JP6915325B2 - Copolymer and its production method - Google Patents

Description

The present invention relates to a novel copolymer and a method for producing the same. More specifically, the present invention relates to a vinylcyclohexane-α-olefin copolymer and a method for producing this copolymer.

It is known that excellent mechanical properties and high heat resistance can be obtained by giving a branched structure such as graft polymerization or cross polymerization to a copolymer of an aromatic olefin and various α-olefins. In Patent Document 1, in particular, as a coordination polymerization step, a styrene monomer, an olefin monomer, and a diene monomer are copolymerized using a single-site coordination polymerization catalyst to synthesize an olefin-styrene-diene copolymer, and then cross. As a chemical conversion step, we have succeeded in obtaining a cross copolymer of olefin-styrene-diene by polymerizing a vinyl compound monomer. This cloth copolymer has a star-shaped branched structure, and is a copolymer having superior breaking strength, tensile elasticity, hardness, heat resistance, etc., as compared with a copolymer having a conventional branched structure.

On the other hand, by hydrogenating the aromatic ring in a block copolymer of an aliphatic olefin-aromatic olefin such as SIBS, transparency, optical properties, flexibility, mechanical properties, moldability, heat resistance, gas barrier property, and low It is known that a hydrogenated block copolymer having an excellent balance of hygroscopicity and non-adsorption of chemicals can be prepared (Patent Document 2).

International Publication No. 2000/37517 Japanese Unexamined Patent Publication No. 2013-216902

The conventional cross-polymer of an aromatic olefin and an α-olefin has excellent mechanical strength, but its gas barrier property is not sufficient. On the other hand, the conventional hydrogenated block copolymer as shown in Patent Document 2 has a very excellent gas barrier property, but has a problem that the adhesiveness is not sufficient depending on the application.

An object of the present invention is to solve the above problems and to provide a copolymer having an excellent balance of mechanical strength, optical properties, flexibility, heat resistance, compatibility and adhesiveness, and a high gas barrier property.

The present inventors have diligently studied in order to solve the above-mentioned problems, and have found that a copolymer having a specific structure can solve the above-mentioned problems, and have completed the present invention.

That is, the gist of the present invention is as follows.

[1] A copolymer containing a structural unit represented by the following formula (1) and / or a structural unit represented by the following formula (2) and a structural unit represented by the following formula (3).

[In the formula (1), R ¹ represents an alkyl group having 1 or more carbon atoms and 10 or less carbon atoms, n ¹ represents an integer of 0 or more and 4 or less, and X ¹ represents a structural unit represented by the following formula (5) and /. Alternatively, it is a group containing a structural unit represented by the following formula (6). ]

[In the formula (2), R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X ² is a structural unit represented by the following formula (5) and / or represented by the following formula (6). It is a group containing a structural unit. ]

[In the formula (3), R ³ represents an alkyl group having 1 or more and 10 or less carbon atoms, and n ² represents an integer of 0 or more and 5 or less. ]

[In the formula (5), R ⁶ represents an alkyl group having 1 or more and 10 or less carbon atoms, and n ³ represents an integer of 10 or more and 5 or less. ]

[In the formula (6), R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms. ]

[2] Aroma of a copolymer containing a structural unit represented by the following formula (7) and / or a structural unit represented by the following formula (8) and a structural unit represented by the following formula (9). A method for producing a copolymer, which comprises a step of hydrogenating a ring.

[In the formula (7), R ¹¹ represents an alkyl group having 1 or more carbon atoms and 10 or less carbon atoms, n ¹¹ represents an integer of 0 or more and 4 or less, and X ¹¹ represents a structural unit represented by the following formula (10) and /. Alternatively, it is a group containing a structural unit represented by the following formula (11). ]

[In the formula (8), R ¹² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X ¹² is a structural unit represented by the following formula (10) and / or represented by the following formula (11). It is a group containing a structural unit. ]

[In the formula (9), R ¹³ represents an alkyl group having 1 or more and 10 or less carbon atoms, and n ¹² represents an integer of 0 or more and 5 or less. ]

[In the formula (10), R ¹⁶ represents an alkyl group having 1 or more and 10 or less carbon atoms, and n ¹³ represents an integer of 0 or more and 5 or less. ]

[In the formula (11), R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms. ]

According to the present invention, it is possible to obtain a copolymer having an excellent balance of mechanical strength, optical properties, flexibility, heat resistance, compatibility and adhesiveness, and having a high gas barrier property. Moreover, the above-mentioned copolymer can be obtained by using the production method of this invention.

Hereinafter, the present invention will be specifically described, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

The copolymer of the present invention is a polymer having a repeating unit having a vinylcyclohexane skeleton. In the copolymer of the present invention, the aromatic ring moiety or the aromatic ring moiety and the olefin moiety contained in the copolymer having a repeating unit having a styrene skeleton are hydrogenated and converted into a saturated hydrocarbon moiety. Also includes.
The copolymer of the present invention is not particularly limited as long as it satisfies the above-mentioned constitutional requirements. The arrangement of the repeating unit in the copolymer is also not particularly limited, and examples thereof include random and block. Among these, block copolymers are preferable because the physical properties of the copolymers can be easily adjusted.
Further, each of the structural units described later contained in the copolymer of the present invention may have a single structure having the same substituents or the like, or may contain a plurality of different structures such as substituents or the like. May be good.

[Copolymer]
The copolymer of the present invention contains a structural unit represented by the following formula (1) and / or a structural unit represented by the following formula (2) and a structural unit represented by the following formula (3). ..

[In the formula (1), R ¹ represents an alkyl group having 1 or more carbon atoms and 10 or less carbon atoms, n ¹ represents an integer of 0 or more and 4 or less, and X ¹ represents a structural unit represented by the following formula (5) and /. Alternatively, it is a group containing a structural unit represented by the following formula (6). ]

[In the formula (2), R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X ² is a structural unit represented by the following formula (5) and / or represented by the following formula (6). It is a group containing a structural unit. ]

[In the formula (3), R ³ represents an alkyl group having 1 or more and 10 or less carbon atoms, and n ² represents an integer of 0 or more and 5 or less. ]

[In the formula (5), R ⁶ represents an alkyl group having 1 or more and 10 or less carbon atoms, and n ³ represents an integer of 0 or more and 5 or less. ]

[In the formula (6), R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms. ]

<Structure of copolymer>
The copolymer of the present invention forms a copolymer in the above-mentioned structural units. The copolymer may be a random copolymer or a block copolymer, but as described above, a block copolymer is preferable because the physical properties of the copolymer can be easily adjusted. Further, the polymerization may be carried out in two or more stages.
In a block copolymer, one or more segments of the above-mentioned structural units form a copolymer. The combination is not particularly limited as long as the effects of the present invention can be obtained.

The reason why the copolymer of the present invention exerts the effect of the present invention is not clear, but the following can be considered.
By containing a cyclohexane ring, the copolymer of the present invention is imparted with a hydrophobic characteristic, and mainly improves the gas barrier property against water vapor. Further, by having a branched structure, compatibility and adsorptivity are improved, and polishing resistance and fracture resistance are improved. Further, by adjusting the combination of each structural unit and its content, the weather resistance, heat resistance, flexibility, and mechanical strength are improved. The copolymer of the present invention satisfies the above-mentioned physical properties in a very well-balanced manner.

The copolymer of the present invention may be in any of atactic, isotactic and syndiotactic forms, and these may be mixed. The ratio of the above-mentioned forms in the copolymer is not particularly limited, and can be appropriately adjusted depending on the intended use and the like.
Increasing the proportion of the syndiotactic form raises the melting point of the copolymer, which tends to give a copolymer with high heat resistance. On the other hand, when the proportion of the atactic form is increased, the melting point is lowered and the heat resistance is lowered, but the moldability tends to be improved. Further, when the proportion of the isotactic form is increased, the crystallization of the copolymer is likely to proceed, and the heat resistance, chemical resistance and the like are improved, but the moldability tends to be lowered.
By appropriately adjusting the proportion of the syndiotactic form, it may be possible to prepare an adhesive polymer having reflow solder resistance.
The above-mentioned form in the copolymer can be confirmed by using NMR or the like.

The copolymer of the present invention has a branched structure, and has a branched structure starting from the structural unit represented by the formula (1) and / or the structural unit represented by the formula (2). The form of the branched structure is not particularly limited, and examples thereof include a graft polymer and a star polymer. The rate of grafting is not particularly limited.

The copolymer of the present invention is not particularly limited as long as it has the above-mentioned specific structural unit, but the structural unit represented by the above formula (1) and / or the structural unit represented by the formula (2) can be used. As a starting point, the structural unit represented by the formula (5) and / or the structural unit represented by the formula (6) are polymerized so as to have a branched structure. The terminal of the copolymer is not particularly limited, and may have any structure such as an alkyl group, a hydroxyl group, a carboxyl group, a chloro group, a bromo group, an amino group, an epoxy group, an ether group, a carbonyl group, a fluoro group, and an iodo group.

<Constituent unit represented by equation (1)>
Equation (1) in the structural unit represented by (hereinafter, may be represented by the structural unit A.) Is a constituent unit of the polymer to a repeating unit derived structure vinylcyclohexane, substituents R ¹ cyclohexane ring in the skeleton And X ¹ are included.

(R ¹ )
In the formula (1), R ¹ represents an alkyl group having 1 or more carbon atoms and 10 or less carbon atoms. The carbon number of R ¹ is not particularly limited, but is preferably 8 or less, and more preferably 6 or less. Within the above range, the copolymer tends to have an excellent balance of gas barrier properties, heat resistance, and the like.
The alkyl group may have a substituent. Specific examples of the substituent that the alkyl group may have include a hydroxyl group, a carboxyl group, a chloro group, a bromo group, an amino group, an epoxy group, an ether group, a carbonyl group, a fluoro group, an iodo group and the like. Be done. Although not particularly limited, for example, for the purpose of imparting water solubility to the copolymer, it is preferable to have a hydroxyl group.
The substitution position of R ¹ is not particularly limited, but the 2-position and / or 4-position are preferable because the stability of the copolymer tends to be improved.

(N ¹ )
n ¹ represents an integer of 0 or more and 4 or less. Although not particularly limited, n ¹ is preferably 0 or more and 3 or less. Within the above range, the heat resistance and compatibility of the copolymer tend to be improved due to the stereoelectronic effect of the substituent. In the structural unit A, when n ¹ is 2 or more and has a plurality of R ¹ , the R ¹ may be the same or different.

(X ¹ )
X ¹ is a group containing the structural unit represented by the formula (5) and / or the structural unit represented by the formula (6) (the structural unit represented by the formula (5) is the structural unit E, the formula. The structural unit represented by (6) may be referred to as a structural unit F). Although not particularly limited, it is preferable that X ¹ contains at least the structural unit E because the gas barrier property of the copolymer tends to be enhanced due to the hydrophobic effect of the cyclohexane ring.

X ¹ may have a structural unit other than the structural unit E and / or the structural unit F as long as the effect of the present invention is not significantly impaired. Specific examples of the structural unit other than the structural unit E and / or the structural unit F that X ^{1 may have include 4-monochlorostyrene, 4-chloromethylstyrene, 4-hydroxymethylstyrene, and 4-t.} -Aromatic rings of the above constituent units such as butoxystyrene, dichlorostyrene, 4-monofluorostyrene, 4-phenylstyrene, vinylnaphthalene, vinylanthracene, acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester are hydrogenated. Examples include structural units derived from things and the like.

<Constituent unit represented by equation (5)>
Structural unit represented by the formula (5) (building block E) is a structural unit of a polymer with repeating units derived structure vinylcyclohexane, those containing a substituent R ⁶ in the cyclohexane ring in the skeleton.

(R ⁶ )
In the formula (5), R ⁶ represents an alkyl group having 1 or more carbon atoms and 10 or less carbon atoms. The preferable number of carbon atoms of R ^6, the substituents that the alkyl group may have, the substitution positions, and the preferable reasons for them are the same as those of R ¹ of the above formula (1).

(N ³ )
n ³ represents an integer of 0 or more and 5 or less. Although not particularly limited, n ³ is preferably 0 or more and 3 or less. Within the above range, the heat resistance and compatibility of the copolymer tend to be improved due to the stereoelectronic effect of the substituent. In the structural unit E, when n ³ is 2 or more and has a plurality of R ⁶ , the R ⁶ may be the same or different.

<Constituent unit represented by equation (6)>
The structural unit (constituent unit F) represented by the formula (6) is a structural unit of a polymer having an ethylene-derived skeleton as a repeating unit, and contains substituents R ⁷ and R ⁸ in carbon atoms in the skeleton.

(R ⁷ and R ⁸ )
In formula (6), R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms. The preferable number of carbon atoms when R ⁷ and R ⁸ are alkyl groups, the substituents that the alkyl group may have, and the preferable reasons for them are the same as those of R ¹ of the above formula (1).

<Constituent unit represented by equation (2)>
The structural unit represented by the formula (2) (hereinafter, may be referred to as structural unit B) is a structural unit of a polymer having an ethylene skeleton as a repeating unit, and substituents R ² and X ^{2 are added to carbon atoms in the skeleton.} Is included.

(R ² )
In the formula (2), R ² represents a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms. When R ² is an alkyl group, the preferred number of carbon atoms, the substituents that the alkyl group may have, and the preferable reasons for them are the same as those of R ¹ of the above formula (1).

(X ² )
X ² is a group containing the structural unit E and / or the structural unit F. Although not particularly limited, it is preferable that X ² contains at least the structural unit E because the gas barrier property of the copolymer tends to be enhanced due to the hydrophobic effect of the cyclohexane ring.
X ² may have a structural unit other than the structural unit E and / or the structural unit F as long as the effect of the present invention is not significantly impaired. The specific structural unit other than the structural unit E and / or the structural unit F that X ^{2 may have is other than the structural unit E and / or the structural unit F that X 1} may have. It is the same as the one listed as the constituent unit of.

In the copolymer of the present invention, the structural unit A and / or the structural unit B serves as the starting point of the branched structure of the copolymer, and the structural unit A and / or the structural unit B forms a graft polymer or a star polymer. NS.
The copolymer of the present invention may contain the above-mentioned structural unit A and / or the structural unit B, but it is preferable that the copolymer contains at least the structural unit A due to the hydrophobic effect of the cyclohexane ring and thus the gas barrier property of the copolymer. Is preferable because it tends to increase.

<Constituent unit represented by equation (3)>
The structural unit represented by the formula (3) (hereinafter, may be referred to as structural unit C) is a structural unit of a polymer having a skeleton derived from vinylcyclohexane as a repeating unit, and has a substituent R ^{3 on a carbon atom in the skeleton.} Is included.

(R ³ )
In the formula (3), R ³ represents an alkyl group having 1 or more carbon atoms and 10 or less carbon atoms. The preferable number of carbon atoms of R ^3, the substituents that the alkyl group may have, the substitution positions, and the preferable reasons for them are the same as those of R ¹ of the above formula (1).

(N ² )
n ² represents an integer of 0 or more and 5 or less. Although not particularly limited, n ² is preferably 0 or more and 3 or less. Within the above range, the heat resistance and compatibility of the copolymer tend to be improved due to the stereoscopic effect of the substituent, which is preferable. In the structural unit C, when n ² is 2 or more and has a plurality of R ³ , the R ³ may be the same or different.

<Ratio of constituent units A to C, E and F>
The content ratios of the constituent units A to C, E and F in the copolymer of the present invention are not particularly limited.

When the copolymer contains the constituent unit A or the constituent unit B, the content ratio of the constituent unit A or the constituent unit B is preferably 0.001 mol% or more and 10 mol% or less with respect to all the constituent units of the copolymer. It is more preferably 1 mol% or less, still more preferably 0.1 mol% or less. When the content ratio of the structural unit A or the structural unit B is within the above range, the crosslinked structure does not become excessive, and the desired copolymer physical properties tend to be obtained.
When the copolymer contains the constituent unit A and the constituent unit B, the total content ratio of the constituent unit A and the constituent unit B is preferably 0.001 mol% or more and 10 mol% with respect to all the constituent units of the copolymer. It is more preferably 1 mol% or less, still more preferably 0.1 mol% or less. When the total content ratio of the structural unit A and the structural unit B is within the above range, the crosslinked structure does not become excessive and the desired copolymer physical properties tend to be obtained.

The content ratio of the structural unit C is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% or more, based on all the structural units of the copolymer. Further, it is preferably 50 mol% or less, more preferably 40 mol% or less, and further preferably 30 mol% or less.

When the content ratio of each of the above constituent units is larger than the above lower limit, the gas barrier property tends to be improved. Further, when the content ratio of each of the above-mentioned structural units is smaller than the above-mentioned upper limit, the flexibility of the copolymer tends to be improved.

The copolymer of the present invention is not particularly limited, but it is preferable that the constituent units A and / or B contain at least the constituent unit A because the cross-linking point of the copolymer tends to be easily controlled.

The content ratio of the constituent unit E in the copolymer of the present invention is not particularly limited, but the content ratio of the constituent unit E is preferably 1 mol% or more, more preferably 3 mol, based on all the constituent units of the copolymer. % Or more, more preferably 5 mol% or more. Further, it is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, based on all the constituent units of the copolymer. When the content ratio of the structural unit E is not more than the above upper limit value, the flexibility of the copolymer tends to be improved. When the content ratio of the structural unit E is equal to or higher than the above lower limit value, the gas barrier property tends to be improved.

The content ratio of the constituent unit F in the copolymer of the present invention is not particularly limited, but the content ratio of the constituent unit F is preferably 1 mol% or more, more preferably 3 mol, based on all the constituent units of the copolymer. % Or more, more preferably 5 mol% or more. Further, it is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, based on all the constituent units of the copolymer. When the content ratio of the structural unit F is not more than the above upper limit value, the gas barrier property tends to be improved. When the content ratio of the structural unit F is at least the above lower limit value, the flexibility of the copolymer tends to be improved.

When the copolymer contains the constituent unit E and the constituent unit F, the total content ratio of the constituent unit E and the constituent unit F is preferably 1 mol% or more, more preferably 1 mol% or more, based on all the constituent units of the copolymer. Is 3 mol% or more, more preferably 5 mol% or more. Further, it is preferably 20 mol% or less, more preferably 15 mol% or less, and further preferably 10 mol% or less with respect to the constituent unit. When the total content ratio of the structural unit E and the structural unit F is within the above range, a copolymer having a good balance between gas barrier properties and flexibility tends to be obtained.

<Other ingredients>
The copolymer of the present invention may contain other components in addition to the above-mentioned structural units A to C as long as the effects of the present invention are not significantly impaired.
Specific examples of the components other than the structural units A to C that may be contained in the copolymer of the present invention include a polymerization initiator, a polymerization catalyst, a stabilizer, a neutralizing agent, a terminal encapsulant, and a composition. Examples include structural units other than units A to C. The content of other components is not particularly limited.

<Structural example of copolymer>
The structure of the copolymer of the present invention is not particularly limited, and examples of preferable structures include the following structures.
The first-stage polymerized chain (hereinafter, may be referred to as “main chain”) includes the structural unit A and / or the structural unit B and the structural unit C, and the second-stage polymerized chain (hereinafter, “side”). A copolymer having a structural unit E and / or a structural unit F as a "chain").
In this copolymer, the structural unit A and / or the structural unit B serves as the starting point of the branched structure of the copolymer, and a graft polymer or a star-shaped polymer is formed.
The ratio of each structural unit contained in the first-stage and second-stage polymerized chains is not particularly limited and can be appropriately adjusted.

The ratio of the main chain constituent unit to the side chain constituent unit in the copolymer of the present invention is not particularly limited, but the main chain constituent unit is preferably 80 mol% or more with respect to all the constituent units of the copolymer. Yes, more preferably 85 mol% or more, still more preferably 90% or more. Further, it is preferably 99 mol% or less, more preferably 97 mol% or less, and further preferably 95 mol% or less. When the ratio of the constituent units of the main chain is not more than the above upper limit value, the mechanical properties of the obtained copolymer tend to be improved. Further, when the ratio of the constituent units of the main chain is equal to or more than the above lower limit value, the flexibility of the obtained copolymer tends to be improved.

<Constituent unit represented by equation (4)>
In addition to the above-mentioned structural units A to C, the copolymer of the present invention may be further referred to as a structural unit represented by the following formula (4) in the main chain portion of the copolymer (hereinafter, referred to as structural unit D). ) May be included. The structural unit D is a structural unit of a polymer having an ethylene skeleton as a repeating unit, and contains substituents R ⁴ and R ⁵ in carbon atoms in the skeleton. Including the structural unit D in the main chain tends to improve the flexibility of the copolymer, which is preferable.

[In the formula (4), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms. ]

(R ⁴ and R ⁵ )
In the formula (4), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms. The preferable number of carbon atoms when R ⁴ and R ⁵ are alkyl groups, the substituents that the alkyl group may have, and the preferable reasons for them are the same as those of R ¹ of the above formula (1).

(Ratio of structural unit D)
When the main chain of the copolymer of the present invention has a constituent unit D, the content ratio of the constituent unit D is preferably 50 mol% or more, more preferably 60 mol% or more, based on all the constituent units of the copolymer. It is more preferably 70 mol% or more. Further, it is preferably 99 mol% or less, more preferably 90 mol% or less, and further preferably 92 mol% or less. When the content ratio of the structural unit D is at least the above lower limit value, the flexibility of the copolymer tends to be improved. Further, when it is not more than the above upper limit value, the gas barrier property tends to be improved.

<Other building blocks>
Specific examples of the structural units that the copolymer of the present invention may have other than the structural units A to D include the structural units E and / or the structural units F other than the structural units E and / or the structural units F that the ^{X 1 may have.} Examples are given as the constituent units.

The ratio of alicyclic hydrocarbons derived from hydrogenated aromatic rings and aromatic rings contained in the copolymer of the present invention is not particularly limited, but alicyclic hydrocarbons are the aromatic rings and fats. With respect to the sum of the ring hydrocarbons, it is usually 5 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, particularly preferably 95 mol% or more, and particularly preferably 99. It is mol% or more, and the upper limit is not particularly limited. When the ratio of the alicyclic hydrocarbon is in the above range, the gas barrier property of the copolymer of the present invention tends to be improved. The above ratio can be calculated, for example, by ¹ H-NMR from the integrated value of the aliphatic-derived peak in the vicinity of 0.5 to 2.5 ppm and the aromatic-derived peak in the vicinity of 6.0 to 8.0 ppm.
The alicyclic hydrocarbon derived from a hydrogenated aromatic ring or the like includes both an alicyclic hydrocarbon obtained by hydrogenating an aromatic ring and an alicyclic hydrocarbon obtained by another method. ..

<Molecular weight of copolymer>
The copolymer of the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, preferably 10,000 or more, more preferably 30,000 or more, and further. It is preferably 50,000 or more, preferably 200,000 or less, more preferably 150,000 or less, still more preferably 130,000 or less. When the Mw of the copolymer of the present invention is at least the above lower limit value, the mechanical strength, heat resistance, and moldability of the obtained molded product are good, and when it is at least the above upper limit value, at the time of processing. The melt viscosity tends to decrease and the moldability tends to be good.

[Method for producing copolymer]
The method for producing the copolymer of the present invention is not particularly limited. For example, a method obtained by copolymerizing a vinyl cyclohexane-based monomer and an α-olefin-based monomer, a method obtained by hydrogenating a vinyl aromatic copolymer, and the like can be mentioned.

<Method obtained by hydrogenating a vinyl aromatic copolymer>
As a method obtained by hydrogenating the vinyl aromatic copolymer, the structural unit represented by the following formula (7) and / or the structural unit represented by the following formula (8) and the following formula (9) are used. The aromatic ring of a vinyl aromatic copolymer containing a constituent unit represented by the present invention (hereinafter, this vinyl aromatic copolymer may be referred to as a hydrogenation raw material copolymer of the present invention) is hydrogenated. There is a way to get it. The molecular structure of the vinyl aromatic copolymer may be branched, radial, or any combination thereof.

[In the formula (7), R ¹¹ represents an alkyl group having 1 or more carbon atoms and 10 or less carbon atoms, n ¹¹ represents an integer of 0 or more and 4 or less, and X ¹¹ represents a structural unit represented by the following formula (10) and /. Alternatively, it is a group containing a structural unit represented by the following formula (11). ]

[In the formula (8), R ¹² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and X ¹² is a structural unit represented by the following formula (10) and / or represented by the following formula (11). It is a group containing a structural unit. ]

[In the formula (9), R ¹³ represents an alkyl group having 1 or more and 10 or less carbon atoms, and n ¹² represents an integer of 0 or more and 5 or less. ]

[In the formula (10), R ¹⁶ represents an alkyl group having 1 or more and 10 or less carbon atoms, and n ¹³ represents an integer of 0 or more and 5 or less. ]

[In the formula (11), R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms. ]

<Constituent unit represented by equation (7)>
The structural unit represented by the formula (7) (hereinafter, may be referred to as structural unit A') is a structural unit of a polymer having a styrene-derived skeleton as a repeating unit, and has a substituent R ^{11 on the benzene ring in the skeleton.} And X ¹¹ are included. R ¹¹ , X ¹¹ and n ¹¹ are synonymous with ^{R 1} , X ¹ and n ^{1 of the} structural unit A represented by the equation (1), respectively.
X ¹¹ is a group containing a structural unit represented by the formula (10) and / or a structural unit represented by the formula (11). The structural unit represented by 11) may be expressed as the structural unit F'), but the one containing at least the structural unit E'is a copolymer due to the hydrophobic effect of the cyclohexane ring obtained by hydrogenation. It is preferable because the gas barrier property of the above tends to increase.

<Constituent unit represented by equation (10)>
Structural unit represented by the formula (10) (building block E') is a constituent unit of the polymer to a repeating unit derived structure vinylbenzene, is intended to include substituents R ¹⁶ vinyl benzene ring in the skeleton. R ¹⁶ and n ¹³ are synonymous with ^{R 6} and n ³ of the structural unit E represented by the equation (5), respectively.

<Constituent unit represented by equation (11)>
The structural unit (constituent unit F') represented by the formula (11) is a structural unit of a polymer having an ethylene-derived skeleton as a repeating unit, and contains substituents R ¹⁷ and R ¹⁸ in carbon atoms in the skeleton. R ¹⁷ and R ¹⁸ are synonymous with ^{R 7} and R ⁸ of the structural unit F represented by the formula (6), respectively.

<Constituent unit represented by equation (8)>
The structural unit (constituent unit B') represented by the formula (8) is a structural unit of a polymer having an ethylene-derived skeleton as a repeating unit, and contains substituents R ¹² and X ¹² in carbon atoms in the skeleton. R ¹² and X ¹² are synonymous with ^{R 2} and X ² of the structural unit B represented by the equation (2), respectively.
X ¹² is a group containing the structural unit E'and / or the structural unit F', and is not particularly limited, but it is preferable to include the structural unit E'at least.

<Constituent unit represented by equation (9)>
The structural unit represented by the formula (9) (hereinafter, may be expressed as the structural unit C') is a structural unit of a polymer having a skeleton derived from vinylbenzene as a repeating unit, and has a substituent R on a carbon atom in the skeleton. ¹³ is included. R ¹³ and n ¹² are synonymous with ^{R 3} and n ² of the structural unit C represented by the formula (3), respectively.

The hydrogenated raw material copolymer of the present invention as described above has a branched structure, and for example, a branched structure can be obtained by crossing as shown in Patent Document 1. Crossing is a step of forming a polymer of the main chain in advance with structural units A', B', C'and the like, and then crossing a star-shaped branched structure starting from the structural units A'and / or the structural unit B'. It is formed by.

<Combination of each structural unit>
The combination of the structural units A', B'and C'is not particularly limited as long as the effects of the present invention can be obtained. It is sufficient that at least one of the constituent unit A'and the constituent unit B'is included, but the one containing the constituent unit A'is the hydrophobicity of the cyclohexane ring contained in the constituent unit obtained by hydrogenating the constituent unit A'. Due to the effect, the gas barrier property of the obtained copolymer tends to be enhanced, which is preferable. X ¹¹ and X ¹² of the structural unit A'and the structural unit B'are not particularly limited, but those containing at least the structural unit E'are more hydrophobic of the cyclohexane ring contained in the obtained copolymer of hydrogenated aromatic ring. Due to the effect, the gas barrier property of the copolymer tends to be enhanced, which is preferable.
Among the above, particularly preferably, the structural unit A'includes a structural unit derived from divinylbenzene, that is, X ¹¹ of the structural unit A'is the structural unit E', which is a structural unit derived from styrene. Examples of the unit C'include a structural unit derived from styrene. These combinations are preferable because the weather resistance, heat resistance, flexibility and strength of the obtained hydrogenated copolymer tend to be good.

<Ratio of structural units A'to C', E'and F'>
When the hydrogenated raw material copolymer of the present invention contains a constituent unit A'or a constituent unit B', the content ratio of the constituent unit A'or the constituent unit B'is preferably relative to all the constituent units of the copolymer. It is 0.001 mol% or more and 10 mol% or less, more preferably 1 mol% or less, still more preferably 0.1 mol% or less. When the content ratio of the structural unit A'or the structural unit B'is within the above range, the crosslinked structure does not become excessive, and the desired copolymer physical properties tend to be obtained.
When the hydride raw material copolymer of the present invention contains the constituent unit A'and the constituent unit B', the total content ratio of the constituent unit A'and the constituent unit B'is preferable with respect to all the constituent units of the copolymer. Is 0.001 mol% or more and 10 mol% or less, more preferably 1 mol% or less, still more preferably 0.1 mol% or less. When the total content ratio of the structural unit A'and the structural unit B'is within the above range, the crosslinked structure does not become excessive and the desired copolymer physical properties tend to be obtained.

The content ratio of the constituent unit C'is preferably 1 mol% or more and 50 mol% or less, more preferably 5 mol% or more and 40 mol% or less, still more preferably 8 mol, based on all the constituent units of the hydrogenated raw material copolymer. % Or more and 30 mol% or less.

When the content ratio of each of the above constituent units is larger than the above lower limit, the gas barrier property of the obtained copolymer tends to be improved. Further, when the content ratio of each of the above-mentioned structural units is smaller than the above-mentioned upper limit, the flexibility of the obtained copolymer tends to be improved.

The content ratio of the constituent unit E'in the hydrogenated raw material copolymer of the present invention is not particularly limited, but the content ratio of the constituent unit E'is preferably 1 mol% or more with respect to all the constituent units of the hydrogenated raw material copolymer. It is more preferably 3 mol% or more, and further preferably 5 mol% or more. Further, it is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, based on all the constituent units of the hydrogenated raw material copolymer. When the content ratio of the structural unit E'is equal to or less than the above upper limit value, the flexibility of the obtained copolymer tends to be improved. When the content ratio of the structural unit E'is equal to or higher than the above lower limit value, the gas barrier property of the obtained copolymer tends to be improved.

The content ratio of the constituent unit F'in the hydrogenated raw material copolymer of the present invention is not particularly limited, but the content ratio of the constituent unit F'is preferably 1 mol% or more with respect to all the constituent units of the hydrogenated raw material copolymer. It is more preferably 3 mol% or more, and further preferably 5 mol% or more. Further, it is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, based on all the constituent units of the hydrogenated raw material copolymer. When the content ratio of the structural unit F'is equal to or less than the above upper limit value, the gas barrier property of the obtained copolymer tends to be improved. When the content ratio of the structural unit F'is equal to or higher than the above lower limit value, the flexibility of the obtained copolymer tends to be improved.
When the hydride raw material copolymer of the present invention contains the constituent unit E'and the constituent unit F', the total content ratio of the constituent unit E'and the constituent unit F'is the total content ratio of the hydride raw material copolymer with respect to all the constituent units. It is preferably 1 mol% or more, more preferably 3 mol% or more, and further preferably 5 mol% or more. Further, it is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, based on all the constituent units of the hydrogenated raw material copolymer. When the total content ratio of the structural unit E'and the structural unit F'is within the above range, a copolymer having a good balance between gas barrier properties and flexibility tends to be obtained.

<Other ingredients>
The hydrogenated raw material copolymer of the present invention may contain other components in addition to the above-mentioned structural units A'to C'as long as the effects of the present invention are not significantly impaired.
Specific examples of the components other than the structural units A'to C'that may be contained in the hydrogenated raw material copolymer of the present invention include a polymerization initiator, a polymerization catalyst, a stabilizer, a neutralizing agent, and a terminal. Examples thereof include a sealing material and structural units other than the structural units A'to C'. The content of other components is not particularly limited.

<Structural example of hydrogenated raw material copolymer>
The structure of the hydrogenated raw material copolymer of the present invention is not particularly limited, and examples of preferable structures include the following structures.
The first-stage polymerized chain (hereinafter, may be referred to as "main chain") includes the structural unit A'and / or the structural unit B'and the structural unit C', and the second-stage polymerized chain (hereinafter, referred to as "main chain"). , May be referred to as a "side chain"), a copolymer having a structural unit E'and / or a structural unit F'.
In this copolymer, the structural unit A'and / or the structural unit B'is the starting point of the branched structure of the copolymer, and a graft polymer or a star-shaped polymer is formed.
The ratio of each structural unit contained in the first-stage and second-stage polymerized chains is not particularly limited and can be appropriately adjusted.

The ratio of the main chain constituent unit and the side chain constituent unit in the hydride raw material copolymer of the present invention is not particularly limited, but the main chain constituent unit is relative to the ratio of all the constituent units of the hydride raw material copolymer. , It is preferably 80 mol% or more, more preferably 85 mol% or more, and further preferably 90% or more. Further, it is preferably 99 mol% or less, more preferably 97 mol% or less, and further preferably 95 mol% or less. When the ratio of the constituent units of the main chain is not more than the above upper limit value, the mechanical properties of the obtained copolymer tend to be improved. Further, when the ratio of the constituent units of the main chain is equal to or more than the above lower limit value, the flexibility of the obtained copolymer tends to be improved.

<Constituent unit represented by equation (12)>
In the hydrogenated raw material copolymer of the present invention, in addition to the above-mentioned structural units A'to C', a structural unit represented by the following formula (12) (hereinafter, may be referred to as a structural unit D') is mainly used. It may be contained in a chain. The structural unit D'is a structural unit of a polymer having an ethylene skeleton as a repeating unit, and contains substituents R ¹⁴ and R ¹⁵ in carbon atoms in the skeleton. By including the structural unit D', the flexibility of the copolymer obtained by hydrogenation tends to be controlled, which is preferable.

[In the formula (12), R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms. ]

(R ¹⁴ and R ¹⁵ )
In formula (12), R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms. The preferred carbon numbers of R ¹⁴ and R ^15, the substituents that the alkyl group may have, and their preferred reasons are the same as for R ⁴ and R ^{5 of building block D.}

(Ratio of structural unit D')
When the hydrogenated raw material copolymer of the present invention has a constituent unit D'in the main chain, the content ratio of the constituent unit D'is preferably 50 mol% with respect to all the constituent units of the hydrogenated raw material copolymer of the present invention. The above is more preferably 60 mol% or more, still more preferably 70 mol% or more. Further, it is preferably 99 mol% or less, more preferably 90 mol% or less, and further preferably 92 mol% or less. When the content ratio of the structural unit D'is equal to or higher than the above lower limit value, the flexibility of the obtained copolymer tends to be improved. Further, when it is not more than the above upper limit value, the gas barrier property of the obtained copolymer tends to be improved.

<Other building blocks>
Specific examples of the structural units that the hydride raw material copolymer of the present invention may have in addition to the above structural units A'to D'are 4-monochlorostyrene, 4-chloromethylstyrene, and 4-hydroxymethylstyrene. , 4-t-butoxystyrene, dichlorostyrene, 4-monofluorostyrene, 4-phenylstyrene, vinylnaphthalene, vinylanthracene, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester and the like. ..

<Weight average molecular weight>
The hydrogenated raw material copolymer of the present invention has a polystyrene-equivalent weight average molecular weight (Mw) of preferably 10,000 or more, more preferably 30,000, as measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. Above, it is more preferably 50,000 or more, preferably 200,000 or less, more preferably 150,000 or less, still more preferably 130,000 or less. When the Mw of the hydride raw material copolymer of the present invention is at least the above lower limit value, the heat resistance and moldability of the copolymer of the present invention obtained by hydrogenating the copolymer can be obtained by molding the copolymer. When the mechanical strength of the molded product becomes good and is not more than the above upper limit value, the melt viscosity at the time of processing is lowered, and the moldability tends to be good.

<Method for Producing Hydrogenated Raw Material Copolymer of the Present Invention>
The hydrogenated raw material copolymer of the present invention can be produced by carrying out polymerization according to a conventional method using a monomer containing the above-mentioned structural unit, other monomers used as necessary, and the like as raw materials.

<Hydrogenation method of the hydrogenation raw material copolymer of the present invention>
The copolymer of the present invention can be obtained by nuclear hydrogenating the copolymer of the hydrogenated raw material of the present invention. The method for hydrogenating the hydrogenation raw material copolymer of the present invention is not particularly limited.

Nuclear hydrogenation refers to the conversion of an aromatic ring contained in the vinyl aromatic copolymer, which is the raw material copolymer of the present invention, into a saturated hydrocarbon skeleton by hydrogenation. Examples of the aromatic ring contained in the copolymer include those formed by a carbon skeleton such as a benzene ring, a naphthalene ring, and an anthracene ring. Only one type of these aromatic rings may be contained in the hydrogenated raw material copolymer of the present invention, or two or more types may be contained in an arbitrary ratio.

For example, in the case of polystyrene, nuclear hydrogenation converts the benzene ring portion into a cyclohexane ring portion.
When an aliphatic unsaturated hydrocarbon (olefin) moiety is contained in an arbitrary moiety in the polymer skeleton, this moiety may become a saturated hydrocarbon moiety at the same time as nuclear hydrogenation.

The nuclear hydrogenation rate is not particularly limited, but is usually 5 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more, and further, among the aromatic rings contained in the copolymer of the hydrogenation raw material of the present invention. It is preferably 80 mol% or more, more preferably 95 mol% or more, particularly preferably 99 mol% or more, and the upper limit is not particularly limited. When the nuclear hydrogenation rate is within the above range, the gas barrier property of the obtained hydride copolymer tends to be improved. The nuclear hydrogenation rate can ^{be calculated, for example, by 1} H-NMR from the integrated values of the aliphatic-derived peaks around 0.5 to 2.5 ppm and the aromatic-derived peaks around 6.0-8.0 ppm. can.
The method of nuclear hydrogenation is not particularly limited, and for example, there is a method of hydrogenating an aromatic ring in the presence of a catalyst, hydrogen, or the like. Pressurization or heating may be performed as needed.
The specific method of nuclear hydrogenation will be described below.

(catalyst)
A catalyst may be used for nuclear hydrogenation, and a metal catalyst can be used as the catalyst. Examples of the metal catalyst include an alloy catalyst, a supported metal catalyst in which an active metal species is supported on a carrier, and the like.
The metal component of the metal catalyst is not particularly limited as long as it can hydrogenate the aromatic ring in the vinyl aromatic copolymer, but is usually ruthenium, nickel, copper, palladium, gold, platinum, iron, osmium, cobalt. , Rhodium, iridium and other metals can be used. Among them, it is preferable to contain at least one metal element selected from the group consisting of the 8th group, the 9th group, the 10th group and the 11th group of the periodic table as those exhibiting the hydrogenation ability. Since it has a particularly high hydrogenating ability, it is preferable to contain at least one metal element selected from the group consisting of groups 8, 9 and 10 of the periodic table, and since it has a particularly high selectivity, ruthenium, Rhodium, nickel, palladium or platinum is preferable, and ruthenium, nickel or palladium is particularly preferable because of its high ability against nuclear hydrogenation.

As the metal catalyst used in nuclear hydrogenation, one type of the above-mentioned metal may be used, or two or more types may be used. When two or more kinds of metals are used, the combination thereof is not particularly limited, and even if each metal has catalytic activity (cocatalyst), the catalytic activity of one or more kinds of metals is improved (auxiliary catalyst). Although it may be used, a co-catalyst is preferable.

The alloy catalyst is not particularly limited, but an alloy of a metal such as ruthenium, nickel, copper, palladium, gold, or platinum is used. Specific examples thereof include generally known Raney catalysts and copper chromium catalysts.

The metal catalyst may be a supported metal catalyst in which an active metal species is supported on various carriers described later, and is supported from the viewpoint that it can be easily separated from the reaction solution and the catalyst can be easily reused. It is preferable to use a metal catalyst.

The carrier is not particularly limited, and examples thereof include carbon-based carriers such as activated carbon, carbon black, and silicon carbide; and metal oxide carriers such as alumina, silica, zirconia, niobia, titania, ceria, diatomaceous earth, and zeolite. Among them, it is preferable to use at least one selected from the group consisting of activated carbon, silica and alumina as a carrier in terms of expression of reaction activity and stabilization of catalyst activity.

The content of the metal in the supported metal catalyst is not particularly limited, but is usually 0.5% by mass or more, preferably 1% by mass or more, based on the total mass of the carrier and the metal in terms of mass percentage in terms of metal. Further, it is usually 50% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less. Sufficient catalytic activity can be obtained by setting the metal content within the above range. In the description of the catalyst below, the value described as% by mass indicates the metal content with respect to the total mass of the carrier and the metal of the catalyst.

The specific surface area of the carrier used for the metal catalyst is not particularly limited, but is usually 1 m ² / g or more, preferably 10 m ² / g or more, and more preferably 50 m ² / g or more. Further, it is preferably 2000 m ² / g or less, more preferably 1500 m ² / g or less, and further preferably 1000 m ² / g or less. By using a specific surface area equal to or greater than the lower limit, it is possible to support the metal on the carrier with a high degree of dispersion, which is preferable in obtaining sufficient catalytic activity. Further, it is preferable to use one having a value equal to or less than the upper limit value in that the pores usually contained in the carrier can be effectively used.

The average pore size of the carrier used for the supported metal catalyst is not particularly limited, but is usually 200 Å or more, preferably 250 Å or more. Further, it is preferably 1000 Å or less, and more preferably 600 Å or less. When the average pore diameter is at least the above lower limit, the copolymer of the hydrogenated raw material of the present invention is sufficiently taken in, and the treatment efficiency tends to be maintained. A carrier having an average pore diameter larger than the above range can be used, but it is preferably less than or equal to the above upper limit from the viewpoint of effectively using the carrier surface.

The method for producing a metal catalyst used in nuclear hydrogenation is not particularly limited as long as the active ingredient functions as a catalyst in a metallic state. For example, it can be obtained by reducing a metal, a metal compound, or the like.

When the supported metal catalyst is used, the production method thereof is not particularly limited, and general methods can be appropriately combined for production. Usually, a metal compound serving as a metal source is supported on a carrier, and after treatments such as drying, washing, and firing, it is converted into a metal state by a reduction treatment and used.

The method for supporting the metal compound on the carrier is not particularly limited, and for example, a known method commonly used for preparing a supported metal catalyst such as an impregnation method, an ion exchange method, a spray method, and a coprecipitation method can be used. By reducing the carrier on which the metal compound is supported, the metal compound supported on the carrier is converted into a metal, so that the desired catalyst can be obtained.

The reduction treatment can be carried out in either the liquid phase or the gas phase, but the gas phase reduction is reduced by using a reducing gas such as hydrogen, or the liquid phase is reduced by using alcohol, formate, sodium formate or the like. Is preferable.

The reduction temperature in the reduction treatment is not particularly limited, but is usually 20 ° C. or higher, preferably 100 ° C. or higher, more preferably 250 ° C. or higher, and usually 600 ° C. or lower, preferably 500 ° C. or lower.

The shape of the metal catalyst used in nuclear hydrogenation is not particularly limited, and can be appropriately selected and used according to the type of reaction carried out using the metal catalyst. Specific shapes of the metal catalyst include, for example, powder, particle, pellet, and the like, and among them, powder, which is less affected by intrapore diffusion, is preferable.

Further, the particle size of the metal catalyst used in nuclear hydrogenation is not particularly limited. Depending on the type of reaction using the metal catalyst, it can be appropriately selected and used, but usually, a catalyst having an average particle size of 30 μm or more and 20 mm or less is used.

The amount of the metal catalyst used in nuclear hydrogenation is not particularly limited as long as the aromatic ring can be hydrogenated within an appropriate time, but is not particularly limited, with respect to the mass of the hydride raw material copolymer of the present invention. , Usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more. Further, it is preferably 50% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less.

(Hydrogenation reaction conditions)
Nuclear hydrogenation may be carried out in a hydrogen atmosphere. The hydrogen source is not particularly limited, but it is desirable to use gaseous hydrogen that does not need to be separated and purified after the reaction is completed.

The hydrogen gas pressure is not particularly limited, but is usually carried out under pressurized conditions with hydrogen gas. The pressure of the hydrogenation reaction is not particularly limited, but is usually 1 MPa or more, preferably 3 MPa or more, and more preferably 5 MPa or more. Further, it is preferably 30 MPa or less, more preferably 20 MPa or less, still more preferably 15 MPa or less.
In general, increasing the reaction pressure promotes the supply of hydrogen to the metal catalyst and improves the reaction rate of nuclear hydrogenation. On the other hand, in order to carry out at a high reaction pressure, equipment such as a reactor having a specially enhanced pressure resistance is required, and there is a possibility that a decomposition reaction of the copolymer may occur under the condition of a high reaction pressure.

The hydrogen concentration of the hydrogen gas in a hydrogen atmosphere is not particularly limited, but is usually 70% by volume or more, preferably 80% by volume or more, more preferably 90% by volume or more, and the upper limit is usually 100% by volume, which is preferable. Is 95% by volume or less.

The temperature at which the copolymer of the hydrogenated raw material of the present invention is nuclear-hydrogenated is not particularly limited, but is usually 20 ° C. or higher, preferably 50 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 150 ° C. or higher. Further, it is preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 220 ° C. or lower. When the reaction temperature is within the above range, efficient nuclear hydrogenation tends to be achieved while suppressing the decomposition reaction of the copolymer.

The reaction time for nuclear hydrogenation of the hydrogenated raw material copolymer of the present invention is not particularly limited as long as nuclear hydrogenation of the copolymer is achieved. The reaction time is preferably 30 minutes or more, more preferably 1 hour or more, preferably 24 hours or less, and more preferably 12 hours or less.

Solvents may be used in nuclear hydrogenation. The solvent is not particularly limited, but for example, alcohols such as methanol, ethanol, 1,4 butanediol, 2,3-butanediol, 1,2-butanediol, and 1,3-butenediol; tetrahydrofuran, dioxane and diethylene glycol dimethyl ether. , Ethers such as triethylene glycol dimethyl ether; hydrocarbons such as hexane, cyclohexane, decalin; and the like. These solvents can be used alone or as a mixed solvent of two or more kinds. From the viewpoint of solubility of the hydrogenated raw material copolymer of the present invention, it is preferable to use tetrahydrofuran (THF) or cyclohexane as the solvent.

When a solvent is used in nuclear hydrogenation, the concentration of the hydride raw material copolymer of the present invention is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more. .. Further, it is preferably 70% by mass or less, and more preferably 50% by mass or less. When the concentration of the hydrogenated raw material copolymer of the present invention is within the above range, the increase in the viscosity of the hydrogenated raw material copolymer reaction solution of the present invention is suppressed while maintaining the productivity, and the handling property of the reaction solution is suppressed. Tends to be able to maintain.

(Reactor)
The reactor used in nuclear hydrogenation is not particularly limited, but an autoclave capable of high-pressure reaction is usually used. A loop reactor may also be used. A continuous reactor can also be used, and the reactor can be filled with a catalyst, and the raw material liquid and hydrogen can be circulated to carry out the reaction. In the case of a continuous reactor, a catalyst separation step is not required, so that a continuous reactor is preferable for mass production. Although SUS is usually used as the material of the reactor, acid-resistant SUS such as Hastelloy may be used. As a countermeasure against the generated acid, a glass-lined container or a Teflon-coated container can also be used.

(Catalyst separation)
After nuclear hydrogenation, the catalyst may be separated from the resulting hydrogenated copolymer. The specific method for separating the catalyst is not particularly limited, and examples thereof include filtration with a filter, decantation, and centrifugation. The copolymer of the present invention may be very difficult to filter due to its branched structure. In that case, separation by decantation or centrifugation is particularly desirable.

[Resin composition]
The copolymer of the present invention can be a resin composition containing other resin components, various additives and the like, if necessary.

Other resin components contained in the resin composition containing the copolymer of the present invention (hereinafter, may be referred to as the resin composition of the present invention) include ethylene / vinyl acetate copolymer and ethylene / acrylic acid. Polymers, ethylene / methacrylic acid copolymers, ethylene / acrylic acid ester copolymers, ethylene / α-olefin copolymers such as ethylene / methacrylic acid ester copolymers, polyethylene, polypropylene, polybutene-1 resin, etc. Polyethylene resin, polyphenylene ether resin, polyamide resin such as nylon 6, nylon 66, aramid resin, aromatic polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polylactic acid, polybutylene succinate, and aliphatic such as polycaprolactone. Polyester resin, polycarbonate resin, polyarylate resin, modified polyphenylene oxide resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone resin, polyether ketone resin, polyether ether ketone resin, polyimide resin, polyoxymethylene homopolymer , Polyoxymethylene resins such as polyoxymethylene copolymers, polymethylmethacrylate resins, silicon-containing soft polymers such as dimethylpolysiloxane, diphenylpolysiloxane, dihydroxypolysiloxane, vinyl aromatic polymers such as polystyrene, ethylene / propylene Ethylene-based elastomers such as copolymerized rubber (EPM), ethylene / propylene / non-conjugated diene copolymerized rubber (EPDM), ethylene / butene copolymerized rubber (EBM), ethylene / propylene / butene copolymerized rubber, styrene-butadiene-styrene Block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene / butylene-styrene block copolymer, styrene-based elastomer such as styrene-ethylene / propylene-styrene block copolymer, polybutadiene, vinyl hydride aroma Examples thereof include group polymers, other vinyl hydride aromatic block copolymers including hydride / butadiene or styrene / isoprene block copolymers, cycloolefin polymers, cycloolefin copolymers and the like. One of these may be used alone, or two or more thereof may be used in combination.

Among them, since it has an excellent balance of transparency, heat resistance, gas barrier property, and non-adsorption property of chemicals, all of vinyl hydride aromatic polymers, vinyl hydride aromatic block copolymers, cycloolefin polymers, and cycloolefins are used. Polymers and polyolefin resins are preferable, and vinyl hydride aromatic polymers are particularly preferable.

Examples of the monomeric vinyl aromatics constituting the above-mentioned vinyl hydride aromatic polymer and vinyl hydride aromatic block copolymer include styrene, α-methylstyrene, 2-methylstyrene, and 3-methyl. Styrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, 4-monochromelostyrene, dichlorostyrene, 4-mono Fluorostyrene, 4-phenylstyrene, vinylnaphthalene, vinylanthracene and the like can be mentioned, and among them, styrene, α-methylstyrene and 4-methylstyrene are preferably used. One of these vinyl aromatics may be used alone, or two or more thereof may be used in combination.

Additives include antioxidants, heat stabilizers, light stabilizers, UV absorbers, fillers such as fillers, neutralizers, lubricants, antifogging agents, antiblocking agents, slip agents, dispersants, colorants, etc. Flame retardant, antistatic agent, conductivity imparting agent, cross-linking agent, cross-linking aid, metal inactivating agent, molecular weight modifier, antibacterial agent, anti-mold material, fluorescent whitening agent, organic diffusing agent, inorganic diffusing agent, etc. Examples include the light diffusing agent of.

The resin composition of the present invention can be produced, for example, by a method of mechanically melt-kneading each of the above components. Examples of the melt kneader that can be used here include a single-screw extruder, a twin-screw extruder, a lavender, a Banbury mixer, a kneader blender, a roll mill, and the like. The lower limit of the kneading temperature is usually 100 ° C. or higher, preferably 145 ° C. or higher, and more preferably 160 ° C. or higher. The upper limit of the kneading temperature is usually 350 ° C., preferably 300 ° C., more preferably 250 ° C. In kneading, each component may be kneaded all at once, or a multi-stage split kneading method may be used in which any component is kneaded and then the other remaining components are added and kneaded.

[Molded product]
The resin composition of the present invention is, for example, injection molding (insert molding method, two-color molding method, sandwich molding method, gas injection molding method, etc.), extrusion molding method, inflation molding method, T-die film molding method, laminate molding method, etc. It can be processed into various molded bodies (hereinafter, may be referred to as the molded body of the present invention) by a molding method such as a blow molding method, a hollow molding method, a compression molding method, or a calendar molding method. The shape of the molded body of the present invention is not particularly limited, and examples thereof include a sheet, a film, a plate, a particle, a mass, a fiber, a rod, a porous body, a foam, and the like, preferably a sheet, a film, and a plate. be. The molded film can also be uniaxially or biaxially stretched. Examples of the stretching method include a roll method, a tenter method, a tubular method and the like. Further, surface treatments such as corona discharge treatment, flame treatment, plasma treatment, and ozone treatment, which are usually used industrially, can be applied.

The application of the molded product of the present invention is not particularly limited, and examples thereof include the following applications. That is, electric wires, cords, coating materials such as wire harnesses in the field of electrical and electronic parts, insulating sheets, displays and touch panels of OA equipment, membrane switches, photo covers, relay parts, coil bobbins, IC sockets, fuse cases, camera pressure plates, etc. FDD collet, floppy hub, optical disk substrate in the field of optical components, pickup lens for optical disk, optical lens, LCD substrate, PDP substrate, TV screen for projection TV, retardation film, fog lamp lens, illumination switch lens, sensor switch lens, full flannel Lenses, protective glasses, projection lenses, camera lenses, sunglasses, light guide plates, camera strobe reflectors, LED reflectors, head lamp lenses for automobile parts, blinker lamp lenses, tail lamp lenses, resin window glasses, meter covers, outer panels, door handles, Rear panels, wheel caps, visors, roof rails, sun roofs, instrument panels, panels, control cable coverings, airbag covers, mudguards, bumpers, boots, air hoses, lamp packings, gaskets, window moldings, and other moldings, sight shields , Weather strips, glass run channels, glomets, vibration control / sound insulation materials, joint materials in the field of building materials, handrails, windows, table edge materials, sashes, bathtubs, window frames, signs, lighting covers, water tanks, staircase wainscots, carports, Highway sound insulation walls, multi-wall sheets, steel wire coating materials, lighting gloves, switch breakers, protective covers for machine tools, industrial deep-drawing vacuum-formed containers, pump housings, home appliances, various packings in the light electrical field, grips, belts , Foot rubber, rollers, protectors, suckers, gaskets for refrigerators, switches, connector covers, game machine covers, pachinko stands, OA housings, notebook PC housings, HDD head trays, instrument windows, transparent housings, etc. Rollers with gears for OA, switch case sliders, gas cock knobs, clock frames, clock wheel train placement, amber caps, various rolls for OA equipment, tubular molded bodies such as hoses and tubes, deformed extruded products, leather-like articles, occlusion Ingredients, toys such as dolls with a soft touch, pen grips, straps, suckers, watches, umbrella bones, cosmetic cases, general miscellaneous goods such as toothbrush patterns, containers such as house wear and tapper wear, binding bands, cables Various bottles such as raw infusion bottles, food bottles, water bottles, bottles for personal care such as cosmetics, catheters for medical parts, syringes, syringe gaskets, drip tubes, tubes, ports, caps, rubber stoppers, diamonds Examples include risers, blood connectors, artificial teeth, disposable containers, etc. The resin composition of the present invention can also be applied to applications by foam molding.

The application of the molded product of the present invention in the field of film / sheet is not particularly limited, and examples thereof include the following applications. That is, packaging stretch film, commercial or household wrap film, pallet stretch film, stretch label, shrink film, shrink label, sealant film, retort film, retort sealant film, fragrance-retaining heat seal film, A- PET sealant, frozen food container / lid, cap seal, heat welding film, heat adhesive film, heat sealing film, bag-in-box sealant film, retort pouch, standing pouch, spout pouch, laminated tube, heavy bag , Foods such as textile packaging film, packaging field such as miscellaneous goods, agricultural film field such as house film, multi-film, infusion bag, multi-chamber container for high calorie infusion and peritoneal dialysis (CAPD), drainage for peritoneal dialysis Liquid bag, blood bag, urine bag, surgical bag, ice pillow, ampoules case, medical film / sheet field such as PTP packaging, civil engineering impermeable sheet, waterproof material, mat, joint material, floor material, roofing, makeup Building material related fields such as film, skin film, wallpaper, leather, ceiling material, trunk room lining, interior skin material, vibration control sheet, sound insulation sheet and other automobile parts field, display cover, battery case, mouse pad, mobile phone case, Weak electricity fields such as IC card holders, floppy disk cases, CD-ROM cases, toothbrush cases, puff cases, cosmetic cases, eye medicine cases, tissue cases, face packs and other toiletry or sanitary fields, stationery films / sheets, clear files , Pen cases, notebook covers, desk mats, keyboard covers, book covers, binders and other office supplies, furniture leather, beach balls and other toys, umbrellas, raincoats and other rain gear, table cloths, blister packages, bath lids , Towel case, fancy case, tag case, pouch, protective bag, insurance card cover, passbook case, passport case, knife case, etc. for general household use, miscellaneous goods field, retroreflective sheet, synthetic paper, etc. Further, as an adhesive composition, or as a film / sheet field in which an adhesive material is applied to a base material to impart adhesiveness, a carrier tape, an adhesive tape, a marking film, a semiconductor or glass dicing film, a surface protective film, etc. Steel plate / plywood protective film, automobile protective film, packaging / binding adhesive tape, office / household adhesive tape, bonding adhesive tape, paint masking adhesive tape, surface protection adhesive tape, sealing adhesive tape, anticorrosion / waterproof Adhesive tape for medical and electrical insulation, adhesive tape for electronic devices, adhesive film, adhesive tape for medical and sanitary materials, adhesive tape for identification and decoration, display tape, packaging tape, surgical tape, etc. Adhesive tape for labels and the like can be mentioned.

The use of the molded product of the present invention in the field of fibers and non-woven fabrics is not particularly limited, and examples thereof include the following uses. That is, by making fibers such as continuous spinning, continuous crimping yarn, short fibers, monofilaments, and non-woven fabrics by the flat yarn, melt blow method, and spunbond method, protective materials such as disposable diapers, surgical clothes, gloves and the like for medical use, Applications such as inner gloves, carpets, their linings, and ropes can be mentioned. Further, knitted fabrics such as non-woven fabrics, monofilaments, flat yarns and slit tapes, and canvases, tent materials, hoods, flexible containers, leisure sheets, tarpaulins and the like made by laminating film sheets can be mentioned.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

In the following Examples and Comparative Examples, various physical properties were measured by the following methods.

<Nuclear hydrogenation rate measurement (NMR) method>
The hydrogenation rate of the aromatic ring is determined by ¹ H-NMR from the integrated value of the peak derived from the aliphatic ring around 0.5 to 2.5 ppm and the peak derived from the aromatic ring around 6.0 to 8.0 ppm. Calculated. The measurement conditions of the NMR spectrum are as follows.
(NMR spectrum measurement conditions)
Equipment: BRUKER Ultra Sheld
Frequency: 400MHz
Solvent: CDCl ₃

<Total light transmittance (transparency)>
Using a press sheet having a thickness of 1 mm of the copolymer before and after hydrogenation, the total light transmittance was measured and the transparency was evaluated in accordance with JIS K7375.

<Gas barrier property (water vapor permeability)>
Using a press sheet having a thickness of 0.1mm hydrogenation before or after the copolymer, JIS K7129 B method gas permeability by an infrared sensor method that complies with (MOCON ^{method) (g / (m 2 ·} 24h)) I asked.

<Gas barrier property (oxygen permeability)>
Using a press sheet having a thickness of 0.1mm hydrogenation before or after the copolymer, JIS K7126-2 method (MOCON method) Gas permeability by an infrared sensor method that complies with ^{(cm 3 / (m 2 ·} 24h · atm)) was requested.

The catalyst a and catalyst b used in the following Examples and Comparative Examples were prepared by the following methods.

[Catalyst preparation]
<Immersion process>
2.85 g of silica (Fuji Silysia Chemical Carrier Act Q30, 75-150 μm product) carrier and 0.25 g of palladium chloride (Nippon Engelhard Co., Ltd.) as a palladium raw material were weighed in a 100 ml eggplant flask, and 0.9 g of concentrated hydrochloric acid, 6.6 ml of water was added and stirred (the amount of water added corresponds to 130% by mass of the amount of water absorbed by the silica carrier). After the entire stirring solution had become familiar, the inside of the eggplant flask was heated in a hot water bath (80 ° C.) while reducing the pressure to impregnate the silica carrier with the palladium raw material solution and remove excess water. The amount of palladium supported on the silica carrier was charged as metallic palladium so as to be 5% by mass in terms of mass percentage.

The silica carrier impregnated with the palladium raw material solution was packed in a glass tube (manufactured by Pyrex), dried under the flow of argon gas, cooled to room temperature, and then taken out. Hereinafter, this is referred to as a catalyst precursor.
The details of the drying conditions are as follows.
Gas flow rate: Argon gas 83 ml / min Drying temperature: The temperature was raised from room temperature to 150 ° C. over 15 minutes, held at 150 ° C. for 1 hour, and then allowed to cool to 50 ° C.

<Reduction process and stabilization process>
The catalyst precursor that had undergone the above drying step was subjected to a reduction treatment. Reduction treatment, again the catalyst precursor, packed in a glass tube (Pyrex Corp.), while passing _{H 2} gas at 83 ml / min, and after heating over 30 minutes to 300 ° C. from the reduction temperature 50 ° C., 300 The temperature was maintained at ° C. for 2 hours. Then, the flowing gas was switched to argon, and the mixture was allowed to cool to room temperature under a flow rate of 83 ml / min.
_{Subsequently, nitrogen gas containing 5% by volume O 2} was passed through the same glass tube (manufactured by Pyrex) for 30 minutes to perform stabilization treatment _{to obtain 5% by volume Pd / SiO 2} catalyst a.

As the carrier, a catalyst was prepared in the same manner as the _{5 mass% Pd / SiO 2} catalyst a except that the above silica (Fuji Silysia Chemical Carrier Act Q30: 75-150 μm product) was pulverized to 45-75 μm. A 5 mass% Pd / SiO ₂ catalyst b was obtained.

[Example 1]
<Manufacturing of hydrogenated copolymer>
In a 200 ml Erlenmeyer flask containing cyclohexane, SE polymer AC25SX005 manufactured by Denka Co., Ltd. (hereinafter, may be referred to as (A-1)) represented by the following structural formula as a hydrogenation raw material vinyl aromatic copolymer is 12 It was dissolved so as to be by mass% to obtain a copolymer solution. _{A stirring device is used to stir the 5% by mass Pd / SiO 2} catalyst a in an amount that is 6% by mass with respect to the copolymer (A-1) contained in the copolymer solution and the copolymer (A-1) solution. The raw material mixture a was prepared by putting the mixture in an autoclave made by Hasteroy and mixing the mixture.

<Structure of (A-1)>
(A-1) is a copolymer having a star-shaped branch produced by two-step polymerization. First, coordination polymerization was carried out using ethylene, styrene and divinylbenzene using a single-site polymerization catalyst, and then styrene was further polymerized from the divinylbenzene portion as a second-step crossing step to extend the polystyrene chain. be. The polymerized chain extended by crossing has a structure extended in a star shape (also referred to as a star structure) with respect to the first-stage polymerized chain. The polystyrene unit of the second-stage polymerized chain occupies 15% by mass in the copolymer, and the styrene content in the first-stage polymerized chain is 25 mol%. The divinylbenzene unit is 0.1 mol% or less in the polymer.
In (A-1), the structural unit A', the structural unit C', the structural unit E', and the structural unit D'are included. The structural unit A'is 0.1 mol% or less, the structural unit C'is 23 mol%, and the branched structure of the structural unit A'(X ^{11 in the} equation (7)) is the structural unit E'. The building block E'contains 7.4 mol%. It also contains 70 mol% of the unit D'.

After sealing the autoclave containing the raw material mixture a, he was charged with _{H 2} so with _{H 2} pressure 1 MPa. The temperature of the autoclave was raised to 210 ° C., which is the reaction temperature, and H ₂ was introduced from that point so that the total pressure became 10.2 MPa. _{During the reaction, H 2} was introduced and controlled by an auto pressure controller so that the pressure in the reaction vessel became constant at 10.2 MPa. The hydrogen consumption in the reaction was constantly monitored by the pressure change of the accumulator installed on the primary side of the auto pressure controller, and the reaction was carried out for 2.3 hours.

After the reaction, the catalyst a was removed by centrifugation to obtain (A-1) hydrogenation reaction solution 1.

(A-1) A solution prepared by mixing 100% by mass of THF with 1 of the hydrogenation reaction solution was prepared. The mixed solution was put in 500% by mass of methanol with respect to this mixed solution to precipitate a copolymer. The obtained copolymer was dried under reduced pressure to remove the solvent in the solid.
The nuclear hydrogenation rate of the aromatic ring in this solid copolymer was determined from the results of NMR measurement and found to be 72 mol%.
Hereinafter, this hydrogenated copolymer may be referred to as (X-1).

<Making a press sheet>
The obtained hydrogenated copolymer (X-1) was preheated for 2 minutes, pressed for 5 minutes, and cooled by a cooling press 3 at a temperature of 200 ° C. using an NSF-100 type single-acting compression molding machine manufactured by Shinto Metal Industry Co., Ltd. A press sheet having a thickness of 200 mm × 200 mm × a thickness of 1 mm and a press sheet having a thickness of 200 mm × 200 mm × a thickness of 0.1 mm were produced by compression molding under the condition of minutes. Using this press sheet, physical properties were evaluated based on the above measurement method.

Hydrogenated copolymer (X-1) The total light transmittance of 60.6% of the water vapor permeability is ^{6.3g / (m 2 · 24h)} , the oxygen permeability ^{1300cm 3 / (m 2 · 24h} · atm )Met.

[Example 2]
The reaction was carried out in the same manner as in Example 1 except that the 5% by mass Pd / SiO ₂ catalyst b was used instead of the 5% by mass Pd / SiO _{2 catalyst a as the hydrogenation catalyst and the reaction time was set to 6 hours.} , A hydrogenated copolymer (X-2) was obtained. The nuclear hydrogenation rate of this hydrogenated copolymer (X-2) was 97 mol%.

A press sheet was prepared for the hydrogenated copolymer (X-2) in the same manner as in Example 1, and the physical properties were evaluated based on the above-mentioned measurement method.

Hydrogenated copolymers total light transmittance of 83.7% of the (X-2), water vapor permeability is ^{3.9g / (m 2 · 24h)} , oxygen permeability ^{1200cm 3 / (m 2 · 24h} · atm) Met.

[Comparative Example 1]
A press sheet was prepared in the same manner as in Example 1 using the Denka SE polymer AC25SX005 (A-1), which is a copolymer before hydrogenation, and the physical properties were evaluated based on the above measurement method.

The total light transmittance of 80.9 percent hydrogenated copolymer before (A-1), the water vapor permeability ^{20.0g / (m 2 · 24h)} , the oxygen permeability 1400cm ³ / ^(m 2 · 24h・ Atm).

The above results are summarized in Table 1.

As can be seen from the above results, it was shown that the copolymer of the present invention had significantly reduced water vapor permeability. It was also shown that oxygen permeability was low.

Claims (4)

As a main chain, seen containing a structural unit A represented by the following formula (1), and a constitutional unit C represented by the following formula (3), as a side chain, a structural unit represented by the following formula (5) A copolymer having E.

[In formula (1), ^{R 1} represents an alkyl group having 1 to 10 carbon atoms, ^{n 1} represents an integer of 0 to 4, ^{X 1} is a configuration Unit represented by the following formula (5) It is a group containing. ]

[In the formula (3), R ³ represents an alkyl group having 1 or more and 10 or less carbon atoms, and n ² represents an integer of 0 or more and 5 or less. ]

[In the formula (5), R ⁶ represents an alkyl group having 1 or more and 10 or less carbon atoms, and n ³ represents an integer of 0 or more and 5 or less. ] The copolymer according to claim 1, wherein the nuclear hydrogenation rate is 50 mol% or more. As a main chain, structure 'and the structural unit C represented by the following formula (9)' units A represented by the following formula (7) viewed contains a, as a side chain, represented by the following formula (10) A method for producing a copolymer, which comprises a step of hydrogenating the aromatic ring of a hydrogenated raw material copolymer having a structural unit E'.

[In formula ^{(7), R 11} represents an alkyl group having 1 to 10 carbon ^{atoms, n 11} represents an integer of 0 to ^{4, X 11} is a structure unit of which is represented by the following formula (10) It is a group containing. ]

[In the formula (9), R ¹³ represents an alkyl group having 1 or more and 10 or less carbon atoms, and n ¹² represents an integer of 0 or more and 5 or less. ]

[In the formula (10), R ¹⁶ represents an alkyl group having 1 or more and 10 or less carbon atoms, and n ¹³ represents an integer of 0 or more and 5 or less. ] The third aspect of the present invention comprises a crossing step of forming a main chain of the hydride raw material copolymer in advance before the hydride step and then forming a branched structure of a side chain of the hydride raw material copolymer. The method for producing a copolymer according to the above.