WO2017170903A1

WO2017170903A1 - Thermoplastic resin composition and molded object thereof

Info

Publication number: WO2017170903A1
Application number: PCT/JP2017/013332
Authority: WO
Inventors: 賢一瀬野
Original assignee: 住友化学株式会社
Priority date: 2016-03-31
Filing date: 2017-03-30
Publication date: 2017-10-05
Also published as: JP6835069B2; JPWO2017170903A1

Abstract

The present invention provides: a thermoplastic resin composition which comprises an amorphous thermoplastic resin (A) having a weight-average molecular weight of 50,000-500,000 and a molecular-weight distribution of 1.0-3.5 and an amorphous thermoplastic resin (B) having a weight-average molecular weight of 500 or higher but lower than 50,000 and in which, when the total amount of the amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B) is taken as 100 mass%, then the content of the amorphous thermoplastic resin (A) is 25-85 mass% and the content of the amorphous thermoplastic resin (B) is 15-75 mass%, the composition satisfying the following requirements (1) and (2); and a molded object comprising the thermoplastic resin composition. Requirement (1): the thermoplastic resin composition has a glass transition temperature of 0-200°C. Requirement (2): a 1 mm-thick sheet formed from the thermoplastic resin composition has a haze less than 8.0%.

Description

Thermoplastic resin composition and molded article thereof

The present invention relates to a thermoplastic resin composition capable of self-healing even if a scratch occurs, and a molded body thereof.

There is a growing need for self-healing materials that can self-repair even if scratches occur, with the goal of developing products that do not spoil the beauty of the long-term. As a self-healing material, for example, Patent Document 1 describes an incompatible composition composed of poly (styrene-butadiene) and sulfonated poly (styrene-butadiene).

International Publication No. 2014/113432

In recent years, transparency is also required for self-healing materials. However, the composition described in Patent Document 1 is opaque because it is incompatible, and a necessary polymer is designed according to a temperature at which self-repair occurs (hereinafter, referred to as a repair temperature). There is a problem that it is necessary to synthesize and it is difficult to adjust the repair temperature.

An object of the present invention is to provide a thermoplastic resin composition that can give a molded article that is transparent and has self-healing performance, and that can easily adjust the repairing temperature by adjusting the content of its constituent components. And a molded article comprising the thermoplastic resin composition.

The present invention provides the following thermoplastic resin composition and molded article.
[1] Amorphous thermoplastic resin (A) having a weight average molecular weight of 50,000 to 500,000 and a molecular weight distribution of 1.0 to 3.5, and a weight average molecular weight of 500 to 50, An amorphous thermoplastic resin (B) that is less than 000, the total amount of the amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B) being 100% by mass, The content of the crystalline thermoplastic resin (A) is 25% by mass to 85% by mass, the content of the amorphous thermoplastic resin (B) is 15% by mass to 75% by mass, and the following requirements Thermoplastic resin composition satisfying (1) and requirement (2):
Requirement (1) The glass transition temperature of the thermoplastic resin composition is 0 ° C. or higher and 200 ° C. or lower; and Requirement (2) The haze of a 1 mm thick sheet made of the thermoplastic resin composition is less than 8.0% It is.
[2] The thermoplastic resin composition further contains a crystalline thermoplastic resin (C),
The thermoplastic resin composition according to [1], wherein the total amount of the thermoplastic resin in the thermoplastic resin composition is 100% by mass, and the content of the crystalline thermoplastic resin (C) is 0.01 to 9% by mass. object.
[3] A molded article comprising the thermoplastic resin composition according to [1] or [2].

ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition which can give the molded object which is transparent and has self-repair performance, and can perform adjustment of repair temperature easily, and shaping | molding which consists of this thermoplastic resin composition The body can be provided.

Hereinafter, embodiments of the present invention will be described in detail.

In the present specification, the amorphous thermoplastic resin is a thermoplastic resin having a crystal melting enthalpy (hereinafter sometimes referred to as ΔH) observed by differential scanning calorimetry of 40 J / g or less. From the viewpoint of enhancing the self-repairing performance, ΔH of the amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B) is preferably 10 J / g or less, more preferably 1 J / g or less.
In this specification, the melting enthalpy is obtained by analyzing a portion in the temperature range of −50 ° C. or higher and 200 ° C. or lower of a melting curve measured by the following differential scanning calorimetry by a method based on JIS K7122. Heat of fusion.
[Differential scanning calorimetry]
By means of a differential scanning calorimeter, an aluminum pan encapsulating about 5 mg of sample in a nitrogen atmosphere was (1) held at 200 ° C. for 5 minutes, then (2) from 200 ° C. to −50 at a rate of 10 ° C./min. Then, the temperature is lowered to (3) -50 ° C for 5 minutes, and (4) the temperature is raised from -50 ° C to 200 ° C at a rate of 10 ° C / min. The differential scanning calorimetry curve obtained by calorimetry in step (4) is taken as the melting curve.

Next, a specific configuration of the thermoplastic resin composition of the present invention will be described.

The thermoplastic resin composition of the present invention contains an amorphous thermoplastic resin (A) having a weight average molecular weight of 50,000 to 500,000 and a molecular weight distribution of 1.0 to 3.5. .

The weight average molecular weight of the amorphous thermoplastic resin (A) is 50,000 or more and 500,000 or less, and the self-repairing performance and molding processability are improved, and the rigidity of the molded body made of the resin composition is increased. From the viewpoint, it is preferably 75,000 or more and 400,000 or less, more preferably 100,000 or more and 300,000 or less.

The viewpoint of the molecular weight distribution of the amorphous thermoplastic resin (A) being 1.0 or more and 3.5 or less, improving the self-repairing performance and molding processability, and increasing the rigidity of the molded body made of the resin composition. Therefore, it is preferably 1.0 or more and 3.0 or less, and more preferably 1.0 or more and 2.5 or less. The molecular weight distribution is the ratio of the weight average molecular weight to the number average molecular weight.
In this specification, the weight average molecular weight is a polystyrene equivalent weight average molecular weight measured by gel permeation chromatography, and the molecular weight distribution is a polystyrene equivalent number average measured by gel permeation chromatography. It is the ratio of the weight average molecular weight in terms of polystyrene to the molecular weight. A polymer soluble in chloroform is subjected to gel permeation chromatography using chloroform as a solvent. Of the olefin resins described below, those insoluble in chloroform are dissolved in xylene and then subjected to gel permeation chromatography using chloroform as a solvent.

The melt flow rate of the amorphous thermoplastic resin (A) measured at a temperature of 190 ° C. and a load of 21 N in accordance with JIS K7210 is preferably 0.01 g / 10 minutes from the viewpoint of improving moldability. As mentioned above, More preferably, it is 0.05 g / 10min or more, More preferably, it is 0.1 g / 10min or more. The melt flow rate of the amorphous thermoplastic resin (A) is preferably 500 g / 10 min or less, more preferably from the viewpoint of improving the molding processability and increasing the rigidity of the molded body made of the resin composition. Is 50 g / 10 min or less, more preferably 10 g / 10 min or less.

The glass transition temperature of the thermoplastic amorphous resin (A) is preferably −70 ° C. or higher and 150 ° C. or lower, more preferably −50 ° C. or higher and 120 ° C. or lower, and further preferably −30 ° C. or higher and 100 ° C. or lower. It is below ℃.
In this specification, the glass transition temperature is an intermediate glass transition temperature obtained by analyzing a melting curve measured by the following differential scanning calorimetry method by a method based on JIS K7121.
[Differential scanning calorimetry]
By means of a differential scanning calorimeter, an aluminum pan encapsulating about 5 mg of sample in a nitrogen atmosphere was (1) held at 200 ° C. for 5 minutes, then (2) from 200 ° C. to −50 at a rate of 10 ° C./min. Then, the temperature is lowered to (3) -50 ° C for 5 minutes, and (4) the temperature is raised from -50 ° C to 200 ° C at a rate of 10 ° C / min. The differential scanning calorimetry curve obtained by calorimetry in step (4) is taken as the melting curve.

Examples of the amorphous thermoplastic resin (A) include olefin resins, styrene elastomers, acrylic resins, polyester resins, polyamide resins, styrene / acrylonitrile resins, engineering plastics, polyvinyl chloride, chlorinated rubber, natural rubber, and chloroprene. Examples thereof include rubber, fluorine rubber, silicon rubber, and urethane rubber. Among these, olefin resin, styrene elastomer, acrylic resin, and engineering plastic are preferable. These may be used alone or in combination of two or more. Moreover, the amorphous thermoplastic resin (A) may be cross-linked. The copolymer exemplified below may be a random copolymer or a block copolymer.

The olefin resin is a resin containing monomer units derived from olefins. Examples of the olefin resin include amorphous propylene resin, amorphous ethylene resin, amorphous cyclic olefin resin, butyl rubber, polybutadiene, and isoprene resin.
The amorphous propylene resin is a polymer containing monomer units derived from propylene and having a ΔH of 40 J / g or less. Amorphous propylene resins include propylene homopolymer, propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer , Propylene-vinylcyclohexane copolymer, propylene-4-vinylcyclohexene copolymer, propylene-norbornene copolymer, propylene-styrene copolymer, maleic anhydride modified propylene homopolymer, maleic anhydride modified propylene-ethylene copolymer Polymer, maleic anhydride modified propylene-butene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer, ethylene-propylene-1-octene copolymer, ethylene-propylene -4-methyl-1-pentene copolymer, Tylene-propylene-styrene copolymer, ethylene-propylene-norbornene copolymer, ethylene-propylene-4-vinylcyclohexene copolymer, ethylene-propylene-vinylcyclohexane copolymer, ethylene-propylene-5-ethylidene-2- Norbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-1,4-hexadiene copolymer, ethylene-propylene-5-vinyl-2-norbornene copolymer, maleic anhydride modified ethylene- And propylene-butene copolymer. The amorphous propylene resin is, for example, an atactic propylene resin.
The amorphous ethylene resin is a polymer containing 100% by mass of the amorphous ethylene resin, containing 50% by mass or more of monomer units derived from ethylene, and ΔH of 40 J / g or less. Amorphous ethylene resins include ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene- Vinylcyclohexane copolymer, ethylene-4-vinylcyclohexene copolymer, ethylene-norbornene copolymer, ethylene-tetracyclododecene copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer Ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and the like.
The amorphous cyclic olefin resin is a polymer having a mass of the cyclic olefin resin of 100% by mass, containing 50% by mass or more of monomer units derived from the cyclic olefin, and a ΔH of 40 J / g or less. Examples of the amorphous cyclic olefin resin include a norbornene ring-opening polymer, a tetracyclododecene ring-opening polymer, a norbornene-ethylene copolymer, a tetracyclododecene-ethylene copolymer, and the like.
Examples of the isoprene resin include polyisoprene, a copolymer of a C10 alicyclic compound that is a dimerized product of isoprene and a C10 chain compound, and the like.
The olefin resin is preferably an amorphous propylene resin, more preferably a propylene homopolymer, a propylene-1-butene copolymer, or an ethylene-propylene-1-butene copolymer.

Examples of the styrene elastomer include styrene-butadiene-styrene triblock copolymer (SBS), styrene-isoprene-styrene triblock copolymer (SIS), styrene-butadiene random copolymer (SBR), and styrene- Isobutylene-styrene block copolymers (SIBS), hydrogenated products in which some or all of the carbon-carbon double bonds of these SBS copolymers are hydrogenated, maleic anhydride modified styrene-isoprene-styrene block copolymers Examples thereof include a polymer (MAH-SIS) and a maleic anhydride-modified styrene-butadiene-styrene block copolymer (MAH-SBS).
These hydrogenated products include styrene- (ethylene / propylene) -styrene block copolymer (SEPS; SIS hydrogenated product), styrene- (ethylene / butylene) -styrene block copolymer (SEBS; hydrogenated SBS). ), Styrene-ethylene- (ethylene / propylene) -styrene block copolymer (SEEPS; hydrogenated styrene-butadiene / isoprene-styrene block copolymer), hydrogenated SBR, maleic anhydride modified styrene- ( And ethylene / butylene) -styrene block copolymer (MAH-SEBS), maleic anhydride-modified styrene- (ethylene / propylene) -styrene block copolymer (MAH-SEPS), and the like.
Among them, a styrene-butadiene-styrene triblock copolymer, a styrene-isoprene-styrene triblock copolymer, a styrene-butadiene random copolymer, a styrene- (ethylene / propylene) -styrene block copolymer, A styrene- (ethylene / butylene) -styrene block copolymer, a hydrogenated product in which part or all of these carbon-carbon double bond portions are hydrogenated.

Examples of the acrylic resin include polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, methyl acrylate-methyl methacrylate copolymer, and the like. . Of these, polybutyl methacrylate and polybutyl acrylate are preferable.

Examples of the polyester resin include amorphous polyethylene terephthalate.

Examples of the polyamide resin include amorphous polyamide.

Examples of the styrene / acrylonitrile resin include polystyrene, α-methylstyrene-vinyltoluene copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-acrylonitrile-indene copolymer, polyacrylonitrile and the like. Can be mentioned.

Examples of the engineering plastic include polysulfone, polyethersulfone, polyarylate, polyamideimide, polyetherimide, modified polyphenylene ether, and polycarbonate. Of these, polycarbonate is preferable.

The thermoplastic resin composition of the present invention contains an amorphous thermoplastic resin (B) having a weight average molecular weight of 500 or more and less than 50,000.

The weight average molecular weight of the amorphous thermoplastic resin (B) is 500 or more and less than 50,000, and is preferably 700 from the viewpoint of improving self-healing performance, increasing the strength of the molded product, and suppressing tackiness. It is 40,000 or less, and more preferably 900 or more and 30,000 or less.

The glass transition temperature of the amorphous thermoplastic resin (B) is preferably 0 ° C. or higher and 200 ° C. or lower, more preferably 30 ° C. or higher and 150 ° C. or lower, and further preferably 40 ° C. or higher and 120 ° C. or lower. is there.

The molecular weight distribution of the amorphous thermoplastic resin (B) is preferably 1.0 or more and 4.5 or less, more preferably 1.0 or more, from the viewpoint of increasing the strength of the molded body and suppressing the adhesiveness. 4.0 or less, more preferably 1.0 or more and 3.5 or less.

Examples of the amorphous thermoplastic resin (B) in the present invention include the olefin resin, styrene elastomer, acrylic resin, polyester resin, polyamide resin, styrene / acrylonitrile resin, engineering plastic, polyvinyl chloride, and chlorinated rubber. Natural rubber, chloroprene rubber, fluorine rubber, silicon rubber, urethane rubber, rosin resin, terpene resin, petroleum resin, coumarone resin, xylene resin, styrene / maleic anhydride resin, and the like. Among them, rosin resin, terpene resin, styrene-maleic anhydride resin and the like are preferable. These may be used alone or in combination of two or more. The amorphous thermoplastic resin (B) may be cross-linked. When the amorphous thermoplastic resin (B) is a copolymer, the copolymer may be a random copolymer or a block copolymer.

Examples of the rosin resin include natural rosin, polymerized rosin, partially hydrogenated rosin, fully hydrogenated rosin, esterified products of these rosins (for example, glycerin ester, pentaerythritol ester, ethylene glycol ester, methyl ester), rosin derivatives (for example, Disproportionated rosin, fumarized rosin, lime rosin).

Examples of the terpene resin include homopolymers of cyclic terpenes such as α-pinene, β-pinene, and dipentene, copolymers of cyclic terpenes, and copolymers of cyclic terpenes and phenolic compounds such as phenol and bisphenol (for example, Terpene-phenol resins such as α-pinene-phenol resins, dipentene-phenol resins and terpene-bisphenol resins), aromatic modified terpene resins which are copolymers of cyclic terpenes and aromatic monomers, and carbons thereof A hydrogenated terpene resin which is a hydrogenated product in which part or all of the intercalated double bond portion is hydrogenated can be mentioned.

Examples of the petroleum resin include homopolymers and copolymers of naphtha cracked oil C5 fraction, C6 to C11 fraction and other olefinic fractions, and carbon-carbon double bond portions of these homopolymers and copolymers. Examples thereof include aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, and aliphatic-alicyclic copolymer resins, which are hydrogenated products in which a part or all of them are hydrogenated. The synthetic petroleum resin further includes a copolymer of naphtha cracked oil and the above terpene, and a copolymer petroleum resin that is a hydrogenated product of the copolymer.

Examples of the coumarone resin include a polymer having one or more monomer units selected from the group consisting of coumarone, indene and styrene.

The thermoplastic resin composition of the present invention is the amorphous thermoplastic resin (A), wherein the total amount of the amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B) is 100% by mass. Is 25 mass% or more and 85 mass% or less, and content of the said amorphous thermoplastic resin (B) is 15 mass% or more and 75 mass% or less. From the viewpoint of the strength of the molded body made of the thermoplastic resin, the content of the amorphous thermoplastic resin (A) is preferably 30% by mass or more, more preferably 35% by mass or more. From the viewpoint of the self-healing performance of the molded body made of the thermoplastic resin, the content of the amorphous thermoplastic resin (A) is preferably 80% by mass or less, more preferably 70% by mass or less.

The thermoplastic resin composition of the present invention satisfies the requirements (1) and (2).
Requirement (1) The glass transition temperature of the thermoplastic resin composition of the present invention is 0 ° C. or higher and 200 ° C. or lower.
The glass transition temperature of the thermoplastic resin composition is preferably 0 ° C. or higher and 150 ° C. or lower, more preferably 0 ° C. or higher and 100 ° C. or lower.
In order for the thermoplastic resin composition of the present invention to satisfy the requirement (1), only one glass transition temperature of the thermoplastic resin composition is observed within a temperature range of −50 ° C. to 200 ° C. Is preferred. Only one glass transition temperature of the thermoplastic resin composition is observed within a temperature range of −50 ° C. or higher and 200 ° C. or lower, which means that the thermoplastic resin contained in the thermoplastic resin composition is compatible. Means that

Requirement (2) The haze of a sheet having a thickness of 1 mm made of a thermoplastic resin composition is less than 8.0%.
The haze is preferably less than 7%, more preferably less than 5%.
The amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B) are in phase so that the haze of the 1 mm thick sheet made of the thermoplastic resin composition of the present invention is less than 8.0%. Select a combination to dissolve. When the thermoplastic resin composition further contains a crystalline thermoplastic resin (C) described later, the crystallinity is set so that the haze of the 1 mm thick sheet made of the thermoplastic resin composition is less than 8.0%. The content of the thermoplastic resin (C) is adjusted. The crystalline thermoplastic resin (C) and the amorphous thermoplastic resin (A) are amorphous so that the haze of the 1 mm thick sheet made of the thermoplastic resin composition of the present invention is less than 8.0%. It is preferable to be compatible with the thermoplastic resin (B).

The combination of the amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B) contained in the thermoplastic resin composition of the present invention includes olefin resin and olefin resin, styrene elastomer and styrene elastomer, acrylic Resin and acrylic resin, polycarbonate and polycarbonate, olefin resin and rosin resin, olefin resin and terpene resin, olefin resin and petroleum resin, styrene elastomer and rosin resin, styrene elastomer and terpene resin, styrene elastomer and petroleum resin, acrylic resin And rosin resin, acrylic resin and terpene-phenol resin, polycarbonate and styrene-maleic anhydride resin.

The melt flow rate of the thermoplastic resin composition of the present invention measured at a temperature of 190 ° C. and a load of 21 N in accordance with JIS K7210 is preferably 0.05 to 300 g / 10 minutes, more preferably 0.1 to It is 200 g / 10 minutes, and more preferably 0.2 to 100 g / 10 minutes.

The thermoplastic resin composition of the present invention may contain a crystalline thermoplastic resin (C) in order to increase the rigidity of the molded body made of the thermoplastic resin composition.
In the present specification, the crystalline thermoplastic resin is a thermoplastic resin having a ΔH greater than 40 J / g. The ΔH of the crystalline thermoplastic resin (C) is preferably 80 J / g or more.

As said crystalline thermoplastic resin (C), crystalline olefin resin, wax, and paraffin are mentioned.
A crystalline olefin resin is a polymer containing monomer units derived from olefins and having a ΔH greater than 40 J / g.
Examples of the crystalline olefin resin include crystalline propylene resin and crystalline ethylene resin.
The crystalline propylene resin is a polymer containing monomer units derived from propylene and having a ΔH of greater than 40 J / g. The crystalline propylene resin includes a propylene homopolymer, a propylene copolymer containing a monomer unit derived from propylene, and a monomer unit selected from the group consisting of ethylene and an α-olefin having 4 to 10 carbon atoms. A polymer is mentioned. Examples of the propylene-based copolymer include a propylene-ethylene copolymer. The propylene-based copolymer may be a random copolymer or a block copolymer. The crystalline propylene resin may be modified with at least one compound selected from unsaturated carboxylic acids and derivatives thereof. The at least one compound selected from unsaturated carboxylic acids and derivatives thereof includes maleic anhydride.
The crystalline ethylene resin is a polymer containing 50% by mass or more of monomer units derived from ethylene with a mass of the crystalline ethylene resin of 100% by mass and a ΔH of greater than 40 J / g. Examples of the crystalline ethylene resin include high-density polyethylene, high-pressure low-density polyethylene, and ethylene-α-olefin copolymer. The crystalline ethylene resin may be modified with at least one compound selected from unsaturated carboxylic acids and derivatives thereof. The at least one compound selected from unsaturated carboxylic acids and derivatives thereof includes maleic anhydride.
These resins may be used alone or in combination of two or more. The crystalline thermoplastic resin (C) may be cross-linked.

As one aspect, from the viewpoint of increasing the rigidity of the obtained molded body, the total amount of the thermoplastic resin in the thermoplastic resin composition is 100% by mass, and the content of the crystalline thermoplastic resin (C) is 0. The content is preferably 0.01 to 9% by mass, more preferably 0.01 to 8% by mass, and still more preferably 0.01 to 6% by mass.
As one aspect, from the viewpoint of increasing the flexibility of the obtained molded body, the total amount of the thermoplastic resin in the thermoplastic resin composition is 100% by mass, and the content of the crystalline thermoplastic resin (C) is as follows. The content is preferably 0 to less than 0.01% by mass.

In the thermoplastic resin composition of the present invention, if necessary, an antioxidant, an ultraviolet absorber, a crosslinking agent, a thermal stabilizer, a photodegradation inhibitor, an impact modifier, a plasticizer, a lubricant, a mold release agent, Nucleating agents, halogen-based flame retardants and non-halogen (polyphosphoric acid-based, red phosphorus-based, etc.) flame retardants, flame retardant aids, colorants such as pigments and dyes, mineral oil-based softeners, foaming agents, processing aids, An antistatic material or the like may be added.
The total amount of the thermoplastic resin composition of the present invention is 100% by mass, and the total content of the amorphous thermoplastic resin (A), the amorphous thermoplastic resin (B), and the crystalline thermoplastic resin (C). The amount is preferably 90% by mass or more, more preferably 91% by mass or more, further preferably 95% by mass or more, and further preferably 98% by mass or more.

As one aspect of the present invention, the following thermoplastic resin composition and molded article are also included.
[4] Amorphous thermoplastic resin (A) having a weight average molecular weight of 50,000 to 500,000 and a molecular weight distribution of 1.0 to 3.5, and a weight average molecular weight of 500 to 50, Amorphous thermoplastic resin (B) that is less than 000, no filler, and the total amount of the amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B). As 100 mass%, the content of the amorphous thermoplastic resin (A) is 25 mass% or more and 85 mass% or less, and the content of the amorphous thermoplastic resin (B) is 15 mass% or more and 75 mass%. % Thermoplastic resin composition satisfying the following requirement (1) and requirement (2):
Requirement (1) The glass transition temperature of the thermoplastic resin composition is 0 ° C. or higher and 200 ° C. or lower; and Requirement (2) The haze of a 1 mm thick sheet made of the thermoplastic resin composition is less than 8.0% It is.
[5] The thermoplastic resin composition further contains a crystalline thermoplastic resin (C),
The thermoplastic resin composition according to [4], wherein the total amount of the thermoplastic resin in the thermoplastic resin composition is 100% by mass, and the content of the crystalline thermoplastic resin (C) is 0.01 to 9% by mass. object.
[6] A molded article comprising the thermoplastic resin composition according to [4] or [5].
Examples of the filler include inorganic fillers and organic fillers.

The thermoplastic resin composition is obtained by melt-mixing an amorphous thermoplastic resin (A), an amorphous thermoplastic resin (B), and a crystalline thermoplastic resin (C) as necessary. can get. The method of melt mixing is not particularly limited, and examples thereof include known mixing methods, for example, a mixing method using an extruder, an open roll mill, a Banbury mixer, a kneader, or a melt mixing tank. The temperature at the time of melt mixing is usually from 100 to 250 ° C., preferably from 130 to 200 ° C.

The molded body composed of the thermoplastic resin composition can self-repair not only the surface of the molded body but also the internal damage of the molded body.

The shape of the molded body includes a sheet, mat, film, pipe, tube, container, net, fiber, connector and the like.

Examples of the method for producing the molded body include injection molding, injection compression molding, press molding, and extrusion molding.

The above thermoplastic resin composition may be dissolved in a good solvent and used as a coating liquid. A coating film formed by applying the coating liquid to a substrate and removing the solvent from the obtained coating film is also an example of the molded body.

When the molded body composed of the thermoplastic resin composition is a sheet, the sheet composed of the thermoplastic resin composition may be used as a single layer, or the sheet composed of the thermoplastic resin composition is used as at least one layer. You may use as a multilayer sheet containing. When the multilayer sheet is a multilayer sheet having three or more layers, an adhesive layer may be provided as one layer.
The thickness of the sheet made of the thermoplastic resin composition is not particularly limited, but is usually 0.5 to 500 mm. In a multilayer sheet including the sheet made of the thermoplastic resin composition as at least one layer, the thickness of the layer made of the sheet made of the thermoplastic resin composition is usually 0, with the thickness of the multilayer sheet being 100%. 0.01 to 99.99%.

When the molded body made of the thermoplastic resin composition is a film, the film made of the thermoplastic resin composition may be used as a single layer, or the film made of the thermoplastic resin composition is used as at least one layer. It may be used as a multilayer film. When the multilayer film is a multilayer film having three or more layers, an adhesive layer may be provided as one layer.
The thickness of the film made of the thermoplastic resin composition is not particularly limited, but is usually 10 to 500 μm. In a multilayer film including the film composed of the thermoplastic resin composition as at least one layer, the thickness of the multilayer film is 100%, and the thickness of the layer composed of the film composed of the thermoplastic resin composition is usually 0. 0.01 to 99.99%.

In the above-mentioned multilayer film or multilayer sheet, the layer composed of the film or sheet made of the thermoplastic resin composition of the present invention is applied by applying a coating liquid containing the thermoplastic resin composition of the present invention to the substrate. It may be a layer formed by removing the solvent from the film.
In the above multilayer film or multilayer sheet, the resin constituting the layer different from the layer composed of the film or sheet made of the thermoplastic resin composition of the present invention includes olefin resin, acrylic resin, styrene / acrylonitrile resin, polysulfone. , Polyethersulfone, polyetheretherketone, polyester resin, polyamide resin, polyamideimide, polyimide, polyphenylene ether, polyphenylene sulfide, polyacetal, polycarbonate, polyarylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyurethane, fluorine-based Examples thereof include resins, rubbers, liquid crystal polymers, epoxy resins, melamine resins, urea resins, phenol resins, and silicon resins.
Examples of the olefin resin include ethylene resin, propylene resin, polybutene resin, and poly (4-methyl-1-pentene) resin. The olefin resin may be modified with at least one compound selected from unsaturated carboxylic acids and derivatives thereof. The olefin resin may be an amorphous olefin resin or a crystalline olefin resin.
Examples of the ethylene resin include high-density polyethylene, high-pressure low-density polyethylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene -Methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-acrylic acid ester-glycidyl methacrylate copolymer.
Examples of the styrene / acrylonitrile resin include polystyrene, styrene-acrylonitrile copolymer, and styrene-acrylonitrile-butadiene copolymer.
Examples of the polyester resin include polyethylene terephthalate and polybutylene terephthalate.
Rubbers include natural rubber, polybutadiene rubber, polyacrylonitrile rubber, acrylonitrile-butadiene copolymer rubber, partially hydrogenated acrylonitrile-butadiene copolymer rubber, butyl rubber, chloroprene rubber, fluoro rubber, chlorosulfonated polyethylene, silicon rubber, Examples thereof include urethane rubber, isobutylene-isoprene copolymer rubber, halogenated isobutylene-isoprene copolymer rubber, chlorinated rubber, and styrene rubber.

Examples of the method for producing the multilayer film or multilayer sheet include a coextrusion inflation molding method, a coextrusion T-die casting molding method, a dry laminating method, a wet laminating method, a sand laminating method, and a hot melt laminating method.

The molded body may be subjected to surface treatment such as corona discharge treatment, flame treatment, plasma treatment, ozone treatment on the surface of the molded body. Moreover, in the manufacturing method of said multilayer film or multilayer sheet, you may perform the said surface treatment to at least one layer before lamination | stacking.
The molded body may be coated on the surface of the molded body. Coating treatment includes antistatic treatment, insulating treatment, conductive treatment, antiglare treatment, antireflection treatment, antifogging treatment, rustproofing treatment, waterproof treatment, antifouling treatment, antibacterial treatment, water repellent treatment, hydrophilic treatment, oil repellent treatment Treatment, water / oil repellency treatment, hydrophilic / lipophilic treatment, hard coat treatment, gas barrier treatment, sound absorption / vibration treatment, high refractive index treatment, scratch resistance treatment, weather resistance treatment, mold release treatment, biocompatibility treatment, etc. .

The use of the molded product of the present invention will be described below.
Specific applications include sealing materials, heat insulation materials, soundproofing materials, shoe soles, packaging materials, coating materials, patches, bandages, hose clips, fluid transport pipes, flexible hoses, asphalt additives, hot melt adhesives, and adhesives Additives for agents, articles that generally need to exhibit good fracture resistance and / or fatigue resistance, and the like.

Optical applications include optical films, optical sheets, optical filters, high-intensity prism sheets, optical condensing spheres, antireflection optical articles, light controllable laminates, transparent daylighting materials, antiglare films, protective films, and pen input. Examples include surface materials for devices.

Electrical equipment relations include electrical cables, sheaths, wire coating materials, electrical insulation members, electronic equipment casings, machine parts, vibration-resistant fatigue members, capacitors, solid electrolytes, and the like.

Tire materials include tire tubes and tire puncture sealing.

Others include fiber reinforced materials, rust preventives, corrosion inhibitors, spray pigments, paints such as barrier materials (organic matter, gas, humidity), pet building materials, building materials such as floors, walls, doors, waterproof sheets, waterproofing Sheet, Actuator, Cleaning pad, Automobile material, Artificial leather, Synthetic leather, Artificial skin, Endovascular stent, Septum, Dental composite restoration material, Sleeve material, Laminated glass, Transfer foil, Flame retardant film, Writing instrument shaft Tube, cushion material, cushioning agent, agricultural film, decorative film, decorative sheet, greenhouse sheet, insect net, furniture, clothes, bag, shoes, sports equipment, container, cutting board, cutting board, antibacterial film, antibacterial molding Body, barrier film, packing and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Measurement and evaluation method]

(1) Melting point, glass transition point (Tg, unit: ° C)
With a differential scanning calorimeter (TA Instruments, DSC Q100), under an atmosphere of nitrogen, an aluminum pan containing about 5 mg of sample was held at (1) 200 ° C. for 5 minutes, and then (2) 10 ° C. / The temperature is lowered from 200 ° C to -50 ° C at a rate of minutes, then (3) held at -50 ° C for 5 minutes, and then (4) the temperature is raised from -50 ° C to about 200 ° C at a rate of 10 ° C / minute did. The differential scanning calorimetry curve obtained by calorimetry in step (4) was taken as the melting curve. The melting curve was analyzed by a method based on JIS K7121, and the melting point and glass transition temperature were determined.
The melting enthalpy ΔH (J / g) was obtained by analyzing the melting curve by a method based on JIS K7122.

(2) Molecular weight, molecular weight distribution After calibrating with a polystyrene standard substance using a gel permeation chromatograph (GPC), a molecular weight distribution curve was measured under the following conditions. The molecular weight distribution was evaluated by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). A thermoplastic resin soluble in chloroform was dissolved in chloroform, and a molecular weight distribution curve was measured under the following conditions. The best plast, which is hardly soluble in chloroform, was dissolved in xylene, and the molecular weight distribution curve was measured under the following conditions. For TOPAS 9506, the molecular weight distribution curve was measured under the same conditions as described below except that one separation column was used.
<Conditions>
Equipment: SHIMADZU LC
Separation column: 2 Agilent Polypores Measurement temperature: 30 ° C
Eluent: Chloroform flow rate: 1.0 mL / min Sample solution concentration: about 1 mg / 1 mL
Sample injection volume: 100 μL
Detector: Differential refraction

(3) Styrene content in polymer ¹ H NMR measurement of the polymer was performed to calculate the styrene content in the polymer.
Apparatus: Nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., JNM-AL400)
Measuring solvent: Deuterated chloroform Measuring temperature: 35 ° C

(4) Melt flow rate (MFR, unit: g / 10 minutes)
According to the method defined in JIS K7210, measurement was performed by the A method under the conditions of a load of 21 N and a temperature of 190 ° C. or 230 ° C.

(5) Production of a press sheet (thickness: 1 mm) of the resin composition The obtained composition was sandwiched between a PET film or a release PET film, an aluminum plate, and a steel plate, and a hot press at 190 ° C. for 5 minutes. After preheating, the pressure was applied for 5 minutes. After completion of pressurization, the sheet was cooled with a cooling press at 30 ° C. to obtain a press sheet. At this time, the thickness of the press sheet was adjusted to 1 mm using a steel spacer.

(6) Punching workability (formability)
When the press sheet (thickness 1 mm) obtained by the above (5) was punched with a punching blade for producing a dumbbell-shaped No. 2 test piece of JIS K6251, the one that was not broken was represented by the symbol “◯” and cracked. The product was designated as “x crack”, and the press sheet was highly sticky and could not be punched out.
Those that are cracked at the time of punching, or those that are highly sticky and cannot be punched cannot be used as a molded body.

(7) Haze per 1 mm thickness (unit%)
Using the press sheet (thickness 1 mm) obtained by the above (5), haze was measured using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7105. The smaller the haze, the better the film is.

(8) Repair rate evaluation (tensile test)
A dumbbell-shaped No. 2 type test piece of JIS K6521 was produced from the press sheet obtained by the above (5). A 50% cut in the thickness direction perpendicular to the parallel part of the test piece was applied to the center of the obtained test piece with a cutter knife (OLFA, non-slip H type, product number: 151BG), and a scratch test was performed. A piece was made. What was heated for 17 hours at a predetermined temperature with a blow dryer was used as a test piece after repair. Each test piece was subjected to a tensile test using a tensile testing machine (RTF-1325-PL-WS, manufactured by A & D) at a distance between grips of 60 mm and a speed of 100 mm / min. The measurement was performed at a temperature of 23 ° C. ± 2 ° C. and a humidity of 50% ± 5%. In addition, the said tension test was complete | finished when the distance between grips became 600 mm, even if the test piece did not cut | disconnect for the convenience of an apparatus.
The initial elastic modulus (Young's modulus) was measured from the slope of the tangent at the zero point of the tensile-stress curve by a method according to JIS K7161, and the elongation at break was measured by a method according to JIS K6521.
The repair rate was calculated by the following equation using the elongation at break of the scratch-free test piece, the scratched test piece, and the post-repair test piece.
Repair rate (%) = ((Elongation when cutting a sample after repair) − (Elongation when cutting a damaged sample)) / ((Elongation when cutting without a scratch) − (Elongation when cutting with a wound)) × 100
Hereinafter, the repair rate calculated by measuring elongation at break using a test piece heated at 40 ° C. for 17 hours in a blow dryer is referred to as a repair rate (40 ° C.). The repair rate calculated by measuring the elongation at break using a test piece heated at 80 ° C. for 17 hours in a blow dryer is referred to as the repair rate (80 ° C.).

[Synthesis Example 1] Synthesis of amorphous propylene-1-butene copolymer In a 100 L SUS polymerizer equipped with a stirrer, propylene and 1-butene were used as molecular weight regulators and hydrogen as the following method. To obtain an amorphous propylene-1-butene copolymer.
From the bottom of the polymerization vessel, hexane as a polymerization solvent was continuously fed at a feed rate of 100 L / hr, propylene was fed at a feed rate of 24.00 kg / hr, and 1-butene was fed at a feed rate of 1.81 kg / hr. Supplied.
From the top of the polymerization vessel, the reaction mixture was continuously withdrawn so that the reaction mixture in the polymerization vessel maintained an amount of 100 L.
From the lower part of the polymerization vessel, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride as a component of the polymerization catalyst at a supply rate of 0.005 g / hour, Triphenylmethyltetrakis (pentafluorophenyl) borate was continuously fed at a feed rate of 0.298 g / hr and triisobutylaluminum was fed at a feed rate of 2.315 g / hr.
The copolymerization reaction was carried out at 45 ° C. by circulating cooling water through a jacket attached to the outside of the polymerization vessel.
A small amount of ethanol was added to the reaction mixture continuously extracted from the upper part of the polymerization vessel to stop the polymerization reaction, and then the monomer was removed and washed with water. Next, the solvent was removed with steam in a large amount of water, and further dried under reduced pressure at 80 ° C. for 24 hours to obtain an amorphous propylene-1-butene copolymer. The production rate of the copolymer was 7.10 kg / hour.
As a result of analyzing the obtained amorphous propylene-1-butene copolymer, the content of 1-butene was 4 mol%, Mw 219000, Mw / Mn = 2.1, ΔH = 0 J / g, MFR = 3 g / 10 minutes (190 ° C., 21 N).

[Synthesis Example 2] Synthesis of Styrene-Butadiene Copolymer After heating and drying, a stirrer was placed in an eggplant-shaped flask having an internal volume of 300 ml substituted with nitrogen, and 146 mL of tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) and styrene (Tokyo Kasei). Kogyo Co., Ltd.) 24 mL was added, and then 130 mL of a butadiene toluene solution (Aldrich, butadiene concentration 20 mass%) was added. Add n-butyllithium n-hexane solution (Tokyo Chemical Industry Co., Ltd., n-butyllithium concentration 1.6 mol / L) until it is colored, scavenge impurities contained in the system, add 0.05 mL, 30 Polymerization was started by raising the temperature to 0 ° C. After 300 minutes, 1 mL of Echinen F-6 (Nihon Alcohol Sales) was added to stop the polymerization. After the termination of the polymerization, 600 mL of toluene was added to the tetrahydrofuran solution containing the polymer, and the resulting solution was washed with about 500 mL of pure water until the solution became neutral. The polymer was precipitated by adding the washing liquid into Echinen F-6, and the polymer separated by filtration was further washed twice with Echinen F-6. The obtained polymer was vacuum dried at 80 ° C. to obtain 35 g of a polymer. As a result of analyzing the obtained polymer, the styrene content was 34 mol%, Mw 663,000, Mw / Mn = 3.3, Tg = 26 ° C., and ΔH = 0J. The MFR could not be measured because the sample did not flow under the conditions of 190 ° C. and 21N.

Synthesis Example 3 Synthesis of Styrene-Butadiene Copolymer 115 mL of tetrahydrofuran, 28 mL of styrene, 120 mL of toluene solution of butadiene (Aldrich, butadiene concentration 20% by mass), 37.5 mL of n-hexane solution of n-butyllithium The synthesis was performed in the same manner as in Synthesis Example 2 except that the polymerization time was 120 minutes. 40 g of polymer was obtained. As a result of analyzing the obtained polymer, the styrene content was 39 mol%, Mw 27,000, Mw / Mn = 1.2, Tg = 35 ° C., and ΔH = 0J.

[Synthesis Example 4] Synthesis of Sulfonated Styrene-Butadiene Copolymer Sodium Salt Sulfonation of the polymer obtained in Synthesis Example 3 is described in J. Am. App. Polym. Sci. , Vol. 96, 1398, (2005). It carried out according to. As a result of measuring the sulfonation rate, it was 31 mmol-OH / 100 g-polymer. Neutralization of the sulfonated styrene-butadiene copolymer is described in Macromolecules, Vol. 40, 6401, (2007). It carried out according to. Sodium acetate was added so that the degree of neutralization was 100. The MFR of the obtained sulfonated styrene-butadiene copolymer sodium salt was measured and found to be 1000 or more (190 ° C., 21 N).

[Example 1]
39% by mass of the amorphous propylene-1-butene copolymer produced in Synthesis Example 1 as the amorphous thermoplastic resin (A), and the hydrogenated terpene resin “Clearon P— as the amorphous thermoplastic resin (B). 105 ”(manufactured by Yasuhara Chemical Co., Ltd.) and 3% by mass of“ Sumitomo Nobrene FLX80E4 ”as the crystalline thermoplastic resin (C), kneader (Toyo Seiki Laboplast Mill (C model), mixer: R- 100H), kneading was performed under the conditions of a resin temperature at the time of kneading of 190 ° C., a kneading time of 5 minutes, and a screw rotation speed of 80 rpm to obtain a resin composition. MFR of the obtained resin composition was 50 g / 10min (190 degreeC, 21N), and Tg was 3.2 degreeC. The press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 100%, Young's modulus 59 MPa, and haze 3.4%.

[Example 2]
48% by mass of the amorphous propylene-1-butene copolymer produced in Synthesis Example 1 as the amorphous thermoplastic resin (A), and the hydrogenated terpene resin “Clearon P— as the amorphous thermoplastic resin (B). 150 ”(manufactured by Yasuhara Chemical Co., Ltd.) 48% by mass, and 4% by mass of“ Sumitomo Nobrene FLX80E4 ”was used as the crystalline thermoplastic resin (C). MFR of the obtained resin composition was 22 g / 10min (190 degreeC, 21N), and Tg was 9.1 degreeC. The press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 74%, the repair rate (40 ° C.) was 0%, the Young's modulus was 250 MPa, and the haze was 4.0%.

[Example 3]
57% by mass of the amorphous propylene-1-butene copolymer produced in Synthesis Example 1 as the amorphous thermoplastic resin (A), and the hydrogenated terpene resin “Clearon P— as the amorphous thermoplastic resin (B). 105 ”38% by mass and 5% by mass of“ Sumitomo Nobrene FLX80E4 ”as the crystalline thermoplastic resin (C) were mixed uniformly, and a twin-screw kneader with an inner diameter of 15 mm (Technobel KZW15-45MG, inner diameter: 15 mm, L / D = 45) at a set temperature of 190 ° C. and a screw rotation speed of 500 rpm, and melted and kneaded to obtain a resin composition. MFR of the obtained resin composition was 15 g / 10min (190 degreeC, 21N), and Tg was 5.0 degreeC. The press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 100%, the repair rate (40 ° C.) was 40%, the Young's modulus was 35 MPa, and the haze was 3.7%.

[Example 4]
Styrene-isoprene-styrene block copolymer “Hibler 5127” (manufactured by Kuraray Co., Ltd.) 60% by mass as the amorphous thermoplastic resin (A), hydrogenated terpene resin “Clearon P” as the amorphous thermoplastic resin (B) The same procedure as in Example 1 was carried out except that 40% by mass of “−105” was used. MFR of the obtained resin composition was 54 g / 10min (190 degreeC, 21N), and Tg was 19.3 degreeC. The press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 61%, Young's modulus 374 MPa, and haze 7.8%.

[Example 5]
Hydrogenated styrene-isoprene-styrene block copolymer “HIBLER 7311F” (manufactured by Kuraray Co., Ltd.) 40% by mass as the amorphous thermoplastic resin (A), hydrogenated terpene resin “Amorphous thermoplastic resin (B)” The same procedure as in Example 1 was performed except that 60% by mass of Clearon P-150 was used. MFR of the obtained resin composition was 37 g / 10min (190 degreeC, 21N), and Tg was 19.4 degreeC. The press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 97%, Young's modulus 556 MPa, and haze 2.6%.

[Comparative Example 1]
40% by mass of the styrene-butadiene copolymer produced in Synthesis Example 2 as an amorphous thermoplastic resin (A) and the sulfonated styrene-butadiene produced in Synthesis Example 4 as an amorphous thermoplastic resin (B) 60% by mass of sodium salt of copolymer is kneaded twice using a small kneader (Xplore, manufactured by DSM) under conditions of a resin temperature of 130 ° C., a kneading time of 5 minutes, and a screw rotation speed of 100 rpm. A resin composition was obtained. The obtained resin composition had a Tg of 29.3 ° C. The press sheet produced from the obtained resin composition was punchable, and the repair rate (40 ° C.) was 50%, Young's modulus was 1615 MPa, and haze was 14.1%.

[Comparative Example 2]
19% by mass of the amorphous propylene-1-butene copolymer produced in Synthesis Example 1 as the amorphous thermoplastic resin (A), and the hydrogenated terpene resin “Clearon P— as the amorphous thermoplastic resin (B). The same procedure as in Example 1 was carried out except that 105 ”79% by mass and 2% by mass of“ Sumitomo Nobrene FLX80E4 ”were used as the crystalline thermoplastic resin (C). The obtained resin composition had an MFR of 2000 g / 10 min (190 ° C., 21 N) or more and a Tg of 19.6 ° C. The press sheet produced from the obtained resin composition was cracked at the time of punching, and the repair rate could not be measured. The haze was 1.4%.

[Comparative Example 3]
84% by mass of the amorphous propylene-1-butene copolymer produced in Synthesis Example 1 as the amorphous thermoplastic resin (A), and the hydrogenated terpene resin “Clearon P— as the amorphous thermoplastic resin (B). Example 10 was carried out in the same manner as in Example 1 except that 9% by mass of 105 ”and 7% by mass of“ Sumitomo Nobrene FLX80E4 ”were used as the crystalline thermoplastic resin (C). The obtained resin composition had an MFR of 6.2 g / 10 min (190 ° C., 21 N), and a Tg of −7.5 ° C. The press sheet produced from the obtained resin composition had high adhesiveness, was not stampable, and the repair rate could not be measured. The haze was 9.2%.

[Comparative Example 4]
50% by mass of propylene resin “Best Plast 703” (manufactured by Evonik) as amorphous thermoplastic resin (A) and 50% by mass of hydrogenated terpene resin “Clearon P-150” as amorphous thermoplastic resin (B) The same operation as in Example 1 was carried out except that it was used. The obtained resin composition had an MFR of 2000 g / 10 min (190 ° C., 21 N) or more, and a Tg of −2.5 ° C. The press sheet produced from the obtained resin composition was cracked at the time of punching, and the repair rate could not be measured. The haze was 15.6%.

[Comparative Example 5]
As amorphous thermoplastic resin (A), 50% by mass of propylene resin “Best Plast 708” (Evonik) and 50% by mass of hydrogenated terpene resin “Clearon P-150” as amorphous thermoplastic resin (B). The same operation as in Example 1 was carried out except that it was used. The obtained resin composition had an MFR of 2000 g / 10 min (190 ° C., 21 N) or more, and a Tg of −5.3 ° C. The press sheet produced from the obtained resin composition was cracked at the time of punching, and the repair rate could not be measured. The haze was 56.4%.

[Comparative Example 6]
50% by mass of propylene resin “Best Plast 792” (manufactured by Evonik) as amorphous thermoplastic resin (A), and 50% by mass of hydrogenated terpene resin “Clearon P-150” as amorphous thermoplastic resin (B) The same operation as in Example 1 was carried out except that it was used. The obtained resin composition had an MFR of 904 g / 10 min (190 ° C., 21 N), and a Tg of −3.1 ° C. The press sheet produced from the obtained resin composition was cracked at the time of punching, and the repair rate could not be measured. The haze was 55.0%.

[Comparative Example 7]
35% by mass of the amorphous propylene-1-butene copolymer produced in Synthesis Example 1 as the amorphous thermoplastic resin (A), and the hydrogenated terpene resin “Clearon P— as the amorphous thermoplastic resin (B). 105 ”52% by mass, 3% by mass of“ Sumitomo Nobrene FLX80E4 ”and 10% by mass of maleic anhydride-modified crystalline propylene resin“ Yumex 1010 ”(manufactured by Sanyo Chemical Industries, Ltd.) as the crystalline thermoplastic resin (C) Except for this, the same procedure as in Example 1 was performed. The obtained resin composition had an MFR of 124 g / 10 min (190 ° C., 21 N), and a Tg of 5.0 ° C. The press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 0%, Young's modulus 118 MPa, and haze 8.3%.

[Comparative Example 8]
31% by mass of the amorphous propylene-1-butene copolymer produced in Synthesis Example 1 as the amorphous thermoplastic resin (A), and the hydrogenated terpene resin “Clearon P— as the amorphous thermoplastic resin (B). 105 ”46% by mass, the same as in Example 1 except that 3% by mass of“ Sumitomo Nobrene FLX80E4 ”and 20% by mass of maleic anhydride-modified crystalline propylene resin“ Yumex 1010 ”were used as the crystalline thermoplastic resin (C). Carried out. MFR of the obtained resin composition was 321 g / 10 minutes (190 degreeC, 21N), and Tg was 7.0 degreeC. The press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 0%, Young's modulus 98 MPa, and haze 33.5%.

[Comparative Example 9]
42% by mass of propylene resin “Tufselen X1107” (manufactured by Sumitomo Chemical Co., Ltd.) as the amorphous thermoplastic resin (A), and hydrogenated petroleum resin “Arcon P-125” (Arakawa Chemical) as the amorphous thermoplastic resin (B) This was carried out in the same manner as in Example 1 except that 30% by mass of Kogyo Co., Ltd. and 28% by mass of crystalline propylene resin “Sumitomo Nobrene FLX80E4” (Sumitomo Chemical Co., Ltd.) were used as the crystalline thermoplastic resin (C). . The obtained resin composition had an MFR of 5 g / 10 min (190 ° C., 21 N), and a Tg of −13.9 ° C. The press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 0%, Young's modulus 70 MPa, and haze 10.0%.

[Comparative Example 10]
As amorphous thermoplastic resin (A), 41% by mass of the amorphous propylene-1-butene copolymer produced in Synthesis Example 1, and as the amorphous thermoplastic resin (B), a hydrogenated petroleum resin “Alcon P— 90 "(Arakawa Chemical Industries, Ltd.) 45% by mass, 4% by mass of Sumitomo Nobrene FLX80E4 as crystalline thermoplastic resin (C), and 10% by mass of petroleum wax" Paraffin Wax 155 "(Nippon Seiwa Co., Ltd.) The same procedure as in Example 1 was performed except that% was used. MFR of the obtained resin composition was 132 g / 10min (190 degreeC, 21N). The haze of the press sheet produced from the obtained resin composition was 77.2%.

[Comparative Example 11]
Hydrogenated styrene-isoprene block copolymer “Septon 2004F” (manufactured by Kuraray Co., Ltd.) 12.5% by mass as the amorphous thermoplastic resin (A), and hydrogenated terpene resin as the amorphous thermoplastic resin (B) “Clearon P-125” (manufactured by Yashara Chemical Co., Ltd.) 62.5% by mass, and crystalline propylene resin “Wintech WFX4” (manufactured by Nippon Polypro Co., Ltd.) 25% by mass was used as the crystalline thermoplastic resin (C). Was carried out in the same manner as in Example 1. MFR of the obtained resin composition was 196 g / 10min (190 degreeC, 21N), and Tg was 2.2 degreeC. The press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 0%, Young's modulus 1100 MPa, and haze 36.1%.

[Comparative Example 12]
As the amorphous thermoplastic resin (A), 5.6% by mass of the propylene resin “Tough Selenium X1107”, as the amorphous thermoplastic resin (B), 55.5% by mass of the hydrogenated terpene resin “Clearon P-125”, crystalline Example except that 16.7% by mass of crystalline propylene resin “Wintech WFX4” and 22.2% by mass of crystalline propylene resin “Biscol 660P” (manufactured by Sanyo Chemical Industries, Ltd.) were used as the thermoplastic resin (C). 1 was carried out. The MFR of the obtained resin composition was 2000 g / 10 min (190 ° C., 21 N) or more. The press sheet produced from the obtained resin composition was cracked at the time of punching, and the repair rate could not be measured. The haze was 3.7%.

[Comparative Example 13]
62% by mass of propylene resin “Best Plast 792” as amorphous thermoplastic resin (A), 26% by mass of hydrogenated petroleum resin “Alcon P-125” as amorphous thermoplastic resin (B), crystalline thermoplastic resin The same procedure as in Example 1 was performed except that 12% by mass of petroleum-based wax “paraffin wax 155” (manufactured by Nippon Seiwa Co., Ltd.) was used as (C). The obtained resin composition had an MFR of 1183 g / 10 min (190 ° C., 21 N), and a Tg of −16.9 ° C. The press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 0%, Young's modulus 39 MPa, and haze 88.8%.

[Comparative Example 14]
45% by mass of propylene resin “Best Plast 792” as amorphous thermoplastic resin (A), 45% by mass of hydrogenated petroleum resin “Alcon P-90” as amorphous thermoplastic resin (B), crystalline thermoplastic resin The same procedure as in Example 1 was performed except that 10% by mass of petroleum-based wax “paraffin wax 155” (manufactured by Nippon Seiwa Co., Ltd.) was used as (C). The obtained resin composition had an MFR of 2000 g / 10 min (190 ° C., 21 N) or more and a Tg of −12.8 ° C. The press sheet produced from the obtained resin composition had high adhesiveness, was not stampable, and the repair rate could not be measured. The haze was 31.4%.

[Comparative Example 15]
48% by mass of the amorphous propylene-1-butene copolymer produced in Synthesis Example 1 as the amorphous thermoplastic resin (A), and the cyclic olefin resin “TOPAS 9506” as the amorphous thermoplastic resin (B) ( This was carried out in the same manner as in Example 1 except that 48% by mass of Polyplastics Co., Ltd. and 4% by mass of “Sumitomo Nobrene FLX80E4” were used as the crystalline thermoplastic resin (C). The obtained resin composition had an MFR of 3 g / 10 min (190 ° C., 21 N), and Tg of −8.7 ° C. and 65.1 ° C. The press sheet produced from the obtained resin composition was punchable, and the repair rate (80 ° C.) was 26%, Young's modulus 71 MPa, and haze 93.7%.

<Explanation of symbols>
A-1: Amorphous propylene polymer resin (1-butene content 4 mol%, Mw 219000, Mw / Mn = 2.1, ΔH = 0 J / g, MFR = 3 g / 10 min (190 ° C., 21N) (Synthesis Example 1)
A-2: Styrene-isoprene-styrene block copolymer “Hibler 5127” (styrene content 20%, Mw 109,000, Mw / Mn = 1.5, ΔH = 0 J / g, MFR = 4 g / min (190 (C, 21N) (Kuraray Co., Ltd.))
A-3: Hydrogenated styrene-isoprene-styrene block copolymer “HIBLER 7311F” (styrene content 12%, Mw 132,000, Mw / Mn = 1.1, ΔH = 0 J / g, MFR = 0.4 g) / Min (190 ° C, 21N) (Kuraray Co., Ltd.))
A-4: Styrene-butadiene copolymer (styrene content 34 mol%, Mw 663,000, Mw / Mn = 3.3, ΔH = 0 J / g, MFR does not flow and cannot be measured (190 ° C., 21 N)) (synthesis Example 2)
A-5: Propylene resin “Best Plast 703” (Mw 41,600, Mw / Mn = 5.6, ΔH = 35 J / g, MFR = 1000 g / 10 min or more (190 ° C., 21 N)) (manufactured by Evonik)
A-6: Propylene resin “Best Plast 708” (Mw 56,900, Mw / Mn = 3.6, ΔH = 28 J / g, MFR = 1000 g / 10 min or more (190 ° C., 21 N)) (manufactured by Evonik)
A-7: Propylene resin “Best Plast 792” (Mw 141,000, Mw / Mn = 4.5, ΔH = 18 J / g, MFR = 500 g / 10 min (230 ° C., 21 N), 220 g / 10 min (190 ° C.) 21N)) (Evonik)
A-8: Propylene resin “Tufselen X1107” (Mw 321,000, Mw / Mn = 2.1, ΔH = 0 J / g, MFR = 1.2 g / 10 min (190 ° C., 21 N)) (Sumitomo Chemical Co., Ltd.) Made)
A-9: Hydrogenated styrene-isoprene block copolymer “Septon 2004F” (styrene content 18%, Mw 78,700, Mw / Mn = 1.0, ΔH = 0 J / g) (manufactured by Kuraray Co., Ltd.)
B-1: Hydrogenated terpene resin “Clearon P-105” (Mw 1,100, Mw / Mn = 2.8, ΔH = 0 J / g) (manufactured by Yashara Chemical Co., Ltd.)
B-2: Hydrogenated terpene resin “Clearon P-150” (Mw 1,200, Mw / Mn = 2.3, ΔH = 0 J / g) (manufactured by Yashara Chemical Co., Ltd.)
B-3: Sodium salt of sulfonated styrene-butadiene copolymer (styrene content 39 mol% (before sulfonation), Mw 27,000 (before sulfonation), Mw / Mn = 1.2 (before sulfonation), ΔH = 0 J / g (before sulfonation), sulfonation rate 31 mmol-OH / 100 g-polymer, neutralization degree 100%, MFR 1000 g / 10 min or more (190 ° C., 21 N)) (Synthesis Example 4)
B-4: Hydrogenated petroleum resin “Alcon P-125” (Mw 1,400, Mw / Mn = 3.2, ΔH = 0 J / g) (Arakawa Chemical Industries, Ltd.)
B-5: Hydrogenated petroleum resin “Alcon P-90” (Mw 900, Mw / Mn = 3.2, ΔH = 0 J / g) (Arakawa Chemical Industries, Ltd.)
B-6: Hydrogenated terpene resin “Clearon P-125” (Mw 1,100, Mw / Mn = 2.9, ΔH = 0 J / g) (manufactured by Yashara Chemical Co., Ltd.)
B-7: Cyclic olefin resin “TOPAS 9506” (Mw = 107,000, Mw / Mn = 1.9, ΔH = 0 J / g) (manufactured by Polyplastics Co., Ltd.)
C-1: Crystalline propylene resin “Sumitomo Nobrene FLX80E4” (melting point: 163 ° C., ΔH = 120 J / g, MFR = 8 g / 10 min (230 ° C., 21 N)) (manufactured by Sumitomo Chemical Co., Ltd.)
C-2: Maleic anhydride-modified crystalline propylene resin “Yumex 1010” (melting point 140 ° C., ΔH = 74 J / g) (manufactured by Sanyo Chemical Industries, Ltd.)
C-3: Petroleum wax “paraffin wax 155” (melting point 68 ° C., ΔH = 218 J / g) (manufactured by Nippon Seiwa Co., Ltd.)
C-4: Crystalline propylene resin “Wintec WFX4” (melting point: 123 ° C., ΔH = 79 J / g) (manufactured by Nippon Polypro Co., Ltd.)
C-5: Crystalline propylene resin “Biscol 660P” (melting point 131 ° C., ΔH = 79 J / g) (manufactured by Sanyo Chemical Industries, Ltd.)

* Observe only crystallization and melting peaks

Claims

An amorphous thermoplastic resin (A) having a weight average molecular weight of 50,000 to 500,000 and a molecular weight distribution of 1.0 to 3.5; and a weight average molecular weight of 500 to less than 50,000 Containing an amorphous thermoplastic resin (B),
The total amount of the amorphous thermoplastic resin (A) and the amorphous thermoplastic resin (B) is 100% by mass, and the content of the amorphous thermoplastic resin (A) is 25% by mass to 85% by mass. %, And the content of the amorphous thermoplastic resin (B) is 15 mass% or more and 75 mass% or less,
Thermoplastic resin composition satisfying the following requirement (1) and requirement (2):
Requirement (1) The glass transition temperature of the thermoplastic resin composition is 0 ° C. or higher and 200 ° C. or lower; and Requirement (2) The haze of a 1 mm thick sheet made of the thermoplastic resin composition is less than 8.0% It is.
The thermoplastic resin composition further contains a crystalline thermoplastic resin (C),
The thermoplastic resin composition according to claim 1, wherein the total amount of the thermoplastic resin in the thermoplastic resin composition is 100% by mass, and the content of the crystalline thermoplastic resin (C) is 0.01 to 9% by mass. object.
A molded article comprising the thermoplastic resin composition according to claim 1 or 2.