WO2019082385A1 - Anti-blocking agent, molding material, and molded article - Google Patents

Abstract

Provided is an anti-blocking agent characterized by including a powder of (co)polymer hydride obtained by hydrogenating a (co)polymer having, as a main component, a structural unit derived from an aromatic vinyl compound, wherein the softening temperature of the (co)polymer hydride is 120°C or more.

Description

Antiblocking agent, molding material, and molded body

The present invention relates to an antiblocking agent, a molding material, and a molded body. More specifically, the present invention relates to a molding composition comprising an antiblocking agent for preventing blocking of pellets, and an external addition of an antiblocking agent to pellets containing a specific block copolymer hydride as a main component. And a molded body obtained by melt-molding the molding material.

Conventionally, the main chain and the side of a block copolymer comprising a polymer block mainly composed of a structural unit derived from an aromatic vinyl compound and a polymer block mainly composed of a structural unit derived from a chain conjugated diene compound The specific block copolymer hydride obtained by hydrogenating the carbon-carbon unsaturated bond of the chain and the carbon-carbon unsaturated bond of the aromatic ring, and the specific block copolymer hydride modified with silane are medical grade It is known that it can be used for applications requiring transparency, such as containers, optical films, solar cell sealing materials, laminated glass interlayers, sealing materials for organic electroluminescent elements, light guide plates, etc. (Patent Documents 1 to 6) ).
For example, by bonding a block copolymer hydride to a glass sheet as a base material or the like, it is used for applications such as a solar cell sealing material, a laminated glass intermediate film, and a sealing material of an organic electroluminescent element.
In addition to high transparency, the block copolymer hydride used for such applications is also required to be excellent in flexibility in order to prevent adhesion to the substrate and cracking of the substrate due to temperature changes. .

In order to apply the above-mentioned block copolymer hydride to the above-mentioned application, usually, the block copolymer hydride in pellet form is processed into a sheet by extrusion molding or calendar molding, and laminated with a substrate Used.
However, since the pellets made of hydrogenated block copolymer have flexibility, they can be packed in packaging bags, flexible container bags, etc. and transported by truck or ship, or in the warehouse for a long time in summer In the case of storage, blocking due to consolidation may occur, and the pellet may not be able to be subjected to molding processing using it. In particular, when sealing properties at relatively low temperatures of about 100 ° C. are required, such as sealing materials for organic electroluminescent elements, the block copolymer hydride used has a low softening temperature Therefore, blocking is more likely to occur.
For this reason, in order to transport and store pellets of the transparent and flexible block copolymer hydride without blocking, it is essential to prevent blocking of the pellet which does not impair the transparency of the melt-molded product. It had become.

In order to prevent blocking of pellets made of a flexible block copolymer hydride, an external antiblocking agent consisting of fine powder such as talc or fatty acid amide is usually externally added to the pellets to adhere to the surface, Methods are taken to prevent direct contact.
However, when an antiblocking agent incompatible with a specific block copolymer hydride is used as in the above-mentioned components, the sheet of the block copolymer hydride to be formed becomes hazy and the transparency is impaired was there.

In order to solve this problem, Patent Document 7 discloses a polymer containing a vinyl aromatic hydrocarbon monomer unit and a conjugated diene monomer unit or a thermoplastic elastomer pellet which is a hydrogenated product thereof as an antiblocking agent. A method of adding polyolefin particulates is disclosed.

International Publication No. 2000/077094 JP 2002-105151 A JP, 2006-189523, A International Publication No. 2011/096389 International Publication No. 2013/176258 International Publication No. 2014/091941 JP, 2015-151519, A

Here, the present inventors add polyolefin fine particles as an antiblocking agent described in Patent Document 7 to a block copolymer hydride to obtain a molding material, and the obtained molding material is obtained. A melt-molded product was produced using this. As a result, it became clear that the obtained melt-formed product had significant turbidity and insufficient transparency.
Therefore, the present invention is an antiblocking agent capable of enhancing the antiblocking properties of pellets containing a block copolymer hydride as a main component, and can provide a molded article having less turbidity and excellent transparency. The purpose is to provide an antiblocking agent.
Another object of the present invention is to provide a molding material which is sufficiently high in antiblocking properties and can give a molded article having little turbidity and excellent transparency.
Furthermore, an object of the present invention is to provide a molded article having less turbidity and excellent transparency.

The inventors of the present invention conducted intensive studies on antiblocking agents externally added to pellets of block copolymer hydride in order to achieve the above object. As a result, a powder of (co) polymer hydride which is a (co) polymer hydride having as a main component a structural unit derived from an aromatic vinyl compound, and having a softening temperature of 120 ° C. or higher, By using as an antiblocking agent, while being able to reduce blocking generation | occurrence | production of a pellet, it discovers that a haze can produce a molded object excellent in transparency with little turbidity, and came to complete this invention.

The object of the present invention is to advantageously solve the above-mentioned problems, and the antiblocking agent of the present invention is obtained by hydrogenating a (co) polymer comprising an aromatic vinyl compound-derived structural unit as a main component And a powder of (co) polymer hydride, and a softening temperature of the (co) polymer hydride is 120 ° C. or more. Thus, the antiblocking agent which is a hydride of the (co) polymer which has a specific structural unit as a main component and whose softening temperature is 120 ° C. or more has a block copolymer hydride as a main component The blocking resistance of the pellet can be enhanced, and a shaped body with less turbidity and excellent transparency can be provided.
The “softening temperature of (co) polymer hydride” can be measured by the method described in the examples.

Here, in the antiblocking agent of the present invention, the (co) polymer hydride is obtained by hydrogenating 90% or more of all carbon-carbon unsaturated bonds contained in the (co) polymer (co) It is preferable that it is a polymer hydride. If the hydrogenation rate of the (co) polymer hydride is 90% or more, a molded article with less turbidity and excellent transparency can be obtained more favorably.

The object of the present invention is to advantageously solve the above-mentioned problems, and the molding material of the present invention comprises two or more polymer blocks (A) mainly composed of structural units derived from aromatic vinyl compounds. And a block copolymer (C) having one or more polymer blocks (B) mainly composed of structural units derived from chain conjugated diene compounds, wherein the total amount of the polymer blocks (A) is a block Assuming that the mass fraction occupied in the whole copolymer (C) is wA, and the mass fraction occupied in the whole amount of the polymer block (B) in the whole block copolymer (C) is wB, wA and wB The block copolymer (C) having a ratio (wA: wB) of 15:85 to 70:30 is hydrogenated to 100 parts by mass of a block copolymer containing a hydrogenated block copolymer (D) as a main component , Any blocking mentioned above The sealant is characterized by being externally added in an amount of less than 15 parts by mass or more 0.01 part by mass. A molding material obtained by externally adding any of the above-described antiblocking agents in an amount of 0.01 parts by mass or more and 15 parts by mass or less to 100 parts by mass of pellets of the specific composition described above has sufficiently high antiblocking properties. In addition, it is possible to provide a molded article with less turbidity and excellent transparency.

Here, in the molding material of the present invention, 90% or more of all carbon-carbon unsaturated bonds contained in the block copolymer (C) are hydrogenated in the block copolymer hydride (D). And block copolymer hydrides. If the hydrogenation rate of the block copolymer hydride (D) is 90% or more, it is possible to provide a molded article having less turbidity and excellent transparency.

In the molding material of the present invention, the block copolymer hydride (D) may have a functional group. If the block copolymer hydride (D) has a functional group, the molded article obtained using the molding material can be given a desired attribute.

An object of the present invention is to advantageously solve the above-mentioned problems, and the molded article of the present invention is characterized in that any of the above-mentioned molding materials is melt-molded. Such molded articles are less turbid and excellent in transparency.

According to the present invention, it is an antiblocking agent capable of enhancing the antiblocking properties of pellets containing a block copolymer hydride as a main component, and can provide a molded article with less turbidity and excellent transparency. An antiblocking agent can be provided.
Further, according to the present invention, it is possible to provide a molding material capable of providing a molded article having sufficiently high antiblocking properties and low turbidity and excellent transparency.
Furthermore, according to the present invention, it is possible to provide a molded article having less turbidity and excellent transparency.

Hereinafter, the present invention will be described in detail in terms of (1) hydrogenated block copolymer, (2) antiblocking agent, (3) molding material, and (4) molded body.

(1) Block copolymer hydride The block copolymer hydride (D) to be added to the molding material of the present invention is a polymer obtained by hydrogenating the precursor block copolymer (C). Furthermore, preferably, the block copolymer hydride (D) is a polymer in which 90% or more of all carbon-carbon unsaturated bonds contained in the block copolymer (C) are hydrogenated.

[Block copolymer (C)]
The block copolymer (C) is a polymer mainly composed of two or more polymer blocks (A) mainly composed of a structural unit derived from an aromatic vinyl compound and a structural unit derived from a chain conjugated diene compound It is a polymer having one or more blocks (B).

A polymer block (A) is a polymer block which has a structural unit (a) derived from an aromatic vinyl compound as a main component. The content of the structural unit (a) in the polymer block (A) is usually 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass, based on 100% by mass of the entire polymer block (A). % Or more. The polymer block (A) may be formed of only the structural unit (a). If the content of the structural unit (a) in the polymer block (A) is not less than the above lower limit value, the heat resistance of the block copolymer hydride (D) to be blended in the molding material of the present invention can be improved. it can.

The polymer block (A) may contain components other than the structural unit (a). Other components include structural units (b) derived from chain conjugated dienes and / or structural units (v) derived from other vinyl compounds. The content of the structural unit (b) and / or the structural unit (v) in the polymer block (A) is usually 10% by mass or less, preferably 5% by mass, based on 100% by mass of the entire polymer block (A). % Or less, more preferably 1% by mass or less. If the content of the structural unit (b) and / or the structural unit (v) in the polymer block (A) is not more than the above upper limit value, the block copolymer hydride (D) to be blended in the molding material of the present invention Heat resistance can be improved.

The plurality of polymer blocks (A) contained in the block copolymer (C) may be identical to or different from one another as long as they satisfy the above range.

A polymer block (B) is a polymer block which has a structural unit (b) as a main component. The content of the structural unit (b) in the polymer block (B) is usually 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass, based on 100% by mass of the entire polymer block (B). % Or more. The polymer block (B) may be formed of only the structural unit (b).
When the content of the structural unit (b) in the polymer block (B) is in the above range, the flexibility of the block copolymer hydride (D) to be blended in the molding material of the present invention can be improved. .

The polymer block (B) may contain components other than the structural unit (b). Other components include structural unit (a) and / or structural unit (v). The content of the structural unit (a) and / or the structural unit (v) in the polymer block (B) is usually 30% by mass or less, preferably 20% by mass, based on 100% by mass of the whole polymer block (B). % Or less, more preferably 10% by mass or less. When the content of the structural unit (a) and / or the structural unit (v) in the polymer block (B) is not more than the above upper limit value, the softness of the block copolymer hydride (D) used in the present invention It is possible to improve the quality.

When the block copolymer (C) has a plurality of polymer blocks (B), the polymer blocks (B) may be identical to or different from each other.
Also, structural unit (b) and / or structural unit (v) that may be contained in polymer block (A), and structural unit (a) and / or structural unit (v) that may be contained in polymer block (B) And may be identical to or different from each other.

The aromatic vinyl compound which can be used to form the structural unit (a) derived from the aromatic vinyl compound is not particularly limited, and styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene Alkyl group having 1 to 6 carbon atoms as a substituent such as 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene and the like Styrenes having 1 to 6 carbon atoms as a substituent such as 4-methoxystyrene; styrenes having an aryl group as a substituent such as 4-phenylstyrene; 1-vinylnaphthalene, 2- Vinyl naphthalenes such as vinyl naphthalene; and the like.
Among these, from the viewpoint of hygroscopicity, aromatic vinyl compounds having no polar group such as styrene and styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent are preferable, and from the viewpoint of industrial availability. And styrene are particularly preferred.

The chain conjugated diene compound which can be used to form the structural unit (b) derived from the chain conjugated diene is not particularly limited, and 1,3-butadiene, isoprene, 2,3-dimethyl-, and the like. 1,3-butadiene, 1,3-pentadiene and the like can be mentioned. Among these, from the viewpoint of hygroscopicity, chain-like conjugated diene compounds containing no polar group are preferable, and from the industrial availability, 1,3-butadiene and isoprene are particularly preferable.

Examples of other vinyl compounds include linear vinyl compounds, cyclic vinyl compounds, unsaturated cyclic acid anhydrides and unsaturated imide compounds. These compounds may have a substituent such as a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group or a halogen atom. Among them, from the viewpoint of hygroscopicity, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene, 4- Linear olefins having 2 to 20 carbon atoms such as methyl-1-pentene and 4,6-dimethyl-1-heptene; cyclic olefins having 5 to 20 carbon atoms such as vinylcyclohexane and norbornene; 1,3-cyclohexadiene and norbornadiene And cyclic diene compounds such as, and the like, which do not contain a polar group are preferable.

The number of polymer blocks (A) in the block copolymer (C) is usually 3 or less, preferably 2, and the number of polymer blocks (B) in the block copolymer (C) is Usually, two or less, preferably one. If the number of polymer blocks (A) and polymer blocks (B) in the block copolymer (C) is equal to or less than the above upper limit, a block copolymer obtained by hydrogenating the block copolymer (C) In the hydride (D), a clear phase separation structure can be formed by the hydrogenated polymer block derived from the polymer block (A) and the hydrogenated polymer block derived from the polymer block (B); The glass transition temperature on the high temperature side of the polymer hydride (D) can be increased to improve the heat resistance of the block copolymer hydride (D) used in the present invention.

The form of the block of the block copolymer (C) is not particularly limited, and may be a chain block or a radial block, but a chain block is preferable because of excellent mechanical strength. Preferred forms of the block copolymer (C) are a triblock copolymer (A)-(B)-(A) in which a polymer block (A) is bonded to both ends of the polymer block (B), and a polymer A pentablock copolymer (A)-in which a polymer block (B) is bonded to both ends of the block (A), and further, a polymer block (A) is bonded to the other end of both polymer blocks (B). (B)-(A)-(B)-(A), and a more preferable form is triblock copolymer (A)-(B)-(A).

Here, the mass fraction of the total amount of the polymer block (A) in the entire block copolymer (C) is wA, and the total amount of the polymer block (B) in the entire block copolymer (C) When the ratio is wB, the ratio of wA to wB (wA: wB) is 15:85 to 70:30, preferably 18:82 to 65:35, more preferably 20:80 to 60:40. is there. If the ratio of wA is equal to or less than the above upper limit, the flexibility of the block copolymer hydride (D) obtained by hydrogenating the block copolymer (C) is enhanced, for example, a solar cell sealing material, The sealing performance in the case of applying to a laminated glass intermediate film, a sealing material of an organic electroluminescent element, etc. can be improved. On the other hand, when wA is at least the above lower limit value, the blocking resistance of the block copolymer hydride (D) itself obtained by hydrogenating the block copolymer (C) is enhanced to prevent blocking of the present invention described later When the inhibitor is externally added and used in combination, it is possible to express synergetically high antiblocking effect.

The molecular weight of the block copolymer (C) is usually 40,000 or more as the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. Or less, preferably 45,000 or more and 150,000 or less, more preferably 50,000 or more and 100,000 or less. The molecular weight distribution (Mw / Mn) of the block copolymer (C) is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. When Mw and Mw / Mn are in the above ranges, the block copolymer hydride (D) used in the present invention has better heat resistance and mechanical strength.

The manufacturing method of a block copolymer (C) is not specifically limited, A well-known method is employable. For example, methods described in WO 2003/018656 pamphlet, WO 2011/096389 pamphlet and the like can be mentioned.

[Block copolymer hydride (D)]
The block copolymer hydride (D) is a polymer obtained by hydrogenating the above-mentioned block copolymer (C). More specifically, the block copolymer hydride (D) is obtained by hydrogenating carbon-carbon unsaturated bonds in the main chain and side chains, and / or carbon-carbon unsaturated bonds in an aromatic ring Preferably, at least main chain and side chain carbon-carbon unsaturated bonds are hydrogenated, more preferably, main chain and side chain carbon-carbon unsaturated bonds, and aromatic rings The carbon-carbon unsaturated bond of is formed by hydrogenation. If the carbon-carbon unsaturated bond of at least the main chain and the side chain is hydrogenated, the light resistance and the thermal degradation resistance of the block copolymer hydride (D) can be enhanced, and the transparency can be enhanced. . Furthermore, if the main chain and side chain carbon-carbon unsaturated bonds and the aromatic ring carbon-carbon unsaturated bonds are hydrogenated, the heat resistance and the weather resistance of the block copolymer hydride (D) are improved. It can be further enhanced.

The hydrogenation rate of the block copolymer hydride (D) is preferably 90% or more, more preferably 97%, based on 100% total carbon-carbon unsaturated bonds contained in the block copolymer (C). The above, more preferably 99% or more. The term “all carbon-carbon unsaturated bonds contained in block copolymer (C)” means carbon-carbon unsaturated bonds in the main chain and side chains of block copolymer (C), and aromatic rings Refers to the entire carbon-carbon unsaturated bond.
The hydrogenation rate of carbon-carbon unsaturated bonds in the main chain and side chains of the block copolymer (C) is preferably 97% or more, more preferably 99% or more. The carbon-carbon unsaturated bond of the aromatic ring of the block copolymer (C) may not necessarily be hydrogenated, but in the case where the carbon-carbon unsaturated bond of the aromatic ring is hydrogenated, The hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring is preferably 90% or more, more preferably 97% or more, and particularly preferably 99% or more.
The higher the ratio of hydrogenation when the total carbon-carbon unsaturated bond contained in the block copolymer (C) is 100% (ie, the "hydrogenation ratio of the block copolymer hydride (D)"), The block copolymer hydride (D) to be added to the molding material of the present invention is excellent in light resistance and heat degradation resistance, and maintains excellent colorless transparency even in long-term use or use at high temperature.
Hydrogenation ratio of carbon-carbon unsaturated bond of main chain and side chain of block copolymer hydride (D); Hydrogenation ratio of carbon-carbon unsaturated bond of aromatic ring; Block copolymer hydride (D) Can be determined by measuring ¹ H-NMR of the block copolymer hydride (D), respectively.
Each hydrogenation rate can be controlled by changing various conditions such as hydrogenation time, hydrogenation temperature and hydrogen pressure.

The hydrogenation method and reaction form of the unsaturated bond in a block copolymer (C) are not specifically limited, What is necessary is just to carry out according to a well-known method, A desired hydrogenation rate can be achieved, and a polymer A hydrogenation method with less chain scission reaction is preferred. As such a hydrogenation method, for example, the methods described in WO 2011/096389 pamphlet, WO 2012/043708 pamphlet and the like can be mentioned.

The molecular weight of the block copolymer hydride (D) is usually 40,000 or more and 200,000 or less, preferably 45,000 or more, as the polystyrene equivalent weight average molecular weight (Mw) measured by GPC using THF as a solvent It is 150,000 or less, more preferably 50,000 or more and 100,000 or less. The molecular weight distribution (Mw / Mn) of the block copolymer hydride (D) is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less.
When Mw and Mw / Mn are in the above ranges, the heat resistance and the mechanical strength of the block copolymer hydride (D) to be added to the molding material of the present invention become good.

After completion of the hydrogenation reaction, the hydrogenation catalyst or the hydrogenation catalyst and the polymerization catalyst are removed from the reaction solution, and then the solvent is removed from the resulting solution to recover the block copolymer hydride (D). Can.
The recovered block copolymer hydride (D) can be generally formed into a pellet shape, blended into a molding material, and the molding material can be subjected to a subsequent molding process.

[Functionalized block copolymer hydride]
The block copolymer hydride (D) to be mixed with the molding material of the present invention may have a functional group [hereinafter, this may be referred to as "block copolymer hydride (Dβ)". ] May be sufficient.
Block copolymer hydride (D) which does not have a functional group (or before introducing a functional group) [Hereafter, this thing may be called "block copolymer hydride (Dα)". By introducing the above-mentioned functional group, it is possible to impart adhesiveness to an inorganic base such as glass, ceramic, metal or the like, or an organic base such as a thermoplastic resin or a thermosetting resin.

The block copolymer hydride (Dβ) can be obtained, for example, by introducing a functional group such as an alkoxysilyl group or an acid anhydride group into the above-mentioned block copolymer hydride (Dα).
The method for introducing a functional group such as an alkoxysilyl group or an acid anhydride group into the block copolymer hydride (Dα) is not particularly limited. For example, an alkoxysilyl group or an acid anhydride is obtained by grafting the ethylenically unsaturated silane compound or the unsaturated carboxylic acid anhydride with the block copolymer hydride (Dα) in the presence of an organic peroxide. Functional groups such as substance groups can be introduced.

As the ethylenically unsaturated silane compound, unsaturated carboxylic acid anhydride and the like used for the grafting reaction, the block copolymer hydride (Dα) undergoes a grafting reaction, and the block copolymer hydride (Dα) is alkoxylated. It is not particularly limited as long as it introduces a silyl group, an acid anhydride group or the like.

Ethylenically unsaturated silane compounds include, for example, vinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; allyltrialkoxysilanes such as allyltrimethoxysilane and allyltriethoxysilane; dimethoxymethylvinylsilane and diethoxymethyl Dialkoxyalkylvinylsilanes such as vinylsilane; Styryltrialkoxysilanes such as p-styryltrimethoxysilane and p-styryltriethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxy ((Meth) acryloxyalkyl) trils such as propyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane and the like Alkoxysilane; 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl and methyl diethoxy silane ((meth) acryloxy alkyl) alkyl dialkoxy silane; and the like. These ethylenically unsaturated silane compounds may be used alone or in combination of two or more. Among them, vinyltrialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane are preferable, and vinyltrimethoxysilane is more preferable. In the present specification, “(meth) acryloxyalkyl” means acryloxyalkyl or methacryloxyalkyl.

As unsaturated carboxylic acid anhydride, for example, maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 2,3-dimethylmaleic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, allyl succinic acid anhydride And 2-phenylmaleic anhydride, and cis-aconitic anhydride and the like. Among these, maleic anhydride, itaconic anhydride and 5-norbornene-2,3-dicarboxylic acid anhydride are preferably used from the viewpoint of industrial availability. These unsaturated carboxylic acid anhydrides may be used alone or in combination of two or more.

As the organic peroxide used for the grafting reaction, one having a half-life temperature of 1 minute to 170 ° C. to 190 ° C. is preferably used.
Examples of the organic peroxide include t-butylcumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and di-t-butylperoxide. Preferred are t-butyl peroxide, di (2-t-butylperoxyisopropyl) benzene and the like. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane is preferable.
These peroxides may be used alone or in combination of two or more.

The amount of functional groups such as alkoxysilyl groups and acid anhydride groups introduced into the block copolymer hydride (Dα) is usually 0.1 parts by mass with respect to 100 parts by mass of the block copolymer hydride (Dα) The content is 10 parts by mass or less, preferably 0.5 parts by mass to 5 parts by mass, and more preferably 1 part by mass to 3 parts by mass.
When the introduction amount of the alkoxysilyl group or the acid anhydride group is within the above range, the block copolymer hydride into which these groups are introduced is an inorganic base material such as glass, ceramics, metal or the like, a thermoplastic resin or Adhesiveness to an organic substrate such as a thermosetting resin is imparted.

The method of reacting the block copolymer hydride (Dα) with the ethylenically unsaturated silane compound or the unsaturated carboxylic acid anhydride in the presence of a peroxide is not particularly limited. For example, kneading a mixture of a block copolymer hydride (Dα), an ethylenically unsaturated silane compound or an unsaturated carboxylic acid anhydride, and a peroxide in a molten state in a twin screw kneader for a desired time Thus, an alkoxysilyl group or an acid anhydride group can be introduced into the block copolymer hydride (Dα).

The kneading temperature by the twin-screw kneader is usually 180 ° C. or more and 220 ° C. or less, preferably 185 ° C. or more and 210 ° C. or less, more preferably 190 ° C. or more and 200 ° C. or less. The heating and kneading time is usually 0.1 minutes to 10 minutes, preferably 0.2 minutes to 5 minutes, and more preferably 0.3 minutes to 2 minutes. The kneading and extrusion may be continuously performed with the heating and kneading temperature and the heating and kneading time (residence time) being in the above ranges.

[Additive]
The block copolymer hydride (D) used by this invention can be mix | blended with various additives generally mix | blended with resin.
Additives include adhesion modifiers for controlling the adhesion and the like with metals, as well as suppressing the decrease in flexibility and adhesion temperature; UV absorbers for shielding ultraviolet rays; oxidation for enhancing processability etc. And inhibitors, and light stabilizers for enhancing the durability.

As a tackiness modifier, hydrocarbon polymers having a number average molecular weight of 300 to 5,000 are preferable. Specific examples of the tackiness modifier include low molecular weight products such as polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, ethylene-α-olefin copolymer, and their hydrides; polyisoprene, polyisoprene And low molecular weight products such as butadiene copolymers and hydrides thereof. Among these, low molecular weight polyisobutylene hydride and low molecular weight polyisoprene hydride are preferable, in particular, in terms of maintaining transparency and light resistance and being excellent in softening effect.

The blending amount of the low molecular weight hydrocarbon-based polymer is usually 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 10 parts by mass or less based on 100 parts by mass of the block copolymer hydride (D) is there. If the amount of the low molecular weight hydrocarbon-based polymer is increased, pellets containing the block copolymer hydride (D) as the main component may be easily blocked even if the antiblocking agent of the present invention is added. is there.

As the ultraviolet absorber, an oxybenzophenone compound, a benzotriazole compound, a salicylic acid ester compound, a benzophenone compound, a triazine compound, and the like can be used.
As the antioxidant, phosphorus-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants and the like can be used. As a light stabilizer, a hindered amine light stabilizer etc. can be used.

The ultraviolet absorber, the antioxidant, the antiblocking agent, the light stabilizer, etc. to be mixed with the block copolymer hydride (D) can be used singly or in combination of two or more. . The blending amount of these additives is usually 5 parts by mass or less, preferably 3 parts by mass or less, and more preferably 1.5 parts by mass or less, with respect to 100 parts by mass of the block copolymer hydride (D).

The method of mix | blending an additive with block copolymer hydride (D) can apply the well-known method generally used as a manufacturing method of a resin composition. For example, after uniformly mixing pellets of block copolymer hydride (D) and additives, the additives are melt mixed by a continuous melt kneader such as a twin-screw extruder and extruded into pellets. The blended block copolymer hydride (D) can be produced.

The “pellets mainly composed of hydrogenated block copolymer (D)” obtained as described above contain hydrogenated block copolymer (D), and optionally, the additive as described above, And block copolymer hydride (D) may contain other resin components having different compositions and properties. The content of the block copolymer hydride (D) in the pellet is preferably 60% or more, more preferably 70% or more, and still more preferably 75% or more, substantially 100%. It may be.

(2) Antiblocking agent The antiblocking agent of this invention is used in order to prevent the blocking of the pellet which has a block copolymer hydride (D) as a main component.
The antiblocking agent of the present invention may be referred to as a polymer having a structural unit (a ′) derived from an aromatic vinyl compound as a main component (hereinafter, “(co) polymer (CA)”). And a powder of (co) polymer hydride (hereinafter sometimes referred to as “(co) polymer hydride (DA)”) obtained by hydrogenating And the softening temperature of (co) polymer hydride (DA) is characterized by being 120 degreeC or more.

As the (co) polymer (CA), a polymer composed of one or more structural units (a ′), and a structural unit (b ′) and / or a structural unit (a ′) as a main component Random copolymer containing structural unit (v '), and block copolymer containing structural unit (b') and / or structural unit (v ') as the main component of structural unit (a') Can be mentioned.
Among these, the (co) polymer (CA) is preferably a block copolymer. When the (co) polymer (CA) is a block copolymer, specific examples thereof include a polymer block (A ′) mainly composed of a structural unit (a ′) and a structural unit (b ′) Diblock copolymers, triblock copolymers, pentablock copolymers and the like consisting of a polymer block (B ') as the main component can be mentioned.

The content of the structural unit (a ′) in the (co) polymer (CA) is usually 75% by mass or more, preferably 80% by mass or more, and more preferably 85% by mass or more.
When the content of the structural unit (a ′) in the (co) polymer (CA) is the above lower limit value or more, the softening temperature of the (co) polymer hydride (DA) to be blended in the molding material of the present invention It can be enhanced and can function well as an antiblocking agent.

As an aromatic vinyl compound which can be used to form a structural unit (a '), the structural unit (a) of the block copolymer (C) mentioned above by the item of "(1) block copolymer hydride" Compounds similar to the aromatic vinyl compounds that can be used to form can be used. Moreover, as a chain conjugated diene compound and other vinyl compounds that can be used to form the structural unit (b ′) and the structural unit (v ′), in the item “(1) block copolymer hydride” The same compounds as the chain conjugated diene compound and other vinyl compounds which can be used to form the structural unit (b) and the structural unit (v) of the block copolymer (C) described above can be used. .
In addition, when the said block copolymer hydride (D) and the (co) polymer (CA) are used for a molding material, structural-unit (a ') which is a main component of (co) polymer (CA) ) May be the same as or different from the structural unit (a) which is the main component of the polymer block (A) of the block copolymer (C) described above. Furthermore, when the (co) polymer (CA) contains the structural unit (b ′) and / or the structural unit (v ′), the structural unit (b ′) contained in the (co) polymer (CA) and The structural unit (v ′) may be identical to or different from the structural unit (b) and the structural unit (v) contained in the block copolymer (C), respectively.

The molecular weight of the (co) polymer (CA) is, in terms of polystyrene equivalent weight average molecular weight (Mw) measured by GPC, usually 10,000 or more and 100,000 or less, preferably 11,000 or more and 80,000 or less, Preferably it is 12,000 or more and 60,000 or less. The molecular weight distribution (Mw / Mn) of the (co) polymer (CA) is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. When Mw and Mw / Mn are in the above ranges, the (co) polymer hydride (DA) used in the present invention has high heat resistance, and the effect as an antiblocking agent is good.
When the molecular weight is at least the above lower limit value, the softening temperature can be sufficiently raised to allow the function as an antiblocking agent to be exhibited well. In addition, when the molecular weight is equal to or less than the above upper limit, the antiblocking agent of the present invention is externally added to the pellet containing the block copolymer hydride (D) as a main component, and when melt-molding the molding material And, it is possible to suppress the remaining unmelted material and to well suppress the occurrence of molding defects.

The method for producing the (co) polymer (CA) is not particularly limited, and known methods can be adopted. For example, methods described in JP-A-2000-169521, WO 2003/018656 pamphlet, WO 2011/096389 pamphlet and the like can be mentioned.

Here, the (co) polymer hydride (DA) is a polymer which is a hydride of the above (co) polymer (CA). Here, the (co) polymer hydride (DA) is an aromatic ring when the (co) polymer (CA) comprises (i) one or more structural units (a ′) Of a carbon-carbon unsaturated bond of (ii) containing structural unit (b ') and / or structural unit (v') while having structural unit (a ') as the main component In the case of a copolymer, or (iii) a block copolymer containing the structural unit (b ') and / or the structural unit (v') while having the structural unit (a ') as the main component, It means that the carbon-carbon unsaturated bond of the main chain and the side chain and the carbon-carbon unsaturated bond of the aromatic ring are hydrogenated. In the (co) polymer hydride (DA) obtained by hydrogenating the (co) polymer (CA) having the structure according to (ii) (iii) above, the carbon-carbon unsaturated bond of the aromatic ring is not necessarily hydrogen It does not have to be standardized.
The hydrogenation rate of (co) polymer hydride (DA), that is, the hydrogenation rate when all carbon-carbon unsaturated bonds contained in (co) polymer (CA) are 100%, 90 % Or more is preferable, 97% or more is more preferable, and 99% or more is more preferable. The higher the hydrogenation rate of the (co) polymer hydride (DA), the better the light resistance and the thermal degradation resistance of the (co) polymer hydride (DA) used in the present invention.
More specifically, (co) polymer hydride (DA) obtained by hydrogenating (co) polymer (CA) having a structure according to (i) above, and a structure according to (ii) (iii) above In the case where the (co) polymer hydride (DA) obtained by hydrogenating the (co) polymer (CA) is obtained by hydrogenating the carbon-carbon unsaturated bond of the aromatic ring during hydrogenation Preferably, the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring is 90% or more, more preferably 97% or more, and still more preferably 99% or more.
In addition, carbon-carbon unsaturation in the main chain and side chain of (co) polymer hydride (DA) obtained by hydrogenating the (co) polymer (CA) having the structure according to (ii) (iii) above The hydrogenation rate of the bond is preferably 90% or more, more preferably 97% or more, and still more preferably 99% or more.
Hydrogenation rates of carbon-carbon unsaturated bonds of (co) polymer hydrides (DA) and side chains; hydrogenation rates of carbon-carbon unsaturated bonds of aromatic rings; and (co) polymer hydrides The hydrogenation rate of (DA) can be determined by measuring ¹ H-NMR of (co) polymer hydride (DA).
Each hydrogenation rate can be controlled by changing various conditions such as hydrogenation time, hydrogenation temperature and hydrogen pressure.

The method for reacting unsaturated bonds in the (co) polymer (CA), the reaction form, and the like are not particularly limited, and may be performed according to known methods, and a desired hydrogenation rate can be achieved. A hydrogenation method with less coalescing chain cleavage reaction is preferred. As such a hydrogenation method, for example, the methods described in WO 2011/096389 pamphlet, WO 2012/043708 pamphlet and the like can be mentioned.

The molecular weight of the (co) polymer hydride (DA) is usually 10, a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. 000 or more and 100,000 or less, preferably 11,000 or more and 80,000 or less, more preferably 12,000 or more and 60,000 or less. The molecular weight distribution (Mw / Mn) of the (co) polymer hydride (DA) is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less.
When Mw and Mw / Mn are in the above ranges, the (co) polymer hydride (DA) used in the present invention is in the form of powder and is a pellet mainly composed of the block copolymer hydride (D) When added externally, the effect of enhancing the antiblocking property can be exhibited well. Moreover, (co) polymer hydride (DA) which becomes Mw and Mw / Mn in the said range is excellent in the compatibility with respect to a block copolymer hydride (D). For this reason, a melt-molded product obtained by using a molding material in which powder of (co) polymer hydride (DA) is externally added to a pellet containing block copolymer hydride (D) as the main component is Excellent transparency.

After completion of the hydrogenation reaction, after removing the hydrogenation catalyst or the hydrogenation catalyst and the polymerization catalyst from the reaction solution, the solvent is removed from the resulting solution to recover the (co) polymer hydride (DA). be able to.
The recovered (co) polymer hydride (DA) can be processed into powder by any method described later and used as an antiblocking agent.

The average particle diameter of the powder of (co) polymer hydride (DA) is 1 μm to 500 μm, preferably 10 μm to 400 μm, and more preferably 50 μm to 350 μm. When the particle size is equal to or more than the above lower limit value, it is suppressed that the (co) polymer hydride (DA) soars when externally added to the pellet containing the block copolymer hydride (D) as the main component However, the workability can be further enhanced by suppressing the adhesion due to charging from becoming excessively strong. When the particle size is equal to or less than the above upper limit value, the blocking preventing effect can be favorably exhibited when externally added to a pellet containing the block copolymer hydride (D) as a main component.
Moreover, the antiblocking agent containing the powder of (co) polymer hydride (DA) is (co) in the state (for example, pellet-like) before processing into powder, as long as the effect mentioned above is not impaired. It may contain a polymer hydride (DA).
The average particle diameter of the powder of (co) polymer hydride (DA) is, for example, from the small diameter side in the particle diameter distribution (volume basis) measured by the dynamic light scattering method according to JIS Z 8828. Indicates the particle size (D50) at which the calculated cumulative volume is 50%.

The content ratio of the (co) polymer hydride (DA) in the antiblocking agent of the present invention is preferably 95% by mass or more, based on 100% by mass of the total mass of the antiblocking agent, and is 99% by mass. It is preferable that it is the above and 100 mass% may be sufficient. Further, as described above, the antiblocking agent of the present invention may contain pelletized (co) polymer hydride (DA) in addition to powder of (co) polymer hydride (DA) In the case where a pellet-like (co) polymer hydride (DA) is contained, it is preferable that the total content of these is within the above range.

As a method of obtaining powder of (co) polymer hydride (DA) having a predetermined particle diameter, any known method may be used as long as it is a known method, for example, solution reprecipitation method, freezing Pulverizing methods using a crusher, a low temperature crusher, a hammer crusher and the like can be mentioned.
In order to produce a powder of (co) polymer hydride (DA) having a desired particle size, grinding conditions can be adjusted as necessary. In addition, for example, the powder can be classified using a sieve or the like.

60 ° C. assumed in the step of transporting and storing the resulting molding material by externally adding the antiblocking agent of the present invention to the pellet containing the block copolymer hydride (D) as the main component Even after storage for a long time under high temperature, occurrence of blocking of pellets can be reduced.

(3) Molding Material In the molding material of the present invention, the antiblocking agent consisting of the (co) polymer hydride (DA) is externally added to the pellet mainly comprising the block copolymer hydride (D). It is a material.
The external addition amount of the antiblocking agent consisting of (co) polymer hydride (DA) is 0.01 parts by mass or more and 15 parts by mass with respect to 100 parts by mass of the pellet mainly composed of the block copolymer (D) Or less, more preferably 0.05 to 15 parts by mass, further preferably 0.1 to 10 parts by mass, particularly preferably 0.1 to 5.0 parts by mass is there.
If the external addition amount of the (co) polymer hydride (DA) is too small, there is a possibility that the antiblocking effect may be insufficient.
If the external addition amount is too large, the blocking inhibitor composed of the pellet mainly composed of the block copolymer hydride (D) and the powder of the (co) polymer hydride (DA) separates and melt molding There is a possibility that defects such as transparent streaks and unevenness may occur in the molded product.

The method of externally adding the antiblocking agent containing the powder of (co) polymer hydride (DA) to the pellet containing the block copolymer hydride (D) as the main component is not particularly limited. For example, it may be externally added using a mixer such as a tumbler mixer, ribbon blender, Henschel mixer, or the like. For example, it can be produced by adding (or while adding) a predetermined amount of an antiblocking agent to a pellet containing a block copolymer hydride (D) as a main component, and mixing with a mixer.

According to the molding material of the present invention, in the step of melt-molding the same to produce a molded article, the molding material storage container, the pneumatic feeding piping from the molding material storage container to the molding machine, the hopper of the molding machine, etc. The occurrence of blocking of the pellet due to
Further, by melt-molding the molding material of the present invention, it is possible to produce a molded body having less turbidity and excellent transparency.

(4) Molded Article The molded article of the present invention is a molded article produced by melt-molding the molding material of the present invention.
The method for producing the molded body is not particularly limited, and a conventionally known molding method can be adopted. For example, known methods of molding in a molten state such as injection molding, blow molding, injection blow molding, inflation molding, and extrusion molding can be mentioned.
A molded article produced by molding the molding material of the present invention does not impair the excellent transparency of a molded article made of a specific block copolymer hydride.

The molded article of the present invention is less turbid and excellent in transparency, and also excellent in heat resistance, mechanical strength, light resistance, moisture resistance, low moisture absorption, etc. Can be used preferably. Specific applications include, for example, optical films, polarizing plate protective films, solar cell sealing materials, adhesive sheets for laminated glass, sealing materials for organic electroluminescent elements, light guide plates, OCA (optical clear adhesive), transparent Adhesive sheet, optical lens, prism, optical components for terahertz wave transmission because of excellent transmittance of terahertz waves with a frequency of 100 GHz to 10 THz, window materials for vehicles, window materials for buildings, window materials for light receiving elements, liquid crystal display element substrates , Medical optical inspection containers, and pharmaceutical containers, and the like.

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to the following examples. In addition, "part" and "%" are mass references | standards unless there is particular notice.

The evaluation in the present embodiment is performed by the following method.
(1) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
The molecular weight of the block copolymer (C), block copolymer hydride (D), (co) polymer (CA) and (co) polymer hydride (DA) is the standard by GPC using THF as the eluent. It was measured at 38 ° C. as a polystyrene conversion value. As a measuring device, HLC8020GPC manufactured by Tosoh Corporation was used.

(2) Hydrogenation ratio The hydrogenation ratio of the main chain, side chain and aromatic ring of block copolymer hydride (D) and (co) polymer hydride (DA) is determined by measuring ¹ H-NMR spectrum. Calculated.

(3) Softening temperature (Ts)
A (co) polymer hydride (DA) used as an antiblocking agent was press-formed to prepare a test piece of 5 mm in length, 5 mm in width, and 2 mm in thickness. Using this test piece, a thermomechanical analyzer (TMA SS 6100, indenter tip diameter 1.0 mm, Seiko Instruments Inc.) based on JIS K 7196 method (thermomechanical analysis of softening temperature of thermoplastic films and sheets). The softening temperature (Ts) was measured in the needle penetration mode in the range of + 30 ° C. to + 200 ° C. at a heating rate of 5 ° C./min.

(4) Evaluation of antiblocking property The pellet (P) containing the block copolymer hydride (D) as the main component and the powder (DAPC) containing the (co) polymer hydride (DA) as the main component The amount was externally added to prepare a molding material (M). 40 g of a molding material (M) was placed in a stainless steel tube (inner diameter 51 mm, length 150 mm) with a bottom lid, and then a stainless steel inner lid 50 mm in diameter and a weight of 532 g were placed on the top of the material. (In this state, a load of 27 g / cm ² (corresponding to a load of about 0.5 m high packed pellets) is applied to the lowermost part of the pellet in the tube.)
With this load maintained, the molding material (M) was held in an oven at a temperature of 60.degree. After holding for 96 hours, the environment was returned to 25 ° C., the bottom lid of the stainless steel pipe was removed, the molding material (M) was taken out, and the blocking resistance was evaluated according to the following criteria.
A: There is a blocked pellet, but the blocked pellet is easily broken when touched with a finger.
B: There is a blocked pellet, and the blocked pellet is not easily disintegrated even if it is touched with a finger.

(5) Evaluation of turbidity of molded body The turbidity of the molded body is a test piece obtained by sandwiching a sheet (S) having a thickness of 0.76 mm made of the molding material (M) of the present invention between two glass plates. The haze was measured and evaluated.
The test piece was produced by the following method.
Using the molding material (M) of the present invention, a 300 mm wide T-die is connected to a single-screw extruder equipped with a 20 mmφ full flight screw, a sheet winding machine is installed, and a 0.76 mm thick sheet (S ) Was produced.
A sample of 60 mm long and 50 mm wide was cut out from the sheet (S), and placed and laminated between two white plate glasses of 60 mm long, 50 mm wide, and 2 mm thick. Next, the laminate is placed in a 75 μm thick resin bag having a layer configuration of nylon (NY) / adhesive layer / polypropylene (PP), and a sealed packer (BH-951, manufactured by Panasonic Corporation) is used. While the inside of the bag was degassed, the opening was heat sealed to seal and package the laminate. Thereafter, the sealed package was placed in an autoclave and heated and pressurized at a temperature of 140 ° C. and a pressure of 0.8 MPa for 30 minutes to prepare a laminated glass test piece in which the sheet (S) was in close contact with the glass surface.
The haze of the obtained laminated glass test piece was measured using a haze meter (NDH7000SP, manufactured by Nippon Denshoku Kogyo Co., Ltd.) according to JIS K7136, and evaluated according to the following criteria.
A: The haze value is 1% or less.
B: Haze value is over 1%.

Production Example 1 Production of Pellet (P1) Composed of Block Copolymer Hydride (D1) (Production of Block Copolymer (C1))
A reactor equipped with a stirrer and sufficiently nitrogen-substituted inside was charged with 400 parts of dehydrated cyclohexane which is an inert solvent, 10 parts of dehydrated styrene which is an aromatic vinyl compound, and 0.475 parts of dibutyl ether. While stirring the entire volume at 60 ° C., 0.88 parts of n-butyllithium (15% by mass cyclohexane solution) as a polymerization initiator was added to initiate polymerization. Subsequently, while stirring the entire volume at 60 ° C., 15 parts of dehydrated styrene was continuously added to the reactor over 40 minutes to advance the polymerization reaction, and after the addition was completed, the entire volume was stirred for another 20 minutes at 60 ° C. . The reaction solution was measured by gas chromatography (GC), and the polymerization conversion ratio at this point was 99.5%.
Next, 50 parts of dehydrated isoprene, which is a chain conjugated diene compound, was continuously added to the reaction solution over 130 minutes, and stirring was continued for 30 minutes after the addition was completed. At this time, the reaction solution was analyzed by GC, and as a result, the polymerization conversion was 99.5%.
Thereafter, 25 parts of dehydrated styrene was further added continuously to the reaction solution over 70 minutes, and after completion of the addition, the mixture was stirred for 60 minutes as it was. At this time, the reaction solution was analyzed by GC, and as a result, the polymerization conversion was approximately 100%.

Here, 0.5 parts of isopropyl alcohol was added to stop the reaction to obtain a polymer solution containing a block copolymer (C1) of the (A)-(B)-(A) type. The weight average molecular weight (Mw) of the block copolymer (C1) was 47,800, the molecular weight distribution (Mw / Mn) was 1.02, and wA: wB = 50: 50.

(Production of block copolymer hydride (D1))
Next, the above polymer solution is transferred to a pressure resistant reactor equipped with a stirrer, and a diatomaceous earth supported nickel catalyst (product name "E22U", nickel supported amount 60% as a hydrogenation catalyst, manufactured by JGC Catalysts Chemical Co., Ltd.) 4.0 parts and 30 parts of dehydrated cyclohexane were added and mixed. The inside of the reactor was replaced with hydrogen gas, and while stirring the solution, hydrogen was supplied to carry out a hydrogenation reaction at a temperature of 190 ° C. and a pressure of 4.5 MPa for 6 hours.
The weight average molecular weight (Mw) of the block copolymer hydride (D1) contained in the reaction solution obtained by the hydrogenation reaction was 50, 100, and the molecular weight distribution (Mw / Mn) was 1.04.

(Manufacture of pellets (P1))
After completion of the hydrogenation reaction, the reaction solution is filtered to remove the hydrogenation catalyst, and then pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl), which is a phenolic antioxidant, is removed. Propionate] 2.0 parts of a xylene solution in which 0.1 part of 0.1 part of a propionate (product name “Songnox (registered trademark) 1010”, manufactured by Matsubara Sangyo Co., Ltd.) was dissolved was added and dissolved.
Subsequently, the above solution was subjected to removal of cyclohexane, xylene and other volatile components from the solution at a temperature of 260 ° C. and a pressure of 0.001 MPa or less using a cylindrical concentrator dryer (product name “Contro”, manufactured by Hitachi, Ltd.) did. The molten polymer was extruded from the die into strands, and after cooling, 95 parts of a pellet (P1) consisting of a block copolymer hydride (D1) was produced by a pelletizer.
The weight average molecular weight (Mw) of the pellet-like block copolymer hydride (P1) thus obtained was 49,600, the molecular weight distribution (Mw / Mn) was 1.05, and the hydrogenation rate was almost 100%.

Production Example 2 Production of Pellet (P2) Consisting of Block Copolymer Hydride (D2) 14 parts of styrene, 80 parts of isoprene and 6 parts of styrene are added in this order over a total of 240 minutes, n-butyllithium Polymerization, hydrogenation, concentration drying, extrusion, cooling, and pelletizing are performed in the same manner as in Production Example 1 except that (the 15 mass% cyclohexane solution) is changed to 0.55 parts, block copolymer hydride (D2) is obtained. 94 parts of pellets (P2) consisting of Pellets (P2) were stored refrigerated at 5 ° C.

In the block copolymer (C2) which is a precursor of the block copolymer hydride (D2), wA: wB = 20:80. The weight average molecular weight (Mw) of the manufactured pellet-like block copolymer hydride (P2) was 75,700, the molecular weight distribution (Mw / Mn) was 1.05, and the hydrogenation rate was almost 100%.

Preparation Example 3 Preparation of Powder (DAPC1) Composed of Polymer Hydride (DA1) 100 parts of styrene, which is an aromatic vinyl compound, was continuously added over a total of 240 minutes to obtain n-butyllithium (15%) In the same manner as in Production Example 1 except that the compounding amount of the cyclohexane solution was changed to 2.8 parts, polymerization, hydrogenation, and a hydrogenation catalyst were removed from the reaction solution to obtain a polymer hydride (DA1) The resulting solution was obtained.
100 parts of a solution containing the obtained polymer hydride (DA1) is poured into 400 parts of isopropyl alcohol while stirring to coagulate the polymer hydride (DA1), and after filtering off, it is vacuum dried at 60 ° C. Thus, 17.3 parts of polymer hydride (DA1) was produced.

The weight average molecular weight (Mw) of the produced polymer hydride (DA1) was 16,600, the molecular weight distribution (Mw / Mn) was 1.04, and the hydrogenation rate was almost 100%. Further, the softening temperature (Ts) of the polymer hydride (DA1) was 122 ° C.

The polymer hydride (DA1) was freeze-crushed to obtain a powder (DAPC1) having an average particle diameter of 120 μm.

Production Example 4 Production of Powder (DAPC2) Composed of Polymer Hydride (DA2) A total of 240 parts of styrene as an aromatic vinyl compound, 15 parts of isoprene as a chain conjugated diene compound, and 77 parts of styrene. Polymerization, hydrogenation, concentration drying, and extrusion were carried out in the same manner as in Production Example 1 except that the amount of n-butyllithium (15% by mass cyclohexane solution) was changed to 0.82 parts by adding in this order over a minute. Cooling and pelletizing were carried out to produce pellets (DAP2) consisting of block copolymer hydride (DA2).

The weight average molecular weight (Mw) of the produced polymer hydride (DA2) was 55,800, the molecular weight distribution (Mw / Mn) was 1.05, and the hydrogenation rate was almost 100%. Moreover, the softening temperature (Ts) of the polymer hydride (DA2) was 128 ° C.

The pellet (DAP2) was freeze-crushed to obtain a powder (DAPC2) having an average particle diameter of 120 μm.

Preparation Example 5 Preparation of Powder (DAPC3) Composed of Polymer Hydride (DA3) Preparation Example 3 and Example 5 except that the blending amount of n-butyllithium (15% by mass cyclohexane solution) was changed to 5.7 parts. In the same manner, 16.9 parts of polymer hydride (DA3) was produced.

The weight average molecular weight (Mw) of the produced polymer hydride (DA3) was 8,200, the molecular weight distribution (Mw / Mn) was 1.04, and the hydrogenation rate was almost 100%. Further, the softening temperature (Ts) of the hydrogenated polymer (DA3) was 110 ° C.
The polymer hydride (DA3) was freeze-crushed to obtain a powder (DAPC3) having an average particle diameter of 100 μm.

Production Example 6 Production of Pellet (P3) Composed of Functionalized Block Copolymer Hydride (D3) Based on 100 parts of the block copolymer hydride (D1) pellet produced in Production Example 1 2.0 parts of vinyltrimethoxysilane which is an ethylenically unsaturated silane compound, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane which is an organic peroxide (product name “perhexa (product name) 0.2 part of (registered trademark) 25B "(manufactured by NOF Corporation) was added. This mixture was kneaded at a resin temperature of 200 ° C. and a residence time of 60 to 70 seconds using a twin-screw extruder (product name “TEM 37B”, manufactured by Toshiba Machine Co., Ltd.). The obtained kneaded product was extruded in the form of a strand, air-cooled, and then cut by a pelletizer to obtain 97 parts of a pellet (P3) consisting of a block copolymer hydride (D3) having a functional group.

After dissolving 10 parts of the pellet (P3) in 100 parts of cyclohexane, the obtained solution was poured into 400 parts of dehydrated methanol to coagulate the modified block copolymer hydride (D3), and the coagulated material was collected by filtration. . The filtrate was vacuum dried at 25 ° C. to isolate 9.0 parts of a crumb of a functional block copolymer hydride (D3).
When the FT-IR spectrum of the block copolymer hydride (D3) having a functional group was measured, it was newly derived from Si-OCH ₃ group at 1090 cm ^-1 and Si-CH ₂ group at 825 cm ^-1 and 739 cm ^-1 An absorption band was observed at a position different from the absorption bands (1075 cm ^-1 , 808 cm ^-1 and 766 cm ^-1 ) derived from Si-OCH ₃ group and Si-CH ₂ group of vinyltrimethoxysilane.
In addition, when the ¹ H-NMR spectrum (in deuterated chloroform) of the block copolymer hydride (D3) having a functional group was measured, a peak based on the proton of a methoxy group was observed at 3.6 ppm. From the peak area ratio, it was confirmed that 1.9 parts of vinyltrimethoxysilane was bonded to 100 parts of the block copolymer hydride (D3).

Example 1
0.6 parts by mass of the powder (DAPC1) prepared in Preparation Example 3 was added to 100 parts by mass of pellets (P1) containing the block copolymer hydride (D1) prepared in Preparation Example 1 as the main component A molding material (M1) was produced by mixing using a mixer (manufactured by Daiko Seiki Co., Ltd .: DMV-25). The molding compound (M1) was used to evaluate the antiblocking properties and the haze of the molding as described above.

In the antiblocking test, there were many blocked pellets, but the blocked pellets were easily broken when touched with a finger. The evaluation of antiblocking properties was acceptable (A). In the haze test of the molded body, the haze of the test piece was 0.1%. The evaluation of the turbidity of the molded body was good (A).
The results are shown in Table 1.

Example 2
0.1 parts by mass of the powder (DAPC2) prepared in Preparation Example 4 is the same as Example 1 with respect to 100 parts by mass of pellets (P1) made of block copolymer hydride (D1) prepared in Preparation Example 1 Were externally added to produce a molding material (M2). The molding compound (M2) was used to evaluate the antiblocking properties and the haze of the molding as described above. The results are shown in Table 1.

[Example 3]
In the same manner as in Example 1, 4.0 parts by mass of the powder (DAPC1) prepared in Preparation Example 3 was used with respect to 100 parts by mass of pellets (P2) consisting of the block copolymer hydride (D2) prepared in Preparation Example 2 Were externally added to produce a molding material (M3). The molding compound (M3) was used to evaluate the antiblocking properties and the haze of the molding as described above. The results are shown in Table 1.

Example 4
The powder (DAPC2) 1.8 parts by mass prepared in Preparation Example 4 is the same as Example 1 with respect to 100 parts by mass of pellets (P2) consisting of the block copolymer hydride (D2) prepared in Preparation Example 2 Were externally added to produce a molding material (M4). The molding compound (M4) was used to evaluate the antiblocking properties and the haze of the molding as described above. The results are shown in Table 1.

[Example 5]
1.2 parts by mass of the powder (DAPC2) prepared in Preparation Example 4 with respect to 100 parts by mass of pellets (P3) consisting of the block copolymer hydride (D3) having an alkoxysilyl group prepared in Preparation Example 5 Externally added as in Example 1 to produce a molding material (M6). The molding compound (M6) was used to evaluate the antiblocking properties and the haze of the molding as described above. The results are shown in Table 1.

Comparative Example 1
The same procedure as in Example 1 was applied 1.0 parts by mass of the powder (DAPC3) prepared in Preparation Example 5 to 100 parts by mass of pellets (P1) consisting of the block copolymer hydride (D1) prepared in Preparation Example 1 Were externally added to produce a molding material (M5). Molding materials (M5) were used to evaluate the antiblocking properties and the haze of the moldings.
As a result, in the molding material (M5), a part of the powder (DAPC3) was separated from the molding material (M5), and although the external addition amount was sufficient, in the antiblocking test, the blocked pellets The blocked pellets did not break easily when touched with a finger. The evaluation of antiblocking properties was poor (B). In the haze test of the molded body, the haze of the test piece was 0.1%. The evaluation of the turbidity of the molded body was good (A). The results are shown in Table 1.

Comparative Example 2
The antiblocking agent was not externally added to the pellet (P1) consisting of the block copolymer hydride (D1) produced in Production Example 1, and the antiblocking property and the turbidity of the molded product were evaluated according to the above.
In the antiblocking test, many blocked pellets were not easily broken even when the blocked pellets were touched with a finger. The evaluation of antiblocking properties was poor (B). In the haze test of the molded body, the haze of the test piece was 0.1%. The evaluation of the turbidity of the molded body was good (A). The results are shown in Table 1.

Comparative Example 3
The antiblocking agent was not externally added to the pellet (P2) comprising the block copolymer hydride (D2) produced in Production Example 2, and the antiblocking property and the turbidity of the molded product were evaluated according to the above. In the antiblocking test, the whole pellet was blocking, and the blocked pellet did not collapse easily. The evaluation of antiblocking properties was poor (B). Since the pellets (P2) easily block even at normal temperature (25 ° C.), the sheet was formed by feeding the pellets (P2) stored in a cold storage little by little to the hopper of the extruder. The formed sheet was not wound up, was cut into a length of 30 cm, and was stored by sandwiching a release film. In the haze test of this sheet, the haze of the test piece was 0.1%. The evaluation of the turbidity of the molded body was good (A). The results are shown in Table 1.

Comparative Example 4
The antiblocking agent was not externally added to the pellet (P3) comprising the block copolymer hydride (D3) having an alkoxysilyl group produced in Production Example 6, and the antiblocking property and the turbidity of the molded product were evaluated according to the above.
In the antiblocking test, many blocked pellets were not easily broken even when the blocked pellets were touched with a finger. The evaluation of antiblocking properties was poor (B). In the haze test of the molded body, the haze of the test piece was 0.1%. The evaluation of the turbidity of the molded body was good (A). The results are shown in Table 1.

 

From the results of Examples 1 to 5 and Comparative Examples 1 to 4, the following can be seen.
The molding of Examples 1 to 5 in which a powder consisting of (co) polymer hydride having a softening temperature of 120 ° C. or higher was externally added as a blocking inhibitor to 100 parts by mass of pellets consisting of block copolymer hydride The material is highly antiblocking and less turbid to melt-formed molded articles.
On the other hand, the molding material of Comparative Example 1 to which a polymer hydride having a softening temperature of less than 120 ° C. was externally added causes blocking, and the blocked block does not easily collapse and is inferior in antiblocking properties. I understand. Furthermore, it can be seen that the molding materials of Comparative Examples 2 to 4 in which the antiblocking agent of the present invention was not externally added were susceptible to blocking.

According to the present invention, it is an antiblocking agent capable of enhancing the antiblocking properties of pellets containing a block copolymer hydride as a main component, and can provide a molded article with less turbidity and excellent transparency. An antiblocking agent can be provided.
Further, according to the present invention, it is possible to provide a molding material capable of providing a molded article having sufficiently high antiblocking properties and low turbidity and excellent transparency.
Furthermore, according to the present invention, it is possible to provide a molded article having less turbidity and excellent transparency.

Claims (6)

1. An antiblocking agent, wherein the antiblocking agent is
   (H) a powder of a (co) polymer hydride obtained by hydrogenating a (co) polymer having as a main component a structural unit derived from an aromatic vinyl compound, and
   The softening temperature of the (co) polymer hydride is 120 ° C. or higher,
   An antiblocking agent characterized by
2. The (co) polymer hydride is
   The antiblocking agent according to claim 1, which is a (co) polymer hydride obtained by hydrogenating 90% or more of all carbon-carbon unsaturated bonds contained in the (co) polymer.
3. Two or more polymer blocks (A) mainly composed of structural units derived from aromatic vinyl compounds, and one or more polymer blocks (B) mainly composed of structural units derived from chain conjugated diene compounds Block copolymer (C), wherein the mass fraction of the total amount of the polymer block (A) in the entire block copolymer (C) is wA, and the total amount of the polymer block (B) is a block co-polymer The block copolymer (C), in which the ratio of wA to wB (wA: wB) is 15:85 to 70:30, where wB is the mass fraction of the polymer (C), is hydrogen The antiblocking agent according to claim 1 or 2 is externally added at a ratio of 0.01 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the pellet mainly composed of hydrogenated block copolymer (D) A molding material to be added.
4. The block copolymer hydride (D) is a block copolymer hydride in which 90% or more of all carbon-carbon unsaturated bonds contained in the block copolymer (C) are hydrogenated. The molding material of Claim 3.
5. The molding material of Claim 3 or 4 in which the said block copolymer hydride (D) has a functional group.
6. A molded body obtained by melt-molding the molding material according to any one of claims 3 to 5.