KR102156564B1 - Composition and molded body - Google Patents

Abstract

Molding capable of producing a molded article with excellent properties (low hardness, good visibility, heat resistance, good molded appearance, etc.), while improving productivity by suppressing blocking in the pellet drying process or hopper Provides a composition excellent in processability. The composition according to the present invention is a composition containing a thermoplastic resin (A) having an iodine value of 2 to 150 and water, and contains 100 to 2000 ppm of the water based on 100 parts by mass of the composition, The thermoplastic resin (A) has a repeating unit derived from the conjugated diene compound, the thermoplastic resin (A) has a crystal melting peak temperature of 50° C. to 95° C., and the crystal melting heat amount is 10 J/g to 40 J. It is characterized by /g.

Description

Composition and molded body

The present invention relates to a composition and a molded article made using the composition.

Conventionally, in order to protect the lens surface of a prism sheet used in a liquid crystal display, a surface protection film is used. Since this surface protective film is for protecting the lens surface of the prism sheet from scratches and contamination in the manufacturing process, it peels off when the manufacturing process is completed, and does not remain in the final product. Therefore, in the surface protection film, (1) hardness is low; The contact area with the adherend can be sufficiently secured, (2) good visibility; Easy to perform work process or visual inspection, (3) having heat resistance; The shape is stable even at high temperatures, no foreign matter is generated, and (4) the molded appearance is good.

As such a surface protection film, it is known that, for example, a molded article made of an ethylene-vinyl acetate copolymer (EVA) or a conjugated diene polymer is formed on one side of a substrate layer made of a thermoplastic resin such as an olefin resin. have.

As a manufacturing method of an adhesive film such as a surface protection film, a method of manufacturing by applying an adhesive to a base layer (for example, see Patent Document 1), and collectively forming the base layer and the molded body by coextrusion method. A method (see, for example, Patent Document 2 and Patent Document 3), etc. are mentioned. In particular, the method of manufacturing a molded article by coextrusion has recently attracted attention because it is simple and can reduce manufacturing cost.

Japanese Unexamined Patent Publication No. 2003-238927 Japanese Unexamined Patent Publication No. 2003-041216 Japanese Laid-Open Patent Publication No. 2010-255007

However, even in the case of manufacturing a molded article by any of the manufacturing methods, blocking is likely to occur in a hopper, etc., during the process of manufacturing pellets of the raw material composition or when the pellets are introduced into the manufacturing apparatus, and productivity decreases. There was a problem.

In addition, the properties of the molded body (low hardness, good visibility, heat resistance, good molding appearance, etc.) and molding processability (solution storage stability, solvent resistance, etc.) are required with the recent rapid development of technology. ) Level is also increasing, so further improvement is required.

Therefore, several aspects according to the present invention provide a composition having excellent molding processability capable of producing a molded article having excellent properties while improving productivity by suppressing blocking in a hopper or the like by solving at least some of the above problems. do.

The present invention has been made to solve at least some of the above-described problems, and can be realized as the following aspects or application examples.

[Application Example 1]

One aspect of the composition according to the present invention,

As a composition containing a thermoplastic resin (A) having an iodine number of 2 to 150 and water,

Contains 100 to 2000 ppm of the water with respect to 100 parts by mass of the composition,

The thermoplastic resin (A) has a repeating unit derived from a conjugated diene compound,

The thermoplastic resin (A) has a crystal melting peak temperature of 50°C to 95°C, and a crystal melting heat amount of 10 J/g to 40 J/g.

[Application Example 2]

In the composition of the application example,

In addition, it contains an anti-blocking agent (B),

When the content of the thermoplastic resin (A) is Ma (parts by mass) and the content of the antiblocking agent (B) is Mb (parts by mass), Ma/Mb may be 200 to 4000.

[Application Example 3]

In the composition of the application example,

It may further include at least one selected from the group consisting of polyethylene wax, polypropylene wax, fatty acid amide, fatty acid ester and fatty acid metal salt.

[Application Example 4]

In the composition of the application example,

The thermoplastic resin (A),

0.3 to 10% by mass in a molecular weight range of 2×10 ⁴ or more and less than 8×10 ⁴ and,

It may have a distribution present in a molecular weight range of 8×10 ⁴ or more and 1×10 ⁶ or less in a range of 90 to 99.1 mass%.

[Application Example 5]

In the composition of the application example,

The thermoplastic resin (A) may further have a repeating unit derived from an aromatic vinyl compound.

[Application Example 6]

The composition of the application example can be used in a coextrusion method.

[Application Example 7]

One aspect of the molded article according to the present invention,

It is characterized in that it is prepared using the composition of the above application example.

According to the composition according to the present invention, blocking in a hopper, etc. can be suppressed when the pellet is produced by molding the composition or the pellet is put into a production apparatus for producing a molded article, and as a result, the productivity of the molded article is improved. . Further, according to the composition according to the present invention, it is possible to produce a molded article having low hardness, excellent visibility, heat resistance, and excellent molded article properties such as good molded appearance, and also good molding processability.

(Form for carrying out the invention)

Hereinafter, preferred embodiments according to the present invention will be described in detail. In addition, it should be understood that the present invention is not limited only to the embodiments described below, but also includes various modifications implemented within a range that does not change the gist of the present invention. In addition, "(meth)acryl-" in this specification is a concept encompassing both "acrylic-" and "methacryl-". In addition, "-(meth)acrylate" is a concept encompassing both "-acrylate" and "-methacrylate".

1. Composition

The composition according to the present embodiment is a composition containing a thermoplastic resin (A) having an iodine value of 2 to 150 (hereinafter, also simply referred to as "component (A)") and water, based on 100 parts by mass of the composition. 100 to 2000 ppm of the water, the thermoplastic resin (A) has a repeating unit derived from the conjugated diene compound, the crystal melting peak temperature of the thermoplastic resin (A) is 50 to 95°C, and , Crystal melting heat is characterized in that 10J/g to 40J/g.

Hereinafter, each component contained in the composition according to the present embodiment will be described in detail.

1.1. Thermoplastic resin (A)

The thermoplastic resin (A) contained in the composition according to the present embodiment has an iodine value of 2 to 150, contains a repeating unit derived from a conjugated diene compound, and has a crystal melting peak temperature of 50°C to 95°C, and , It is a thermoplastic resin having a crystal fusion heat of 10 J/g to 40 J/g, and is used to produce a molded article.

The component (A) has a repeating unit derived from the conjugated diene compound, but may further have a repeating unit derived from an aromatic vinyl compound as necessary. Hereinafter, the repeating unit constituting the component (A) and the structure and properties of the component (A) will be described in order.

1.1.1. Repeating unit derived from conjugated diene compound

Component (A) has a repeating unit derived from a conjugated diene compound. Examples of the conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, and the like. , It may be one or more selected from these. As the conjugated diene compound, 1,3-butadiene is particularly preferable.

In the component (A), the content ratio of the repeating unit derived from the conjugated diene compound is preferably 30 to 100 parts by mass, and 35 to 100 parts by mass when the total repeating units of the component (A) are 100 parts by mass. More preferable. When the content ratio of the repeating unit derived from the conjugated diene compound is within the above range, it becomes easy to produce a molded article excellent in viscoelasticity and strength.

1.1.2. Repeating units derived from aromatic vinyl compounds

Component (A) may further have a repeating unit derived from an aromatic vinyl compound. As an aromatic vinyl compound, for example, styrene, tert-butyl styrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1,1-diphenylstyrene, vinylnaphthalene, vinylanthracene, N, N-diethyl-p-aminoethyl styrene, vinylpyridine, etc. are mentioned. Among these, styrene is particularly preferred.

In the component (A), the content ratio of the repeating unit derived from the aromatic vinyl compound is preferably 0 to 70 parts by mass, and 0 to 60 parts by mass when all repeating units of the component (A) are 100 parts by mass. More preferable.

1.1.3. Other repeat units

Component (A) may have repeating units other than the above. Examples of the repeating unit other than the above include a repeating unit derived from an unsaturated carboxylic acid ester, a repeating unit derived from an unsaturated carboxylic acid, and a repeating unit derived from an α,β-unsaturated nitrile compound.

As said unsaturated carboxylic acid ester, it is preferable that it is a (meth)acrylic acid ester. As specific examples of such (meth)acrylic acid ester, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, ( Meth) acrylate i-butyl, (meth) acrylate n-amyl, (meth) acrylate i-amyl, (meth) acrylate hexyl, (meth) acrylate cyclohexyl, (meth) acrylate 2-ethylhexyl, (meth) acrylate n -Octyl, (meth) acrylate nonyl, (meth) acrylate decyl, (meth) acrylate hydroxymethyl, (meth) acrylate hydroxyethyl, (meth) acrylate ethylene glycol, di(meth) acrylate ethylene glycol, di(meth) Propylene glycol acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, aryl (meth)acrylate, and the like, and one selected from these It can be more than that. Among these, it is preferable that it is one or more types selected from methyl (meth)acrylate, ethyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, and it is especially preferable that it is methyl (meth)acrylate.

Specific examples of the unsaturated carboxylic acid include mono or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, and at least one selected from them. In particular, it is preferably at least one selected from acrylic acid, methacrylic acid and itaconic acid.

Specific examples of the α,β-unsaturated nitrile compound include, for example, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, vinylidene cyanide, and the like, selected from these It may be one or more. Among these, it is preferable that it is one or more types selected from acrylonitrile and methacrylonitrile, and it is especially preferable that it is acrylonitrile.

In addition, component (A) may further have a repeating unit derived from the compound shown below. Examples of such compounds include fluorine-containing compounds having ethylenically unsaturated bonds such as vinylidene fluoride, ethylene tetrafluoride, and propylene hexafluoride; Alkylamides of ethylenically unsaturated carboxylic acids such as (meth)acrylamide and N-methylolacrylamide; Vinyl carboxylic acid esters such as vinyl acetate and vinyl propionate; Acid anhydrides of ethylenically unsaturated dicarboxylic acids; Monoalkyl ester; Monoamide; And aminoalkylamides of ethylenically unsaturated carboxylic acids such as aminoethylacrylamide, dimethylaminomethylmethacrylamide, and methylaminopropylmethacrylamide, and the like, and may be at least one selected from these.

1.1.4. Structure, properties and synthesis method of thermoplastic resin (A)

The thermoplastic resin (A) in the present embodiment is not particularly limited, but a block copolymer consisting of a block consisting of repeating units derived from an aromatic vinyl compound and a repeating unit mainly derived from a conjugated diene compound, or a conjugated diene A hydrogenated product of a block copolymer having a block of repeating units derived from a compound and a low vinyl bond amount and a block of repeating units derived from a conjugated diene compound and a high vinyl bond amount is preferably used. Specifically, a block copolymer of a conjugated diene compound such as butadiene or isoprene, a block copolymer of styrene and a conjugated diene compound such as butadiene or isoprene, or a hydrogenated product thereof is preferable, and a butadiene-butadiene-butadiene block from the viewpoint of durability A hydrogenated product of a copolymer, a styrene-butadiene-butadiene block copolymer, and a styrene-butadiene-styrene block copolymer is more preferable. These thermoplastic resins (A) can be synthesized by a method described in Japanese Patent Publication No. 33303467, Japanese Patent Publication No.3282364, Japanese Patent Publication No. 2010-255007 or International Publication No. 2007/126081.

The content of the repeating unit derived from the aromatic vinyl compound in such a styrene-conjugated diene block copolymer is usually 5 to 40% by mass, and preferably in the range of 10 to 35% by mass. If the content of the repeating unit derived from the aromatic vinyl compound is within the above range, the adhesive strength can be further increased, and there is a tendency that a glue residue does not occur due to cohesive failure.

The iodine value of the component (A) needs to be 2 to 150, preferably 2 to 100, and more preferably 2 to 70. When the iodine value of the component (A) is within the above range, it is difficult to block and provide a composition having good heat resistance, flexibility, and transparency. In addition, since the iodine value is a value expressed by converting the amount of halogen reacting with 100 g of the target substance to the number of grams of iodine, the unit of the iodine value is "g/100 g". In this specification, for example, "the iodine value is 2 to 150" means the effect that "the iodine value is 2 to 150 g/100 g".

When the iodine number is not in the above range, the blocking property tends to deteriorate. This is thought to be because the shape retention of the thermoplastic resin decreases due to influences such as lowering the woven density of the main chain due to the large amount of unsaturated bonds in the main chain, or lowering the crystallinity due to the division of the ethylene chain into unsaturated bonds. . In addition, when the iodine value is not in the above range, it is confirmed that the heat resistance is also deteriorated, and thus it may not be able to withstand a processing process at a high temperature such as coextrusion. This is considered to be the effect of the reaction of the unsaturated bond contained in the thermoplastic resin at high temperature.

In addition, when the iodine value is not in the above range, a tendency for hardness to increase or Haze value to deteriorate is observed. In addition, the iodine value of the thermoplastic resin (A) in this invention can be measured according to the method described in "JIS K 0070:1992".

In manufacturing a molded article, when extrusion molding the composition using a melt extrusion device or the like, the melt flow rate (MFR) of the component (A) contained in the composition, measured at 230° C. and 21.2 N load, is 0.1 It is preferably -100 g/10 minutes, more preferably 1.0 to 50 g/10 minutes, particularly preferably 2.0 to 30 g/10 minutes. If the MFR is less than 0.1 g/10 minutes, the load at the time of extrusion molding may become excessive. On the other hand, when the MFR exceeds 100 g/10 minutes, there is a tendency to cause problems in extrusion moldability such as drawdown.

The mass average molecular weight (Mw) of the component (A) is preferably 1×10 ^{5 to} 1×10 ⁶ , and more preferably 2×10 ^{5 to} 5×10 ⁵ . When the mass average molecular weight (Mw) of the component (A) is in the above range, it is easy to obtain a molded article excellent in molding processability. In addition, the "mass average molecular weight" here refers to the mass average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

Further, it is preferable that the molecular weight distribution of the component (A) satisfies the following requirements [1] and [2].

[1] In a molecular weight range of 2×10 ⁴ or more and less than 8×10 ⁴ , the component (A) should be present in an amount of 0.3 to 10% by mass, preferably 0.5 to 4.5% by mass.

[2] In a molecular weight range of 8×10 ⁴ or more and 1×10 ⁶ or less, the component (A) should be present in a range of 90 to 99.1 mass%, preferably 95 to 99.5 mass%.

When the abundance ratio of the component (A) in the requirements of the above [1] and [2] is within the above range, elution of the composition when contacted with a solvent can be effectively suppressed, and the viscosity of the composition can be reduced. Accordingly, there is a tendency to obtain a composition excellent in the balance of the physical properties of the solvent resistance and processability.

Component (A) has at least one melting peak (crystal melting peak) in the range of 50 to 95°C. This melting peak temperature is measured by differential scanning calorimetry (DSC method). Specifically, using a differential scanning calorimeter (DSC), after preserving the component (A) as a sample at 200°C for 10 minutes, cooling to -80°C at a rate of 10°C/min, then -80°C It is the peak temperature of the heat flow rate (crystal fusion heat quantity) when the temperature was raised at a rate of 10°C/min after storage and maintenance at 10 minutes. In addition, the amount of heat of crystal melting at the melting peak is 10 to 40 J/g, preferably 15 to 35 J/g.

The content rate of the component (A) in the composition according to the present embodiment, when the total mass of the composition is 100% by mass, preferably 50 to 100% by mass, more preferably 55 to 100% by mass, particularly preferably Is 60 to 100% by mass.

1.2. Anti-blocking agent (B)

The composition according to the present embodiment may contain an antiblocking agent (B) (hereinafter, also simply referred to as "component (B)"). The composition according to the present embodiment may contain at least one selected from the group consisting of polyethylene wax, polypropylene wax, fatty acid amide, fatty acid ester, and fatty acid metal salt. When the composition contains such a compound, blocking (clogging) in a hopper or the like can be suppressed, and the productivity of the molded article can be further improved.

Examples of the anti-blocking agent (B) include synthetic hydrocarbon-based waxes such as fluoropolymers, polyethylene waxes, polypropylene waxes, ethylene-propylene copolymer waxes, Fischer-Tropsch waxes and partial oxides thereof or copolymers with ethylenically unsaturated carboxylic acids; Modified waxes such as montan wax derivatives, paraffin wax derivatives, and microcrystalline wax derivatives; Hydrogenated waxes such as hydrogenated castor oil and hydrogenated castor oil derivatives; Higher fatty acids and alcohols such as cetyl alcohol, stearic acid, and 12-hydroxystearic acid; Fatty acid esters such as glyceryl stearate, polyethylene glycol stearate, stearyl stearate, and isopropyl palmitate; Fatty acid amides such as stearic acid amide; Fatty acid metal salts such as calcium stearate and lithium stearate; Phthalic anhydride imide; And chlorinated hydrocarbons.

Among these, it is preferably at least one selected from the group consisting of polyethylene wax, polypropylene wax, fatty acid amide, fatty acid ester, and fatty acid metal salt. When these components are added to the composition according to the present embodiment, blocking in a hopper or the like can be more effectively suppressed in a pellet manufacturing process or a manufacturing apparatus for manufacturing a molded article.

The content ratio of the component (B) in the pressure-sensitive adhesive composition according to the present embodiment is preferably 0.02 parts by mass or more and 0.5 parts by mass or less, and 0.03 parts by mass or more and 0.4 parts by mass with respect to the total 100 parts by mass of the component (A). It is more preferable that it is the following. When the content of the thermoplastic resin (A) in the composition according to the present embodiment is Ma (parts by mass) and the content of the blocking agent (B) is Mb (parts by mass), the thermoplastic resin (A) and the blocking agent It is preferable that it is 200-4000, and, as for the quantity ratio (Ma/Mb) of (B), it is more preferable that it is 250-3500.

1.3. water

The composition according to the present embodiment contains 100 to 2000 ppm of water based on 100 parts by mass of the composition, but it is preferably 130 to 1000 ppm, and more preferably 150 to 600 ppm. When the moisture content is within the above range, when the composition is molded, it is excellent in molding processability, and a molded article having a good appearance can be produced. If the moisture content exceeds the above range, there is a possibility that moisture is heated in the cylinder of the injection molding machine to form bubbles in the thermoplastic elastomer, and rupture on the surface of the molded article, resulting in deterioration of Haze or poor appearance (silver streak).

In addition, in the present invention, "the moisture content of the composition" means the same as the moisture content of the pellets of the composition. The moisture content of the composition in the present invention is a value measured in accordance with JIS K7251 "Plastic-How to Determine the Moisture Content".

The moisture content of the composition can be controlled by subjecting the composition to a pellet dryer such as a dehumidifying dryer, a vacuum dryer, or a hot air dryer, and heating the composition at a temperature and time suitable for the thermoplastic elastomer to be used. If the drying temperature is high and the drying time is long, the moisture content can be drastically reduced, but there is a possibility that the pellets of the composition may cause blocking or deterioration such as bleed out. Further, when the drying temperature is low and the drying time is short, the moisture content tends to increase. Either way, the moisture content can be controlled by controlling the drying temperature and the drying time in this way.

1.4. Other ingredients

To the composition according to the present embodiment, in addition to the above components, if necessary, known components such as a radical generator, an anti-aging agent, a filler, a colorant, a flame retardant, and a tackifier may be added.

The radical generator can control the hardness and heat resistance of the molded article by generating a radical by irradiating radiation such as heating or ultraviolet rays, and crosslinking the component (A) to adjust the degree of crosslinking when producing a molded article. As the radical generator, a photo radical generator that generates radicals by irradiating light such as ultraviolet rays is preferable. Specific examples of the photo radical generator include hydroxy ketones, benzyl dimethyl ketals, amino ketones, acyl phosphine oxides, benzophenones, and the like. These photo-radical generators can be used alone or in combination of two or more.

As the radical generator, it is particularly preferable that it is an oligomer type photo radical generator. The oligomeric type photo-radical generator is a low molecular weight polymer of a monomer having a functional group capable of generating radicals by irradiation with light such as ultraviolet rays. Since these oligomer-type photo-radical generators have a plurality of radical generation points in a molecule, they are less susceptible to crosslinking inhibition by oxygen, and can be crosslinked in a small amount. It is preferably used in that it does not scatter even in a hot melt state and is not extracted from the polymer.

As a specific example of an oligomer-type photo radical generator, an oligomer obtained by polymerization of acrylated benzophenone (manufactured by UCB, brand name "EbecrylP36"), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy- Oligomer, 2-hydroxy-2-methyl, obtained by polymerizing the reaction product of 2-methyl-1-propan-1-one (manufactured by BASF, brand name “Irgacure2959”) with a primary hydroxyl group and 2-isocyanatoethyl methacrylate -[4-(1-methylvinyl)phenyl]propanol oligomer (manufactured by Lamberti, brand name "EsacureKIP150"), and the like. It is preferable that the molecular weight of these oligomer type photo-radical generators is up to about 50000.

As the anti-aging agent, for example, an antioxidant such as hindered phenol-based or phosphite-based, ultraviolet absorber such as benzotriazole-based, benzophenone-based and salicylic acid ester-based, and a light stabilizer such as hindered amine-based are suitably added.

As the filler, inorganic fillers such as talc, silica, and calcium carbonate, and organic fillers such as carbon fibers and amide fibers can be used.

2. Molded body

The molded article according to the present embodiment is produced using the above-described composition by a known method. For example, when the molded article is an adhesive film, it becomes a film provided with a base layer and an adhesive layer formed on one or both sides of the base layer. Hereinafter, a method for producing a substrate layer, a composition for a substrate, and an adhesive film will be described.

<Base layer and composition for substrate>

It is preferable that the composition for a substrate for producing a substrate layer contains a thermoplastic resin. Among thermoplastic resins, olefin resins are preferred.

As the olefin-based resin, for example, a polyethylene, polypropylene, or polybutene-based copolymer can be suitably used. Specifically, propylene-ethylene copolymer, propylene-butene-1 copolymer, butene-1-ethylene copolymer, propylene-ethylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer , An ethylene-ethyl methacrylate copolymer, an ethylene-methyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, and an ethylene-n-butyl acrylate copolymer. These thermoplastic resins can be used alone or in combination of two or more.

The substrate composition contains a thermoplastic resin as a main component, but for the purpose of preventing deterioration, for example, an antioxidant, an ultraviolet absorber, a light stabilizer such as a hindered amine light stabilizer, an antistatic agent, etc., for example, Fillers such as calcium oxide, magnesium oxide, silica, zinc oxide, and titanium oxide, pigments, anti-glare agents, lubricants, anti-blocking agents, and the like can be appropriately added.

The MFR of the thermoplastic resin contained in the substrate composition, measured at 230° C. and a load of 21.2 N, is preferably 0.01 to 100 g/10 minutes, and more preferably 0.1 to 80 g/10 minutes. In addition, the thermoplastic resin contained in the base material composition may be composed of only one type of thermoplastic resin, or may be formed by mixing two or more types of thermoplastic resins. The base layer may be a single layer, or may be a multilayer of two or more layers. In addition, it is also possible to select a foam layer as the base layer.

<Production method of adhesive film>

The adhesive film according to the present embodiment is a film having a so-called laminated structure comprising a substrate layer and an adhesive layer formed on one or both sides of the substrate layer. Therefore, the adhesive film according to the present embodiment includes: (1) a coating method; A method of forming a pressure-sensitive adhesive layer by applying a composition for an adhesive to one or both sides of a previously prepared substrate layer, and then winding up, (2) coextrusion; The substrate composition and the pressure-sensitive adhesive composition can be produced by a method such as a method of forming an adhesive layer on one or both sides of the substrate layer by coextrusion molding using a melt coextrusion device or the like. In addition, as the composition for an adhesive, the composition according to the present embodiment described above can be used.

In the case of manufacturing an adhesive film by a coating method, apply the above adhesive composition to one or both sides of a substrate layer having a thickness of about 2 to 150 μm, and if necessary, energy such as ultraviolet (UV) or electron beam (EB). It can be produced by irradiating a line and crosslinking to form an adhesive layer having a thickness of 5 to 200 µm. Moreover, it can also be set as the pressure-sensitive adhesive film for transfer by subjecting one side of the substrate layer to a release treatment. When applying the pressure-sensitive adhesive composition as a base layer, it can be applied in a state where the viscosity is lowered by heating if necessary. Specifically, hot melt coater, comma roll, gravure coater, roll coater, kiss coater, slot die coater , A squeeze coater, etc. can be used.

When manufacturing a pressure-sensitive adhesive film by collectively molding the base material composition and the pressure-sensitive adhesive composition by coextrusion, if necessary, crosslinking treatment by irradiating energy rays such as ultraviolet (UV) or electron beam (EB), and a thickness of 5 to 200 It can be manufactured by forming an adhesive layer which becomes µm.

The ultraviolet irradiation can be performed using an appropriate ultraviolet source such as a high-pressure mercury lamp, a low-pressure mercury lamp, an excimer laser, and a metal halide lamp. The irradiation amount of ultraviolet rays is determined according to the degree of crosslinking required, but is preferably 10 mJ/cm 2 to 5000 mJ/cm 2, more preferably 100 mJ/cm 2 to 5000 mJ/cm 2. Further, if necessary, a filter or a polyester sheet that cuts ultraviolet rays on the short wavelength side can also be used. In addition, the temperature at the time of ultraviolet irradiation is not particularly limited, and heating conditions from room temperature to 140°C can be appropriately selected.

As a source of electron beams, for example, a method using hot electrons generated from a commercially available tungsten filament, a cold cathode method generated through a high voltage pulse to a metal, and a collision between an ionized gaseous molecule and a metal electrode. The secondary electron method using secondary electrons generated by this is mentioned. The electron dose is determined according to the required degree of crosslinking, but is preferably 10 to 1000 kGy, more preferably 100 to 500 kGy.

In the case of irradiation with energy rays in the above-described method for producing an adhesive film, electron beam (EB) irradiation is more suitable than ultraviolet (UV) irradiation in that crosslinking of the adhesive layer is likely to proceed. The adhesive layer irradiated with an electron beam is advantageous in that it can make the generation|occurrence|production of a gel component in a very small amount and can suppress the generation|occurrence|production of a foreign matter originating from a gel component. On the other hand, in the case of ultraviolet irradiation, the radical generator may decompose at the extrusion temperature, and there are manufacturing problems, such as the need to manufacture in a light-shielding environment.

According to the above-described method for producing an adhesive film, an adhesive layer having improved adhesive properties and heat resistance can be produced by irradiating energy rays such as ultraviolet (UV) or electron beam (EB) with the adhesive layer formed of the adhesive composition. In that case, after energy ray crosslinking, it is good to make the solvent-soluble content of the block copolymer 5 to 60 mass%, preferably 10 to 50 mass%. In order to make such a solvent-soluble component, the degree of crosslinking may be appropriately adjusted, such as selecting the amount of the radical generator used or the amount of energy ray irradiation.

In addition, when a sulfur, sulfur-based vulcanizing agent or vulcanization accelerator, which is generally used for crosslinking rubber, is used instead of a radical generator, a large amount of sulfide ions or sulfate ions are generated, which may bleed out from the adhesive layer. Not desirable. Further, with crosslinking using peroxide, it may become difficult to obtain sufficient heat resistance.

In addition, the adhesive film manufactured in this way can be used in a shape such as a tape shape or a sheet shape, if necessary.

3. Examples

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. "Parts" and "%" in Examples and Comparative Examples are based on mass unless otherwise noted.

3.1. Preparation of thermoplastic resin

3.1.1. Synthesis Example 1

To a nitrogen-substituted reaction vessel, 800 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 parts of tetrahydrofuran were put, and 0.09 parts of n-butyllithium was added at a polymerization initiation temperature of 70° C., followed by temperature-raising polymerization. . After the polymerization conversion ratio reached 99% or more, the reaction solution was cooled to 25°C to prepare a polymer before hydrogenation. Subsequently, 80 parts of 1,3-butadiene and 5 parts of tetrahydrofuran were added, and further temperature-raising polymerization was performed. After the polymerization conversion ratio reached 99% or more, 0.06 part of dichloromethylsilane was added, and temperature-raising polymerization was further performed. Then, 0.04 parts of diethylaluminum chloride and 0.06 parts of bis(cyclopentadienyl)titanium furfuryloxychloride were added and stirred into the reaction vessel. Thermoplastic resin A-1 by starting the hydrogenation reaction at a hydrogen gas supply pressure of 0.7 MPa-Gauge and a reaction temperature of 80°C, and taking the reaction solution to 60°C and atmospheric pressure after 3 hours, and extracting it from the reaction vessel. Got it.

3.1.2. Synthesis Example 2

To a nitrogen-substituted reaction vessel, 800 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 parts of tetrahydrofuran were put, and 0.09 parts of n-butyllithium was added at a polymerization initiation temperature of 70° C., followed by temperature-raising polymerization. . After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 45°C, 80 parts of 1,3-butadiene and 1 part of tetrahydrofuran were added, and further temperature-raising polymerization was performed. After the polymerization conversion ratio reached 99% or more, 0.06 part of dichloromethylsilane was added, and temperature-raising polymerization was further performed. Then, 0.04 parts of diethylaluminum chloride and 0.06 parts of bis(cyclopentadienyl)titanium furfuryloxychloride were added and stirred into the reaction vessel. After that, hydrogenation reaction was performed in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-2.

3.1.3. Synthesis Example 3

Thermoplastic resin A-3 was obtained in the same manner as in Synthesis Example 1 except that the hydrogenation reaction time was set to 2 hours.

3.1.4. Synthesis Examples 4, 5, 6

Thermoplastic resins A-4, A-5, and A-6 were obtained in the same manner as in Synthesis Example 2, except that the hydrogenation reaction time was changed to 2 hours, 1 hour, and 40 minutes, respectively.

3.1.5. Synthesis Example 7

To a nitrogen-substituted reaction vessel, 600 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 parts of tetrahydrofuran were put, and 0.10 parts of n-butyllithium was added at a polymerization initiation temperature of 70° C., followed by temperature-raising polymerization. . After the polymerization conversion ratio reached 99% or more, the reaction solution was cooled to 10°C, and then 80 parts of 1,3-butadiene and 15 parts of tetrahydrofuran were added, and further temperature-raising polymerization was performed. After the polymerization conversion ratio reached 99% or more, 0.06 part of tetrachlorosilane was added, and temperature-raising polymerization was further performed. Then, 0.03 parts of diethylaluminum chloride and 0.06 parts of bis(cyclopentadienyl)titanium furfuryloxychloride were added and stirred into the reaction vessel. Thereafter, a hydrogenation reaction was performed for 1 hour in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-7.

3.1.6. Synthesis Example 8

To a nitrogen-substituted reaction vessel, 600 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 parts of tetrahydrofuran were put, and 0.06 parts of n-butyllithium was added at a polymerization initiation temperature of 70° C., followed by temperature-raising polymerization. . After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 10° C., and then 0.05 parts of n-butyllithium, 80 parts of 1,3-butadiene, and 15 parts of tetrahydrofuran were added, followed by further heating-up polymerization. Did. After the polymerization conversion ratio reached 99% or more, 0.06 part of tetrachlorosilane was added, and temperature-raising polymerization was further performed. Then, 0.03 parts of diethylaluminum chloride and 0.06 parts of bis(cyclopentadienyl)titanium furfuryloxychloride were added and stirred into the reaction vessel. After that, hydrogenation reaction was performed in the same manner as in Synthesis Example 1 to obtain thermoplastic resin A-8.

3.1.7. Synthesis Example 9

To a nitrogen-substituted reaction vessel, 600 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 parts of tetrahydrofuran were put, and 0.10 parts of n-butyllithium was added at a polymerization initiation temperature of 70° C., followed by temperature-raising polymerization. . After the polymerization conversion ratio reached 99% or more, the reaction solution was cooled to 10°C, and then 50 parts of 1,3-butadiene, 30 parts of styrene, and 15 parts of tetrahydrofuran were added, and further temperature-raising polymerization was performed. After the polymerization conversion ratio reached 99% or more, 0.06 part of tetrachlorosilane was added, and temperature-raising polymerization was further performed. Then, 0.03 parts of diethylaluminum chloride and 0.06 parts of bis(cyclopentadienyl)titanium furfuryloxychloride were added and stirred into the reaction vessel. After that, hydrogenation reaction was performed in the same manner as in Synthesis Example 1 to obtain thermoplastic resin A-9.

3.1.8. Synthesis Example 10

To a nitrogen-substituted reaction vessel, 800 parts of degassed and dehydrated cyclohexane, 40 parts of 1,3-butadiene, and 0.03 parts of tetrahydrofuran were put, and 0.09 parts of n-butyllithium was added at a polymerization initiation temperature of 70° C., followed by temperature-raising polymerization. . After the polymerization conversion ratio reached 99% or more, the reaction solution was cooled to 10°C, 60 parts of 1,3-butadiene and 15 parts of tetrahydrofuran were added, and further temperature-raising polymerization was performed. After the polymerization conversion ratio reached 99% or more, 0.06 part of dichloromethylsilane was added, and temperature-raising polymerization was further performed. Then, 0.04 parts of diethylaluminum chloride and 0.06 parts of bis(cyclopentadienyl)titanium furfuryloxychloride were added and stirred into the reaction vessel. Thereafter, hydrogenation reaction was performed in the same manner as in Synthesis Example 1 to obtain thermoplastic resin A-10.

3.1.9. Synthesis Example 11

To a nitrogen-substituted reaction vessel, 500 parts of degassed and dehydrated cyclohexane, 6 parts of styrene, and 13 parts of tetrahydrofuran were put, and 0.10 part of n-butyllithium was added at a polymerization initiation temperature of 40° C., followed by temperature-raising polymerization. After the polymerization conversion ratio reached 99% or more, the reaction solution was cooled to 10°C, then 94 parts of 1,3-butadiene were added, and further temperature-raising polymerization was performed. After the polymerization conversion ratio reached 99% or more, 0.07 part of dichlorodimethylsilane was added, and temperature-raising polymerization was further performed. Then, 0.03 parts of diethylaluminum chloride and 0.06 parts of bis(cyclopentadienyl)titanium furfuryloxychloride were added and stirred into the reaction vessel. Thereafter, a hydrogenation reaction was performed in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-11.

3.1.10. Synthesis Example 12

To a nitrogen-substituted reaction vessel, 800 parts of degassed and dehydrated cyclohexane, 15 parts of 1,3-butadiene, and 0.03 parts of tetrahydrofuran were put, and 0.09 parts of n-butyllithium was added at a polymerization initiation temperature of 70° C., followed by temperature-raising polymerization. . After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 15°C, 70 parts of 1,3-butadiene and 15 parts of tetrahydrofuran were added, and further temperature-raising polymerization was performed. After the polymerization conversion ratio reached 99% or more, 15 parts of styrene were added, and temperature-raising polymerization was further performed. Then, 0.04 parts of diethylaluminum chloride and 0.06 parts of bis(cyclopentadienyl)titanium furfuryloxychloride were added and stirred into the reaction vessel. After that, hydrogenation reaction was performed in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-12.

3.1.11. Synthesis Example 13

Thermoplastic resin A-13 was obtained in the same manner as in Synthesis Example 11 except that the hydrogenation reaction time was set to 15 minutes.

3.1.12. Synthesis Example 14

Thermoplastic resin A-14 was obtained in the same manner as in Synthesis Example 10 except that the hydrogenation reaction time was set to 12 hours.

3.2. Evaluation of thermoplastic resin

The total bonded styrene content, vinyl bond content, iodine value, crystal melting peak temperature, crystal melting calorific value, and molecular weight of the produced thermoplastic resin were measured by the following method. The results are shown in Tables 1 and 2.

3.2.1. Evaluation of total bound styrene content

The polymer before hydrogenation was dissolved in carbon tetrachloride, and the total bound styrene content was calculated from a 270 MHz, ¹ H-NMR spectrum. The results are shown in Tables 1 and 2.

3.2.2. Evaluation of vinyl bond (1,2 bond and 3,4 bond) content

Vinyl bonds (1,2 bonds and 3,4 bonds) were calculated for the polymer before hydrogenation by the Hampton method using an infrared analysis method. The results are shown in Tables 1 and 2.

3.2.3. Evaluation of iodine number

The iodine number was calculated for the thermoplastic resin according to the method described in "JIS K 0070:1992". The results are shown in Tables 1 and 2.

3.2.4. Evaluation of crystal melting peak temperature/calorie of crystal melting

After storing and maintaining the thermoplastic resin at 200°C for 10 minutes using a differential scanning calorimeter (DSC), it is cooled to -80°C at a rate of 10°C/min, and then stored and maintained at -80°C for 10 minutes. The peak temperature in the heat flow rate (crystal fusion heat amount (J/g)) when the temperature was raised at a rate of °C/min was taken as the crystal melting peak temperature (°C). The results are shown in Tables 1 and 2.

3.2.5. Molecular weight evaluation of thermoplastic resin

GPC analysis of the thermoplastic resin was performed. Specifically, using gel permeation chromatography (GPC, brand name "HLC-8120GPC", manufactured by Tosoh Finechem, column: manufactured by Tosoh Corporation, GMH-XL), in terms of polystyrene, number average molecular weight (Mn), mass average The molecular weight (Mw) and molecular weight distribution (Mn/Mw) were determined. Tetrahydrofuran was used as a solvent.

The entire area of the molecular weight distribution curve was calculated from the chromatogram measured in the molecular weight evaluation of the thermoplastic resin. 2 × 10 ⁴ or more was less than 8 × 10 ⁴ of the peak area S1 in the molecular weight region and a calculating a 8 × 10 ⁴ or more 1 × 10 ⁶ or less the peak area of the molecular weight range of S2. By dividing S1 by the total area, a content ratio having a molecular weight of 2×10 ⁴ or more and less than 8×10 ⁴ was calculated. Further, by dividing S2 by the total area, the content ratio of molecular weight of 8×10 ⁴ or more and 1×10 ⁶ or less was calculated.

3.3. Reference Example 1

After adding 0.05 part of calcium stearate to the produced thermoplastic resin, poured into a 40 mm single screw extruder manufactured by Ikegai, melt-kneaded, extruded into a strand shape, cooled and solidified in water, and then a strand cutter manufactured by Kikenkoki And pelletized to obtain a columnar undried pellet.

100 parts by mass of undried pellets and 0.10 parts by mass of calcium stearate (manufactured by Wako Junyaku Kogyo Co., Ltd.) were added to the SMV-20 super mixer, stirred at a stirring speed of 300 rpm for 5 minutes, and calcium stearate was applied to the surface of the undried pellets. did. Thereafter, it was sieved with a 3.5 mesh made of stainless steel having a graduation spacing of 6.0 mm, and further sifted through a 12 mesh made of stainless steel having a graduation gap of 1.5 mm. A composition in which a size that does not pass through 12 mesh was dried under a drying temperature of 80°C using a dryer (trade name “parallel batch dryer”, manufactured by Satake Chemical Industry Co., Ltd.), and the moisture content was adjusted to 500 ppm. (Pellets) were prepared. In addition, the moisture content of the composition thus produced can be measured in accordance with the moisture vaporization method described in JIS K7251 "Plastic-How to Determine the Moisture Content".

3.3.1. Blocking evaluation of composition (pellet)

Blocking is preferably less because it causes deterioration in workability when recovering from the dryer or an error in inputting the extruder hopper. For this reason, the blocking state of the composition (pellet) was confirmed by the following method, and it evaluated according to the following index. Table 3 shows the results.

-"A": The adhesion of the pellets is not confirmed, and it can be judged to be excellent.

-"B": A few order-shaped pellets are confirmed, but since adhesion between pellets is eliminated by loosening, productivity is inferior, but it can be judged as good because it can be practical.

-"C": The pellets adhere and are integrated, and the integrated pellets cannot be released and cannot be provided for practical use, so it can be judged as defective.

3.3.2. Evaluation of the hardness of the composition (pellet)

When used as a pressure-sensitive adhesive, the molded article and the adherend are pressed under a predetermined pressure, but if the amount of deformation of the molded article is large, the contact area with the adherend can be sufficiently secured, and good adhesion performance can be expected, so that the hardness is preferably low. For this reason, hardness evaluation of a composition (pellet) was performed according to the following method, and it evaluated according to the following index. Table 3 shows the results.

The prepared composition (pellet) and a spacer having a thickness of 2 mm were placed on the mirror plate, and then hot pressed at 190° C. for 30 minutes using a hot press molding machine “AT-37” manufactured by Iwaki Kogyo Co., Ltd. Got it. The prepared sheets were stacked on top of each other to have a thickness of 6 mm, and the value after 15 seconds was read using a Type A durometer described in JIS 6253.

-"AA": The hardness is 50 or less, and since the contact area with the adherend can be greatly improved in bonding with the adherend, it can be judged to be very excellent.

-"A": The hardness is more than 50 and not more than 65, and since the contact area with the adherend can be improved in bonding with the adherend, it can be judged to be excellent.

-"B": The hardness is more than 65 and not more than 75, and the contact area with the adherend is small in bonding with the adherend, but it can be judged as good because it can be practical.

-"C": The hardness is more than 75, the shape change to the adherend cannot be caused, and since it cannot be provided for practical use, it can be judged as a defect.

3.3.3. Haze evaluation of composition (pellet)

It is preferable that the Haze value is low in consideration of the visibility in the processing process of the optical member and the visual inspection. For this reason, it evaluated according to the following index. Table 3 shows the results.

The sheet prepared above was measured using "HAZEMETER HM-150" manufactured by Murakami Shiki Saigi Jutsu Genkyusho in conformity with JIS-K7136 (2000).

-"A": Haze is 15 or less, and it can be judged that visibility is very excellent.

-"B": Haze is more than 15 and 20 or less, and the visibility is inferior, but it can be judged as good because it can be practical.

-"C": Haze is more than 20 and visibility is poor, so it cannot be provided for practical use and can be judged as a defect.

3.3.4. Preparation of molded body (adhesive film) and evaluation of heat resistance and molded appearance

Using polyethylene (manufactured by Mitsubishi Chemical Co., Ltd., brand name ``YF30'') as the base layer, and the composition (pellet) prepared above as the adhesive layer, by a two-layer coextrusion device equipped with a feed block type T-die, The base material layer and the adhesive layer were coextruded under molding conditions at a cylinder temperature of 190°C and a die temperature of 190°C so that the thickness of the base layer was 100 μm and the thickness of the adhesive layer was 10 μm, and an adhesive film was prepared.

On the other hand, the composition (pellet) prepared above was cut, weighed 20.0 mg, immersed in 20 mL of orthodichlorobenzene at 135°C for 1 hour, and filtered to recover the eluted component A. On the other hand, the adhesive film produced above was cut, weighed 20.0 mg, immersed in 20 mL of orthodichlorobenzene at 135°C for 1 hour, and filtered to collect the eluted component B. The GPC measurement of elution components A and B was performed, the presence or absence of a gel component in a film formation process was evaluated as follows, and the heat resistance of a composition (pellet) was evaluated. Table 3 shows the results.

-"A": Almost no change was observed in both the GPC strength ratio and GPC shape of the eluted component A and the eluted component B, and the gel component was very small. Since the amount of foreign matter is very small, it can be judged to be excellent.

-"B": Almost no change was observed in the GPC intensity ratio between the eluted component A and the eluted component B, and although the gel component was a small amount, generation of a multimer was confirmed from the GPC shape. Although the formation of a multimer is confirmed, since the gel component is a trace amount, the amount of foreign matter is small and it can be judged as good because it can be practical.

-"C": The GPC strength of the eluted component B is very small, and because there are very many gel components due to multimerization, it cannot be provided for practical use, so it can be judged as a defect.

It is preferable that the amount of foreign matter generated during the pelletizing or film-forming process causes defects in the film or poor yield. In addition, in the evaluation of GPC, the high-temperature GPC measuring system "PL-GPC220" manufactured by Polymer Laboratory, the column "MIXED-B" manufactured by Polymer Laboratory, and the measurement temperature were 135°C.

Moreover, the surface of the adhesive film produced above was observed with an optical microscope, and it evaluated as follows. Table 3 shows the results.

-"A": On the film surface, abnormalities, such as air bubbles, are not recognized, and it can be judged that it is excellent.

-"B": Although some air bubbles existed on the film surface, since it can be practical, it can be judged as favorable.

-"C": A lot of air bubbles are observed on the film surface, and it cannot be provided for practical use, so it can be judged as a defect.

In consideration of the adhesive performance of the adhesive film and the visibility in the process of using the adhesive film, it is preferable that the surface roughness or turbidity due to air bubbles on the film surface is small.

3.3.5. Solution storage stability

15 g of the composition and 85 g of cyclohexane were added to a separator, and heated to 80°C to dissolve. Thereafter, the cyclohexane solution was collected in a 250 mL poly bottle, cooled to 40°C, and allowed to stand at 40°C for 24 hours. From the appearance of the polymer solution after standing and the solution viscosity, the solution storage stability was judged as follows. In addition, for the measurement of the solution viscosity, the Tokisan Corporation viscometer TVB10M was used, and the measurement temperature was performed at 40°C.

-"A": When the poly bottle was inclined 90 degrees, the polymer solution flowed. The viscosity of the solution was 3,000 mPa·s or less, and the fluidity of the solution was high, and it was judged that the solution storage stability was excellent. Since the solution storage stability is excellent, it is excellent because it is easy to transfer from a pipe or transfer liquid to a container, and a wet process such as casting or coating can be easily performed.

-"B": When the poly bottle was tilted 90 degrees, the polymer solution flowed. Since the viscosity of the solution was more than 3,000 mPa·s, the fluidity of the solution was slightly low, but the solution storage stability was judged to be good. Since the solution storage stability is good, it is good because it can be applied to a wet process.

-"C": When the poly bottle was tilted 90 degrees, the polymer solution did not flow. Since the solution did not flow and the viscosity of the solution could not be measured, it was judged that the solution storage stability was poor.

3.3.6. Solvent resistance

The prepared composition (pellet) and a spacer having a thickness of 2 mm were placed on the mirror plate, and then hot pressed at 190° C. for 30 minutes using a hot press molding machine “AT-37” manufactured by Iwaki Kogyo Co., Ltd. Got it. The produced press sheet was cut out into 10 mm x 30 mm, and immersed in 50 g of oleic acid for 72 hours in an environment at 30°C. The press sheet after immersion was taken out with tweezers, and solvent resistance was judged as follows from the appearance of the press sheet and the amount of dimensional change. In addition, the amount of dimensional change was evaluated as follows.

Dimensional change (%) = ((Sheet area after immersion-Sheet area before immersion)/Sheet area before immersion) × 100

-"A": The amount of dimensional change was 200% or less, and it was judged that it was possible to take out while maintaining the shape of a press sheet using tweezers, and was excellent in solvent resistance. It is excellent as a material for various molded products because it has high resistance to swelling when a solvent adheres to a molded article, a change in physical properties is suppressed, and a shape retention is also excellent.

-"B": The dimensional change amount was more than 200%, and it was judged that it was able to take out while maintaining the shape of a press sheet using tweezers, and the solvent resistance was good. When a solvent adheres to a molded article, a change in physical properties due to swelling occurs, but since the solvent is excellent in storage retention and shape retention, it is suitable as a material for various molded articles.

-"C": When taking out the press sheet using tweezers, the sheet shape collapsed, the amount of dimensional change could not be measured, and it was judged that the solvent resistance was poor. Since the solvent resistance is poor, the shape of the molded article cannot be maintained when the solvent adheres to the molded article, and the change in physical properties is large, and thus it is defective as a material for various molded articles.

3.4. Reference Examples 2 to 6, Examples 3 to 8, Comparative Examples 1 to 8

A composition (pellet) was prepared in the same manner as in Reference Example 1 except that thermoplastic resins A-2 to A-14 were used, and the type and amount of the anti-blocking agent (B) and the moisture content were changed to the components and amounts in Tables 3 to 4. It produced and evaluated in the same manner as in Reference Example 1. The results are shown in Tables 3-4.

In addition, the moisture content was adjusted by changing the drying time of the composition (pellet) appropriately.

3.5. result

According to Reference Examples 1 to 6 and Examples 3 to 8, the compositions according to the present invention are excellent in productivity and workability in pellet production, high adhesion to an adherend, and gel resistance during extrusion film molding. It was able to manufacture an extruded product which was excellent in quantity and appearance, and was excellent in visibility at the time of using a film.

According to Comparative Examples 1 to 8, when the moisture content is large, appearance defects occur during extrusion film molding, when the moisture content is low, blocking occurs during pellet drying, and when the iodine value of the thermoplastic resin is high, the yield is reduced or blocking or solvent resistance Deterioration, furthermore, foreign matters of the extruded film were generated, and it was found that when the iodine value of the thermoplastic resin was low, the hardness, haze, and solution storage stability were deteriorated.

The present invention is not limited to the embodiments described above, and various modifications are possible. The present invention includes substantially the same configuration as the configuration described in the embodiment (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect). In addition, the present invention includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration. In addition, the present invention includes a configuration that produces the same operational effects as the configuration described in the above-described embodiment or a configuration capable of achieving the same object. In addition, the present invention includes a configuration in which a known technique is added to the configuration described in the above embodiment.

Claims (7)

As a composition containing a thermoplastic resin (A) having an iodine number of 27 to 150 and water,
Contains 100 to 2000 ppm of the water with respect to 100 parts by mass of the composition,
The thermoplastic resin (A) has a repeating unit derived from a conjugated diene compound,
The composition wherein the thermoplastic resin (A) has a crystal melting peak temperature of 50° C. to 95° C., and a crystal melting heat amount of 10 J/g to 40 J/g. The method of claim 1,
In addition, it contains an anti-blocking agent (B),
When the content of the thermoplastic resin (A) is Ma (parts by mass) and the content of the blocking inhibitor (B) is Mb (parts by mass), Ma/Mb = 200 to 4000. The method of claim 1,
The composition further comprises at least one selected from the group consisting of polyethylene wax, polypropylene wax, fatty acid amide, fatty acid ester and fatty acid metal salt. The method according to any one of claims 1 to 3,
The thermoplastic resin (A),
0.3 to 10% by mass in a molecular weight range of 2×10 ⁴ or more and less than 8×10 ⁴ and,
A composition having a distribution present in a molecular weight range of 8×10 ⁴ or more and 1×10 ⁶ or less in a range of 90 to 99.3% by mass. The method according to any one of claims 1 to 3,
The composition, wherein the thermoplastic resin (A) further has a repeating unit derived from an aromatic vinyl compound. The method according to any one of claims 1 to 3,
Composition for use in coextrusion. A molded article made using the composition according to any one of claims 1 to 3.