JP7196604B2 - molding material - Google Patents

Description

The present invention relates to molding materials.

Pellets of a soft resin such as hydrogenated block copolymer (hydrogenated SIS) deteriorate workability when the pellets stick together and block when stored in a container. In such a case, a dusting agent such as talc or metallic soap is added to the soft resin pellets to suppress blocking due to adhesion between the pellets for a long time (see, for example, Patent Document 1). .
Moreover, in order to improve light resistance, an ultraviolet absorber (light stabilizer) is added to soft resin pellets (see, for example, Patent Document 1).

International Publication No. 2015/182695

However, even if the addition of a dusting agent to soft resin pellets can suppress blocking due to mutual adhesion between pellets, depending on the amount of dusting agent added, desired optical properties (haze, transmittance) It was sometimes impossible to form a sheet having
Furthermore, depending on the timing of adding the ultraviolet absorber (light stabilizer) to the soft resin pellets, it may not be possible to form a sheet having a desired shrinkage rate.

Therefore, the present invention can suppress blocking due to mutual adhesion of molding materials during storage and transportation, and can mold a sheet having desired optical properties (haze, transmittance) and shrinkage. The object is to provide a molding material.

The inventor of the present invention has made intensive studies in order to achieve the above object. And, the present inventor consists of a core part containing a soft resin as a main component and a bleed part covering the core part and containing the ultraviolet absorber as a main component, and the content of the ultraviolet absorber is a predetermined amount By using a molding material (masterbatch pellet) in which at least part of the dusting agent is present in the bleeding portion, it is possible to suppress blocking due to mutual adhesion of the molding materials during storage and transportation, The inventors have found that it is possible to form a sheet having desired optical properties (haze, transmittance) and shrinkage, and have completed the present invention.

That is, an object of the present invention is to advantageously solve the above problems, and a molding material of the present invention is a molding material containing a soft resin, an ultraviolet absorber, and a dusting agent, A molding material comprising a core portion containing the soft resin as a main component and a bleed portion covering the core portion and containing the ultraviolet absorber as a main component, wherein the content of the ultraviolet absorber is It is more than 5 parts by mass and not more than 40 parts by mass with respect to 100 parts by mass of the soft resin, and at least part of the dusting agent is present in the bleeding part. Thus, it consists of a core part containing a soft resin as a main component and a bleed part covering the core part and containing the ultraviolet absorber as a main component, and the content of the ultraviolet absorber is a predetermined amount, By using a molding material (masterbatch pellet) in which at least part of the dusting agent is present in the bleeding portion, it is possible to suppress blocking due to mutual adhesion of the molding materials during storage and transportation, and to achieve the desired optical properties. Sheets can be molded with properties (haze, transmittance) and shrinkage.
In the present invention, "containing a soft resin as a main component" means that the content of the soft resin is more than 50% by mass, and "containing an ultraviolet absorber as a main component" means that the ultraviolet absorbing It means that the content of the agent is more than 50% by mass.
Furthermore, in the present invention, the "bleeding portion" corresponds to the surface portion of the core portion, and includes components that bleed out from the core portion and components that are added later and adhere to the core portion.
In the present specification, the "molding material" of the present invention is the "masterbatch pellet C", the "soft resin pellet" is the "raw material pellet A", and the "pellet used when molding a sheet or the like" and the "masterbatch pellet Raw material pellets at the time of masterbatch pellet production to be blended with" are referred to as "raw material pellets B".

Here, in the molding material of the present invention, the content of the dusting agent is preferably 0.0040 parts by mass or more and 0.0220 parts by mass or less with respect to 100 parts by mass of the soft resin. If the content of the dusting agent is 0.0040 parts by mass or more and 0.0220 parts by mass or less with respect to 100 parts by mass of the soft resin, blocking due to adhesion of the molding materials to each other during storage and transfer is ensured. , and a sheet having desired optical properties (haze, transmittance) can be reliably formed.

Here, in the molding material of the present invention, the soft resin preferably contains hydrogenated block copolymer as a main component. If the soft resin contains a hydrogenated block copolymer as a main component, a sheet having desired optical properties (haze, transmittance) can be more reliably formed.
In the present invention, "mainly composed of a hydrogenated block copolymer" means containing more than 50% by mass of a hydrogenated block copolymer.

Here, in the molding material of the present invention, the block copolymer hydride comprises at least two polymer blocks [A] mainly composed of aromatic vinyl monomer units and chain conjugated diene monomer units. The mass fraction of all the aromatic vinyl monomer units in the block copolymer [C] consisting of at least one polymer block [B] mainly composed of The ratio of wA to wB, where wA is the mass fraction of all chain conjugated diene monomer units in the block copolymer [C] in the entire block copolymer [C]. It is preferably obtained by hydrogenating the carbon-carbon unsaturated bonds in the main chain and side chains of the block copolymer [C] in which (wA:wB) is 10:90 to 70:30. The hydrogenated block copolymer comprises at least two polymer blocks [A] mainly composed of aromatic vinyl monomer units and at least one polymer block mainly composed of linear conjugated diene monomer units. Let wA be the mass fraction of the total aromatic vinyl monomer units in the block copolymer [C] consisting of [B] and the block copolymer [C]. The ratio of wA to wB (wA:wB) is 10:90 to 70:30, where wB is the mass fraction of the total linear conjugated diene monomer units of the block copolymer [C]. If the carbon-carbon unsaturated bonds in the main chain and side chains of the block copolymer [C] are hydrogenated, a sheet having desired optical properties (haze, transmittance) can be more reliably formed. can be done.
In the present invention, "mainly composed of aromatic vinyl monomer units" means containing more than 50% by mass of aromatic vinyl monomer units, and "chain conjugated diene monomer units "Containing as a main component" means containing more than 50% by mass of linear conjugated diene monomer units.

Here, in the molding material of the present invention, it is preferable that at least part of the block copolymer hydride is silane-modified. If at least part of the hydrogenated block copolymer is silane-modified, a sheet having desired optical properties (haze, transmittance) can be more reliably formed.

Here, in the molding material of the present invention, the ultraviolet absorber present in the bleeding portion is preferably a linear material having a width of 0.01 μm or more and 3.00 μm or less. If the UV absorber present in the bleed portion is a linear substance with a width of 0.01 μm or more and 3.00 μm or less, blocking due to adhesion of molding materials during storage and transportation can be suppressed more reliably. At the same time, a sheet having desired optical properties (haze, transmittance) can be formed more reliably.

Here, in the molding material of the present invention, it is preferable that the coverage of the core portion with the bleed portion is 90% or more. If the coverage of the bleed portion of the core portion is 90% or more, it is possible to more reliably suppress blocking due to mutual adhesion of the molding materials during storage and transportation, and desired optical properties (haze, transmittance ) can be formed more reliably.

According to the molding material of the present invention, it is possible to suppress blocking due to adhesion of molding materials to each other during storage and transportation, and to mold a sheet having desired optical properties (haze, transmittance) and shrinkage. be able to.

It is an example of a photograph taken when observing the surface of the molding material (masterbatch pellet C) of the present invention with an electron microscope. It is an example of the SEM image of the surface of the molding material (master batch pellet C) of this invention, and shows the state where the dusting agent was buried in the bleeding ultraviolet absorber. 3 is a photograph taken when the surface of raw material pellet B coated with an ultraviolet absorber used in Comparative Example 3 was observed with an electron microscope. 10 is an SEM image of the surface of raw material pellet B coated with an ultraviolet absorber used in Comparative Example 3. FIG.

(molding material)
The molding material of the present invention contains a soft resin, an ultraviolet absorber and a dusting agent, and may further contain other optional components.
In addition, the molding material of the present invention consists of a core portion containing a soft resin as a main component, and a bleed portion covering the core portion and containing an ultraviolet absorber that bleeds out as a main component, and any other portion. means a masterbatch pellet that may further have a

The coverage of the core portion with the bleed portion is preferably 90% or more, more preferably 94% or more, and particularly preferably 98% or more. If the coverage of the bleed portion of the core portion is at least the above lower limit, it is possible to more reliably suppress blocking due to mutual adhesion of the molding materials, and a sheet having desired optical properties (haze, transmittance) can be produced more effectively. It can be molded reliably.

<Soft resin>
"Soft resin" is a general term for resins that can adhere to each other and block at room temperature.

The molecular weight of the soft resin is a polystyrene equivalent weight average molecular weight (Mw) measured by GPC using THF as a solvent, and is preferably 35,000 or more, more preferably 38,000 or more. 000 or more, preferably 200,000 or less, more preferably 150,000 or less, and particularly preferably 100,000 or less. Also, the molecular weight distribution (Mw/Mn) of the soft resin is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.7 or less.
When Mw and Mw/Mn are within the above ranges, the heat resistance, mechanical strength and workability of pellets containing the soft resin are good.

The softening temperature of the soft resin is preferably 90° C. or higher, more preferably 95° C. or higher, particularly preferably 100° C. or higher, from the viewpoint of heat resistance and workability. Therefore, the temperature is preferably 170° C. or lower, more preferably 160° C. or lower, and particularly preferably 150° C. or lower.
In addition, the "softening temperature" is measured using a softening temperature measuring device (product name "CFT-500EX", manufactured by Shimadzu Corporation) in the range of 30 ° C. to 200 ° C., a temperature increase rate of 5 ° C./min, and a measurement load. The softening temperature can be calculated by measuring the softening temperature at 100 kgf/cm ² (9.8 MPa) and using the offset method.

The soft resin preferably contains hydrogenated block copolymer as a main component. If the soft resin contains a hydrogenated block copolymer as a main component, a sheet having desired optical properties (haze, transmittance) can be more reliably formed.

<<block copolymer hydride>>
At least a portion of the block copolymer hydride is preferably silane-modified.
That is, the block copolymer hydride may be (i) an entirely unmodified block copolymer hydride (block copolymer hydride [D]), or (ii) an unmodified block copolymer It may be a mixture of the combined hydride [D] and the silane-modified form of the block copolymer hydride [D] (modified block copolymer hydride [E]); It may be a polymer hydride [E], but (ii) it is a mixture of an unmodified block copolymer hydride [D] and a modified block copolymer hydride [E], or ( iii) All are preferably hydrogenated modified block copolymers [E].
The hydrogenated block copolymer comprises at least two polymer blocks [A] mainly composed of aromatic vinyl monomer units and a chain conjugated diene (linear conjugated diene, branched conjugated diene) monomer. It is preferable to hydrogenate the carbon-carbon unsaturated bonds of the main chain and side chains of the block copolymer [C] consisting of at least one polymer block [B] mainly composed of the polymer unit.

-Aromatic Vinyl Monomer Unit-
Examples of aromatic vinyl monomers capable of forming aromatic vinyl monomer units include styrene and derivatives thereof, specifically styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, 4-monochlorostyrene, dichlorostyrene, 4-monofluorostyrene , and 4-phenylstyrene. Among these, those containing no polar group to reduce hygroscopicity, specifically styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropyl Styrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, and 4-phenylstyrene are preferred, and styrene is particularly preferred because of its industrial availability. One of these may be used alone, or two or more of them may be used in combination at any ratio.

- Chain conjugated diene monomer unit -
The chain conjugated diene monomer that can form the chain conjugated diene monomer unit is not particularly limited, but those containing no polar group are preferable in order to reduce hygroscopicity. 3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene and 1,3-pentadiene are preferred. Among these, 1,3-butadiene and isoprene are particularly preferred because of their industrial availability. One of these may be used alone, or two or more of them may be used in combination at any ratio.

-Polymer block [A]-
Here, the polymer block [A] is a polymer block mainly composed of aromatic vinyl monomer units. The content of the aromatic vinyl monomer unit in the polymer block [A] is preferably 80% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 100% by mass. If the content of the aromatic vinyl monomer units in the polymer block [A] is 80% by mass or more, the polymer block [A]-derived microphase-separated domains in the hydrogenated copolymer can be maintained. can maintain the tensile strength and heat resistance of the aromatic monomer block.

The polymer block [A] may contain monomer units other than aromatic vinyl monomer units, and such other monomer units are chain conjugated diene monomer units. There may be. Further, as the monomer capable of forming other monomer units, those not containing a polar group are preferable in order to reduce hygroscopicity. Linear olefins such as hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene; vinyl Cyclic olefins such as cyclohexane can be mentioned.
The content of the monomer units other than the aromatic vinyl monomer units in the polymer block [A] is preferably 20% by mass when the total repeating units in the polymer block [A] are 100% by mass. % or less, more preferably 10 mass % or less, still more preferably 5 mass % or less, and particularly preferably 0 mass %.
In addition, when the copolymer which is a block copolymer has a plurality of polymer blocks [A], the monomer compositions of the plurality of polymer blocks [A] may be the same or different.
Here, the content ratio of structural units in the polymer block [A] can be measured using, for example, NMR and gel permeation chromatography (GPC). In addition, the polymer block [B], which will be described later, can also be measured in the same manner.

-Polymer block [B]-
The polymer block [B] is a polymer block mainly composed of chain conjugated diene monomer units. The content of the linear conjugated diene monomer units in the polymer block [B] is preferably 60% by mass or more, more preferably 100% by mass, based on the total repeating units in the polymer block [B]. is 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 100% by mass. When the content of the linear conjugated diene monomer unit in the polymer block [B] is 60% by mass or more, the softening temperature derived from the polymer block [B] in the copolymer can be obtained. Impact strength and workability can be maintained.

Incidentally, the polymer block [B] may contain monomer units other than the linear conjugated diene monomer units, and such other monomer units are aromatic vinyl monomer units. Other monomer units may be formed from the chain olefins and cyclic olefins described above in the section "Polymer block [A]".
The content of the monomer units other than the aromatic vinyl monomer units in the polymer block [B] is preferably 40 mass% when the total repeating units in the polymer block [B] are 100 mass%. % or less, more preferably 20 mass % or less, still more preferably 10 mass % or less, and particularly preferably 0 mass %.
In addition, when the copolymer which is a block copolymer has a plurality of polymer blocks [B], the monomer compositions of the plurality of polymer blocks [B] may be the same or different.

-Block copolymer [C]-
Block copolymer [C] is a precursor of block copolymer hydride [D] and is a polymer containing at least two polymer blocks [A] and at least one polymer block [B]. is.
Here, the number of polymer blocks [A] in the block copolymer [C] is usually 5 or less, preferably 4 or less, more preferably 3 or less, still more preferably 2.
The number of polymer blocks [B] in the block copolymer is usually 4 or less, preferably 3 or less, more preferably 2 or less, and still more preferably 1. .

The form of the blocks of the block copolymer [C] is not particularly limited, and may be a chain block or a radial block, but the chain block is preferable because of its excellent mechanical strength.
In addition, the block copolymer [C] has at least one structure in which the polymer block [A] is bonded to both ends of the polymer block [B] (that is, a structure arranged in the order of ABA). is preferred.
A particularly preferred form of the copolymer, which is a block copolymer, is a triblock copolymer (ABA) in which the polymer block [B] is bound to both ends of the polymer block [A], and a pentablock in which a polymer block [B] is bonded to both ends of the polymer block [A], and a polymer block [A] is bonded to the other end of each of the two polymer blocks [B]. Copolymers (ABABA) are mentioned, with triblock copolymers (ABA) being most preferred.

--wA:wB--
Let wA be the mass fraction of all the aromatic vinyl monomer units in the block copolymer [C] with respect to the entire block copolymer [C], and all the linear conjugated diene units in the block copolymer [C] When wB is the mass fraction of the monomer unit in the block copolymer [C], wA is preferably 10% or more, more preferably 20% or more, and 25% or more. more preferably 40% or more, particularly preferably 70% or less, more preferably 60% or less, wB is preferably 30% or more, and 40% or more is more preferably 90% or less, more preferably 80% or less, even more preferably 75% or less, and particularly preferably 60% or less.
When wA is equal to or less than the upper limit, it is possible to suppress the decrease in the impact resistance of the hydrogenated block copolymer [D] obtained from the block copolymer [C] at low temperatures. On the other hand, when wA is equal to or higher than the lower limit, it is possible to suppress a decrease in rigidity of the block copolymer hydride [D] obtained from the block copolymer [C].
Regarding the "ratio of wA to wB (wA:wB)", in the process of producing the block copolymer [C], the aromatic vinyl monomer used for the polymerization of the block copolymer [C], The number of parts of the linear conjugated diene monomer and other vinyl compounds, and the number of monomers used in the polymerization completion stage of each block of the block copolymer [C] measured using gas chromatography (GC) The mass fraction of each monomer unit can be calculated from the polymerization conversion rate to the polymer.

The molecular weight of the block copolymer [C] is 35,000 or more in polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. is preferably 38,000 or more, particularly preferably 40,000 or more, preferably 200,000 or less, more preferably 150,000 or less, 100,000 The following are particularly preferred. Also, the molecular weight distribution (Mw/Mn) of the block copolymer [C] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.7 or less.
When Mw and Mw/Mn are within the above ranges, the heat resistance, mechanical strength and workability of the pellets made of the soft resin are good.
In the present invention, "weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn)" refers to the weight average molecular weight of the sample to be measured (block copolymer [C], block copolymer hydride [D]). (Mw) and number average molecular weight (Mn) can be measured at 40° C. using tetrahydrofuran (THF) as an eluent, and standard polystyrene conversion values can be calculated. As a measuring device, for example, a gel permeation chromatography (GPC) device (HLC8320GPC, manufactured by Tosoh Corporation) can be used.

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

-Hydrogenation of block copolymer [C] (block copolymer hydride [D])-
The block copolymer hydride [D] is a polymer obtained by selectively hydrogenating only the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound of the block copolymer [C]. may be present, the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound of the block copolymer [C] and the carbon-carbon unsaturated bonds of the aromatic ring derived from the aromatic vinyl compound It may be a polymer with hydrogenated bonds or a mixture thereof.

When selectively hydrogenating only the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound of the block copolymer [C], the carbon-carbon unsaturated bonds of the main chain and side chains The hydrogenation rate of is usually 95% or more, preferably 97% or more, more preferably 99% or more, and the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound is usually 10 % or less, preferably 5% or less, more preferably 3% or less.
The higher the hydrogenation rate of the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound, the weather resistance and heat deterioration resistance of the pellets containing the soft resin and the sheets formed using the pellets. is good. In addition, by suppressing the hydrogenation of the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl compound, the heat deterioration resistance of the pellet containing the soft resin and the sheet molded using the pellet can be easily maintained. Become.
Here, "hydrogenating the carbon-carbon unsaturated bonds of the main chain and the side chain" means "hydrogenating the double bond derived from the chain conjugated diene compound in the block copolymer [C]. ", and "hydrogenating the carbon-carbon unsaturated bond of the aromatic ring" means "hydrogenating the double bond derived from the aromatic ring in the block copolymer [C]".

When hydrogenating the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene compound of the block copolymer [C] and the carbon-carbon unsaturated bonds of the aromatic ring derived from the aromatic vinyl compound , the hydrogenation rate of all carbon-carbon unsaturated bonds is 90% or more, preferably 95% or more, more preferably 99% or more.
If the hydrogenation rate of the block copolymer hydride [D] is within this range, the pellet containing the soft resin will be excellent in transparency and resistance to heat deterioration, and the carbon-carbon heterogeneous structure derived from the chain conjugated diene compound will Compared to pellets using a block copolymer hydride [D] in which only saturated bonds are selectively hydrogenated, it is particularly preferable because it has excellent light resistance and a high heat distortion temperature.

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

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

After the completion of the hydrogenation reaction, after removing the hydrogenation catalyst or the hydrogenation catalyst and the polymerization catalyst from the reaction solution, the solvent is removed from the resulting solution to recover the hydrogenated block copolymer [D]. be able to.

The molecular weight of the hydrogenated block copolymer [D] is preferably 35,000 or more, more preferably 38,000 or more, as a polystyrene equivalent weight average molecular weight (Mw) measured by GPC using THF as a solvent. 40,000 or more is particularly preferable, 200,000 or less is preferable, 150,000 or less is more preferable, and 100,000 or less is particularly preferable. The molecular weight distribution (Mw/Mn) of the hydride block copolymer [D] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.7 or less.
When Mw and Mw/Mn are within the above ranges, the heat resistance, mechanical strength and processability of the pellets containing the soft resin are good.

-Silane modification of block copolymer hydride [D] (modified block copolymer hydride [E])-
It is preferred that the block copolymer hydride [D] and an ethylenically unsaturated silane compound are reacted (silane-modified) in the presence of a peroxide to introduce an alkoxysilyl group into the copolymer hydride. .
By introducing an alkoxysilyl group into the hydrogenated block copolymer [D], the modified hydrogenated block copolymer [E] is imparted with strong adhesion to glass and metal.

--alkoxysilyl group--
Alkoxysilyl groups include tri(C1-6 alkoxy)silyl groups such as trimethoxysilyl group and triethoxysilyl group; methyldimethoxysilyl group, methyldiethoxysilyl group, ethyldimethoxysilyl group, ethyldiethoxysilyl group; (C1-20 alkyl) di(C1-6 alkoxy)silyl group such as propyldimethoxysilyl group and propyldiethoxysilyl group; phenyldimethoxysilyl group and phenyldiethoxysilyl group (aryl ) di(C1-C6 alkoxy)silyl group; and the like. Among these, a trimethoxysilyl group is particularly preferable from the viewpoint of imparting strong adhesiveness to the glass plate to the intermediate film. Further, the alkoxysilyl group is bonded to the block copolymer hydride [D] via a divalent organic group such as an alkylene group having 1 to 20 carbon atoms or an alkyleneoxycarbonylalkylene group having 2 to 20 carbon atoms. You may have

The amount of the alkoxysilyl group introduced into the hydrogenated block copolymer [D] is generally preferably 0.1 part by mass or more, and 0.1 part by mass or more per 100 parts by mass of the hydrogenated block copolymer [D]. It is more preferably 5 parts by mass or more, particularly preferably 1 part by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and 3 parts by mass or less. is particularly preferred. If the amount of alkoxysilyl groups introduced is too large, cross-linking between the alkoxysilyl groups decomposed with a trace amount of moisture or the like proceeds before the hydrogenated modified block copolymer [E] obtained is melt-molded into a desired shape. Problems such as gelation and deterioration of moldability due to deterioration of fluidity during melting tend to occur. On the other hand, if the amount of alkoxysilyl groups to be introduced is too small, the problem of not being able to obtain sufficient adhesive strength of the molded product of the hydrogenated modified block copolymer [E] tends to occur. The introduction of alkoxysilyl groups can be confirmed by IR spectrum. Also, the introduction amount can be calculated from the ¹ H-NMR spectrum.

[Ethylenically unsaturated silane compound]
The ethylenically unsaturated silane compound used for silane modification is a compound capable of reacting (for example, graft polymerization) with the block copolymer hydride [D] to introduce an alkoxysilyl group into the block copolymer hydride [D]. is not particularly limited. Examples of such ethylenically unsaturated silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, and the like. Among these, vinyltrimethoxysilane and vinyltriethoxysilane are preferred, and vinyltrimethoxysilane is more preferred. One of these may be used alone, or two or more of them may be used in combination at an arbitrary ratio.
The amount of the ethylenically unsaturated silane compound used is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, per 100 parts by mass of the block copolymer hydride [D]. It is particularly preferably 3 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less.

[Peroxide]
Peroxides used for silane modification preferably have a one-minute half-life temperature of 170 to 190° C. Examples include t-butylcumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2 ,5-dimethyl-2,5-di-(t-butylperoxy)hexane, di-t-butylperoxide, di-(2-t-butylperoxyisopropyl)benzene and other organic peroxides. . One of these may be used alone, or two or more of them may be used in combination at an arbitrary ratio.
The amount of peroxide used is preferably 0.05 parts by mass or more, more preferably 0.08 parts by mass or more, and 0.1 parts by mass or more per 100 parts by mass of the copolymer hydride. It is particularly preferably 2 parts by mass or less, more preferably 1 part by mass or less, and particularly preferably 0.5 parts by mass or less.

--molecular weight--
The weight-average molecular weight (Mw) of the hydrogenated modified block copolymer [E] (silane-modified product) obtained by the above-mentioned silane modification is usually less than the amount of alkoxysilyl groups introduced, so the block used as a raw material is It is not much different from that of the copolymer hydride [D], preferably 25,000 or more, more preferably 30,000 or more, particularly preferably 35,000 or more, and 200,000 It is preferably 150,000 or less, more preferably 100,000 or less, particularly preferably 100,000 or less. When the polymerization average molecular weight of the silane modified product is 35,000 or more, the mechanical strength of the silane modified product can be enhanced, and when it is 200,000 or less, the workability of the silane modified product can be ensured.
Also, the molecular weight distribution (Mw/Mn) of the modified silane is preferably 3.5 or less, preferably 3.0 or less, and particularly preferably 2.5 or less. If the molecular weight distribution is 3.5 or less, the workability and mechanical strength of the modified silane obtained from the block copolymer hydride [D] can be enhanced.
In addition, the molecular weight distribution (Mw/Mn) of the silane-modified product is the block copolymer It tends to be larger than that of the hydride [D].

<<Method for producing block copolymer hydride [D]>>
The method for producing the block copolymer hydride [D] is a production method for producing the block copolymer hydride [D], and includes a copolymerization step and a hydrogenation step, and, if necessary, silane modification. Including other steps such as steps.

- Copolymerization step -
The copolymerization step is a step of copolymerizing an aromatic vinyl monomer and a chain conjugated diene monomer using an initiator containing an organic lithium compound.
The method of copolymerization is not particularly limited as long as it is copolymerization using an initiator containing an organolithium compound, and a monomer composition containing an aromatic vinyl monomer and a chain conjugated diene monomer, Copolymers can be prepared by polymerizing by known methods.

--organolithium compounds--
The organolithium compound is generally used for anionic polymerization, and is not particularly limited. Examples include n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium, benzyllithium. mono-organolithium compounds such as; , 1,4-dilithiobenzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, 1,3,5-trilithio - polyfunctional organolithium compounds such as 2,4,6-triethylbenzene; Among these, monoorganolithium compounds such as n-butyllithium and sec-butyllithium are preferred. One of these may be used alone, or two or more of them may be used in combination at an arbitrary ratio.

-Hydrogenation process-
The hydrogenation step is a step of hydrogenating the block copolymer [C] obtained in the copolymerization step.
The method for hydrogenating the unsaturated bonds in the block copolymer [C] (hydrogenation method) is not particularly limited, and known methods can be employed. A hydrogenation method capable of suppressing coalescing chain scission reactions is preferred. Examples of such a hydrogenation method include methods described in International Publication No. 2011/096389, International Publication No. 2012/043708, and the like.

-Silane modification step-
The silane-modifying step is a step of silane-modifying the hydrogenated block copolymer [D] obtained in the hydrogenation step.
The method for silane-modifying the block copolymer hydride [D] is not particularly limited. An alkoxysilyl group can be introduced into the hydrogenated block copolymer [D] by kneading with a screw extruder. The kneading temperature is preferably 230° C. or higher, preferably 240° C. or higher, particularly preferably 250° C. or higher, preferably 300° C. or lower, and more preferably 280° C. or lower. , 270° C. or lower. The kneading time is preferably 0.3 minutes or longer, more preferably 0.5 minutes or longer, particularly preferably 0.8 minutes or longer, preferably 10 minutes or shorter, and 5 minutes. It is more preferably less than or equal to, and particularly preferably about 2 minutes or less. The kneading temperature and the kneading time may be appropriately set so as to be kneaded and extruded continuously.

As the organic peroxide, one having a 1-minute half-life temperature of 170° C. or higher and 190° C. or lower is preferably used. For example, 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 organic peroxides may be used alone or in combination of two or more.
The amount of the organic peroxide used is preferably 0.05 parts by mass or more, more preferably 0.08 parts by mass or more, relative to 100 parts by mass of the block copolymer hydride [D]. It is particularly preferably 0.1 parts by mass or more, preferably 2 parts by mass or less, more preferably 1 part by mass or less, and particularly preferably 0.5 parts by mass or less.

The method for reacting the block copolymer hydride [D] and the ethylenically unsaturated silane compound in the presence of an organic peroxide is not particularly limited. For example, an alkoxysilyl group can be introduced into the block copolymer hydride [D] by kneading at a desired temperature for a desired time in a twin-screw kneader. The kneading temperature by the twin-screw kneader is preferably 230° C. or higher, more preferably 240° C. or higher, particularly preferably 250° C. or higher, preferably 300° C. or lower, and 280° C. or lower. more preferably, and particularly preferably 270° C. or lower. The heat-kneading time is preferably 0.1 minutes or longer, more preferably 0.2 minutes or longer, particularly preferably 0.3 minutes or longer, and preferably 10 minutes or shorter. Minutes or less is more preferable, and 2 minutes or less is particularly preferable.
Specifically, the introduction of the alkoxysilyl group into the block copolymer hydride [D] is carried out by setting the temperature and the residence time within the above ranges, the block copolymer hydride [D], the ethylenically unsaturated The silane compound and the organic peroxide may be continuously kneaded and extruded.

Since the polymer is reacted with an ethylenically unsaturated silane compound in the presence of an organic peroxide, a cross-linking reaction and a cleavage reaction of the polymer occur simultaneously. It becomes larger than the value of molecular weight distribution of copolymer hydride [D].

これらの中でも、所望の光学特性（ヘイズ、透過率）を有するシートを確実に成形することができる点で、構造式（１）で表される２－（５－クロロ－２－ベンゾトリアゾリル）－６－ｔｅｒｔ－ブチル－ｐ－クレゾール等のベンゾトリアゾール系物質が好ましい。 <Ultraviolet absorber>
The ultraviolet absorber is not particularly limited as long as it is a substance that absorbs ultraviolet rays. For example, 2-(5-chloro-2-benzotriazolyl)-6-tert represented by the following structural formula (1) - Benzotriazole-based UV absorbers such as butyl-p-cresol (BASF Japan Ltd., Tinuvin (registered trademark) 326); compounds represented by the following structural formula (2) (e.g., BASF Japan Ltd., Tinuvin ( (registered trademark) 1600); benzophenone-based UV absorbers such as compounds represented by the following structural formula (3) (eg, Chimassorb 81, manufactured by BASF Japan Ltd.); One of these may be used alone, or two or more of them may be used in combination at any ratio.

Among these, 2-(5-chloro-2-benzotriazolyl represented by Structural Formula (1) can be reliably formed into a sheet having desired optical properties (haze, transmittance). )-6-tert-butyl-p-cresol are preferred.

The ultraviolet absorber present in the bleeding portion is preferably a linear substance having a width within a predetermined range.
The width of the ultraviolet absorber present in the bleeding portion is preferably 0.01 μm or more, more preferably 0.50 μm or more, particularly preferably 1.00 μm or more, and 3.00 μm or less. is preferably 2.50 μm or less, and particularly preferably 2.00 μm or less.
When the width of the ultraviolet absorber present in the bleed portion is at least the above lower limit, it is difficult to separate from the surface and can cover the surface, and when it is at most the above upper limit, the surface can be densely covered, It can contribute to bridging resistance.
The width of the ultraviolet absorber present in the bleed portion was measured by a scanning electron microscope (manufactured by JEOL Ltd., "JEM-7800F Prime") with a degree of vacuum of 280 kPa and no pretreatment (non-deposition) molding material. SEM observation of the ultraviolet absorber on the surface (bleed portion) was performed.

The content of the ultraviolet absorber in the molding material is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and particularly preferably 9 parts by mass or more with respect to 100 parts by mass of the soft resin. , is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, and particularly preferably 30 parts by mass or less.
When the content of the ultraviolet absorber in the molding material is at least the above lower limit, the bridge resistance and light resistance can be reliably improved, and when it is at most the above upper limit, kneading can be performed without problems.

<Dusting agent>
Dusting agents include, for example, stearic acid monoamide, stearic acid amide (stearic acid amide) such as stearic acid monoamide, styrene/bisstearic acid amide, ethylene/bisstearic acid amide; magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate , calcium oleate, calcium laurate, 12-hydroxy calcium stearate, calcium montanate, barium stearate, barium oleate, barium laurate, barium arachidate, barium behenate, zinc stearate, zinc oleate, zinc laurate metal soaps such as , lithium stearate, sodium stearate, sodium palmitate, sodium laurate, potassium stearate, potassium laurate; talc; One of these may be used alone, or two or more of them may be used in combination at an arbitrary ratio. Among these, stearic acid amide is preferable from the viewpoint of reducing haze.

The dusting agent is at least partially present in the bleed portion.
The content of the dusting agent in the molding material (the total amount present in the core portion and the bleeding portion) is preferably 0.0040 parts by mass or more, and preferably 0.0100 parts by mass or more, relative to 100 parts by mass of the soft resin. It is more preferably 0.0150 parts by mass or more, more preferably 0.0220 parts by mass or less, and more preferably 0.0185 parts by mass or less. By setting the content to be equal to or higher than the above lower limit, blocking due to adhesion between molding materials can be reliably suppressed. On the other hand, by making the content equal to or less than the above upper limit value, it is possible to prevent the transparency of the molding material from being lowered, and it is possible to reliably mold a sheet having desired optical properties (haze, transmittance). can be done.

The dusting agent preferably has a particle size that allows 85% or more of it to pass through a 200-mesh net, more preferably 90% or more. By making the particle size equal to or larger than the above lower limit, the blocking resistance of the molding material can be exhibited.

<Other ingredients>
Other components include, for example, phosphorus antioxidants, phenolic antioxidants, processing aids, polymers other than block copolymer hydrides, infrared shielding/absorbing agents, colorants, acid anhydrides, inorganic oxidation substances (pulverized silica, fired silica, etc.), and the like. One of these may be used alone, or two or more of them may be used in combination at any ratio.

<<Phosphorus-based antioxidant>>
Phosphorus-based antioxidants are not particularly limited. -di-t-butylphenyl)phosphite, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like. Phosphite compounds, 4,4'-butylidene-bis(3-methyl-6-tbutylphenyl-di-tridecylphosphite) 4,4'-isopropylidene-bis(phenyl-di-alkyl (C12-C15 ) Phosphite) and other diphosphite compounds; 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetrakis-t-butyldibenzo[d , f][1.3.2]dioxaphosphepin, 6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-2,4,8,10-tetrakis- and t-butyldibenzo[d,f][1.3.2]dioxaphosphepin. One of these may be used alone, or two or more of them may be used in combination at an arbitrary ratio.

<<Phenolic antioxidant>>
Phenolic antioxidants are not particularly limited. (3,5-di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis{2-[ 3-(3-t-butyl-4-hydroxy-5-methylphenyl)proonyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 1,3 ,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene and the like. One of these may be used alone, or two or more of them may be used in combination at any ratio.

The total content of the phosphorus antioxidant and the phenolic antioxidant with respect to 100 parts by mass of the soft resin is not particularly limited, but is preferably 0.001 parts by mass or more, and is 0.003 parts by mass or more. is more preferably 0.005 parts by mass or more, particularly preferably 1.0 parts by mass or less, more preferably 0.8 parts by mass or less, and 0.5 parts by mass or less is particularly preferred. If the total content of the phosphorus antioxidant and the phenolic antioxidant with respect to 100 parts by mass of the soft resin is 0.001 parts by mass or more, oxidation can be prevented, and if it is 1.0 parts by mass or less , the bleeding to the resin surface can be suppressed.

<<Processing aid>>
The processing aid is preferably one that can be uniformly dissolved or dispersed in the hydrogenated block copolymer [D], more preferably a hydrocarbon polymer having a number average molecular weight of 300 or more and 5,000 or less.

Specific examples of hydrocarbon polymers include polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, polyisoprene, ethylene/α-olefin copolymers, polyisoprene-butadiene copolymers, and the like. low molecular weight compounds and hydrides thereof; and the like. One of these may be used alone, or two or more of them may be used in combination at an arbitrary ratio.
Among these, low molecular weight (number average molecular weight is preferably 500 or more and 3,000 or less, more preferably 500 or more and 2,500 or less) in terms of maintaining transparency and light resistance and being excellent in softening effect. Polyisobutylene hydrides and low-molecular-weight polybutene hydrides (having a number average molecular weight of preferably 500 or more and 3,000 or less, more preferably 500 or more and 2,500 or less) are preferred.

The content of the low molecular weight hydrocarbon polymer relative to 100 parts by mass of the soft resin is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less. . If the content of the low-molecular-weight hydrocarbon-based polymer is increased, the heat resistance of the interlayer film for laminated glass tends to be lowered and the elution tends to increase.

<Method for manufacturing molding material>
A molding material is manufactured as follows.
First, pellets of the soft resin (raw material pellets A) are obtained by pelletizing the prepared soft resin. Next, raw material pellets B are obtained by adding additives such as modifiers and dusting agents to the raw material pellets A, if necessary. A UV absorber is added to a part of the obtained raw material pellets B, and then pelletized (by making a masterbatch) to obtain a molding material (masterbatch pellet C) containing a high concentration of the UV absorber. manufacture.

<Sheet molding method using molding material>
The obtained molding material (masterbatch pellet C) is blended with the raw material pellet B and formed into a sheet to form a resin sheet [F]. Here, the blending ratio of the masterbatch pellets C and the raw material pellets B is 0.005 parts by mass or more and 0.010 parts by mass of the ultraviolet absorber with respect to 100 parts by mass of the total soft resin contained in the masterbatch pellets C and the raw material pellets B. It is preferable to set the compounding ratio so as to be equal to or less than the mass.

The molding material of the present invention includes an intermediate film for laminated glass (the laminated glass may contain a heat ray reflective film, a transparent conductive film, a light control film, a highly elastic resin layer, etc.), a sealing material (solar power generation elements, OLEDs, etc.), optical films (retardation films, polarizing plate protective films, etc.), medical moldings (vials, syringes, infusion bags, culture container adhesives, etc.), adhesive sheets, adhesives, etc. be done.

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. In the following description, "%" and "parts" representing amounts are based on mass unless otherwise specified. Measurements and evaluations in the examples were carried out by the following methods.

<(1) Weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn)>
It was measured at a rate of 0.6 cc/min at 40° C. as a standard polystyrene conversion value by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent. As the measurement device, "HLC8320GPC" manufactured by Tosoh Corporation is used, and three columns of "TSKgel SuperH" type "G5000HLX", "G4000HLX", and "G2000HLX" manufactured by Tosoh Corporation are connected in series, and the polymer The concentration was adjusted to 4 mg/1 cc and measured.

<(2) Ratio of wA and wB (wA:wB)>
The content (mass fraction) wA of aromatic vinyl compound monomer units in block copolymer [C] and the content (mass fraction) of linear conjugated diene compound monomer units in block copolymer [B] Regarding the “ratio of wA and wB (wA:wB)” when the mass fraction) is wB, the aromatic The number of parts of vinyl compounds, acyclic conjugated diene compounds and other vinyl compounds, and the polymerization conversion rate of the monomers used in the final stage of each polymer block polymerization to polymer as measured using gas chromatography (GC). The content (mass fraction) of the aromatic vinyl compound monomer unit and the content (mass fraction) of the chain conjugated diene compound monomer unit were calculated.

<(3) Hydrogenation rate>
The block copolymer [C] used in the hydrogenation reaction of Production Example and the hydrogenated block copolymer [D] obtained by the hydrogenation reaction were subjected to ¹ H-NMR measurement using deuterated chloroform as a solvent. Hydrogenation of block copolymer hydride [D] is performed by calculating the proportion of unsaturated bonds that have disappeared among all unsaturated bonds present in the main chain, side chains and aromatic rings of block copolymer [C]. asked for a rate.

<(4) Amount of dusting agent>
An FT-IR apparatus ("FT/IR-4600" manufactured by JASCO Corporation) was used to analyze the surface of the obtained molding material by FI-IR reflection type analysis. A calibration curve was prepared from the peak intensity ratio derived from the dusting agent and the polymer, and the amount of the dusting agent before bleeding of the molding material was calculated. Regarding the measurement, "preparation of alkoxysilane modified product (modified block copolymer hydride [E])" and "molding material (masterbatch pellet C) or preparation of raw material pellet B used in Comparative Example 3 described later , and the content of the dusting agent in the molding material (the total amount present in the core portion and the bleed portion) was measured.

<(5) Blocking property during storage of molding material (masterbatch pellet C) or raw material pellet B used in Comparative Example 3 described later>
A rectangular parallelepiped container of 1.5 m ³ (bottom area 0.36 m ² ) is filled with the molding material (masterbatch pellet C) or the raw material pellet B used in Comparative Example 3 described later and left to stand for 10 minutes. was opened to evaluate the presence or absence of fluidity of the molding material.
"OK" indicates that there is fluidity (that is, masterbatch pellet C or blocking resistance of raw material pellet B used in Comparative Example 3 described later), and "NG" indicates fluidity (that is, masterbatch pellet C or It indicates that there is no blocking resistance of the raw material pellet B used in Comparative Example 3, which will be described later.

<(6) Sheet haze (%)>
Using the molding material (masterbatch pellet C) and raw material pellet B (raw material pellet B and ultraviolet absorber in Comparative Example 3), under the same conditions as <Production of resin sheet [F1]> described in Example 1, the thickness A sheet molded sample having a thickness of 500 μm and a length and width of 50 mm was produced, and the haze of the produced sheet molded sample was measured using a haze meter (“NDH2000” manufactured by Nippon Denshoku Industries Co., Ltd.). The haze of the sheet should be 1.0% or less.

<(7) Sheet transmittance (410 nm) (%)>
Using the molding material (masterbatch pellet C) and raw material pellet B (raw material pellet B and ultraviolet absorber in Comparative Example 3), under the same conditions as <Production of resin sheet [F1]> described in Example 1, the thickness A sheet-molded sample having a thickness of 500 μm and a length and width of 50 mm was prepared, and the transmittance at 410 nm was measured using an ultraviolet-visible-near-infrared spectrophotometer (JASCO Corporation “V-670”) for the sheet-molded sample thus prepared. did. Note that the transmittance of the sheet must be 80% or less.

<(8) Maximum Shrinkage of Sheet (%)>
Using the molding material (masterbatch pellet C) and raw material pellet B (raw material pellet B and ultraviolet absorber in Comparative Example 3), under the same conditions as <Production of resin sheet [F1]> described in Example 1, the thickness A sheet molded sample having a thickness of 500 μm and a length and width of 100 mm was prepared and treated in an oven at 110° C. for 3 minutes. After that, the maximum shrinkage rate of the sheet molded sample was calculated by the following formula (1). The maximum shrinkage of the sheet should be 4.0% or less.
"Maximum shrinkage rate (%)" = (length of sheet-molded sample before treatment - length of sheet-molded sample after treatment) / length of sheet-molded sample before treatment x 100 (1)

<(9) Width of UV absorber>
Using a scanning electron microscope (manufactured by JEOL Ltd., "JEM-7800F Prime"), the degree of vacuum is 280 kPa, and the UV absorber on the surface (bleed part) of the molding material without pretreatment (non-deposition) is observed by SEM. did. The width of the ultraviolet absorber was measured at a magnification of 2000 times. In addition, about a measurement, it implemented using the molding material after one week after manufacture.
"OK" indicates that the width of the ultraviolet absorbent in the bleed portion is 3.00 μm or less, and "NG" indicates that the width of the ultraviolet absorbent exceeds 3.00 μm.
The width of the ultraviolet absorber is defined as the length (diameter) of the shorter side of the string.

<(10) Presence or absence of masterbatch>
Regarding "presence or absence of master batch" in the table, "presence" means that pellets kneaded with an ultraviolet absorber are used regardless of whether or not they correspond to the molding material of the present invention.

(Example 1)
Block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E]), and molding material (masterbatch pellet C) were prepared by the method shown below. A resin sheet [F1] was prepared by the method shown below. After that, block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E]), molding material (masterbatch pellet C), and resin sheet [ F1], each measurement and each evaluation were performed.

<Preparation of block copolymer [C]>
550 parts of dehydrated cyclohexane, 25.0 parts of dehydrated styrene, and 0.820 parts of n-butyl ether are added to a sufficiently nitrogen-substituted reactor equipped with a stirrer, and n-butyllithium (15 % n-hexane solution) was added to initiate polymerization. A polymerization reaction was carried out at 65° C. for 60 minutes. The polymer addition rate at this point was 99.9% as determined by gas chromatography. Next, 50.0 parts of dehydrated isoprene was added, and stirring was continued for 40 minutes. The polymerization addition rate at this point was 99.6%. After that, 25.0 parts of dehydrated styrene was further added and reacted for 60 minutes. The polymerization addition rate at this point was almost 100%. Here, 2.0 parts of methanol was added to stop the reaction.
The obtained block copolymer [C] has a weight average molecular weight (Mw) of 42900, a molecular weight distribution (Mw/Mn) of 1.03, and is represented by SIS (styrene block-isoprene block-styrene block) was a triblock copolymer.

<Preparation of block copolymer hydride [D]>
The block copolymer [C] solution obtained in the above "preparation of block copolymer [C]" is transferred to a pressure-resistant reaction vessel equipped with a stirrer, and silica-alumina-supported nickel as a hydrogenation catalyst is transferred. 5 parts of a catalyst (“T-8400RL” manufactured by Clariant Catalyst Co., Ltd.) and 100 parts of dehydrated cyclohexane were added and mixed. The inside of the reactor was replaced with hydrogen gas at room temperature, and the temperature was raised to 180° C. while the gauge pressure was 2 MPa. When the internal temperature of the pressure-resistant reactor reached 180°C, the temperature was kept constant at 180°C without supplying hydrogen for 20 minutes. After 20 minutes, the hydrogen pressure was increased to 4.5 MPa and hydrogenation reaction was carried out for 6 hours (hydrogenation rate: 99.5%). The GPC elution curve of the hydrogenated copolymer after the hydrogenation reaction showed a molecular weight distribution (Mw/Mn) of 1.66 and a weight average molecular weight (Mw) of 37,800.
After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and then pentaerythritol tetrakis[3-(3,5-di-t-butyl- 2.0 parts of a xylene solution containing 0.1 part of 4-hydroxyphenyl)propionate] ("AO60" manufactured by ADEKA) was added and dissolved.
Next, the above solution is treated with a cylindrical concentrator dryer (“Control” manufactured by Hitachi, Ltd.) at a temperature of 260 ° C. and a pressure of 0.001 MPa or less to remove cyclohexane, xylene and other volatile components from the solution. to obtain a molten polymer. The resulting molten polymer was cut into round pellets by an underwater cutter to obtain raw material pellets A of hydride of block copolymer [C] (hydride of block copolymer [D]).

<Preparation of modified alkoxysilane (hydrogenated modified block copolymer [E])>
2.0 parts of vinyltrimethoxysilane and 2,5-dimethyl-2,5-di(t-butylperoxy) are added to 100 parts of raw material pellets A of the obtained hydrogenated block copolymer [D]. 0.1 part of hexane ("Perhexa (registered trademark) 25B" manufactured by NOF Corporation) was added. This mixture is kneaded using a twin-screw extruder ("TEM37B" manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 250 ° C. and a kneading time of 60 to 70 seconds to obtain an alkoxysilane modified block copolymer hydride (X ), 17 parts of hydrogenated polybutene (manufactured by NOF Corporation, trade name: NOF Polybutene 10SH) is added, melt extrusion is performed with a single screw or single tube, and the resulting kneaded product is cut with an underwater cutter. Form round pellets, remove water on the surface by centrifugal dehydration, and use as a dusting agent (antiblocking agent) ethylene bisstearic amide (ethylene bisstearic amide) (manufactured by Kao Corporation, trade name: Kaowax) EB-FF) is added in an amount of 0.0116 parts per 100 parts of a soft resin containing no dusting agent (“block copolymer hydride alkoxysilane modified product (X)” to obtain a block copolymer hydride. A raw material pellet B of the alkoxysilane modified product of [D] (modified block copolymer hydride [E]) was obtained.

<Preparation of molding material (masterbatch pellet C)>
The "block copolymer "Tinuvin (registered trademark) as an ultraviolet absorber so that "Tinuvin (registered trademark) 326" as an ultraviolet absorber is 11.755 parts with respect to 100 parts of hydride alkoxysilane modified product (X)" ) 326” was added to the modified block copolymer hydride [E]. This mixture was kneaded using a twin-screw extruder (“TEM37B” manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 200° C. for a kneading time of 60 to 70 seconds. The resulting kneaded product is made into round pellets by an underwater cutter, the water on the surface is separated by centrifugal dehydration, and ethylene / bis stearamide (ethylene / bis stearamide) ( Kao Corporation, trade name: Kaowax EB-FF) is added to 100 parts of a soft resin that does not contain a dusting agent (“alkoxysilane-modified hydrogenated block copolymer (X)”) at 0.0066 was added to obtain a molding material (masterbatch pellet C).
In addition, as shown in Table 1A, the molding material (masterbatch pellet C) is a soft resin not containing a dusting agent (“alkoxysilane modified product of block copolymer hydride (X)”) per 100 parts by mass. 11.755 parts by mass of an ultraviolet absorber and 0.0182 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

<Production of resin sheet [F1]>
The "raw material pellet B of the modified alkoxysilane (modified block copolymer hydride [E])" and the "molding material (masterbatch pellet C)" obtained above are included in the raw material pellet B and the masterbatch pellet C. 0.008 parts by mass of the ultraviolet absorber is blended in advance with respect to 100 parts by mass of the soft resin, and a T-die film melt extruder ("TEM37B" manufactured by Toshiba Machine Co., Ltd.; T die width 400 mm). was used to perform extrusion molding under the conditions of a molten resin temperature of 180° C. and a T-die temperature of 180° C. to obtain a resin sheet [F1] (thickness: 500 μm). The obtained resin sheet [F1] was wound up on a roll and collected.

(Example 2)
In Example 1, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin not containing a dusting agent, as an ultraviolet absorber 11.755 parts of "Tinuvin® 326" and adding 0.0066 parts of a dusting agent (anti-blocking agent) instead of adding 0.0066 parts of a dusting agent-free soft resin "block copolymerization 7.053 parts of "Tinuvin (registered trademark) 326" as an ultraviolet absorber was added to 100 parts of alkoxysilane modified product (X) of coalescing hydride, and 0.00 of a dusting agent (antiblocking agent) was added. Block copolymer [C], hydrogenated block copolymer [D], modified alkoxysilane (hydrogenated block copolymer [E] ), and a molding material (masterbatch pellet C) are prepared, a resin sheet [F1] is produced, a block copolymer [C], a block copolymer hydride [D], an alkoxysilane modified product (modified block copolymer Each measurement and each evaluation were performed for the hydrogenated polymer [E]), the molding material (masterbatch pellet C), and the resin sheet [F1].
In addition, as shown in Table 1A, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) that does not contain a dusting agent. On the other hand, it contains 7.053 parts by mass of an ultraviolet absorber and 0.0136 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Example 3)
In Example 1, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin not containing a dusting agent, as an ultraviolet absorber 11.755 parts of "Tinuvin® 326" and adding 0.0066 parts of a dusting agent (anti-blocking agent) instead of adding 0.0066 parts of a dusting agent-free soft resin "block copolymerization 7.053 parts of "Tinuvin (registered trademark) 326" as an ultraviolet absorber was added to 100 parts of alkoxysilane modified product (X) of coalescing hydride, and 0.00 of a dusting agent (antiblocking agent) was added. Block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E] ), and a molding material (masterbatch pellet C) are prepared, a resin sheet [F1] is produced, a block copolymer [C], a block copolymer hydride [D], an alkoxysilane modified product (modified block copolymer Each measurement and each evaluation were performed for the hydrogenated polymer [E]), the molding material (masterbatch pellet C), and the resin sheet [F1].
In addition, as shown in Table 1A, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) that does not contain a dusting agent. On the other hand, it contains 7.053 parts by mass of an ultraviolet absorber and 0.0178 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Example 4)
In Example 1, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin not containing a dusting agent, as an ultraviolet absorber 11.755 parts of "Tinuvin® 326" and adding 0.0066 parts of a dusting agent (anti-blocking agent) instead of adding 0.0066 parts of a dusting agent-free soft resin "block copolymerization 35.264 parts of "Tinuvin (registered trademark) 326" as an ultraviolet absorber was added to 100 parts of the alkoxysilane modified product (X) of coalescing hydride, and 0.264 parts of a dusting agent (antiblocking agent) was added. Block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E] ), and a molding material (masterbatch pellet C) are prepared, a resin sheet [F1] is produced, a block copolymer [C], a block copolymer hydride [D], an alkoxysilane modified product (modified block copolymer Each measurement and each evaluation were performed for the hydrogenated polymer [E]), the molding material (masterbatch pellet C), and the resin sheet [F1].
In addition, as shown in Table 1A, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) that does not contain a dusting agent. On the other hand, it contains 35.264 parts by mass of an ultraviolet absorber and contains 0.0139 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Example 5)
In Example 1, in "Preparation of molding material", instead of using benzotriazole-based "Tinuvin (registered trademark) 326" as an ultraviolet absorber, triazine-based "Tinuvin (registered trademark) 326" was used as an ultraviolet absorber. Block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E] ), and a molding material (masterbatch pellet C) are prepared, a resin sheet [F1] is produced, a block copolymer [C], a block copolymer hydride [D], an alkoxysilane modified product (modified block copolymer Each measurement and each evaluation were performed for the hydrogenated polymer [E]), the molding material (masterbatch pellet C), and the resin sheet [F1].
In addition, as shown in Table 1A, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) that does not contain a dusting agent. On the other hand, it contains 11.755 parts by mass of an ultraviolet absorber and contains 0.0182 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Example 6)
In Example 5, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin not containing a dusting agent, as an ultraviolet absorber 11.755 parts of "Tinuvin® 1600" and adding 0.0066 parts of a dusting agent (anti-blocking agent) instead of adding 0.0066 parts of a dusting agent-free soft resin "block copolymerization 7.053 parts of "Tinuvin (registered trademark) 1600" as an ultraviolet absorber was added to 100 parts of the alkoxysilane modified product (X) of coalescing hydride, and 0.00 of a dusting agent (antiblocking agent) was added. Block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E] ), and a molding material (masterbatch pellet C) are prepared, a resin sheet [F1] is produced, a block copolymer [C], a block copolymer hydride [D], an alkoxysilane modified product (modified block copolymer Each measurement and each evaluation were performed for the hydrogenated polymer [E]), the molding material (masterbatch pellet C), and the resin sheet [F1].
In addition, as shown in Table 1A, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) that does not contain a dusting agent. On the other hand, it contains 7.053 parts by mass of an ultraviolet absorber and 0.0178 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Example 7)
In Example 5, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin not containing a dusting agent, as an ultraviolet absorber 11.755 parts of "Tinuvin® 1600" and adding 0.0066 parts of a dusting agent (anti-blocking agent) instead of adding 0.0066 parts of a dusting agent-free soft resin "block copolymerization 35.264 parts of "Tinuvin (registered trademark) 1600" as an ultraviolet absorber was added to 100 parts of the alkoxysilane modified product (X) of coalescing hydride, and 0.00 of a dusting agent (antiblocking agent) was added. Block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E] ), and a molding material (masterbatch pellet C) are prepared, a resin sheet [F1] is produced, a block copolymer [C], a block copolymer hydride [D], an alkoxysilane modified product (modified block copolymer Each measurement and each evaluation were performed for the hydrogenated polymer [E]), the molding material (masterbatch pellet C), and the resin sheet [F1].
In addition, as shown in Table 1A, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) that does not contain a dusting agent. On the other hand, it contains 35.264 parts by mass of an ultraviolet absorber and contains 0.0139 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Example 8)
In Example 1, in "Preparation of molding material", instead of using benzotriazole-based "Tinuvin (registered trademark) 326" as an ultraviolet absorber, benzophenone-based "Chimassorb 81" was used as an ultraviolet absorber. Block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E]), and molding material were prepared in the same manner as in Example 1 except that (Master batch pellet C) is prepared, resin sheet [F1] is produced, block copolymer [C], block copolymer hydride [D], alkoxysilane modified (modified block copolymer hydride [ E]), the molding material (masterbatch pellet C), and the resin sheet [F1] were measured and evaluated.
In addition, as shown in Table 1A, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) that does not contain a dusting agent. On the other hand, it contains 11.755 parts by mass of an ultraviolet absorber and contains 0.0182 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Example 9)
In Example 8, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin that does not contain a dusting agent, as an ultraviolet absorber "Chimassorb 81" 11.755 parts of "Chimassorb 81" of "block copolymer hydride alkoxy With respect to 100 parts of modified silane (X), 7.053 parts of "Chimassorb 81" as an ultraviolet absorber were added, and 0.0064 parts of a dusting agent (antiblocking agent) was added. In the same manner as in Example 8, block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E]), and molding material (masterbatch pellet C ) to prepare a resin sheet [F1], block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E]), molding Each measurement and each evaluation were performed for the material (masterbatch pellet C) and the resin sheet [F1].
In addition, as shown in Table 1A, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) that does not contain a dusting agent. On the other hand, it contains 7.053 parts by mass of an ultraviolet absorber and 0.0180 part of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Example 10)
In Example 8, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin that does not contain a dusting agent, as an ultraviolet absorber "Chimassorb 81" 11.755 parts of "Chimassorb 81" of "block copolymer hydride alkoxy 35.264 parts of "Chimassorb 81" as an ultraviolet absorber was added to 100 parts of modified silane (X), and 0.0023 parts of a dusting agent (antiblocking agent) was added. In the same manner as in Example 8, block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E]), and molding material (masterbatch pellet C ) to prepare a resin sheet [F1], block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E]), molding Each measurement and each evaluation were performed for the material (masterbatch pellet C) and the resin sheet [F1].
As shown in Table 1A, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) containing no dusting agent. On the other hand, it contains 35.264 parts by mass of an ultraviolet absorber and contains 0.0139 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Comparative example 1)
In Example 1, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin not containing a dusting agent, as an ultraviolet absorber 11.755 parts of "Tinuvin® 326" and adding 0.0066 parts of a dusting agent (anti-blocking agent) instead of adding 0.0066 parts of a dusting agent-free soft resin "block copolymerization 3.526 parts of "Tinuvin (registered trademark) 326" as an ultraviolet absorber was added to 100 parts of alkoxysilane modified product (X) of coalescing hydride, and 0.00 of a dusting agent (antiblocking agent) was added. Block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E] ), and a molding material (masterbatch pellet C) are prepared, a resin sheet [F1] is produced, a block copolymer [C], a block copolymer hydride [D], an alkoxysilane modified product (modified block copolymer Each measurement and each evaluation were performed for the hydrogenated polymer [E]), the molding material (masterbatch pellet C), and the resin sheet [F1].
As shown in Table 1B, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) containing no dusting agent. On the other hand, it contains 3.526 parts by mass of an ultraviolet absorber and contains 0.0135 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Comparative example 2)
In Example 1, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin not containing a dusting agent, as an ultraviolet absorber 11.755 parts of "Tinuvin® 326" and adding 0.0066 parts of a dusting agent (anti-blocking agent) instead of adding 0.0066 parts of a dusting agent-free soft resin "block copolymerization 41.142 parts of "Tinuvin (registered trademark) 326" as an ultraviolet absorber was added to 100 parts of the alkoxysilane modified product (X) of coalescing hydride, and 0.00 of a dusting agent (antiblocking agent) was added. Block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E] ), and a molding material (masterbatch pellet C) are prepared, a resin sheet [F1] is produced, a block copolymer [C], a block copolymer hydride [D], an alkoxysilane modified product (modified block copolymer Each measurement and each evaluation were performed for the hydrogenated polymer [E]), the molding material (masterbatch pellet C), and the resin sheet [F1].
As shown in Table 1B, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) containing no dusting agent. On the other hand, it contains 41.142 parts by weight of an ultraviolet absorber and 0.0195 parts by weight of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Comparative Example 3)
In Example 1, in (i) "Preparation of molding material", ultraviolet rays Add 11.755 parts of "Tinuvin (registered trademark) 326" as an absorbent and add 0.0066 parts of a dusting agent (antiblocking agent) to obtain a molding material (masterbatch pellet C). (The "raw material pellet B" obtained in Example 1 was used as it was as "the pellet used for sheet molding"), and (ii) instead of "manufacturing the resin sheet [F1]", the following "resin sheet [F2 ] Production” was performed in the same manner as in Example 1 to produce block copolymer [C], hydrogenated block copolymer [D], and modified alkoxysilane (hydrogenated modified block copolymer [E]), block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E]), and resin sheet [F2] Each measurement and each evaluation were performed.
In addition, as shown in Table 1B, the raw material pellet B was dusted with respect to 100 parts by mass of a soft resin (“alkoxysilane modified product of hydrogenated block copolymer (X)”) containing no dusting agent. agent (antiblocking agent) 0.0116 parts. Further, it was confirmed by SEM observation that the dusting agent was present in the surface layer of the raw material pellet B. Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the surface layer portion was an ultraviolet absorber.
<Production of resin sheet [F2]>
The "raw material pellet B" obtained in Example 1 was melted at a resin temperature of 160 using a T-die film melt extruder ("TEM37B" manufactured by Toshiba Machine Co., Ltd.; T die width 400 mm) equipped with a side feeder. °C and a T-die temperature of 160°C. Further, from a side feeder, Tinuvin (registered trademark) 326 as an ultraviolet absorber was added to 100 parts of the "alkoxysilane-modified block copolymer hydride (X)" as a soft resin containing no dusting agent. The resin sheet [F2] (thickness: 500 µm) was obtained by continuously adding and kneading so as to obtain 0.009 parts by mass. The obtained resin sheet [F2] was wound up on a roll and collected.

(Comparative Example 4)
In Example 1, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin not containing a dusting agent, as an ultraviolet absorber 11.755 parts of "Tinuvin® 326" and adding 0.0066 parts of a dusting agent (anti-blocking agent) instead of adding 0.0066 parts of a dusting agent-free soft resin "block copolymerization 2.351 parts of "Tinuvin (registered trademark) 326" as an ultraviolet absorber was added to 100 parts of alkoxysilane modified product (X) of coalescing hydride, and 0.00 of a dusting agent (antiblocking agent) was added. Block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E] ), and a molding material (masterbatch pellet C) are prepared, a resin sheet [F1] is produced, a block copolymer [C], a block copolymer hydride [D], an alkoxysilane modified product (modified block copolymer Each measurement and each evaluation were performed for the hydrogenated polymer [E]), the molding material (masterbatch pellet C), and the resin sheet [F1].
As shown in Table 1B, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) containing no dusting agent. On the other hand, it contains 2.351 parts by mass of an ultraviolet absorber and contains 0.0225 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Comparative Example 5)
In Example 5, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin not containing a dusting agent, as an ultraviolet absorber 11.755 parts of "Tinuvin® 1600" and adding 0.0066 parts of a dusting agent (anti-blocking agent) instead of adding 0.0066 parts of a dusting agent-free soft resin "block copolymerization 41.142 parts of "Tinuvin (registered trademark) 1600" as an ultraviolet absorber was added to 100 parts of the alkoxysilane modified product (X) of the combined hydride, and 0.00 of a dusting agent (antiblocking agent) was added. Block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E] ), and a molding material (masterbatch pellet C) are prepared, a resin sheet [F1] is produced, a block copolymer [C], a block copolymer hydride [D], an alkoxysilane modified product (modified block copolymer Each measurement and each evaluation were performed for the hydrogenated polymer [E]), the molding material (masterbatch pellet C), and the resin sheet [F1].
As shown in Table 1B, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) containing no dusting agent. On the other hand, it contains 41.142 parts by mass of an ultraviolet absorber and 0.0195 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Comparative Example 6)
In Example 5, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin not containing a dusting agent, as an ultraviolet absorber 11.755 parts of "Tinuvin® 1600" and adding 0.0066 parts of a dusting agent (anti-blocking agent) instead of adding 0.0066 parts of a dusting agent-free soft resin "block copolymerization 3.526 parts of "Tinuvin (registered trademark) 1600" as an ultraviolet absorber was added to 100 parts of the alkoxysilane modified product (X) of coalescing hydride, and 0.00 of a dusting agent (antiblocking agent) was added. Block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E] ), and a molding material (masterbatch pellet C) are prepared, a resin sheet [F1] is produced, a block copolymer [C], a block copolymer hydride [D], an alkoxysilane modified product (modified block copolymer Each measurement and each evaluation were performed for the hydrogenated polymer [E]), the molding material (masterbatch pellet C), and the resin sheet [F1].
As shown in Table 1B, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) containing no dusting agent. On the other hand, it contains 3.526 parts by mass of an ultraviolet absorber and contains 0.0135 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Comparative Example 7)
In Example 5, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin not containing a dusting agent, as an ultraviolet absorber 11.755 parts of "Tinuvin® 1600" and adding 0.0066 parts of a dusting agent (anti-blocking agent) instead of adding 0.0066 parts of a dusting agent-free soft resin "block copolymerization 2.351 parts of "Tinuvin (registered trademark) 1600" as an ultraviolet absorber was added to 100 parts of the alkoxysilane modified product (X) of the combined hydride, and 0.00 of a dusting agent (antiblocking agent) was added. Block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E] ), and a molding material (masterbatch pellet C) are prepared, a resin sheet [F1] is produced, a block copolymer [C], a block copolymer hydride [D], an alkoxysilane modified product (modified block copolymer Each measurement and each evaluation were performed for the hydrogenated polymer [E]), the molding material (masterbatch pellet C), and the resin sheet [F1].
In addition, as shown in Table 1B, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) containing no dusting agent. On the other hand, it contains 2.351 parts by mass of an ultraviolet absorber and contains 0.0225 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Comparative Example 8)
In Example 8, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin that does not contain a dusting agent, as an ultraviolet absorber "Chimassorb 81" 11.755 parts of "Chimassorb 81" of "block copolymer hydride alkoxy With respect to 100 parts of modified silane (X), 41.142 parts of "Chimassorb 81" as an ultraviolet absorber were added, and 0.0079 parts of a dusting agent (antiblocking agent) was added. In the same manner as in Example 8, block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E]), and molding material (masterbatch pellet C ) to prepare a resin sheet [F1], block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E]), molding Each measurement and each evaluation were performed for the material (masterbatch pellet C) and the resin sheet [F1].
As shown in Table 1B, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) containing no dusting agent. On the other hand, it contains 41.142 parts by weight of an ultraviolet absorber and 0.0195 parts by weight of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Comparative Example 9)
In Example 8, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin that does not contain a dusting agent, as an ultraviolet absorber "Chimassorb 81" 11.755 parts of "Chimassorb 81" of "block copolymer hydride alkoxy With respect to 100 parts of modified silane (X), 3.526 parts of "Chimassorb 81" as an ultraviolet absorber were added, and 0.0019 parts of a dusting agent (antiblocking agent) was added. In the same manner as in Example 8, block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E]), and molding material (masterbatch pellet C ) to prepare a resin sheet [F1], block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E]), molding Each measurement and each evaluation were performed for the material (masterbatch pellet C) and the resin sheet [F1].
As shown in Table 1B, the molding material (masterbatch pellet C) contains 100 parts by mass of a soft resin (“alkoxysilane-modified block copolymer hydride (X)”) containing no dusting agent. On the other hand, it contains 3.526 parts by mass of an ultraviolet absorber and contains 0.0135 parts of a dusting agent (antiblocking agent). Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

(Comparative Example 10)
In Example 8, in "Preparation of molding material", 100 parts of "block copolymer hydride alkoxysilane modified product (X)" as a soft resin that does not contain a dusting agent, as an ultraviolet absorber "Chimassorb 81" 11.755 parts of "Chimassorb 81" of "block copolymer hydride alkoxy With respect to 100 parts of modified silane (X), 2.351 parts of "Chimassorb 81" as an ultraviolet absorber were added, and 0.0109 parts of a dusting agent (antiblocking agent) was added. In the same manner as in Example 8, block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E]), and molding material (masterbatch pellet C ) to prepare a resin sheet [F1], block copolymer [C], block copolymer hydride [D], alkoxysilane modified product (modified block copolymer hydride [E]), molding Each measurement and each evaluation were performed for the material (masterbatch pellet C) and the resin sheet [F1].
As shown in Table 1B, the molding material (masterbatch pellet C) contained 2.351 parts by mass of an ultraviolet absorber and 0.2 parts by mass of a dusting agent (antiblocking agent) with respect to 100 parts by mass of the soft resin. 0225 parts. Further, it was confirmed by SEM observation that the dusting agent was present in the bleeding portion of the molding material (masterbatch pellet C). Further, it was confirmed by an infrared microscope Spotlight 200i manufactured by PerkinElmer that the main component of the core portion was a soft resin and the main component of the bleed portion was an ultraviolet absorber.

From Tables 1A and 1B, when the molding materials of Examples 1 to 10 are used, (i) the content of the ultraviolet absorber is more than 5 parts by mass and 40 parts by mass or less with respect to 100 parts by mass of the soft resin, and (ii) Since at least a part of the dusting agent is present in the bleeding portion that covers the core portion containing a soft resin as a main component and contains an ultraviolet absorber as a main component, blocking due to adhesion between molding materials can be suppressed, and a sheet having desired optical properties (haze, transmittance) and shrinkage can be molded.

According to the molding material of the present invention, it is possible to suppress blocking due to adhesion between molding materials, and to mold a sheet having desired optical properties (haze, transmittance) and shrinkage.

Claims (7)

A molding material containing a soft resin, an ultraviolet absorber, and a dusting agent,
A molding material comprising a core portion containing the soft resin as a main component and a bleed portion covering the core portion and containing the ultraviolet absorber as a main component,
The content of the ultraviolet absorber is more than 5 parts by mass and 40 parts by mass or less with respect to 100 parts by mass of the soft resin,
The content of the dusting agent is 0.0220 parts by mass or less with respect to 100 parts by mass of the soft resin,
A molding material, wherein at least part of the dusting agent is present in the bleeding portion. 2. The molding material according to claim 1, wherein the content of said dusting agent is 0.0040 parts by mass or more with respect to 100 parts by mass of said soft resin. The molding material according to claim 1 or 2, wherein the soft resin is mainly composed of hydrogenated block copolymer. The hydrogenated block copolymer comprises at least two polymer blocks [A] mainly composed of aromatic vinyl monomer units and at least one polymer mainly composed of linear conjugated diene monomer units. The mass fraction of all the aromatic vinyl monomer units in the block copolymer [C] consisting of the block [B] and the block copolymer [C] is defined as wA, and the block copolymer [C ], where wB is the mass fraction of all linear conjugated diene monomer units in the block copolymer [C], the ratio of wA to wB (wA:wB) is from 10:90 to 4. The molding material according to claim 3, which is obtained by hydrogenating the carbon-carbon unsaturated bonds in the main chain and side chains of the block copolymer [C] with a ratio of 70:30. 5. The molding material according to claim 3, wherein at least a portion of said block copolymer hydride is silane-modified. 6. The molding material according to any one of claims 1 to 5, wherein the ultraviolet absorber present in said bleeding portion is a linear material having a width of 0.01 µm or more and 3.00 µm or less. 7. The molding material according to any one of claims 1 to 6, wherein a coverage of said bleed portion of said core portion is 90% or more.

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