WO2012141264A1

WO2012141264A1 - Laminated body and medical device

Info

Publication number: WO2012141264A1
Application number: PCT/JP2012/060066
Authority: WO
Inventors: 中川　淳
Original assignee: 三菱化学株式会社
Priority date: 2011-04-15
Filing date: 2012-04-12
Publication date: 2012-10-18
Also published as: JP2013014127A; JP5929447B2

Abstract

Disclosed is a laminated body which has excellent flexibility, hygienic properties and shock resistance, in addition to outstanding adhesion between layers. Also disclosed is a medical device. Further disclosed is a laminated body having outstanding flexibility, hygienic properties, transparency and low-temperature shock resistance, in addition to excellent adhesion between layers, and which is suited to use in infusion bags.

Description

Laminate and medical container

The present invention relates to a laminate and a medical container that have good flexibility, hygiene, transparency and impact, and good adhesion between layers. In particular, the present invention relates to a laminate that has good flexibility, hygiene, transparency, and low-temperature impact resistance, and good adhesion between layers and can be suitably used for an infusion bag.

Conventionally, infusion bags for medical use have been made of soft vinyl chloride resin having good flexibility. However, since the soft vinyl chloride resin contains a large amount of plasticizer in order to impart flexibility, there is a concern that the plasticizer leaks into the infusion depending on the type of infusion.

As an infusion bag using a resin that does not contain a plasticizer, a polyolefin bag such as polyethylene or polypropylene is used. However, the infusion bag made of polyolefin has good hygiene because it does not contain a plasticizer, but it is low in flexibility and has insufficient impact resistance, particularly low temperature impact resistance. Absent.

In order to obtain an infusion bag having both of these advantages, for example, it is conceivable to use a layer made of a soft vinyl chloride resin and a layer made of polyolefin as a laminate. However, since the soft vinyl chloride resin and polyolefin have low affinity and poor adhesion and fusion properties, when these resins are used as a laminate for an infusion bag, they peel at the interface between them, The target performance cannot be obtained.

In order to improve this, an adhesive layer having good adhesion to both the soft vinyl chloride resin layer and the polyolefin layer is expected.

As a composite material with improved adhesion between a vinyl chloride resin layer and another resin layer, for example, Patent Document 1 discloses a material useful for sealing and construction as a hard vinyl chloride resin and a copolyester elastomer or a styrene block. A fusion-bonded copolymer or the like is disclosed.

Patent Document 2 discloses a multilayer film having a polypropylene resin layer as a surface layer through a sulfone group-containing polyester resin layer and a modified polyolefin layer (adhesive layer) as an antifouling film for vinyl chloride resin wallpaper. Has been.

Further, Patent Document 3 discloses various bonds between a poly (vinylidene chloride) layer and a polypropylene homopolymer layer as a second layer as a multi-layer structure for producing a medical solution container. Layers are illustrated.

On the other hand, in Patent Document 4, as a medical device, a multilayer film having a connecting layer containing polyester between a vinyl chloride resin layer as a first layer and a layer containing polyolefin as a second layer. Tubing is disclosed.

Japanese National Table 2010-516523 Japanese Unexamined Patent Publication No. 2009-208446 Japanese National Special Table 2010-526669 Japan Special Table 2006-500442

However, in the method of Patent Document 1, no study has been made on the fusing property and adhesiveness with a soft vinyl chloride resin suitable for an infusion bag or the like, and in the art, the adhesiveness with polyolefin is not at all. Not improved.

Further, in the method of Patent Document 2, an adhesive force between the vinyl chloride resin layer and the polypropylene resin layer is expressed, but when used as a laminate for an infusion bag, a sulfone group-containing polyester resin layer and a modified resin layer are used. There is a concern that substances contained in the polyolefin layer affect the chemical solution.

Furthermore, the multi-layer structure disclosed in Patent Document 3 can be used even when any bonding layer is used, even when stress is applied to the structure or when a delamination test is performed between layers. It does not have enough adhesiveness to withstand. Therefore, when this was used for an infusion bag, there was anxiety in practical use. Further, the laminate manufactured in Patent Document 4 has insufficient transparency and adhesiveness.

Thus, at present, there is a situation in which a laminated body having flexibility, hygiene, transparency and impact resistance and suitable for an infusion bag has not yet been found.

The present invention has been made in view of such a situation, and its problem is to provide a laminate and a medical container having good flexibility, hygiene, transparency and impact resistance, and good adhesion between layers. It is to provide. In particular, the present invention is to provide a laminate that has good flexibility, hygiene, transparency, and low temperature impact resistance, and good adhesion between layers, and can be suitably used for an infusion bag. .

As a result of intensive studies in view of the above problems, the present inventor can solve the above problems by using an adhesive resin layer made of a specific resin composition for the soft vinyl chloride resin layer and the polyolefin layer. The headline and the present invention were completed. That is, the gist of the present invention resides in the following [1] to [14].

[1] It has a soft vinyl chloride resin layer (A), an adhesive resin layer (B1) containing a cycloaliphatic polyester and a styrene elastomer, and a polyolefin layer (C), and the melting point of the cycloaliphatic polyester is 130 to 200. And a number average molecular weight of the styrene elastomer is 190,000 or less.

[2] The laminate according to [1], wherein in the adhesive resin layer (B1), the alicyclic polyester has a unit derived from 1,4-cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol. .

[3] In the adhesive resin layer (B1), the alicyclic polyester includes a segment mainly composed of units derived from 1,4-cyclohexanedicarboxylic acid and units derived from 1,4-cyclohexanedimethanol; The laminate according to [1] or [2], comprising a polyalkylene ether polyol segment.

[4] In the adhesive resin layer (B1), the styrenic elastomer is composed of at least two polymer blocks P mainly composed of a vinyl aromatic compound and at least one heavy body mainly composed of butadiene and / or isoprene. [1] to [1] to [1] to [1] to [1] to [1] to [1] to [5] a block copolymer comprising the combined block Q and the polymer block P occupying 5 to 55% by weight. 3] The laminate according to any one of [1].

[5] A laminate having a soft vinyl chloride resin layer (A), an adhesive resin layer (B2), an adhesive resin layer (B3), and a polyolefin layer (C) in this order, and the adhesive resin layer (B2) A laminate comprising an alicyclic polyester and an adhesive resin layer (B3) containing a styrene elastomer and a modified polyolefin resin.

[6] The laminate according to [5], wherein in the adhesive resin layer (B2), the alicyclic polyester has a unit derived from 1,4-cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol. .

[7] In the adhesive resin layer (B2), the alicyclic polyester includes a segment mainly composed of units derived from 1,4-cyclohexanedicarboxylic acid and units derived from 1,4-cyclohexanedimethanol; The laminate according to [5] or [6], comprising a polyalkylene ether polyol segment.

[8] The laminate according to any one of [1] to [7], wherein the polyolefin layer (C) is an ethylene resin and / or a propylene resin.

[9] A medical container comprising the laminate according to any one of [1] to [8].

[10] An infusion bag containing the laminate according to any one of [1] to [9] as a constituent.

[11] A resin composition comprising an alicyclic polyester and a styrene elastomer, wherein the alicyclic polyester has a melting point of 130 to 200 ° C., and the styrene elastomer has a number average molecular weight of 190,000 or less. object.

[12] The resin composition according to [11], wherein the alicyclic polyester has a unit derived from 1,4-cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol.

[13] The alicyclic polyester has a segment mainly composed of a unit derived from 1,4-cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol, and a polyalkylene ether polyol segment [ [11] or [12].

[14] The styrenic elastomer comprises 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. The block copolymer in which P accounts for 5 to 55% by weight and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer according to any one of [11] to [13] Resin composition.

In the following, the invention according to [1] is referred to as “first aspect of the present invention”, and the invention according to [5] is referred to as “second aspect of the present invention”. Further, the laminate according to the first aspect of the present invention and the laminate according to the second aspect of the present invention may be collectively referred to as the “laminate of the present invention”. Further, the invention according to the above [11] is referred to as “third aspect of the present invention”.

According to the present invention, there are provided a laminate and a medical container that have good flexibility, hygiene, transparency and impact resistance, and good adhesion between layers. Moreover, according to this invention, the softness | flexibility, hygiene, transparency, and low temperature impact resistance are favorable, and the laminated body which can be used conveniently for an infusion bag with the favorable adhesiveness of an interlayer is provided.

The laminate according to the first aspect of the present invention includes an adhesive resin layer containing a soft vinyl chloride resin layer (A), an alicyclic polyester having a melting point of 130 to 200 ° C., and a styrene elastomer having a number average molecular weight of 190,000 or less. It has (B1) and a polyolefin layer (C).

The laminate according to the second aspect of the present invention includes a soft vinyl chloride resin layer (A), an adhesive resin layer (B2) containing an alicyclic polyester, an adhesive resin containing a styrene elastomer and a modified polyolefin resin. It has a layer (B3) and a polyolefin layer (C) in this order.

Furthermore, the resin composition according to the third aspect of the present invention includes an alicyclic polyester and a styrene elastomer, the alicyclic polyester has a melting point of 130 to 200 ° C., and the number average of the styrene elastomer. The molecular weight is 190,000 or less.

Hereinafter, the laminate according to the first aspect and the second aspect of the present invention and the resin composition according to the third aspect of the present invention will be described.

<Soft vinyl chloride resin layer (A)>
The soft vinyl chloride resin layer (A) in the present invention contains at least a vinyl chloride resin. Although the vinyl chloride resin which comprises a soft vinyl chloride resin layer (A) is not limited, The homopolymer or copolymer of vinyl chloride is mentioned.

Monomers that can be copolymerized with vinyl chloride are not limited, and examples include ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid or an ester thereof, acrylic acid or an ester thereof, methacrylic acid or an ester thereof, and vinylidene chloride.

Alternatively, a partially crosslinked resin may be used. Further, a polymer blend of a polyvinyl chloride resin, for example, a polymer blend composed of a vinyl chloride resin and polyvinylidene chloride may be used. Among these, as the vinyl chloride resin used for the soft vinyl chloride resin layer (A), a vinyl chloride homopolymer is preferable.

The average degree of polymerization of the vinyl chloride resin used for the soft vinyl chloride resin layer (A) is not limited, but is preferably 500 to 6000, more preferably 800 to 3000.

The reduced viscosity (K value) of the vinyl chloride resin used in the present invention is not limited, but is preferably 50 to 110, more preferably 60 to 90 as a value based on JIS K7367-2 (1999). .

The production method of the vinyl chloride resin is not limited, and examples thereof include a production method such as a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method. Further, it may be a plastisol or an aqueous latex in which vinyl chloride resin fine particles are dispersed in an organic medium.

The soft vinyl chloride resin layer (A) in the present invention preferably contains a plasticizer together with the vinyl chloride resin.

The plasticizer used for the soft vinyl chloride resin layer (A) is not limited, but specific examples include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate. Phthalates having 1 to 12 carbon atoms such as diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate, diundecyl phthalate, ditridecyl phthalate, didodecyl phthalate, diisocumyl phthalate and dinonyl phthalate Acid esters; diisobutyl adipate, dibutyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate, dibutyl diglycol adipate, di-2-ethylhexyl a Rate, dihexyl azelate, diisooctyl azelate, triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, acetyl trioctyl citrate, dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl seba Fatty acid esters such as keto, methyl acetyl ricinolate and butyl acetyl ricinolate; tri- (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, tetra- (2-ethylhexyl) pyromellitate, tetra -N-octyl pyromellitate, tetraisooctyl pyromellitate, biphenyltetracarboxylic acid tetrabutyl ester, biphenyltetracarboxylic acid tetrape Aromatic carboxylic esters such as tilester and biphenyltetracarboxylic acid tetrahexyl ester; tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl Orthophosphates such as diphenyl phosphate, xylenyl diphenyl phosphate and 2-ethylhexyl diphenyl phosphate; chlorinated paraffin; chlorinated fatty acid ester; epoxidized soybean oil; epoxidized linseed oil; epoxy butyl stearate, epoxy octyl stearate Examples include methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate The These plasticizers may be used alone or in combination of two or more compounds.

The amount of the plasticizer used in the present invention is not limited, but it is preferably 1 to 150 parts by weight, more preferably 15 to 120 parts by weight, still more preferably 20 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin. 100 parts by weight.

By setting the blending amount of the plasticizer to be equal to or more than the lower limit, the flexibility of the laminate of the present invention is improved. On the other hand, by making the compounding quantity of a plasticizer below the said upper limit, while preventing a plasticizer from bleeding out from the laminated body of this invention, the deterioration of a moldability can be prevented.

The soft vinyl chloride resin layer (A) in the present invention may contain a stabilizer together with the vinyl chloride resin.

The stabilizer used for the soft vinyl chloride resin layer (A) is not limited, but can be appropriately selected from known stabilizers for vinyl chloride resin, such as tribasic lead sulfate and dibasic phthalates. Lead silicate, lead silicate, lead orthosilicate-silica gel coprecipitate, dibasic lead stearate, cadmium-barium stabilizer, barium-zinc stabilizer, calcium-zinc stabilizer, tin stabilizer, and Examples thereof include stabilizers mainly composed of inorganic salts such as magnesium, aluminum or silicon such as hydrotalcite. These stabilizers may use only 1 type of compound, or may use 2 or more types of compounds together.

The amount of the stabilizer used in the present invention is not limited, but it is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, still more preferably 3 to 3 parts by weight based on 100 parts by weight of the vinyl chloride resin. 15 parts by weight. When the stabilizer is blended in the above range, the thermal stability or moldability tends to be good.

<Adhesive resin layer (B1)>
The adhesive resin layer (B1) in the present invention contains at least an alicyclic polyester and a styrene-based elastomer. In the present invention, by using an alicyclic polyester and a styrene-based elastomer in combination as the adhesive resin layer (B1), both the vinyl chloride resin layer (A) and the polyolefin layer (C) can exhibit good adhesiveness. It becomes possible.

Although the cause is not clear, alicyclic polyester expresses an affinity and adhesive effect with soft vinyl chloride resin, while styrene elastomer expresses an affinity and adhesive effect with polyolefin, Moreover, it is considered that the alicyclic polyester and the styrene elastomer have a good affinity.

In addition, the resin composition containing the alicyclic polyester and styrene elastomer used for the adhesive resin layer (B1) is the resin composition according to the third aspect of the present invention.

[Alicyclic polyester]
The alicyclic polyester in the present invention is not limited as long as it is a polyester obtained by using an alicyclic compound as a raw material monomer, but is preferably a polyester having an alicyclic compound as a main component. Here, “having an alicyclic compound as a main component” means a polyester containing 50% by weight or more of an alicyclic compound as a structural unit of the polyester (in other words, as a raw material monomer).

The content of the alicyclic compound constituting the alicyclic polyester is preferably 60% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more. The adhesive performance as an adhesive resin layer (B1) can be improved by making the content rate of the alicyclic compound which comprises alicyclic polyester more than the said lower limit. In addition, the upper limit of the content rate of the alicyclic compound which comprises this alicyclic polyester is 100 weight% normally.

Here, as described later, when the alicyclic polyester in the present invention contains a polyalkylene ether polyol as a soft segment, when calculating the content of the alicyclic compound constituting the alicyclic polyester, The weight of the alkylene ether polyol is excluded and handled.

The alicyclic compound constituting the alicyclic polyester in the present invention may be any of dicarboxylic acid, diol, oxycarboxylic acid and caprolactone as a raw material monomer, and further, as a compound other than an ester-forming monomer. An alicyclic compound may be used. Preferably, an alicyclic compound is used as any one of dicarboxylic acid, diol, and oxycarboxylic acid, and further, an alicyclic compound is used as at least one of dicarboxylic acid and diol. It is.

When alicyclic dicarboxylic acid is used as a raw material monomer constituting alicyclic polyester, the compound is not limited. For example, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Cyclohexanedicarboxylic acids such as acids; decahydro such as 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalenedicarboxylic acid and 2,7-decahydronaphthalenedicarboxylic acid And naphthalenedicarboxylic acids. Of these, cyclohexanedicarboxylic acid is preferred, and 1,4-cyclohexanedicarboxylic acid is particularly preferred. Two or more of these alicyclic dicarboxylic acids can be used in combination.

When the alicyclic diol is used as a raw material monomer constituting the alicyclic polyester, the compound is not limited. For example, cyclopentane diol such as 1,2-cyclopentanediol and 1,3-cyclopentanediol; 5-membered ring diols such as 2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol and cyclopentanedimethanol bis (hydroxymethyl) tricyclodecane; 1,2-cyclohexanediol, 1,3-cyclohexanediol and 1 Cyclohexanediol such as 1,4-cyclohexanediol; cyclohexanedimethanol such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol; 2,2-bis- (4-hydroxy Kurohekishiru) biscyclohexyl diol such as propane.

Of these, cyclohexanedimethanol is preferred, and 1,4-cyclohexanedimethanol is particularly preferred. Two or more of these alicyclic diols can be used in combination.

These alicyclic dicarboxylic acids and alicyclic diols may be ester-forming derivatives as raw material monomers.

When the alicyclic compound constituting the alicyclic polyester is a 6-membered ring, the 6-membered ring compound may be a trans isomer, a cis isomer, or a mixture thereof. For both the alicyclic dicarboxylic acid and the alicyclic diol, the trans isomer content is preferably 50 mol% or more, more preferably 60 mol% or more, based on the total amount of the trans isomer and the cis isomer. Preferably, it is 70 mol% or more.

When the ratio of the trans form is not less than the lower limit, the heat resistance and moldability of the alicyclic polyester tend to be improved. Further, the trans isomer content is usually 100 mol% or less, and more preferably 85 mol% or less. When the ratio of the transformer body is not more than the above upper limit value, the moldability during coextrusion tends to be improved.

In the alicyclic polyester used in the present invention, a compound other than the alicyclic compound can be used in combination as a raw material monomer. The compound that can be used as the raw material monomer for the alicyclic polyester is not limited, and various dicarboxylic acids, diols, oxycarboxylic acids, caprolactones, polyfunctional compounds, and the like can be used.

Examples of dicarboxylic acids other than alicyclic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, phenylenedioxydicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and 4,4 ′. Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, 4,4′-diphenyl ketone dicarboxylic acid, 4,4′-diphenoxyethane dicarboxylic acid and 4,4′-diphenylsulfone dicarboxylic acid; succinic acid, glutaric acid, adipic acid And aliphatic dicarboxylic acids such as pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid and dodecadicarboxylic acid. Among these, terephthalic acid or 2,6-naphthalenedicarboxylic acid is preferable, and terephthalic acid is particularly preferable. Two or more dicarboxylic acids other than these alicyclic dicarboxylic acids can be used in combination.

As diols other than alicyclic diols, in addition to polyalkylene ether polyols described later, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, Aliphatic diols such as decamethylene glycol, neopentyl glycol and diethylene glycol; xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyphenyl) propane, 2,2-bis (4′- and aromatic diols such as β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone and bis (4-β-hydroxyethoxyphenyl) sulfonic acid.

Among these, 1,4-butanediol or ethylene glycol is preferable in addition to the polyalkylene ether polyol described later, and 1,4-butanediol is particularly preferable. Two or more diols other than these alicyclic diols can be used in combination.

Examples of the polyfunctional compound include polyols such as trimellitic acid, pyromellitic acid, and pentaerythritol, tricarboxylic acid, and tetracarboxylic acid.
In addition, you may use raw material monomers other than these alicyclic compounds as an ester-forming derivative.

Among these, as the alicyclic polyester used for the adhesive resin layer (B1), units derived from 1,4-cyclohexanedicarboxylic acid are preferably 50 mol% or more, more preferably 60 mol%, in all dicarboxylic acid units. As mentioned above, it is more preferable that it is 70 mol% or more.

The upper limit of the proportion of units derived from 1,4-cyclohexanedicarboxylic acid in all dicarboxylic acid units is 100 mol%. If the proportion of units derived from 1,4-cyclohexanedicarboxylic acid in the total dicarboxylic acid units is within the above range, the proportion of unreacted substances or low molecular weight components is small, so that hygiene tends to be good.

In addition, as the alicyclic polyester, 1,4-cyclohexanedimethanol is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol in all diols excluding the polyalkylene ether polyol described later. % Or more is preferable.

The upper limit of the proportion of 1,4-cyclohexanedimethanol-derived units in all diol units is usually 100 mol%. When the proportion of units derived from 1,4-cyclohexanedimethanol in all diol units excluding polyalkylene ether polyol is within the above range, the proportion of unreacted substances and low molecular weight components is small, and thus hygiene tends to be good. It becomes.

The alicyclic polyester used for the adhesive resin layer (B1) in the present invention may be a so-called block copolymer having a hard segment and a soft segment and containing a polyalkylene ether polyol as the soft segment. Here, the structure of the alicyclic polyester described above corresponds to the hard segment.

It is preferable that the alicyclic polyester contains a polyalkylene ether polyol as a soft segment because the crystallization speed is improved and the transparency after heat sterilization tends to be good. The polyalkylene ether polyol is an embodiment of “diol other than alicyclic diol” as described above.

Thus, by including a polyalkylene ether polyol as a soft segment, the laminate of the present invention can further improve flexibility, impact resistance, soft touch, and the like.

The polyalkylene ether polyol constituting the soft segment is not limited, but among them, polyalkylene ether glycol is preferable.

Examples of the polyalkylene ether glycol include polyethylene ether glycol, polypropylene ether glycol, polytrimethylene ether glycol, polytetramethylene ether glycol, and polyhexamethylene ether glycol. Particularly preferred is polytetramethylene ether glycol. These polyalkylene ether glycols may be used in combination.

When a block copolymer having a hard segment and a soft segment is used as the alicyclic polyester in the present invention, in particular, as the hard segment, a structure derived from 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedimethanol Is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, and polytetramethylene ether glycol is preferably used as the soft segment.

The number average molecular weight of the soft segment, that is, the number average molecular weight of the polyalkylene ether polyol is preferably 200 to 4000, more preferably 300 to 3000, and still more preferably 500 to 2500.

Good flexibility can be obtained by setting the number average molecular weight of the polyalkylene ether polyol to the lower limit value or more. Moreover, by making a number average molecular weight below the said upper limit, the phase-separation within alicyclic polyester can be suppressed and it can prevent that the transparency or heat resistance of a laminated body falls.

In addition, the “number average molecular weight” referred to here is measured by gel permeation chromatography (GPC). For calibration of GPC, a POLYTETRAHYDROFURAN calibration kit manufactured by POLYMERLABORATORIES, UK may be used.

The content of the polyalkylene ether polyol in the alicyclic polyester is not limited, but is preferably 3 to 40% by weight, more preferably 6 to 30% by weight.

When the content of the polyalkylene ether polyol that is a soft segment is set to the above lower limit value or more, the flexibility, adhesiveness, and tackiness tend to be improved. Moreover, it can suppress that transparency and heat resistance of a laminated body fall by making content of a soft segment below the said upper limit.

The content of the structural unit derived from the polyalkylene ether polyol can be calculated from the charged ratio at the time of production or quantified by an instrumental analysis method such as ¹ H-NMR spectrum analysis.

The alicyclic polyester used for the adhesive resin layer (B1) in the present invention has a melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg (kgf) according to test condition 4 of JIS K7210 (1999). Preferably, it is in the range of 0.1 to 100 (g / 10 minutes), more preferably 0.5 to 80 (g / 10 minutes), and still more preferably 1.0 to 60 (g / 10 minutes). Is preferred.

When the MFR is not more than the above upper limit value, the moldability of the laminate can be improved, and further the mechanical strength of the laminate can be improved. On the other hand, by making MFR more than the said lower limit, fluidity | liquidity becomes favorable and the moldability of a laminated body improves.

The melting point of the alicyclic polyester used for the adhesive resin layer (B1) in the present invention is 130 ° C. or higher, preferably 160 ° C. or higher, and 200 ° C. or lower, in terms of the balance between processability and transparency. Preferably it is 190 degrees C or less. Further, when the laminate is manufactured by co-extrusion of the adhesive resin layer (B1) together with the soft vinyl chloride resin layer (A) because the melting point is not more than the above upper limit value, molding at a low temperature is possible. In addition, generation of hydrogen chloride gas derived from a soft vinyl chloride resin can be prevented, and deterioration of the molding machine can be prevented.

The melting point of the alicyclic polyester was determined by using a differential scanning calorimeter (DSC) or the like at a rate of temperature increase of 100 ° C./min from room temperature to 250 ° C. and held for 3 minutes, and then cooled to −100 ° C. It is the temperature of the melting peak when the temperature is raised to 250 ° C. at a rate of temperature increase of 10 ° C./min after cooling at 10 ° C./min.

[Styrene elastomer]
The styrenic elastomer in the present invention is not limited as long as it has a polymer block mainly composed of a vinyl aromatic compound and a polymer block imparting flexibility, and specifically, for example, vinyl aromatic A block copolymer having at least two polymer blocks P mainly composed of a compound and at least one polymer block Q mainly composed of butadiene and / or isoprene and / or hydrogenating the block copolymer. (Hereinafter, the polymer block P may be abbreviated as “block P” and the polymer block Q may be abbreviated as “block Q”).

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 a styrene derivative such as styrene or α-methylstyrene is 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 butadiene alone, isoprene alone, butadiene or isoprene. The block Q may contain monomers other than butadiene and isoprene as raw materials.

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%, more preferably 80 to 100%.

By hydrogenating the block Q within the above range, the thermal stability of the laminate of the present invention 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 styrenic elastomer is not limited, but is preferably 5% by weight or more, more preferably 10% by weight or more, on the other hand, 55% by weight or less, preferably 50% by weight. More preferably, it is more preferably 45% by weight or less. When the weight ratio of the block P is in the above range, the adhesiveness of the laminate of the present invention tends to be good.

When the block Q is a hydrogenated derivative and is mainly composed of butadiene, the 1,2-addition structure of butadiene 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.

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, the adhesiveness of the laminate of the present invention tends to be good by setting the ratio of 1,2-addition structure within the above range.

When the copolymer having the block P and the block Q is used as the styrenic elastomer, the chemical structure may be any of linear, branched or radial, but the following formula (1) or ( The block copolymer represented by 2) is preferable, and the structure of the following formula (1) is more preferable from the viewpoint of adhesiveness.

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 adhesiveness of the laminate of the present invention tends to be good.

P- (QP) 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 formula (1) or (2), m and n are preferably larger in terms of lowering the order-disorder transition temperature as a rubbery polymer, but smaller in terms of ease of production and cost. . In the present invention, m and n are preferably given as integers of 1 to 5, more preferably 2 to 4.

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 styrene elastomer in the first embodiment of the present invention is 190,000 or less. If the number average molecular weight of the styrene-based elastomer exceeds the upper limit, the fluidity is lowered. As a result, the styrene-based elastomer forms a domain in the adhesive resin layer (B1), so that the adhesiveness to other resin layers is reduced. In particular, the adhesion with the polyolefin layer is deteriorated.

The number average molecular weight of the styrene-based elastomer is preferably 150,000 or less, more preferably 120,000 or less, still more preferably 100,000 or less, and particularly preferably 90000 or less, for the same reason as described above.

The lower limit of the number average molecular weight of the styrene-based elastomer is not limited, but is preferably 20000 or more, more preferably 40000 or more, and further preferably 50000 or more. When the number average molecular weight of the styrene elastomer is less than the lower limit, the material strength tends to be low.

The number average molecular weight of the styrene elastomer is a value in terms of polystyrene measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC) under the following conditions.

(Measurement condition)
Equipment: “150C ALC / GPC” manufactured by Nihon Millipore Corporation
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
Add 0.2% by weight of 2,6-di-t-butyl-p-phenol as an antioxidant.

The production method of the styrene elastomer 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. In addition, a known method such as hydrogenation (hydrogenation) of the block copolymer can be employed, for example, in an inert solvent in the presence of a hydrogenation catalyst.

Examples of commercially available hydrogenated block copolymers include “KRATON (registered trademark) -G” manufactured by Kraton Japan Co., Ltd., “Septon (registered trademark)” and “Hibler (registered trademark)” manufactured by Kuraray Co., Ltd. And “Tuftec (registered trademark)” manufactured by Asahi Kasei Corporation.

In addition, examples of commercially available non-hydrogenated block copolymers include “KRATON (registered trademark) -A” manufactured by Kraton Japan Co., Ltd., and some grades of “Hylar (registered trademark)” manufactured by Kuraray Co., Ltd. Asahi Kasei Corporation "Tufprene (registered trademark)" and the like.

In the present invention, a rubber softener may be contained in the adhesive resin layer (B1) within the range where the effects of the present invention are exhibited. Usable rubber softeners are not limited as long as the flexibility of the adhesive resin layer (B1) can be adjusted, and among them, hydrocarbon rubber softeners are preferable.

The hydrocarbon rubber softener is preferably a mineral oil or synthetic resin softener and more preferably a mineral oil softener because of its high affinity for styrene elastomers.

[Combination ratio]
The blending ratio (weight ratio) of the alicyclic polyester and the styrenic elastomer in the present invention is not limited, but is preferably in the range of 95/5 to 35/65, and preferably 90/10 to 40/60. More preferred.

Adhesiveness to the polyolefin layer (C) can be improved by setting the blending ratio of the styrene elastomer to the lower limit value or more. Moreover, affinity with a soft vinyl chloride resin can be improved by making the mixture ratio of a styrene-type elastomer below the said upper limit.

The blending of the alicyclic polyester and the styrene elastomer constituting the adhesive resin layer (B1) in the present invention may be made in advance as a uniform resin composition, or when molding a laminate described later, May be used by appropriately blending (dry blending).

When the adhesive resin layer (B1) in the present invention is previously formed as a uniform resin composition, the method is not limited. For example, a method of mixing with a Henschel mixer, a V-blender, a ribbon blender or a tumbler blender, The mixture obtained by such a method can be obtained by further kneading with a single screw extruder, twin screw extruder, kneader or Banbury mixer, and then granulating. Moreover, it can also mix using a kneader or a roll.

The production conditions for producing the resin composition by these methods are not limited, and can be appropriately set under known conditions. The temperature at the time of melt mixing may be any temperature at which at least one of the raw material components is in a molten state, but usually the temperature at which all the components used are melted is selected, and the temperature is generally 150 to 250 ° C.

<Adhesive resin layer (B2)>
The adhesive resin layer (B2) in the second aspect of the present invention contains at least alicyclic polyester. In the present invention, by containing alicyclic polyester as the adhesive resin layer (B2), the vinyl chloride resin layer (A) and the adhesive resin layer (B3) can exhibit good adhesiveness and / or affinity. It becomes possible. Although the cause is not clear, it is considered that the alicyclic polyester has high affinity with both the soft vinyl chloride resin (A) and the resin constituting the adhesive resin layer (B3).

The content of the alicyclic polyester in the adhesive resin layer (B2) is not limited, but is preferably 50% by weight or more, and more preferably 70% by weight or more. The upper limit is preferably 100% by weight.

[Alicyclic polyester]
Although the alicyclic polyester in this invention will not be limited if it has an alicyclic compound as a raw material monomer, It is preferable that it is polyester which has an alicyclic compound as a main component.

Here, “having an alicyclic compound as a main component” means a polyester containing 50% by weight or more of an alicyclic compound as a structural unit of the polyester (in other words, as a raw material monomer). The content of the alicyclic compound constituting the alicyclic polyester is preferably 60% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more.

Adhesive performance as the adhesive resin layer (B2) can be improved by setting the content of the alicyclic compound constituting the alicyclic polyester to the lower limit value or more. In addition, the upper limit of the content rate of the alicyclic compound which comprises the said alicyclic polyester is 100 weight% normally.

The alicyclic compound constituting the alicyclic polyester in the present invention is the same as that described in the adhesive resin layer (B1) in the laminate according to the first aspect of the present invention as a raw material monomer. Can do.

When the alicyclic compound constituting the alicyclic polyester is a 6-membered ring, the 6-membered ring compound may be a trans isomer or a cis isomer, or a mixture thereof. For both the cyclic dicarboxylic acid and the alicyclic diol, the trans isomer content is preferably 50 mol% or more, more preferably 60 mol% or more, based on the total amount of the trans isomer and the cis isomer. 70 mol% or more is more preferable.

When the ratio of the trans form is not less than the lower limit, the heat resistance and moldability of the alicyclic polyester tend to be improved. Moreover, the upper limit of the trans isomer content is usually 100 mol%, and more preferably 85 mol% or less. When the ratio of the transformer body is not more than the above upper limit value, the moldability during coextrusion tends to be improved.

In the alicyclic polyester used in the present invention, a compound other than the alicyclic compound can be used in combination as a raw material monomer. The compounds other than the alicyclic compounds that can be used here are the same as those mentioned in the description of the adhesive resin layer (B1). In the alicyclic polyester used for the adhesive resin layer (B2), the unit derived from 1,4-cyclohexanedicarboxylic acid is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably, among all dicarboxylic acid units. It is 70 mol% or more. The upper limit of the proportion of units derived from 1,4-cyclohexanedicarboxylic acid in all dicarboxylic acid units is usually 100 mol%.

If the proportion of units derived from 1,4-cyclohexanedicarboxylic acid in the total dicarboxylic acid units is within the above range, the proportion of unreacted substances and low molecular weight components is small, and thus hygiene tends to be good.

In addition, as the alicyclic polyester, 1,4-cyclohexanedimethanol is preferably 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol in all diols excluding the polyalkylene ether polyol described later. % Or more is preferable. The upper limit of the proportion of 1,4-cyclohexanedimethanol-derived units in all diol units is usually 100 mol%.

When the proportion of units derived from 1,4-cyclohexanedimethanol in all diol units excluding polyalkylene ether polyol is within the above range, the proportion of unreacted substances or low molecular weight components is small, so that hygiene is good. There is a tendency.

The alicyclic polyester used for the adhesive resin layer (B2) in the present invention may be a so-called block copolymer having a hard segment and a soft segment and containing a polyalkylene ether polyol as the soft segment.

Here, the structure of the alicyclic polyester described above corresponds to the hard segment. When the alicyclic polyester contains a polyalkylene ether polyol as a soft segment, the crystallization speed is improved and the transparency after heat sterilization tends to be good, which is preferable. The polyalkylene ether polyol is an embodiment of “diol other than alicyclic diol” as described above.

The polyalkylene ether polyol constituting the soft segment is not limited, but the same as those mentioned in the description of the adhesive resin layer (B1) can be used.

Sufficient flexibility can be obtained by setting the number average molecular weight of the polyalkylene ether polyol to the lower limit value or more. Moreover, by making a number average molecular weight below the said upper limit, the phase-separation within alicyclic polyester can be suppressed and it can prevent that the transparency or heat resistance of a laminated body falls.

When the content of the polyalkylene ether polyol, which is a soft segment, is set to the above lower limit or more, flexibility, adhesiveness, and tackiness tend to be improved. Moreover, it can suppress that transparency and heat resistance of a laminated body fall by making content of a soft segment below the said upper limit.

Although the melting point of the alicyclic polyester used for the adhesive resin layer (B2) in the present invention is not limited, it is preferably 130 ° C. or higher, more preferably 160 ° C. or higher from the viewpoint of the balance between processability and transparency. 210 ° C. or less, more preferably 200 ° C. or less. Further, when the laminate is manufactured by co-extrusion of the adhesive resin layer (B1) together with the soft vinyl chloride resin layer (A) because the melting point is not more than the above upper limit value, molding at a low temperature is possible. In addition, generation of hydrogen chloride gas derived from a soft vinyl chloride resin can be prevented, and deterioration of the molding machine can be prevented.

The adhesive resin layer (B2) in the present invention has a melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg (kgf) in accordance with JIS K7210 (1999), preferably 0.1 to It is preferably 100 (g / 10 minutes), more preferably 0.5 to 80 (g / 10 minutes), and still more preferably 1.0 to 60 (g / 10 minutes).

When the MFR is not more than the above upper limit value, the moldability of the laminate can be improved, and further the mechanical strength of the laminate can be improved. By making MFR more than the said lower limit, fluidity | liquidity becomes favorable and the moldability of a laminated body improves.

<Adhesive resin layer (B3)>
The adhesive resin layer (B3) in the present invention contains at least a styrene elastomer and a modified polyolefin resin. Since the styrenic elastomer and the modified polyolefin resin have good affinity, the adhesive resin layer (B3) containing these as essential components can exist in a state where the phase structure is stable.

In the present invention, the adhesive resin layer (B3) contains both a styrene elastomer and a modified polyolefin resin, thereby exhibiting good adhesiveness and / or affinity with the adhesive resin layer (B2) and the polyolefin layer (C). It becomes possible to do.

Although the cause is not clear, the styrene elastomer in the adhesive resin layer (B3) exhibits tackiness, while the modified polyolefin resin chemically reacts with the alicyclic polyester constituting the adhesive resin layer (B2). It is considered that good adhesiveness with the adhesive resin layer (B2) is expressed. Moreover, since the modified polyolefin in the adhesive resin layer (B3) has high affinity with the polyolefin layer (C), it is considered that good adhesiveness is expressed.

The total content of the styrene-based elastomer and the modified polyolefin resin in the adhesive resin layer (B3) is not limited, but is preferably 20% by weight or more, more preferably 30% by weight or more, and further preferably 40% by weight or more. The upper limit is 100% by weight.

[Styrene elastomer]
The styrenic elastomer in the present invention is not limited as long as it has a polymer block mainly composed of a vinyl aromatic compound and a polymer block imparting flexibility, except for the number average molecular weight described below, The thing similar to what was mentioned in description of the said adhesive resin layer (B1) can be used.

Although the number average molecular weight of the styrene-based elastomer in the present invention is not limited, it is preferably 20000 or more, more preferably as a value in terms of polystyrene measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC). 40,000 or more, more preferably 50,000 or more, preferably 300,000 or less, more preferably 200,000 or less, still more preferably 150,000 or less, particularly preferably 100,000 or less.

When the number average molecular weight of the styrene-based elastomer is within the above range, the adhesiveness and / or affinity with the adhesive resin layer (B2) and the polyolefin layer (C) tend to be good.

Examples of commercially available non-hydrogenated block copolymers include “KRATON (registered trademark) -A” manufactured by Kraton Japan Co., Ltd. Asahi Kasei Co., Ltd. “Tufprene (registered trademark)” and the like.

In the present invention, a rubber softener may be contained in the adhesive resin layer (B3) within the range where the effects of the present invention are exhibited. Usable rubber softeners are not limited as long as the flexibility of the adhesive resin layer (B3) can be adjusted, and among them, hydrocarbon rubber softeners are preferable.

[Modified polyolefin resin]
The modified polyolefin resin in the present invention is obtained by reacting a polyolefin resin and an unsaturated compound.

The polyolefin resin used for the production of the modified polyolefin resin is selected from known polyolefin resins, and specifically, the resins exemplified as the raw material of the polyolefin layer (C) described later can be used similarly.

Among these, the polyolefin resin is preferably a propylene resin. Here, the propylene-based resin means a polymer obtained from a monomer mainly composed of propylene, specifically, a propylene homopolymer, a propylene / ethylene copolymer, a propylene / 1-butene copolymer or a propylene / ethylene. -1-butene copolymer is preferred. Among them, a propylene homopolymer is particularly preferable.

The polyolefin resin may be any one of the above-mentioned various polyolefin resins, or may be a mixture of plural kinds.

The melt flow rate (MFR) of the polyolefin resin is not limited, but is preferably 0.01 to 80 g / 10 minutes, more preferably 0.1 to 40 g / 10 minutes from the viewpoint of moldability.

Here, MFR means a value at 190 ° C. and a load of 2.16 kg when the polyolefin resin is ethylene or an α-olefin having 3 or more carbon atoms (molar conversion), and the polyolefin resin is propylene. Is the value at 230 ° C. and a load of 2.16 kg.

The unsaturated compound used in the present invention is not limited as long as it is an unsaturated compound that can react with the polyolefin resin. Here, “can react” includes not only the case of reacting with the polyolefin resin by the unsaturated group constituting the unsaturated compound, but also the case of reacting with the polyolefin resin without passing through the unsaturated group. .

Specific examples of reactive compounds include, but are not limited to, unsaturated carboxylic acids or derivatives thereof, and ethylenically unsaturated silane compounds. Of these, unsaturated carboxylic acids or derivatives thereof are preferred.

Examples of the unsaturated carboxylic acid or derivative thereof include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid TM (endocis-bicyclo [2,2,1 And unsaturated carboxylic acids such as hept-5-ene-2,3-dicarboxylic acid) and derivatives thereof such as acid halides, amides, imides, anhydrides and esters thereof. As the derivative, an acid anhydride is preferable.

Specific examples of the unsaturated carboxylic acid or derivative thereof include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. Of these, maleic acid or its anhydride is particularly preferred.

In the present invention, any method may be used for the reaction between the polyolefin resin and the unsaturated compound, and the reaction can be obtained by reaction only with heat, but an organic peroxide or the like that generates radicals during the reaction is used as a reaction aid. It may be added as Examples of the reaction method include a solution modification method in which a reaction is performed in a solvent or a melt modification method that does not use a solvent, but other methods may be used.

Examples of the melt modification method include, for example, a method in which a polyolefin resin and an unsaturated compound, and if necessary, an organic peroxide are mixed in advance and then reacted by melting and kneading in a kneader, and a polyolefin resin melted in the kneader, Examples thereof include a method in which a mixture of an organic peroxide and an unsaturated compound dissolved in a solvent or the like is added from the inlet and reacted.

The kneader is not particularly limited, and for example, a single or twin screw extruder, a roll, a Banbury mixer, a kneader, and a Brabender mixer can be used.

Examples of the solution modification method include a method in which a polyolefin resin is dissolved in an organic solvent or the like, an organic peroxide and an unsaturated compound are added thereto, and graft copolymerization is performed. The organic solvent is not particularly limited, and examples thereof include alkyl group-substituted aromatic hydrocarbons and halogenated hydrocarbons.

The blending ratio of the polyolefin resin and the unsaturated compound is not limited, but the unsaturated compound is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 5 parts by weight, and still more preferably 100 parts by weight of the polyolefin resin. Is preferably blended at a ratio of 0.1 to 1 part by weight.

The reaction aid for generating radicals is not limited, and specific examples include benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate). ) Hexin-3, lauroyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert- Organic peroxides or organic peresters such as butyl perbenzoate, tert-butyl perisobutylate, tert-butyl perpivalate, and cumyl perpivalate, and azobisisobutyronitrile and dimethylazoisobutylene And azo compounds such as

These reaction aids can be appropriately selected according to the type of polyolefin resin, the type of unsaturated compound, and the reaction conditions, and two or more types may be used in combination. The compounding amount of the reaction aid is preferably 0.001 to 3 parts by weight, more preferably 0.005 to 0.5 parts by weight, and still more preferably 0.01 to 0 parts by weight based on 100 parts by weight of the polyolefin resin. .2 parts by weight, particularly preferably 0.01 to 0.1 parts by weight.

[Polyolefin resin]
The adhesive resin layer (B3) in the present invention preferably contains an unmodified polyolefin resin in addition to the styrene elastomer and the modified polyolefin resin. Here, as the unmodified polyolefin resin contained in the adhesive resin layer (B3), the resins exemplified as raw materials for the polyolefin layer (C) described later can be similarly used. By using an unmodified polyolefin resin in combination in the adhesive resin layer (B3), it becomes easy to control the melt fluidity and the moldability tends to be improved.

The non-modified polyolefin resin used for the adhesive resin layer (B3) may be the same as or different from the polyolefin resin used as the raw material of the modified polyolefin resin, but when the same kind of polyolefin resin is used, the polyolefin layer Adhesiveness with (C) may improve.

Further, the unmodified polyolefin resin used for the adhesive resin layer (B3) may be the same as or different from the polyolefin resin used for the polyolefin layer (C) described later. Adhesiveness with a layer (C) may improve.

[Combination ratio]
The blending ratio (weight ratio) of the styrene elastomer and modified polyolefin resin in the present invention is not limited, but is preferably in the range of 5/95 to 80/20, more preferably 5/95 to 60/40. preferable.

Formability can be improved by setting the blending ratio of the modified polyolefin resin to the lower limit value or more. Moreover, the adhesiveness with respect to an adhesive resin layer (B2) can be improved by making the mixture ratio of modified polyolefin resin into the said upper limit or less.

The content when the unmodified polyolefin resin is contained in the adhesive resin layer (B3) is not limited, but is preferably 10% by weight or more, more preferably 20% by weight or more in the adhesive resin layer (B3). More preferably, it is 30% by weight or more, preferably 90% by weight or less, more preferably 80% by weight or less, and still more preferably 70% by weight or less.

In the present invention, the styrene elastomer, the modified polyolefin resin, and the unmodified polyolefin resin used as necessary may be preliminarily made into a uniform resin composition to constitute the adhesive resin layer (B3) in the present invention. These may be appropriately blended (dry blended) when used to form a laminate described later.

When the adhesive resin layer (B3) in the present invention is previously formed as a uniform resin composition, the method is not limited, and examples thereof include a method of mixing with a Henschel mixer, a V-blender, a ribbon blender or a tumbler blender. In addition, for example, a mixture obtained by such a method may be further granulated after melt-kneading with a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, or the like. Moreover, the method of mixing using a kneader or a roll is mentioned, for example.

The production conditions for producing the resin composition by these methods are not limited, and can be appropriately set under known conditions. 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 it is generally preferable to carry out at 150 to 250 ° C.

The adhesive resin layer (B3) in the present invention has a melt flow rate (MFR) measured according to JIS K7210 (1999) test condition 4 of preferably 0.1 to 100 (g / 10 min), more preferably 0. It is preferably in the range of 5 to 80 (g / 10 minutes), more preferably 1.0 to 60 (g / 10 minutes).

When the MFR is not more than the above upper limit value, the moldability of the laminate can be improved and the mechanical strength of the laminate can be improved. By making MFR more than the said lower limit, fluidity | liquidity becomes favorable and the moldability of a laminated body can be improved.

As described above, the adhesive resin layer (B3) in the present invention may be produced by appropriately blending a styrene-based elastomer, a modified polyolefin resin, and an unmodified polyolefin resin contained as necessary. May be used. As a commercial item, what corresponds to an adhesive resin layer (B3) can be selected and used from Mitsubishi Chemical Corporation "Zeras" etc.

<Polyolefin layer (C)>
The polyolefin layer (C) in the present invention contains at least a polyolefin resin. The polyolefin resin that can be used for the polyolefin layer (C) is not limited, but for example, homopolymers of α-olefins such as ethylene, propylene, or 1-butene, the α-olefins or the α-olefins thereof. Other α-olefins having about 4 to 20 carbon atoms such as 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene or 1-decene, vinyl acetate, vinyl Examples thereof include a copolymer with alcohol, (meth) acrylic acid or (meth) acrylic acid ester.

Specific examples of polyolefin resins include, for example, ethylene homopolymers such as low, medium and high density polyethylene (branched or linear), ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene- 4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer (ethylene-vinyl acetate copolymer) Polymer saponified products), ethylene-based resins such as ethylene- (meth) acrylic acid copolymers and ethylene- (meth) acrylic acid ester copolymers; propylene homopolymers, propylene-ethylene copolymers and propylene- Propylene resins such as ethylene-1-butene copolymer; and 1-butene homopolymer, 1-butene-ethylene copolymer Coalescence and butene - propylene copolymer 1-butene-based resin of the polymer and the like; ring-opening metathesis polymer and a norbornene derivative of norbornene - such as so-called cyclic polyolefin resins such as ethylene copolymers.

Further, as the polyolefin resin used for the polyolefin layer (C), similarly to the modified polyolefin resin contained in the adhesive resin layer (B3), these polyolefin resins are unsaturated carboxylic acids such as maleic anhydride, maleic acid or acrylic acid. Alternatively, it may be modified with a derivative thereof or an unsaturated silane compound.

Here, the ethylene-based resin means a polymer containing ethylene as a main component as a raw material monomer, and preferably containing 50 mol% or more of ethylene. The propylene resin means a polymer containing propylene as a main component as a raw material monomer, and preferably containing 50 mol% or more of propylene. The same applies to 1-butene resins.

These polyolefin resins may be used alone or in combination of two or more.

The polyolefin resin suitable for the polyolefin layer (C) varies depending on the use and required characteristics of the laminate of the present invention, but when used for an infusion bag, an ethylene resin or a propylene resin is preferable.

The ethylene resin is more preferably a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, and the propylene resin is a copolymer of propylene and ethylene or an α-olefin having 4 to 8 carbon atoms. Is more preferable.

Further, the chain form in the case of using a copolymer as the polyolefin resin is not limited and may be any of a block copolymer, a random copolymer, a graft copolymer, etc., but the block copolymer or the random copolymer may be used. Polymers are preferred.

The polyolefin resin used for the polyolefin layer (C) has a melt flow rate (MFR) of preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more, and further preferably 0.5 g / 10 min. Above, preferably 50 g / 10 min or less, more preferably 30 g / 10 min or less, and still more preferably 10 g / 10 min or less.

By setting the MFR of the polyolefin resin to be equal to or higher than the lower limit, the fluidity is increased and the molding becomes easy. Further, by setting the MFR to be equal to or less than the upper limit value, fluidity is suppressed and molding becomes easy.

<Laminated body>
The laminate according to the first aspect of the present invention includes at least the soft vinyl chloride resin layer (A), the adhesive resin layer (B1), and the polyolefin layer (C) described above. The laminate according to the second aspect of the present invention has at least each of the soft vinyl chloride resin layer (A), the adhesive resin layer (B2), the adhesive resin layer (B3), and the polyolefin layer (C) described above. . Furthermore, in any of the laminated body according to the first aspect of the present invention and the laminated body according to the second aspect, any layer other than these layers (hereinafter sometimes referred to as “other layers”) is arbitrarily used. You may have.

The configuration of the layer in the laminate according to the first aspect of the present invention is not limited, but the soft vinyl chloride resin layer (A) and the adhesive resin layer (B1) are preferably adjacent to each other, and the adhesive resin layer It is preferable that (B1) and the polyolefin layer (C) are adjacent to each other. In particular, the soft vinyl chloride resin layer (A), the adhesive resin layer (B1), and the polyolefin layer (C) are preferably adjacent to each other in this order. By adopting such a layer configuration, the soft vinyl chloride resin layer (A) and the polyolefin layer (C) can have the respective characteristics, and the flexibility, impact resistance, transparency and hygiene are good. It can be set as a laminated body.

The layer structure of the laminate according to the second aspect of the present invention is preferably such that the soft vinyl chloride resin layer (A) and the adhesive resin layer (B2) are adjacent to each other, and the adhesive resin layer (B2). And the adhesive resin layer (B3) are preferably adjacent to each other, and the adhesive resin layer (B3) and the polyolefin layer (C) are preferably adjacent to each other. By adopting such a layer configuration, the soft vinyl chloride resin layer (A) and the polyolefin layer (C) can have the respective characteristics, and the flexibility, impact resistance, transparency and hygiene are good. It can be set as a laminated body.

Each of the laminates according to the first aspect and the second aspect of the present invention is not limited in shape, and may be a planar shape such as a film, a sheet, or a plate shape, a pipe shape, a bag shape, or an indefinite shape. Either may be sufficient.

In the laminate of the present invention, the material constituting the other layer is not limited, but specifically, a thermoplastic resin such as a polyamide resin, a polyester resin, a styrene resin, an acrylic resin, or a polycarbonate resin is used. These resins may be a resin composition layer containing a plurality of resins.

The polyamide resin used for the other layers is not limited. Specifically, nylon 6, nylon 66, nylon 610, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 66/610, nylon 6/11, MXD nylon, amorphous nylon or terephthalic acid / adipic acid / hexamethylenediamine copolymer is preferably used. These polyamide resins may be used alone or in combination. Among these, nylon 6, nylon 66, or nylon 6/66, which has an excellent melting point and rigidity, is preferable.

The thickness (total thickness) of the laminate of the present invention is not limited and can be arbitrarily set depending on the layer structure, application, shape of the final product, required physical properties, and the like.
The total thickness of the unstretched laminate is preferably 30 to 500 μm, more preferably 40 to 400 μm, and particularly preferably 50 to 300 μm. The total thickness of the stretched laminate (stretched film) is preferably 5 to 400 μm, more preferably 10 to 300 μm, and particularly preferably 20 to 200 μm.

The thickness of each layer of the laminate of the present invention is not limited, and can be arbitrarily set depending on the layer configuration, application, final product shape, required physical properties, and the like.

In the laminate according to the first aspect of the present invention, the thickness of the soft vinyl chloride resin layer (A) is preferably 50% or more, more preferably 55% or more, and preferably 94% or less with respect to the total thickness. More preferably, it is 90% or less. When the thickness of the soft vinyl chloride resin layer (A) is not less than the above lower limit value, the flexibility tends to be improved, and when it is not more than the above upper limit value, the hygiene tends to be improved.

In the laminate according to the first aspect of the present invention, the thickness of the adhesive resin layer (B1) is preferably 1% or more, more preferably 5% or more, preferably 20% or less, more preferably relative to the total thickness. 10% or less. When the thickness of the adhesive resin layer (B1) is equal to or greater than the lower limit value, the adhesiveness tends to be improved. When the thickness is equal to or smaller than the upper limit value, the film strength tends to be improved, and the cost is also advantageous. There is a tendency.

In the laminate according to the first aspect of the present invention, the thickness of the polyolefin layer (C) is preferably 5% or more, more preferably 10% or more, preferably 49% or less, more preferably 20%, based on the total thickness. % Or less. When the thickness of the polyolefin layer (C) is not less than the lower limit value, heat seal failure tends to be difficult to occur, and when it is not more than the upper limit value, flexibility tends to be improved.

In the laminated body according to the first aspect of the present invention, the thickness of the soft vinyl chloride resin layer (A) is preferably 50% or more, more preferably 100% or more, preferably with respect to the thickness of the polyolefin layer (C). It is 2800% or less, more preferably 2000% or less. When the thickness of the soft vinyl chloride resin layer (A) is not less than the above lower limit value, the flexibility tends to be improved, and when it is not more than the above upper limit value, the heat sealability tends to be improved.

In the laminate according to the second aspect of the present invention, the thickness of the soft vinyl chloride resin layer (A) is preferably 50% or more, more preferably 55% or more, preferably 93% or less, more than the total thickness. Preferably it is 90% or less. When the thickness of the soft vinyl chloride resin layer (A) is not less than the lower limit, flexibility tends to be improved, and when it is not more than the upper limit, hygiene tends to be improved.

In the laminate according to the second aspect of the present invention, the thickness of the adhesive resin layer (B2) is preferably 1% or more, more preferably 5% or more, preferably 20% or less, more preferably relative to the total thickness. It is 15% or less, more preferably 10% or less. When the thickness of the adhesive resin layer (B2) is equal to or greater than the lower limit value, the adhesiveness tends to be improved, and when it is equal to or smaller than the upper limit value, the film strength tends to be improved, and further advantageous in terms of cost. It becomes.

In the laminate according to the second aspect of the present invention, the thickness of the adhesive resin layer (B3) is preferably 1% or more, more preferably 5% or more, preferably 20% or less, more preferably relative to the total thickness. It is 15% or less, more preferably 10% or less. When the thickness of the adhesive resin layer (B3) is not less than the lower limit value, the adhesion tends to be improved, and when it is not more than the upper limit value, the film strength tends to be improved, and further, it is advantageous in terms of cost. It becomes.

In the laminate according to the second aspect of the present invention, the thickness of the polyolefin layer (C) is preferably at least 5%, more preferably at least 10%, preferably at most 48%, more preferably at 30% of the total thickness. % Or less. When the thickness of the polyolefin layer (C) is not less than the lower limit value, heat sealing failure tends to be difficult to occur, and when the thickness is not more than the upper limit value, flexibility tends to be improved.

In the laminate according to the second aspect of the present invention, the thickness of the soft vinyl chloride resin layer (A) is preferably 50% or more, more preferably 100% or more, preferably with respect to the thickness of the polyolefin layer (C). It is 2800% or less, more preferably 2000% or less. When the thickness of the soft vinyl chloride resin layer (A) is not less than the lower limit, flexibility tends to be improved, and when it is not more than the upper limit, heat sealability tends to be improved.

<Method for producing laminate>
As a method for producing the laminate of the present invention, various conventionally known methods can be employed. For example, a method of forming an inflation film, a T-die film, a sheet or a pipe by a coextrusion method in which individual molten resins melted by an extruder are supplied to a multilayer die and laminated in the die are formed. Examples thereof include co-injection molding in which individual molten resins are injected into the same mold with a time lag.

It is also possible to employ extrusion laminate molding in which a resin film constituting any one of the layers is formed in advance, and the other layers are melt extruded. Furthermore, it is also possible to form a laminate by previously forming a resin film constituting each layer and laminating these layers by applying heat.

Moreover, the laminated body of this invention can also be made into an extending | stretching laminated body by extending | stretching this, after obtaining a laminated body by the above shaping | molding. The stretched laminate may be heat-set, or may be a product without being heat-set. In the case where heat setting is not performed, the stretched laminate is heated to release stress and shrink, so that it can be used as a shrink film.
Furthermore, these can be made into a draw-formed container or the like through secondary processing such as vacuum forming or pressure forming.

<Molded body>
The shape and use of the molded product obtained from the laminate of the present invention are not limited, but are suitable as a medical container, food packaging material or pharmaceutical packaging material because of its good flexibility, hygiene, transparency and impact resistance. And is particularly suitable for an infusion bag.

An infusion bag is usually composed of a main body of an infusion bag, a port for injecting a chemical solution, a cap including a rubber stopper for taking out the chemical solution, etc., but the laminate of the present invention is suitable as a main body of an infusion bag. Can be used.

The method for forming an infusion bag with the laminate of the present invention is not limited, but a method of forming a tubular (cylindrical) inflation film by the above-described coextrusion method and fusing the ends can be preferably employed. .

When the laminate of the present invention is used for an infusion bag, the polyolefin layer (C) having good hygiene is on the inside, that is, the side in contact with the infusion, and the soft vinyl chloride resin layer (A) having good flexibility is on the outside. It is preferable to use it as a configuration.
As a molded object obtained from the laminated body of the present invention, as a preferable application other than the infusion bag, for example, a packaging material such as food or electronic parts can be mentioned.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In addition, the values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

In the examples and comparative examples of the present invention, the following raw materials were used.

-Evaluation of the laminate according to the first aspect of the present invention <Soft vinyl chloride resin layer (A)>
(Α-1) “1170M55” manufactured by Mitsubishi Chemical Corporation: soft vinyl chloride resin.

<Adhesive resin layer (B1)>
[Alicyclic polyester]
(A-1) A polyether ester block copolymer comprising a polymer of 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedimethanol as a hard segment and polytetramethylene ether glycol (number average molecular weight: 2000) as a soft segment. Polymer. The content of polytetramethylene ether glycol is 15% by weight. Melt flow rate measured at 230 ° C. and 2.16 kg load (kgf) 30 g / 10 min. Melting point 197 ° C.

[Aromatic polyester] (for comparative example)
(A-2) A block copolymer of polybutylene terephthalate and polytetramethylene ether glycol. Content of polytetramethylene ether glycol (number average molecular weight: 2000) is 77% by weight.

[Styrene elastomer]
(B-1) “KRATON (registered trademark) -G1645MO” manufactured by Kraton Japan Co., Ltd .: a styrene-butadiene-styrene hydrogenated block copolymer. It has the structure of the formula (1). Styrene (block P) content: 13% by weight (measured by ¹³ C-NMR), number average molecular weight: 64000.

(B-2) “H7125F” manufactured by Kuraray Co., Ltd .: Styrene-isoprene-butadiene-styrene hydrogenated block copolymer. It has the structure of the formula (1). Styrene (block P) content: 20% by weight (measured by ¹³ C-NMR), number average molecular weight: 82000.

(B-3) “KRATON (registered trademark) -G1641H” (for comparative example) manufactured by Kraton Japan Co., Ltd .: styrene-butadiene-styrene hydrogenated block copolymer. It has the structure of the formula (1). Styrene (block P) content: 33% by weight (measured by ¹³ C-NMR), number average molecular weight: 200000.

(B-4) “H7135” (for comparative example) manufactured by Kuraray Co., Ltd .: Styrene-isoprene-butadiene-styrene hydrogenated block copolymer. It has the structure of the formula (1). Styrene (block P) content: 30% by weight (measured by ¹³ C-NMR), number average molecular weight: 210000.

(B-5) “KRATON (registered trademark) -G1651” (for comparative example) manufactured by Kraton Japan Co., Ltd .: styrene-butadiene-styrene hydrogenated block copolymer. It has the structure of the formula (1). Styrene (block P) content: 33% by weight (measured by ¹³ C-NMR), number average molecular weight: 200000.

(B-6) “KRATON (registered trademark) -A1535HU” (for comparative example) manufactured by Clayton Japan Co., Ltd .: styrene- (butadiene-styrene) -styrene hydrogenated block copolymer. It has the structure of the formula (1). Styrene (block P) content: 18% by weight (measured by ¹³ C-NMR), number average molecular weight: 200000.

<Polyolefin layer (C)>
(Γ-1) “Zeras (registered trademark) 7025” manufactured by Mitsubishi Chemical Corporation: propylene-ethylene block copolymer, MFR (230 ° C., 2.16 kg) 1.6 g / 10 min)

Example 1-1
In advance, the alicyclic polyester polymer (a-1) and the styrene elastomer (b-1) were mixed with a twin-screw extruder (Nippon Steel Works, Ltd.) based on the blending ratio (parts by weight) shown in Table 1. The resin composition pellets used for the adhesive resin layer (B1) were obtained by melting and kneading at a set temperature of 200 ° C. using “TEX-30αII” (manufactured by cylinder 30 mm). Hereinafter, the pellets of the obtained resin composition are expressed as “β-1”.

[Adhesion to PVC] and [Adhesion to PP] Evaluation Using the materials for the soft vinyl chloride resin layer (A), the adhesive resin layer (B1) and the polyolefin layer (C), GSI Creos Co., Ltd., T-die Single layer films each having a thickness of 100 μm were obtained using a molding machine. The molding temperature was set to 190 ° C., and the molding speed was set to 5 m / min.
The single-layer film of the adhesive resin layer (B1) obtained above and the single-layer film of the soft vinyl chloride resin layer (A) or the polyolefin resin layer (C) are stacked and heated under the conditions of 210 ° C. and 2 kg / cm ^2. Sealing was performed.

A sample of the obtained laminated film was cut into a width of 15 mm, and a 180 ° peel test was performed at a speed of 100 mm / min in a 23 ° C. atmosphere.

The evaluation result of the laminated film of the adhesive resin layer (B1) and the soft vinyl chloride resin layer (A) is “adhesive to PVC”, and the laminated film of the adhesive resin layer (B1) and the polyolefin resin layer (C) is evaluated. The result was defined as “adhesiveness to PP”. The results are shown in Table 1.

[Japanese Pharmacopoeia Container Test]
Using the single-layer film of the adhesive resin layer (B1) obtained above, the item of “1.2 Elution Test” in the “7.02 Plastic Drug Container Test Method” of the 16th revision of the Japanese Pharmacopoeia Was evaluated. A case where all the standards were passed was indicated as “◯”, and a case where there was at least one rejected item was indicated as “X”. The evaluation results are shown in Table-1.

[Haze]
A single-layer film having a thickness of 100 μm for the soft vinyl chloride resin layer (A), the adhesive resin layer (B1), and the polyolefin layer (C) used in the above-described evaluation of adhesiveness was used. Haze was measured with a haze meter (product name: NDH2000) according to ISO 14782 (1999). The results obtained are shown in Table 2. In addition, it is evaluated that it is excellent in transparency, so that the value of haze is small, and the thing whose haze of the single layer film used as an adhesive resin layer is 30 or less is especially preferable.

(Example 1-2, Comparative Examples 1-1 to 1-6)
Resin composition pellets used for the resin composition (B1) were produced in the same manner as in Example 1-1 except that the raw materials used were as shown in Table 1.
In Comparative Examples 1-5 and 1-6, a-1 or a-2 was used as it was as the adhesive resin layer (B1).

Further, a laminate was produced in the same manner as in Example 1-1, and evaluation of “adhesiveness to PVC”, “adhesiveness to PP” and “Japanese Pharmacopoeia Container Test” was performed. The results are shown in Table 1.

[Evaluation of results 1]
As shown in Table 1, in Examples 1-1 and 1-2, the adhesion between each layer was good, and also passed in the Japanese Pharmacopoeia container test. Accordingly, it was confirmed that the laminate has sufficient physical properties and can be suitably used as a medical container.

Further, as shown in Table 2, in Example 1-1, all the layers exhibited good transparency. Usually, in a resin composition using a combination of a plurality of resins, the transparency deteriorates, but a single layer film using (β-1) corresponding to the adhesive resin layer (B1) in the present invention is good. Transparency.

Comparative Example 1-6 was evaluated as “x” in the “Japanese Pharmacopoeia Container Test” because it did not satisfy the standards in the potassium permanganate consumption test and the ultraviolet absorption spectrum test.

-Evaluation of the laminate according to the second aspect of the present invention <Soft vinyl chloride resin layer (A)>
(A-1) “1170M55” manufactured by Mitsubishi Chemical Corporation: soft vinyl chloride resin.
<Adhesive resin layer (B2)>
(B-1) Cycloaliphatic Polyester A polymer comprising 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedimethanol as a hard segment and polytetramethylene ether glycol (number average molecular weight: 2000) as a soft segment Ether ester block copolymer. The content of polytetramethylene ether glycol is 15% by weight. Melt flow rate measured at 230 ° C. and 2.16 kg load (kgf) 30 g / 10 min. Melting point 197 ° C.

<Adhesive resin layer (B3)>
(C-1) “Zeras (registered trademark) MC748AP” manufactured by Mitsubishi Chemical Corporation: a resin composition containing a styrene elastomer and anhydrous maleic modified polypropylene. MFR (230 ° C, 2.16 kg) 2.0 g / 10 min)
(C-2) “Modic (registered trademark) F512” manufactured by Mitsubishi Chemical Corporation: polyolefin adhesive resin (modified polyolefin resin). MFR (190 ° C., 2.16 kg) 1.5 g / 10 min) (for comparative example)

<Polyolefin layer (C)>
(D-1) “Zeras (registered trademark) 7025” manufactured by Mitsubishi Chemical Corporation: propylene-ethylene block copolymer, MFR (230 ° C., 2.16 kg) 1.6 g / 10 min)

Example 2-1
[Adhesion evaluation]
Using the materials for the soft vinyl chloride resin layer (A), the adhesive resin layer (B2), the adhesive resin layer (B3), and the polyolefin layer (C), the thickness is 100 μm by GSI Creos and T-die molding machine. A single layer film was obtained. The molding temperature was set to 190 ° C., and the molding speed was set to 5 m / min.

By using these single-layer films, the adhesive strength between the respective layers was measured by the following method, thereby schematically evaluating the adhesive strength between the respective layers when the laminate was formed. That is, a single layer film of a soft vinyl chloride resin layer (A) and a single layer film of an adhesive resin layer (B2), a single layer film of an adhesive resin layer (B2) and a single layer film of an adhesive resin layer (B3), an adhesive resin One pair of single layer films of the single layer film of the layer (B3) and the single layer film of the polyolefin layer (C) were stacked, and heat-sealed under the conditions of 210 ° C. and 2 kg / cm ² .

A sample of the obtained laminated film was cut into a width of 15 mm, and a 180 ° peel test was performed at a speed of 100 mm / min in a 23 ° C. atmosphere. The results are shown in Table 2.

[Japanese Pharmacopoeia Container Test]
Using the single layer film of the adhesive resin layer (B2) or the adhesive resin layer (B3) obtained as described above, the “1. Evaluation of the item “2 eluate test” was performed. A case where all the standards were passed was indicated as “◯”, and a case where there was at least one rejected item was indicated as “X”. The evaluation results are shown in Table 2.

[Haze]
About each using the 100-micrometer-thick single-layer film for the soft vinyl chloride resin layer (A), the adhesive resin layer (B2), the adhesive resin layer (B3), and the polyolefin layer (C) used in the evaluation of adhesiveness. The haze was measured according to ISO 14782 (1999) using a haze meter (product name: NDH2000) manufactured by Nippon Denshoku Industries Co., Ltd. The results obtained are shown in Table 4. In addition, it is evaluated that it is excellent in transparency, so that the value of haze is small, and the thing whose haze of the single layer film used as an adhesive resin layer is 30 or less is especially preferable.

(Comparative Examples 2-1 to 2-4)
The adhesion between the respective layers was evaluated in the same manner as in Example 2-1, except that the layer configuration was as shown in Table 2. Further, in the same manner as in Example 2-1, the “Japanese Pharmacopoeia Container Test” was evaluated for the resin corresponding to the adhesive resin layer (B2) or the adhesive resin layer (B3). The results are shown in Table 3.

[Evaluation of results 2]
As shown in Table 3, in Example 2-1, the adhesion between the layers was good, and also passed in the Japanese Pharmacopoeia container test. Therefore, it was confirmed that the laminate had sufficient physical properties and could be used as a medical container without problems.

Furthermore, as shown in Table 4, Example 2-1 showed good transparency in any layer. Usually, in a resin composition using a combination of a plurality of resins, transparency is deteriorated, but a single layer film using (C-1) corresponding to the adhesive resin layer (B3) in the present invention is good. Transparency.

On the other hand, in Comparative Examples 2-1 to 2-3, the adhesion between the layers was poor, so that the physical characteristics as a laminate could not be satisfied. In Comparative Example 2-4, in the “Japanese Pharmacopoeia Container Test”, the test for the consumption of potassium permanganate and the test for the ultraviolet absorption spectrum did not satisfy the standard, and the result was “x”.

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2011-091395) filed on April 15, 2011 and a Japanese patent application (Japanese Patent Application No. 2011-128696) filed on June 8, 2011. , Which is incorporated by reference in its entirety.

Claims

It has a soft vinyl chloride resin layer (A), an adhesive resin layer (B1) containing an alicyclic polyester and a styrene elastomer, and a polyolefin layer (C), and the melting point of the alicyclic polyester is 130 to 200 ° C. And the number average molecular weight of this styrene-type elastomer is 190,000 or less, The laminated body characterized by the above-mentioned.
The laminate according to claim 1, wherein in the adhesive resin layer (B1), the alicyclic polyester has a unit derived from 1,4-cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol.
In the adhesive resin layer (B1), the alicyclic polyester comprises a segment mainly composed of units derived from 1,4-cyclohexanedicarboxylic acid and units derived from 1,4-cyclohexanedimethanol, and a polyalkylene ether. The laminated body of Claim 1 or 2 which has a polyol segment.
In the adhesive resin layer (B1), the styrene elastomer comprises 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. A block copolymer comprising 5 to 55% by weight of a polymer block P and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer. The laminate according to Item 1.
A laminate having a soft vinyl chloride resin layer (A), an adhesive resin layer (B2), an adhesive resin layer (B3), and a polyolefin layer (C) in this order, and the adhesive resin layer (B2) is an alicyclic type A laminate comprising polyester, wherein the adhesive resin layer (B3) contains a styrene elastomer and a modified polyolefin resin.
The laminate according to claim 5, wherein, in the adhesive resin layer (B2), the alicyclic polyester has a unit derived from 1,4-cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol.
In the adhesive resin layer (B2), the alicyclic polyester comprises a segment mainly comprising units derived from 1,4-cyclohexanedicarboxylic acid and units derived from 1,4-cyclohexanedimethanol, and a polyalkylene ether. The laminated body of Claim 5 or 6 which has a polyol segment.
The laminate according to any one of claims 1 to 7, wherein the polyolefin layer (C) is an ethylene resin and / or a propylene resin.
A medical container comprising the laminate according to any one of claims 1 to 8.
An infusion bag comprising the laminate according to any one of claims 1 to 9 as a constituent.
A resin composition comprising an alicyclic polyester and a styrene elastomer, wherein the alicyclic polyester has a melting point of 130 to 200 ° C., and the styrene elastomer has a number average molecular weight of 190,000 or less.
The resin composition according to claim 11, wherein the alicyclic polyester has a unit derived from 1,4-cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol.
The alicyclic polyester has a segment mainly composed of a unit derived from 1,4-cyclohexanedicarboxylic acid and a unit derived from 1,4-cyclohexanedimethanol, and a polyalkylene ether polyol segment. 12. The resin composition according to 12.
The styrenic elastomer comprises at least two polymer blocks P mainly composed of vinyl aromatic compounds and at least one polymer block Q mainly composed of butadiene and / or isoprene. The resin composition according to any one of claims 11 to 13, which is a block copolymer occupying ˜55% by weight and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer.