JP2018111798A - Composition for adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for adhesive capable of manufacturing an adhesive film having an adhesive layer excellent in adhesive property (hardness is low, visibility is good, heat resistance exists, molding appearance is good or the like) together with enhancing productivity by suppressing blocking with a pellet drying process, a hopper or the like.SOLUTION: A composition for adhesive contains a thermoplastic resin (A) having iodine value of 2 to 150 and an antiblocking agent (B), and has Ma/Mb=200 to 4000, when content of the thermoplastic resin (A) is Ma (pts.mass) and content of the antiblocking agent (B) is Mb (pts.mass).SELECTED DRAWING: None

Description

  The present invention relates to a pressure-sensitive adhesive composition.

  Conventionally, a surface protective film has been used to protect the lens surface of a prism sheet used in a liquid crystal display. Since this surface protective film is for protecting the lens surface of the prism sheet from scratches and dirt in the manufacturing process, it is peeled off after the manufacturing process is completed and does not remain in the final product. Therefore, the surface protective film has (1) low hardness; a sufficient contact area with the adherend can be secured, (2) good visibility; work process and appearance inspection are easy, (3) Adhesive properties such as heat resistance; stable shape, no generation of foreign matter, and (4) good molded appearance are required.

  As such a surface protective film, for example, an adhesive layer made of, for example, an ethylene-vinyl acetate copolymer (EVA) or a conjugated diene polymer is provided on one surface of a base material layer made of a thermoplastic resin such as an olefin resin. What is formed is known.

  As a method for producing a pressure-sensitive adhesive film such as a surface protective film, a method in which a pressure-sensitive adhesive is applied to a base material layer (see, for example, Patent Document 1), and a method in which the base material layer and the pressure-sensitive adhesive layer are collectively formed by a coextrusion method. (For example, refer to Patent Document 2 and Patent Document 3). In particular, a method for producing an adhesive layer by a co-extrusion method has been attracting attention in recent years because it is simple and can suppress production costs.

JP 2003-238927 A Japanese Patent Laid-Open No. 2003-041216 JP 2010-255007 A

  However, even if the adhesive layer is manufactured by any manufacturing method, blocking is likely to occur in the process of manufacturing pellets of the pressure-sensitive adhesive as a raw material or when the pellets are put into the manufacturing apparatus, and production is There was a problem that the performance would be lowered.

  Also, the level of pressure-sensitive adhesive properties (low hardness, good visibility, heat resistance, good molding appearance, etc.) required with the recent rapid technological development progress is high. Therefore, further improvement is required.

  Therefore, some aspects according to the present invention have an adhesive layer that is excellent in the above-described characteristics while improving productivity by suppressing blocking by a hopper or the like by solving at least a part of the problems. A pressure-sensitive adhesive composition capable of producing a pressure-sensitive adhesive film is provided.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the composition for pressure-sensitive adhesives according to the present invention is:
A thermoplastic resin (A) having an iodine value of 2 to 150;
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 = 200 to 4000. And

[Application Example 2]
In the pressure-sensitive adhesive composition of the above application example,
The antiblocking agent (B) may be 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 3]
In the pressure-sensitive adhesive composition of the above application example,
The thermoplastic resin (A) can have a repeating unit derived from a conjugated diene compound.

[Application Example 4]
In the pressure-sensitive adhesive composition of the above application example,
The thermoplastic resin (A) may further have a repeating unit derived from an aromatic vinyl compound.

[Application Example 5]
One aspect of the composition for pressure-sensitive adhesives according to the present invention is:
A polymer having a repeating unit derived from a conjugated diene compound having an iodine value of 2 to 150;
A component that is 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 content of the polymer is M1 part by mass, and the content of at least one component selected from the group consisting of the polyethylene wax, polypropylene wax, fatty acid amide, fatty acid ester, and fatty acid metal salt is M2 part by mass M1 / M2 = 200 to 4000.

[Application Example 6]
In the pressure-sensitive adhesive composition of the above application example,
The polymer may further have a repeating unit derived from an aromatic vinyl compound.

[Application Example 7]
In the pressure-sensitive adhesive composition of the above application example,
Furthermore, water can be contained at 100 to 2000 ppm.

[Application Example 8]
The pressure-sensitive adhesive composition of the above application example can be used in a co-extrusion method.

According to the composition for pressure-sensitive adhesives according to the present invention, blocking in a hopper or the like can be suppressed when the pellets are introduced into a production apparatus for producing pressure-sensitive adhesive pellets or a pressure-sensitive adhesive layer, and as a result. Productivity of adhesive film is improved. Moreover, according to the composition for pressure-sensitive adhesives according to the present invention, a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer having excellent pressure-sensitive adhesive properties such as low hardness, excellent visibility, heat resistance, and good molded appearance is produced. can do.

  Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be understood that the present invention is not limited to only the embodiments described below, and includes various modifications that are implemented without departing from the scope of the present invention. In the present specification, “(meth) acrylic” is a concept encompassing both “acrylic” and “methacrylic”. Further, “˜ (meth) acrylate” is a concept encompassing both “˜acrylate” and “˜methacrylate”.

  In the present invention, the “adhesive film” refers to a film having an adhesive layer formed on at least one surface of a base material layer.

1. Composition for Adhesive The composition for an adhesive according to the first embodiment of the present invention is a thermoplastic resin (A) having an iodine value of 2 to 150 (hereinafter also simply referred to as “component (A)”). And an anti-blocking agent (B) (hereinafter also simply referred to as “component (B)”), the content of the thermoplastic resin (A) is Ma (parts by mass), and the anti-blocking agent (B ) Is Mb (parts by mass), Ma / Mb = 200 to 4000.

In addition, the pressure-sensitive adhesive composition according to the second embodiment of the present invention includes a polymer having a repeating unit derived from a conjugated diene compound having an iodine value of 2 to 150, polyethylene wax, polypropylene wax, fatty acid amide, and fatty acid. And at least one component selected from the group consisting of an ester and a fatty acid metal salt, and the content of the polymer is M1 part by mass, the polyethylene wax, polypropylene wax, fatty acid amide, fatty acid ester, and fatty acid metal salt When the content of at least one component selected from the group consisting of is M2 parts by mass, M1 / M2 = 200 to 4000.
Hereinafter, each component contained in the composition for pressure-sensitive adhesives according to the first and second embodiments (hereinafter collectively referred to as “the composition for pressure-sensitive adhesives according to this embodiment”) will be described in detail.

1.1. Thermoplastic resin (A)
The thermoplastic resin (A) contained in the composition for pressure-sensitive adhesives according to this embodiment is a thermoplastic resin having an iodine value of 2 to 150, in order to produce a pressure-sensitive adhesive layer constituting a part of the pressure-sensitive adhesive film. Used. When the iodine value of the thermoplastic resin (A) is in the above range, it is difficult to block, and it is possible to provide a pressure-sensitive adhesive composition having good heat resistance, flexibility and transparency.

  When the iodine value is not within the above range, the blocking characteristics tend to deteriorate. This is because thermoplastic resins are affected by the fact that the main chain contains many unsaturated bonds and the entanglement density of the main chain decreases, and the crystallinity decreases when the ethylene chain is broken by unsaturated bonds. This is thought to be due to a decrease in shape retention. In addition, when the iodine value is not within the above range, the heat resistance tends to be deteriorated, and it may not be able to withstand a high temperature processing step such as coextrusion. This is considered to be the effect that the unsaturated bond contained in the thermoplastic resin reacts at a high temperature.

  Moreover, when an iodine value is not the said range, the tendency for hardness to increase or for a Haze value to deteriorate is recognized. This is considered to be due to the fact that the chain formed by the ethylene structure, which is a hydrogenated 14-added butadiene, is lengthened and the crystallinity becomes too high.

Component (A) preferably has a repeating unit derived from a conjugated diene compound, and 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) preferably 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. , One or more selected from these. As the conjugated diene compound, 1,3-butadiene is particularly preferable.

  In the component (A), the content of the repeating unit derived from the conjugated diene compound is preferably 30 to 100 parts by mass when the total repeating unit of the component (A) is 100 parts by mass, and is preferably 35 to 100 parts by mass. More preferably, it is a part. When the content ratio of the repeating unit derived from the conjugated diene compound is in the above range, it becomes easy to produce an adhesive film excellent in viscoelasticity and strength, and the adhesive properties of the adhesive layer are further improved.

1.1.2. Repeating Unit Derived from Aromatic Vinyl Compound Component (A) may further have a repeating unit derived from an aromatic vinyl compound. Examples of the aromatic vinyl compound include styrene, tert-butylstyrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1,1-diphenylstyrene, vinylnaphthalene, vinylanthracene, N, N— Examples thereof include diethyl-p-aminoethylstyrene and vinylpyridine. Among these, styrene is particularly preferable.

  In the component (A), the content of the repeating unit derived from the aromatic vinyl compound is preferably 0 to 70 parts by mass when the total repeating unit of the component (A) is 100 parts by mass. More preferably, it is part by mass. When the content ratio of the repeating unit derived from the aromatic vinyl compound is in the above range, the tackiness of the adhesive layer becomes better.

1.1.3. Other repeating units Component (A) may have other repeating units. 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.

  The unsaturated carboxylic acid ester is preferably a (meth) acrylic acid ester. Specific examples of such (meth) acrylic acid esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth ) N-butyl acrylate, i-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylic Ethylene glycol, di (meth) acrylic acid ethylene glycol, di (meth) acrylic acid propylene glycol , Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl (meth) acrylate, and the like. Can be one or more. Among these, one or more selected from methyl (meth) acrylate, ethyl (meth) acrylate and 2-ethylhexyl (meth) acrylate is preferable, and methyl (meth) acrylate is particularly preferable. preferable.

  Specific examples of the unsaturated carboxylic acid include mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and the like. One type selected from these That can be the end. In particular, at least one selected from acrylic acid, methacrylic acid and itaconic acid is preferable.

  Specific examples of the α, β-unsaturated nitrile compound include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, vinylidene cyanide, and one or more selected from these. Can be. Of these, at least one selected from acrylonitrile and methacrylonitrile is preferable, and acrylonitrile is particularly preferable.

  Moreover, a component (A) may further have a repeating unit derived from the compound shown below. Examples of such compounds include fluorine-containing compounds having an ethylenically unsaturated bond such as vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene; ethylenically unsaturated carboxylic acids such as (meth) acrylamide and N-methylolacrylamide. Acid alkyl amides; Vinyl acetates, vinyl acetates, vinyl propionates, etc .; Acid anhydrides of ethylenically unsaturated dicarboxylic acids; Monoalkyl esters; Monoamides; Aminoethylacrylamide, dimethylaminomethylmethacrylamide, Methylaminopropylmethacrylamide Examples thereof include aminoalkylamides of ethylenically unsaturated carboxylic acids such as, and can be one or more selected from these.

1.1.4. The structure, properties and synthesis method of the thermoplastic resin (A) The thermoplastic resin (A) in the present embodiment is not particularly limited, but is mainly composed of a block composed of repeating units derived from an aromatic vinyl compound and a conjugated diene compound. A block copolymer comprising a repeating unit derived from the above, a block of a repeating unit derived from a conjugated diene compound and having a low vinyl bond, and a block of a repeating unit derived from a conjugated diene compound and having a high vinyl bond. A polymer hydrogenated product 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. From the viewpoint of durability, butadiene- A hydrogenated product of a butadiene-butadiene block copolymer, a styrene-butadiene-butadiene block copolymer, or a styrene-butadiene-styrene block copolymer is more preferable. Such a thermoplastic resin (A) can be synthesized by the methods described in Japanese Patent No. 3303467, Japanese Patent No. 3282364, Japanese Patent Application Laid-Open No. 2010-255007, and 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. When the content of the repeating unit derived from the aromatic vinyl compound is in the above range, the adhesive force can be further increased, and there is a tendency that no adhesive residue occurs 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, the composition for pressure-sensitive adhesive of the present invention is applied to a substrate and then irradiated with energy rays such as UV (ultraviolet rays) and EB (electron beams). The surface of the adhesive layer can be partially crosslinked. Thereby, it is possible to produce an adhesive layer excellent in heat resistance and high-temperature holding power while maintaining appropriate flexibility on the surface of the adhesive layer. When the component (A) is a hydrogenated product of a styrene-conjugated diene block copolymer, the iodine value of the component (A) is appropriately adjusted by changing the hydrogenation rate by controlling the hydrogenation conditions. can do. In addition, the thermoplastic resin (A
) Can be measured according to the method described in “JIS K 0070: 1992”. The iodine value is a value representing the amount of halogen that reacts with 100 g of the target substance in terms of grams of iodine, so the unit of iodine value is “g / 100 g”. In this specification, for example, “the iodine value is 2 to 150” means “the iodine value is 2 to 150 g / 100 g”.

  In the production of the pressure-sensitive adhesive film, when the substrate composition and the pressure-sensitive adhesive composition are co-extruded using a melt co-extrusion apparatus or the like, the component (A) contained in the pressure-sensitive adhesive composition The melt flow rate (MFR) measured at 230 ° C. and 21.2 N load is preferably 0.1 to 100 g / 10 minutes, more preferably 1.0 to 50 g / 10 minutes. It is particularly preferably 0 to 30 g / 10 minutes. If the MFR is less than 0.1 g / 10 minutes, the load during coextrusion may be excessive. On the other hand, if the MFR exceeds 100 g / 10 min, there is a tendency to cause problems in coextrusion moldability such as drawdown.

The weight 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 weight average molecular weight (Mw) of the component (A) is in the above range, an adhesive film excellent in molding processability and adhesive strength can be easily obtained. When this Mw is less than the above range, tackiness is excellent, but adhesive residue or the like may occur during peeling. If Mw exceeds the above range, the moldability or adhesive strength may not be sufficiently increased. In addition, "weight average molecular weight" here refers to the weight average molecular weight of polystyrene conversion measured by GPC (gel permeation chromatography).

  The component (A) preferably has at least one melting peak (crystal melting peak) in the range of 50 to 150 ° C. This melting peak temperature is measured by differential scanning calorimetry (DSC method). Specifically, using a differential scanning calorimeter (DSC), the sample component (A) was held at 200 ° C. for 10 minutes, then cooled to −80 ° C. at a rate of 10 ° C./minute, and then −80 This is the peak temperature of the heat flow rate (heat of crystal melting) when the temperature is raised at a rate of 10 ° C./min after being held at ° C. for 10 minutes. The crystal melting heat amount of the melting peak is in the range of 5 to 70 J / g, preferably 8 to 55 J / g.

  The content ratio of the component (A) in the pressure-sensitive adhesive composition according to this embodiment is preferably 50 to 100% by mass, more preferably 55 to 100% by mass when the total mass of the composition is 100% by mass. %, Particularly preferably 60 to 100% by mass.

1.2. Antiblocking agent (B)
The antiblocking agent (B) contained in the pressure-sensitive adhesive composition according to this embodiment 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 the composition for pressure-sensitive adhesives contains such an anti-blocking agent (B), blocking (clogging) with a hopper or the like can be suppressed and the productivity of the pressure-sensitive adhesive film can be further improved.

Anti-blocking agent (B) includes fluoropolymer, polyethylene wax, polypropylene wax, ethylene-propylene copolymer wax, Fischer-Tropsch wax and their partial oxides or copolymers with ethylenically unsaturated carboxylic acids. Synthetic hydrocarbon waxes such as; modified waxes such as montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives; hydrogenated waxes such as hardened castor oil and hardened castor oil derivatives; cetyl alcohol, stearic acid, 12-hydroxystearic acid, etc. Higher fatty acids and alcohols; fatty acid esters such as glyceryl stearate, polyethylene glycol stearate, stearyl stearate, isopropyl palmitate; fatty acid amino acids such as stearamide ; Calcium stearate, fatty acid metal salts of lithium stearate; phthalic anhydride imide, chlorinated hydrocarbons, and the like.

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

  The content ratio of the component (B) in the composition for pressure-sensitive adhesives according to this embodiment needs to be 0.02 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass as a total of the components (A). It is preferable that it is 0.03 mass part or more and 0.4 mass part or less. When the content of the thermoplastic resin (A) in the composition for pressure-sensitive adhesives according to this embodiment is Ma (parts by mass) and the content of the antiblocking agent (B) is Mb (parts by mass), the thermoplastic resin The amount ratio (Ma / Mb) of (A) to the anti-blocking agent (B) needs to be 200 to 4000, and preferably 250 to 3500. When not within the above range, when pelletized with a strand cutter, workability deteriorates due to an increase in fine pellets, and the yield of undried pellets deteriorates due to an increase in bead-like defective pellets. there's a possibility that. Moreover, there is a possibility that blocking cannot be prevented in drying of undried pellets. Furthermore, the haze and appearance of the molded film may be deteriorated.

1.3. Water content The pressure-sensitive adhesive composition according to this embodiment preferably contains 100 to 2000 ppm of water, more preferably 130 to 1000 ppm, and particularly preferably 150 to 600 ppm. When the moisture content is within the above range, a molded article having excellent appearance and excellent appearance can be produced when the pressure-sensitive adhesive composition is molded. If the moisture content exceeds the above range, the moisture is heated in the cylinder of the injection molding machine and becomes bubbles in the thermoplastic elastomer, and bubbles are broken on the surface of the molded product, resulting in deterioration of the haze and poor appearance (siriburst leak). there is a possibility.

  In the present invention, the “water content of the pressure-sensitive adhesive composition” is synonymous with the water content of the pressure-sensitive adhesive composition pellets. The water content of the pressure-sensitive adhesive composition in the present invention is a value measured according to JIS K7251 “Plastics—How to Obtain Water Content”.

  The moisture content of the pressure-sensitive adhesive composition is determined by heating the pressure-sensitive adhesive composition at a temperature and time suitable for the thermoplastic elastomer to be used, using a pellet dryer such as a dehumidifying dryer, a vacuum dryer, or a hot air dryer. Can be processed and controlled. If the drying temperature is high and the drying time is long, the amount of water can be greatly reduced, but the pellet of the pressure-sensitive adhesive composition may cause blocking or change in quality such as bleed out. Further, when the drying temperature is low and the drying time is short, the moisture content tends to increase. In any case, the moisture content can be controlled by controlling the drying temperature and the drying time.

1.4. Other components In the composition for pressure-sensitive adhesives according to the present embodiment, in addition to the above-described components, as necessary, radical generators, anti-aging agents, fillers, colorants, flame retardants, tackifiers, and the like. Known components may be added.

The radical generator is formed by generating radicals by irradiating radiation such as heating or ultraviolet rays and crosslinking the component (A) when preparing an adhesive layer constituting a part of the adhesive film. It is possible to effectively reduce the adhesion progress of the adhesive layer. As the radical generator, a photo radical generator that generates radicals by irradiation with 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 singly or in combination of two or more.

  The radical generator is particularly preferably an oligomer type photoradical generator. The oligomer 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. Such an oligomer type photo radical generator has a plurality of radical generation points in one molecule, so it is not easily affected by cross-linking inhibition by oxygen and can be cross-linked with a small amount. In particular, it is preferably used because it does not scatter in a solvent-free hot melt state and is not extracted from the polymer.

  Specific examples of the oligomer type photo radical generator include oligomers obtained by polymerizing acrylated benzophenone (trade name “Ebecryl P36” manufactured by UCB), 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- An oligomer obtained by polymerizing a reaction product of a primary hydroxyl group of 2-methyl-1-propan-1-one (trade name “Irgacure 2959” manufactured by BASF Corporation) and 2-isocyanatoethyl methacrylate, 2-hydroxy-2-methyl- [4 -(1-Methylvinyl) phenyl] propanol oligomer (manufactured by Lamberti, trade name “EsacureKIP150”) and the like. The molecular weight of these oligomer-type photoradical generators is preferably up to about 50,000.

  As the anti-aging agent, for example, antioxidants such as hindered phenols and phosphites, UV absorbers such as benzotriazoles, benzophenones, and salicylic acid esters, and light stabilizers such as hindered amines are suitably added. .

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

2. Adhesive film The adhesive film which concerns on this embodiment is a film provided with the base material layer and the adhesive layer formed in the single side | surface or both surfaces of the said base material layer. The composition for the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer is as described above. Hereinafter, the manufacturing method of a base material layer, the composition for base materials, and an adhesive film is demonstrated in this order.

<Base material layer and base material composition>
It is preferable that the composition for base materials for producing a base material layer contains a thermoplastic resin. Of the thermoplastic resins, olefin resins are preferred.

  As the olefin resin, for example, polyethylene, polypropylene, and polybutene copolymers 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, ethylene-ethyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-n-butyl acrylate copolymer, etc. can be mentioned. These thermoplastic resins can be used alone or in combination of two or more.

The composition for a substrate 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, and the like. For example, fillers such as calcium oxide, magnesium oxide, silica, zinc oxide, and titanium oxide, pigments, anti-tarnish agents, lubricants, anti-blocking agents, and the like can be appropriately added.

  It is preferable that MFR measured by 230 degreeC and a 21.2N load of the thermoplastic resin contained in the composition for base materials is 0.01-100 g / 10min, 0.1-80 g / 10min It is more preferable that Moreover, the thermoplastic resin contained in the base composition may be composed of only one kind of thermoplastic resin, or may be composed by mixing two or more kinds of thermoplastic resins. The base material layer may be a single layer or a multilayer of two or more layers. It is also possible to select a foam layer as the base material layer.

<Method for producing adhesive film>
The adhesive film which concerns on this embodiment is a film which has what is called a laminated structure provided with the base material layer and the adhesive layer formed in the single side | surface or both surfaces of the said base material layer. Therefore, the pressure-sensitive adhesive film according to this embodiment is obtained by (1) a coating method; a method in which a pressure-sensitive adhesive composition is formed on one surface or both surfaces of a base material layer prepared in advance and then wound up, and (2) ) Coextrusion method; a method of forming an adhesive layer on one or both sides of a substrate layer by coextruding the composition for a substrate and the composition for an adhesive using a melt coextrusion apparatus or the like, It can be manufactured by such a method.

  When producing an adhesive film by a coating method, the above adhesive composition is applied to one or both sides of a base material layer having a thickness of about 2 to 150 μm, and ultraviolet (UV) or electron beam (EB) is applied as necessary. ), Etc., to form a pressure-sensitive adhesive layer having a thickness of 5 to 200 μm. Moreover, it can also be set as the adhesive film for transcription | transfer by giving a mold release process to the single side | surface of a base material layer. When applying the pressure-sensitive adhesive composition to the base material layer, it can be applied in a state where the viscosity is reduced by heating if necessary. Specifically, a hot melt coater, a comma roll, a gravure coater, A roll coater, kiss coater, slot die coater, squeeze coater or the like can be used.

  When producing a pressure-sensitive adhesive film by co-extrusion of the substrate composition and the pressure-sensitive adhesive composition, irradiate energy rays such as ultraviolet rays (UV) or electron beams (EB) as necessary. It can manufacture by forming a pressure-sensitive adhesive layer having a thickness of 5 to 200 μm by crosslinking treatment.

The ultraviolet irradiation can be performed using an appropriate ultraviolet ray source such as a high-pressure mercury lamp, a low-pressure mercury lamp, an excimer laser, or a metal halide lamp. Dose of ultraviolet light is determined according to the degree of crosslinking in need, preferably ^{10mJ / cm 2 ~5000mJ / cm 2} , more preferably ^{100mJ / cm 2 ~5000mJ / cm 2} . In addition, a filter or a polyester sheet that cuts ultraviolet rays on the short wavelength side may be used as necessary. Furthermore, 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 an electron beam source, for example, a method using thermal electrons generated from a commercially available tungsten filament, a cold cathode method in which metal is generated through a high voltage pulse, and collision between ionized gaseous molecules and a metal electrode. A secondary electron system using secondary electrons generated can be given. 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.

When irradiating energy rays in the method for producing an adhesive film, electron beam (EB) irradiation is more preferable than ultraviolet (UV) irradiation from the viewpoint of easy progress of crosslinking of the adhesive layer. The pressure-sensitive adhesive layer irradiated with an electron beam is advantageous in that the generation of a gel component can be made extremely small, and the generation of a foreign substance derived from the gel component can be suppressed. On the other hand, in the case of ultraviolet irradiation, the radical generator may be decomposed at the extrusion temperature, and there are production problems such as the necessity of producing in a light-shielding environment.

  According to the above method for producing an adhesive film, the adhesive properties and heat resistance are improved by irradiating the adhesive layer formed of the adhesive composition with energy rays such as ultraviolet rays (UV) or electron beams (EB). An adhesive layer can be prepared. At that time, after the energy beam cross-linking, the solvent-soluble content of the block copolymer is 5 to 60% by mass, preferably 10 to 50% by mass. In order to obtain such a solvent-soluble component, the degree of crosslinking may be adjusted as appropriate by selecting the amount of radical generator used or selecting the amount of energy ray irradiation.

  In place of radical generators, if sulfur, sulfur vulcanizing agents, or vulcanization accelerators generally used for rubber crosslinking are used, a large amount of sulfide ions and sulfate ions are generated and bleed out from the adhesive layer. Since it may be, it is not preferable. In addition, it may be difficult to obtain sufficient heat resistance by crosslinking using a peroxide.

  In addition, the adhesive film manufactured in this way can be used in shapes, such as a tape form and a sheet form, as needed.

3. EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. “Part” and “%” in Examples and Comparative Examples are based on mass unless otherwise specified.

3.1. Production of thermoplastic resin 3.1.1. Synthesis example 1
A nitrogen-substituted reaction vessel was charged with 800 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.09 part of n-butyllithium at a polymerization start temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 10 ° C., 80 parts of 1,3-butadiene and 15 parts of tetrahydrofuran were added, and further temperature-programmed polymerization was performed. After the polymerization conversion rate reached 99% or more, 0.06 part of dichloromethylsilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.04 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. The hydrogenation reaction is started at a hydrogen gas supply pressure of 0.7 MPa-Gauge and a reaction temperature of 80 ° C., and after 3 hours, the reaction solution is brought to 60 ° C. and normal pressure, and is taken out from the reaction vessel to obtain a thermoplastic resin A-1. It was.

3.1.2. Synthesis example 2
A reaction vessel purged with nitrogen was charged with 800 parts of degassed and dehydrated cyclohexane, 30 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.09 part of n-butyllithium at a polymerization start temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 10 ° C., 70 parts of 1,3-butadiene and 15 parts of tetrahydrofuran were added, and further temperature-programmed polymerization was performed. After the polymerization conversion rate reached 99% or more, 0.06 part of dichloromethylsilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.04 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a 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
A reaction vessel purged with nitrogen was charged with 800 parts of degassed and dehydrated cyclohexane, 8 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.09 part of n-butyllithium at a polymerization start temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 10 ° C., 92 parts of 1,3-butadiene and 15 parts of tetrahydrofuran were added, and further temperature-programmed polymerization was performed. After the polymerization conversion rate reached 99% or more, 0.06 part of dichloromethylsilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.04 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was performed in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-3.

3.1.4. Synthesis example 4
A nitrogen-substituted reaction vessel was charged with 800 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.09 part of n-butyllithium at a polymerization start temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 25 ° C., 80 parts of 1,3-butadiene and 5 parts of tetrahydrofuran were added, and further temperature-programmed polymerization was performed. After the polymerization conversion rate reached 99% or more, 0.06 part of dichloromethylsilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.04 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was performed in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-4.

3.1.5. Synthesis example 5
A nitrogen-substituted reaction vessel was charged with 800 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.09 part of n-butyllithium at a polymerization start temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. 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-programmed polymerization was performed. After the polymerization conversion rate reached 99% or more, 0.06 part of dichloromethylsilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.04 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was performed in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-5.

3.1.6. Synthesis Example 6
A thermoplastic resin A-6 was obtained in the same manner as in Synthesis Example 1 except that the hydrogenation reaction time was 2 hours.

3.1.7. Synthesis Examples 7, 8, 9
Thermoplastic resins A-7, A-8, and A-9 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.

3.1.8. Synthesis Example 10
A reaction vessel purged with nitrogen was charged with 600 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.10 parts of n-butyllithium at a polymerization initiation temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion rate 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, followed by further temperature rising polymerization. After the polymerization conversion rate reached 99% or more, 0.06 part of tetrachlorosilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.03 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was carried out in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-10.

3.1.9. Synthesis Example 11
A thermoplastic resin A-11 was obtained in the same manner as in Synthesis Example 10 except that the hydrogenation reaction time was 1 hour.

3.1.10. Synthesis Example 12
A reaction vessel purged with nitrogen was charged with 600 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.06 part of n-butyllithium at a polymerization start temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion 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, and the temperature was further increased. Warm polymerization was performed. After the polymerization conversion rate reached 99% or more, 0.06 part of tetrachlorosilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.03 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was carried out in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-12.

3.1.11. Synthesis Example 13
A reaction vessel purged with nitrogen was charged with 600 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.10 parts of n-butyllithium at a polymerization initiation temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 10 ° C., and then 65 parts of 1,3-butadiene, 15 parts of styrene, and 15 parts of tetrahydrofuran were added to perform further temperature rising polymerization. . After the polymerization conversion rate reached 99% or more, 0.06 part of tetrachlorosilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.03 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was carried out in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-13.

3.1.12. Synthesis Example 14
A reaction vessel purged with nitrogen was charged with 600 parts of degassed and dehydrated cyclohexane, 20 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.10 parts of n-butyllithium at a polymerization initiation temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion rate 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 rising polymerization was performed. . After the polymerization conversion rate reached 99% or more, 0.06 part of tetrachlorosilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.03 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was carried out in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-14.

3.1.13. Synthesis Example 15
A reaction vessel purged with nitrogen was charged with 800 parts of degassed and dehydrated cyclohexane, 40 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.09 part of n-butyllithium at a polymerization start temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. After the polymerization conversion rate 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-programmed polymerization was performed. After the polymerization conversion rate reached 99% or more, 0.06 part of dichloromethylsilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.04 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was carried out in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-15.

3.1.14. Synthesis Example 16
A nitrogen-substituted reaction vessel was charged with 500 parts of degassed and dehydrated cyclohexane, 6 parts of styrene, and 13 parts of tetrahydrofuran, and 0.10 parts of n-butyllithium was added at a polymerization initiation temperature of 40 ° C. Polymerization was performed. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 10 ° C., and then 94 parts of 1,3-butadiene was added for further temperature rising polymerization. After the polymerization conversion rate reached 99% or more, 0.07 part of dichlorodimethylsilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.03 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was performed in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-16.

3.1.15. Synthesis Example 17
A nitrogen-substituted reaction vessel was charged with 500 parts of degassed and dehydrated cyclohexane, 6 parts of styrene, and 13 parts of tetrahydrofuran, and 0.10 parts of n-butyllithium was added at a polymerization initiation temperature of 40 ° C. Polymerization was performed. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 10 ° C., and then 94 parts of 1,3-butadiene was added for further temperature rising polymerization. After the polymerization conversion rate reached 99% or more, 0.05 part of tetrachlorosilane was added and polymerization was further performed at elevated temperature. Thereafter, 0.03 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was carried out in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-17.

3.1.16. Synthesis Example 18
A nitrogen-substituted reaction vessel was charged with 500 parts of degassed and dehydrated cyclohexane, 6 parts of styrene, and 13 parts of tetrahydrofuran, and 0.06 part of n-butyllithium was added at a polymerization initiation temperature of 40 ° C. to raise the temperature. Polymerization was performed. 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 and 94 parts of 1,3-butadiene were added to carry out temperature-increasing polymerization. . After the polymerization conversion rate reached 99% or more, 0.06 part of tetrachlorosilane was added, and the temperature rising polymerization was further performed. Thereafter, 0.03 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was carried out in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-18.

3.1.17. Synthesis Example 19
A nitrogen-substituted reaction vessel was charged with 800 parts of degassed and dehydrated cyclohexane, 15 parts of 1,3-butadiene, and 0.03 part of tetrahydrofuran, and 0.09 part of n-butyllithium at a polymerization start temperature of 70 ° C. Was added, and the temperature rising polymerization was performed. 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-programmed polymerization was performed. After the polymerization conversion rate reached 99% or more, 15 parts of styrene was added, and the temperature rising polymerization was further performed. Thereafter, 0.04 part of diethylaluminum chloride and 0.06 part of bis (cyclopentadienyl) titanium furfuryloxychloride were added to the reaction vessel and stirred. Thereafter, a hydrogenation reaction was carried out in the same manner as in Synthesis Example 1 to obtain a thermoplastic resin A-19.

3.1.18. Synthesis Example 20
A thermoplastic resin A-20 was obtained in the same manner as in Synthesis Example 16 except that the hydrogenation reaction time was 15 minutes.

3.1.19. Synthesis Example 21
A thermoplastic resin A-21 was obtained in the same manner as in Synthesis Example 15 except that the hydrogenation reaction time was 12 hours.

3.2. Evaluation of Thermoplastic Resin The total bonded styrene content, vinyl bond content, iodine value, crystal melting peak temperature, and crystal melting heat amount of the produced thermoplastic resin were measured by the following methods. The results are shown in Tables 1 and 2.

3.2.1. Evaluation of Total Bonded Styrene Content The thermoplastic resin before the hydrogenation reaction was dissolved in carbon tetrachloride, and the total bonded 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 Calculates vinyl bond (1,2 bond and 3,4 bond) by the Hampton method using infrared analysis of thermoplastic resin before hydrogenation reaction did. The results are shown in Tables 1 and 2.

3.2.3. Evaluation of iodine value The iodine value of a thermoplastic resin was calculated 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 / Crystal Melting Calorie Heat when a thermoplastic resin is held at 200 ° C. for 10 minutes using a differential scanning calorimeter (DSC) and then heated to −80 ° C. at a rate of 10 ° C./min. The peak temperature at the flow rate (crystal melting heat (J / g)) was defined as the crystal melting peak temperature (° C.). The results are shown in Tables 1 and 2.

3.3. Example 1
0.05 parts of calcium stearate is added to the thermoplastic resin produced, put into a 40 mm single screw extruder manufactured by Ikegai, melt kneaded, extruded into a strand, cooled and solidified in water, and then a strand cutter manufactured by Giken Koki Co., Ltd. To obtain a cylindrical undried pellet.
100 parts by weight of undried pellets and 0.10 parts by weight of calcium stearate (manufactured by Wako Pure Chemical Industries, Ltd.) are added to Supermixer SMV-20 and stirred at a stirring speed of 300 rpm for 5 minutes. Was applied. After that, it was sieved with a stainless steel 3.5 mesh having an aperture of 6.0 mm, and further sieved with a stainless steel 12 mesh having an aperture of 1.5 mm. Dry the one that does not pass 12 mesh under the condition of a drying temperature of 80 ° C. using a drier (trade name “Parallel Flow Drier”, manufactured by Satake Chemical Machinery Co., Ltd.). A pressure-sensitive adhesive composition (pellet) adjusted to 500 ppm was prepared. The water content of the pressure-sensitive adhesive composition thus prepared can be measured in accordance with the water vaporization method described in JIS K7251 “Plastics—How to determine water content”.

3.3.1. Blocking evaluation of the pressure-sensitive adhesive composition (pellet) Blocking is desirably small because it causes deterioration in workability when recovered from the dryer and causes an error when the extruder hopper is charged. For this reason, the blocking state of the composition for pressure-sensitive adhesives (pellets) was confirmed by the following method and evaluated according to the following indices. The results are shown in Table 3. “A”: Pellets are not attached to each other, and it can be determined that they are excellent.
-"B": Although some bead-shaped pellets are recognized, since mutual adherence between the pellets is solved by solving, it is inferior in productivity, but can be judged to be good because it can be used practically.
"C": The pellets are attached to each other and integrated, and the integrated pellet cannot be unraveled and cannot be put to practical use, so it can be determined to be defective.

3.3.2. Hardness evaluation of pressure-sensitive adhesive composition (pellet) When used as a pressure-sensitive adhesive, the pressure-sensitive adhesive layer and the adherend are pressure-bonded at a predetermined pressure. If the amount of deformation of the pressure-sensitive adhesive layer is large, the contact area with the adherend is reduced. It is desirable that the hardness be low because sufficient adhesion can be secured and good adhesive performance can be expected. Therefore, the hardness of the pressure-sensitive adhesive composition (pellet) was evaluated according to the following method and evaluated according to the following index. The results are shown in Table 3.

By placing the composition for the pressure-sensitive adhesive (pellet) produced on the mirror surface plate and a spacer having a thickness of 2 mm, and using a hot press molding machine “AT-37” manufactured by Iwaki Industry Co., Ltd., heat-pressing at 190 ° C. for 30 minutes, A 2 mm thick press sheet was obtained. The prepared sheets were overlapped to a thickness of 6 mm, and the value after 15 seconds was read using a type A durometer described in JIS6253.
“AA”: Hardness is less than 50, and it is possible to determine that it is extremely excellent because the contact area with the adherend can be greatly improved in bonding with the adherend.
-"A": Hardness is more than 50 and less than 65, and it can be judged that it is excellent because it can improve the contact area with the adherend in bonding with the adherend.
"B": Hardness is more than 65 and less 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 used practically.
"C": Hardness is over 75, shape change with respect to the adherend cannot be caused, and it cannot be used practically, so it can be determined as defective.

3.3.3. Haze evaluation of composition for pressure-sensitive adhesive (pellet) It is desirable that the haze value is low in consideration of the visibility in the processing step and appearance inspection of the optical member. For this reason, it evaluated according to the following parameters | indexes. The results are shown in Table 3.

Based on JIS-K7136 (2000), the sheet created above was measured using “HAZEMETER HM-150” manufactured by Murakami Color Research Laboratory.
“A”: Haze is less than 15, and it can be determined that the visibility is extremely excellent.
"B": Haze is more than 15 and less than 20, and is inferior in visibility, but can be judged good because it can be used practically.
“C”: Haze is over 20 and the visibility is poor, so it cannot be put to practical use and can be judged as defective.

3.3.4. Production and heat resistance of adhesive film and evaluation of molded appearance Using polyethylene (Mitsubishi Chemical Co., Ltd., trade name “YF30”) as a base material layer, and the adhesive composition (pellet) prepared above as an adhesive layer, Using a two-layer coextrusion device equipped with a feed block type T die, the base layer is 100 μm thick and the adhesive layer is 10 μm thick under the molding conditions of a cylinder temperature of 190 ° C. and a die temperature of 190 ° C. The material layer and the adhesive layer were coextruded to produce an adhesive film.

On the other hand, the pressure-sensitive adhesive 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 collect the eluted component A. On the other hand, the prepared adhesive film was cut and weighed 20.0 mg, immersed in 20 mL of orthodichlorobenzene at 135 ° C. for 1 hour, and filtered to collect the eluted component B. GPC measurement of the elution components A and B was performed, the presence or absence of the gel component in the film forming step was evaluated as follows, and the heat resistance of the pressure-sensitive adhesive composition (pellet) was evaluated. The results are shown in Table 3.
“A”: Almost no change was observed in the GPC intensity ratio and the GPC shape of the elution component A and elution component B, and the gel component was very small. Since the amount of foreign matter is extremely small, it can be judged that it is excellent.
"B": Almost no change was observed in the GPC intensity ratio between the eluted component A and the eluted component B, and the gel component was insignificant, but multimer formation was observed from the GPC shape. Although formation of a multimer is recognized, since the gel component is very small, it can be judged that the amount of foreign matter is small and can be used practically.
“C”: The GPC intensity of the eluted component B is extremely small, and the gel component due to the increase in quantity is extremely large.
It is desirable that the amount of foreign matter generated during the pelletization or film forming process causes a film defect or a yield failure and is small. The evaluation of GPC was carried out at a high temperature GPC measurement system “PL-GPC220” manufactured by Polymer Laboratory, a column “MIXED-B” manufactured by Polymer Laboratory, and a measurement temperature of 135 ° C.

Moreover, the surface of the adhesive film produced above was observed with an optical microscope and evaluated as follows. The results are shown in Table 3.
“A”: No abnormality such as bubbles is observed on the film surface, and it can be determined that the film is excellent.
"B": Although some bubbles existed on the film surface, it can be judged good because it can be used practically. "C": Many air bubbles are observed on the film surface, which cannot be used practically and can be judged as defective.
Considering the adhesive performance of the adhesive film and the visibility in the process of using the adhesive film, it is desirable that the surface roughness and turbidity due to bubbles on the film surface be small.

3.4. Examples 2 to 26, Comparative Examples 1 to 6
Using thermoplastic resins A-2 to A-21, the type and amount of the antiblocking agent (B), and the amount of water were changed to the components and amounts shown in Tables 3 to 5, and the adhesive was applied in the same manner as in Example 1. An agent composition (pellet) was prepared and evaluated in the same manner as in Example 1. The results are shown in Tables 3-5.
The water content was adjusted by changing the drying time of the pressure-sensitive adhesive composition (pellet) as appropriate.
Moreover, as PP powder in Table 5, the brand name “CERAFLOUR970” manufactured by Big Chemie Japan was used. As PE powder in Table 5, the trade name “Accumist B-6” manufactured by Honeywell was used. As the fatty acid amide in Table 5, the trade name “Armoslip E” manufactured by Lion Akzo Corporation was used.

3.5. Results According to Examples 1 to 26, the pressure-sensitive adhesive composition according to the present invention is excellent in productivity and workability in pellet production, exhibits high adhesive strength to adherends, An extruded adhesive film having excellent appearance and excellent visibility when using the film could be produced.
According to Comparative Examples 1 to 6, when the moisture content is large, poor appearance at the time of extrusion film formation occurs, when the moisture content is small, blocking occurs at the time of pellet drying, and when the amount of the antiblocking agent is large, the haze rise of the extrusion film is increased. Appearance defects occur, and if the amount of the antiblocking agent is small, the yield decreases and blocking occurs. If the iodine value of the thermoplastic resin is high, the yield decreases and the blocking deteriorates. It was found that when the iodine value is low, the hardness and the haze are deteriorated.

  The present invention is not limited to the above embodiment, and various modifications can be made. The present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same objects and effects). The present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration. Furthermore, the present invention includes a configuration that achieves the same effects as the configuration described in the above embodiment or a configuration that can achieve the same object. Furthermore, the present invention includes a configuration obtained by adding a known technique to the configuration described in the above embodiment.

Claims (8)

A thermoplastic resin (A) having an iodine value of 2 to 150;
An anti-blocking agent (B),
Adhesive which is Ma / Mb = 200 to 4000 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). Composition.   The pressure-sensitive adhesive composition according to claim 1, wherein the antiblocking agent (B) is 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 composition for adhesives of Claim 1 or Claim 2 in which the said thermoplastic resin (A) has a repeating unit derived from a conjugated diene compound.   The composition for adhesives of Claim 3 in which the said thermoplastic resin (A) further has a repeating unit derived from an aromatic vinyl compound. A polymer having a repeating unit derived from a conjugated diene compound having an iodine value of 2 to 150;
A component that is 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 content of the polymer is M1 part by mass, and the content of at least one component selected from the group consisting of the polyethylene wax, polypropylene wax, fatty acid amide, fatty acid ester, and fatty acid metal salt is M2 part by mass M1 / M2 = 200 to 4000, A composition for pressure-sensitive adhesives.   The composition for adhesives of Claim 5 in which the said polymer further has a repeating unit derived from an aromatic vinyl compound.   Furthermore, the composition for adhesives as described in any one of Claims 1 thru | or 6 containing 100-2000 ppm of water | moisture contents.   The composition for adhesives as described in any one of Claim 1 thru | or 7 used for a coextrusion method.