JP5652173B2 - Resin composition and molded body - Google Patents

Description

  The present invention relates to a resin composition containing an alicyclic polyester block copolymer resin and a molded product thereof. In particular, the present invention relates to a resin composition containing an alicyclic polyester block copolymer resin having transparency, heat resistance, hygiene, and two-color moldability with an aromatic polycarbonate, and a molded product thereof.

  An alicyclic polyester resin (hereinafter sometimes abbreviated as “PCC resin”) composed of a structural unit derived from 1,4-cyclohexanedicarboxylic acid and a structural unit derived from 1,4-cyclohexanedimethanol is an excellent all A modifier that adjusts the refractive index, fluidity, etc. of aromatic polycarbonate resin without impairing transparency, because it has light transmittance and haze value and exhibits high affinity for aromatic polycarbonate resin. Etc. In addition, a block copolymer in which a part of the diol component in the PCC resin is replaced with a structural unit derived from polyalkylene glycol (hereinafter sometimes abbreviated as “PCCP resin”) is a transparency possessed by the PCC resin. In addition to its affinity for aromatic polycarbonate resins, it has excellent heat resistance and heat sealability, so it is used mainly in the medical field such as infusion bags.

  In adapting PCCP resin to multilayer films and sheets, or adapting to two-color molding with engineering plastics, in terms of increasing the degree of freedom of layer structure, the transparency and affinity to polycarbonate are the characteristics of PCCP resin. It is desirable to be able to design materials with a wide range of hardness while maintaining them. On the other hand, it is possible to improve flexibility by increasing the content of structural units derived from polyalkylene glycol contained in the PCCP resin, but the heat resistance is inferior because the melting point of the resin is lowered. It will be. Further, as the number of components derived from polyalkylene glycol increases, hygiene, thermal stability, hue and the like tend to deteriorate, so it is desirable to keep the necessary minimum content. Therefore, it is required to improve flexibility without impairing transparency, which is a characteristic of PCCP resin, by alloying PCCP resin and other flexible resin components.

In the past, no attempt has been made to increase flexibility by adding other resins to PCCP resin, but core-shell type acrylic rubber containing methyl methacrylate in PCC resin or ABS (acrylonitrile-butadiene-styrene). Attempts have been made to improve impact resistance and tensile properties by adding a system modifier or the like (Patent Document 1). However, since this method aims to improve the impact resistance while maintaining a certain degree of rigidity, a sufficient soft effect cannot be obtained. Further, since talc and pigment are generally blended, the transparency of the PCC resin is not fully utilized.
On the other hand, there is disclosed a technique for achieving both transparency and impact resistance by adding an epoxidized diene block copolymer to a mixture of a PCC resin and an aromatic polycarbonate resin (Patent Document 2). However, this method is intended to improve the impact resistance of a hard resin mainly composed of an aromatic polycarbonate resin, and does not take into account the improvement of flexibility.

As described above, it has excellent total light transmittance and haze value, expresses high affinity for aromatic polycarbonate resin, has excellent heat resistance and heat sealability, and a flexible resin or resin composition has been conventionally used. It was not achieved.
Further, as a result of investigation by the present inventors, it has been found that even if the transparency is good immediately after molding, the transparency may be lowered when the molded product is placed in a high temperature environment. Accordingly, it has been more difficult to obtain a resin or resin composition that achieves the above required characteristics and can maintain transparency even under high temperature conditions.

JP-A-5-287182 JP 2008-222775 A

  The present invention has been made in view of such circumstances, and the problem is that it has flexibility, excellent transparency not only at room temperature but also at high temperatures, and high affinity with aromatic polycarbonate resins and the like. The object is to provide a resin composition.

As a result of intensive studies in view of the above-mentioned problems, the present inventor can solve the above problems by using a resin composition containing a specific PCCP resin and a block copolymer having a specific structure. The headline and the present invention were completed.
That is, the gist of the present invention is the following [1] to [7].
[1] The following component (A), component (B) and component (C) are contained, and the weight ratio of component (A) / [component (B) + component (C)] is 95/5 to 35/65. And the weight ratio of component (B) / component (C) is 99/1 to 63/37.
Component (A): having a segment mainly composed of units derived from 1,4-cyclohexanedicarboxylic acid and units derived from 1,4-cyclohexanedimethanol and a polyalkylene polyol segment, and 7-30 polyalkylene polyols Aliphatic polyester block copolymer resin having a melting point of 160 ° C. to 210 ° C. Component (B): at least two polymer blocks P mainly composed of vinyl aromatic compound, butadiene and / or isoprene A block copolymer comprising 34 to 55% by weight of the polymer block P and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer. Polymer Component (C): Hydrocarbon softener

[2] A resin composition in which the component (B) in [1] is represented by the following formula (1).
P- (Q-P) m (1)
(Wherein P represents the polymer block P, Q represents the polymer block Q, and m represents an integer of 1 to 5)
[3] The resin composition according to [1] or [2], wherein the polyalkylene polyol component contained in the component (A) is polytetramethylene ether glycol.
[4] The resin composition according to any one of [1] to [3], wherein the total light transmittance measured in accordance with JIS-K7105 is 75% or more .
[5] The resin composition according to any one of [1] to [4], wherein the component (B) has a weight average molecular weight of 60,000 or more and 550,000 or less.
[6 ] A molded article obtained by molding the resin composition according to any one of [1] to [ 5 ].
[ 7 ] A jack cover for a mobile phone formed by molding the resin composition according to any one of [1] to [ 5 ].
[ 8 ] A laminate comprising a layer containing the resin composition according to any one of [1] to [ 5 ] and a layer containing an aromatic polycarbonate or an acrylonitrile-styrene copolymer.

According to the present invention, an alicyclic polyester-based resin composition that is excellent in heat resistance and flexibility and excellent in transparency not only at room temperature but also at high temperature is provided. By using this, it is possible to provide films and sheets suitable for medical bags, packaging materials, containers, labels, building materials, members for electrical and electronic equipment, information recording films, adhesive tape substrates, injection molded products, etc. It becomes.
Further, the resin composition of the present invention can be compatible and fused with an aromatic polycarbonate resin, an acrylonitrile-styrene copolymer or the like while maintaining properties such as heat resistance and flexibility, and can be used for home appliances, etc. It is possible to provide resin materials applicable to various uses. From these characteristics, it is possible to provide a resin material that can be suitably used particularly as a jack cover for a mobile phone.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following description, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

The resin composition of the present invention comprises the following component (A), component (B) and component (C).
Component (A): having a segment mainly composed of units derived from 1,4-cyclohexanedicarboxylic acid and units derived from 1,4-cyclohexanedimethanol and a polyalkylene polyol segment, and 7-30 polyalkylene polyols An alicyclic polyester block copolymer resin having a melting point of 160 ° C. or higher and 210 ° C. or lower. Component (B): at least two polymer blocks P mainly composed of a vinyl aromatic compound, butadiene and / or isoprene A block copolymer comprising 34 to 55% by weight of the polymer block P and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer. Ingredient Component (C): Hydrocarbon softener

<Component (A): Alicyclic polyester-based block copolymer resin>
The component (A) in the present invention comprises a hard segment comprising 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid component and 1,4-cyclohexanedimethanol as a diol component as main constituent units, and a soft segment comprising a polyalkylene polyol. And an alicyclic polyester block copolymer resin having 7 to 30% by weight of the polyalkylene polyol.
Here, “main” means the proportion of structural units derived from 1,4-cyclohexanedicarboxylic acid in all dicarboxylic acid structural units in the hard segment, or in the structural units derived from all diol components in the hard segment. The proportion of structural units derived from 1,4-cyclohexanedimethanol is 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, and particularly preferably 80 mol%. The upper limit is 100 mol%.

The higher the proportion of 1,4-cyclohexanedicarboxylic acid in all the dicarboxylic acid constituent units in the hard segment in the alicyclic polyester block copolymer resin, the more preferable in terms of the heat resistance of the molded article.
Examples of dicarboxylic acid components other than 1,4-cyclohexanedicarboxylic acid that can be used in the alicyclic polyester block copolymer resin used in the present invention include 1,2-cyclohexanedicarboxylic acid and 1,3-cyclohexane. Alicyclic dicarboxylic acids such as dicarboxylic acid, 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid; terephthalic acid, phthalic acid, isophthalic acid, phenylenedioxydicarboxylic acid, 4,4′- Diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl ketone dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 2,6-naphthalene dicarboxylic acid Aromatic dicarboxylic acids such as acids; succinic acid, glutaric acid Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecalactone dicarboxylic acid include aliphatic dicarboxylic acids such as dodeca dicarboxylic acid. These dicarboxylic acid components can be used alone or in combination of two or more.
As the dicarboxylic acid, aliphatic dicarboxylic acid or alicyclic dicarboxylic acid is preferably used.

In addition, when the dicarboxylic acid component is an alicyclic dicarboxylic acid, the ratio of the trans isomer in the dicarboxylic acid is arbitrary, and it is desirable that the ratio of heat resistance of the resin composition of the present invention is large. From the standpoint of suppression, the lower one is preferable. Specifically, the ratio of the trans form of the alicyclic dicarboxylic acid is preferably 60 mol% or more, more preferably 70 mol% or more, and on the other hand, it is 98 mol% or less. preferable.
In the present invention, the dicarboxylic acid may be used as an alkyl ester having 1 to 4 carbon atoms, a halide thereof, or the like in the production of an alicyclic polyester block copolymer resin.

  Examples of diol components other than 1,4-cyclohexanedimethanol that can be used in the alicyclic polyester block copolymer resin used in the present invention include 1,2-cyclopentanediol and 1,3-cyclopentane. Diol, 1,2-cyclopentanedimethanol bis (hydroxymethyl) tricyclo [5.2.1.0] decane, 1,3-cyclopentanedimethanol bis (hydroxymethyl) tricyclo [5.2.1.0] 5-membered ring diols such as decane; 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol (1,2-CHDM), 1,3-cyclohexanedi Methanol (1,3-CHDM), 2,2-bis- (4-hydroxycyclohexyl) ) -6-membered ring diol such as propane; aliphatic diol such as ethylene glycol, trimethylene glycol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol Xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl); ) Aromatic diols such as sulfone and bis (4-β-hydroxyethoxyphenyl) sulfonic acid. These diol components can be used alone or in combination of two or more.

Among these, from the viewpoint of imparting flexibility, aliphatic diols such as pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, and diethylene glycol are preferable.
When the diol component is an alicyclic diol, the proportion of the trans isomer in the diol is arbitrary, but for the same reason as the proportion of the trans isomer contained in the above alicyclic dicarboxylic acid component, the proportion of the trans isomer Is preferably 60 mol% or more, more preferably 70 mol% or more, and preferably 98 mol% or less.

In the present invention, examples of the polyalkylene polyol constituting the soft segment of the alicyclic polyester block copolymer resin include polyethylene glycol, poly (1,2 and / or 1,3) propylene ether glycol, polytetramethylene ether. Examples include glycol and polyhexamethylene ether glycol. Of these, polytetramethylene ether glycol is preferred.
The amount of the polyalkylene polyol in the alicyclic polyester block copolymer resin is preferably larger from the viewpoint of the flexibility of the resin composition. On the other hand, if the polyalkylene polyol is excessively large, the alicyclic polyester block Since the melting point of the copolymer resin is lowered, the heat resistance and transparency of the resin composition may be impaired. Further, when the amount of the polyalkylene polyol is excessively small, the growth of microcrystals during molding is inhibited, so that there is a possibility of whitening in the heat resistance test.

Specifically, the content of the polyalkylene polyol contained as a soft segment in the alicyclic polyester block copolymer resin of the component (A) is 7% by weight or more, preferably 9% by weight or more. On the other hand, the content is 30% by weight or less, and preferably 25% by weight or less. In addition, the content of the polyalkylene polyol in the alicyclic polyester block copolymer resin can be calculated from the charge ratio at the time of production or quantified by an instrumental analysis method such as ¹ H-NMR spectrum analysis. it can.
The molecular weight of the polyalkylene polyol is not limited, but the number average molecular weight is preferably 200 or more from the viewpoint of toughness and impact resistance, while the number average molecular weight is preferably 3000 or less from the viewpoint of polymerization reactivity. .

  The melting point of the alicyclic polyester block copolymer resin used in the present invention is 160 ° C. or higher, more preferably 180 ° C. or higher. If the melting point of the alicyclic polyester block copolymer resin is less than the lower limit, the heat resistance is poor, which is not preferable. In addition, the melting point of the alicyclic polyester block copolymer resin is 210 ° C. or less, preferably 205 ° C. or less, from the viewpoint of the heat deformation rate and the transparency after the heating test. When the melting point exceeds the above upper limit, the crystallization rate becomes slow, so the crystallinity of the molded product becomes low, and as a result, the heat deformation rate and the transparency after the heat test are inferior. In addition, melting | fusing point can be measured by a conventional method, for example by using a differential scanning calorimeter (DSC) etc., Usually, it means the temperature of the melting peak top when measuring with the temperature increase rate of 10 degreeC / min.

  The intrinsic viscosity (IV) of the alicyclic polyester-based block copolymer resin used in the present invention is arbitrary, but a lower one is preferable from the viewpoint of easy molding because the melt viscosity is also low. Specifically, it is an inherent characteristic obtained by measuring an alicyclic polyester block copolymer resin at 30 ° C. using an Ubbelohde viscometer with a phenol / tetrachloroethane (weight ratio 1/1) mixture as a solvent. The viscosity (IV) is preferably 1.5 dl / g or less. On the other hand, from the viewpoint of physical properties such as strength of a molded product obtained from the resin composition of the present invention, it is preferably 0.5 dl / g or more.

<Component (B): Block copolymer>
Component (B) in the present invention is a block copolymer having at least two polymer blocks P mainly composed of a vinyl aromatic compound and at least one polymer block Q mainly composed of butadiene and / or isoprene. And / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer (hereinafter, polymer block P may be abbreviated as “block P”, and polymer block Q may be abbreviated as “block Q”. is there).
Here, “a polymer mainly composed of a vinyl aromatic compound” means a polymer obtained by polymerizing a monomer mainly composed of a vinyl aromatic compound, and “a polymer mainly composed of butadiene and / or isoprene”. The term “polymerized” means a monomer mainly composed of butadiene and / or isoprene. In addition, “mainly” here means 50 mol% or more.

  The monomeric vinyl aromatic compound constituting the block P is not limited, but styrene derivatives such as styrene and α-methylstyrene are preferable. Of these, styrene is the main component. The block P may contain a monomer other than the vinyl aromatic compound as a raw material.

The block Q is more preferably any one of butadiene alone, isoprene alone, butadiene and isoprene. The block Q may contain monomers other than butadiene and isoprene as raw materials.
The block Q may be a hydrogenated derivative obtained by hydrogenating a double bond having after polymerization. The hydrogenation rate of the block Q is not limited, but is preferably 50 to 100% by weight, and more preferably 80 to 100%. By hydrogenating the block Q within the above range, the thermal stability of the resulting resin composition tends to be improved. The same applies to the case where the block P uses a diene component as a raw material. The hydrogenation rate can be measured by ¹³ C-NMR.

  The weight ratio of the block P in the component (B) is 34% by weight or more, preferably 35% by weight or more, while it is 55% by weight or less, preferably 50% by weight or less, 45% by weight. % Or less is more preferable. When the weight ratio of the block P in a component (B) is the said range, the haze and total light transmittance of the resin composition of this invention become favorable. The feature of the present invention is that the transparency is good not only at room temperature but also at high temperature. In order to impart this characteristic, the weight ratio of the block P in the component (B) is within the previous range. This is very important.

  When block Q is a hydrogenated derivative and is composed mainly of butadiene, the 1,2-addition structure of butadiene in the microstructure of block Q is preferably 20% by weight or more, more preferably 30% by weight. % Or more. The upper limit is 100% by weight. Similarly, when the block Q is composed of isoprene, the 1,2-addition structure of isoprene in the microstructure of the block Q is preferably 20% by weight or more, more preferably 30% by weight or more. The upper limit is 100% by weight. In any case, by setting the ratio of 1,2-addition structure within the above range, it is possible to obtain higher transparency of the obtained resin composition.

Component (B) in the present invention is not limited as long as it has a structure having at least two polymer blocks P and at least one polymer block Q, and may be any of linear, branched, radial, etc. However, it is preferably a block copolymer represented by the following formula (1) or (2), and more preferably a structure of the following formula (1) from the viewpoint of the holding power of the rubber softener. .
Furthermore, the block copolymer represented by the following formula (1) or (2) is more preferably a hydrogenated derivative (hereinafter sometimes abbreviated as a hydrogenated block copolymer). When the copolymer represented by the following formula (1) or (2) is a hydrogenated block copolymer, the thermal stability is improved.
P- (Q-P) m (1)
(PQ) n (2)
(Wherein P represents the polymer block P, Q represents the polymer block Q, m represents an integer of 1 to 5, and n represents an integer of 2 to 5)
In the formula (1) or (2), m and n are preferably large in terms of lowering the order-disorder transition temperature as a rubbery polymer, but small in terms of ease of production and cost. . In the present invention, m and n are preferably given by integers of 1 to 5, more preferably 2 to 4.

When component (B) is a hydrogenated block copolymer represented by formula (1) or (2) and block Q is composed of butadiene, 1,2-addition of butadiene in the microstructure of block Q The structure is preferably 20% by weight or more, more preferably 30% by weight or more. The upper limit is 100% by weight. Similarly, when the block Q is composed of isoprene, the 1,2-addition structure of isoprene in the microstructure of the block Q is preferably 20% by weight or more, more preferably 30% by weight or more. The upper limit is 100% by weight. In any case, by setting the ratio of 1,2-addition structure within the above range, it is possible to obtain higher transparency of the obtained resin composition.
The block copolymer or hydrogenated block copolymer (hereinafter collectively referred to as “(hydrogenated) block copolymer”) is represented by the formula (2) because it has excellent rubber elasticity. ) A (hydrogenated) block copolymer represented by formula (1) is preferred to a block copolymer, and (hydrogenated) block copolymer represented by formula (1) wherein m is 3 or less. (Hydrogenated) block copolymer represented by the formula (1) in which m is 2 or less is more preferable.

The number average molecular weight of the component (B) in the present invention is not limited, but is usually 30,000 or more, preferably 50,000 or more, more preferably 80,000 or more, and usually 500,000 or less, preferably 400,000. In the following, it is desirable that it is 300,000 or less. When the number average molecular weight of the component (B) is within the above range, it is desirable because moldability and heat resistance are good.
Although Weight average molecular weight of the component (B) is not limited in the present invention, typically 60,000 or more, preferably 80,000 or more, more preferably 100,000 or more, usually 550,000 or less, preferably 500, It is desirable that it is 000 or less, more preferably 400,000 or less. When Weight average molecular weight of the component (B) is within the range, is desirable because a good moldability and heat resistance.

The number average molecular weight and the weight average molecular weight of the component (B) are weight average molecular weights in terms of polystyrene measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC) under the following conditions.
(Measurement condition)
Equipment: Nippon Millipore "150C ALC / GPC"
Column: Showa Denko Co., Ltd. “AD80M / S” 3 detectors: FOXBORO infrared spectrophotometer “MIRANIA” measurement Wavelength: 3.42 μm
Solvent: o-dichlorobenzene Temperature: 140 ° C
Flow rate: 1 cm ³ / min Injection amount: 200 microliters Concentration: 2 mg / cm ³
As an antioxidant, 0.2% by weight of 2,6-di-t-butyl-p-phenol was added.

The method for producing the component (B) in the present invention is not particularly limited as long as the above structure and physical properties can be obtained. Specifically, for example, it can be obtained by performing block polymerization in an inert solvent using a lithium catalyst or the like by the method described in Japanese Patent Publication No. 40-23798.
The block copolymer may be hydrogenated (hydrogenated), for example, as described in JP-B-42-8704, JP-B-43-6636, JP-A-59-133203, and JP-A-60-79005. Can be carried out in the presence of a hydrogenation catalyst in an inert solvent.

Examples of such commercially available hydrogenated block copolymers include “KRATON-G” manufactured by Shell Chemicals Japan Co., Ltd., “Septon”, “Hibler” manufactured by Kuraray Co., Ltd., and “Tuftec” manufactured by Asahi Kasei Co., Ltd. .
Examples of commercially available non-hydrogenated type block copolymers include “KRATON-A” manufactured by Shell Chemicals Japan Co., Ltd., some grades of “Hibler” manufactured by Kuraray Co., Ltd., and “Tufprene” manufactured by Asahi Kasei Co., Ltd. .

<(Component (C): Softener for hydrocarbon rubber>
In the present invention, a hydrocarbon rubber softener is used as the component (C). In the present invention, the term “hydrocarbon rubber softener” means that the weight ratio of the hydrocarbon structure in the molecular structure is 90% or more, and the hardness of the resin composition comprising the component (A) and the component (B) is adjusted. It means a compound capable of performing the function and the function of improving moldability. Component (C) may be a single compound, but is usually a mixture of compounds having different molecular structures and molecular weights.
The hydrocarbon rubber softener is preferably a mineral oil-based or synthetic resin-based softener, more preferably a mineral oil-based softener because of its high affinity for the component (B). Mineral oil softeners are generally a mixture of aromatic hydrocarbons, naphthenic hydrocarbons and paraffinic hydrocarbons, with paraffinic oils in which 50% or more of all carbon atoms are paraffinic hydrocarbons,
About 30 to 45% of all carbon atoms are naphthenic hydrocarbons (cycloparaffinic hydrocarbons), and more than 35% of all carbon atoms are aromatic hydrocarbons. Each called. Of these, paraffinic oil is preferred because of its good hue. Examples of the synthetic resin softener include polybutene and low molecular weight polybutadiene. The hydrocarbon rubber softener may be any one of the above-mentioned various softeners or a mixture of plural kinds.

  Examples of the compound constituting the paraffinic softener include paraffinic compounds having 4 to 155 carbon atoms, preferably paraffinic compounds having 4 to 50 carbon atoms, and specifically include butane, pentane, hexane, and heptane. , Octane, nonane, decane, undecane, dodecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosan, heneicosan, docosan, tricosan, tetracosan, pentacosan, hexacosan, heptacosan, octacosan, nonacosan, triacontane, hentria contane, N-paraffins (linear saturated hydrocarbons) such as detriacontane, pentatriacontane, hexacontane, heptacontane, etc .; isobutane, isopentane, neopentane, isohexane, isope Tan, neohexane, 2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3, 3-dimethylpentane, 2,2,3-trimethylbutane, 3-methylheptane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,4 -Dimethylhexane, 2,2,3-trimethylpentane, isooctane, 2,3,4-trimethylpentane, 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, isononane, 2-methylnonane, isodecane, Isoundecane, isododecane, isotridecane, isotetradecane, isopentadecane, isoocta Kang, Isonanodekan, isoeicosane, isoparaffins such as 4-ethyl-5-methyl-octanoic (branched saturated hydrocarbons); and, may be mentioned derivatives of these saturated hydrocarbons. These paraffins are usually used in a mixture and are preferably liquid at room temperature.

  In addition, a small amount of unsaturated hydrocarbons and derivatives thereof may coexist in the non-aromatic hydrocarbon softener (softener for hydrocarbon rubber other than aromatic oil). Unsaturated hydrocarbons include ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 3-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2 -Ethylene hydrocarbons such as butene, 1-hexene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 1-nonene, 1-decene, acetylene, methylacetylene, 1-butyne, 2- Examples thereof include acetylene hydrocarbons such as butyne, 1-pentyne, 1-hexyne, 1-octyne, 1-nonine and 1-decyne.

The kinematic viscosity at 40 ° C. of the hydrocarbon rubber softener is preferably lower from the viewpoint of moldability, but higher from the viewpoint of sanitary properties such as eluted fine particles. Specifically, it is preferably 20 cSt (20 × 10 ⁻⁶ m ² / s) or more, more preferably 50 cSt (50 × 10 ⁻⁶ m ² / s) or more, and on the other hand, 800 cSt ( 800 × 10 ⁻⁶ m ² / s) or less, and preferably 600 cSt (600 × 10 ⁻⁶ m ² / s) or less.
The flash point (COC method) of the hydrocarbon rubber softener is not limited, but is preferably 200 ° C. or higher, and more preferably 250 ° C. or higher.

<Combination ratio>
The blending ratio of component (A) and component (B) + component (C) in the present invention is 95/5 to 35/65 (weight) as component (A) / [component (B) + component (C)]. Ratio), preferably 90/10 to 40/60, more preferably 85/15 to 45/55. When the blending ratio of component (B) + component (C) is less than the lower limit value, the heat resistance and chemical resistance are greatly deteriorated, which is not preferable. On the other hand, blending of component (B) + component (C) When the ratio exceeds the above upper limit value, the impact resistance and flexibility are not sufficiently improved, which is not preferable.
The blending ratio of component (B) / component (C) is preferably 99/1 to 63/37 by weight, more preferably 97/3 to 70/30, and most preferably 95/5. ~ 76/24. When the ratio of a component (B) and a component (C) is less than the said lower limit and more than the said upper limit, since it is inferior to initial transparency and transparency after aging, it is unpreferable.

The feature of the resin composition of the present invention is that it is excellent in transparency not only at room temperature but also at high temperature. In other words, this characteristic means that the resin composition or a molded product obtained from the resin composition can be aged, that is, can maintain transparency even when heated or exposed to a high temperature environment. As a result of the study by the present inventor, it becomes clear that the higher order structure, crystal structure, etc. of component (A) and component (B) change due to aging, thereby changing the transparency of the resin composition and molded product. It was. Based on this finding, it has been clarified that the transparency after aging can be maintained by optimizing the component (B) and adding an appropriate amount of the component (C).
The content of component (C) in the resin composition of the present invention is usually 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight or more, and usually 20% by weight. Hereinafter, it is preferably 15% by weight or less, more preferably 10% by weight or less. If the content of the component (C) in the resin composition is less than the lower limit, the transparency after aging tends to deteriorate, and if it exceeds the upper limit, the initial total light transmittance tends to be impaired. is there.

<Other ingredients>
In the resin composition of the present invention, resins and additives other than the above-mentioned component (A), component (B), and component (C) may be used as long as the effects of the present invention are not significantly impaired.
Specific examples of the resin other than the component (A) and the component (B) include, for example, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, and ethylene / acrylic acid. Ethylene copolymers such as ester copolymers and ethylene / methacrylate copolymers; polyolefin resins such as polyethylene and polypropylene; polyphenylene ether resins; polyamide resins such as nylon 66 and nylon 11; polyethylene terephthalate and polybutylene Examples thereof include thermoplastic resins such as polyester resins such as terephthalate and acrylic / methacrylic resins such as polymethyl methacrylate resins. Moreover, you may use various thermoplastic elastomers other than a component (A) and a component (B).

Examples of additives include various heat stabilizers, antioxidants, ultraviolet absorbers, anti-aging agents, nucleating agents, plasticizers, light stabilizers, impact modifiers, pigments, lubricants, antistatic agents, Examples include flame retardants, flame retardant aids, fillers, and compatibilizers. These other resins and additives may be used alone or in combination of two or more in any combination and ratio.
Examples of the heat stabilizer and the antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and the like.

Flame retardants are roughly classified into halogen-based flame retardants and non-halogen-based flame retardants, and non-halogen-based flame retardants are preferable in terms of the environment. Non-halogen flame retardants include phosphorus flame retardants, hydrated metal compounds (aluminum hydroxide and magnesium hydroxide) flame retardants, nitrogen-containing compounds (melamine and guanidine) flame retardants and inorganic compounds (borate and molybdenum) Compound) flame retardant and the like.
Fillers are roughly classified into organic fillers and inorganic fillers. Examples of the organic filler include naturally occurring polymers such as starch, cellulose fine particles, wood flour, okara, fir husk, bran, and modified products thereof. Inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon Examples thereof include black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fiber, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite, and carbon fiber.

  Examples of nucleating agents include sorbitol compounds and metal salts thereof; benzoic acid and metal salts thereof; phosphoric acid ester metal salts; ethylene bisoleic acid amide, methylene bisacrylic acid amide, ethylene bisacrylic acid amide, hexamethylene bis-9,10 -Dihydroxystearic acid bisamide, p-xylylene bis-9,10-dihydroxystearic acid amide, decanedicarboxylic acid dibenzoyl hydrazide, hexanedicarboxylic acid dibenzoyl hydrazide, 1,4-cyclohexanedicarboxylic acid dicyclohexylamide, 2,6-naphthalenedicarboxylic acid Dianilide, N, N ′, N ″ -tricyclohexyltrimesic acid amide, trimesic acid tris (t-butylamide), 1,4-cyclohexanedicarboxylic acid dianilide, 2,6-naphthalenedicarbo Acid dicyclohexylamide, N, N′-dibenzoyl-1,4-diaminocyclohexane, N, N′-dicyclohexanecarbonyl-1,5-diaminonaphthalene, ethylenebisstearic acid amide, N, N′-ethylenebis (12- Amide compounds such as hydroxystearic acid) amide and octanedicarboxylic acid dibenzoylhydrazide. Examples of the inorganic crystal nucleating agent include talc, kaolin, and silica.

  Even when a resin or additive other than the component (A), the component (B), and the component (C) is used in the production of the resin composition of the present invention, the component (A in the raw material of the resin composition of the present invention (A) ), The total amount of component (B) and component (C) is preferably 60% by weight or more, and preferably 80% by weight or more from the viewpoint of ease of expression of the excellent effects of the present invention. Is more preferable. The upper limit here is usually 100% by weight.

<Resin composition>
The resin composition of the present invention can be obtained by mixing the above-described components at a predetermined ratio.
The mixing method is not particularly limited as long as the raw material components are uniformly dispersed. That is, a composition in which each component is uniformly distributed can be obtained by mixing the above-described raw material components simultaneously or in any order.
For more uniform mixing and dispersion, it is preferable to melt and mix a predetermined amount of the above raw material components. For example, the raw material components of the resin composition of the present invention are mixed in an arbitrary order and then heated. Alternatively, all raw material components and the like may be mixed while being sequentially melted, or the mixture of each raw material component and the like may be pelletized or melted and mixed at the time of molding when producing a target molded product.

  The mixing method and mixing conditions are not particularly limited as long as each raw material component is uniformly mixed, but from the viewpoint of productivity, continuous kneaders such as single-screw extruders and twin-screw extruders, mill rolls, and Banburys. A known melt-kneading method such as a batch kneader such as a mixer or a pressure kneader is preferred. The temperature at the time of melt mixing may be a temperature at which at least one of the raw material components is in a molten state, but usually a temperature at which all the components used are melted is selected, and in general, the temperature is often set at 150 to 250 ° C.

The resin composition of the present invention desirably has high transparency. Transparency is evaluated by haze and total light transmittance. Specifically, the total light transmittance measured in accordance with JIS K7105 when a molded product having a thickness of 2 mm is preferably 75 or more, more preferably 80 or more. It is more preferable. Further, the haze is preferably 50 or less, more preferably 40 or less, and still more preferably 30 or less.
In addition, the resin composition of the present invention is characterized by good transparency even when kept at a high temperature. That is, a haze measured according to JIS K7105 when a molded product having a thickness of 2 mm is aged (heat treatment) at 120 ° C. for 1 hour is preferably 45 or less, more preferably 42 or less, and 40 or less. Is more preferable, and 30 or less is particularly preferable.
The resin composition of the present invention has good flexibility and transparency. In particular, when used in combination with an aromatic polycarbonate resin, the compatibility between the resin composition of the present invention and the aromatic polycarbonate resin is good, so that a molded article with good transparency can be obtained.

<Molded body>
The molded body of the present invention can be obtained by molding the above-described resin composition of the present invention. Here, the manufacturing method of the molded body of the present invention is not particularly limited as long as the resin composition of the present invention can be molded. Specific examples include various molding methods such as injection molding, blow molding, extrusion molding, inflation molding, and vacuum molding after sheet molding, pressure molding, and vacuum / pressure molding. Of these, in consideration of manufacturing a grip member, a film, and the like, injection molding or extrusion molding is preferable.

  The temperature of the cylinder and the die at the time of molding is preferably a high temperature from the viewpoint that appearance failure due to surface deposition of unmelted material is unlikely to occur, and the melting point of the highest melting point component among the components contained in the molten resin It is more preferable that the temperature is higher, particularly preferably 10 ° C. or higher than the melting point of the component having the highest melting point, and most preferably 20 ° C. or higher than the melting point of the component having the highest melting point. On the other hand, in order not to cause discoloration or deterioration of physical properties due to thermal decomposition of the contained components, the temperature of the cylinder and the die during molding is preferably low. Specifically, since the melting point of the component (A) is generally 160 ° C to 240 ° C, it is preferably 170 ° C or higher, more preferably 190 ° C or higher, and 200 ° C or higher. Is particularly preferred. The upper limit of the cylinder and die temperature during molding is preferably 250 ° C. or lower, and more preferably 240 ° C. or lower. Further, the mold temperature when performing injection molding is preferably 60 ° C. or less, and more preferably 45 ° C. or less.

<Shape of molded product>
The molded body of the present invention may have any shape as long as it is a molded body obtained by molding the resin composition of the present invention, but in particular, a tube, a film or sheet, a container shape, a fin (fin) shape A molded product having a shape such as a grip shape or a jack cover shape is preferable because flexibility and transparency, which are one of the characteristics of the resin composition of the present invention, are easily utilized.
The thickness of the molded product of the present invention is preferably thinner in terms of utilizing transparency, but thicker in terms of obtaining a good tactile sensation by taking advantage of flexibility. Since the molded article of the present invention is excellent in transparency, it is easy to ensure practically sufficient transparency even if it has a certain thickness.

Moreover, the molded object of this invention is good also as a laminated body of the layer containing the resin composition of this invention, and another layer. In this case, layers formed individually may be laminated, other layers may be laminated on a previously molded layer, or a plurality of layers may be molded simultaneously to form a laminate. As a molding method in the case of a laminated body, specifically, for example, two-color co-extrusion molding using a single-screw or twin-screw extruder, two colors for injecting a molten resin into a previously molded layer Examples include molding, laminate molding, and multilayer inflation molding.
Examples of the other layers include layers formed from aromatic polycarbonate, acrylonitrile-styrene copolymer, ethylene / α-olefin copolymer, styrene-ethylene-butylene copolymer, and the like. Especially, the laminated body formed by laminating | stacking the layer containing an aromatic polycarbonate or an acrylonitrile-styrene copolymer is suitable.
Since the resin composition of the present invention has excellent compatibility particularly with aromatic polycarbonate resins and acrylonitrile-styrene copolymers, when it is a laminate with these resin layers, it has high interlayer adhesion. Can be obtained.

  Since the molded product of the present invention is excellent in flexibility and transparency, medical containers such as infusion bags, various packaging containers, labels, building materials, members for electrical / electronic devices, films for information recording, adhesive tapes, etc. It can be suitably used as a base material or the like. In addition, the resin composition of the present invention can be fused with an aromatic polycarbonate resin, an acrylonitrile-styrene copolymer or the like while maintaining properties such as heat resistance and flexibility. As a body or a resin composition, it can be suitably used for various uses such as home appliances. In particular, the jack cover for mobile phones is becoming more transparent as mobile phone colors are diversified, and can be fused with aromatic polycarbonate, acrylonitrile-styrene copolymer, etc. The product of the present invention can be suitably used.

EXAMPLES Hereinafter, although this invention is demonstrated still in detail using an Example, this invention is not limited by a following example, unless the summary is exceeded.
In the examples and comparative examples of the present invention, the following raw materials were used.
<Component (A)>
(A-1) PCCP-1
A polyether ester block copolymer comprising a polyester comprising 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedimethanol as a hard segment and polytetramethylene ether glycol as a soft segment.
(Content of polytetramethylene ether glycol quantified by ¹ H-NMR: 15% by weight. Trans rate of 1,4-cyclohexanedicarboxylic acid: 88%. Trans rate of 1,4-cyclohexanedimethanol: 69%. Melting point measured with a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min was 200 ° C. Melt flow measured at 230 ° C. and 2.16 kg load (kgf) in accordance with test condition 4 of JIS standard K7210 (The rate is 35 g / 10 min.)

<Component (B)>
(B-1) “Clayton A-1536HU” manufactured by Shell Chemical Co., Ltd .: a styrene-butadiene-styrene hydrogenated block copolymer. It has the structure of the formula (1), and m = 2. (Styrene (block P) content: 42% by weight)
(B-2) “Clayton A-1535HU” manufactured by Shell Chemical Co., Ltd .: a styrene-butadiene-styrene hydrogenated block copolymer. It has the structure of the formula (1), and m = 2. (Styrene (block P) content: 58% by weight)
(B-3) “Clayton G-1641HU” manufactured by Shell Chemical Co., Ltd .: a styrene-isoprene-styrene hydrogenated block copolymer. It has the structure of the formula (1), and m = 1. (Styrene (block P) content: 33% by weight (catalog value))
(C-1) “PW-90” manufactured by Idemitsu Kosan Co., Ltd .: Paraffinic process oil.

(Examples 1 and 2 and Comparative Examples 1 to 5)
Based on the blending ratio (parts by weight) shown in Table 1, the resin composition was melt-kneaded at a set temperature of 200 ° C. with a twin-screw extruder (“TEX-30αII” manufactured by Nippon Steel Works, Ltd., cylinder diameter 30 mm). Pellets were obtained.
Using this pellet, an 80 mm × 120 mm × 2 mm plate and an 80 mm × 10 mm × 4 mm test piece were molded by an injection molding machine (“IS-130t” manufactured by Toshiba Machine Co., Ltd.). The injection molding conditions were resin temperature: 180-240 ° C., injection time: 2-20 seconds, mold temperature: 25 ° C., cooling time: 10-40 seconds.

<Evaluation of molded body>
(1) Haze and total light transmittance In accordance with JIS K7105, haze and total light transmittance were measured using a plate of 80 mm × 120 mm × 2 mm.
(2) Haze after aging An 80 mm × 120 mm × 2 mm plate obtained by injection molding is aged in air in a gear oven (“GPH-100” manufactured by Tabai) at a temperature of 120 ° C. and a heating time of 1 hour. The haze of the subsequent plate was measured according to JIS K7105.

(3) Tensile properties In accordance with JIS K6251, a test piece of No. 3 dumbbell obtained by punching a plate of 80 mm × 120 mm × 2 mm obtained by injection molding was pulled at a speed of 500 mm / min using an autograph, and ruptured. The elongation rate until tensile strength (tensile elongation rate) and the strength at break (tensile fracture strength) were measured. Moreover, the stress (100% modulus) obtained when showing 100% elongation and the stress (300% modulus) obtained when showing 300% elongation were also measured.

(4) Bending properties In accordance with JIS K7171, 80 mm x 10 mm x 4 mm test pieces obtained by injection molding were subjected to vertical displacement at a rate of 2 mm / min using an autograph, and 0.1-0.5 mm displacement The bending elastic modulus was measured from the stress at, and the maximum bending strength was measured from the obtained maximum stress.
<Evaluation of molded body>
The results of evaluating the resin compositions and molded bodies obtained in Examples 1 and 2 and Comparative Examples 1 to 5 by the above method are shown in Table 1.

The resin composition of the present invention has both flexibility and transparency, and not only has excellent physical properties of molded products such as films, sheets and injection molded products obtained directly from the composition, but also the resin of the present invention. It is also possible to produce two-color molded products such as laminates, polymer blend molded products, and portable jack covers that make use of the compatibility of the composition with aromatic polycarbonate resins and acrylonitrile-styrene copolymers. .

Claims (8)

The following component (A), component (B) and component (C) are contained, and the weight ratio of component (A) / [component (B) + component (C)] is 95/5 to 35/65, And the weight ratio of a component (B) / component (C) is 99/1-63/37, The resin composition characterized by the above-mentioned.
Component (A): having a segment mainly composed of units derived from 1,4-cyclohexanedicarboxylic acid and units derived from 1,4-cyclohexanedimethanol and a polyalkylene polyol segment, and 7-30 polyalkylene polyols Aliphatic polyester block copolymer resin having a melting point of 160 ° C. to 210 ° C. Component (B): at least two polymer blocks P mainly composed of vinyl aromatic compound, butadiene and / or isoprene A block copolymer comprising 34 to 55% by weight of the polymer block P and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer. Polymer Component (C): Hydrocarbon softener The resin composition according to claim 1, wherein the component (B) is represented by the following formula (1).
P- (Q-P) m (1)
(Wherein P represents the polymer block P, Q represents the polymer block Q, and m represents an integer of 1 to 5)   The resin composition according to claim 1 or 2, wherein the polyalkylene polyol component contained in component (A) is polytetramethylene ether glycol.   The resin composition according to any one of claims 1 to 3, wherein a value of total light transmittance measured based on JIS-K7105 is 75% or more. The weight average molecular weight of a component (B) is 60,000 or more and 550,000 or less, The resin composition in any one of Claims 1-4. The molded object formed by shape | molding the resin composition in any one of Claims 1-5 . A jack cover for a mobile phone formed by molding the resin composition according to any one of claims 1 to 5 . A laminate comprising a layer containing the resin composition according to any one of claims 1 to 5 and a layer containing an aromatic polycarbonate or an acrylonitrile-styrene copolymer.