group consisting of plasma irradiation, ultraviolet irradiation, corona discharge, and flame spraying in the presence of a silicon compound. and a treatment of contacting the surface with a silicon compound after performing at least one selected from the group consisting of plasma irradiation, ultraviolet irradiation, corona discharge and flame spraying on the surface of the resin molded body [G] ( performing at least one treatment of ii).
Step 2: The resin molded body [G] that has undergone the step 1 and the molded body [F] are subjected to at least one of the treatments (i) and (ii) of the resin molded body [G]. and the molded body [F] are laminated so as to be in contact with each other, and are heat-pressed.
(2) The method for producing a bonded body according to (1), wherein the bonding surface between the molded body [F] and the resin molded body [G] in the bonded body [H] has a peel strength of 4 N/cm or more.
(3) The hydrogenated modified block copolymer [E] contains at least two polymer blocks [A] mainly composed of structural units [a] derived from an aromatic vinyl compound, and a chain conjugated diene compound derived A block copolymer [C] consisting of at least one polymer block [B], which is mainly composed of the structural unit [b] of ], and the mass fraction of the total amount of the structural unit [b] in the block copolymer [C] is wb, the ratio wa:wb between wa and wb is 20: A block copolymer hydride [D] obtained by hydrogenating 90% or more of the carbon-carbon unsaturated bonds derived from the structural unit [b] of the block copolymer [C] having a ratio of 80 to 60:40, an alkoxy A method for producing a conjugate according to (1) or (2), which is a hydrogenated modified block copolymer into which a silyl group is introduced.

According to the method for producing a bonded body of the present invention, a molded body mainly composed of a hydrogenated modified block copolymer into which an alkoxysilyl group is introduced and a resin molded body are stably and firmly adhered to each other, A joined body of the molded article and the resin molded article can be manufactured.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. In the method for producing a joined body of the present invention, a molded body [F] mainly composed of a hydrogenated modified block copolymer [E] into which an alkoxysilyl group has been introduced is bonded to a resin molded body [G]. This is a method for manufacturing a conjugate [H]. The method for manufacturing a joined body of the present invention is characterized by including at least the following steps 1 and 2.

Step 1: A treatment (i ), and/or
After performing at least one surface treatment selected from the group consisting of plasma irradiation, ultraviolet irradiation, corona discharge and flame spraying on the surface of the resin molded body [G], the surface subjected to the surface treatment (hereinafter referred to as " A treatment (ii) in which the surface to be processed" is brought into contact with a silicon compound,
the process of carrying out
Step 2: The surface of the resin molded body [G] subjected to the above treatment (i) and/or the above treatment (ii) (hereinafter referred to as , referred to as the “surface to be treated”) and the molded body [F] are laminated so as to be in contact with each other, and are heat-pressed.

Then, through the above-described steps 1 and 2, the molded article [F] mainly composed of the hydrogenated modified block copolymer [E] into which an alkoxysilyl group has been introduced, and the resin molded article [G] It is possible to stably manufacture a joined body in which the two are strongly bonded together.

(Molded body [F])
Molded article [F] is mainly composed of hydrogenated modified block copolymer [E]. The molded article [F] may contain components other than the hydrogenated modified block copolymer [E] (hereinafter referred to as "other components").
In the present invention, the expression that the molded article "contains a specific polymer as a main component" means that the molded article contains 70% by mass or more of the polymer based on 100% by mass of the total mass of the molded article.
The content of the hydrogenated modified block copolymer [E] contained in the molded article [F] is preferably 80% by mass or more, preferably 90% by mass, based on 100% by mass of the entire molded article [F]. % or more is more preferable.

<Modified block copolymer hydride [E]>
The modified block copolymer hydride [E] is a polymer obtained by introducing an alkoxysilyl group into the precursor block copolymer hydride [D].

<<block copolymer hydride [D]>>
Here, the block copolymer hydride [D] is not particularly limited as long as an alkoxysilyl group can be introduced. Polymer block [A] containing structural unit [a] as a main component and structural unit [b] derived from a chain conjugated diene compound (linear conjugated diene compound, branched conjugated diene compound) as main components A polymer obtained by hydrogenating a block copolymer [C] having a polymer block [B] can be preferably used.
In the present invention, the expression that the polymer block "consists of a specific structural unit as a main component" means that "the total structural unit (total repeating unit) constituting the polymer block is 100% by mass, and the structural unit is 70 containing at least % by mass".

[Block copolymer [C]]
The block copolymer [C] preferably has at least two polymer blocks [A] and at least one polymer block [B].

[[polymer block [A]]]
Polymer block [A] is a polymer block mainly composed of structural unit [a] derived from an aromatic vinyl compound. The content of the structural unit [a] in the polymer block [A] must be 70% by mass or more, and 90% by mass, based on 100% by mass of the total structural units constituting the polymer block [A]. % or more, more preferably 95 mass % or more, and even more preferably 98 mass % or more. If the content of the structural unit [a] in the polymer block [A] is too low, the heat resistance of the molded product [F] containing the hydrogenated modified block copolymer [E] as a main component may be lowered. . The upper limit of the content of the structural unit [a] in the polymer block [A] is not particularly limited, and may be 100% by mass or less.

Polymer block [A] may contain structural units (other structural units) other than structural unit [a]. Other structural units that the polymer block [A] may contain include structural units [b] derived from chain conjugated diene compounds and/or structural units [j] derived from other vinyl compounds. The total content of the structural unit [b] derived from the linear conjugated diene compound and the structural unit [j] derived from the other vinyl compound in the polymer block [A] constitutes the polymer block [A]. Based on 100% by mass of all structural units, it is necessary to be 30% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and preferably 2% by mass or less. More preferred.

-Aromatic Vinyl Compound-
Here, the aromatic vinyl compound used to introduce the structural unit [a] includes styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropyl styrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, and other styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent; 4-methoxystyrene; styrenes having an alkoxy group having 1 to 6 carbon atoms as a substituent; styrenes having an aryl group as a substituent such as 4-phenylstyrene; vinyls such as 1-vinylnaphthalene and 2-vinylnaphthalene naphthalenes; and the like. These may be used singly or in combination of two or more.
Among these, aromatic vinyl compounds containing no polar groups, such as styrene and styrenes having an alkyl group having from 1 to 6 carbon atoms as a substituent, from the viewpoint of reducing the hygroscopicity of the molded article [F]. is preferred, and styrene is particularly preferred because of its industrial availability.

- Chain conjugated diene compounds -
The chain conjugated diene compounds (straight chain conjugated diene compound, branched chain conjugated diene compound) used to introduce the structural unit [b] include 1,3-butadiene, isoprene, 2,3 -dimethyl-1,3-butadiene, 1,3-pentadiene, chloroprene and the like. These may be used singly or in combination of two or more.
Among these, chain conjugated diene compounds containing no polar group are preferable from the viewpoint of reducing the hygroscopicity of the molded article [F], and 1,3-butadiene and isoprene are preferable from the viewpoint of industrial availability. Especially preferred.

―Other Vinyl Compounds―
Other vinyl compounds used to introduce the structural unit [j] include vinyl compounds other than aromatic vinyl compounds and chain conjugated diene compounds, such as chain vinyl compounds, cyclic vinyl compounds, Examples include saturated cyclic acid anhydrides and unsaturated imide compounds. These compounds may have substituents such as nitrile groups, alkoxycarbonyl groups, hydroxycarbonyl groups, and halogen atoms. Moreover, you may use these compounds individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of reducing the hygroscopicity of the molded article [F], ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene , 1-dodecene, 1-eicosene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene, chain vinyl compounds (chain olefins) having 2 to 20 carbon atoms; vinylcyclohexane, norbornene Cyclic vinyl compounds (cyclic olefins) having 5 to 20 carbon atoms such as; Cyclic diene compounds such as 1,3-cyclohexadiene and norbornadiene;

[[polymer block [B]]]
Polymer block [B] is a polymer block mainly composed of structural unit [b] derived from a chain conjugated diene compound. The content of the structural unit [b] in the polymer block [B] is required to be 70% by mass or more based on 100% by mass of the total structural units constituting the polymer block [B], and 80% by mass. % or more, more preferably 90 mass % or more. If the content of the structural unit [b] in the polymer block [B] is too low, the molded product [F] may have reduced flexibility. The upper limit of the content of the structural unit [b] in the polymer block [B] is not particularly limited, and may be 100% by mass or less.

Polymer block [B] may contain structural units (other structural units) other than structural unit [b]. Other structural units that may be contained in the polymer block [B] include the structural unit [a] derived from the aromatic vinyl compound and/or other vinyl compounds described above in the section "Polymer block [A]". A structural unit [j] derived from The total content of the structural unit [a] derived from the aromatic vinyl compound and the structural unit [j] derived from the other vinyl compound in the polymer block [B] is the total content of the polymer block [B]. Based on 100% by mass of structural units, the content is required to be 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less.

- Chain Conjugated Diene Compounds, Aromatic Vinyl Compounds, and Other Vinyl Compounds -
Chain conjugated diene compound used to introduce structural unit [b], aromatic vinyl compound used to introduce structural unit [a], and used to introduce structural unit [j] As specific examples of the other vinyl compounds, those described above in the section "Polymer block [A]" can be used, and preferred examples of each can also be described in the section "Polymer block [A]". It is the same as that mentioned as a suitable example.

[[Properties of block copolymer [C]]]
Here, the mass fraction occupied by the block copolymer [C] by the total amount of the structural units [a] derived from the aromatic vinyl compound is wa, and the total amount of the structural units [b] derived from the chain conjugated diene compound is the block copolymer. When the mass fraction occupied in the polymer [C] is wb, the ratio wa:wb between wa and wb is preferably 20:80 to 60:40, and 30:70 to 55:45. is more preferred, and 40:60 to 50:50 is even more preferred.
By setting the mass fraction (wa) of the structural unit [a] derived from the aromatic vinyl compound to 60% or less, the flexibility of the molded product [F] can be ensured. On the other hand, by setting the mass fraction (wa) of the structural unit [a] derived from the aromatic vinyl compound to 20% or more, the heat resistance of the molded product [F] can be ensured.
Regarding the "ratio between wa and wb (wa:wb)", in the process of producing the block copolymer, the aromatic vinyl compound, the 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 the polymerization of each block of the block copolymer measured by gas chromatography (GC) to the polymer. .

Further, the mass fraction of all the polymer blocks [A] in the block copolymer [C] with respect to the entire block copolymer [C] is wA, and the total polymer block [B] is the block copolymer [C] When wB is the mass fraction in the whole, the ratio of wA to wB (wA:wB) is preferably 20:80 to 60:40, and 30:70 to 55:45. more preferably 40:60 to 50:50.
By setting the mass fraction (wA) of the polymer block [A] to 60% or less, the flexibility of the molding [F] can be ensured. On the other hand, by setting the mass fraction (wA) of the polymer block [A] to 20% or more, the heat resistance of the molding [F] can be ensured.

As described above, the number of polymer blocks [A] in the block copolymer [C] is preferably 2 or more, preferably 3 or less, and more preferably 2. . As described above, the number of polymer blocks [B] in the block copolymer [C] is 1 or more, preferably 2 or less, and more preferably 1.
When the number of polymer blocks [A] and polymer blocks [B] in the block copolymer [C] increases, in the block copolymer hydride [D], the hydrogenated polymer derived from the polymer block [A] The phase separation between the coalescing block and the hydrogenated polymer block derived from the polymer block [B] becomes unclear, and the glass transition temperature on the high temperature side based on the hydrogenated polymer block derived from the polymer block [A] decreases. As a result, the heat resistance of the molded product [F] may decrease.

A plurality of polymer blocks [A] contained in the block copolymer [C] may have the same composition and/or different block lengths. Further, when the block copolymer [C] has a plurality of polymer blocks [B], the plurality of polymer blocks [B] are different even if the composition and/or block length are the same. good too.

Moreover, the form of the block of the block copolymer [C] is not particularly limited, and may be a linear block or a radial block. A chain type block is preferable because the molded article [F] has excellent mechanical strength.
The most preferred form of block copolymer [C] is a triblock copolymer ([A]-[B]-[A]) in which polymer block [A] is bound to both ends of polymer block [B]. be.

The molecular weight of the block copolymer [C] is determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent from the viewpoint of improving the heat resistance and mechanical strength of the molded product [F]. The polystyrene equivalent weight average molecular weight (Mw) to be measured is preferably 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, more preferably 100,000 or less. In addition, the molecular weight distribution (Mw/Mn) of the block copolymer [C] is preferably 3 or less, more preferably 2 or less, and still more preferably, from the viewpoint of improving the heat resistance and mechanical strength of the molded article [F]. is 1.7 or less.

[[Method for producing block copolymer [C]]]
The method for producing the block copolymer [C] is not particularly limited, and known methods can be employed. Specifically, as the method for producing the block copolymer [C], the methods described in International Publication No. 2003/018656, International Publication No. 2011/096389, etc. can be employed.

[Hydrogenation of block copolymer [C]]
Hydrogenated block copolymer [D] can be obtained by hydrogenating at least the carbon-carbon unsaturated bond derived from the chain conjugated diene compound of block copolymer [C] described above.
Here, the block copolymer hydride [D] is obtained by selectively hydrogenating only the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound of the block copolymer [C]. It may be a polymer, and the main chain and side chain carbon-carbon unsaturated bonds derived from the chain conjugated diene compound of the block copolymer [C] and the aromatic ring carbon derived from the aromatic vinyl compound- It may be a polymer obtained by hydrogenating a carbon unsaturated bond, or a mixture thereof.

Upon hydrogenation, the hydrogenation rate of the carbon-carbon unsaturated bond derived from the structural unit [b] (structural unit derived from the chain conjugated diene compound) of the block copolymer [C] is the light resistance of the molded product [F]. From the viewpoint of improving durability and heat deterioration resistance, it is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more.
For example, when selectively hydrogenating only the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound of the block copolymer [C], the carbon-carbon unsaturated bonds of the main chain and side chains The hydrogenation rate of the saturated bond is preferably 90% or more, more preferably 95% or more, and still more preferably 98% or more, and the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound is preferably 15% or less, more preferably 10% or less, still more preferably 5% or less.
The block copolymer hydride [D] obtained by hydrogenating the carbon-carbon unsaturated bonds of the main chain and side chain derived from the chain conjugated diene compound has better light resistance than the block copolymer [C]. and heat deterioration resistance are improved. If the hydrogenation rate of the carbon-carbon unsaturated bonds in the main chain and side chains derived from the chain conjugated diene compound is less than 90%, the molded product [F] may have poor light resistance and heat deterioration resistance. . In addition, 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 heat deterioration resistance of the molded product [F].

Further, for example, the carbon-carbon unsaturated bond of the main chain and side chain derived from the chain conjugated diene compound of the block copolymer [C] and the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound are hydrogenated. In the case of hydrogenation, the hydrogenation rate of all carbon-carbon unsaturated bonds is preferably 90% or more, more preferably 95% or more, and even more preferably 98% or more. By setting the hydrogenation rate to 90% or more, the molded article [F] is excellent in light resistance and heat deterioration resistance. Further, a modified block copolymer hydride [E] obtained by using as a precursor a block copolymer hydride [D] obtained by selectively hydrogenating only carbon-carbon unsaturated bonds derived from a chain conjugated diene compound, Compared to the molded article [F], which is the main component, it is particularly preferable because it has superior light resistance and heat deterioration resistance and also has a high heat distortion temperature.

The hydrogenation rate of the carbon-carbon unsaturated bond derived from the chain conjugated diene compound and the hydrogenation rate of the carbon-carbon unsaturated bond derived from the aromatic vinyl compound of the hydrogenated block copolymer [D] are, for example, , can be determined by measuring ¹ H-NMR of the precursor block copolymer [C] and block copolymer hydride [D].

The method for hydrogenating the unsaturated bond in the block copolymer [C], the reaction mode, and the like are not particularly limited, and the hydrogenation may be carried out according to known methods.
As a method for selectively hydrogenating the carbon-carbon unsaturated bonds of the main chain and side chains derived from the linear conjugated diene compound of the block copolymer [C], for example, see JP-A-2015-78090. Mention may be made of the known hydrogenation methods described.
In addition, the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound of the block copolymer [C] and the carbon-carbon unsaturated bonds of the aromatic ring derived from the aromatic vinyl compound are hydrogenated. Examples of the method include those described in International Publication No. 2011/096389, International Publication No. 2012/043708, and the like.

After the completion of the hydrogenation reaction, after removing the hydrogenation catalyst or the hydrogenation catalyst and the polymerization catalyst from the reaction solution, the hydrogenated block copolymer [D] can be recovered from the resulting solution.
The form of the recovered block copolymer hydride [D] is not limited, but it can usually be made into pellets and subjected to the subsequent reaction for introducing alkoxysilyl groups.

The molecular weight of the hydrogenated block copolymer [D] is the polystyrene-equivalent weight-average molecular weight measured by GPC using THF as a solvent, from the viewpoint of imparting sufficient melt moldability and mechanical strength to the molded product [F]. (Mw) is preferably 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, still more preferably 100, 000 or less.
Further, the molecular weight distribution (Mw/Mn) of the block copolymer hydride [D] is preferably 3 or less, more preferably 2 or less, more preferably 1.7 or less.

<<Introduction of alkoxysilyl group to block copolymer hydride [D]>>
A modified block copolymer hydride [E] can be obtained by introducing an alkoxysilyl group into the block copolymer hydride [D] described above.
By introducing an alkoxysilyl group into the hydrogenated block copolymer [D], the modified hydrogenated block copolymer [E] is imparted with strong adhesion to glass and metal.

Alkoxysilyl groups include tri(C1-6 alkoxy)silyl groups such as trimethoxysilyl group and triethoxysilyl group; methyldimethoxysilyl group, methyldiethoxysilyl group, ethyldimethoxysilyl group, ethyldiethoxysilyl group; (C1-20 alkyl) di(C1-6 alkoxy)silyl group such as propyldimethoxysilyl group and propyldiethoxysilyl group; phenyldimethoxysilyl group and phenyldiethoxysilyl group (aryl ) di(C1-C6 alkoxy)silyl group; and the like. Further, the alkoxysilyl group is bonded to the hydrogenated block copolymer [D] 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. It's okay to be Among these, the modified block copolymer hydride [E] is imparted with even better adhesion to glass and metal, and the molded product [F] and the resin molded product [G] are bonded more firmly. A trimethoxysilyl group is more preferable from the viewpoint of stably producing the body. In addition, the alkoxysilyl group introduced into the block copolymer hydride [D] may be of one type alone or of a plurality of types.

Here, the amount of the alkoxysilyl group introduced into the hydrogenated block copolymer [D] is preferably 0.1 parts by mass or more, more preferably 0, per 100 parts by mass of the hydrogenated block copolymer [D]. .2 parts by mass or more, more preferably 0.3 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less. If the amount of alkoxysilyl groups introduced is too large, cross-linking between the alkoxysilyl groups decomposed with a trace amount of moisture or the like proceeds before the hydrogenated modified block copolymer [E] obtained is melt-molded into a desired shape. There is a risk of gelation, or a decrease in moldability due to a decrease in fluidity when melted. On the other hand, if the amount of alkoxysilyl groups to be introduced is too small, there is a possibility that sufficient adhesive strength for adhering the molded article [F] to the resin molded article [G] cannot be obtained.
The introduction of alkoxysilyl groups into the hydrogenated modified block copolymer [E] can be confirmed by an IR spectrum. Also, the introduction amount can be calculated from the ¹ H-NMR spectrum.

A method for introducing an alkoxysilyl group into the hydrogenated block copolymer [D] is not particularly limited. As a preferred method, for example, an ethylenically unsaturated silane compound is reacted (grafting reaction) with block copolymer hydride [D] in the presence of an organic peroxide to introduce an alkoxysilyl group. method.

The ethylenically unsaturated silane compound to be used is not particularly limited as long as it undergoes a grafting reaction with the hydrogenated block copolymer [D] and introduces an alkoxysilyl group into the hydrogenated block copolymer [D]. For example, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxysilane, Roxypropyltriethoxysilane, 3-Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropyltriethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropylmethyldiethoxysilane, 3-Acryloxypropyltrimethoxysilane Silane, etc. are preferably used.
These ethylenically unsaturated silane compounds may be used alone or in combination of two or more. Among these, the modified block copolymer hydride [E] is imparted with even better adhesion to glass and metal, and the molded product [F] and the resin molded product [G] are more strongly bonded. Vinyltrimethoxysilane is particularly preferred from the viewpoint of stably producing a joined body.

As the organic peroxide used in the grafting reaction, one having a 1-minute half-life temperature of 100° C. or higher and 190° C. or lower is preferably used.
Examples of organic peroxides include t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, 1,1-di(t-butyl per oxy)-2-methylcyclohexane, 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 method of reacting the block copolymer hydride [D] and the ethylenically unsaturated silane compound in the presence of an organic peroxide is not particularly limited. For example, a block copolymer hydride [D], an ethylenically unsaturated silane compound and a peroxide mixture are kneaded in a molten state for a desired time in a twin-screw kneader to obtain a block copolymer hydride. An alkoxysilyl group can be easily introduced into [D]. The kneading temperature by the twin-screw kneader is preferably 180° C. or higher, more preferably 185° C. or higher, still more preferably 190° C. or higher, and preferably 220° C. or lower, more preferably 210° C. or lower, and still more preferably 200° C. or lower. is. The heat-kneading time is preferably 0.1 minutes or more and 10 minutes or less, preferably 0.2 minutes or more and 5 minutes or less, more preferably 0.3 minutes or more and 2 minutes or less. The target hydrogenated modified block copolymer [E] is efficiently produced by continuously kneading and extruding the mixture so that the heat-kneading temperature and the heat-kneading time (residence time) are within the above ranges. can be done.
Although the form of the resulting hydrogenated modified block copolymer [E] is not limited, it can usually be made into a pellet shape and used for subsequent molding and blending of other components such as additives. .

The molecular weight of the modified block copolymer hydride [E] does not differ greatly from the molecular weight of the block copolymer hydride [D] used as a starting material, since the amount of alkoxysilyl groups to be introduced is small. However, since the polymer is reacted with an ethylenically unsaturated silane compound in the presence of an organic peroxide, cross-linking reaction and cleavage reaction of the polymer occur simultaneously, and the value of the molecular weight distribution of the modified block copolymer hydride [E] is tend to be large.

The molecular weight of the hydrogenated modified block copolymer [E] is the weight average molecular weight (Mw ), preferably 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, still more preferably 100,000 or less is.
In addition, the molecular weight distribution (Mw/Mn) is preferably 3.5 or less, more preferably 2.5 or less, and still more preferably 2.0 from the viewpoint of improving the heat resistance and mechanical strength of the molded product [F]. It is below.

<Method for producing compact [F]>
Molded article [F] is a resin composition [f] containing hydrogenated modified block copolymer [E], which is a main component, and other components such as various additives and fillers as necessary. It can be obtained by molding.

<<modified block copolymer hydride [E]>>
The content of the hydrogenated modified block copolymer [E] in the resin composition [f] is usually 70% by mass or more, preferably 80% by mass or more, more preferably 100% by mass of the resin composition [f]. It is 90% by mass or more.

<<Other Ingredients>>
〔Additive〕
Additives include tackifiers, ultraviolet absorbers, infrared absorbers, antioxidants, antiblocking agents, light stabilizers, and the like. These can be used singly or in combination of two or more.

[[Tackifier]]
Specific examples of tackifiers include low-molecular-weight compounds such as polyisobutylene, polybutene, poly-1-octene, ethylene/α-olefin copolymers, and hydrides thereof; polyisoprene, polyisoprene-butadiene copolymers, etc. and hydrides thereof. The tackifier can be used singly or in combination of two or more. Among these, polyisobutylene hydride having a low molecular weight (the number average molecular weight is usually 300 or more and 5,000 or less) in that it maintains transparency and light resistance and is excellent in the effect of imparting tackiness at lower temperatures. Polyisoprene hydride having a low molecular weight (generally having a number average molecular weight of 300 or more and 5,000 or less) is preferred.

[[Ultraviolet absorber]]
Examples of ultraviolet absorbers include oxybenzophenone-based compounds, benzotriazole-based compounds, salicylic acid ester-based compounds, benzophenone-based compounds, and triazine-based compounds. Ultraviolet absorbers can be used singly or in combination of two or more.

[[Infrared absorbing agent]]
Infrared absorbing agents include metal oxide fine particles, near-infrared absorbing dyes, and the like.
Metal oxide fine particles include fine particles of tin oxide such as tin oxide, aluminum-doped tin oxide, indium-doped tin oxide, and antimony-doped tin oxide; zinc oxide, aluminum-doped zinc oxide, indium-doped zinc oxide, gallium-doped zinc oxide, fine particles of zinc oxide such as tin-doped zinc oxide and silicon-doped zinc oxide; fine particles of titanium oxide such as titanium oxide and niobium-doped titanium oxide; tungsten oxide, sodium-doped tungsten oxide, cesium-doped tungsten oxide, thallium-doped tungsten oxide, rubidium fine particles of tungsten oxide such as doped tungsten oxide; fine particles of indium oxide such as indium oxide and tin-doped indium oxide;
Examples of near-infrared absorbing dyes include phthalocyanine compounds, naphthalocyanine compounds, imonium compounds, diimonium compounds, polymethine compounds, diphenylmethane compounds, anthraquinone compounds, pentadiene compounds, azomethine compounds, lanthanum hexaboride, and the like.
The infrared absorbers can be used singly or in combination of two or more.

〔〔Antioxidant〕〕
Antioxidants include phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, and the like. Antioxidants can be used singly or in combination of two or more.

[[Anti-blocking agent]]
Antiblocking agents include ethylene bisstearate amide, lithium stearate, sodium stearate, potassium stearate, magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, barium stearate, calcium laurate, zinc laurate, barium laurate, zinc myristate, calcium ricinoleate, zinc ricinoleate, barium ricinoleate, zinc behenate, sodium montanate, magnesium 12-hydroxystearate, calcium 12-hydroxystearate, zinc 12-hydroxystearate, etc. be done. An antiblocking agent can be used individually by 1 type or in combination of 2 or more types.

[[Light stabilizer]]
As the light stabilizer, a hindered amine light stabilizer or the like can be used. A light stabilizer can be used individually by 1 type or in combination of 2 or more types.

[[Addition amount]]
The amount of the tackifier to be added is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, relative to 100 parts by mass of the hydrogenated modified block copolymer [E]. The amount to be added can be appropriately selected according to the required adhesiveness.
Addition amounts of ultraviolet absorbers, infrared absorbers, antioxidants, antiblocking agents, light stabilizers, etc. are preferably such that the total of these additives is based on 100 parts by mass of the modified block copolymer hydride [E]. is 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, still more preferably 0.05 parts by mass or more, preferably 5 parts by mass or less, more preferably 4 parts by mass or less, still more preferably 3 parts by mass It is below the department.

〔filler〕
Fillers include organic fibers, inorganic fibers and inorganic layered compounds for improving mechanical strength; pigments, dyes and hollow particles for imparting design; metal fibers, carbon fibers and carbon nanotubes; and the like. A filler can be used individually by 1 type or in combination of 2 or more types.

[Method of blending other ingredients]
As a method for blending the modified block copolymer hydride [E] with other components such as the above-described additives and fillers, a generally used known method can be applied.
For example, pellets of the modified block copolymer hydride [E] and other components are uniformly mixed using a mixer such as a tumbler, ribbon blender, and Henschel type mixer, and then a continuous type such as a twin-screw extruder. A method of melting and mixing with a melt kneader and extruding into pellets, or a method of continuously adding compounding agents from a side feeder to a hydrogenated modified block copolymer [E] using a twin-screw extruder equipped with a side feeder. On the other hand, a resin composition (f) for producing a molded article [F] in which other components are uniformly dispersed can be produced by a method such as melt-kneading, extruding, and pelletizing.

<<Method for producing compact [F]>>
The method for producing the molded article [F] by molding the resin composition (f) is not particularly limited, and known molding methods such as a melt extrusion molding method, an inflation molding method, a calendar molding method, an injection molding method, and the like can be used. is applicable. Among them, when the molded article [F] has a sheet-like shape, a melt extrusion molding method is preferable as a method for molding the molded article [F], and T A method of extruding from a die onto a cast roll surface is preferably used.

When the sheet-shaped molding [F] is formed by a melt extrusion molding method, the resin temperature is preferably 170° C. or higher and 250° C. or lower, more preferably 180° C. or higher and 240° C. or lower, still more preferably 190° C. or higher and 230° C. C. or lower temperature range is selected as appropriate.
If the resin temperature is too low, the flowability deteriorates, and defects such as citrus peel and die lines are likely to occur in the obtained sheet-shaped molded body [F], and the extrusion speed of the sheet-shaped molded body [F] is reduced. It cannot be increased, and there is a possibility that it will be industrially disadvantageous. If the resin temperature is too high, the adhesion of the sheet-shaped molded product [F] to glass and metal may be poor, or the storage stability of the sheet-shaped molded product [F] may be deteriorated. Adhesion to glass and metal may deteriorate after long-term storage in the environment.

<<Properties of compact [F]>>
The surface of the sheet-like molding [F] can be planar or embossed. In addition, in order to prevent blocking between the sheet-shaped moldings [F], a release film may be layered on one side of the sheet-shaped moldings [F] for storage.

The thickness of the sheet-shaped molding [F] 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 5 mm or less, more preferably 3 mm or less.
If the thickness of the sheet-shaped molded body [F] is within the above range, for example, it is placed between the glass plate and the sheet-shaped resin molded body [G] and used as an adhesive, and the resin sheet improves penetration resistance. It can be suitably used as tempered laminated glass or the like.
The thickness of the sheet-shaped molding [F] may be uniform or non-uniform. Moreover, the sheet-like molded body [F] may have uneven structures such as uneven patterns, embossed shapes, steps, groove shapes, and through-holes.

(Resin molding [G])
The resin molding [G] is mainly composed of a resin material other than the hydrogenated modified block copolymer [E] described above.
The resin molding [G] contains a resin material (thermoplastic resin and/or thermosetting resin, etc.), and is obtained by molding a resin composition that optionally contains various additives, fillers, and the like. The resin molded product [G] may be a sheet-like molded product with uniform thickness or a molded product with uneven thickness at each part.
When the resin molded product [G] is a film made of a thermoplastic resin such as polycarbonate or polyethylene terephthalate, the bonded product [H] obtained by the production method of the present invention can be used as an interlayer film for laminated glass. , effects such as improving the penetration resistance of the laminated glass can be expected.

The resin molded article [G] used in the production method of the present invention may be transparent or opaque, but a transparent one is particularly preferred.
For example, when the joined body [H] obtained by the production method of the present invention is used in applications requiring light transmittance and transparency, such as laminated glass, a transparent sheet-like resin molded body [H] G] can be used to obtain a joined product [H] with good transparency by joining with the molded product [F].

<Resin material>
Here, as the resin material which is the main component of the resin molding [G], 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 copolymers, ethylene/1-butene/dicyclopentadiene copolymers, ethylene/1-butene/5-ethylidene-2-norbornene copolymers, and ethylene/1-butene/vinylnorbornene copolymers system resin;
Cycloolefin polymers such as ethylene/norbornene copolymers, ethylene/tetracyclododecene copolymers, ring-opening metathesis polymer hydrides of norbornene derivatives, and cyclohexadiene polymers;
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 are exemplified. olefin-(meth)acrylic acid ester copolymer;
an 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, polycyclohexanedimethylene 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 ,5-dibromo-4-hydroxyphenyl)propane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 3,3′-dimethyl-4,4′ -Polycarbonate resins obtained by reacting bisphenols such as dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl oxide and 9,9-bis(4-hydroxyphenyl)fluorene with carbonyl compounds such as carbonyl chloride;
Styrenic resins such as polystyrene, styrene/methyl methacrylate copolymer, and styrene/acrylonitrile copolymer;
(meth)acrylic ester (co)polymers such as polymethyl methacrylate, polymethyl acrylate, methyl methacrylate/glycidyl methacrylate copolymer, and 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, and ethylene/tetrafluoroethylene copolymer;
polyurethane resin;
Aromatic resins such as polyetheretherketone resins, polysulfone resins, polyethersulfone resins, polyarylate resins, polyimide resins, and polyetherimide resins;
polyamide-based resins such as nylon 6, nylon 66, nylon 11, nylon 12, and nylon 6T;
As a thermosetting resin,
epoxy resin, urea resin, melamine resin, phenol resin, unsaturated polyester resin;
These resin materials can be used singly or in combination of two or more.
Among these, polycarbonate resins, polyester resins, and (meth)acrylic acid ester (co)polymers are more preferable from the viewpoint of excellent transparency, mechanical strength, etc., when used by being laminated with a glass plate, for example. .
In the present invention, "(meth)acryl" means acryl and/or methacryl, and "(co)polymer" means homopolymer and/or copolymer.

When the resin molded product [G] contains a thermoplastic resin as a main component, the content of the thermoplastic resin in the resin molded product [G] is preferably 70 mass% when the resin molded product [G] is taken as 100% by mass. % or more, more preferably 80 mass % or more, and still more preferably 90 mass % or more.
When the resin molded body [G] contains a thermosetting resin, the content of the thermosetting resin in the resin molded body [G] is preferably 15% by mass when the resin molded body [G] is taken as 100% by mass. Above, more preferably 20% by mass or more, still more preferably 30% by mass or more.

<Other ingredients>
Additives contained in the resin molding [G] are not particularly limited, but may include antioxidants, ultraviolet absorbers, light stabilizers, and the like. Specific examples thereof include those similar to those described above in the section of "Molded article [F]".

<Method for producing resin molding [G]>
The molding method for molding the resin composition to obtain the resin molding [G] is not particularly limited, and examples thereof include known molding methods such as melt extrusion molding, inflation molding, calendar molding, and injection molding.

<Properties of Resin Mold [G]>
The thickness of the resin molding [G] is not particularly limited. When the resin molding [G] is a sheet-like molding having a substantially uniform thickness, the thickness is preferably 0.02 mm or more, more preferably 0.05 mm or more, and still more preferably 0.1 mm or more. Yes, preferably 20 mm or less, more preferably 15 mm or less, still more preferably 10 mm or less. The thickness of the sheet-shaped resin molding [G] may be uniform or non-uniform. Moreover, the resin molding [G] may have uneven structures such as uneven patterns, embossed shapes, steps, groove shapes, and through holes.
If the thickness of the sheet-shaped resin molded body [G] is within the above range, for example, the sheet-shaped molded body [F] is used to bond the glass plate and the resin molded body [G] to manufacture laminated glass. In this case, the penetration resistance and impact resistance of the laminated glass can be sufficiently enhanced.

(Step 1)
In the method for producing a bonded body of the present invention, before bonding (heating and pressing) the molded body [F] described above and the resin molded body [G] described above, a , the step of applying a predetermined surface treatment is essential.
Specifically, in step 1, at least part of the surface of the resin molding [G] is exposed to at least one selected from the group consisting of plasma irradiation, ultraviolet irradiation, corona discharge and flame spraying in the presence of a silicon compound. Treatment (i) for performing one surface treatment and/or at least one selected from the group consisting of plasma irradiation, ultraviolet irradiation, corona discharge and flame spraying to at least part of the surface of the resin molded body [G] It is a step of performing at least one treatment of the treatment (ii) of contacting the surface with a silicon compound after performing one surface treatment.

<Plasma irradiation>
Examples of plasma irradiation include normal pressure plasma irradiation in which plasma irradiation is performed under atmospheric pressure, and low pressure plasma irradiation in which plasma irradiation is performed under reduced pressure. From the viewpoint of performing plasma irradiation more simply and uniformly, normal pressure plasma irradiation is preferable.
Atmospheric 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. Under atmospheric pressure, nitrogen and dry air or nitrogen and oxygen It is more preferable to carry out in 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 resin molding [G] is preferably 1 mm or more and 20 mm or less.

When plasma irradiation is performed under reduced pressure, plasma irradiation is preferably performed using a low-pressure gas (eg, argon, oxygen, nitrogen, or a mixed gas thereof) of 0.001 kPa to 10 kPa (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 low-pressure plasma irradiation, the output of plasma irradiation is preferably 50 W or more and 500 W or less.

<Corona discharge>
Corona discharge is preferably performed in a dry air atmosphere.
The corona discharge output is preferably 50 W or more and 1000 W or less, and the discharge power is preferably 20 W·min/m ² or more and 550 W·min/m ² or less. The distance between the electrode and the resin molding [G] is preferably 1 mm or more and 20 mm 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% by volume or more and 15% by volume or less, more preferably 0.05% by volume or more and 5% by volume or less.
The distance between the excimer ultraviolet lamp and the irradiated surface of the resin molding [G] is preferably 10 mm or less, more preferably 1 mm or more and 5 mm or less.
The irradiation intensity (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.

<Flame Spray>
The flame spraying is carried out by spraying the flame of the fuel gas onto the surface of the resin molding [G]. The flame temperature is preferably 500° C. or higher and 1,500° C. or lower, more preferably 550° C. or higher and 1,200° C. or lower, and still more preferably 600° C. or higher and 900° C. or lower. The temperature of the flame can be appropriately adjusted according to the type of fuel gas used and the flow rates of the fuel gas and air.
The flame treatment time is preferably 0.1 to 100 seconds, more preferably 0.3 to 30 seconds, and even more preferably 0.5 to 20 seconds.

The surface treatment described above 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 joined body in which the molded body [F] and the resin molded body [G] are more strongly bonded. Plasma irradiation and corona discharge are more preferred.

<Silicon compound>
The silicon compound used in the method for producing a conjugate of the present invention is a compound having at least one of an alkoxysilyl group and an alkylsilyl group.

When the surface of the resin molding [G] is subjected to a predetermined surface treatment in the presence of a silicon compound (i.e., when treatment (i) is employed), for example, the silicon compound is vaporized and then nitrogen, It can be introduced into the surface treatment apparatus together with a carrier gas such as argon or helium. In particular, when flame spraying is employed, a combustible gas such as natural gas or propane gas, or a combustion-supporting gas such as air or oxygen may be used as the carrier gas.
When the silicon compound is brought into contact with the surface of the resin molded body [G] after being subjected to a predetermined surface treatment (that is, when the treatment (ii) is adopted), for example, the surface of the resin molded body [G] is Applying a method of contacting the processed surface with the vaporized silicon compound together with the carrier gas and/or a method of contacting the silicon compound dissolved in a solvent (water, water-alcohol mixed solvent, etc.). can be done.

When the silicon compound is used in a vaporized state, the boiling point of the silicon compound is preferably 300° C. or lower, more preferably 250° C. or lower, and still more preferably 200° C. or lower. If the boiling point exceeds 300° C., the concentration of the silicon compound in the carrier gas cannot be sufficiently increased, and the effect of the surface treatment using the silicon compound may not be obtained. Also, the lower limit of the boiling point of the silicon compound is not particularly limited, but is, for example, -111°C or higher.
In addition, in this invention, a "boiling point" means the boiling point in a normal pressure.

Specific examples of silicon compounds include silane (boiling point: -111°C), methylsilane (boiling point: -57°C), disilane (boiling point: -15°C), trimethylsilane (boiling point: 7°C), tetramethylsilane (boiling point: 28°C), dimethyldimethoxysilane (boiling point: 81°C), methyltrimethoxysilane (boiling point: 102°C), hexamethyldisilane (boiling point: 113°C), dimethyldiethoxysilane (boiling point: 114°C), tetramethoxysilane ( boiling point: 121°C), vinyltrimethoxysilane (boiling point: 123°C), hexamethyldisilazane (boiling point: 125°C), methyltriethoxysilane (boiling point: 143°C), tetraethylsilane (boiling point: 155°C), vinyltri Ethoxysilane (boiling point: 161°C), tetraethoxysilane (boiling point: 168°C), hexyltrimethoxysilane (boiling point: 202°C), 3-aminopropyltrimethoxysilane (boiling point: 215°C), 3-aminopropyltriethoxy Silane (boiling point: 217°C), N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (boiling point: 234°C), phenyltriethoxysilane (boiling point: 236°C), 3-methacryloxypropyltrimethoxysilane (boiling point: 255°C), 3-glycidoxypropylmethyldimethoxysilane (boiling point: 259°C), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (boiling point: 259°C), 3-methacryloxy Propylmethyldiethoxysilane (boiling point: 265°C), 3-glycidoxypropyltrimethoxysilane (boiling point: 290°C), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (boiling point: 310°C), N -phenyl-3-aminopropyltrimethoxysilane (boiling point: 312°C), and the like. These can be used singly or in combination of two or more.

When the vaporized silicon compound is used as part of the mixed gas, the concentration of the silicon compound in the mixed gas (for example, the concentration of the silicon compound in the mixed gas of the carrier gas and the vaporized silicon compound) is preferably is 1×10 ⁻⁵ g/L or more and 5×10 ⁻¹ g/L or less, more preferably 1×10 ⁻⁴ g/L or more and 2×10 ⁻¹ g/L or less, further preferably 1×10 ⁻³ g/L or more and 1×10 ⁻¹ g/L or less.
If the concentration of the silicon compound is too low, the effect of the surface treatment using the silicon compound may not be sufficiently exhibited. If the concentration of the silicon compound is too high, the consumption of the silicon compound increases, which may result in poor economy.
The concentration of the silicon compound in the mixed gas can be measured, for example, by gas chromatography.

When the silicon compound is used in the form of a solution, the boiling point of the silicon compound is not particularly limited. When using a silicon compound in a solution state, in addition to the silicon compounds specifically exemplified above, for example, as a silane coupling agent described in JP-A-2015-155196, JP-A-2015-211940, etc. Known compounds can be used.

The silicon compound solution is obtained by diluting the above silicon compound with a solvent. As a specific example of the solvent, water or an organic solvent can be used alone or in combination of two or more. Examples of organic solvents include alcohols such as methanol, ethanol, isopropanol and n-butanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; glycol ethers such as ethylene glycol and propylene glycol; aromatic hydrocarbons such as toluene and xylene; and ethers such as diethyl ether, diisopropyl ether and di-n-butyl ether. Organic acids such as formic acid, acetic acid, propionic acid and oxalic acid, pH adjusters such as aqueous ammonia, surfactants, and the like can also be added to the silicon compound solution.

The concentration of the silicon compound in the silicon compound solution is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 5% by mass or less, and still more preferably 0.3% by mass or more and 2% by mass. % or less.
If the concentration of the silicon compound is too low, the effect of the surface treatment using the silicon compound may not be sufficiently exhibited. If the concentration of the silicon compound is too high, the consumption of the silicon compound increases, which may result in poor economy.

As the silicon compound used in step 1, tetramethylsilane, dimethyldimethoxysilane, methyltrimethoxysilane, hexamethyldisilane, dimethyldiethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane Silane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-Epoxycyclohexyl)ethyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane are preferred.
More specifically, when the silicon compound is used in a vaporized state, the silicon compound used in step 1 includes tetramethylsilane, dimethyldimethoxysilane, methyltrimethoxysilane, hexamethyldisilane, dimethyldiethoxysilane, tetramethoxysilane, Silane and vinyltrimethoxysilane are preferable, and when the silicon compound is used in a solution state, the silicon compound used in step 1 is 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-amino propylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane are preferred.

(Step 2)
In step 2 of the method for manufacturing a joined body of the present invention, the resin molding [G] that has undergone step 1 described above and the molding [F] described above are subjected to treatment (i) and/or treatment (ii) in step 1. ) is laminated so that the surface to be treated and the molded body [F] are in contact with each other, and then heat-pressed.
Here, according to the production method of the present invention, immediately after the surface of the resin molded body [G] is subjected to the treatment (i) and/or the treatment (ii) in step 1, the resin molded body [G] has a molded body Even if it takes a long time until [F] is laminated and heat-pressed, the compact [F] and the resin compact [G] can be strongly bonded. The time from surface treatment (treatment (i) and/or treatment (ii)) to lamination and thermocompression bonding is not particularly limited. It is preferably within 7 days, more preferably within 5 days, and still more preferably within 3 days from the viewpoint of strong adhesion.
A sufficiently long period of time from surface treatment to lamination and thermocompression bonding for strong bonding allows stable production of a joined body in which the hydrogenated modified block copolymer and the resin molding are firmly bonded. be able to.

The method of laminating the molded product [F] and the resin molded product [G] and heat-pressing them is not particularly limited.
For example, if both the molded body [F] and the resin molded body [G] are sheet-like, the molded body [F] and the resin molded body [G] are divided into the molded body [F] and the resin molded body [G]. The surfaces to be treated are superimposed so that they are in contact with each other, and the obtained laminate is placed in a flexible bag (hereinafter sometimes referred to as "bag"), and heated and pressed while removing air from the bag. A method in which the laminate obtained in the same manner as described above is placed in a bag, the air in the bag is degassed, and then heated and pressed together in an autoclave to form a bonded body. ; a method of bonding the laminate obtained in the same manner as above under heat and pressure with a hot press to form a joined body, and the like. Alternatively, a laminate obtained in the same manner as described above may be heat-pressed using a pressure machine such as a vacuum laminator, a vacuum press, or a roll laminator.
The joined body of the molded body [F] and the resin molded body [G] may be made into a multi-material joined body by further superimposing other members at the same time, if necessary.
Here, the method of putting in a bag and thermocompression bonding to obtain a bonded body is particularly useful as a method of manufacturing a bonded body having a curved surface shape. Further, when manufacturing a bonded body having a curved surface shape by bonding the planar resin molded body [G] to the molded body [F], the resin molded body [G] that has undergone step 1 is heated and softened. It is also possible to obtain a joined body having a curved surface shape by laminating it with the molded body [F] and bonding it together.

The temperature at which the molded product [F] and the resin molded product [G] are heated and pressed together (thermocompression temperature) is preferably 80° C. or higher and 180° C. or lower, more preferably 90° C. or higher and 170° C. or lower, and still more preferably It is 90°C or higher and 160°C or lower.
If the thermocompression bonding temperature is within the above range, sufficient bonding strength can be obtained, and defects such as air bubbles are less likely to occur on the bonding surface.

The pressure during 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 still more preferably 0.3 MPa or more and 1.0 MPa or less. If the pressure during thermocompression bonding is within the above range, sufficient adhesive strength can be obtained, and defects such as air bubbles are less likely to occur on the adhesive surface.
The pressure at the time of thermocompression bonding using a hot 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 still more preferably 0.3 MPa or more and 2 MPa or less. If the pressure during thermocompression bonding is within the above range, sufficient adhesive strength can be obtained, and defects such as air bubbles are less likely to occur on the adhesive surface.
The time for thermocompression bonding in an autoclave (thermal 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, still more preferably 20 minutes, from the viewpoint of maintaining sufficient productivity. minutes or more and 40 minutes or less.
From the viewpoint of maintaining sufficient productivity, the time for performing thermocompression bonding using a hot press device (thermal compression bonding time) 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.

(Conjugate [H])
The joined body [H] obtained by the production method of the present invention has sufficient adhesive strength between the molded body [F] containing the modified block copolymer hydride [E] as a main component and the resin molded body [G]. It is joined. The bonded body [H] is not particularly limited in the peel strength of the adhesive surface between the molded body [F] and the resin molded body [G], but is preferably 4 N/cm or more, more preferably 6 N/cm or more, and still more preferably. is 8 N/cm or more, particularly preferably 10 N/cm or more. If the peel strength of the adhesive surface is 4 N/cm or more, in the bonded body [H], the molded body [F] and the resin molded body [G] are not easily separated. The peel strength can be measured, for example, by a method such as JIS6854-3:1999 described in Examples.
Although the upper limit of the peel strength between the adhesive surfaces of the molded product [F] and the resin molded product [G] is not particularly limited, it is, for example, 30 N/cm or less.

The joined body [H] obtained by the production method of the present invention includes at least one or more molded bodies [F] and at least one or more resin molded bodies [G]. It is a conjugate having a portion where parts or all of the surfaces where the bodies [G] are in contact with each other are adhered.
The molded body [F] and/or the resin molded body [G] are made of glass, metal, other resin, etc. on a surface different from the surface in contact with each other (in the case of a sheet, the surface on the opposite side). Other members may be joined.

The bonded body [H] obtained by the production method of the present invention specifically includes a two-member bonded body composed of molded body [F]/resin molded body [G]; molded body [F]/resin molding Body [G] / molded body [F], resin molded body [G] / molded body [F] / resin molded body [G], glass plate / molded body [F] / resin molded body [G], metal plate / Molded body [F]/Resin molded body [G], Resin molded body [G]/Molded body [F]/Three-member bonded body (three-layer bonded body) composed of other resin molded bodies having metal-plated parts, etc. ; Glass plate / molded body [F] / resin molded body [G] / molded body [F], metal plate / molded body [F] / resin molded body [G] / molded body [F], resin molded body [G ]/Molded body [F]/Resin molded body [G]/Molded body [F], hard coat layer/Resin molded body [G]/Molded body [F]/Construction of other resin molded bodies having metal-plated parts A four-member bonded body (four-layer bonded body) consisting of: glass plate / molded body [F] / resin molded body [G] / molded body [F] / glass plate, glass plate / molded body [F] / resin molded body [G] / molded body [F] / metal plate, glass plate / molded body [F] / resin molded body [G] / molded body [F] / resin molded body [G], metal plate / molded body [F] / Resin molding [G] / Molding [F] / Five-member bonded body (five-layer bonded body) composed of metal plates, etc.; Molded body [F] between glass plates / Resin molded body [G] multi-member (six or more members) bonded body (multilayer bonded body) in which a large number of layers are laminated;

When the joined body [H] obtained by the production method of the present invention is, for example, laminated glass, the two or more glass plates used may have the same thickness, material, etc., but may differ from each other. good too. Although the thickness of the glass plate to be used is not particularly limited, it is preferably 0.05 mm or more and 10 mm or less. In addition, for example, a glass plate/sheet-shaped molded body [F]/sheet-shaped polycarbonate resin molded body [G]/sheet-shaped molded body [F]/glass plate. Laminated glass with excellent penetrability (each thickness is, for example, 1 mm (glass plate) / 0.8 mm (molded body [F]) / 2 mm (polycarbonate resin molded body [G]) / 0.8 mm (molded body [ F])/1 mm (glass plate)) or the like.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited only to the following examples. "Parts" and "%" are based on mass unless otherwise specified.

Evaluations in the examples were performed by the following methods.
(1) Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn)
The molecular weights of block copolymer [C] and block copolymer hydride [D] were measured at 38° C. as standard polystyrene conversion 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 block copolymer hydride [D] is ¹ H of the block copolymer [C] and the block copolymer hydride [D]. - Calculated by measuring NMR.
(3) Adhesiveness (peel strength after holding under predetermined conditions)
The resin molding [G] that had undergone the surface treatment in step 1 was held in the atmosphere at a temperature of 25° C. and a humidity of 50% RH. The peel strength of the joined body [H] obtained by thermocompression bonding with the sheet-shaped molded body [F] using the resin molded body [G] with the holding time of 1 hour, 24 hours, and 48 hours, respectively. was measured and evaluated. The peel strength was measured as follows.
A test piece having a length of 200 mm and a width of 25 mm was taken from the resulting joined body [H]. JIS K6854-3: 1999 (adhesive- Peeling adhesive strength test method-Part 3: T-type peeling) Using Autograph (manufactured by Shimadzu Corporation, product name "AGS-X"), molded body [F] at a peeling speed of 100 mm / min and the resin molding [G] were peeled off, and the peel strength was measured.
The adhesion was evaluated as "good" when the peel strength was 4 N/cm or more, and as "poor" when the peel strength was less than 4 N/cm. In particular, when the peel strength is 4 N/cm or more even when the holding time is 48 hours, the bonded body formed by firmly bonding the molded body [F] and the resin molded body [G] is sufficiently It can be said that stable production is possible.

[Production Example 1] Production of Molded Product [F1] Containing Hydrogenated Modified Block Copolymer [E1] as Main Component (Preparation of Block Copolymer [C1])
550 parts of dehydrated cyclohexane, 25.0 parts of dehydrated styrene, and 0.475 parts of n-dibutyl ether are placed in a sufficiently nitrogen-substituted reactor equipped with a stirrer, and 15 parts of n-butyllithium are added while stirring at 60°C. % cyclohexane solution was added to initiate polymerization.
The mixture was reacted at 60° C. for 60 minutes while stirring. The polymerization conversion 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%.
After that, 25.0 parts of dehydrated styrene was further added and stirred for 60 minutes. The polymerization conversion rate at this point was almost 100%. Here, 0.096 part of isopropyl alcohol was added to terminate the reaction. The obtained block copolymer [C1] had a weight average molecular weight (Mw) of 61,600, a molecular weight distribution (Mw/Mn) of 1.05, and wa:wb = 50:50.
In the above "wa:wb", the mass fraction of the structural unit [a] derived from styrene as the aromatic vinyl compound in the block copolymer [C1] is wa, and isoprene as the chain conjugated diene compound. represents the ratio (wa:wb) between wa and wb, where wb is the mass fraction of the structural unit [b] derived from the block copolymer [C1]. The same applies to Production Example 2 below.

(Preparation of block copolymer hydride [D1])
Next, the polymer solution obtained as described above was transferred to a pressure-resistant reactor equipped with a stirrer, and bis(cyclopentadienyl)titanium dichloride was added in 1.0 parts of toluene as a hydrogenation catalyst. A mixed solution of 0.042 parts and 0.122 parts of diethylaluminum chloride was added and mixed. The inside of the reactor was replaced with hydrogen gas, hydrogen was 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 hydrogenated block copolymer [D1] after the hydrogenation reaction had a weight average molecular weight (Mw) of 62,900 and a molecular weight distribution (Mw/Mn) of 1.06.

After completion of the hydrogenation reaction, 0.10 part of water was added to the reaction solution and stirred at 60° C. for 60 minutes. After that, it is cooled to 30 ° C. or less, and 1.5 parts of activated clay (product name “Galeon Earth (registered trademark)”, manufactured by Mizusawa Chemical Industry Co., Ltd.) and talc (product name “Micro Ace (registered trademark)”, Nippon Talc Co., Ltd. ) was added, and the reaction solution was filtered to remove insoluble matter. Pentaerythrityl tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by SONGWON, product name "Songnox1010"), a phenolic antioxidant, 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 is filtered through a metal fiber filter (pore size 0.4 μm, manufactured by Nichidai Co., Ltd.) to remove minute solids, and then a cylindrical concentration dryer (product name “Kontoro” manufactured by Hitachi, Ltd.) ), the solvent cyclohexane, xylene and other volatile components are removed from the solution at a temperature of 260 ° C. and a pressure of 0.001 MPa or less, extruded in a molten state into strands from a die directly connected to a concentration dryer, After cooling, it was cut with a pelletizer to obtain 92 parts of pellets of hydrogenated block copolymer [D1]. About 100 ppm of finely divided ethylene bisstearic acid amide was added to the pellets as an antiblocking agent. The resulting hydrogenated block copolymer [D1] had a weight average molecular weight (Mw) of 62,300 and a molecular weight distribution (Mw/Mn) of 1.11. The hydrogenation rate of the carbon-carbon double bonds in the main chain and side chains derived from the chain conjugated diene compound is 99%, and the hydrogenation rate of the carbon-carbon double bonds in the aromatic ring derived from the aromatic vinyl compound is 5. %.

(Preparation of modified block copolymer hydride [E1])
2.0 parts of vinyltrimethoxysilane and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (product name 0.2 part of "PERHEXA (registered trademark) 25B" manufactured by NOF CORPORATION) was added to obtain a mixture. This mixture is 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, air-cooled, and then pelletized by a pelletizer. By cutting, 97 parts of pellets of hydrogenated modified block copolymer [E1] having an alkoxysilyl group were obtained. About 100 ppm of an antiblocking agent (ethylene bis stearamide fine powder) was additionally added to the pellets.

After dissolving 10 parts of the obtained hydrogenated block copolymer [E1] pellets in 100 parts of cyclohexane, the solution is poured into 400 parts of dehydrated methanol to solidify the hydrogenated modified block copolymer [E1], followed by filtration. After separation, 9.0 parts of crumbs of hydrogenated modified block copolymer [E1] were isolated by vacuum drying at 25°C. In the FT-IR spectrum, new absorption bands originating from Si—OCH ₃ groups at 1090 cm ⁻¹ and Si—CH ₂ groups at 825 cm ⁻¹ and 739 cm ⁻¹ are observed in those of vinyltrimethoxysilane at 1075 cm ⁻¹ and 808 cm −1 . ⁻¹ , and 766 cm ⁻¹ at different positions. Also, 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. It was confirmed that 1.8 parts of silane had bound.

(Preparation of compact [F1])
An ultraviolet absorber 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3- 0.2 part of tetramethylbutyl)phenol (Tinuvin (registered trademark) 329, manufactured by BASF Japan) was added and mixed evenly. The resulting mixture was passed through a film forming machine ( Product name: "SZW20-25MG" manufactured by Technobell), a sheet-like molded body [F1] (thickness 0 .40 mm, width 230 mm). The compact [F1] was wound up into a roll and collected.

[Production Example 2] Production of Molded Product [F2] Containing Hydrogenated Modified Block Copolymer [E2] as Main Component (Preparation of Block Copolymer [C2])
Using the same apparatus as in Production Example 1, 0.59 parts of n-dibutyl ether, 1.04 parts of 15% cyclohexane solution of n-butyllithium, and 0.5 parts of isopropyl alcohol were used. Polymerization was carried out in the same manner as in Production Example 1 except that the content was changed to 43 parts. The polymerization conversion rate was almost 100%.
The obtained block copolymer [C2] had a weight average molecular weight (Mw) of 40,000, a molecular weight distribution (Mw/Mn) of 1.15, and wa:wb = 50:50.

(Preparation of block copolymer hydride [D2])
Next, the above polymer solution is transferred to the same pressure-resistant reactor as in Production Example 1, and a diatomaceous earth-supported nickel catalyst (product name “E22U”, nickel loading 60%, JGC Catalyst Kasei Co., Ltd.) and 80 parts of dehydrated cyclohexane were added and mixed. The inside of the reactor is replaced with hydrogen gas, hydrogen is supplied while stirring the solution, hydrogenation reaction is carried out at a temperature of 150° C. and a pressure of 3.0 MPa for 1 hour, followed by a temperature of 190° C. and a pressure of 4.5 MPa. The temperature was elevated to 100°C and the hydrogenation reaction was carried out for 6 hours.
The hydrogenated block copolymer [D2] contained in the reaction solution obtained by the hydrogenation reaction had a weight average molecular weight (Mw) of 41,900 and a molecular weight distribution (Mw/Mn) of 1.20.

After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and pentaerythrityl tetrakis[3-(3,5-di-t-butyl 2.0 parts of a xylene solution containing 0.1 part of 4-hydroxyphenyl)propionate] was added and dissolved to obtain a solution.
Next, the above solution was treated in the same manner as in Production Example 1 to produce 93 parts of pellets of hydrogenated block copolymer [D2].
The produced pellet-shaped block copolymer hydride [D2] has a weight average molecular weight (Mw) of 41,400, a molecular weight distribution (Mw/Mn) of 1.25, and a main chain derived from a chain conjugated diene compound and The hydrogenation rate of the carbon-carbon double bond of the side chain and the hydrogenation rate of the carbon-carbon double bond of the aromatic ring derived from the aromatic vinyl compound were both approximately 100%.

(Preparation of modified block copolymer hydride [E2])
Modified block copolymer hydride [E2] having an alkoxysilyl group in the same manner as in Production Example 1, except that pellets of block copolymer hydride [D2] are used instead of block copolymer hydride [D1] 96 parts of pellets of About 100 ppm of an antiblocking agent (ethylene bis stearamide fine powder) was additionally added to the pellets.

As a result of analysis in the same manner as in Production Example 1, it was confirmed that 100 parts of hydrogenated block copolymer [E2] and 1.8 parts of vinyltrimethoxysilane were bonded to 100 parts of hydrogenated block copolymer [D2]. rice field.

(Preparation of molded article [F2] containing hydrogenated modified block copolymer [E2] as main component)
2-(2H-benzotriazole, which is an ultraviolet absorber, is prepared in the same manner as in Production Example 1, except that the modified block copolymer hydride [E2] is used instead of the modified block copolymer hydride [E1]. -2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol was added to prepare a sheet-like compact [F2] (thickness: 0.40 mm, width: 230 mm).

[Example 1]
(Step 1) Corona discharge and contact with silicon compound (treatment (ii))
A sheet-shaped test piece with a length of 300 mm and a width of 200 mm was prepared from a polycarbonate resin molded body [G1] (manufactured by Teijin Chemicals, product name “Panlite Sheet”, PC-2151, sheet with a thickness of 0.5 mm). , On one side of this test piece, using a corona surface treatment device (manufactured by Wedge, product name “A3SW-LW”), surface processing by corona discharge (output: 60 W, electrode and polycarbonate resin molded body [G1] distance: 10 mm, processing speed: 1 m/min).
The surface to be processed of the resin molding [G1c] subjected to the above corona discharge was immersed in an aqueous solution (concentration: 2%) of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM903"), which is a silicon compound. After immersion, it was dried in an oven at 110°C for 5 minutes.

The resin molding [G1cs] subjected to the treatment (ii) by the above corona discharge and subsequent contact with a silicon compound was held under environmental conditions of 25° C. and 50% RH for 1 hour, 24 hours and 48 hours. .

(Step 2) Lamination and thermocompression bonding The treated surface of the sheet-shaped resin molding [G1cs-1h] held for 1 hour in the above environment of 25 ° C. and 50% RH, and the sheet-shaped molding prepared in Production Example 1 A test piece having a length of 300 mm and a width of 200 mm cut out from the body [F1] was sandwiched with a release film at 50 mm of the longitudinal end portion, and the pieces were stacked to form a laminate.

A laminate of this molded body [F1] and resin molded body [G1cs-1h] was placed in a 75 μm thick resin bag having a layer structure of NY (nylon)/adhesive layer/PP (polypropylene). After heat-sealing both sides with a heat sealer while leaving a 200 mm width at the center of the opening of the bag, use a sealed packer (manufactured by Panasonic, product name "BH-951") to deaerate the inside of the bag. The laminate was hermetically packaged by heat sealing the opening. Thereafter, the hermetically-packaged laminate was placed in an autoclave and heat-pressed at a temperature of 140° C. and a pressure of 0.8 MPa for 30 minutes to produce a joined body H (F1/G1cs-1h).

A T-shaped peel test piece was cut out from the resulting joined body H (F1/G1cs-1h), and the adhesion between the molded body [F1] and the resin molded body [G1cs-1h] was evaluated. As a result, the peel strength was It was 17 N/cm, and the evaluation of adhesiveness was good.

Resin moldings [G1cs-24h] that were held in an environment of 25° C. and 50% RH for 24 hours and 48 hours after the treatment (ii) was performed in the same manner as in the production of joined body H (F1/G1cs-1h), and Bonded body H (F1/G1cs-24h) in which molded body [F1], resin molded body [G1cs-24h] and resin molded body [G1cs-48h] are bonded using resin molded body [G1cs-48h] and Conjugate H (F1/G1cs-48h) was made.
As a result of evaluating the adhesiveness of the adhesive surfaces of the conjugate H (F1/G1cs-24h) and the conjugate H (F1/G1cs-48h) in the same manner as the conjugate H (F1/G1cs-1h), the peel strength was The bond H (F1/G1cs-24h) was 16 N/cm, and the bond H (F1/G1cs-48h) was 15 N/cm.

[Comparative Example 1]
Corona discharge was applied to one side of the polycarbonate resin molding [G1] similar to that of Example 1 in the same manner as in Example 1 except that it was not brought into contact with the silicon compound.

As in Example 1, the resin molding [G1c] subjected to surface processing by corona discharge was held under environmental conditions of 25° C. and 50% RH for 1 hour, 24 hours and 48 hours. After that, the compacts [F1] prepared in Production Example 1 were superimposed, and joined body H (F1/G1c-1h), joined body H (F1/G1c-24h), and joined body H in the same manner as in Example 1. (F1/G1c-48h) was produced.

In the same manner as in Example 1, the adhesiveness of the adhesive surface was evaluated for conjugate H (F1/G1c-1h), conjugate H (F1/G1c-24h), and conjugate H (F1/G1c-1h). .
The peel strength of the bonded body H (F1/G1c-1h) was 12 N/cm, and the evaluation of adhesiveness was good. 48h), the peel strength was all less than 4 N/cm, and the evaluation of adhesiveness was unsatisfactory.

[Example 2]
(Step 1) Plasma irradiation in the presence of a silicon compound (treatment (i))
A test piece with a length of 200 mm and a width of 100 mm was prepared from the same polycarbonate resin molding [G1] as used in Example 1, and one side of the test piece was treated with an atmospheric pressure plasma treatment apparatus (manufactured by AcXys Technologies , product name “UL-Coat”), plasma irradiation was performed in the presence of hexamethyldisilane, which is a silicon compound, under the following conditions.
Output: 0.2kW,
Nozzle-substrate distance (distance between plasma generation source and polycarbonate resin molding [G1]): 15 mm,
table speed: 320mm/min,
air flow rate: 5 L/min,
Silicon compound (hexamethyldisilane) flow rate: 0.12 g/min The concentration of the silicon compound in the mixed gas of the carrier gas (air) and the vaporized silicon compound was 2.4×10 ⁻² g/L. rice field.

In the same manner as in Example 1, the resin molding [G1sp] subjected to the treatment (i) by plasma irradiation in the presence of the silicon compound was subjected to environmental conditions of 25° C. and 50% RH for 1 hour, 24 hours, or and held for 48 hours.

(Step 2) Lamination and thermocompression bonding After that, the compacts [F1] prepared in Production Example 1 were stacked, and joined body H (F1/G1sp-1h) and joined body H (F1/ G1sp-24h) and conjugate H (F1/G1sp-48h) were generated.

In the same manner as in Example 1, conjugate H (F1/G1sp-1h), conjugate H (F1/G1sp-24h) and conjugate H (F1/G1sp-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of conjugate H (F1/G1sp-1h) is 16 N/cm, the peel strength of conjugate H (F1/G1sp-24h) is 15 N/cm, and the peel strength of conjugate H (F1/G1sp-48h) is It was 15 N/cm, and all evaluations of adhesiveness were good.

[Comparative Example 2]
In the same manner as in Example 2 except that the silicon compound was not introduced, one surface of the polycarbonate resin molding [G1] similar to that in Example 2 was irradiated with plasma.

As in Example 2, the resin molding [G1p] surface-treated by plasma irradiation was held under the environmental conditions of 25° C. and 50% RH for 1 hour, 24 hours and 48 hours. After that, the compacts [F1] prepared in Production Example 1 were superimposed, and joined body H (F1/G1p-1h), joined body H (F1/G1p-24h), and joined body H in the same manner as in Example 1. (F1/G1p-48h) was produced.

In the same manner as in Example 1, conjugate H (F1/G1p-1h), conjugate H (F1/G1p-24h) and conjugate H (F1/G1p-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of the conjugate H (F1/G1p-1h) was 11 N/cm, and the evaluation of adhesion was good. 48h), the peel strength was all less than 4 N/cm, and the evaluation of adhesiveness was unsatisfactory.

[Example 3]
(Step 1) Flame spraying in the presence of a silicon compound (treatment (i))
A test piece with a length of 200 mm and a width of 200 mm was prepared from the same polycarbonate resin molding [G1] as used in Example 1, and one side of the test piece was treated with a flame treatment device (manufactured by Itro Co., Ltd., product Flame spraying was carried out in the presence of hexamethyldisilane, which is a silicon compound, under the following conditions using the name "Itro processing apparatus".
Distance from burner nozzle to object to be treated: 50 mm,
air flow rate: 150 L/min,
Combustible gas (LPG) flow rate: 8 L / min,
Silicon compound (hexamethyldisilane) flow rate: 4.7 g/min Table speed: 760 mm/sec Number of treatments: 1 reciprocation Incidentally, the concentration of the silicon compound in the mixed gas of the carrier gas (air and LPG) and the vaporized silicon compound was , 3.0×10 ⁻² g/L.

In the same manner as in Example 1, the resin molding [G1sf] subjected to the surface treatment by flame spraying in the presence of the silicon compound was subjected to environmental conditions of 25° C. and 50% RH for 1 hour, 24 hours and 48 hours. held.

(Step 2) Lamination and thermocompression bonding After that, the compacts [F1] prepared in Production Example 1 were respectively stacked, and in the same manner as in Example 1, joined body H (F1/G1sf-1h), joined body H (F1/ G1sf-24h) and conjugate H (F1/G1sf-48h) were generated.

In the same manner as in Example 1, conjugate H (F1/G1sf-1h), conjugate H (F1/G1sf-24h) and conjugate H (F1/G1sf-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of conjugate H (F1/G1sf-1h) is 16 N/cm, the peel strength of conjugate H (F1/G1sf-24h) is 14 N/cm, and the peel strength of conjugate H (F1/G1sf-48h) is It was 13 N/cm, and all evaluations of adhesiveness were good.

[Comparative Example 3]
The same polycarbonate resin molding [G1] as in Example 3 was subjected to flame spraying in the same manner as in Example 3, except that no silicon compound was introduced.

As in Example 3, the resin molding [G1f] subjected to surface treatment by flame spraying was held under environmental conditions of 25° C. and 50% RH for 1 hour, 24 hours and 48 hours. After that, the compacts [F1] prepared in Production Example 1 were superimposed, and joined body H (F1/G1f-1h), joined body H (F1/G1f-24h), and joined body H in the same manner as in Example 1. (F1/G1f-48h) was produced.

In the same manner as in Example 1, conjugate H (F1/G1f-1h), conjugate H (F1/G1f-24h) and conjugate H (F1/G1f-48h) were evaluated for adhesiveness of the adhesive surfaces.
The peel strength of the joined body H (F1/G1f-1h) was 10 N/cm, and the adhesive evaluation was good. 48h), the peel strength was all less than 4 N/cm, and the evaluation of adhesiveness was unsatisfactory.

[Example 4]
Joined body H (F2/ G1cs-1h), H(F2/G1cs-24h) and H(F2/G1cs-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G1cs-1h), conjugate H (F2/G1cs-24h), and conjugate H (F2/G1cs-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of conjugate H (F2/G1cs-1h) is 16 N/cm, the peel strength of conjugate H (F1/G2cs-24h) is 15 N/cm, and the peel strength of conjugate H (F1/G2cs-48h) is It was 15 N/cm, and all evaluations of adhesiveness were good.

[Comparative Example 4]
Joined body H (F2/ G1c-1h), H(F2/G1c-24h) and H(F2/G1c-48h) were generated.

In the same manner as in Example 1, the adhesiveness of the adhesive surface was evaluated for conjugate H (F2/G1c-1h), conjugate H (F2/G1c-24h), and conjugate H (F2/G1c-1h). .
The peel strength of the conjugate H (F2/G1c-1h) was 12 N/cm, and the evaluation of adhesion was good. 48 h), the peel strength was less than 4 N/cm, and the evaluation of adhesiveness was unsatisfactory.

[Example 5]
Joined body H (F2/ G1sp-1h), H(F2/G1sp-24h) and H(F2/G1sp-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G1sp-1h), conjugate H (F2/G1sp-24h) and conjugate H (F2/G1sp-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of conjugate H (F2/G1sp-1h) is 16 N/cm, the peel strength of conjugate H (F1/G2sp-24h) is 15 N/cm, and the peel strength of conjugate H (F1/G2sp-48h) is It was 14 N/cm, and all evaluations of adhesiveness were good.

[Comparative Example 5]
Joined body H (F2/ G1p-1h), H(F2/G1p-24h) and H(F2/G1p-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G1p-1h), conjugate H (F2/G1p-24h) and conjugate H (F2/G1p-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of the conjugate H (F2/G1p-1h) was 10 N/cm, and the evaluation of adhesion was good. 48h), the peel strength was all less than 4 N/cm, and the evaluation of adhesiveness was unsatisfactory.

[Example 6]
Joined body H (F2/ G1sf-1h), H(F2/G1sf-24h) and H(F2/G1sf-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G1sf-1h), conjugate H (F2/G1sf-24h), and conjugate H (F2/G1sf-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of conjugate H (F2/G1sf-1h) is 15 N/cm, the peel strength of conjugate H (F2/G1sf-24h) is 13 N/cm, and the peel strength of conjugate H (F2/G1sf-48h) is It was 13 N/cm, and all evaluations of adhesiveness were good.

[Comparative Example 6]
Joined body H (F2/ G1f-1h), H(F2/G1f-24h) and H(F2/G1f-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G1f-1h), conjugate H (F2/G1f-24h), and conjugate H (F2/G1f-48h) were evaluated for adhesiveness of the adhesive surfaces.
The peel strength of the conjugate H (F2/G1f-1h) was 10 N/cm, and the evaluation of adhesion was good. 48h), the peel strength was all less than 4 N/cm, and the evaluation of adhesiveness was unsatisfactory.

[Example 7]
Same as Example 4, except that a polyethylene terephthalate resin molded product [G2] (manufactured by Acrysunday Co., Ltd., product name "Sunday PET", sheet shape with a thickness of 0.5 mm) was used instead of the polycarbonate resin molded product [G1]. Conjugates H(F2/G2cs-1h), H(F2/G2cs-24h) and H(F2/G2cs-48h) were produced by

In the same manner as in Example 1, conjugate H (F2/G2cs-1h), conjugate H (F2/G2cs-24h), and conjugate H (F2/G2cs-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of conjugate H (F2/G2cs-1h) is 18 N/cm, the peel strength of conjugate H (F2/G2cs-24h) is 17 N/cm, and the peel strength of conjugate H (F2/G2cs-48h) is It was 15 N/cm, and all evaluations of adhesiveness were good.

[Comparative Example 7]
Joined bodies H (F2/G2c-1h) and H (F2/G2c-24h) were prepared in the same manner as in Comparative Example 4, except that polyethylene terephthalate resin molded body [G2] was used instead of polycarbonate resin molded body [G1]. and H(F2/G2c-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G2c-1h), conjugate H (F2/G2c-24h), and conjugate H (F2/G2c-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of the joined body H (F2/G2c-1h) was 13 N/cm, and the adhesive evaluation was good. 48 h), the peel strength was less than 4 N/cm, and the evaluation of adhesiveness was unsatisfactory.

[Example 8]
Joined bodies H (F2/G2sp-1h) and H (F2/G2sp-24h) were prepared in the same manner as in Example 5, except that polyethylene terephthalate resin molded body [G2] was used instead of polycarbonate resin molded body [G1]. and H(F2/G2sp-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G2sp-1h), conjugate H (F2/G2sp-24h) and conjugate H (F2/G2sp-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of conjugate H (F2/G2sp-1h) is 19 N/cm, the peel strength of conjugate H (F2/G2sp-24h) is 17 N/cm, and the peel strength of conjugate H (F2/G2sp-48h) is It was 16 N/cm, and all evaluations of adhesiveness were good.

[Comparative Example 8]
Joined bodies H (F2/G2p-1h) and H (F2/G2p-24h) were prepared in the same manner as in Comparative Example 5, except that polyethylene terephthalate resin molded body [G2] was used instead of polycarbonate resin molded body [G1]. and H(F2/G2p-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G2p-1h), conjugate H (F2/G2p-24h), and conjugate H (F2/G2p-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of the conjugate H (F2/G2p-1h) was 11 N/cm, and the evaluation of adhesion was good. 48h), the peel strength was all less than 4 N/cm, and the evaluation of adhesiveness was unsatisfactory.

[Example 9]
Joined bodies H (F2/G2sf-1h) and H (F2/G2sf-24h) were prepared in the same manner as in Example 6, except that polyethylene terephthalate resin molded body [G2] was used instead of polycarbonate resin molded body [G1]. and H(F2/G2sf-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G2sf-1h), conjugate H (F2/G2sf-24h), and conjugate H (F2/G2sf-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of conjugate H (F2/G2sf-1h) is 16 N/cm, the peel strength of conjugate H (F2/G2sf-24h) is 14 N/cm, and the peel strength of conjugate H (F2/G2sf-48h) is It was 13 N/cm, and all evaluations of adhesiveness were good.

[Comparative Example 9]
Joined bodies H (F2/G2f-1h) and H (F2/G2f-24h) were prepared in the same manner as in Comparative Example 6, except that polyethylene terephthalate resin molded body [G2] was used instead of polycarbonate resin molded body [G1]. and H(F2/G2f-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G2f-1h), conjugate H (F2/G2f-24h), and conjugate H (F2/G2f-48h) were evaluated for adhesion of the adhesive surfaces.
The peel strength of the joined body H (F2/G2f-1h) was 12 N/cm, and the adhesive evaluation was good. 48 h), the peel strength was less than 4 N/cm, and the evaluation of adhesiveness was unsatisfactory.

[Example 10]
Except for using a rigid vinyl chloride resin molded body [G3] (manufactured by Acrysunday Co., Ltd., product name "Sunday Sheet", transparent type, sheet shape with a thickness of 0.5 mm) instead of the polycarbonate resin molded body [G1] Similar to Example 4, conjugates H(F2/G3cs-1h), H(F2/G3cs-24h) and H(F2/G3cs-48h) were produced.

In the same manner as in Example 1, conjugate H (F2/G3cs-1h), conjugate H (F2/G3cs-24h), and conjugate H (F2/G3cs-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of conjugate H (F2/G3cs-1h) is 20 N/cm, the peel strength of conjugate H (F2/G3cs-24h) is 18 N/cm, and the peel strength of conjugate H (F2/G3cs-48h) is It was 17 N/cm, and all evaluations of adhesiveness were good.

[Comparative Example 10]
Joined bodies H (F2/G3c-1h) and H (F2/G3c-24h) were prepared in the same manner as in Comparative Example 4, except that the rigid vinyl chloride resin molded body [G3] was used instead of the polycarbonate resin molded body [G1]. ) and H(F2/G3c-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G3c-1h), conjugate H (F2/G3c-24h), and conjugate H (F2/G3c-48h) were evaluated for adhesiveness of the adhesive surfaces.
The peel strength of the conjugate H (F2/G3c-1h) was 15 N/cm, and the evaluation of adhesion was good. 48 h), the peel strength was less than 4 N/cm, and the evaluation of adhesiveness was unsatisfactory.

[Example 11]
Joined bodies H (F2/G3sp-1h) and H (F2/G3sp-24h) were prepared in the same manner as in Example 5, except that the rigid vinyl chloride resin molded body [G3] was used instead of the polycarbonate resin molded body [G1]. ) and H(F2/G3sp-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G3sp-1h), conjugate H (F2/G3sp-24h) and conjugate H (F2/G3sp-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of conjugate H (F2/G3sp-1h) is 21 N/cm, the peel strength of conjugate H (F2/G3sp-24h) is 19 N/cm, and the peel strength of conjugate H (F2/G3sp-48h) is It was 18 N/cm, and all evaluations of adhesiveness were good.

[Comparative Example 11]
Joined bodies H (F2/G3p-1h) and H (F2/G3p-24h) were prepared in the same manner as in Comparative Example 5, except that the rigid vinyl chloride resin molded body [G3] was used instead of the polycarbonate resin molded body [G1]. ) and H(F2/G3p-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G3p-1h), conjugate H (F2/G3p-24h) and conjugate H (F2/G3p-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of the conjugate H (F2/G3p-1h) was 13 N/cm, and the evaluation of adhesion was good. 48h), the peel strength was all less than 4 N/cm, and the evaluation of adhesiveness was unsatisfactory.

[Example 12]
Joined bodies H (F2/G3sf-1h) and H (F2/G3sf-24h) were prepared in the same manner as in Example 6, except that the rigid vinyl chloride resin molded body [G3] was used instead of the polycarbonate resin molded body [G1]. ) and H(F2/G3sf-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G3sf-1h), conjugate H (F2/G3sf-24h), and conjugate H (F2/G3sf-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of conjugate H (F2/G3sf-1h) is 16 N/cm, the peel strength of conjugate H (F2/G3sf-24h) is 13 N/cm, and the peel strength of conjugate H (F2/G3sf-48h) is It was 12 N/cm, and all evaluations of adhesiveness were good.

[Comparative Example 12]
Joined bodies H (F2/G3f-1h) and H (F2/G3f-24h) were prepared in the same manner as in Comparative Example 6 except that the rigid vinyl chloride resin molded body [G3] was used instead of the polycarbonate resin molded body [G1]. ) and H(F2/G3f-48h) were generated.

In the same manner as in Example 1, conjugate H (F2/G3f-1h), conjugate H (F2/G3f-24h), and conjugate H (F2/G3f-48h) were evaluated for adhesion of the adhesive surfaces.
The peel strength of the joined body H (F2/G3f-1h) was 10 N/cm, and the adhesive evaluation was good. 48h), the peel strength was all less than 4 N/cm, and the evaluation of adhesiveness was unsatisfactory.

[Example 13]
(Step 1) Plasma irradiation and contact with a silicon compound (treatment (ii))
The same polycarbonate resin molding [G1] as in Example 2 was irradiated with plasma in the same manner as in Example 2, except that no silicon compound was introduced.

The surface to be processed of the resin molding [G1p] subjected to the above plasma irradiation was immersed in an aqueous solution (concentration: 2%) of 3-aminopropyltrimethoxysilane, which is a silicon compound, and then placed in an oven at 110°C for 5 hours. Dried under conditions of minutes.

(Step 2) Lamination and thermocompression bonding The resin molded product [G1ps] subjected to the treatment (ii) by the above plasma irradiation and subsequent contact with a silicon compound under environmental conditions of 25 ° C. and 50% RH for 1 hour, Hold for 24 hours and 48 hours. After that, the compacts [F1] prepared in Production Example 1 were superimposed, and in the same manner as in Example 1, joined body H (F1/G1ps-1h), joined body H (F1/G1ps-24h) and joined body H ( F1/G1ps-48h) was produced.

In the same manner as in Example 1, the adhesiveness of the bonding surface was evaluated for conjugate H (F1/G1ps-1h), conjugate H (F1/G1ps-24h) and conjugate H (F1/G1ps-48h).
The peel strength of bonded body H (F1/G1ps-1h) is 18 N/cm, the peel strength of bonded body H (F1/G1ps-24h) is 16 N/cm, and the peel strength of bonded body H (F1/G1ps-48h) is It was 16 N/cm, and the evaluation of adhesiveness was good.

[Example 14]
(Step 1) UV irradiation and contact with a silicon compound (treatment (ii))
A sheet-shaped test piece of 200 mm long × 100 mm wide was prepared from the same polycarbonate resin molded product [G1] as used in Example 1, and one side of this test piece was irradiated with a xenon excimer ultraviolet irradiation device (M · Ultraviolet irradiation (excimer ultraviolet irradiation) was performed under the following conditions using a product name "MECL-M-1-200" manufactured by Di-Excima.
Illuminance: 140 mW/cm ² ,
Stage temperature: 100°C,
The distance between the sample and the light source (the distance between the excimer ultraviolet lamp and the irradiated surface of the polycarbonate resin molded body [G1]): 2 mm,
Processing environment: nitrogen gas atmosphere, oxygen concentration 0.1% by volume,
Stage movable speed: 10 mm/sec,
Accumulated amount of excimer light exposure: 6500 mJ/cm ²

After immersing the processed surface of the resin molding [G1uv] irradiated with the above excimer ultraviolet rays in an aqueous solution (concentration: 2%) of 3-aminopropyltrimethoxysilane, which is a silicon compound, in an oven at 110 ° C. It was dried under the conditions of 5 minutes.

(Step 2) Lamination and thermocompression bonding The resin molded body [G1uvs] subjected to the above treatment (ii) by irradiation with excimer ultraviolet rays and subsequent contact with a silicon compound was placed under environmental conditions of 25° C. and 50% RH for 1 hour. , 24 hours and 48 hours. After that, the compacts [F1] prepared in Production Example 1 were superimposed, and in the same manner as in Example 1, joined body H (F1/G1uvs-1h), joined body H (F1/G1uvs-24h), and joined body H ( F1/G1uvs-48h) was generated.

In the same manner as in Example 1, conjugate H (F1/G1uvs-1h), conjugate H (F1/G1uvs-24h) and conjugate H (F1/G1uvs-48h) were evaluated for adhesiveness of the adhesive surface.
The peel strength of conjugate H (F1/G1uvs-1h) is 14 N/cm, the peel strength of conjugate H (F1/G1uvs-24h) is 13 N/cm, and the peel strength of conjugate H (F1/G1uvs-48h) is It was 12 N/cm, and the evaluation of adhesiveness was good.

The results of Examples 1-14 and Comparative Examples 1-12 described above are shown in Tables 1 and 2 below, respectively. In Tables 1 and 2,
"APTM" denotes 3-aminopropyltrimethoxysilane;
"HMDS" denotes hexamethyldisilane,
"PC" indicates a polycarbonate resin,
"PET" indicates polyethylene terephthalate resin,
"PVC" indicates rigid vinyl chloride resin.

The results of this example and comparative example reveal the following.
In the absence of a silicon compound, the resin molded product [G] whose surface was subjected to corona discharge, plasma irradiation, or flame spraying was kept under environmental conditions of 25 ° C. and 50% RH for 1 hour. Although it can be strongly adhered to the molded article [F] containing the copolymer hydride [E] as a main component, it cannot be firmly adhered to the molded article [F] after being held for 24 hours or more (Comparative Examples 1 to 9).
On the other hand, in the presence of a silicon compound, the resin molding [G] subjected to treatment (i) of plasma irradiation or flame spraying on the surface was subjected to environmental conditions of 25 ° C. and 50% RH for 1 hour. , 24 hours, or 48 hours, it can be stably and strongly adhered to the molded article [F] containing the hydrogenated modified block copolymer [E] as a main component (Examples 2, 3, 5, 6, 8, 9, 11, 12). In addition, the resin molded body [G] subjected to the treatment (ii) in which the surface was subjected to corona discharge, plasma irradiation, or excimer ultraviolet irradiation and then contacted with a silicon compound was subjected to environmental conditions of 25 ° C. and 50% RH. Even after holding for any time of 1 hour, 24 hours, or 48 hours, it can be stably and strongly adhered to the sheet-like molded product [F] containing the hydrogenated modified block copolymer [E] as a main component (practical Examples 1, 4, 7, 10, 13, 14).
Also, after performing at least one of the treatment (i) and treatment (ii) on the surface of the resin molded body [G], it is adhered to the molded body [F] to produce the joined body [H]. According to the production method of the present invention, the resin molded body [G] and the molded body [F] which have been subjected to only surface treatment (the surface is subjected to corona discharge, plasma irradiation, or flame spraying) in the absence of a silicon compound. There is also an effect that a bonded body having stronger adhesiveness can be obtained compared to the method of manufacturing a bonded body [H] by bonding with , Example 3 and Comparative Example 3, Example 4 and Comparative Example 4, Example 5 and Comparative Example 5, Example 6 and Comparative Example 6, Example 7 and Comparative Example 7, Example 8 and Comparative Example 8, Example For Example 9 and Comparative Example 9, Example 10 and Comparative Example 10, Example 11 and Comparative Example 11, Example 12 and Comparative Example 12, "Peel strength (N/cm)" in Table 1 "After holding for 1 hour" ”).

According to the method for producing a bonded body of the present invention, a molded body mainly composed of a hydrogenated modified block copolymer into which an alkoxysilyl group is introduced and a resin molded body are stably and firmly adhered to each other, A joined body of the molded article and the resin molded article can be manufactured. For this reason, the method for producing a bonded body of the present invention comprises a molded body [F] mainly composed of a specific hydrogenated modified block copolymer [E] into which an alkoxysilyl group has been introduced, and a resin such as polycarbonate or polyethylene terephthalate. Useful for encapsulation of solar cell modules, encapsulation of organic EL elements, encapsulation of electronic components, lamination of penetration-resistant laminated glass, etc., which require strong adhesion to the molded product [G]. .

Claims (3)

A bonded product obtained by bonding a molded body [F] containing ethylene bisstearic acid amide, which is mainly composed of a modified block copolymer hydride [E] into which an alkoxysilyl group is introduced, and a resin molded body [G]. A method for producing [H], comprising steps 1 and 2 below.
Step 1: The surface of the resin molding [G] is selected from the group consisting of plasma irradiation, corona discharge, and flame spraying in the presence of at least one of hexamethyldisilane and 3-aminopropyltrimethoxysilane. performing at least one process (i);
Step 2: The resin molded body [G] that has undergone the step 1 and the molded body [F] are separated from the surface of the resin molded body [G] subjected to the treatment (i) and the molded body [F] A step of laminating the layers so that they are in contact with each other and heat-pressing them. 2. The method for producing a bonded body according to claim 1, wherein the bonding surface between said molded body [F] and said resin molded body [G] in said bonded body [H] has a peel strength of 4 N/cm or more. The hydrogenated modified block copolymer [E] comprises at least two polymer blocks [A] mainly composed of structural units [a] derived from an aromatic vinyl compound and structural units derived from a chain conjugated diene compound. A block copolymer [C] comprising [b] as a main component and at least one polymer block [B], wherein the entire amount of the structural unit [a] accounts for the block copolymer [C] When the mass fraction is wa and the mass fraction of the total amount of the structural unit [b] in the block copolymer [C] is wb, the ratio wa:wb between wa and wb is 20:80 to 60. : 40, the block copolymer hydride [D] obtained by hydrogenating 90% or more of the carbon-carbon unsaturated bonds derived from the structural unit [b] of the block copolymer [C] has an alkoxysilyl group. 3. The method for producing a conjugate according to claim 1, wherein the introduced modified block copolymer is a hydrogenated product.