JP2018048236A - Antiblocking agent, molding material and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel antiblocking agent for improving antiblocking property of a pellet consisting of specific block copolymer hydride, a molding material manufactured by outside adding the antiblocking agent to the pellet consisting of specific block copolymer hydride, and a molded body manufactured by melting molding the molding material, small in turbidity and excellent in transparency.SOLUTION: There is provided an antiblocking agent consisting of a powder of (co)polymer hydride having the softening temperature of 120°C or more obtained by hydrogenating 90% or more of all carbon-carbon unsaturated bonds of a (co)polymer mainly containing a structural unit derived from an aromatic vinyl compound.SELECTED DRAWING: None

Description

  The present invention relates to an anti-blocking agent for pellets mainly composed of a specific block copolymer hydride, and a molding material obtained by externally adding the anti-blocking agent to pellets mainly composed of a specific block copolymer hydride. 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 composed mainly of a structural unit derived from a chain conjugated diene compound A specific block copolymer hydride obtained by hydrogenating a carbon-carbon unsaturated bond of a chain and a carbon-carbon unsaturated bond of an aromatic ring is used as a medical container. It is known that it can be used for applications requiring transparency, such as optical film, solar cell encapsulant, laminated glass intermediate film, organic electroluminescent element encapsulant, and light guide plate (Patent Documents 1 to 6). .
For example, by sticking a block copolymer hydride to a glass sheet or the like as a base material, it is used for applications such as a solar cell sealing material, a laminated glass intermediate film, an organic electroluminescence element sealing material, and the like.
The block copolymer hydride used for such applications is required to have excellent flexibility in addition to high transparency, in order to prevent adhesion to the substrate and cracking of the substrate against temperature changes. .

In order to apply the block copolymer hydride to the above-mentioned application, the block copolymer hydride is usually processed into a sheet by extrusion molding or calendar molding and laminated with a base material. Used.
However, since the pellets made of the above block copolymer hydride are flexible, they can be packed in packaging bags, flexible container bags, etc., and transported by truck or ship, or in a warehouse for a long time in summer. In the case of storage, blocking due to compaction may occur, and it may not be possible to use the molding using the pellet. In particular, when a sealing property at a relatively low temperature of about 100 ° C. is required like a sealing material of an organic electroluminescence element, the block copolymer hydride to be used has a low softening temperature. Therefore, blocking is more likely to occur.
Therefore, in order to transport and store transparent and flexible block copolymer hydride pellets without blocking, it is essential to prevent blocking of the pellets without impairing the transparency of the melt-formed product. It was.

In order to prevent blocking of pellets made of a flexible block copolymer hydride, usually, an antiblocking agent made of fine powder such as talc or fatty acid amide is externally added to the pellets and adhered to the surface. A method is taken to prevent direct contact.
However, if a blocking inhibitor that is incompatible with a specific block copolymer hydride is used, such as the above components, turbidity occurs in the molded block copolymer hydride sheet, and 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 as an antiblocking agent. A method of adding polyolefin fine particles is disclosed.

WO2000 / 077094 pamphlet JP 2002-105151 A JP 2006-189523 A WO2011 / 096389 pamphlet WO2013 / 176258 pamphlet WO2014 / 091941 pamphlet Japanese Patent Laying-Open No. 2015-151519

The present inventors applied the method described in Patent Document 7 to obtain a molding material by adding polyolefin fine particles to a specific block copolymer hydride having transparency used in the present invention. When a melt-molded body was produced using the molding material, the resulting melt-molded body was markedly turbid and the transparency was not maintained.
The present invention has been made in view of such circumstances, and even when stored for a long period of time at a high temperature of 60 ° C. assumed in the transportation and storage process, the blocking property of pellets made of a block copolymer hydride is prevented. A new anti-blocking agent that improves the process, a molding material obtained by externally adding the anti-blocking agent to pellets made of a specific block copolymer hydride, and a low turbidity produced by melt molding the molding material It aims at providing the molded object excellent in transparency.

  In order to achieve the above-mentioned object, the present inventors have made extensive studies on an anti-blocking agent that is externally added to a block copolymer hydride pellet. As a result, a (co) polymer hydride obtained by hydrogenating 90% or more of all carbon-carbon unsaturated bonds of a (co) polymer having a structural unit derived from an aromatic vinyl compound as a main component, and Use of (co) polymer hydride powder with a softening temperature of 120 ° C or higher as an anti-blocking agent to reduce pellet blocking even when stored at a high temperature of 60 ° C for a long period of time. As a result, the present invention has been completed.

Thus, according to the present invention, the following (1) antiblocking agent, (2) molding material, and (3) molded body are provided.
(1) A polymer hydride obtained by hydrogenating 90% or more of the total carbon-carbon unsaturated bonds of a polymer having a structural unit derived from an aromatic vinyl compound as a main component and having a softening temperature of 120 ° C. An anti-blocking agent comprising a polymer hydride powder as described above.
(2) At least two polymer blocks (A) mainly composed of a structural unit derived from an aromatic vinyl compound and at least one polymer block composed mainly of a structural unit derived from a chain conjugated diene compound ( B)
The weight fraction of the total amount of the polymer block (A) in the entire block copolymer (C) is wA, and the weight fraction of the total amount of the polymer block (B) in the entire block copolymer (C) is wB. Of the block copolymer (C) in which the ratio wA: wB of wA to wB is 15:85 to 70:30,
100 parts by weight of pellets mainly composed of hydrogenated block copolymer (D) in which 90% or more of carbon-carbon unsaturated bonds in the main chain and side chains and carbon-carbon unsaturated bonds in the aromatic ring are hydrogenated On the other hand, a molding material obtained by externally adding 0.01 to 15 parts by weight of the antiblocking agent described in (1).
(3) The molding material according to (2), wherein the block copolymer hydride (D) is a block copolymer hydride (D) having a functional group.
(4) A molded product obtained by melt-molding the molding material according to (2) or (3).

According to the anti-blocking agent of the present invention, this is externally added to pellets mainly composed of the block copolymer hydride (D), and the resulting molding material is assumed in the transportation and storage process. Even when stored at a high temperature of 60 ° C. for a long time, the occurrence of blocking of the pellets can be reduced.
According to the molding material of the present invention, in the step of melt molding this to produce a molded body, in the molding material storage container, the air feed pipe from the molding material storage container to the molding machine, the hopper of the molding machine, etc. Occurrence of pellet blocking due to crystallization is reduced.
Further, according to the present invention, by molding the molding material, a molded body having low turbidity and excellent transparency can be produced.

  Hereinafter, the present invention will be described in detail by dividing it into (1) a hydride of a block copolymer, (2) an antiblocking agent, (3) a molding material, and (4) a molded body.

(1) Block copolymer hydride The block copolymer hydride (D) used in the present invention is composed of a carbon-carbon unsaturated bond in the main chain and side chain of the block copolymer (C) as a precursor. It is a polymer in which 90% or more of the carbon-carbon unsaturated bonds of the aromatic ring are hydrogenated.

[Block copolymer (C)]
The block copolymer (C) is mainly composed of at least two polymer blocks (A) mainly comprising an aromatic vinyl compound-derived structural unit and at least one structural unit derived from a chain conjugated diene compound. And a polymer block (B).

A polymer block (A) is a polymer block which has the 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 weight or more, preferably 95% by weight or more, more preferably 99% by weight or more.
When there is too little content of the structural unit (a) in a polymer block (A), there exists a possibility that the heat resistance of the block copolymer hydride (D) used by this invention may fall.

The polymer block (A) may contain components other than the structural unit (a). Examples of the other component include a structural unit (b) derived from a chain conjugated diene and / or a structural unit (v) derived from another vinyl compound. The content of the structural unit (b) and / or the structural unit (v) in the polymer block (A) is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less.
When the content of the structural unit (b) and / or the structural unit (v) in the polymer block (A) is excessive, the heat resistance of the block copolymer hydride (D) used in the present invention is lowered. There is a fear.

  The plurality of polymer blocks (A) contained in the block copolymer (C) may be the same as or different from each other 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 weight or more, preferably 80% by weight or more, more preferably 90% by weight or more.
When the content of the structural unit (b) in the polymer block (B) is in the above range, the block copolymer hydride (D) used in the present invention exhibits flexibility.

The polymer block (B) may contain components other than the structural unit (b). Examples of the other component include the structural unit (a) and / or the structure (v). The content of the structural unit (a) and / or the structural body (v) in the polymer block (B) is usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less.
When the content of the structural unit (a) and / or the structural unit (v) in the polymer block (B) is too much, the flexibility of the block copolymer hydride (D) used in the present invention is impaired. There is a fear.

  When the block copolymer (C) has a plurality of polymer blocks (B), the polymer blocks (B) may be the same as or different from each other.

As the aromatic vinyl compound, styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, Styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent such as 5-t-butyl-2-methylstyrene; styrenes having an alkoxy group having 1 to 6 carbon atoms as a substituent such as 4-methoxystyrene; Styrenes having an aryl group as a substituent such as 4-phenylstyrene; vinylnaphthalenes such as 1-vinylnaphthalene and 2-vinylnaphthalene; and the like.
Among these, from the viewpoint of hygroscopicity, aromatic vinyl compounds that do not contain a polar group, such as styrene and styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, are preferable, because of industrial availability. Styrene is particularly preferred.

  Examples of the chain conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and the like. Among these, a chain conjugated diene compound not containing a polar group is preferable from the viewpoint of hygroscopicity, and 1,3-butadiene and isoprene are particularly preferable from the viewpoint of industrial availability.

  Examples of other vinyl compounds include chain 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 these, from the viewpoint of hygroscopicity, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene, C2-C20 chain olefins such as 4-methyl-1-pentene and 4,6-dimethyl-1-heptene; C5-C20 cyclic olefins such as vinylcyclohexane and norbornene; 1,3-cyclohexadiene And those containing no polar group, such as cyclic diene compounds such as norbornadiene;

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.
Block copolymer hydride (D) obtained by hydrogenating block copolymer (C) when the number of polymer blocks (A) and polymer blocks (B) in block copolymer (C) increases , The phase separation between the hydrogenated polymer block derived from the polymer block (A) and the hydrogenated polymer block derived from the polymer block (B) becomes unclear, and the high temperature of the block copolymer hydride (D) The glass transition temperature on the side is lowered, and the heat resistance of the block copolymer hydride (D) used in the present invention may be lowered.

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

The weight fraction of the total amount of the polymer block (A) in the block copolymer (C) is wA, and the weight fraction of the total amount of the polymer block (B) in the block copolymer (C) is wB. Sometimes, the ratio wA: wB of wA to wB is 15:85 to 70:30, preferably 18:82 to 65:35, more preferably 20:80 to 60:40.
When wA is too much, the block copolymer hydride (D) obtained by hydrogenating the block copolymer (C) has low flexibility, for example, a solar cell sealing material, a laminated glass interlayer film, There is a possibility that it cannot be applied to a sealing material of an organic electroluminescence element.
On the other hand, when wA is too small, the block copolymer hydride (D) obtained by hydrogenating the block copolymer (C) is excessively easy to block, and even when the anti-blocking agent of the present invention is externally added. There is a possibility that a sufficient anti-blocking effect is not exhibited.

  The molecular weight of the block copolymer (C) is a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and usually 40,000 to 200. , Preferably 45,000 to 150,000, more preferably 50,000 to 100,000. Further, 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 within the above ranges, the block copolymer hydride (D) used in the present invention has good heat resistance and mechanical strength.

  The manufacturing method of a block copolymer (C) is not specifically limited, A well-known method is employable. Examples thereof include the methods described in WO2003 / 018656 pamphlet, WO2011 / 096389 pamphlet and the like.

[Block copolymer hydride (D)]
The block copolymer hydride (D) is obtained by hydrogenating the carbon-carbon unsaturated bond of the main chain and the side chain of the block copolymer (C) and the carbon-carbon unsaturated bond of the aromatic ring. It will be. The hydrogenation rate is usually 90% or more, preferably 97% or more, more preferably 99% or more.
The hydrogenation rate of the carbon-carbon unsaturated bonds in the main chain and side chain of the block copolymer (C) is preferably 97% or more, and more preferably 99% or more. Further, the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring of the block copolymer (C) is preferably 97% or more, and more preferably 99% or more.
The higher the hydrogenation rate, the better the block copolymer hydride (D) used in the present invention has light resistance and heat deterioration resistance, and excellent colorless transparency is maintained even when used for a long time or under high temperature. The
The hydrogenation rate of the block copolymer hydride (D) can be determined by measuring ¹ H-NMR of the block copolymer hydride (D).

  The hydrogenation method and reaction mode of the unsaturated bond in the block copolymer (C) are not particularly limited, and may be carried out according to a known method, the hydrogenation rate can be increased, and the polymer chain scission reaction is small. The method is preferred. Examples of such hydrogenation methods include the methods described in WO2011 / 096389 pamphlet, WO2012 / 043708 pamphlet and the like.

The molecular weight of the block copolymer hydride (D) is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC using THF as a solvent, and is usually 40,000 to 200,000, preferably 45,000 to 150. 1,000, more preferably 50,000 to 100,000. 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 within the above ranges, the heat resistance and mechanical strength of the block copolymer hydride (D) used in the present invention are improved.

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 block copolymer hydride (D). Can do.
The recovered block copolymer hydride (D) can usually be formed into a pellet shape and subjected to subsequent molding.

[Block copolymer hydride having a functional group]
The block copolymer hydride (D) used in the present invention has a functional group [hereinafter, this may be referred to as “block copolymer hydride (Dβ)”. It is preferable that
Block copolymer hydride (D) having no functional group (or before introduction of a functional group) [Hereinafter, this may be referred to as “block copolymer hydride (Dα)”. ], By introducing the functional group, adhesion to an inorganic substrate such as glass, ceramics or metal, or an organic substrate such as a thermoplastic resin or a thermosetting resin can be imparted.

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 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, the block copolymer hydride (Dα) may be grafted with an ethylenically unsaturated silane compound or an unsaturated carboxylic acid anhydride in the presence of an organic peroxide to produce an alkoxysilyl group or an acid anhydride. Functional groups such as physical groups can be introduced.

  The ethylenically unsaturated silane compound or unsaturated carboxylic acid anhydride used for the grafting reaction is grafted with the block copolymer hydride (Dα) to form an alkoxy on the block copolymer hydride (Dα). There is no particular limitation as long as a silyl group or an acid anhydride group is introduced.

  Examples of the ethylenically unsaturated silane compound include vinyl trialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; allyltrialkoxysilanes such as allyltrimethoxysilane and allyltriethoxysilane; dimethoxymethylvinylsilane and diethoxymethyl. Dialkoxyalkyl vinyl silanes such as vinyl silane; styryl trialkoxy silanes such as p-styryltrimethoxysilane and p-styryltriethoxysilane; 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxy ((Meth) acryloxyalkyl) tria such as propyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane Kokishishiran; 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.

  Examples of the unsaturated carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 2,3-dimethylmaleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and allyl succinic anhydride. , 2-phenylmaleic anhydride, cis-aconitic anhydride and the like. Among these, maleic anhydride, itaconic anhydride, and 5-norbornene-2,3-dicarboxylic 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, those having a 1-minute half-life temperature of 170 to 190 ° C. are preferably used.
Examples of the organic peroxide include t-butyl cumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di- -T-butyl peroxide, di (2-t-butylperoxyisopropyl) benzene and the like are preferably used.
These 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 to 10 parts per 100 parts by weight of the block copolymer hydride (Dα). Parts by weight, preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight.
If the introduction amount of an alkoxysilyl group or an acid anhydride group is within the above range, the block copolymer hydride into which these groups have been introduced can be used for inorganic substrates such as glass, ceramics, metals, thermoplastic resins, Adhesiveness to an organic substrate such as a thermosetting resin is imparted.

  The method for reacting the block copolymer hydride (Dα) with the ethylenically unsaturated silane compound or unsaturated carboxylic acid anhydride in the presence of a peroxide is not particularly limited. For example, a mixture of a block copolymer hydride (Dα), an ethylenically unsaturated silane compound or an unsaturated carboxylic acid anhydride, and a peroxide is kneaded in a molten state in a biaxial 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 biaxial kneader is usually 180 to 220 ° C, preferably 185 to 210 ° C, more preferably 190 to 200 ° C. The heat kneading time is usually about 0.1 to 10 minutes, preferably about 0.2 to 5 minutes, and more preferably about 0.3 to 2 minutes. What is necessary is just to knead | mix and extrude continuously so that heat-kneading temperature and heat-kneading time (residence time) may become the said range.

[Additive]
In the block copolymer hydride (D) used in the present invention, various additives generally blended with the resin can be blended.
Additives include: tackiness modifier for adjusting flexibility, lowering of bonding temperature and adhesion to metal, etc., ultraviolet absorber for shielding ultraviolet rays, antioxidant for improving processability, durability Examples thereof include a light stabilizer for enhancing the properties.

  As the tackifier, a hydrocarbon polymer having a number average molecular weight of 300 to 5,000 is preferable. Specific examples of the tackifier include low molecular weight substances such as polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, and ethylene-α-olefin copolymer, and hydrides thereof; polyisoprene, polyisoprene. -Low molecular weight substances such as butadiene copolymers and hydrides thereof. Among these, a low molecular weight polyisobutylene hydride and a low molecular weight polyisoprene hydride are preferable because they maintain transparency and light resistance and are excellent in softening effect.

  The blending amount of the low molecular weight hydrocarbon polymer is usually 20 parts by weight or less, preferably 15 parts by weight or less, more preferably 10 parts by weight or less with respect to 100 parts by weight of the block copolymer hydride (D). is there. If the blending amount of the low molecular weight hydrocarbon polymer is increased, the pellet mainly composed of the block copolymer hydride (D) may be easily blocked even when the anti-blocking agent of the present invention is added. is there.

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

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

  As a method of adding an additive to the block copolymer hydride (D), a known method generally used as a method for producing a resin composition can be applied. For example, the block copolymer hydride (D) pellets and additives are mixed evenly, then melt-mixed by a continuous melt kneader such as a twin screw extruder, and extruded to form pellets. A blended block copolymer hydride (D) can be produced.

(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 anti-blocking 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 referred to as “(co) polymer (CA)”). ) Of (co) polymer hydride obtained by hydrogenating 90% or more of the total carbon-carbon unsaturated bonds, and having a softening temperature of 120 ° C. or more (hereinafter referred to as “(co)). Polymer hydride (DA) ")).

The (co) polymer (CA) is a polymer composed of one or more structural units (a), the structural unit (a) as a main component, the structural unit (b) and / or the structural unit (v). And a random copolymer with the structural unit (a) as a main component and a block copolymer with the structural unit (b) and / or the structural unit (v).
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) having the structural unit (a) as a main component and a structural unit (b) as a main component. Examples thereof include a diblock copolymer, a triblock copolymer, a pentablock copolymer, and the like, which are composed of the polymer block (B).

The content of the structural unit (a) in the (co) polymer (CA) is usually 75% by weight or more, preferably 80% by weight or more, more preferably 85% by weight or more.
When the content of the structural unit (a) in the (co) polymer (CA) is too small, the softening temperature of the (co) polymer hydride (DA) used in the present invention is lowered, and as an antiblocking agent. May stop functioning.

  As the aromatic vinyl compound for introducing the structural unit (a), the same compounds as those described for the block copolymer hydride (D) can be used. The chain conjugated diene compound and / or other vinyl compound into which the structural unit (b) and / or the structural unit (v) is introduced are the same as those described for the block copolymer hydride (D). These compounds can be used.

The molecular weight of the (co) polymer (CA) is a weight average molecular weight (Mw) in terms of polystyrene measured by GPC, and is usually 10,000-100,000, preferably 11,000-80,000, more preferably. 12,000-60,000. Further, 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 within the above ranges, the (co) polymer hydride (DA) used in the present invention has high heat resistance and good antiblocking effect.
If the molecular weight is too small, the softening temperature is lowered and the function as an antiblocking agent may not be sufficiently exhibited. If the molecular weight is too high, molding defects such as unmelted material remaining may occur during molding of the molding material comprising the block copolymer hydride (D) externally added with the antiblocking agent of the present invention. .

  The manufacturing method of (co) polymer (CA) is not specifically limited, A well-known method is employable. For example, the method as described in Unexamined-Japanese-Patent No. 2000-169521, WO2003 / 018656 pamphlet, WO2011 / 096389 pamphlet etc. is mentioned.

The (co) polymer hydride (DA) is obtained by hydrogenating all carbon-carbon unsaturated bonds of the above (co) polymer (CA). Here, “hydrogenated all carbon-carbon unsaturated bonds” means an aromatic ring when the (co) polymer (CA) is composed of one or more of the structural units (a). Is a random copolymer or block copolymer of the structural unit (a) and the structural unit (b) and / or the structural unit (v). In some cases, it means that the main chain and side chain carbon-carbon unsaturated bonds and the aromatic ring carbon-carbon unsaturated bonds are hydrogenated.
The hydrogenation rate of the carbon-carbon unsaturated bonds in the main chain and the side chain is usually 90% or more, preferably 97% or more, more preferably 99% or more. The hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring is usually 90% or more, preferably 97% or more, more preferably 99% or more.
The higher the hydrogenation rate, the better the light resistance and heat deterioration resistance of the (co) polymer hydride (DA) used in the present invention.
The hydrogenation rate of the (co) polymer hydride (DA) can be determined by measuring ¹ H-NMR of the (co) polymer hydride (DA).

  The hydrogenation method and reaction mode of the unsaturated bond in the (co) polymer (CA) are not particularly limited, and may be carried out according to a known method, the hydrogenation rate can be increased, and hydrogen with little polymer chain scission reaction. Is preferred. Examples of such hydrogenation methods include the methods described in WO2011 / 096389 pamphlet, WO2012 / 043708 pamphlet and the like.

The molecular weight of the (co) polymer hydride (DA) is a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and is usually 10. 000 to 100,000, preferably 11,000 to 80,000, more preferably 12,000 to 60,000. 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 within the above ranges, the (co) polymer hydride (DA) used in the present invention is powdered and externally added to the block copolymer hydride (D) pellets. In this case, the antiblocking effect can be increased, and since the compatibility with the block copolymer hydride (D) is excellent, the (co) polymer hydride is added to the block copolymer hydride (D). The melt-molded body of the molding material to which (DA) powder is externally added maintains excellent transparency.

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 (co) polymer hydride (DA). be able to.
The recovered (co) polymer hydride (DA) can be processed into a powder and used as an anti-blocking agent.

The average particle size of the antiblocking agent comprising (co) polymer hydride (DA) is 1 to 500 μm, more preferably 10 to 400 μm, and still more preferably 50 to 350 μm.
If the particle size is too small, the (co) polymer hydride (DA) is likely to float when externally added to the pellet containing the block copolymer hydride (D) as a main component, and adherence by charging. Becomes stronger and workability becomes very poor. If the particle size is too large, the anti-blocking effect may not be exhibited even when externally added to the pellet containing the block copolymer hydride (D) as a main component.
In addition, the anti-blocking agent comprising the (co) polymer hydride (DA) may contain the above average particle size powder even when the total amount is not composed of the above average particle size powder. For example, unpulverized pellets may be mixed.

As a method for obtaining a powder of (co) polymer hydride (DA) having a predetermined particle size, any known method may be used, such as a solution reprecipitation method, a freeze pulverizer, Examples thereof include a pulverization method using a low temperature pulverizer, a hammer type pulverizer, and the like.
In order to produce a powder of (co) polymer hydride (DA) having a desired particle size, the pulverization conditions can be adjusted as necessary. Moreover, it can also classify with a sieve.

  By externally adding the anti-blocking agent of the present invention to pellets mainly composed of the block copolymer hydride (D), the resulting molding material can be obtained at a high temperature of 60 ° C. assumed in the transportation and storage process. Even after storage for a long time, the occurrence of blocking of the pellet can be reduced.

(3) Molding material In the molding material of the present invention, an antiblocking agent composed of the (co) polymer hydride (DA) is externally added to the pellets mainly composed of the block copolymer hydride (D). Material.
The external addition amount of the antiblocking agent comprising (co) polymer hydride (DA) to 100 parts by weight of pellets mainly composed of block copolymer hydride (D) is 0.01 to 15 parts by weight, Preferably, it is 0.05-15 weight part, More preferably, it is 0.1-10 weight part.
If the external addition amount of the (co) polymer hydride (DA) is too small, the anti-blocking effect may be insufficient.
If the amount of external addition is too large, pellets mainly composed of block copolymer hydride (D) and antiblocking agent composed of (co) polymer hydride (DA) will be classified, and a melt molded molded body. May cause problems such as transparent streaks and unevenness.

  There is no particular limitation on the method of externally adding an anti-blocking agent made of (co) polymer hydride (DA) to pellets mainly composed of block copolymer hydride (D). For example, the external addition may be performed using a mixer such as a tumbler mixer, a ribbon blender, a Henschel mixer, or the like. For example, a predetermined amount of powder of an anti-blocking agent made of (co) polymer hydride (DA) is added (or added) to pellets mainly composed of block copolymer hydride (D). However, it can be manufactured by mixing with a mixer.

According to the molding material of the present invention, in the step of melt molding this to produce a molded body, in the molding material storage container, the air feed pipe from the molding material storage container to the molding machine, the hopper of the molding machine, etc. Occurrence of pellet blocking due to crystallization is reduced.
In addition, by melt-molding the molding material of the present invention, a molded body having low turbidity and excellent transparency can be produced.

(4) Molded body The molded body of the present invention is a molded body produced by melt-molding the molding material of the present invention.
The manufacturing method of a molded object is not specifically limited, A conventionally well-known shaping | molding method is employable. For example, a known method of molding in a molten state such as injection molding, blow molding, injection blow molding, inflation molding, extrusion molding or the like can be mentioned.
The molded body produced by molding the molding material of the present invention does not impair the excellent transparency of the molded body made of a specific block copolymer hydride.

  The molded article of the present invention is less turbid and excellent in transparency, and also has good heat resistance, mechanical strength, light resistance, moisture resistance, low hygroscopicity, etc., and therefore optical applications that require high transparency, etc. Can be preferably used. Specific applications include, for example, an optical film, a polarizing plate protective film, a solar cell encapsulant, an adhesive sheet for laminated glass, an organic electroluminescence element encapsulant, a light guide plate, an OCA, a transparent adhesive sheet, an optical lens, Prism, terahertz wave transmission optical component, vehicle window material, building window material, light receiving element window material, liquid crystal display element substrate, medical optical inspection container because it has excellent transmittance of terahertz wave with a frequency of 100 GHz to 10 THz , Pharmaceutical containers, and the like.

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

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

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

(3) Softening temperature (Ts)
A (co) polymer hydride (DA) used as an antiblocking agent was press-molded to prepare a test piece having a length of 5 mm, a width of 5 mm, and a thickness of 2 mm. Using this test piece, based on JIS-K7196 method (softening temperature test method by thermomechanical analysis of thermoplastic film and sheet), a thermomechanical analyzer (TMA SS6100, indenter tip diameter 1.0 mm, manufactured by Seiko Instruments Inc.) ), 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 blocking property A predetermined amount of powder (DAPC) containing (co) polymer hydride (DA) as the main component is added to the pellet (P) containing block copolymer hydride (D) as the main component. The molding material (M) was prepared by adding.
40 g of the molding material (M) was put in a stainless steel tube (inner diameter 51 mm, length 150 mm) with a bottom lid, and then a stainless steel inner lid with a diameter of 50 mm and a weight of 532 g were placed on top of the material. (In this state, a load of 27 g / cm ² (corresponding to a load of a filled pellet having a height of about 0.5 m) is applied to the lowest part of the pellet in the tube.)
The molding material (M) was held in an oven at a temperature of 60 ° C. while maintaining this load state. After holding for 96 hours, the temperature was returned to 25 ° C., and the bottom cover of the stainless steel tube was removed to take out the material. Evaluation is good (◎) when there is no blocked pellet, there is a blocked pellet, but when the blocked pellet is easily disintegrated when touched with a finger, (Yes), there is a blocked pellet, blocking A case where the pellets did not disintegrate easily even when touched with a finger was judged as defective (x).

(5) Evaluation of Turbidity of Molded Body Turbidity of the molded body is a test piece in which a 0.76 mm thick sheet (S) made of the molding material (M) of the present invention is sandwiched between two glass plates and adhered. Haze was measured and evaluated.
The test piece was produced by the following method.
Using the molding material (M) of the present invention, a T-die having a width of 300 mm was connected to a single-screw extruder equipped with a 20 mmφ full flight screw, a sheet winder was installed, and a 0.76 mm thick sheet (S ) Was produced.
A sample having a length of 60 mm and a width of 50 mm was cut out from the sheet (S) and placed between two white glass plates having a length of 60 mm, a width of 50 mm, and a thickness of 2 mm and laminated. Next, this laminate is put into a 75 μm thick resin bag having a layer structure of NY / adhesive layer / PP, and the inside of the bag is removed using a sealed pack device (BH-951, manufactured by Panasonic Corporation). The opening was heat-sealed in a state of care, and the laminate was hermetically packaged. Thereafter, the hermetically sealed laminate 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 produce 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 Industries Co., Ltd.).
In the evaluation, a case where the haze was 1% or less was judged as good (◯), and a case where it exceeded 1% was judged as defective (x).

[Production Example 1] Production of pellets (P1) made of block copolymer hydride (D1) (Production of block copolymer (C1))
A reactor equipped with a stirrer and sufficiently purged with nitrogen inside was charged with 400 parts of dehydrated cyclohexane, 10 parts of dehydrated styrene and 0.475 part of dibutyl ether. While stirring the whole volume at 60 ° C., 0.88 part of n-butyllithium (15% by weight cyclohexane solution) was added to initiate polymerization. While continuously stirring the whole volume at 60 ° C., 15 parts of dehydrated styrene was continuously added to the reactor over 40 minutes to proceed the polymerization reaction. After the addition was completed, the whole volume was further stirred at 60 ° C. for 20 minutes. . When the reaction solution was measured by gas chromatography (GC), the polymerization conversion rate at this point was 99.5%.
Next, 50 parts of dehydrated isoprene was continuously added to the reaction solution over 130 minutes, and stirring was continued for 30 minutes as it was after the addition was completed. At this time, as a result of analyzing the reaction solution by GC, the polymerization conversion rate was 99.5%.
Thereafter, 25 parts of dehydrated styrene was continuously added to the reaction solution over 70 minutes, and the mixture was stirred as it was for 60 minutes after the addition was completed. At this point, the reaction solution was analyzed by GC. As a result, the polymerization conversion rate was almost 100%.

  Here, 0.5 parts of isopropyl alcohol was added to stop the reaction, thereby obtaining a polymer solution containing the block copolymer (C1) of type (A)-(B)-(A). 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%, manufactured by JGC Catalysts & Chemicals, Inc.) as a hydrogenation catalyst. ) 4.0 parts and 30 parts of dehydrated cyclohexane were added and mixed. The inside of the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the solution. A hydrogenation reaction was performed 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 pellet (P1))
After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and then the phenol-based antioxidant pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl). ) Propionate] (product name “Songnox 1010”, manufactured by Matsubara Sangyo Co., Ltd.) 2.0 parts of xylene solution in which 0.1 part was dissolved was added and dissolved.
Next, the above solution is 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 concentrating dryer (product name “Contro”, manufactured by Hitachi, Ltd.). did. The molten polymer was extruded into a strand shape from a die, and after cooling, 95 parts of a pellet (P1) made of a block copolymer hydride (D1) was produced by a pelletizer.
The pelletized block copolymer hydride (P1) had a weight average molecular weight (Mw) of 49,600, a molecular weight distribution (Mw / Mn) of 1.05, and a hydrogenation rate of almost 100%.

[Production Example 2] Production of pellet (P2) composed of block copolymer hydride (D2) 14 parts of styrene, 80 parts of isoprene, and 6 parts of styrene were added in this order over a total of 240 minutes to obtain n-butyllithium. Except for changing the (15% by weight cyclohexane solution) to 0.55 parts, in the same manner as in Production Example 1, polymerization, hydrogenation, concentration drying, extrusion, cooling, and pelletizing were carried out to obtain a block copolymer hydride (D2 94 parts of pellets (P2) consisting of The pellet (P2) was refrigerated at 5 ° C.

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

[Production Example 3] Production of powder (DAPC1) made of polymer hydride (DA1) 100 parts of styrene was added continuously over a total of 240 minutes, and n-butyllithium (15% cyclohexane solution) was added. Except for changing to 8 parts, in the same manner as in Production Example 1, the hydrogenation catalyst was removed from the polymerization, hydrogenation, and reaction solution to obtain a solution containing a polymer hydride (DA1).
100 parts of a solution containing the obtained polymer hydride (DA1) was poured into 400 parts of isopropyl alcohol with stirring, the polymer hydride (DA1) was solidified, filtered, and vacuum dried at 60 ° C. As a result, 17.3 parts of a polymer hydride (DA1) was produced.

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

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

[Production Example 4] Production of powder (DAPC2) comprising polymer hydride (DA2) 8 parts of styrene, 15 parts of isoprene, and 77 parts of styrene were added in this order over a total of 240 minutes, and n-butyllithium ( 15% by weight cyclohexane solution) was changed to 0.82 parts, and the same procedure as in Production Example 1, followed by polymerization, hydrogenation, concentration drying, extrusion, cooling, and pelletizing was carried out from the block copolymer hydride (DA2). The resulting pellet (DAP2) was produced.

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

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

[Production Example 5] Production of powder (DAPC3) comprising polymer hydride (DA3) In the same manner as in Production Example 3, except that n-butyllithium (15 wt% cyclohexane solution) was changed to 5.7 parts. 16.9 parts of a polymer hydride (DA3) were produced.

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

[Production Example 6] Production of pellet (P3) composed of functional block-containing block copolymer hydride (D3) With respect to 100 parts of block copolymer hydride (D1) pellets produced in Production Example 1, 2.0 parts of vinyltrimethoxysilane and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (product name “Perhexa (registered trademark) 25B”, manufactured by NOF Corporation) 0.2 Parts were added. This mixture was kneaded using a twin screw extruder (product name “TEM37B”, manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 200 ° C. and a residence time of 60 to 70 seconds. The obtained kneaded product was extruded into a strand shape, air-cooled, and then cut by a pelletizer to obtain 97 parts of a pellet (P3) made of a block copolymer hydride (D3) having a functional group.

After dissolving 10 parts of the pellet (P3) in 100 parts of cyclohexane, the resulting solution was poured into 400 parts of dehydrated methanol to coagulate the modified block copolymer hydride (D3), and the coagulated product was collected by filtration. . The filtrate was vacuum-dried at 25 degreeC, and 9.0 parts of crumbs of the block copolymer hydride (D3) which has a functional group were isolated.
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 groups at 1090 cm ⁻¹ and Si—CH ₂ groups at 825 cm ⁻¹ and 739 cm ^−1. A large absorption band was observed at a position different from the absorption bands (1075 cm ⁻¹ , 808 cm ⁻¹ and 766 cm ⁻¹ ) derived from the Si—OCH ₃ group and Si—CH ₂ group of vinyltrimethoxysilane.
Further, when a ¹ H-NMR spectrum (in deuterated chloroform) of the block copolymer hydride (D3) having a functional group was measured, a peak based on a 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 weight of the powder (DAPC1) produced in Production Example 3 was added to 100 parts by weight of the pellet (P1) mainly composed of the block copolymer hydride (D1) produced in Production Example 1. Then, a molding material (M1) was produced by mixing with a mixer (manufactured by Daiko Seiki Co., Ltd .: DMV-25). Using the molding material (M1), blocking property and turbidity of the molded product were evaluated.

In the blocking property test, there were many blocked pellets, but they easily collapsed when the blocked pellets were touched with a finger. The evaluation of blocking property was acceptable (◯). In the test for turbidity of the molded product, the haze of the test piece was 0.1%. The evaluation of the turbidity of the molded product was good (◯).
These results are shown in Table 1.

[Example 2]
As in Example 1, 0.1 part by weight of the powder (DAPC2) produced in Production Example 4 is used per 100 parts by weight of the pellet (P1) made of the block copolymer hydride (D1) produced in Production Example 1. Was added externally to produce a molding material (M2). Using the molding material (M2), blocking property and turbidity of the molded product were evaluated.
These results are shown in Table 1.

[Example 3]
In the same manner as in Example 1, 4 parts by weight of the powder (DAPC1) produced in Production Example 3 is added to 100 parts by weight of pellets (P2) made of the block copolymer hydride (D2) produced in Production Example 2. This was added to produce a molding material (M3). Using the molding material (M3), blocking property and turbidity of the molded product were evaluated.
These results are shown in Table 1.

[Example 4]
As in Example 1, 1.8 parts by weight of the powder (DAPC2) produced in Production Example 4 is used per 100 parts by weight of the pellet (P2) made of the block copolymer hydride (D2) produced in Production Example 2. Was added externally to produce a molding material (M4). Using the molding material (M4), blocking property and turbidity of the molded product were evaluated.
These results are shown in Table 1.

[Example 5]
1.2 parts by weight of the powder (DAPC2) produced in Production Example 4 is added to 100 parts by weight of the pellet (P3) made of the block copolymer hydride (D3) having an alkoxysilyl group produced in Production Example 5. Externally added in the same manner as in Example 1 to produce a molding material (M6). Using the molding material (M6), blocking property and turbidity of the molded product were evaluated.
These results are shown in Table 1.

[Comparative Example 1]
As in Example 1, 1.0 part by weight of the powder (DAPC3) produced in Production Example 5 is used per 100 parts by weight of the pellet (P1) made of the block copolymer hydride (D1) produced in Production Example 1. Was added externally to produce a molding material (M5). Using the molding material (M5), blocking property and turbidity of the molded product were evaluated.
As a result, in the molding material (M5), a part of the powder (DAPC3) was separated from the molding material (M5) and the external addition amount was sufficient, but in the blocking test, the blocked pellets Many of the blocked pellets did not collapse easily when touched with a finger. The evaluation of blocking property was poor (x).
In the test for turbidity of the molded product, the haze of the test piece was 0.1%. The evaluation of the turbidity of the molded product was good (◯).
These results are shown in Table 1.

[Comparative Example 2]
No blocking inhibitor was added externally to the pellet (P1) made of the block copolymer hydride (D1) produced in Production Example 1, and the blocking property and turbidity of the molded product were evaluated.
In the blocking property test, there were many blocked pellets, and even when the blocked pellets were touched with a finger, they did not collapse easily. The evaluation of blocking property was poor (x).
In the test for turbidity of the molded product, the haze of the test piece was 0.1%. The evaluation of the turbidity of the molded product was good (◯).
These results are shown in Table 1.

[Comparative Example 3]
No blocking inhibitor was added externally to the pellet (P2) made of the block copolymer hydride (D2) produced in Production Example 2, and the blocking property and turbidity of the molded product were evaluated.
In the blocking test, the whole pellet was blocked, and the blocked pellet did not collapse easily. The evaluation of blocking property was poor (x).
Since the pellet (P2) is easily blocked even at room temperature (25 ° C.), the sheet was formed by feeding the pellet (P2) stored in a refrigerator to the hopper of the extruder little by little. The molded sheet was not wound up, but was cut to a length of 30 cm and stored with a release film in between. In the turbidity test of this sheet, the haze of the test piece was 0.1%. The evaluation of the turbidity of the molded product was good (◯).
These results are shown in Table 1.

[Comparative Example 4]
No blocking inhibitor was added externally to the pellet (P3) made of the block copolymer hydride (D3) having an alkoxysilyl group produced in Production Example 6, and the blocking property and turbidity of the molded product were evaluated.
In the blocking property test, there were many blocked pellets, and even when the blocked pellets were touched with a finger, they did not collapse easily. The evaluation of blocking property was poor (x).
In the test for turbidity of the molded product, the haze of the test piece was 0.1%. The evaluation of the turbidity of the molded product was good (◯).
These results are shown in Table 1.

The following can be seen from the results of this example and the comparative example.
Powder (DAPC) made of (co) polymer hydride (DA) having Ts in the range of the present invention as an antiblocking agent for 100 parts by weight of pellets (P) made of block copolymer hydride (D) ) Was added externally within the scope of the present invention, and the molding materials (M) of Examples 1 to 5 have improved blocking resistance and less melt-formed molded bodies.
On the other hand, the molding material (M) of Comparative Example 1 to which a polymer hydride (DA) having Ts lower than Ts within the scope of the present invention was externally added caused blocking, and the blocked mass was not easily broken. The effect as an antiblocking agent is low.
The molding materials (M) of Comparative Examples 2 to 4 in which the anti-blocking agent of the present invention is not externally added are likely to cause blocking.

  According to the present invention, the main component is a hydride of a specific block copolymer obtained by hydrogenating 90% or more of the carbon-carbon unsaturated bond of the main chain and the side chain and the carbon-carbon unsaturated bond of the aromatic ring. By externally adding a specific anti-blocking agent to the pellets contained, a molding material having improved anti-blocking properties under high-temperature environments is provided, and turbidity is obtained by melt molding the molding material. Is provided with a small and excellent transparency.

Claims (4)

  A (co) polymer hydride obtained by hydrogenating 90% or more of the total carbon-carbon unsaturated bonds of a (co) polymer having a structural unit derived from an aromatic vinyl compound as a main component, and having a softening temperature An anti-blocking agent comprising a powder of a (co) polymer hydride having a temperature of 120 ° C. or higher. At least two polymer blocks (A) mainly composed of structural units derived from an aromatic vinyl compound, and at least one polymer block (B) composed mainly of structural units derived from a chain conjugated diene compound Consists of
The weight fraction of the total amount of the polymer block (A) in the entire block copolymer (C) is wA, and the weight fraction of the total amount of the polymer block (B) in the entire block copolymer (C) is wB. Of the block copolymer (C) in which the ratio wA: wB of wA to wB is 15:85 to 70:30,
100 parts by weight of pellets mainly composed of hydrogenated block copolymer (D) in which 90% or more of carbon-carbon unsaturated bonds in the main chain and side chains and carbon-carbon unsaturated bonds in the aromatic ring are hydrogenated On the other hand, a molding material obtained by externally adding 0.01 to 15 parts by weight of the anti-blocking agent according to claim 1.   3. The molding material according to claim 2, wherein the block copolymer hydride (D) is a block copolymer hydride (D) having a functional group.   A molded product obtained by melt molding the molding material according to claim 2.